Professional Documents
Culture Documents
*
**
*
*
European Commission
STEEL RESEARCH
European Commission
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
A great deal of additional information on the European Union is available on the Internet.
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
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.
Control of these operations requires understanding of the properties and mastery of specific advanced technologies.
1.1
1.1.1
1.1.2
PASSIVITY
1.2
1.2.1
10
1.2.2
11
13
1.3.1
- Iron-Oxygen Diagram
14
1.3.2
15
1.3.3
16
INDUSTRIAL SCALE
17
18
1.3
1.4
1.4.1
- Kinetic aspects
1.4.2.1 - Growth
21
mechanism
and
thickness
of
the
22
1.4.3
24
26
1.4.4
27
29
29
29
31
32
- Oxidation of
enviroTTmari t
stainless
steel
in
an
industrial
33
33
35
36
sures
1.4.5
depletion
phenomena
40
-
41
Fundamental aspects
1.4.6
42
43
44
47
1.4.8
49
1.4.9
- Anti-scale products
54
1.1. -
Disoriented region
Disoriented region
Onented region
Oriented region
j
Intact crystal
ADSORBED OXYGEN
MOLECULES
CHEMISORBED OXYGEN
ATOMS
>
SURFACE METAL
ATOMS
stability
of
the
chemical
bond
of
the
oxygen may
be
:o:
. L1." . 'i'.''
\ AAA A/
AAA
M.
Mv
MA/VW
\
A0VY\A
/ \/ \/ \/ \ / \ /
\ /
Chemisorbed oxygen
Oxide film
(1)
which
change
towards
(2)
(3)
thermody
TRANSPASSIVITY
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
)
11
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)
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
1200-
formed
mainly
between
475C
and
375C. The
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
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
Sound metal
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 -
f -
diffusion of cations
dizing atmosphere
g -
GAS O 2
0 2 2 0(ads.)
0(ads.) + 2 e" 0 s
M M z + + e-
METAL M
*** + 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
..
(5)
AGj = -RT In
= -RT In K
(6)
VPo 2
(7)
(8)
,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
20
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
Kinetic aspects
21
period of induction, O + A
period of formation, A > B, the weight
linearly with time
increasing
period of retardation, C.
T, lt
22
th.p
cr
S Diffusion
grows :
by diffusion of
magnetite;
(PAIDASSI21) .
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)
changes.
The
protoxide
changes
as
result
of
two
transformations :
the shrinkage of its field of existence
temperature decreases (cf. Fe0 diagram);
as the
4 FeO * Fe 3 0 4 + Fe
with precipitation of interfacial magnetite.
,Fe,0,
Fe304
Metal/scale
interface
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
Metal
b)
Layer of 3 0
at the metal/scale
interface
slow cooling;
partially decomposed
protoxide
25
overall
reaction
of
formation
of
an oxide may
xM + V4y02 -* M ^ y + AG T
be
(13)
c -
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
m.
*&
r r r z
m %
Spinel
.BO
Sol. Sol.
*? =v/pT
(14)
the various
oxides
formed depending
on the
(Fe,Cr) 2 0 3
F*0.(F.^r)203
F0
Mm^M Cr
c
23
'23
Fe-Cr a l l o y
(Fe,Cr)203 or
due
to
31
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
1.4.4
Oxidation
of
stainless
steel
in
an
industrial
e n v i * t-
However,
AISI 304
(25% Cr,
reaction
34
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:
35
% o2
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
Austenitic
steels
Continuum annealing,
2 to 2.58 02, 1100C,
2 =IL, va tax qaench
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
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
Ferritic
steels
Bogie-bearth furnace
annealing, 2 to 7-s o2
750 to 850"C, 2 to 4 h
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)
(16)
39
possibly
oxidizable
elements
are
Mn
and
Si, with
the
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.
(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
41
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
that nickel
increases
the diffusion of
Continuous annealing
Temperature: 1140C
Duration: 85 seconds
Furnace supplied with natural gas.
43
05
IO
15
Depth (um)
4
6
8
Depth (tim)
10
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
Inside
Outside
Edge
Edge
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
-SX\\\\\S\\\
I-++
-M-
Magnetite
+++
++
*-++
Haematite
Magnetite
Protoxide
Hot structure
Iron + Magnetite
Iron + Magnetite
46
non-uniformity between
edges
co|s
47
in
oxygen
"physically"
Cracks : two-dimensional
described
defects
in terms of a
which
appear
in
specific
micrograph
concept
allowing
evaluation
of
the con-
in the
scale.
