ISSN 1018-5593

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**

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European Commission

technical steel research

Properties and service performance

Surface treatments for stainless steel state

of the art developments and trends

STEEL RESEARCH

European Commission

Properties and service performance

Surface treatments for stainless steel state

of the art developments and trends
D. Henriet
Directorate-General XII
Sciences, Research and Development
200 rue de la Loi
B-1040 Brussels
Edited by

R. Nauche

Contract No 7210-ZZ/604
1 July 1993 to 15 November 1995

Final report

Directorate-General XII
Science, Research and Development

1996

EUR 17248 EN

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It can be accessed through the Europa server (http://europa.eu.int.)

LEGAL NOTICE
Neither the European Commission nor any person acting on
behalf of the Commission is responsible for the use which might be made of the
following information

Cataloguing data can be found at the end of this publication

Luxembourg: Office for Official Publications of the European Communities, 1997

ISBN 92-827-6941-0
ECSC-EC-EAEC, Brussels Luxembourg, 1997
Reproduction is authorized, except for commercial purposes, provided the source is acknowledged
Printed in Luxembourg

ACKNOWLEDGEMENTS

This
treatise
was
undertaken
with
the
help
of
Directorate-General XII of the Commission of the European Communities which we wish to thank.
In a steelmaking plant, particularly when manufacturing
stainless steel, the surface-treatment shops are at the
interface between hot plant and cold plant.

Surface treatment is an important phase in the manufacture of

these products since surface preparation affects the results of
the subsequent steps, from smelting to the sale of the
product...

Control of these operations requires understanding of the properties and mastery of specific advanced technologies.

- OXIDATION OF STAINLESS STEELS

CONTENTS

1.1

THE ADSORPTION OF OXYGEN

1.1.1

- Constitution of the adsorbed oxide film

1.1.2

- From ch^imi sorbed oxygen film to oxide film

PASSIVITY

1.2

1.2.1

- Demonstration of the passive layer

10

1.2.2

- Properties of the passive layer

11

HIGH-TEMPERATDRE OXIDATION - IRON-OXYGEN DIAGRAM

13

1.3.1

- Iron-Oxygen Diagram

14

1.3.2

- Reactions between iron oxides and the other elements

15

1.3.3

- Mechanisms and modelling

16

INDUSTRIAL SCALE

17

- ThermodynaTTn*c aspects - Change in the free energy of

18

1.3

1.4
1.4.1

formation of oxides with temperature - OLETTE-ANCEY

diagrams
1.4.2

- Kinetic aspects
1.4.2.1 - Growth

21
mechanism

and

thickness

of

the

22

scale on carbon steels

1.4.2.2 - Change in the scale during cooling

1.4.3

- The scale on stainless steels

24

26

1.4.4

1.4.3.1 - Classification of the oxides

27

1.4.3.2 - Oxidation of chromium

29

1.4.3.3 - Oxidation of nickel

29

1.4.3.4 - Oxidation of Fe-Cr alloys

29

1.4.3.5 - Oxidation of Fe-Cr-Ni alloys

31

1.4.3.6 - Influence of addition elements

32

- Oxidation of
enviroTTmari t

stainless

steel

in

an

industrial

33

1.4.4.1 - Influence of water vapour

33

1.4.4.2 - Oxidation in air and in 0 2

35

1.4.4.3 - Industrial annealing at low oxygen pres-

36

sures
1.4.5

- Chromium depletion of stainless steels

1.4.5.1 - Chromium

depletion

phenomena

40
-

41

Fundamental aspects

1.4.6

1.4.5.2 - Influence of the main factors

42

1.4.5.3 - An example of chromium depletion

43

- The influence of treatment and cooling conditions on

44

the change in structure of the scale

1.4.7

- The formation of defects in the scale

47

1.4.8

- The study of scale

49

1.4.9

- Anti-scale products

54

OXIDATION OF STAINLESS STEELS

Review of the main concepts
Oxidation phenomena in stainless steels

1.1. -

THE ADSORPTION OF OXYGEN

The assumed "ideal" surface does not exist in practice. It is an

"approximate" theoretical concept. This is because there are
always a few imperfections of a chemical, physical or crystallographic nature which may alter the surface of the metal. The
most obvious of these imperfections is due to the fact that a
metal atom incorporated into the body of a crystalline structure
has a defined number of neighbours (for example 12 for iron in
the face-centred cubic lattice). As a result of imperfections,
the surface crystal has properties different from the crystal
lying within the body of the lattice (variations in the
attractive forces). We may consider the surface of an industrial
product as comprising three regions:
a contamination region: this is the first layer where
pollutants coming from the ENVIRONMENT are deposited.
The chemical nature of the metal results in a very
strong reaction of the surface atoms which tend to
combine with any element gravitating towards the
vicinity (monomolecular film of a fatty acid).
a chemically altered region: this is the oxidation
region.
a physically altered region: this is for example
altered by rolling or generally by any treatment which
results in working.

Figure 1 - Model of an industrial surface

CHAUDRON, BENARD and LACOMBE1 and MOREAU2 have shown that
extremely careful polishing results in a high degree of abrasion
of the surface and in surface working.

Disoriented region

Disoriented region

Onented region
Oriented region

j
Intact crystal

Figure 2 - Modification of the surface structure of a steel by

polishing.
Depending on the extent of abrasion (working), the affected
region may be some ten microns in thickness (according to
reference 1 ) .
The build-up of films of adsorbed oxygen has formed the subject
of a considerable amount of research3'4,5. These studies have
shown that the fixation of oxygen, at the steel surface exposed

to a molecular atmosphere at room temperature, results from the

competition of three separate processes:
chemical adsorption and formation of a film of oxygen
which is dissociated to a greater or lesser extent
physical adsorption and fixation of 0 2
oxidation reaction:
2M (bare surface) + 0 2 (gas) - 2M0 (adsorbed surface)

ADSORBED OXYGEN
MOLECULES
CHEMISORBED OXYGEN
ATOMS

>

SURFACE METAL
ATOMS

Figure 3 - Coexistence of the chemical adsorption of atoms and

the physical adsorption of oxygen molecules at the surface of a
metal at low temperature (reference 3 ) .
1.1.1 - Constitution of the adsorbed oxide film
BENARD2 has shown that the composition of the film of adsorbed
oxygen is markedly different from that of the oxide of the
metal.
The film of chemically adsorbed oxygen should be regarded as a
special species endowed with a defined structure of its own;
this depends in the first place on the nature of the chemical
bond which unites the oxygen to the surface atoms of the metal,
this bond being only ionic.

The transfer of electrons from the metal to the oxygen is mainly

due to the :
increase in resistivity of the thin film;
increase in the metal extraction potential;
reduction in the photoelectric sensitivity threshold.
This

stability

of

the

chemical

bond

of

the

oxygen may

be

attributed to its covalent character6'3.

:o:

. L1." . 'i'.''

'. '.- ---T-''.

Figure 4 - Diagram showing the exchange of electrons during

the chemical adsorption of an oxygen atom and of a water
vapour molecule on a metal 3 .
1.1.2. - From chemj sorbed oxygen film to oxide film
According to reference 3, the transition from one configuration
to the other probably takes place depending on the crystallographic orientation of the surface subjected to the oxidation;
this would be easy if the orientation is favourable to their
being continuity between the metal lattice and the oxide lattice
(for example the formation of FeO x on a [100] face of -iron).

\ AAA A/
AAA

M.

Mv

MA/VW
\

A0VY\A

/ \/ \/ \/ \ / \ /

\ /

Chemisorbed oxygen

Oxide film

Figure 5 Diagrammatic comparison of the composition of a

chemisorbed film with an oxide film (after BENARD3) .
1.2 PASSIVITY7,8
A metal immersed in water changes towards an oxidized form, this
reaction corresponding to metal ions passing into solution
according to the reaction:
M * M z + s o l + ze"
where

(1)

M is the metal, is the valency of the metal and

M z + s o l is the corresponding ion in solution.

This reaction depends on the potential difference between the

metal and the solution and therefore on the experimental con
ditions, mainly the pH.
In the case of iron, simple mechanisms have been proposed

which

involve adsorbed intermediate metallic species, for example:

(Fe) m + (H 2 0) s Fe(OH) + a d s + (H+) + 2e'
Fe(OH) + a d g + H + + (Fe ++ ) g + H 2 0
The adsorbed species may in turn
namically stable forms:
Fe(OH) 2 and Fe(OH) 3 .

change

towards

(2)
(3)
thermody

These "hydroxide" forms create, at the surface of the metal, a

compact insulating film - the "PASSIVE" film.

By referring to POURBAIX8 diagrams it is possible to know under
which conditions the passive film exists. The addition of highly
oxidizable elements, such as chromium, into iron reinforces the
tendency to form very stable, highly adherent and relatively
thin oxides. In the case of stainless steel, the thickness of
the passive layer is of the order of a few nanometres.
1.2.1 - Demonstration of the passive layer
The most conventional method of demonstrating the passive layer
is
to plot
the
current
density/potential
curve
under
"potentiokinetic" conditions.
The current density/potential curve of a stainless steel is
given below; it comprises 4 regions:
- activity;
- prepassivity;
- passivity;
- transpassivity.

TRANSPASSIVITY

Figure 6 - An example of a potentiokinetic curve for an

AISI 316 type stainless steel in a dilute acid medium.
10

Description
Corresponding to the "activity peak" is the critical passivation
current (Icrit) and the critical potential E c r i t ; this arises from
the phenomenon of oxidation, a thermodynamically stable state.
E c r i t corresponds to the potential at which the dominant phenom
enon is passivation of the metal and I cr i t corresponds to the
current density necessary to stabilize the PASSIVE state.
1.2.2 - Properties of the passive layer
The composition and constitution of the passive layers in
stainless steel determine the extent of the corrosion resistance
of stainless steel. The thickness of the passive layer ranges
from a few nanometres to 10 nm.
These films consist of water molecules, cations, anions and
highly oxidizable metals, such as iron, chromium, aluminium,
silicon, etc.
The ambient medium (wet air) reacts with the metallic surfaces,
especially with chromium which is more easily oxidizable than
iron.
Several structural models of the passive film have been pro
posed7, two types being mainly mentioned:
(Fe,Cr)203
(Fe,Cr)(0H)n
Other models are mentioned in the literature, for example:
a)
the formation of a passive film by "change of place",
according to the model proposed by UHLIG9 and SATO 10 (Figure 7)
in which:
a)
the oxygen of the water is fixed by adsorption on the
surface of the metal
)

exchange between O "

ions and metal ions, with the

11

mechanism being repeated according to the diagram below:

- adsorption of OH" ions, forming an amorphous layer
- migration and fixation of Fe + + + and Cr + + + ions coming
from the basis metal.
In brief, the most recent studies 11 confirm these data - the
passive film is a hydrated oxide having the structure of a gel
or micelle.
Li u u U M M

MMMMMM
MMMMMM

(a)

000 000
MMM MMM
MMMMMM

000000
MMMMMM

(b)

000000
MMMMMM
000000

(0

MMMMMM
00000 0
MMMMMM
00000 0
MMMMMM

M MMM M M

(d)

le)

Figure 7 - Passive film forming on a "free" metal 7 ' 9 by

a) adsorption of oxygen,
b) change of place; and
c) repetition of the process (d+e)
Although the passive film is not an insulator in the electrical
sense of the term, it is subject to ion transfer and is therefore the site of material transport. An increase in the flux of
material can generate instabilities leading to rupture of the
passive film (this is the case with CI" ions).
Rupture of the passive film
The main parameters involved in the rupture of the passive layer
are:
the metal/solution potential
the redox potential of the solution
the pH of the solution
12

the F", Cl" and cation concentrations.

A depassivation pH or critical pH may be defined which corresponds to the dissolution of the oxide.
1.3 -

HIGH-TEMPERATURE OXIDATION - IRON-OXYGEN DIAGRAM12'13

In the field of steelmaking, the reference system for studies on

high-temperature oxidation is the iron-oxygen diagram. In the
case of stainless steel, we will choose the Fe-Cr-0 and Fe-Ni-0
diagrams (Section 1.4).
The Fe-0 diagram shows that 3 iron oxides may be encountered
(Figure 8 ) :
the protoxide or wustite, represented by the formula
Fe1_xO since it is lacking in iron. It crystallizes in
the face-centred cubic system, of the NaCl type, at
570C; FeO decomposes according to the eutectoid
reaction4:
4FeO -* Fe 3 0 4 + Fe (4)
from 0.1 to 27.7% oxygen (Figure 8 ) .
magnetite, Fe 3 0 4 , having a cubic structure of the
spinel type. This oxide also exhibits non-stoichiometry. In the diagram, we see that the oxygen-rich
part leads to the formation of Fe 3 0 4 at high temperature (temperature > 850C).
ematite'

Fe 2 0 3 ,

which

is

encountered

in

two

allotropie forms:
a-Fe 2 0 3 , of rhombohedral structure; this oxide forms
at high temperature
y-Fe 2 0 3 , of cubic structure, which is metastable.
13

1.3.1 - Iron-Oxygen Diagram13

1200-

Figure 8 - Cooling in the Fe-0 system13:

1) Fe x _ x 0, rich in 0 2
2) Fex.x0 - Fe + Fe 3 0 4
Decomposition at the metal oxides interphase (scale)
In this case, the decomposition of the protoxide does not end up
with the formation of the Fe 3 0 4 + Fe eutectoid but the precipitation of magnetite, epitaxially with FeO. This magnetite film
is

formed

mainly

between

475C

and

375C. The

magnetite regions allow precipitation of hematite

oxygen-rich
^2

>

^ 7 % of

0 2 atoms).
Low oxygen content (internal oxidation)
To complete the equilibrium diagram, it is necessary to consider
the region of low oxygen contents, corresponding to the region
in which oxygen is soluble in iron.
14

In this region, elements which are more oxidizable than iron,

such as aluminium, silicon and titanium, are oxidized: this is
the phenomenon of internal oxidation.
1.3.2 -

Reactions between iron oxides and the other elements

The iron oxides, FeO, Fe 3 0 4 and Fe 2 0 3 , form solid solutions with

the manganese oxides, MnO, Mn 3 0 4 and Mn 2 0 3 . Chromium and aluminium form spinels: FeCr 2 0 4 and FeAl 2 0 4 . FeO reacts with Si0 2 to
give fayalite (2Fe0'Si02), hence the advantageous role of HF in
the pickling operation.
Figure 9 shows an interesting example:
the outer part consists mainly of Fe 2 0 3 and then Fe 3 0 4 ;
the mixed region, lying close to the metal, is formed
by a mixture of wustite (Fe-^^) and the reaction
products of FeO with other metals;
the so-called "altered" region; this is altered by
other phenomena, particularly by internal oxidation
and decarburation;
the basis metal.
The case of chromium is examined in Section 1.4.3.

15

Atmosphere

Fe,0,

-Fe.O.
Precipitates of Fe 3 0

Outer region

FeO
PL-

diffusion
O

Mixed region
Penetration at grain boundaries
and internal oxidation

Altered region

Deca rbu ration

Sound metal

Figure 9 Diagrammatic crosssection through reheating scale

and the underlying metal (according to reference 14).
1.3.3 Mechanisms and modelling64
PHILIBERT has recently proposed a simple model based on the
diffusion of the metal and oxygen and on the reactions at the
atmosphere/oxide and oxide/metal interfaces. This model predicts
the growth kinetics of the oxide film on the metal.
In contrast, the formation of industrial scale does not
currently lend itself to modelling.
The basics of the model, to which reference may be made, are
summarized in the diagram below (Figure 10):
a

absorption of oxygen molecules at the surface and dis

sociation into atoms
0 2 (gas) 20 (ads)

ionization of oxygen
O (ads) + 2e 0 2
ionization of the metal at the metal/oxide interface

16

M -* M z + + ze
d -

diffusion

of

oxygen

ions

through

the

oxide

skin

to

the

metal substrate
e -

formation of oxide by reaction of 0 2 with the metal

V2ZO"" + M -* M01/2Z + ze

f -

diffusion of cations

through the oxide skin to the oxi

dizing atmosphere
g -

formation of oxide by reaction of these cations with oxygen

M + + + + ^zO(ads) + ze * %zM0

GAS O 2
0 2 2 0(ads.)
0(ads.) + 2 e" 0 s

M M z + + e-

METAL M

Figure 10 - Principle of the oxidation phenomenon: flow of

both electrons and ions 64
1.4

INDUSTRIAL SCALE 14,15,3

A thorough understanding of industrial scale is essential in

order to undertake a study on surface treatments. This is
because the nature and properties of the scale have an influence
on the descaling and pickling behaviour. Industrial scale is
complex and its composition depends on the cooling conditions
The presence of addition elements usually modifies the structure
17

and growth kinetics of the oxidized layers; in addition, the

metal beneath the scale is often altered by internal oxidation.
The annealing atmosphere may also have a considerable influence
on the structure and growth kinetics of the scale, especially if
this ambient atmosphere contains oxidizing gases such as C0 2 and
H 2 0.
1.4.1 -

Thermodynamic aspects - Change in the free energy of

formation of oxides with temperature -OLETTE-ANCEY
Diagrams 17

The thermochemical properties of the elements and their com

pounds form a source of information for the metallurgist study
ing the physico-chemical oxidation reactions.
The changes in free energy provide essential information for a
study on scale formation. To make it easier to understand the
phenomena involved, we propose to use OLETTE-ANCEY diagrams, the
principle of which will be viewed below.
Consider the general reaction for formation of an oxide:

*** + 2 " M A
The change in free energy, AG T , which accompanies such a reac
tion at constant and constant P, is related to the change in
standard free energy AG by an equation of the form:

AG T
x

where

a
o
Mvo,
}
= AG" + RT In
L-

J.

M* p o 2

is the temperature in kelvin,

p 0 is the partial pressure of oxygen,
a 0 is the activity of the metal oxide and
a M is the activity of the metal.
18

..
(5)

If AGT is negative, the reaction is thermodynamically possible

(but it may still not occur if the kinetics are very slow).
If AGT is positive, the reaction will not take place. When the
metal, the oxygen and the oxide are in equilibrium at a tempera
ture , AGT = 0.
Equation (5) then becomes:

AGj = -RT In

= -RT In K

(6)

VPo 2

where K is then the equilibrium constant of the reaction.

Thus:
AG = RT In p 0

(7)

We therefore see that the formation of the oxide depends on the

partial pressure of oxygen and on the temperature. A G may be
expressed in terms of the change in the free enthalpy and in the
entropy under standard conditions:
AG = ? - TAS

(8)

The OLETTE-ANCEY curves take account of these parameters and

show that, for a given temperature, it is possible to calculate
the values of AG with sufficient accuracy to direct industrial
processes.
By examining the diagrams (Figure 11), it is possible to deter
mine the relative stability of the oxides with respect to one
another. It will be recalled that the more negative the value of
the free energy of formation of an oxide under standard con
ditions the more stable is the oxide. The value of the oxygen/
metal/oxide equilibrium potential serves to determine the
direction of the reactions.
19

,H,W

-BO .
-U0

200
U
WO
TWElttTUtt *C.
0

WO

ISO U M

io- i o

WO

--

\
p0.

V Vi
1

"* to

W**

\
io-

W*10

,\

aftn

Figure 11 - Equilibrium diagram for the formation of a few

oxides 17 .

20

lOg P O 2 (p&2 in atm.)

FeaCU/Fe^Oa.

Cu /C LU O

-lOf-N'/NiO
3 /soa
FeO/Fe, Q,.
Sn/SnOj
Fe/FeO
P/FjOj

c/co
-20"

-30

Cr/Cr 2 03
Mn/MnO
V/ViOs
_/3
Oj
Tl/TlOa

Aj/AljOa

-40

Figure 12 - Section through the diagram at 1000C 15

1.4.2

Kinetic aspects

Thermodynamic data give us an idea of the direction of the

reactions. On the other hand, they do not give any information
about the rate of the reactions. The thermodynamic data are
therefore of limited value. Between 1960 and 1980 many
researchers3'18'19,20 have studied the oxidation kinetics in Fe-Cr
and Fe-Cr-Ni alloys; in the case of ferritic and austenitic
steels, they have shown that oxidation takes place in successive
steps.
Figure 13 gives a diagrammatic example of the oxidation kinetics
in iron-chromium alloys18. depending on the industrial con
ditions, the rate of oxidation may increase very markedly. The
kinetics are as follows:

21

period of induction, O + A
period of formation, A > B, the weight
linearly with time

increasing

period of retardation, C.

T, lt

Figure 13 Oxidation kinetics in FeCr alloys and stainless

steels18
1.4.2.1 Growth mechanism and thickness of the scale on carbon
steels 15 ' 21
Two situations are possible:
oxidation below 570C, the scale then consisting of
Fe 3 0 4 and Fe 2 0 3 ;
oxidation above 570C, the scale consisting of F e ^ ^ ,
Fe 3 0 4 , Fe 2 0 3 .
Industrial scale corresponds to this situation. GALDN15 mentions
that, for a given industrial process (running conditions and
constant composition), the distribution in the thicknesses of
the various oxides is substantially constant:

22

- approx. 95% for FeO

- approx. 4% for Fe 3 0 4
- approx. 1% for Fe 2 0 3 .
This situation is obtained after one minute at 1100C. An
empirical formula allows us to calculate the thickness of the
metal layer consumed by oxidation:
(9)

th. Fe = 0.54 th. s c a l e

where

th.p

= thickness of the layer of oxidized metal and

th. s c a l e = thickness of the layer of scale formed.

Figure 14 gives a diagrammatic representation of the oxidation
mechanism for iron in oxygen.

cr

S Diffusion

Figure 14 - Diagram of the oxidation mechanism for iron in

oxygen21:
LJ" vacancies, positive charge defects, - negative charge
defects
Growth mechanism
For steels, the scale growth mechanisms are known. The scale
23

grows :
by diffusion of
magnetite;

iron in the protoxide and in the

by diffusion of oxygen in the hematite

(PAIDASSI21) .

Oxygen diffusion mechanisms are provided by dislocations, grain

boundaries or microcracks. The diffusion of iron in 1- 0 is
possible due to vacancies. It should be pointed out that these
mechanisms are valid only if the scale is adherent 16,22 ' 64 .
Growth kinetics
For the oxide layers, which adhere to the basis metal and grow
under isothermal conditions, the thickness of the scale depends
on the duration of the oxidation through a law of the form:
th. =

v/Et

(10)

In this equation:
th. = thickness of the scale
k
= oxidation constant
t
= time.
The oxidation constant k depends on temperature,
Between 700C and 1250C, it has been found that21:
k = 6.03 exp(-Q/RT)

(11)

k being expressed in cm 2 /s, T is expressed in K and Q = 40,500

calories/mole/degree.
1.4.2.2 - Change in the scale during cooling14'15
The modifications observed relate solely to the protoxide layer;
the other oxides, Fe 3 0 4 or Fe 2 0 3 , do not undergo obvious major
24

changes.

The

protoxide

changes

as

result

of

two

transformations :
the shrinkage of its field of existence
temperature decreases (cf. Fe0 diagram);

as the

the eutectoid reaction at 570C:

(12)

4 FeO * Fe 3 0 4 + Fe
with precipitation of interfacial magnetite.

For the oxygenrich region (02 = 27.7% by weight), Fe 3 0 4 can also

precipitate above 570C.
Although the decomposition of Fe 1x 0 takes place at the
metal/scale interface, it does not stop with the formation of
the Fe 3 0 4 + Fe eutectoid but with the precipitation of magnetite
epitaxially with e
F ^yO.
The two modes of cooling which are particularly important for
scale removal are shown in Figures 15 and 16.

,Fe,0,
Fe304

Metal/scale
interface

r " -->>' ?*5,3.. - 's_i

ffti

F e , 0 . dendrites
Undecomposed
protoxide

.-

^rSs^S^Fff-vXXj

a)

Eutectoid region
(Fe 3 0 4 *Fe)

Layer of
protoxide
(either
decomposed or
undecomposed)

Undecomposed
protoxide

'i '".J

Layers of
higher
oxides

Rapid cooling;
undecomposed protoxide

Figure 15 Rapid cooling;

undecomposed protoxide 14,15

Metal

b)

Layer of 3 0
at the metal/scale
interface

slow cooling;
partially decomposed
protoxide

Figure 16 slow cooling;

decomposed protoxide 14,15

25

The first figure, Figure 15, relates to RAPID cooling in which

Fej_ 0 is not decomposed. The second figure deals with SLOW
cooling; in this case Fe 3 0 4 precipitates and interfacial
magnetite precipitation is observed between the undecomposed
protoxide and the metal. We will see that the oxidation phe
nomena in stainless steels are much more complicated. The
presence of addition elements leads to modifications in both the
structure and the growth kinetics. Likewise, the atmosphere in
which the alloy steel oxidizes may also have an influence on the
structure. This is found to be the case, for example, in the
presence of an oxidizing gas (C02) or water vapour.
1.4.3 - The scale on stainless steel
The scale on stainless steel is tackled by taking as a reference
the Fe-O, Fe-Cr-0 and Fe-Ni-0 systems 13,24,25 .
Reminder
a - The
written:

overall

reaction

of

formation

of

an oxide may

xM + V4y02 -* M ^ y + AG T

be

(13)

This reaction is possible only if AG T (change in free energy at

a temperature is negative). The value of AG therefore gives an
indication of whether or not a reaction is possible.
b -

The oxide is more stable the more negative AG T is.

c -

Even if the reaction is thermodynamically possible, it can

take place only if the kinetics are fast enough.

d - The more stable and adherent the oxide layer is and the
more impermeable it is to the migration of solid or gaseous
molecules or atoms, in one direction, and to diffusion of the
metal ions of the alloy, in the other direction, the higher the
oxidation resistance will be.
26

e - The oxidation resistance becomes even more effective the

lower the density of defects (vacancies etc.), that is to say
departure from stoichiometry, in the oxides.
1.4.3.1 - Classification of the oxides 26
PILLING and BEDWORTH27 have classified layers of metal oxides
into 2 separate categories:
- those whose specific volume is greater than that of
the metal giving rise to it, the oxide then being
under compression;
- those whose volume is less than that of the original
metal, the layer then having cracks through which
oxygen penetrates.
The PILLING and BEDWORTH27 coefficient gives a first indication
about the texture of the layer formed.

Oxides

MgO

0.81

A1 2 0 3

1.28

Zr0 2

1.56

Cu 2 0

1.64

NiO

1.65

Ti0 2

1.76

CoO

1.86

Cr 2 0 3

2.07

3.19

25

Table I - PILLING and BEDWORTH27 coefficients

For alloy steels, the compounds formed during the reaction of
27

certain metallic elements with oxygen may give rise to solid

solutions or to multiphase layers.
According to BENARD3, for binary alloys there are three cases
which can be shown diagrammatically:
1st case: Class I, only A oxidizes and forms AO.
2nd case: Class IIa, the substances A and both
oxidize and form two insoluble oxides AO and
BO.
3rd case: Class lib: both oxides AO and BO are soluble
and then form a spinel.
The following diagram summarizes these various possibilities3.

Class I = only A oxidizes and forms AO

m.

Class Ila = A and form two insoluble

oxides AO and BO

*&

Class IIb = the oxides AO and BO are

soluble or form a spinel

r r r z
m %

Spinel

.BO
Sol. Sol.

Figure 17 - Oxidation diagram for binary alloys"

28

These cases correspond to a simple oxidation law of the type:

*? =v/pT

(14)

in which: AW is the weight change per unit area, Kp is a

constant related to the diffusion coefficients of oxygen and of
the metal in the oxide, and t represents the oxidation time.
For ternary alloys, the oxidation laws are complicated and the
diffusion coefficients in such media are not known with any
accuracy.
1.4.3.2 - Oxidation of chromium
Chromium crystallizes in the body-centred cubic system,
Melting point 1900C
Relative density 7.19.
Main oxide, Cr 2 0 3 .
PILLING and BEDWORTH coefficient = 2.07.
Above 1100C, chromium can volatilize in the form of CrO, Cr0 3
and Cr 2 0 5 (reference 2 6) .

1.4.3.3 - Oxidation of nickel

Nickel crystallizes in the face-centred cubic system
Melting point 1453C
Relative density 8.9
Oxide formed NiO
PILLING and BEDWORTH coefficient = 1 . 6 5 (reference 26)

1.4.3.4 - Oxidation of Fe-Cr alloys 3,26

The oxidation resistance of Fe-Cr alloys varies depending on the
chromium content, the temperature, the oxidizing atmosphere and
29

on the other elements present (BENARD )

Figure 18 gives

the various

oxides

formed depending

on the

chromium content and the temperature .

(Fe,Cr) 2 0 3

F*0.(F.^r)203
F0

Mm^M Cr
c

23

'23

Fe-Cr a l l o y

Figure 18 - Oxidation diagram for an Fe-Cr alloy (scale layers

formed on this alloy3)
low contents (approx. 0.5%): the oxides formed have
the same appearance and a composition similar to those
formed on pure iron;
2% < Cr < 3%: the oxide layer consists of (Fe,Cr)304
spinels; if the temperature is below 850C, the major
oxides are Fe 2 0 3 and Fe 3 0 4 ; in contrast, if the temperature
is above 950C, the oxides consist of (Cr,Fe)304 and Fe 2 0 3 ;
Cr > 13%: the main oxide formed is
(Fe,Cr)304, depending on the authors 28,29 ;

(Fe,Cr)203 or

Cr > 26%: the oxide consists mostly of (Fe,Cr)203, but

thermodynamically the (Fe,Cr)304 spinel can exist if the
30

basis metal contains more than 13% of chromium.

1.4.3.5 - Oxidation of Fe-Cr-Ni alloys 3 , 2 4 , 3 0 , 3 1 , 3 2
Most authors 24,30 state that the oxidation of Fe-Cr-Ni alloys is
similar, in principle, to that of Fe-Cr alloys and depends
mostly on the selective oxidation of chromium.
For austenitic steels, the oxides divide into two layers:
a -

an outer solid solution of (Fe,Cr,Ni)203

b - a spinel of approximate formula (Fe,Cr,Ni) 3 0 4 . GENDRON

and AJERSCH31 and CHAUDANSON24 have confirmed, for example,
that in an AISI 316L steel the oxidation comprises two
steps:
- formation of an outer oxide, Fe 3 0 4
- formation of the spinel
(Fe,Cr)304,
diffusion of 0 2 .

due

to

In contrast, for an AISI 310 grade, the outer layer is a spinel

of the (Mn,Fe)Cr304 type.
The role of nickel would seem to be to promote the formation of
Fe-Cr-0 solid solutions by reducing the oxygen diffusion rate.
BENARD3 has shown that, for an AISI 304 alloy oxidized in air,
nickel was not present in the products formed at the start of
oxidation; since nickel is more noble than iron, it would be
rejected to the metal/oxide interface. This phenomenon is
confirmed by the concentration of nickel in the chromiumdepleted region. The oxidation mechanisms in Fe-Cr-Ni steels are
governed both by kinetic parameters, mentioned previously24, and
by the presence of other elements: Al, Si, Mn, Mo and rare
earths.

31

1.4.3.6 - Influence of addition elements

Role of aluminium 33,24
The role of aluminium is predominant; in trace amounts, its role
will also be very important in internal oxidation. For Fe-Cr-Al
steels, the surface oxidation kinetics are seen to be very slow
because of the presence of a protective layer of Al 2 0 3 .
Cr < 13%, Al < 2.5%: The outer layer consists of Fe 2 0 3 , an
intermediate layer of FeCr 2 0 4 spinel is then observed and finally
another, highly protective, spinel FeAl 2 0 4 .
Cr > 13%, Al < 2.5%: The outer layer consists of Cr 2 0 3 and the
intermediate layer consists of FeCr 2 0 4 and FeAl 2 0 4 .
Cr > 13%, Al > 2.5%: These steels lead to the formation of a
highly protective layer of the oxide Al 2 0 3 .

Role of silicon3
Silicon is selectively oxidized and consequently increases the
oxidation resistance. Like aluminium, silicon plays a major role
in internal oxidation. The protective nature of silicon is due
to the presence of Si0 2 at the metal/oxide interface; however,
the nature of silicon at the metal/oxide interface remains a
controversial subject since, for some authors, it is silica
which is believed to be responsible for this protection while
for other authors it is believed to be an amorphous oxide at the
metal/oxide interface.

Role of manganese35
Depending on the oxidation temperature and the manganese
content, an internal oxide may be obtained which contains Mn 2 0 3
and more generally a spinel of formula MnCr 2 0 4 . According to
CAPLAN et al. 3 6 , in the presence of a high (2 6%) chromium

32

content, an MnCr 2 0 4 spinel is formed on the outermost surface, to

the detriment of an (FeCr)203 solid solution.
Role of molybdenum
The advantage of additions of molybdenum is due to its effect on
the mechanical behaviour and on the corrosion resistance.
Moderate contents of molybdenum have a favourable effect but, in
contrast, for high concentrations (> 2%) the volatile oxide Mo0 3
may form.
Role of rare earths35
There are many mechanisms relating to the role of rare earths,
some being highly controversial:
- anchoring of oxides
- growth of seeds
- trapping of impurities.
Role of sulphur
The role of sulphur has not been envisaged (the case for resulphurized martensitic stainless steels). Sulphur gives porous
scale with formation of an oxysulphide.

1.4.4

Oxidation

of

stainless

steel

in

an

industrial

e n v i * t-

It is well known (HATFIELD37) that the scale on an AISI 3 04 grade

steel is seven times greater at 900C in the presence of 5% of
water vapour 24 ' 38 .
1.4.4.1 - Influence of water vapour
The influence of water vapour is felt:
- on the oxidation kinetics
33

However,
AISI 304
(25% Cr,
reaction

although it has a very strong effect on steels of the

and AISI 316 type, it is slight for AISI 310 grades
20% N i ) . The greater the iron content the greater the
with water vapour.

In contrast, contradictory39 reactions are observed in Fe, 14%

Cr, 35% Ni alloys.
- on the nature of the scale
Water vapour promotes the formation of spinels for AISI 3 04
steels, the oxide formed being an (Fe,Ni)Cr204 spinel.
- on the morphology of the scale 40
Water vapour promotes increase in porosity and the formation of
so-called "cellular" oxides.
The kinetics of oxide growth are also modified. The porosity of
the oxide layers is a key parameter. It is well known that
porous scale easily "desquamates" in pickling baths.
- on the first stages of oxidation
The role of water vapour varies with temperature, influencing
especially the level of diffusion of 0 2 and H 2 0 species through
the pores.
This information is collated in Figure 19 which shows the fields
of existence of the surface oxides formed at 1200C on an AISI
43 0 steel, depending on the water vapour pressure and the
oxidation time 24 .
In conclusion, the reader is reminded of the favourable role
played by water vapour, during annealing, on the "pickleability"
of these steels.

34

Oxidation time (sec)

Figure 19 - Fields of existence of the surface oxides formed

at 1200C in the presence of water vapour (AISI 430 steel) 2
1.4.4.2

Oxidation in air and in pure oxygen

A review of the literature shows that the results differ according to the authors 41 ' 42 ' 43 ' 44 . According to CHAUDANSON24, YEARSIAN
et al. 43 and KURODA et al. 4 4 , oxidation in air is complex, the
time and temperature parameters governing, for the most part,
the kinetics of scale formation.
The most recent work 4

seems to confirm:

at 1000C, going from the atmosphere towards the

metal, the presence of the following oxides (in the case of
AISI 304 and 310 steels):
- FeCr 2 0 4 and MnCr 2 0 4 spinels
- oxide Cr 2 0 3

35

1.4.4.3 - Industrial annealing at low oxygen pressures

a - Atmospheres dilute in 0 2
CASTRO and DECROIX45 have studied the annealing of AISI 43 0 and
AISI 3 04 grade steels in a neutral gas containing 1% of oxygen
between 1000C and 1300C.
The scale is composed of:
FeCr 2 0 4 and MnCr 2 0 4 spinels
a layer rich in silicon at the metal/oxide interface.
The most recent work has shown that, in addition to the spinels,
the oxide Cr 2 0 3 and fayalite, 2FeO*Si02 were observed; however,
the spinel MnCr 2 0 4 was not detected.

Role of the oxygen content in continuous annealing

In this field, the work by HABRAKEN et al. 46 is authoritative.
This team has studied the relationship between the nature of the
scale and pickling for the purpose of identifying an oxide
structure which exhibits good pickleability. HABRAKEN has shown
that the pickling capability depends on the presence of manganese and silicon in the scale; the effect of these elements
depends on the time and temperature of the anneal.
b - Annealing at low oxygen pressure
FERNANDO and ZAREMSKI47 have carried out a very exhaustive study
on the influence of the annealing conditions on the nature of
the oxides and the pickling of AISI 304 and AISI 430 steels.
The key parameters are, in order of importance:
the temperature
the duration of the annealing treatment
the amount of oxygen in the annealing gas.
36

Temperature mainly has an effect on the thickness of the scale,

As an example, for the AISI 3 04 grade:
Outer layer: the spinels FeCr 2 0 4 , (Fe,Cr)203 and Mn 3 0 4
Metal/oxide interface: presence of fayalite.
Manganese was detected only if was above 1120C.
For the AISI 43 0 grade:
Outer layer: FeCr 2 0 4
Metal/oxide interface: presence of silica

% o2

AISI 430 grade

steel

AISI 304 grade

steel
FeCr 2 0 4 , Cr 2 0 3 , MnO

6
Cr 2 0 3
4
Cr 2 0 3

FeCr 2 0 4 , Cr 2 0 3 , MnO

2
0
00

Cr 2 0 3
FeCr 2 0 4 , (Fe,Cr)203
FeCr 2 0 4 , (Fe,Cr)203

FeCr 2 0 4 , Cr 2 0 3 , MnO
FeCr 2 0 4 , (Fe,Cr)203,
MnO, NiO

Table 2 - Nature of the scale on AISI 3 04 and AISI 43 0 steels

as a function of the percentage of oxygen in the annealing
atmosphere24 ' 45
We give below a few examples of industrial annealing. Furnaces in Europe - are supplied with natural gas and corresponds to a
treatment atmosphere containing:
2 to 7% of oxygen
some C0 2
some water vapour.
Each plant chooses an amount of oxygen compatible with the
annealing treatment and, above all, one which gives the best
37

pickleability. The pickling process is therefore carried out at

this level.

