CN1047537A - Zinc phosphide combination and method - Google Patents

Zinc phosphide combination and method Download PDF

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Publication number
CN1047537A
CN1047537A CN90103728A CN90103728A CN1047537A CN 1047537 A CN1047537 A CN 1047537A CN 90103728 A CN90103728 A CN 90103728A CN 90103728 A CN90103728 A CN 90103728A CN 1047537 A CN1047537 A CN 1047537A
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Prior art keywords
aqueous composition
oxyamine
composition
ion
amount
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Pending
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CN90103728A
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Chinese (zh)
Inventor
汤姆斯·W·突尔
鲍尔·A·库龙欧斯基
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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
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations 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
    • C23C22/07—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
    • C23C22/22—Orthophosphates containing alkaline earth metal cations

Abstract

Contain in the zinc phosphatization liquid of the promotor beyond the hydroxyl-removal amine and can reduce its recrement growing amount greatly by adding the 0.02-0.4wt% oxyamine.

Description

Zinc phosphide combination and method
The application is the unsettled U.S. Patent application No.06/834 that submitted on February 24th, 1986,491 part continuation application, and its whole disclosures are for this reference.
The present invention relates at iron, form the improved method of phosphoric acid zinc protective layer on steel and other metal products surface.These layers are enough all even can to form the effectively lubricating matrix when fine and close before follow-up drawing or similar forming process.More particularly, the present invention relates to decrease in the phosphatization operation treatment solution composition and the method for slag shape amount.
Metal phosphorizing liquid is widely used at metal products, particularly forms coating on iron and the carbon steel product surface.Metal phosphorizing liquid is generally phosphoric acid and other chemical, often comprises zinc, the dilute aqueous soln of calcium and other metal ion, and by dip-coating, spraying or similar fashion can contact it with the metallic surface.Metallic surface and this solution reaction and under proper condition this reaction can form various metals from the teeth outwards, an if phosphating metal part, then often comprise some iron, and the monoblock coating of the insoluble basically crystal phosphoric acid salt of any metal that exists as positively charged ion in the solution.
The coating of Xing Chenging can be used as subsequent paint like this, effective matrix of lubricant and other material.Anticorrosion in the various environment that these coatings often can usually be in when metal products is used, And stops the metal below it to be corroded.These coatings are used widely industrial having obtained.
The mature special application field of phosphate coating is manufactured to draw the metal with other similar forming operation, wherein requires to reduce surface friction.Among some this class is used, found to contain the cationic phosphatization liquid of zinc and calcium and be better than most other phosphatization liquid.For example, the USP 4,688,411 that authorized Hagita etal on August 25th, 1987 has illustrated the application of blending calcium and zinc phosphatization liquid, and wherein the ratio of calcium/zinc is 0.3-1 down for 70-90 ℃.Shown in Figure 4 as this Hagita patent, the ratio of calcium/zinc is big more, and the coating wt that then any non-zero reached in the concrete treatment time is just low more.
The known oxyamine of can using in phosphatization liquid promotes phosphating reaction in this specialty, thus can be under specified criteria with other not the similar solution of hydroxyl amine compare and increase phosphate coating formation amount in the phosphatization liquid of hydroxyl amine.
Except its require effect and, during using, all known phosphatization liquid all can generate the waste material that this specialty is commonly referred to as " sludge ", non-miscible compound of the metal phosphate that is settled out when using for phosphatization liquid and other material sometimes must be removed this waste material in case of necessity to reach gratifying operate continuously.Surpass certain level if sludge gathers, then wherein a part of regular meeting is bonded at some by on the phosphating metal goods, thereby forms nonconforming surface blot on these goods.Get rid of sludge expense costliness, because the toxic metal ion of its middle and high concentration has environmental practice by the current law requirement.Therefore, recrement formation amount is the very high target of improvement phosphating process in the minimizing operation.
Clear and definite opposite explanation is arranged in operational example in addition and, all numerical value that inventory or reaction or application conditions be described herein need be interpreted as " approximately ".
