02 - Materials Used in Refining

Refining-Petrochemicals-Chemicals-Engineering
MATERIALS USED IN REFINING
I - INTRODUCTION.............................................................................................................................1
1 - Non-uniform distribution of tensile stresses in PE............................................................................1
2 - Local behaviour of metal under the effects of induced tensile stress .............................................1
II - GRANULAR AND CRYSTALLINE STRUCTURE OF METALS...................................................3

1 - Granular structure ..............................................................................................................................3
2 - Crystalline structure ...........................................................................................................................3
III - CRYSTALLINE DISCONTINUITIES ..............................................................................................5
1 - Punctual discontinuities .....................................................................................................................5

2 - Linear defects .....................................................................................................................................5
3 - Planar defects.....................................................................................................................................6
IV - ELASTIC AND PLASTIC DEFORMATIONS .................................................................................7

1 - Deformation in a crystal grain............................................................................................................7
2 - Plastic deformations...........................................................................................................................8
V - HARDENING MECHANISM ...........................................................................................................9
1 - The intrinsic elastic limit of the grain .................................................................................................9

2 - Effect of grain boundaries................................................................................................................10
VI - CHARACTERISTICS OF METALS AND MECHANICAL TESTS...............................................11

1 - Tension tests ....................................................................................................................................11
2 - Creep tests .......................................................................................................................................13
3 - Charpy tests .....................................................................................................................................14
4 - Hardness tests .................................................................................................................................17
MX TYP - 00529_A_A - Rev. 2 15/06/2009

2009 - IFP Training
II
VII - IRON-CARBON ALLOY................................................................................................................21

1 - Production of cast iron and steel.....................................................................................................21
2 - Crystalline structure of iron - Carbon alloys....................................................................................25
3 - Stage change diagram in the solid state of the iron-carbon alloy .................................................27
4 - Effect of addition elements ..............................................................................................................29
5 - CCT diagram ....................................................................................................................................31
6 - Structure changes in the vicinity of a weld .....................................................................................34
VIII - INTRINSIC BRITTLENESS OF METALLIC STRUCTURES ......................................................35

1 - Risks of brittle fracture .....................................................................................................................35
2 - Stress level .......................................................................................................................................35
3 - Defects that concentrate stresses...................................................................................................35
4 - Ductile-to-brittle transition point.......................................................................................................36
5 - Precautions to be taken on equipments in service ........................................................................36
6 - Extract from french pressure vessel code CODAP........................................................................38
IX - SELECTION OF CONSTRUCTION MATERIALS FOR PRESSURE VESSELS ......................41

1 - General considerations ....................................................................................................................41
2 - Materials used in refinery complying with ASTM ...........................................................................42
3 - Ferrous and non ferrous alloys used in petroleum refining and petrochemical operations .........45
4 - Integrally applied cladding ...............................................................................................................50
5 - Material selection guide ...................................................................................................................52
X - MAIN METALLURGICAL DEGRADATIONS...............................................................................54
00529_A_A 2009 - IFP Training

1
I- INTRODUCTION
1- NON-UNIFORM DISTRIBUTION OF TENSILE STRESSES IN PE
D MAC 2130 A
2 - LOCAL BEHAVIOUR OF METAL UNDER THE EFFECTS OF INDUCED TENSILE
STRESS
F
F
Reversible Irreversible
elastic plastic
elongation elongation
D MAC 2131 C
F F

2
F F
Reversible Brittle
elastic rupture
elongation
D MAC 2131 D
F F
If the local tensile stresses exceed the metals elastic limit will be:
- local plastic elongation if the metal is ductile

- local fissuring of the metallic structure if the metal is brittle

3
II - GRANULAR AND CRYSTALLINE STRUCTURE OF METALS

1- GRANULAR STRUCTURE
A metal is made up of many small polyhedral volumes called grains, whose size varies generally from
2 to 20 m, and are limited by surfaces called grain boundaries.
Surface observed
with a scanning electron
Microscope
ENSAM Doc.
a) Rupture along the grain boundaries
Surface observed with

an optical light
microscope
ENSAM Doc.
D MAC 200 E
b) Grain plane cross section
2- CRYSTALLINE STRUCTURE
Each grain is in fact a monocrystal, that is, a regular stacking of metal ions whose cohesion is
ensured by a gas of electrons.
These free electrons explain, for example, the properties of thermal and electric conductivity of
metals.
This ion stacking leads to compact structures which may be represented by a regular stacking of hard
spheres.

4
D MAC 217 B
The orientation of the crystalline network specific to each grain is different and the material is said to be
polycrystalline. In the very special case where the material is composed of only one grain, it is said
to be monocrystalline.
Grain boundary
Grain Grain
D MAC 201 C
D MAC 200 F
Monocrystal Monophased polycrystal

5
III - CRYSTALLINE DISCONTINUITIES

1- PUNCTUAL DISCONTINUITIES
Foreign atom
Foreign atom
Gap
D MAC 1009 B
2- LINEAR DEFECTS
D MAC 1010 A
Dislocation - Wedge Dislocation - Screw
Density of dislocations
The density of dislocations that is expressed as the length of dislocation lines per unit volume (usually
in centimetres per cubic centimetre: cm/cm3 or cm2) is of the order of 106 to 108 cm/cm3 in a
tempered metal and from 1011 to 1012 in a very deformed metal.

6
3- PLANAR DEFECTS
a - Free surfaces
Surface
These separate the solid from the gas. They are rarely
smooth and have steps at the atomic scale.
D MAC 1013 A
As the surface atoms are not entirely surrounded by
neighbours, they have more energy than atoms
inside the mass of the metal.
b - Grain boundaries
These boundaries have an interface

energy and represent a metastable
metal state. They can move under the
effect of temperature and are the favoured
site of segregation for foreign atoms;
they form obstacles to the propagation
of dislocations.
Grain boundaries therefore play an

D MAC 1011 A
important role in the mechanical properties

of the polycrystal.
c - Interfaces between 2 phases
The interface separates two different phases. Two limiting cases can be distinguished:
- the incoherent interface, across which there is no continuity in the crystal lattice of the two
phases
- the coherent interface, where the adjacent phases have crystal lattices whose directions
and spacings coincide. As the structures of the two phases are never strictly identical, the
passage from one to the other across a coherent interface usually leads to the existence of
a local deformation field
D MAC 1012 B
a) Coherent b) Coherent with c) Incoherent

interface dislocations

7
IV - ELASTIC AND PLASTIC DEFORMATIONS

1- DEFORMATIONS IN A CRYSTAL GRAIN
Force S
When a tensile test is conducted
on a metal material, two main R
zones are distinguishable on the E
recorded graph:
Constriction
- a zone of elastic
deformation in which the
deformation is reversible 0
Elongation
- a zone of plastic Permanent
deformation corresponding
D MAC 203 E
deformation
to a permanent deformation
of the metal OE : zone of elastic elongation
ESR : zone of plastic deformation
SR : local zone deformation known as constriction (necking)
Plastic
elongation P
Elastic
elongation P
P
Within the crystal, plastic

deformation occurs mainly by a
sliding of one part of the crystal
against another.
D MAC 216 D
P P P
(a) (b) (c)

8
2- PLASTIC DEFORMATIONS
Three types of dislocations can occur:
D MAC 1017 A
Network of dislocations in a nickel sample
D MAC 1010 C
These dislocations form during solidification

and also during plastic deformation. Their high
Wedge Screw Mixed number (106 to 108 in tempered steel) allows
dislocation dislocation dislocation
the development of severe plastic deformation.

9
V- HARDENING MECHANISM
The elastic limit y is reached when the applied stress field leads to an irreversible displacement of the
dislocation throughout the structure. If this limit is to be increased (macroscopic parameter), the difficulty
in displacing dislocations has to be increased at the microscopic scale. Obstacles have to be created.
The problem can be explained by considering that the elastic limit of a polycrystalline material (mono or
polyphasic) is composed of two parts:
- the intrinsic elastic limit y of the monocrystal (grain)

- the polycrystalline effect mainly related to grain boundaries
1- THE INTRINSIC ELASTIC LIMIT OF THE GRAIN

a - The effect of Peierls-Nabarro forces
In a relatively perfect crystal, a force known as the Peierls-Nabarro force, which is related to the
rupture of bonds within the heart of the dislocation, has to be exerted for an isolated dislocation to
move.
b - Effect producing solid solutions
The introduction of foreign atoms into the structure by substitution or insertion creates a stress field
around the impurity that interacts with the stress field of the moving dislocation, making it
more difficult to move.
c - The effect of precipitation of a second phase
This is one the best methods for increasing the resistance to plastic deformation in a material.
When shear-resistance particles are dispersed in a matrix, the crossing of a precipitate boundary by
a dislocation can only occur if the dislocation curves between the particles, which requires an extra
force.
e
Critical dispersion of coherent
Uniform solid or semi-coherent precipitates
d
solution
c
b Zone where Precipitates
Precipitates precipitates incoherent
a coherent
D MAC 1020 B
Resistance to dislocation movement Changes in the intrinsic elastic limit

Dislocation
by the presence of shear-resistant in relation to precipitate size
precipitates
d - The effect of the dislocations themselves
When a material is deformed beyond its elastic limit, the resistance continues to increase. This is a
consolidation effect, which is a hardening caused by the interaction between the dislocations
themselves.
If the temperature of an already deformed metal is gradually increased, the dislocations tend to
re-arrange themselves or even disappear, this leads to a progressive lowering of the elastic
limit. This is the phenomenon of restoration that proceeds recrystallization (formation of new
grains and sudden lowering of the materials elastic limit).

