Advanced Materials Opportunities and Challenges

Jonathan Parker Structural Integrity Associates, Inc

Advanced Boiler Steels

Greater Strength with good ductility allows higher allowable stresses, thinner wall and higher operating temperatures and pressures

Parker 3C-1/2

Summer Workshop 2005 Annapolis, MD

Advanced 2%Cr Steels

Element C% Si % Mn % P% S% Cr % Mo % Ti % Nb % V% W% Al % N% B% Grade 22 0.15 max 0.50 max 0.30-0.60 0.030 max 0.030 max 1.9 -2.6 0.87-1.13 Grade 23 0.04-0.10 0.50 max 0.10-0.60 0.030 max 0.010 max 1.9 - 2.6 0.05-0.30 0.02-0.08 0.20-0.30 1.45-1.75 0.030 max 0.030 max 0.0005-0.0060 Grade 24 0.05-0.10 0.15-0.45 0.30-0.70 0.020 max 0.010 max 2.2 - 2.6 0.90-1.10 0.05-0.10 0.20-0.30 0.020 max 0.012 max 0.0015-0.0070
Parker 3C-1/3

Summer Workshop 2005 Annapolis, MD

Advanced 2%Cr Steels

Grade 23
C 0,07 Si 0,28 Mn 0,54 P 0,008 S 0,004 Al 0,018 Cu 0,041 Cr 2,08 Ni 0,047 Mo 0,08 V 0,22 W 1,65 B 0,002 Nb 0,026 N 0,011

Parker 3C-1/4

Summer Workshop 2005 Annapolis, MD

Advanced 2%Cr Steels

Grade 24
C 0,08 Si 0,21 Mn 0,53 P 0,004 S 0,004 Al 0,004 Cu 0,09 Cr 2,44 Ni 0,18 Mo 0,95 V 0,26 B 0,004 Nb 0,002 Ti 0,053 N 0,0073

Parker 3C-1/5

Summer Workshop 2005 Annapolis, MD

Advanced 2%Cr Steels

Grade 23 has shown problems of Stress Relief Cracking
1000
heating rate 80 - 120C/h 740C 540 - 560C min. 1h

800
Temperature [C]

600

cooling rate 100 - 150C/h

400
250 - 300C

uniform wall thickness

intermediate stress relieving PWHT-time depends on wall thickness

200
preheating
welding

time
Parker 3C-1/6

Summer Workshop 2005 Annapolis, MD

Advanced 2%Cr Steels

Can occur where there are significant changes in section, where beads overlap etc

Parker 3C-1/7

Summer Workshop 2005 Annapolis, MD

Tube Cracking in Service

T23

T23

P91 Cracking on tube side of weld typically due to excessive systems or thermal stress
Parker 3C-1/8

Summer Workshop 2005 Annapolis, MD

Advanced 2%Cr Steels

Creep Strength
300

105h Creep rupture strength [MPa]

250 200 150 100 50 0 500 510 520 530 540 550 560 570 580 590 600
T/P91 T/P24 T/P23 T/P22

Temperature [C]
Parker 3C-1/9

Summer Workshop 2005 Annapolis, MD

Advanced 9 to 12 %Cr Steels

Parker 3C-1/10

Summer Workshop 2005 Annapolis, MD

Advanced 9 - 12%Cr Steels

Grade 91

Parker 3C-1/11

Summer Workshop 2005 Annapolis, MD

Grade 91 Metallurgy

Martensitic structure brittle so tempering required Normalizing @1040 1100oC, typically 1050oC. Need to control cooling to ensure complete transformation Tempering @ 740 780oC, typically 750 to 760oC ~ 1-2 hr Need to avoid nucleation of new austenite during temper
Parker 3C-1/12

Summer Workshop 2005 Annapolis, MD

9 12%Cr Steel Metallurgy

Investigation of Z-Phase - Cr(V,Nb)N
EELS
C

chemical analysis
NK V L2,3 Cr L2,3 Cr
300 400 500

EDX
Cr V Fe Nb Cr Fe
4000 8000

E /eV
0

CK

E/eV

C Cr Cr L2,3 Fe L2,3 Cr
0

Fe W Mo
4000

Cr

300

400

500

600

E /eV

Fe
8000

E/eV

Fe L2,3 OK Cr L2,3

RGB-Image with EELSand EDX-analysis blue: Z-Phase red : M23C6 black: matrix

Fe C Fe Cr
0 4000

400

500

600

700

E /eV

Cr Cr

Fe
8000

E/eV

G-X12, HAZ (soft zone), 600C / 90 MPa / 26.000 h

Parker 3C-1/13

Summer Workshop 2005 Annapolis, MD

9 12%Cr Steel Metallurgy

G-X12, HAZ (soft zone), 600C / 90 MPa / 26.094 h.The development of Cr,V,N Z phase coincides with a loss of creep strength