Found that the lubricated required phosphate coating of gratifying pre-drawing can be at 3-15g/m 2Low coating wt in the coat weight range on surface in formation and this scope is more preferred sometimes, as long as it is just feasible to have formed continuous fine and close phosphate layer.Also find zinc phosphatization liquid, comprise going back existing limited amount oxyamine can reduce sludge formation amount in the operation greatly in calcic and/or some other metal ion solution, and can not bring disadvantageous effect simultaneously to phosphating process.
One of preferred embodiment of the invention is pH1-3.7, the more preferably phosphatization liquid of 2.5-3.5, comprising or more preferably it becomes following composition substantially mutually: (A) 1-4wt% zine ion; (B) maximum 3wt% calcium ions; (C) 1-7.5wt% phosphate radical; (D) 0.02wt% oxyamine at least; (E) hydroxyl-removal amine and outer promotor is known for this specialty wherein can comprise more than one chemical of effective promotion amount; (F) about at most 0.1wt% nickel and/or copper positively charged ion; (G) about at most 0.2wt% manganese positively charged ion; And (H) water.Herein, all to be interpreted as be phosphoric acid and the non-PO that becomes the various ion sums of acid composition in the solution to any " phosphate radical " amount -3 4The stoichiometry equivalent.And, should see also there is the corresponding ion that must occur in the solution of the present invention that this does not chemically have harm in parkerizing process, corresponding to it is said any composition that occurs with ionic forms.
Preferred accelerators is a nitrate radical, is the 1-7.5wt% of phosphatization liquid.Other suitable promotor include but not limited to inferior sulfate radical, picratol, vanadate, and/or molybdate.
In above-mentioned preferred compositing range, the total amount of nickel and copper positively charged ion is 0.001-0.01wt% more preferably, and most preferably value is 0.006wt%.If calcium ion exists in solution, then its concentration is preferably 0.5wt% at least.
The oxyamine amount preferably should make all oxyamines all be replaced and by solution generate at least 50% the sludges of its amount for the displaced equal zinc phosphatization liquor ratio hydroxyl amine of nitrite anions of the 3wt% that replaced oxyamine more, wherein in the phosphated metal surfaces of equivalent.The oxyamine of the no more than 0.4wt% of general preferred employing in the solution, and the most preferably value of oxyamine is 0.05wt%.
Can adopt immersion with hydroxyl amine phosphatization liquid of the present invention to the processing of metallic surface, spray, associated form, or any other can reach the method for effective contact, and it is identical that temperature, time and other treatment condition solution general and that this specialty usefulness contains isoconcentration same metal ion and other promotor are carried out parkerized condition.And bonderizing of the present invention is other known process steps of coupling advantageously, as cleaning before the phosphatization, pickling and conditioning operation and phosphatization post-flush, chromium phosphoric acid or other coating Passivation Treatment, be coated with lubricant, japanning etc. all carry out in the mode that this specialty is known.
The suitable practicality of special composition in the phosphatization liquid of the present invention and preferred source are known in that this specialty is known.For example, oxyamine preferably derives from storage stability salt or title complex, wherein severally puts goods on the market.Most preferably be the sulfuric acid oxyamine, being also referred to as the sulfuric acid oxyamine sometimes is (NH with basic chemical formula 2OH) 2(H 2SO 4) or (NH 3OH) 2SO 4Oxyamine.The sulfuric acid oxyamine is designated hereinafter simply as " HAS ".
The method that the recrement volume that produces between the phosphatization liquid usage period is known with this specialty is measured.In general, from carry out this process vessel, take out the aliquot sample liquid, note guaranteeing being representative sample.To contain waiting separatory to change in the transparent conical graduate and being allowed to condition in the environment under the influence of gravity sedimentation about 24 hours of suspended solids.This sedimentation operates in and produces a boundary line that is easy to discern between container bottom and the liquid layer.On the scale marks of container, can read the recrement amount.
Phosphatization liquid typical of the present invention produces 7-11ml sludge/m 2Phosphating metal, and common phosphoric acid zinc coating liquid produces 14-25ml sludge/m 2Phosphating metal.
Below the present invention is described in detail in detail with non-limiting operational example.
Example 1-5
These example explanation phosphatization liquid method for making of the present invention and application.These solution composition such as tables 1 are done the zinc source with zinc oxide, make the nitric acid root with nitric acid, and phosphoric acid is made the phosphoric acid root, and calcium hydroxide is as calcium ion source, and nickelous nitrate is as nickel ion source, and HAS is as the oxyamine source.Use some result such as table 2 of these solution.
Example 6-7 and comparative example 1C-3C
