EP0713539A1

EP0713539A1 - Phosphate treatment process for steel strip with one galvanised surface

Info

Publication number: EP0713539A1
Application number: EP94924298A
Authority: EP
Inventors: Klaus Bittner; Walter K.M. Jansen; Klaus-Peter Mohr; Thomas Wendel; Hardy Wietzoreck
Original assignee: Metallgesellschaft AG
Current assignee: Chemetall GmbH
Priority date: 1993-08-06
Filing date: 1994-07-29
Publication date: 1996-05-29
Anticipated expiration: 2014-07-29
Also published as: ATE170931T1; DE59406893D1; DE4326388A1; JPH09501202A; ES2122318T3; EP0713539B1; US5795408A; JP3372954B2; ZA945881B; WO1995004842A1; CN1131444A

Abstract

PCT No. PCT/EP94/02510 Sec. 371 Date Jul. 8, 1996 Sec. 102(e) Date Jul. 8, 1996 PCT Filed Jul. 29, 1994 PCT Pub. No. WO95/04842 PCT Pub. Date Feb. 16, 1995The process forms a phosphate coating on a steel strip or sheet having a galvanized or alloy galvanized side and a steel side so that the phosphate coating is only present on the galvanized or alloy galvanized side. This process includes contacting the galvanized or alloy galvanized side of the steel strip or sheet with a phosphatizing solution for 4 to 20 seconds at a temperature of from 45 DEG C. to 80 DEG C. The phosphatizing solution has an S value of from 0.08 to 0.30 and contains 0.5 to 5 g/l zinc, 3 to 20 g/l P2O5, 0.020 to 0.2 g/l nitrite, 3 to 30 g/l nitrate and 0.2 to 2.5 g/l complexing agent for iron. Chelate forming substances, such as tartaric acid, citric acid, ethylenediamine-tetraacetic acid, nitrilotriacetic acid and/or oxalic acid, may be used as the complexing agent for iron. The phosphatizing solutions may also contain other bivalent cations, particularly manganese and/or nickel cations.

Description

Process for the phosphating treatment of one-sided galvanized steel strip

The invention relates to a method for the phosphating treatment of one-sided galvanized or alloy-galvanized steel strip or sheet with the aid of phosphating solutions which contain zinc, nitrate and nitrite.

The phosphating of metals pursues the goal of producing firmly adherent metal phosphate layers on the metal surface, which in themselves improve the corrosion resistance and, in conjunction with paints and other organic coatings, contribute to a significant increase in the adhesion and resistance to infiltration when exposed to corrosion. In addition, phosphate layers serve as insulation against the passage of electrical currents and, in conjunction with lubricants, to facilitate sliding processes.

For the pretreatment before painting, the low-zinc phosphating processes are particularly suitable, in which the phosphating solutions contain comparatively low zinc ion contents of e.g. B. 0.5 to 1.5 g / 1 (DE-C-22 32 067, EP-B-39 093). Under these conditions, phosphate layers with a high content of phosphophyllite (Zn-Fe (P0 ₄ ) ₂ • 4 H ₂ 0) are produced on steel, which is considerably more corrosion-resistant than the hopite (Zn- (PO.) ~ • deposited from zinc-rich phosphating solutions. 4 H ₂ 0). By using nickel and / or manganese ions in the

Low-zinc phosphating solutions can further increase the protection quality in connection with paints (EP-A-228 151, EP-B-414 296, EP-B-414 301, EP-A-544 650, DE-A-39 18 136) . Low zinc process with the addition of z. B. 0.5 to 1.5 g / 1 manganese ions and z. B. 0.3 to 2.0 g / 1 of nickel ions are widely used as a so-called trication process for preparing metal surfaces for painting, for example for the cathodic electrocoating of car bodies.

Especially for the phosphating of electrolytically galvanized or hot dip galvanized steel strip

Procedures have been developed that involve the training of a

Allow phosphate layer within short treatment times. For example, it is from the

DE-A-32 45 411 known, in particular electrolytically galvanized steel strips with a phosphate layer

To provide 2 layer weight below 2 g / m, using solutions that are about 1 to

Contain 2.5 g / 1 zinc ions, content of free

Acidity of 0.8 to 3 points and an acid ratio

Have total acid / free acid from 5 to 10. The duration of treatment should not be significantly longer

5 seconds. Another method for

Phosphating of electrolytically and / or hot-dip galvanized steel strip provides for phosphating solutions to be applied over a period of 2 to 30 seconds in the temperature range from 40 to 70 ° C., which contain 0.02 to 0.75 g / 1 zinc, 0.2 to

2.0 g / 1 manganese, 0.1 to 2.0 g / 1 nickel, 10 to

Contain 20 g / 1 phosphate and 0.5 to 30 g / 1 nit ions. The free acid content in the

Range from 1.6 to 3.0 points, the content of Total acid in the range from 12 to 40 points and the weight ratio of nickel ions to nitrate ions in the range from 1:10 to 1:60 and the weight ratio of manganese ions to nitrate ions in the range from 1: 1 to 1:40 (DE-A-39 27 131).