(diallyl phthalate,
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
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
40
BO
120
160
200 240
280
40
80
120
160
200 240
280
diagrams
reveal
the
51
specimen of known
52
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
descaling
and
- 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
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
56
Parameters
Effects observed
Water vapour
Dilute oxygen
atmospheres
57
BIBLIOGRAPHY - Chapter I
1.
2.
3.
Ch
e m.],
J. BENARD
Oxydation des mtaux [Oxidation
of e
m tals]
Pub. GauthierVillars Paris, 1962
4.
5.
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
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
, October, 1983
21. J. PAIDASSI
Monographie sur l'oxydation du fer [Monograph
dation
of
on the
oxi-
iron]
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]
61
Corrosion],
and
silicat
e s]
(1975),
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),
64
CLEANING
CONTENTS
Page
1.
2.
69
1.1
59
1.2
71
2.1
7I
2.2
Thermal processes
71
2.3
Chemical processes
72
2.3.1
72
2.3.2
82
R7
2.4
Electrolytic cleaning
2.4.1
2.4.2
90
2.4.3
Plants
gi
2.4.4
Checking - Establishing a
specification - Quality assurance
2.5
2.6
3.
94
96
2.5.1
Microorganisms
96
2.5.2
Proteins
97
2.5.3
Lipases
97
2.5.4
CAMEX process
98
98
iQO
BIBLIOGRAPHY
103
USEFUL ADDRESSES
106
67
CLEANING
1.
CLEANING
1.1 The purpose of cleaning
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-|
Products discharge
time
Start of the reaction
. 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.
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
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
cleaning,
Detergent
Oil
surface to be cleaned
Metal
"xn_p
t
t t
73
Oil
Water
Lipophilic
chain
H dro n lic
y P '
group
Figure 3 - Adsorption of
the surface-agents2
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
C
R
T
=
=
=
=
CH, - (Oy,, - ( ) - SC V
Na
Cationic :
Nonionic :
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
b)
c)
d)
e)
80
Desludger - Deoilor
Block diagram
OD
Deconcenlrating
circuit
Ultrafiltration
module
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
83
Trichloromethane Perchloroethylene
CHC1-CC12
CC12=CC12
1.46
1.62
Boiling point
(760 mm of Hg)
87C
121C
58
14
F1ammabi1ity
none
none
Decomposition temperature
125C
145C
Formula
84
b)
c)
distillation
entrainment using steam, distillation of an azeotrope
(73C for trichloroethylene and 88C for perchloroethylene) and then separation of the solvent from the
water.
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
2.4
Electrolytic cleaning2'13'11
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
For water:
H20 H+ +
* + H20 H30* (hydroxonium ions)
c)
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
**cell
>
^reaction '
- 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
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/
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
- 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.
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
Mechanical action of 0 2
Short duration
Speed of ion transfer
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
2 pay-offs
1 shear cutter
1 welder
Treatment
Output
Shear cutter
2 take-ups
Fluid circuit
Effluents
92
^=8=
^^--U^-U-tf-^^^i
5t^vvV77/^^
ELECTROLYTIC TANK
DTANK
PAYOFF
U3
#P^^^^^uS
7"*/ / V / C 7 * 7 r / ' 7 ^~/~7
Mi
/ / =
/
2nd i BRUSHING UNIT
DRYERS
TENSIONER
/
/
/
/
TAKE-UP
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)
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.
activity % =
100
using
activity % =
100
b)
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
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
Glycerol
+ 3H*
/}
\>-
Fatty acids
Rj, Rj, Rj are identical or different organic radicals, possibly containing long chains
97
2.6
3.
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
101
LIST OF FIGURES
LIST OF TABLES
Table I
Table II
- Modern hydrocarbons
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.
6.
C. LE BORDAYS
Surfaces, No. 159, 64
7.
[Surface
for
the
[Surface
treatment
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.
13.