10
2- EFFECT OF GRAIN BOUNDARIES

Grain A is subject to plastic deformation, which usually does not spread to grain B, because there is no
continuity in the slippage plane.
The plastic deformation propagates from one grain to another at a critical scission value that is related
to the mean dimension d of the grains.
1
y = f
d
This experimentally well-respected law shows that the finer the grains the higher the elastic limit.

11
VI - CHARACTERISTICS OF METALS AND MECHANICAL TESTS

Various tests are used to determine the mechanical properties of metals, including the following:
- tension tests
- creep tests
- Charpy compression tests
- hardness tests
1- TENSION TESTS
These tests consist of subjecting a standard sample, usually a cylinder or prism to a tensile force F,
exerted along its longitudinal axis and recording the resulting deformation L.
Cross-sectional
area So
F F
D MAC 202 C
Length between marks o
Standard cylindrical test specimen
Test graph
(MPa)
R
Rm B
C
A
Re
Elongation
of constriction
General elongation
L - Lo
0 Lo
A%
Lo
Lu
So S Su
L
D MAC 203 F

12
This graph shows the following zones:

L Lo
- OA: the elastic domain with reversible deformation where R = E L (E = young modulus)
o
- the point A is the limit of the elastic domain (Re)
- ABB: the domain of general plastic deformation
- point B, point of maximum loading of start of constriction (Rm)
- BC: the domain of constriction or local plastic deformation
- point C, the sample rupture point
It can be used to determine the following properties:
- the apparent elastic limit Re in N/mm2 or MPa
1 MPa = 106 Pa = 10 bar = 1 N/mm2 = 0.1 kgf/mm2
R - the conventional elasticity of

0.2% elongation
Rp
0.2 This is the elastic limit that is
generally used in the production of
standards and in the calculation of
rules used in construction codes.
0.2 % e
D MAC 204 B
elastic zone
- the resistance to tension Rm in N/mm2 or MPa

Lu Lo
- the percentage elongation at rupture A % = L . 100
o
So Su
- the constriction coefficient Z % = S . 100
o
The temperature has an overwhelming effect on variations in the elastic limit and the force at
rupture.
T1C < T2C < T3C
T1 C T2 C T3 C
D MAC 205 A

13
At high temperatures there is a very large fall in all these resistance measurements plus a
phenomenon of creep at about 450C in may steels.
At low temperatures, there is an increase in resistance to rupture and the elastic limit, with a lowering
of throughness (tendency to brittle rupture).
2- CREEP TESTS
At high temperatures (> 0.4 to 0.5 of the melting point) a metal subject to a stress lower than or greater
than the elastic limit can show an elastic deformation that progresses with time and can lead to rupture.
This phenomenon is called creep.
During the test, the sample similar to that used in the tension test is maintained at a high temperature
and is subjected to tensile stress.
l/l Increase in the stress Rupture by creep

0 ure
o at
per at constant temperature of carbon steel
C
Te m
40
at Tertiary
0C
c lo s e to 40 creep
ature
Temper
Secondary
creep Stress and
Primary temperature
creep constant
D MAC 207 C
Time
Changes in elongation with time at high temperature
The test duration can exceed 10000 hours.
Furnace pipes that are brought to a high temperature are particularly sensitive to creep. An excessive
temperature increase in the wall leads to an increase in this phenomenon and greatly decreases the
life of the pipes.
This is the explanation for blistering that appears on boiler and furnace pipes when there is an internal
deposit of lime scale or coking, that has a major influence on heat transfer and therefore on the
temperature of the metal.
D MAC 206 A
To improve creep resistance in materials, elements such as chromium, molybdenum tungsten and
titanium are incorporated into alloys.
14
3- CHARPY TESTS
a - Introduction
Knowledge of the properties derived from tension tests can be sufficient because ruptures can occur
below the elastic limit in special conditions that make the metal brittle.
Factors that make metals brittle include:
- three-dimensional stresses (a notch made on the sample in Charpy tests simulates this
three-dimensional system)
- low temperatures
- an increase in the speed of deformation
- an increase in component size
The brittleness of a notched metal sample is determined by a dropping blade Charpy test.
The test consists of measuring the energy of the blade absorbed by the sample at the time of impact.
Scale
Angle de la pointe
du couteau
X
Blade Blade
30
Blade
2 to 2.5
X
10
55 10
8
2
Specimen 0.25
Specimen XX 45
D MAC 208 C
o 1.5
1t 40

15
b - Principle of the test
The blade held on a pendulum is displaced to a height of h0 corresponding to a starting energy of W0

(usually 300 Joules).
The blade is released. In its fall as it reaches the vertical position it breaks the sample. The height to
which the pendulum reaches in its swing is measured to calculate the energy not absorbed W1. The
difference between W0 and W1 is calculated.
W (energy absorbed) = W0 W1 = P (h0 h1) in Joules
G
ho
G
h1
W=Pxh Wo = P x ho
D MAC 209 C
P = weight in N P = weight in N
h1 = height (m) ho = height (m)

16
c - Influence of temperature
At a certain temperature, the elastic limit and the rupture force are equal. There is no more elastic
deformation; the rupture is said to be brittle. The temperature at which this phenomenon occurs is
called the transition temperature.
The transition temperature is frequently arbitrarily chosen as being the temperature at which the
energy needed for rupture is equal to 27 J.
KC (J) Crystallinity %
150 0
100
50
50
28 TK 50%
100
0
-100 TK 28 -40 0 40 T C
Brittle breakage Semi-brittle breakage Ductile breakage
K KV
Charpy U
CFC CC
D MAC 210 B
Charpy V
High resistance
0 T 0 T

17
d - Example: changes in Charpy rupture energy of an A 37 FP steel in relation to temperature
Temperature + 20C 0C 20C 40C
Charpy rupture energy (J) 16 4 3.2 2.8
Steel ages with time, which is reflected by slight increases in the transition temperature.
A steel might have a transition temperature of 15C now, but + 5C in twenty years.
Among other components this phenomenon affects furnace pipes. For example, a steel with 4-6%
chromium, but no molybdenum, with a transition temperature of 10C when coming into service.
After 2.5 years of operating at a temperature of 565C, the transition temperature has become + 15C.
This of course results in reduced elongation.
It is recommended not to exceed temperature changes of more than 50C/hour to avoid thermal
shocks.
4- HARDNESS TESTS
a - The Brinell test
The test consists of pressing a steel ball

of diameter D onto the test sample at a
standard loading of F, and measuring the
diameter of the impression left on the
surface after removing the load.
The Brinell hardness BH is the ratio of F/A

(A = area of impression in mm2).
Photo Malicet Blin (SKF)
F
Thickness
D
h
D MAC 211 B
d
h

18
Diameter D of ball
F in Newtons
in mm Uses
for steel
For steel
10 0.0045 29400 Normal
5 0.004 7355
2.5 0.003 1840 For special cases
1 0.003 294
Uses
On laminated components or mouled components with a large grain size.
b - The Vickers test
The test consists of stamping the test sample with a square pyramid shaped diamond tool, with an
angle of 136 at the tip, with a force F and measuring the diagonal of the impression left on the surface
after removing the load.
The Vickers hardness is equal to the ration F/A (A = area of the impression considered to be a square
pyramid.
F
136
d1
D MAC 212 A
d2
Uses
Not to be used on coarse-grained items (moulded components).
There can be differences in the length of the diagonal in the case of very anisotropic metals.
The need to very carefully prepare the surface by rectification and polishing is a disadvantage of the
Vicker test, although it is the most precise.
There are correction factor tables for measuring the hardness of spherical or cylindrical items.
Matching the hardness of welding assemblages.

19
c - Rockwell test
Principle
The test consists of stamping the superficial layer of the test sample twice with a standardized tool
(cone or ball) and measuring the remanent increase in the depth of penetration e.
Fo Fo + F1 Fo
e = c-a
Surface of the
a
b
c
sample magnified
Hardness 100
0.2 mm

Hardness 0
Fo Fo + F1 Fo

e = c-a
Surface of the
a
b
sample magnified
Hardness 130

0.26 mm
D MAC 213 E

Hardness 0
Uses
Only coarse-grained items (moulded components) cannot be tested using this method. The marks left
of the samples are small. Provides a direct reading.
d - Equivalence between hardness measurements
Hardness depends both on the elastic limit and the capacity for hardening by deformation.
In practice, deformations of about 8 to 10% are produced during tests.
It is therefore difficult to quantitatively relate hardness measurements made on the same

material using different methods. There are however useful conversion tables although they are only
approximate (see table on next page: NFA 03-172 for non-alloyed or lightly alloyed steels).

