CA1206852A - Process and composition for phosphating metal surfaces - Google Patents

Process and composition for phosphating metal surfaces

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Publication number
CA1206852A
CA1206852A CA000450436A CA450436A CA1206852A CA 1206852 A CA1206852 A CA 1206852A CA 000450436 A CA000450436 A CA 000450436A CA 450436 A CA450436 A CA 450436A CA 1206852 A CA1206852 A CA 1206852A
Authority
CA
Canada
Prior art keywords
liter
nitrobenzenesulfonate
phosphating
weight
nitrite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA000450436A
Other languages
French (fr)
Inventor
Gerd Muller
Werner Rausch
Wolfgang Wuttke
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel Corp
Original Assignee
Parker Chemical Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Parker Chemical Co filed Critical Parker Chemical Co
Application granted granted Critical
Publication of CA1206852A publication Critical patent/CA1206852A/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical 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
    • C23C22/08Orthophosphates
    • C23C22/12Orthophosphates containing zinc cations
    • C23C22/13Orthophosphates containing zinc cations containing also nitrate or nitrite anions
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C22/00Chemical 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
    • C23C22/05Chemical 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
    • C23C22/06Chemical 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
    • C23C22/07Chemical 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
    • C23C22/08Orthophosphates
    • C23C22/12Orthophosphates containing zinc cations
    • C23C22/14Orthophosphates containing zinc cations containing also chlorate anions

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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)

Abstract

ABSTRACT OF THE DISCLOSURE

In a process for applying phosphate coatings to metal surfaces by means of nitrite-accelerated phosphating solutions based on zinc phosphate, the layer weight on iron or steel is reduced and controlled by bringing the metal surfaces in contact with a phosphating solution which addi-tionally contains a nitrobenzenesulfonate and in which the nitrobenzenesulfonate content is such that the weight of the resulting layer is less than 2 g/m2, preferably less than 1.5 g/m .
The content of nitrobenzenesulfonate is greater than 100 mg/liter and that of nitrite should preferably be 10 to 300 mg/liter. The process according to the invention is applicable both to low zinc and high zinc phosphating solutions.

Description

Case: P30,029 ~Z~85Z

PROCESS AND COMPOSITION FOR Foisting METAL SURFACES

Background of the In notion The invention relates Jo a composition and process for applying phosphate coatings to metal surfaces by means ox nitrite-accelerated phosphating solutions based on zinc phosphate.
It is known to add nitrites, in particular alkali metal nitrites to aqueous acid solutions of zinc phosphate in order to accelerate layer formation and to oxidize the dissolved iron into the trivalent form (German Patent Specifications 845,135 and 907,966~ German Auslegeschriften 1,031,083 and 1~277,645 and German Offenlegungsschrift 1,771,769)~ The processes are used in industry on a large scale. They are distinguished by a high speed of phosphating, but give phosphate layers having relatively high weights per unit area, unless special layer-improving substances, for example polyphosphates (German Auslegeschrift 1,062,083), are added.
Admittedly the weight of the phosphate layer can be somewhat reduced by the concomitant use of chlorates in nitrite-accelerated phosphating solutions German Auslegeschrift 1,521~678). However, this procedure has the disadvantage that I; major reductions in the weight of the layer are only possible using high concentrations of chlorate, and thereby the side reaction between chlorate and nitrite, with the formation of chloride and nitrate, assumes undesirably high proportions.
In a recent phosphating~process a mixture of chlorate and an organic vitro compound, for example a nitrobenzenesulfonate, is used for acceleration (European Laid-Open Specification 36,689).

,. . _ .

" .

I issue Thin, finely crystalline phosphate layers are produced by this means. Here too, however, a disadvantage is the accumulation of chloride in the treatment baths; in major amounts this can have an adverse effect on the quality ox the layer.
The object of the invention is to provide a process which does not have the disadvantages ox the known processes and which has a high accelerating effect and gives extremely finely gained, flexible phosphate layers having a low weight per unit area.

