EP2243863A1

EP2243863A1 - Continuous chemical patination/satinising treatment process for zinc-titanium alloys

Info

Publication number: EP2243863A1
Application number: EP10159892A
Authority: EP
Inventors: Ernesto Caldana; Angelo Grandini; Matteo Damiani; Marco Bianchi
Original assignee: Simar - Metalli Marghera SpA Soc; NP Coil Dexter Industries SRL
Current assignee: Simar - Metalli Marghera SpA Soc; NP Coil Dexter Industries SRL
Priority date: 2009-04-21
Filing date: 2010-04-14
Publication date: 2010-10-27
Anticipated expiration: 2030-04-14
Also published as: IT1393946B1; EP2243863B1; ITMI20090665A1

Abstract

Disclosed is a continuous chemical patination/satinising treatment process for zinc-titanium alloys, comprising the following stages:
- degreasing with alkaline grease-removal liquid in aqueous solution;
- first rinse with continuously fresh water;
- acid treatment involving chemical patination/satinising;
- second rinse with continuously fresh water;
- pre-passivation treatment with a chromium-free bath containing zirconium and/or titanium and aluminium compounds;
- air drying;
- passivation treatment comprising a first stage of treatment with a conventional inorganic component based on chromium 3 and/or 6 or chromium-free, and a second stage of treatment with an antifinger agent consisting of an aqueous solution of an acrylic resin consisting of monomers based on butylacrylate, methylmethacrylate and acrylic acid, having the following characteristics:
pH < 6; MW ≥ 250000; TG (glass transition temperature) between 30 and 45°C; dry residue between 30 and 50%, possibly mixed with corrosion inhibitors such as zinc oxide and P₂O₅;

- drying of wet film.

Description

The present invention relates to a continuous chemical patination/satinising treatment process for zinc-titanium alloys used in the construction industry, in particular for roofs, facades, guttering, interiors or architectural works.

Prior art

Zinc-titanium alloy laminates are widely used in the construction industry, especially for roofing and cladding. The natural appearance of these claddings can be varied by particular pre-patination surface treatments.
Said processes must give coil surfaces having a chemical composition complying with Standard EN 988 - 1998 (see Table 1) an attractive appearance with a patinated effect, specific colouring, such as antique-look zinc, excellent antifinger properties, and high corrosion resistance. Table 1

Element Standard EN 988 - 1998

Al < 0.0150%

Cu 0.0800 - 1.0000%

Pb < 0.0030%

Cd < 0.0030%

Fe < 0.0020%

Sn < 0.0010%

Ti 0.0600 - 0.2000%
The known process normally comprises the following stages:

degreasing with an alkaline grease-removal liquid in aqueous solution
first rinse with continuously fresh water
acid treatment involving chemical patination/satinising with specific products
second rinse with continuously fresh water
final passivation treatment
drying of wet film.

EP 827785 describes a process for the treatment of zinc-titanium laminates characterised by the use of a pickling bath based on nitric and sulphuric acid and a passivation stage with a polymer containing chromate.

Disclosure of the invention

An improved process has now been found which is characterised, after the second rinse with water, by a pre-passivation stage followed by drying with hot air to prevent the formation of surface zinc oxides, and the use of a polyacrylic resin as antifinger agent in the final passivation treatment.
The process of the invention comprises the following stages in particular:

degreasing;
first rinse with continuously fresh water;
acid treatment involving chemical patination/satinising;
second rinse with continuously fresh water;
pre-passivation treatment with a chromium-free bath containing zirconium and/or titanium and aluminium compounds;
air drying;
passivation treatment comprising a first stage of treatment with a conventional inorganic component based on chromium 3 and/or 6 or chromium-free, and a second stage of treatment with an antifinger agent consisting of an aqueous solution of an acrylic resin consisting of monomers based on butylacrylate, methylmethacrylate and acrylic acid, having the following characteristics:
- pH < 6;
- MW ≥ 250000;
- TG (glass transition temperature) between 30 and 45°C;
- dry residue between 30 and 50%;
possibly mixed with corrosion inhibitors such as zinc oxide and P205;
drying of wet film.