20
Hardness Tensile Hardness Tensile

HV Hardness Hardness Hardness Hardnes Hardnes strength HV Hardness Hardness Hardnes Hardness strength
HB HRA HRB s HRC s HRD Rm (MPa) HB HRA s HRC HRD Rm (MPa)
F 98,1 N F 98,1 N
80 76,0 260 350 332,5 68,1 35,5 51,9 1160

85 80,7 280 360 342,0 68,7 36,6 52,8 1190
90 85,5 300 370 351,5 69,2 37,7 53,8 1220
95 90,2 310 380 361,0 69,8 38,8 54,4 1260
100 95,0 330 390 370,5 70,3 39,8 55,2 1290
105 99,8 350 400 380,0 70,8 40,8 56,0 1320
110 104,5 62,0 360 410 389,5 71,4 41,8 56,8 1360
115 109,3 64,6 380 420 399,0 71,8 42,7 57,5 1390
120 114,0 67,0 400 430 408,5 72,0 43,6 58,2 1420
125 118,8 69,0 410 440 418,0 72,3 44,5 58,8 1450
130 123,5 71,0 430 450 423,0 73,3 45,3 59,4 1490
135 128,3 73,1 450 460 432,0 73,6 46,1 60,1 1520
140 133,0 75,1 460 470 442,0 74,1 46,9 60,7 1550
145 137,8 77,0 480 480 450,0 74,5 47,7 61,3 1590
150 142,5 78,8 500 490 456,0 74,9 48,4 61,6 1620
155 147,3 80,5 510 500 466,0 75,3 49,1 62,2 1650
160 152,0 82,1 430 510 475,0 75,7 49,8 62,9 1680
165 156,8 83,5 550 520 483,0 76,1 50,5 63,5 1720
170 161,5 85,0 560 530 492,0 76,4 51,1 63,9 1750
175 166,3 86,1 580 540 500,0 76,7 51,7 64,4 1790
180 171,0 87,3 590 550 509,0 77,0 52,3 64,8 1820
185 175,8 88,5 610 560 517,0 77,4 53,0 65,4 1850
190 180,5 89,6 630 570 526,0 77,8 53,6 65,8 1880
195 185,3 90,7 640 580 535,0 78,0 54,1 66,2 1920
200 190,0 91,8 660 590 543,0 78,4 54,7 66,7 1950
205 194,8 92,8 680 600 552,0 78,6 55,2 67,0 1980
210 199,5 93,7 690 610 560,0 78,9 55,7 67,5 2020
215 204,3 94,6 710 620 569,0 79,2 56,3 67,9 2050
220 209,0 95,5 730 630 577,0 79,5 56,8 68,3 2080
225 213,8 96,3 740 640 586,0 79,8 57,3 68,7 2120
230 218,5 760 650 80,0 57,8 69,0 2140
235 223,3 780 660 80,3 58,3 69,4
240 228 60,7 20,3 40,3 790 670 80,6 58,8 69,8
245 232,8 61,2 21,3 41,1 810 680 80,8 59,2 70,1
250 235,5 61,6 22,2 41,7 830 690 81,1 59,7 70,5
255 242,2 62,0 23,1 42,2 840 700 81,3 60,1 70,8
260 247,0 62,4 24,0 43,1 860 720 81,8 61,0 71,5
265 251,7 62,7 24,8 43,7 880 740 82,2 61,8 72,1
270 256,5 63,1 25,6 44,3 890 760 82,6 62,5 72,6
275 261,2 63,5 26,4 44,9 910 780 83,0 63,3 73,3
280 266,0 63,8 27,1 45,3 930 800 83,4 64,0 73,8
285 270,7 64,2 27,8 46,0 950 820 83,8 64,7 74,3
290 275,5 64,5 28,5 46,5 960 840 84,1 65,3 74,8
295 280,2 64,8 29,2 47,1 970 860 84,4 65,9 75,3
300 285,0 65,2 29,8 47,5 990 880 84,7 66,4 75,7
310 294,5 65,8 31,0 48,4 1030 900 85,0 67,0 76,1
320 304 66,4 32,2 49,4 1060 920 85,3 67,5 76,5
330 313,5 67,0 33,3 50,2 1090 940 85,6 68,0 76,9
340 323,0 67,6 34,4 51,1 1120
e - Relation between hardness measurement and tensile strength
Similarly, and for the same reasons, it is difficult to correlate hardness with tensile properties (Rp,
Rm).
However, for a given type of alloy, such correlations do exist. In particular, there are tables for either
raw, rolled or heat treated carbon steels. Such tables are not valid for hammered steel, stainless
steel or non-ferrous alloys.

21
VII - IRON-CARBON ALLOY

1- PRODUCTION OF CAST IRON AND STEEL
CAST IRON PRODUCTION LINE SCRAP IRON PRODUCTION LINE
Iron mineral Mineral preparation
Scrap iron
Charcoal Coking oven
1250 C
Liquid cast iron Prparation
Blast furnace
Electrodes
Hopper car
Liquid steel Liquid steel
1600 C
D MAC 1041 B
Secondary
Oxygen storage tank Oxygen-based metallurgical
converter electric
furnace Electric furnace
Refining
station
CASTING
Casting in ingot molds Continuous casting
Removal of ingots Reheating furnaces

from molds
Slabs
Blooms Reheating
Lingot reheating Bloomings stabling
Slabs
Flat profile
sections
D MAC 1042 B
Continuous wide-band conveyor

Profile sections
Profile section conveyor Blooms

22
b - Steel working
The transition from liquid cast iron to steel requires a reduction in content of practically all the elements
such as the following comparative table shows:
%C % Si % Mn %P %S
Cast irons 3-4 0.5 to 2.5 1 to 2 2 to 0.1 0.05
Steels 0.05 - 1.5 0 to 0.5 0.3 to 1.5 < 0.05 < 0.05
The working process generally consists of two distinct and separate phases:
- oxidation phase: elimination of C, Si, Mn and P along with a simultaneous action of CaO
for the latter.
Cast iron refining consists of very rapid oxidation reactions caused by placing gaseous
oxygen in contact with the liquid metal under conditions extremely far from the
thermodynamic equilibrium with other elements present. These reactions may be written as
follows:
C + 1/2 O2 CO
C + O2 CO2
Si + O2 SiO2
Mn + 1/2 O2 MnO
Fe + 1/2 O2 FeO
2 Fe + 3/2 O2 Fe2O3
The gases CO and CO2 are conveyed into the capturing enclosure.
The oxides produced by the last four reactions contribute, along with the other oxides
constituting the converters load, particularly in limestone, to the formation of liquid slag, of
a lower density than the liquid metal, and which floats on its surface.
The dephosphorylation reaction, 2 P + 5/2 O2 P2O5, is only possible thanks to the

presence of this liquid slag: the phosphorus pentoxide must be neutralized as it gradually is
formed by the reaction with basic constituents, essentially CaO, contained in the liquid slag.
However, the presence of FeO yields an unforgeable product and a large release of CO
gas (reduction of FeO by C): effervescent steels. It will be necessary to proceed with a
deoxidation of the bath (reduction phase).

23
The liquid cast iron, at an average temperature of 1250C, is inserted in a converter on a bed of
scrap iron to be recast in order to limit the baths temperature to 1650C despite the exothermicity of
the oxidation reactions. Some pure oxygen is forced under pressure at the same time as the
insertion of limestone in massive or powder form.
Lancer holder bucket

Monorail
Refining
Hopper
Cast iron looding crane
Trmie
Gas
Example : Lancer blocking system

Converter
(LD Salmer) Lancer with O2
280 tons
Height : 11.67 m Suction hood
Outer dia ext. : 8.16 m
Protective apron
Casting hole
Wear profile
Sheet metal Loading floor

lining (A 42)
D MAC 1044 A
Metal Casting ladle
The scrap iron resmelting production line uses electric arc furnaces equipped with a refractory
hearth on which the materials to be resmelted are placed. The scrap iron is preheated to 250C
300C in a reheating furnace using the produced gases or, in a more effective way, by employing two
paired electric arc furnaces operating alternately together.
The refining reactions are quite similar to those of the converter. The impurities are oxidized by means
of:
- the oxygen conveyed by the impurities oxidized from the load

- the pure oxygen conveyed by the lancers, or by the channels placed at the hearth base
- the oxygen from the air, which penetrates through the side door and the diverse furnace
openings
This last source of oxygen, which leads to the useless heating of nitrogen and hence must then be
collected and cooled in the smoke treatment circuits, tends to be strongly reduced in the most modern
furnaces, which are endowed with airproof devices.

24
A following drawing of an electric arc furnace is represented. It is the example of a recent DC single-
electrode furnace with a nominal capacity of 150 tons. The inner diameter is 6.5 m. The hearth is lined
with refractories, the side walls and a part of the dome are quenched by the circulation of water. The
graphite electrode above the bath may attain a diameter of 750 mm for high power single-electrode
furnaces (140 MVA), which may implement currents attaining 140 kA.
Refractory electrode
Liquid slag Electric arc
D MAC 1045 B
Steel
Reduction phase
The previous phase leads to a highly oxidized metal (rich in FeO) which has to be reduced.
The growing demand for high-grade steels has led to the development of a ladeled refining which is
based essentially on vacuum degassing treatments combined or not with the actions of synthetic slags
and the reheating of the liquid bath.
Deoxidization (or reduction) takes place during this phase by the introduction of deoxidant additions
such as ferrosilicon or aluminum; killed steels are obtained with silicon or aluminum.
Grading takes place during this phase by additions of ferro-alloys or others such as Fe-Mn, Fe-
Nb, = Fe-V, Si-Mn, etc. The addition of manganese allows trapping the sulfur in the form of MnS and
preventing the formation of FeS, which constitutes with iron a eutectic with a low melting point, and
whose presence compromises the aptitude to work the steel when hot.
After ladeling, the total content of the residual elements, S, P, O, N, H, may attain very low levels on
the order of 50 ppm.

