Super Critical Boiler Materials –

Metallurgical Aspects

R N Mehrotra,
GM
Energy Technology
 Boiler Materials
a. Introduction
b.Design Consideration
c. Materials Consideration
 Thermal Power Plant
Recent Design of Thermal Power Plants
Based on
 Higher Thermal Efficiency
 Global Environmental Concern
Required Material
Sub-Critical High Creep Strength,
oxidation and corrosion
Super-Critical resistance
Ultra Super Stable Microstructure at
Critical Boiler High temperature
Considerations
Tube wall thickness
Weldability
Achieved
By
Precipitation strengthening
(Nb, V,Ti, Mo, W etc. form stable
carbide & inter-metallics)
Solution Strengthening
(Ni, Cr, Mo, W gives Solution
strengthening)
Interstitial Element
Strengthening
(B & N gives interstitial
Elemental strengthening)
 What is Super critical
Super Critical Fluid is defined as a substance:

Above critical Temperature (Tc) &

Above critical Pressure (Pc)

At which Liquid & Gas states are in equilibrium

For CO2 Tc= 31.1 deg C & Pc = 73.8 bar
 Super critical and ultra supercritical conditions

Critical Conditions Ultra super critical conditions

•Temperature -374.150C •Temperature above 5600C
•Pressure-225.56kg/cm2 •Pressure above 306kg/cm2

Improvement of thermal efficiency

•Increasing the steam temperature (ή increases 0.31%
every 100C of increase of main steam temperature &
0.24% every 100C of increase of reheat steam
temperature )
•Increasing in the steam pressure (ή increases 0.1%
increase with increase of 10 bar pressure)
 Efficiency in USC Boiler

• European and Japanese

USC PC Experience Base
– 580-600°C high
availability, good load
followers
In Development:
– European Advanced
700°C (1292°F) PC
plant stalled?
– DOE EIO/ EPRI 760°C
(1400°
(1400 F) boiler
materials program

Improvement of power plant heat

rate with increase in temp. and
pressure to turbine
 Efficiency in USC Boiler

47 34.5/760/760/760
Efficiency, %, HHV

34.5/704/704/704
45

34.5/648/648/648
Pressure- MPa

24.1/565/565 Temperature-0C

24.1/565/565
40

16.5/537/537

37

537 648 760

Temperature, 0 C
Efficiency in USC Boiler

Plant Efficiency
 Efficiency in USC Boiler

Improvement of steam conditions in Japan

b.Design Consideration
 For super critical Boiler materials

• Wall thickness
– Heat transfer
– Welding
• Corrosion (Oxidation)
• Erosion – Gas Velocity
 Consideration Of Boiler Tube Design

t= (PD/2S+P) + 0.005D +e
P=S [2t-0.01D-2e/{D-(t-0.005D-e)}]
D= Original O.D
t= Thickness of tube
C= Minimum allowance for threading and structural stability
P=Maxm. Allowable working pressure
R=Inside radius
S=Maxm. Allowable stress value at the design temp. of metal
t will decrease if S will increase; S can be increased by changing
material chemistry e.g by solid solution strengthening and or
precipitation strengthening but we have to consider CEV also for
weldability.
 Steam Generating Tube

Requirements for Steam generating

Tube materials
Creep properties and weldability
Erosion resistance in context of Indian high ash coal

Materials Temp. (C ) Allowable stress(105hr )

T22 500 103 MPa
T23 500 111 MPa
T24 550 95 MPa
P92 550 103 MPa

Chemical composition of candidate

water wall materials for USC Boiler
 Header and Steam Pipes

Requirements
Creep, thermal fatigue, weld ability
Component Phase 0 Phase I Phase II
(31 MPa, (31MPa, (34.5MPa,
5650C) 5930C) 6500C)

Header and P22, P23, P91, P92, SAVE12, NF12

Pipes P91, P92, P122, E911
P122

Evolution of Chromium steel

Chemical composition of Candidate materials for Header
 Thickness
820
720
620
Thickness, Cm

