METALLURGY

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 Presentation Outline

Requirement of metallurgy for boiler

Present Limitation

Future Development

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 Requirements of Materials

The following major properties of materials is of

interest in the choice of materials for Boiler and
Pressure Vessel applications:
Strength at room temperature and elevated/
service temperature
Corrosion/ Oxidation resistance
Stability of structure over a service period
normally about 30 years
Ease of fabrication including welding

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 Effect of Common Alloying Elements

Carbon: This is the main element which provides strength.

For considerations of weldability the carbon content is
restricted to 0.25% in IBR and in many of the European
codes.
American Code (ASME B&PV) allows carbon up to 0.35%.
The purchase specifications of BHEL restricts the carbon
to a maximum value of 0.30%.
Carbon has a major bearing on the high temperature
strength also, for example a minimum of 0.04% of carbon
is required as per ASME B&PV code to ensure the high
temperature creep properties of austenitic SS grades.
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 Effect of Common Alloying Elements
Chromium: This is the major alloying element conferring
the oxidation /corrosion resistance to the steel. This
element also provides resistance to corrosion in sulphur
rich flue gases.

1100 27
Oxidation temperature (under

These temperatures are based on

1000
oxidation/ corrosion by flue gases
flue gases) deg.C

900 wherever applicable.

In case of plain air as in pent
800 house region, higher metal
17
12 temperatures can be tolerated.
700
9
600 5
1 2.25
500 0
Continuous oxidation temperature vs the Chromium content
400
0 5 10 15 20 25 30
Weight % Chromium
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 Effect of Common Alloying Elements
Molybdenum: The main alloy element which confers creep
resistance for the steel. 100,000 hrs rupture strength is used in these
presentations for the purpose of various comparisons

Effect of Mo on 100,000hrs, rupture strength

300 Carbon 0.30Mo Steel,
100,000hrs. rupture strength,

15Mo3
250
Carbon Steel,
200 St35.8,45.8
N/ sq.mm

150

100

50

0
440 450 460 470 480 490
Temperature deg. C
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 Effect of Common Alloying Elements

The other common alloying elements used for

enhancing the creep resistance are Nb, V, and
W. Similar to Mo these are strong carbide
formers, providing a fine network of carbides in
the matrix impeding the dislocation movement
thus enhancing resistance to creep deformation.
Nitrogen is used in order to substitute the
carbon and form nitrides which provide creep
resistance similar to carbides.

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 Effect of De-oxidation Practice & Grain Size

Fully killed steels are preferred for high

temperature application in view of their
homogeneity.
The higher creep strength of silicon-killed steels
has been attributed to the free nitrogen available
in these. This superiority is seen only in short
term tests. In the long term, there is no
difference.

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 Effect of De-oxidation Practice & Grain Size

Aluminum killed steels because of their fine grain

size have better toughness as well as matching
strength at higher temperatures with silicon
killed steels, hence can be used at higher
temperatures.
Higher proneness to graphitisation of aluminum
treated steels, however, is to be kept in mind.

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 The problem of graphitisation

There had been failures in Carbon and Carbon

Moly steel piping operating at temperatures
beyond 425 deg C by this phenomenon.
Graphite being the more stable phase than
cementite there is a tendency during high
temperature service after long times for the
carbides in these steels to separate out as iron
and carbon (graphite)

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 The problem of graphitization
Weld HAZ of multi layer joints where the metal
temperature has reached just above the lower
critical temperature are the preferred regions
for graphitisation.
Cold worked bands in base materials are also
locations where chain type graphitisation has
been observed.
Based on a study of various failures of this type
and also examination of piping, working in this
temperature range, the time temperatures
required for such material degradation has been
worked
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 Conventional Boiler Materials
Area of Application Material type Typical spec. for Upper limit Temp. Guiding Reason for
Plates, Tubes, Pipes deg C(Heat Upper Limit
Absorbing Surface)
Drum C Steel/ Low Alloy SA299 425
Steel
Water walls, C Steel SA192, SA210, 425 Graphitisation
Economiser SA106
Superheater and C Mo steel A209 T1 465 Graphitisation
Reheater
1Cr Mo SA213T11, 565 Oxidation/
SA335P11 corrosion, Flue gas
2 Cr 1Mo SA213T22, 580 Oxidation/
SA335P22 corrosion, Flue gas
18 Cr 8 Ni SA213 TP304 H 704

