1

??? ? ?

????????????????????????????

??????????????????????????????

??????????????????????????????

??????????????????????????????

??????????????????????????????

???????????????????

????????????????????????????

??? 40 ?????????????????????????

?????????????????(Stress Corrosion Cracking,

SCC)?????????????????????????(Vessel

Internal Cracking?VIC) ?????????? VIC ???????

??????????????????????????????

?????????????????(Fatigue)???(Wear)???

???????????????????(1)????(2)?????

????????????????

???????????????????????????

2

??IGSCC ? IASCC ????????????????????

??????????????????????????????

?????????

???????????????????????????

??????????????????????????????

????????????????????????? SCC ??

??????????????????????????????

?????????????????????????????

??????????????????? (Hydrogen Water

Chemistry, HWC)??????(3,4)????HWC ?????????

????????????(??? 0.6ppm ??)????????

??????????????????????-16 ??????

???????????-60?????????????

?? HWC ???????????????????????

??????????????????????????????

???? IGSCC ??????????? HWC ????????

??????(5-13)??????????????????????

????(Primary Coolant Circuits, PCCs)???????? HWC ?

3

??????????????????????????????

??????????????????????????????

(Catalytic)????(Inhibitive)????????????(5,11,12)???

???????????? IGSCC ??????????????

??????????????????????????????

????????????????????(Noble Metal Chemical,

NMCA)(19-23)?? Pt?????????????????????

????????????????

?????????????????????????NMCA

??????????????????????????????

????? NMCA ????????????????????

??????????????????????????????

??????????????????????????????

??????????????????????????????

?(7,8)?????????????????????? IGSCC ??

?????????????????? HWC ?????????

??????????????????????????????

??????????????????????????????

?????????

4

???? HWC ????????????????????

????????????????????? IGSCC ?????

???????(ZrO2)????(TiO2)????????(ZrO(NO3)2)

????????????????????? BWR ??????

???????? 150??????? 304???????????

????????????????????? 304 ??????

HWC ? BWR ???????????????????????

?????????304???????????????????

5

??? ? ?

2.1 ??????

???????? BWR ?????????????? SCC

??????????????????????????????

??????????????(Tensile Stress)??????(Corrosive

Environment)????????(Susceptible Material)??? 2-1 ??

????????????? SCC??????????????

SCC ???????????????

? 2-1 ?????????

2.1.1 ????

BWR ???? SCC ????????

(1) ???

BWR ????????????????????????

Tensile

stress

Susceptible

material

Corrosive

environment

SCC

6

??????????????????????????????

??????????????????????? SCC ????

??????????? SCC ????????????????

????????????????????????? (Heat-

Affected Zone,HAZ)????????????????????

SCC ????

(2) ?????

BWR ???????????????????? (Radiolysis)

??????????????????????????????

??????????????????????????????

????????????????????? SCC ???

(3) ???????

BWR ?????????????? 304?304L?316?316L ?

????? Inconel 600?X-750 ????????????????

??????????????????? 500?? 850?????

??????????????????????????????

??????????????????(Sensitization)??????

7

?? HAZ ?????????????????????????

??????????????????????????????

?????? IGSCC????????????????????

??????????????????????????????

?(Radiation-Induced Segregation, RIS)?????????????

? IASCC?

2.1.2 ????

???????SCC ???????????????????

?????????????????????? SCC ?????

????????????? SCC ????????????

(1) ???

????????????????????????????

????????????????????????????

????????????????

(2) ???

????????????????????????????

?????? IGSCC ???????????????????

8

???????????????????? BWR ?????

??????????? 0.1S/cm?????????????

????????????????????????????

????????????????????????????

????????? IGSCC ?????????? IGSCC ??

????????????? HWC ????

(3) ???

?????????????????? SCC ????????

(

9

?????????????????????????????

-n neMM + + (1)

-+ + eHH2 (2)

-- ++ 4OH4eO2HO 22 (3)

O2H2e2HOH 222 ++-+ (4)

??????????????????????????????

?(Radiolysis)????????????????????????

?????????????????????????

OHO21

OH 2222 + (5)

??????????????????????????????

(1)?(3)??(4)???????????????????????

??????????????????????????????

??????????????? ECP?? ECP ????????

???????(3)??(4)???????????????(1)??

??????????

??? ECP ??? Macdonald ??????????(Mixed

Potential Model, MPM)????(25)?MPM???????????

10

??????????????????/???????????

????????????????????????

0)()(1

,/ =+=

EiEi corrn

jjOR

(6)

iR/O, j????? j ????????R/O????????? icorr??

??????????????????????/???????

????

????????????????

eOR n+ (7)

?? R ??????????O ????????????????

?????????? Butler-Volmer ??????

c

eORa

eOR

ce

ORae

OR

bEE

r

bEE

fOR

bEEbEE

OR

ei

eii

eei

/)(

,

/)(

,/,0

/)(/)(

///

//

111 ---

---

-+

-=

ll

(8)

i0,R/O ???????(? ECD)?il,f? il,r ????????????