P22
520
P92
420
P122
320
NF709
220
120
20
400 450 500 550 600 650 700
Temperature, C

800
700 P22
600 P92
500
Thickness, Cm

400
300
200
100 Temperature Vs Thickness Temperature Vs Allowable stress
0
400 450 500 550 600 650 700
Temperature,C

Allowable Stress and Thickness Requirement at three conditions of

materials P22, and P92, P122, NF709 (with increase in Cr content)
Conditions
a. (172 kg/cm2, 4500C), b. (250 kg/cm2, 5500C), c. 306 kg/cm2, 6500C)
 Contd.
For Same Materials like P22
•Higher temp. and pressure thickness
requirement is higher
Issue with Higher
Thickness
•Heat transfer affected
•Chance of thermal Fatigue
•Weld ability may be affected

Require
•Lower thickness
•Higher allowable stress
•Materials of High Cr content like P92
c.Materials Property
Considerations
 Consideration Of Material Property

 Creep
 Fatigue
 Corrosion
 Erosion
 Oxidation
Weldability
Creep
Oxidation

Remaining life due to change in microstructure due to creep

 Erosion

Erosion
For 200/210 MW unit

Issue
Indian coal has higher ash content
Ash is higher abrasive index

For 500 MW unit

Tube failure & Loss of availability

Target 0%
Current – 1.43%
C-200- 1.02%
C-500 – 1.62%
 Creep and fatigue
Creep strength requirement with increase
in temperature and pressure
Crack due to thermal fatigue
Enhancement of Creep
strength by
Decreasing stacking fault energy
By stable precipitation
By restricting dissolution and
coarsening of precipitate
By restricting grain boundary
sliding
By high dislocation density
Delaying recovery of dislocation
structure
Thermal fatigue Influence
By
Thermal conductivity of
materials
Thermal expansion co-efficient
of materials
Strength of materials
 Oxidation and Corrosion

Oxidation is controlled by Corrosion is controlled by

By formation of stable protective oxide layer Formation of stable oxide layer, which
will hinder diffusion of iron and electron
(By alloying addition like Cr, Al, Si)

Effective way
to control
By
Chromising

Weight loss with chromium content

 Boiler Tube Erosion

Tube failure analysis Tube erosion

Depend on
•Fly ash particle size
•Hardness
•Velocity of propagation
Materials wear
 Components
•Steam generating tube
•Header and Steam Pipe
•Super-heater and Re-heater tube
 Steam Generating Tube

Requirements for Steam generating

Tube materials
Creep properties and weldability
Erosion resistance in context of Indian high ash coal

Materials Temp. (C ) Allowable stress(105hr )

T22 500 103 MPa
T23 500 111MPa
T24 550 95MPa
P92 550 103 MPa

Chemical composition of candidate

water wall materials for USC Boiler
 Header and Steam Pipes

Requirements
Creep, thermal fatigue, weld ability
Component Phase 0 Phase I Phase II
(31 MPa, (31MPa, (34.5MPa,
5650C) 5930C) 6500C)

Header and P22, P23, P91, P92, SAVE12, NF12

Pipes P91, P92, P122, E911
P122

Evolution of Chromium steel

Chemical composition of Candidate materials for Header
 Header and Steam Pipes

Thermal conductivity of some proposed header and

steam separator materials

Thermal expansion coefficient of some Evolution of Cr-bearing steel

proposed header and steam separator
materials
 Super-Heater and Re-heater Tube

Component Phase 0 Phase I Phase II

(31 MPa, (31MPa, (34.5MPa, Requirements
5650C) 5930C) 6500C)
Creep
resistance
Super heater T91, 304H, TP347HFG, NF709,
and Reheater 347 ( for non   Inconel 617 Corrosion
tube corrosive 310NbN, resistance
part) SS347 (for
310NbN (for corrosive) Oxidation
corrosive)
resistance

Austenitic steel are candidate materials for final stages, Nickel base
super alloy can be used at still higher temperature