Parker 3C-1/14

Summer Workshop 2005 Annapolis, MD

9 12%Cr Steel Metallurgy

Cromocord 10M, weld deposit

as received condition

3.919 h / 150 MPa

8.065 h / 130 MPa

12.271 h / 120 MPa

26.094 h / 90 MPa

G-X12 CrMoWVNbN 10.1.1, HAZ (soft zone)

as received condition

3.919 h / 150 MPa

8.065 h / 130 MPa

12.271 h / 120 MPa

26.094 h / 90 MPa
Parker 3C-1/15

Summer Workshop 2005 Annapolis, MD

9 12%Cr Steel Metallurgy

M23C6 (Cr, Mo, W, Fe) MX (V, Nb), (Nb, V) Laves Phase (Mo, W, Cr, Fe) Z-Phase (Cr, V, Nb, N)
0 20 000 40 000

Duration at 600C, h
Parker 3C-1/16

Summer Workshop 2005 Annapolis, MD

Creep Behaviour

Life with Larson Miller Constant of 20 is one third life with Larson Miller Constant of 32 Alternative to describe life with stress and temperature.

Parker 3C-1/17

Summer Workshop 2005 Annapolis, MD

Stress for 100 000 hr Rupture P92

300

550C

1 00 000 h rupture stre ss, M Pa

200

600C

650C
100

0 0 - 1000 h (276) 0 - 3000 h (334) all data (408) > 1000 h (132) > 3000 h (74)

range of rupture times in extrapolation (number of data points in brackets)

(Ref Ennis 2004)

Parker 3C-1/18

Analysis with all rupture data indicates over estimation of long-term strength
Summer Workshop 2005 Annapolis, MD

Creep Cavitation Damage

Long term failure occurs by the development, growth and link up of creep cavities on prior austenite grain boundaries, lath boundaries and inclusions

Parker 3C-1/19

Summer Workshop 2005 Annapolis, MD

Creep Cavitation Damage

Monitoring the development of cavities offers the opportunity for assessment - must take appropriate care

Parker 3C-1/20

Summer Workshop 2005 Annapolis, MD

Creep Cavitation Damage

Monitoring the development of cavities offers the opportunity for assessment - must take appropriate care

Parker 3C-1/21

Summer Workshop 2005 Annapolis, MD

Oxidation Behaviour
Significant improvement in oxidation resistance above about 12%Cr Useful operating metal temperature for Grade 91 600oC, 1112oF?

Parker 3C-1/22

Summer Workshop 2005 Annapolis, MD

Oxidation Behaviour
Rate influenced by alloying elements such as Silicon Variation of 2 times for Si levels within specification

Parker 3C-1/23

Summer Workshop 2005 Annapolis, MD

Oxidation Behaviour
Rate influenced by trace elements such as Sulphur

Parker 3C-1/24

Summer Workshop 2005 Annapolis, MD

Oxidation Behaviour
Exfoliation can cause - tube blockages-rapid overheating and failure - erosion in downstream components Thick scale will cause tube overheating & accelerated creep

Eg Ennis 2002
Summer Workshop 2005 Annapolis, MD

Parker 3C-1/25

Oxidation Behaviour

ID scale can also act as initiation site for cracking

Parker 3C-1/26

Summer Workshop 2005 Annapolis, MD

Bends
History of in-service failures in pipe bends with precipitation strengthened alloys such as CrMoV steel problems typically due to bending and subsequent HT

Parker 3C-1/27

Summer Workshop 2005 Annapolis, MD

Bends
Problems of cracking, prior to, or very soon after start of service with Grade 91 tube bends due to stress corrosion cracking,

Pictures Alstom
Parker 3C-1/28

Summer Workshop 2005 Annapolis, MD

Bends
Problems of cracking very soon after service with Grade 91 tube bends due to very rapid creep because of incorrect heat treatment Post bend heat treatment frequently requires a full renormalization and tempering. Important to ensure proper control of heat treatment

Examples of the microstructure in nominally identical bends

Parker 3C-1/29

Summer Workshop 2005 Annapolis, MD

Creep - Fatigue
Interaction leads to similar life reduction to P22

Data N.Taylor et al
Summer Workshop 2005 Annapolis, MD

Parker 3C-1/30

Creep - Fatigue

In Grade 91 interaction leads to similar life reduction to P22 i.e.