???????????(Limiting Current Density)?ba? bc????

??? Tafel???E R Oe/ ?? Nernst???????????????

?????????????

11

bb -= 10/,0 ROOR CCnFki (9)

?? F ? Faraday ??? k0 ???????????(Intrinsic

Electrochemical Rate Constant)?CO? CR????????????

???????b ??????(Transfer Coefficient)?Tafel ????

??????

nFRTba )1/(303.2 b-= (10)

nFRTbc b/303.2-= (11)

?? R ??????T ?????????(Turbulent Flow)????

??????????????????

dScRenFDCi ROROl /0165.033.086.0

//, = (12)

??????????(?)???????(?)?D ???????

?????(Diffusion Coefficient)? ROC / ? O ? R ???(Bulk)???

Re? Reynolds ?(Re?ud/v)?Sc? Schmidt ?(Sc?v/D)?d ????

???????u????? v ????????????????

???

12

)log(303.20 //O

RRO

eRO a

anF

RTEE -=

(13)

?? aR? aO??? R? O ???????E R O/0 ??????

????????????????????????? ECP ?

??????????(E R Oe/ )? Tafel ??(ba? bc)????????

??????????????????????????(il,f? il,r)

??????????????????(8)??? k0 ??????

??????????(i0,R/O)?????????????????

???????

??????????????????????? ECP ??

????????????( ORi /,0 )??

ORORIOR iFi /,0/,/,0 = (14)

?? FI,R/O????????? ECD??????

?? 2-2?????????(? Evans Diagram)??????

?????????????? ECP ??????????????

? 2-1??????????? A?B?C ????? A?????

??????B??????????????C ????????

13

?????????????????? A ??????????

??????????????????????????????

????????(?? A)?????????(?? O1)????

Ecorr1A????????????ECP?? icorr1A????????(?

??????????)?

? BWR ?? HWC ???????????????????

??????????????????????????????

???????? (?? B)????? O1 ???????

ECP(Ecorr1B)???? ECP ?????????????????

(icorr1B)???????????????? ECP ??????????

????????????????????????????

???????????? ECD ???????????????

ECD ?????????????????????????? 3

?????ECD ? 1/HH0, 2

+i ??? 2 /HH0, 2 +i ??? O1???? 3 ????

?? O2?ECD ? 1 /OO0, 22 -i ???2

/OO0, 22-i ??????????????

???????????????????????? Tafel ???

????????????????(?????)????????

???? A??????? O2??????(? ECP)?? Ecorr2A??

14

?????????????? icorr2C????????????

??????????????? ECP ????????????

???

??????????????????? HWC??????

???? C ??????? O2??????(? ECP)?? Ecorr2C??

???????? A????????? icorr2C?????????

? ECP ????????????????????

????????????????????????????

????????????????ECD??????????ECP

?????????????????????????????

ECD ????

15

2

2-/OO0, 2i 1, -22 /OO0i

+ni M/M 0,

1+/HH0, 2

2+/HH0, 2

i

log i (A/cm2)

-12 -11 -10 -9 -8 -7 -6 -5 -4 -3 -2 -1 0 1

-22 /OO

E

+/HH2E

+nEM/M

A. Metal Oxidation

B. Metal +H2 Oxidation on Metal

C. Metal + H2 Oxidation Inhibitive Coating

Ecorr1A

Ecorr2A

icorr1B

O2

O1

icorr1A icorr2A

icorr2C

Ecorr1B

Ecorr2C

? 2-2 ??????????????? ECP ?????????

????????????

16

??? ????

3.1 ?????

??? BWR ??????????????????????

??????????????????????????????

????????????? IGSCC ??????? BWR ????

????????? 200 ? 300ppb??????????????

??? IGSCC ???????????????????????

????(26)???? BWR ??????????????????

??????????????????????????????

??????????????????????????????

??????????????????????????????

??????????????????????????????

????? ECP ????(27)?ECP ? IGSCC ??????????

?? ECP ?????????????????(28)???????

???-230 mVSHE? 304 ????? IGSCC ??????(Ecrit)??

??????? ECP ??? Ecrit ???????????????

????

17

??? HWC ?????????????????????

??????????????????? HWC ? BWR ????

????HWC ???????????????????????

??????????????????????????????

??????????????????????????????

??????????????????????????????

??????????????????????????????

???? HWC ????????? ppb????????????

??????????????????????????????

????????????? ECP ??????? HWC ????

??????(Upper Downcomer)??????????(10)?

????????????????????????????

?????????(28)????????????????-16 ??

???????????????????-60 ?????????

??????????????????????????????

???? BWR ???????? N16?????????????

???? HWC???????????????? N16?????

?? NH3? NOX ??????????????????????

18

????????? R. L. Cowan(24)??? HWC ????304???

???????????????????..??????????

? MCr2O4???????????????? CoCr2O4?????

??????? 3-1??????? Co60????????????

?????????????????????????NWC ?

HWC ?????????? Co60?????? 3-1???

