Cryogenic Steel

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Steels for cryogenic applications Page 2
1 Introduction
Steels, which are used at low temperatures, are called cryogenic steels, low-temperature resistant
steels or steels that are tough at sub-zero temperatures. Their most important property is sufficient
toughness at operating temperature. Associated with this, is a considerable sensitivity to brittle
fracturing. Furthermore, they are characterised in some cases by high strengths and their suitability for
welding. These materials are used particularly in machinery for liquefying gas, for pipes, pumps, fittings
of cooling industry as well as for bearing, transport and pressure vessels of the liquidated gases (Figure
1, Figure 2). Nuclear research and engineering is also a special application of these steels.
Figure 1: LPG tanker (liquefied petroleum gas) with Figure 2: Tank for liquefied petroleum gas of a self-
gas tanks made of low-temperature resistant pressure service autogas filling station
vessel steels
For low-temperature applications, various materials can be chosen depending on the operating temperature.
These also include non-ferrous materials such as:
– Copper and copper alloys (cf. Chapter 2.18)

– Nickel and nickel alloys (cf. Chapter 2.19)
– Aluminium and aluminium materials (cf. Chapter 2.20)
To improve its toughness at subzero temperatures, the element nickel, in particular, is added to the
steel, in addition to other materials-technical measures. If the nickel content is below 10% and if no
further property-determining elements (like e.g. chromium) are added, the microstructure remains
ferritic-pearlitic at room temperature under conditions of equilibrium (Figure 16) and has a cubic body
centred elementary cell. Due to their preferred application as pressure vessel material steels, these
steels are organised, in accordance with CEN ISO/TR 15 608 (grouping metallic materials for
welding), into material group 9 and its subgroups 9.1 to 9.3 (Table 1).
Table 1: Material group 9 according to CEN ISO/TR 15 608 and important European material standards
Low-temperature resistant pressure vessel steels – nickel-alloyed
Standard steels
Group Sub-group Steel grades
(examples)
Nickel-alloyed steels with Ni  10%
EN 10 028-4
9.1 Nickel-alloyed steels with Ni  3% (13MnNi6-3)
EN 10 028-4
9 9.2 Nickel-alloyed steels with 3.0% < Ni  8% (X12Ni5)
EN 10 028-4
9.3 Nickel-alloyed steels with 8.0% < Ni  10% (X8Ni9)
Materials and their behaviour during

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2 Definitions
In addition to their strength, the terms and properties defined below are particularly important for steels
that are tough at subzero temperatures.
Cryogenic engineering (low-temperature engineering)
The term cryogenic engineering should, according to the NIST (National Institute for Standards and
Technology, USA) only be applied to applications below -150 °C. This is why this chapter does not speak
of low-temperature toughness but rather toughness at subzero temperatures (see below).
Deformability
The deformation of a body is understood to be the change in its shape as a result of the influence of an
external force. The deformation can manifest as a change in length or angle.
Ductility
The term ductility describes the resistance of a material to fracture or crack propagation. The ductility
mostly occurs through the absorption of energy in plastic deformation. For numerous materials, including
in particular all cubic-body-centred metals (and therefore also the non-alloy structural steels), the ductility
is heavily dependent on temperature.
Toughness at subzero temperatures
The term toughness at subzero temperatures is not clearly defined. In the specifications, two limit val-
ues are defined for it. In accordance with SEW 680 steels are tough at subzero temperatures, if they still
display an impact energy of 27 J (at the cross specimen) at temperatures  -10 °C. Contrary to this DIN
17280 specifies as a limit value for toughness at subzero temperatures a temperature  -60 °C.
Note: The term 'toughness at subzero temperatures' is no longer included in the European standard DIN
EN 10 028-4. For this reason, reference is made to the withdrawn standards DIN 17 280 and SEW 680.
It is recommended to use the limit temperature -60 °C.
3 Verification of toughness
The toughness of steel materials is tested by proving a minimum value for impact energy in the
notched-bar impact test (cf. Chapter 2.23), which is required in the respective standards and regula-
tions (e.g. EN 10 028-4).
Depending on the crystal lattice structure and the test temperature, the notched-bar impact test produces
different curves, as shown in . These have the following meanings:
– Curve : Fine grain structural steels in the cbc lattice structure

– Curve : Metals with cbc or hdg lattice structure, e.g. non-alloy structural steels, chromium steels,
magnesium
– Curve : Metals with cfc lattice structure, e.g. austenitic Cr-Ni steels, aluminium, copper, nickel
– Curve : Brittle materials, e.g., cast iron
In particular non-alloy structural steels, like all other materials with cubic body centred elementary
cells (cf. Chapter 2.01) display a marked dependence between temperature and their toughness. The
transition between the tough "high" and the brittle "low" in the impact energy consumed/temperature
curve is described by the transition temperature Tü or Tt of impact energy (). This is defined as a tem-
perature between the high and the low of the impact energy consumed/temperature curve. The
following allocations are common in accordance with Chapter 2.23:

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Tü27 Temperature, at which the impact energy reaches a defined limit value (e.g. 27 J, )
Tü50 Temperature, at which a certain amount of matt or fibrous fracture area occurs, e.g. 50%
Tü0.4 Temperature, at which a defined measure of lateral widening is obtained, e.g. 0.4 mm
Tü50% Temperature, at which the size of the crystalline patch is 50% (amount of crystalline patch is
estimated)
The application temperature of a given material should therefore always be above the respective defined
transition temperature. In other words: Materials for low-temperature applications must be resistant
to embrittlement fractures.
80
High altitude
 70
 High altitude
Impact energy KV in J
 60
Impact energy KV in J
50
40
Steep drop Steep drop
30
27
20
Low altitude Low altitude
10