Austenitic
steels

Continuum annealing,
2 to 2.58 02, 1100C,
2 =IL, va tax qaench

D e s c a l i n g . Prepickling . Pickling, then

passivation
treatments

Box annealing,
N2 or H, 800C,
6 h

D e s c a l i n g P r e p i c k l i n g P i l i n g , then
treatments!
^passivation
1
1

HR
Ferritic
steels

Table 3: Examples of industrial processes, after hot rolling

(HR), used for flat stainless steels

AnaaaliEg, 2 t o l

Austenitic
steels

HWD

0;,

9S0 t o 1050-C,
depending on the
grades

Prepickling
(molten s a l t s )

Pickling, then
passivation

Prepickling
(molten s a l t s )

Pickling, then
passivation

Box anneal iag,

750 to B50"C,
2 to 4 h

Ferritic
steels
Bogie-bearth furnace
annealing, 2 to 7-s o2
750 to 850"C, 2 to 4 h

Table 4: Examples of industrial processes, after hot wire

drawing (HWD), used for stainless steel wire rod
c Reducing annealing (box annealing, bright annealing)
This is the case for ferritic flat products annealed in H 2 + N 2
atmospheres, with a percentage of hydrogen varying from 4 to
100%: this is socalled "box" annealing. The treated coils come
from hot rolling and must be annealed and then pickled before
cold rolling. The iron oxide is then subjected to a partial
pressure of hydrogen, and therefore to a medium which is
reducing with respect to this compound.
38

After annealing for 815C for 12 hours, the oxide layer was
analysed, using glow discharge mass spectroscopy (GDMS) 48 , and
shown to have a metal/oxide interfacial region rich in silicon
and in chromium; in contrast, the outer region contained only
iron and manganese. The scale thus obtained is cracked and
porous 49,50 .
d - Thermodynamic aspects of reducing annealing51'52
The oxidizability of the elements is calculated by comparing the
oxygen potential of the annealing atmosphere, at a given tem
perature.
In order to evaluate the oxidizability of a medium, we use the
reaction:
H 2 0 *- y>2 + H 2
where :
p

H2o

s
Po 2 -P H a

(15)

and = absolute temperature

The value of P 0 is determined from the partial pressures of
hydrogen and water vapour, the partial pressure of H 2 0 being
determined by measuring the dew point and the constants being
obtained from tables, using the equation:
lnp 0 = 2In _ ^ 1
PH 2

(16)

Examples of the oxidizability of the elements Cr, Si and Mn are

found in the literature53'54'55'56. These articles may be consuited for specific studies.

39

Constitution of the phases oxidized in reducing atmospheres

We give below a few examples relating to defined grades, under
conditions which are also defined24 :
AISI 420 steel - Annealed in an H 2 /N 2 atmosphere, with dew points
between -3 6 and -25C (see CHAUDANSON24) .
The

possibly

oxidizable

elements

are

Mn

and

Si, with

the

formation of silica and the spinel (Mn,Cr)204.

It should be pointed out that statistically the silicon oxide
(Si02) content increases as the temperature of the dew point
decreases.
AISI 304 steel - Annealed in an H 2 /N 2 atmosphere; dew point above
-40C.
The oxides possibly formed are:
- FeCr 2 0 4 spinels
- Silicon oxide,Si02.
All the studies show that, when annealing in a reducing atmosphere, the addition elements Si, Al, Mn and Cr may, possibly,
oxidize whereas, in agreement with the thermodynamic data, the
iron oxides are reduced (BRIGHT annealing). The iron oxides are
reduced further the lower the dew points.
1.4.5 - Chromium depletion of stainless steels
The surface oxidation of stainless steels leads to chromium
depletion at the metal/oxide interface - the "chromium-depleted"
region. This region seems to play an important role (VICENTINI
and BOMBARA57) during the pickling process, because it is more
soluble in acids than the basis metal. It is now accepted (cf.
"PICKLING" Chapter) that pickling does not take place by dissolution of the scale layer but by exfoliation of the latter after
attack of the chromium-depleted region. It has been shown
that

40

the pickleability of AISI 304 and AISI 430 grade steels, after
annealing, is improved when the amount of chromium in the
chromium-depleted region decreases.

1.4.5.1 - Chromium depletion phenomena - Fundamental aspects

The formation of an oxide containing chromium, due to the effect
of temperature, is accompanied by the formation of a region in
the metal impoverished in this element as a result of a
continuous increase in chromium in the oxide.
Studies on the chromium depletion phenomena make use of the
theory proposed by WAGNER59 and to the laws of solid-state
diffusion. We will not repeat here the diffusion study, but an
appreciation of these phenomena may be obtained by consulting
specialized works. However, we do give, in Table 4, the
diffusion coefficients of chromium in the main stainless steels.
Steel grade Temperature

(C)

D(cm 2 /sec)

References

AISI 430

1200C
1000C

3.4 10" 1 0
2.9 10" 1 0

60

AISI 410

1200C
1000C

3.4 1 0 - 1 0
2.9 10" 1 0

60

AISI 316

1000C

3 10" 1 2

61

AISI 321

1000C

3 10' 1 2

61

Table 5 - Diffusion coefficients of chromium in stainless

steels

41

1.4.5.2 - Influence of the main factors

The

parameters

influencing

the

chromium

depletion

are

the

following:
- The nature of the steel. For a given treatment, chromium
depletion is greater for austenitic steels than for
ferritic steels. This phenomenon may be explained by the
difference between the interdiffusion values in the alloy.
- The treatment temperature. The relationship between
temperature and the thickness of the chromium-depleted
region has never been formally demonstrated. However, it is
known that the diffusion coefficient of chromium increases
with temperature62.
- The treatment duration. For a given temperature, the
Cateel/C chromium depletion is a maximum for heat treatments
of short duration. This phenomenon may be explained by the
rapid formation of a Cr203 layer which results in strong
chromium depletion of the matrix but which also forms a
diffusion barrier.
- The annealing atmosphere. The effect of a reducing
atmosphere is greater for the AISI 430 steel than for the
AISI 304 steel.
- The

residual

elements.

The

effect

of

the

residual

elements may be seen:

- in the chromium diffusion rate,
- in the nature of the oxide layer.
It will be recalled
chromium.

that nickel

increases

the diffusion of

- The initial surface finish. It is known3,24 that working

(rolling) promotes the diffusion of chromium in Fe-Cr
42

alloys. This phenomenon may be explained by the formation,

during the mechanical treatment, of dislocations promoting
the diffusion of the elements Cr and Mn.
1.4.5.3 - An example of chromium depletion63 is given below.
Conditions:
- Steel: AISI 304
-

Continuous annealing
Temperature: 1140C
Duration: 85 seconds
Furnace supplied with natural gas.

The results of the chromium depletion measurements give:

- a chromium depletion profile extending over 1.7 /m
- amount of chromium at 50 nm from the metal/oxide interface is approximately 4% (compared to 18%) , while at 200 nm
the amount of chromium reaches 12%.
The following figures20,21 show examples of chromium depletion
profiles obtained for an AISI 304 steel at 1140C and an AISI
430 steel at 870C, after 90 seconds, for various annealing
atmospheres.

43

05

IO
15
Depth (um)

4
6
8
Depth (tim)

10

1.4.6 - The influence of treatment and cooling conditions on the

change in structure of the scale
It may be easily understood that the reheating conditions before rolling - and the cooling conditions of the coils,
bundles or bars play a key role on the nature, composition,
heterogeneity, etc. of the scale.
Scale inlay
After hot rolling, the scale may appear as various layers of
varied colours65. These various colours are due to the fact that
rolling inlays the oxides into the metal (Figure 22); KITAGAWA65
and LUYCHX66 have shown that the main factors responsible for the
inlaying are the composition of the metal and the reheating
conditions (temperature, time and oxygen partial pressure).
Cooling conditions
Likewise, the conditions under which the product is cooled have
a very significant effect on the nature and homogeneity of the
scale-covered surface. Examination of a stainless steel coil
entering a pickling tank reveals various colorations between the

44

edges and the central axis and between the faces. For example,
the lower face often undergoes chafing on the spraying table. We
will see that axis/edge non-uniformities are often observed as
a result of the differences in constitution of the scale, that
of the edges always being more oxidized than that along the
axis. The edge oxides are richer in iron chromites, FeCr204, and
Fe203. The oxides away from the edges (cooling protected from the
air) are richer in protoxide F e ^ O , which undergoes the eutectoid decomposition with the formation of interfacial magnetite.

Formation mechanism
Rolling-mill roll

Scale

^^aaa^a

Rolling direction

"Waves" of inlaid scale

Figure 22 - Mechanism for the formation of inlaid scale

(according to reference 66)

Inside

Outside

Edge

Edge

Overoxldlzed scale (higher oxides)

Fig. 23 - Example of non-uniformity of the edge/axis surface

The scale on edges is always more oxidized16
In a study on flat products, QUANTIN and BECOT16 have shown that
the cooling conditions have a significant effect on the constitution of the scale; depending on the cooling kinetics adopted,
45

it is possible to obtain:
- scale of different compositions and constitution
- scale of very varied thickness.
The following example is a good illustration of the effect of
cooling conditions.
Cooling in the
presence of air:
higher oxides
Haematite

Very slow cooling, protected from

the air: total decomposition of
the protoxide

-SX\\\\\S\\\
I-++

-M-

Magnetite

+++
++

*-++
Haematite

Magnetite

Protoxide

Hot structure

Iron + Magnetite

Iron + Magnetite

Very rapid (quench)

cooling: hot structure
preserved

Rapid cooling: partial

decomposition of
the protoxide

Slow cooling: almost

complete decomposition
of the protoxide

Figure 24 - Effect of cooling conditions on the structure of

the scale16
The corollary of this study relates to the method of storing
coils or bundles after rolling or wire drawing, or heat treat
ments. Depending on the cooling method adopted, the scale formed
will be reproducible (similar composition and constitution) or
random.
Figure 25 shows the various cases observed.

46

non-uniformity between
edges

idem, except for

the central coil

rapid cooling of the edges, with

good reproducibility: air circulates
between the uniformly spaced coils

co|s

non-uniformity between edges:

the coils cool differently depending
on their position

arranged randomly: no reproducibility

Figure 25 - Example of methods of storing coils: effect on the

constitution and composition of the scale16
1.4.7 - The formation of defects in the scale
The defects observed in the layers of scale are due to:
- the metal
- the environment of the metal during oxidation.
- Role of the metal: It is known that working accelerates the
oxidation rate3; the same applies to the geometrical shape and to
the impurities which come into play to form:

47

- mixed oxides or spinels

- inclusions.
- The environment during oxidation:
The first defects formed are due to:
- constraint of the growth;
- evolution of gas at the metal/oxide interface. The
ambient gas may thus form pustules filled with C0 2 , CO or
nitrogen;
- temperature, as a result of a difference between the
expansion coefficients of the metal and the oxide, and
sometimes also as a result of melting of the oxide. This is
the case, for example, for fayalite, Fe2Si04, which melts at
1170C. Thus in the presence of silicon, we observe:
- formation of fayalite at > 1170C
- melting of fayalite
- crystallization when < 1170C;
- the atmosphere, particularly to variations
partial pressures and to water vapour.

in

oxygen

Appearance of the scale

The scale is
vocabulary:

"physically"

Cracks : two-dimensional

described

defects

in terms of a

which

appear

in

specific

micrograph

sections as black lines with parallel edges.

Pores : more or less round interstices, often aligned in a string
Cavities : defects within the volume of the scale (voids, devoid
of material)
48

Pustules : protuberances or eruptions at the surface of the scale

Disbondment: rupture of material leading to a scaly or flaky
structure
Adhesion: practical

concept

allowing

evaluation

of

the con-

tinuity of material between basis metal and scale

Uniformity: depends on the scale of observation; irregularities
may be distinguished by their shape, frequency and amplitude.
"Cat's whiskers" or WHISKERS: oxide needles observed

in the

scale.

1.4.8 - The study of scale

The study of scale demands specific techniques and operating
methods which we will briefly review below:
Metallographic examination
Specimen preparation varies depending on the structure of the
scale studied:
- thick scale
- thin scale
- porous or powdery scale.
The coating methods take these properties into account:
Thick scale: use of thermosetting resins
epoxy resin, etc.).

(diallyl phthalate,

Porous scale: there is a risk of this being damaged by hot

rolling. Operate under vacuum using so-called "cold" resins (for
example LAMPLAN 607) .
49

Polishing:
- prepolishing using 240 - 400 - 800 - 1200 paper
- polishing using diamond paste: METAPLAST SAT or B.ESCIL.
Analysis :
- Optical examination
- Etching using reagents of the NITAL or CHLORAL type
- Scanning electron microscopy, the microscope being
equipped with an energy-dispersive X-ray probe (EDX). The
results are expressed in the form of energy spectra,
overall pointwise analysis and concentration profiles
- Glow

- discharge optical spectroscopy.

This method is complementary to the other means of investigation. It makes it possible, without any special preparation of the specimens, to monitor simultaneously the
change in the elements going from the surface of the scale
down to the metal. We give two examples of GMDS curves
(Figures 26 and 27) relating to scale, showing concentration profiles as a function of the erosion time.

50

Concentration (arbitrary units)

Scale

40

BO

120

160

200 240

280

Emson time (s)

40

80

120

160

200 240

280

Figures 26 and 27G D O S curves showing the concentration

profile as a function of erosion time67
- X-ray diffraction: Debye-Scherrer
constitution of the scale.

diagrams

reveal

the

- the other physical methods are mentioned only as a

reminder. Reference may be made to specialized publications68 :
-

photoelectron spectroscopy (ESCA)

Auger electron spectroscopy
secondary-ion mass spectroscopy (SIMS)
nuclear microanalysis.

Chemical analysis - Oxygen assay 69

We have developed a method allowing us to measure the thickness
of the scale, by quantitative'analysis of the surface oxygen,
before pickling. The LEC0 TC 43 6 analyser is used for this type
of operation.

51

The method consists in quantitatively measuring:

a the total oxygen from a scalecovered
surface area
b the residual oxygen
basis metal).

specimen of known

(the oxygen in inclusions within the

From the difference we obtain the surface oxygen. In order to be

specific, the surface oxygen of a scalecovered specimen (hot
rolled) may be between 1000 and 10,000 g/cm2, the residual
oxygen being about 10 to 20 /g/cm2, i.e. a ratio of more than
100:1. Moreover, knowing the constitution of the scale, it is
easy to calculate from this its thickness. The method is useful
because it is quick and simple.

52

Physical properties of the pure oxides (after BENARD3)

Formula

Hame

Colour

Stability
range

Relative
density

Pilling and
Bedworth
coefficient

Hardness
(Mohs)

OfAljOj

corundum

colourless

2050C

3.97

1.28

-1 2 0 3

alumina

to RT

3.50

1.45

CaO

chalk

colourless

2580C

3.37

0.64

Ce 2 0 3

trigonal

grey

1692C

6.9

1.15

cubic

grey

6.1

1.30

5.21

2.00

Cr 3 0,

black

Cr 2 0 3

green

2275C

Fe^O

wustite

black

2050C

Fe 3 0 <

magnetite

black

1600C

o-Fe203

haematite

red/brown

7-Fe 2 0 3

haematite

red/brown

MgO

periclase

colourless

MnO

manganosite

6.55

to 7.4 0.91 to

4.5

0.81

5.18

2.10

1457C

5.24

2.14

5 to 6

1457C

4.59

2.45

2800C

3.58

0.81

6.5
5 to 6

green

1780C

5.43

1.77

Mn 2 0 3

black

d=1350C

4.50

2.38

M0O3

white/yellow

7950C

4.69

3.27

NiO

bunsenite

green/black

1990-C

6.72

1.68

5.5

Si0 2

O-crystobalite

colourless

220C

2.32

2.15

6 to 7

Si0 2

0-crystobalite

colourless

1713C

2.20

2.27

Si0 2

-quartz

colourless

573C

2.66

1.88

Si0 2

/S-guartz

colourless

175uC

2.50

2.00

Si0 2

a-tridymite

colourless

117C

2.26

2.21

Si0 2

/S-tridymite

colourless

2.20

2.27

anatase

brown/black

Ti0 2

brookite

yellow/black

rutile
Zr0 2

zirconia

Table 6 Physical properties of pure oxides (after BENARD3)

Other methods :
Electrochemical methods of analysis, selective dissolution and
solubility tests, in the various acids, are simple methods of
53

investigation which may be employed.

Physical properties
Table 6 gives a list of a few properties of pure oxides, listed
alphabetically, the values mentioned having been taken from
reference 3 and are given only by way of example. It may be seen
that there are differences in the literature values. The same is
true for the properties, such as the colour, it being known that
this is strongly influenced by:
- the nature and amount of impurities (small fractions of
parts per thousand of impurities modify the colour: for
example ruby and sapphire);
- the thickness of the oxide layer (reflection phenomenon).
1.4.9 - Anti-scale products
The current chapter concludes with various
prepickling processes (see PICKLING chapter)

descaling

and

Anti-scale products are substances which protect the metal from

oxidation or, in contrast, serve to remove scale.
We may distinguish:
Protective coatings: the purpose of these coatings is to limit
the diffusion of 0 2 , by the formation of a protective layer; a
very thin fluid and impermeable surface film is formed, which
solidifies very rapidly.
Protective coatings comprise:
- glasses (sodium aluminosilicates and alkali-metal or
alkaline-earth-metal
borates;
Si02-Al203-CaO-B203
phase
diagram study)
- magnesium phosphosilicates;
54

- molten nitrates, oxides and chlorides;

- Fe 2 0 3 ,nCaO s o l i d s o l u t i o n .
These products may be applied by spraying70.
"Reactive" coatings: These anti-scale products do not act as a
protective coating but as "reactants": they decompose, giving
off C02, hydrogen or chlorine; this is the case, for example,
with methylchlorosilane.
These substances have a thermal expansion coefficient different
from that of the metal; as a result, there is spontaneous
detachment of the oxides, leaving - according to the sales
literature - a clean unoxidized surface.

55

Visual examination
- Defects
(incrustations)
Macrography
Binocular examination
Macrography, Colour

.Examination of sections

Surface examination

SEM - X-ray microanalysis <

X-ray diffraction
Composition of the
oxides

Elemental analysis

Micrography

SEM
Defects,
local analysis

Thickness, structure

Electron microprobe

GDMS

Distribution of the
elements

Surface analysis

Analytical methods
Surface O2 assay
oxide solubility
electrochemical
dissolution methods
pickleability tests
(weight loss)
thermogravimetric analysis

Table 7: Methods for studying scale

56

SUMMARY of the phenomena of oxidation in stainless steels

The table below summarizes the action of the important parameters modifying the oxidation phenomena.

Parameters

Effects observed

Water vapour

- modifies the nature of the oxide layers.

- modifies the distribution of the elements
at the metal/oxide interface.
- increases the porosity of the oxides.
- promotes the formation of spinels.
- makes pickling easier.

Dilute oxygen
atmospheres

- at low oxygen partial pressures, promote

the formation of spinels.
- modify the nature of the scale.

Annealing in N2/H2 - promotes the formation of spinels.

atmospheres
- reduces the iron oxides.
- the nature of the oxides depends on the
dew point.
- acts on the easily oxidizable elements:
Si, Al and Mn.
Chromium
depletion

- a phenomenon associated with diffusion,

- varies depending on the nature of the
steel
- increases with the duration of the
treatment.
- influences working
- influences the diffusion barrier.

57

BIBLIOGRAPHY - Chapter I

1.

G. CHAUDRON, J. BENARD and P. LACOMBE

Comm. journes des Etats de surface
[Comm., Surface
finish
workshop]
Paris 1945 73

2.

J. MOREAU and J. BE NARD

Journ. Chim. Phys. [J. Phys.

3.

Ch
e m.],

1956, 53, 787

J. BENARD
Oxydation des mtaux [Oxidation
of e
m tals]
Pub. GauthierVillars Paris, 1962

4.

B.M. DELL, F.S. STONE and P.F. TILE Y

Trans. Farad. Soc. 1953, 49, 195

5.

P.H. EMMET and S. BRUNAUER

J. Amer. Chem. Soc. 1956, 78, 4533

6.

L. PAULING
T r a i t de c h i m i e m i n r a l e
chemistry]

7.

[Tre atise

on

. BAROUX, G. BRANGER and C. LEMATRE

Les a c i e r s i n o x y d a b l e s [Stainle ss
steels]
E d i t i o n s d e p h y s i q u e s [Physics
Publications],

8.

inorganic

Paris

1990

M. POURBAIX
Atlas d'quilibres lectrochimiques [Atlas of e
el ctroc

hemical e quilibria]
Editions GauthierVillars, Paris, 1963
9.

H.H. UHLIG
Corrosion Sci. 1979, 19., 777

10. N. SATO
Electrochem. Acta 1971, 16, 1683

59

11. OKAMATO
Corrosion Sci. 1973, 13, 47
12. P. PASCAL
Nouveau trait de chimie minrale [New treatise
inorganic
chemistry],
Volume XVII,
Pub. Masson, Paris, 1967

on

13. M. HANSEN
Constitution of binary alloys
2nd Edit., Metallurgy and Metallurgical Engineering,
McGraw-Hill, (1958)
14. J. BAUD, A. FERRIER and J. MANENC
Mem. Scient. Rev. Mt. (1978), 371
See also J. MOREAU and M. CAGNET, Rev. Mt. (1957), 54
No. 5, 383
15. F. GALDN
CESSID notebooks
Le dcapage de produits plats [The pickling
ducts]

of

flat

pro-

of

flat

pro-

, October, 1983

16. D. QUANTIN and J. BCOT

CESSID notebooks
Le dcapage de produits plats [The pickling
ducts]

, October, 1983

17. M. OLETTE, M.F. ANCEY-MORET

Rev. Mt. (1963), June, 60, 6, 569
18. G.C. WOOD
Corrosion Science (1961) - Vol. 2, 173
19. J. BENARD, J. HERTZ, Y. JEANNIN and J. MOREAU
Mem. Sci. Rev. Mt. (1960), No. 5, LVII, 389
2 0. D. CAPLAN and M. COHEN
Corrosion (1959), Vol. 15, No. 3, 141
60

21. J. PAIDASSI
Monographie sur l'oxydation du fer [Monograph

dation

of

on the

oxi-

iron]

In "Oxydation des mtaux [Oxidation

BENARD
Ed. Gauthier-Villars, Paris, 1969

of metals]

"by J.

22. J. PAIDASSI
Rev. Mt. (1957) - LIV No. 8, 569
23. J. BAUD
La calamine : formation - structure [Scale ; formation

structure]
IRSID - RF. p. 95, January, 1974
24. H. CHAUDANSON
- Thesis, University of Paris, XI, 1990
- IRSID Report, 1991, No. 91340
25. M. TACHIKART
Thesis, Compigne Technology University, 1989
26. F. ARMANET and J.H. DAVIDSON
in "Les aciers inoxydables [Stainless
Les Editions de Physiques [Physics
Paris, 1990

steels]"
Publications]

27. N.B. PILLING and R.B. BEDWORTH

J. Inst. Mt. (1923), 29, 529
28. H.J. YEARIAN, E.C. RANDELL and T.A. LONGO
Corrosion (1956), Vol. 12, 515
29. K.A. HAY, F.G. HICKS and D.R. HOLMES
Werkstoffe und Korrosion [Materials and
(1979), 21,11,917

61

Corrosion],

and

30. W.A. SHARP

High temperature oxidation of Fe-Cr-Ni alloys in 0 2
4th Int. Congress on Metallic Corrosion (1972), 291
31. S. GENDRON and F. AJERSCH
"Proceedings of the international symposium on high
temperature oxidation"
Hamilton, Ontario, Canada (1990), August, 155
32. M.C. HOBBY and G.C. WOOD
Oxidation of Metals (1969) - Vol. 1, 1, 23
33. J.P. LARPIN, G. AGUILAR, H. BUSCAIL and J. COLSON
"Proceedings of the international symposium on high
temperature oxidation"
Hamilton, Ontario, Canada (1990), August, 337
34. H.E. EVANS, D.A. HILTON, R.A. HOLM and S.J. WEBSTER
Oxidation of metals (1983) - Vol. 19, No. 1/2, 1
35. F.H. STOTT
"Materials Science and Technology" (1989) - Vol. 5 - 734
36. D. CAPLAN, P.E. BEAUBIEN and M. COHEN
Trans, of the Metallurgical Society of AIME (1965) - Vol,
233, 766
37. S. HATFIELD
Reported by ARMANET (loc. cit.)
Thesis, Compigne Technology University, 1984
38. J.T. BITTEL, L.H. SJDAHL and J.F. WHITE
Corrosion NACE (1969), 25, No. 1, 7
39. D. CAPLAN and M. COHEN
Journal of Metals (1952), Vol. 4, 1057
40. M. DAUZAT
IRSID Report (1991), RI 91.306
62

41. A.U. SEYBOLT

Journal of the Electrochemical Society
(1960) No. 3, Vol. 107, 147
42. U. LEROY, J.P. SERVAY et al.
Silicates industriels [Industrial
Vol. 40, 37

silicat
e s]

(1975),

43. H.J. YEARIAN, W.D. DERBYSHIRE and J.F. RADAVICH

Corrosion (1957) 597
44. K. KURODA, P.A. LABUN et al.
Oxidation of Metals (1983), 16, 117
45. R. CASTRO and J. DECROIX
Oxydation l'air et en atmosphre pauvre en 0 2 d'un acier

Fe Cr [Oxidation of an Fe Cr ste e l in air and in an 02

depleted
atmosph
e
er ]
Corrosion et anticorrosion [Corrosion and Corrosion
Pro
tection]

, (1963) Vol. 11, No. 6, 219

46. L. HABRAKEN, T.D. SHUNGU and V. LEROY

Le vide les couches minces [Vacuum Thin

films]

199, 385
47. L.A. FE RNANDO and D.R. ZARE MSKI
Metallurgical Trans (1988), Vol. 19A, 1083
48. R. BERNERON, . CHETREFF, J.P. COLIN, P. DE GELIS,
H. HOCQUAUX, F. HOFFERT and S. MATHIEU
XXIV C.S.I. GarmishPartenkirchen (1985)
49. H. SHAY, T.L. ELLISON and K.R. BERGER
Progress in powder metallurgy (1983), Vol. 39, 411
50. J.P. MERLIN
IRSID Report S.C.A. 1994 84/94

63

(1979),

51. J.F. KIRNER, E.J. KARWACKI and A.L. CABRERA

Applied Surface Science (1988), Vol 32, 239
52. J.F. KIRNER, M.R. ANEWALT, E.J. KARWACKI and A. CABRARA
Metallurgical Transactions (1988), Vol. 19A, 3045
53. J.F. KIRNER and A.L. CEGRERA
J. Heat Treat. (1989), Vol. 7, 27
54. J. YANCAI
Iron and Steel (1986), Vol. 31, No. 3, 35
55. R. TODOROKI, T. SAKAMOTO, ZAIZEN and T. SOMURA
Trans. ISIJ. (1982), Vol. 22, 364
56. C D . STARR
Wire Journal (1977), 50
57. B. VICENTINI and G. BOMBARA
Electrochim, Metallorum, 1968, 3, 313
58. B.S. COVINO
Pubi. Bureau of Mines - Chicago, 1987, 8-12, 39
59. C. WAGNER
J. Electrochem. Soc. (1952), Oct., 369
60. G.L. WULF, M.B. McGIRR and G.R. WALLWORK
Corrosion Science (1969), Voi. 9, 739

64

CLEANING

CONTENTS
Page

1.

2.

CONSIDERATIONS OF A GENERAL NATURE

69

1.1

The purpose of cleaning

59

1.2

The origin of surface grease and dirt

GENERAL CLEANING METHODS

71

2.1

Mechanical or physical processes

7I

2.2

Thermal processes

71

2.3

Chemical processes

72

2.3.1

Alkaline chemical cleaning

72

2.3.2

Cleaning using organic solvents

82
R7

2.4

Electrolytic cleaning
2.4.1

The principles involved

2.4.2

The important parameters

90

2.4.3

Plants

gi

2.4.4

Checking - Establishing a
specification - Quality assurance

2.5

2.6
3.

94

Biological cleaning processes

96

2.5.1

Microorganisms

96

2.5.2

Proteins

97

2.5.3

Lipases

97

2.5.4

CAMEX process

98

Choosing the cleaning method - Future

HEALTH AND SAFETY AT WORK WITH RESPECT TO CLEANING

98
iQO

BIBLIOGRAPHY

103

USEFUL ADDRESSES

106

67

CLEANING
1.

CLEANING
1.1 The purpose of cleaning

The cleaning of stainless steels is not an end in itself

but an essential step before surface treatment. Its purpose is
to remove the fatty substances and thus to help guarantee the
quality of the surface finish for subsequent operations.
When do you clean?
Why?
How?
Cleaning is an essential operation in the following
cases :
- bright annealing
- after cold rolling or cold wire drawing,
depending on the customer's requirements.
The purpose of cleaning is to remove fatty substances of
whatever origin in order to:
- avoid modifying the partial pressure of the ambient
gases during annealing (pH , p 0 ) ;
- avoid forming CO and C0 2 ;
- removing rolling residues;
- removing surface carbon.
To do this, the following types of cleaning processes
may be employed:
-

mechanical or physical
thermal
chemical
electrochemical
69

- biological.
The use of ultrasound is not a method per se but helps
to increase the kinetics and the quality of the descaling.
The cleaning is carried out in a reactor (Figure 1) and
causes an INITIAL STATE to pass into a FINAL STATE using
stoichiometric, equilibrium and conversion reactions. This
reactor allows energy balances and "mass" balances, and hence
evaluation of the yields.

Reagent A-|

Charging with some

of the reagents

The reaction continues,

while reagents are
added

Products discharge

time
Start of the reaction

End of the reaction

Figure 1: The "CLEANING" reactor

(semicontinuous operation)1
1.2 The origin of surface grease and dirt2
There are several origins of fatty substances present on the
surface of stainless steel:
- animal or vegetable origin: These are combinations of
fatty acids and of glycerine or of metal soaps (mixed
compounds of fatty acids and metals). Most of these fatty
substances can be saponified, and therefore decomposed by
alkalis, giving soluble soaps. The fatty acids encountered
are:
. oleic acid
. palmitic acid
70

. stearic acid,
or their salts:
. oleates, palmitates, etc.
. triglycerides.
These oils are mostly protective oils.
- mineral origin. In this category, we find hydrocarbons and
paraffinie compounds. The latter cannot be saponified and
it is impossible to dissolve them by the action of
alkalis. However, in contrast, they do form emulsions
which can be separated by physical methods. These oils are
used for cold rolling. They contain many polar additives
and esters, for example, emulsifiers, "anti-wear" agents,
anti-carbon agents and corrosion inhibitors.
2.

GENERAL CLEANING METHODS

2.1 Mechanical or physical processes

Mechanical
cleaning
is in fact a
"precleaning"
operation, consisting in "scraping" the metal sheet with various
tools in order to remove most of the oil. The term "wiping" is
also used.
Brushing is often used, supplemented with adsorption of
oil by means of a paper insert.
The BUVARD effect makes it possible:
- to adsorb most of the oil, and
- to protect the surface.
2.2 Thermal processes
In the
oxidized in air
formation of CO,
allow catalytic

thermal processes, the greases and oils are

at a moderate temperature (T < 400C) with
C0 2 and H 2 0. Special enclosures and refractories
combustion without passing through a high71

temperature stage ( < 130C) .

2.3

Chemical processes
The chemical cleaning processes comprise two types of

process :
- alkaline chemical cleaning
- chemical cleaning using organic solvents.
2.3.1 Alkaline chemical cleaning2,3'4
Chemical cleaning relies, for the most part, on two
principles of extractive/reactive chemistry:
- dissolving in an aqueous medium or by means of
organic solvents
- saponification, that is to say a chemical treatment
which allows a grease to be decomposed into a soap
which, in turn, may be decomposed into glycerol and
an acid (the reverse reaction to esterification):

R-COOR' +
NaOH
-> R-COO"Na+ + R"0H
Fatty acid + sodium hydroxide -> Soap
+ alcohol
2.3.1.1 Cleaning in an alkaline medium5,6
Solubilizing in an alkaline aqueous medium involves
complex physico-chemical processes which remove the fatty film
via the following three major steps:
- penetration and wettability
- displacement
- dispersion.
Wettability: This consists in decreasing the surface
tension of the oil on the surface of the metal so as to allow
72

the chemical reagent to act. The low surface tension of a

detergent allows it to come into contact with the grease and to
infiltrate into it2.
Figures 2, 3 and 4 show the various steps in alkaline

cleaning,
Detergent
Oil

surface to be cleaned

penetration of the fatty

film by
surface-active
molecules (wetting)

displacement of the fatty

film
from
the
metal
surface to the detergent
solution

Metal

"xn_p
t

t t

Figure 2 - First steps of the cleaning mechanism2

73

Oil

Water

Lipophilic
chain

H dro n lic
y P '
group

Figure 3 - Adsorption of
the surface-agents2

Figure 4 - Double electric layer

in an oil droplet surrounded by
an anionic wetting agent2,
according to reference 2

2.3.1.2 Emulsification
Oil, isolated from the surface, tends to "rise" and form
a fatty layer. In order to avoid the latter redepositing,
attempts are made to absorb it using surface-active agents
forming a micelle. This phenomenon is comparable to the role
played by lymphocytes in biology. It is limited by the oil/water
partition coefficient if the bath is excessively laden with
micelles and becomes milky, surface salting-out being observed.
Surface agent

O Aqueous phase

Oil

Figure 5 - The principle of emulsification6

In summary, emulsif ication is the displacement of the
surface film towards the detergent solution followed by reten74

tion, as fine droplets, of the phases formed. These reactions

are controlled by many mechanisms. The diagram (Figure 5)
explains the phenomenon. The molecule of the cleaning agent is
adsorbed
on
the
greasy
film
by
modification
of
the
grease/solution interfacial tension.
2.3.1.3 Surface-active agents
Definition: A surface-active molecule consists of two
parts:
- a hydrophilic polar part which is soluble in water
- a lipophilic non-polar part which is soluble in the
organic phase.
Surface-active agents are usually classified according
to the nature of their hydrophilic part, which may be cationic,
anionic, nonionic and amphoteric.
General properties of surface-active agents:
The character common to all surface-active agents is
AMPHIPHILICITY, that is to say the presence in the molecule of
two groups possessing different solubilities. Surface-active
agents modify the liquid/liquid interfacial tension.
The GIBBS
equation relates
the
surface
tension
2
(expressed in mol.cm" ) and to the interfacial tension y in N.m"1:
C d7_
RT dc

C
R
T

=
=
=
=

surface tension expressed in mol.cm"2

concentration of surface-active agent (mol.m"3)
the gas constant (j .mol^.K"1)
absolute temperature (K).
Molecules exposed to surface-active agents form aggre75

gations of molecules, or micelles, which are limited by the

critical micelle concentration (CMC).
The essential property of micelles is to solubilize
products which are barely soluble in aqueous phase but soluble
in organic phase. Experts in surface-active agents have intro
duced an empirical concept in order to quantify these reagents
in cleaning products: "the hydrophilic/lipophilic balance" (HLB,
Griffin).
Examples of surface-active agents:
The table below gives a few examples of surface-active
molecules.
Amphoteric: CH3 - NH - (CH2)2 - COOH
Anionic :

CH, - (Oy,, - ( ) - SC V

Na

sodium dodecylbenzene sulphonate

Cationic :

[ (CH^ - NH - CH2 H @ > ] * CI

dimethylbenzylammonium chloride

Nonionic :

_ {CH^ -<0>- O - (CH, - CH2 - 0)9H

nonylphenol

containing

mols

of

ethylene oxide
In recent years, novel surface-active agents have been
prepared, among which we mention:
- betaines
- lecithins
- phospholipids.
If the surface-active agent is anionic, the negatively
polarized hydrophilic group creates repulsive forces within the
76

detergent liquid, thus promoting dispersion of the dirt particles. Anionic surface-active agents are highly sensitive to
the hardness of the water, but are also highly stable in alkaline medium.
Anionic surface-active agents may be divided into three
main groups :
- soaps,
- sulphonate compounds,
- sulphate compounds.
2.3.1.4 Soaps3,6,8
Soaps are salts of long-chain fatty acids having the
general structure [RCOO"]M+ where R is the lipophilic part. The
cation M* is usually sodium, ammonium or potassium.
Sulphonate compounds :
These compounds, of general formula R-S03-Na+, form most
of the household and industrial detergents. The main sulphonate
compounds are :
- taurates, of structure : R-CO-NCH3-CH2-CH2-S03-Na+
- alkylsulphonates :
R-CHOH-CH2-S03-Na+
- ethanol sulphonates:
R-C00-CH2-CH2-SO3-Na+
2.3.1.5 Sulphate compounds7,8,10,11
Sulphate compounds come from the sulphation of an
alcohol, their foaming power being very high. Examples are
sodium lauryl sulphate or sodium dodecyl sulphate, SDS.
In summary, the role of surface-active agents is
essential in the cleaning process, this role being due to the
presence of two groups :
- a hydrophilic group, therefore having an affinity for
77

water
- a hydrophobic and lipophilic group, therefore having
an affinity for grease.
Cationic (quaternary ammonium) surface-active agents are
stable, very soluble in water and contain a "halogen" functional
group.
Nonionic surface-active agents, having no charges, are
mostly molecules of ethylene oxide (hydrophilic part) on an
alkylphenol (hydrophobic part). Their efficacy corresponds to a
given temperature range, with a maximum detergency for a minimum
wetting power. It is therefore necessary to use these surfaceactive agents at the recommended temperatures. Nonionic surfaceactive agents are barely soluble in very alkaline medium.
The benefit of nonionic surface-active agents is that
they do not give rise to any ions in solution (thus beneficial
for the ENVIRONMENT).
2.3.1.6 Complexing agents6
The purpose of complexing agents is not directly
connected with the saponification reaction; above all they
prevent precipitation of alkaline-earth metals with the soaps
formed.
A few years ago, ethylenediaminetetraacetic acid or its
sodium salt2, Complexon III, used to be used. This compound is
particularly toxic and it is therefore preferred to use sodium
gluconate, NaC6Hi:L07 (or gluconic acid) , which is biodegradable.
Baths used2,6
Cleaning agents
Cleaning agents have two functions :
to yield OH" ions to the medium, so as to ensure
saponification
to enhance the efficacy of the surface-active agents.
78

The following are used:

a)

sodium phosphates and polyphosphates (pH = 10 to 12)

-

b)
c)
d)
e)

monobasic sodium phosphate, NaH2P04

dibasic sodium phosphate, Na2HP04
tribasic sodium phosphate, Na3P04
tripolyphosphate, NasP3O10
hydrogen pyrophosphate, Na2H2P207

- neutral pyrophosphate, Na4P207

sodium silicate, Na2Si03
sodium borate, Na2B407
sodium carbonate, Na2C03, (or potassium carbonate)
sodium hydroxide, NaOH (pH 14).

Currently, the authorities limit the use of phosphates

and polyphosphates. This is because their disposal leads to
EUTROPHICATION of the rivers (development of certain algae).
2.3.1.7 The main parameters of chemical cleaning in
aqueous medium2,3,5,7
The main parameters are:
- the surface finish of the underlying metal: polished,
brushed, scaled, etc.;
- the thickness and nature of the film of fatty substance;
- the concentration of the reagents: the cleaning
kinetics depend on the concentration of the reagents,
but a reagent excess also limits the kinetics and
makes rinsing difficult;
- the temperature: the dominant effect of temperature
is on the efficacy of cleaning (Arrhenius law), the
temperature furthermore allowing:
. better viscosity of the oils
. reduction in surface tension.
79

A temperature above 90C may cause seif-drying or the

formation of an adherent film;
- the duration: this depends on:
. the thickness of the layer of fatty substance
. the nature of the fatty substance;
- stirring: this allows the metal/solution interface to
be renewed, many means of stirring being used, such
as mechanical, pneumatic and ultrasonic stirring.