?3-1 ???????????????????????(24)

? 3-1 NWC ? HWC ????? Co60?????(24)

19

3.2 ?????

?????????????????????? 200 ? 300

ppb ????????????????????????????

??????????????????????????????

??????????????????????????????

??????????????????????????????

??????????????????????????????

??????????????????????????

3.2.1 ?????(Sol-gel Method)

???????????? TiO2(29,30) ? ZrO2

(9,32,33) ? ?

TiO2-SiO2(34-37)????????????????????????

?????????? (38-41)???????????????(?

?)???????(??)????????(???)????????

?????????Sol-gel???????????

Formula?Zr(OC3H7)4+C3H7OH??????CH3COOH ????

?H2O

Concentration?0.025 to 0.9M ZrO2

Volume ratio? H2O/ CH3COOH?2

20

H2O/ C3H7OH?1

??????? Sol-gel????????? 20?????????

??????????????????????????????

??????????? 40 oC ? 70 oC ???? 15???????

?????????????????????? 400 oC ?? 1?

????????? Tg(?????)??????????????

??????????????????(Densification)?

????????????????????????????

(Amorphous)?????(Porous)?? Sol-gel ??????????

????? (42-46)? 1.????? (Spin Coating)? 2.??? (Dip

Coating)?3.?????(Spray Coating)?4.???(Electrophoresis)?

????????????????????????????

??????? 2?????????????????? Cr2O3?

??????????????????????????????

? 800 oC ?????????????????????????

?????????????????????????Fe2O3??

???????????(38)?

21

? X????(X-ray Diffraction, XRD)???????????

(Fourier Transform Infrared Spectrum, FTIR)???????????

???? 3-2(38)? ZrO2????????????????????

?????? XRD????(a)????????????????

????(b)?(c)????????????????????T(111)

?? ZrO2?????(d)???????????????????

? XRD??????????????????????????

??????????? ZrO2??? 316L???????????

?????????? 40 nm ?????????????????

??????????????????????????????

??????????? ZrO2 ????????(38)??? Zr-O-Fe

??????????? ZrO2 ????????????????

??????????????? 3-3(38)???? 3-4(38)?????

????????? ZrO2?????? FTIR ????(a)????

???????(b)??????????????(c)??????

???????????? FTIR ???????????????

??????????????????????????????

Zr-O-C ????????? Zr-O-Zr??????????????

?? ZrO2 ?????????????????????????

22

Sol-gel?? TiO2-SiO2???????????????(38)??? 3-5

?????????????????????????????

????????????????????????????

?(9)?? Sol-gel?????? 304???????????????

?(288 oC ???? 0.1 mS/cm???????)?????????

?? ECP????????????????

? 3-2 ???????? ZrO2???? XRD??(38)

23

? 3-3 ??????????????????? (38)

? 3-4 ??????? ZrO2 ?????? FTIR ??(38)

24

? 3-5 ???? 1 mVs-1?15%?????? 250C(a)???? 316L

SS(b)316L SS ?? 8000C ??? 2??(c)? TiO2-SiO 2 ?

?? 316L SS ????????(34)

3.2.2 ?????(Plasma Spray)

???????????????????????????

??????????????????????????????

?????????(8,51)????? 200 ppb ??????????

???????(??500 mVSHE)??????? 200-300 ppb ??

??????????????????????????????

??????????? 3-6?????????????????

??????????????????????????????

????????????????(TiO2)???? n-type??

25

???????????(??410 nm)???????????? ECP

????? 3-7(53)??????? TiO2?????????????

??????????????????????????????

??? Evan Diagram ????? 3-8(53)????? 3-9(53)?????

TiO2 ??? 304 ??????????????????????

??????????????????????? TiO2 ????

?????? ECP ???????????? TiO2???????

? ECP ?????????

????????????????????????????

?????(42)???????????????? pin-hole ????

????????????????????(microcrack)?????

??????????????????????????????

??????????????????????????????

???????????(42)?

26

? 3-6 ????????????? YSZ(Yttria stabilized zirconia)

????????? ECP ?(8)

? 3-7 ? TiO2???????????????(??410 nm)??

???????? ECP ?(53)

27

? 3-8 ? TiO2?????????????????? ECP ??

? Evan Diagram ???(53)

? 3-9 ? TiO2???????????????????????

???????(53)

28

3.2.3. ?????(Alloying)

?????????(Zirconium)? 304 ???????????

0.5~3.0 wt?????????????????????????

???? ECP ????(8)???????????????????

???????? ECP ?????? 3-10(8)???

? 3-10 ?????????? Zr??? 304 ?????????

???????????? ECP ??(8)

3.2.4. ?????(Chemical addition)

????????????????????????????

??????????????????????????????

? Kim ??? 1 mM? ZrO(NO3)2???? 10 ppm???????

????????????(8)?????????????????

29

????(288 oC???? 200 ppb?2?)????????????

???? 60 oC ?? 10 ppm?????????????? 10??

20 ????????? ECP ???????? 3-11?3-12(8)???

?????????????? ECP ?????????????

