20160502 2nd Seminar : General Topic [CSSM]

Heat resistant materials

&
Creep behavior
Min-Gu Jo
Contents

• Thermal power station & Heat resistant materials

• Creep deformation

• HEA for Creep-resistant material

Energy consumption & Thermal power station
• IEO Energy consumption prospect • ‘14 Korea 1st Energy supplement ratio

International Energy Outlook 2014 2015 Korea Energy Handbook

• Thermal power station

• CCT (Clean Coal Technology)

 HELE coal technology (High Efficiency Low
Emission coal technology)
 CCS(CO2 Capture & Storage)

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Coal thermal power station & Heat resistant materials

SC(Supercritical)
: 538℃↓
USC(Ultra-supercritical)
: 566℃↑
HSC(Advanced-USC)
: 704℃↑

T ↑  Efficiency ↑  CO2 emission ↓

• Heat resistant materials

• Current state of Korea

- SC  USC
- 6000 ton CO2/MW
- 30% efficiency (ave)

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• Coal thermal power station - Boiler (tube, pipe)
Boiler Generator
Turbine

- Welding part - Turbine

- Bending part - Corrosion - Oxidation

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Creep
• Definition
: Phenomenon which materials gradual are changed(are deformed) under a constant applied load(stress)
Normally, under a constant applied load at an elevated temperature (T > 0.4 Tm)
 a time dependent dimensional change
Jet engine (1% in 10,000 hrs), steam tube (1% in 100,000 hrs)
To determine the engineering creep curve of metal, a constant load is applied to a tensile specimen
maintained at constant temperature and the strain of the specimen is determined as a function of time

Tensile test
: constant displacement determined stress

Creep test
: constant stress determined strain and time

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 • Creep stages (3 steps)
Primary creep (Transient)
: strain rate decreases with increasing time  work hardening
Secondary creep (Steady-state)
: balance between work hardening and recovery
Tertiary creep (Acceleration)
: strain rate increases due to creep damage (effective area
decrease, metallurgical change)

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• Creep mechanisms

- Dislocation glide (σ/G > 10-2)

Involves dislocation moving along slip planes and
overcoming barriers by thermal activation
Occurs at high stress and low T

- Dislocation creep (climb, 10-1> σ/G >10-4)

Involves dislocation movement to overcome barriers by
thermally assisted mechanisms involving diffusion of
vacancies or interstitials

- Diffusion creep (10-4 > σ/G)

Involves the flow of vacancies and interstitials through a
crystal under the influence of applied stress
Favored at high T and low stress
Bulk diffusion (Nabarro-Herring creep), GB diffusion
(Coble creep)

- Grain boundary sliding

Involves the sliding of grains past each other

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Josh Kacher, Acta Materialia 60 (2012) 6657–6672

C.M. Hu, Materials Characterization 61 (2010) 1043 – 1053

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Strengthening mechanism

Solid Solution Hardening

Substitutional solid solution (Mo, W, Co..)
Interstitial solid solution (C, N, B) But, Creep is time-dependent deformation
 Microstructure changes are effective
Precipitation(Dispersion) Hardening
σ = 0.8MGb/λ

Work Hardening(Dislocation Hardening)

σ0 = σi + αGbρ1/2

Grain Size Refinement Hardening Microstructural degradation  heterogeneous  failure

σy = σ0 + kD-1/2

Secondary Phase Hardening

σave = f1σ1 + f2σ2 f : volume fraction

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Carbo-Nitride
M23C6 ((Cr,Fe,Ni,Mo)23C6 )
Crystal structure : FCC (a=10.57~10.68Å)
Precipitation site : Grain boundary, Twin boundary
Shape : Globular, Plate
Typical Size : 200~500nm

Initial stage : Precipitation hardening

Precipitate at grain boundary  depletion zone  Coarsening  Decreasing strength

MX precipitates (MC, MN, M(CN), M1M2(CN))