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-
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]
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
CFPI
2 8 Bd Camlinat
92233 GENNEVILLIERS
- Fax 610626
Dow Chemicals SA
42 rue Emeriau
75723 PARIS CEDEX
- Fax 200677
FRAPPAZ
23 alle du Mens
69606 VILLEURBANNE CEDEX
- Fax 72 04 48 48
PENN CHIMIE
3 Impasse du quai de l'Industrie
91200 ATHIS-MONS
- Fax 60 48 02 85
TEC'S
8 rue du Languedoc
BP 423
95005 CERGY PONTOISE
SOLVAY et Cie
12 Cours Albert 1er
75383 PARIS CEDEX 08
- Fax 45 63 57 28
For recovery:
CARBONE-LORRAINE - Chemical Engineering Department
Tour MANHATTAN Cedex 21 F92005
PARIS-LA DEFENSE
- Fax 33.1.47.73.55.54
106
DESCALING
CONTENTS
Page
1.
DEFINITION - OBJECTIVE
109
2.
109
110
....
no
HO
2.1.3
113
2.1.4
Skin pass
114
2.1.5
2.2
115
Shot peening
115
2.2.1
Principle
115
2.2.2
2.2.3
116
. .
120
122
. .
123
RECENT IMPROVEMENTS
121
121
131
3.2.1
Principle
131
3.2.2
3.2.3
131
133
135
3.2.5
Raw materials
136
3.2.6
Existing plants
13 6
107
137
140
140
ENVIRONMENTAL ASPECTS
142
USEFUL ADDRESSES
145
LIST OF FIGURES
146
BIBLIOGRAPHY
147
108
DESCALING
1.
DEFINITION - OBJECTIVE
2.
Descaling
actions :
processes
involve
109
the
following
mechanical
2.1
2.1.1
2.1.2
Movable descaling
roll
Planishing rolls
Pay-off mandrel
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)
/
of three
by support
and cracks
the outer
rolls of
rolls. It
the scale
fibre and
113
To the output
S-block
Overlap
To the input
S-block
Tensioner
Tensioners
OD PO
r
*77777
W777Z
114
Shot peening
2.2.1
Principle
115
2.2.2
a)
Important
peening
parameters
associated
with
shot
b)
1mm
criteria
116
are
taken
into
account
when
Shot velocity:
rotor
blades (generally 4, 6 or 8)
Injection cage
CI
intensity curve
sheath of trajectories
relative intensity of shot peening
depending on the trajectory locus
.J
inpact
trajectories of the particles
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)
UA.
\J~
* > M W S**JVsV
round shot
b
spherical impression
">y^"
angular shot,
angular impression
blasting velocity
shot
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
Purpose :
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
0,5
2 to 6
depending on the
steel tested
Permanent strain
imposed
where
D +d
d =
D =
brush
121
working
with
adjustable
Weaknesses
2.2.4
Hydraulic descaling
so as to
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.
Work sequence
Peripheral velocity
(m/s)
Rough grinding
25 - 30
Ceramic binder
Rough grinding
45 - 65
Rough grinding
80
Surface grinding
18 - 25 - 63
Internal grinding
20 - 50 - 63
Grinding
28 - 50 - 63
Centreless
30 - 63
Between centres
We therefore
distinguished:
-
cleaning grinding
pregrinding
finish grinding
fine grinding.
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
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
for
- 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
3.
RECENT IMPROVEMENTS16'18'19
3.1
SIMON-HOUGARDY Process16
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|
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
129
Fixed feeding
head
Oscillating
feeding head
Connecting
rod
Nozzle
#*rA wwmmzsM
Figure 13 - Industrial prototype with rotary seals3
130
3.2
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
Step 3:
Step 4:
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
2. Descaling
Scale
Metal
Metal I
3.2.3
ring
comprising
six orifices
acting
as
the
the
the
the
the
- the
Pressurized supply
Helix angle
3.2.4
Descaling parameters
Degree of descaling, %
200
100
0.2 0.4 06 1
1.6
Blasting time, s
135
3.2.5
Raw materials
=]
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
~3ffp
Classifier
f ,1,' .'
Precipitation
and settling
Filtration
I* /.'J
t<ft
" "
3.2.6
E xisting pianti
3.2.7
Advantages:
3.3
3.3.1
Principle
3.3.2
Realization
137
138
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 :
- no dust
Drawbacks:
3.4
Descaling
using
molten
salts
Thin-film
(spray)
4.
