Conventional Power Plant Materials Course:

P22 and P91

GLOW

Frdric Vanderlinden
 Introduction
BOILER
Superheater 3
Lifetime
Reheater 2 Superheater 2
125k oh Convection
Radiation +
convection
200k oh
Superheater 1
250k oh convection
? Reheater 1
Convection

Temperatures: 550-600C
700C
ECO
Evaporator
Pressure: 130-200bar 365 bar Radiation +
convection
Water/steam: 540 tons/hour
Coal consumption: 80-100
tons/hour

Re-design vs. new PP

Bio-mass
Type of coal 2
 Most used materials in Power generation

C /C-Mn & Mo
Carbon
steels/Low
alloy
CrMo Ferritic

Martensitic
Stainless
steel
Austenitic

Super Duplex
Ni alloys
alloys

5/09/2014 4
Introduction
BOILER - MATERIALS
Steels
carbon vs. alloyed steels
ferrite, martensite, austenite
<650C steam
Examples: St35.8, 13CrMo45, 10CrMo910, 14MoV63, T/P91, T/P92, S304H
Nickel alloys
> 650C steam
Examples: A617, A740,

Costs - /kg
16Mo3: 5
T/P92: 10
S304H: 20
A617: 70
7
According to EN10216-5

8
 Introduction: Steel
Metal:
grains with crystal structure
Fe-C diagram

Steel:
Fe + C
ferrite, pearlite
Alloying:
Fe + C + Mn, Si, Cr, Ni, Mo, V, Ti, Nb
increase strength, corrosion resistance, ...
ferrite, pearlite, austenite
Heat treatment:
increase strength
martensite, bainite
9
 Source: Metallurgy for the non-metallurgist, Harry Chandler
Date
 P22

5/09/2014 11
 P22 content

Background of P22

Properties

Manufacturing Fabrication

Ageing

Failure Case

5/09/2014 12
 Background grade 22

Standardized for over 50 years (ASTM: P22/T22, DIN: 10CrMo9-10, BS: 622, etc.)

Used in high-capacity power stations with excellent operating behaviour for pipes
and tubes (and bars, forgings, castings, plates, sheets)

Based on steel in combination of Cr and Mo

Mainly superheaters and reheaters

Source: V&M book

5/09/2014 13
 P22 content

Background of P22

Properties

Manufacturing Fabrication

Ageing

Failure Case

5/09/2014 14
10CrMo9-10 = T22 = 1.7380

Chemical composition*

Main characteristics
High-temperature strength primarily because of dispersion of fine Mo carbide precipitates
Resistance to oxidation due to higher %Cr
Used to temperatures up to 600 C, although design allows more
Ferrite bainite structure (Martensite when cooled rapidly)

*SOURCE: EN10216-2 15
 T22 Chemical composition

Chemical composition remained practically unchanged since introduction 50 years

ago

Trace elements are better controlled now (S, P) toughness increase

Hardness requirement for new P22 = 170 - 180HV

Creep characteristics result from precipitations (nitrides and carbonitrides) which will
pin down mainly the grain boundaries.

During long term high temperture exposure precipitates will coarsen (large number of
small precipitates will be replaced by a small number of large precipitates).

This results in a lose of strength

Date
 T22 Allowable stresses

5/09/2014 17
 P22 content

Background of P22

Properties

Manufacturing Fabrication

Ageing

Failure Case

5/09/2014 18
 T22 Manufacturing and fabrication

5/09/2014 SOURCE: EPRI and EN10216-2

19
 T22 Manufacturing and fabrication

Microstructures from T22 will depend on the heat treatment, grain size and chemical
composition

Rolling, forging, extrusion are performed at high temperatures (austenite region)

After initial manufacturing further fabrication (bending, welding, forging) will alter
microstructure and properties
E.g.Casting is different from forging and extrusion

Therefore final heat treatment is of utmost importance

Transformation temperatures are very important (e.g. Ac1 = ~799 - 821C)

Altough design codes (e.g. ASME I) are not always clear on these subjects it is still
very important