I
Summary of the Invention The object is achieved by modifying the process of the type initially mentioned, in accordance with the invention, in such a way that the metal surfaces are brought in contact lo with a phosphating solution which additionally contains a I` nitrobenzenesulfonate and in which the nitrobenzenesulfonate content is such that the weight of the resulting layer on iron or steel is less than 2 g/m2.
, Admittedly it is known from German Offenlegungsschrift ~3~004~927/ for a special, so-called low-zinc process, to employ a phosphating solution which also embraces the accelerator combination of a nitrite and an aromatic vitro compound, such as a nitrobenzenesulfonate. It is evident/ however, that neither the significance of precisely this special combination nor the possibility of being able to reduce the weight of the layer for iron or steel below 2 g/m2 by controlling the dosage of nitrobenzenesulfonate has been recognized (cf., in particular, also the illustrative embodiments in this text).
-2-: .

Detailed Description of the I've 8 52 The process according to the invention is intended particularly for the treatment of iron and steel. However, it is also suitable or phosphating zinc and aluminum materials and also steel using coatings produced by a very wide variety of processes and composed of zinc, zinc alloys, aluminum and aluminum alloys.
The treatment of the metal surfaces can be carried out by the spray-coating process, the flow-coating process and also by the dip-coating process. However, it is also applicable in combined procedures, for example spraying-dipping, dipping-spraying, spraying-dipping-spraying and the like.
The contact times for the phosphating solution with the metal surface are within the usual limits and can be, for example, 45 seconds to 3 minutes for spraying, 2 to 10 minutes for dipping and 20 seconds of spraying and 3 minutes of dipping for spraying-dipping.
The temperatures of the phosphating solutions used in the process according to the invention are usually between 30 and 60C. The lower the temperature, the longer the contact time must be, in general.
When carrying out phosphating of iron or steel with the accelerators nitrite and nitrobenzenesulfonate, it is possible to obtain the layer weights below 2 g/m which are desired in a particular case by suitable metering. Layer weights down to about 1 g/m2 can be obtained.

.
-3 With regard to particularly hug lily of the phosphate layer produced, as well as high gloss, but also a low consumption of chemicals, an advantageous embodiment of the invention envisages bringing the iron or steel surface in contact with a phosphating solution in which the nitrobenzenesulfonate content is such that the weight of the resulting layer on iron or steel is less than 1.5 g/m . It is advantageous for this purpose to bring the metal surfaces into contact with a phosphating solution in which the content of nitrobenzenesulfonate is at least 300 mg/liter.
The contents of the individual active ingredients of the bath vary within the customary limits. The nitrite content is preferably within the range from 10 to 300 mg/liter. The upper limit for the nitrobenzenesulfonate content is about 2 g/liter. Higher contents are associated in practice with no additional effect.
The nitrite and nitrobenzenesulonate accelerators are usually added to the phosphating bath in the form of their alkali metal salts. The nitrobenzenesulfonate can however, also be added in the form of the corresponding sulfonic acid. In special cases it is possible to generate the nitrite within the phosphating bath by auto catalytic formation from nitrate and, if necessary, to add nitrite separately only when starting the phosphating baths after prolonged interruptions in working.
The aqueous acid solutions, to be used within the scope of the invention, based on zinc phosphate contain primary zinc phosphate and a certain amount of free acid, this amount being adjusted to the particular bath concentration, mode of use .

issue and bath -temperature. Depending on the process conditions, the pi of the-baths it, for instance, between 2.0 and 3.9.
The baths can also contain further cations which are known in the technology of phosphating, for example Nix Co, Cut My, Cay My, Fe, Nay K, H, NH4 and others. In order to adjust the acidity and to achieve special technical effects it can be necessary or desirable to use concomitantly further anions other than phosphate, for example NO, C103, Of, Suave F, BF4, Sift, citrate, tart rate and others.
lo It has been found, surprisingly, that the accelerator combination nitrite/nitrobenzenesulfonate is effective in the same manner either in conjunction with the suckled low-zinc technology or in conjunction with the standard zinc technology.
Accordingly, advantageous embodiments of the invention envisage bringing the metal surfaces in contact with a phosphating solution in which the ratio by weight of Zen to P205 has been adjusted to l : I to 85), or bringing the metal surfaces in contact with a phosphating solution in which the ratio by weight of Zen to P205 has been adjusted to l : (OWE to 7).
In the first case, phosphate layers containing a high proportion of phosphophyllite to hopeite are produced on steel.
Because of their excellent resistance to corrosion, these coatings are particularly suitable as a preparatory measure for painting, the best protective properties being achieved in conjunction with cathodic application of paint by electrode position.
In the second case the result is phosphating processes which are distinguished by a higher speed of phosphating compared with the low zinc processes. The phosphate layers produced by I: ' sluice these processes possess good properties for a broad spectrum of use in the fields of corrosion resistance and cold deformation without machining.
The process according to the invention is exemplified and illustrated in detail on the basis of the hollowing examples.