18 Cr 10 Ni Cb SA213 TP347 H 704

Modified 9Cr SA213T91, 650 ASME code

SA335P91
12%Cr X20CrMoV12 1 700 German Code

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 Heat Absorbing Surfaces
To withstand higher
temperatures expected
inside the gas path,
higher grade material,
T91, is given inside the
flue gas path,
(as compared to T22
material inside the
penthouse, i.e. above
roof)

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Reasons for development of newer grades

Following are some of the issues which led to the development of

newer grades.
1. Beyond 6000C only austenitic stainless grades have the necessary
corrosion/ oxidation resistance and creep strength.
2. However austenitic stainless steels have the following limitations:
Higher thermal expansion and lower thermal conductivity
Higher affinity for carbon of austenitic grades causes carbon
migration to austenitic area, causing decarburisation in the
ferritic side HAZ, leading to poorer creep strength of this
region

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 Reasons for development of newer grades

Stresses due to the differential thermal expansion and also lower

high temperature strength of the decarburised zone leads to creep
fracture along this zone and this type of failure is called Dissimilar
Metal Weld failures or DMW.
Use of Ni base (inconel) filler has been found to improve the
situation by delaying the onset of failure, and the failure situation
was not fully eliminated.
The other problem is the proneness of austenitic stainless steel to
SCC.
Development of ferritic grades of steel with improved creep
strength, matching that of austenitic grades was necessitated for
the above reasons.

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 Evolution of Ferritic Steels for Boilers
105 h Creep Rupture Strength at 6000 C
30 MPa 60-80 MPa 80-100 MPa 120-140 MPa 140-180 MPa
-C +W
2.25 Cr 1 Mo +V -Mo +Nb 2.25Cr-1.6WVNb
ASME T/P22 2.25 Cr 1MoV HCM2S
(STBA24) (ASME T23, STBA 24J1)

9Cr 2Mo
+ Mo HCM9M
(STBA27)

9Cr 1Mo + Mo 9Cr2MoVNb

ASME T9
+V EM12
+ Nb -Mo
(STBA26) NFA 49213 +W
9Cr1MoVNb 9Cr0.5Mo1.8WVNb
9Cr1MoVNb +V ASME T91 E911, NF616
+V
+ Nb Tempaloy F-9 + Nb STBA28 ASME T92, STBA 29
Optimised
-W
+ Co
12Cr0.5Mo1.8WVNb 12CrWCoNiVNb
12Cr + Mo 12Cr-0.5Mo - Cu (TB12) (NF12)
+W
AISI 410 +Mo + Nb
- Mo
+V +W
+W + Cu +W
12Cr1MoV 12Cr1MoWV 12Cr1Mo1WVNb 12Cr0.5Mo2WCuVNb + Co
HT91 HT9 HCM12A, ASME T122 12CrWCoVNb
HCM12
X20CrMoV121 X20CrMoWV121 SUS410J3TB SAVE 12
SUS410J2TB

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 Evolution of Stainless Steels for Boilers
105 h Creep Rupture Strength at 6000 C
Sub 80 MPa 80-120 MPa 120-140 MPa 140-190 MPa

18Cr-8NiNb
18Cr-8Ni, C<0.08 ASME TP347 HFG
-C Heat Treatment
AISI 304
18Cr-8NiNbTi
+ Ti 18Cr-8Ni, Ti Tempaloy A-1
AISI 321 18Cr-8Ni, SUS321J1HTB
+C C-0.04-0.10 Chem. Optimisation
+ Nb 18Cr-8Ni, Nb H Grade
18Cr-8Ni 18Cr-8NiCuNbN
AISI 347
AISI 302 Super 304H
18Cr-8Ni, Mo SUS304J1HTB
+ Mo Cu Addition
AISI 316
25Cr-20NiNbN
+ Cr 22Cr-12Ni + Cr 25Cr-20Ni
+ Ni + Ni HR3C
AISI 309 AISI 310
SUS310J1HTB

20Cr-25NiMoNbTi
NF709
SUS310J2HTB
21Cr-32NiTiAl
Alloy 800H
22Cr-15NiNbN
Tempaloy A-3
SUS309J4HTB