?????? 100 ppb ?????ECP ??????? IGSCC ??

???(-230 mVSHE)?? 3-13(8)? 1 mM? ZrO(NO3)2???????

???????????(Auger Depth Profile)???? Zr????

? 3-11 ?? 1 mM ? ZrO(NO3)2??????????????

?????? ECP ?(8)

30

? 3-12 ?? 10 ppm????????????????????

??????? ECP ?(8)

? 3-13 1 mM? ZrO(NO3)2???????????????? (8)

????????????????????????????

?????????????(47)????????????????

????????????(????????)??????????

??????? pH? 2.8? 7.1???? 160 oC ?????? 6?

12 ????????????(Interfacial Resistance)???????

31

? 300 ????????? ECP ???????????????

??? ECP ????????? 400 mV????? 3-14????

??????? B. Stellwag(48)???????????????

??????????????? ZrO2 ????????????

?????????? ECP ?????????????????

?? K3Fe(CN)6/K4Fe(CN)6 ??????????????? ZrO2

??????????????????????????????

?????????????????? 3-15?????? ZrO2?

??????????????????????????????

?? ECP ?????????????????????????

?? Kim ????? ECP ??????????????????

???? Prefilm ??????? ECP ???? 3-11?3-12????

???? B. Stellwag ??????? ECP ???????????

? 3-16????????????????? ZrO2???????

??????? Prefilm ????? ECP ??????????(54)

???????????? ECP ?? Prefilm ??????????

??????????????????????????????

??????????????????????????????

??????????????

32

? 3-14 ??????????????? 304??? ECP ???

????(47)

? 3-15 ZrO2???????????????????????

??(48)

33

? 3-16 ZrO2?????????????? ECP ?(48)

3.2.5.?????(Electrophoretic Deposition)

???????? ZrO2??????????? HCl????

pH ????????????????????????????

????????????????

???????? ZrO2 ??(50)???????? 150m ??

???????????(Electrochemical Impedance Spectroscopy, EIS)

????????? ZrO2 ??????????????????

?? 1000 ?????? 3-17?????????(Constant Load)??

????????????? 220 S/cm????????????

ZrO2???????? 400??????????????????

??? 3.9210-7cm/s???? ZrO2??????????????

34

????? 3-18??????? ZrO(NO3)2???????????

(52)?????????????

? 3-17 ????????????????????? ZrO2??

(??)??????(??)????(50)

35

? 3-18 ?????????? ZrO2?????????????

?????(50)

????????????(11)???????????????

?????????????????????????????

(12)?????????????????????????????

??????????????????????????????

??????????????????????????????

??????????????????????????????

???????????????????? ECP ??????

??????????????????????????????

?????????????

36

3.3 ?????????(SSRT)

??????? SSRT ??????????????????

?????????????????? SCC ?????????

????? SSRT ???????????????????????

ECP ??????????????-?????????????

10-2sec-1?SSRT ??????????? 10-5~10-7sec-1??????

?????????????????????????? SCC??

??????????????????????????????

?????????????????????????? SCC?

??????????????????EPR????? EIGSCC

??? ECP?????????? EPR ?????? SSRT ??(31)?

????? IGSCC ??? ECP ?(EIGSCC)??? 3-19(31)??????

??? SSRT ?????????(18)?????? IGSCC ????

???????(Crack Growth Rate, CGR)?????? TGSCC ?

??

37

? 3-19 ????????? EPR???? IGSCC? EIGSCC???

?(31)

???????????????????(13-17)???????

??????????????(Crack tip)???????????

(Crack mount)???????????????????PH???

??????????????????D. D. Macdonald (17)????

??????????????????????(Induction stage)?

???????????(Crack propagation stage)????????

?????????????????????????????

3-20 ????????????????????????????

??????????????????????????????

?????????????????????????????

??????????????????????????????

38

?????????????????????????? 3-21 ?

??

? 3-20 ??????????(17)

? 3-21 ????????????(17)

39

??? ??

4.1 ??

??????????? 304???????????????

?????????????????????? 304??????

??????????????????????????????

???? 4-1????????????????????????

650???? 24 ??????????????????SiC???

????????????? 1200 ??????????????

??????????????????????????????

??????(Electrochemical Potentiokinetic Reactivation, EPR)??

??(24)?????????(Degree of Sensitization, DOS)?

4.2 ?????(Insulated Protective Coatings)

????????????????????????????

??????????????????????????????

??????? 288?????????? 300ppb????????

??(prefilm)????????????????????????

??????????????????????? 10 ?????

????????????????? 10???????????

40

? 4.1 ?????

650? 24hr ????

+ ??

????

?????

14days ? 288? [O2]dis=300ppb

???????

14 days ?150?

SSRT

1.[O2]dis=300ppb,[H2]dis=10ppb

2.[O2]dis=300ppb,[H2]dis=25ppb

ECP

[O2]dis=100~1000ppb

1.[H2]dis=0ppb, 2.[H2]dis=10ppb

3.[H2]dis=25ppb,4.[H2]dis=50ppb

SEM fracture surface examination IGSCC% Max.stress Elongation

ECP value AES maps, depth profile

Type 304 SS

41

?????????????????????????????

