(19)

TEPZZ_55 Z¥5B_T
(11) EP 1 552 035 B1
(12) EUROPEAN PATENT SPECIFICATION

(45) Date of publication and mention (51) Int Cl.:

of the grant of the patent: C23C 22/34 (2006.01) C23F 3/06 (2006.01)
25.08.2010 Bulletin 2010/34 C23G 1/08 (2006.01)

(21) Application number: 03727360.4 (86) International application number:

PCT/EP2003/004306
(22) Date of filing: 25.04.2003
(87) International publication number:
WO 2004/035861 (29.04.2004 Gazette 2004/18)

(54) PICKLING SOLUTION AND PROCESS FOR STAINLESS STEEL

LÖSUNG UND VERFAHREN ZUM BEIZEN VON ROSTFREIEM STAHL
SOLUTION ET PROCEDE DE DÉCAPAGE D’ACIER INOXYDABLE

(84) Designated Contracting States: (56) References cited:

AT BE BG CH CY CZ DE DK EE ES FI FR GB GR EP-A- 0 167 751 EP-A- 0 505 606
HU IE IT LI LU MC NL PT RO SE SI SK TR EP-A- 0 582 121 EP-A- 0 596 273
EP-A- 0 769 574 WO-A-01/49899
(30) Priority: 15.10.2002 PCT/EP02/11483 BE-A- 1 003 954 DE-C- 19 828 811
GB-A- 1 449 525 US-A- 2 276 353
(43) Date of publication of application: US-A- 3 025 189 US-B1- 6 312 812
13.07.2005 Bulletin 2005/28
• PATENT ABSTRACTS OF JAPAN vol. 2002, no.
(73) Proprietor: Henkel AG & Co. KGaA 08, 5 August 2002 (2002-08-05) -& JP 2002 121689
40589 Düsseldorf (DE) A (KAWASAKI STEEL CORP;NEC CORP), 26 April
2002 (2002-04-26)
(72) Inventors: • G.KREYSA, M.SCHÜTZE: "Corrosion Handbook"
• GIORDANI, Paolo 1987, WILEY-VCH, 2004 DECHEMA E.V.,
I-26013 Crema (IT) SOCIETY FOR CHEMICAL ENGINEERING AND
• RIGAMONTI, Mauro BIOTECHNOLOGY , 60486 FRANKFURT (MAIN),
I-20090 Opera (IT) GERMANY 1 * page 300 - page 301 * * page 422 *
• GASPARETTO, Valentino
I-23887 Olgiate Molgora (IT)
EP 1 552 035 B1

Note: Within nine months of the publication of the mention of the grant of the European patent in the European Patent
Bulletin, any person may give notice to the European Patent Office of opposition to that patent, in accordance with the
Implementing Regulations. Notice of opposition shall not be deemed to have been filed until the opposition fee has been
paid. (Art. 99(1) European Patent Convention).

Printed by Jouve, 75001 PARIS (FR)

 EP 1 552 035 B1

Description

[0001] This invention relates to a process for pickling stainless steel. In general, technical steels are termed non-
rusting or stainless if rust formation is prevented under normal environmental conditions, for example in the presence
5 of atmospheric oxygen and moisture and in aqueous solutions. Most high-alloy, so-called corrosion-resistant or acid-
resistant steels withstand relatively severe corrosion conditions, for example acids and salt solutions. These steels are
generically referred to as special steels or stainless steels. A list of the technically most important special steels, together
with the material numbers, identifications and alloy components, as well as the mechanical and chemical properties
thereof are given in Ullmanns Encyklopädie der technischen Chemie, 4th Edition, Vol. 22, pp. 106-112 and in German
10 Industrial Standard DIN 17440, July 1985. Special steels are iron based alloys containing at least 10% chromium. The
formation of chromium oxide on the material surface imparts to the special steels the corrosion-resistant character thereof.
[0002] Special steels may be sub-divided into the following families: austenitic steels, ferritic steels, martensitic steels,
precipitation hardened steels and duplex steels. These groups differ in the physical and mechanical properties thereof,
as well as in corrosion resistance, as a result of the various alloying constituents. Austenitic special steels are listed as
15 special steels of the 200 and 300 Series. They are the most widely employed special steels and represent 65 to 85%
of the special steel market. They are chemically characterized by a chromium content of > 17% and a nickel content of
> 8%. They have a cubic face-centered structure and are outstandingly ductile and weldable. The most widely used of
these steels is probably Type UNS S 30400 (Type 304), or "18/8". Modifications include S 32100 (stabilized with titanium)
and S 34700 (stabilized with niobium). Alloys having higher contents of chromium, nickel or molybdenum are available
20 and provide increased corrosion resistance. Examples are S 31600, S 31700, S 30900 and S 31000. The 200 Series
of austenitic special steels has, on the other hand, a reduced nickel content and contains manganese instead. When
special steel is annealed, hot rolled, etc., a layer of scale forms on the surface, which destroys the desired shiny metallic
appearance of the steel surface. This surface layer must therefore be removed after this production step by a pickling
process. The oxide-containing surface layer to be removed differs fundamentally from the oxide layer on low-alloy steels
25 or on carbon steels. Apart from iron oxides, the surface layer contains oxides of the alloying elements, for example
chromium, nickel, aluminum, titanium or niobium. Particularly in hot rolling, there is an accumulation of chromium oxide
in the surface layer. The oxide layer is accordingly enriched with chromium rather than iron. Conversely, this means
that the steel layer immediately underneath the oxide layer is depleted in chromium. A pickling process using suitable
acidic pickling solutions preferentially dissolves this chromium-depleted layer underneath the oxide layer, with the result
30 that the oxide layer is removed.
[0003] Pickling processes for special steel are well-known in the art. Earlier processes use nitric acid-containing
pickling baths. These often additionally contain hydrofluoric acid, which on account of its complexing action with respect
to iron ions promotes the pickling process. Although such pickling baths are economically efficient and technically
satisfactory, they have the serious ecological disadvantage that they emit considerable amounts of nitrogen oxides and
35 release large amounts of nitrates into the waste water.
[0004] Intensive efforts have therefore been made in the art to find alternative pickling processes that do not use nitric
acid. Fe(III) ions are a possible substitute for the oxidizing action of nitric acid. The concentration of Fe(III) ions is
maintained by hydrogen peroxide, which is added continuously or batch wise to the treatment baths. Such pickling or
passivating baths contain about 15 to about 65 g/l of trivalent iron ions. During the pickling process, trivalent iron ions
40 are converted to the divalent form. At the same time, further divalent iron ions are dissolved out from the pickled surface.
The pickling bath is thereby depleted in trivalent iron ions during the operation, while divalent iron ions accumulate. The
redox potential of the treatment solution is thereby displaced, with the result that the solution finally loses its pickling
action. Divalent iron ions are oxidized back to the trivalent state by the continuous or batch wise addition of oxidizing
agents, for example hydrogen peroxide, or other oxidizing agents, such as perborates, peracids or also organic peroxides.
45 In this way, the redox potential necessary for the pickling or passivating action is maintained.
[0005] EP-B-505 606 describes a nitric acid-free process for the pickling and passivation of stainless steel, in which
the material to be treated is immersed in a bath at a temperature of between 30 and 70 ˚C and which contains, at least
at the beginning of the pickling process, at least 150 g/l of sulfuric acid, at least 15 g/l of Fe(III) ions, and at least 40 g/l
HF. This bath furthermore contains up to about 1 g/l of additives, such as non-ionic surfactants and pickling inhibitors.
50 Hydrogen peroxide is added continuously or batch wise to the bath in such amounts that the redox potential remains in
the desired range. The other bath constituents are also replenished so that the concentration thereof remains within the
optimum operating range. The pickling bath is agitated by blowing in air. Agitation of the pickling bath is necessary in
order to achieve a uniform pickling result. A similar process, which differs from the above-described process basically
only in the adjusted redox potential, is described in EP-A-582 121.
55 [0006] After the pickling, the surface is chemically activated, which means that, in air, the surface once again becomes
coated with an optically interfering surface layer. This may be prevented by passivating the freshly pickled surfaces after
or during the pickling. This may be performed in treatment solutions similar to the pickling solutions, a higher redox
potential being used for the passivation than for the pickling process. This special passivation step forms an optically