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 Table 2: Chemical composition of the new materials being used
C Si Mn P S Ni Cr Mo V Nb N Al W Cu
2.25 Cr Steels
Min - 0.25 0.30 - - - 1.90 0.87 - - - - - -
T22
Max 0.15 1.00 0.60 0.030 0.030 - 2.60 1.13 - - - - - -
Min 0.04 - 0.10 - - - 1.90 0.05 0.20 0.02 - - 1.45 -
T23*
Max 0.10 0.50 0.60 0.030 0.010 - 2.60 0.30 0.30 0.08 0.03 0.03 1.75 -
Min 0.05 0.15 0.30 - - - 2.20 0.90 0.20 - - - - -
T24**
Max 0.10 0.45 0.70 0.020 0.010 - 2.60 1.10 0.30 - 0.012 0.020 - -
* T23 material additionally contains 0.0005-0.0006 Boron.
** T24 has Boron in the range of 0.0015 to 0.0070 and Ti in the range of 0.05 to 0.10.
9 Chrome Steels
Min 0.08 0.20 0.30 - - - 8.00 0.85 0.18 0.06 0.03 - - -
T91
Max 0.12 0.50 0.60 0.020 0.010 0.40 9.50 1.05 0.25 0.10 0.07 0.04 - -
EM12
Min - 0.20 0.80 - - - 8.50 1.70 0.20 0.30 - - - -
Max 0.17 0.65 1.30 0.030 0.030 0.30 10.50 2.30 0.40 0.55 - - - -
Min 0.09 - 0.30 - - - 8.00 0.30 0.15 0.03 0.03 - 1.50 -
T92
Max 0.13 0.50 0.60 0.020 0.010 0.40 9.50 0.60 0.25 0.10 0.07 0.04 2.50 -
12 Chrome Steels
Min 0.17 - - - - 0.30 10.00 0.80 0.25 - - - - -
X20
Max 0.23 0.75 1.00 0.030 0.030 0.80 12.50 1.20 0.35 - - - - -
Stainless Steels
Super Min 0.07 - - - - 7.5 17.00 - - 0.30 0.05 - - 2.5
304H Max 0.13 0.30 0.50 0.045 0.030 10.5 19.00 - - 0.60 0.12 - - 3.5
Min - - - - - 17.0 23.00 - - 0.20 0.15 - - -
HR3C
Max 0.10 1.50 2.00 0.030 0.030 23.0 27.00 - - 0.60 0.35 - - -
Min 0.04 - - - - 9.00 17.00 - - Nb+Ta - - - -
347 8xC
HFG Max 0.10 0.75 2.00 0.040 0.030 13.00 20.00 - - Nb+Ta - - - -
1.0
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 Hardness vs. tempering temperature-T/ P91 weld

380
360
340 345
Hardness HV10

332
320 322
300 304
280 283
As welded Hardness 473 HV10
260 254
240
220
200
500 550 600 650 700 750 800 850
Temperature Deg C (2hours)

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 Hardness vs Tempering temperature (T/ P91 HAZ)

380
360
340
Hardness HV10

336 333 336

320
300 302
280
As Welded Hardness 380 HV 10 268
260 254
240
220
200
500 550 600 650 700 750 800
Temperature deg C (2hours)

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 Future Development
Supercritical cycles

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 Realising higher steam parameters is
dependent, to a great extent on the
availability of materials to withstand the
demanding service conditions

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 Requirements of Materials
for Supercritical cycles
Strength to resist rupture at design condition
Fatigue strength to withstand cycling stresses
Ability to resist stress concentrations
Resistance to oxidation,corrosion and erosion
Ability to withstand damaging metallurgical
changes.
Ease of fabrication
Good physical properties to minimise thermal
stresses.

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 Low Alloy steels
Can meet live steam temperatures of 540 Deg.C.
Reduced creep strength at higher temperatures
calls for high thickness
Poor resistance to oxidation at high
temperatures
Good workability & high thermal conductivity

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 Austenitic steels
Superior high temp. strength
High Steam side oxidation
High temperature corrosion
Susceptibility to stress corrosion cracking
Expensive.