0
Temperature T Tü27
Temperature T
Figure 3: Schematic illustration of curves of im- Figure 4: Curve of impact energy consumed as a
pact energy consumed as a function of the tem- function of temperature, with example for the tran-
perature for different materials sition temperature Tü27
Figure 5: Broken up Liberty-T2-tanker S.S. Figure 6: Broken up Liberty freighter S.S “Charles S.
“Schenectady” in the port of Portland, USA Haight” near to Cape Ann, USA (picture: Ted Dow, USA)
(picture: Library of Congress, USA)
Before the phenomenon of the transition temperature was known, ships kept breaking apart in Arctic
waters due to embrittlement. Typical examples of this are the Liberty freighter and T2 tanker: these
World War 2 era ships broke apart with hardly deformation or obvious reason in wet dock or on calm
seas, but at low temperatures (Figure 5 and Figure 6). The sinking of the RMS “Titanic” on 15 April 1912
is ultimately due to a material embrittlement due to the low water temperatures of -4 °C in the North
Atlantic (Figure 7 and Figure 8). The steels used were not sufficiently tough at low temperatures.

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Figure 7: The RMS “Titanic” leaving Southampton on Figure 8: Iceberg, with which the RMS “Titanic” is pre-
10 April 1912 (picture: F. G. O. Stuart, U.K.) sumed to have collided (picture: Wikimedia)
4 Measures for achieving toughness at subzero temperatures

4.1 General possibilities for increasing strength and toughness
The metallurgical options for increasing strength presented in Chapter 2.10 do not always have a benefi-
cial effect on the toughness properties, as shown in Table 2. When using the respective mechanisms, it
is important to pay attention how these are influencing the use and processing properties, the toughness
at subzero temperatures and the suitability for welding.
Table 2: Options for changing the mechanical-technological properties of steel

Increase in Improvement in toughness
Mechanism
strength properties properties
alloying with existing
Solid solution hardening yes
elements
Strain hardening yes no
through special Ms-
Solidification by microstructural transformation yes
microstructure
Hardening yes very limited
Grain refining yes yes
4.2 Particular options for increasing toughness at subzero temperatures
An improvement in the impact energy values and thus an increased resistance to brittle fracturing at low
temperatures on non-alloy and low-alloy steels, i.e. steels with cbc elementary cell, can be achieved by
the following metallurgical measures:
Improvement in purity, inter alia by:

– lowering trace and impurity elements (phosphorus, sulphur each  0.025%)
Changing the alloy potential:

– Setting a (very) low carbon content (increase in strength by grain refining)
– Alloying with nickel and/or manganese (cf. Section 4.3)

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Setting a fine-grained microstructure, inter alia by:

– alloying with aluminium (0.02%)
– adding fine-grained additives (e.g. carbide formers such as niobium, vanadium, titanium, etc.)
– normalising, quenching and tempering, thermomechanical treatment
In most cases, a targetted heat treatment improves the toughness at subzero temperatures. In particular
with the low-alloy steels (Ni  1%) the homogeneity of the microstructure can be improved by normalising,
which then improves the toughness. On the other hand, the alloyed steels (Ni  3.5%) are generally
quenched and tempered. The resultant martensitic or martensitic-bainitic microstructure offers significant-
ly better toughness properties with simultaneoulsy high strength values than the normalised microstructure.
4.3 Influences of nickel and manganese on the toughness of steels with cbc elementary cell
4.3.1 Influence of nickel on the the impact energy curve
Nickel is the only element, through which the toughness of an iron-based material can be improved even
at falling temperatures. By adding nickel, the curve of the impact energy moves to the left over the tem-
perature line, i.e. the transition temperature and with it therefore the risk of the formation of brittle
fractures is moved to lower temperatures. In accordance with Figure 9 the transition temperature
Tü27 of a steel with 2% nickel and 0.15% carbon is about -120 °C. A steel with 13% nickel and 0.01%
carbon on the other hand does, up to a temperature of -196°C, not anymore display up a drop in the
course of the curve due to its austenitic microstructure (and therefore also no embrittlement at low tem-
peratures.) Nickel also brings about a lowering of the A1 and A3 temperature, with which a considerable
supercooling of the austenite transformation is associated. As a result, steels alloyed with sufficient nick-
el can already tend to form martensite (cubic martensite) during air cooling.
4.3.2 Influence of manganese on the impact energy curve
Manganese in quantities of up to approx. 2% impacts positively on the toughness of steels (Figure 10).
By adding this element the fineness of grain is improved, thus lowering the transition temperature Tü.
The reason for this is the reduction in the transformation temperature of austenite, which leads to a
significant delay in the diffusion processes during transformation. The result is a smaller secondary grain
size and a very fine formation of pearlite. Manganese content above 2% however leads, due to the
significantly lower transformation temperature of austenite, to the formation of intermediate stage (bain-
ite) or martensite, with which an increasing embrittling effect is associated. For this reason, the man-
ganese content is to be limited to maximum 1.7%, to guarantee the toughness of steels with a cbc ele-
mentary cell at subzero temperatures.
Note: To guarantee sufficient toughness at subzero temperatures, it is important to lower the share of
manganese in the steel further as the nickel content increases, as otherwise this would lead to an in-
crease in solid solution hardening and the associated drop in toughness.

