PP継手Series チューブフィッティングPP 標準 ミニ 耐腐蝕 用 ル 用 クリーン 環境用 ーブ 219 継 手 注文形式（例） PP C 6 01 ②.チューブサイズ
IGSCC 腐蝕防治
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1 第一章 前 言 電力是社會文明的生命力，也是帶動國家經濟發展的原動力，一 個電廠規劃與興建時程長達五至十年，若包括廠址勘選與土地取得， 則時程更長達十至廿年，因此規劃長期電源開發之期間至少要涵蓋未 來十年以上，由於核能發電計畫之興建問題在國內爭議已久，因環保 意識高漲，在環境保護及維持並提高電廠供電品質的前提下，延長現 役核電廠的運轉年限為目前世界性的趨勢。 核電廠在設計建造時，採用的為抗蝕不銹鋼材料，理論上電廠應 可以有 40 年的運轉年限，不會有腐蝕劣化而影響安全之虞。但近年 來沸水式反應器陸續出現應力腐蝕龜裂(Stress Corrosion Cracking, SCC) 的劣化問題，隨著運轉年限的增加，壓力槽內部組件龜裂(Vessel Internal Cracking ，VIC) 問題日益嚴重，而出現 VIC 的位置逐漸擴大 且頻率也不斷增加，壓力槽內部組件的劣化形式大致有：主循環迴路 內爐水高流速產生組件震動導致的疲勞(Fatigue)、磨耗(Wear)，及在 高溫高輻射環境所造成的熱脆化、輻射脆化 (1) 、氫脆化 (2) ，但是應力 腐蝕龜裂仍是造成組件劣化的主因。 應力腐蝕龜裂包括了沿晶應力腐蝕龜裂與輻射促進應力腐蝕龜
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IGSCC 腐蝕防治
Transcript of IGSCC 腐蝕防治
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1
??? ? ?
????????????????????????????
??????????????????????????????
??????????????????????????????
??????????????????????????????
??????????????????????????????
???????????????????
????????????????????????????
??? 40 ?????????????????????????
?????????????????(Stress Corrosion Cracking,
SCC)?????????????????????????(Vessel
Internal Cracking?VIC) ?????????? VIC ???????
??????????????????????????????
?????????????????(Fatigue)???(Wear)???
???????????????????(1)????(2)?????
????????????????
???????????????????????????
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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 ?
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3
??????????????????????????????
??????????????????????????????
(Catalytic)????(Inhibitive)????????????(5,11,12)???
???????????? IGSCC ??????????????
??????????????????????????????
????????????????????(Noble Metal Chemical,
NMCA)(19-23)?? Pt?????????????????????
????????????????
?????????????????????????NMCA
??????????????????????????????
????? NMCA ????????????????????
??????????????????????????????
??????????????????????????????
??????????????????????????????
?(7,8)?????????????????????? IGSCC ??
?????????????????? HWC ?????????
??????????????????????????????
??????????????????????????????
?????????
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4
???? HWC ????????????????????
????????????????????? IGSCC ?????
???????(ZrO2)????(TiO2)????????(ZrO(NO3)2)
????????????????????? BWR ??????
???????? 150??????? 304???????????
????????????????????? 304 ??????
HWC ? BWR ???????????????????????
?????????304???????????????????
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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
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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)??????
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7
?? HAZ ?????????????????????????
??????????????????????????????
?????? IGSCC????????????????????
??????????????????????????????
?(Radiation-Induced Segregation, RIS)?????????????
? IASCC?
2.1.2 ????
???????SCC ???????????????????
?????????????????????? SCC ?????
????????????? SCC ????????????
(1) ???
????????????????????????????
????????????????????????????
????????????????
(2) ???
????????????????????????????
?????? IGSCC ???????????????????
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8
???????????????????? BWR ?????
??????????? 0.1S/cm?????????????
????????????????????????????
????????????????????????????
????????? IGSCC ?????????? IGSCC ??
????????????? HWC ????
(3) ???
?????????????????? SCC ????????
(
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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???????????
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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???????????????
?????????????
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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 ????????????????
???
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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 ????????
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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??
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14
?????????????? icorr2C????????????
??????????????? ECP ????????????
???
??????????????????? HWC??????
???? C ??????? O2??????(? ECP)?? Ecorr2C??
???????? A????????? icorr2C?????????
? ECP ????????????????????
????????????????????????????
????????????????ECD??????????ECP
?????????????????????????????
ECD ????
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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 ?????????
????????????
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??? ????
3.1 ?????
??? BWR ??????????????????????
??????????????????????????????
????????????? IGSCC ??????? BWR ????
????????? 200 ? 300ppb??????????????
??? IGSCC ???????????????????????
????(26)???? BWR ??????????????????
??????????????????????????????
??????????????????????????????
??????????????????????????????
??????????????????????????????
????? ECP ????(27)?ECP ? IGSCC ??????????
?? ECP ?????????????????(28)???????
???-230 mVSHE? 304 ????? IGSCC ??????(Ecrit)??
??????? ECP ??? Ecrit ???????????????
????
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??? HWC ?????????????????????
??????????????????? HWC ? BWR ????
????HWC ???????????????????????
??????????????????????????????
??????????????????????????????
??????????????????????????????
??????????????????????????????
???? HWC ????????? ppb????????????
??????????????????????????????
????????????? ECP ??????? HWC ????
??????(Upper Downcomer)??????????(10)?
????????????????????????????
?????????(28)????????????????-16 ??
???????????????????-60 ?????????
??????????????????????????????
???? BWR ???????? N16?????????????
???? HWC???????????????? N16?????
?? NH3? NOX ??????????????????????
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????????? 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)
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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)?
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? 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 ?????????????????????????
-
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Sol-gel?? TiO2-SiO2???????????????(38)??? 3-5
?????????????????????????????
????????????????????????????
?(9)?? Sol-gel?????? 304???????????????
?(288 oC ???? 0.1 mS/cm???????)?????????
?? ECP????????????????
? 3-2 ???????? ZrO2???? XRD??(38)
-
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? 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??
-
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???????????(??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)?
-
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? 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)?????????????????
-
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????(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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