2
 EP 1 552 035 B1

invisible passivation layer on the metal surface, and the steel surface thereby preserves its shiny metallic appearance.
Whether a treatment solution behaves in a pickling or passivating manner with respect to special steel depends mainly
on the established redox potential. Acidic solutions having pH values below about 2.5 have a pickling action if, on account
of the presence of oxidizing agents, they have a redox potential in the range from about 200 to about 350 mV with
5 respect to a silver/silver chloride electrode. If the redox potential is raised to values above about 300 to 350 mV, depending
on the type of the stainless steel, the treatment solution has a passivating effect on the base alloy. In case of less noble
materials (ferritic, martensitic grades) this inferior limit will shift to higher values.
[0007] During the pickling of stainless steel, in particular during the pickling of ferritic and martensitic stainless steel,
but also during the pickling of austenitic stainless steel containing sulfur in the alloy, a gray black smut is formed during
10 the pickling itself. This is due to the formation of by-products on the surface due to the pickling reaction. In particular
ferritic and martensitic grades must be passivated after the pickling using high oxidizing chemical solutions in a separate
step. This step provides both the bleaching of the material and the passivation of the surface.
[0008] In recent years nitric acid free pickling processes were successfully applied in the stainless steel industry in
order to solve the ecological problems caused by the presence of nitric acid. One of the remaining open problems for
15 the complete removal of HNO3 from the industrial plant was just the substitution of nitric acid in the passivation step.
The problem solutions proposed were substantially based on acid solutions containing hydrogen peroxide as the oxidizing
agent. However, the performance of these solution showed to be constantly inferior to the nitric acid containing solutions
for two fundamental reasons:

20 a) The low stability of hydrogen peroxide during the use due to the destroying effect of the metal ions slowly dissolved
from the outer surface during the process;
b) The poorer surface finishing quality of the ferritic/martensitic grades compared to the HNO3 based solutions.

[0009] Possible solutions exist to solve problem a) (see, e.g., WO 01/49899 and GB 1,449,525), enabling hydrogen
25 peroxide based solutions to tolerate iron ion concentrations as high as 10-15 g/l without destroying the excess of hydrogen
peroxide necessary to get passivation. However, it is clear that a suitable industrial problem solution requires to have
both problem a) and b) solved at the same time.
[0010] This difficulty is increased by the fact that in any case, when using nitric acid free passivation solutions for
ferritic and martensitic grades, for many grades there always exists the need to add some HF to allow the bleaching of
30 the surface, as for HNO3 containing solutions. The addition of HF has the drawback to dissolve much more iron from
the substrate, decreasing at the same time the shelf life of the hydrogen peroxide based passivation solution. In any
case the surface quality obtained is normally lower than using HNO3 based solutions.
[0011] The subject matter of the present invention is a process solution for pickling stainless steel comprising:

35 a) one or more strong acids other than the complex fluoro acids of group c), and different from nitric acid, in a total
concentration of at least 10 g/l and at most 200 g/l.
e) iron(III) cations in concentration from at least 3 g/l and at most 100 g/l, wherein the process solution contains no
other oxidizing agent than the iron(III) ions and dissolved oxygen,
characterized in that the process solution additionally comprises
40 c) one or more complex fluoro acids of Si and/or anions thereof in concentrations from 50 to 500 mmoles per liter,
f) fluoride ions that amount to a fraction of at least 1 % of the iron(III) cations being present as fluoride complexes
and to less than 1 g/l of free fluoride,
wherein the process solution has a redox potential, measured at its working temperature with a Pt/Ag/AgCl electrode,
of at least 280 mV.
45
[0012] These process solutions for pickling contain one or more strong acids (always meaning: other than the complex
fluoro acids throughout this disclosure) (defined as equally strong or stronger than phosphoric acid) in order to have a
pH-value not higher than 2.5, preferably not higher than 1. This ensures high pickling power of the process solution.
Additionally, the strong acids keep the ionic strength of the solution approximately constant Concentrations of the strong
50 acids in the range of 10 to 200 g/l (as the total of the strong acids) in solutions for pickling are usually sufficient. The
strong acids may, for example, be selected from nitric acid, phosphoric acid, hydrochloric acid, and sulfuric acid and
mixtures thereof. Hydrochloric acid is less preferred, because it might lead to chloride pitting. Nitric acid works well as
a strong acid to give the required low pH-value and/or as an oxidizing agent for the oxidation of Fe(II) ions to Fe(III) ions.
But for the ecological reasons referred to above it is preferred that strong acids different from nitric acid are used, and
55 also a different oxidizing agent than nitric acid.
[0013] In any aspect of the present invention, the complex fluoro acids of Si or anions thereof can be added as free
acids or as salts, preferably alkaline metal salts, provided that they are soluble in the process solution at least in an
amount to result in the indicated concentration of complex fluoro acids and/or anions thereof. In any case an equilibrium