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250 50
Impact energy (ISO-V-Probe) in J
200 0
Transition temperature Tü27 in °C

5 % Ni
150 8,5 % Ni -50

Fine granularity
13 % Ni
Bainite,
100 Martensite formation
- 150
2 % Ni
0 % Ni
3,5 % Ni
50 - 200
0 - 250
- 200 - 160 - 120 -80 -40 0 40 0 1,0 2,0 3,0
Test temperature In °C Weight content of manganese in %
Figure 9: Influence of nickel on the impact energy Figure 10: Influence of manganese on the transi-
according to EBERT tion temperature of the impact energy
5 Behaviour of metals at falling temperature

5.1 Influence of falling temperatures on mechanical properties
The temperature-dependence of the mechanical properties of metallic materials must be known if these
materials are to be used properly. Incidences of embrittlement in the thermally unaffected base material,
in the weld metal and in the heat-affected zone of welded joints are a key problem and should not occur
at operating temperature. Thus as the temperature falls, the resistance to shape change, the yield
strength and the tensile strength of metallic materials more or less increases. Under no circumstances
are these properties less than at room temperature, so that components that are sufficiently dimensioned
at room temperature can also withstand the stresses at low temperatures. For static stress, however, this
is only theoretically correct and is not necessarily the case in practice. The reason lies in the defor-
mation
behaviour. Whereas in metals and alloys with cubic-face-centred elementary cell the deformation
parameters either increase slightly or stay the same as the temperature falls, for metals and alloys with
a cubic body or hexagonal crystal structure, the ductility suddenly falls more or less strongly below
certain temperatures. The susceptibility of such materials to the formation of brittle fractures therefore
increases considerably (cf. Section 5.2).
Figure 11: Material parameters of S235, X2NiCr18-16 and TiAl6V4 as a function of temperature
(acc. to FREY and HAEFER)

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Figure 11 shows the curve of the strength and

deformation parameters as a function of temperature
using the example of three metallic materials with
different lattice structures. The marked steep drop
of the deformation parameters of non-alloy structural
steel S235 at falling temperature is clearly evident.
Figure 12 schematically illustrates what is known as

the “embrittlement temperature”. As can be
seen, as the temperature falls the yield point Re
increases faster than the tensile strength Rm. The
temperature, at which both strength values col-
lapse, is called the “embrittlement temperature”.
Figure 12: Schematic illustration of the term
“embrittlement temperature”
5.2 Brittle fracture
As the temperature drops, cubic-body-centred materials, in particular, lose the ability at atomic level to
glide under loading conditions (cf. Chapter 2.01). They lose their ductility and toughness. As a result,
any loading condition lead to a splitting of the grains. This in turn leads to the formation of an unstable,
propogating crack. The splitting of the grains produces the typical fracture appearance, the cleavage
fracture (this is brittle, because zero-deformation fractures develop, with few exceptions, in a transcrystal-
line fashion Figure 13). Brittle fractures occur without plastic deformations and require only a little energy
to form. Selected influences on this fracture type are compared with deformation fractures in Table 3.
Figure 13: Typical fracture area of a brittle fracture Figure 14: Typical fracture area of a ductile fracture
(cleavage fracture), SEM micrograph (honeycomb fracture), SEM micrograph
5.3 Deformation fracture
If the flowing of a material that takes place during plastic deformation processes is regarded as sliding
of the crystal planes on one another and therefore as the process of passing through dislocations, the
crack initiation can by explained by the collision of dislocations at, e.g. grain boundaries. These combine
into cavities and the material plastifies (i.e. it deforms). If the tension is high enough locally, the faces
between these cavities tear off. This results in deformation fractures with their typical honeycomb struc-
ture (Figure 14). A strong constriction in the area of the fracture zone is typical of this type of fracture.
Parameters that influence the formation of deformation fractures are contained in Table 3 and compared
to brittle fractures.

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Table 3: Selected parameters that influence the formation of brittle and deformation fractures (overview)
Variable Brittle fracture Deformation fracture
Temperature: Low temperatures Dependent on the type of elementary cell
Component thickness: Thick components Dependent on the load
Notches: Sharp notches Favourable influence
Residual stress state: High residual stress states Uniaxial stress conditions
Microstructure: Imbalanced micro structure Dependent on the microstructure hardness
(e.g. martensite)
Purity Embrittling inclusions Type, quantity, size of inclusions
Grain size: Coarse grain Dependent on the size and shape of the grain
Material (elementary cell): cbc, hdP Temperature-dependent (cbc, hdP, cfc)
Chemical composition: High carbon content Dependent on the type of elementary cell
Stress: Abrupt (fast) Static (slow)
6 Overview of materials for low-temperature applications