80

Desludger - Deoilor

Block diagram

OD

Deconcenlrating
circuit
Ultrafiltration
module

Figure 6 - Chemical cleaning line (alkaline cleaning)

2.3.1.8 Use of ultrasound

The use of ultrasound increases the efficacy of socalled "immersion" chemical cleaning. Powerful stirring is
generated by the phenomenon of cavitation caused by the ultrasonic waves due to the acoustic vibrations at frequencies above
the audible, preferably between 20 and 50 kHz. Ultrasound causes
regions of underpressure and overpressure, the bubbles of
emulsions imploding under the effect of the overpressure and
thus expelling the adherent dirt particles, even if they are
concealed in very narrow pores.
Rinsing:
Rinsing takes place either by immersion or by spraying
in one or more tanks. Preferably,
the water used is
demineralized and heated to 90C; it may be sprayed onto the
metal sheet or the bundles of wire. The optimum pH for avoiding
deposition (silica or carbonate) is approximately 7. On leaving
the tank, after the wiper rollers, the metal is dried in hot
forced air.
2.3.2 Cleaning using organic solvents14
Solvent cleaning is in the process of disappearing, not
for reasons connected with efficacy but for ENVIRONMENTAL
reasons. Replacement solutions are being made which should
result in the use of solvents which are less toxic than those
normally used.
In cleaning operations, the solvents may be used in
three forms:
- in the pure state: they then act by solubilization of
the fatty substances
- as an emulsion: the solvent is then dispersed in
water in the form of fine droplets
- as a mixture: one or more surface-active agents are
then added to the solvent, giving it emulsifying
properties while at the same time maintaining its
intrinsic properties.
82

2.3.2.1 Brief review of the properties of solvents

A solvent is characterized by its "solvent power". In
this case there is no ionic reaction, rather dissolving without
association.
It is more common to use a solvent value or kauributanol value, this having a 100 base for benzene2.
Substances whose kauri-butanol value is < 100 are not
very effective cleaning agents while substances having a value
> 100 are powerful cleaning agents, for example:

Commercial name

Formula

Kauri-butanol

value

(KBV)

dichloromethane
trichloromethane
benzene
perchloroethylene
1,2,2-trifluorotrichloroethane
(Freon 113)

CH 2 C1 2

136

CHC1-CC1 2

129

C6H6

100

CC1 2 =CC1 2

90

CFC12-CF2C1
CFC1,-CF,C1

31

Three types of solvent may be distinguished:

- aliphatic hydrocarbons
- halogen-containing aliphatic hydrocarbons
- aromatic hydrocarbons.
By way of example, we give the relevant properties of
two solvents :

83

Trichloromethane Perchloroethylene
CHC1-CC12

CC12=CC12

Relative density, 20C

1.46

1.62

Boiling point
(760 mm of Hg)

87C

121C

58

14

F1ammabi1ity

none

none

Decomposition temperature

125C

145C

Formula

Vapour pressure at 20C

(mm of Hg)

The temperatures of use are limited by the FLASH POINT of

the mixtures
and
their volatility.
For health
reasons
(TOXICITY), these cleaning methods are currently in the process
of being abandoned.
Additives are often combined with non-aqueous solvents,
such as :
- emulsifiers
- agents for lowering the surface tension
- stabilizers (e.g., sodium dodecylbenzenesulphonate).
The concentration and amount of cleaning agent decrease
with entrainment and evaporation so that it is therefore necessary periodically to add fresh product. Despite these additions,
a high degree of contamination is rapidly reached and the
solutions must be renewed. Legislation is now very strict and
the disposal of spent solvents into the drains is prohibited. It
is absolutely necessary to call on the services of companies
expert in solvent recovery according to standardized procedures.
2.3.2.2 Processes
Solvent cleaning processes require "cleaning machines".
A cleaning machine is a sealed tank consisting of three zones:
a)

a lower zone consisting of a heater with automatic

control

84

b)

a central zone or vapour collection zone

c)

an upper zone consisting of a condenser (cold-water

tubing or serpentine coil). The condensate then falls
under gravity into the lower part.

Cleaning may be carried out14:

- BY DIPPING, i.e. by immersion in the solvent
- IN VAPOUR,
- by a JET/VAPOUR combination.
2.3.2.3 Solvent regeneration
Solvents are deemed to be saturated when the maximum
acceptable content of oils and greases is about 20%. Two processes are used for solvent regeneration:
-

distillation
entrainment using steam, distillation of an azeotrope
(73C for trichloroethylene and 88C for perchloroethylene) and then separation of the solvent from the
water.

2.3.2.4 Modern hydrocarbons15

"Modern" hydrocarbons are an effective alternative to
halogenated solvents; they are also called "specialty fluids".
These hydrocarbons contain few aromatic functional groups, among
which may be mentioned:
eyelane compounds
isoparaffins (from Exxon Chemical)
- n-paraffins.
These products are used at room temperature. They are
odourless and have high flash points and acceptable degrees of
evaporation.
85

Tables II and III give examples of the use of modern

hydrocarbons, compared with halogenated solvents15.

Product
(Exxon Chemical)

ACTREL 2221

Inflammable
product hazard
classification

Evaporation
number
(Ether = 1)
17

Surface
tension
(mN/m)

Exposure limi t

300
300
300

value
(ppm. vol.)

ACTREL 3338
ACTREL 2240

A II
A II

38

A II

44

23
23
27

ACTREL 335SL

A III

65

23

300

ACTREL 22 56L
ACTREL 1188L

A III
A III

193
500

30
27

300
300

ACTREL 3310L
ACTREL 1111L

Product not
classified as

> 1000
> 1000

25
28

300
300

hazardous

Table II
(According to Exxon Chemical)
Product

Evaporation number

KB I

(ether = 1)

Surface
tension
(mN/m)

Exposure limit

17

500

value
(ppm. vol.)

FREON 113

1.3

31

1,1,1-Trichloroethane

2.5

124

22.5

200

Perchloroethylene

9.5

90

31.7

50

Table III

2.3.2.5 Biosanes 16
Biosanes are solvents free of hydrocarbons and of
halogenated compounds; these new cleaning agents are rapidly
biodegradable in naturally occurring environments. Biosanes are
not subject to any labelling regulation by way of their
toxicological properties, according to EC Decree 883679, and
they
are
therefore
excellent
from
an
ecotoxicological
standpoint. Because none of their constituents is involved in a
statutory chemical activity, they may be regarded as non-toxic.
86

Their flash points are between +3 0C and greater than

100C. However, the literature is still silent on the cleaning
properties of biosanes.

2.4

Electrolytic cleaning2'13'11

2.4.1 The principles involved

Electrolytic cleaning is cleaning under the action of an
electric field.
The twin purpose of the electrical current is:
- to cause dissociation of the species (protonization)
- to cause migration of the ions.
In electrolytic cleaning, the reactions take place at the
electrodes and both energy and species are supplied at the
interface between the solution and the metal to be cleaned.
Brief review of concepts in electroch^tni stry
a)

If the reaction takes place reversibly, with current transfer, the energy (electromotive force of the system) is
given by the equation:

AG = -n F E
where

b)

AG
n
F

= free energy
= number of electrons exchanged
= 96,500 coulombs

= electromotive force of the system.

Dissociation of the electrolytes:

An electrolyte MA dissociates according to:
MA - M* + A"
87

For water:
H20 H+ +
* + H20 H30* (hydroxonium ions)
c)

Electrochemical effect of the electrical current:

Due to the current, the species decompose and move to the
cathode and anode.
The amount of matter participating in the reaction is
proportional to the intensity of the current and to time:
m = k.I.t
where Am = amount of matter
k
= coefficient of proportionality
I
= intensity of the current
t = time.

d)

Thermodynamic aspects:
Since only a fraction of the molecules in solution
react, it is therefore necessary to introduce an acti
vity coefficient:
A = (c) ()
where A = activity of the molecules
C = concentration
= activity coefficient.
The DebyeHckel law (ionic interactions) shows that the
value may be calculated from the equation: log = b/c

It should be pointed out that the work potential is

always higher than the reaction potential:

**cell

>

^reaction '

This difference is due to the various overpotentials :

88

- concentration overpotential, nc
transport overpotential, nt
- diffusion overpotential, nd
- capacitive overpotential, ncap.
AS = nc + nt + n d + ncap
where AS = sum of the overpotentials.
The experimental potential of the reaction is therefore:
RT Log [M+] + AS
E = E0+-=fnF

where E, E0, R, T, F, n have the usual meanings.

e)

Kinetic aspects:
These relate to the migration phenomena (transport number)
and the reaction rates.

f)

Cleaning reactions:
a)

Ionic dissociation:
H20 H+ + OH"
NaOH ^ Na+ + OH"
Na3P04 - P0 4 + 3Na+

Anodic reactions:
40H" -* 02t + 2H20 + 4e
M* + OH" -> M (OH)
(R-CnH2n+1) + 0 2 - oxidized fatty substance

89

) Cathodic reactions:
4Na+ + 4H20 + 4e -* 4NaOH + 2H2t
(the nascent hydrogen being able to diffuse into the
crystal lattice and cause embrittlement).
The various reaction steps are as follows :
transport of the reacting species to the electrode/
electrolyte interface,
adsorption of the species on the surface of the
electrode,
oxidation and reduction reactions,
desorption of the species formed at the surface of
the electrode,
removal of the products
electrolyte interface.

from

the

electrode/

The electrolytes (concentrations expressed in g/1)

NaOH
Na2C03
Na3P04
Na4P207
Complexing agents
Na2Si03

10 to 80
20
25
20
10
30

2.4.2 T h e important p a r a m e t e r s
-

Temperature: 85C + 5C
Concentration of the reagents
Duration
pH

Concentration of the complexing agents

Concentration of the surface-active agents
Nature of the electrodes
Current density: 10 to 2 0 A/dm2
Direct polarization or induced polarization
90

- Alternating polarization:
phase, 15 A/dm2 - 4 minutes
e phase, 15 A/dm2 - 3 minutes
- Electrode spacing
- Brushing
- Nature of the rinsing water: deionized water
. pH 5 to 6.5
. Ca < 100 mg/1
. S04"" < 80 mg/1
- Possibility of recycling the rinsing water.

Advantages and disadvantages of changing polarity

In the cathodic phase
Advantages

Disadvantages

Mechanical action of H2
Short duration
Speed of ion transfer
Effective saponification

Dissolving action
More complex plant
Higher cost
Solubility of certain species
H, embrittlement

In the anodic phase

Tarnishing of some grades

Mechanical action of 0 2
Short duration
Speed of ion transfer

Solubility of certain species

2.4.3 Plants
We give below an example of an industrial cleaning line
(separate line).

91

a)

General characteristics
Type of metal cleaned: stainless steel sheet (a and )
Speed
Width
Thickness
Nature of the oil

b)

maximum 5 0 m/min ;
running speed 45 m/min
minimum, 400 mm; maximum, 1100 mm
minimum, 0.2 0 mm; maximum, 2.8 mm
Quaker

Configuration of the line

Input

2 pay-offs
1 shear cutter
1 welder

Treatment

1 chemical precleaning unit

Electrolytic cleaning two 15 m3 tanks
CLEANER solution (25 g/ml)
Temperature 95C
Current 8000 A at 40 volts
Planar anodes: current density of
10 A/dm2
Brushing: 2 counter-rotating brushes
Rinsing at high pressure and then dip
ping (80C water)
Wiping: 3 rollers
Drying: 10 0C hot air

Output

Shear cutter
2 take-ups

Fluid circuit

12 0 m3/h for the cleaning

2 0 m3/h for the rinsing

Effluents

Discharge of the rinsing water to the

neutralizing station

92

^=8=

^^--U^-U-tf-^^^i

/ ' / TV'/ >V ? ^V /*/ V / ' / ^ y V ^ ; 1 / / /

5t^vvV77/^^

ELECTROLYTIC TANK
DTANK

PAYOFF

U3

#P^^^^^uS
7"*/ / V / C 7 * 7 r / ' 7 ^~/~7

Mi

/ / =

/
2nd i BRUSHING UNIT

IMMERSION RINSING SPRAY RINSING

DRYERS

TENSIONER

/
/

/
/

TAKE-UP

Figure 7 - Typical diagram of an electrolytic cleaning line

Examples of reagents used:

The products, whose commercial names are taken from the
specialized literature, are only given by way of documentary
example.

Products

Concentration

SPEPS
DE 466

24

SPEPS
DE 467

CFPI
PROGAL
W207DF

CFPI
PROGAL
W317DF

HENKEL
P3
VR 6334

25

20

20

25

PENCHIMIE
CLEANER
SM97L
19

g/i
Types

non-silicatesolid
solid
solid
solid
solid
phosphates phosphates phosphates phosphates phosphates containing liquid
phosphates

Cleaning power,

70

71

72

58

76

59

39

40

40

53

32

54

%
Surface tension,
dynes/cm

Table IV
2.4.4 Checking - Establishing a specification - Quality
Assurance
a)

Acceptance checking - Checking the baths

The checking and measurements necessary for establishing

a specification relate to:
- the appearance of the product (colour, particle size,
uniformity, etc.);
the solubility in water, generally 20 g/1;
the salting-out in water;
- the ionic concentration;
the concentration of OH" ions (OH" assay, "free" ions) ;
- measurement of the surface tension.
Ten drops of the cleaning solution and ten drops of
distilled water are weighed out and the following equa94

tion is applied:

where :
. = surface tension of the cleaning agent in dynes/cm
= surface tension of distilled water at 20C
m'
m

(73 dynes/cm)
= mass of ten drops of cleaning agent
= mass of ten drops of water.

(Several methods may be found in the literature in the

"Measurement of the surface tension - STALAGNOMETRY"
chapter).
The cleaning power (level 60%) is given by:

activity % =

residue, electrolytic degreasing

residue, using ultrasound

We take as reference the ultrasonic cleaning

trichloroethane at 60C for three minutes.

100

using

The cleaning power may also be determined by comparing

the mass of two small plates of stainless steel having
the same area and oiled:

activity % =

mass of oil removed by cleaning

mass of oil initially present

100

- the foaming power: the height of the foam is measured

under defined conditions.
95

Post-cleaning checking - Surface appearance2'18'19

b)

The post-cleaning checks relate mainly to the presence of

the following elements: so-called "surface" carbon, iron,
sulphur, phosphorus and silicon, the thiosulphate content and
species added as antigraphytizing agent.
It is important to remove these elements for the
subsequent operations, especially C and Si, the latter element
modifying the surface oxygen partial pressure and allowing
internal oxidation of the highly oxidizable elements, such as
titanium and aluminium.
The most commonly employed surface inspection methods
20

are :
glow-discharge mass spectroscopy (GDMS);
secondary ion mass spectroscopy (SIMS);
Raman spectroscopy;
photoelectron spectroscopy (ESCA);
Auger electron spectroscopy;
all infrared methods;
anodic dissolution and quantitative analysis of the
surface elements by molecular plasma spectroscopy;
reflectance measurements.
2.5

Biological cleaning processes16

Biotechnologies could, in the future, provide solutions

to the problems of pollution by halogenated solvents. Depending
on the nature of the oils, advanced techniques are being
directed towards the use of enzymes or of enzyme-producing
bacteria in a closed medium (bioreactor).
From the literature, we find cleaning processes using:
2.5.1 Microorganisms
These are prokaryotes, such as the eukaryotes bacteria
96

(microscopie fungi), yeasts, and algae. These have slow

kinetics, but the bacteria are easy to produce, to manipulate
genetically and to cultivate. Microorganisms would be required
for destroying spent oils or greases or for rehabilitating
polluted sites16'21'22.
2.5.2 Proteins
All enzymes are proteins (20 amino acids). These amino
acids are bonded together to form polypeptide chains having a
three-dimensional structure. The enzymes play a particular
autocatalytic role and act on the cleaning kinetics21.
2.5.3 Lipases
Lipases are a class of enzymes, and therefore proteins.
They are sought after for their use in oleochemistry and will be
used in future detergents. They are also called lipolytic
enzymes. Lipases are substances produced by plants. The
advantage of lipases stems from the fact that they possess a
"genetic reactor" allowing them to be manufactured for an
industrial use. By means of genetic manipulation, it is known
how to make them more effective at a given pH, with beneficial
economic implications for the user. Industrial production is
carried out in fermenters or bioreactors21.

CHj-O-C-R,

+ 3H 2 0
R^-O-CH
o
I
CHj-O-C-R,

CHjOH

Lipase*

>

,
R,-C /
\5.

HO-CH
+ R.-C
t
\>CH 2 OH
R,-C

Triglyceride* '_> * *' " " o11

C or monoglyceride or diglyceride)

Glycerol

+ 3H*

/}

\>-

Fatty acids

Rj, Rj, Rj are identical or different organic radicals, possibly containing long chains

Hydrolysis of a triglyceride by a lipase

97

2.5.4 CAMEX process23

In the CAMEX process, the spent oils and greases are
continuously removed. The cleaning agent CAMEX BIO 104 is an
alkaline agent which is effective between 2 0 and 80C, having a
low foaming power and able to be used in immersion or spraying
processes.
CAMEX BIO 10423 contains special components which create
the optimum conditions for growing bacteria. According to the
literature on this subject, the oil is consumed by the bacteria
and "the more oil introduced the more active the bacteria are".
The grease and oil content may fall to 100/500 mg/1.
In
addition to CAMEX BIO 104, surface-active agents, phosphates,
silicates, and proteins serving for bacteria development may be
added.
Biological separation

Figure 8 - Diagram of the CAMEX process

2.6

Choosing the cleaning method - Future22,25

The choice of cleaning method must take into account the

following requirements:
technical requirements: types of greases and oils to
98

be removed, degree of cleanliness desired, subsequent

treatments and especially flow of material (surface
to be cleaned), cleaning kinetics;
economic requirements : plant available within the
framework of an industrial site, manufacturing cost
per m2 (or per tonne) , cost of treating the spent
baths and effluent;
ecological requirements and those relating to the
working conditions: Chlorinated solvents, fluorinated
solvents and chlorofluorocarbons (CFCs) have, for a
number of years, been the subject of international
pressure with regard to their impact on the
environment and, in general, because they create a
nuisance. This pressure is resulting in strict
European directives and legislation; we are moving
towards a total ban on the use of halogenated
solvents. We point out, however, that replacements
for halogenated solvents do exist.
The current thrust is towards methods using:
biotechnology
genetic engineering
clean processes.
Thus, recent patents have shown the advantage of
cryogenic spray cleaning using balls of ice or dry ice (C02) .
The device comprises four parts:
a liquid nitrogen supply,
a pressurized-water supply,
a storage container, the balls thus stored being
entrained by means of an Archimedean screw to
an injector gun (at -140C).
The balls blasted have a diameter of 1 mm.
99

FTIR spectra show excellent results on stainless steel

sheets.

3.

HEALTH AND SAFETY AT WORK WITH RESPECT TO CLEANING

(These regulations apply for the most part to non-aqueous

solvents)
Toxicological aspects
They relate to:
inhalation: organic solvents are toxic and adversely
affect the respiratory pathways and the nervous
centres
(narcotic
action).
There
are
strict
provisions with regard to trichloroethylene;
direct

ingestion,

which

is

very

serious

(fatal

intoxication);
direct contact: repeated handling of solvents may
cause dehydration of the epidermis (dissolution of
the lipoacid layer); prevention consists in using
gloves.
Prevention and Safety24
The limiting flux of allowed solvents is fixed by
legislation. This imposes the use of vapour recovery plants.
Likewise, many standards fix the use conditions and state the
personnel exposure limits; generally, these are average concen
trations for a given work period. For example 5 days 8 h = 40
hours.
Discharge: Discharge is strictly controlled. Discharge into the
drains is banned for three reasons:
the risk of pollution
100

the risk of explosion

the risk of fire.
Preventative measures
The main preventative measures are the following:
effective suction of vapours
detection of the degree of pollution in workshops
(Drager tubes),
ventilation of workshops
wearing of masks and goggles
authorized storage
unauthorized discharge, but recovery treatment by
authorized companies
medical surveillance of personnel (checking of blood
composition)
fire protection.

101

LIST OF FIGURES

Figure 1 - The "cleaning" reactor

Figure 2 - First steps of the cleaning mechanism
Figure 3 - Adsorption of surface-active agents
Figure 4 - Electrical double layer in an oil droplet
Figure 5 - Principle of emulsification
Figure 6 - Chemical cleaning line
Figure 7 - Diagram of an electrochemical cleaning line
Figure 8 - Block diagram of the CAMEX process

LIST OF TABLES

Table I

- Examples of surface-active molecules

Table II

- Modern hydrocarbons

Table III - Conventional hydrocarbons

Table IV

- Examples of commercial reagents used

102

BIBLIOGRAPHY

1.

2.

P. TRAMBOUZE et al.
Les racteurs chimiques [Chemical
TECHNIP Publications, Paris, 1984

reactors]

D. HENRIET
Les a c i e r s i n o x y d a b l e s [Stainless
steels]
E d i t i o n s de P h y s i q u e [ P h y s i c s P u b l i c a t i o n s ] ,

Paris,

1990,

855

3.

4.

5.

J . J . DUPRAT and G. GARNIER

Les T e c h n i q u e s
de l ' I n g n i e u r
[Technologies
Engineer]
Mtallurgie [Metallurgy], Volume 4
R. WILMOTTE and J. BENEZECH
Pratique et thorie des traitements de surface
treatments: theory
and
practice]
Volume 1 - Cleaning; Paint guide
CETIM Publications
R. WILMOTTE and J. BENEZECH
P r a t i q u e d e s t r a i t e m e n t s de s u r f a c e
practice]
Galvano-Organo (1994), Oct., 448

6.

C. LE BORDAYS
Surfaces, No. 159, 64

7.

A. COHEN and K. HOOK

[Surface

for

the

[Surface

treatment

Optimization of alkaline soak cleaners for ferrous metal

surface Plating and Surface finishing (1985), 3
8.

J.C. REMONNAY
Traitements de surface [Surface
treatments]
Galvano-Organo (1987), D e c , 581

103

9.

D. FRYMERMAN
Surface (1970), No. 58
(1971), No. 60

10.

D. FRYMERMAN
Les techniques de
Engineer],
M 147 0

l'Ingnieur

[Technologies

for

the

G. DAVID
Les techniques de
Engineer],
M 1492

l'Ingnieur

[Technologies

for

the

11.

12.

L. ADES and G. DAVID

Dgraissage de la surface mtallique avant dpt lectrolytique [Cleaning
metal
surfaces
before
electroplating]
C.P.I. Lectures.

13.

N. MULLER and T. ROSSMANN

Le dgraissage eleetrolytique [Electrolytic
cleaning]
Traitements de surface [Surface treatments], March, 1969

14.

E. LUTTER
Le dgraissage par dtergence [The cleaning
gents]
Galvanotechnik (1975), March, 66, No. 3

15.

[PRAXIS - FORUM

J. TARDIF
T r a i t e m e n t s de s u r f a c e [Surface t r e a t m e n t s ]
G a l v a n o - O r g a n o ( 1 9 9 0 ) , D e c , 6 1 1 , 991

17.

deter-

M. SCHAICH and A.A. EGGINK

Confrences PRAXIS - FORUM
Bad Nauheim, (FRG)
Exxon Chemical (1985)

16.

using

H.G. GERMSCHEID
M e t a l l o b e r f l c h e [Metal s u r f a c e s ] ( 1 9 7 5 ) ,
No. 3 , March 1975 a n d No. 4 , A p r i l 1975
104

Conferences],

18.

D. DAVID
Mthodes
[Common
EYROLLES

19.

D. DAVID
Mthodes avances de caractrisation des surfaces
[Advanced methods for surface
characterization]
EYROLLES Publications, Paris, 1992

20.

R. BERNERON
Spectrochimica Acta (1978), 33 , 665

21.

S. NAUCHE
Communication p e r s o n n e l l e

22.

23.

24.

and R. CAPLAIN
usuelles de caractrisation des surfaces
methods in surface
characterization]
Publications, Paris, 1988

P. DOUZOU et al.
Les biotechnologies
PUF, Paris, 1983

[Personnel

communication]

[Biotechnologies]

F. SEGUIN
Traitements de surface [Surface
Ga Ivano-Organo (1990), D e c , 1017

treatments]

Safety Data Sheets

(INRS - 30 rue Olivier Noyer - 75680 PARIS CEDEX 14)

25.

A. GOUCHET
T r a i t e m e n t s de s u r f a c e [Surface
treatments]
Galvano-Organo (1990), D e c , 981

105

A FEW USEFUL ADDRESSES

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92233 GENNEVILLIERS

- Fax 610626

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106

DESCALING

CONTENTS

Page

1.

DEFINITION - OBJECTIVE

109

2.

CONVENTIONAL DESCALING METHODS

109

2.1 Processes associated with rolling

110

2.1.1 Descaling using simple tension

2.1.2 Bending around a roll

....

no
HO

2.1.3

The "PROCESSOR" system

113

2.1.4

Skin pass

114

2.1.5

Descaling using a planishing

stand or oxide breaker

2.2

115

Shot peening

115

2.2.1

Principle

115

2.2.2

Important parameters associated with

shot peening

2.2.3

116

Mechanical descaling of long products

. .

2.2.4 Hydraulic descaling

2.2.5
3.

Processes common to metals and alloys

120
122

. .

123

RECENT IMPROVEMENTS

121

3.1 SIMON-HOUGARDY Process

121

3.2 Descaling using wet shot peening - The

ISHICLEAN process

131

3.2.1

Principle

131

3.2.2

The process - the steps in the ISHICLEAN

process

3.2.3

Description of the technology

131
133

3.2.4 Descaling parameters

135

3.2.5

Raw materials

136

3.2.6

Existing plants

13 6

3.2.7 Advantages and disadvantages of the process

107

137

3.3 Wire descaling using ferromagnetic particles

- A.P.O. process
-"7
137
3.3.1 Principle
137
3.3.2 Realization
3.3.3 Advantages and disadvantages of the process ^ 3 9
3.4 Cryogenic descaling
^40
3.5 Descaling using molten salts - Thin-film (spray)
descaling - Anti-scale products

140

DESCALING AND SURFACE FINISH

140

ENVIRONMENTAL ASPECTS

142

USEFUL ADDRESSES

145

LIST OF FIGURES

146

BIBLIOGRAPHY

147

108

DESCALING

1.

DEFINITION - OBJECTIVE

Descaling is the removal of scale using processes not

associated with chemical reactions in an ionized medium. This is
a "preparatory" or "roughing" operation. Apart from sandblasting, grinding and brushing, it is rarely used alone but
often precedes a pickling operation. Unlike polishing and
brightening, it is not a finishing operation and therefore does
not lead to a "final" surface finish.
Objective of descaling
The objective of descaling is to crack the scale in order
to allow acid to flow and come into contact with the metal, and
thus accelerate the process of dissolving the oxides. It is
known that the chemical pickling mechanism comprises three main
steps :
- the infiltration of the acid or acid mixtures into the
cracked oxide layers;
- the dissolving of the protoxide and mixed iron-chromium oxides;
- the detachment of the outermost oxides, Cr203 FeO.
These three steps show the importance of infiltration of
the acid and therefore the importance of scale cracking. The
first approaches related to improving the pickling operation
must indeed target the metal/solution interfacial reaction.

2.

CONVENTIONAL DESCALING METHODS

Descaling
actions :

processes

involve

109

the

following

mechanical

- destruction of longitudinal cohesion by tensionflexure

- fragmentation and crushing by compression
- disbondment and fracture of interfaces by shearing.
The study deals with:
- the processes associated with rolling:
. tension
. bending around a roll
. processor
. skin pass
. oxide breaker
- the processes associated with shot peening and
sand blasting
- the processes associated with grinding and brushing.

2.1

Processes associated with rolling

2.1.1

Descaling using simple tension2

This is mostly used for wires. The difference in the

mechanical properties between metal and scale causes the latter
to crack. In general, it is necessary to slightly exceed the
yield point of the metal without going as far as forming Lders
bands since the deformation is then heterogeneous. According to
MONTAGUT2, in order to reduce the pickling time by 3 0% it is
necessary to impose a strain of about 6 to 7%.
This method is not used for flat products.

2.1.2

Bending around a roll6'7

The principle of this method is shown diagrammatically in

Figure 1. The purpose of the method is to form very slight
110

crazing, the crazes being uniformly spaced, because of their

controlled formation and therefore not appearing as a surface
defect.
Drive rolls

Movable descaling
roll

Planishing rolls

Pay-off mandrel

Figure 1 - Device for bending over a roll2

The most important parameter is the roll diameter (50 to
100 mm) . For strip, two successive rolls are used, the outer
fibre is then in tension while the inner fibre is in
compression6. The strains are about 0.4% for the two rolls.
The important parameters are:
- the roll diameters
- the winding angle
- torque control.
Formulae involving the roll diameter and the thickness
may be used to calculate the total strain. The maximum strain
which may be given to a sheet by pressing it against a roll and
then straightening it out is equal to the strain of the external
shape :
e =

2R

111

where

t
= thickness and
2 R = roll diameter.

Small Roll:
It was in 1980 that JUTTEAU1 showed that a "small roll"
could descale flat steel products8.
Results:
The "small roll" can increase the strain by several %,
leading to a very pronounced improvement in planarity.
It is observed that passing over a "small roll" results
in an appreciable improvement in pickleability1,2. Figure 2 shows
an example of a "small roll".

112

'<0
I 1 V Wear piale (attack side)
/

' 20 Minimum deviation

Running direction

Figure 2 - Example of a "small roll" plant.

2.1.3 The "PROCESSOR" system2
The "PROCESSOR" system consists
approximately 100 mm in diameter supported
imposes on the strip three successive bends
by alternating tension and compression of
inner fibre.

of three
by support
and cracks
the outer

rolls of
rolls. It
the scale
fibre and

According to reference 2, one drawback of the system is

that the effectiveness at the edges is limited.
Figure 3 shows a diagram of the "PROCESSOR" system.

113

To the output
S-block

Overlap

To the input
S-block

Figure 3 - Diagram of the principle of the "PROCESSOR" system2

2.1.4 Skin pass3'4,5
Basically this is a cold rolling mill leading to small
deformations of about 2 to 3% strain.
The skin pass operation improves the planarity of strip.
The main adjustment parameters are:
- the pressure applied
- the diameter of the rolls.

Tensioner

Tensioners

OD PO

r
*77777

W777Z

Figure 4 - Diagram of the principle of a skin pass2

Results :
The skin pass operation is most effective for a 2%
strain. There is uniformity from the edges to the centre.
In the best cases, the maximum reduction in pickling time

114

is approximately 50%. The skin pass operation is therefore a

particularly effective way of increasing the rate of pickling.
2.1.5 Descaling using a planishing stand or oxide
breaker2
Principle:
The planishing stand, or oxide breaker, operates according to a principle similar to that of the PROCESSOR system. The
main deformation is produced on two small rolls by reverse
bending. The third roll produces a transverse or "anti-tiling"
offset, its diameter, 250 mm, being greater and the deformations
imposed being smaller than those on the two "small rolls". The
effectiveness of the oxide breaker requires strains of 1.5 to
2%; for this value, the pickling time is reduced by a factor of
three. Some lines currently use a so-called "oxide-breaker"
descaling process consisting of two small "oxide-breaking"
rolls, one able to move upwards and the other downwards, which
force the strip to adopt a high degree of curvature in one
direction and then in the opposite direction so as to break the
oxides and to work the metal.
2 .2

Shot peening

2.2.1

Principle

Shot peening consists in blasting particles of highly

carburized steel, of a given diameter, onto the metal (strip or
wire bundle) so as to crack the scale and detach it. The purpose
of shot peening is therefore to remove the oxides, especially
those formed during hot rolling. From a mechanical standpoint,
shot peening always causes the surface to be work-hardened.
Since shot peening is not sufficient to remove the oxide completely, this operation is very often followed by a pickling
operation.

115

2.2.2

a)

Important
peening

parameters

associated

with

shot

Nature of the shot:

Two types of shot may be used:
- either spherical shot
- or angular shot.
Two grades of steel are used for the shot:
6 C 17
6 CM 18.8

b)

Particle size and appearance of the shot:

The shot particles most commonly used have diameters

ranging from 0.25 to 0.75 mm. The average Vickers hardness is
500.
Figure 5 shows a few examples of the appearance of the
shot used9.

1mm

Figure 5 - Appearance of typical shot9

The following
selecting the shot:

criteria

116

are

taken

into

account

when

- the nature and type of the workpieces to be shot

peened (wire, sheet, workpieces of various shape)
- continuous or discontinuous shot peening
- the size and number of shot blasters.
c)

Shot velocity:

The shot is directed onto the metal sheet by the centri

fugal force of a turbine. The metal balls are blasted with a
velocity of between 50 and 100 m/s. The trajectory of the shot
varies depending on the point of impact. Figure 6 shows the
trajectories of the shot particles coming from a turbine: note
the intensity of the shot peening varies depending on the
trajectories and on the impact, that is to say depending on the
blasting angle.

rotor

blades (generally 4, 6 or 8)

Injection cage

CI

intensity curve

distributor or auxiliary turbine

sheath of trajectories
relative intensity of shot peening
depending on the trajectory locus

.J

inpact
trajectories of the particles

Figure 6 - Trajectory of the shot from a turbine

117

According to BOUHIER9, it has been demonstrated that

there is a relationship between the area shot peened and the
number n of shot blasters, this being of the form:
Sn = 1 - (1 - Sx)n
S1 being the surface fraction cleaned by one shot blaster.
d)

Blasting angle and shape of the shot

The blasting angle has an effect of the effectiveness of

the shot peening and the working of the oxidized metal.
A round shot will give a spherical impression and an
angular shot will lead to an impression of similar shape, very
powerful shot peening leading to regions of marked compression.
Figure 7 shows a few characteristic examples relating to the
shape of the shot and the wear of the particles: too great a
shot wear leads to the particles shattering and to intense
abrasion.
e)

Industrial realization (of flat products):

A stainless steel descaling line comprises 1 to 4 shotpeening booths. Each booth is sealed and consists of:
- four turbines (2 per face) whose function is to blast
the shot onto the metal sheet, maintaining a certain
blasting angle;
- a shot recovery and recycling unit;
- a dust collection unit common to all the booths (suction and filtration of the dust particles).
The distance between the injectors and the walls of the
chamber must be such that the deleterious effects of the shot
rebounding are small. Adjustments must be optimized so as to
reduce the costs.
f)

Optimization - Computer control:

118

Tight control of the parameters is necessary if it is

desired to obtain reproducible results. Computercontrolled
operation has enabled the performance of plants to be improved.

UA.

\J~

* > M W S**JVsV

round shot
b
spherical impression

">y^"

angular shot,
angular impression

Impressions resulting from shot particles on the metal.

blasting velocity

shot

metal surface to be shot peened V2 rebound velocity (V2 < )

hatched regions = regions of compression

- Effects of shot peening.

I Grenailles liminer

i
Shot to be removed
a round shot
b angular shot
Reduction in size of the shot particles by abrasion and shattering.

119

Figure 7 - Impressions formed by the shot on the metal, the

effect of shot peening and the reduction in size of the shot
by abrasion and shattering (after PRONER10)
2.2.3
a)

Mechanical descaling of long products

Purpose :

The cold transformation of wire stock (wire drawing) or

bar stock (drawing) requires that the scale arising from hot
drawing be removed beforehand.
The objective to be achieved is the removal of a scale
layer with a thickness of between 5 to 20 ..
Application: the method is little used for stainless steels, but
should be mentioned.
b)

Suitability for descaling:

LAPOSTOLLE13
has
proposed
the
following
test: a
tensile test is carried out on carefully taken specimens,
giving them a permanent strain of 2 to 6%. By determining the
amount of residual scale (by dissolving and weighing), a
"residual scale" = f(A%) curve may be plotted.
The curve having the shape below is obtained:

120

Residual scalei (kg/t)

= 5

0,5

2 to 6
depending on the
steel tested

Permanent strain
imposed

Figure 8 - "Residual scale" = f(A%) curve enabling the

suitability for descaling to be assessed (according to
LAPOSTOLLE13)
c)

Methods quoted in the literature12,13,14 ,

Bending (for wires having a diameter of < 12 mm) . This

consists in passing the wire, under tension, over several
rollers, mounted in series, in two (vertical and horizontal)
planes. The strain imposed by the bending is given by the
equation:
A % =

where

D +d

d =

diameter of the wire

D =

diameter of the roller.

Brushing: this is carried out:

- using steel wool
- using a rotating
pressure.

brush

121

working

with

adjustable

Shot peening: This method is similar in its principle to

that used for flat products. The superposition of the turns (in
the case of coils) limits the use of the method.
Given below are the advantages and disadvantages of the
mechanical descaling of long products:
Strengths

Weaknesses

reduction in the harmful effects of pickling atmospheric pollution

(atmospheric and aqueous pollution)
lower wire-drawing speed

lower manufacturing cost

no need to keep aqueous baths running

reduction in water cost

2.2.4

for descaled wire than for pickled

wire
problems caused by the turns (coils)

Hydraulic descaling

There are two aspects raised by hydraulic descaling:

- the first relates to reactions during cooling
- the second relates to the mechanical action of the
water jet.
Reactions occurring when cooling: These relate to the
formation or thermal decomposition of oxides, for example the
ternary eutectic FeOCr2O3'Si02 whose melting point is about
1150C or the eutectic FeO'FeS which crystallizes at 1180C;
these solidification reactions lead to a change in volume, and
hence to the oxides shattering. It will be recalled that all
these phenomena are manifested by a large change in volume, the
scale thus being in compression while the metal is in tension.
Reactions due to mechanical stresses: These relate to the
deformation, vibration, shock, compression, tearing and expulsion of the scale.
Hydraulic descaling equipment: The main items of equipment in a hydraulic descaling plant are:
- filters: these are located upstream of the pumps and
must retain the solid particles likely to damage the
apparatus and to block up the nozzles
122

- accumulators: these serve to adjust the flow rate and

the pressure
- pumps: the speed of the fluid is about 4 to 8 m/s
- nozzles: these must deliver extremely fine sheets of
water and the areas of impact must overlap
- valves: these must open and close slowly

so as to

avoid pressure surges in the plant.

Water pressure: Tables are available for the operators
running the plants. Pressures of 150 bar are now conventional,
the jets being almost vertical (9010).
2.2.5

Processes common to metals and alloys

Sand blasting:
This consists in blasting the steel with sand particles,
iron-based compounds, alumina, etc., using a pressurized fluid:
dry sand blasting uses air entrainment, wet sand blasting uses
water or oil.
The pressures used are generally from 5 to 15 bar for
air, the pressures increasing for wet sand blasting.
Grinding17 :
Grinding is not a process specific to stainless steel,
but is used for most metals and alloys.
Grinding consists in abrading the surface of the metal
using a grinding wheel rotating at high speed. The grinding
wheel generally consists of abrasive materials of the carborundum type (silicon carbide) or of the corundum type (alumina) or
of boron carbide.
Other abrasive materials are used, namely;
123

zirconia
diamond powder
Vosgian sandstone
granite powder.