Importance of manufacturing material certificate

More a contractual agreement between supplier and client

5/09/2014 20
 T22 Manufacturing and fabrication

675C

675C 675 750 C

675C 675 750 C

675 950C

950C 1040C

5/09/2014 SOURCE: EN12952 21

 Welding Requirements

Preheat minimum 200C

Interpass temperature Maximum 350C

PWHT according to EN12952-3 = 680-730C

But not required when wall thickness is <13mm, diameter is <120mm and design temperture
is >480C
During 2 x wall thickness (minutes) when wall thickness is 13 < WT < 60
During 120 + (WT 60) (mintues) when wall thickness is > 60mm

5/09/2014 22
 P22 content

Background of P22

Properties

Manufacturing Fabrication

Ageing

Failure Case

5/09/2014 23
 T22 Ageing

Creep characteristics result from precipitations (nitrides and carbonitrides) which will
pin down mainly the grain boundaries.

During long term high temperture exposure precipitates will coarsen (large number of
small precipitates will be replaced by a small number of large precipitates).

This results in a lose of strength which is related to hardness reduction

Microstructure follow up according to VGB TW507

5/09/2014 24
 Identification
Microscopic:
Micropores/voids (isolated, aligned, micro cracks, macro cracks)

Cfr.
Laborelec
report CFB1
Microstructural plastic deformation at location of leak

Possible graphitization in carbon and low-alloy steel:

graphite nodules
generally at microstructural defects & weld points

5/09/2014 25
 Real Cases

5/09/2014 26
 P22 content

Background of P22

Properties

Manufacturing Fabrication

Ageing

Failure Case

5/09/2014 28
Non GDF-Suez plant Piping T-parts
240.000 OH
Steam temp. 540 C
10CrMo9-10
Severe creep damage at
welds
Accelerated creep process

29
Damage mechanisms
High temperature corrosion
coal ash corrosion

35 LABORELEC
Phenomenon
Coal combustion: at high temperature minerals (in coal)
form volatile alkali compounds and sulphur oxides
Metal temperature: 560-730 C
The volatile components deposit on the fly ash, react at the
interface between metal/deposit and form complex alkali
sulphates (K,Na)3Fe(SO4)3 - low melting point salts: 552 C
Molten slag attacks the protective iron oxides fast
oxidation of metal reduction in wall thickness increase
in stress creep damage

36
Identification
Slag deposits on outer wall of boiler pipes
Loss of thickness of tube walls
Low alloy carbon steel pipes:
smooth areas with loss of wall thickness on the fire
side
30-45 away from the fire side: rough & corroded
surfaces
Strongly adhering sintered or slag-like deposits
Built up of 3 layers:
porous fly ash
white, water-soluble, corrosive alkali sulphates (0.8 -
6 mm thick)
glass, black iron oxides and sulphides (< 3.2 mm)
US wall thickness measurements on 30-45 away from the
fire side min. thickness
Maximum corrosion damage @ 680 - 730 C
37
Conditions
Metal temperatures:
560 - 730 C
Locations:
Superheater and reheater tubes
Also their mountings (higher surface temperatures)

38
Prevention/elimination

Avoid the use of the following coal types:

bituminous coal

coal with > 3.5% S and > 0.25% Cl

Chemical analysis of the coal and the fly ash

Determine the melting temperature of the ash

US wall thickness measurements: determine extent + severity

Non-severe corrosion:

replace the pipes periodically

use thicker pipes

use coating or cladding

Prevention/elimination

Use additives: not feasible economically

Mix the coal so as to lower the % of corrosive
components
Decrease the metal temperature:
steam temperature
clean the tubes periodically
redesign the damaged area: heat transfer
 Case study

Superheater tube
SA-213 T22 Cr-Mo steel
in service for 23 years

Dr. Rama S. Koripelli, Dr. David C. Crowe, Dr. David N. French, and Jonathan Brand
The Role of Fireside Corrosion on Boiler Tube Failures, Part I, Coal Power, April 2010.
 P91