6.1 Typical application temperatures and suitable steel materials
As already described in Section 1, materials that are tough at subzero temperatures are used in particular
for gas liquefaction systems and for transporting and storing liquefied gasses. The need to liquefy
gasses results from the fact that the volume of liquid gas is many times smaller than that of the gaseous
phase. Thus, for example, 600 m³ of natural gas (comprising mainly methane, CH4) is reduced, at a
temperature of -163 °C, to 1 m³ of liquefied petroleum gas. Depending on the respective boiling or
condensation temperature, special steels have proven to be successful for this (Table 4).
Table 4: Application areas of selected materials that are tough at subzero temperatures compared to the
boiling temperatures of technical gases
Boiling tem-
Application limit Yield strength:
Gas perature Steel or material type
temperature in °C Re in N/mm²
in °C
Ammonia -33.4 -40 Fine grain structural steel (QL) 460 – 960
Propane -42.1 -50 Fine grain structural steels (NL, ML) 275 – 460
Carbon
-50.2 Fine grain structural steel (QL1) 460 – 890
disulphide -60
Radon -61.7 Ni-alloy pressure vessel steel (1% Ni) 285 – 355
Carbon
-78.5
dioxide
-100 Ni alloy pressure vessel steel (3.5% Ni) 355
Acetylene -83.6
Ethane -88.6
Ethylene
-103.8 -120 Ni-alloy pressure vessel steel (5% Ni) 390
(LEG)
Krypton -151.0
Methane -163.0
Ni-alloy pressure vessel steel (9% Ni) 490 – 585
(LNG)
-196 Austenitic Cr-Mn steels 300 – 320
Oxygen -182.9
Austenitic Cr-Ni-steels 200 – 350
Argon -185.9
Nitrogen -195.8
Neon -246.1 Austenitic Ni-Cr steels and alloys 250 – 300
-253
Hydrogen -252.8 Nickel and Ni alloys 80 – 300
Helium -268.9 -273 Nickel and Ni alloys 80 – 300

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6.2 Low-temperature properties of non-alloy and alloyed fine grain structural steels
The characteristics of high-strength fine grain structural steels are discussed in detail in Chapter 2.10.
Taking into consideration their use in the refrigeration technology, it is important to consider that these
can be used, depending on the way in which they are manufactured and their treatment status, down as
low as temperatures of -60 °C (QL1) (Table 4).
Due to their cubic-body-centre lattice all fine grain steels with particular toughness at subzero
temperatures also display a steep drop in the curve of impact energy consumed over temperature. This
is however moved to lower temperatures compared to non-alloy structural steels by the measures
described in Section 4.2 (cf. , curves  and . Depending on their manufacturing technology,
fine grain structural steels can be categorised into three main types (the fourth type, i.e. precipitation-
hardenable fine grain structural steels, is no longer standardised):
Normalised or normalised rolled fine structural steels (N) – EN 10 025-3:

– N: Cvtransverse at -20 °C  20 J
– NL: Cvtransverse at -50 °C  16 J
Thermomechanical rolled fine grain structural (M) – EN 10 025-4:

– M: Cvtransverse bei -20 °C  20 J
– ML: Cvtransverse bei -50 °C  16 J
Fluid or water-quenched and tempered fine grain structural steels (Q) – EN 10 025-6:
– Q: Cvtransverse at -20 °C  27 J
– QL: Cvtransverse at -40 °C  27 J
– QL1: Cvtransverse at -60 °C  27 J
6.3 Low-temperature properties of stainless steels
The properties of stainless steels in accordance with DIN EN 10 088-1 are discussed in detail in Chapter
2.15. Due to their austenitic micro structure with cubic-face-centred elementary cell, the austenitic
chromium-nickel materials in particular, display a tough behaviour even at temperatures in the vicinity of
absolute zero to (approx. 10 K). As can be seen in , curve , the curve of impact energy consumed over
temperature does not have a steep drop. Depending on their chemical composition, the austenitic
micro structure of these steels remains stable even at low temperatures. Affected by their micro
structural structure at room temperature, the stainless steels can be categorized into four main types.
Ferritic chromium steels:

– Application temperatures to: approx. -50°C
Martensitic chromium steels:

– Application temperatures of martensitic chromium steels to: approx. 0°C
– Application temperatures of soft-martensitic chromium steels to: approx. -50 °C
Austenitic chromium-nickel steels:

– Application temperatures up to: approx. 10 K
Ferritic-austenitic chromium-nickel steels:

– Application temperatures up to: approx. -200°C

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6.4 Low-temperature properties of non-ferrous metals that are tough at subzero temperatures
For use at low temperatures, however, a range of non-ferrous metals and their alloys with cubic-face-
centred lattice structure are suitable. These include in particular:
Copper and copper alloys

– Application temperatures up to: approx. -200 °C
Nickel and nickel alloys

– Application temperatures up to: approx. -273 °C (0 K)
Aluminium and aluminium alloys

– Application temperatures up to: approx. -200 °C
Note: these non-ferrous materials are discussed in detail in chapters 2.18, 2.19 and 2.20.
7 Nickel-alloy pressure vessel steels that are tough at low temperatures

7.1 Overview of material group
Through the development of pressure vessel steels with different nickel contents, materials are available,
which have sufficient impact properties at low operating temperatures (EN 10 028-4). These can be
classified according to their nickel content into four groups:
– 1% nickel steels
– 3.5% nickel steels
The alloying element nickel influences the transformation sequence and the quenching and tempering
of these steels, giving more favourable microstructure characteristics, in particular a fine-grained result.
In addition to the resultant improvement in toughness properties, the strength properties can also be
enhanced, even with the same contents of the other elements present in these steels, such as carbon,
silicon and manganese (solid solution hardening).
By increasing the nickel content, the transition temperature in the curve of impact energy consumed over
temperature can be moved to lower temperatures, without a marked prominent steep drop occurring.
With that, the application temperatures of such steels can be reduced, in some cases significantly ( and
Figure 9). In addition to the chemical composition, the microstructure formation, the
heat-treatment and stress states also impact on the position of the steep drop of the impact energy
(transition temperature) for these materials.
7.2 Properties of nickel-alloyed pressure vessel steels that are tough at subzero temperatures
Table 5, Table 6 and Table 7 provide information on the chemical composition and on selected mechani-
cal properties of nickel-alloyed steels that are tough at subzero temperatures. In terms of toughness at
subzero temperatures, these steels possess a high level of purity, i.e. low content of phosphorous
and sulphur as well as very precisely coordinated content of the main alloying elements, nickel
and manganese as well as carbon.