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 New Materials
Optimised to achieve :
Greater long-term rupture strength
Improved resistance to high temperature
corrosion
Lower oxide film growth

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 T91/P91
Bridged the gap between Low alloy ferritic
steels and Austenitic steels
Higher Creep strength compared to the earlier
ferritic steels
Lower thickness resulting from the higher creep
strength advantageous in meeting transient
temperature changes

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 T92/P92
Development on T91/P91
Creep rupture strength higher than T91/P91(20
to 30% higher at 600 Deg C)
Will facilitate raising steam temperature by 20
deg C over T91/P91 capability

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 T23/T24
Higher Creep Rupture Strength compared to
T22.
Potential candidate for use in evaporator walls.

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 Steam temperature range for Materials

MATERIAL LIVE STEAM TEMPERATURE

X20CrMo V12-1 < 565 Deg.C (< 545 Deg.C for SH)
X3CrNiMoN17-13 565 Deg.C 580 Deg.C
Esshete 1250
TP 347 H FG, SUPER 304 H 580 Deg.C - 600 Deg.C
HR 3C (25 Cr 20 Ni Nb N) 600 Deg.C - 620 Deg.C
AC 66 (27 Cr 30 Ni Nb Ce)
NF 709 (20 Cr 25 Ni Mo Nb Ti)
Incoclad 671/ Incoloy 800 HT
Compound Tubes 620 Deg.C 720 Deg.C
Coextruded Tubes
Alloy 617 (NiCr 23 Co 12 Mo)

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 Candidate Materials for Advanced Supercritical Plants for various Steam Conditions

Component 31MPa, 31 MPa, 31 MPa, 34.5 MPa, 35Mpa

565/565/565 C 593/593/593 C 620/620/620C 650/650/650C 732/760/760C

Headers/ P22, HCM2S P91, P92, P122, P92, P122, SAVE12, NF12 Haynes 230,
Steam Pipes (P23), E911 E911, NF12, INCO 740,
P91, P92, P122 SAVE12 CCA617

Finishing T91, 304H, 347 TP347HFG NF709, Super NF709, Haynes 230,
Superheater Super 304H, 304H Inconel 617 INCO 740,
/ Reheater P-122 CCA617,
non- HR6W,
corrosive Super 304H

Corrosive 310NbN (HR3C) HR3C HR3C CR30A

SS347/IN72 (Weld Super304H/IN7 NF709/IN72(Wel
overlay) 2 (Weld d overlay)
overlay)

Waterwall
Lower Wall C Steel T11, T12, T22
Upper Wall T11, T12, T22 T23 (HCN12) T92, T23

For low NOx Clad with alloy Clad with alloy Clad with alloy Clad with alloy
Boilers + containing >20% containing >20% containing containing >20%
High S Coal
26 October 2017
Cr or chromised Cr or chromised >20% Cr or
PMI Revision 00
Cr or chromised 37
chromised
 Materials for Advanced Supercritical Plants

12 Cr Steels 15Cr-15Ni

Temple F12M 12Cr-Mo-W 17Cr-14Ni-2Mo-Nb-Ti-B-

HCM12 12Cr-1Mo-1W-VNbN 3Cu
12Cr-0.5Mo-2W- 17-14CuMo 15Cr-10Ni-6Mn-1Mo-W-
HCM12A,
VNbBN Eshete1250 1V-Ti
T122
12Cr-W-Co-V-Nb-N Tempaloy A2 18Cr-14Ni-Mo-Nb-Ti
Save 12
NF12 12Cr-W-Co-V-Nb-N

20-25Cr High Cr-High Ni

Alloy 800H 32Ni-21Cr-Ti-Al HR6W 43Ni-23Cr-6W-Nb-Ti-

Tempaloy A3 15Ni-22Cr-Nb-B-N CCA617/ Inconel B55Ni-22Cr-0.3W-8Mo-
NF707 35Ni-21Cr-Mo-Nb-Ti 617 11Co-Al
NF709 25Ni-20Cr-Mo-Nb-Ti INCO 740 50Ni-25Cr-20Co-2Ti-2Nb-
SAVE25 18Ni-23Cr-W-Nb- Haynes 230 V-Al
HR3C 3Cu-N 57Ni-22Cr-14W-2Mo-La
25Cr-20Ni-Nb-N
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 THANK YOU

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