We have extracted from the technical guide on stainless

steels a few indicators given for these steels:
17

Work sequence

Peripheral velocity
(m/s)

Rough grinding

25 - 30

Ceramic binder

Rough grinding

45 - 65

Synthetic resin binder

Rough grinding

80

Synthetic resin binder

Surface grinding

18 - 25 - 63

Internal grinding

20 - 50 - 63

Grinding

28 - 50 - 63

Centreless

Grinding of round bar

30 - 63

Between centres

We therefore
distinguished:
-

see that four types of grinding may be

cleaning grinding
pregrinding
finish grinding
fine grinding.

The parameters to be taken into consideration are, in

order of importance:
-

the
the
the
the
the
the
the

grade of steel
thickness of the scale
initial surface finish
desired surface finish
type of grinding wheel used
speed of rotation
additives used.
124

Grinding using abrasive belts15:

This consists in grinding the stainless steel using
abrasive belts which may or may not be driven in translational
motion. It is applied to the grinding of weld beads, to the fine
polishing of metal sheets and to the repair of surfaces, and
encompasses all the processes which use sheets of cloth or paper
under mechanical pressure.
The materials are extremely diverse, depending on whether
they use endless belts, discs or flap wheels.
The abrasive consists of corundum, carborundum, boron
carbide, etc.
Brushing15 :
Brushing is used for two purposes :
- obtaining a characteristic surface finish
- cleaning a surface.
It is carried out using a stainless steel brush driven in
a rapid rotational motion.
Brushing is not carried out dry but in the presence of
descaling pastes composed of solid chemical reagents, tallow,
etc., for example sodium fluoride, nitrates or phosphates.
Operating recommendations :
Grinding

and

brushing

treatments

require

specific

operating experience.
For example:
- Avoid excessive local pressures and do not exceed the
tangential velocities indicated by the manufacturers
so as not to cause local overheating likely to modify
125

the planari ty of the metal, colour - sometimes randomly - the surface, or create non-uniform surface
areas which act as local corrosion initiators.
- Use a specific item of equipment and dedicate it
strictly for this use so as to prevent encrustation of
various metals or oxides, some of these being harder
than iron oxides. Within the same spirit, efforts
should be made to use abrasives which are free of iron
so as not to create an electrochemical couple favourable to corrosion.
- Grinding and brushing operations are generally followed by nitric passivation for a few seconds.
- It will

be

worthwhile

referring

to

the

technical

instructions of the machine manufacturers.

Main abrasives and polishing tools:
We give below the name of a few abrasives used
polishing:
-

for

Quartz: hardness 7, used in roughing

Natural corundum (Al203, hardness 9)
Artificial corundum (Al203, hardness 9)
Emery: natural rock, very widespread on the island of
Naxos (Greece)

- Silicon carbide
- Tripoli (a mixture of silica and alumina)
- Alumina
- Chalk (Paris white: Si02 + A1203)
- Chromium oxide
- Ferric oxide.
Polishing tools:
The following tools may be adopted:
126

grinding wheels, consisting of a mixture of abrasive

and a binder, compression moulded
buffs: leather buffing discs, glued and stitched
felt buffing discs
spuds : these consist of a stitched pad with emerized
edges
flap wheels
abrasive belts: these consist of three elements:
. the backing (made of paper or cloth)
. the adhesive
. the abrasive.

3.

RECENT IMPROVEMENTS16'18'19
3.1

SIMON-HOUGARDY Process16

Conventional descaling, using pressurized water18, cools

the product significantly. Methods using less energy and cooling
the products less are therefore sought.
Basic principle:
The proposed idea consists in replacing the flat-jet
nozzles used conventionally by "coherent" cylindrical-jet
nozzles of small diameter and high energy density; the proposed
nozzles are mounted side by side and oscillate. The main characteristic of this novel process stems from the fact that the
entire surface is not in direct contact with the descaling
water; it takes account of two essential characteristics of
descaling:
- the specific flow rate of water (1/m2)
- the jet impact pressure (N/mm2) , that is to say the
impact force of the jets divided by the impact area of
the jets. The heat shock created by the impact leads
to displacement of the scale. Figure 9 shows a typical
example of the trace of the jet impacts.
127

30% of the area undei

direct impact from
the jets

Figure 9 - Trace of the jet impact areas 16

Hydraulic development:
This novel process is based on the use of a jet having a
very small impact area and a very high impact pressure.
Figures 10 and 11 give the results obtained by SIMON and
HOUGARDY16 using a 1.5 mm diameter jet. Figure 10 shows the
fraction of the total flow passing through the orifice (Q0/Qt) as
a function of the diameter of the orifice. The change in slope
corresponds to the loss of coherence of the jet. On impacting
the product, the 1.5 mm coherent jet is spread out and the
diameter of the coherent part of the jet becomes approximately
2 mm. Figure 11, due to the same authors, shows that the speed
of the water in the jet ranges from 5 m/s to 20 m/s.

128

Oo/Ot
1.0
0.9

= 1.5 mm

-HSe

<
->::p

.'''..**" ^

0.7

^t

0.E

G2"

0.S

Without stabilizer
With stabilizer

Coherent jet

-s

0.3 1.0
1 4
18 2.2

2.6

3.0

34 3a
0 lmm|

Figure 10 Flows passing through the calibrated orifice16

Water speed (m/s)

1

30

n
0J

>

[Flat jet I

I
|

-1

OS

1
t

09

i
...

0.7

H?,jat =1 - 5mm

1.1

I
I

"

13

US

~",l
I
17

1.9

Distance from the axis of the jet (mm)

Figure 11 Water speed in the jet 16

Industrial realization16 :
Figure 12 shows a diagrammatic view of the industrial
prototype: a row of nozzles, individually supplied by a high
pressure hose, oscillates using a specially designed system. The
working pressure is about 50 bar.

129

Figure 12 - Industrial prototype with hoses 16

Figure 13 shows a diagram of the industrial process. Note
the "oscillating feeding head" allowing the nozzle to move. The
number of nozzles depends on the width of the strip and on the
running speed. The process could be applied to wire in bundles,
the nozzles being installed at the very centre of the bundles.
Figure 13 relates to a diagram of an industrial prototype
with rotary seals.
Rotary
seal
/
[

Fixed feeding
head

Oscillating
feeding head

Connecting
rod

Nozzle

#*rA wwmmzsM
Figure 13 - Industrial prototype with rotary seals3

130

3.2

Descaling using wet shot peening18 - the ISHICLEAN

19.20

process '
Context: Acid pickling, both as a means for removing
scale and for giving a surface quality, is satisfactory. However, in the current state of legislation, descaling processes
may become advantageous alternatives, particularly wet descaling
operations which, by definition, do not involve the harmful
effects of dust.
The ISHICLEAN process was developed by the Harima Heavy
Ind. (IHI) company and Nippon Steel Corporation (NSC). This
process may also be designated by the term NID (Nippon Steel
Ishiclean/Descaling).
3.2.1

Principle

The ISHICLEAN process is specific to the descaling of hot

sheet: it is a wet descaling operation. The product to be
descaled is subjected to a bombardment of shot by two rails of
nozzles. A mixture of an iron-based grit and water is blasted
onto the sheet at high pressure (- 100 bar). The scale is broken
off and entrained by the water jet.
The mixture, grit + water + scale, drops into a particlesize separator.
Three phases are recovered:
- the water, which is recycled back to the nozzles
- the grit, also recycled, and
- a mixture of broken grit + scale.
3.2.2

The process: the steps in the ISHICLEAN18 process

The ISHICLEAN process comprises four steps:

Step 1:

Break-up of the oxide due to the collision of abrasive

particles with the surface of the scale. This then
131

undergoes cracking (Figure 15) .

Step 2:

Descaling. The scale flakes off and no longer adheres

to the metal; it is entrained by the pressurized
water.

Step 3:

Abrasion of the basis metal.

This step must not be continued for long. It results
in work hardening of the metal and a significant loss
of mass from the sheet.

Step 4:

Complete entrainment of the grit/oxides/water mixture,

settling and recycling of the species.
Shot
Water under high pressure

Steel

F i g u r e 14 - P r i n c i p l e of t h e ISHICLEAN p r o c e s s 3

132

1. Cracking of the scale

Removal of
material
Crack
Scale
Basis
metal

2. Descaling

Scale
Metal

3. Descaling + abrasion of the basis metal

Metal I

Figure 15 - The steps in the ISHICLEAN process3

3.2.3

Description of the technology

The key point in the ISHICLEAN process is formed by the

injection nozzles. Figure 16 shows a diagram of a nozzle, which
consists of:
- a central orifice serving to inject grit and water
- a circular

ring

comprising

six orifices

acting

as

water injectors (90 1/m, 1000 kg/cm ) .

It is this second circuit which imparts its energy to the
shot. The nozzles are grouped together in orientable rails of 38
jets.
An ISHICLEAN unit may comprise two to four rails of 38
jets
133

The nozzle adjustment parameters are:

-

the
the
the
the
the
- the

blasting distance (300 to 700 mm)

focusing distance
blasting angle
helix angle a, the angle which the rail makes with
direction in which the sheet moves
water pressure.

There are other types of nozzles, variations relating to

the water inlet orifices.
Supply with shot

Pressurized supply

Helix angle

Figure 16 - Injection nozzles and position of an ISHICLEAN

rail with respect to the steel strip18
134

3.2.4

Descaling parameters

The descaling kinetics are proportional to the flow rate

of abrasive agent and water.
The efficiency depends on:
- the water pressure
- the nozzle/sheet distance.
Optimum descaling is achieved with a blasting angle of
45.
It is necessary to adjust the number and distance of the
nozzles so as to obtain complete overlap of the impact areas.
Partial or total removal of the oxides can be achieved in
one or more passes, that is to say passing under several rails.
Figure 17 shows the effect of water pressure on the
descaling.

Degree of descaling, %

200

100

0.2 0.4 06 1

1.6

Blasting time, s

Figure 17 - Effect of water pressure on descaling

135

3.2.5

Raw materials

Abrasive agent: The abrasive agent recommended by ISHI is

an ironbased grit from New Zealand. This grit also contains
titanium which is an excellent tracer for checking that the
surface of the descaled sheets is clean. The desired particle
size is 150 /m; after wet shot peening, the grit particles have
partially broken up.
Recycling: After descaling, the combination of water +
grit + oxide particles drops into a hopper and the various
particles are separated, by density difference, in a settling
tank and then in a cyclone separator.
Figure 18 shows the entire ISHICLEAN plant18'19'20.
Water under high pressure
Cyclone

=]

Scalecovered strip

:.
;:

ST
V
./

Descaled strip

\^S

'I

Highdensity abrasive

Sludge
recycling
pump

Lowdensity abrasive

Descaling tower
%

Cyclones

Clean water
Highpressure
pump for the
water

Washing the grit

Supply of
flocculating agent

~3ffp
Classifier

I' l' l'j' l' l' l' I' l' l' | f ,1 Q

f ,1,' .'

Precipitation
and settling

Filtration
I* /.'J

t<ft
" "

Storage of discharged sludge

Figure 18 General diagram of an ISHICLEAN plant18'19'20

3.2.6

E xisting pianti

According to the literature (1992) several industrial

plants equipped with the ISHICLEAN process have been installed.
136

In Japan, we may mention the YAWATA, NAGOYA and HIKARI

plants.

3.2.7

Advantages and disadvantages of the process

Advantages:

- low cost of capital investment

- absence of pollution

Disadvantages: - running cost (energy and grit)

- surface rugosity: this requires a
finishing acid "flash" and passivation.

3.3

Wire descaling using ferromagnetic particles - A.P.O.

process"

3.3.1

Principle

The stainless steel wire passes through a cell containing

ferromagnetic abrasive particles (steel shot of angular shape).
This highly abrasive powder is subjected to an intense magnetic
field and to mechanical pressure.

3.3.2

Realization

Figure 19 shows a typical diagram of a plant12. According

to the authors of the patent12, the magnetic field enhances the
abrasive properties of the shot, especially if this is subjected
to high pressure. The shot circulates in the cell at high speed;
once it is contaminated by the oxides it is treated and then
reused (the shot lasts from 2 to 4 weeks).
Figure 2 0 shows the diagram of a complete plant for the
A.P.O. process.

137

Figure 19 - Typical diagram and principle of the A.P.O.

process12
1
2
3
4
5
6
7

Direction of movement of the strip

Strip leaving the module
Abrasive particles
Powder/strip compressive forces
Torn-off scale particles
Strip entering the module
Layer of scale

138

Figure 20 - Block diagram of an A.P.O. plant12

1 2 3 4 5 6 7 8 9 10 11 12 13 -

3.3.3

A.P.O. module
Drive rollers
Treated strip
Recovery of the scale
Spent powder
Unit for separating the scale from the powder
Reusable powder
Powder conveyor
Strip with scale
Tank
Powder charging unit
Powder compression unit
Electromagnet acting on the powder

Advantages and disadvantages of the process

Advantages :

effective (low-throughput plant)

139

- no dust
Drawbacks:

3.4

- the process is slow (low throughput)

- adjustment difficulties
- expensive process.

Cryogenic descaling (ice and dry ice)

The literature reveals the filing of patents21 relating to

cryogenic descaling using:
- balls of ice
- balls of dry ice.
These processes are only suitable for low-tonnage plants
and for subcontracting units.
The only advantages are :
- the absence of waste (except for the scale)
- the absence of atmospheric pollution.
These are, in fact, "laboratory processes".
3.5

Descaling

using

molten

salts

Thin-film

(spray)

descaling - Anti-scale products

This type of descaling will be dealt with in the "PICKLING" chapter.

4.

DESCALING AND SURFACE FINISH

Appearance of the metal after shot peening:

During shot peening, the metal undergoes work hardening.
The work-hardened layer increases with the shot velocity and the
duration of the treatment, the thickness affected possibly being
up to 200 /xm. The surface rugosity increases with the duration
140

of the operation and the size of the particles.

The "pits" of encrusted oxides are not removed by the
shot peening.
Shot peening and Fretting:
Controlled shot peening is very effective for combating
fretting.
Brief reminder about fretting:
This type of metal-surface destruction is also called
"rubbing wear" (wear induced by small rubbing movements) and
"rubbing crack" (a crack induced by small rubbing movements).
The surface finish and the coefficient of friction are
modified by shot peening. The same applies to the work hardening
of the surface, the depth of which may be up to 1 mm. This work
hardening has an influence on the microstructure of the
material, the surface hardness of which increases11.
The effects of fretting and shot peening are summarized
below:
Shot peening

Fretting
contact pressure
nominal stresses
displacement amplitude
debris
lubrication
crack
hardness
rubbing

lift
residual stresses
elasticity of the peaks
absorption of the debris
lubricant retention
blockage of cracks

- microstructure
- surface finish

The main role of shot peening is to promote lubricant

retention during cold rolling; this is because the very high
local pressures on asperities very often lead to rupture of the
141

oil film or expulsion of the lubricant. Maintaining "pockets of

oil" in the immediate vicinity of the regions of maximum
pressure allows better lubrication of the compressed surfaces.
Rugosity and planaritv:
The rugosity and planarity of a surface may be highly
variable, depending on the descaling process. The measures used
to compare rugosities are:
- the average rugosity RA
- the rugosity depth R,
- the rugosity Rz.
The average rugosity corresponds to the distance separating two parallel lines right along the measurement profile, the
total being divided by a number N representing the number of
peaks above or below this average line:

yt

y2

y3

y*

y5

Checking the surfaces :

Consult the "PICKLING" chapter.

5.

ENVIRONMENTAL ASPECTS

Over the coming years, there could be a renewed interest

in "dry" treatments (descaling) - as opposed to wet treatments
(pickling) - for at least two reasons related mainly to environmental legislation:
- significant increase in the cost of water, as a solvent, even with recycling; consumption limited, by
legislation, to 8 1/m2 could lead to a very high
142

manufacturing cost for removing the scale from flat

products via a wet route;
- pickling baths and the rinsing water will have to be
treated, which will have the following consequences :
. construction of a treatment unit
. purchase of reagents (Ca(OH)2, flocculating agent,
etc.),
. cost of energy
. a filtration operation
. the expensive discharging of hydroxides and other
compounds, etc.
Since the ratio Fe(OH)3/Fe is 1.9, to which it is necessary to
add an equivalent mass of water, 1 tonne of steel thus results
in 3.8 tonnes of wet hydroxides. A similar calculation shows
that the H* ions of the residual acids are neutralized into the
following forms: CaF2 and CaS04; the mass of the residues is then
multiplied by large factors related to the molecular weights (96
for S04") and to the water of crystallization and of hydration.
If we add:
-

the cost of acid or acid mixtures

the heating of the baths
the ancillaries (hot air, etc.)
the capture and neutralization of the vapours
the neutralization of the baths
the separation, transportation and discharge (expensive) of the hydroxides and calcium compounds,

we can then see the advantage of shot peening.

The following comparison shows, in terms of manufacturing
cost, the most important units in each technique: the SHOT
PEENING process may be advantageous in this regard. To be sure,
the final outcome of each process is not the same:
143

- shot peening is an operation preparatory to pickling,

leading to known technical problems: work hardening of
the product
- pickling is a "final" or "smoothing" operation.
The following table allows qualitative comparison of the
two processes, in terms of manufacturing cost.

Descaling

Shot peening
- Plant depreciation
- Purchase of shot

- Plant depreciation

- Manufacturing cost of fluids

- Storage of acids
- Heating and temperature hold of baths
- Capture and neutralization of the
vapours

- Purchase of reagents

- Capture of dust
- Discharge of waste (spent shot,
scale, dust) or recycling in steelworks
- No water

The mass ratio:

- Neutralization of baths
- Filtration
- Discharge of sludge (-4:1
respect to the steel)

Pickling by-products
Shot-peening by-products

144

ratio with

is between 6 and 10

USEFUL ADDRESSES
BLASBERG - FRANCE
25, rue Georges Bizet
92000 NANTERRE
CAPOL
BP 10
38360 NOYAREY
VAPOR BLAST
Z.A.I, des Bruyres
7 8190 TRAPPES
L'ABRASIENNE
20, avenue Reille
75014 PARIS
WHEELABRATOR ALLEVARD
BP 3
3 8570 LE CHEYLAS
SEMANAZ
11 bis, quai du Rancy
94388 BONNEUIL-S-MARNE CEDEX
DELEY/SABLAJET
11, rue de la Marne
94146 ALFORTVILLE
SECOMAT
77, rue de l'Epineuil
16710 SAINT-YRIEIX-SUR-CHARENTE
BIPOL
3, rue St-Remi
51430 BEZANNES
ROTOFINISH RSLER
BP 513
89105 SENS CEDEX
145

LIST OF FIGURES

Figure
Figure
Figure
Figure
Figure
Figure
Figure
Figure
Figure
Figure

1
2
3
4
5
6
7
8
9
10

Figure
Figure
Figure
Figure
Figure
Figure
Figure
Figure
Figure
Figure

11
12
13
14
15
16
17
18
19
20

Device for bending around a roll

Example of a "small roll" plant
Diagram of the principle of the "PROCESSOR" system
Diagram of the principle of a SKIN PASS
Appearance of typical shot
Trajectories of the shot from a turbine
Impressions formed by the shot on the metal
"Residual scale" = f(A%) curve
Trace of the jet impact areas
Flows passing through the calibrated
orifice
(SIMON-HOUGARDY process)
Water speed in the jet
Industrial prototype with hoses
Industrial prototype with rotary seals
Principle of the ISHICLEAN process
Steps in the ISHICLEAN process
Injection nozzles (ISHICLEAN process)
Effect of water pressure on descaling
General diagram of an ISHICLEAN plant
Typical diagram and principle of the APO process
Block diagram of an APO plant

146

BIBLIOGRAPHY

1.

C. JUTTEAU, M. GRUMBACH, A. LE BON and M. PRUDHOMME

Rev. Met. (1992), 991

2.

J.L. MONTAGUT and A. ADINE

CESSID Seminar, October, 1983

3.

R.M. HUDSON and C.J. WARNING

Metal Finish (1980), 2128

4.

F. WEBER, H. SCHMITZ and M. E SPE NHAN

Stahl u. Eisen [Iron and Ste e l],
96, No. 12, 577

5.

G. KOHLER and W. ZIMNIK

Stahl u. Eisen [Iron and Ste e l],

6.

96, No. 21, 1010

O. NOE

S t a h l u . E i s e n [Iron and S t e e l ] , 9 1 , No. 16, 916

7.

E .J. PATULA
Journal of Engineering for Industry (1971) , 101, 269

8.

C. HUBER
CESSID Seminar, October, 1983

9.

P. BOUHIER
CESSID Notebooks, 7177, October, 1983

10.

R. PRONE R
Les Techniques de l'Ingnieur

[Te chnologie s

for

th
e

Engi

neer]
Metallurgy, M4 1494
11.

Y. LE GUERNIC
GalvanoOrgano Surface treatments, 615, 445, April 1991

12.

Patent SU 296163 (1988)

13.

. LAPOSTOLLE
CESSID Seminar "The control of scale", 1921, June, 1990
147

14.

G. DI CAPRIO
Gli Acciai inossidabili [Stainless
steels]
2nd edition, Published by Ulrico Hoepli, Milan

15.

J. REMMELTS
Brit. Corr. J., 199-206, 4 July, 1969

16.

P. SIMON and A. HOUGARDY

La Revue de Metallurgie [Metallurgy
C.I.T., April, 1994

17.

Review]

Guide Technique des aciers inoxydables [Technical

stainless

guide

on

of

flat

steels]

UGINE SA - Immeuble PACIFIC

13 Cours VALMY - TSA 3 0003
F92070 La Defense 7 Cedex
18.

D. QUANTIN
In "Le dcapage des produits plats [The pickling

products] "
CESSID Notebook, 1983
19.

T. FURUYA, T. KAWANANI and M. HIGASHI

IHI Engineering review (1979), April, 15-21

20.

T. FUJIKI
IHI Engineering review (1982), January, 469-474

21.

J. BODIN
Galvano-Organo, Surface treatments, 139-140, February, 1995

22.

B. BAROUX
Mtaux [Metals], No. 646-238, June, 1979

23.

T. ASAMURA, S. YAMAGUCHI, K. OYA and M. IYAZAKI

Nippon Steel Corporation
Seitetsu Kenkyu, 304, June, 1981

148

Pickling

PICKLING

Contents
1. GENERAL COMMENTS: Definitions - CHEMICAL REACTION ENGINEERING - REACTOR DESIGN

153

1.1 How do you pickle? Aspects related to "process

engineering"
1.2 Thermodynamic aspect

153
156

1.3 Chemical kinetics

1.4 Development of a pickling reactor

157
162

DESIGN OF A PICKLING LINE

168

2.1 Examples of processes

2.1.1 Process for flat products
2.1.2 Process for wire

168
172
172
173

2.2 Descaling
2.3 Roughing

I74

2.3.1 Acid baths

. -.
2.3.2 Oxide conditioning using alkaline solutions

174
182

2.3.3 Treatments using molten salts

2.3.3.1 Scientific bases
2.3.3.2 The chemistry of molten salts . . .

187
187
188

2.3.3.3 Descaling - Thermochemical pickling

2.3.4 Electrolytic pickling
2.3.4.1
process
2.3.4.2
2.3.4.3
2.3.4.4
2.3.4.5

190
198

The electrochemical bases of the

Research on electrolytic pickling .
Media used
Raw materials - energy balance
. .
Operating conditions

151

198
199
202
209
210

2.3.4.6 The state of knowledge

2.3.4.7 A few ideas on which to focus . . .
2.4 Chemical pickling

214
222
230

2.4.1 The role and place of chemical pickling in a

process for finishing stainless steels
. .

230

2.4.2 Review of a few typical baths

2.4.2.1 Nitric/hydrofluoric acid pickling

23 0
23 0

2.4.2.2
2.4.2.3
2.4.2.4
2.4.2.5
world

The UG3P process

232
The UG3P+ process
237
Other processes
239
Examples of baths used throughout the
241

946
2.4.3 General theory - Mechanisms proposed

...

2.4.4 The parameters involved in pickling . . . .

2.4.5 Methods used for studying and investigating
pickling
2.4.6 Passivation
2.4.7

OCT

253
259

Finishing operations: brushing, rinsing, drying,

final inspection

2 64

152

1 - GENERAL COMMENTS - PROCESS ENGINEERING

1.

GENERAL COMMENTS:
Definitions
ENGINEERING - REACTORS DESIGN

CHEMICAL

REACTION

According to LAROUSSE, pickling is an "operation whose

purpose is to remove the oxides covering a metal surface and, by
extension, to clean any surface so as to expose the bare metal" .
Pickling operations are very important in the process for
manufacturing stainless steels. They provide the transition
between hot plant and cold plant, coming after the annealing
operations.
Within our framework, pickling is the final operation
which leads to the formation of a clean surface - that is to say
a surface free of scale - thus allowing cold rolling or any
other subsequent operation.
An alternative term which is sometimes encountered and,
has the same definition as above, is "ETCHING" - this term being
used, for example, in metallography, engraving, etc.
This definition answers the question:
What is the purpose of pickling?
The other question raised is:
How do you pickle?

1.1 How do you pickle? Aspects related to "process engineering"

Pickling is carried out in one or more reactors and
involves several reactions.

153

The following diagram explains the two elements of the

system:
reactions

Thermal reactions

Mass balance

reactors

Chemical reactions
in solution:
Equilibria

Instrumentation
H* control
E
rdox control

Electrochemical reactions
Metal/solution interface
Oxidation/reduction

Heat transfer
Transfer of the reactants
Purge
Overflow
Entrainment

The pickling reactor allows the pickling reactions to be

known p r e c i s e l y and allows the operating p o i n t s to be defined.

The factors governing the process are as follows1:

154

Hydrodynamic d a t a
C i r c u l a t i o n and c o n t a c t i n g
0 t ^ e phases

Thermodynamic and k i n e t i c
r e a c t i o n data

Operating parameters :
_ .,
nature o f the r e a c t a n t s
INPUT
conjurations
flow rates
r e s i d e n c e time

,-

m *~-J*

"

REACTOR

%,

/
'

CTK-DT

\ "^~*-^
\

\OUTPUT
- ^ - > =

^*r
s^^

Nature o f t h e p r o d u c t s
Degree o f c o n v e r s i o n o f
t h . reactants

- 1TTVJTCU D i s t r i b u t i o n o f t h e
I r i n l o n
^ ^
Yields

Data on mass transfer.

heat, and momentum

Geometric structure
o f
" "*=tor

The quality of the pickling must remain constant and we

must therefore take into account the main parameters involved in
the operation:
a)

The reactor gives rise to chemical and electrochemical

reactions - stoichiometric reactions, equilibrium reac
tions, complexing reactions - quantities are therefore
associated with these reactions;

b)

The mass balance relating to each category of atom;

c)

The concept of driving forward the reactions

aspect)

d)

Conversion, selectivity, yield, etc.

(kinetic

A pickling bath, as a reactor, is a SEMI-OPEN system. The

number (nl) of moles initially present is replaced by the
concept of molar flow rate. It is then possible to work out
yields, by calculating the INPUT/OUTPUT fluxes, and perform mass
balances.

155

1.2 Thermodynamic aspect

We define, for the PICKLING reactor:
a)

An INITIAL STATE:
scale-covered metal
- concentration of the H + ions and anions in solution
- concentration of the metal ions
- redox potential
temperature

b)

A FINAL STATE:
- non-oxidized metal
concentration of the H + ions
solution
- concentration of the metal ions
- redox potential
temperature

and

the

anions

in

The change in enthalpy associated with this reaction is:

(AH R ) T = E v i t e i )
where

(AH R ) T

is

expressed

in

joules and

h^A^

denotes

the

partial molar enthalpy of the compound A at constant T.

The change in enthalpy associated with this equation
written as Ev^A^ = 0 corresponds to complete conversion of a
fraction of the reactants (a state of equilibrium is established) .
It is necessary to introduce the TIME parameter in order
to define the reaction volume useful for the chemical conversion
to a point where the reaction has been driven forward to a
defined extent (from oxidized metal.... to descaled metal).
The laws of chemical kinetics therefore also apply to
156

pickling. Introducing these concepts is necessary in order to

understand the phenomena and to establish the "mass balances"
and requires knowing the main characteristics of the reaction:
1)

nature of the reacting phases

2)

localization (in our case, the metal/solution interface)

3)

possibly the intermediate forms, for example the presence of TRANSIENT species which are often highly
reactive and detectable only with difficulty, but which
play an essential role in controlling the passage of the
reactants into products - this corresponds in practice
to the case when pickling is blocked by the build-up of
species.
Equilibrium constant

The law of mass action teaches that an equilibrium (or

equilibria) exists between the reactants and the products
formed.
The change in standard
single reaction:

free energy corresponds

to a

(AG)T = -RT In K a
where K a is the equilibrium constant for a given reaction. We
will see that this concept is of paramount importance for
quantitative measurements on the baths and for monitoring them,
especially for nitric/hydrofluoric acid baths.
1.3 hemjcal kinetics
We will define the general ways of expressing the mass
balances (stoichiometric or non-stoichiometric) and the thermal
balances corresponding to transformations involving one or more
reactions being driven forwards.
157

We will therefore also have to define and explain the

laws governing how reactions are driven forwards as a function
of the residence time of the reactants (including the metal)
within the reactor.
A pickling bath is a HYBRID reactor. With regard to the
metal sheet to be descaled, it is an OPEN reactor, in the STEADY
state: the characteristic of such a system is that there is no
build up metal (continuous running). The mass flow rate at the
input I is approximately equal to the mass flow rate at the
output O.
The stoichiometric constraints of the reaction apply
therefore to the amounts of chemical species consumed or produced within the system.
- dissolution of the oxides
- dissolution of the metal.
flow
flow
flow
flow
flow

rate
rate
rate
rate
rate

of
of
of
of
of

the
the
the
the
the

metal at the INPUT

metal at the OUTPUT
metal in solution
oxides in solution
insoluble oxides

=
=
=
=
=

fmx
fn^
fm sol
fox sol
fox ins

fmx = fmo + fm sol + fox sol + fox ins ,

where fm sol + fox sol + fox ins < fn^.
With regard to the pickling solution, we consider two
cases :
1st case:
The solution is not stirred and the system does not
include a circulation pump; this is the case of a uniform SEMIOPEN reactor in plug flow. In this reactor, conservation of
matter requires, at any instant:

158

Incoming flux
of acid .

Rate of
consumption
of A T

Outgoing flux ,
of acid
"
A

Rate of
accumulation
of A

Rate of
J" evaporati on
of A T

Accumulation of product
Input flu:
of acid

Fe++ - Fe*** - tit** - C:

Anions
Evaporation

Output flux of acid

The reactor term "uniform" assumes that the H + concen

tration and the temperature are held constant (this is only
partly true for H+) . However, the term "plug flow" means that
the reaction products progress (expenditure of the bath) and
that the system will be purged at a time:
o + tx

fc

where tQ corresponds to the fresh bath

t x corresponds to the time it is operated for
2nd case:
The solution is stirred and the system includes a
circulation pump. The reactor is also described as being "well
mixed" or a "homogeneous" reactor (further terms are BACK MIX
REACTOR or CONTINUOUSLY STIRRED TANK REACTOR (CSTR)).
This reactor is characterized by a composition and an
instantaneous state of the reaction mixture which is perfectly
uniform throughout the volume which is presented to it. This
condition is fulfilled if the added reactants are mixed in an
infinitely short time and if the internal recirculation is such
that the time taken by a molecule to go from any point in the
reactor to another point is infinitely short compared to the
time for the metal sheet to pass through the reactor.
Under these conditions:

159

jl

Fjj
VR =
Rj
Fj 0

RRj =

jO

= input flux
volume of the reagents
= chemical reagents
= output flux

The case of "dip"-descaled wires

The system may also move towards a transient regime, in
terms of driving the reaction forward (simple reaction). This is
specifically the case of wire bundles - the reaction is generally in the steady state but the system is subjected to
programmed operating fluctuations. In this case, it is necessary
to consider the reactor at time "t" and to do a balance on what
has happened since the initial time t = 0.
At time "t", there are n^ mols of Aj in the reactor while
there were nj 0 at t = 0.
Let us denote by n? and n? the number of moles which
entered the reactor and which left after the start of the
operation. These are given by:
n^ = SI F jx dt

and

n? = Fjodt

Figure 1 gives an example of the reactor used:

160

Supply
reservoirs

Figure 1 - Treatment, in batch mode, of a finite

quantity of material
In general, for any reactor, the following balance may be
written:

I *> * L
incoming
flux

flow
rate
relating
to production

- . * /,
Va

outgoing
flux

rate
of
accumulation

The rational analysis of pickling therefore

establishing the mass balances and energy balances.

requires

The combination of these balances allows the mechanisms

to be interpreted and the consumptions to be actually quantified.
Periodic supply
This is the case, in pickling, of adding an acid, after

161

quantitative measurement, at a work station. The diagram repre

sents a socalled "pulsed" reagent supply.
In practice, the difference CgCjj must be as small as
possible so as to satisfy the fixed setpoints.
Figure 2(c) shows the almost ideal solution. It is
therefore necessary to fix the frequency of and the amplitude
o f

S-CM

(a)

(b)

(c)

K k k k
>NKNNKSE'Z

CM

V^fsfNTslSlsisj*^.

Figure 2 Diagram of pulsed reagent supply1

1.4 D evelopment of a pickling reactor

We give below a model of the development of a reactor and
the approach to be followed in the form of a block diagram. The
approach proposed derives from VILLERMAUX1 and SMITH2.
First step: Laboratory feasibility
Analysis of the scale
thickness).

(constitution composition

Kinetic and thermodynamic aspects Mechanisms

Stoichiometry of the reactions Measurement methods
Weight loss Control of the surface finish Analysis
of the reactants Parametrized analysis of the key
factors (H+, Fe + + , Fe + + + , Ni + + , Cr + + + , Cr 6+ concen
162

rations), redox potential, equilibrium

temperature, time, stirring, etc.).

potential,

Second step: Design of a pilot plant

Industrial engineering requirements - Analysis of the key
factors - Mathematical model of the reactor - Mass transfer Automation - ENVIRONMENTAL implications - Yield analysis.
Third step: Construction of the reactor
Choice of the constructor - Supply for the reactor (metal
and reagents) - Control and regulation system - Run speed Resistance and properties of the materials - By-products ENVIRONMENTAL problems - Technical and economic assessments.
The following block diagram shows
rational design of a pickling reactor.

163

an

example

of

Knowledge about the

calo

Phases of the project

1
Preliminary

Mechanisms
S t o i chi on try

Thai iiiKlynamlc aspects

studies

in the
laboratory

Measurement method*
ffeight-loas probes

Kinetic aspects

Parametriled analysis
Key factors
Balances

Analysis of the
reagents

Design of a
p i l o t plant

"
Construction

Industrial engineering*
requirements

Heat, mass and energy

transfer

An-kiyn* of the key f*ctoi-

M i L l e m i u c i l M x k l o* t h

:..-tor

of a
pilot plant

Environment
Pollution

1'

Rates - Yield
Assessments

Automation
Preparation of the
programs

Additional analyses

Preparation

Supply of metal
and reagents

Use of the final

form of the model

of the

Ron speed

final

I
t

design

Control and measurement

system

By-products
Purification

\
Resistance and properties
of the materials

Design of the
industrial reactor

Automation

"

Construction of the
industrial reactor

ENVIRONMENTAL
problems

Technical and economic

assessments
Quality assurance

Rational design of a p i c k l i n g r e a c t o r
Pickling f a c t o r s
There are about a dozen f a c t o r s which have an e f f e c t .
The parametrized analyses
account the following f a c t o r s :

164

must

therefore

take

into

 grade of the metal and thickness of the chromium

depleted region
nature, composition, constitution and thickness of the
scale
concentration of the H + ions
concentration of the associated anions: NOj, F", S0
concentration of the cations: Fe + + + , Fe ++ , Ni + + , Cr+"t"t'
redox potential
potential of the basis metal
temperature
time
stirring (replenishment of the metal/solution inter
face)
additives (surfactants, etc.)
The pickling efficiency may be quantified using the so
called "massloss" method, expressed in g/m2. The dimensions of
the typical specimen (for the case of metal sheets) are 50 mm
50 mm, the thickness being that of the metal sheet to be
descaled. After pickling, the surface is examined using the
following standard methods:
visual examination
micrographie examination
microprobe examination
Glow discharge optical spectroscopy.(G D 0 S)
physical properties: rugosity, colour, etc.
inspection Quality Assurance

165

BIBLIOGRAPHY

General Points

1. J. VILLERMAUX
Gnie de la raction chimique. Conception et fonctionnement
des racteurs.

[Chemical reaction

engineering.

Reactor design and

Pub. Lavoisier, Paris

2. J.M. SMITH
Chemical engineering kinetics
Pub. McGraw-Hill, 1970
3. P. TRAMBOUZE et al.
Les racteurs chimiques [Chemical
Pub. TECHNIP, Paris, 19 84

reactors]

4. R. NICOLLE
Le Gnie des procds dans: Le livre de l'acier

[Process engineering

in "The steel

Pub. TEC and DOC, Lavoisier, 1993

167

book"]

operation]

2. DESIGN OF A PICKLING LINE

The pickling of stainless steel rarely employs a single
treatment, using a single solution. In most cases it is accomplished in a system of reactors forming an "ANNEALING PICKLING
LINE" (APL).
A pickling line is a series of reagents and reactors
whose purpose is to produce a metal free of scale.
2.1 Examples of processes
Figure 1 shows a diagram of an annealing pickling line.
In general, it consists of three sections:
a)

"INPUT" Section consisting of:

2
1
1
1
1

b)

pay-offs
planisher
shear
welder
looper characterized by the number of runs

"CENTRAL" Section
1 bank of furnaces (heated by natural gas)
1 bank of coolers
1 to 3 electrolytic
roughing tanks
1 to 2 pickling tanks
1 passivation tank
1 rinsing unit.

c)

"OUTPUT" Section
1 looper
1 shear
2 take-ups.

Variants involve:
168

pickling

tanks

or

to

the possible presence of molten-salt baths

- installation of more

sophisticated

systems

(spray,

ultrasound, etc.).
There are specific lines for austenitic or ferritic
steels and so-called "hybrid" lines which handle all grades of
stainless steel:
ferritic steels
-

austenitic steels
austeno-ferritic steels
martensitic steels
etc.

A process is adapted to each grade and depends on the

concentration of acids, the immersion time, the temperature,
etc.
Finally, there is also a classification relating to the
shape of the products:
flat product
long product (wire)
- bar
thick sheet
tube
- castings (valve bodies, foundry castings and other
workpieces descaled "in drums" or "in baskets").
All the types of species will not be studied in detail in
this treatise simply because pickling may give rise to many
combinations of treatments :
acid treatments
- alkaline treatments
- electrolytic treatments
- molten-salt treatments.
Each factory adopts a process pertinent to the metallurgical history of the products and increasingly takes into
169

account economie considerations having an impact on the ENVIRONMENT.