Degreasing serves to eliminate all trace of oils, fats, cleaning paste, oxides and any other impurities from the coil surface, in order to have a perfectly clean metal surface ready for subsequent treatments.
Normally, said degreasing is performed with liquid products in aqueous solution at an alkaline pH (10-14). The use concentration is between 1% and 10%, and the temperature of the working bath between 50°C and 70°C, for a treatment time of between 5 and 40 seconds, with spray pressures of between 1 and 4 bars. The main elements of the degreasing bath are listed in Table 2 below. Table 2

Element Concentration

KOH or NaOH 2 - 20 g/l

P₂O₅ 2 - 20 g/l

Surfactants 200 - 3000 ppm

Sequestering additives 1 - 10 g/l
P₂O₅ is present either as orthophosphates (monosodium, disodium or trisodium phosphate) or as polyphosphates (tripolyphosphate or neutral pyrophosphate), all in the form of sodium or potassium salts.
The most commonly used surfactants are ethoxylated fatty alcohols with alcohol C9-C11 chain, C12-C13 or C12-C18, having different degrees of ethoxylation or containing different numbers of ethylene oxide moles.
The sequestering additives are organic compounds selected from nitriloacetic acid, sodium gluconate, gluconic acid, ethylenediaminetetraacetic acid disodium, ethylenediaminetetraacetic acid trisodium, phosphonates, acrylates and polyacrylates.
The first rinse with continuously fresh water serves to eliminate all trace of the preceding stage; the temperature is normally between 30°C and 60°C, with times ranging between 5 and 30 seconds, and spray application.
The chemical patination/satinising treatment is performed by pickling the zinc-titanium alloy with a surface attack between 5 and 20 g/m².
The treatment is usually performed with a specific product at a pH of between 0 and 2, used at concentrations of between 10 and 15%. The temperature of the working bath can be between 50% and 70%, for a reaction time of between 10 and 30 seconds; the spray pressures must be between 1 and 4 bars.

The main elements of the patination/satinising bath are listed in Table 3 below.

Table 3

Element	Concentration
H₂SO₄	10-150 g/l
Surfactants	1 - 15 g/l
Process accelerant as NO₃	100 - 6000 ppm
Sequestering agents	1 -100 g/l
Elements deriving from pickling of the alloy
Zn	< 100 g/l
Other metals originating from the alloy	< 100 mg/l

The process accelerator can consist of NO₃ donor compounds such as nitric acid, ammonium nitrate, nickel nitrate, sodium nitrate, zinc nitrate, iron nitrate or cobalt nitrate, or nitrogenous organic compounds such as nitroguanidine, used alone or mixed together. The surfactants and agents are the same as already described.
The second rinse with continuously fresh water is performed as for the first rinse, to eliminate all trace of the preceding stage; the temperature is normally between 30°C and 60°C, with times ranging between 5 and 30 seconds, and spray application.
Pre-passivation, which prevents the formation of zinc-oxides on the surface by increasing the anti-corrosion properties of the coil, is performed by treatment with a chromium-free bath containing zirconium and/or titanium and aluminium compounds.
The typical composition of a pre-passivation bath according to the invention is set out in Table 4 below. The concentration of the product ranges between 1 and 5%, the temperature between 30 and 60°C, and the treatment times between 1 and 10 seconds; the product can be applied by spraying or immersion, and the pH value is < 5. Table 4

Element Concentration

Zr 100 - 5000 mg/l

Ti 100 - 5000 mg/l

Al 10 - 500 mg/l

NH₃ 100 - 1000 ppm
The zirconium compounds are preferably selected from fluorozirconic acid, ammonium zirconium carbonate and potassium fluozirconate; the aluminium compounds are selected from aluminium oxide of various extractions (aluminas), aluminium fluoride and aluminium bifluoride; the titanium compounds are selected from fluotitanic acid, titanium oxalate, titanium oxide and potassium fluotitanate.
Drying is then performed with hot air from 50 to 90°C.

