MATERIALS FOR HIGH TEMPERATURE

HIGH PRESSURE APPLICATIONS AND

THEIR WELDABILTY

BY
DR.V.R.KRISHNAN
ENGINEERS INDIA LIMITED
NEWDELHI
SOJOM Conference- 2012
 High Temperature High pressure Applications
encountered in many Industries such as

 Chemical
 Petrochemical
 Gas Processing
 Metallurgical
 Power generation
 Energy Conversion
 Waste Incineration
 Heat Recovery
 Heat Treatment
 Nuclear,…etc.
 High Temperature Material used in chemical
process Industry can be broadly classified into:

 Materials used for high pressure applications

for their higher long term high temperature
properties.

 Materials used for their improved high

temperature degradation resistance in specific
environments.

 Material combinations that combine both the

above properties
 Mechanical Property Requirements of Materials
to be considered for High Temperature uses

 High Temperature Strength

 Stress Rupture Strength
 Creep Strength
 Fatigue properties
 Thermal stability
 Thermal Shock Resistance
 Toughness
 Other properties as specified by the designers
Corrosion Resistance Properties of Materials
to be considered for High temperature use

 Oxidation
 Carburization
 Nitriding
 Sulfidation
 Halogenation
 Molten salt Attack
 Liquid Metal Attack
 Fuel Ash Corrosion
 Metal Dusting
 Carbon steels

 Cost Effective Work Horse Material

 Rapidly looses its strength with increase in
temperature
 Under normal circumstances can be used up to
400 Deg. C
 Attacked by H2S above 260 Deg. C
 Attacked by Oxygen and air above 540 Deg. C
 Attacked by Nitrogen above 980Deg.C
 Generally not preferred for high temperature
applications.
 Low alloy Chromium-Molybdenum Steels

 Better understanding of effects of alloying elements and

damage mechanisms gained
 Development of new generation Cr-Mo steels for high
pressure –high temperature Applications.
 Steels should resist the following damage mechanisms:
Temper Embrittlement
Sigma Phase Embrittlement
Hydrogen Embrittlement
Hydrogen attack
Creep Embrittlement
Weld Overlay Disbonding
Low alloy Cr-Mo steels used for high temperature
high pressure applications.

2.25Cr-1Mo steel Standard

2.25Cr-1Mo steel Standard Enhanced

ASME Code Case 1960-3

2.25Cr-1Mo V
ASME Code Case 2098-2

3Cr-1Mo V Ti B
ASME Code Case 1961-1

3Cr-1Mo V Nb Ca
ASME Code Case 2151
 Requirements for Cr-Mo steels high temperature
high pressure Hydrogen Service

 The steel should killed and normalized and tempered

 Made through an ultra clean steel making process
 Vanadium modified steels should be preferred
 Chemical composition shall have the following
restrictions:
C = 0.15 % max.
P = 0.007 % max.
S = 0.002 % max.
Mn= 0.52-0.56 %
P+Sn = 0.012 % max.
 Impurity elements such as Si, Sn, Sb and As should be
restricted to very low values
 Additional requirements for Cr-Mo steels for High
temperature high pressure service
 Temper embrittlement resistance should be ensured by
J-Factor which should be less than 100:
[J = ( Si+ Mn) (P+Sn) X 10^4 ,]
 A separate temper embrittlement susceptibility test ,
called Step cooling Treatment test shall be conducted to
evaluate the shift in ductile brittle transition temperature
of the material after exposure to the elevated
temperature.
 The weld metal used shall be evaluated by the X-Factor
that should be less than 10.
 [ X = (10P+5Sb+4Sn+As) ÷100 ]
 The weldment shall also be evaluated for temper
embrittlement resistance through Step cooling treatment
and DBT shift .
 Higher Chromium Grades for high temperature
applications