Date
 P91 content

Background of P91

Properties

Manufacturing Fabrication

Ageing

Failure Case

5/09/2014 43
 Background information on P91

P22 and X20 widely used

Further increase in temperature required a new steel

Mid seventies development at Oak Ridge National Laboratory (USA) of a 9Cr-1Mo

material

Approved by ASTM in 1983 (Tube) and 1984 (Pipe)

Worldwide installed during the early 90ties

Overcome the difficulties in welding of X20 (%C)

5/09/2014 44
 P91 content

Background of P91

Properties

Manufacturing Fabrication

Ageing

Failure Case

5/09/2014 45
X10CrMoVNb9-1 = P/T91 = 1.4903
Application: Ansaldo and BWE-STF headers

1. Chemical composition

2. Main characteristics
First use in 1986 and today numerous applications in HRSG and coal plants for headers and tubing

9%Cr - 1% Mo steel with strengthening alloying elements (V, Nb, Mo, N)

Higher creep resistance and oxidation resistance

Good experiences provided the complete manufacturing and fabrication specifications are respected because creep
strength is governed by chemical composition + heat treatments

Can be used up to 600C but at higher temperatures creep strength is insufficient

Long term creep resistance is sensitive to composition changes; EN10216-2 needs to be followed + supplementary
requirements:

N/Al ratio >2 Al-nitrides formation can reduce VN particle precipitation

Cu 0.30% weldability

Si > 0.20%
 Microstructure is key !

MX carbides (formed during

tempering) are the principal creep
resistance promoting elements

MX = Nb(C,N) and V(C,N)

5/09/2014 47
5/09/2014 48
Specific explanation 9%Cr steels - Awareness
Type IV cracking

Fine grain heat affected zone has the lowest creep strength due to low carbon martensite and smaller grains. This
is a priority in lifetime follow up.

Intermetallic Z-phase formation

At temperatures >600C formation of large Z phase (= Cr(V, Nb)N) precipitates over time can dissolve the fine MX
carbo-nitrides resulting in a steep drop in creep properties.

This effect is even larger at higher Cr contents.

Delta ferrite

Cooling rate from the austenite is critical to obtain 100% Martensite.

Too slow cool down can result in a larger fraction of delta ferrite with lower creep strength.

Therefore the qualification of heavy wall components is important.

Laves phase

After 10 to 20kOH Laves phase can form above 600C reducing the creep strength because of the removal of solid
solution strengthening elements W and Mo
5/09/2014 50
 Hardness
Hardness translates the tensile strength of the material into a non destructive
measureble method
Used for QA-QC and lifetime calculation due to correlation

IP GDF Suez and Laborelec recommendation: The following guidelines can be

followed in case of hardness measurements lower than 200HV or higher than 270HV
in the base material for new material:

hardness<190HV: reject component

190HV<hardness<200HV: investigate further

270HV<hardness<300HV: investigate further

hardness>300HV: reject component

5/09/2014 51
 P91 content

Background of P91

Properties

Manufacturing Fabrication

Ageing

Failure Case

5/09/2014 52
 Levels of subcontracting !

5/09/2014 53
X10CrMoVNb9-1 = P/T91 = 1.4903
Bending operation shall be qualified for the relevant thickness and lot in production

This shall include all the crucial parameters (methods, temperatures, PBHT and thermocouples)

Qualification shall be tested destructively and non destructively

Location of mechanical specimens shall be in the zone with the maximum straining

For in production heat treatment all essential parameters shall be included in the final documentation (type
of furnace, atmosphere, t-T records, cooling method, thermocouples, calibration certificates)

Effectiveness of heat treatments shall be demonstrated per lot by micrographic examination and hardness

Welding processes TIG, SMAW and SAW are allowed but root pass is to be done with TIG

Thin layers are preferred to allow good toughness properties

Backing gas is mandatory up till 6mm of weld metal deposited

Filler metals: Mn + Ni content < 1.5% because of long term creep properties

Filler metal Ac1 transformation temperature shall be determined per lot of filler metal