Final passivation treatment

The antifinger passivating product is applied with a Chem-Coater machine in two separate application stages, with a wet film drying step between each stage.
The inorganic component is applied at the first stage. Depending on the process required, the inorganic component can be one of three different types:

"Chromium 3 - Chromium 6 Version" (Version 1)

The product consists of chromic acid, chromium phosphate, corrosion inhibitors such as zinc phosphate and zinc chromate, and reducing agents such as gluconic acid, citric acid, saccharose, hydroxylamine, methanol, hydrogen peroxide and starch. The application takes place continuously at a temperature of between 15°C and 40°C; the concentration used depends on the wet film applied, which ranges between 2 and 10 ml/m²; it is generally between 10 and 50%, so that the end result is a total chromium deposit of 20 to 100 mg/m²; its value is calculated from the mg of chromium, on the basis that 1 mg/m² of Cr = 16 mg/ m² of total coating.
An example of the composition of the bath is shown in Table 5 below. Table 5

Element Concentration

Total chromium (= chromium 3 + chromium 6) 5 - 20%

P₂O₅ 1 - 5%

Zinc 2 - 8%

"Chromium 3 Version" (Version 2)

The product consists of phosphoric acid, chromium phosphate, chromium nitrate, complexing agents selected from salified phosphonates or acids, gluconic acid, citric acid, tartaric acid, EDTA, glycolic acid and/or polyacrylates, corrosion inhibitors such as colloidal silicon dioxides in suspension, possibly having different particle sizes, generally below 30 µm, and with a SiO₂ content of between 10 and 50%, and finally, organic wetting agents based on alkoxypolypropoxypolyethoxy-ethyl-benzylether or belonging to the perfluoroderivative family. The application takes place continuously at a temperature of between 15°C and 40°C; the concentration used depends on the wet film applied, which ranges between 2 and 10 ml/m²; it is generally between 30 and 70%, so that the end result is a total chromium deposit of 30 to 80 mg/m²; its value is calculated from the mg of chromium, on the basis that 1 mg/m² of Cr = 32 mg/ m² of total coating.
An example of the composition of the bath is shown in Table 6 below. Table 6

Element Concentration

Total chromium (= chromium 3) 20 - 200 g/l

P₂O₅ 10-150 g/l

NO₃ 3 - 50 g/l

SiO₂ 20 -200 g/l

"Chromium-free - Chromium Version" (Version 3)

The product consists of silanes, selected from the families of 1-propylamine,3-(triethoxysilyl)-silane and trimethoxy[3-(oxiranylmethoxy)-propyl]-silane, titanium salts deriving from fluotitanic acid, titanium oxalate, titanium oxide or potassium fluorotitanate, alkaline phosphates such as monobasic or dibasic ammonium phosphate, mono-, bi- or tribasic sodium phosphate, acid or neutral potassium pyrophosphate, alkaline nitrates such as ammonium nitrate, sodium nitrate or potassium nitrate, sequestering agents selected from nitriloacetic acid, sodium gluconate, gluconic acid, ethylenediaminetetraacetic acid disodium, ethylenediaminetetraacetic acid trisodium, phosphonates, acrylates and polyacrylates, and corrosion inhibitors based on heavy metals such as vanadium, molybdenum, tungsten and cerium. The product should be applied at room temperature, in concentrations ranging between 80 and 100%, in such a way that the titanium deposit is between 4 and 8 mg/m² and the SiO₂ deposit between 70 and 140 mg/m²; its value is calculated from the mg of titanium, on the basis that 1 mg/m² of Ti = 160 mg/m² of total coating.
An example of the composition of the bath is shown in Table 7 below. Table 7

Element Concentration

SiO₂ 10 - 150 g/l

P₂O₅ 10-150 g/l

V ≤ 100 ppm

Ti ≤ 200 ppm
Drying is then performed with hot air from 50 to 90°C.
An antifinger agent is applied at the second stage, namely an aqueous solution of corrosion inhibitors such as zinc oxide and P₂O₅ and an acrylic resin consisting of monomers based on butylacrylate, methylmethacrylate and acrylic acid, having the following characteristics:

pH < 6; MW ≥ 250000; TG (glass transition temperature) between 30 and 45°C; dry residue between 30 and 50%.

In the case of version 1 only, the antifinger passivation product can also be applied in a single stage, with a Chem-Coater machine. Depending on the final chromium deposit desired, the bath is prepared with 1 part inorganic to 2 parts organic component, or 1 part inorganic to 3 parts organic component. The quantity of mixture applied is 2 to 6 ml/m². There is a partial reduction of chromium from 6 to 3 during this stage.
The wet film is then dried at a belt temperature of 80 to 140°C.