Thus,
the
current
trend
is
to
get
rid
of
nitric/hydrofluoric
acid baths and baths which generate
hexavalent chromium.
We give below several examples of pickling processes
described in the specialized literature12.

170

Q)

-H
H

tn
t

H
H

BB

tn
t V
H
t
H
)
0)

0)

o
)
t

i'. '

t
"

-.VW-V'''-iV.

TV
CENTRAL SECTION

CA

J:

Running direction

OUTPUT SECTION

(d
M-l
O

INPUT SECTION

2.1.1

Process for flat products

Example No. 1: Annealing pickling line for hot-rolled

flat austenitic stainless steels (sheet).
3
Shot
peening

Pickling

Passivation

Rinsing

Drying

Annealing ovens - 2 or 3 cells - for example, heated

using natural gas
Quench - water/air coolers
Shot peening - several turbines (at least 2)
Roughing: 1 to 3 tanks
4.1 using an acid or acid mixtures (H2S04, etc.)
4.2 or by electrolytic means in acid or neutral medium
4.3 or using molten-salt baths
Pickling: 1 or 2 tanks
5.1 using a nitric/hydrofluoric acid mixture brushing rinsing
5.2 using the UG3P process
|_ at the cutputof pickling
Passivation, mostly using HN0 3
Final rinsing: pressurized water, cold water and/or hot
water
Hot-air drying

2
3
4

6
7

N.B.

4
Roughing *

between

brushing
2.1.2

each

roughing

tank

there

is

often

double-

uni t .
Process for wire

Pickling line for hot-wire-drawn

Example No
tenitic stainless steels (0.5 tonne wire bundles).

172

aus

1
Annealing

~1

Stoving

1
2
3
4

5
6
7
8
9
10 -

Quench

Holten salts

Quench

Roughing

HP rinsing

i
Pickling

10

Rinsing

Drying

Annealing: controlled atmosphere furnace

Quench: water
160C stoving
Treatment using: molten soda + sodium nitrate at 500C
or molten sodium hydride
Quench: water or dilute acid
Roughing: H 2 S0 4 or HCl (Japan) , 1 or 2 tanks
Rinsing using pressurized water
Pickling: HN0 3 - HF or UG3P (1 or 2 tanks)
Rinsing with high-pressure water
Air drying

N.B. - These diagrams are conventional

and correspond
confidential
bibliographic
data. Each factory
own "recipes"
with respect to additives.
In
some processes correspond to published patents
be implemented only by means of a licence.

2.2

to nonhas
its
contrast,
and may

Descaling

The reader should refer to the chapter on this subject

(Chapter 3 ) . It is explained that dry descaling could experience
a resurgence of interest because of its less stressful impact on
the ENVIRONMENT than pickling processes. This is because the byproducts are a mixture of scale and shot (no water) , while
pickling involves neutralization and filtration of large volumes
of solution. In this regard, the descaling treatments are
particularly advantageous.

173

2.3

Roughing
Roughing is the first pickling operation.
*

The role of "roughing" baths is to modify the scale in

order to make descaling easier (the term "oxide conditioning" is
often employed).
The conditioning consists of:
- modifying the nature and structure of the scale
(modification of the lattice)
- strongly oxidizing the FeOx- and Cr203-type scale
- destroying the mixed compounds (spinels)
- dissolving the oxidized regions which are preferentially soluble, so as to allow basis metal/acid
contact.
The scale conditioning methods use the following:
acid solutions
- basic solutions
- molten-salt baths
- electrolytic baths.
2.3.1 Acid baths
We compile below the characteristics of "roughing" baths
employed, specifying for each of them the "strengths" and
"weaknesses".
The assessment criteria involved are:
the ease of implementation
the efficacy and quality of the results
- the ENVIRONMENTAL, pollution, health
aspects

and

the methods of treating the spent solutions

the fields of application
174

safety

the manufacturing cost.

We will not consider all "roughing" baths, but by means
of a few examples we indicate the current trends :
a) Sulphuric acid (reducing bath)
Commercially available solution: 96 to 98% H 2 S0 4 ,
18 M, r.d. = 1.84
Price (1995) - $110/t
Concentration range

1.6 to 4 M/l

Temperature range

55 to 95C

Strengths:

- efficacy
- low cost

Weaknesses :

- reducing bath, therefore redeposition of the

metals Fe, Ni, Cu, Sb, Sn and As (stains)
- in finishing, the workpieces may
suffer
hydrogen embrittlement
- H 2 S0 4 cannot be used in a finishing bath.

Methods of control: quantitative measurement of total H + , Ni,

++
!
Cr, Fe...
tot and Fe

Improvements : - turbulent
baths
(replenishment
of
the
metal/solution interface)
- use in an oxidizing medium1. In this case, the
Fe ++ /Fe +++ redox potential is controlled.
ENVIRONMENTAL aspects:
- neutralization of the baths using Ca(0H) 2 or
NaOH, but Na 2 S0 4 is very soluble;
- high molecular weight of CaS0 4 2H 2 0;
- it is possible to transfer spent baths to a
sulphate plant, but there is the problem of
obtaining ferrous sulphate which also contains
175

chromium sulphate and nickel sulphate. It is

strictly forbidden to distribute these products;
- there are possibilities to treat spent baths
electrochemically (electrodialysis, etc.).
b) Hydrochloric acid
Commercially available solution: 36%, 12N, r.d. = 1.18
A roughing bath little used in Europe, but thought highly
of in Japan (Nippon Steel Corporation and Kawasaki Steel2'3) .
This is the process most used for mild steel, in the
presence of an inhibitor in order to remedy over-pickling during
line stoppages. It also has the advantage that effective systems
for recycling it exist (RUTHNER process, LURGI process, etc.).
There are two trends :
Reducing bath: HCl, 2 to 8 M/l
40 to 60C use temperature
Strengths

not very heavy and very effective

chromium oxides are soluble in HCl
inexpensive.

Weaknesses:

risk of pitting of the metal

high vapour pressure, hence damage to workshop
structures (covers over baths)
HCl requires effective rinsing operations
prohibited for steel intended for the nuclear
industry.

Improvements :

The Japanese school is increasingly using HCl, in

an oxidizing medium (H202) or as an HCl/Fe +++
mixture.

176

Method of control:
- H + (automatic control)
- metals: Fe t o t , Fe + + , Ni, Cr
- redox potential.
ENVIRONMENTAL aspects
- neutralization of spent baths using Ca(OH) 2 or
NaOH or Na 2 C0 3 . The chlorides formed are
soluble and pass into the effluents;
- non-utilization of the oxides during HCl
recycling using the RUTHNER process.
c) Nitric/Hydrofluoric acid bath
This is the bath most often used for stainless steels,
especially in finishing.
Highly oxidizing bath:

70% HN0 3 (- 14M), r.d. = 1.41

70% HF
r.d. = 1.16

Range for prepickling

HN0 3 :
HF:

1.5 to 3 M/l
0.5 to 2.5 M/l

Temperature: 40 to 60C.
Strengths:
HP role:

- powerful depassivating agent

- H + supplier
- Fe + + + , Cr"1"1"1" and Ni + + complexing agent
- lowers the redox potential;

HNQ3 role:

- H + generator
- powerful oxidizing agent
- brightener for the descaled product.

177

Weaknesses :
Hazard problems and ENVIRONMENTAL problems :
- evolution of 0 and N0 2
- presence of NO^ and N0 3 in effluents.
Improvements :

- stirring

of

the

solution

(tightly

sealed

tanks)
- N0 X oxidation using H 2 0 2
urea

or reduction using

- electrodialysis of spent baths.

Methods of control5:
There are no rigorous methods of quantitative
analysis
Good approach using the SCANACON4 apparatus
Problems due to dilution of the baths and to
modification of the equilibria5. Analysis of
the species in solution.
Use of so-called H + and F" "selective" elec
trodes .
d) UG3P process (Ugine Peroxy Pickling Process) 6
Basically, the UG3P bath is a nitric/hydrofluoric acid
bath in which the nitric acid is replaced by air and possibly
hydrogen peroxide. The pickling agents are H + and Fe + + + .
The basic reaction is: 2Fe +++ + Fe - 3Fe ++
Fe ++ may be reoxidized by air, the kinetics being fast,
in an HF medium and only in this medium (complexing of the Fe ++
ions and lowering of the redox potential).
The UG3P bath is described in Section 2.4 in the current
chapter; it is mostly used as a finishing bath. It is preferred
to use the UG3P+ bath, which is much more efficient and, above
all, highly effective in attacking oxides.
178

Concentration range:
HF
Fe

tot

Fe + + +

1 to 5 M/l
> 20 g/i
> 15 g/i

(20 to 80 g/1)
(15 to 80 g/1)

The "in situ" redox potential is controlled, the addi

tions of H 2 0 2 being slaved to the redox potential.
Operating conditions:
- air sparging
- temperature range, 50 to 7 0C
- H 2 0 2 , 200 volumes.
The characteristics of the UG3P process are described in
several patents 6,7 ' 8 .
Strengths :
- strict control of the parameters
- absence of contamination by nitrate compounds
- production of a white and bright product
- CaF2 is insoluble and of low molecular weight
- UG3P is an effective finishing bath.
Weaknesses:

- HF is an expensive reagent
- low pickleability in roughing bath.
Method of control:
- total acidity = HF
- measurement of the redox (Fe+++/Fe++) potential
- Fe t o t , Fe + + , Ni and Cr.
ENVIRONMENTAL aspects:
Effective solution of the problems posed by:
- atmospheric pollution, , N0 2
- aqueous pollution, NO^, N0 3
- working conditions and health
179

total absence of F" in effluents after neutra

lization using Ca(OH) 2 (since CaF2 is insoluble).
Future improvements :
recycling of solutions
recovery of F" by electrodialysis
spraying.
UG3P+ process 1
The pickleability of the UG3P process may be improved by
adding H 2 S0 4 .
An HF/H 2 S0 4 /Fe +++ mixture is then used, with:
injection of air (effective stirring)
- addition of H 2 0 2 , 2 00 volumes.
Concentration range :
HF
H 2 S0 4

Fe + + +
Fe +++ /Fe ++

1 to 2.5 M/l
2 to 3 M/l
60 to 65C
> 20 g/1
> 4

It is also possible to use FeS0 4 or Fe 2 (S0 4 ) 3 in order to

prepare the bath. By shifting the equilibria, an HF/H 2 S0 4 /Fe +++
mixture is obtained, the ferrous iron formed is reoxidized by
H202.
There are numerous patents, subsequent to UG3P, using the
same principle (Fe+++ and descaling agent) 9 . These patents extol
the virtues of H 2 0 2 stabilizers, but these stabilizers are
unnecessary since H 2 0 2 is already stabilized for being trans
ported and the UG3P bath does not contain H 2 0 2 in excess.

180

Acid or
acid
mixture

Concentration
range
temperature

H2SO

1.6 to 3 M/l
55 to 95C
1.5 to 8 M/l
(alloy)
40 to 60C

HCl

UG3P
(HF + Fe***)

UG3P*

Other
processes
H* + H 2 0 2

HF alone
1 to 2.5M
55 to 70C

Weaknesses

Proposed improvements
ENVIRONMENTAL aspects

Efficacy
Low cost

Reducing bath
Redeposition

Air stirring
CaS0 4 solubility
Oxidation Fe*** by H 2 0 2

Efficacy

Pitting

Air stirring

Corrosive
vapours

Solubility of CaCl2
Addition of H 2 0 2

Low efficacy
in roughing bath

f HF (3.5M)
Fe*** > 100 g/1
H 2 0 2 savings

Strengths

Absence of
pollution
Air stirring
Oxidation

H 2 S0 4 , 2M
HF, 2M
60 to 75C

H 2 S0 4
H 3 P0 4

H 2 S0 4 , 2M
H 3 P0 2 , 2M

16

Expensive
(stabilizer)

H ; 0 ; stabilization

Very good
pickle
ability

N0 X and
N0 2 , NO3
contami nation

Air stirring
Treatment by urea
or by H 2 0 2

13

Used in
"deglassing"

Redeposition

Turbulence
Addition of H 2 0 2 (UG3P)

12
2
16

Co-based
alloys

Redeposition
Expensive

t H 3 P0 4

13

Cr-based
alloys

Redeposition

t HCl

13

Cr-based
alloy

Air stirring

12
16

H 2 S0 4
1 to 2.5M
60C - Fe***

H 2 S0 4
HF

3
15

HF 1 to 2M

HNO3 1 to 3M
HF, 0.5 to 2M
40 to 55C

1-2

Very good pickleability

Fe*** > 100 g/1

HF, 1 to 2.5M
No pollution Expensive (HF)
H 2 S0 4
Very
1 to 3 M = 70C effective

HN0 3
HF

Ref.

is pointless
Similar to TJG3P

60 to 70C
H 2 S0 4
HCl

H 2 S0 4 , 2M
HCl, 2M
60 to 65"

H204
HCl
HF

H 2 S0 4 , 2M
HCl, 3M
HF, IM
60C

H 3 P0 4
HCl
HF

2M
3M
IM
60C

Ni-based
alloy

Addition of H 2 SiF 6

Organic

6M
70 o C

Aggressive

Addition of H2SiF6

acids
HCOOH

12

11

Types of baths used for roughing

181

2.3.2

Oxide conditioning using alkaline solutions

The object of this treatment, which is particularly

selective for martensitic stainless steels, is to oxidize the
iron chromites and to form soluble alkali-metal chromtes and
hydroxide compounds.
Operating conditions:
Application to grades:

AISI 410
AISI 416
AISI 42 0

Oxidizing solution:

NaOH,

40 to 200 g/1

KMn0 4 ,

15 to 60 g/1

Temperature: 60 to 85C
Immersion time: 5 to 20 minutes.
The oxidation kinetics are slow, a characteristic colour
change appearing after a few minutes. Some authors 13,14 recommend
adding sodium fluoride (50 g/1), the desired purpose being to
destroy the spinel lattice by preferential attack of the silicates .
Strict control of this bath is difficult; Mn0 4 can be
quantitatively analyzed using FeS0 4 , in 6N H 2 S0 4 medium. This
bath is often prematurely expended as a result of the presence
of reducing agents which cause significant precipitation of
Mn(OH) 3 .
Various attempts have been aimed at replacing Mn0 4 by
other oxidizing agents, in alkaline medium: perborates, percarbonates, addition products of hydrogen peroxide in the presence
of KOH and NaOH. These compounds are powerful oxidizing agents
which are easier to use than permanganates; the by-products
formed are sodium or potassium salts, thus getting round the
problem of manganese salts.
182

Treatment of the baths after use:

The aim is to be able to use spent acid baths coming from
pickling plants.
The experimental procedure is:
acidification by spent baths (H2S04)
reduction of Cr 6+ by FeS0 4 (or sodium bisulphite).

183

BIBLIOGRAPHY
Roughing
1.

P. WILLEMIN, M. DESCEMOND and M. MASSON

La Revue de Mtallurgie

[Metallurgy

Review]

, 415, March,

1995
2.

Swedish Patent SE 800/911

3.

Japanese Patents - (Sumitomo Kinzoku)

Appi. No. 56.171638
JP-50,071,1524

4.

SCANACON Ltd
Box 36, 17221 Syndbyberg, Sweden

5.

D. HENRIET, L .
C. SCHOENHUT

MEUNIER,

A.M.

PRAT,

M.A.

CUCHEVAL

and

IRSID (1978), RI 756-757

6.

.
BOUSQUET,
P.
BOUHIER,
H.
G. KACZOROWSKI and M. VILLERET

GIRAUD,

D.

HENRIET,

Coram., Inter. Rolling Congress, Deauville, 1987

7.

European Patent 0,236,354

8.

European Patent Applications: 9102222 and 9113757

9.

S. FORTUNATI, E. NOVARO, C. PEDRAZZINI and A. POLLASTRELLI

Comm. Innovation Stainless Steel
Florence 11 Oct., 1993, Italy

10. L . L ACOURCEL L E
Galvano-Organo, 737, Oct., 1995
11. European Patent 91400252.2

185

12. Handbook of Stainless Steels

Pub. McGraw-Hill, New York
13. K. SAKURAI and S. IIZUMI
Nisshin Seiko Giho
No. 62, 38-52, (1990)
14. R. SANTHOLZER
Oberflche [Surfaces], 15, No. 6, 312, 1975
15. H. NISHIMURA, T. SAWATANI and T. MIZUNUMA
Trans. I.S.I.J. Jap. B292, 20, 7, (1980)
16. French Patent 2,399,466 (HCl/FeCl3)
US Patent 2,186,546 (H2S04/HC1/HN03)
Italian Patent 1,319,217 (H2S04/HN03/HF)

186

2.3.3

Treatments using molten salts

2.3.3.1

Scientific bases and aim of the treatments

As with aqueous solutions, molten salts may give rise to

chemical and electrochemical reactions.
a)

Acid/base reactions involving protons, H + .

define, in "molten salt" medium, scales of
and basicity which are based on a concept
to the theory proposed by BRNSTE D and
(ionic dissociation).

b)

Dissolution and complexing reactions

c)

Redox reactions:
a Ox.l + ne
b Red.2

* a Red.l,
at El
b Ox.2 + ne, at E2

a Ox.l + b Red.2

and K =

We thus
acidity
similar
OSTWALD

* a Red.l + b Ox.2

[Red.l]*. [Ox.2]>
[Ox.l]a.[Red.2]b

If E l and E 2 are the potentials

obtain:

for reactions 1 and 2, we

,
log K_ = E l E2
0.058 n

Thus, molten NaN0 3 gives

NO;

+ 2e

NO;

+ 02"

Nitrates, which do not oxidize Cr 3+ to Cr 6+ , in aqueous

187

medium, react in molten-salt medium to give:

3N0 3 + Cr 3+

- Cr0 3 + 3N0 2 t

The molten salts form, with the oxides, compounds which

are soluble in water and in dilute acids; thus, chromium oxide
Cr 2 0 3

reacts with sodium hydroxide

to give a soluble sodium

Chromate :
Cr 2 0 3 + 4NaOH + 3/202

-* 2Na 2 Cr0 4 + 2H 2 0

The oxides may therefore be dissolved by

temperature treatment using molten salts.

this high-

One particular aspect in this field is the need to

operate at quite a high temperature (between 500 and 1200C).
The use of binary or ternary eutectics enables the
melting point of the mixtures to be lowered considerably. Likewise, a similar technique, known by the name FSFM (Fused Salt
Film Method) enables the oxides to be treated using a thin film
of molten salts after evaporating the water.

2.3.3.2

The chemistry of molten salts

The chemistry of molten salts is treated in many specialized publications1,2. We give below some data relating to the
decomposition voltages for the main ionized molten salts.

Dlten sa]Lts
KCl
NaCl
CaCl 2
MgCl 2
NaOH
KOH

Decomposition
voltage E d
(in volts)

Use temperature
(in C)

3.37
3.25
3.23
2.55
2.31
1.58

800
800
800
800
480
430

188

Alkali-metal halides are particularly aggressive with

respect to ferric oxides.
We give below a few mixtures quoted in the literature :
a) 50% KCl/50% NaCl eutectic

MP = 670C

b) 60% AlCl3/26% NaCl/14% KCl

MP = 94C
This eutectic dissolves Fe 2 0 3 , MgO and Cr 2 0 3
c) Cryolite
Cryolite, Na 3 AlF 6 , corresponds to the mixture:
25% AlF 3 /75% NaF,

MP = 1009C

Advantage : Ionization of the main known oxides, in particular cryolite allows decomposition of corundum and beryl.
d) Alkali-metal amides
Molten alkali-metal amides are very good solvents for
oxides. They are not used very much because they are tricky
to handle (risk of explosion).
sodium amide

MP = 22 0C

potassium amide

MP = 338C

The eutectic of the two compounds melts at 92C.

Amides are powerful reducing agents for oxides.
e) Sulphates
The 71.6% LiS04/28.4% K 2 S0 4 eutectic melts at 535C.
The melting point of the 80% Na2SO4/2 0% K 2 S0 4 eutectic is
much higher than 830C. At this temperature, S0" is oxidized
according to the reaction:
189

2S0 4 " -* S207_ + O""

f) Nitrates
The 27% LiN0 3 /18% NaN0 3 /55% KN0 3 eutectic melts at 127C, but
its ability to dissolve oxides is low.
g) Carbonates
The 43.5% LiC03/31.5% Na 2 C0 3 /25% K 2 C0 3

eutectic melts at

397C.
Carbonates are good solvents for iron oxides.
h) Borates
It is well known to analytical chemists that mixtures of
alkali-metal borates form excellent fluxes for ores, refrac
tories, slags and scoria and, in general, for all oxides.
Chemical analysis of these products, using X-ray fluor
escence, requires forming a homogeneous bead using a flux.
The boron compounds used are:
borax, Na 2 B 4 0 7 10H 2 O
kernite, Na 2 B 4 0 7 4 2 0
colemanite, Ca 2 B 6 0 11 *5H 2 0 (calcium hexaborate)
Molten kernite dissolves all metal oxides encountered in the
iron and steel industry.
2.3.3.3

Descaling - Thermochemical pickling - Indus

trial processes

Three types of process are currently used in industry:

immersion in oxidizing molten-salt medium
- immersion in reducing molten-salt medium
- spraying (fused salt film method).
190

The treatment of steel using molten salts may be said to

be an "oxide conditioning and transformation" operation. This is
a treatment "preparatory" to the chemical pickling in solution
and it serves to modify the nature and structure of the surface
oxides.
a) Oxidizing molten salts - KOLENE Salt
The 85% NaOH/14% NaN0 3 /l% NaCl eutectic is mostly used.
Chromium

oxides

(or mixed

chromium-iron

oxides)

are

converted into hexavalent soluble compounds:

Cr 2 0 3 + 4NaOH + 3/202 -* 2Cr04Na2 + 2H20
Industrial realization:
Refractory tank, from 5 to 15 m 3 in volume (depending on
the capacity of the line), closed using a folding-down cover and
heated using natural gas.
- Bundles are predried in an oven (15 minutes at 200C) .
- The bundles are lowered, using a preprogrammed
electromechanical system, and immersed for 4 minutes.
- The bundles are removed and immersed in a cold dilute
solution of H 2 S0 4 .
This treatment causes the scale to shatter, and hence to
deteriorate.

b) Reducing molten salts

The "reducing" treatment is, by its very principle, the
opposite of the oxidizing treatment.
The salt bath used is a mixture of:
191

98% NaOH/2% NaH, temperature 490C.

The metal oxides are reduced to the metallic state by
sodium hydride, according to the reaction:
M 2 0 3 + 3NaH - 2M + 3NaOH
This treatment is not used very much in Europe.
It is difficult to implement and the objective dangers
are real (explosion).
Molten-salt

baths

are

very

effective

but

their

use

remains limited for the following reasons:

- high cost;
- pollution problems.

c) Spraying or thin-film thermochemical treatments

(Fused Salt Film Method or FSFM)
Principle: The sprays were
during the eighties 3,4 .

proposed

by

Russian

researchers

The principle of this treatment is as follows:

A saturated aqueous solution of a salt or mixtures of
alkali-metal or alkaline-earth metal salts:
KCl
NaCl
MgCl 2 + NaCl
CaCl2 + NaN0 3 , etc.
is finely sprayed onto the scale-covered metal at high temperature.
At

elevated

temperature,
192

the

water

evaporates

very

rapidly in the spray chamber. The molten salts then react with
the scale to give compounds soluble in the pickling acids.
Realizations :
There are many variants and many patents relating both to
realizations and to the processes. Figure 1 shows an example of
a

set-up

proposed

by

YAMAZAKI

and

MIYAKE 3 .

The

sheet

(or

workpiece to be pickled) is introduced into a high-temperature

furnace.
On

leaving

the

furnace,

the

sheet

is

sprayed

with

solution of mineral salts so as to form, after evaporation, a

thin film of molten salts. The water evaporates instantaneously
and is removed by a suction system. The drop in temperature of
the steel is only a few tens of degrees so that the system can
be

used

for

the

pickling-annealing

of

austenitic

steels.

Deposition
of molten
salts

sheet to be pickled

solution (air/solution mixture) sprayer

tank of solution and compressor

gas scrubbing - removal of fume

furnace

deposition of molten salts

Figure 1
193

stainless

Important parameters:
The

success

of

the

method

depends

on

the

following

parameters :
constitution and composition of the aqueous solutions
temperature of the treatment furnace
size of the spray nozzles

(VENTURI effect)

angle of injection of the spray

pressure of the liquid
running speed of the metal
duration of

the

reaction between

oxides

and

molten

salts
efficacy of the quenching and brushing system
efficacy of the pickling system used downstream.
Improvements proposed, developments and trends:
The improvements relate to:
installing the furnace within the entire system, and
new heating systems
installation
extractors
the

of

(induction furnace)

molten-salt

injectors

and

fume

(at the furnace inlet and outlet)

number,

arrangement

and

performance

of

the

injectors
a patent filed by Kawasaki
sheet

in

concentrated

(CaCl2) , drying

it

in

an

relates to immersing the

aqueous
oven

solution

and

of

salts

then passing

it

through a high-temperature furnace.

Currently, it is recommended abandoning the solvent (H20)
and implementing an extremely fine "dry spray"
+ borates or of MgO + borates).

194

(mixture of CaO

These oxides react in the solid state with the metal

oxides to give ferrites or boroferrites which are soluble in
acids.
The following diagram represents
recommended by Kawasaki Steel6.

AISI 304 grade steel

hot rolled

I
Furnace temperature 1180C
15% CaCl2 spraying at the
outlet
Velocity 30 m/min
Contact time 10 seconds

I
Dipping in 2% H 2 S0 4
(or water)
Brushing

Chemical pickling
HNO3/HF
or HCl/FeCl 3
Passivation - rinsing

195

a process

proposal

BIBLIOGRAPHY

Treatments using molten salts

G. CHARLOT and B. TREMILLON

Les ractions chimiques dans

fondus. [Chemical

reactions

les

in solvents

solvants

and molten

Pub. Gauthier-Villars, Paris, 1963

2

J.D. MACKENZIE
Chem. Rev. (1956), 56, 455

T. YAMAZAKI and M. MIYAKE

J. Met. Finishing Soc. of Jap.
(1983), Vol. 34, No. 10, 21

N.N. KARAGODIN and M.I. IGONIKIN

USSR Steel (1974), 12, 1106

Patents
5

JP 271935 (31.05.1988)

JP 104626/90 - PN 0.453321 Al
Kawasaki Steel Corp. Patent

US 2,395,694 (1947)

JP 34167 (1978)

197

et

les

sels

salts]

2.3.4

Electrolytic pickling

Definition: Electrolytic pickling is a descaling process under

the influence of an electric field and in the presence of an
electrolyte.
2.3.4.1 Electrochemical bases of the process
Electrolytic pickling relies on
dynamics and electrochemical kinetics.

the

laws

of thermo-

The thermodynamic data are:

the
the
the
the
the
the

concepts of decomposition potentials

redox reactions
equilibrium potentials
concepts of activity
phenomena of overpotential
Faraday's laws

The kinetic data are:

the ionic dissociation (Oswald's laws)
the ion mobility and the phenomena of transfer
the fundamental laws of diffusion
the electrokinetic phenomena (electrochemical double
layer).
Electrochemical
advantages :

polarization

provides

the

following

acceleration of the electrochemical phenomena at the

metal/solution interface and in the solution,
- gas evolution leading to desquamation of the oxides
- precise control of the parameters.
According to ANTROPOV1, the electrochemical dissolution
of metals comprises two groups of phenomena:
198

- dissolution

caused

by

the

effect

of

the

external

current (anodic dissolution)

- so-called "spontaneous" dissolution, arising from
interactions with the ambient medium, or chemical
dissolution.
Often a superposition of the two phenomena is observed.
It is also found that metals dissolve at the anode at more
positive potentials than the corresponding equilibrium potentials, dissolution always being accompanied by a very high
anodic overpotential.
The anodic dissolution of iron comprises several stages,
involving anions and, in the first instance, hydroxide ions.
For example, the anodic dissolution of iron from the
metals of the ternary alloy, in sulphuric medium, is given by
the following reactions:

FeOH+

Fe + OH" -> FeOH ads + e

FeOH ads -* FeOH+ ads
ads + n H 2 0 - Fe ++ , nH 2 0 + OH"

For stainless steel,

depassivation of the metal.

this

reaction

requires

prior

2.3.4.2 Electrolytic pickling study

The development of industrial processes requires a prior
electrochemical study, using the plotting and interpretation of
I = f (E) curves under various galvanokinetic and potentiokinetic
conditions and in various media (H2S04, H 2 S0 4 + HN0 3 , Na 2 S0 4 ,
(NH4)2S04, HN0 3 , etc.
Figure 1 represents
potential curves2.
Electrolytic

pickling

an

is
199

example

mostly

of

current-density/

carried

out

under

galvanostatic conditions in which the potential of the metal is

then not imposed and pickling takes place preferentially in a
region of high overpotential, that is to say in the
transpassivity region and beyond (this is confirmed by the
oxidation of Cr +++ ) .

i (mA.cm

re
Cr
(Ni

Fe

2+

3 +
__*. r
Cr
+
.2+
_. Ni +

2e~
3e~
2e" )
E

-0.5

-1.5

CrVI+ 6e .

2H 0 + 2 e " _ ^
r. 3 + +
Cr

Cr

+1

CrVl + 3e

OH

(V/SCE)

+1.5
3+
Cr

pH > 4
pH < A

3e~ Cr

Figure 1 I = f(E) curve for an AISI 304 stainless steel;

Na 2 S0 4 electrolyte (170 g/1) at 70C, pH > 4 and pH < 4
(after MYSSON2) .
Figure 2 is a summary of the reactions counted in the
imposed potential ranges of 1.5 to +1.5 volts/SCE. in a S0 4 "
medium. For potentials above the passivation plateau, we enter
the transpassivity region in which trivalent chromium is oxi
dized into hexavalent chromium. Useful information may also be
provided by POURBAIX3 potentialpH curves.

200

We give below the curves relating to iron and chromium.

These curves delimit the immunity, metaldissolution, passi
vation and hydroxideprecipitation regions.

.1.5
l(V/scE)_
* 1/202 *

H20

: >

Eo - 1.228 - 0.0591 pH
Crl

2rT * 2 r
E0 CV/SH E)

CrVl

pH < 2
2Cr3**7H20

[Pourbaix]

pH>2

* Cr207 2 "- 14 H* * 6

CI2Q3-5H20

*- 2CrO<2-. 1 0 H * - 6 e

E o - 1.244-0.0985pH

* <v/s) [pouxbaix]

Passivation plateau

pH>4

pH<4
Fe

*- Fe2* 2 r

Cr

- C r > * 3 r

.Ni
E

fr.

N2'2e-

Comment: for a few (1 in 10)

specimens of the grade Z8C17
-FellandCr

(Z2CN1810)

Cr III

Eo fZ2CN1810) - - 0.45 ( V / S C E )
Eo(28C17)

--0.8

(V/SCE)

O VI

Cr III
pH>2

pH2
Cr2C7 2 -* 1 4 r T - 6 e -

Cr VI

- 2 Cf3* 7 H 2 0

*-

CrVl
Cr042--8H*8eE o - 0 . 3 6 8 - 0 . 0 7 8 pH

2 H 2 0 - 2er
E o - 0 - 0 . 0 5 9 1 pH

Om

Cr(OH

*- Cr
*-

O*4H20

* WSH )

IPourbaix)

* H 2 - 2 0 H o (V/SH E)

[Pooxbaijc]

-+- Cr

-1.5
CV/SCE)

Figure 2 Summary of the reactions counted in the range

of imposed potentials from 1.5 to +1.5 volts/SCE.
(after MYSSON2) , in SO^, for AISI 304 grade steel.

201

I
!

!%

i ! 1

\ !

\ n

!
'

I
Cr0
1

:: Cri OH!,

e
1.

-0?
1

>

'-

-II)

">4

1
1

'
intexmediate oxides
Miur.fi

1 Cr*

-ns

I0" : M

C-,,'-

! 1 4

ns

DyCrCJji

UN

-I.W

>~
10

12

CrK

pH

10'

F (OH ii

\
\
F.'

*.

"

**.
7.

^ * ,
Ft i
ID

pH

1?

Figure 3 PotentialpH diagrams for chromium and iron

(after POURBAIX3)

2.3.4.3 Media used

Electrolytic pickling comprises:

202

 processes carried out in neutral medium

processes carried out in acid medium.
For each medium, the system can operate:
under indirect polarization, also called: "induced
polarization", that is to say without any metallic
connection between the current source and the metal to
be pickled, the current being provided entirely by
ionic conduction;
under direct polarization or polarization via direct
connection.
In indirect polarization, the metal strip or wire is
polarized by means of electrodes arranged more or less judi
ciously on each side.
Figure 4 shows a diagram of a setup for a pair of
electrodes and the metal strip to be pickled, according to an
arrangement which has become conventional.

Electrodes . ^

Electrolyte

.
*^M

Metal strip to be pickled

Anodic polarization

Figure 4 Diagram of the principle of the electrode setup

(indirect polarization)
In direct polarization, the metal strip is directly
connected to a DC power supply via a solid conductor, of greater
or lesser efficiency (metal or graphite pads or conductive
brushes).
203

a)

Electrolytic pickling
process)

in neutral medium

(RUTHNER

Electrolytic pickling in neutral medium is the most used

in the world, known as the RUTHNER4 process, the associated
anion in most cases being a sulphate or nitrate.
We will take as an example the electrolytic pickling of
stainless steels in the presence of sodium sulphate (150 g/1) at
pH 5.5.
The anodic polarization (40 A/dm2) causes the formation
of chemical species in the vicinity of the metal, the highly
active nascent sulphuric acid dissolving the oxides.
Figure 5 shows a diagram of the various reactions
proposed by RUTHNER under the following operating conditions:
Na 2 S0 4 electrolyte: 150 g/1 pH 5.5
Temperature: 85C
c d . = 40 A/dm2

G
NojSO,

S O / - 2'
H.O

+ ++
OH-, Ot>
H*, H,

20-22Na*SO<'

H*,H 2
OH-, O /

i
H*, H /

OH-, O /

+ ++

Figure 5 - Diagram of the various reactions

proposed by RUTHNER4

204

Cathodic reaction:
2H + + 2e" H2t
2OH" + 2Na+ 2NaOH
Because of the high overpotential, we have:
4H20 + 4e * 2H2 + 40H"
Anodic

reaction:
20H" -* H 2 0 + 2 e + Y>2
2H+ + S 0 4 " * H 2 S0 4
If the overvoltage is low:
2Fe + 4H 2 0 + 2Fe(OH) 2 + 4H + + 4e
For a h i g h

overpotential:
2H 2 0 -* 0 2 + 4H+ + 4 e

At

the

scale,

the

simplified

reactions

RUTHNER are as follows:

Cr 2 0 3 + 3H 2 S0 4 * Cr 2 (S0 4 ) 3 + 3H20
In anodic mode (strip):
F e 2 0 3 - 6e - 2 F e + + + + 3 / 2 0 2
C r 2 0 3 - 6e -* 2Cr + + + + 3 / 2 0 2
NiO - 2 e -> N i + + + V>'
>2

The metal ions then react by hydrolysis:

Fe + + + + 3H20 Fe (OH) 3 * + 3H+
Cr +++ + 3H 2 0 * Cr (OH) 3 * + 3H+

205

proposed

by

In cathodic mode:

2Na+

Na 2 S0 4 -* 2Na+ + S0 4 "
+ 2H20 + 2e" -> 2NaOH + H2t

The evolution of hydrogen tends to desquamate the oxide.

The actual mechanism seems to be much more complicated, but more
comprehensible if reference is made to the potentiokinetic and
galvanokinetic curves9. As already mentioned, in reality there
will be both electrochemical and chemical reactions: the electrolysis is carried out at I = constant, and therefore the
actual value of the potential of the metal is not known and
consequently, at a given instant, the "actual" pickling reactions are not known either. For example, experimentally it is
observed that most of the chromium is in hexavalent form, which
necessarily means:
- either the anodic formation of peroxidisulphuric acid,
an oxidizing agent for Cr + + + , according to the reaction:
2H 2 S0 4 - H 2 S 2 0 8 + 2H + + 2e"
however, it is known that the electrolysis of
moderately concentrated H 2 S0 4 may lead to the formation of the peroxidisulphuric ion, S 2 0 8 ", a powerful
oxidizing agent for Cr +++ at 80C;
- or an electrochemical oxidation of trivalent chromium,
according to the reaction16:
Cr+++ +

4H2O

_ HCr0 4 + 7H + + 3e"

The potentiokinetic curves show that this reaction does

indeed take place.
In both cases, oxidation by S20 or electrochemical
oxidation, these reactions lead to the formation of Cr 6+ to the
cost of the coulombic efficiency of the pickling and the cost
206

for the ENVIRONMENT.

In
polarized
hand, the
the other

conclusion, it may be assumed that the metal is highly

in the transpassive zone, which explains, on the one
oxidation of chromium to the hexavalent state and, on
hand, the dissolution of the metal.

b) Electrolytic pickling in acid medium16

The literature mentions many studies on electrolytic
pickling in acid medium. The electrolyte generally consists of
a sulphuric acid solution at 150-250 g/litre.
It

is

pointed

out

that

two

dissolution

phenomena,

electrochemical and chemical, coexist.

The electrochemical phenomenon relates to the electrolysis of water while the chemical phenomenon is a dissolution of
the oxides and of the basis metal, after depassivation, by
sulphuric acid. The latter reaction lasts only a few seconds,
which avoids powerful evolution of hydrogen by attack of the
metal.
Recent studies14, carried out in Europe and elsewhere,
show the advantage afforded by direct polarization, which leads
to higher coulombic efficiencies. It will be recalled that the
current efficiency of indirect polarization processes is about
3 0%. There are large leakage currents and a large Joule effect,
these being due to poor distribution of the current lines.
Other acids have been proposed; in a recent study, the
company Kawasaki Steel proposed an electrolysis in an HN0 3
(150 g/1)/HCl (20 to 70 g/1) medium for the AISI 409 grade. The
results were interesting (no pitting) despite the presence of
CI" ions.

207

c) Electrolytic pickling in H 2 S0 4 or HNO3/HF medium under

potentiostatic conditions and with direct polarization
The most recent studies are those of AZZERRI and TAMBA6.
These authors have shown that:
the pickling kinetics are more rapid in an electric
field
the potential to be imposed on the scale-covered
metal should correspond to the potential for dissolving the chromium-depleted region, plus a slight
overpotential.
The table below summarizes
defined by AZZERRI and TAMBA6.