Insofar as the aforementioned phosphating solutions which permit short-term treatment and which are galvanized on both sides or hot-dip galvanized are used, there are no major complications. In recent times, however, steel strips that are only galvanized on one side are increasingly being used, particularly in the automotive industry. However, when the abovementioned short-term processes are applied to strips galvanized on one side, there is a strong formation of phosphate sludge in the phosphating solution, which interferes to this extent. In addition, phosphate layer formation begins on the steel side, which is particularly undesirable if subsequent phosphating, e.g. the automobile body, is intended.

The object of the invention is to provide a method for the phosphating treatment of one-sided galvanized or alloy-galvanized steel strip or sheet, which largely suppresses sludge formation, prevents the formation of a phosphate layer on the steel side, and the formation and quality of the phosphate layer on the galvanized or alloy-galvanized steel side is not impaired and is nevertheless simple and economical to carry out the process. The object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the galvanized or alloy-galvanized steel strip or sheet is baked for 4 to 20 seconds with a solution of a temperature of 45 to 80 ° C. Brings contact that

0.5 to 5 g / 1 zinc

3 to 20 g / 1 P ₂ 0-.

0.005 to 0.2 g / 1 N0 ₂

3 to 30 g / 1 N0 ₃

0.2 to 2.5 g / 1 complexing agent for iron

contains an S-value of 0.08 to 0.30 and in the case of the phosphating treatment of hot-dip galvanized or hot-dip galvanized steel strip or sheet, an additional content of 0.2 to 4 g / 1 complex and / or simple fluoride (calc. as F).

In the design of the present invention, it was found that in the above-mentioned measurement of the concentrations of complexing agents for iron and nitrite, the iron going from the non-galvanized or alloy-galvanized side of the steel strip or sheet is largely bound in a complex manner. A layer formation on the steel side cannot be determined. The formation of phosphate sludge in the phosphating solution is completely prevented or reduced to a value that makes up a maximum of 10% of the otherwise observed amount of sludge. The desired phosphating result on the galvanized or alloy-galvanized side is not affected. The limits of the specified ranges for complexing agents are important insofar as too high complexing agent concentrations impair the formation of the phosphate layer by complexing the layer-forming cations. If the amount of complexing agent added is too low, phosphate sludge formation in the phosphating solution and starting phosphate layer formation on the steel side cannot be avoided. With a higher or lower setting of the nitrite concentration, the phosphating on the galvanized or alloy-galvanized steel side and the complexation of the detached iron can be adversely affected. So z. B. with an excessive nitrite concentration, an incipient layer formation on the steel side cannot be avoided. Such beginning layer formation can impair the subsequent phosphating in the automotive plant, but in any case leads to undesirable sludge formation.

In order to prevent the nitrite concentration from rising above the upper limit as a result of autocatalytic nitrite formation at normal throughput, it will usually be necessary to take suitable countermeasures. A particularly suitable countermeasure is to keep the nitrite concentration of the phosphating solution within the limits mentioned by means of nitrite-degrading substances such as urea and / or amidosulfonic acid. This can be done by continuous or discontinuous addition. A particularly elegant method provides for the nitrite concentration to be kept within the required limits by having a urea concentration of 1 to 3 g / l and / or in the phosphating solution Amidosulfonic acid concentration of 0.5 to 2 g / 1. This creates a steady state in that as much nitrite is broken down by the urea or amidosulfonic acid content as is produced by autocatalysis.

The steel strips or sheets to be used within the method according to the invention can have layers of electrolytic zinc (ZE), hot zinc (Z), or alloys based on zinc / nickel (ZNE), zinc / iron (ZF) or zinc / Have aluminum (ZA or AZ). The latter are usually alloys with z. B. 55 wt .-% Al and 45 wt .-% Zn counted.