Allowable stress value

Evolution of austenitic steel

State of the Art Materials
Welding Aspects
Weldability
Issue
Weld ability Require
•Type IV Cracking
•Crack free weld
•SCC of weldment
•Achieve adequate mechanical property
•Weld resistance to service degradation

PWHT is always required for

advanced high chromium alloy
Weded joint creep rupture
strength should be considered
 Welding

Require
• Proper welding process for joining of
materials of different Cr content
•Proper Choice of filler materials
•Minimum Hardness requirement of HAZ
Issue
•Micro structural degradation
•Type IV cracking
•Over tempering of base
materials during PWHT

Cause of Type IV cracking

•Undissolved Precipitates
•Grain-boundary sliding Type IV cracking

•Impurity segregation
•High stress in weldment
 Welding

Welding Processes for

Consideration
Chromium steel
Pre-heat temperature
GTAW
Post weld heat-treatment
SMAW temperature & Time

FCAW
SAW
Why Pre-heat? Why PWHT?
To resist hydrogen assisted  To improve toughness of HAZ
cold cracking
Lower the hardness of HAZ
 Welding

Postweld heat treatment requires controlling temperature in four phases to

relieve the stress caused by welding for P91 steel

Why PWHT?
 Welding

Welding parameter
Material: P92
Welding process: SMAW, SAW, GTAW
Pre-heat treatment: For 350mm dia & 50mm. thickness 1500C for SMAW
and 1000C for GMAW process, for thickness upto 6-8mm GMAW process
and no pre-heat treatment
PWHT: 7500 C -7600C for 2-4 hrs. for 50mm & above thick

Material: P23
Welding Process: SMAW, SAW, GTAW
Pre-heat treatment: 1500C for higher thickness,
PWHT: 7150C for 2hrs for 50mm thick
 Welding (P-92)

600
Ms

400
T Mf
E
M 300
P.
(0C)
200

Hardness vs cooling time

HAZ microstructure is martensitic at
500
all cooling rate,
400
HAZ hardness is higher than 350HV
Hardness, HV

300

200 HAZ have lower impact toughness

100

0
0 50 100 150 200 250
It indicates PWHT is required for all cooling
Cooling time, second
rate as HAZ has higher hardness and lower
toughness
 Welding

Reported welding Parameter for SMAW process for P92 grade

Welding Electrode: Composition almost similar to base metal

Welding current: 140-180A
Welding voltage: 18-26V
Travel speed: 4-15cm/min
Pre-heat and interpass Temperature: 200-3000C
Diameter of Electrode: 4.0mm
Heat input: 40-54kJ/cm
Welding Pass: 30
PWHT: 7600C for 5hrs

As transformed hardness of martensite in weld metal and HAZ in P92 is 350- 450HV

& Higher tensile strength than acceptable value

 Welding

600

400
T
E
M 300
P.
(0C) 200

Hardness vs cooling time

CCT diagram of T24 steel
400
350
300
Hardness, HV

250
200
150
100
50 HAZ microstructure is Bainitic
0
0 50 100 150 200 250
Cooling time, second
 Welding

Silent feature of Weding Parameter for P23/T23 steel

Bainitic transformation takes place in HAZ
Hardness of HAZ is <350HV
Tube of smaller thickness not required Pre-heat-treatment
PWHT is also not required for small thickness some time
Good brittle fracture resistance of HAZ
For higher thickness a PWHT at 7400C for 2 hrs in SMAW and 4 hrs
for SAW process
Welding

Welding consumable for X20 & P91

CCT diagram of X-20

and P91 steel
 Conclusions

Higher steam temperature and pressure require materials

having higher allowable stress at higher temperature
High Chromium ferritic steel is used header and steam
pipes
Proper welding flux selection is required for welding of
materials of dissimilar Chromium content
High Chromium Austenitic steel is used for super-heater
and reheater tubes
Higher temperature of operation beyond 7500C may
require Ni-base alloy