Examples:
Steel sheets were degrade in an aqueous alkaline cleansing agent, rinsed with water and then treated by spraying with various phosphating solutions for 2 minutes at 55C.

Bath solution 1:
1.4 g/liter of Zen 0.4 g/liter of No 17.8 g/liter of P205 6.0 g/liter of NO
100 mgjliter of NO as Nina + Noah to adjust the phosphating equilibrium.
Added quantity of No nutria benzenesulfonate (mg/liter) 0 200 400 600 800 Weight of phosphate layer (g/m ) 4.1 3.9 2.9 1.7 1.3 Appearance of the phosphate layer: increase in fineness of grain I with increasing amount of nitrobenzenesulfonate .

Bath solution I 685~
. . .
0.8 g/liter of Zen 0.5 g/liter of No 1.5 g/liter of Clue 14 g/liter of P205 2 g/liter of N03 100 mg/liter of N02 as Nina + Noah to adjust the phosphating equilibrium.
Added quantity of No m-nitrobenzenesulfonate (mg/liter) o 100 200 30V 400 500 Weight of phosphate layer (g/m ) 2.5 2.1 1.8 1.6 1.4 1.2 Appearance of the 15 phosphate layer: increase in fineness of grain with increasing amounts of nitrobenzenesulfonate Bath solution 3:
3 g/liter of Zen 20 0.012 g/liter of No 1.5 g/liter of Clue 7.2 g/liter f~P205 :: 1.3 g/liter of N03 133 mg/liter of NO as Nina + Noah to adjust the phosphating equilibrium.
Added quantity of No m-nitrobenzenesulfonate (mg/liter) 0 100 200 300 400 500 700 Weight of phosphate layer ~g/m2) 3.5 3.1 2.6 2.2 1.9 1.6 1.2 7_ I
Appearance of the phosphate layer: increase in fineness of grain with increasing amounts of nitrobenzenesul~onate Bath solution 4:
3.2 g/liter of Zen 6.8 g/liter of P205 2~6 g/liter of N03 150 mg/liter of N02 as Nina Noah to adjust the phosphating equilibrium.
Added quantity of No m-nitrobenzenesulfonate (mg/liter) o 100 200 400 600 800 Weight of phosphate layer (g/m2) 3.8 3.5 3.2 2.5 2.0 1.4 : Appearance of the phosphate layer: increase in fineness of grain with increasing amounts of nitrobenzenesulfonate "Bath solution 1" and "bath solution 2" correspond to low-zinc technology, while "bath solution 3" and "bath solution 4"
: correspond to standard zinc technology. The data shows that, ; within both procedures, the controlled addition of nitrobenzene-~;~ 25 sulfonate is effective in the same manner and is associated with I: a considerable reduction in the layer weight.

:

:

:

Claims (8)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows.
1. A process for applying phosphate coatings to metal surfaces by means of nitrite-accelerated phosphating solutions based on zinc phosphate, which comprises bringing the metal surfaces in contact with a phosphating solution which additionally contains a nitrobenzenesulfonate compound in an amount so that the weight of the resulting layer on iron or steel is less than 2 g/m2.
2. The process as in Claim 1, wherein the nitro-benzenesulfonate content is an amount such that the weight of the resulting layer is less than 1.5 g/m2.
3. The process of Claim 1, wherein the content of nitrobenzenesulfonate is greater than 100 mg/liter.
4. The process of Claim 1, wherein the nitrite content is 10 to 300 mg/liter.
5. The process of Claim 1, wherein the weight ratio of Zn to P2O5 is 1 : (8 to 85).
6. The process of Claim 1, wherein the weight ratio of Zn to P2O5 is 1 : (0.3 to 7).
7. An aqueous acidic composition comprising in dis-solved form zinc, phosphate, nitrite and a nitrobenzenesulfonate compound in an amount sufficient to generate a coating weight less than 2 g/m when contacted with an iron or steel surface.
8. The composition of Claim 7, wherein the nitro-benzenesulfonate compound is present in a content greater than 100 mg/l.
CA000450436A 1983-03-31 1984-03-23 Process and composition for phosphating metal surfaces Expired CA1206852A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP3311738.1 1983-03-31
DE19833311738 DE3311738A1 (en) 1983-03-31 1983-03-31 METHOD FOR PHOSPHATING METAL SURFACES