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Table 5: Chemical composition (ladle analysis) to DIN EN 10 028-4

Steel grade Mass fraction in %)
C Si Mn P S Altot Mo Nb Ni V
Short name Mat. no.:
max. max. max. max. min. max. max. max.
0.70 to 0.30 to
11MnNi5-3 1.6212 0.14 0.50 0.025 0.015 0.020 — 0.05 0.05
1.50 0.80
0.85 to 0.30 bis
13MnNi6-3 1.6217 0.16 0.50 0.025 0.010 0.020 — 0.05 0.05
1.70 0.85
0.80 to 1.30 to
15NiMn6 1.6228 0.18 0.35 0.025 0.010 — — — 0.05
1.50 1.70
0.30 bis 3.25 to
12Ni14 1.5637 0.15 0.35 0.020 0.005 — — — 0.05
0.80 3.75
0.30 bis 4.75 to
X12Ni5 1.5680 0.15 0.35 0.020 0.005 — — — 0.05
0.80 5.25
0.30 bis 8.50 to
X8Ni9 1.5662 0.10 0.35 0.020 0.005 — 0.10 — 0.05
0.80 10.00
0.30 bis 8.50 bis
X7Ni9 1.5663 0.10 0.35 0.015 0.005 — 0.10 — 0.01
0.80 10.00
Table 6: Mechanical properties at room temperature to DIN EN 10 028-4

Product thickness ReH Rm A
Steel grade
Usual delivery state*) [mm] min. min.
Short name Mat. no.: Over To [N/mm²] [N/mm²] [%]
30 285
11MnNi5-3 1.6212 +N (+NT) 30 50 275 420 to 530 24
50 80 265
30 335
13MnNi6-3 1.6217 +N (+NT) 30 50 345 490 to 610 22
50 80 335
30 355
+N
15MnNi6 1.6228 or +NT 30 50 345 490 to 640 22
or +QT
50 80 335
30 355
+N
12Ni14 1.5637 or +NT 30 50 345 490 to 640 22
or +QT
50 80 335
+N 30 390
X12Ni5 1.5680 or +NT 530 to 710 20
30 50 380
or +QT
+N 30 490
+NT640
plus +NT 30 50 480
640 to 840 18
30 490
X8Ni9 1.5662 +QT640 +QT
30 50 480
30 585
+QT680 +QT 680 to 820 18
30 50 575
30 585
X7Ni9 1.5663 +QT 680 to 820 18
30 50 575
*) +N = normalised; +NT = normalised and tempered; +QT = quenched and tempered; +NT640/+QT640/+QT680 = heat treatment type with minimum tensile
strength of 640 or 680 N/mm²

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Table 7: Minimum values of impact energy (ISO V specimens) according to DIN EN 10 028-4
Steel grade Heat- Minimum values of impact energy Cv in J at test temperature in °C
Position of
treatment
Short name Mat. no.: test pieces 20 0 -20 -40 -50 -60 -80 -100 -120 -150 -170 -196
condition*)
11MnNi5-3 1.6212 longitudinal 70 60 55 50 45 40 — — — — — —
+N (+T)
13MnNi6-3 1.6217 transverse 50 50 45 35 30 27 — — — — — —
+N longitudinal 65 65 65 60 50 50 40 — — — — —
15NiMn6 1.6228 or +NT
or +QT transverse 50 50 45 40 35 35 27 — — — — —
+N longitudinal 65 60 55 55 50 50 45 40 — — — —
12Ni14 1.5637 or +NT
or +QT transverse 50 50 45 35 35 35 30 27 — — — —
+N longitudinal 70 70 70 65 65 65 60 50 40 — — —
X12Ni5 1.5680 or +NT
or +QT transverse 60 60 55 45 45 45 40 30 27 — — —
longitudinal 100 100 100 100 100 100 100 90 80 70 60 50

1.5662 +NT640
transverse 70 70 70 70 70 70 70 60 50 50 45 40
longitudinal 100 100 100 100 100 100 100 90 80 70 60 50

X8Ni9 1.5662 +QT640
transverse 70 70 70 70 70 70 70 60 50 50 45 40
longitudinal 120 120 120 120 120 120 120 110 100 90 80 70
1.5662 +QT680
transverse 100 100 100 100 100 100 100 90 80 70 60 50
longitudinal 120 120 120 120 120 120 120 120 120 120 110 100
X7Ni9 1.5663 +QT
transverse 100 100 100 100 100 100 100 100 100 100 90 80
*) +N = normalised; +NT = normalised and tempered; +QT = quenched and tempered; +NT640/+QT640/+QT680 = heat treatment type with minimum tensile
strength of 640 or 680 N/mm².
7.3 Heat-treatment states of nickel-alloyed pressure vessel steels that are tough at subzero
temperatures
Nickel-alloyed steels are used in accordance with Table 6 and Table 7 in the normalised (+N) as well as
in the normalised and tempered (+NT) or in the liquid-hardened and tempered state (+QT). The following
examples describe typical states during heat treatments:
Example 1: 12Ni14+NT:
The heat treatment +NT for the steel 12Ni14 prescribes that this is to be austenitised in the temperature
range between 830 and 880 °C and subsequently cooled in air. Tempering occurs at temperatures between
580 and 640 °C. After tempering, the steel can be cooled either in air or quenched in water.
Example 2: X8Ni9+QT640:
The steel X8Ni9 exists in the quenched and tempered state as indicated by the code +QT. The tempering
and quenching treatment is carried out as follows:
– Austenitising between 770 and 830 °C with water or oil quenching.

