Nofrijon Sofyan, Ph.D.

Introduction
Steel for cryogenic applications is a steel used at
very low temperatures around -200 C.
At this very low temperature, the materials
commonly become brittle.
Because of that, for this low-temperature service,
the materials are required to give a specific high
strength, ductility, and toughness.
Carbon and alloy grades for low-temperature service
are required to provide the high strength, ductility, and
toughness in vehicles, vessels, and structures that must
serve at -45C and lower.
At temperature below ambient, a metals behavior is
characterized somewhat by crystalline structure.
The yield and tensile strengths of metals that crystallize
in the body-centered cubic from iron, molybdenum,
vanadium and chromium depend greatly on
temperature.
4
These metals display a loss of ductility in a narrow
temperature region below room temperature.
The tensile strength of metals with face-centered
cubic structures - aluminum, copper, nickel and
austenitic stainless steel - is more temperature
dependent than their yield strength, and the metals
often increase in ductility as temperature decrease.
Cryogenic properties
5
Transformation occurring in compositions that are normally
stable at room temperature, but metastable at cryogenic
temperatures can greatly alter their behavior.
For example, the combination of gross plastic deformation
and cryogenic temperatures can cause a normally ductile
and tough stainless steel, such as 301, 302, 304, 321, to
partially transform to bcc structure, resulting in an
impairment of ductility and toughness.
A fully stable stainless steel 310 cannot be transformed at
cryogenic temperatures.
6
The 300 series steels offer a fine combination of
toughness and weldability for service to the lowest
temperatures.
In the annealed condition, their strength properties are
adequate for ground-based equipment but inadequate
for lightweight structures.
For aerospace applications, fabricators can take
advantage of the alloys strain-hardening characteristics
and use them in highly cold-worked condition.
7
The principal shortcomings of cold-worked materials
are: low weld-joint efficiencies caused by annealing
during welding and the transformation to martensite
that occurs during cryogenic exposure.
Selection of fully stable grade type 310, overcomes the
transformation problem.
Precipitation-hardening A286 stainless has even higher
strength when cold worked before aging.
The alloy steel recommended for cryogenic service is
9% nickel steel.
8
It is satisfactory for service down to -195C and is
used for transport and storage of cryogenics
because of its low cost and ease of fabrication.
Other alloy steels are suitable for service in the
low-temperature range.
The steels A201 and T-1 can suffice to -45C, nickel
steels with 2.25% Ni can suffice to -59C, and
nickel steels with 3.5% Ni to -101C.
Design for cryogenic applications
9
Designers of cryogenic assemblies base their stress
calculations on the room-temperature properties of
the material.
The reason is that it is the highest temperature the
material will encounter.
10
And it stands that if a higher-strength material that
stands up to super cold conditions were available,
designers might specify it.
At 26C austenitic stainless steel has tensile and
yield strengths that are 172 MPa greater than the
corresponding strengths for type 304 stainless.
At -100C its tensile and yield strength exceed
those of type 304 by 550 MPa and 276 MPa
respectively.
11
A grade with following chemical composition shows
good mechanical properties at cryogenic temperatures:
C - 0.072%, Mn - 16%, P - 0.02%, S - 0.008%, Si -
0.41%, Ni - 5.85%, Cr - 17.8%, N - 0.36%, Fe -
Remainder
The composition is given for plates with 12.7mm
thickness
The material combination of high strength, good
toughness, and weldability should prompt designers to
specify it for welded pressure vessels for the storage of
cryogens.
Ductility and temperature
12
Ductility is a critical property for cryogenic
applications.
In general, BCC metals such as Fe, Carbon and low-
alloy steels, Molybdenum, and Niobium become
brittle at low temperatures.
13
FCC metals such as Cu, Ni, Cu-Ni alloys, Al and its
alloys, and austenitic stainless steels remain ductile
at low temperatures.
Most plastics and elastomers become brittle at low
temperatures.
Ceramics and glasses are already brittle at room
temperature and become slightly more so at
cryogenic temperatures.
Brittle materials
14
In brittle materials, the maximum load is the same as:
the yield strength,
the tensile strength
the breaking strength
Yield in brittle materials such as ceramics does not occur
by the motion of dislocations but by planar defects such
as cracks.
The effect of temperature on the stress-strain curve and tensile
properties of an aluminum alloy.
Brittle materials bend test
16
The bend test is used to measure the properties of brittle
materials where a flat specimen is put under load and bent.
The bend test for measuring the strength of brittle materials
and the deflection, d, obtained by bending.
Brittle Materials
Low alloy steel
17
Low-alloy steels constitute a category of ferrous
materials that exhibit mechanical properties
superior to plain carbon steels as the result of
additions of alloying elements such as nickel,
chromium, and molybdenum.
Total alloy content can range from 2.07% up to
levels just below that of stainless steels, which
contain a minimum of 10% Cr.
18
For many low-alloy steels, the primary function of
the alloying elements is to increase hardenability in
order to optimize mechanical properties and
toughness after heat treatment.
