Nickel & Special HT steels for Petrochemical Applications

Nickel & Special HT steels
Petrochemical applications
UTP Schweissmaterial
Application Technology
Contents
1 Requirements of petrochemical processes
2 Base material selection
3 Welding consumables for petrochemical appliances
4 Examination of long-term behaviour of welding consumables
5 Other aspects to be considered
6 Summary
2 | UTP Schweissmaterial | Nickel for HT applications I June 2012

Oil processing in refinery
Distillation takes place at different temperature and

pressure levels.
E.g.: Ammonia synthesis at 100 bar and 600C
Therefore, petrochemical plants are composed of

different base metals.
An oil refinery is a combination of all these units.
Source: howstuffworks.com

Temperature: from RT up to 1200C

Pressure: up to 600 bar

In order to guarantee reliable and

safe processing conditions, base
materials and welding consumables
are selected to fulfil the following
requirements:
Oxidation resistance
Carburisation resistance
Low embrittlement tendency
Creep rupture strength

Contents
6 Summary

Operating temperatures for different materials
Temperature F
2192
1050-1100C 900-1200C
1832 centrifugal
casting
CrNi NiCr
1472 alloys alloys
700C
G-X40CrNiSi2520 X10NiCrAlTi3220
600C stainless ASTM A531 Grade
1112 steels HK40 NiCr15Fe
high-temperature
resistant G-X40NiCrNb3525 NiCr22Mo9Nb
CrMo ASTM A297 HP40
752 NiCr23Fe
steels
X6CrNi1811 NiCr23Co12Mo
ASTM A240 304H
X20CrMoV121 NiCr25FeAlY
392 X6CrNiMo1713
X10CrMoVNb91 ASTM A240 316H X5NiCrCeNb3227

Chemical composition of iron-base alloys
Chemical composition
Iron Base Alloys
Main alloying elements in wt %
Material ASTM
EN Designation Ni Cr Fe C Nb Si Others
No. Designation
1.4859 GX10NiCrNbSi32-20 CT 15C 32 20 R 0,10 1,0 1,0 Mn<2,0
1.4848 GX40CrNiSi25-20 HK 40 20 25 R 0,40 1,8 Mn<2,0
1.4857 GX45NiCrSi35-25 HP 40 34 25 R 0,4 1,8 Mn<2,0
1.4868 GX50CrNiSi30-30 30 30 R 0,5 1,8 0,5<Mn<1,5
1.4889 GX45NiCrNbSiTi45-35 35/45 45 35 R 0,45 1,7 1,8 Mn < 1,5

Chemical composition of nickel-base alloys
Nickel base alloys
Common UNS Mat. EN
Ni Cr Fe C Al Ti Others
name No. No. Designation
Alloy 601 N06601 2.4851 NiCr23Fe R 23 16 0,08 1,4 0,4
0,08%Y
Alloy 602CA N06602 2.4633 NiCr25FeAlY R 25 9,5 0,2 2,1 0,14
0,07%Zr
Alloy 600 L N06600 2.4817 LC-NiCr15Fe R 15 8 <0,025 <0,3
2.4815 G-NiCr15 R 15 22 0,5
NA22H 2.4879 G-NiCr28W R 29 11 0,45 4,5%W
9%Mo
Alloy 625 N06625 2.4856 NiCr22Mo9Nb R 22 <3 <0,025
3,5%Nb
9%Mo
Alloy 617 N06617 2.4663 NiCr23Co12Mo R 22 <2 0,05-0,1 1 0,4
12%Co
1,5%Nb
Alloy 657 2.4680 G-NiCr50Nb R 50 <1,0 <0,1
0,15%N

Requirements for high-temperature alloys
Carburising resistance
Low embrittlement tendency
Creep rupture strength

Oxidation
In order to reduce oxidation rate, you need elements which hinder the diffusion of
O2 inside the material and which have a high affinity to O2
(e.g. Al, Si, Nb)
Influence of alloying elements:
Cr > 25 %; higher Cr content stabilizes oxide films but causes sigma phase
Ni has a beneficial effect on cyclic oxidation
Higher Si-content promotes oxidation resistance, esp. bonding of oxide layer
Rare earth elements enhance oxide stability

Comparison of corrosion attack on Chipped-off

Nicrofer 6023 H (alloy 601) and material
Nicrofer 6025 HAT (alloy 602 CA)
after 1000 h at 1200C (2192F)
in air
Initial dimension
Main alloying elements in wt%
Common
Ni Cr Fe C Al Ti Others Chipped-off
name material
Alloy 601 R 23 16 0,08 1,4 0,4
Alloy 0,08%Y
R 25 9,5 0,2 2,1 0,14
602CA 0,07%Zr

Test medium: Air
Air temperature: 1200C
Time: 1000 hrs

Mechanism of carburization
Decomposition of hydrocarbons creates free carbon,

which diffuses through the grain boundaries into the material.
Carburization increases with rising temperature;