???????????????? 150????????????

???? ZrO2?TiO2?? ZrO(NO3)2?????? 10 ppm?10 ppm

? 1 mM?????????? 14??

4.3 ?????(Recirculation Loop)

?????? BWR ???????????????????

??????????????????????????????

??????????????????????????????

????????????????????????(SSRT)???

? SSRT ???????????????????(ECP)????

????????????????????? ECP ??????

??????????????????????????????

???????????????????????? 4-2 ? SSRT

???????????? 4-3? ECP ???????????

4.3.1 ?????

SSRT ???

????????? 316?????????????????

42

??????? 4000psi????? 15?????????????

??????????????????????????????

???????????(Damper)????(Safety Valve)??????

??????????????????????????(Heat

Exchanger)?????(Pressure Regulator)????????????

??????????????????????????????

??????????????????????????????

???????????????????

ECP ???

ECP ?????????? SSRT ????????????

??ECP ???????????????????

4.3.2 ????

SSRT ???

????????????????????????????

??????????????????????????????

????????????????????????? PULSAR

25HJ???????????????????????? 2095psi?

?????? 1.93 gallon/hour????????????????

43

N2 H2 O2

Gas Vent

Water

Tank

Deionizer

Conductivity H2 O2

Recirculation Pump

High Pressure

Pump

Damper

Heat Exchanger

Flower Meter

IBM Compatible

Keyboard

Multimeter

PC

SSRT Contrller

TempertureController

Cooler

Load

? 4-2 SSRT ??????????

IBM Compatible

Keyboard

Mass Flow Controller

N2 H2 O2

Gas Vent

Water

Tank

Deionizer

Conductivity H2 O2

Recirculation Pump

High Pressure

Pump

Damper

Heat Exchanger

Flower Meter

Autoclave

Nanovolt Tmeter

Switch System

PC

Cooler

TempertureController

? 4-3 ECP ??????????

44

??????? 1200psi???????????????????

????????????????????????? 1500psi?

??????????????????????????????

?????????????????????????????

1800psi?????????

ECP ???

????? PULSA Series 680 ??????????? 1800psi?

?????? 1 gallon/hour?

4.3.3 ????

?????????????????????????? 1?

??????? 1/4 ?????????? 1/2 ?????????

??????????????????????????????

????? 500W?220V ?????????? 288???????

???????????????????????????? 380

?? 450??????? SSRT ????????????????

?????????????????????????????

??????????????????????????????

??????????????????????ECP ??????

45

????????????????

4.3.4 ????

SSRT ???

????????????????????????????

??????????? GLI Model C53 ????????????

??????????????????????????????

?????????????????????? GLI Model C53

???? ORION Series1816 ????????? Orbisphere

Laboratories3600 ??????????????????????

???????????????????

ECP ???

??? GLI Model D63 ????????? SSRT ?????

?????????

4.3.5 ????

???????????????????????????

???????????????? 16M????????????

?????????????????? BARNSTEAD D8901 High

46

Capacity Cartridge????? D8911 Ultrapure Cartidge??????

??????? 0.1?S/cm??????????????????

??????????????????????????????

????????????????????

4.3.6 ????

SSRT ???

????????????????????????????

??????????????????????????????

SSRT ???????????????????????????

??????????????????????????????

?????????????????? Parker ?????????

????????????????????????????

ECP ???

???????????????????????????

ECP ????? MKS Model 247C 4-Channel???????? MKS

Mass-Flow Controller ????????????????????

4.3.7 ????

47

SSRT ???

?? KEITHLEY 2700 Multimeter?????????????

????? 20 ????????? GPIP ???????????

?????????????????????

ECP ???

?? KEITHLEY 2182?????(NANOVOL TMETER)? 7001

?????????(SWITCH SYSTEM)????????????

?????????????? ECP ????????

4.4 ?????????

SSRT ???????? 4-4?????????? 316???

??????????????????????????????

?????????? 1.67?10-7 s-1????? 288????? 1100psi?

??????? 40ml/min???? Linear Voltage Displacement

Transducer(LVDT)??????????????????? 20 ?

??????????????????????????????

??????????????????????????????

????????????????(Scanning Electron Microscope,

HITACHI S-4000)???????????? IGSCC ???????

48

??????????????????????????????

?????????? 304 ?????????????????

??

? 4-4 ???????

4.5 ???????????

? ECP ????????????????????????

??????????????????????? 316?????

?????? 1100psi???????? 20ml/min????????

Conax ???????????????????????????

???????????????????/??????????

????????? 288???????? 123 mVSHE??????

????????????????????????ECP ????

??????????????????? 10 ?????????

49

???????????????

4.6 ????

????????????????? X ???? (Energy

Dispersive X-Ray Spectrometer, EDX)??????(55)???? Auger

?????(Physical Electronics, Auger 670 PHI Xi)???????

