13

Corrosion degradation of nuclear structural materials
Structural Integrity: Corrosion assisted degradations / failures
A) Introduction to corrosion in NPPs:

F) Corrosion in secondary circuit of NPPs:
Ø Forms of corrosion
Ø Structural materials used in PHWR, PWR, BWR Ø FAC of carbon steel
B) Water chemistry in Nuclear power plants: Ø SG tube degradation
ØPrimary and secondary circuit of PHWR
G) Corrosion in Fire water line, corrosion under
ØPrimary and secondary circuit of PWR insulation of stainless-steel pipeline
ØBWR
Conclusions
C) Corrosion degradation in primary circuit of
PHWR:
ØOxidation of Zr – alloy and hydrogen pickup
ØFlow accelerated corrosion of carbon steel
Dr. Supratik Roychowdhury,
D) Corrosion degradation in primary circuit of PWR:
Head, Corrosion Engineering Section,
ØPWSCC of SG tube
MP&CED, BARC
ØPossible primary water effects on RPV steel
ØSCC in Alloy 600 welds
HBNI-INSTN course on
E) Corrosion in BWR: IGSCC of stainless steel Structural Integrity Assessment of Mechanical Components: Concepts & Procedures, March 11-15, 2024
Introduction
v Corrosion degradation: Interaction of material with its environment
resulting in the degradation of the material
v Driving force: Metals extracted from its ore tend to interact with
environment to revert back to its natural state Aqueous environment
v Thermodynamically favourable phenomenon
v Materials behave differently when exposed to a corrosive environment:

• In presence of a corrosive environment a material can fail by SCC at
stress levels much below the yield strength (cannot be eliminated by
design)
Metal/Alloy
• Toughness of materials can reduce drastically if prone of hydrogen
embrittlement
v Understanding of degradation modes essential for residual life
estimation, designing future reactors (aggressive environments)
Subcritical crack growth mechanisms..

Brittle failure of ductile materials – Corrosion Fatigue, Stress Corrosion Cracking, Hydrogen embrittlement
2

ØBWR
Conclusions
PHWR:
ØPWSCC of SG tube
MP&CED, BARC
1) Uniform corrosion
Metal
No Corrosion
2) Galvanic corrosion 3) Crevice corrosion

More Noble Metal / Non-metal /
metal Crud /deposit
A B A B
Crevice = 0.1-100 µm
4
4) Pitting corrosion
Pitting
Cross-section of pits Pit
Inclusion
PREN = %Cr + 3.3 x (%Mo + 0.5%W) + 16 x %N
PREN
•SS, Al more prone to pitting in presence of Cl 304 17.5-20.8

304LN 19.4-23.0
•For more pitting resistance – Hastelloy F, C
316/316L 23.1-28.5
• Titanium has best pitting resistance in sea water 316L (2.5% min Mo) 25.3-30.7
316LN 25.0-30.3
DSS 2205 30.8-38.1
DSS 2507 >40
5
Sanicro 28 35.9-43.0
5) Intergranular corrosion Sensitisation during welding
• Precipitation of Cr23C6 at the grain boundary → Cr depletion
• Temperature range: 500-8500C.
• At Cr concentration < 12%, passive film becomes weak and prone to
Corrosion rate at gb >> within grain attack in aggressive environment.
Sensitisation due to carbon pickup

• Grease, oil, lubricants (hydrocarbons) are commonly used during SS
rolling, pilgering, machining etc.
• Improper cleaning of hydrocarbons will lead to carbon pickup during
subsequent heat treatment® Sensitisation
• Other sources of contamination - Crayon markings, Paint, Adhesive tape 6
6) Dealloying / Selective Leaching
Cu
Brass
Dezincification of Brass (Cu-Zn)
7) Erosion corrosion
• Mechanical (high flow rate with abrasives) + electrochemical
effects
Flow
• Corrosion products may spall, aggravating the abrasive effect
• Can occur in gases too, no specific surface pattern
• Stainless steels are also prone
7
8) Environmental assisted cracking (SCC, CF, HE)
Tensile stress
Cyclic stress
SCC
Corrosion
Fatigue
500 µm
• Cracking due to synergistic action of tensile stress, susceptible material and corrosive environment
• Stress: Cyclic – Corrosion Fatigue, Static – SCC
• Ductile material fail in brittle manner
Crack initiation: Thin cracks with crack tip