25
2- CRYSTALLINE STRUCTURE OF IRON - CARBON ALLOYS

a - Structure of iron at a temperature < 900C Fe
(a) (c)
D MAC 217 C
(b)
b - Structure of iron at a temperature > 900C Fe
(a)
(c)
D MAC 218 B
(b)

26
c - Structure of the iron-carbon alloy (steel)
Between 727C and 1487C according to the carbon content
Iron atom
Carbon atom
D MAC 219 E
Carbon atoms in gamma iron (Fe "") AUSTENITE (A)
(maximum possible content 2.11 % at 1148 C)
Between ambient temperature and 912C according to the carbon content
Iron atom
Carbon atom
D MAC 219 F
Carbon atoms in alpha iron (Fe "") FERRITE (F)
(maximum possible content 0.0218 % at 727 C)
D MAC 219 G
Carbon atoms in iron CEMENTITE (Fe3C)
Cementite, or the iron carbide Fe3C, has a composition equal to 6.67% carbon in weight; this carbide is
an interstitial compound with an orthorhomic crystalline structure.
Cementite is a metastable iron carbide which has a tendency to decompose into ferrite (or austenite)
and graphite.
Fe3C 3 Fe + Cgr H = - 23 kJ/mol-1
This transformation takes place only at a sufficiently high temperature under special circumstances.

27
3- STATE CHANGE (TRANSFORMATION) DIAGRAM IN THE SOLID STATE OF THE

IRON-CARBON ALLOY
a - Iron-carbon binary phase diagram (see next page)
The dotted lines correspond to iron graphite equilibrium, while the solid lines correspond to iron
cementite equilibrium.

28
Austenite (a) (b) (c)

White cast iron Perlitic cast iron Ferritic cast iron
(with cementile) (with laminated graphite) (with spherodal graphite)
1800
1600 1538 1495 Liquid Graphite

(Fer - ) solubility
1400 in liquid iron
1394
4,26 1227
1200 2,08 1154
(Fer - ) 2,11 1148 4,30 6,67
Austenite
Temperature (C)
1000
912
A3
Austenite Cementite
0,68 Acm
+ cementite + (Fe3C)
800 738
Ferrite + Austenite
0,77 A1 727
600
(Fer - )
ferrite Ferrite + cementite
400
Ferrite Perlite
+ +
200 perlite cementite
(a) (b) (c)
0
0,0 1,0 2,0 3,0 4,0 5,0 6,0 7,0
D MAC 1046 B
Carbone in weight
Steels Cast iron
Ferrite
Ferrite + perlite Perlite

29
4- EFFECT OF ADDITION ELEMENTS

Effect on the extension of the domains of existence of the solid solutions CFC ( ) and CC (,
):
lments gamagnes
1400 Ni 1400 Mn
1200 1200
Sol Sol
1000 1000 4,5
0 0 AC
800 3 2 AC1 800 1
600 600
0 0,4 0,8 1,2 1,6 0 0,4 0,8 1,2 1,6
%C %C
lments alphagnes
1400 Si
1200
8 6,5
1000 2 0
800 0 AC
1 1400 Cr
19
600 1200
0 0,4 0,8 1,2 1,6 12
%C 15 5
1000
%C 0
1400 800 AC1
Mo
1200 600
4 0 0,4 0,8 1,2 1,6
2 %C
1000
Sol
D MAC 1049 A
800 0 AC
1
600
0 0,4 0,8 1,2 1,6
%C
Changes in the domain by Ni, Mn, Si, Mo, Cr

30
SUMMARY TABLE OF THE EFFECT OF ADDITION ELEMENTS ON STEEL PROPERTIES
C Mn Si Al Ni Cr Mo V W Co Cu S P Ti Ta Nb
Yield point
Tensile strength (R)
Elongation
R at high temperature
Creep resistance
Fatigue resistance
AC1
AC3
Austenitic range
Grain size
Overheating trend
Oxidation resistance
Brittleness to heat
Critical quenching rate
Hardenability
Hardness
Tempering stability
Formation of carbides
Shock resistance
Effect : increased decreased

strongly increased strongly decreased

31
5- CCT DIAGRAM
Anisothermal transformation of austenite (CCT curves: continuous cooling transformation curve)
Austenitized at 850 C, 30 min.

Grain size : 9
Ferrite
Perlite
Bainite
Martensite
D MAC 1060 B
Time (in seconds)
CCT Diagram of Steel 43 Cr4 (42C4) (Atlas IRSII)

32
The evolution of A is read along the cooling laws carried over onto the diagram.
Law 1 corresponds approximately to evolution (t) at the center of the round bar of 10 mm cooled in
water. Law 12 corresponds approximately to evolution (t) at the surface of a round bar of 900 mm
cooled in air. The beam 1 to 12 represents therefore an extended range of cooling conditions.
The numbers indicated along a particular curve correspond to the mass percentages of the constituent
formed in the domain just exited.
Curve 8: after an incubation time of 200 s, the transformation of A begins at 675C by the formation of
15% (yF = 0.15) of properlitic ferrite, and then 20% of perlite (yF = 0.20). No transformation takes place
between 580C, the end of the perlitic domain, and 485C. At this last temperature, the bainitic domain
is entered, which terminates at 360C, after a bainite formation of 40% (yB = 0.40). After a new domain
of stability (360C 285C), the non-transformed austenite (25%) will yield between 285C (MS) and
the ambient temperature 25% martensite (yM = 0.25). For this grade the possible presence of Aresidual
is neglected. The steel will have at the ambient temperature the following constitution:
yF = 0.15; yP = 0.20; yB = 0.40; yM = 0.25
and its hardness will be 36 HRC.
The table below summarizes the constitutions obtained after quenching down to the ambient
temperature according to laws 1 to 12 assuming yA res = 0.
Curves yF yP yB yM HRC
1 0 0 0 1 59
2 0 0 0 1 59
3 0 0 0 1 56
4 0 0 0.07 0.93 53
5 0 0 0.20 0.80 50
6 0.02 0 0.40 0.58 42
7 0.03 0.04 0.60 0.33 38
8 0.15 0.20 0.40 0.25 36
9 0.25 0.50 0.05 0.10 27
10 0.40 0.60 0 0 20
11 0.40 0.60 0 0 18
12 0.40 0.60 0 0 214 HRC
The dotted line in the bainitic and ferrite / perlitic domains corresponds to the transformation rate of
austenite [from 0.5 (50%)]. For the same steel and under identical austenitization conditions, the
beginnings of the austenite transformation under continuous cooling are moved downward to the
right with respect to the transformations under isothermal conditions. In fact, a continuous cooling
corresponds to a serious of elementary isothermal stays at temperatures where the incubation times
are very long.

33
c - Micrographies of the structures mentioned above
MARTENSITE FERRITE + BAINITE
D MAC 1065 B
MARTENSITE + BAINITE FERRITE + PERLITE

34
6- STRUCTURE CHANGES IN THE VICINITY OF A WELD
HAZ
I II III IV V
Weld
Initial state
of the base metal
D MAC 1089 B
Ac3 1100 C
600C Ac1
Area I: the temperature does not exceed approximately 600C; no change is discernible in the
base metal.
Area II: the temperature is between 600C and Ac1. Some changes are discernible according to
the initial state of the base metal: precipitations, tempering, spheroidizing.
Area III: the temperature is between Ac1 and Ac3. The changes are of major importance (cf.:
phase diagram). The partial austenitization may lead to a structural refinement during cooling. The
area is the beginning of the HAZ: Heat Affected Zone.
Area IV: the temperature is between Ac3 and approximately 1100C. After cooling, standardized
structures and rough structures are obtained according to the temperature attained.
Area V: the temperature is between 1100C and 1500C (smelting). The austenitic grain size is
such that the metals hardenability is considerably increased and the structures obtained in this
area after cooling vary from very rough acicular structures to cooled structures for the highest rates.