Alloy : Ti, Nb, V, Zr, Ta.. (strong carbide/nitride former)
Crystal structure : FCC (a=4.40~4.47Å)
Precipitation site : dislocation, stacking faults. Twin or grain boundary
Shape : Cuboidal shape after sufficient aging

Providing good strengthening effect

Stabilizing the alloy against intergranular corrosion

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Z-Phase (CrNbN)
Crystal structure: Tetragonal (a=3.037Å, C=7.391Å)
Precipitation site : grain boundaries, twin boundary, dislocation
Shape : Rodlike, Cuboidal
Typical Size : 20~50nm

Z phase forms Nb stabilised steel with N at low temperature than MX particles.

Modified Z- phase : (Cr(Nb,V)N), CrVN
MX precipitates  Z-phase after long time annealing (stable phase below 1000oC)

M2N (Cr2N)
Crystal structure: Hexagonal close packed (a=4.78Å c=4.44Å)
Precipitation site : grain boundaries, twin boundary, dislocation
Shape : Rodlike, Cuboidal
Typical Size : 20~50nm

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Intermetallic compound
Laves phase (Fe2Mo, Fe2Nb, Fe2W, Fe2Ta, Fe2Ti)
Crystal structure : Hexagonal (a=4.73Å, C=7.72Å)
Precipitation site : Grain boundary,
Mo added steel : formation after a minimum of 1000h between 625~800oC
Nb stabilized steel : after long time aging, 5000~10000h between 625~800oC
 However, NbC and Z phase are more stable than Laves phase

σ-Phase (Fe,Ni)x(Cr,Mo)y
Crystal structure : Tetragonal (a=8.80Å, C=4.54Å)
Precipitation site : Grain boundary, Twin boundary, Inclusion
The precipitates form after long term aging at high temperature (10,000~15,000h, 600oC)

G Phase (Ni16Nb6Si, Ni16Ti6Si7, (Ni,Fe,Cr)16(Nb,Ti)6Si7) (austenitic stainless steel)

Crystal structure : FCC Phase (a=1.115~1.12Å)

T. Sourmail, Precipitation in creep resistant austenitic

stainless steels, Materials Science and Technology, 17
(2001) 1-14

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 D-B Park, PhD thesis, Korea univ (2013)
Typical creep curve
0.30 0.50
150MPa 80MPa
200MPa
650oC 0.45 100MPa 800oC
0.25 250MPa 120MPa
0.40
300MPa 150MPa
0.35
0.20

Strain (mm/mm)
Strain (mm/mm)

0.30
0.15 0.25
0.20
0.10
0.15
0.10
0.05
0.05

10-1 100 101 102 103 104 105 10-1 100 101 102 103 104 105

100 Time (h) 100 Time (h)

10-1
650oC -1
800oC
10
-2
10
10-2

Creep rate (h-1)

10-3
Creep rate (h-1)

10-3
10-4
-5
10-4
10
10-5
10-6 80MPa
150MPa
200MPa 10-6 100MPa
10-7 250MPa 120MPa
300MPa 150MPa
10-8 -1 0 1 2 3 4 5
10-7 -1
10 10 10 10 10 10 10 10 100 101 102 103 104 105
Time (h) Time (h)

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Stress dependences of minimum creep rates
10-1
Norton law (Power law)
10-2
εm = Aσ n

10-3

Minimum creep rate (h-1)

ε = 5.88 × 10−22 σ 8.33 ε = 1.98 × 10−19 σ 6.59
Dislocation creep
10-4
n=3~5 ε = 1.95 × 10−19 σ 6.02
: pure metal, simple alloy 10-5 ε = 7.08 × 10−27 σ 8.6

n=3~12 10-6
austenitic stainless steel
10-7 800°C
In this study 750°C
n=6~8.6 10-8 700°C
650°C
10-9
100 200 300 400
Stress (MPa)
Dae-Bum Park, Materials Characterization 93 (2014) 52 – 61