A preferred embodiment of the invention consists in bringing the galvanized or alloy-galvanized steel strip or sheet into contact with a phosphating solution which

1 to 2.5 g / 1 zinc

10 to 20 g / 1 P ₂ 0 ₅ 0.020 to 0.060 g / 1 N0 ₂

5 to 15 g / 1 N0 ₃

0.2 to 2.5 g / 1 complexing agent for iron

contains and has an S value of 0.12 to 0.20. This embodiment of the invention has the advantage that the sludge formation is particularly low and that good phosphate layers are also formed on the galvanized or alloy-galvanized side.

Particularly advantageous results are achieved if, according to an advantageous embodiment of the invention, the galvanized or alloy galvanized Steel strip or sheet is brought into contact with a solution which, as a complexing agent, contains chelating agents such as tartaric acid, citric acid,

Ethylenediaminetetraacetic acid, nitrilotriacetic acid and / or oxalic acid contains. The contents of the phosphating solutions in the aforementioned complexing agents should preferably be used

0.5 to 2.5 g / 1 tartaric acid

0.2 to 0.4 g / 1 citric acid

0.2 to 2.5 g / 1 nitrilotriacetic acid or

Ethylenediaminetetraacetic acid

(calculated as

Ethylenediaminetetraacetic acid)

be.

The quality of the phosphate layer produced can be improved if, in accordance with a further embodiment of the invention, the galvanized or alloy-galvanized steel strip or sheet is brought into contact with a phosphating solution which contains further divalent cations, in particular manganese and or nickel ions. In this case it is advantageous to reduce the concentrations in the phosphating solution to 1 to 3 g / 1, in particular 1.5 to 2.5 g / 1 of manganese ions, and / or 0.1 to 2.5 g / 1, in particular 0, Adjust 5 to 1.5 g / 1 nickel ions.

Because of the need for the higher aggressiveness of the phosphating solution, it is essential in the treatment of hot-dip galvanized or hot-dip galvanized steel strip or sheet to work with phosphating solutions which contain complex and / or simple fluoride. According to a further advantageous embodiment of the invention, however, phosphating solutions which contain complex and / or simple fluoride, preferably in amounts of 0.1 to 3 g / l (calculated as F ), contain. Fluoroborate, fluorosilicate, is a complex fluoride. Fluorotitanate and / or fluorozirconate preferred.

The phosphating treatment of the strip or sheet can be carried out by conventional methods, that is to say in immersion or spraying. However, it is particularly advantageous to apply the solution by spraying.

The phosphating solution is usually supplemented by a supplementary concentrate, with the control e.g. B. is done automatically via a conductivity measurement. A suitable supplement concentrate contains e.g. B. 10 to 30 wt .-% P ₂ ° 5 ' ^{3 to 20 wt} - ^{-% N0} 3 ^and ° to 2 wt .-% zinc. The zinc content in the supplemental concentrate depends essentially on the reactivity of the zinc or alloy zinc layer on the steel strip or sheet. If this layer has a higher reactivity and thus larger amounts of zinc get into the bath due to the pickling attack of the phosphating solution, a supplementary solution with lower zinc concentrations within the range of 0 to 2% by weight is possible. In an extreme case, ie in particular in the case of a phosphating treatment immediately after galvanizing the steel strip, the supplemental concentrate can also be zinc-free.

In the preferred embodiment of the method according to the invention - with a content of Phosphating solution on nickel and / or manganese ions - the supplementary concentrate also contains 0.2 to 2% by weight of nickel and / or 1 to 4% by weight of manganese.

In principle, the supplementary solution can also already contain the complexing agent for iron and, if necessary, the N0 ₂ -degrading substance; however, for reasons of better adjustability of the required concentrations, it will generally be preferable to supplement these two substances separately.

With the help of the method according to the invention

Generates phosphate layers whose layer weight is about 1

Is 2 to 2 g / m.

The invention is illustrated by the following example, for example and in more detail.

Example:

Immediately after the electrolytic galvanizing of steel strip, phosphating was carried out with a solution which had the following components:

Zinc: 1.8 g / i

P ₂ 0 ₅ : 14.5 g / i

Nickel: 1.3 g / i

Manganese: 2.0 g / i

Tartaric acid: 1 g / i

Urea: 1 g / i

N0 ₃ : 7 g / i

NO-: 0.040 g / i The S value of the phosphating solution was 0.17 and the temperature of the phosphating solution was set at 50 to 55 ° C. The application was carried out by spraying for 8 seconds.

The phosphating treatment was carried out over a period of time

3 out of 16 hours with a bath size of 25 m. Thereafter, a wet sludge amount of 2 ml / 1

Phosphating solution determined. This corresponds to approx.

2 0.6 ml of sludge per m of penetrated steel surface.

