Boiler Materials

P.Sundaramoorthy
BHEL, Tiruchirappalli

1
 Introduction

The following topics are planned to be covered in

this talk:
1. Selection of materials for high temperature
service
2. Limitations of the conventional materials
3. Development of new materials
4. Some of the problems due to the weldments
during high temperature service
5. Some of the weldability aspects of the newer
grades
2
 General Considerations: 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

3
 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.
4
 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
5
 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
6
 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.

7
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.

8
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.

9
 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)

10
 The problem of graphitisation
Weld HAZ of multi layer joints where the metal
temperature has reached just above the lower
critical temperature (7500C inter critical
temperature zone) 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 out.
11
 The problem of graphitisation

Time-Temperatures for different levels of graphitisation

Graphitisation level 20%

1E+07

Initiation of graphitisation
Log time (hours)

Graphitisation level 30%

100000
0

Graphitisation level 50%

10000 100000

320 370 420 470 520 570

Temperature deg C

12
13
 Conventional Boiler Materials
Area of Material type Typical spec. for Upper limit Temp. Guiding Reason
Application Plates, Tubes, deg C(Heat for Upper Limit
Pipes Absorbing
Surface)
Drum C Steel/ Low SA299 425
Alloy Steel
Water walls, C Steel SA192, SA210, 425 Graphitisation
Economiser SA106
Superheater and C ½ Mo steel A209 T1 465 Graphitisation
Reheater
1Cr ½ Mo SA213T11, 565 Oxidation/
SA335P11 corrosion, Flue
gas
2 ¼ 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 SA213 T91, T92 650 ASME code

SA335 P91, P92
12%Cr X20CrMoV12 1 700 German Code
14
 Heat Absorbing Surfaces
To withstand higher
temperatures expected
inside the gas path,
higher grade material,
T91, is given inside the
flue gas path,
ROOF (as compared to T22
material inside the
penthouse, i.e. above
roof)
Gas Flow

15
 Creep rupture strength of conventional
ASTM materials
100 000 hrs Creep rupture stress of conventional ASTM materials

Carbon steel
300
1.25 Cr 0.5 Mo Si Steel (T11/ P11)
250 2.25 Cr 1 Mo Steel (T22/ P22)
Rupture stress MPa

Carbon 0.3 Mo Steel (German Steel 15 Mo3)

200
304 H Steel (min)
150

100

50

0
325 375 425 475 525 575 625 675 725
Temperature deg C

16
 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

17
Steel Type Type α λ at 20°C Ω at 20°C E at 20°C
X10-6 °C W/m.°C nΩm kN/mm²
(Conductivity)

Carbon 1016 13 47 150 205

Steel
Ferritic S44400 12.5 24 600 225
Ferritic 329 13.5 20 850 205
Austenitic
Austenitic 304 19.5 15 700 200

18
 304H 304H

T22
T22

304H T22

19
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 failures.
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.
20
SH Bifurcate Assembly Less than one month service- SCC
due to welding stress in HAZ
SS347H Insert
Ø 51 x 6 mm
SS 347H
Bifurcate
Ø 51 x 7.5 mm

SS347H Tube
Ø 63.5 x 8.0 mm

Weld
joint
SS347H Insert
STBW Ø 63.5 x 12.5 mm
joint (8mm near STBW)

SS347H Tube

SS347H Insert

OD

21
ID

SS347H Insert
Ø 51 x 6 mm

22
23
 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

Ref: Cerjak H., Letofsky E., Schuster F., “Basic aspects of the weldability of 9-10% Cr Steels 24
for advanced Power Generation”, Indian Welding Journal, 1999, pp. 17-24
 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

25
 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
26
 Chemical Composition of High Temperature Materials
Specn C Si Mn P S Ni Cr Nb N Fe Co Ti Al B Cu

HR3C 0.10 1.50 2.00 0.030 0.030 17.0 23.0 0.20 0.15 3.0 10.0 0.60 0.80 0.006 0.50
max max max max max 23.0 27.0 0.60 0.35 max 15.0 max 1.50 max max

IN617 0.05 0.50 0.50 0.015 0.015 Base 20.0

0.15 max max max max 24.0

IN740 0.034 0.45 0.27 Bal 24.31 1.83 1.02 19.63 1.58 0.75
Nominal

27
 MICROSTRUCTURES OF NEW MATERIALS

T22 T23 T91

P91 F91 T92 28

 MICROSTRUCTURES OF NEW MATERIALS

X20

ASS – Proper SAHT ASS – Improper SAHT

29
 MICROSTRUCTURES OF NEW MATERIALS

ASS Pipe Material ASS HAZ + Weld Metal Weld Metal + Inc Pipe

Inc Pipe Material 30

 100000 hrs creep rupture strengths of
different high temperature steels

100 000 hrs Creep rupture strength of different high temp. steels
10 CrMo 910 (Eq. P22)
200 X20 CrMoV12 1
P91
150
Stress MPa

NF 616 (Eq P92)

100 347 SS
ASME 304H
50

0
500 550 600 650 700
Temperature deg C

31
Allowable Stress Levels of different high
temperature ferritic steels
140

120
T 24
Allowable stress (MPa)

T 23

100

T 22
80

60
T 91

40

20

0
400 450 500 550 600 650

Tem perature (Deg.C)

32
Allowable Stress Levels of different high
temperature stainless steels
140

120
TP347HFG
100
Allowable stress (MPa)

80 SUPER304H

T91
60
T92
40

TP 347H
20

0
550 575 600 625 650 675 700
Tem perature (deg.C)

33
34
Nickel Alloys are having good amount of corrosion
resistance and strength at temperatures above 600°C

35
AC1: 820°C
AC3: 851°C
36
Welding cycle for X20CrMoV12 1 Steel

37
AC1: 810°C
AC3: 930°C

38
If PWHT is possible within 8Hrs

39
If PWHT is not possible within 8Hrs

40
 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)

41
 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)

42
Different types of damages in high
temperature weldments

Type IV cracking
in FGHAZ of P91
and P92 steels

43
44
 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 620/620/620°C 650/650/650C 732/760/760C

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 Cr or chromised Cr or chromised >20% Cr or Cr or chromised 45
chromised
 Materials for Advanced Supercritical Plants

12 Cr Steels 15Cr-15Ni

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

F12M 12Cr-1Mo-1W-VNbN 3Cu
HCM12 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 12Cr-W-Co-V-Nb-N
NF12

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
46
THANK YOU

47