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 Dae-Bum Park, Materials Characterization 93 (2014) 52 – 61
Activation energy for dislocation creep
−Q
ε = Aσ n exp 
10-2
 RT 
560
540
10-3

Activation energy (kJ/mol⋅K)

520
Minimum creep rate (h-1)

500
10-4 480
460
10-5 440
420
10-6 400
120MPa 380
-7 150MPa
10 360
200MPa
340
250MPa
10-8 320
0.92 0.94 0.96 0.98 1.00 1.02 1.04 1.06 1.08 1.10 100 120 140 160 180 200 220 240 260 280

1000/T (K-1) Applied stress (MPa)

γ-Fe self diffusion activation energy : 295kJ/mol

14Cr-15Ni-Ti austenitic stainless : 460kJ/mol
347H austenitic stainless steel : 441~461kJ/mol
TP347H austenitic stainless steel : 385~463kJ/mol

The similarly value of apparent activation energy (465~485kJ/mol)

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Kyu-Ho Lee, Materials Characterization 102 (2015) 79–84

Fig. 4. (a) Creep rate versus time tested at 866 K and (b) creep-
rupture plot of the Steel Aand Steel B acquired at various creep Fig. 5. XRD profiles of the powders electrolytically extracted from
conditions. the gauge part of creep specimens of (a) Steel A and (b) Steel B
tested at 866 K.

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Kyu-Ho Lee, Materials Characterization 102 (2015) 79–84

Fig. 8. Development of phase fraction of the precipitates in (a)

Fig. 7. Equilibrium phase fraction of high-Cr martensitic heat-resistant steels, Steel A, (b) Steel B and (c) chemical composition ofM2N in Steel
(a) Steel A and (b) Steel B calculated by MatCalc. B during aging at 866 K calculated by thermo-kinetic simulation.
Monkman-Grant relationship (predict the rupture time)
0.30
5
10 150MPa
200MPa 650oC

ε t = K
0.25 250MPa
n 300MPa

4 m r 0.20

Strain (mm/mm)
10
0.15
Time to rupture (h)

0.10
103
εm−1.006tr = 0.184 0.05

102 10-1 100 101 102 103 104 105

Time (h)
100
101 10-1
650oC
800°C 10-2

750°C 10-3

Creep rate (h-1)

0
10
700°C 10-4

650°C 10-5
10-1 -8 -7 -6 -5 -4 -3 -2
10-6
150MPa
10 10 10 10 10 10 10 10-7 200MPa
250MPa

Minimum creep rate (h-1)

300MPa
10-8 -1
10 100 101 102 103 104 105
Dae-Bum Park, Materials Characterization 93 (2014) 52 – 61 Time (h)

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Larson-Miller plot (predict the rupture time)
T (logt r + C ) = K
500
304HV
400
Super304H[1]
300 SUS 347H[2]
SUS 316[3]
Applied stress (MPa)

200

100

23000 24000 25000 26000 27000 28000 29000 30000 31000

LMP=(T)(logtr+25) (K,h) [1] NRIM Creep data sheep No. 56
[2] NRIM Creep data sheep No. 28B
Dae-Bum Park, Materials Characterization 93 (2014) 52 – 61 [3] NRIM Creep data sheep No. 6B

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High Entropy alloy(HEA) Introduction
Definition
B. Cantor, Materials Science and Engineering A 375–377 (2004) 213–
: At least five major metallic element having an 5-35 at% 218
 FeCrMnNiCo

Yeh, Advanced Engineering Materials, 6, 5 (2004) 299-303

 High-Entropy alloys (HEAs)
N
∆Sconf = −R ∑ ni ln ni
i =1
 Core effect
1) Solid solution strengthening
2) Distorted lattice structure
3) Cocktail effect
4) Sluggish effect

5) Nanoscale deformation twin (Cantor alloy)