– Tempering between 540 and 600 °C with cooling in air or quenching in water.
Note: The number “640” means that the minimum tensile strength must be Rm = 640 N/mm².

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7.4 Microstructure formation of nickel-alloyed steels
Figure 15 provides information regarding the influence of the nickel and carbon content on the micro struc-
ture formation of steel materials. It is clear that steels with high nickel and carbon contents have a fully aus-
tenitic microstructure. As the content of carbon decreases and the nickel content stays at the same level,
the tendency to form martensite increases. This is due to the supercooling of the - transformation in the
iron-nickel binary system (Figure 16). More nickel-rich and therefore tougher (more cubic) martensite may
form. Therefore these steels can be quenched and tempered depending on the nickel content.
Figure 15: Influence of the Ni and C-content on the micro Figure 16: Binary equilibrium system iron nickel
structure formation (acc. to GUILLET) (acc. to MASSALSKI)
7.5 Types of nickel-alloy pressure vessel steels that are tough at subzero temperatures
1% nickel steels
Alloying small quantities of nickel improves the hardenability of these steels. They are used both in the
quenched and tempered and in the normalised state. Their good behaviour up to temperatures of -60 °C
is achieved as a result of the tough, nickel-alloyed ferrite. Figure 17 shows the transformation behaviour
of the steel 13MnNi6-3. The steels are used for liquid propane and butane applications, among others.
A typical example of the 1% nickel steels is the material 13MnNi6-3.
3.5% nickel steels
The 3.5% nickel-alloyed steels are used in the temperature range from -50°C to -100°C. Thus they can
be used e.g. for the liquefying of carbon dioxide, acetylene and ethane. The materials have a terrific
combination of high strength and good toughness. A typical example of the 3.5% nickel steels is the
material 12Ni14.
5% nickel steels
These steels are used up to temperatures of minimum -120 °C. Compared with the 9% nickel steels,
these steels are more economical due to their lower nickel content, but they are not as strong. A typical
application of these materials is the construction of tanks for ethylene gas tankers. The only 5% nickel
steel standardised in EN 10 028-4 is the material X12Ni5.

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9% nickel steels
The application temperatures of steels with 9% nickel go as low as -196 °C. The extraordinary low tem-
perature properties of these materials are based on the high toughness of the low-carbon, tempered
(cubic) Ni-martensite. In this context, Figure 18 shows the transformation behaviour of the steel X8Ni9 in
the continuous TTT diagram. It is clear that this material is an air-hardening steel (cf. also section 4.3.1).
Typical applications of these materials include stationary storage tanks for very cold gasses, such as
liquid nitrogen. Due to their insensitivity to stress cracking corrosion (cf. Chapter 2.14), 9% Ni steels
can also be used in alkaline environments.
900 900
Austenitisation: 900 °C / 5 min Austenitisation: 790 °C / 5 min
800
800 A3 A3
700
700 A1
Temperature in °C
A F
Temperature in °C
600 A A1
P
600 500
500 Zw 400 Ms Zw
Ms
300
400 M
M Zw= bainite 200
Zw= bainite
300
HV1 430 295 274 210 170 160 100
HV1 360 350 320 300 300 290 280
200 0
1 10 10² 10³ 104 1 10 10² 10³ 10 4
105
106
Time in s
Time in s
Figure 17: Continuous TTT diagram for the steel Figure 18: Continuous TTT diagram for the steel X8Ni9
13MnNi6-3 (source: Heat treatment atlas) (source: Heat treatment atlas)
8 Welding of nickel-alloyed pressure vessel steels that are tough at subzero

temperatures
8.1 General notes on welding fabrication
The successful welding of nickel-alloyed pressure vessel steels that are tough at subzero temperatures
depends on a range of variables. These include, in particular:
– the steel grade,

– the manufacturing process and the delivered state,
– the remanent (remaining) magnetism,
– thermal conductivity and thermal expansion,
– the welding process and the filler metal,
– the heat controlling and the heat input and the
– cooling rate.
The choice of filler metals depends on the following criteria:
– toughness properties of the base materials,

– application temperature,
– costs,
– weldability with alternating current --> thorough knowledge of the magnetic specifics of the 9 % steel
(remanent magnetism),
– welding position --> suitability for out-of-position welding
– hot crack resistance and
– type of powder in submerged arc welding.

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8.2 Remanent magnetism and effective counter measures
The nickel steels that are tough at subzero temperatures, in particular the materials X12Ni5 and X8Ni9,
tend to build up a remanent magnetism, which can impair the welding process because of the blow
effect. They must therefore be welded in the demagnetized state. Here, a remnant magnetic field
strength of 1,600 A/m (corresponding to 20 Oe) as a mean value with respect to the disruptive magnetic
fields during welding should not in principle be exceeded.
Note: When ordering these materials, in addition to the usual material certificate according to EN 10204
“Types of inspection documents”, an inspection document about the magnetic field strength must be
agreed when accepting the semi-finished product.
During transport, storage and further processing, magnetisation of materials is to be avoided, which
could e.g. occur by rounding on bending rollers, transporting with magnet cranes, thermal cutting with
magnet roll guidance or the influence of current-carrying welding cables and the like. Prior to welding,
the magnetic fields between the joint edges should be checked. A field strength of max. 4800 A/m
(60 Oe) does not yet impair welding considerably. Stronger magnetic fields may be influenced by the
position of the antipole or respectively weakened by mounting permanent magnets or by creating a
closed field. Also, fitting a strip of non-alloyed sheet steel to the back of the weld reduces the blowing
effect in the welding gap by displacing the field lines. The stripe thickness shall correspond to at least the
thickness of the sheet to be welded and the stripe width to at least four times the thickness of the sheet
to be welded. If the measures stated do not lead to success, an improvement can be achieved by the
following approach:
– Welding with alternating current,