The solution composition of these examples sees Table 3.Adopt the described identical component of example 1-5 source, and make the nitrous acid root with Sodium Nitrite.
Comparative example is all used solution well known in the prior art.Comparative example 1C carries out high coating wt phosphatization with common zinc solution, and 2C hangs down the coating wt coating with common solution, in two examples all without calcium.Comparative example 3C calcic, but other quite is bordering on 1C.All these comparative examples contain nitrite as promotor.Coupling nitrate.
Some that obtains with these solution the results are shown in Table 4.Example 7 usefulness are equal to the solution of comparative example 3C, and just oxyamine replaces with nitrite anions in comparative example 3C solution in example 7 solution; Used nitrite anions amount is the 3wt% that is replaced the oxyamine amount.Basic identical with phosphate coat weight and quality that two kinds of solution obtain, but the recrement amount has reduced more than 40% in example 7.Example 6 understood with comparative example 1C comparison sheet generally speaking use high zinc: it is basic identical that calcium reaches true effect than solution.
Example 8
This example has illustrated integrated processes, comprises using phosphatization liquid of the present invention, and this is effective especially when making follow-up drawing or cold-drawing technology with steel pipe or line.
Steel should advance to clean to guarantee removing all greases and oil, generally are to adopt this professional known tensio-active agent.After crossing tensio-active agent, reusable heat water is rinsed well.Also have indentation or rust staining if go up on the surface, then use conventional pickling and handle, preferably in thermal resistance sulfuric acid or hydrochloric acid, carry out.After the pickling, metal must be rinsed well, pollutes phosphatization liquid to prevent too many acidic substance.The twice water flushing washing is carried out in suggestion, uses cold water for the first time, for the second time on demand with hot water or cold water.
After the flushing, metal is immersed in the phosphatization liquid of the present invention like this, keep about 71-93 ℃, and in solution, stop about 30 seconds to about 5 minutes to obtain requiring coating.Preferred coatings weight depends on the accurate composition of pending metal, pretreatment operation, and pending following process on the metal to be treated, and mode is generally those skilled in the art and knows.
In more preferred, in stainless steel processing jar, will prepare separately to cooperate and promptly can be made into phosphatization liquid with additive liquid.In typical facility, in this jar, be filled with water to 3/4ths of its volume, add 12.2 gallons of preparation liquid composed as follows then and promptly can be made into 100 gallons of working fluids.Afterwards about 3.7 gallons of additive liquid composed as follows are finished the preparation process of phosphatization mixture.
The preparation liquid of this preferred embodiment is by 87.5 parts of zinc oxide, 2.3 part contains the nickel nitrate aqueous solution of 13.7wt% nickel ion, 211.0 part of 75% phosphate aqueous solution, 6.0 parts of HAS, form with 113 parts of 42 ° of Baume nitric acid, all the components is dissolved in the enough water to reach 1000 parts altogether.Additive liquid is 261.7 parts of calcium hydroxides and 665.4 parts of 42 ° of Baume nitric acid are mixed with enough water and to reach 1000 parts altogether.(owning " parts " in this section all by weight).
After carrying out phosphate coat, treatment articles fully washes and removes and prevent anyly may carry phosphatization liquid secretly.Coat suitable lubricant with the soap aqueous solution then.The goods that obtain so just can make its drawing that meets with stresses or the operation of other forming process.
In this method operation, gather some recrements.This should regularly remove before polluting on the coating reaching q.s.And when using continuously, concentration can change, and should be equipped with every locating to add more above-mentioned additive liquid to compensate some former variation with composition in phosphatization liquid at reasonable time.
Table 1
Solution composition among the example 1-5
Each composition weight percent of composition
1 2 3 4 5
Zine ion 1.3 1.7 2.0 2.1 2.7
Calcium ion 1.3 0.9 0.7 0.5 does not have
Nickel ion 0.006 0.006 0.006 0.006 0.006
Nitrate radical 3.5 3.5 3.5 3.5 3.5
Phosphate radical 3.3 3.3 3.3 3.3 3.3
Oxyamine 0.05 0.05 0.05 0.05 0.05
All the other are water
Table 2
Example 1-5 floating coat weight and sludge volume sludge volume
Example coating wt g/m 2Ml/m 2
1 3-5 10
2 8-10 10
3 9-13 11
4 12-15 10
5 12-20 9
Table 3
Solution composition among example 6-7 and the 1c-3c
Composition
6 1C 2C 3C 7
Zine ion 1.5 3.0 1.9 1.2 1.2
Calcium ion 0.8 does not have 1.2 1.2
Nickel ion 0.006 0.006 0.006 0.006 0.006
Nitrate radical 4.3 3.6 2.9 4.7 4.7
Phosphate radical 3.4 3.4 0.6 3.2 3.2
Oxyamine 0.05 does not have 0.05
Nitrite anions does not have .0015 .0015 .0015 and does not have
Table 4
Example 6-7 and 1C-3C floating coat weight and sludge volume
The sludge volume
Example coating wt g/m 2Ml/m 2
6 8-10 8.4
1C 9-14 14
2C 6-9 25
3C 4-8 14
7 4-8 7.9