3
 EP 1 552 035 B1

state between the acid and the anionic form of the complex fluoride ions will be established, depending on the pH value
of the process solution and the dissociation constant of the complex fluoro acid. For reasons of availability, the complex
fluoro acids of Si or anions thereof are for economic and ecological reasons preferably selected from SiF62- either in
the form of the corresponding acid or of their salts. Most preferably, the complex fluoro acid themself is used to make
5 up or to replenish the process solutions
[0014] A hydrogen peroxide stabilizer d) is optional, as its presence is only advantageous when the oxidation if iron
(II) ions formed in the pickling process are oxidized to iron(III) by using H2O2 in free or bound form. But this oxidation
could be carried out by using other chemical oxidants like nitric acid, ozone, permanganate ions, perchloric acid, peroxo-
acids of sulfur or phosphorous or the like. Or the oxidation of iron(II) may be performed electrochemically, e.g. in a way
10 analogous to the disclosure of WO97/43463 or of WO98/26111. Finally, this oxidation may be carried out using oxygen
or an oxygen containing gas like air or air enriched with oxygen. In this case the oxidation occurs more efficiently if either
a homogeneous or heterogeneous catalyst is present. The teaching of WO99/31296, of the unpublished PCT application
PCT/EP02/09730, or of EP 795 628 may be applied analogously.
[0015] Iron(II) ions form in the pickling solution by the pickling reaction
15
2 Fe(III) + Fe(0) → 3 Fe(II)

where the base metal underlying the surface scale layer (in case of stainless steel: mainly the chromium depleted layer)
is dissolved mainly by oxidation by Fe(III) ions. This reaction reduces the concentration of Fe(III) ions and increases the
20 concentration of Fe(II) ions. Therefore, the redox potential will decrease according to the Nernst equation. To restore
the redox potential and to have a sufficient "pool of redox power" available, Fe(II) ions have to be oxidized to Fe(III) ions
by one of the ways outlined in the previous paragraph. A concentration of least 3 g/l, preferably at least 5 g/l, more
preferably at least 10 g/l of Fe(III) ions is required to assure a sufficient "pool of redox power" for the pickling reaction.
In a working pickling solution according to the invention, the concentration of Fe(III) ions will usually be in the range of
25 20 to 40 g/l. Maximum concentrations of 100 g/l or even of 60 g/l are usually sufficient for this purpose, and are rarely
exceeded in practice.
[0016] A usual and convenient way to carry out the oxidation of Fe(II) is the addition of a hydrogen peroxide solution
(e.g. as the technical product, which usually contains a conventional stabilizer added by the manufacturer, or one or
more of the stabilizers described more above), either directly into the agitated pickling bath or, more preferably, into a
30 conduit through which pickling solution is circulated. This addition of H2O2 does usually not lead to an excess of it in the
bulk of the pickling solution. Instead, H2O2 is only added (continuously or at intervals) in an amount necessary to give
the required concentration of Fe(III) ions and the required redox potential. To achieve this it is usually not necessary to
oxidize all iron ions in the pickling solution to the trivalent state, even if this is possible. Instead, more preferably, a
fraction of the total iron ions will still be present in the divalent state. In a working pickling solution the concentration of
35 Fe(II) ions may be in the range of from about 5 to about 80 g/l. It is preferred, however, that the ratio of the concentrations
of Fe(III) : Fe(II) ions is at least 0.1, more preferably at least 0,3.
[0017] The concentration of total Fe ions (divalent and trivalent) is held below the upper limit (normally lower than 130
g/l and more preferably less than 100 g/l) mostly by drag-out of pickling solution adhering to the pickled surfaces, and
by replenishment of the pickling solution with a replenisher solution not containing Fe ions. Alternatively, part of the
40 spent pickling solution may be dumped and replaced by fresh pickling solution, or iron salts may be crystallized (e.g. by
cooling the pickling solution) and removed.
[0018] The presence of Fe(II) ions in the working pickling solutions precludes the presence of excess H2O2, as this
would oxidize the Fe(II) immediately. Despite of this it is still advantageous to use a hydrogen peroxide stabilizer in the
pickling solution, e.g. one of those mentioned more above. The reason for this is that freshly added H2O2 will not only
45 be used up by the oxidation of Fe(II), but also by spontaneous decomposition favored by the presence of transition metal
ions in the pickling solution. The presence of a stabilizer in the bulk of the picking solution will slow down the decomposition
reaction and will, therefore, increase the yield of the oxidation of Fe(II). Thus, the overall process needs less H2O2 and
is, therefore, more economical when a hydrogen peroxide stabilizer is present.
[0019] Thus, a preferred pickling solution according to the present invention does not contain any other oxidant (defined
50 as being able to oxidize Fe(II) to Fe(III) in the pickling solution) than the Fe(III) ions themselves and possibly oxygen
which will be dissolved in the pickling solution by its contact with air, especially in the case of air-blowing or in spray
application. However, if environmental concerns are less important or may be overcome by technical means, nitric acid
may be used as an efficient and economic oxidant.
[0020] The pickling solution may comprise further additives or auxiliaries which are conventional in pickling solutions
55 of the state of the art. For example, surfactants or emulsifiers may improve the wetting of the substrate, especially if
tightly wound wire coils are pickled. Nonionic surfactants, e.g. polyethoxylated alkyl alcohols containing about 8 to about
22 C-atoms in the alkyl chain, may be used. Other useful additives include polishing agents and acid attack inhibitors.
The total concentration of these additives is usually in the range of 0.1 to 2 g/l in the bath, and may be retained by

4
 EP 1 552 035 B1

feeding additive solutions if required.