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
yt
y2
y3
y*
y5
5.
ENVIRONMENTAL ASPECTS
Descaling
Shot peening
- Plant depreciation
- Purchase of shot
- Plant depreciation
- 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
- 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
146
BIBLIOGRAPHY
1.
2.
3.
4.
5.
6.
O. NOE
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.
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.
17.
Review]
stainless
guide
on
of
flat
steels]
D. QUANTIN
In "Le dcapage des produits plats [The pickling
products] "
CESSID Notebook, 1983
19.
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.
148
Pickling
PICKLING
Contents
1. GENERAL COMMENTS: Definitions - CHEMICAL REACTION ENGINEERING - REACTOR DESIGN
153
153
156
157
162
168
168
172
172
173
2.2 Descaling
2.3 Roughing
I74
174
182
187
187
188
190
198
151
198
199
202
209
210
214
222
230
230
23 0
23 0
2.4.2.2
2.4.2.3
2.4.2.4
2.4.2.5
world
946
2.4.3 General theory - Mechanisms proposed
...
OCT
253
259
2 64
152
1.
GENERAL COMMENTS:
Definitions
ENGINEERING - REACTORS DESIGN
CHEMICAL
REACTION
153
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
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
Geometric structure
o f
" "*=tor
b)
c)
d)
(kinetic
155
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
(AH R ) T
is
expressed
in
joules and
h^A^
denotes
the
2)
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
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
rate
rate
rate
rate
rate
of
of
of
of
of
the
the
the
the
the
=
=
=
=
=
fmx
fn^
fm sol
fox sol
fox ins
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
Anions
Evaporation
fc
159
jl
Fjj
VR =
Rj
Fj 0
RRj =
jO
= input flux
volume of the reagents
= chemical reagents
= output flux
and
n? = Fjodt
160
Supply
reservoirs
I *> * L
incoming
flux
flow
rate
relating
to production
- . * /,
Va
outgoing
flux
rate
of
accumulation
requires
161
S-CM
(a)
(b)
(c)
K k k k
>NKNNKSE'Z
CM
V^fsfNTslSlsisj*^.
(constitution composition
potential,
163
an
example
of
1
Preliminary
Mechanisms
S t o i chi on try
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
:..-tor
of a
pilot plant
Environment
Pollution
1'
Rates - Yield
Assessments
Automation
Preparation of the
programs
Additional analyses
Preparation
Supply of metal
and reagents
of the
Ron speed
final
I
t
design
By-products
Purification
\
Resistance and properties
of the materials
Design of the
industrial reactor
Automation
"
Construction of the
industrial reactor
ENVIRONMENTAL
problems
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
165
BIBLIOGRAPHY
General Points
1. J. VILLERMAUX
Gnie de la raction chimique. Conception et fonctionnement
des racteurs.
[Chemical reaction
engineering.
reactors]
4. R. NICOLLE
Le Gnie des procds dans: Le livre de l'acier
[Process engineering
in "The steel
167
book"]
operation]
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
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.
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
Pickling
Passivation
Rinsing
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
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
2.2
to nonhas
its
contrast,
and may
Descaling
173
2.3
Roughing
Roughing is the first pickling operation.
*
and
safety
1.6 to 4 M/l
Temperature range
55 to 95C
Strengths:
- efficacy
- low cost
Weaknesses :
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
Weaknesses:
Improvements :
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:
1.5 to 3 M/l
0.5 to 2.5 M/l
Temperature: 40 to 60C.
Strengths:
HP role:
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
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)
- 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
Fe + + +
Fe +++ /Fe ++
1 to 2.5 M/l
2 to 3 M/l
60 to 65C
> 20 g/1
> 4
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
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
181
2.3.2
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
183
BIBLIOGRAPHY
Roughing
1.
[Metallurgy
Review]
, 415, March,
1995
2.
3.
4.
SCANACON Ltd
Box 36, 17221 Syndbyberg, Sweden
5.
D. HENRIET, L .
C. SCHOENHUT
MEUNIER,
A.M.
PRAT,
M.A.
CUCHEVAL
and
.
BOUSQUET,
P.
BOUHIER,
H.