– Using modern welding power sources, e.g. “square wave” and
– Buffering the weld faces with the prescribed filler metal.
8.3 Welding 1% and 3.5% nickel steels
Usable welding processes:
E, SAW, TIG, MAG-M, MIG, ...
Welding consumables:
mostly same type (alloy type: 1 to 3.5% nickel)
– Very similar linear expansion coefficient as base material.

– For metal arc welding, hydrogen-controlled filler metals are to be used.
– For mixed compounds with austenites, nickel-based filler metals are to be preferred.
Examples of the same type of filler metals for 1% and 3.5% nickel steels that are tough at subzero tem-
peratures are listed in Table 8.
Table 8: Fillers of the same or similar type for 1% and 3.5% nickel steels (EN ISO 2560)
Alloying content in weight-%
Filler metal
%C % Si % Mn % Cr % Ni % Mo %W Others
E 46 8 2Ni B 0.05 0.3 1.4 — 1.8-2.6 — — —
E 50 8 3Ni B 0.05 0.2 1.4 — 2.6-3.8 — — —

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Heat treatment of the base material:
If the impact energy needs to meet high requirements around the fusion line, a quenched and
tempered base material is recommended.
Heat input during welding:
– Q  20 kJ/cm
Preheating and interpass temperature:
– Pre-heating temperature: is to be adapted to the plate/sheet thickness, temperature should not

go below 100°C.
– Interpass temperature:  180 °C
Note: If the interpass temperature is higher, the toughness properties of the heat-affected zone are
influenced negatively at operating temperature due to retarded cooling (risk of coarse grain formation).
In addition, cooling rates that are too high have a disadvantageous impact on the toughness of the
welded joint (risk of formation of brittle martensite).
8.4 Welding 5% and 9% nickel steels
Usable welding processes:
E, SAW, TIG, MAG-M, MIG, ...
Welding consumables:
The choice of filler metals for this steel group depends on various factors. These include:
– the component safety

(coefficient of expansion, hydrogen sensitivity, hot crack safety, deformability, impact energy, behaviour of
fracture mechanics, etc.)
– the design
(yield point, tensile strength, impact energy at design temperature, etc.)
– the cost effectiveness

(welding processes, deposition rate, frequency of repairs, price of the filler material, etc.)
Same-type welding (filler metals with 5 or 9% nickel; alloying type: same type):
To fully utilise the base material strength and toughness properties of the 9% Ni steels, same-type weld-
ing is recommended. However, it has only become common practice for special applications (problem:
weld metal toughness). Table 9 provides an example of such a filler metal.
Table 9: Filler metal of the same type for 9% nickel steels

Filler metal
SG Ni 9* 0.02 0.04 0.40 — 11.0 — — —
*) non-standardised commercial alloy

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SFI / IWE 2.13
Different-type welding (austenitic filler metals; alloying type: Cr-Ni):
Austenitic filler materials of this alloy group show good yield strength and toughness values in the weld
metal. They cannot however achieve the high strength of the base material in all cases. The weld metal
shows high impact properties for temperatures up to -196 °C. Table 10 provides examples of austenitic
filler metals.
However it must be taken into consideration that austenitic filler metals and thus their weld metal too,
depending on the degree of dilution (cf. Chapter 2.05) of the 5% and 9% nickel steels display deviating
linear thermal expansion coefficients. If this is not taken into account, material fatigue due to different
thermal expansion during alternating temperature loading may occur.
Note: Different-type austenitic welded joints on 5% and 9% nickel steels that are tough at subzero tem-
peratures are not resistant to changes in temperature.
Table 10: Different-type filler materials for 5% and 9% nickel steels (alloy type Cr-Ni, EN ISO 3581)
Filler metal
E 18 14 MnW B* 0.20 0.60 9.0 18.0 14.0 — 3.50 —
E 20 16 3 Mn L B 0.04 1.20 5.0-8.0 18.0-21.0 15.0-18.0 2.5-3.5 — 0.20 N
*) non-standardised commercial alloy, on the basis of EN ISO 3581
Different-type welding (Ni-based filler metals; alloying type: nickel alloy):
Different-type welding is preferred for 5% or 9% nickel steels. This is due to the better resistance to
changing temperatures. Ni-based metals thus display almost the same linear thermal expansion
coefficients as 9% Ni steels (Table 11). Moreover, Ni-based filler metals have a significantly lower crack
propagation speed than the other alloy types. Table 12 contains examples of such filler metals.
Table 11: Linear thermal expansion coefficients for different materials

Temperature range Coefficient of linear thermal expansion
Material -6
in °C in 10 /K
9% nickel steel 20 to -196 8 to 10
Chromium-nickel steel 20 to -196 14 to 16
Nickel-based alloy 20 to -196 9 to 11
Note: Temperature change-stressed welded joints with low-temperature resistant 5% and 9% nickel
steels can only be executed using the same type of steel or with nickel-based alloys.
Table 12: Different-type filler materials for 5% and 9% nickel steels (alloy type Ni-basis, EN ISO 14 172)
Filler metal
2.00 18.0 4.0 Fe
E Ni 6082 (NiCr20Mn3Nb) 0.10 0.80 Balance 2.00 —
6.00 22.0 3.0 Nb
20.0 8.5 3.5 Fe
E Ni 6012 (NiCr22Mo9) 0.03 0.70 1.00 Balance —
23.0 10.5 1.5 Nb