Df + Dc = 0.25
Creep with cycling reduces life by 75% (or more)
Parker 3C-1/31

Summer Workshop 2005 Annapolis, MD

Welds
Control of thermal cycles - required microstructure and precipitation. Typical PWHT ~ 750 760oC
1000
Temperature [C]

800 600 400 200

Heating rate 80 - 120C/h

760C - 10 2-4h Cooling rate 100 - 150C/h

+ 0

slow 250 - 300C cooling rate < 400C cooling in still air

20 - 100C

Preheating necessary cooling down after welding 00,511,522,533,544,555,566,577,588,599,5 10,511,522,533,5 10 1 11 11 Welding or soaking

Time
Parker 3C-1/32

Summer Workshop 2005 Annapolis, MD

Welds
E911 multipass weld
fusion line Ac1 Ac3 between Ac1 and Ac3 red line green line blue line black area

Parker 3C-1/33

Summer Workshop 2005 Annapolis, MD

Weld Creep
Properties below parent, P91 40-60% reduction factor ?

Parker 3C-1/34

Summer Workshop 2005 Annapolis, MD

HAZ Weak Zone

Type IV cracking - weak zone caused by overaging during welding in a narrow zone within the HAZ

Parker 3C-1/35

Summer Workshop 2005 Annapolis, MD

Weld Creep

Weld HAZ very susceptible to Type IV creep Cracking Life reduction proposed of 40 60%

Parker 3C-1/36

Summer Workshop 2005 Annapolis, MD

Tube Cracking in Service

Stub Tube-to-Header Welds Recent experience shows > 100 welds cracked in P91 header after around 60 000 hrs

Header side cracking of stub tube welds

Parker 3C-1/37

Summer Workshop 2005 Annapolis, MD

Type IV Cracking in Service

Plant failures have been reported:
In US, early failures associated with high system loading, poor heat treatment In Europe, first failure after 20 000 hrs was attributed to incorrect heat treatment, Others in header end plate welds occurred after 36 500 hrs (with 469 hot and 72 cold starts). Nominal operating conditions for the headers were 568C 1055oF, and 160bar. The failed weld had been inspected with standard UT and found clear 8,663 hrs prior to failure. Following the failure, High sensitivity UT was carried out on the three other modified 9Cr headers on the affected unit and the equivalent headers on another unit. This led to the discovery of further damaged end plate welds
Parker 3C-1/38

Summer Workshop 2005 Annapolis, MD

Type IV Cracking in Service

Cracks after 36,500h, 469 hot + 72 cold starts

Brett RWE npower

Parker 3C-1/39

Summer Workshop 2005 Annapolis, MD

Type IV Cracking in Service

Creep Strength of Grade 91 linked to N : Al ratio With High Al, limited N Available to form Carbo Nitrides and Nitrides, lower Hardness and, more importantly, Low creep strength

Data RWE npower

Summer Workshop 2005 Annapolis, MD

Parker 3C-1/40

Summary
Advanced Steels typically exhibit excellent parent creep properties in straight sections with correct composition and heat treatment, but

Long Term life - Larson Miller Constant Oxidation temperature limit, thick scale leads to problems with Exfoliation Cracking Over temperature Creep Fatigue interaction gives Life at Df + Dc=0.25
Parker 3C-1/41

Summer Workshop 2005 Annapolis, MD

Summary

Bending introduces complexities which in Grade 91 can severely reduce life Hot bend , need full renormalize and temper Cold bend, heat treatment depends on strain Welding can lead to problems due to Residual Stress PWHT Type IV cracking Repair, Joining to P22 Inspection, need to use validated high sensitivity ultrasonic technique to ensure accurate volumetric damage assessment
Parker 3C-1/42

Summer Workshop 2005 Annapolis, MD

Type IV Cracking in Service

Parker 3C-1/43

Summer Workshop 2005 Annapolis, MD

Type IV Cracking in Service

Parker 3C-1/44

Summer Workshop 2005 Annapolis, MD

Weld Issues - P91/ P22

Parker 3C-1/45

Summer Workshop 2005 Annapolis, MD