G. KACZOROWSKI and M. VILLERET
GIRAUD,
D.
HENRIET,
8.
9.
10. L . L ACOURCEL L E
Galvano-Organo, 737, Oct., 1995
11. European Patent 91400252.2
185
186
2.3.3
2.3.3.1
b)
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
,
log K_ = E l E2
0.058 n
+ 2e
NO;
+ 02"
187
- Cr0 3 + 3N0 2 t
Chromate :
Cr 2 0 3 + 4NaOH + 3/202
-* 2Na 2 Cr0 4 + 2H 2 0
this high-
2.3.3.2
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
MP = 670C
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
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
oxides
(or mixed
chromium-iron
oxides)
are
baths
are
very
effective
but
their
use
proposed
by
Russian
researchers
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
leaving
the
furnace,
the
sheet
is
sprayed
with
used
for
the
pickling-annealing
of
austenitic
steels.
Deposition
of molten
salts
sheet to be pickled
furnace
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)
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
number,
arrangement
and
performance
of
the
injectors
a patent filed by Kawasaki
sheet
in
concentrated
(CaCl2) , drying
it
in
an
aqueous
oven
solution
and
of
salts
then passing
it
194
(mixture of CaO
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
fondus. [Chemical
reactions
les
in solvents
solvants
and molten
J.D. MACKENZIE
Chem. Rev. (1956), 56, 455
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
the
laws
of thermo-
polarization
provides
the
following
- dissolution
caused
by
the
effect
of
the
external
FeOH+
this
reaction
requires
prior
pickling
an
is
199
example
mostly
of
current-density/
carried
out
under
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
200
.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-
(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)
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?
202
Electrodes . ^
Electrolyte
.
*^M
a)
Electrolytic pickling
process)
in neutral medium
(RUTHNER
G
NojSO,
S O / - 2'
H.O
+ ++
OH-, Ot>
H*, H,
20-22Na*SO<'
H*,H 2
OH-, O /
i
H*, H /
OH-, O /
+ ++
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
205
proposed
by
In cathodic mode:
2Na+
Na 2 S0 4 -* 2Na+ + S0 4 "
+ 2H20 + 2e" -> 2NaOH + H2t
4H2O
_ HCr0 4 + 7H + + 3e"
is
pointed
out
that
two
dissolution
phenomena,
207
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
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
respect
to a
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,
211
material to be pickled
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 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
using
parameters)
low pollution compared to other processes.
are as follows:
-
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.
electrolytic
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:
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
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
17
60 sec
600
304
17
60 sec
2000
430
17
60 sec
550
304
17
60 sec
1200
430
17
120 sec
1100
304
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
17
120 sec
550
430
600
60C
Fe 2 (S0 4 ) 3
100 g/1
60C
218
Treatments
Solutions
(g/D
Immersion or
electrolytic
treatments in
acid baths
Electrolytic
treatments in
baths of
ferric salts
HN03/HF
70/5
H 2 S0 4
230
HCl
100
HF/H 2 S0 4
10/230
80C HN03/HF
HC1/HN0 3
300/100
X
Pickling power comparable to HN03/HF
60C Pitting - Environmental problem
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
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
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
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
221
200 g/1
40C
situ
generation of H 2 S0 4
222
form
of
hydrated
precipitates
therefore
depend
on
the
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.
7.
Dcapage
des produits
plats
[The
pickling
of
flat
of
flat
products]
CESSID Seminar, Maizires-les-Metz, 1983
8.
227
9.
D. HENRIET
Les traitements de surface des aciers inoxydables
[Surface treatments for stainless
steel]
steels]"
Publications]
11.
12.
13.
14.
15.
S. HASUNO, M. ISHIKAWA, M.
S. SHIIBA and T. SHIOKAWA
MURABAYASHI, Y. YAMAGUCHI,
17.
H. HUGDAHL
Wire J o u r n . I n t e r n .
(1985), J u n e ,
228
62-67
18.
19.
Y. UBARA
Published in ISIJ (1990), Vol. 31, 771
20.
