12.

1 Basics

Institut fr Eisenhttenkunde
der RWTH Aachen
Topic 12:
Development of Technical Surfaces
Prof. Dr.-Ing. Wolfgang Bleck

Process steps and their impact on surface

12.2 Oxidation and Pickling

Scale build up during hot strip processing
Pickling reactions

12.3 Gas - Metal Reactions

Batch annealing and continuous annealing
Surface reactions during batch annealing

12.4 Rolling
Surface topography
Texturing methods

Outline

12.1 Basics
Process steps and their impact on surface

12.2 Oxidation and Pickling

Scale build up during hot strip processing
Pickling reactions

C.C.

Hot-Rolling

Temper
Rolling

Pickling

Cold Rolling

Batch
Annealing

Continuous
Annealing

Hot-Dip
Galvanizing

Electrolytic
Galvanizing

12.3 Gas - Metal Reactions

Batch annealing and continuous annealing
Surface reactions during batch annealing

CoilCoating

12.4 Rolling
Surface topography
Texturing methods

Shipment

Outline

slab casting: solidification structure, oscillation, non-metallic inclusions,

cracks, scale build up
hot rolling: scale build up, surface enrichment/depletion of elements, roll
contact, descaling

Processing of cold rolled steel strip

Manufacturing
stage
Reheating before hot
rolling
Acid pickling,
followed by oiling

pickling: reaction with acids, mechanical treatment of scale

Indigenous factors
(originating in the
base metal)
Diffusion to the surface
Selective Oxidation
Rolled-in scale
Redeposition of Cu, Ni
Elements left at the
interface (C, As, P)
Residual scale
(insufficient pickling)
Surface roughness
(pitting, overpickling)

temper rolling: mechanical roughening due to roll contact

surface coating: reactions with molten metals, metallic electrolytes, glass
melts organic substances

Cold rolling

cold rolling: roll contact, abrasion, reaction with lubricants

batch/continuous annealing: gas-metal reactions, selective oxidation,
segregation of alloying elements

Annealing
(batch, or continous
after electrolytic
degreasing)
Skin-pass

Segregation of
elements
Selective oxidation
(internal and external)
Mn, Si, Al, Cr, P

Development of technical surfaces

Exogenous factors
(originating in the outside
medium)
Mechanical defects (scales,
slivers, roll-marks)
Residual inhibitors
Oil
Salts from the bath (Cl-, SO42-)
Ca (rinsing water)
Roughness due to skin pass
Diverse contaminations (C,
iron oxyhydroxide film)
Aging of the oil during storage
before cold rolling
Polluted oil from the rolling mill
Oil cracked in the roll-gap
Fine abraded Fe particles
Metallic soaps
Final roughness, depending
on rolls and lubricant
Silica gel, if electrolytic
degreasing
C (cracking of oils)
Ca, S, N from cold-rolling oils
and additives
Dry skin-pass: repetitive
marks, roughness of rolls
Wet skin-pass: pollutants
already present + additional
organic compound, giving a
uniform layer
No marking of the sheet

Indigenous and exogenous factors

Most metals are thermodynamically unstable in presence of

oxygen ions and tend to oxidize. Electrons are released which
changes the oxidation state of the elements.
Examples:
Fe
>
Fe2+ + 2e2+
Fe
> Fe3+ + 1eZn
> Zn2+ + 2eThe reaction between iron and oxygen can lead to three
possible types of iron oxides:
FeO
Fe3O4
Fe2O3

wustite
magnetite
hematite

(Fe2+)
(Fe2+, Fe3+)
(Fe3+)

The iron oxides wustite, magnetite and hematite have

different physical and mechanical properties.