Claims (20)

1, metal surface phosphating aqueous composition, the about 1-of its PH about 3.7, comprising (A) at least about the 1wt% zine ion; (B) maximum 3wt% calcium ions; (C) 1wt% phosphate radical at least; (D) 0.02wt% oxyamine at least; (E) effectively promotion amount hydroxyl-removal amine and outer promotor; (F) about at most 0.1wt% is selected from the positively charged ion of nickel and copper; (G) about at most 0.2wt% manganese positively charged ion; And (H) water, this aqueous composition feature is that this aqueous composition and another composition are compared, another composition is called and substitutes composition, its composition is same as this aqueous composition substantially, just all oxyamine content all replace with nitrite anions in this aqueous composition, its amount is about 3wt% of the oxyamine that replaced, measure under the same terms in the time of relatively, comprise the recrement amount that each composition equal volume is produced when carrying out phosphatization under about 71-93 ℃ the phosphatization temperature on the equal area surface of metal of the same race, substitute the recrement amount that composition produces and Duo 50% at least than the recrement amount of this aqueous composition generation.
2, the aqueous composition of claim 1 is comprising altogether at least about the positively charged ion that is selected from nickel and copper of 0.001wt%.
3, the aqueous composition of claim 2, the about 2.5-of its pH is about 3.5, comprising the about 4wt% zine ion of about 1-; The about 7.5wt% phosphate radical of about 1-; The about 0.4wt% oxyamine of about 0.02-; With the about 7.5wt% nitrate radical of about 1-.
4, the aqueous composition of claim 1 is comprising about 1-4wt zine ion; The about 7.5wt% phosphate radical of about 1-; The about 0.4wt% oxyamine of about 0.02-; With the about 7.5wt% nitrate radical of about 1-.
5, the aqueous composition of claim 4 is comprising the about 3wt% calcium ion of about 0.5-.
6, the aqueous composition of claim 3 is comprising the about 3wt% calcium ion of about 0.5-.
7, the aqueous composition of claim 6 is comprising about 0.05wt% oxyamine.
8, the aqueous composition of claim 5 is comprising about 0.05wt% oxyamine.
9, the aqueous composition of claim 4 is comprising about 0.05wt% oxyamine.
10, the aqueous composition of claim 3 is comprising the 0.05wt% oxyamine.
11, metal contacted with aqueous composition and make the method for its phosphatization, the about 1-of this aqueous composition pH about 3.7, comprising zine ion, phosphate radical, hydroxyl-removal amine and outer promotor, and water, its improvement is that this aqueous composition also contains at least about the 0.02wt% oxyamine and it is characterized in that this aqueous composition and another composition are compared, another composition is called and substitutes composition, its composition is same as this aqueous composition substantially, just all oxyamine content of this aqueous composition all replace with nitrite anions, its amount is about 3wt% of the oxyamine that replaced, measure under the same terms in the time of relatively, comprise the recrement amount that each composition equal volume is produced when carrying out phosphatization on the equal area surface of metal of the same race under about 71-93 ℃ the phosphatization temperature, substitute the recrement amount that composition produces and Duo 50% at least than the recrement amount of this aqueous composition generation.
12, the method for claim 11, wherein this aqueous composition also contains the positively charged ion that is selected from nickel and copper at least about 0.001wt%.
13, the method for claim 12, wherein the about 2.5-of this aqueous composition pH is about 3.5, comprising the about 4wt% zine ion of about 1-; The about 0.01wt% of about altogether 0.001-is selected from the positively charged ion of nickel and copper; The about 7.5wt% phosphate radical of about 1-; The about 0.4wt% oxyamine of about 0.02-; With the about 7.5wt% nitrate radical of about 1-.
14, the method for claim 11, wherein the about 2.5-of this aqueous composition pH is about 3.5, comprising the about 4wt% zine ion of 1-; The about 0.01wt% of about altogether 0.001-is selected from the positively charged ion of nickel and copper; The about 0.4wt% oxyamine of the about 0.02-of the about 7.5wt% phosphate radical of about 1-; With the about 7.5wt% nitrate radical of about 1-.
15, the method for claim 14, wherein this aqueous composition comprises the about 3wt% calcium ion of about 0.5-.
16, the method for claim 13, wherein this aqueous composition comprises the about 3wt% calcium ion of about 0.5-.
17, the method for claim 16, wherein this aqueous composition comprises about 0.5wt% oxyamine.
18, the method for claim 15, wherein this aqueous composition comprises about 0.5wt% oxyamine.
19, the method for claim 14, wherein this aqueous composition comprises about 0.5wt% oxyamine.
20, metal is contacted with aqueous composition so that the method for its phosphatization, the about 1-of this aqueous composition pH is about 3.7, comprising zine ion, and phosphate radical, hydroxyl-removal amine and outer promotor, and water, its improvement is that said parco-lubrizing produces about 13ml recrement/m 2Phosphated metal surfaces.
CN90103728A 1989-05-19 1990-05-19 Zinc phosphide combination and method Pending CN1047537A (en)

