igscc 腐蝕防治
DESCRIPTION
IGSCC 腐蝕防治TRANSCRIPT
-
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
????
1. M. Shindo et al, Journal of Nuclear Materials 233-237 (1996) 1393-1396. 2. M.A. Al-Anezi, G.S. Frankel and A.K. Agrawal, Corrosion . Vol.55 No.11
pp.1101-1109.
3. R. L. Cowan, Nuclear Engineering International, January 1986, p. 26.
4. M. E. Indig, Proc. 4th Intl. Symposium on Environmental Degradation of
Materials in Nuclear Power Systems - Water Reactors, NACE, Jekyll Island,
GA.,Aug. 6-10, 1989.
5. L. W. Niedrach, Corrosion, Vol. 47, p. 162 (1991).
6. Y. J. Kim, L. W. Niedrach, M. E. Indig, and P. L. Andresen, Journal of
Metals ,Vol. 44, No. 2, p. 14 (1992).
7. T.K. Yeh and D. D. Macdonald, Proc. 7th International Symposium on
Environmental Degradation of Materials in Nuclear Power Systems - Water
Reactors, NACE, Breckenridge, Colorado, Aug. 6-10, 1995, p. 909.
8. Y. J. Kim and P. L. Andresen, CORROSION/96 , NACE, Denver, Colorado,
Mar.24-29, 1996, Paper Number 105.
9. R. Pathania, Zirconium Oxide Deposition to Mitigate IGSCC, BWRVIP Mitigation Committee Meeting, Atlanta, GA, October 1-3, 1997, EPRI.
10. B. Stellwag, M. Lasch, and U. Staudt, 1998 JAIF Conference p186-193.
11. Peter L. Andresen and Tom Angeliu, GE Corp. Research and Development Center,
-
78
Corrosion96, The NACE International Annual Conference and Exposition, Paper No.84.
12. Peter L. Andresen, GE Corp. Research and Development Center, Corrosion95,
The NACE International Annual Conference and Corrosion Show, Paper No.412. 13. D. D. Macdonald, SRI International, and Menlo Park, Corrosion Science, Vpl.32,
No.1, pp.51-81, 1991. 14. D. D. Macdonald Electrochimica Acta, Vol.31, No.8, pp.1079-1086, 1986. 15. D. D. Macdonald, J. Electrochem. Soc., Vo;.139, No.12, December 1992. 16. Mirna Urquidi-Macdonald and D. D. Macdonald, J. Electrochem. Soc., Vo;.136,
No.4, April 1989. 17. H. S. Kwon A. Wuensche, and D. D. Macdonald, Corrosion-Vol.56, No.5,
pp.482-491, 2000. 18. J. R. Galvele, Corrosion Science 41(1999)191-195. 19. S. Hettiarachchi et al., Proc. 7th International Symposium on Environmental
Degradation of Materials in Nuclear Power Systems - Water Reactors, NACE, Breckenridge, Colorado, Aug. 6-10, 1995, p. 735.
20. Y. J. Kim, L. W. Niedrach, and P. L. Andresen, CORROSION/95, NACE,
Orlando, Florida, Mar. 26-31, 1995, Paper No. 99. 21. Y. J. Kim et al., CORROSION/96, NACE, Denver, Colorado, Mar. 24-29, 1996,
Paper Number 107. 22. T. K. Yeh, C. H Liang, M. S. Yu, and D. D. Macdonald, Proceedings of the 8th
Intl. Symp. Environ. Degrad. Matls. in Nuclear Power Systems - Water Reactors, Amelia Island, Florida, August 10-14, 1997, American Nuclear Society, p. 559.
23.S. Hettiarachchi et al., Proceedings of the 8th Intl. Symp. Environ. Degrad. Matls. in Nuclear Power Systems - Water Reactors, Amelia Island, Florida, August
-
79
10-14, 1997, American Nuclear Society, p. 581.
24. R. L. Cowan et al, GE Nuclear Energy, Vallecitos Nuclear Center, Nuclear Engineering and Design 166(1996)31-36.D. D. Macdonald, Corrosion, Vol. 48, No. 3, p. 194 (1992).
25. Electric Power Research Institute, EPRI TR-103315-R1,1996.
26. C. C. Lin, Proc. of the 1998 JAIF Water Chemistry Conference, JAIF,Kashiwazaki, Japan, Oct.11-16, 1998, p211.
27. R. L Cowan, Nuclear Energy,36,No.4(1997)p.257.
28. Y. J. Kim and Lorraine Falter Franc is, Journal of the American Ceramic Society, Vol.76, No.3, pp.737-742(1993).
30. K. Kato et al, Journal of Materials Science , 29(1994)5911-5915. 31. N. Saito et al, Corrosion(2000)-Vol.56, No.1, pp.57-69.
32. R. D. Maggio et al, Surface and Coatings Technology 89(1997)292-298.
33.Dibyendu Ganguli and Debtosh Kundu, Central Glass and Ceramic Research Institute, India, Journal of Materials Science Letters, 3(1984)503-504.
34. M. Atik et al., Journal of applied electrochemistry , Vol. 25, p. 142 (1995).
35.M. Atik and J. Zarzycki, Journal of Materials Science Letters, 13(1994)1301-1304.
36. M. Guglielmi et al, Journal of Materials Science, 27(1992)5052-5056.
37. M. A. Sainz et al, Journal of Non-Crystalline Solids 121(1990)315-318.
-
80
38. M. Atik and M. A. Aegerter, Journal of Non-Crystalline Solids 147?148(1992)813-819.
39. F. Perdomo L. et al, Journal of materials science letters, 17(1998)295-298.
40. M. Zaharescu et al, Journal of Non-Crystalline Solids 160(1993)162-166.
41. A. Julbe et al, Journal of Membrane Science, 77(1993)137-153.
42. A. Sanjurjo et al, SRI International, Surface and Coatings Technology, 49(1991) 116-120.
43.Y. Takahashi and K. Yamaguchi, Journal of materials science 25(1990)3950-3955. 44. F. Bel Hadj et al, Journal of Non-Crystalline Solids 82(1986)417-425. 45. C. J. Brinker and A. J. Hurd, Journal De Physique III, 4(1994)1231-1242. 46. O. Reglat , R. Labrie, and P. A. Tanguy, Journal of computational physics
109,238-346(1993).
47. R. Pathania, BWRVIP Mitigation Committee Meeting, Lake Buena Vista, FL, December 1-2, 1999, EPRI.
48. B. Stellwag and R. Kilian, Siemens Nuclear Power GmbH U.Staudt, VGB Germany3rd Workshop on LWR Coolant Water Radiolysis and Electrochemistry.
49. G. L. Song et al, Institute of Corrosion and Protection of Metals, State Key
Laboratory for Corrosion and Protection, Chinese Academy of Sciences, Shenyang, China, Corrosion Science, Vol.40, No.7, pp.1109-1117, 1998.
50. X. Zhou, I. Balachov, and D. D. Macdonald, Corrosion Science. Vol.40 No.8 pp. 1349-1362.
-
81
51. Y. J. Kim and Peter L. Andresen, CORROSION/98 Paper No.507. 52. S. K. Yen and T. Y. Huang, Institute of Materials Engineering, National Chung
Hsing University, Taiwan, Materials Chemistry and Physics 56(1998)214-221. 53. M. Andritschky et al, Surface and Coatings Technology, 68/69(1994)81-85.
54.???, ??????????304????????????????
??,??????????,2001????