Color

Melting
temperature
(C)

Density
(g/cm)

PillingBedworth
ratio
Coefficient of
(volume
thermal
of oxide /
expansion
volume of
iron)

Thermal
conductivity
(Cal/K.mole)

5.24

2.14

9.6 13.9*10-6

0.035 to 30C

25

36

Fe3O4

black

1600

5.18

2.10

8*10-6

36.3

48

178 at room
temperature

FeO

black

1371 - 1424

5.52 7.50
(depending
on vacancy
content)

1.83
1.67

11*10-6
independent of
temperature

11.5

14.2

90 to 200

Physical properties of iron oxides

volume of ironoxide
volume of iron

Pilling-Bedworth-Ratio (PBR)

Sauerstoffgehalt

Temperatur

1400

54

56

60 Atom-%

flssiges Oxid +
Sauerstoff

flss. Oxid +
Magnetit
I
G
H
N J
-Eisen +
Magnetit
flss. Oxid

B -Eisen +
flss. Oxid

58

flssiges Oxid

R` R
Y

Electrical
conductivity
(W-1.cm-1)

Room temperature

52

to
1000C

Brown/red
(in divided
form)
Black (bulk
form)

Hardness

flss. Eisen
50
1800
flssiges
C
Eisen +
flssiges
Oxid
1600
A

to
25C

`Fe2O3

Oxidation of metals

PBR =

Specific heat
(Cal/cm.s.K)

Magnetit+
Sauerstoff
Z

Vickers
kgf/mm

Mohs

Fe2O3

P 9861219

5 to 6

Fe3O4

M 500
P 690

FeO

P 388

E
Youngs
modulus
10 kgf/m
M 23
P 21.4
30.5
M 21.7 to
24.7
P 23.5
P 12.6

800C
Ultimate
tensile
strength
kg/mm

G
Shear
modulus
10
kgf/mm

Hardness
kgf/mm

M 8.6 to 9
P 9.4 to 9.6

M 8.9 to
9.9
P 9.3

GFeo=GFe/2

P 30

P 0,11
0,12

P 0.12
0.25

P 2.5
3.4

Youngs modulus
10 kg/mm
Tension

Yield strength
kg/mm

Compression Tension Compression Tension

P 9.6 10.7 P 3 3.7

Mechanical properties of iron oxides

Wustite (FeO) is thermodynamically unstable below 570C.

At higher temperatures a more exact specification for the
stoichiometric composition is Fe1-xO (x > 0), due to the wide
range of the wustite phase region.
Hematite (Fe2O3) and magnetite (Fe3O4) are also stable at room
temperature.

1200
Wstit

-Eisen +
Wstit

Wstit +
Magnetit

1000
L
800

Magnetit +
Hmatit

In thermodynamic equilibrium an oxide layer consists of 3

superposed layers:

-Eisen +
Wstit

600
Q
-Eisen + Magnetit
FeO

400
0 0,2 0,4

22

24

Fe3O4
26

Fe2O Z`
28

Fe / FeO / Fe3O4 / Fe2O3 / O2

30 Massen-%

Sauerstoffgehalt

Fe-O phase diagram

Oxide Layer

During casting, hot-strip processing and annealing treatments

scale builds up. Scale is the product of a high temperature
corrosion reaction in oxidizing atmospheres. Thickness and
composition depends on the process properties.

Scale thickness is a function of temperature and follows

(if diffusion controlled) a parabolic law:

Example: Scale in the pusher type funace consists of

D = Kt

Scale from slab casting + new scale from slab reheating

D = thickness, t = time, K = constant

Scale

Scale thickness

Material loss resulting from scale, kg/m2

12.1 Basics
Process steps and their impact on surface

1310C
3

12.2 Oxidation and Pickling

1250C

Scale build up during hot strip processing

Pickling reactions

1200C

12.3 Gas - Metal Reactions

1150C

Batch annealing and continuous annealing

Surface reactions during batch annealing

1100C

1050C
975C
925C
875C

0
0

12.4 Rolling
3

Time, h

Surface topography
Texturing methods

Material losses resulting from scale

Outline

Scale build up in slab

reheating furnace

thickness ~ 3 mm

Scale build up during hot strip processing

Scale build up in
roughing stand

thickness ~
0.25-0.75 mm

Scale build up at different temperatures

Scales, build up during hot rolling process, can be classified

into three types:
Primary (furnace) scale
(during slab reheating, 1200 - 1250C)
Secondary scale
(during hot rolling, 850 - 1150C)

Primary scale builds up during reheating of already oxidized

slabs to 1200 - 1250C.