[0021] The gist of this invention mainly lies in the replacement of free HF in pickling solutions, due to health and
environmental impacts of free HF. Therefore, it is preferred that the pickling solution contains as little free HF as possible
due to the equilibrium reactions in the pickling solution. "Free HF" means HF molecules or fluoride ions (able to form
5 HF by reaction with hydronium cations in the acidic pickling solution) which are not used up for complex formation, e.g.
with Fe(III) or Cr(III) ions in the pickling solution. Therefore, even if HF is added into the bath, this will not lead to the
presence of "free HF" as long as it is used up to form these complexes. In extremely difficult pickling cases, however,
it may be necessary to provide small concentrations of free HF for technical efficiency.
[0022] However, for some stainless steel grades (e.g. austenitic grades, or grades of the 4xx series which have not
10 been mechanically or chemically pretreated after annealing) the pickling speed increases when HF is added in an amount
to complex a fraction or all of the Fe(III) and Cr(III) ions, but not necessarily to result in an excess of free HF. Therefore,
according to this invention the pickling solution contains at least a fraction of 1 % of the Fe(III) ions and preferably at
most all of the Fe(III) ions are present as fluoride complexes.
[0023] It is known from EP 1 050 605 that catalytic concentrations of chloride ions in concentrations of between 0.1
15 to 10 g/l may increase the pickling speed. This is also true for pickling solutions according to the present invention.
Therefore, the process solution of the present invention may additionally comprise chloride ions or hydrochloric acid in
a total concentration of from 0.1 to 10g/l, more preferably from 1 to 5 g/l.
[0024] The redox potential of the process solution for pickling (measured at the working temperature with a PdAg/
AgCl electrode and relative to this electrode, i.e. the potential of this - secondary electrode is taken to be zero) is set
20 and maintained at least 280 mV, preferably at least 300 mV. In practice, it will usually not be higher than 800 mV. As
described above, the redox potential is managed by the addition of oxidants to the pickling solution in order to oxidize
a fraction of the Fe(II) ions to Fe(III) ions.
[0025] Furthermore, the present invention comprises a process for pickling stainless steel wherein the steel is brought
into contact with a process solution as described here above. Preferably the pickling solution has a temperature between
25 20 and 80 ˚C, more preferably between 30 and 70 ˚C. The optimum temperature range may depend on the substrate
and may be found empirically. The pickling may be carried out as a dip or as a spray process. Pickling times strongly
depend on the type of steel, on its shape, and on the pretreatment between rolling or annealing and pickling. In practice,
the time required for complete pickling will normally be in the range of from 1 to 90 Minutes. Pickling times may also
depend on the presence of fluoro complexes of Fe(III) and/or on the presence of chloride ions. They will have to be
30 optimized empirically.
[0026] Bath agitation or other means for moving the process solution relative to the pickled surfaces may shorten the
time required for complete pickling. Therefore, it is preferred that the pickling solution is moved relatively to the surface
of the steel. In spray application this happens automatically. It is also possible to move the material to be pickled within
the bath solution. Other efficient means for agitation are stirring, pumping pickling solution in a loop, and especially
35 blowing of air. In the latter case it is preferred that air is injected in the order of at least 3 m3/m3 bath per hour, e.g. in
the order of 10 to 40 m3/m3 bath per hour.
[0027] During the pickling process the concentration of Fe(III) will diminish and the concentration of Fe(II) ions increase,
as described above. This would lower the redox potential and diminish the pickling efficiency. Therefore, it is preferred
that at least a fraction of the iron(II) formed during the pickling are oxidized to iron(III) ions. How this can be done has
40 been explained above in connection with the pickling solution.
[0028] It should be evident from the description above that the process according to the present invention is part of
the treatment chain: pretreatment (acid treatment, molten salt treatment, shot peening, mechanical cracking of the scale,
and the like), pickling (in one ore more steps, e.g. using pickling solutions as quoted in the introductory part or according
to the invention), bleaching/passivating according to the state of the art, water rinse, and drying. At least one pickling
45 step has to be carried out according to the invention.
[0029] The invention for pickling stainless steel can be applied to the production of stainless steel in any form, such
as wire, rod, tube, plate, coil, and finished articles.
[0030] If the pickling step is carried out according to the present invention, the composition of the pickling solution
may be adjusted according to the material to be pickled and/or according to the pretreatment before pickling. E.g. it may
50 not be necessary at all to add HF in order to complex iron(III) ions when stainless steel grades of the 4xx series are
pickled, if they have previously been pretreated (molten salts, shoot blasting, KMnO4/NaOH solutions, scale breaking ,
etc). Especially when not pretreated 4xx grades are pickled, faster pickling is obtained when HF is added to the pickling
solution in such an amount that at least a fraction of the iron(III) ions are complexed, but no free fluoride (i.e. fluoride
ions not involved in complex formation) is present in the pickling solution. For the pickling of austenitic stainless steel,
55 faster pickling also occurs when HF is added to the pickling solution in such an amount that at least a fraction of the iron
(III) ions are complexed, but no free fluoride is present in the pickling solution. The presence of free fluoride or free HF,
preferably at a concentration lower than 10 g/l, will be thus limited to specific critical situations that could be found in the
practical industrial realty

5
 EP 1 552 035 B1

[0031] Depending on the substrate and on the type of pretreatment before pickling, pickling may be carried out in one
or more steps, e.g. in two steps. The same or different bath compositions may be chosen for the different steps. The
redox potential may also change from step to step and is usually higher in subsequent steps than in the first step.
However, the total concentration of divalent and trivalent iron ions may be higher in the first step than in the subsequent
5 steps.
[0032] It is well known in the art of pickling that the process solutions can be present in the form of a gel or a paste.
For the process solution according to the present invention this is possible as well, and this is one possible embodyment
of the present invention. Thickeners to be added to bring the process solution into this physical state are known in the
art of pickling. Examples are inorganic thickeners based on aluminum, magnesium, or calcium oxides or mixtures thereof,
10 organic thickeners like polyvinylpyrrolidone, cellulose ethers, and modified polyacrylic acids. Of course, mixtures of
organic and inorganic thickeners may be used as well.
[0033] The active ingredients of the process solutions for pickling of stainless steel are partly used up during the
process. Therefore, they have to be replenished periodically or more or less continuously, either as a result of bath
analysis or according to experience. For this purpose, the single components can be added separately, as required.
15 However, it is usually preferred to add at least some of the components together in a replenisher solution, as this
minimizes the number of different solutions which have to be added to the process solutions. Usually, the oxidizing agent
is added separately from the other ingredients due to its instability. However, it may be added together with a hydrogen
peroxide stabilizer. It is very practical, however, to add the strong acid, the complex fluoro compounds, and the hydrogen
peroxide stabilizer together in one solution.
20
Examples