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US35455089A 1989-05-19 1989-05-19
US07/354,550 1989-05-19

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111009371A (en) * 2019-12-27 2020-04-14 浙江工业大学 Preparation method of soft magnetic composite material based on novel phosphating solution process

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5234509A (en) * 1984-12-20 1993-08-10 Henkel Corporation Cold deformation process employing improved lubrication coating
DE4210513A1 (en) 1992-03-31 1993-10-07 Henkel Kgaa Nickel-free phosphating process
DE19606018A1 (en) * 1996-02-19 1997-08-21 Henkel Kgaa Zinc phosphating with low levels of nickel and / or cobalt
DE19716075A1 (en) * 1997-04-17 1998-10-22 Henkel Kgaa Phosphating process accelerated with hydroxylamine and chlorate

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DE3407513A1 (en) * 1984-03-01 1985-09-05 Gerhard Collardin GmbH, 5000 Köln METHOD FOR ZINC-CALCIUM PHOSPHATION OF METAL SURFACES AT LOW TREATMENT TEMPERATURE
CA1257527A (en) * 1984-12-20 1989-07-18 Thomas W. Tull Cold deformation process employing improved lubrication coating
US4793867A (en) * 1986-09-26 1988-12-27 Chemfil Corporation Phosphate coating composition and method of applying a zinc-nickel phosphate coating
US4865653A (en) * 1987-10-30 1989-09-12 Henkel Corporation Zinc phosphate coating process

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111009371A (en) * 2019-12-27 2020-04-14 浙江工业大学 Preparation method of soft magnetic composite material based on novel phosphating solution process

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JP2994428B2 (en) 1999-12-27
AU5577890A (en) 1990-11-22

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