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8.5 Notes on the choice of filler metals
Figure 19 contains generally valid information on the choice of filler metals for nickel-alloy pressure ves-
sel steels that are tough at subzero temperatures.
1% nickel steels 3.5% nickel steels 5% nickel steels 9% nickel steels
Same-type welding Different-type welding Same-type welding Different-type welding
deviating properties of deviating properties of

same properties of base same properties of base
base material and weld base material and weld
material and weld metal material and weld metal
metal metal
Filler with 1 - 3.5% Ni Ni-based filler Filler with 5 - 9% Ni Cr-Ni filler Ni filler
Bonds are tough at

Bonds between 1 to
Usually with 1 to 3.5% subzero temperatures Use at T = Use at T =
3.5% Ni steels and
nickel steels and high-strength at the constant change
Cr-Ni steels
same time
Figure 19: Choice of the filler metals for nickel-alloyed pressure vessel steels that are tough at subzero tem-
peratures
8.6 Notes on quality assurance of welding work
As for all welding work, the quality assurance measures as described in more detail in Chapters 4.1 and
4.2 should always be implemented. Given the specifics of their use at low temperatures, however, it
must also be ensured that e.g. within the framework of the work and procedural tests to EN ISO 15 614-
1, the focus is placed in particular on verifying the toughness of the welded joints (impact energy) at the
intended operating temperature. On the other hand, the strength properties can be verified at room tem-
perature, as these do not deteriorate at lower temperatures (cf. Section 5.1). Special attention should
also be paid to the influence of the heat-treatment state of quenched and tempered base materials to-
wards the HAZ of the welded joints in the metallographic microsection.
Given their categorisation as pressure vessel steels and at operating pressures that exceed atmos-
pheric pressure by at least 0.5 bar, additional requirements are to be taken into consideration. These are
stipulated, inter alia, in the Pressure Equipment Directive 97/23/EG (European Pressure Equipment Di-
rective) and in the AD 2000 regulations (cf. Chapter 3.09).
Note: The information contained in this document is to be treated as such and does not replace any
technical regulations and specifications. The most recent editions apply in each case.
Note: During the welding fabrication of pressure vessel steels that are tough at subzero temperatures,
the user information from the respective manufacturer of the base material and/or filler metal should be
respected.

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SFI / IWE 2.

– Copper and copper alloys (cf. Chapter 2.18)

Materials and their behaviour during

Cryogenic engineering (low-temperature engineering)

Toughness at subzero temperatures

– Curve : Fine grain structural steels in the cbc lattice structure

Materials and their behaviour during

Materials and their behaviour during

4 Measures for achieving toughness at subzero temperatures

Table 2: Options for changing the mechanical-technological properties of steel

4.2 Particular options for increasing toughness at subzero temperatures

Improvement in purity, inter alia by:

Changing the alloy potential:

Materials and their behaviour during

Setting a fine-grained microstructure, inter alia by:

4.3.2 Influence of manganese on the impact energy curve

Materials and their behaviour during

Transition temperature Tü27 in °C

150 8,5 % Ni -50

5 Behaviour of metals at falling temperature

Materials and their behaviour during

Figure 11 shows the curve of the strength and

Figure 12 schematically illustrates what is known as

5.2 Brittle fracture

5.3 Deformation fracture

Materials and their behaviour during

6 Overview of materials for low-temperature applications

Materials and their behaviour during

Normalised or normalised rolled fine structural steels (N) – EN 10 025-3:

Thermomechanical rolled fine grain structural (M) – EN 10 025-4:

6.3 Low-temperature properties of stainless steels

Ferritic chromium steels:

Martensitic chromium steels:

Austenitic chromium-nickel steels:

Ferritic-austenitic chromium-nickel steels:

Materials and their behaviour during

Copper and copper alloys

Nickel and nickel alloys

Aluminium and aluminium alloys

7 Nickel-alloy pressure vessel steels that are tough at low temperatures

Materials and their behaviour during

Table 5: Chemical composition (ladle analysis) to DIN EN 10 028-4

Table 6: Mechanical properties at room temperature to DIN EN 10 028-4

11MnNi5-3 1.6212 +N (+NT) 30 50 275 420 to 530 24

13MnNi6-3 1.6217 +N (+NT) 30 50 345 490 to 610 22

Materials and their behaviour during

longitudinal 100 100 100 100 100 100 100 90 80 70 60 50

longitudinal 100 100 100 100 100 100 100 90 80 70 60 50

– Austenitising between 770 and 830 °C with water or oil quenching.

Materials and their behaviour during

7.4 Microstructure formation of nickel-alloyed steels

3.5% nickel steels

Materials and their behaviour during

8 Welding of nickel-alloyed pressure vessel steels that are tough at subzero

– the steel grade,

The choice of filler metals depends on the following criteria:

– toughness properties of the base materials,

Materials and their behaviour during

8.2 Remanent magnetism and effective counter measures

– Welding with alternating current,

8.3 Welding 1% and 3.5% nickel steels

Usable welding processes:

E, SAW, TIG, MAG-M, MIG, ...

mostly same type (alloy type: 1 to 3.5% nickel)