35
VIII - INTRINSIC BRITTLENESS OF METALLIC STRUCTURES

1- RISKS OF BRITTLE FRACTURE
A structure must not be brittle during various operating conditions (including starting and
stopping) nor during hydraulic testing. Three conditions are needed to produce a brittle fracture
and must occur simultaneously:
- a temperature below the minimum permissible temperature for the structure
- a level of stress sufficiently high in the regions where Re
- the presence of a sufficiently acute defect (discontinuity) or a concentration of stressess
The design of a structure, its dimension and complexity play a major role; for a given defect and similar
ductile properties of the material, a brittle fracture is more likely if the structure is large in size and
especially if it has thick walls, and also if it has large openings or if it has not been de-stressed
after welding.
2- STRESS LEVEL
A brittle fracture only starts under the effect of tensile forces close to the elastic limit in a region
where there is a discontinuity or concentration of stresses.
The forces liable to start a brittle fracture can be stresses caused working forces or residual
stresses or a combination of the two. Residual welding stresses are particularly dangerous, firstly
because of their severity and secondly because they affect a metal that has been subjected to plastic
deformation during cooling at a temperature where it could have been subject to ageing. Hence the
importance of annealing to remove stresses.
3- DEFECTS (discontinuities) THAT CONCENTRATE STRESSES

The term discontinuity includes any discontinuity in shape having the same effect on stress
distribution as a cut on or in the material:
- sharp changes in angle in the shape or thickness of the wall (nozzle, welded manhole,
sheet metal reinforcing an opening)
- stiffeners, insulation attachments, poorly design supports
- defects affecting welds:
surface irregularities: excessive or poorly aligned bulges and troughs
lack of penetration of internal or external welds
inclusions and voids
In addition to geometric discontinuities, metallurgical discontinuities also have to be taken into

consideration. These are sudden changes in the mechanical properties, such as those produced in the
structure by tempering following the use of an unsuitable welding process:
- on steels sensitive to tempering, the most dangerous welding beads are those conducted
without precautions, i.e. without preheating and a too low an intensity (e.g. tack welds and
welds for secondary attachments)
- metallurgical discontinuities caused by an annealing effect can be aggravated by voids
below welding beads caused especially in ferritic steels by the influence of hydrogen
- the production of welding beads in dangerous on steels sensitive to ageing which have
been hammered during working (e.g. rounded bottoms)
- superficial scratches and stamping marks are also dangerous, the latter not only forming a
physical discontinuity but also a metallurgical discontinuity caused by the impact and by
ageing
36
4- DUCTILE-TO-BRITTLE TRANSITION POINT

The transition temperature is the temperature above which the material becomes ductile and below
which the material is brittle.
It is important to distinguish between the ductile-to-brittle transition point of the material, which is
one the materials intrinsic properties and what is called the ductile-to-brittle point of the
construction, which is the temperature below which the structure itself becomes liable to brittle
fracture, as a result not only of the material but also its dimensions, any discontinuities and the
stresses to which it is subjected.
In practice it is the transition temperature of the construction that is most important; a structure
under pressure must never descend to a lower temperature. To determine this temperature you
start the transition temperature of the material and then determine the transition temperature of the
construction taking into account its dimensions and the stresses put upon it.`
This minimum permissible temperature of the construction can be determined from existing
tables in construction codes for pressure vessel such as the french code CODAP.
5- PRECAUTIONS TO BE TAKEN ON EQUIPMENTS IN SERVICE

For old equipment whose characteristics (material, welding conditions, etc.) may be poorly known, an
attempt must be made to identify as best as possible the true state of the walls:
- the nature of the original material, chemical analysis, hardness, resilience
- current ductility, taking into account possible degradation in use
- presence of progressing defects that must always be feared, in relation to the required
quality in service. Some can appear during the service of the equipment (e.g. if it is to
alternating temperatures or mechanical stresses leading to fatigue phenomena). These
defects must be detected during NDT before the hydraulic testing
- deterioration of the properties of shock resistance of the material during service. This
is reflected in the movement of variable extent of the transition curves to the right in
the case of:
brittleness that has become reversible again (temper embrittlement) of Cr-Mo

steels that can experience a shift in transition temperature of several tens of degrees
ageing following hammering of non-detressed steels working at between 150C

and 250C. The transition temperature increases by 15C to 30C depending on
steel quality (hence once again the importance of the PWHT)
a delayed rupture on equipment in contact with hydrogen. The highest risk

occurs during cooling of a reaction vessel, to temperatures below 200C. Stabilized
structures (standardized + tempered) are required plus a PWHT of welded joints
which restores the brittle structures of the HAZ
Precautions must especially be taken in certain transition stages and also during hydraulic
retesting.

37
THE ORIGINS OF FRACTURES
Sharp angles
Brittleness caused by design
Change of section
(Area with concentrated stresses leading to Notch effect
Joint area (welding)
the start of fracture)
Three-dimensional stress zone
Heterogeneity (inclusions)
Brittleness caused by the intrinsic Nitrogen content (killed steel)
properties of the material Coarse grains
Internal and external hairline cracks
Cutting out
Brittleness caused by construction or Shaping, bending (before and after heating)
Welding (role of flux, metal added, welding defects)
maintenance
Heat treatment (brittleisation temperature)
Surface defects
Working temperature
- low
- transition zone
- high (graphitization 450-650C)
Brittleness occurring during use
Ferritic brittleization
Sigma phase of austenitic steels between 425 and
875C
Precipitation of carbides in grain boundaries
(austenitic steels at 600C)
Fatigue (alternating stress, vibration)
Intergranular corrosion of stainless steel in aqueous

solution
Corrosion under stress (transgranular) by caustic
(soda, chlorides, etc.)
Corrosion by fatigue (caused by pitting and
alternating stresses)
Attack by hydrogen:
- at high temperature:
Brittleness caused by corrosion
* decarburation
* intergranular attack
* blister
- at ordinary temperature
* H2 blistering
* H2 blistering + pitting (corrosion by
fatigue, brittlelization by H2S under
stress
Reminder:
- brittleness = tendency for a material to propagate cracks without significant plastic

deformation
- brittleization = reduction of the ductility of a material by a physical or chemical reaction
38
6- EXTRACT FROM FRENCH PRESSURE VESSEL CODE CODAP
ANNEXE MA2
PREVENTING THE RISK OF BRITTLE FRACTURE
MA2.4.2 - Minimum Permissible Temperature (MPT)
This is the lowest temperature that can be reached without the risk of brittle fracture of the walls of an
apparatus or one of its components in each of the situations defined in C1.1.5.
MA2.4.3. - Reference temperature (RTe)
This is the temperature at which the Charpy tests are conducted meeting the rupture energy values
required in MA2.5.1 for basic materials and welds (deposited metal and area affected by heat).
MA2.4.4. - Reference thickness (RTh)
This is the minimum thickness possible on an apparatus as defined in C1.9.2.
MA2.5.1. - Charpy rupture energy value required
The Charpy tests are conducted in accordance with EN 10045-1 (A 03-011) on V-notched samples
under the conditions defined in section M and F of the code.
At the reference temperature Rte, the average value of the Charpy rupture energy on three samples of
normal cross section must be at least equal to 27 Joules and no value on any sample must be less
than 20 Joules.
MA2.5.3.2 - The determination of the MPT is conducted as follows.
T (C)
RT e
MPT
D MAC 1062 C
RTu e(mm)

39
MPT (C)
40 = 20
RTe
= 0
20 RTe
0
0
e = -2
RT 00
Te = -4 0
-20 R = -6
RTe
-40 = -80
RTe
-60
Ni
1.5
-80
D MAC 1336 B
0 10 20 30 40
RTh (mm)

MPT
100
00529_A_A
RTe = 20
80
60
RTe = 0
40
RTe = -20
20
RTe = -40
0
40
-20
2009 - IFP Training

-29 RTe = -60
-40
-43
-56
-60
-80
-84
-100
0 10 20 30 40 50 60 70 80 90 100 110
D MAC 1515 A
RTh (min)
41
IX - SELECTION OF CONSTRUCTION MATERIALS FOR PRESSURE VESSELS

1- GENERAL CONSIDERATIONS
The selection of construction materials for Code pressure vessels has to be made from Code approved
material specifications. A metallurgical engineer usually specifies the most economical materials of low
first cost and/or low future maintenance cost that will be satisfactory under operating conditions and
will meet other requirements.
There are many factors supported by experience and laboratory test results that must be considered in
selecting the most suitable materials. They include the following:
corrosion resistance in the service corrosive environment

strength requirements for design temperature and pressure
cost
ready market availability
fabricability
quality of future maintenance
Generally, process equipment is designed for a certain minimum service life under specific operating
conditions. Based on a corrosion rate in mils (0.001 in.) per year (MPY) a total corrosion allowance is
established which is added to the calculated required thickness. Typical design lives are given below
for several types of petrochemical equipment:
20 years: Fractionating towers reactors, high-pressure heat-exchange shells, and other

major equipment which is hard to replace
10-15 years: Carbon-steel drums, removable reactor parts, and alloy or carbon-steel tower
internals
5-10 years: Carbon steel piping, heat-exchanger tube bundles, and various process column
internals.
The selected material must be suitable for services of different levels of severity from the standpoint of
pressure, temperature, corrosive environments, cyclic or steady operations, etc. Obviously, a number
of divisions is possible. However, since the choice of material for a vessel depends primarily on the
service environment, it would seem practical to classify construction materials according to service;
non-corrosive, with corrosion rates negligible or very low and definitely established (for carbon steel, a
maximum of 1/4 in. total; otherwise an alternative material with a better corrosion resistance is used) or
corrosive, requiring special materials other than carbon steels or low-alloy steels.