229
2.4
2.4.1
in a
2.4.2.1
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"
the replacement
of
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
234
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
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
2.4.2.3
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
2.4.2.4
Other processes
the
potential
239
makes
such
stabilization
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
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
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
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)
Low pickleability in
roughing bath
It is necessary to
increase the HF concentration
Fe+++/air
22,
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)
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)
Fe +++
22
HF (1 to 2M)
Good pickleability
Precipitation of CaF2 and
sulphates
HF is excellent as a
complexing agent
HNO,
Good pickleability
HCl
(Fe++)
H 2 S0 4
In combination with:
Table 3
243
Acid, alone
or in cambi nation
HCl
Strengths
Weaknesses
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
H 2 S0 4
Effective as a roughing
bath
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
Fe + + +
Pickleability enhancement
Redox control
Pyrolysis of the bath
(of benefit to the
environment)
Table 5
245
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 .
acid
infiltrates
via
248
300mV(//Ag/AgCI)
HN03
HF
F 40g. I
Time (seconds)
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.
scale residues
J.
%>>
250
^H*
Cc
Ca
Eredox
E
=
=
=
=
=
=
t
A
to
f[(Ps)
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.
2.4.5
Methods used
pickling
for
studying
and
investigating
with
the
naked
eye:
brightness
and
glow-discharge
first rank. It
obtained very
nanometres to
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
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
(the included
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
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
2.4.6
Passivation
259
Logi
r
Ho
PASSIVITY
TRANS
PAssrviTY
PRE
PAssrviTY
Simplified
known
'
mechanisms
have
been
proposed
and
it
is
structure,
+ ( H + ) s + 2e"
structure, H 2 0MH 2 0,
ending
up,
after
towards
deprotonization,
oA/OHj
Sit"'
^^O
UnHj u n
(H?0)
OH,OH2
O^OH:
261
evolves
the
with
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
H 2 O 2 (50%)
2.4.7
Brushing
The aim of brushing is to make it easier to detach the
oxides and salts deposited during pickling.
264
the presence
of
a back-up
roller.
Water
is
injected
at the
and
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
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
- 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.
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
In-laboratory
inspection:
this
involves
inspection
268
BIBLIOGRAPHY
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 -
3.
4.
5.
. CHETREFF
Le dcapage des produits plats
[The pickling
of flat
product
s]
Les Cahiers du CESSID [CESSID
Notebook
s]
IRSID, 1983
6.
7.
B.
BOUSQUET,
P.
BOUHIER,
H.
GIRAUD, D.
G. KACZOROWSKI and M. VILLERET
International Rolling Congress, Deauville, 1987
269
HENRIET,
8.
9.
M. POURBAIX
Atlas d'quilibres lectrochimiques 25C
[Atlas of electrochemical
equilibria
at 25C]
European Patent
EP 582,121 Al
11.
12.
13.
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.
17.
D. QUANTIN
CESSID Notebooks: Pickling of flat products, 85-102, 1983
18.
270
19.
20.
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.
24.
[Standard
methods
of surface
characterization]
R. BERNERON
Spectrochimi Acta, 1978, 33, 19, 665
27.
[Communication,
Autumn Metallurgy
Workshop]
28.
N. PHILLIPS
Trainee Report
IRSID SCA 90/144, August 1990
29.
271
Paris, 1990
Publications]
30.
31.
G. OKAMOTO
Corrosion - Sci (1973) 13, 471
32.
33.
34.
E. PRAT
Le Dcapage des produits plats [Pickling
IRSID, CESSID Notebook, October 1983
35.
of
flat
products]
[The technical
evolution
pickling
lines]
in high-performance
SACK Documentation
272
continuous
HISTORICAL BACKGROUND
3.2
Preliminary operations
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
4.2.2
4.2.3
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
4.4
Painted
Varnish
stainless
steels
4.3.2
- Lacquering
4.4.2
5 -
molecular
INSPECTION METHODS
5.1
5.2
Physical methods
5.3
Electrochemical
or
physico-chemical
quantitative analysis
6 -
7 -
274
methods
of
enamels, etc.
- or
to enhance
the passive
film exposed
to inter-
ferential phenomena.
276
Is
it
necessary
to
colour
stainless
steels?
Is
have colored
waiting for
stainless
it".
steels
because
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:
- austeno-ferritic steels
3.2 - Preliminary operations
(alkaline
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
JS)
Immersion
in
sulphuric
280
acid/chromic
acid/manganese
sulphate mixture:
-
H2S04
18N
H2Cr207
90
g/1
MnS0 4
20
g/1
50% by weight
50% by weight
[Technologies
for
the Engineer],
M 1514).