A. Chemical equilibria and Redox Potential values (Pt/Ag/AgCl)

25 [0034] One of the aspects different compared to the traditional technology according to EP 505 606 is that the con-
centration of Fe3+ available as free (i.e. uncomplexed) in the pickling solution is much higher. From the literature data
and from the experimental ones in the system:

Fe3+ - Fe2+ - H2SO4 - H2SiF6

30
there is no remarkable complex formation between Fe3+ and H2SiF6. The redox potential measurements gives a clear
indication of that:

Data 1.
35
[0035]

Solution H2SO4 = 120 g/l

H2SiF6 = 0
40
Fe3+, g/l Fe2+ g/l E (mV)
33,97 14,7 472

45
Solution H2SO4 = 120 g/l
H2SiF6 = 50 g/l
Fe3+, g/l Fe2+ g/l E (mV)
50 30,86 12,79 464

Data 2.

55
[0036] In a solution containing initially H2SO4 = 120 g/l and H2SiF6 = 34 g/l were added 26,7 g of Fe2+ (added as
FeSO4 * 7 H2O) and the redox potential measured. Step by step part of the bivalent iron was oxidized with Hydrogen
peroxide and the redox potential read at each oxidation step:

6
 EP 1 552 035 B1

Fe3+, g/l Fe2+, g/l E (mV)

0 26,7 270
5 0,3 26,4 337
5,5 20,9 402
11,9 14,6 425
19,4 6,9 467
10
25,6 1,0 537

[0037] The data obtained for Fe3+ = 0 was possible only using fresh analytical grade reagent. On the contrary using
an industrial raw material a very small amount of Fe3+ (as in the second experimental data) is sufficient to get a redox
15
potential value higher than 300 mV.
[0038] There is no special influence of the single acids on the redox potential value in absence of trivalent iron:

Solution H2SO4 = 0 g/l

20 H2SiF6 = 34 g/l
Fe3+, g/l Fe2+ g/l E (mV)
0 26 265

25

Solution H2SO4 = 120 g/l

H2SiF6 = 0
Fe3+, g/l Fe2+ g/l E (mV)
30
0 26 271

Solution H2SO4 = 0
35
H2SiF6 = 0
Fe3+, g/l Fe2+ g/l E (mV)
0 26 260

40
[0039] The strong effect of Fe3+ on the redox potential compared to traditional pickling solution according to EP 505
606 should be due to the fact that there is no strong complex between Fe3+ and the anions in the solution.
[0040] The influence of the addition of HF to the solution confirmed its stronger influence on the redox potential value
due to the Fe3+ complexation, as can be seen in the following experiment, in which HF was added at different step to
45 a solution originally without HF.

Fe3+ Fe2+ H2SO4 H2SiF6 HF added

E, mV
g/l g/l g/l g/l g/l

50
9,9 37,8 120 34 0 0,390
1 0,390
5 0,373
10 0,347
55
20 0,303
37,2 0,249

7
 EP 1 552 035 B1

[0041] By adding HF the redox potential starts to decrease. For HF = 10 g/l all the Fe3+ present was theoretically
complexed and the redox potential decreased of about 50 mV compared to the starting solution. Adding other 10 g/l
more of HF (20 as total and 10 as theoretical HF free) the redox potential value decreased by other 50 mV.

5 B. PICKLING DATA

Example B1

[0042] STAINLESS STEEL GRADES 400

10 [0043] Stainless steel wire samples AISI 416 and AISI 420 were pickled in different solutions, after pre-treatment in
reduction molten salts (Ferropur). Two different pickling temperature (30˚C, 40˚C) were also investigated.

F1 F2 F3 (comparative)

15 H2SO4, g/l 120 120 120

H2SiF6, g/l 50 17 50
Fe3+g/l 30,8 30,8 <1
Fe2+ g/l 12,8 12,8 13,11
20
Total F- (added as HF), g/l 0 0 0

[0044] At the end of the pickling cycle the samples were bleached and passivated in a solution according to the
"bleaching aspect" of this invention:
25
H2SO4

H2SiF6

30 H2O2

Stabilizer

[0045] These cycle was compared with a CleanoxR 352 (a process according to EP 505 606) pickling cycle using the
35 following pickling and bleaching solutions:

Parameter Cleanox 352 pickling solution (comparative) Cleanox 352 bleaching solution (comparative)
Fe3+ g/l 25
40 Fe g/l 35
H2SO4 free g/l 100 30
HFftee g/l 25
Total F- g/l 50
45
H2O2 g/l 6,0

[0046] The results are summarized in the tables below (CX = Cleanox; m.p.t. = minimum pickling time; n.d. = not
determined)
50

T = 30˚C AISI 416 AISI 420 F

F1 F2 F3 (comparative) CX 352 F1 F2 F3 (comparative) CX 352

55
Minimum Pickling 600 600 » 1000 480 300 300 » 1000 480
time, seconds

8
 EP 1 552 035 B1

(continued)

T = 30˚C AISI 416 AISI 420 F

Weight loss at m.p.t. 85,7 106,9 n.d. 142 30,7 37,3 n.d. 124
5
g/m2

T = 40˚C AISI 416 AISI 420 F

10
F1 F2 F1 F2
Minimum Pickling time, g seconds 300 300 180 240
Weight loss at m.p.t. g/m2 84,9 85,9 47,5 63

15
[0047] The following general observation can be made:
[0048] There was a negligible pickling reaction in absence of Fe3+ ions (F3 comparative solution) The minimum pickling
time to get a completely de-scaled surface can be decreased compared to the reference for any concentration of H2SiF6
by changing the temperature The weight loss at the minimum pickling time is strongly reduced with the new process
20 compared to a process according to the state of the art (CleanoxR). An increase of the temperature using CleanoxR on
these grades is not possible because it will cause over-pickling of the surface.