42
2- MATERIALS USED IN REFINERY COMPLYING WITH ASTM (American Society for

Testing Materials)
Stainless steels
Carbon steels Alloy steels
(Ferritic) (Ferritic) Heat resisting
Austenitic Ferritic Duplex Martensitic
austenitic
Fe Fe Fe Fe Fe Fe Fe
C 0.25% C 0.25% C 0.05% C 0.05% C ~ 0.1% C 0.05% C = 0.1 0.2%
(Mn < 1.2%) Cr 9% Cr = 16 18% Cr = 17 25% Cr = 10.5 29% Cr = 20 25% Cr = 10.5 17%
Si < 0.16% Mo 1% Ni = 8 13% Ni = 8 20% (Mo) Ni = 4 7% (Mo)
(for high temp.) (Mo 3) (Si) (Ai) (Mo) (V)
2.5 Ni 9% (Ti) (Ti) (Cu)
(for low temp.) (Nb) (Nb) (N)
(Mn) (Zr)
(N)
(Cu)
S 0.05% S 0.05% S 0.05% S 0.05% S 0.05% S 0.05% S 0.05%
P 0.05% P 0.05% P 0.05% P 0.05% P 0.05% P 0.05% P 0.05%
Material Plate Pipe Tube Forging

Carbon steels
Carbon steel A285 Gr A, B, C A53 Gr B A214 (soud) A105
A179 (sans soudure) A266 Cl I, II, III
Low temperature, A333 Gr 6 A350 Gr LF2
carbon steel
Killed carbon steel A516 Gr 55,70 A106 Gr B A179 A105
A266 Cl I, II, III

Low alloyed steels
1 Cr - 1/2 Mo A387 Gr 12 A335 Gr P12 A213 Gr T12 A182 Gr F1
A336 Gr F1
11/4 Cr - 1/2 Mo A387 Gr 11 A335 Gr P11 A199 Gr T11 A 182 Gr F11

A213 Gr T11
21/4 Cr - 1 Mo A387 Gr 22 A335 Gr P22 A199 Gr T22 A182 Gr F22

A213 Gr T22 A336 Gr F22
3 Cr - 1 Mo A387 Gr 21 A335 Gr P21 A199 Gr T21 A182 Gr F21
A213 Gr T21 A336 Gr F21
5 Cr - 1/2 Mo A387 Gr 5L A335 Gr P5 A199 Gr T5 A182 Gr F5
A213 Gr T5 A336 Gr F5
8 Cr - 1 Mo A387 Gr 9 L A335 Gr P9 A199 Gr T9 A182 Gr F9
A213 Gr T9
31/2 Ni A203 Gr D, E, F A333 Gr 3 A334 Gr 3 A350 Gr LF 3
9 Ni A353 A333 Gr 8 A334 Gr 8 A522 Gr I

A553 TP I

43
Ferritic stainless steels
Type 405
A240 TP405 A268 Gr TP405 A268 Gr TP 405
12 Cr
Type 410 A182 Gr F6a

A240 TP 410 A268 Gr TP410 A268 Gr TP410
13 Cr A336 Gr F6a
Type 410 S
A240 TP 410S
13 Cr
Type 430
A240 TP 430 A268 Gr TP430 A268 Gr TP430 A182 Gr F430
17 Cr
Material Tle Canalisation Tube Forging
Austenitic stainless steels
Type 304 A312 Gr TP 304 A213 Gr TP304 A182 Gr F304

A 240 TP304
18 Cr - 8 Ni A376 Gr TP304 A249 Gr TP304 A336 Gr F304
Type 304 L A213 Gr TP304L

A240 TP304L A312 Gr TP304L A182 Gr F304L
18 Cr - 8 Ni A249 Gr TP304L
Type 304H A312 Gr TP304H A213 Gr TP304H

A240 TP304H A182 Gr F304H
18 Cr - 8 Ni A376 Gr TP304H A249 Gr TP304H
Type 309S
A240 TP309S A312 Gr TP309S A249 Gr TP309S
23 Cr - 12 Ni
Type 310 A213 Gr TP310 A182 Gr F310

A240 TP310S A312 Gr TP310
25 Cr - 20 Ni A249 Gr TP310 A336 Gr F25
Type 316 A213 Gr TP316 A182 Gr F316

A240 TP316 A312 Gr TP316
16 Cr - 12 Ni - 2 Mo A249 Gr TP316 A336 Gr F316
Type 316L A213 Gr TP316L

A240 TP316L A312 Gr TP316L A182 Gr F316L
16 Cr - 12 Ni - 2 Mo A249 Gr TP316L

A240 TP316H A182 Gr F316H
16 Cr - 12 Ni - 2 Mo A376 Gr TP316H A249 Gr TP316H
Type 317
A240 TP 317 A312 Gr TP 317 A249 Gr TP 317 A276 TP317
18 Cr - 13 Ni - 3 Mo
Type 317L
A240 TP317L A312 Gr TP317L A249 Gr TP317L
18 Cr - 13 Ni - 3 Mo
Type 321 A312 Gr TP321 A213 Gr TP321 A182 Gr F321

A240 TP321
18 Cr - 10 Ni - Ti A376 Gr TP321 A249 Gr TP 321 A336 Gr F8t

A240 TP321H A182 Gr F321H
18 Cr - 10 Ni - Ti A376 Gr TP321H A376 Gr TP321H
Type 347 A312 Gr TP347 A312 Gr TP347 A182 Gr F347

A240 TP347
18 Cr - 10 Ni - Cb A376 Gr TP347 A376 Gr TP347 A336 Gr F8c

A240 TP347H A182 Gr F347H
18 Cr - 10 Ni - Cb A376 Gr TP347H A376 Gr TP347H

44
Nickel based alloys
Hastelloy B-2
B333 B619 B622
(67 Ni-28 Mo) - 2 Fe-1 Cr
Hastelloy C-4
B575
(Ni-Mo-Cr)
Inconel 600 B167

B-168 B516 B166
(72 Ni - 18 Cr - 10 Fe) B517
Chrome based alloys
Incoloy 800, B407 B564

B409 B515
800 H (30 Ni-23 Cr-Fe) B514
Alloy 20
B463 B464 B468 B462
(Cr-Ni-Fe-Mo-Cu-Cb)
Copper alloys
Laiton damiraut B171 alloy 443, B111 alloy 443, 444,

(Cu - 30 Zn - 15 n) 444, 445 445
Laiton B171 alloy 464

(Cu - 402 n - 0,755 n)
Cupro-nickel
B171 alloy 706 B466 alloy 706 B111 alloy 706
(90 Cu - 10 Ni)
Cupro-nickel
B466 alloy 710 B111 alloy 710
(80 Cu - 20 Ni)
Cupro-nickel
B171 alloy 715 B466 alloy 715 B111 alloy 715
(70 Cu - 30 Ni)
Monel B564 alloy Ni-Cu

B127 B165 B163 alloy Ni-Cu
(Ni-Cu) B164

00529_A_A
3-
MATERIAL REASON OF USE USED FOR INCONVENIENTS OR PRECAUTION
CARBON STEEL INEXPENSIVE 80% OF ALL COMPONENTS IN USE LIMITED TO 480C

REFINERIES AND
READILY AVAILABLE PETROCHEMICAL PLANTS POOR RESISTANCE TO
CORROSION
EASILY FABRICATED IN REFINERIES: FRACTIONATION
TOWERS, SEPARATOR DRUMS, H2 BLISTERING OR H 2
HEAT EXCHANGER SHELLS, EMBRITTLEMENT RISK WITH
STORAGE TANKS, MOST PIPING HUMID H2S
AND ALL STRUCTURES
PETROCHEMICAL OPERATIONS
45
CARBON MOLYBDENUM USE AT 0 = 425 450C REACTOR VESSELS, HEAT QUESTION RAISED REGARDING
STEEL: (C - 0.5 MO GRADE) EXCHANGER SHELLS, THE EFFECT OF LONG TERM H2
RESISTANCE TO HIGH- SEPARATOR DRUMS, PIPING EXPOSURE
FOR PROCESS INVOLVING
2009 - IFP Training

TEMPERATURE
HYDROGEN ATTACK H2 AT > 260C
LOW-ALLOY STEELS : EXCELLENT RESISTANCE REACTOR VESSELS AT HIGH

TO CERTAIN TYPES OF AND HIGH PRESSURE:
Cr-Mo CONTAINING < 10 % HIGH-TEMPERATURE
SULFIDE CORROSION AND OVERLATED WITH STAINLESS
2.25 Cr-1 Mo WIDELY HIGH TEMP, H2 ATTACK STEEL TO IMPROVE CORR.
USED RESIST.
TO IMPROVE RESISTANCE
TO H2 STRESS CRACKING FURNACE TUBES, HEAT
(HSC) POST WELD HEAT EXCHANGERS SHELLS, PIPING,
TREATMENT SEPARATOR DRUMS
FERROUS AND NON FERROUS ALLOYS USED IN PETROLEUM REFINING AND
00529_A_A
STAINLESS STEELS: RESISTANCE TO EXTENSIVELY USED IN WILL PIT IN PRESENCE OF

(CR > 11%) CORROSION IN MANY PETROCHEMICAL PLANTS CHLORIDES
OPERATING CONDITIONS (BECAUSE HIGHLY CORROSIVES
NATURE OF THE CATALYST AND
SOLVENTS OFTEN USED)
IN REFINERIES PRIMARILY
LIMITED TO APPLICATIONS
INVOLVING HIGH SULFIDIC
CORROSION AND OTHERS
HIGH ATTACK
46
MARTENSITIC SS PUMP COMPONENTS, VALVE POSWELD HEAT TREATMENT TO