Daniel B. Miracle, “Exploration and Development of High Entropy

Alloys for Structural Applications”, Entropy (2014), 16, 494-525

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Initial specimen information
• EBSD IQ(Microstructure) • XRD

40000

35000

30000

25000

Intensity
20000

15000

10000

5000

0
30 40 50 60 70 80 90 100

Diffraction angle 2-Theta

50.34㎛±19.89
FCC singe phase
• EDS Lattice parameter* : 3.58238 Å
Element Wt% At% (*:Bragg’s law와 d-spacing으로 얻은 각각의 면들의 lattice
CrK 18.30 19.76 parameter의 평균)
MnK 18.36 18.75
FeK 19.95 20.80 • Vickers hardness
CoK 21.18 20.92
NiK 19.94 19.78
Matrix Correction ZAF 161Hv±2.677

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Tensile results
600 1000

800

True Stress (MPa)

Eng Stress (MPa)

400
600

400
200 RT RT
500 ℃ 200 500 ℃
600 ℃ 600 ℃
700 ℃ 700 ℃
0 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.0 0.1 0.2 0.3 0.4

Eng Strain True Strain

600 1200

550
1000
500
800
UTS (MPa)

UTS (MPa)
450

400 600

350
400
300 Cantor
27 ℃ Ni-based super alloy (KIST)
500 ℃ 200 Austenite (NIMS)
250 600 ℃ High Cr (NIMS)
700 ℃ Low Cr (NIMS)
200 0
10-4 10-3 10-2 0 100 200 300 400 500 600 700 800 900

Strain rate (S-1) Temperature ( ℃)

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 Tensile results compared with S304H
700

RT
600
 Cantor
RT
Eng Stress (MPa)

450℃
500 Strain rate : 8.333x10-4
550℃
 S304H
400
600℃ Strain rate : 6.666x10-4
600℃ 650℃
500℃
300
700℃
200
Cantor
700
S304H
100
Cantor (This stduy)
S304H (KEPCO) 600
0

UTS (MPa)
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
500

Eng Strain
400

300

0 100 200 300 400 500 600 700 800

Temperature ( ℃)

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Creep results
103
102
-1
10
101
100

Creep rate (1/h)

10-2 10-1
10-2
Strain

10-3
10-3
10-4
10-5
10-4 100MPa 200MPa
10-6
200MPa 100MPa
10-7
T=650 ℃ T=650 ℃
10-5 10-8
10-3 -2
10 -1
10 0
10 10 1
10 2 3
10 10-3 10-2 10-1 100 101 102 103

400
Time (hr) Time (hr)
Cantor
350 Ni-based super alloy (NIMS)
Austenitre (NIMS)
High Cr (NIMS)
300 Low Cr (NIMS)
Stress (MPa)

250

200

150

100

50

0
100 101 102 103 104 105

Rupture Time (hr)

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 XRD results after creep test
Relative Intensity

Specimen Initial 100MPa 200MPa

Crystal
FCC FCC FCC
200MPa
structure
100MPa Lattice
Initial 3.58238 3.58729 3.59578
parameter*(Å)
(*:Bragg’s law와 d-spacing으로 얻은 각각의 면들의 lattice
parameter의 평균)

40 50 60 70 80 90 100

Diffraction angle 2-theta

Relative Intensity
200MPa
100MPa
Initial

45 48 51

Diffraction angle 2-theta

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Summary
• To improve efficiency of coal thermal power station, increase of operating
temperature is required. Therefore, research on heat-resistant material should be
preceded.

• Materials with high heat-resistance, oxidation-resistance, corrosion-resistance,

weldability and especially creep-resistance are required as the structural materials for
the thermal power station application.

• Creep phenomenon is a time-dependent deformation behavior and microstructural

change is dominant effect on the failure of materials.

• Through the creep test condition under high temperature and constant load compare
to the real operating condition, we expect to predict the lifetime of structural
materials for the thermal power station.

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Thank you for your attention