Localized film breakdown Crack Propagation: radius of atomic
(Cl-/halides/sulfides At Slip dissolution/Film rupture dimensions, minimum
inhomogeneities, slip steps etc.) ~10 % of life crack mouth opening.
~90 % of life 8
Hot conditioning of PHT circuit of PHWRs
• System integrity check at high temperature and pressure
• Crud removal
• Grow magnetite of thickness 0.5-0.6 micrometer thick
pH 10.2 at 25ºC, corresponding to 7.3 at
230oC (by adding 1 ppm Li+ as LiOH)
conductivity at 250C, µS cm-1 On the average about 60
Dissolved Oxygen, (ppb) <5
Chloride, (ppm) < 0.2
Crud, (ppm) 140 to begin with and < 0.1 at the end
Hydrazine, (ppm) 5. begin with and < 0.2 at the end

9

ØBWR
Conclusions
PHWR:
ØPWSCC of SG tube
MP&CED, BARC
HBNI-INSTN
Common structural materials in PHWR Zr-2.5Nb-0.5Cu
Pressure tube - Zr-2.5Nb

Garter spring - Zr-2.5Nb-0.5Cu
Calandria tube – Zr-4
Fuel cladding – Zr-4
Feeder – A 333 Gr-6 (Primary circuit)
Feed water line – A 106 Gr B (secondary circuit)
SG tube – Alloy 800
11
Common structural materials: PWR
VVER:
Fuel cladding – Zr-1Nb
RPV – SS clad LAS
SG tube – SS321
D. Feron, R. Staehle
In-core structural material
12 – SS
Common structural materials: BWR
Fuel cladding – Zr-2

BWR – Boiling Water Reactor RPV – SS clad LAS
In-core structural material – SS 13

ØBWR
Conclusions
PHWR:
ØPWSCC of SG tube
MP&CED, BARC
Purpose of maintaining primary
circuit water chemistry
Assure integrity Assure fuel Minimize out of

clad integrity
of pressure core radiation
and good fuel
boundary fields
performance
Cost of repair >> cost of maintaining water chemistry!! 15

Primary Water chemistry in NPPs Light Water Reactor (LWR)
PHWR PWR BWR
TAPS 3&4 KKNP TAPS 1&2
Primary coolant: D2O Primary coolant: H2O Primary coolant: H2O

Temperature: 249 – 305 °C Temperature: 280 – 330 C Temperature: 270 - 300 °C
Pressure: 10 MPa Pressure: 20 Mpa Pressure: 7 Mpa
Water Chemistry: D2O (97% min) Water Chemistry: Water Chemistry:

LiOH: 1-2 ppm Li as LiOH: 2 ppm DM water
pH @25 ºC: 10 – 10.5 B as H2BO3: 1200 ppm pH @25 ºC: 7.0
H2: ~ 2 ppm pH @25 ºC: 6.9-7.4 H2: In case of HWC
DO < 10 ppb H2: ~ 2 ppm DO: 200-300 ppb (NWC)
DO < 10 ppb <10 ppb (HWC, NMCA)16
Purpose of maintaining
secondary circuit water
chemistry
Minimize Ensure Maintain heat

corrosion due material (SG exchange
to water tube) integrity performance
Cost of repair >> cost of maintaining water chemistry!! 17

