Boiler Materials

P.Sundaramoorthy BHEL, Tiruchirappalli

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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
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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.
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
Oxidation temperature (under flue gases) deg.C

1000 900 800 700 600 500 400 0 5 10 15 20 25 0 1 2.25 5 9 12 17

27 These temperatures are based on oxidation/ corrosion by flue gases wherever applicable. In case of plain air as in pent house region, higher metal temperatures can be tolerated.

Continuous oxidation temperature vs the Chromium content 30

Weight % Chromium

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

100,000hrs. rupture strength, N/ sq.mm

300 250 200 150 100 50 0 440

Carbon 0.30Mo Steel, 15Mo3 Carbon Steel, St35.8,45.8

450

460

470

480

490

Temperature deg. C

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.

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.

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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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 11 worked out.

The problem of graphitisation

The problem of graphitisation

Time-Temperatures for different levels of graphitisation
100000 10000 100000 0 1E+07

Graphitisation level 20% Initiation of graphitisation Graphitisation level 30% Graphitisation level 50%

Log time (hours)

320

370

420

470

520

570

Temperature deg C

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13

Conventional Boiler Materials

Area of Application Material type Typical spec. for Plates, Tubes, Pipes SA299 SA192, SA210, SA106 A209 T1 SA213T11, SA335P11 SA213T22, SA335P22 SA213 TP304 H Upper limit Temp. deg C(Heat Absorbing Surface) 425 425 465 565 Graphitisation Graphitisation Oxidation/ corrosion, Flue gas Oxidation/ corrosion, Flue gas Guiding Reason for Upper Limit

Drum Water walls, Economiser Superheater and Reheater

C Steel/ Low Alloy Steel C Steel C Mo steel 1Cr Mo

2 Cr 1Mo

580

18 Cr 8 Ni

704

18 Cr 10 Ni Cb
Modified 9Cr 12%Cr

SA213 TP347 H
SA213 T91, T92 SA335 P91, P92 X20CrMoV12 1

704
650 700 ASME code 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
Rupture stress MPa

1.25 Cr 0.5 Mo Si Steel (T11/ P11) 2.25 Cr 1 Mo Steel (T22/ P22) Carbon 0.3 Mo Steel (German Steel 15 Mo3) 304 H Steel (min)

250 200 150 100 50 0 325 375 425 475 525

575

625

675

725

Temperature deg C

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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. 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

2. However austenitic stainless steels have the following limitations:

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Steel Type

Type

at 20C at 20C nm X10-6 C W/m.C

(Conductivity)

E at 20C kN/mm

Carbon Steel
Ferritic Ferritic Austenitic Austenitic

1016
S44400 329 304

13
12.5 13.5 19.5

47
24 20 15

150
600 850 700

205
225 205 200

18

304H T22

304H

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

SS347H Tube 63.5 x 8.0 mm

STBW joint

SS347H Insert 63.5 x 12.5 mm (8mm near STBW)

Weld joint

SS347H Tube SS347H Insert

OD

21

ID

SS347H Insert 51 x 6 mm

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23

Evolution of Ferritic Steels for Boilers

105 h Creep Rupture Strength at 6000 C 30 MPa 2.25 Cr 1 Mo ASME T/P22 (STBA24)
+V

60-80 MPa
-C +W -Mo +Nb

80-100 MPa

120-140 MPa

140-180 MPa

2.25 Cr 1MoV 9Cr 2Mo HCM9M (STBA27)

2.25Cr-1.6WVNb HCM2S (ASME T23, STBA 24J1)

+ Mo

9Cr 1Mo ASME T9 (STBA26)

+ Mo +V + Nb

9Cr2MoVNb EM12 NFA 49213 9Cr1MoVNb Tempaloy F-9

+V + Nb Optimised

-Mo +W

+V + Nb

9Cr1MoVNb ASME T91 STBA28

9Cr0.5Mo1.8WVNb E911, NF616 ASME T92, STBA 29 12Cr0.5Mo1.8WVNb (TB12)