In some cases, however, alloy additions are used to
reduce environmental degradation under certain
specified service conditions.
Classification of low alloy steels
19
As with steels in general, low-alloy steels can be
classified according to:
Chemical composition, such as nickel steels, nickel-
chromium steels, molybdenum steels, chromium-
molybdenum steels
Heat treatment, such as quenched and tempered,
normalized and tempered, annealed.
20
Because of the wide variety of chemical compositions
possible and the fact that some steels are used in more
than one heat-treated, condition, some overlap exists
among the alloy steel classifications.
Thus, four major groups of alloy steels can be
addressed: (1) low-carbon quenched and tempered
(QT) steels, (2) medium-carbon ultrahigh-strength steels,
(3) bearing steels, and (4) heat-resistant chromium-
molybdenum steels.
Low-carbon quenched and tempered steels
21
Low-carbon quenched and tempered steels combine
high yield strength (from 350 to 1035 MPa) and
high tensile strength with good notch toughness,
ductility, corrosion resistance, or weldability.
The various steels have different combinations of
these characteristics based on their intended
applications.
22
However, a few steels, such as HY-80 and HY-100,
are covered by military specifications.
The steels listed are used primarily as plate.
Some of these steels, as well as other, similar steels,
are produced as forgings or castings.
Medium-carbon ultrahigh-strength steels
23
Medium-carbon ultrahigh-strength steels are
structural steels with yield strengths that can exceed
1380 MPa.
Many of these steels are covered by SAE/AISI
designations or are proprietary compositions.
Product forms include billet, bar, rod, forgings,
sheet, tubing, and welding wire.
Bearing steels
24
Bearing steels used for ball and roller bearing
applications are comprised of low carbon (0.10 to
0.20% C) case-hardened steels and high carbon (-
1.0% C) through-hardened steels.
Many of these steels are covered by SAE/AISI
designations.
Cr-Mo heat-resistant steels
25
Chromium-molybdenum heat-resistant steels contain
0.5 to 9% Cr and 0.5 to 1.0% Mo.
The carbon content is usually below 0.2%.
The chromium provides improved oxidation and
corrosion resistance, and the molybdenum increases
strength at elevated temperatures.
26
They are generally supplied in the normalized and
tempered, quenched and tempered or annealed
condition.
Chromium-molybdenum steels are widely used in the
oil and gas industries and in fossil fuel and nuclear
power plants.
Know how
27
Knowing the type of low-alloy steel you have and matching it with the
correct filler metal is critical to achieving weld integrity.
Low-temperature steel
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Designation Lowest usual
service
temperature,
(C)
Min Yield
Strength (MPa)
Tensile
Strength (MPa)
Min
Elongation,
L0= 50 mm
(%)
Uses
A442 Gr. 55 -45 221 379 - 448 26 Welded pressure vessels and storage
tanks; refrigeration; transport
equipment
A442 Gr. 60 -45 221 414 - 496 23
A516 Gr. 55 -45 207 379 - 448 27
A516 Gr. 60 -45 221 414 - 496 25
A516 Gr. 65 -45 241 448 - 531 23
A516 Gr. 70 -45 262 483 - 586 21
A517 Gr. F -45 690 792 - 931 16 Highly stressed vessels
A537 Gr. A -60 345 483 - 620 22 Offshore drilling platforms, storage
tanks, earthmoving equipment A537 Gr. B -60 414 551 - 690 22
29
Designation Lowest usual
service
temperature,
(C)
Min Yield
Strength (MPa)
Tensile
Strength (MPa)
Min
Elongation,
L0= 50 mm
(%)
Uses
A203 Gr. A -60 255 448 - 531 23 Piping for liquid propane, vessels, tanks
A203 Gr. B -60 276 482 - 586 21
A203 Gr. D -101 255 448 - 531 23 Land-based storage for liquid propane,
carbon dioxide, acetylene, ethane and
ethylene
A203 Gr. E -101 276 482 - 586 21
A533 Gr. 1 -73 345 552 - 690 18 Nuclear reactor vessels where low
ambient toughness required for
hydrostatic testing; some chemical and
petroleum equipment
A533 Gr. 2 -73 482 620 - 793 16
A533 Gr. 3 -73 569 690 - 862 16
A543 Gr. 1 -107 586 724 - 862 14 Candidate material with high notch
toughness for heavy-wall pressure
vessels
A543 Gr. 2 -107 690 793 - 931 14
Ferritic cryogenic steels
30
Ferritic cryogenic steels are nickel containing low alloy
steels designed to operate safely at temperatures
substantially below 0C and are characterized by
good tensile properties and high impact strength at low
temperatures.
The nickel content ranges from around 1.5 to 9%,
although there are some fine grained carbon-
manganese steels that may be operated at
temperatures as low as -50C.