Heat treatment

Laboratory oxidation
20 min, 1050C

the

operating

Potentiostatic pickling
H 2 S0 4 , 200 g/1

environment
Cold strip

Potentiostatic
pickling
HNO3, 200 g/1

Tempera ture: 8 0 ' C

HF, 20 g/1
Temperature: 5 5 C

210 seconds
-550 mV

65 seconds
-2 00 mV

Oxidation in an industrial
5 seconds without polarization
environment and shot peening
10 seconds at -100 mV
Hot strip
5 seconds at -400 mV
Oxidation in an industrial

conditions

3 0 seconds
-200 mV

5 seconds without polarization

2 5 seconds at -65 0 mV
45 seconds at -550 mV

Table 1 - Operating conditions for electrolytic pickling

N.B. - The values of potential

are given with
mercurous sulphate electrode:
Hg/Hg2S04 at 20C.

respect

to a

The authors have observed an improvement in the

reflectance and stress the ecological aspect relating to the
208

lifetime of the baths.

On the other hand, industrialization of such a process
seems uncertain since it is virtually impossible - at a reasonable cost - to equip a potentiostatic polarization line. It is
preferred - at a lower cost - to operate under galvanostatic
conditions.
2.3.4.4 Mass balances - Energy balance
Implementation of the processes requires strict monitoring of the baths and therefore having available particularly
powerful analytical methods
(for analysing the following
+++
6+
species: Cr , Cr , S0 4 ", S20", H + , Fe + + + , Ni + + , etc.). Indeed,
the development of analytical techniques over time has been the
result of three elementary processes:
elemental dissolution reaction, oxidation, complexing
removal of substances by entrainment
precipitation of sludge

(scale, hydroxides, defined

compounds).
Measuring the transitory and steady-state compositions
allows us to do the mass balances. The efficiency of the pickling is assessed by measuring the weight loss from a test piece
under defined operating conditions and for a given initial
surface state.
With regard to the composition of the sludge, this varies
depending on the alkali-metal salt associated with the Si 4 ion.
The Na + ion leads to basic mixed sulphates; in contrast, the NH 4
ion gives a well-defined salt, namely ammonium jarosite, a mixed
ammonium and iron sulphate:
NH 4 Fe 3 (S0 4 ) 2 (OH) 6
which explains why these baths contain very little iron in
solution but, in contrast, Cr 6+ and Cr 3+ , the latter precipitating in the form of Cr(OH) 3 and a proportion of nickel having
209

no relation with the composition of the metal (in the metal, the
Ni/Fe ratio is -0.10 while in solution, containing NH 4 ions, it
may be greater than 5 ) .
It is very important to analyse the bath and the various
phases since this enables the reaction mechanisms to be
explained.
The physical analytical methods (Debye-Scherrer examination, and microprobe) are particularly useful for characterizing the solid species present.
2.3.4.5 Operating conditions - Industrial realization
Operating conditions are mentioned in specialized works.
The electrolytic pickling is carried out in tanks having
an ad hoc lining which is itself often covered with carbon
bricks.
The capacity of these tanks
depending on the size of the plant.

is

about

10

to 40

m3,

The important parameters are:

the current density (about 2 to 4 A/dm2 for Itotai = 5
to 8 kA) ,
the nature and concentration of the electrolyte
the duration of polarization
the nature of the electrodes
the potential of the electrodes and the metal
the
the
the
the
the

temperature of the solution

electrode/metal distance
H + concentration
redox potential of the medium
running speed of the metal (25 to 50 m/min)

The most widely employed industrial realization is the

RUTHNER process. Figure 6 shows an embodiment : 2 half-tanks with
210

belt-driving rollers. In the first half-tank, the electrodes are

negatively polarized, the strip therefore being the anode; the
phenomenon observed is dissolution of the subjacent metal and of
the oxides. After drying, the strip enters the 2nd half-tank in
which the electrodes are positively polarized. Exchanger systems
enable the electrolytic solution to be heated.
The plant also comprises a settling tank for separating
out the sludge and pumps for reinjecting the solution.

211

material to be pickled

set of press rollers

partitions

electrode

electrode

bottom draining

surbased reservoir

centrifuge

pump

10

heat exchanger

11

return pipe

12

rectifier

212

Figure 6 - Diagram of
an electrolytic pickling system (from RUTHNER documentation)

Figure 7 - A few examples of electrochemical cells supplied

under direct polarization
(supplied via graphite brushes or pads)

Figure 7 shows several set-up models currently recommended for direct anodic polarization.
Model 2 corresponds to anodic polarization of the metal

213

with injection
space.

of

the

electrolyte

into

the

inter-electrode

Models 3 and 4 correspond to polarization

"tunnel" system and supply via graphite brushes.

using

Model 5 refers to anodic polarization of the metal which

passes through two cathodic polarization cells. The system is
generally vertical and corresponds to a so-called "well" set-up.
The advantage of this system is that there is a high current
efficiency compared to the conventional system. Spray injection
of the electrolyte also improves the coulombic efficiency.
We are very keen on so-called "vertical" set-ups with
looping, since they are very efficient and have an excellent
pickleability/size ratio.
2.3.4.6 The state of knowledge - New thrusts in electrolytic pickling (1994)
There is renewed interest in electrolytic pickling owing
to the :
uniformity of the pickling

(strict control of the

parameters)
low pollution compared to other processes.

Achievements in recent years -in JAPAN

a) SURGIE et al. 1 0 have developed a pickling method based
on the use of polarization curves for grades of stainless
steels, the medium most employed being the S0 4 medium.
b) KAWABATA, OWADA and SATOH 11 have proposed an electrolytic pickling process developed at Chiba Works of Kawasaki
Steels, based on acid pickling in an HN03/HC1 medium. The
operating conditions proposed for the CAPL (continuous annealing
and processing high speed electrolytic pickling line) project
214

are as follows:
-

HN0 3 : 100 to 200 g/1

HCl: 2 to 7 g/1 (above 10 g/1, pitting of the steel
is observed)
current density: 30 A/dm2
E = 1.40 volts (SHE)
grades treated: AISI 409 and AISI 436.

The dissolution equations are as follows:

Cr 2 0 3 + 4H 2 0 -* Cr207_ + 8H+ + 6e"
Fe -* Fe + + + + 3e"
Cr -* Cr 6+ + 6e"
2H 2 0 - 0 2 + 4H + + 4e"
The authors do not specify the polarization conditions.
NAKANORI and OSHIMA12 of Nisshin Steels Ltd (new SHUNAN
line) have proposed a line running at 18,000 tonnes per month at
a speed of 100 metres per minute (APL No. 7, on two levels).
This line includes an electrolytic pickling unit.
Grades treated: ferritic steels
Plant:
a) 1 Na 2 S0 4 tank:
Temperature :
Current density:
Duration:

200 g/1
80C
500 A/m2

b) 1 NaOH tank:
Temperature :
Current density:
Duration:

350 g/1

c) 1 HN0 3 tank:

100 g/1

10 to 30 seconds

80C
500 A/m2
6 to 18 seconds

215

Temperature:

55C

Current density:

400 A/m2

Duration:

10 to 30 seconds.

The authors do not indicate the polarization modes

adopted but do mention the possibilities of iron, copper and
nickel redeposition which implies cathodic polarization of the
strip at the output.
TANO et al 13 have studied the electrolytic pickling of
stainless steels in sulphuric medium in direct or indirect
polarization.
According to TANO, in H 2 S0 4 medium, the dimer is formed:
H 2 S0 4 + H 2 S0 4 -> H 4 S 2 0 8
which dissociates according to the equation:
H 4 S 2 0 8 -> H 2 S 2 0 8 + H2t
In the presence of sulphuric acid, Cr 6+ would always be
formed as a result of the reaction:
Cr 2 0 3 + H 2 S 2 0 8 + H 2 0 + 20 2 + 4e" - 2Cr0 4 + 2H 2 S0 4
This work has confirmed one point, that

electrolytic

pickling occurs in the transpassive region.

HASUNO et al. 15 operate in an (NH4) 2 C0 3 /NH 4 OH medium. The
hydrogen overpotential is high, leading to detachment of the
oxides but also to embrittlement of the pickled metal.
SAKURAI and IIZUMI 14 have published a useful and exhaustive review of the electrolytic pickling of hot-rolled stainless
steels. Tables 2 and 3 relate to this review. Examination of
these tables raises the following points: these data give trends
but they are not sufficient to establish a process for the
following reasons:
216

these are laboratory tests, and therefore the variation in the solutions over time is not known;
despite the "technical" data, the polarization conditions (potential of the electrodes and distribution
of the current lines) are ignored;
absence of electrochemical data, for example the
redox potential which is known to be a key parameter
in pickling, particularly for tests in the presence
of iron (reduction of Fe + + + at the cathode, not compensated for by the anodic oxidation);
the chlorine-containing media seem to have good
pickling power, something which we have confirmed, as
long as the process is limited to low CI" contents and
as long as the materials are protected, especially
the metal framework of the pickling lines.
The authors confirm the advantage of oxidizing media three so-called "promising" processes relate to highly oxidizing
solutions which have proven advantages compared with reducing
solutions for:

obtaining good pickleability

complexing Fe + + + , Cr +++ and Ni + +
high solubility of the compounds formed
relative lack of hydrogen (embrittlement).

217

Operating conditions
Electrolytes

HN03/HF
70 g/1

Grades
cd
Weight loss
2 Duration
mg/dm
A/dm
5
27

60 sec
120 sec

Results

(AISI)

350
480

304

800
1000

430

300

304

Very good surface finish, but

risk of pitting

5 g/1

60C

5
23

60 sec
120 sec

60 sec

Total pickling
Absence of pitting
Excellent results
No spots
Pickling power > immersion
Pickling power < immersion

H 2 S0 4
230 g/1

18

120 sec

500

80C

3
18

120 sec
120 sec

900
1600

430

17

60 sec

300

304

17

60 sec

900

430

Expensive process in roughing

treatment
Formation of sludge

17

60 sec

600

304

Better results than Na 2 S0 4

17

60 sec

2000

430

17

60 sec

550

304

17

60 sec

1200

430

17

120 sec

1100

304

Pickling power comparable to

430

HF/HN0 3
C12t - Baring of the steel

Na 2 S0 4
250 g/1
80C

NaN0 3
100 g/1
80C

NaF
100 g/1
80C

FeCl 3
260 g/1

tl

Results > Na 2 S0 4

17

120 sec

17

120 sec

800

304

Good pickling power

17

120 sec

550

430

Increasing the Fe 2 (S0 4 ) 3 concentration is recommended

600

60C

Fe 2 (S0 4 ) 3
100 g/1
60C

Table 2 - Electrolytic pickling of

hot-rolled stainless steels 14

218

Treatments

Solutions
(g/D

Immersion or
electrolytic
treatments in
acid baths

Electrolytic
treatments in
baths of
ferric salts

High pickling power if HF is high

60C ENVIRONMENTAL problem

HN03/HF
70/5

H 2 S0 4
230

HCl
100

HF/H 2 S0 4
10/230

Pickling power comparable to

80C HN03/HF

HC1/HN0 3
300/100

X
Pickling power comparable to HN03/HF
60C Pitting - Environmental problem

High pickling power, comparable to HN03/HE

60C

H 2 S0 4 /HF
HN0 3
230/10/70

0
Very good pickling power
60C

H 2 S0 4 /HF
HN03HF
230/70/50

Immersion,
mixtures

Electrolytic
treatments in
baths of
neutral salts

Rankina of the process

O Promising
to be studied further
to be abandoned

Low pickling power, AISI 3 04

80C High pickling power, AISI 43 0
X
Low pickling power
60C Pitting

X
Poor pickling power
80C Formation of Cr

Na 2 /S0 4
250

NaN0 3
100

No superiority over Na 2 S0 4
X
80C

NaF
100

X
No superiority over Na 2 S0 4
80C

NaCl
100

Strong pickling power

80C Pitting

NaCl
HN0 3
100/70

O
Strong pickling power
30C No pitting - No Cr 6 +

FeCl 3
260

Fe 2 (S0 4 ) 3
100

X
Low pickling power
60C

Fe(N0 3 ) 3
100

X
Low pickling power
60C

0
Strong pickling power
60C Possible pitting, AISI 304

Table 3 - Electrolytic pickling of

hot-rolled stainless steels 14

219

In
the Eastern
Countries, SHAPOVALOV,
SHLYAMNEV,
16
UL'YANIN, NIKITIN et al. have proposed an electrolytic pickling
process in a neutral medium, under the following conditions:
Na 2 S0 4 electrolyte
pH 4 to 7
7 0C temperature
Lead electrodes
The authors have also confirmed that pickling takes place
in the transpassive region.
JUTKIN5, still in a Na 2 S0 4 medium, has demonstrated
dissolution of a "chemical" origin. Cr 6+ is formed only if the
applied voltage is very high; in fact, referring to POURBAIX3
one would expect a pH of 6 and E > 0.80 volts/H2.
JUTKIN acknowledged that the H 2 S0 4 medium gives good
results in terms of pickleability.
Studies carried out within the framework of research in
the European Community deal mainly with improvements of the
technological kind. AZZERRI and BRUNO7 have developed the PIN
(Pickling In Neutral medium) process, which was subsequently
improved by TAMBA et al. 6 . The objective sought is to develop an
environmentally friendly process using neither strong acid
(HN03) nor strong base.
The reactions proposed are as follows :

220

2,0

Cathode

Anod

2* + 2 # - - * H j

20- - , + 2 - + V i o ,

2,02* + SO,- - - H 2 S0 4

20- + 2* - * 2

NojS04

The authors have undertaken a parametrized study of the

various factors:
- reactions at the electrodes
I = f(E) curves
- adaptation of the POURBAIX curves,
study of the overpotential phenomena
- polarization curves under galvanostatic conditions
sludge treatments
- effect of the polarization mode
effect of temperature.
The operating conditions summarized are as follows:
200 g/1
Na 2 S0 4 electrolyte:
2 0 to 40 A/dm2
Current density:
16 seconds
Duration:
90C
Temperature :
electrical data;
pulsed current
3 cycles of 16 seconds
Voltage: 15 to 20 volts.
To our knowledge, the PIN process has not been utilized
on an industrial scale.
HUGDAHL17 has proposed an electrolytic pickling method
for wire. The proposed reactions are similar to those adopted

221

for flat products, but the cathodic polarization seems to be

higher.
H 2 S0 4 electrolyte:
Temperature:

200 g/1
40C

In the European Community, various electrolytes have been

proposed:
- ternary mixtures: H 2 S0 4 /Na 2 S0 4 /NaN0 3
- mixtures: H 2 S0 4 + SiF6H2 or H 2 S0 4 + Na 2 S0 4 + SiF 6 H 2
- organic acids (gluconic acid + sodium gluconate) with
additions of PO.

2.3.4.7 Assessment - A few ideas on which to focus

Careful examination of the work carried out over the last
ten years shows that there has not been a "process revolution"
in the field of electrolytic pickling.
Three ideas to focus on are:
- the ENVIRONMENTAL aspects: electrolytic pickling
eliminates the vapour problems due to the main acids,
namely HN0 3 , HF and, in part, H 2 S0 4 . However, the
problems associated with the salts have not, for all
that, been solved;
-

the METAL QUALITY aspects: electrolytic pickling does

not lead to a FINAL surface finish but to an INTERMEDIATE surface finish so that imperfections encountered are removed during the final treatment, which is
often a chemical treatment;

- aspects related to the EXPERIMENTAL CONDITIONS and to

the MANUFACTURING COST:
in

situ

generation of H 2 S0 4
222

 reliable control of the parameters.

On the other hand, there are certain difficulties in
operating with direct polarization. With indirect polarization,
the coulombic efficiency is not very high and many species are
formed which come into play and inhibit the fundamental pickling
reactions.
Improvements (and not new ideas) concern:
- direct anodic and/or cathodic polarization
- use of pulsed currents
- enhancement of transfer overpotential
- renewal of the metal/solution interface
increase in the pickling rate
- use of organic reagents and fluorides
improving the transfer technologies
treatment of spent baths and recovery of the metals
internal linings of the tanks
the nature, shape and manufacture of the electrodes
- reduction in the manufacturing cost
improving the working conditions.
Finally, it will be recalled that electrolytic pickling
takes place beyond the "transpassive" region, which explains:
the dissolution of the metal and the oxides
- the oxidation of S0 4 " into S 2 0 8 " and of Cr"1""1"1" into Cr 6+ .
As regards the electrolytic media, it can be stated that
all "commonly used" inorganic acids have been tested: hydrochloric, nitric, sulphuric, boric, hydrofluoric and phosphoric
acids, and their mixtures; organic acids: formic acid, oxalic
acid, acetic acid, gluconic acid, the salts of these acids and
mixtures of salts. Some media have given results which are
interesting in the laboratory but disappointing on an industrial
scale, or vice versa, extrapolation from laboratory to industrial process not being obvious.
223

Electrolytic pickling remains a transitory step in a

pickling process, for the various products treated (flat products or long products). The final industrial step is still an
acid treatment followed by passivation.
Two topics have not been tackled in this chapter:
electrochemical abrasion (or electro-abrasion): this
is a conventional abrasion system having a rotating
abrasive grinding wheel lubricated with an electrically conductive paste. The system has been used by
Kawasaki Steel at their Mizushima factory for abrading
thick sheet. The abrasion machine is made the cathode
and the sheet is made the anode;
- electrochemical machining or electromachining, recommended for workpieces of complex shape.
ENVIRONMENTAL aspects - Manufacturing cost
Within the "ENVIRONMENTAL protection and manufacturing
cost" context, electrolytic pickling is not, a priori,
a system
"holding all the aces", especially compared to so-called "dry"
treatments.
Electrolytic pickling requires the use of salts or acids
which must be:
- removed
in
the
(Fe(OH)3-nH20);

form

of

hydrated

precipitates

- neutralized into a form similar to the salts (hydrated

CaS04) or recycled (electrodialysis, electroosmosis,
etc.). To this should be added the possible formation
of Cr , and hence a reduction process using Fe ++ or
S03"";
a non-negligible consumption of electrical energy.
224

The choice of process will

coulombic efficiency expected.

therefore

depend

on

the

These ENVIRONMENTAL and cost factors may, however, become

insignificant compared to the surface quality of the materials
obtained.

225

BIBLIOGRAPHY
Electrolytic pickling

L. ANTROPOV
Electrochimie thorique [Theoretical
Pub. MIR - MOSCOW, 1979
Pub. Lavoisier, 753 84 Paris Cedex 8

electrochemistry]

C. MYSSON
Doctoral thesis (1989), University of Besanon, No.: 123

M. POURBAIX
Atlas d'quilibres lectrochimiques 25C
[Atlas of electrochemical
equilibria
at 25C]
Pub. GAUTHIER-VILLARS, Paris, 1963

4.

RUTHNER
Consult E. BRAUN
Iron and Steel Engineer (1980), April, 79-81

5.

D.I. JUTKIN
Stal [Steel], No. 3, 262, 1973

6.

N. AZZERI and A. TAMBA

Journ. of Applied Electrochemistry
(1976), 6, 347-352

7.

N. AZZERI, R. BRUNO, P. BERARDI, L. PACELLI and C. SATOLLI

Le

Dcapage

des produits

plats

[The

pickling

of

flat

of

flat

products]
CESSID Seminar, Maizires-les-Metz, 1983
8.

B. BOUSQUET and J. CASTEL

Le Dcapage des produits plats [The pickling
products]
CESSID Seminar, M a i z i r e s - l e s - M e t z , 1983

227

9.

D. HENRIET
Les traitements de surface des aciers inoxydables
[Surface treatments for stainless
steel]

"Les aciers inoxydables [Stainless

Editions de Physique [Physics
10.

steels]"
Publications]

K. SURGIE, I. FUJII and F. YOSHIZAMA

Kinzotu Hyomenshi (1981), 32, 403

11.

Y. KAWABATA, S. OWADA, S. SATOH, F. TOGASHI, O. HASHIMOTO,

S. KAKIHARA and T. KAWASAKI
Comm. 1st European Stainless Steel Conference
AIM - Florence 11-14 October 1993

12.

T. NAKANORI and H. OSHIMA

Comm. 1st European Stainless Steel Conference
AIM - Florence 11-14 October 1993

13.

K. TANO, S. ABE, T. MURASE, T. OKAZAKI, A. MARUTA and

S. KIDO
Nippon Steel Technical Report (1989), 43, 1-7

14.

K. SAKURAI and S. IIZUMI

Nippon Steel Corp.
Nisshin Seiko Giho (1990), 62, 38-58

15.

S. HASUNO, M. ISHIKAWA, M.
S. SHIIBA and T. SHIOKAWA

MURABAYASHI, Y. YAMAGUCHI,

Trans. ISIJ (1991), 23, 1, 29-35

16.

E.T. SHAPOVALOV, A. P. SHLYAMNEV, E. UL'YANIN, V. NIKITIN

et al.
Steel in the USSR (1982), No. 5, May, 215-219

17.

H. HUGDAHL

Wire J o u r n . I n t e r n .

(1985), J u n e ,

228

62-67

18.

S. SHIMADA and A. KAWAGUCHI

Kinzoku Hyomen Gijutsu (1986), 37., 3, 115
IRSID Translation T 4610, 1987

19.

Y. UBARA
Published in ISIJ (1990), Vol. 31, 771

20.

K. SAKAI and R. YOSHIHARA

Tetsu to Hagane (1986), 72., No. 8, 52

229

2.4

Chenu cal pickling

2.4.1

The role and place of chemical pickling

process for finishing stainless steels

in a

In a stainless steel finishing process, chemical pickling

is the FINAL STEP in preparing the surface before cold rolling
or before finishing treatments. It follows the oxide descaling
and conditioning treatments and precedes the passivation
operation.
The aim is to:
- completely remove the oxides
- dissolve the chromium-depleted region
It is used for hot-rolled or hot-drawn products, coldrolled or cold-drawn products and, in general, all products
which have reoxidized during transformation treatments.
Since the properties of the scale are different (in terms
of constitution, composition, structure, thickness, etc.), the
pickling processes are therefore different.
It is therefore necessary to consider:
the chemical pickling of hot-transformed products
the chemical pickling of cold-transformed products.
2.4.2

Review of a few typical baths

2.4.2.1

Nitric/hydrofluoric acid pickling2'3,4

Nitric/hydrofluoric acid pickling is certainly the most

commonly used pickling process in the world.
The operating conditions are:
70% HN0 3 (r.d. = 1.40), 10 to 25% (by weight)
70% HF (r.d. = 1.25), 1 to 6% (by weight)
230

Temperature: 45 to 60C,
The operating conditions vary depending on the grade and
treatment temperature of the products.
Operating mechanisms3
This subject is dealt with as a whole in Section 2.4.3;
however, there are specific reactions corresponding to each type
of bath. We believe that it is necessary to distinguish two
types of reaction:
- reactions in solution
- reactions at the metal/solution interface
a) Reactions in solution
A pickling bath is a mixture of several constituents.
In equilibrium, there are many ionic or molecular species
in an HN03/HF bath:
HF, H + , F", N03", N0 2 , HF, Fe + + + , Cr+++, Ni + + , etc.
In aqueous solution, in the presence of metals, the
nitric acid contains nitrous acid and its dissociation products:
NO, N0 2 , N 2 0 3 , N 2 0 4 , NO + , N0 2 , etc.
The same applies to HF, which reacts with Fe + + + (and with
Cr +++ ) to give complexes:
Fe + + + + F"
Fe + + + + 2F"

- FeF 2+
- FeF 2 +

Fe + + + + 3F"
Fe + + + + 4F"
Fe + + + + 5F"

- FeF3
- FeF
- FeF"

Depending on the respective concentrations of the acids,

we have the following equilibrium:
231

3HF + Fe(N0 3 ) 3 3HN03 + FeF3

This equation is very important and shows that a
nitric/hydrofluoric acid bath recharged simply with HF reforms
nitric acid in situ. We therefore see the importance shown by
analysis when operating these baths: any modification made to
sampling (dilution, neutralization, etc.) changes the analytical
values measured3'5,6.
2.4.2.2

The UG3P* process6'7'8

Ugine SA, the parent company of the "Stainless steels and

alloys" branch of Usinor Sacilor, is using an environmentally
friendly pickling process, called UG3P (Ugine Peroxy Pickling
Process), in its factories.
To simplify matters, this process may be regarded as
consisting in pickling stainless steels in a nitric/hydrofluoric
acid bath in which the nitric acid is replaced with air and
possibly hydrogen peroxide.
a) Fundamental bases relating to
nitric acid with other oxidizing agents

the replacement

of

Use of the electrode potential/pH diagrams, in the form

introduced by POURBAIX9, allows us to predict from thermodynamics, for a given element (in this case iron), the equilibria for all possible reactions between this element and the
other ionic compounds in solution. Examining the POURBAIX9
diagrams shows that it may be envisaged replacing HN0 3 with any
substance lying above the field of nitric acid reduction.
Among these oxidizing agents, we may consider using:
- oxygen (air)

Development carried out with the assistance of the

Commission of European Communities (DG XII)
232

ozone
- hydrogen peroxide and peroxides which may act as an
oxidizing agent, forming water according to the following
equation:
H 2 0 2 + 2H+ + 2Fe ++ -+ 2H 2 0 + 2Fe +++

233

Volt/H:
Mn2?/Mn0

9
0 pF"(

10

11

pH

Figure 1 - Potential-pH diagram for the various compounds

used for pickling stainless steel9,6

234

b) Description of the UG3P process

Reactions in solution
The main reactions in solution are:
- oxidation of Fe ++
- complexing of the ions.
Oxidized metal/solution reactions
This process involves two types of reactions, depending
on the extent to which the Fe ++ oxidation has progressed:
1) if Fe +++ /Fe ++ > 1, then
2Fe +++ + Fe -* 3Fe ++
Fe ++ is then reoxidized into Fe"1"1"1" by the air and H 2 0 2
2) if Fe +++ /Fe ++ < 1, then
Fe + 2HF -* H2t + FeF2
Kinetic aspect
Although the kinetics of oxidation by air in an H 2 S0 4 or
HCl medium are quite slow, in an HF medium f errif luoride
complexes are formed and the redox potential of the Fe +++ /Fe ++
system is substantially lowered (by about 500 mV) . At this
potential, air is a powerful oxidizing agent with respect to
Fe"t"l"/Fe" complexes. The reaction mechanism of the bath will be
described in 2.4.3.
From the electrochemical standpoint, the UG3P process may
be considered as being a potentiostatic process, with no external polarization. Indeed, the bath adjustments and the control
means are such that the main parameters are frozen, namely:
- redox potential
- Fe +++ /Fe ++ ratio
- concentration of H + ions
temperature
235

immersion time
The main variable

is the nature of

the metal to be

pickled.
c) Advantages of the UG3P process
- An environmentally friendly process : The consequence of
removing the nitric acid is the complete elimination of the
products derived from it, such as the nitrogen oxides NOx,
nitrates and nitrites. This innovative process therefore dispenses with having to treat these substances in liquid and solid
pickling waste.
The decomposition of hydrogen peroxide leads to two
natural products - oxygen and water, which are, par
excellence,
environmentally-friendly substances.
Working conditions
The working conditions for operators are greatly improved
for three reasons :
- elimination of nitrogen oxides
- elimination of certain acid handling operations
- fewer sludge scraping operations
Economic aspects
Three factors contribute to savings in the process:
the specific equipment for treating the nitrogen
oxides is no longer necessary. By way of indication, for a line
having an annual capacity of between 200 and 300 kilotonnes, the
capital investment necessary just for treating the nitrogen
oxides is about 5 MF;
in addition to the savings in pollution treatment
there is a saving in direct running cost corresponding to better
236

control of the consumption of reagents;

- increased productivity. Since the UG3P process treats
the pollution at source it may be regarded as the best
technology currently available in this particular field.

N.B. :

The process
and its many applications
are protected
8
patents ,
among which is European Patent 0,236,354
on 19.09.1985
and granted on
12.07.1989.

by
filed

Corollaries of the UG3P process

There are several variants similar to the UG3P process,
these processes using :
- Fe + + + as the oxidizing agent and the reaction10:
2Fe +++ + Fe -* 3Fe ++
- air-stirring of the bath
- hydrofluoric acid as the Fe + + + complexing agent, but
combined with another acid: H 2 S0 4 , H 3 P0 4 , HCl organic acids; it
may be pointed out that the addition of H 2 S0 4 is also provided in
the description of the patents8. Indeed, one of the ways of
preparing the bath consists in dissolving Fe 2 (S0 4 ) 3 in HF, which,
by shifting the equilibria, gives:
Fe 2 (S0 4 ) 3 + 6HF * 2FeF3 + 3H 2 S0 4
The use of a mixture of several acids consequently
reduces the manufacturing cost of pickling by replacing, in
part, an expensive acid (HF) with an inexpensive acid (H2S04) .

2.4.2.3

The UG3P* process

This process, developed by Imphy SA 11 for stainless steel

wire, is an improvement of the UG3P process.
237

It
-

uses:
HF
H 2 S0 4
H 2 0 2 (2 00 volumes).

The

operating

conditions

given

by WILLEMIN11

are

as

follows :
- Application to 43 0 kg bundles of wire stock
- Preferably a "roughing" bath
- Temperature 60C
- Volume of the bath 20 m 3 ; the bath being equipped with
a recycling circuit operating at 80 m /hour
- Redox potential 400 mV(Ag/AgCl)
- Air bubbling.
Inspection of the wire
- Presence or absence of residual scale
- Colour of the metal
- Uniformity in the appearance of the bundles
- Two-dimensional rugosity
- Scanning microscopy
Quality of the pickling
- Surface quality comparable to that obtained with the
nitric/hydrofluoric acid process
- Slightly etched grain boundaries
- Ra = 2 to 2.5 ..
Reaction Mechanism
As a result of the heat treatment prior to the pickling
operation, the oxidized layer consists of:
a) a non-adherent surface layer consisting of oxides of
the Fe 3 0 4 type
b) a region consisting of oxides of the "spinel" type,
FeOCr 2 0 3 , associated with the unoxidized and highly
chromium-depleted metal.
238

Metallographic examination shows, unambiguously, that the

UG3P+ bath attacks only the unoxidized, chromium-depleted
regions, i.e. the regions rich in nickel and iron. These
observations are correlated by quantitative analysis for iron,
chromium and nickel in solution: the nickel content of the bath
is twice as high as the chromium content although the grades in
question contain more chromium than nickel. In this particular
bath, the content, expressed per thousand, is 6%o.

2.4.2.4

Other processes

The companies ITB and ILVA, collaborating with the Centro

Sviluppo Materiali [Materials
Development
Centre], cited, in
1993, the prior art and published a method based on similar
principles 12,13 .
ITB markets various reagents enabling many grades of
stainless steel to be pickled.
In these patents, we find:
HF, as complexing agent for Fe + + + , Cr +++ and Ni + +
air stirring
oxidation by H 2 0 2 (cf. Tokai Denka patent14)
The products marketed bear the following references:
CLEANOX 352 starter (Fe 2 (S0 4 ) 3 + H 2 S0 4 )
CLEANOX 352 A (HF + H 2 S0 4 + inhibitor + wetting agents)
CLEANOX 352 (stabilized H 2 0 2 ) .
This publication provokes two comments: the addition of
H 2 0 2 is slaved to the redox potential of the medium; however, it
is known that hydrogen peroxide is already stabilized following
its manufacture, this procedure being virtually obligatory for
transporting this reagent.
Controlling

the

potential
239

makes

such

stabilization

"pointless". This is because it is enough to operate in the

presence of 1% of Fe + + (of the total iron) in order to avoid
having an excess of peroxide, this being perfectly achievable by
using a measure of the redox potential and by measuring of the
Fe ++ content.
Also to be found in various commercial brochures are a
large number of surprising contradictions: how do you combine,
effectively, in the same solution, on the one hand, a pickling
accelerator and, on the other hand, a pickling inhibitor?
This "contradictory" combination of opposite fundamental
reactions challenges the expert and can only cause contrary
effects. It is quite clear that this combination is counter to
nature, the only outcome being a commercial advantage.

The Fe-1"1"1- HCl process

This process, developed and used in Japan, gives excellent results if the following are controlled:
the concentration of the reagent (HCl)
the pickling time.
The operating conditions are as follows:
HCl:
Fe + + + :

2N to 6N
50 gl (oxidation by H 2 0 2 )

Temperature: 60 to 80C
Bubbling:
air
This highly efficient bath (for dissolving surface Fe 3 0 4
and the chromium-depleted region) causes the appearance of
pitting as soon as there is overpickling. However, it is highly
corrosive, over time, for the structural components (beams) of
the plant as a result of the vapour pressure of FeCl3.

240

2.4.2.5

Examples of baths used throughout the world

We give below some examples of baths used for pickling.

Rather than simply enumerating them, we have collated, in
several tables, the known baths and their main characteristics,
classified into strengths and weaknesses.
Acid, alone
or in combination
HNO3

Strengths
Used for passivation
Low manufacturing cost if
the treatment of the
effluents and vapours is
disregarded.
Efficient
40 to 60C
1 to 4 M

In association with: Good pickleability

HF
Low manufacturing cost
(if the environmental
effect is ignored)

Weaknesses
Atmospheric pollution:
N0 2 , NO x
Aqueous pollution:
NO3, N0 2

Atmospheric pollution:
N0 2 , NO x
Aqueous pollution:
NO, N0 2
High manufacturing cost,
(environmental impact)
Difficult to manage

H 2 S0 4

Good pickleability

Atmospheric pollution
Aqueous pollution
Difficult to manage
(quantitative analysis)

HCl

Good pickleability

Atmospheric pollution
Aqueous pollution
Difficult to manage
(quantitative analysis)

H202

Only for reoxidation of

N0 X to NO ?

COVINO et al. 2 have shown that, for AISI 3 04 steel: an increase in HF

improves the pickleability; if HN0 3 is between 0.4 and 1.5 M, the pickleability improves, but worsens outside this range; iron and chromium in
solution slow down the pickling kinetics. Neither has a small effect

Table 1

241

Acid, alone
or in cambination

Strengths

Weaknesses

Little pollution
0.5 to 5M
50 to 70C

High cost

Fe+++/air
H202
(UG3P)

Little pollution (elimination of nitrogen compounds)

Removal of F" by precipitation of CaF2
The pickling agent is
Fe + + +
Whiteness of the product

Low pickleability in
roughing bath
It is necessary to
increase the HF concentration

Fe+++/air
22,

Very good pickleability

Formation of alkalineearth fluorides and sulphates
Whitener for the product
Little pollution

Precipitation of
CaS042H20

Fe + + +
H 3 P0 4
H202

Good pickleability if
Fe + + + combined with
alkaline-earth metal
phosphates

Difficult to control
(quantitative analysis
of HF/H 3 P0 4 mixtures)

HF

In combination with:

UG3P*
(reference 11)

The brightness and whiteness both increase with E r e d o x

- Solubility of CaF2: 17 mg/litre of H 2 0

Table 2

242

Acid, alone
or in combination

Strengths

Weaknesses

Low cost
Efficient roughing bath
2 to 8 M/l
80 to 90C

Redeposition in reducing
medium (acid black)
Not very effective in a
finishing bath

Fe + + +
H202

Good pickleability
High iron content
Easy to control:
H + redox
(500 mV/Ag/AgCl)

Neutralization and formation of CaS04-2H20

(high molecular weight)

Fe +++
22
HF (1 to 2M)

Good pickleability
Precipitation of CaF2 and
sulphates
HF is excellent as a
complexing agent

More difficult to control

with two acids

HNO,

Good pickleability

Difficult to control (two

acids)
Significant pollution:
NO, NO 2' NO 3' NO,

HCl
(Fe++)

Effective roughing bath

Highly aggressive as a
finishing bath

Very difficult to control

(analytical problems)
Risk of pitting

H 2 S0 4

In combination with:

Whiteness increases with the redox potential

Solubility of CaS04-2H20 in water; 2 g/1
Solubility of CaS04-VH20 in water: 10.4 g/1

Table 3

243

Acid, alone
or in cambi nation

HCl

Strengths

Weaknesses

Much used in Japan

Low cost
Very effective as a
roughing bath
1 to 5M
Oxides soluble in HCl
HCl recycling

High HCl vapour pressure

Pitting of the metal

Fe + + +
H202
(Fe%++, 1 M/l)
(Ref. 15)

Conventional in Japan
Very effective as a
roughing bath
1 to 5M HCl
Control of the redox
potential
Simplified effluent
treatments
HCl recycling

HCl vapour pressure

Risk of pitting of the
metal

H 2 S0 4

Effective as a roughing
bath

HCl vapour pressure

Difficult to control
(analytical problems)

In combination with:

Good results with 12N HCl, but t < 50C and Fe + + + 20 g/1
Solubility of CaCl 2 = 427 g/1

Table 4

244

Acid, alone
or in combination

H 3 P0 4

Strengths

Good pickleability as a
finishing bath and
passivation
Expensive

Weaknesses

Reducing bath
Few studies as an
oxidizing bath

4 to 8 M
60 to 80C

In combination with:
H 2 S0 4

Effective as a reducing
bath

Fe + + +
H202

Effective as an oxidizing
bath

Analytical problems

Redox control

HCOOH

Effective as a finishing
bath

Bath not very aggressive

Fe + + +

Pickleability enhancement
Redox control
Pyrolysis of the bath
(of benefit to the
environment)

Higher cost than

inorganic acids

Table 5

245

2.4.3 General theory - Mechanisms proposed

Although the pickling mechanisms are still the subject of
controversy among the various schools, over the years there has
been a tendency for various theories to converge. FRENIER and
GROWCOCK16 consider that it is necessary to distinguish several
mechanisms depending on the following cases.
a) "freed" oxides at the surface
b) "adherent" oxides at the surface
For each case, it is necessary to consider:
the chemical phenomena
the electrochemical phenomena.
QUANTIN17 gives a few values for the solubility of the
various iron oxides in H 2 S0 4 and HCl media.
According to the data (see Table 6) , the solubilities
increase with temperature and with concentration of the acid17.
The solubility is an important parameter but it does not
completely explain pickleability; this is because the rates of
dissolution measured on industrial scale have shown that it does
not dissolve during the first few minutes of immersion17.
The mechanism of pickling is therefore not just simply
chemical dissolution of the scale.

246

Acid

Concentration

4N

HCl

6N

8N

TC

Fe 3 0 4

Fe203

FeO x

20

0.03

0.18

2.61

41
63

0.79
2.04

2.92
3.98

80

0.23
3.82
3.9

2.99

2.98

20

0.76

1.05

3.3

41

3.75

1.56

3.93

63

3.69

2.65

3.92

80

3.82

3.17

3.99

20

3.63

1.43

4.09

41

3.74
3.75

2.09
3.02

3.86
3.77

63

0.03
0.34

0.03
0.17

1.8
2.28

80

2.15

0.62

3.13

20

0.014

0.02

41
63

0.09
1.83

0.06
0.37

1.11
2.22
3.93

20
41

0.007
2.01

0.03
0.1

0.53
1.09

63

3.72

0.59

0.48

63
41
4.5N

H 2 S0 4

9N

18N

Table 6
Solubility (g/1) of the oxides in hydrochloric
and sulphuric acids
Duration of the treatment: 15 minutes .