Example B2. Not pre-treated 4xx grades

25 [0049] Samples of AISI 430 as rolled and annealed but without any mechanical or chemical-physical pre-treatment
were pickled in solution F1. A second solution was prepared adding to this solution 30 g/l of total fluoride as HF (Solution
F4). This fluoride was complexed by Fe3+ ions present in the solution to form fluorocomplexes FeFx(3-x) in such a way
to have no free HF present in the solution For comparison a CleanoxR solution as in example 1 was tested .The pickling
for which the surface was visually free of oxides was noted as minimum pickling time.
30 [0050] The results are shown in the table below (for abbreviations see Tables above).

T = 30˚C F1 F4 CX 35 (comparison)
H2SO4, g/l 120 120 100
35 H2SiF6, g/l 50 17 -
Fe3+, g/l 30,8 30,8 25
Fe2+, g/l 12,8 12,8 35
Total F- (added as HF), g/l 0 30 50
40
HFfree, g/l 0 0 25
Minimum Pickling time, (minutes) →∞ 15 19
Weight loss at m.p.t. g/m2 n.d. 34,9 226,5
45

[0051] In this case due to the very compact oxide structure the solution tested in example 1 was completely unable
to pickle the surface. The addition of fluoride in FeFx complexed form allowed to get a surface completely free of scale,
decreasing the minimum pickling time compared to the CleanoxR reference solution and with a minimum weight loss of
the sample.
50

Example B3. Austenitic stainless steel

[0052] AISI 304/4 wire samples were pickled by immersion in different solutions in which were kept constant: the
sulphuric acid concentration, Fe3+ and Fe2+ concentration and the pickling temperature (45˚C). The ratio between H2SiF6
55 and the total fluoride was varied. Pickling result was evaluated at steps of 5 minutes and were evaluated when the
surface was completely free of oxide by visual observation.

9
 EP 1 552 035 B1

10

15

20

25

30

35

40

45

50

55 Example B4. Austenitic stainless steel AISI 304 L

[0053] The previous test was repeated by pickling a steel more difficult than 304/4.

10
 EP 1 552 035 B1

10

15

20

25

30

35

40

45

50

[0054] The data confirmed that quite well that in the case of austenitic steel, even if pickling only using H2SiF6 without
the addition of HF is possible, the minimum pickling time is quite longer than the time of the conventional CleanoxR
process. The time decreased to comparable values when fluoride in form of ferric fluoride complexes was added at a
55 concentration of about 20 g/l (as F-), with the advantage to get the pickling with a lower total weight loss (g/m2).
[0055] Apparently the best results where obtained when H2SiF6 was in the range 17-34 g/l.

11
 EP 1 552 035 B1

C. INFLUENCE OF SULPHURIC ACID CONCENTRATION

[0056] Using AISI 304 L austenitic stainless steel the following solutions were compared at a temperature of 45˚C:

5
T=45˚C S13 S14 S15
H2SO4 , g/l 60 120 160
H2SiF6, g/l 34 34 34

10
Fe3+, g/l 30 30 30
Fe2+, g/l 14,5 14,5 14,5
Total F- (added as HF), g/l 20 20 20
HFfree, g/l 0 0 0
15
Minimum Pickling time (minutes) 35 35 35
Weight loss at m.p.t. 157,7 153 149

[0057] These data clearly show that there is no relevant influence of sulphuric acid concentration on the pickling
20
efficiency in the range 60 - 160 g/l, at least when H7SiF6 is kept constant.

D. CATALYTIC EFFECT OF CHLORIDES

[0058] Catalytic amount of chloride were tested in solutions as S13 and S15 adding 2 g/l of cr ions as ferrous chloride
25
(FeCl2). Thus the solutions in the table below were compared and the following results obtained :

T=45˚C S13 S15 S16 S17

H2SO4, g/l 60 160 60 160
30
H2SiF6, g/l 34 34 34 34
Cl-, g/l - - 2 2
Fe3+, g/l 30 30 30 30

35 Fe2+, g/l 14,5 14,5 14,5 14,5

Total F- (added as HF), g/l 20 20 20 20
HFfree, g/l 0 0 0 0
Minimum Pickling time (minutes) 35 35 25 25
40
Weight loss at m.p.t. 157,7 149 157,8 167,4

[0059] In both cases the addition of 2 g/l of chlorides accelerated the process, on this quite common stainless steel
grade , by reducing the minimum pickling time of about 30%.
45

D. EFFECT OF THE TEMPERATURE

[0060] Solution S15 was tested at 3 different temperatures always using 304 L stainless steel wire samples.

50
T=45˚C T=55˚C T=63˚C
Minimum pickling time (minutes) 35 20 15
Weight loss at m.p.t. 149 152 157

55
[0061] By increasing the temperature it was possible to strongly reduce the minimum pickling time without practically
increasing the weight loss and thus in the chemical consumption as normally happens with conventional pickling solutions
according to EP 505 606.

12
 EP 1 552 035 B1

E .PICKLING TESTS USING FLUOBORIC ACID INSTEAD OF FLUOSILICIC ACID

[0062] A comparative test was made at a temperature of 45˚C on AISI 304 L with and without HF added to the solutions
between fluoroboric and fluorosilicic acids using the same molar concentration.
5

T=45˚C S5 S7 S18 S19

H2SO4, g/l 120 120 120 120
H2SiF6, g/l 34 34 - -
10
HBF4, g/l - - 20,7 20,7
Fe3+, g/l 30 30 30 30
Fe2+, g/l 14,5 14,5 14,5 14,5
15 Total F- (added as HF) 0 20 0 20
HFfree, g/l 0 0 0 0
Minimum pickling time (minutes) > 70 35 > 70 45
Weight loss at m.p.t.. g/m2 n.d. 153 n.d. 147,7
20

[0063] The test shows that pickling mechanism is the same and the results are quite similar. Fluorosilicic acid works
a little better concerning both minimum pickling time and surface finishing (brighter surface). This makes it probable that
other complex fluoro acids with similar complex stabilities and acid strenghths, like complex fluoro acids of Ti and Zr,
25 as well as anions thereof, also behave similarly

Effect of the Fe3+/Fe2+ ratio on the pickling result.