TRIM, TURBINES BLADES, TRAY AVOID HSC IF H2S
12 to 17% Cr VALVES, TRAY COMPONENTS IN ENVIRONMENT
2009 - IFP Training

0.5 to 1.1% C FRACTIONATING TOWERS
FERRITIC SS (AISI 405 AND 410) NOT SUBJECT TO HSC VESSEL LININGS
12.5 TO 26% Cr
0.08 TO 0.25% C
AUSTENITIC SS EXCELLENT CORR. LININGS TRAY COMPONENTS IN SUBJECT TO SCC BT CHLORIDE
RESIST. FRACTIONATION TOWERS,
Cr > 17% PIPING HEAT EXCHANGER IF SENSITIZED SUBJECT TO
Ni > 8% TUBES, REACTOR CLADDING, SCC BY POLYTHIONIC ACID
AISI 304 TUBES AND HANGERS IN
AISI 304L (Low Carbon) FURNACE, COMPONENTS FOR
AISI 321 (With TI) COMPRESSOR, TURBINES,
AISI 347 (with Nb) PUMPS, VALVES, REBOILER
AISI 316 (with Mo) TUBES
AISI 309 (25 Ni 12 Cr)
AISI 310 (25 Ni 20 Cr)
00529_A_A
CAST IRON HIGH HARDNESS PUMP, VALVE COMPONENTS, BRITTLENESS, LOW STRENGTH
REDUCES THE VELOCITY EJECTOR, JETS, STRAINERS AND NOT USED FOR PRESSURE
EFFECTS OF CORROSION, FITTINGS RETAINING COMPONENTS FOR
SUCH AS IMPINGEMENT, HANDLING FLAMMABLE
EROSION, AND HYDROCARBONS
CAVITATION
HIGH SILICON CAST IRONS CORROSION RESISTANT REFINERY AND PETROCHEMICAL

(14% Si) (PASSIVE SURFACE, OR PLANT APPLICATIONS INCLUDE
SILICON OXIDE, THAT VALVE AND PUMP COMPONENTS
47
FORMS DURING
EXPOSURE TO MANY
CHEMICAL
ENVIRONMENTS EXCEPT
2009 - IFP Training

HYDROFLUORIC ACID).
HIGH. NICKEL CAST IRONS EXCELLENT CORR. WEAR, VALVE COMPON., PUMP COMPO.
AND HIGH RESIST. DAMPER, DIFFUSERS, TRAY
13 36% Ni COMPON., COMPRESSOR
+ UP TO 6% Cr PARTS
00529_A_A
COPPER AND ALUMINUM TUBES USED IN WATER-COOLED TO APPLICATION BELLOW 260C

ALLOYS: CONDENSERS AND COOLERS AT (STRENGTH LIMITATION)
MOST REFINERIES
ADMIRALTY METAL PERFORMED POORLY IN OVER
HEAD CONDENSERS,
COMPRESSOR AFTER
COOLERS, AND OTHER
LOCATIONS WHERE HIGH
CONCENTRATIONS OF H2S AND
AMMONIA ARE ENCOUNTERED
48
IN AQUEAOUS CONDENSATE
PITTING AND AMMONIA SCC,
DEZINCIFICATION
2009 - IFP Training

ALUMINUM ALLOYS RESISTANCE TO THE VACUUM TOWERS
NAPHTENIC ACID
CORROSION OF TRAY
ALUMINIZED COATING TO
COMPONENTS
PROTECT LOW-ALLOY STEELS
AGAINST HIGH SULFIDIC
CORROSION
NICKEL ALLOY (Ni > 30%) RESIST TO SULFURIC ACID, CAN BE ATTACKED AND
Monel 400 HYDROCHLORIC ACID, EMBRITTLED BY SULFUR
Inconel 600 HYDROFLUORIC ACID AND BEARING
Inconel 625 CAUSTIC SOLUTIONS GASES AT HIGH
Incoloy 800, 801, 825
Hastelloy C276, B2 IMMUNE TO CHLORIDE SCC EXPENSIVE
00529_A_A
ALLOY 400 USED SPECIFIC LINING FOR CARBON STEEL

APPLICATIONS TO OVERCOME EQUIPMENT
UNUSUALLY
SEVERE CORROSION OVER HEAD CONDENSERS
PROBLEMS
49
TITANIUM FULLY RESISTANT TO CERTAIN PETROCHEMICAL NOT A HIGH METAL

MANY PROCESS STREAMS PROCESSES WELDING, CUTTING UNDER
INERT GAS ATMOSPHERES TO
RESISTANT TO SEAWATER TUBES USED IN OVERHEAD
2009 - IFP Training

PREVENT EMBRITTLEMENT
OR BRACKISH WATER COOLERS AND CONDENSERS TO LIMITED TO < 260C
(FOR COOLING) PREVENT CORR. BY AQUEAOUS IF H2 < 175C TO PREVENT
CHLORIDES, SULFIDES AND EMBRITTLEMENT DUE TO
SULFUR DIOXIDES (1) HYDRIDE FORMATION
(1) CAN CORRODE BENEATH
ACIDIC DEPOSITS
50
4- INTEGRALLY APPLIED CLADDING

Integrally clad or rollclad plate is fabricated in a steel mill by hot rolling of assemblies of carbon or low
alloy steel plates (backing) and corrosion resistant sheet (linear) which have been welded at the edges.
In rolling at high temperatures the pressure creates a solid-phase weld between the backing and
cladding metals. The bond strength usually exceeds the minimum 20,000 psi in shear strength required
by the Code. The thickness of the liner can be specified in percent of backing-plate thickness, or more
5 1
often in fractions of an inch. For most applications a thickness of 64 8 in. is quite sufficient and is
3
considered a corrosion allowance. Rarely does the thickness of an integrally applied liner exceed 8 in.
Integrally clad plate has many advantages. It can be hot or cold formed; lightly loaded internal support
clips can be directly attached to the cladding; and the continuous bond eliminates the possibility of any
corrosive substance getting between the cladding and the backing metal. It would seem that
differences in thermal expansion might introduce peak stresses leading to cracks in the cladding,
particularly in the region of welds, but based on practical experience, the integral cladding performs
quite well at the elevated temperature or cyclic service. However, special tests may be prescribed to
prove that integrally clad plate is suitable for the intended operating corrosive conditions. Also, frequent
services inspections of the cladding are recommended. Diffusion of carbon from ferritic backing steels
into austenitic stainless cladding occurs at high bonding temperature, but the carburized zone is very
narrow and does not affect the overall strength of the corrosion resistance of the clad plate. Carbon
diffusion can be minimized by nickel plating of the backing plate.
Where mild corrosion resistance is required, most cladding materials are made of straight chromium
steels, types 405 or 410S. Both have lower thermal expansion than carbon steel. For more severe
corrosive service 18-8 stainless steels are used. The grades with low carbon content or the stabilized
grades have to be used if welding is used in fabrication or a post weld heat treatment is required.
PWHT temperatures may be in the carbide precipitation range for unstabilized austenitic stainless steel
and/or in the range of sigma-phase formation; proper attention has to be given to this in the selection of
the stainless steel cladding material, otherwise heat treatment may result in inferior mechanical and
corrosion properties of the cladding material.
Table 1 lists some frequently used cladding materials; the backing material can be any carbon or low-
alloy steel.
Plain carbon and low-alloy steels are satisfactory for hydrogen service at low operating temperatures
and high pressures or low pressures and high temperatures.

51
Table 1
ASTM (SA) standard Alloy cladding Remarks Maximum

specifications for metal Service
integrally ASTM (SA) temperature
clad plate (F)
Chromium steels, A (SA) Type 410S 0.08 C. max. 1200

A (SA) 263 405 12 Cr-Al 1200, note 4
429 15 Cr notes 3, 5
430 17 Cr notes 3, 5
Chromium-nickel A (SA) 240 Type 304 L 0.03 C. max 800

steels, A (SA) 264 309S 23 Cr-12 Ni note 6
310S 23 Cr-20 Ni note 6
316L 0.03 C. max 800
321 Ti stabilized note 6
347 Cb stabilized note 6
Nickel and nickel-base B (SB) 127 Monel 400 500

alloys, A (SA) 265 168 Incomel 600 1200
409 Incoloy 800 1200
424 Incoloy 825
Copper and copper-base B152 Cu alloy P-deoxidized

alloys, B432 No. 122 copper
No. 102 oxygen-free
B 402 No. 706 90 Cu-10 Ni
No. 715 70 Cu-30 Ni
1. Internals parts (trays, pans, baffles, etc.) are of the same class of alloys as the shell fining.
2. Maximum service temperature of the lining can be controlled by the maximum service temperature allowed for
the backing material.
3. The Code does not recommend the use of the Cr-stainless steels with a content of Cr over 14 percent for
service metal temperature over 800F.
4. Operating temperatures should be outside the temperature range from 750F to 950F, where the material is
subject to embrittlement.
5. Not suitable for welding.
6. Because of the different thermal expansions of austenitic steels and carbon steels and graphitization of carbon
steels the operating temperature is also quite limited to 800F.