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
The
quality
of
the
coloured
film depends
on many
283
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
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
20 g/1
H 2 S0 4 (r.d. = 1.84)
200 ml/1
H 2 0 qs
1000 ml
4.1.4
Hybrid
medium and
processes
described
in
The Inco
process22'23'2*'25
(for
example
obtained
by
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
288
COLOURING
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
The WELCOLOR
process 26
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
(1985)
HF/HNO3 Activation
Oxidation
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
Japanese
companies
Kawasaki Steel
and
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
the "TEMPER
Nippon Stainless
4.2.4.6
this
is
stainless
steel
4.3.1
Painted
stainless
steels
- lacquering
varnish
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
4.4.1
Physical
vapour
deposition
(PVD)29'31
4.4.1.1
Ion plating3
Sputtering29
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
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
Inner cathode
\.
Substrate
Outer cathode
299
Examples of application
- colouring of dental prostheses
process)
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
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
hL
SHEET
I-El \
CA-HnPF
.A.ICPE.
li
Chemical
vapour
deposition
(CVD) 37
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
hydroxides
at pH
8.5
9.5
306
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
b) Motor-vehicle industry
decorative trim
c) Homecraft/hygiene
d) Pharmaceutical industry
and surgery
e) Roadway equipment
road signs
f) National defence
307
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
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.
3.
4.
5.
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.
9.
J.R. CONNER
Belgian Patent (1963), No. 619,691
10.
SMITH
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.
16.
C E . NAYLOR
Piating (1950), 37, 153
17.
18.
C. BATCHELLER
United States Patent (1940), No. 2,219,554
19.
20.
21.
Inco process
Stainless Steel Industry (1982), 10, No. 53
22.
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.
28.
29.
30.
G. DEARNALEY
Electroplat. and Met. Finish., 6, Sept., 1976
31.
J. MACHET
Les Techniques de
Engineer]
M 1663
l'Ingnieur
[Technologie
s
32.
33.
P. de GLIS
for
the
. PIESSLINGER
Stahl Eisen
[Iron
and Steel],
FRG,
35.
POLISPECTRAL process
Marketed by Mcachim, 86600 Lusignan
36.
1095
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
318
319
313
323
323
326
326
327
327
328
BIBLIOGRAPHY
314
1.
ORGANIZATION
1.1
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-
- visit
classified
plants periodically
in order
to
Water Agencies
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
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
3.
Community
3.1
318
3.2
problems
are
dealt
with,
within
the
b) DirectorateGeneral XI:
The E nvironment,
Safety and Consumer
tion.
Nuclear
Protec
c) DirectorateGeneral XII:
20 0 rue de la Loi
1049 BRUSSELS
4.
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:
-
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.
- Abrasion.
Brightening and polishing: polishing wheels
321
Transformation or treatment
Pollution
operations
Hot rolling (HR)
Wire drawing
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
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
Fume scrubbing
Chromium-depleted
Neutralization
Hydroxide precipitation
Acid pickling
Reducing agent or oxidizing
agent
Fume scrubbing
Neutralization
Neutralization of the solutions or
F-,
recovery of Ni
Sludge treatment
NO;
Fume scrubbing
Neutralization
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
322
5.
to surface-
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
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
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
mg/m3 (STP)
0.1 mg/m3 (STP)
10 mg/m3 (STP)
100 ppm.
325
5.2
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
to give an aluminate.
5.4
EEC Directives
5.5
Noise/Noise pollution
6.
(inhalation
of
solvents,
intoxication,
328
BIBLIOGRAPHY
1.
EEC Bulletin
200 rue de la Loi - 1049 Brussels
2.
in the Steel
Industry]
[Technical
notebook
on the p revention
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
Federation
of
Land-decontamination
ADEME Bulletin
27 rue Louis Vicat - 75737 Paris
329
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EUR 17248 Properties and service performance
Surface treatments for stainless steel state of the art
developments and trends
D. Henriet
Luxembourg: Office for Official Publications of the European Communities
1997 II, 329 pp. 21.0 x 29.7 cm
Technical steel research series
ISBN 92-827-6941-0
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