[0064] Three different grades of austenitic stainless steel wire samples were pickled in the following solutions according
30 to the invention:

LK HK
Fe3+, g/l 20,3 36,2
35 Fe2+, g/l 34 11,5
E, mV 363 398
H2SO4, g/l 100 100
H2SiF6, g/l 34 34
40
Total F- g/l (added as HF) 19 30
HFfree, g/l 0 0

45 [0065] The samples were pickled at 45˚C step by step till to get the surface completely free from oxide scale by visual
observation. The table below shows the test results in terms of weight losses at the end of the pickling and the minimum
pickling time (m.p.t.) observed:

Sol. 302BK molten salts pre- E308L molten salts pre-treated E316L8 as annealed
50 treated
m.p.t., minutes 20,0 40,0 60
LK
Weight loss, g/m2 111,7 102,7 171,3
m.p.t., minutes 20,0 35 55
55 HK
Weight loss, g/m2 131,8 112,5 168,4

13
 EP 1 552 035 B1

[0066] The data showed that there is very little or no effect at all of the Fe3+/Fe2+ ratio on the pickling rate.

Claims
5
1. A process for pickling stainless steel wherein the stainless steel is brought into contact with a process solution
comprising:

a) one or more strong acids other than the complex fluoro acids of group c), and different from nitric acid, in a
10 total concentration of at least 10 g/l and at most 200 g/l.
e) iron(III) cations in concentrations from at least 3 g/l to at most 100 g/l, wherein the process solution contains
no other oxidizing agent than the iron(III) ions and dissolved oxygen,
characterized in that the process solution additionally comprises
c) one or more complex fluoro acids of Si and/or anions thereof in concentrations from 50 to 500 mmoles per liter,
15 f) fluoride ions that amount to a fraction of at least 1 % of the iron(III) cations being present as fluoride complexes
and to less than 1 g/l of free fluoride,
wherein the process solution has a redox potential, measured at its working temperature with a Pt/Ag/AgCl
electrode, of at least 280 mV and up to 800 mV.

20 2. A process according to claim 1 wherein the process solution additionally contains a total of from 0.1 to 10 g/l of
chloride ions and/or hydrochloric acid.

3. A process according to one or both of claims 1 and 2 wherein the process solution has a redox potential, measured
at its working temperature with a Pt/Ag/AgCl electrode, of at least 300 mV and up to 800 mV.
25
4. A process according to one or more of claims 1 to 3 wherein the process solution is moved relatively to the surface
of the stainless steel.

5. A process according to one or more of claims 1 to 4 wherein at least a fraction of the iron(II) ions formed during the
30 pickling are oxidized to iron(III) ions.

6. A process solution for pickling stainless steel comprising:

a) one or more strong acids other than the complex fluoro acids of group c), and different from nitric acid, in a
35 total concentration of at least 10 g/l and at most 200 g/l.
e) iron(III) cations in concentration from at least 3 g/l and at most 100 g/l, wherein the process solution contains
no other oxidizing agent than the iron(III) ions and dissolved oxygen,
characterized in that the process solution additionally comprises
c) one or more complex fluoro acids of Si and/or anions thereof in concentrations from 50 to 500 mmoles per liter,
40 f) fluoride ions that amount to a fraction of at least 1 % of the iron(III) cations being present as fluoride complexes
and to less than 1 g/l of free fluoride,
wherein the process solution has a redox potential, measured at its working temperature with a Pt/Ag/AgCl
electrode, of at least 280 mV.

45 7. A process solution according to claim 6 which has a redox potential, measured at its working temperature with a
Pt/Ag/AgCl electrode, of at least 300 mV and up to 800 mV.

8. The process solution according to any of claims 6 and 7, wherein the strong acids other than the complex fluoro
acids of groups c) are selected from sulfuric acid, phosphoric acid, and mixtures thereof.
50
9. The process solution according to any of claims 6 to 8, wherein the process solution is in the form of a gel or a paste.

Patentansprüche
55
1. Verfahren zum Beizen von rostfreiem Stahl, wobei der rostfreie Stahl in Kontakt mit einer Verfahrenslösung gebracht
wird, die Folgendes umfasst:

14
 EP 1 552 035 B1

a) eine oder mehrere starke Säuren, bei denen es sich nicht um die komplexen Fluorosäuren von Gruppe c)
handelt und die sich von Salpetersäure unterscheiden, in einer Gesamtkonzentration von mindestens 10 g/l
und höchstens 200 g/l,
e) Eisen(III)-Kationen in Konzentrationen von mindestens 3 g/l bis höchstens 100 g/l, wobei die Verfahrenslösung
5 kein anderes Oxidationsmittel als die Eisen(III)-lonen und gelösten Sauerstoff enthält,
dadurch gekennzeichnet, dass die Verfahrenslösung zusätzlich Folgendes umfasst:
c) eine oder mehrere komplexe Fluorosäuren von Si und/oder Anionen davon in Konzentrationen von 50 bis
500 mmol pro Liter,
f) Fluoridionen, die eine Fraktion von mindestens 1 % der Eisen(III)-Kationen, die als Fluoridkomplexe vorliegen,
10 und weniger als 1 g/l von freiem Fluorid ausmachen,
wobei die Verfahrenslösung ein Redoxpotential, gemessen bei ihrer Gebrauchstemperatur mit einer Pt/Ag/
AgCl-Elektrode, von mindestens 280 mV und bis zu 800 mV aufweist.

2. Verfahren nach Anspruch 1, wobei die Verfahrenslösung zusätzlich insgesamt von 0,1 bis 10 g/l Chloridionen und/
15 oder Salzsäure enthält.

3. Verfahren nach einem oder beiden der Ansprüche 1 und 2, wobei die Verfahrenslösung ein Redoxpotential, ge-
messen bei ihrer Gebrauchstemperatur mit einer Pt/Ag/AgCl-Elektrode, von mindestens 300 mV und bis zu 800
mV aufweist.
20
4. Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, wobei die Verfahrenslösung im Verhältnis zu der
Oberfläche des rostfreien Stahls bewegt wird.

5. Verfahren nach einem oder mehreren der Ansprüche 1 bis 4, wobei mindestens eine Fraktion der Eisen(II)-Ionen,
25 die während des Beizens gebildet werden, zu Eisen(III)-Ionen oxidiert wird.