 5 Cr- 0.5 Mo steel

 7 Cr- 1Mo steel
 9Cr-1 Mo steel
 Modified 9 Cr-1Mo steels( 91, 92 grades)
 12 Cr steels, etc. , are also used in high temperature
high pressure systems .
 These steels are increasingly difficult to fabricate due to
their air hardening nature .
 Requires specific heat treatments and thermal cycles to
achieve satisfactory properties
 Welded with matching consumables with narrow range
of appropriate parameters
 Materials used for High Temperature
Environmental Corrosion Resistance
 Oxidation
 Most industrial environments Oxidation takes part in the
high temperature corrosion reaction regardless of the
prominent mode of high temp. corrosion.
 Protection against oxidation would again depend on the
selective formation of a thermodynamically stable oxide.
 Cr, Al, and Si are 3 major elements that form stable
passive oxide layer.
 Protective effect of Cr is limited to 950 Deg. C, but when
used with Al/ Si, resists oxidation up to 1200 Deg. C
 Additions of rare earths, further reduces cracking,
fissuring and spalling of the protective oxide layer
 Prominent alloys used for high temperature service
Cost Comparison
 SS 309 ( 25Cr-13Ni-0.5Si-0.15C-Fe alloy) 0.8
 SS 310 ( 25 Cr-20Ni-0.5Si-0.08C-Fe alloy) 1.0
 Alloy 253 ( 21Cr-11Ni-1.7Si-N-Ce-Fe alloy) 1.2
 Alloy DS ( 18Cr-36Ni-2.2Si-0.06C-Fe alloy) 1.5
 Alloy 800/800H (20Cr-31Ni-0.4Al-0.4Si-0.08C-Fe-Ti) 1.5
 45TM (27Cr-23Fe-2.7Si-0.08C-Ni alloy+ RE) 2.1
 Alloy600 (16CR-9Fe-0.07C-Ni alloy) 2.1
 Alloy 601 (23Cr-14Fe-1.4Al-0.06C-Ni alloy) 2.1
 Alloy602A (25Cr-9.5Fe-2.1Al-0.18C-Nialloy+Y,Zr,Ti) 2.5
 AlloyX ( 22Cr-18Fe-9Mo-0.10C-Ni alloy+W,Co) 2.8
 Alloy625 (22Cr-3Fe-9Mo-0.10C-Ni alloy+3.5% Cb) 2.8
 Alloy617 (22Cr-1.5Fe-9Mo-0.06C-Ni alloy+ 12%Co) 3.5
 Sulfidation

 Sulfidation involves interaction of metal with sulfur contaminants in

the environment to form sulfide scale.
 Sulfidation and Oxidation are competing activities.
 Voluminous and porous are formed and flake away.
 Metal sulfides being lower l\melting than oxides or carbides( 635-
1070deg.C)catastropic corrosion can occur due to increase in
diffusion rates.
 High nickel alloys such as 600/601 are susceptible.
 Increasing Cr increases resistance to sulfidation.
 Cobalt additions and cobalt alloys have better resistance.
 Co-Co4S3 eutectic is formed only at 880˚C compared to Ni-Ni3S2
eutectic which forms at 635˚C.
 Si & Al increases resistance in oxidizing cum sulfiding media.
 Mn, Mg, Ca, Ce, Yt which bind S in a stable form prevents further
reaction and thus increase resistance to sulfidation.
 Carburisation

 This is typical phenomenon in steam cracking furnaces

where coking builds up and other C rich environments.
 Carburization mainly occurs above 700ºC.
 Involves dissolution and inward Carbon diffusion which
results in internal formation of carbides in the alloy
 Increase in carbon and formation of inter- dentritic
carbides results in brittleness, volume change and
differences in thermal expansion characteristics, leading
to fissures.
 Depletion of chromium can cause rapid surface oxidation
during cyclic operation.
 Metal Dusting

 Metal dusting is similar to carburization and is

sometimes referred to as catastrophic carburization.
 Occurs at 500-700ºC for a CO/H2 mixture and
at 850-1000ºC for a CH4/H2 mixture
 Metal dusting is a disintegration of carbides in the form
of dust that consists of graphite and metal particles.
 For low alloy steels it starts immediately after exposure.
 For high chromium steels, it is delayed and starts only
formation of chromium rich carbides.
Materials for resisting carburisation and metal
dusting

 24Ni-24Cr-Nb-C alloy
 35Ni-25Cr-Nb-C alloy
 35Ni-25Cr-W-C alloy
 35Ni-25Cr-Nb-Ti-C alloy with RE
 40Ni-30Cr-Nb-Ti-C alloy with RE
 45Ni-35Cr-Nb-Ti-C alloy with RE
 35Ni-26Cr-15Co-W-C alloy
 48Ni-28Cr-3Co-W-C alloy
 NITRIDING

 Nitrogen attack occurs in ammonia cracking. malamine

production, heat treating baths, protective atmospheres
and bright annealing furnaces and others.
 Due to low nitrogen solubility and thermal instability of
Ni-N compound, Ni based alloys are more resistant than
steels.
 Strong Nitride formers such as Cr, Ti, Al, V, Nb and Zr
decrease the resistance to nitriding.
 B, C and Si improve resistance by deducing the rate of
N diffusion.
 High nickel alloys such as 602CA are suitable.
 HALOGENATION