31
These grades of steel are generally found in the oil
and gas and petrochemical industries where they
are used for the handling and storage of liquefied
petroleum gases (LPG) at temperatures down to
approximately -100C and, in the case of the 9%
nickel steel, down to -196C.
They are also found in the gas processing industry
for the production and handling of gases such as
carbon dioxide and oxygen.
Some cryogenic steels
32
Steel Type
Specification
(Plate)
Min service
temperature C
Typical storage/
processing application
Fine grained Al killed C/Mn
steel
EN10028-3
P460NL2
-50 Ammonia, propane (LPG)
1.5% Ni steel EN10028-4 15NiMn6 -60 Ammonia, propane, carbon
disulphide
2.5% Ni steel ASTM A203 GrB -60 Ammonia, propane, carbon
disulphide
3.5% Ni steel ASTM A203Gr E
EN10028-4 12Ni14
-101 Carbon dioxide, acetylene, ethane
5% Ni steel EN10028-4 X12Ni5 -130 Ethylene (LEG)
9% Ni steel ASTM A353/A553Tp1
EN10028-4 X8Ni9
-196 Methane (LNG), oxygen, argon
Austenitic stainless steel ASTM 304L
EN10088-1 1.4305
-273 Nitrogen, hydrogen, helium
Applications
33
The choice of which steel to use for
any particular application depends
not only on the temperature but
also on such aspects as section
thickness required by design and
the possibility of stress corrosion.
Welding for cryogenic
34
The applications of these steels require that the
mechanical properties, in particular the toughness, of
welds and their associated heat affected zones match
or are very close to those of the parent metals.
The fabrication of the cryogenic steels into pipework
and vessels therefore requires careful selection of
welding consumables and close control of welding
parameters.
35
Manual metallic arc (SMAW) electrodes matching the
composition and Charpy-V impact strength of the fine
grained carbon manganese steels at -50C can be
obtained, for example, AWS A5.5 E7018-1 electrodes,
although the addition of a small amount of nickel, up to
1%, will give added confidence in achieving the
required toughness.
Matching C/Mn composition MAG (GMAW), flux cored
(FCAW) and submerged arc (SA) consumables will not
give adequate toughness at -50C and require nickel to
provide the required as-welded toughness.
36
Natural gas is more efficiently stored and
transported in liquid phase, which involves taking
the material to temperatures below -163 C.
This requires economic and materials that work well
at low temperatures, such as steel to 9% Nickel
37
This material has been developed to have good
toughness and impact resistance at low
temperatures to prevent the spread of cracks, good
ductility and strength traction.
Metallurgy and weldability of the steel for
cryogenic applications, general welding and the
precautions, need to be taken into account to make
a weld with this steel.
Cryogenic metallurgy
38
The most critical property of steels for cryogenic
applications is their tenacity.
Ferritic materials show a change in their mechanical
behavior when exposed to low temperatures, and this is
manifested by a reduction in the toughness of steel,
characterized by a change from ductile to brittle
behavior as the temperature decreases below the
critical temperature of transition.
39
This temperature can not be assessed on all
materials depending on their crystal structure, in the
case of steels, this temperature is presented in
ferritic steels while not shown in the austenitic.
Welding of steel to 9% nickel
40
Usually these steels are welded in the condition
after heat treatment.
The preparation of the board must be done
carefully, should be avoided sharp edges to try to
induce no magnetization in the plates.
41
Surfaces must be carefully cleaned with acetone or
some organic solvent to remove contaminants that
can cause defects in the weld.
Aspects in the manufacture of welding:
Evaluation of the welding processes to use
Material supply to use
Welding Procedure
Welding processes
42
Evaluation of welding processes to employ: Welding
processes such as submerged arc welding (SAW),
shielded metal arc welding gas (GMAW), arc welding
electrode tungsten (GTAW) and coated electrode
welding (SMAW) can be employed, however the
SMAW process turns out to be a viable and flexible to
weld in any position or material and field.
For these processes are commonly used basic
electrodes.
Filler material
43
Input materials to vary from those of ferritic alloys
high percentage of Ni (80Ni/20Cr/0.26C), they
are generally used in high temperature
applications.
Ferritic alloys around 12% Ni are cheap, but they
are not accepted for the sizes of storage tanks
today.
44
The primary objective in selecting the filler metal is to
get a counterpart to the base metal that is tenacious,
ductile to reduce residual stresses in the HAZ (heat
affected zone) (elongation > 35%), and with a
coefficient of thermal expansion low and similar to the
base metal to prevent thermal fatigue in the union.
Because the liquid natural gas tanks are subject to
continual expansion and contraction, the constant of
thermal expansion filler materials should be similar to
the base material.
References
W.D. Callister, Jr.. Fundamentals of Materials Science
and Engineering, John Wiley & Sons, Inc., New York,
2001
R.C. Reed: The Superalloys, Fundamentals and
Applications, Cambridge University Press, Cambridge,
UK, 2006.
J.R. Davis: Heat-Resistant Materials, ASM Specialty
Handbook, 1997.