Typical thickness is about 3 mm.

The scale does not have the equilibrium composition due to

the reaction with scale which build up during the slab casting
process.

The primary scale is removed by water pressure before the

first pass.

The scale is a function of temperature, time and reactions

Tertiary scale
(during cooling, < 750C)

between the different oxide phases

Scale types

Secondary scale builds up during hot rolling. Especially the

scale which develops during roughing operation (high
temperature revese rolling) is an important process parameter.

formation at 1000 - 1150C, mostly FeO

At high temperatures the secondary scale (thickness about
0.2 mm) acts as lubrication during forming.

The secondary scale is removed by water pressure before

entering the finishing train.

Secondary scale

Primary scale

Tertiary scale builds up after finishing during the cooling

process.

Composition of ternary scale depends on cooling rate and

coiling temperature.
Example:
Coiling > 570C: Fast FeO-growth and decomposition during
slow cooling
Fe1-x O Fe1-yO + n Fe3O4 (y < x)

FeO

Fe3O4 + Fe (eutectoid wustite decomp.)

Tertiary scale

Hot rolling of silicon containing steels can lead to the formation

of a red scale. This is caused by a silicon enrichment at the
Fe/FeO interface at temperatures > 1170C.

Scale contains the phase Fayalit (Fe2SiO4)

Easy to remove at high temperatures because of liquid scale
Critical at low temperatures because of strong adhesive
strength due to the formation of silicates

Red scale formation in Si steels

Transport mechanisms
in different scale types

Phase diagram SiO2 - FeO

Effect of red scale on roughness

12.1 Basics
Process steps and their impact on surface

12.2 Oxidation and Pickling

Scale build up during hot strip processing
Pickling reactions
Pickling line (Neuwied)

12.3 Gas - Metal Reactions

Batch annealing and continuous annealing
Surface reactions during batch annealing

12.4 Rolling

total length
thickness (hot strip)
width (hot strip)
speed (max.)

Surface topography
Texturing methods

Pickling line (Andernach)

190 m
1.5-5.0 m
610-1630 mm

entry section
270 m/min

pickling section
160 m/min
HCl
20-120 g HCl/l
65-75 C
3000 kVA

etchant
concentration
temperature
input power

speed (max.)

207 m
1.5-3.0 m
600-1250 mm
entry section
610 m/min

etchant
concentration
temperature
input power

pickling section
245 m/min
H2SO4
15-25 %
100-105 C
4800 kVA

Pickling lines

Outline

Potential E/SCE in mV

1. Acid filters through micro-cracks in the magnetite

total length
thickness (hot strip)
width (hot strip)

-400

+300

Fe3O4
a

FeO

20 m

Metal

a
b

2. Dissolution of FeO below the magnetite

3. Acid reaches the metallic surface and attacks the iron

Scale
before
pickling

The acid filters through

micro-cracks in the
magnetite

Dissoltion of FeO
beneath the magnetite

The acid reaches the

scale/metal interface and
attacks the iron, creating
a hemispherical pit

Absence of preferential
dissolution at the
scale/metal interface

Metal surface
after pickling

c
d

e
f

reddish
flakes
beak off
Time,t

3-step pickling reaction

Potential-time-curve
of a pickling reaction

Hydrochloric acid + iron oxides:

2 FeCl3 + 3 H2O
Fe2O3 + 6 HCl
Fe2O3 + 8 HCl

2 FeCl3 + FeCl2 + 4 H2O

FeO + 2 HCl

FeCl2 + H2O

a high amount of wustite

a thin scale
a lot of micro-cracks and pores
... are reducing the necessary pickling time!