6. Verfahrenslösung zum Beizen von rostfreiem Stahl, die Folgendes umfasst:

a) eine oder mehrere starke Säuren, bei denen es sich nicht um die komplexen Fluorosäuren von Gruppe c)
30 handelt und die sich von Salpetersäure unterscheiden, in einer Gesamtkonzentration von mindestens 10 g/l
und höchstens 200 g/l,
e) Eisen(III)-Kationen in einer Konzentration von mindestens 3 g/l und höchstens 100 g/l, wobei die Verfah-
renslösung kein anderes Oxidationsmittel als die Eisen(III)-Ionen und gelösten Sauerstoff enthält,
dadurch gekennzeichnet, dass die Verfahrenslösung zusätzlich Folgendes umfasst:
35 c) eine oder mehrere komplexe Fluorosäuren von Si und/oder Anionen davon in Konzentrationen von 50 bis
500 mmol pro Liter,
f) Fluoridionen, die eine Fraktion von mindestens 1 % der Eisen(III)-Kationen, die als Fluoridkomplexe vorliegen,
und weniger als 1 g/l von freiem Fluorid ausmachen,
wobei die Verfahrenslösung ein Redoxpotential, gemessen bei ihrer Gebrauchstemperatur mit einer Pt/Ag/
40 AgCl-Elektrode, von mindestens 280 mV aufweist.

7. Verfahrenslösung nach Anspruch 6, die ein Redoxpotential, gemessen bei ihrer Gebrauchstemperatur mit einer
Pt/Ag/AgCl-Elektrode, von mindestens 300 mV und bis zu 800 mV aufweist.

45 8. Verfahrenslösung nach einem der Ansprüche 6 und 7, wobei die starken Säuren, bei denen es sich nicht um die
komplexen Fluorosäuren von Gruppe c) handelt, aus Schwefelsäure, Phosphorsäure und Gemischen davon aus-
gewählt sind.

9. Verfahrenslösung nach einem der Ansprüche 6 bis 8, wobei die Verfahrenslösung in der Form eines Gels oder
50 einer Paste ist.

Revendications

55 1. Procédé pour le décapage d’acier inoxydable, dans lequel l’acier inoxydable est mis en contact avec une solution
de procédé comprenant :

a) un ou plusieurs acides forts autres que les fluoroacides complexes du groupe c), et différents de l’acide

15
 EP 1 552 035 B1

nitrique, en une concentration totale d’au moins 10 g/l et d’au plus 200 g/l,
e) des cations de fer (III) en des concentrations d’au moins 3 g/l à au plus 100g/l, la solution du procédé ne
contenant pas d’autre agent d’oxydation que les ions de fer (III) et l’oxygène dissous,
caractérisé en ce que la solution de procédé comprend en outre
5 c) un ou plusieurs fluoroacides complexes de Si et/ou leurs anions en des concentrations de 50 à 500 mmoles
par litre,
f) des ions fluorure qui forment une fraction d’au moins 1% des cations de fer (III) présents sous forme de
complexes de fluorure et moins de 1 g/l de fluorure libre,
dans lequel la solution de procédé présente un potentiel redox, mesuré à sa température de travail avec une
10 électrode de Pt/Ag/AgCl, d’au moins 280 mV et jusqu’à 800 mV.

2. Procédé selon la revendication 1 dans lequel la solution de procédé contient en outre un total de 0,1 à 10 g/l d’ions
chlorure et/ou d’acide chlorhydrique.

15 3. Procédé selon l’une ou les deux revendications 1 et 2, dans lequel la solution de procédé présente un potentiel
redox, mesuré à sa température de travail avec une électrode de Pt/Ag/AgCl, d’au moins 300 mV et jusqu’à 800 mV.

4. Procédé selon l’une ou plusieurs des revendications 1 à 3, dans lequel la solution de procédé est déplacée par
rapport à la surface en acier inoxydable.
20
5. Procédé selon l’une ou plusieurs des revendications 1 à 4 où au moins une fraction des ions de fer (II) formés
pendant le décapage est oxydée en ions de fer (III).

6. Solution de procédé pour le décapage d’acier inoxydable, comprenant :

25
a) un ou plusieurs acides forts autres que les fluoroacides complexes du groupe c), et différents de l’acide
nitrique, en une concentration totale d’au moins 10 g/l et d’au plus 200 g/l,
e) des cations de fer (III) en une concentration d’au moins 3 g/l et d’au plus 100 g/l, la solution du procédé ne
contenant pas d’autre agent d’oxydation que les ions de fer (III) et l’oxygène dissous,
30 caractérisé en ce que la solution de procédé comprend en outre
c) un ou plusieurs fluoroacides complexes de Si et/ou leurs anions en des concentrations de 50 à 500 mmoles
par litre,
f) des ions fluorure qui forment une fraction d’au moins 1% des cations de fer (III) présents sous forme de
complexes de fluorure et moins de 1 g/l de fluorure libre,
35 dans lequel la solution de procédé présente un potentiel redox, mesuré à sa température de travail avec une
électrode de Pt/Ag/AgCl, d’au moins 280 mV.

7. Solution de procédé selon la revendication 6, qui présente un potentiel redox, mesuré à sa température de travail
avec une électrode de Pt/Ag/AgCl, d’au moins 300 mV et jusqu’à 800 mV.
40
8. Solution de procédé selon l’une quelconque des revendications 6 et 7, où les acides forts autres que les fluoroacides
complexes du groupe c) sont choisis parmi l’acide sulfurique, l’acide phosphorique et leurs mélanges.

9. Solution de procédé selon l’une quelconque des revendications 6 à 8, où la solution de procédé est sous forme
45 d’un gel ou d’une pâte.

50

55

16
 EP 1 552 035 B1

REFERENCES CITED IN THE DESCRIPTION

This list of references cited by the applicant is for the reader’s convenience only. It does not form part of the European
patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be
excluded and the EPO disclaims all liability in this regard.

Patent documents cited in the description

• EP 505606 B [0005] • WO 9931296 A [0014]

• EP 582121 A [0005] • EP 0209730 W [0014]
• WO 0149899 A [0009] • EP 795628 A [0014]
• GB 1449525 A [0009] • EP 1050605 A [0023]
• WO 9743463 A [0014] • EP 505606 A [0034] [0039] [0045] [0061]
• WO 9826111 A [0014]

Non-patent literature cited in the description

• Ullmanns Encyklopädie der technischen Chemie. Ju-

ly 1985, vol. 22, 106-112 [0001]

17