Publications (1)

Publication Number Publication Date
CA1206852A true CA1206852A (en) 1986-07-02

Family

ID=6195182

Family Applications (1)

Application Number Title Priority Date Filing Date
CA000450436A Expired CA1206852A (en) 1983-03-31 1984-03-23 Process and composition for phosphating metal surfaces

Country Status (9)

Country Link
EP (1) EP0121274A1 (en)
AU (1) AU2629184A (en)
BR (1) BR8401487A (en)
CA (1) CA1206852A (en)
DE (1) DE3311738A1 (en)
ES (1) ES531002A0 (en)
GB (1) GB2137231B (en)
PT (1) PT78335B (en)
ZA (1) ZA842173B (en)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3408577A1 (en) * 1984-03-09 1985-09-12 Metallgesellschaft Ag, 6000 Frankfurt METHOD FOR PHOSPHATING METALS
US5234509A (en) * 1984-12-20 1993-08-10 Henkel Corporation Cold deformation process employing improved lubrication coating
CA1257527A (en) * 1984-12-20 1989-07-18 Thomas W. Tull Cold deformation process employing improved lubrication coating
US4595424A (en) * 1985-08-26 1986-06-17 Parker Chemical Company Method of forming phosphate coating on zinc
USRE35958E (en) * 1985-08-26 1998-11-17 Henkel Corporation Method of forming phosphate coating on zinc
GB8523572D0 (en) * 1985-09-24 1985-10-30 Pyrene Chemicals Services Ltd Coating metals
DE3630246A1 (en) * 1986-09-05 1988-03-10 Metallgesellschaft Ag METHOD FOR PRODUCING PHOSPHATE COVER AND ITS APPLICATION
US5236565A (en) * 1987-04-11 1993-08-17 Metallgesellschaft Aktiengesellschaft Process of phosphating before electroimmersion painting
DE3712339A1 (en) * 1987-04-11 1988-10-20 Metallgesellschaft Ag METHOD FOR PHOSPHATIZING BEFORE ELECTROPLATING
DE3871031D1 (en) * 1987-08-19 1992-06-17 Metallgesellschaft Ag METHOD FOR PHOSPHATING METALS.

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2884351A (en) * 1956-01-25 1959-04-28 Parker Rust Proof Co Method of cold rolling ferrous strip stock
FR1258855A (en) * 1960-02-18 1961-04-21 Parker Ste Continentale Advanced process for phosphating metal surfaces
FR2110784A5 (en) * 1970-10-30 1972-06-02 Parker Ste Continentale
NL7114590A (en) * 1971-10-22 1973-04-25
SE441105B (en) * 1976-04-05 1985-09-09 Amchem Prod PROCEDURE FOR PREPARING AN AMORPH, LIGHT, HARD FIXED PHOSPHATE COATING
GB1542222A (en) * 1977-01-06 1979-03-14 Pyrene Chemical Services Ltd Phosphate coating compositions
JPS5456038A (en) * 1977-10-12 1979-05-04 Nippon Paint Co Ltd Controlling method for acidic phosphate film forming liquid
DE2908376C2 (en) * 1979-03-03 1985-09-26 Akzo Gmbh, 5600 Wuppertal Process for making an antistatic carpet fiber
DE3016576A1 (en) * 1980-04-30 1981-11-05 Metallgesellschaft Ag, 6000 Frankfurt METHOD FOR PHOSPHATING METAL SURFACES AND THE USE THEREOF
US4498935A (en) * 1981-07-13 1985-02-12 Parker Chemical Company Zinc phosphate conversion coating composition

Also Published As

Publication number Publication date
AU2629184A (en) 1984-10-04
ES8504270A1 (en) 1985-05-01
GB2137231B (en) 1986-06-18
ES531002A0 (en) 1985-05-01
EP0121274A1 (en) 1984-10-10
PT78335A (en) 1984-04-01
DE3311738A1 (en) 1984-10-04
BR8401487A (en) 1984-11-13
ZA842173B (en) 1984-10-31
GB8408006D0 (en) 1984-05-10
GB2137231A (en) 1984-10-03
PT78335B (en) 1986-04-30

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