Hydrochloric acid + iron:

Fe
+ 2 HCl

FeCl2+ H2

Factors influencing the pickling

process (mild steels)

Reactions

10.04

Light intensity (AU)

8.03
Cu
6.02

Fe
Ni

4.02

2.01
As
0.00
0.00

0.64

1.29

1.93

2.57

3.21

3.86

Erosion time (s)

GDOS-profile of a hot rolled

and pickled steel surface

Necessary pickling time

12.1 Basics

Weathering steel, best-known

under the trademark Cor-Ten
steel, is a group of steel alloys
which were developed to obviate
the need for painting, and form a
stable rust-like appearance if
exposed to the weather for
several years.

Process steps and their impact on surface

12.2 Oxidation and Pickling

Scale build up during hot strip processing
Pickling reactions

12.3 Gas - Metal Reactions

Batch annealing and continuous annealing
Surface reactions during batch annealing

12.4 Rolling
Fulcrum (1987) by Richard Serra, is a site
specific sculpture commissioned for the
west entrance to Liverpool Street station in
the Broadgate complex.

COR-TEN

Surface topography
Texturing methods

Outline

batch-type annealing furnace

continuous annealing line

batch annealing process

700-850C

Cold rolling mill

continuous annealing line

ca. 10K/h

<150C

ca. 50K/h

10-100K/s

temperature, C

1
5

temperature, C

<720C

>10 K/s
300-400C
1000K/s
<40C

<40C

1)
2)
3)
4)

batch-type annealing furnace

cooling
temper rolling mill
recoiling, trimming, inspection, oiling

5)
6)
7)
8)
9)

cleaning
annealing
cooling
temper milling
trimming, inspection, oiling

Batch annealing and

continuous annealing process

heating

soaking

1. cooling

2. cooling

heating soaking 1. cooling 2. cooling

overaging
time, <10min

time, up to 4 days

Temperature cycles for batch annealing

and continuous annealing

12.1 Basics
Process steps and their impact on surface

12.2 Oxidation and Pickling

Scale build up during hot strip processing
Pickling reactions

12.3 Gas - Metal Reactions

Batch annealing and continuous annealing
Surface reactions during batch annealing

12.4 Rolling
Surface topography
Texturing methods
Quelle: www.msm.cam.ac.uk

Batch Annealing Furnaces

Name
HNX

composition
N2, 2-7% H 2

function
prevent oxidation

dewpoint: -40C

prevent decarburization

20C
DX

N2, 12% H2, 10% CO, 5%

Outline

comment

prevent oxidation

CO2, 0,5% CH4

carburizing
atmospheres

100% H 2

CO, CO 2, CH4 u.o. C3H8,

Isotope

B
P
S
Cr
Fe
Ni
Zn

11
31
33
52
56
60
66

outdated, problems
with cleanliness of
strip surface

H2

Element

decarburization

prevent oxidation

short annealing time

cleaning

(thermal conductivity)

carburizing

H2O, H2, N2

mixture
solids
xylene/ethanol
/water (total)
<47-64
<0,8-4
<70-210
51-72
200-400
<3-6
50-106
<4-724
29000-74000
2-42
93-150
11-182
87-120

vacuum
air

78% NO 2, 22% O2

Annealing atmospheres

oxidation

composition of lubricating film

after cold rollling in g/m

Measurement of gas composition

during batch annealing I

Measurement of gas composition

during batch annealing II

<200C

vaporization of residues from aqueous emulsions

280-400C

decomposition of oil CO and CO2

protective gas can be oxidizing in this temperature range:
x CO2 + Fe
>
x CO + FeOx
CO2 + H2
>
CO + H2O
>
x H2 + FeOx
x H2O + Fe