???????????????????????? IGSCC ??

??

50

??? ?????

304 ????????? 5-1???????????????

??????????????????? 650???? 24 ???

???? 5-2 ?????????????????????

DL-EPR ?????(54)???????? 24?? 650???????

?????? 46%??????????????????????

??????(prefilm)????? 150?????????????

??????????????? 10ppm? ZrO2?10ppm? TiO2?

?? 1 mM? ZrO(NO3)2???????????????????

??????????????????????????????

????????

5.1 ?????????

?????????(SSRT)???????????????

????????? 300ppb????? 10ppb??????????

?? 1????????????? 300ppb????? 25ppb???

???????? 1? 2????? 5-3????????????

???????(ZrO2,TiO2,ZrO(NO3)2)? SSRT ???

51

? 5-1 304??????

Fe C Cr Ni Mn Co Si Cu Mo P S

Mass% 68.9 0.075 17.1 7.55 1.10 0.088 0.427 0.239 0.222 0.191 0.019

? 5-2 ???????????? DL-EPR ?????(54)

Sensitization Time (at 650?) As Received

With Solution Annealing (1050?,0.5hr)

0 hr 2.67*10-2% 0

22% 6.1% 1 hr

21% 5.3%

42% 8.8% 8 hrs

35%

24 hrs 46%

? 5-3 SSRT ????????????

? ? [O2]dis=300ppb [H2]dis=10ppb

[O2]dis=300ppb [H2]dis=25ppb

Prefilm ~ 0.5 > 1

IPC-ZrO2 ~ 0.5 > 1

IPC-ZrO(NO3)2 ~ 0.5 > 1

IPC-TiO2 ~ 0.5 > 1

5.1.1 ???????????????

52

? 5-4(54)???????? 300ppb ???????? SSRT ?

????????????? 90??150??200??? 5-1????

?????? 150??????????????? 5-4?????

??????????????????????????????

IGSCC ????? prefilm ?????????????????

IGSCC ???

5.1.2 ???? 300ppb ???? 10ppb? SSRT

? 5-5 ???????? 300ppb ????? 10ppb(?????

?? 1)???? SSRT ???? 5-2 ????? 300ppb ?????

10ppb ? SSRT ???????????????????????

??????????????????????????? Prefilm

??????? Prefilm ??????????????? 280 ??

? 155 MPa ????? 9.65%????????????????

????????? 315~335 ?????????? 165~180 MPa?

???? 10.91%~11.55%??????????????????

IGSCC ??????????? Prefilm ????????????

????????????? IGSCC ???????????

300ppb ???????? SSRT ?????? IGSCC ??????

53

?????? IGSCC ????

5.1.3 ???? 300ppb ???? 25ppb ? SSRT

? 5-6 ???????? 300ppb ????? 25ppb(?????

?? 1 ??? 2)???? SSRT ???? 5-3 ????? 300ppb ?

???? 25ppb ? SSRT ????????? SSRT ???????

??????????????????????????????

?????? 1 ? SSRT ?????????????? Prefilm ?

?????? Prefilm ??????????????? 320 ???

175 MPa ????? 11.15%?????????????????

?????? 339~345 ?????????? 180~186 MPa????

? 11.77%~11.92%?????????????????? IGSCC

??????????? Prefilm ?????? IGSCC ?????

???????????? 1 ? SSRT ???????????

?????????????????? IGSCC ????????

???????????? IGSCC ????????????

IGSCC ?????????????? IGSCC ?????????

??????????????????

54

? 5-4 ???? 300ppb ? SSRT ??(54)

? ? Time to fracture (hr) Elongation

(%) IGSCC

(%)

Prefilm 220 7.55 52

ZrO2-150? 320 10.97 40

ZrO(NO3)2-150

? 295 10.11 48

TiO2-150? 308 10.56 42

0

50

100

150

200

250

300

350

400

TiO2

TiO2

ZrO(NO3)2

ZrO(NO3)2

ZrO2

ZrO2

Prefilm

Prefilm

Prefilm

ZrO(NO3)2TiO2ZrO2

IGSCC%Elongation(%)Fracture Time

hr

0

20

40

60

80

100

Type304SS[O

2]dis

:300ppb

288oC Strain rate=1.67*10-7S-1

IPC

%

? 5-1 ???? 300ppb ? SSRT ???????

55

? 5-5 ???? 300ppb ????? 10ppb ? SSRT ??

? ? Time to fracture(hr) Max.

Stress(MPa)

Elongation (%)

IGSCC (%)

Prefilm 280 155 9.65 40

ZrO2-150? 335 180 11.55 32

ZrO(NO3)2-150

? 315 165 10.91 30

TiO2-150? 322 172 11.11 34

56

0

50

100

150

200

250

300

350

400

Prefilm

ZrO2

ZrO(NO3)

2

TiO2

Max. Stress

TiO2

TiO2

ZrO(NO3)2

ZrO(NO3)

2

ZrO2

ZrO2

PrefilmPrefilm

Prefilm

ZrO(NO3)2TiO

2ZrO

2

IGSCC%Elongation(%)Fracture Time

hr,

MP

a

0

20

40

60

80

100

Type304SS[O

2]dis

:300ppb[H2]dis:10ppb

288oC Strain rate=1.67*10-7S-1

IPC

%

? 5-2 ???? 300ppb ????? 10ppb ? SSRT ??????