-W + Co

12Cr AISI 410

+ Mo

12Cr-0.5Mo
+Mo +V +W

- Cu +W + Nb

12CrWCoNiVNb (NF12)

12Cr1MoV HT91 X20CrMoV121

12Cr1MoWV HT9 X20CrMoWV121

- Mo +W + Cu

12Cr1Mo1WVNb HCM12 SUS410J2TB

12Cr0.5Mo2WCuVNb HCM12A, ASME T122 SUS410J3TB

+W + Co

12CrWCoVNb SAVE 12

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

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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 ASME TP347 HFG
Heat Treatment

-C

18Cr-8Ni, C<0.08 AISI 304 18Cr-8Ni, Ti AISI 321

+C

+ Ti

18Cr-8Ni AISI 302

+ Nb

18Cr-8Ni, Nb AISI 347 18Cr-8Ni, Mo AISI 316 22Cr-12Ni AISI 309

+ Cr + Ni

18Cr-8Ni, C-0.04-0.10 H Grade

18Cr-8NiNbTi Tempaloy A-1

SUS321J1HTB
Chem. Optimisation

18Cr-8NiCuNbN Super 304H

SUS304J1HTB
Cu Addition

+ Mo

+ Cr + Ni

25Cr-20Ni AISI 310

25Cr-20NiNbN HR3C
SUS310J1HTB

20Cr-25NiMoNbTi NF709 21Cr-32NiTiAl Alloy 800H

SUS310J2HTB

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

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 T23* Max 0.10 0.50 0.60 0.030 0.010 2.60 0.30 0.30 0.08 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 * 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 T91 Max 0.12 0.50 0.60 0.020 0.010 0.40 9.50 1.05 0.25 0.10 Min 0.20 0.80 8.50 1.70 0.20 0.30 EM12 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 T92 Max 0.13 0.50 0.60 0.020 0.010 0.40 9.50 0.60 0.25 0.10 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 Min 0.07 7.5 17.00 0.30 Super 304H Max 0.13 0.30 0.50 0.045 0.030 10.5 19.00 0.60 Min 17.0 23.00 0.20 HR3C Max 0.10 1.50 2.00 0.030 0.030 23.0 27.00 0.60 Nb+Ta Min 0.04 9.00 17.00 347 HFG

W
1.45 1.75 -

Cu
-

0.03 0.012

0.03 0.020

0.03 0.07 0.03 0.07 0.05 0.12 0.15 0.35 -

0.04 0.04 -

1.50 2.50 -

2.5 3.5 -

Max

0.10

0.75

2.00

0.040

0.030

13.00

20.00

8xC Nb+Ta 1.0

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Chemical Composition of High Temperature Materials

Specn HR3C C 0.10 max Si 1.50 max Mn 2.00 max P 0.030 max S 0.030 max Ni 17.0 23.0 Cr 23.0 27.0 Nb 0.20 0.60 N 0.15 0.35 Fe 3.0 max Co 10.0 15.0 Ti 0.60 max Al 0.80 1.50 B 0.006 max Cu 0.50 max

IN617

0.05 0.15

0.50 max
0.45

0.50 max
0.27

0.015 max

0.015 max

Base

20.0 24.0
24.31 1.83 1.02 19.63 1.58 0.75

0.034 IN740 Nominal

Bal

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MICROSTRUCTURES OF NEW MATERIALS

T22

T23

T91

P91

F91

T92

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MICROSTRUCTURES OF NEW MATERIALS

X20

ASS Proper SAHT

ASS Improper SAHT

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MICROSTRUCTURES OF NEW MATERIALS

ASS Pipe Material

ASS HAZ + Weld Metal

Weld Metal + Inc Pipe

Inc Pipe Material

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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) 200 150 100 50 0 500 X20 CrMoV12 1 P91 NF 616 (Eq P92) 347 SS ASME 304H