The rate roughly doubles for every 38C tube metal temperature increase.
Consequences of carburization:
Decrease of melting point

Carbide formation with chromium depletion
Loss of ductility due to carbide formation

Carburization
3,5
Carburized at temperature for
260 hours in carbon granulate
3,0
Increase in carbon [%]
2,5 HK-40
25/20
HP-45 Increase of alloy carburization
2,0 25/35 mod.
under rising temperature
35/45
1,5
1,0
0,5
0,0
950 1050 1150 [C]
1800 1900 2000 2100 [F]

Temperature

Carburization
There are Synergistic additions of

Cr, Ni and Si are
numerous & complex W, Nb, Ti and Zr
effective barriers
factors: considerably improve
resistance to carburization

Creep behaviour
Creep is the tendency of a solid material to slowly deform

permanently under the influence of stresses (and temperature).
Strengthening mechanisms against creep:
Solid solution hardening (Cr, Mo, Co, W)

Precipitation hardening (Al, Ti, Nb)
Formation of carbides (Ti, Nb, V, B)
Manipulation of grain size (coarse / fine)
Purity to trace elements

Metallographic explanation for creep behaviour
Microstructure of alloy 800H

after 33470 h, 650C (1202F), 11 N/mm.
On the grain boundaries,
slight formation of chromium carbides
visible, grain size about 170 m,
Initially: 140 m
Mag. 500:1
Microstructure of alloy 800H

after 25760h, 850C (1562F), 1.8 N/mm.
On the grain boundaries,
agglomeration of carbides,
the grains have grown,
grain size about 220 m
Mag. 500:1
Requirements for high-temperature alloys
They should be still weldable!

How to weld these
materials - similar
or dissimilar?

Contents
6 Summary

UTP welding consumables for Fe-base alloys
Iron Base Metals Filler metal
Material No. EN Designation ASTM Des. C Si Cr Ni Nb Others
1.4859 GX10NiCrNbSi32-20 CT 15C 0,1 1 20 32 1 Mn < 2.0
UTP 2133 Mn 0,14 0,3 21 33 1,3 4,5 % Mn
1.4848 GX40CrNiSi25-20 HK 40 0,4 1,8 25 20 - Mn < 2.0
UTP 2535 Nb 0,4 1 25 35 1,2 1,5 % Mn
1.4857 GX45NiCrSi35-25 HP 0,4 1,8 25 34 - Mn < 2.0
UTP 2535 Nb 0,4 1 25 35 1,2 1,5 % Mn
1.4889 GX45NiCrNbSiTi45-35 35/45 0,5 2 35 45 2 Mn < 1.5
UTP 2535 Nb 0,45 1 35 45 0,9 0,8 % Mn

UTP welding consumables for Ni-base alloys
Nickel base alloys Filler metals Chemical composition

Common name Material No. EN Designation Ni Cr Fe C Al Ti Others
Alloy 601 2.4851 NiCr23Fe R 23 16 0,08 1,4 0,4
0,08%Y;
UTP 6225 Al R 25 10 0,8 1,8 0,1 0,07%Zr
0,08%Y;
Alloy 602CA 2.4633 NiCr25FeAlY R 25 9,5 0,2 2,1 0,14 0,07%Zr
0,08%Y;
UTP 6225 Al R 25 10 0,8 1,8 0,07%Zr
Alloy 600 L 2.4817 LC-NiCr15Fe R 15 8 <0,025 <0,3
2.4815 G-NiCr15 R 15 22 0,5
6,2%Mn
UTP 7015 Mo R 16 6 0,04 2,2%Nb
NA22H 2.4879 G-NiCr28W R 29 11 0,45 4,5%W
UTP 2949W R 29 15 0,45 4,5%W
9%Mo;
Alloy 625 2.4856 NiCr22Mo9Nb R 22 <3 <0,025 3,5%Nb
3,3%Nb
UTP 6222 Mo R 22 1,5 0,03 9%Mo
9%Mo;
Alloy 617 2.4663 NiCr23Co12Mo R 22 <2 0,05-0,1 1 0,4 12%Co
9%Mo
UTP 6170 Co R 21 1 0,6 0,7 0,3 12%Co
1,5%Nb
Alloy 657 2.4680 G-NiCr20Nb R 50 <1 <0,1 0,15%N
UTP 5848 Nb R 50 - <0,1 1,5%Nb
Creep strength
Creep rupture strength and high-temperature plastic deformation are

the key properties to determine the tube wall thickness.
The design is usually made for 100,000 hours of service life.
Cr and C control the rupture strength through carbide formation.
Nb is a solid solution strengthener as are W and Mo.
Nb and additions of Ti and Zr produce extremely fine carbides and participate in

the formation and strengthening of the alloy (temperature-stable carbides).

Contents
6 Summary

Creep strength
To increase the working temperature of a weld material,
TV requests creep strength values after
minimum 30,000 hrs at different temperatures.