To date, the mechanisms proposed for stainless steels

derive from studies relating to non-alloy steels.
We give here the main points :
ENGELL proposes an acid reaction mechanism based on the
kinetics of oxide dissolution.
The acid infiltrates into the scale and causes a galvanic
cell to be set up. This cell discharges and results in the
electrochemical dissolution of the steel/oxide interface.
247

Currently, this mechanism is highly contested, the mechanism

proposed by FERRIER and BAUD 19 ' 20 being preferred to it.
The potential/time curve of a scale-covered specimen of
AISI 304 grade is shown in Figure 2. The end of pickling corresponds to a change in the potential of the specimen and to
stabilization21.
Figure 3 shows the three steps in pickling:
an initiation step in which the
microcracks in the outer oxide layers;

acid

infiltrates

via

- a chemical dissolution step in which protoxide FeOx is dissolved;

- a chemical dissolution and electrochemical step which begins
when the acid has reached the chromium-depleted region.

248

300mV(//Ag/AgCI)

Composition of the solution

HN03
HF
F 40g. I

Time (seconds)

Figure 2 - Equilibrium potential curve as a function of time

in HNO3/HF medium for a scale-covered grade AISI 304 steel

249

Higher oxides

decomposed
protoxide
1 - Initiation stage : infiltration of the acid via the
ncrocracJcs in the layers of higher oxides which do
not dissolve.

enlargement of the microcracDcs and dissolution of the

protoxide
2 - chemical dissolntion of the protoxide

scale residues

J.

%>>

final pic3cling state

3 - When the acid reaches the b a s i s metal, there i s

electrochemical
d i s s o l u t i o n of
the p r o t o x i d e . An
FeO/acid/Fe c e l l would have been formed.
H2S04

Figure 3 - Mechanism of p i c k l i n g - Steps i n the process

250

An interesting point, due to PRIGENT22, allows us to

explain the interpretation of the phenomena associated with the
metal/solution interface. PRIGENT has demonstrated the existence
of a blocking phenomenon in pickling, due to a high concentration of H + : this blocking is attributed to a build-up of Fe ++
ions at the metal/oxide interface and to local precipitation of
FeS04'nH20 which is not very soluble in the acid (viscous layer) .
This precipitation strongly inhibits continuation of pickling
process.
In summary, the kinetics of metal attack are faster than
the kinetics of Fe + + oxidation, the system stopping by precipitation of insoluble compounds.
2.4.4

The parameters involved in pickling

a) Quantification of the efficacy of chemical pickling

We define two important concepts:
pickleability
aggressiveness.
These two concepts allow us to assess the effectiveness
of a pickling solution with respect to two aspects examined
previously:
with respect to the scale
with respect to the basis metal.
Pickleability is defined as the weight loss measured for
an oxidized specimen in a pickling test carried out, in the
laboratory, under defined conditions:
AW, expressed in mg/cm2/min, with S, CH+, C c , C a , E r e d o x ,
E , T, t and A all constant.
In this expression:
AW
= weight loss
S
= area of the specimen (cm2)
251

concentration of H + expressed in mol/1

concentration of cations expressed in mol/1
concentration of anions expressed in mol/1
redox potential of the solution
equilibrium potential of the specimen
temperature

^H*
Cc
Ca
Eredox
E

=
=
=
=
=
=

t
A

= immersion time expressed in minutes

= operating
conditions
(factors
related
stirring).

to

In reality, this concept covers the efficacy of the bath

with respect to the combination of oxide + basis metal.
Aggressivity is defined as the weight loss measured for
a non-oxidized specimen (basis metal) in a pickling test carried
out, in the laboratory, under the conditions defined above.
We observe three types of parameters involved in pickling:
- parameters relating to the scale
- parameters relating to the basis metal
- parameters relating to the solution.
The parameters relating to the scale involve:
the constitution of the oxides
the composition
the physical and mechanical properties
the chemical and electrochemical properties
(stoichiometry of the compounds, solubility in acids)
The parameters related to the basis metal are:
- the constitution
the composition
- the prior treatments
- the thickness of the chromium-depleted region.
The parameters related to the solution, already men
tioned, are:
the concentration of hydrogen ions
252

the concentration of anions (NO3, F", etc.)

the concentration of cations (Fe+++, Ni + + , Cr +++ )
the redox potential (Fe+++/Fe++ ratio)
the temperature: pickleability increases with
(Arrhenius law) as does the solubility of the oxides
the immersion time
the experimental factors: stirring or spraying of the
solution, use of ultrasound, etc.

f[(Ps)

+ (Pm) + (CH*, CAn-, C c n-, E r e d o x , E

K
Ps
Pm

, T, t . A)] f o r c o n s t a n t S

= efficacy of pickling
= properties of the scale
= properties of the basis metal.

The other symbols have the meanings already mentioned.

It is possible to compare results only if the operating
conditions are well defined. For example, it is also necessary
to specify the rinsing and passivation conditions.

2.4.5

Methods used
pickling

for

studying

and

investigating

There are many excellent publications24'25 on this theme.

We simply propose to give here these techniques and to recommend
that those interested should consult the specialized publi
cations.
The following should be distinguished:
a) examination
whiteness

with

the

naked

eye:

brightness

and

b) gravimetric methods and pickleability tests

The weight loss of a metal specimen, with and without
scale, is determined for various immersion times under the
following strictly defined operating conditions:
253

composition of the solution, pickling time, temperature, etc.

Next, the following curves are plotted:
- weight loss = f(immersion time)
and/or weight loss = f(H + ).
c) physical analytical methods
Optical microscopy: on the oxides
- examination in differential contrast
- examination in polarized light.
Surface preparation is particularly important: the
methods used to take a sample may damage it thermally or mechanically (sawing, fracture, etc.).
Scanning electron microscopy
fraction in reflection

(SEM) and electron dif-

Scanning microscopy makes it possible to describe all

aspects of a solid, such as the topography, crystallography,
chemical composition and chemical bonding, characteristic of the
volume.
Glow-discharge mass spectroscopy
Among the surface analysis techniques,
mass spectroscopy (GDMS) occupies a place in the
allows a very great deal of information to be
rapidly concerning surface layers from a few
several tens of micrometres in thickness.

glow-discharge
first rank. It
obtained very
nanometres to

This method makes it possible to produce concentration

profiles through the depth. It was developed by BERNERON et al. 26
for the surface analysis of iron and steel materials.
Photoelectron spectroscopy (ESCA)
254

ESCA (Electron Spectroscopy for Chemical Analysis) is

also called XPS (X-ray photoelectron spectroscopy).
The method is based on the high-resolution determination
of binding energies using a beam of monochromatic X-rays.
The advantage of
energies vary depending
this examination carries
the first few monolayers

the technique is that these binding

on the chemical environment. However,
analytical information regarding only
of atoms.

ESCA spectroscopy has become one of the main tools in

surface analysis because of its two major assets - quantitative
analysis and information regarding the chemical nature of the
elements.
Auger electron spectroscopy (AES)
Laser impact microprobe (LAMMA)
The ions generated by the impact of a laser beam, focused
onto a metal specimen, are analysed in vacuo
using a mass
spectrometer (LAser Microprobe Mass Analysis).
Applications: the microanalysis of scale
Weaknesses: modification (oxidation) of the scale by the
laser beam.
Transmission electron microscopy and electron diffraction - Energy-dispersive X-ray analysis

Ellipsometry
Ellipsometry is an optical method of analysis based on
measuring the change in the state of polarization of an incident
light beam reflected by a surface.
255

It thus makes it possible to measure the change in the

state of polarization of the light upon reflection.
It is therefore possible to show that:
a surface is clean
a surface is covered with a film.

Electrochemical methods
The electrochemical methods pertain:
on the one hand, to the metal, with or without scale
on the other hand, to the pickling solution.
Investigation methods pertaining to the metal:
plotting of potentiokinetic or galvanokinetic curves
attack at a controlled potential
potential time curve
coulometry at constant E and/or at constant I.
Investigation methods pertaining to the solution:
analysis of the following species: H ot , F", HF, S0 4 ",
+1+ +1
NJ, Fe"
NO3,
Fe1"
"", Fe ++ , Cr3 and Cr 6 (selective electrodes
are used);
the literature and certain patents 12,13 mention pH
measurement: it should be pointed out that in the current state
of the art there are no reliable methods of measuring the pH in
a hydrofluoric acid medium and in the presence of the Fe ++ /Fe +++
pair. This point is developed further in the "Analysis of the
baths" section:
redox potential
coulometry at constant E and/or at constant I
256

conductimetry

Chemical methods
The chemical methods used are also specific:
to the metal
to the solution.
Metal-specific methods:
- spectrometric analysis (or other methods)
- measurement of the surface oxygen content.
Measuring

the

surface

oxygen

content

allows

us

to

27

determine the thickness of the scale .

The proposed method consists in:
- measuring the total oxygen content of a scale-covered
specimen of known area
- measuring the residual oxygen content

(the included

oxygen in the basis metal).

The difference in these measurements gives the surface
oxygen content.
Apparatus: LECO TC 436
(Reducing smelt, in helium - oxidation of CO to C0 2 measurement of the C0 2 concentration using an absorption
cell working in the infrared).
Solution-specific methods:
elemental quantitative measurement of the elements in
solution:
F e t o t , C r ( C r + + + a n d Cr 6 ) , N i , Mn, Cu, Sn, e t c .
257

Oxide solubility tests

The solubility tests can provide information useful in
developing a pickling process 28 .
These are tests which make it possible to assess, in the
first instance, the solubility of the scale in an acid.
The operating methodology proposed29 is very simple and
consists in placing 500 to 1000 mg of scale in a reflux device
containing a refrigerant and in heating the acid under defined
operating conditions (temperature, time, etc.).
The presence of a refrigerant allows operation at the
temperature of condensation of the azeotrope (special set-up in
HF medium etc.) and quantitative assessment of the aggressiveness of the acids to the scale.
The results of these tests may be expressed in summary
form as :
Solubility of the oxides in the acids
HF > HCl > H 2 S0 4 > HNO3
These tests could also be carried out on binary
ternary mixtures of acids and at various redox potentials.
The values obtained are used
balances and the efficiencies.

258

for compiling

or

the MASS

UG1NE-GUEUGN0N S - A .

n-<wt-M ten
o

03133

>-co-arro 110
N12
CR2
r

<
>i
-

Ol

SI

0
FE

AL

-
C
\

C W

+J

XI
Cn
H
rA

z'

xJ^

(X

~?i

kr-^/^C^-*

rP

S . 00

a
1

4 . RO

9.60

71

14.40

-1

"
;

r~

IS.20

Erosion time (s)

is-nut-M

ton

SOI 347
21--DtC. CIX

N12
CR2
MN
SI

0
FE
AL

0.00

1.60

Z-40

3-20

4.00

I.

1.15
0.M
1.00
1.05
0-1
I.O
1.01
O.M

4.10

Erosion time (s)

Figure 4 - Examples of analysis using glow-discharge

mass spectroscopy26

2.4.6

Passivation

259

The aim of passivation is to form a protective layer on

the surface of the metal, and guarantee that it is stable over
time. The terms:
- passive layer
- passive film (or passivating film)
are also encountered.
The non-oxidizability of (stainless) steel is caused by
the metal developing a surface layer which is highly adherent
and relatively thin (about 1 to 10 nanometres), but which has a
very low ion permeability. Transfer of cations from the metal to
the solution is extremely small, or indeed, in some cases,
negligible.
According to the actual words of some authors 29 ' 30 ,
"paradoxically, the non-oxidizability of stainless steel stems
from the "oxidizable" character of one of its constituents,
namely chromium" .

The passive film29

The physico-chemical characteristics of the passive
layers determine their protective properties and therefore, to
a greater or lesser extent, their corrosion resistance.
The protective film has to acquire certain properties
even if this layer is very far from metal/film/solution
thermodynamic equilibrium; a steady state is necessarily
obtained, its disturbance being counterbalanced by its reformation.

A reminder about the nature of the passive film29

The electrochemical manifestation of the passive film is
given by the conventional plot of the I = f(E) curve for stain260

less steel. The segment E E t

represents the passivity range.

Logi

r
Ho
PASSIVITY
TRANS
PAssrviTY

PRE
PAssrviTY

Figure 5 Electrochemical manifestation of the

passivity phenomena

Simplified
known

'

mechanisms

have

been

proposed

and

it

is

that the passive layer consists of a stable hydrous

oxide formed by the reaction:

(M) m + (H 2 0) s M ( O H ) + a d s
The primary
OHMOH

structure,

+ ( H + ) s + 2e"

structure, H 2 0MH 2 0,
ending

up,

after

towards

deprotonization,

structure of the OM0 type.

oA/OHj

Sit"'

^^O
UnHj u n
(H?0)
OH,OH2
O^OH:

261

evolves

the

with

Figure 6 - Structure of the passive layer [After OKAMOTO31]

A

Partially formed film

Consolidated film

Industrial advantage and methods of passivation

Passivation is a state of thermodynamic stability of the
stainless steel, hence a method of protecting it.

A few examples of passivating baths:

Austenitic and ferritic stainless steels
a) 70% nitric acid (r.d. = 1.41), 20% (by volume)
Temperature: 40 to 60C
Time : 1 to 2 minutes
In continuous processes, the passivation time is often
increased to 1 to 3 minutes.
b) mixture of acids
. 70% nitric acid (r.d. = 1.41), 20% (by volume)
. 85% phosphoric acid (r.d. = 1.70), 40% (by volume)
. glacial acetic acid (r.d. = 1.05), 40% (by volume)
Temperature: 50C
Time: 1 to 10 minutes.

Martensitic steels
a) 70% nitric acid (r.d. = 1.41), 20% (by volume)
5% potassium dichromate
temperature: 60C
time: 10 minutes
b) 10% ethylenediamjnetetraacetic acid (sodium salt)
temperature: 60C
time: 15 minutes
262

c) 2% potassium permanganate
7% citric acid
the pH is adjusted to 3 using aqueous ammonia
temperature: 40C
time : 5 minutes

Lines of development - New thrusts

Simplified, less expensive and above all less polluting
solutions have been proposed in recent years :
Phosphoric compounds have been envisaged, in reducing
medium and oxidizing medium:
* M H 3 P 0 4 + 0.5M H 2 N a P 0 4
* M H 3 P 0 4 + 2%

H 2 O 2 (50%)

It has also been proposed to use:

* M H 2 S 0 4 + 2% H 2 O 2 (50%)
* M HC10 4

Peroxides (H202, etc.) or peracids (peracetic, perboric

or persulphuric acids) have formed the subject of patents ' in
the field of passivation.
We also refer here to an interesting study by BELOZERSKII
et al. . These authors study the mechanisms of iron passivation
by hydrogen peroxide using Mssbauer gamma-ray spectroscopy; the
thickness of the passivated layer reaches between 5 and 100 nm
for very low hydrogen peroxide concentrations (0.1%). The
constitution of the passive layer would be a hydroperoxide of
formula or-FeOOH-Fe203 .
33

Peroxymonopersulphuric acid, H 2 S0 5 , known commercially as

Caro's acid, gives interesting results at very low concentrations (0.5%) . The instability of H 2 0 2 is often mentioned, as is,
consequently, the need to add stabilizers to this reagent: these
263

additions are not necessary since H 2 0 2 is already stabilized by

the manufacturers for obvious reasons related to transporting
this compound.
Passivation must be carried out on clean and rinsed metal
and it is known that, for example, halides in solution destroy
the passive layer by forming a haloferric complex. In this case,
rinsing with water containing 1% of NaHC0 3 will eradicate the
effect of the halides.

2.4.7

Finishing operations: brushing - rinsing - drying

- final inspection

These operations are particularly important in a pickling

process. They concern all kinds of baths, such as basic, acidic
or electrolytic baths, and all types of product, such as flat
product, long product, castings, etc.
The desired aim is the complete removal of all substances
coming from the pickling operation:
scale
- salts from oxide or metal dissolution.

Solubility of the salts

The first criterion for removing salts is their
solubility in water; it is therefore essential to prevent
evaporation of water and crystallization of the salts.
Strip and bundles must maintain a high moisture content;
to use the phrase from the shop floor: "the strip must be wet" 34 .

Brushing
The aim of brushing is to make it easier to detach the
oxides and salts deposited during pickling.
264

On leaving a tank, a rotary brush (made of nylon) comes

into contact with the strip. Pressure is applied to the strip:
- on the one hand, by a clamping system
- on

the other hand, by

the presence

of

a back-up

roller.
Water

is

injected

at the

same time as brushing

and

entrains the oxide particles.

Wiping
Wiping is carried out at various points:
- on entering and leaving the tanks
- between rinses
- before drying.
The strip passes between two rollers coated with an
organic material. Entrainment of the liquid is limited to a film
2 0 . thick on each face of the metal.
Precise clamping of the wiper rollers is essential.

Rinsing34'35
The partition coefficient rule governs the method of
rinsing. Several rinsing systems may be distinguished:
- open-loop rinsing
cascade rinsing
- high-pressure rinsing.

Open-loop rinsing
Figure 7 shows the principle of operation of open-loop
265

rinsing. As a general rule, it is carried out in two tanks, as

in the figure:
First tank: spraying of cold water by two systems of spray
booms placed on either side of a deflector roller:
- the water flow rate is 40 to 60 m3/hour (but this may
vary depending on the capacity of the line)
- the pressure is 5 to 10 bar.
Second tank:

Spraying of hot water (60 to 80C) in a

closed circuit
or
immersion in a hot-water tank (60 to 80C)
condensates or injection of steam

60 to 14 0 nr/h river water

Figure 7 - Example of open-loop rinsing 34

Cascade rinsing
This system, while still guaranteeing effective rinsing,
allows important water savings to be made.
The water from the first (least polluted) tank is
conveyed to the most polluted rinsing tanks, that is to say at
the output of a pickling bath. '
Nowadays, the systems include many servocontrol devices;
electrochemical sensors (H+, Cl", F", etc.) transmit instructions
266

for opening or closing solenoid valves,

High-pressure (HP) rinsing

Directives regarding surface treatments are becoming
increasingly strict; we therefore have to move towards systems
which reduce water consumption.
The "HP" rinsing technique makes use both of the mechanical action produced by the water blast and of the diluting
action:
-

flow rate: 10 m 3 /h at 3 0 to 50 bar

- temperature: 20 to 60C
The advantages are :
effective rinsing
reduction in water consumption (between 50 and 80%)
possible recycling.
"High-pressure"
designed to reconcile
consumption.

rinsing represents the best solution

effectiveness and reduction in water

Final rinsing
In some applications, final rinsing is carried out using
80C ion-exchanged water. This protocol prevents surface redeposition of F", S0", NO", Cl", Fe + + + or Cr +++ ions.

Drying
Drying is mostly carried out by blowing hot air, using
variously shaped sets of drying nozzles.
267

New ways of drying have been proposed by line designers :

- infrared drying
- microwave drying.
As a general rule, these systems are more expensive, the
factories making use of extensive sources of water vapour.

Final inspection, surface finish after pickling

In-line inspection: the surface quality of the products
being produced is checked during an in-line inspection
operation:
- measurement of the grain size
- general appearance
- logging the position and size of defects
taking the values of stipulated parameters for comparison with the standard values set up by the metallurgical inspection departments (QA etc.).

In-laboratory

inspection:

this

involves

inspection

operations aiming to check:

- the composition, grades (chemical analysis)
the surface properties
- the metallurgical and mechanical properties

268

BIBLIOGRAPHY

Chenu cal pickling

1.

D. HENRIET
Les traitements de surface des acier inoxydables
dans "Les aciers inoxydables"
[Surface

treatment
s

for s tainle
s
s

s teel,

in

"Stainle
s
s

Steels"]
Les Editions de Physique

[Phys ics

Publication
s ],

BP112 -

F 91944, Les Ulis - Cedex A

2.

B.S. COVINO, J.V. SCALER, T.J. DRISCOLL and J.P. CARTER

Met. Trans A 17 A (1986) 137

3.

D. HENRIET, L. MEUNIER, A.M. PRAT and M.A. CUCHEVAL

IRSID, RE 661 and 662 (1979)

4.

D. PECKNER and I.M. BERNSTEIN

Handbook of stainless steels
McGraw-Hill Book Company
New York, 1977

5.

. CHETREFF
Le dcapage des produits plats
[The pickling
of flat
product
s]
Les Cahiers du CESSID [CESSID
Notebook
s]
IRSID, 1983

6.

B. BOUSQUET, . GIRAUD, D. HENRIET, G. K ACZOROWSK I and

M. VILLERET
CECA Final research report, No. 7210 GD 304 1583, 1988

7.

B.
BOUSQUET,
P.
BOUHIER,
H.
GIRAUD, D.
G. KACZOROWSKI and M. VILLERET
International Rolling Congress, Deauville, 1987

269

HENRIET,

8.

European and French patents :

EP 188,975
FR-A-2,587,369 and EP 236,354

9.

M. POURBAIX
Atlas d'quilibres lectrochimiques 25C

[Atlas of electrochemical

equilibria

at 25C]

Pub. Gauthier-Villars, Paris, 1963

10.

European Patent
EP 582,121 Al

11.

P. WILLEMIN, M. DESCEMOND and M. MASSON

Rev. Met., March, 415, 1995

12.

S. FORTUNATI, E. NOVARO, C. PEDRAZZINI and A. POLLASTRELLI

Comm. Innovation Stainless Steel
11-14 October, 1993, Florence, Italy

13.

Italian Patent No. 002340

14.

British Patent
GB-A-2,000,196
(TOKKAI DENKA KOGYOKK)

15.

Japanese Patent
JP 048563 (09.09.1988), Sumitomo
Appi. No. 56,171,63 8

16.

W.W. FRENIER and F.B. GROWCOCK

Corrosion - Nace (1984), Dec. Vol. 40, 12, 663

17.

D. QUANTIN
CESSID Notebooks: Pickling of flat products, 85-102, 1983

18.

H.I. ENGELL and F. WEVER

Arch fr Eisen [Steel Archives], 1956, 27, 475

270

19.

J. BAUD and A. FERRIER

C.I.T. of the C.D.S. (1978), 10, 1817

20.

J. BAUD and A. FERRIER

C.I.T. of the C.D.S. (1978), 11, 2035

21.

S. LECOURT
Le livre de l'acier [The steel
book],
Chapter 24
Pub. Lavoisier, 11 rue Lavoisier, Paris

22.

P. PRIGENT
CNAM Report, Paris, 1991

23.

D. HENRIET and D. PAUL

Seminar conference "Scale control"
CESSID - IRSID, 21 June 1990

24.

D. DAVID and R. CAPLAIN

Mthodes usuelles de caractrisation des surfaces

[Standard

methods

of surface

characterization]

Pub. EYROLLES, Paris, 1992

26.

R. BERNERON
Spectrochimi Acta, 1978, 33, 19, 665

27.

D. HENRIET, L. PROST, D. PAUL and H. GIRAUD

Comm. Journes d'Automne de la Mtallurgie

[Communication,

Autumn Metallurgy

Workshop]

28.

N. PHILLIPS
Trainee Report
IRSID SCA 90/144, August 1990

29.

B. BAROUX, G. BERANGER and C. LEMAITRE

Les aciers inoxydables [Stainless steels]
Les Editions de Physique [Physics
BP 112 - F 91944 Les Ulys Cedex A

271

Paris, 1990

Publications]

30.

G. BERANGER and F. DABOSI

CNRS Summer School, Les Houches, 1981

31.

G. OKAMOTO
Corrosion - Sci (1973) 13, 471

32.

Air Liquide documentation (hydrogen peroxide)

33.

G. BELOZERSKII, C. BOHM, T. EKDAHL and D. LILJEQUIST

Corrosion Science (1982) - Vol. 22, 9_, 844

34.

E. PRAT
Le Dcapage des produits plats [Pickling
IRSID, CESSID Notebook, October 1983

35.

of

flat

products]

F.A. SCMIDT, F.W. DELWIG, F.G. BEMPERA and V. RIADESEL

Evolution technique des lignes de dcapage en continu
haute performance

[The technical
evolution
pickling
lines]

in high-performance

SACK Documentation

272

continuous

COLOURING OF STAINLESS STEELS

Contents
1 -

HISTORICAL BACKGROUND

THE PASSIVE LAYER

THE COLOURING OF STAINLESS STEELS - OBJECTIVES SOUGHT

3.1

The steels in question

3.2

Preliminary operations

STAINLESS STEEL COLOURING PROCESSES

4.1

4.2

Conventional processes
4.1.1

Thermal processes :

4.1.2
4.1.3
4.1.4

A) Direct oxidation
B) Treatments using molten salts
C) Enamels on stainless steels
Chemical processes
Electrochemical processes
Hybrid processes

New processes
4.2.1

The Inco process

4.2.2
4.2.3

The WELCOLOR process

The COLORINOX process

4.2.4

Japanese companies
4.2.4.1 Kawasaki Steel
4.2.4.2 LUMINA-COLOR products
4.2.4.3 Nisshin Steel

273

4.2.4.4 Nippon Yakin Kogyo

4.2.4.5 Nippon Stainless
4.2.4.6 Other coloured stainless products
4.3

4.4

Particular types of deposition

4.3.1

Painted
Varnish

stainless

steels

4.3.2

Adhesive coatings - Varnish

- Lacquering

Physical colouring methods

4.4.1

Physical vapour deposition (PVD)

4.4.1.1 Ion plating
4.4.1.2 Sputtering
4.4.1.3 Surface treatment using
plasma
4.4.1.4 Vacuum evaporation

4.4.2

5 -

molecular

Chemical vapour deposition (CVD)

INSPECTION METHODS
5.1

Tests normally carried out

5.2

Physical methods

5.3

Electrochemical

or

physico-chemical

quantitative analysis

6 -

SAFETY AND THE ENVIRONMENT

7 -

FUTURE TRENDS - APPLICATIONS

274

methods

of

COLOURING OF STAINLESS STEELS

1 - HISTORICAL BACKGROUND: Why colour steels?

Since ancient times, man has sought to colour metals for
various reasons; for example for:
- protection
- aesthetic appearance
- monetary value
differentiation.
In a publication entitled "Secrets d'ateliers perdus et
retrouvs [Workshop secrets
lost
and rediscovered]",
BOURDAIS
cites, somewhat poetically, "Florentine
bronzing",
"fireblacking
of
iron",
"sodium
hyposulphite
and lead
acetate
blueing"
and "bronzing
of gun barrels"
achieved using "butter of
antimony". By dipping the object for various lengths of time,
yellow, purple, violet or black surfaces were obtained.
In those days, concern for the environment, ecological
impact and safety were unheard of. We read with horror of
methods of operation, which mention the use by young apprentices
of lead
salts, mercury
salts, cadmium
salts, etc. in
unventilated workshops, etc.
Patination2 is a particular form of colouring associated
with the artificial ageing of an object by imitating its surface
change due to contact with a given atmosphere, for example
housing, cowsheds, etc. The antiquarian seeks "old silver"
patinas while the numismatist is interested in the "coppered"
patinas of coins.
From a scientific point of view, patina is due to a
thermodynamic instability in the medium of use 2 . This phenomenon
may advantageously be employed for decorative purposes. The
patina colour actually results from the composition of the
oxides; but there is also an optical phenomenon due to their
thickness (cf. M1750 refr).
275

THE PASSIVE LAYER3

Stainless steel does not oxidize because the alloy
develops a highly adherent but relatively thin
(a few
nanometres) surface layer which has a low ionic permeability the passive layer - the transfer of ions from the metal to the
external medium being virtually zero. The physicochemical
characteristics of the passive layer gives stainless steel its
protective properties and hence its corrosion resistance. This
film is mainly composed of oxygen ions 0~", hydroxide groups OH",
anions and cations, such as those of chromium, iron, nickel,
silicon and aluminium (studies carried out using Auger spectroscopy, ion spectroscopy, SIMS, etc.).
Structure of the passive layer: several structural models
of the passive film have been proposed3. They are divided into
two categories, depending on whether the passive film consists
of a crystalline oxide of the (Fe,Cr)203 type or of a largely
disordered hydrated oxide.
Since stainless steel is "automatically patined", because
of the formation of the passive film, colouring is therefore
much more intended for aesthetic and decorative purposes than
for surface protection. In colouring processes, the aim is:
- either

to cover the passive

film: paint, varnish,

enamels, etc.
- or

to enhance

the passive

film exposed

to inter-

ferential phenomena.

3 - THE COLOURING OF STAINLESS STEELS - OBJECTIVES SOUGHT

The colouring of stainless steels is a controversial
operation, being the subject of reciprocal observations on the
part of sheet manufacturers.

276

Is

it

necessary

to

colour

stainless

steels?

Is

colouring a commercial and technical trump card?

Back in 1976, the company Inco, in an article which
appeared in ELECTROPLATING and METAL FINISHING4, wrote "We must

have colored
waiting for

stainless
it".

steels

because

the world has got to be

The reasons most often mentioned are:

decoration:

architecture

and

the

building

and

motor-vehicle industries
reliability: scheduling and sorting
visual indication
camouflage
The properties sought are the following:
colour uniformity
corrosion resistance
shapability
resistance to rubbing
temperature stability
no fingerprints.
3.1. - The steels in question
Colouring relates to:

- ferritic stainless steels

Grade AISI 43 0
austenitic stainless steels
Grade AISI 304 316

decoration, flatware and

sanitary ware
decoration, sanitary ware and
medical prostheses
industrial chemistry

- austeno-ferritic steels
3.2 - Preliminary operations

Colouring requires a series of preliminary operations

277

a) cleaning: various processes can be used:

chemical cleaning in an alkaline medium
phosphate or borate)

(alkaline

electrolytic cleaning under potentiostatic or galvanostatic conditions and in an alkaline medium.

Cleaning using halogenated solvents is no longer used
because of legislation with regard to the safety of personnel
and because of environmental reasons.
b) pickling: all the techniques deemed to be effective can be
used:
- roughing:
- using electrolysis in an acid or neutral medium
- using molten salts
- using acids or mixtures of acids
finishing, in acid medium:
- UG3P or UG3P+ (HF/H2S04/Fe+++ mixtures)
- nitric acid passivation and rinsing in water.
c) brightening:
Colouring mostly pertains to a so-called "bright" surface
finish. From an industrial standpoint, this appearance is
achieved by annealing in the presence of ammonia.

4 - STAINLESS STEEL COLOURING PROCESSES

Stainless steel colouring processes may be separated into
two categories :
- c onven t i ona1 processes going back some twenty years
- novel processes (including current trends)
278

In each category we may also distinguish:

- processes leading to very thin (100 to 1000 ) oxide
layers giving rise to colouring by interference of
light;
- processes leading to thick (several micrometres)
coloured oxide layers or to coloured coverings (enamels,
paint, plastic coating).
4.1 - 'Conventional* processes
4.1.1 Thermal

processes5'6'7,8

A) Direct oxidation
Principle: the metal, prepolished, is heated to a predetermined
temperature for a given time.
The oxidation layer then refers to the Fe-Cr-0 and Fe-CrNi -O diagrams.
Execution: the main parameters are:
temperature
composition of the basis metal
- duration of the treatment
the oxygen partial pressure.
Table I shows the colours obtained by leaving the specimen for
10 minutes at the following temperatures:

279

TABLE IColour

Temperature (C)

Pale yellow
pink
deep yellow

290
340
370

red-brown

390

violet

420

deep violet
blue
deep blue

450
540
600

If the temperature rise is very rapid, the colour darkens very

quickly.
Results:
The colours obtained are not very resistant to slight
abrasion; however, the oxide film is sufficiently thick to
enhance the corrosion resistance. The resulting rugosity allows
an oil film to be retained, and therefore allows drawing to be
carried out, if necessary. This process proved to be satisfactory, some twenty years ago, for the building industry: the
colours obtained are strong and decorative.
Improvements :
Two improvements may be mentioned:
a)

heating for 10 minutes at 540C

- air cooling the stainless steel plate
spraying a solution of sodium silicate
annealing for 5 minutes at 315C
slow cooling, in air ' ' .

JS)

Immersion

in

sulphuric

280

acid/chromic

acid/manganese

sulphate mixture:
-

H2S04

18N

H2Cr207

90

g/1

MnS0 4

20

g/1

heating at 500C for 10 minutes 10

B) Treatment s using molten salts5'6'11'12
These treatments may be likened to so-called "burnishing"
or surface-blacking processes11.
Principle: oxidation in molten-salt medium
Execution: a highly oxidizing mixture is used:
Na 2 Cr 2 0 7
K 2 Cr 2 0 7

50% by weight
50% by weight

Immersion time: 10 minutes (320C).

Results: There is complete blacking. This process is used to
"burnish" the transmission components of a mechanical assembly
and for certain artillery pieces. The process is rapid and
inexpensive.
Improvements : By reducing the immersion time, various colours
may be obtained:
straw colour, after 3 minutes
gold colour, after 4 minutes
blue colour, after 6 minutes.
Safety points:
- avoid any contact of the bath with powerful reducing agents
(greases and oils)
- removal of molten salts: remove hexavalent chromium by means
281

of a treatment using ferrous iron,

C) Enamels on stainless steels1
Under thermal methods, we may include the deposition of
enamels as thin layers on stainless steels. These techniques are
used in jewellery and involve mixtures of oxides and borates,
silicates, alkali-metal carbonates, etc. These mixtures are made
into a uniform powder and then melted; the articles to be
coloured are then dipped into the melt.
The colours obtained are as follows :
blue for cobalt oxide (Thenard's blue)
green for copper oxide
violet for manganese oxide
yellow for antimony oxide
The enamelled layer, unlike in air annealing, is a few
tenths of a mm in thickness (cf. Techniques de l'Ingnieur

[Technologies

for

the Engineer],

M 1514).

We give below an example of the composition of an enamel

deposited on an austenitic stainless steel for the purpose of
improving the decorative effect:

sio 2

55 t o 75%

L i 0 2 15 t o 20
CoO 3 t o 5
3
23
Ti0 2 3 to 10
B

NaF

4.1.2

Chemical

2 to 5

processes5'1*'15'16

Principle: The basis of chemical processes is to "convert" the

surface of the metal into a stable oxide by immersing the metal
in an aqueous solution containing chromium (Cr6+) salts.
282

Execution: Prepolished components or sheets are immersed in a

mixture of chromic acid and sulphuric acid, for example:
- 200 parts of chromic acid
- 490 parts of sulphuric acid (r.d. = 1.87)
- 1000 parts of water
temperature: 85C
time: 15 to 20 minutes.
Results:

The

quality

of

the

coloured

film depends

on many

factors; these are mainly:

the temperature of the solution
the immersion time
the concentration of chromic acid and sulphuric acid.
The colours obtained depend on:
the temperature
the immersion time (Figure 1)

283

time (in minutes)

Figure 1: Colours obtained - Influence of
temperature and time5
Improvements :
It has

been

proposed 15

to add 2 to 5% of ammonium
molybdate in order to improve the brightness of coloured steel.
The addition of a manganese salt (MnS04) is recommended10 for
accelerating the formation of the coloured film. It is also
possible to add Cu, Ni or Co ions, in a reducing medium, and
thus allow more uniform colouring to be obtained10'17. It has
been shown
that immersing the stainless steel in a mixture
containing:
- H 2 Cr 2 0 7 , 250 g/1
- H 2 S0 4 , 490 g/1 (r.d. = 1.87)
at a temperature of between 60 and 95C makes it possible to
obtain more varied ranges of colours, namely:
- bronze
284

- blue
- gold
red
- violet
- green.
Other variants have been proposed:
H 2 S0 4 , 400 g/1
H 3 P0 4 , 90 g/1
H 2 Cr 2 0 7 , 250 g/1
and

H 2 S0 4 , 350 g/1
HCOOH, 100 g/1
H 2 Cr 2 0 7 , 200 g/1.

4.1.3

Electrochemical

processes5

Principle: the metal is oxidized, under anodic polarization;

Execution: a current
of specimen are used
lines (equipotential
the anode and a lead

generator and a cell suitable for the type

to obtain good distribution of the current
plot). The stainless steel specimen is made
plate forms the cathode.

The operating conditions are as follows16 :

H 2 S0 4 (r.d. = 1.82)
Na 2 Cr 2 0 7
H 2 0 qs

250 litres
60 kg
1000 litres

temperature: 80C
anode current density: 0.06 A/dm2 at 1.2 volts.
Continuously stirring the bath allows a uniform colour
and better corrosion resistance to be obtained. It also allows
use of a mixture of potassium dichromate and sodium dichromate
containing vanadium salts 18 ; similarly, the addition of nitric
acid is mentioned.
285

It is possible to operate with a modulated current in a

sodium chloride medium or in a sulphuric/chromic acid medium19.
Good results have been obtained20 in electrolysis, at constant
current density, with a platinum cathode (in search of a uniform
blue colour) . Other bath formulae are mentioned, such as, for
example:
Cr 2 0 7 "

20 g/1

H 2 S0 4 (r.d. = 1.84)

200 ml/1

H 2 0 qs

1000 ml

current density: 5 A/dm2, for 10 to 2 0 seconds.

A bright blue colour is obtained. Note the very high
current density and the very short duration of this "flash"
oxidation.
In all cases, colouring is performed in a Cr
in the presence of a high H

4.1.4

Hybrid

medium and

ion activity (> 5N H 2 S0 4 ) .

processes

By "hybrid" processes we mean the combination of a

chemical process (conversion) with an electrochemical process
(fixation)5'22'23. It has been found that the colouring obtained
using a chemical route can be "fragile". It has therefore been
proposed to "electrochemically harden" the oxide microlayer; the
term "fixation" may also be found in the literature.
We give below a few proposed compositions:
a) Chemical treatment: immersion in 3N H 3 P0 4 for 2 minutes
b) Electrolysis
Composition of the bath:
Na 2 Cr 2 0 7 , 250 g/1
H 2 S0 4 , 100 g/1
286

- current density: 5 A/dm2

- temperature: 80C
- time: 5 minutes
or in a bath of composition:
H 2 Cr 2 0 7 , 750 g/1
H 2 S0 4 , 2 00 g/1
- current density: 3 A/dm2
- temperature: 40C
- time: 15 minutes
Some authors add selenium or arsenic salts, or sodium
metasilicate, which act as surfactants.
The (patented) Inco process, which is
4.2.1, may be regarded as a "hybrid" process.

described

in

4.2 - New processes

4.2.1

The Inco

process22'23'2*'25

In 1972, Inco developed, at its Research Centre in

Birmingham, a colouring and hardening process for stainless
steel. This process is used under licence in many countries.
Starting products
- bright polished products
eleetropolisning)

(for

example

obtained

by

- products which are bright annealed in a reducing atmosphere .

Colouring:
1st phase: colouring
- H 2 Cr 2 0 7
- H 2 S0 4

287

temperature: 90C
2nd phase : cathodic hardening
- cathodic polarization of the coloured steel
- anode: lead or a Pb-Sn-Sb alloy
- electrolyte:
H 2 Cr 2 0 7 , 250 parts (by weight)
H 3 P0 4 ,
2.5 parts
H 2 0,
1000 parts
- current density: 0.2 to 0.4 A/dm2
- time : 5 to 6 minutes
- finishing: washing in water and drying.
Three problems had to be solved:
- making the colouring uniform
- making the colour reproducible from one bath to another
- reducing the fragility of the coloured film.
Making use of masking, using a varnish,
obtain:

it is possible

to

- coloured patterns of the desired shape

- various colours within the range mentioned.
Results : The process can be applied to austenitic and martensitic steels. However, for the latter, the colouring is always
more delicate (depending on the carbon content, areas of surface
attack may appear).
Inspection of the film: A simple specific method has been
developed for inspecting the coloured film (Figure 3 ) 2 4 . The
variation in potential between a platinum electrode and a given
specimen in a colouring bath is recorded as a function of time.
The E = f (time) curve has the form shown below. The colour
depends on the value of -B. The period of immersion is brought
to an end when the identified potential is reached.