Laboratory test procedures

Degreasing:

Element	Concentration
KOH	4 g/l
P₂O₅ from neutral potassium pyrophosphate	5 g/l
Surfactants with C9-C11 chain + 5 and 6 moles of OE = ethylene oxide	500 ppm
Sodium gluconate	3 g/l

Use concentration of product	3 - 5%
Temperature	50 - 60°C
Treatment time	10 sec.
Spray pressure	2 bars

First rinse

Continuously fresh water	-
Temperature	30°C
Treatment time	10 sec.
Spray pressure	2 bars

Chemical patination/satinising treatment:

Element	Concentration
H₂SO₄	60 g/l
HNO₃	6 g/l
Surfactants with C9-C11 chain + 5 and 6 moles of OE = ethylene oxide	1500 ppm
Sodium gluconate	10 g/l

Use concentration of product	10%
Temperature	60 - 70°C
Treatment time	10 sec.
Spray pressure	2 bars

Second rinse

Pre-passivation

Element	Concentration
Zr (from fluorozirconic acid)	500 mg/l
Ti (from fluotitanic acid)	300 mg/l
Al (from alumina)	50 mg/l
NH₃	50 ppm

Use concentration of product	2 - 3%
Temperature	50°C
Treatment time	2 sec.
pH	4

Drying is typically performed with hot air at a temperature of between 60 and 80°C.

Final passivation

First stage: "Chromium 3 - Chromium 6 Version"

Element	Concentration
Total chromium (= chromium 6 + chromium 3)	13%
P₂O₅	3%
Zinc	3%

Reducing agent used	starch
Wet film applied	1 - 4 ml/m²
Temperature	room

First stage: "Chromium 3 version"

Element	Concentration
Total chromium (= chromium 3)	40 g/l
P₂O₅	20 g/l
NO₃	5 g/l
SiO₂	40 g/l

Complexing agent used	Citric acid
Type of silica used	Particle size 15 µm - dry 30%
Type of wetting agent	perfluoroderivative
Wet film applied	1 - 4 ml/m²
Temperature	room

First stage: "Chromium-free version"

Element	Concentration
SiO₂ (from 1-propylamine,3-(triethoxysilyl)-silane and/or trimethoxy[3-(oxiranylmethoxy)propyl]-silane	100 g/l
P₂O₅ (from monobasic ammonium phosphate)	20 g/l
V	100 ppm
Ti (from fluotitanic acid)	200 ppm

Complexing agent used	phosphonate
Nitrate used	ammonium nitrate
Type of inhibitor selected	vanadium
Temperature	room

Second stage: all versions.

Resin used	Pure acrylic, new formulation, inhibited, with dry residue = 30%, pH = 4, TG = 32°C
Wet film applied	3-6 ml/m²

Single-stage application: "Chromium 3 - Chromium 6 Version"

Dose ratios	Inorganic ingredient 1 part -
	Organic ingredient 2 parts

	Inorganic ingredient 1 part -
	Organic ingredient 3 parts
Wet film applied	3 - 4 ml/m²
Temperature	room

Drying can be performed with hot air at a temperature of between 100 and 120°C.

Examples

The laboratory tests were performed to compare the results obtained with (i) cycles not including the pre-passivation stage (conventional cycle) and (ii) other cycles which were identical to the preceding ones except that they included the pre-passivation stage and subsequent drying.
Two-stage application of the final passivating product and single-stage application were tested in the cycles relating to the "Chromium 3 - Chromium 6 version"; 1:2 and 1:3 dose ratios of the two components were tested in the latter case.
Both the above-mentioned silanes, subsequently marked α and β, were tested in the cycles relating to the "chromium-free version", both separately and in combined.
Only the acrylic resin according to the invention was used in the organic component of the final passivation stage in all the cycles.

For convenience, the way in which the various cycles tested were marked is shown in Table 8 below.