?

? 5-6 ???? 300ppb ????? 25ppb ? SSRT ??

? ? Time to fracture(hr) Max.

Stress(MPa)

Elongation (%)

IGSCC (%)

Prefilm 320 175 11.15 29

ZrO2-150? 341 180 11.77 23

ZrO(NO3)2-150

? 339 180 11.79 21

57

TiO2-150? 345 186 11.92 18

0

50

100

150

200

250

300

350

400

Prefilm ZrO2

ZrO(NO3)2TiO

2

Max. Stress

TiO2

TiO2

ZrO(NO3)2

ZrO(NO3)2

ZrO2

ZrO2

Prefilm

Prefilm

Prefilm

ZrO(NO3)2

TiO2ZrO2

IGSCC%Elongation(%)Fracture Time

hr,

MP

a

0

20

40

60

80

100

Type304SS[O

2]dis

:300ppb[H2]dis:25ppb

288oC Strain rate=1.67*10-7S-1

IPC

%

? 5-3 ???? 300ppb ????? 25ppb ? SSRT ??????

?

? 5-4 ?? 5-11 ??? prefilm?IPC-ZrO2?IPC-ZrO(NO3)2?

IPC-TiO2??????????????????????????

????????? SEM ??????????????????

????????? 5-4(c)?? 5-7(c)?????????????

58

??????????????????????????????

??????????????????????????????

??????????????????????????????

??????????????????????????????

??????????????????????????????

??????????? IGSCC ???????????

?????????????????????? 304????

??? IGSCC ???????

59

(a)

(b)

(c)

? 5-4 prefilm ??????? 300ppb ????? 10ppb ? SSRT ?

??(a)IGSCC(b)?????(c)??? SEM???

60

(a)

(b)

(c)

? 5-5 IPC-ZrO2??????? 300ppb ????? 10ppb ? SSRT

???(a)IGSCC(b)?????(c)??? SEM ???

61

(a)

(b)

(c)

? 5-6 IPC- ZrO(NO3)2??????? 300ppb ????? 10ppb ?

SSRT ???(a)IGSCC(b)?????(c)??? SEM???

62

(a)

(b)

(c)

? 5-7 IPC- TiO2??????? 300ppb ????? 10ppb ? SSRT

???(a)IGSCC(b)?????(c)??? SEM ???

63

(a)

(b)

(c)

? 5-8 prefilm ??????? 300ppb ????? 25ppb ? SSRT ?

??(a)IGSCC(b)?????(c)??? SEM???

64

(a)

(b)

(c)

? 5-9 IPC- ZrO2??????? 300ppb ????? 25ppb ? SSRT

???(a)IGSCC(b)?????(c)??? SEM ???

65

(a)

(b)

(c)

? 5-10 IPC- ZrO(NO3)2??????? 300ppb ????? 25ppb

? SSRT ???(a)IGSCC(b)?????(c)??? SEM??

?

66

(a)

(b)

(c)

? 5-11 IPC- TiO2??????? 300ppb????? 25ppb? SSRT

???(a)IGSCC(b)?????(c)??? SEM???

67

5.2 ???????????

?????? ECP ???????????????????

???????????????????? 5-12?5-13 ????

5-12 ?????????????????????? ECP? ECORRA

??? ECORRB?? 5-13 ????????????????????

? ECP ? ECORRA ??? ECORRB??????????????????

???

5.2.1 ??????????? ECP ??

? 5-14????????????????????????

????? ECP ????????????? 100ppb ? 1000ppb?

Prefilm ??????????????????????????

?? ECP ??????? 300ppb? 1000ppb??Prefilm???

??????????????ECP????304?????IGSCC

??????(Ecrit) -230 mVSHE???Prefilm?? ECP ??????

300ppb?-50 mVSHE??????? 1000ppb? 50 mVSHE??????

????? ECP ???-150 mVSHE? 20 mVSHE??????? ECP ??

???????????????? ECP ????????????

200ppb??Prefilm?? ECP ?-130 mVSHE?????? ECP ???

68

??? IGSCC ?????-230 mVSHE???????? 100ppb??

Prefilm??? ECP ????????-230 mVSHE?????????

??-230 mVSHE???-320 mVSHE????????????? ECP ??

???-230 mVSHE ??????????????????????

ECP ????????????????????????? ECP ?

???????????????? ECP ??????? ECP ??

5.2.2 ???? 10ppb ???????? ECP ??

????? 10ppb ????????? ECP ?????? 5-15?

????? ECP ???????????????????? ECP

???????????????? 1000ppb?500ppb?300ppb??

????????????? 0.32?0.16?0.53 ??? 1?????

1000ppb ??Prefilm ?? ECP ??? 20 mVSHE????? ECP ??