Grinding flush of all welds is advised (avoiding stress concentration)

190HV is accepted as minimum HV but 200HV is advised to have some margin

Typical heat treatment chart of P91-92

Very important region: cool down shall allow complete Martensite transformation
minimum 1h below 100C

Period cannot be too long, maximum 1 week in dry conditions to avoid risk of SCC

Importance of QA-QC
 Temp, C

5/09/2014
300
500
800

100
200
400
600
700

0
-
Heat min of 50mm pipe on either
side of weld to preheat temp of
200 C
Hold at 200C f or 2h bef ore commencing welding

temp
of 300 C
interpass
Weld, max

10.0
'Hot grind' and Hydrogen bake-out at 300-316 C for 4 h

20.0

56
30.0
Time, h
Repair all def ects.
Cool to below 95 C and
carryout 100% MPI + UT inspection.

Handle with care to minimise stresses.

Maintain temperature above dewpoint.
Thermal Cycle for P91-P91 Welds

40.0

Controlled heating f rom 300 to

760 C at no more than 160 C/h

Hold at 760 C for 4 h

Controlled cooling f rom 760 C to

50.0

400 C at at least 1 C/min

60.0
5/09/2014 58
 Example Live steam Piping
Laborelec Material specification for high temperature
ferritic/martensitic steels
Based on the standards but with all needed supplementary
requirements
Kick off meeting at OEM supplier together with Owner engineer
and NoBo
Review of procedures and implementation on the work
floor
Review of certificates
Advice towards NoBo and Owner engineer QA/QC
department
Witness of first induction bend welding NDT
Follow up meeting
Review of test results
Review and witness of on site installation
Guarantee Zero Reference sample - relevance
 IP GDF Suez Guideline

http://sharedoc.electrabel.suez/projects/CC
/Internal%20Access/2013/P1310-
28%20material%20specifications%20for%
20high%20temperature%20ferritic%20mart
ensitic%20steels.docx

11/04/2011 60 60
 P91 content

Background of P91

Properties

Manufacturing Fabrication

Ageing

Failure Case

5/09/2014 61
5/09/2014 62
 Replication void density

5/09/2014 63
 P91 Ageing: Laborelec HaVoC
methodology
To answer the need for a practical approach:
LABORELEC proposal: Combination of Hardness measurements and Replication
HaVoC method: Hardness and Void density Creep assessment
Goal: Evaluate by means of zones with intervals for next inspections / actions
Zero-reference highly recommended (Hardness and Replica)
So far only results
on Base Material

Hardness
used as
first
indication

64
 P91 content

Background of P91

Properties

Manufacturing Fabrication

Ageing

Failure Case P91 Mismanagment

5/09/2014 65
Context

Combined water and power plant

2 years after commissioning: leak in P91 hot reheat steam
line
Leak location at a weld of a lateral T-piece
29 bar, 560 C

66
Context

OEM project

Subcontractor piping

Supplier Lateral T
prefab

Local contractor on site

welding

67
Context

68
Context

69
70
Further inspection results
Local repair is not an option
Design is not according to best practice: welds concentration
Hardness drops below requirement values
After taking a boat sample erroneous filler metal is noticed in
the root
Nothing found in QA documents
After further inspection: NOT a single case!

71
Corrective measures
Check and repair of all P91 welds for erroneous filler metal
Rework of lateral T (taper end) with smooth thickness
transition + Normalizing & Tempering (South Korea)

72
Conclusions

Design constraints of ASME are a minimum construction code

Case indicates that descent QA and QC is mandatory
Increased necessity with sub-contracting structure
Other power plant in construction was also affected

73
 Heat Treatment

5/09/2014 74
 Warmtebehandeling hooks and eyes

What is it?
Why?
Mechanism
Execution
Hooks and eyes (pitfalls)
What is it?