52
5- MATERIAL SELECTION GUIDE

00529_A_A
6-
TYPE DESIGNATION VOLUMIC WEIGHT COST RELATIVE TO

(g/cm3) CARBON STEEL COST
IRON BASED CARBON STEEL 7.85 1

COST OF METALS
STAINLESS STEEL Z3 CN 18.10 (304 L) 7.9 3 to 5

STAINLESS STEEL Z3 CND 17.12 (316 L) 7.9 4 to 6
STAINLESS STEEL (Z3 INCDU 25.20) (URANUS B6) 8.0 6 to 8
ACIER INOX (CRONIFER 19.25 HMO) 8.0 6 to 8
DUPLEX STAINLESS STEEL 7.85 8 to 12
(URANUS 45 N AND 47 N)
53
NICKEL BASED NICKEL 200 8.9 19 to 38

MONEL 400 8.8 14 to 18
2009 - IFP Training

INCONEL 600 8.4 16 to 20
INCOLOY 825 8.2 12 to 16
HASTELLOY C 276 AND C 22 8.9 25 to 30
HASTELLOY B2 9.2 25 to 38
EXOTIC TITANIUM (GRADE 2) 4.5 40

ZIRCONIUM 6.5 60
TANTALUM 16.6 800
OTHERS ALUMINUM 2.7 2

COPPER 8.9 3
LEAD 11.3 1
GOLD 19.3 14 000
PLATINUM 21.5 17 000
00529_A_A
X - MAIN METALLURGICAL DEGRADATIONS
MATERIAL EFFECT TEMPERATURE INCUBATION TIME CAUSE REMEDY
CARBON STEEL AND LOW ALLOYED STEEL
Carbon and manganese Ageing : Room Few years Precipitation of phases made up To choose steels with low TK27
carbon steel H, Re, Rm in crease of iron, carbon, and nitrogen
%, KV, decrease Between 150C and 250C Few weeks Normalizing heat treating (HT)
TK27 increase
Increased phenomena in
bended areas
Low alloyed steels with Temper embrittlement: Between 175C and 550C About 10 years, less P and with a lower effect Bruscato factor =
Cr (2 to 9%) and Mo, like A%, KV, decrease with a maximum effect at time if P > 0.015% As, Sb, Sn segregate in the (10P+5Sb+4Sn+As)/100 =
2.25 Cr - 1 Mo, tempered TK27 increase 470C grain boundaries 20 ppm max (15 is the best)
or welded Cracks and brittle fracture J factor = (Mn+Si) x (P + Sn) x
54
when pressure vessel is 104 = 150 max (80 is the best)

under pressure Step cooling HT: from 593C to
315C and air cooling
2009 - IFP Training

To pressurize the pressure
vessel at TC > its transition
TC
STAINLESS STEELS
Ferritic and austenitic Chromium carbide 425 to 870C: close to It depends on Depletion of Cr (<11%) in the Low carbon steels (< 0.03% C):
precipitates and sensitizing welds, in service content 18Cr-10Ni grain boundary regions around 304L, 316L
to intergranular corrosion temperature of pressure between 550C and the chromium carbide Stabilized Ti(321) or Nb(347)
vessel 680C: precipitates (Cr23C6 ) no steels
- 8 mn / 0.06% passive film at the grain Solution annealing
- 8 h / 0.03% boundaries HT (~ 1050C+ rapid cooling)
- 120 h / 0.02%
00529_A_A
MATERIAL EFFECT TEMPERATURE INCUBATION TIME CAUSE REMEDY
STAINLESS STEELS (Continued)
Ferritic, Duplex, austenitic Sigma phase formation in Between 590C and 930C It depends on TC: Hard and brittle sigma phase Gow / Harder formula:
with a small content of ferritic grains. (maximum effect at 760C) few hours in formation (50%Cr, 50%Fe) Cr+4Mo+3(Si-1)-16C /
ferrite and Cr > 16% At room TC: Welding areas operating Ni+(Mn-1)/S < 1.7
304, 316 hardly sensitive H, Re, Rm increase temperatures Solution annealing HT of
25Cr 20Ni more sensitive A%, KV decrease austenitic steels with 10% ferrite
than 20Cr 35Ni (~ 0.1%) (~ 1100C+ rapid cooling)
between 600C and 900C Not to pressurize pressure
vessels at room temperature
use 321, 347, 800H(Ni base, Cr,
Fe), 800HT
> 12% Cr ferritic steels 475C embrittlement: 320C at 550C (maximum 10 to 100 hours Decay of ferrite to: To use > 12% Cr steels at
and DUPLEX H, Re, Rm increase effect at 475C) - a high content of Cr phase TC < 320C
55
A%, KV decrease - a high content of Fe phase HT at 815C followed by rapid

TK27 increase so the metal cooling to restore ductility
is brittle at room TC
2009 - IFP Training

DISBOUNDING
Interface formed by 2.25Cr Intergranular cracks in the Cooling phases of the Few hours after 3 conditions must occur Thin clad (3 to 6 mm): to diffuse
1Mo and austenitic stainless interface: pressure vessel to room cooling to room TC simultaneously: hydrogen more easily inside the
steel: 304, 316, 321, 309, - in the martensitic layer of TC during shutdown - hydrogen in high temperature pressure vessel.
347 the base metal, austenite phase (which has Decrease C content < 0.15% in
- in the grain boundaries of relatively high hydrogen the interface at the base metal
the stainless steel clad solubility relative to ferrite) surface
along the martensitic layer - high strength or hard 321, 347 steels: fine Nb or Ti
structures (steels sensitive to carbides and low Si, P and S
tempering) content
- high stress level 2.25Cr 1Mo V speed cooling:
Hydrogen absorbed embrittles 20C/h to 40C/h allows
martensitic layer of base dissolved hydrogen to escape
metal and stresses cause
cracks and disbounding
during cooling

02 - Materials Used in Refining

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02 - Materials Used in Refining

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Refining-Petrochemicals-Chemicals-Engineering

MATERIALS USED IN REFINING

II - GRANULAR AND CRYSTALLINE STRUCTURE OF METALS...................................................3

III - CRYSTALLINE DISCONTINUITIES ..............................................................................................5

1 - Punctual discontinuities .....................................................................................................................5

IV - ELASTIC AND PLASTIC DEFORMATIONS .................................................................................7

V - HARDENING MECHANISM ...........................................................................................................9

1 - The intrinsic elastic limit of the grain .................................................................................................9

VI - CHARACTERISTICS OF METALS AND MECHANICAL TESTS...............................................11

MX TYP - 00529_A_A - Rev. 2 15/06/2009

VII - IRON-CARBON ALLOY................................................................................................................21

VIII - INTRINSIC BRITTLENESS OF METALLIC STRUCTURES ......................................................35

IX - SELECTION OF CONSTRUCTION MATERIALS FOR PRESSURE VESSELS ......................41

X - MAIN METALLURGICAL DEGRADATIONS...............................................................................54

00529_A_A 2009 - IFP Training

00529_A_A 2009 - IFP Training

- local plastic elongation if the metal is ductile

00529_A_A 2009 - IFP Training

II - GRANULAR AND CRYSTALLINE STRUCTURE OF METALS

a) Rupture along the grain boundaries

Surface observed with

00529_A_A 2009 - IFP Training

Monocrystal Monophased polycrystal

00529_A_A 2009 - IFP Training

III - CRYSTALLINE DISCONTINUITIES

Dislocation - Wedge Dislocation - Screw

00529_A_A 2009 - IFP Training

These boundaries have an interface

Grain boundaries therefore play an

important role in the mechanical properties

c - Interfaces between 2 phases

a) Coherent b) Coherent with c) Incoherent

00529_A_A 2009 - IFP Training

IV - ELASTIC AND PLASTIC DEFORMATIONS

Within the crystal, plastic

00529_A_A 2009 - IFP Training

These dislocations form during solidification

00529_A_A 2009 - IFP Training

- the intrinsic elastic limit y of the monocrystal (grain)

1- THE INTRINSIC ELASTIC LIMIT OF THE GRAIN

b - Effect producing solid solutions

c - The effect of precipitation of a second phase

Resistance to dislocation movement Changes in the intrinsic elastic limit

d - The effect of the dislocations themselves

00529_A_A 2009 - IFP Training

2- EFFECT OF GRAIN BOUNDARIES

00529_A_A 2009 - IFP Training

VI - CHARACTERISTICS OF METALS AND MECHANICAL TESTS

Standard cylindrical test specimen

00529_A_A 2009 - IFP Training

This graph shows the following zones:

It can be used to determine the following properties:

- the apparent elastic limit Re in N/mm2 or MPa

1 MPa = 106 Pa = 10 bar = 1 N/mm2 = 0.1 kgf/mm2

R - the conventional elasticity of

- the resistance to tension Rm in N/mm2 or MPa

T1C < T2C < T3C

00529_A_A 2009 - IFP Training

l/l Increase in the stress Rupture by creep

Changes in elongation with time at high temperature

The test duration can exceed 10000 hours.

Factors that make metals brittle include:

00529_A_A 2009 - IFP Training

Tensile strength (R)

Critical quenching rate