300-450C

10

Fe + x H2O
H2 + CO

a catalytic reaction is possible on the strip surface

>

CH4 + H2O

H2+H2O

-20

-10

-50 -30
-60 -40
-50

-20
-30
-40

-60

-50
-60

-40

10

10

11

100 150 200 300

H2+H2O=1

5%H2+H2O+N2=1

109
1010

Si

108

50%H2+H2O+N2=1

10

107

SiOx

pH2O/pH2

10

>620C

>
>

-10 +10 (C)

-20
0 +10
0
-30 -10

Fe

Mn

Mn

102

+10
0

C CO

5%H2+(N2)

10-1

x
eO

reactions:
FeOx + x H2
H2O + C

Gas-metal reactions II

50%H2+(N2)

Gas-metal reactions I

101

protective gas is reducing Fe but oxidizing Mn, Cr, Si and

Al selective oxidation (depends on dewpoint)

reaction:
CO + 3 H2

distillation of oil CH4 and C2H4

100

420-650C

500 700 1,000(C)

Equilibrium conditions
during batch annealing of steel

Glow discharge optical

spectroscopy (GDOS)

12.1 Basics
Massenanteil [%]

100

Process steps and their impact on surface

90

Mastab:

80

Fe : 100%
Mn : 1%
Al : 1%
Si : 0.5%

70

Cr : 0.1%
Ni : 1%
C : 1%
P : 1%

60
50

Scale build up during hot strip processing

Pickling reactions

12.3 Gas - Metal Reactions

Batch annealing and continuous annealing
Surface reactions during batch annealing

40
30
20

12.2 Oxidation and Pickling

Mn
C

Mn

Cr

Si
Al

10

0.2

Ni

Cr

Si

Ni

Al

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8
2.0
Tiefe [m]

12.4 Rolling
Surface topography
Texturing methods

GDOS-profile of a cold rolled

and batch annealed strip steel

Irregularities of a technical surface (form deviations) can have an

influence on the component function.

Outline

form deviation 1st order

2nd order

3rd order
4th order

abrasion
cleaning, sliding
lubricating power
technical surface

wettability / coatability
fatigue properties
fit
corrosion properties
optical properties

ideal surface

Irregularities of a technical surface

stochastic

deterministic

Form deviations 1.- 4. order

(DIN 4760)

pseudo-stochastic

Stochastic and pseudo-stochastic

surface structures with low root mean
square height show better optical
coating properties

statistic distribution of
different (geometric)
surface characteristics

defined arrangement of
identical (geometric)
surface characteristics,
separated from each other

defined arrangement of
identical (geometric) surface
characteristics, not
separated from each other

Classification of surface textures

Deterministic surface structures

with hydrostatic lubrication
indents show better formability
behaviour

Properties of textures

12.1 Basics

stochastic

SBT

Process steps and their impact on surface

blasting shot

12.2 Oxidation and Pickling

deformation of roll surface by

martensitic blasting shot
spinner

Scale build up during hot strip processing

Pickling reactions

roll

Shot Blast Texturing

12.3 Gas - Metal Reactions

Batch annealing and continuous annealing
Surface reactions during batch annealing

stochastic

EDT

electrons
dielectric

local melting and evaporationof roll

surface by capacitor discharges

12.4 Rolling
Surface topography
Texturing methods

roll

Electric Discharge Texturing

Outline

Texturing methods I

stochastic

Pretex

deposition of a wear resistant

chrome layer

cathode

anode

vacuum

local melting of roll surface by

electron beam

electron beam

roll
Cr

deterministic

EBT

6+

electrodes
roll

Electron Beam Texturing

Precision Texturing

EBT

pseudo-stochastic
cathode

anode

vacuum

local melting of roll surface by

electron beam

deterministic

LT
Laser

chopper wheel

local melting of roll surface by laser

beam

electron beam

inert gas
roll

roll

Electron Beam Texturing

Laser Texturing

Texturing methods II

Texturing methods III

10