Table 8

Code	Pre-passivation	Passivation version	Passivation	Component dose ratio	Type of silane
A 1	No	1	Biphasic
A 1.2	No	1	Monophasic	2 : 1
A 1.3	No	1	Monophasic	3 : 1
A 2	No	2	Biphasic
A 3.1	No	3	Biphasic		α
A 3.2	No	3	Biphasic		β
A 3.3	No	3	Biphasic		α + β
B 1	Yes	1	Biphasic
B 1.2	Yes	1	Monophasic	2 : 1
B 1.3	Yes	1	Monophasic	3 : 1
B 2	Yes	2	Biphasic
B 3.1	Yes	3	Biphasic		α
B 3.2	Yes	3	Biphasic		β
B 3.3	Yes	3	Biphasic		α + β

After application of the cycles, the zinc-titanium alloy panels treated were subjected to corrosion-resistance tests in a salt spray (fog) chamber, in accordance with Standard ASTM B 117, unprotected panels and panels with protected edges being checked for the appearance of the first white oxides.
Table 9 shows the results obtained, expressed as hours of exposure before the appearance of the first white oxidation phenomena. Table 9

Code Hours of exposure Code Hours of exposure

A 1 72 B 1 96

A 1.2 72 B 1.2 96

A 1.3 72 B 1.3 96

A 2 60 B 2 72

A 3.1 60 B 3.1 72

A 3.2 60 B 3.2 72

A 3.3 72 B.3.3 96

Claims

A process of continuous chemical patination/satinising treatment of zinc-titanium alloys comprising the following stages:
- degreasing with alkaline grease-removal liquid in aqueous solution;

- first rinse with continuously fresh water;

- chemical acid patination/satinising treatment;

- second rinse with continuously fresh water;

- pre-passivation treatment with a chromium-free bath containing zirconium and/or titanium and aluminium compounds;

- air drying;

- passivation treatment comprising a first stage of treatment with a conventional inorganic component based on chromium 3 and/or 6 or chromium-free, and a second stage of treatment with an antifinger agent consisting of an aqueous solution of an acrylic resin consisting of monomers based on butylacrylate, methylmethacrylate and acrylic acid, having the following characteristics:
pH < 6;

MW ≥ 250000;

TG (glass transition temperature) between 30 and 45°C;

dry residue between 30 and 50%;
possibly mixed with corrosion inhibitors such as zinc oxide and P205;

- drying of wet film.
A process as claimed in claim 1, wherein the zirconium and/or titanium and aluminium compounds in the pre-passivation bath are selected from fluorozirconic acid, ammonium zirconium carbonate and potassium fluorozirconate; aluminium oxide of various extractions (aluminas), aluminium fluoride and aluminium difluoride; fluorotitanic acid, titanium oxalate, titanium oxide and potassium fluorotitanate.
A process as claimed in claim 1 or 2, wherein the passivation comprises treatment with a bath containing chromium 3 and chromium 6 compounds.
A process as claimed in claim 3, wherein the bath contains chromic acid, chromium phosphate, zinc phosphate and zinc chromate and reducing agents.
A process as claimed in claim 1 or 2, wherein the passivation comprises treatment with a bath containing chromium 3 compounds.
A process as claimed in claim 5, wherein the bath contains phosphoric acid, chromium phosphate, chromium nitrate, complexing agents, corrosion inhibitors and organic wetting agents based on alkoxypolypropoxypolyethoxy-ethyl-benzylether or belonging to the class of perfluoroderivatives.
A process as claimed in claim 1 or 2, wherein the passivation comprises treatment with a chromium-free bath.
A process as claimed in claim 7, wherein the bath contains silanes, selected from the classes of 1-propylamine,3-(triethoxysilyl)-silane and trimethoxy[3-(oxiranylmethoxy)propyl]-silane, titanium salts deriving from fluorotitanic acid, titanium oxalate, titanium oxide or potassium fluorotitanate, alkaline phosphates, alkaline nitrates, sequestering agents selected from nitriloacetic acid, sodium gluconate, gluconic acid, ethylenediaminetetraacetic acid disodium, ethylenediaminetetraacetic acid trisodium, phosphonates, acrylates, polyacrylates, and corrosion inhibitors based on heavy metals selected from vanadium, molybdenum, tungsten and cerium.