Heat Treatment

Normalizing
Tempering

Normalizing & Solution annealing-

Tempering (NT) quenching & Heat Treatment after
Tempering (QT) welding stress relief
heat treatment
TMCP DACQT
Carbon Steel,
Precipitation PWHT Low Alloy Steel and
hardening Martensitic creep
resistant steel
 Non homogeneous cool down
Change in Volume due to
Why? Welding Transformation
Cold Deformation
Casting
Shrinkage

Hardness

Stresses
500
As welded Residual Stresses
450 560C-24u
560C-50u
.

400 560C-500u
560C-1000u
Hardness (HV10)

350

300

250

200
BM HAZ WM HAZ BM
150
Mechanical properties/
Corrosion Behaviour (brittle
Stress Corrosion fracture, fatigue)
Tolerances
Mechanism 1

No change in microstructure

Temperature is below the critical transformation temperature (AC1)

Regrouping from dislocations (grid defects)

Grid defects = metastable

Need to switch over to stable state

Under influence of temperature

Recristalisation of cold deformation

Influence on mechanical properties

Mechanisme 2

Deformation!!!
Cracks !!!

Temperature &
yield strength Decrease in
residual stresses

Regrouping of
dislocations Reheat
cracking
Stress
corrosion
Mechanisme 3

Temperature > Time

Temperature gradients
Execution 1

Temperature Efficiency

Minimum 50C under the critical transformation temperature

Minimum 550C (T<550C limited effect)

Time (holding time)

Discussion: from 30minutes up to several hours

Heating and cooling

Uniform Thermal
Gradients
Heating- and Cooling rate (bv 150C/h)
Execution 2
Critical transformation
temperature ?

X20
 Execution 3

How?

Furnace Heat treatment

Uniform

Yes or no under inert/reducing atmosphere

Controlled quenching possible

Local Heat Treatment

Electric resistance (mats)

Induction

IR, VSR (Vibratory stress relieving), shotpeening

Excecution 4
Standards give guidance (e.g. AWS D10.10) but also recommandation from suppliers (e.g. Superheat)
Excecution 5

Procedure for PWHT

MANDATORY!

Calibration of equipment and thermocouples

Used method(s)

Heat treatment cycle

Dimensions (heated zone, insulation zone, insulation thickness)

Location of Thermocouples (type, number, location)

Programming and control

Documentation and reporting

 Temp, C

300
500
800

100
200
400
600
700

0
-
Heat min of 50mm pipe on either
side of weld to preheat temp of
200 C
Hold at 200C f or 2h bef ore commencing welding
Execution 6

temp
of 300 C
interpass
Weld, max

10.0
'Hot grind' and Hydrogen bake-out at 300-316 C for 4 h

20.0
30.0
Time, h
Repair all def ects.
Cool to below 95 C and

Heat treatment cycle

carryout 100% MPI + UT inspection.

Handle with care to minimise stresses.

Maintain temperature above dewpoint.
Thermal Cycle for P91-P91 Welds

40.0

Controlled heating f rom 300 to

760 C at no more than 160 C/h

Hold at 760 C for 4 h

Controlled cooling f rom 760 C to

50.0

400 C at at least 1 C/min

60.0
Hooks and eyes 1

Deformations

Depending on the level of stresses

Non equilibrated heating and cooling (HR/CR)

Wrong arrangement in furnace

Unavoidable in a lot of circonstances!

Calculation via Finite elements

Free
expansion? Cold
Temper beading repair
 Hooks and Eye s

Temper beading = magic word ?

Controlled deposition !

Demands a lot of experience and knowledgekennis & ervaring !

For P91, extensif research by Laborelec (cold weld repair) and

EPRI
Hooks and Eyes 3

Temperature Rest austenite

Too high (T>Ac1) => transformation ! Untempered
martensite
Influence on microstructure + properties

Mainy due to problems in controling/measuring/follow-up

Too Low

Bad choise: T<550C limited effect

Losses (mainly due to heavy wall thicknesses inner bore of pipe)

Place a thermocouple on the inner

bore
Chimneyeffect Check procedure:
Rain, Wind & Snow - Correct TC placement
Sufficient capacity - Check insulation thickness
Hooks and Eyes 4
Standard X20 10CrMo9.10 10CrMo9.10/X20 G17CrMo9.10(cast)/X20
Tempering heat treatment for wall thickness up to 60mm
DIN17175 720-780C 650-750C
min. 60 min min. 90 min
t>30mm t>30mm