Stress MPa

550

600 Temperature deg C

650

700

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Allowable Stress Levels of different high temperature ferritic steels

140

Allowable stress (MPa)

120 T 23 100

T 24

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

Allowable stress (MPa)

100

80 T91 60 T92 40

SUPER304H

TP 347H 20

0 550

575

600

625 Tem perature (deg.C)

650

675

700

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

35

AC1: 820C AC3: 851C

36

Welding cycle for X20CrMoV12 1 Steel

37

AC1: 810C AC3: 930C

38

If PWHT is possible within 8Hrs

39

If PWHT is not possible within 8Hrs

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Hardness vs. tempering temperature-T/ P91 weld 380 360 345 340 332 322 320 304 300 283 280 As welded Hardness 473 HV10 260 254 240 220 200 500 550 600 650 700 750 Temperature Deg C (2hours)

Hardness HV10

800

850

41

Hardness vs Tempering temperature (T/ P91 HAZ) 380 360 340 336 320 300 280 As Welded Hardness 380 HV 10 260 240 220 200 500 550 600

Hardness HV10

333 336 302 268 254

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

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Candidate Materials for Advanced Supercritical Plants for various Steam Conditions
Component 31MPa, 565/565/565 C P22, HCM2S (P23), P91, P92, P122
T91, 304H, 347

31 MPa, 593/593/593 C P91, P92, P122, E911

31 MPa, 620/620/620C P92, P122, E911, NF12, SAVE12

NF709, Super 304H

34.5 MPa, 650/650/650C SAVE12, NF12

35Mpa 732/760/760C Haynes 230, INCO 740, CCA617

Haynes 230, INCO 740, CCA617, HR6W, Super 304H

Headers/ Steam Pipes

Finishing Superheater / Reheater noncorrosive Corrosive

TP347HFG Super 304H, P-122

NF709, Inconel 617

310NbN (HR3C)

HR3C SS347/IN72 (Weld overlay)

HR3C Super304H/IN7 2 (Weld overlay)

CR30A NF709/IN72(Wel d overlay)

Waterwall Lower Wall Upper Wall For low NOx Boilers + High S Coal

C Steel T11, T12, T22 Clad with alloy containing >20% Cr or chromised

T11, T12, T22 T23 (HCN12) Clad with alloy containing >20% Cr or chromised Clad with alloy containing >20% Cr or chromised Clad with alloy containing >20% Cr or chromised

T92, T23

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Materials for Advanced Supercritical Plants 12 Cr Steels 15Cr-15Ni

Tempaloy F12M HCM12 HCM12A, T122 Save 12 NF12

12Cr-Mo-W 12Cr-1Mo-1W-VNbN 12Cr-0.5Mo-2WVNbBN 12Cr-W-Co-V-Nb-N 12Cr-W-Co-V-Nb-N

17-14CuMo Eshete1250 Tempaloy A2

17Cr-14Ni-2Mo-Nb-Ti-B3Cu 15Cr-10Ni-6Mn-1Mo-W1V-Ti 18Cr-14Ni-Mo-Nb-Ti

20-25Cr

High Cr-High Ni 32Ni-21Cr-Ti-Al 15Ni-22Cr-Nb-B-N 35Ni-21Cr-Mo-Nb-Ti 25Ni-20Cr-Mo-Nb-Ti 18Ni-23Cr-W-Nb3Cu-N 25Cr-20Ni-Nb-N HR6W CCA617/ Inconel 617 INCO 740 Haynes 230 43Ni-23Cr-6W-Nb-TiB55Ni-22Cr-0.3W-8Mo11Co-Al 50Ni-25Cr-20Co-2Ti-2NbV-Al 57Ni-22Cr-14W-2Mo-La
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Alloy 800H Tempaloy A3 NF707 NF709 SAVE25 HR3C

THANK YOU

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