288

COLOURING

irroraion in & solution

containing 490 g/1 of
KjSQ + 2S0 g/1 of Cr03 (8D'C)

immersion time

C/'* C /

ni.

^xis .;;:: q

:*8-"-@

oxide film
Clan
S

Othodic elftc-rolyju
IB a, solution containing
2.S g/1 of HjSOt + 250 g/1
of CrO] (40*C); 3current
density 4.8 A/An ; 7 mintes

77777777777
metal

Fig.2 : Basic principle of the

Inco process
a) colouring
b) hardening

Fig.3 : Colours obtained as a

function of potential and
time.

Applications : The Inco process allows twelve different colours

to be obtained. Among industrial applications (cf. 7) we see
that one of the records of application in architecture1 of this
process is held by the temple of Shakaden in Tokyo which
required 30,000 m 2
(450 tonnes) of coloured stainless steel:
roofing covered with black panels, ceilings consisting of gold
coloured panels.
Making use of masking, using varnish, makes it possible
to obtain:
coloured patterns of the desired shape
various colours over the same area upon successive
immersions.
4.2.2

The WELCOLOR

process 26

The WE LCOLOR process is an improvement of the Inco

process. The novelty of the process resides in the pretreatment,
before colouring. The following block diagram summarizes the
various phases of the process:
1

In France: use at Eurodisney

289

Cleaning
"PERCO CLEANER"
30 g/1

>'
Pretreatment
10% H3PO4
20C
Anodic treatment
1 A/dm2 , 3 minutes

Potential control

""
Colouring
Cr03 , 250 g/1
H 2 S0 4 , 500 g/1
77 - 82C

Fixing
CrQj , 250 g / 1
H3PO4, 2 . 5 g / 1
= 20C, 10 m i n u t e s
c a t h o d i c t r e a t m e n t : 0 . 5 A/dm2

Drying

Results :
v e r y good r e s u l t s on A I S I 43 0 g r a d e s
good c o r r o s i o n r e s i s t a n c e
good t e m p e r a t u r e s t a b i l i t y (200C)
C o m p o s i t i o n of t h e i n t e r f e r e n c e

layer:

12 t o 21% C r , 2 t o 6% Ni a n d 12% Fe
Approximate formula: (Cr,Fe)203 (Fe,Ni)020

290

4.2.3

The COLORINOX process

(1985)

This process was developed and patented by the company

Aquitaine d'Application de Surface (Toulouse). It has been used
for colouring solar absorbers. The various phases in the process
are summarized in the following block diagram:
Cleaning

HF/HNO3 Activation

Oxidation

Colouring (inorganic pigments)

Hardening

Results:
large choice of colours on AISI 316-304 grades
limitation for AISI 430 grades (grey and black)
good heat resistance (black, 400C; colour, 200C)
good resistance to rubbing
However;
lack of transparency of the coating
291

bending is not possible (elongation < elongation of

the basis metal).
4.2.4

Japanese

companies

According to the Japanese technical press, the demand for

coloured stainless steel sheet, for roofing, has increased by
10% each year over a certain period: from 10,200 tonnes for the
financial year 1984/85 it exceeded 11,642 tonnes in 1985/86,
then 12,548 tonnes in 1986/87, etc., since when it seems to have
stabilized. One of the desired aims is to replace coloured
varnished tiles, so common in Japan. We give below the various
processes commercialized in that country. It should be pointed
out that the Japanese have introduced hybrid processes,
including:
colouring
fixing
covering with a polyester
bonded coatings.
4.2.4.1

film or epoxy resin or

Kawasaki Steel

This company is marketing "RIVER LITE COLOR" sheets of

coloured stainless steel, of the silicone or polyester lacquered
type. Production (1991) seems low, about 120 t/month.
Known products:
"RIVER LITE COLOR F" products obtained by application
of fluororesins
"WELCOLOR" products treated with polyesters
silicone resins or epoxy-type resins 27 .
4.2.4.2

and

"LUMINA COLOR" products (Yakuhin patent)

This process would seem to be close to the Inco process

and to comprise two main phases:
292

colouring by H 2 S0 4 /H 2 Cr 2 0 7 treatment
hardening of the film obtained
Colours obtained: black, brown, bronze and gold
AISI 304-316 grades
Tonnage < 50 t/month
4.2.4.3

Nisshin Steel

This company has developed coloured stainless steel tubes

according to the Inco process and by painting.
Grades known: "COLOR SOFTAIR-F": these are "fluororesin"-type
prelacquered stainless steel sheets. Good atmospheric corrosion
resistance. According to the documentation, the cost of the
COLOR SOFTAIR-F process is 40% of the cost of the Inco process.
4.2.4.4

Nippon Yakin Kogyo

In 1975, this company had commercialized

COLOR" process 28 .

the "TEMPER

The bases of the process are:

formation of a coloured
(350C)
treatment in HN0 3 .
4.2.4.5

film by oxidation in air

Nippon Stainless

The most well-known product of this company is

NARCLEAREX-N: this is a stainless steel sheet coated with a 5
thick film consisting of a mixture of a macromolecular resin,
ceramic and pigments 28 .
Characteristics: good adhesion of the film after bending
basic steel AISI 304-430
colour: grey, blue or gold
Price example (1992): 78 F/kg (0.3 mm thickness)
293

4.2.4.6

Other coloured stainless products

- KPK "MIROR COLOR STAINLESS":

coloured by electroplating.

this

is

stainless

steel

- "NAS COAT" and "NIKI COLOR" are stainless steels coloured by

painting.
- POLISPECTRAL process (Mcachim35) :
colours: bronze, steel blue, cobalt blue, brown and grey
coloured grades: AISI 3 02 - 3 04 - 3 04L
principle used: electrochemical colouring.
Comment : In Europe, particularly in France, many surface treatment companies also undertake, on request, to colour stainless
steels. A literature survey shows the existence of a smaller
number of patents filed in France, this being partly due to the
fact that filing a patent in Japan is virtually systematic.
4.3 - Particular types of deposition

4.3.1

Painted

stainless

steels

- lacquering

varnish

The application of paint to stainless steel is regarded,

with justification, as pointless because of the excellent
atmospheric corrosion resistance of most grades. However, it is
possible to find stainless steels which are "painted" for
temporary modification or "technical differentiation" reasons.
If the surface is well prepared (effective cleaning), the paint
is highly adherent, especially on "matt" or "brushed" stainless
steel. Preferably, paints of the "vinyl" or "epoxy" resin type
are used. In order to protect the primary layer from the effect
of ultraviolet radiation, the finishing layer will be of the
Polyurethane type.
The choice of paint may be made in conjunction with the
manufacturers, who are proposing suitable products.

294

Lacguering
This operation is sometimes used for treating large
areas, on which it is desired, for example, to inscribe a set of
initials.
Execution:
effective cleaning
surface preparation
Next, two types of lacquering may be used:
a) air-drying lacguering (satin appearance)
- priming, using a polyvinyl "primary wash"
- secondary lacquering, using an epoxy lacquer
b) hot lacquering
This process is quicker, since it is applied as a
single layer.

4.3.2

Adhesive

coatings

Varnish

Except in special cases, adhesive coatings and varnishes

are used only for temporary protection.
4.4 - Physical colouring methods

4.4.1

Physical

vapour

deposition

(PVD)29'31

For many years, sputtering has been used to decorate and

protect surfaces by applying coloured coatings. There are many
variants of these techniques, which are continuing to evolve;
they have in common the use of vacuum techniques and result in
coatings which are often expensive but of high quality.
The following methods may be distinguished:
295

4.4.1.1

Ion plating3

A DC voltage (between 200 and 6000 volts) is applied

between the evaporation source and the substrate. The generation
of an argon plasma and a reactive gas enables the vapour to be
ionized.
The characteristics of the process are:
rapid deposition kinetics
good adhesion, but often a porous columnar structure
is obtained.
Currently, this process is used on an industrial scale
for ion-based nitriding and carbonitriding. As regards colouring, the most often quoted example relates to the deposition of
titanium nitride which has a yellow colour.
4.4.1.2

Sputtering29

Principle: sputtering is one of the variants of the vacuum

deposition processes. A target is subjected to ion bombardment
of high-energy particles (generally Ar + ions) and the sputtered
atoms from the target material are deposited on a substrate
carrying the material to be coloured. The ions are obtained by
a glow discharge between two electrodes. In general, a diode
arrangement is used in which the material to be sputtered is
fixed to the cathode, the substrates being placed on the anode.
Many improvements exist:
biased diode
alternating-voltage diode
radiofrequency diode
low-pressure triode.
Examples of equipment for colouring using sputtering:
Sputtering installations must meet a certain number of
296

criteria:
coating of three-dimensional objects with uniform
colouring
keeping the substrates at a sufficiently low temperature so that the technique can be applied to
stainless steels
multi-purpose nature of the equipment
reproducibility of the coatings
reduction in "dead" time (pumping time),
and we mention, for example, the IONIMAC 1501 device. The
components to be treated may be arranged on a circular substrate
holder, which is given a circumferential movement, and can thus
move between the cathodes, as shown in Figure 5.
Results
The table below gives a few examples of the colours
obtained29

297

TABLE I I

DECORATIVE PVD LAYERS

Material

Colour

Approx. hardness
(Hv: 0.015 kP/mm2)

TiN
TiN + Au

yellow-gold

2000

gold

--

TiC
Ti
Zr
Hf
Ta (C, N, 0)
W

grey to black

1500 to 2000

grey, black
blue, bronze
copper, yellow
brown ...

1000 to 2000

Al
Cr
Stainless steel
Cr-Ni
Ti
Cr-Co-Fe
IC carbon

grey
grey
grey
grey
black

298

500 to 700
500 to 700
500 to 700
2000 to 4000

Figure 4: IONIMAC I 501 Laboratory equipment29

Inner cathode

\.
Substrate
Outer cathode

Fig.5 : Double-cathode system

for coating threedimensional objects29

299

Fig.6 : In-line deposition

equipment29

Properties of the depositions obtained

hardness, between Hv 600 and 700

chemical stability
various colours
biocompatibility
good adhesion

Examples of application
- colouring of dental prostheses
process)

(TiN + Au) (TITANORE

Disadvantages :
the deposition kinetics are very slow, even using magnetic
cathodes.
4.4.1.3 Surface treatment using a molecular plasma
(IRSID-UGINE S.A. work) 3 2 ' 3 3
Molecular plasma surface treatment (MPST) is similar to
reactive sputtering.
Principle: The subject-matter of the method is a process for
colouring the surface of a metallic material by creating, on the
surface of the said material, a film of oxide having a con
trolled thickness, characterized in that the material, which has
a positive polarity, is subjected to a surface treatment, using
a low-temperature plasma, under conditions for forming a glow
discharge. The ambient atmosphere contains at least one oxidi
zing gas (or gas mixture) . Preferably, an 02/N2 mixture is used.
The operation leads to deposition on the anode 32 , contrary to the
PVD method in which the material has a negative polarity, by ion
bombardment.
Execution:
To achieve this deposition, the stainless steel which it
300

is desired to colour is placed in a chamber containing oxygen

atoms ionized by a glow discharge. The anode is formed by the
material (Figures 7 and 8 ) .
Atmosphere of the chamber : 1000 Pa, containing 2 0% of oxygen.
The colour which appears on the material depends on the
thickness (300 to 2000 ) of the deposition.
The thickness depends on:
the voltage maintained between the anode and cathode
(200 to 3000 volts)
- the current density at the anode (1 to 100 mA/cm2)
- the time (1 to 60 minutes)
- the distance between the anode and cathode
Colours obtained:
yellow to pinky yellow, after 2 to 4 minutes
violet red, after 5 to 6 minutes
pale blue, after 7 to 12 minutes
yellow, after 18 minutes
pink, after 22 minutes
greeny blue, after 27 minutes
green, after 3 0 minutes.
Results :
The MPST treatment is extremely reproducible since the
erosion times measured by glow-discharge spectroscopy have a
standard deviation of less than 4%. The nature of the cathode,
made of stainless steel or pure chromium, is an important
parameter for resistance in the corrosion tests. On the other
hand, the effect of the composition of the gas mixture, for
example:
301

or

Ar + 2 0% of 0 2
N 2 + 2 0% of 0 2

would be negligible33.
The quality of the deposition depends on the anode
temperature. It is necessary to cool the anode (T > 350C) in
order to obtain a satisfactory deposition. Comparative tests
were made, on the one hand, on sheets coloured using the Inco
process and, on the other hand, on material subjected to "cold"
(T < 200C) and hot (T > 350C) MPST.
The parameters were the following:
- colour uniformity
- corrosion test
salt fog
the pH of dissolution in a given reagent
- ability to be bent
the Erichsen test
fingerprints.
It was found that the quality of the two products were
similar (so-called "cold" plasma). The "Inco" colouring being
better in the corrosion test but not so good in wear resistance.
We should point out that these were tests measured on
only a few specimens and not the subject of a statistical
approach.
Constitution of the layer formed:
The layer consists of single crystals of mixed oxide of
the spinel type (Fe, Cr,Ni) 3 0 4 in the case of a stainless steel
cathode and rhombohedral Cr 2 0 3 in the case of a chromium cathode.

302

Disadvantages :
MPST is an expensive and relatively slow treatment. It
would be necessary to carry out the treatment on a wide (about
1000 mm) and continuously moving product.
There are problems associated with fingerprints. It
has been shown that all processes are sensitive to fingerprints.
The currently proposed remedy is to cover the product with a
varnish based on:
resins
Polyurethane or polysiloxane
a film of silica
or to subject the product to slight
("embossed" or "pigskin" sheets).

continuous

Improvements :
Proposed improvements relate to:
the use of a "cold" plasma
magnetic assistance
chromium electrode (cathode)
treatment on running product.

303

embossing

Figure^: Colouring using MPST in a double-cathode arrangement

(After CHARBONNIER et al.36)

hL

STAINLESS STEEL TUBE

SHEET

I-El \

CA-HnPF

.A.ICPE.

li

Figure 8: Colouring using MPST in an arrangement for sheet

(1000 mm in width) (after CHARBONNIER et al.36)
4.4.1.4 Vacuum evaporation
Principle: vacuum deposition of a material vaporized by heating.
This material condenses on a substrate. The evaporation source
depends on the material to be deposited. It is possible to use,
as heat source:
- resistance heating (Joule effect)
- HF induction heating
- electron bombardment
The colouring kinetics are relatively fast (1 M m/minute).
4.4.2

Chemical

vapour

deposition

(CVD) 37

Principle: This involves a vapour-to-solid reaction.

The vaporized compound condenses on a surface, in contact with
a gas, giving a solid layer. Many materials (metals, steels,
stainless steels, oxides, etc.) may be deposited on various
substrates.
304

advantages: thick deposition is possible

drawbacks: expensive process
improvements :
- low-voltage CVD
- plasma-coupled CVD.

5 - INSPECTION METHODS
The inspection and quality assurance methods make use of
all the techniques for studying surfaces38 known to date:
5.1 - tests normally carried out
- visual uniformity
- corrosion tests (Kesternich)
salt fog
the pH of dissolution
- bending
the Erichsen test
- abrasion test.
5.2 - Physical methods
scanning electron microscopy
- glow-discharge mass spectroscopy.
The latter method gives primary information about the
nature and constitution of the coloured layers, especially about
the composition profiles.
Among recent developments, we have adopted:
- Auger spectroscopy (study of chemical bonds)
- ESCA spectroscopy or XPS
- secondary ion mass spectroscopy, which is particularly
useful for studying oxide/metal interfaces.

305

5.3 - Electrochemical or physico-chemical methods of Quantitative analysis

The method involves chemically or electrochemically
dissolving the coloured layer (over an area of several tens of
cm2) .
After dissolving, the solution is:
injected into a plasma torch (continuous analysis
coupling - plasma-torch emission spectroscopy);
- quantitatively analysed by pulsed polarography (sensitivity: 10"9 M/litre).

6 - SAFETY AND THE ENVIRONMENT

Chemical and electrochemical methods of colouring
stainless steels require the use of acids and salts, some of
which are toxic, especially hexavalent-chromium salts.
The effluent from colouring treatments will undergo:
- a chromium depletion treatment (using ferrous iron or
sodium bisulphite)
- neutralization of the H + ions using Ca(OH) 2
- precipitation of the
(Cr(OH)3 and Ni(OH) 2 ).

hydroxides

at pH

8.5

9.5

The standards in force2, relating to surface treatments,

published by the French Ministry for the Environment (Official
Journal of 3. January 1992), will have to be met. For example,
the limiting content for Cr 6+ is fixed at 0.1 mg/litre.

306

7 - FUTURE TRENDS - APPLICATIONS

Worldwide, after a period of development during the
eighties, the colouring of stainless steels seems to be marking
step. Several fields of activity are interested in colouring
stainless steels:
1) the large industrial firms manufacturing

stainless

steels;
2) surface-treatment companies, mostly SMEs. It is
mainly these companies which carry out colouring treatments .
Potential users:
Among these, we may mention:
a) Building, architecture and
decoration industries

Search for attractive surfaces, harmony of colours,

breaking away from the metallic appearance of stainless
steel.

b) Motor-vehicle industry

decorative trim

c) Homecraft/hygiene

decorative appearance (wastepaper bins in Japanese airports) , ease of cleaning

d) Pharmaceutical industry
and surgery

safety: one colour per tool

scheduling

e) Roadway equipment

road signs

f) National defence

search for matt-coloured or

green- or yellow-coloured
equipment

307

TABLE SUMMARIZING THE PROCESSES

An attempt to make comparisons
\ . Processes
Thermal

Molten-salt

Electrochemical

Inco

COLORINO!

MPST

processes

treatments

processes

process

process

process

Reproducibility

XX

XXXX

Corrosion

XX

XX

XXX

XXXX

XX

XXX

Heat resistance

XX

XX

XX

XX

XXX

XXX

Mechanical
strength."

XX

XX

XX

XXX

XXX

XXXX

(with additional

Properties ^ v

resistance

UJ

o
00

treatment)
Wear resistance

XXX

XX

XX

XXX

XX

XXX

Range of colours

XXX

XXX

XXX

XXX

XXX
in

XXX

Fields of
application

Architecture

Architecture,
mechanical engineering

Architecture,
goldsmithery

Architecture

Energy
(solar collectors)

Not mentioned

COMMENTS

Easy to produce

Quick and easy to

Good

Good

Selective

Very expensive

and inexpensive

produce

reproducibility

reproducibility

applications

process

X
XX
XXX

Poor
Good
Very good

xxxx

Excellent

BIBLIOGRAPHY

1.

M. BOURDAIS
Secrets d ' a t e l i e r s perdus et
[Workshop secrets
lost
and
Pub. Dunod, P a r i s , 1978

retrouvs
rediscovered]

2.

G. BRANGER and C. CODDET

Les T e c h n i q u e s d e l ' I n g n i e u r
[Technologies
for the
Engineer]
M t a l l u r g i e [Metallurgy]
, M 1750

3.

B. BAROUX, G. BRANGER and C. LEMAITRE

Les A c i e r s I n o x y d a b l e s [Stainless
Steels],
Chapter V
Les E d i t i o n s d e P h y s i q u e [Physics
Publications],
1990

4.

Inco Communication in:

Electroplating and Metal Finishing, September 1976, p. 23

5.

S. JOHN and B.A. SHENOI

Electroplat. Met. Finish., (Sept 1976), 29 (9) pp 20-22

6.

S.D. FISHLOCK
Electroplat. Met. Finish., (1963), 16 (5), pp 142-145

7.

J.R. CONNER
US Patent (1964), No. 3,125,471

8.

British Patent (1972), No. 1,243,111

9.

J.R. CONNER
Belgian Patent (1963), No. 619,691

10.

T.E. EVANS, H. JAMES and C.G.

SMITH

British Patent (1967), No. 1,122,173

11.

Metal Finishing - Guidebook and Directory (1975), p.483

309

12.

13.

D. FISHLOCK
Galvatechnica

(1964), 15,(2)

pp 2 5 - 3 0

J.P. JACQUET
Les Techniques de l'Ingnieur
[Technologies
for the Engineer],

M 1514

14.

C. BATCHELLER
Electroplat. Metal Finish., (1944), 42, 466

15.

N.E. CLEGG and W.J. GREENING

United States Patent (1965), No. 3,210,220

16.

C E . NAYLOR
Piating (1950), 37, 153

17.

T.E. EVANS, A.C. HART, H. JAMES and V.A. SMITH

Trans. Inst. Met. Finish., (1972), 50, pp 77-79

18.

C. BATCHELLER
United States Patent (1940), No. 2,219,554

19.

T.E. EVANS and H. JAMES

British Patent (1967), No. 1,089,496

20.

T.E. EVANS and W.H. SUTTON

German Patent (1972), No. 2,319,383

21.

Inco process
Stainless Steel Industry (1982), 10, No. 53

22.

R. BLOWER and T.E. EVANS

Sheet Metal Indus. GB (1974), 51, No. 5, 230

23.

M. BLANKFIELD
Sheet Met. Indus. GB (1974), 51, No. 5, 32

24.

Inco process
Nickel Topics, USA, (1976), 23, No. 1, pp 7-10
310

25.

J. SALBAING
Rev. Met. (1977), 74, No. 7, 377

26.

HIK ARI
Nippon Steel Technical Report (1978), No. 12

27.

Japan Metal Bulletin of 9/09/1986

28.

G. BERANGER, X. HENRIET and P. CORBE

Training Report - Initiation to Research
Technical University of Compigne, April 1987

29.

F. AUBERT and J.B. KURETH

Galvano-Organo-Traitements de Surface
[Galvano-organic
Treatment
s
of Surfaces ],

369, April 1991

30.

G. DEARNALEY
Electroplat. and Met. Finish., 6, Sept., 1976

31.

J. MACHET
Les Techniques de
Engineer]
M 1663

l'Ingnieur

[Technologie
s

32.

P. de GLIS and R. BERNERON

French Patent, filed under No. 88/05091

33.

P. de GLIS

for

the

French Patent, filed under No. 89/05430

French Patent, filed under No. 89/08085
34.

. PIESSLINGER
Stahl Eisen

[Iron

and Steel],

FRG,

(1991), 101, 16,

35.

POLISPECTRAL process
Marketed by Mcachim, 86600 Lusignan

36.

J.C CHARBONNIER, H. GIRAUD, D. LOISON and J. PONTET

CECA Convention, No. 7210 (K B), 326
311

1095

ENVIRONMENTAL PROTECTION REGULATIONS

Application to surface treatments

CONTENTS

Page
1. ORGANIZATION
1.1 Ministry of the Environment
1.2 Prefects
1.3 RIREDs
1.4 REDs
1.5 Territorial Organizations
1.6 Water Agencies
1.7 Other Organizations

315
315
315
315
316
316
316
316

2. EXAMPLES IN EUROPE

317

2.1 Germany
2.2 United Kingdom

317
317
318

3. THE ENVIRONMENT IN THE EEC

3.1 The Maastricht Treaty
3.2 Organization in the European Union

318

319

4. FORMS OF POLLUTION AND OF HARMFUL EFFECTS IN THE COURSE OF

THE SURFACE TREATMENT OF STAINLESS STEELS
319
4.1 Aqueous pollution
319
4.2 Atmospheric pollution
320
4.3 Noise pollution
320
5. REVIEW OF THE LEGISLATION IN FORCE
5.1 Decree of 26 September 1985
5.2 Water Law No. 92 of 3 January 1992
5.3 Draft decree of 10 December 1992

313

323
323
326
326

5.4 EEC Directives

5.5 Noise/Noise pollution

327
327

6. HEALTH AND SAFETY AT WORK

328

BIBLIOGRAPHY

314

ENVIRONMENTAL PROTECTION REGULATIONS

Application to surface treatments

1.

ORGANIZATION
1.1

Ministry of the Environment

Created in 1971, the Ministry of the Environment plays

a coordination role in the national environmental policy with
the other Ministries involved (Health, Agriculture, Finance,
etc.).
Its field of competence encompasses the protection of
natural environments and the prevention of pollution, hazards
and risks to the quality of life.
1.2

Prefects

The prefects have an essential function in the environmental field, in terms of:
- Meeting the regulations
- Impact studies
- Granting of operating permits
lations) .
1.3

(classified instal-

RIREDs* (Regional Industry, Research and Environment

Directorates)
Their mission is to:
- participate in preparatory enquiries and to draft
technical requirements to be imposed on industrial
concerns with regard to the environment;

in French, these are "DRIRE" or "Directions Rgionales de

l'Industrie, de la Recherche et de l'Environnement".
315

- visit

classified

plants periodically

in order

to

check whether the imposed regulations are being met;

- draw up reports regarding observed infringements.
1.4

REDs** (Regional Environm^rital Directorates)

Set up in 1992, they have a policing function with

regard to the management and development of water.
1.5

Territorial organizations (communes and regions)

Their power is limited to general policing (in terms of

pollution, noise levels, etc.) and protection of the population.
1.6

Water Agencies

They correspond to the large French river basins; there

are six of them.
They have two functions :
- to collect

fees

from

industrial

enterprises

with

regard to pollution
- to redistribute these monies in the form of aid in
anti-pollution investment.
1.7

Other organizations

Other organizations exist whose missions are associated

with steering and stimulating environmental research, among
which are:
- ADEME (Agence de l'Environnement et de Matrise de
l'Energie [Agency
for
the Environment
and for
the
Control
of
Energy]);

In French these are "DIREN" or "Directions Rgionales de

1'Environnement"
316

INERIS (Institut National de l'Environnement Industriel et des Risques [.National Institute for
the
Industrial
Environment
and for
Hazards]);
IFEN (Institut Franais de l'Environnement
Institute

2.

for

the

[French

Environment].

EXAMPLES IN EUROPE
2.1

Germany

National laws define a general framework. The governments of the regions (LNDER) may decree their own regulations
and define limits and measurements in terms of harmful emissions
(TA - LUFT [Technical
Instructions
relating
to Air
Quality).
- Existence of laws on harmful effects
(BimSchG
[Federal Law on Air Pollution
Control]):
air, noise,
light, vibration, etc.
- Laws with regard to waste
- Laws with regard
Resources
Act]).
2.2

to water management

(WHG [Water

United Kingdom

British legislation derives from the French and European laws (Environmental Protection Act):
- the polluting activity is subject to a prior permit;
- the control of discharge (air, water, waste, etc.) is
subject to a permit granted by a specialized body,
namely Her Majesty's Inspectorate of Pollution
(HMIP);
- the technical regulations are drawn up as per BATNEEC
317

(Best Available Technology Not Entailing Excessive

Cost) .

3.

THE ENVIRONMENT IN THE EEC

Environmental protection was introduced into the Treaty

of Rome on 1 July 1987 by the Single Act.
In terms of Article 13OR, the European
Directives on the environment have three objectives:

Community

a) preserving, protecting and improving the quality of

the environment;
b) protecting the health of people;
c) using natural resources rationally.
In order to achieve these objectives, the EEC proposes
to apply four fundamental principles:
-

3.1

prevention of effects harmful to the environment

fighting pollution at the source
applying the "Polluter Pays" Principle (PPP)
taking account of ecological considerations in every
field (education, transport, etc.).

The Maastricht Treaty

Following the adoption of this treaty, the regulations

on environmental protection are characterized by:
- more pronounced European harmonization
- a global approach to harmful effects.

318

3.2

Organization in the European Union

Environmental

problems

are

dealt

with,

within

the

European Union, by the following organizations:

a) DirectorateGeneral V:

E mployment, Industrial Rela

tions
and
Social
Affairs
(Health and Safety)

b) DirectorateGeneral XI:

The E nvironment,
Safety and Consumer
tion.

Nuclear
Protec

c) DirectorateGeneral XII:

Science, Research and Develop

ment, Industrial Technologies
and Materials.

d) DirectorateGeneral XVII: E nergy.

Useful addresses:

20 0 rue de la Loi
1049 BRUSSELS

4.

Btiment Jean Monnet

Rue Alcide de Gasperi
L 2920 LUXEMBOURG

FORMS OF POLLUTION AND OF HARMFUL EFFECTS IN THE COURSE OF

THE SURFACE TREATMENT OF STAINLESS STEELS
4.1

Aqueous pollution
Origin of the water
Various types of water are used as required:
surface water (rivers, lakes, canals, etc.)
well water
treated water (demineralization), water from steam
319

condensation, etc.
- drinking water.
Use of the water
Water is used:
- for manufacture: preparing treatment baths, adjusting
levels, rinsing manufactured products, etc.
- for cooling: motors, compressors, belt-drive rollers,
quenching products, etc.
4.2

Atmospheric pollution
This concerns mainly the emission of vapours:
-

vapours from acids (HCl, HF, H 2 S0 4 )

vapours from bases (NaOH)
vapours from chlorinated or fluorinated solvents
sublimation
of
certain
salts
(molten
sodium
hydroxide, chromtes, etc.)
- dust (shot peening).
4.3

Noise pollution
Noise pollution occurs mostly from the following:
- Heat treatments : noise emitted from annealing ovens,
rapid quenching baths, coolers, etc.
- Shot peening and sand blasting: the decibel noise
level may be exceeded close to shot-peening turbines.

- Pickling: noise pollution occurs close to:

. fans
. gas extraction and scrubbing systems.
320

- Abrasion.
Brightening and polishing: polishing wheels

321

The forms of pollution and harmful effects in the course of

surface treatment of stainless steels

Transformation or treatment

Pollution

Prevention and Pollution Control

operations
Hot rolling (HR)
Wire drawing

Temperature of the water

SM - COD
Hydrocarbons

Cooling
Filtration/recycling
Breaking down

Noise
Annealing heat treatments

Furnace atmosphere - NH 3
Cooling or quenching water
SM (Suspended Matter)

Fume scrubbing
Recycling
Filtration

Shot peening
Sand blasting

Dust - particles of silica

and oxides
SM (ISHICLEAN)
Noise

Fume scrubbing
Recycling
Filtration

Prepickling
Molten-salt treatments

Vaporization of salts:
Na*, NJ, CrO;
Metals in solution:
Fe***, Ni**, CrSO

Fume scrubbing
OH" neutralization
Chromium-depleted
Hydroxide precipitation

Electrolytic pickling

Acid vapours (SOI")

Cr 6 * or OH"
S0", Cr6*, Fe***, Ni**

Fume scrubbing
Chromium-depleted
Neutralization
Hydroxide precipitation

Acid pickling
Reducing agent or oxidizing
agent

Acid vapours; F", N0, SO4"

Fe**, Cr***, Ni**, S0"
Fe***, Cr***, Ni**, S0"

Fume scrubbing
Neutralization
Neutralization of the solutions or

F-,

recovery of Ni
Sludge treatment

NO;

Passivation and rinsing

Acid vapours: NO;

N0, Fe***, Ni**, Cr***

Fume scrubbing
Neutralization

Cold rolling (CR)

Hydrocarbons
SM - COD
Additives
Noise

Fume capture
Breaking-down of emulsions

Chlorinated or fluorinated
organic solvents
Alkalinity, PO4""

Recycling
Vapour collection
Neutralization
Precipitation

Skin pass

Cleaning

Eutrophication
Brightening
Polishing

Hydrocarbons
Dust
Noise

Fume/vapour collection
Recycling in steelworks

Electropolishing
Colouring

Acid vapours

Vapour scrubbing
Neutralization

Cr6*, Ni**, Fe***

322

5.

REVIEW OF THE LEGISLATION IN FORCE (main texts)

The legislation concerns:
- Decree of 2 6 September 1985 relating
treatment workshops

to surface-

- Water Law No. 92 of 3 January 1992

- the
draft
decree
"amending"
the
decree
of
26 September 1985 relating to surface-treatment workshops
5.1

Decree of 26 September 1985

"The present instruction concerns workshops operating

with
- molten-salt bath treatments;
- the pickling, cleaning and preparing of surfaces".
Title 11 - "The prevention of water pollution must be a major
concern in the design, construction and operation of surfacetreatment plants, with regard to the Environment.
The least polluting treatment processes must be selected.
Recycling, recovery and regeneration techniques must be employed
as many times as is possible."
Art. 2 - Any discharge into the groundwater table, whether
direct or indirect (distribution, infiltration), total or
partial, is forbidden.
Art. 3 - It relates to the discharge limit values:
3.1.1 - The standards for discharge, in terms of
product concentrations, are defined as follows, in
mg/litre of effluent discharged:
Metals: Zn + Cu + Ni + Al + Fe + Cr + Cd + Pb + Sn = 15 mg/1
The following values must not be exceeded:
323

Cr 6+
Cr 3+
Cd
Ni
Cu
Zn
Fe

0.1 mg/l
3 mg/l
0.2 mg/l
5 mg/l
2 mg/l
5 mg/l
5 mg/l

Al

5 mg/l

Pb
Sn

1 mg/l
2 mg/l

Other pollutants are:

SM
CN"
F"

30 mg/1
0.1 mg/1
15 mg/1

NO

1 mg/1
10 mg/1
150 mg/1
5 mg/1

COD
Total hydrocarbons

Provisional derogations may be permitted if the best

known decontamination techniques do not allow these
values to be achieved.
3.1.2

Discharges must meet the following charac

teristics :
the pH must be between 6.5 and 9
the temperature must be less than 30C.
Art. 32 The amount of effluent must correspond to an
average level of less than 8 litres per square metre of
surface treated, for each necessary rinsing function in a
treatment line.
Art. 41 Automatic monitoring:
The operator must ensure that discharge from his operation
is automatically monitored.
324

The effluent shall be tested continuously before discharge.

Monitoring refers to both volumes and pH. The pH is measured
and recorded continuously. The recordings are archived for
a period of at least 5 years. The daily volume is recorded
on a recording medium provided for this purpose (archive
time: five years).
Title III - Prevention of atmospheric pollution
Art. 7 - Atmospheric emissions (vapours, gases, etc.) from
above the baths must, where necessary, be collected, etc.,
by means of the best technologies available before discharge
into the atmosphere.
Art. 11 - The limiting values for discharge into the atmos
phere are:
- total acidity (expressed in H + )
0.5 mg/nm3 (STP)
- HF (expressed in F")
5 mg/m3 (STP)
- C r total
- Cr 6+
- Alkalinity (expressed in OH")
- (N02)

mg/m3 (STP)
0.1 mg/m3 (STP)
10 mg/m3 (STP)
100 ppm.

In this field, the operator must also ensure that discharges

are automatically monitored.
Title IV - Waste
Art. 14 - this relates to all waste: sludge, spent baths,
salts, etc.
The waste from surface-treatment works must be disposed of
in a plant duly authorized for this purpose, according to
the laws on classified plants.
Art. 18 - The prefectorial decree may prohibit any method of
disposal which does not provide the best guarantees and
results in terms of environmental protection.

325

5.2

Water Law No. 92 of 3 January 1992

This law relates to the policing and management of

water. It strengthens the powers of prefects and mayors with
regard to preventing pollution and stipulates the punishments in
the event of pollution (Fines ranging from 2,000 F to 12 0,000
F) .
Imprisonment: 2 months to 2 years; the operator is
responsible for restoring the water environment.
5.3

Draft decree of 10 December 1992

This draft, which is highly contested by operators of

surface-treatment plants, tightens the limit values for elements
in discharges, even making them impossible to meet. This is
because the present draft forgets that any precipitated
hydroxide (Ni(OH)2 or Cr(OH)3) has a solubility product... (the
case for amphoteric compounds).
Limit values
Limit values
mg/l 1992 (draf
mg/l 1985
Al
Cd
Cr 6+
Cr

2
0.2

Cu
Sn

5
0.2
0.1
3
2
2

Fe
Ni

5
5

Pb
Zn

1
5

total

0.1
0.5
0.5
2
0.5
0.5
0.5

Most neutralization plants would then be obsolete, with

regard to the proposed limit values, precipitation using lime or
sodium hydroxide leading to hydroxides for which the solubility
product is not zero: in order to separate nickel quantitatively,
a pH of 9.5 must be reached; but at this pH, Al (OH) 3 redissolves
326

to give an aluminate.

5.4

EEC Directives

The EEC framework directive 80/1107/EEC of 27 November

1980 deals with protection from the risks associated with
exposure to chemical, physical and biological agents. The
permitted values for certain substances in the atmosphere in
places of work have been defined.
Limit value: LV (cm3/m3 or mg/m 3 ).
Two types of values are adopted:
short-term exposure limit values (SELV)
average exposure limit values (AELV).
These values are very important for two products :
asbestos; 0.3 to 0.6 fibres/cm3/8 hours
benzene; 1 ppm/8 hours.

5.5

Noise/Noise pollution

The European Directive 86/188/EEC (closeness to sources

of noise)
Background level at 45 dB
Daytime level at 70 dB
Night-time level at 60 dB
If the source of noise is close to an inhabited area,
these values are reduced by 10 dB.
327

Introducing a new machine must not create an emergence

of more than 3 dB with respect to the prior sound situation.
New regulations: these concern the "place of work":
daily sound exposure level (DSEL)
peak sound pressure level (PSPL)
Above the following thresholds:
DSEL = 85 dB
PSPL = 135 dB
individual measurements are mandatory.
From 1 January 1991, equipment suppliers must be in a
position to give the acoustic properties of new machines. In
tenders, it is therefore necessary, systematically to request
this information.

6.

HEALTH AND SAFETY AT WORK

The various regulations pertaining to health and safety

at work are dealt with at the end of the chapters relating to
the surface-treatment techniques:
- cleaning

(inhalation

of

solvents,

intoxication,

preventative measures, etc.)

- pickling (inhalation of acids, preventative measures,
etc. )
- colouring
- descaling.

328

BIBLIOGRAPHY

1.

EEC Bulletin
200 rue de la Loi - 1049 Brussels

2.

Guide de l'Environnement en Sidrurgie

[Guide on the Environment

in the Steel

Industry]

USINOR - SACILOR, May 1993

3.

Cahier technique de la prvention des pollutions

[Technical

notebook

on the p revention

Ministry for the Environment

Agence de bassin L oire-Bretagne

Brittany

of p ollution]
[Agency

for

the

Loire-

Basin]

4.

M. ROUSSEAU-ROCHEL L I
Traitements de surface [Surface treatment]
Galvano-Organo (1994), D e c , 997

5.

Bulletin

de

la

Fdration

Nationale

des

Syndicats

de

1'Assainissement

[Bulletin of the National

Associations]

Federation

of

Land-decontamination

Official Journal of the French Republic, 4 January 1992

6.

ADEME Bulletin
27 rue Louis Vicat - 75737 Paris

329

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European Commission
EUR 17248 Properties and service performance
Surface treatments for stainless steel state of the art
developments and trends
D. Henriet
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