Testing of creep strength
Plate after welding
1 1 sawn plate
2 2 prepared specimen
3 3 ready specimen
4 4 tested specimen
1000C (1832F), 1071 hrs, 10 N/mm2
Testing of creep strength
Specimen in test

Embrittlement behaviour
Embrittlement tendency is checked after ageing
at different temperatures by Charpy impact test.

Testing of embrittlement behaviour
Plate after welding Plate in oven

Testing of embrittlement behaviour
2 3
1 plate machined UTP 068 HH

2 after 10,000 hrs, 950C 10,000 hrs, 950C
3 - machined after testing

Embrittlement behaviour
Av ( ISO-V ) [ J ]
200
150 950C
750C
850C
Ageing of
550C E NiCrFe-2
100 (UTP 7015 Mo)
650C
50
0
1 10 100 1.000 10.000 100.000
time [ h ] test temperature: RT

Contents
6 Summary

Thermal expansion coefficient
20
19
.
18
thermal expansion coefficient
17
-6
16
m x grd x 10
15
UTP 2133Mn
m
14
alloy 800H
13
1.4859
12 C-steel
11 Alloy 625
10
200 300 400 500 600 700 800 900
temperature C


Base material:
Manaurite 36X
(25Cr 35Ni Nb)

Contents
6 Summary

Summary
For high-temperature application use welding consumables with similar

chemical composition to match the properties of the base metal.
Creep strength plays a key-role in the development of welding

consumables.
Corresponding expansion coefficients are also important for the structure

lifetime.
These filler metals are available for SMAW and GTAW.
Qualification of BWG welding consumables is crucial to meet high quality

requirements.

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Nickel & Special HT steels for Petrochemical Applications

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Nickel & Special HT steels

1 Requirements of petrochemical processes

2 Base material selection

3 Welding consumables for petrochemical appliances

4 Examination of long-term behaviour of welding consumables

5 Other aspects to be considered

2 | UTP Schweissmaterial | Nickel for HT applications I June 2012

Distillation takes place at different temperature and

E.g.: Ammonia synthesis at 100 bar and 600C

Therefore, petrochemical plants are composed of

An oil refinery is a combination of all these units.

3 | UTP Schweissmaterial | Nickel for HT applications I June 2012

Temperature: from RT up to 1200C

4 | UTP Schweissmaterial | Nickel for HT applications I June 2012

In order to guarantee reliable and

5 | UTP Schweissmaterial | Nickel for HT applications I June 2012

1 Requirements of petrochemical processes

2 Base material selection

3 Welding consumables for petrochemical appliances

4 Examination of long-term behaviour of welding consumables

5 Other aspects to be considered

6 | UTP Schweissmaterial | Nickel for HT applications I June 2012

7 | UTP Schweissmaterial | Nickel for HT applications I June 2012

1.4859 GX10NiCrNbSi32-20 CT 15C 32 20 R 0,10 1,0 1,0 Mn<2,0

1.4848 GX40CrNiSi25-20 HK 40 20 25 R 0,40 1,8 Mn<2,0

1.4857 GX45NiCrSi35-25 HP 40 34 25 R 0,4 1,8 Mn<2,0

1.4868 GX50CrNiSi30-30 30 30 R 0,5 1,8 0,5<Mn<1,5

1.4889 GX45NiCrNbSiTi45-35 35/45 45 35 R 0,45 1,7 1,8 Mn < 1,5

8 | UTP Schweissmaterial | Nickel for HT applications I June 2012

9 | UTP Schweissmaterial | Nickel for HT applications I June 2012

Low embrittlement tendency

Creep rupture strength

10 | UTP Schweissmaterial | Nickel for HT applications I June 2012

Influence of alloying elements:

11 | UTP Schweissmaterial | Nickel for HT applications I June 2012

Comparison of corrosion attack on Chipped-off

Alloy 601 R 23 16 0,08 1,4 0,4

12 | UTP Schweissmaterial | Nickel for HT applications I June 2012

Test medium: Air

Air temperature: 1200C

Time: 1000 hrs

13 | UTP Schweissmaterial | Nickel for HT applications I June 2012

Decomposition of hydrocarbons creates free carbon,

Carburization increases with rising temperature;

Decrease of melting point

14 | UTP Schweissmaterial | Nickel for HT applications I June 2012

1800 1900 2000 2100 [F]

15 | UTP Schweissmaterial | Nickel for HT applications I June 2012

There are Synergistic additions of

16 | UTP Schweissmaterial | Nickel for HT applications I June 2012

Creep is the tendency of a solid material to slowly deform

Strengthening mechanisms against creep:

Solid solution hardening (Cr, Mo, Co, W)

17 | UTP Schweissmaterial | Nickel for HT applications I June 2012

Microstructure of alloy 800H

Microstructure of alloy 800H

They should be still weldable!

19 | UTP Schweissmaterial | Nickel for HT applications I June 2012

20 | UTP Schweissmaterial | Nickel for HT applications I June 2012

1 Requirements of petrochemical processes

2 Base material selection

3 Welding consumables for petrochemical appliances