On the zinc side there was a flawless one

Phosphate layer formed, its layer weight

2 was 1.6 g / m. The steel side was in perfect condition

Condition, d. H. showed practically none

Layer training.

In a comparison test without adding

Complexing agent and NO - degrading substance, but otherwise under the same conditions, came about

Wet sludge accumulation of 28 ml / 1 phosphating solution.

2 This corresponds to approximately 8.4 ml of sludge per m of steel surface penetrated. The layer weight on

2 of the zinc side was 1.6 g / m, the

The steel side, however, showed a beginning

Phosphate layer formation.

Claims

1. A method for the phosphating treatment of one-sided galvanized or alloy-galvanized steel strip or sheet with the aid of phosphating solutions containing zinc, nitrate and nitrite, characterized in that the one-sided galvanized or alloy-galvanized steel strip or sheet for a period of 4 to 20 seconds in contact with a phosphating solution at a temperature of 45 to 80 ° C, which

0.5 to 5 g / 1 zinc

3 to 20 g / 1 P ₂ 0 ₅

0.005 to 0.2 g / 1 N0 ₂

3 to 30 g / 1 N0 ₃

0.2 to 2.5 g / 1 complexing agent for iron

contains, an S-value of 0.08 to 0.30 and in the case of the phosphating treatment of hot-dip galvanized or hot-dip galvanized steel strip or sheet, an additional content of 0.2 to 4 g / 1 complex and / or simple fluoride (calc. as F).

2. The method according to claim 1, characterized in that the one-sided galvanized or alloy galvanized steel strip or sheet is brought into contact with a phosphating solution, the nitrite concentration of urea and / or amidosulfonic acid in the range of 0.005 to

0.2 g / 1 is kept. A method according to claim 2, characterized in that the one-sided galvanized or alloy galvanized steel strip or sheet is brought into contact with a phosphating solution, the nitrite concentration of which is adjusted by setting a urea concentration of 1 to 3 g / 1 and / or an amidosulfonic acid concentration of 0.5 to 2 g / 1 is kept within the limits of 0.005 to 0.2 g / 1.

Method according to claim 1, 2 or 3, characterized in that the one-sided galvanized or alloy-galvanized steel strip or sheet is brought into contact with a phosphating solution which

1 to 2.5 g / 1 zinc

10 to 20 g / 1 P ₂ 0 ₅

0.020 to 0.060 g / 1 N0 ₂

5 to 15 g / 1 N0 ₃

0.2 to 2.5 g / 1 complexing agent for iron

contains, and has an S-value of 0.12 to 0.20.

Method according to one or more of Claims 1 to 4, characterized in that the steel strip or sheet which is galvanized or alloy-galvanized on one side is coated with a

Brings in contact phosphating solution which contains chelating agents, such as tartaric acid, citric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid and / or oxalic acid, as complexing agents. A method according to claim 5, characterized in that the one-sided galvanized or alloy galvanized steel strip or sheet is brought into contact with a phosphating solution which

0.5 to 2.5 g / 1 tartaric acid

0.2 to 0.4 g / 1 citric acid

0.2 to 2.5 g / 1 nitrilotriacetic acid or

Ethylenediaminetetraacetic acid

(calculated as

Ethylenediaminetetraacetic acid)

contains.

Method according to one or more of claims 1 to 6, characterized in that the one-sided galvanized or alloy-galvanized steel strip or sheet is brought into contact with a phosphating solution which contains further divalent cations, in particular manganese and / or nickel ions.

Process according to claim 7, characterized in that the one-sided galvanized or alloy-galvanized steel strip or sheet is brought into contact with a phosphating solution which contains 1 to 3 g / 1, preferably 1.5 to 2.5 g / 1 manganese and / or 0 , 1 to 2.5 g / 1, preferably 0.5 to 1.5 g / 1 nickel. 9. The method according to one or more of claims 1 to 8, characterized in that the one-sided galvanized or alloy galvanized steel strip or sheet is brought into contact with a phosphating solution, the complex and / or simple fluoride, preferably in amounts of 0.1 to 3 g / 1 (calculated as F).

10. The method according to claim 9, characterized in that the one-sided galvanized or alloy galvanized steel strip or sheet is brought into contact with a phosphating solution which contains as a complex fluoride, fluoroborate, fluorosilicate, fluorotitanate and / or fluorozirconate.

11. The method according to one or more of claims 1 to 10, characterized in that the one-sided galvanized or alloy galvanized steel strip or sheet is brought into contact with the phosphating solution by spray treatment.