 Halogen and halogen compound attack via the

gaseous phase or molten salt compounds.
 Molten salts cause slagging and disintegration of
oxide layer.
 Gaseous phase halogens penetrate deeply into
the material without destroying the oxide layer.
 Diffused halide ions react to form heavy metal
halides with low melting points and high vapour
pressure that causes very high rates of metal
loss.
 Ni halides have low vapour pressure and hence
high nickel alloys are more resistance.
 Fuel ash Corrosion

 Na and V in the low grade fuel oil used in fired heaters

form sodium-vanadium pentate which would settle in
lower temperature regions of the furnace in molten state
and attack the protective oxide layer, leading to failure of
the components.
 Accelerated corrosion due to ash/salt deposits is
frequently called fuel ash corrosion.
 The only material that can resist fuel ash corrosion is
50cr-50Ni Nb alloy.
 Weldabilty Considerations
 Chrome Moly Steels

- Weldability well studied and documented.

- Low hydrogen SMAW, SAW, GMAW, GTAW,
ESAW,PAW,EBW,LBW, others can be used
- Depending on the alloy content and strength
appropriate preheating post-heating and PWHT are
required.
- Welding Consumables and must meet the X- factor
requirements.
- Welding procedure must also under the temper
embrittlement susceptibility tests.
- Hardness after PWHT shall not exceed 225 BHN
 Weldability Considerations
 Welding procedure qualification test should
include at least 3 heat treatment cycles to
account for repair.
 Temper bead technique that may be required for
repair during service should also be developed
and qualified.
 Separate repair welding qualification would be
required.
 If the materials are used as base materials for
cladded plates, separate hydrogen disbonding
test should be conducted.
 Weldabilty Considerations

High Chrome Steels

- 9Cr-1Mo and modified its modified versions have good
weldability when the code recommended parameters are
followed.
- GTAW, SMAW, EBW, and other Gas Shielded processes
preferred. SMAW can also be used.
- Preheating and PWHT requirements should be strictly
followed.
- For P91 and 92, addition of nitrogen in the shielding gas
desirable.
- A very narrow range of 740+/-10 deg C should be
followed for PWHT of modified grades to ensure requires
micro structural features.
 Weldabilty Coniderations
Stainless Steels

 Austenitic stainless steels are considered some of the most

weldable grades.
 GTAW, GWAW, SMAW, PAW, EBW, FCAW, etc . Can be used with
matching filler metals.
 The weld metal composition should be richer in alloying elements to
account for loss during welding and for segregation.
 Care should taken to avoid segregations as it would affect the creep
properties in high temp. applications.
 The weld surfaces and weld metal should free of any contaminants,
especially halogens, and the gas purity should be maintained.
 Ferrite contents in the weld affect the long term properties of
austenitic SS in high temperature service due to sigmatization.
 With low ferrite contents, weld metal solidification cracking is a
possibility and should be tackled by proper bead sizing and
sequencing .
 Weldability of high temperature alloys
Nickel alloys

 Weldability is rather similar to austenitic stainless steels, but has

higher viscosity requiring care full manipulation of welding heat and
bead size.
 Nickel alloys are richer in molybdenum that tends to segregate and
hence smallest bead and faster cooling, consistent with base metal
fusion characteristics should be adopted.
 Presence higher quantities of Al, Ti, Nb, Zr and other carbide and
oxide forming elements are to be protected against loss by
employing inert Gas shielded processes such as GTAW, GMAW,
EBW, PAW, etc.
 FCAW, SMAW and SAW should be used with care to avoid loss of
alloying elements that would affect creep and high temperature
corrosion resistance.
 Contaminants to watch for are carbon, oxides lead, phosphorus,
sulfur, from grease, crayons, m/c oils, oil mist from compressors,
shop dirt, tempilsticks, etc.
 Weldability Considerations.
 Nickel alloys have large range of solidification and hence
must be welded with least restraint. Proper weld joint
design and use of fixtures that avoid restraint stresses
should be used.
 Increased joint angles to allow puddle manipulation,
relatively thinner land to compensate for lower
penetration, welding currents and heat inputs well within
the approved parameters are essential for producing
sound welds
 Use of hot wire addition and 2% H to shielding gas will
increase the speed and quality of welding
 Welding consumables should be carefully chosen with
assured high temperature properties from reputed
manufacturers only.
 Thorough cleaning of the joints and consumables are of
paramount importance.
 Conclusion

 A wide range of ferritic alloy steels, austenitic

stainless steels and high nickel alloys are to be
used either alone or in combination for high
temperature high pressure applications in
process industries.
 Choice of the material and the welding
procedures to adopted would depend on the
material deterioration mechanisms and the
nature of the alloy behavior.
 Information available in the open literature can
be used for successful fabrication and use of
these alloys.