-50 mVSHE?-25 mVSHE???????? 500ppb??Prefilm ?? ECP

???-30 mVSHE????? ECP ????-120 mVSHE?-80 mVSHE?

??????? 300ppb ??Prefilm ?? ECP ???-100 mVSHE?

???? ECP ????-200 mVSHE?-180 mVSHE??? Prefilm ??

???????? 10ppb ?????????? ECP ???-230

mVSHE????? 304 ????? IGSCC ???????????

69

? 10ppb ???????????????? IGSCC ??????

???? IGSCC ??????????

5.2.3 ???? 25ppb???????? ECP ??

???????????????? 25ppb ?????????

ECP ?????? 5-16?????????? 1000ppb?500ppb?

300ppb??????????????? 0.4?0.8?1.3??????

? 1000ppb ??Prefilm ?? ECP ??? -70 mVSHE????? ECP

??-170 mVSHE?-140 mVSHE??????? 500ppb ??Prefilm ?

? ECP??-123 mVSHE????? ECP??-210 mVSHE?-190 mVSHE

?????????? 1000ppb ? 500ppb ??? ECP ??????

??-230mVSHE???????? 300ppb ??Prefilm ?? ECP ??

-180 mVSHE????? ECP ???-300 mVSHE?-280 mVSHE????

Prefilm ?? ECP ??-230mVSHE ??????????????

-230mVSHE???IGSCC ??????Prefilm ????? ECP ??

?? 100mVSHE?

?????? 300ppb ??????????????????

???? IGSCC ?????????? ECP ??? 304?????

70

IGSCC ??????? 50 mVSHE???????????????

? IGSCC ???????? ECP ?????????? SSRT ??

??????????? ECP ?????? ECP ?????

-230mVSHE???? SSRT ????? IGSCC ???

5.2.4 ???? 50ppb???????? ECP ??

??????? ECP ?????? 5-17??????????

1000ppb?500ppb?300ppb??????????????? 0.8?1.6?

2.7 ??????????????????? 1000ppb ??Prefilm

?? ECP ??? -130 mVSHE ??????-230 mVSHE?????

ECP ????-250 mVSHE?-220 mVSHE????????????

500ppb ??Prefilm ?? ECP ?-210 mVSHE???????????

? ECP ??-330 mVSHE?-290 mVSHE?????????????

??? 300ppb ??Prefilm ???????? ECP ????????

??-230mVSHE????-260mVSHE?-410 mVSHE?-360 mVSHE??

?? ECP ???? 100mVSHE?????????????????

IGSCC ?????????? ECP ??????????????

??????????????????? ECP ??

71

??????????????????????? ECP ??

????????????????? ECP ??????????

????????? IGSCC ????????????????

? 5-12 ?????????????? ECP ???

? 5-13 ??????????????? ECP ???

72

0 200 400 600 800 1000-700

-600

-500

-400

-300

-200

-100

0

100

EC

P(m

V SH

E)

D.O concentration[ppb]

D.H 0ppb Prefilm IPC-ZrO2 IPC-ZrO(NO3)2 IPC-TiO2 Zr

? 5-14 ?????????????????????????

????? ECP ????

0 200 400 600 800 1000-700

-600

-500

-400

-300

-200

-100

0

100

EC

P(m

V SH

E)

D.O concentration[ppb]

D.H 10ppb Prefilm IPC-ZrO2 IPC-ZrO(NO3)2 IPC-TiO2 Zr

? 5-15 ??????????????????????? 10ppb

???????? ECP ????

73

0 200 400 600 800 1000-700

-600

-500

-400

-300

-200

-100

0

100

EC

P(m

V SH

E)

D.O concentration[ppb]

D.H 25ppb Prefilm IPC-ZrO2 IPC-ZrO(NO3)2 IPC-TiO2 Zr

? 5-16 ??????????????????????? 25ppb

???????? ECP ????

0 200 400 600 800 1000-700

-600

-500

-400

-300

-200

-100

0

100

EC

P(m

V SH

E)

D.O concentration[ppb]

D.H 50ppb Prefilm IPC-ZrO2 IPC-ZrO(NO3)2 IPC-TiO2 Zr

? 5-17 ??????????????????????? 50ppb

???????? ECP ????

74

5.3 ????

5.3.1 AES

??????????????????????? AES ? maps

????????????? 5-18 ??? x-??????(x-ray

maps)???????????????????????????

?????????????????????????????

???????????????????? Zr? Ti??????

????????? Zr? Ti????????? 5-19 ?????

???????? AES ??????? Zr? Ti?????????

???? Zr? Ti??????????????????????

Zr? Ti??????????????????????????

Auger??????????? Zr???????(~147 eV)???

????????????????????????

75

? 5-18 AES ???(??)? Zr, Ti maps ???(??)

76

IPC- ZrO2

IPC- ZrO(NO3)2

IPC- TiO2

? 5-19???????????? AES ?????

77

????

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54.???, ??????????304????????????????

??,??????????,2001????