VdTV 451-03/3 12.2003 720-780C 650-750C 700-750C 670-720C

min. 120 min min. 60 min min. 120 min min. 120 min
t>30mm t>30mm t>30mm t>30mm

Mannesmann 432R 720-780C

min. 120 min
t>30mm

EN13480-4 (05/2002) 730-770C 670-730C 700-750C

2,5*t 2*t 2,5*t
min. 60 min min. 60 min min. 60 min

EN10216-2 (2002+A2:2007) 730-780C 680-750C

Filler Metal Suppliers X20

PWHT
Bhler Thyssen 720-760C
3 min/mm
min. 2h
CE, %C, wanddikte
Regelgeving Metrode 730-770C
min. 3h

Thyssen 720-760C
4h
 Hooks and eyes 5

Holding time

Too short

Elongation via additional heat treatment

Too long

Wrong calculation

Multiple repairs (! Covered by PQR?) Multiple

PWHT
Impact on the mechanical properties !

LMP = T (20 + log t)

T= temp (K) en t= tijd (h)
Hooks and eyes 8

Grade P91
 Hooks & Eyes 9

Crack formation

Stress Corrosin Cracking

Hard microstructure shrink stresses corrosive environment (humidity)

Conservation between welding and PWHT

Reheat cracking

Mainly in precipitation hardening creep resistant steels CrMo(V)

Intergranulair cracks in HAZ

Sensitive microstructure: Coarse grain HAZ with strong matrix and weak grain
boundaries
 Hooks & Eyes 10

100

90
.

80

70

60
Reduction of area (Z%)

50

40

30

20

10
Licht Reduction of area (%) > 20
Sterk
Extreem
Unsensitive
0
400 425 450 475 500 525 550 575 600 625 650 675 700 725 750 775 800

Temperature (C)
Hooks & Eyes 11

Intercooling

Martensitic creep resistant steel (X20, P91, P92)

Complete transformation to martensite (untempered)

Tempering of martensite

Grade 91
Hooks & Eyes 12

Tussenkoeling temperatuur ?

T < Mf
Hooks & Eyes 13 X20/10CrMo9.10
P91/P22
P91/Super304H
Dissimilar Welds

Houston, we have a problem!

Different possibilities:

Buttering with Ni-basis Time, Cost

Conclusive solution
Selection of Temperature

Demands lower- and higher

alloyed component
Impacto on mechanical properties
C-migration, thermal expansion
 P91 P22

5/09/2014 98
Hooks & Eyes 14

And a lot more

Presence of aggressive or harmfull substances on the surface (markers...)

Complex structures under high stresses allow intercooling?

Protection of flanges for scaling with compound

Support against deformation (eg. SS at 950C)

Etc.

Q&A
 FROM INNOVATION TO OPERATIONAL
ASSISTANCE IN ENERGY
Laborelec is a leading research and services centre in energy
processes and energy use, with more than fifty years of
experience. We are part of the Research and Innovation Division
of the GDF SUEZ Group, a world leader in the energy sector.

LABORELEC BELGIUM
Rodestraat 125
1630 Linkebeek
Belgium

LABORELEC THE NETHERLANDS

Amerikalaan 35
6199 AE Maastricht-Airport
The Netherlands

LABORELEC GERMANY
Brombergerstrasse 39-41,
42281 Wuppertal
Germany

LABORELEC CHILE SpA

Avenida Parque Antonio Rabat Sur 6165, FIVE REASONS FOR YOU TO CHOOSE LABORELEC
Vitacura, Santiago Wide range of technical competences in Electricity
Chile Generation, Grids and End-Use
Increased profitability and sustainability of your energy
processes and assets
Unique combination of contract research and operational
assistance
www.laborelec.com Independent advice based on certified laboratory and field
analyses all over the world
info@laborelec.com More than 50 years of experience
102