Secondary Water chemistry of PHWR
• The quality of feed water system is very critical as local hot-spots can significantly increase concentration of corrosive
species
• Chemical added are volatile in nature (All Volatile Treatment (AVT)) to prevent deposition in local hot-spots
• Similar water chemistry for PWR and PHWR
Parameter Value Chemical/Source Remarks

pH 8.8-9.5 Mono-ethanolamine To keep the secondary water alkaline
to minimize corrosion rate (FAC)
DO £10 (µg/l) Hydrazine (oxygen To minimize the corrosion rate of SG
ppb scavenger) tubing
Specific £10 (µS/cm) The values is due ionization of
conductivity at chemical added. Higher value indicated
25°C the condenser tube leakage.
Ammonia £300 (µg/l) Decomposition of Higher value of ammonia is deleterious

hydrazine to copper based alloy.
Secondary Water chemistry of PHWR

Silica £20 (µg/l) To control deposition on SG surface
Hydrazine 10 - 100 Hydrazine (oxygen Scavenges dissolved oxygen and also
scavenger) protects SG surfaces from IGC
Fe, Cu, Ni ≤ 20 (µg/l) (of Corrosion of materials To assess the corrosion of materials in
each metal) feed water system
Sodium £100 (µg/l) Higher value indicates the condenser

tube leakage.
Chloride £100 (µg/l) Higher value indicates the condenser
tube leakage.
19
Water Chemistry of secondary circuit of PWR
pH 9.4-9.6 Ammonia To keep the secondary water alkaline
to minimize corrosion rate (FAC)
DO £5 (µg/l) ppb Hydrazine (oxygen To minimize the corrosion rate of SG
scavenger) tubing
Ammonia £1000-2000 Addition for pH
(µg/l)
Hydrazine >20 (µg/l) Hydrazine (oxygen Scavenges dissolved oxygen
scavenger)
Fe ≤ 10 (µg/l) Corrosion of materials To assess the corrosion of materials in
feed water system
Cu £1 (µg/l)
20

ØBWR
Conclusions
PHWR:
ØPWSCC of SG tube
MP&CED, BARC
Zr-alloys in Nuclear power plants
Characteristics Life limiting factors
• Low thermal neutron absorption cross-section Deformation under irradiation (PT)
(capture cross section for thermal neutrons – 0.185 barns) -- Creep (axial and circumferential)
• Corrosion Resistance -- Irradiation growth
• Irradiation Stability (radial creep affects by-pass flow and
reduces CCP)
Oxidation and hydrogen related

damage in high temperature
water/steam
Fuel side corrosion
22
Typical compositions of common Zr alloys
Elements Zircaloy-2 Zircaloy-4 Zr-2.5%Nb Zr-1%Nb

Zr Base Base Base Base
Nb 0. 10 0.05 2.4-2.8 0.9-1.1
Sn 1.2-1.7 1.2-1.7 0.05 0.05
Fe 0.07-0.20 0.18-0.24 0.065 0.05
Cr 0.05-0.15 0.7-0.13 0.02 0.02
Ni 0.03-0.08 0.007 0.007 0.02
N 0.008 0.008 0.0065 0.006
C 0.027 0.027 0.012 0.02
O 0.09-0.16 0.09-0.16 0.09-0.13 0.1
23
Zr alloys used in NPPs
Zircaloy-2: Fuel clad in BWR & was earlier used as

pressure tubes in PHWR
Zircaloy-4: Fuel clad in PHWR, PWR, Calandria Tube &

Square channel for BWR
Zr-2.5%Nb: Pressure Tube in PHWRs
Zr-1%Nb: Fuel clad in VVERs
Zr-2.5%Nb-0.5Cu: Garter Spring in PHWR
24
Zr alloys -- Oxidation Kinetics
W = kLt W2 = kpt + C
Linear Parabolic
Post-transition Oxidation
Rate Laws
W = ke log
W3 = kct + C
Pre-transition (Ct + A)
Cubic
Logarithmic
Linear – Porous or cracked oxide, no diffusion barrier, not

protective
Parabolic – Ionic diffusion controlled oxidation, Protective oxide
Cubic – Protective oxide short exposure period
Logarithmic – Very thin oxides at low temperature, not relevant for
Zr-alloys in NPPs
25
Oxidation behaviour of Zr-2.5Nb and Zircaloys in 3160C and 3600C water
160
Zr-2 at 3600C water
Alloys undergo accelerated corrosion
120 after high initial degree of resistance
During transition
DW, mg/dm2
vBlack ® grey ® white

Zr-2.5Nb at 3600C water vstresses are released
80
Zr-2 at 3160C During Post-Transition

water v Protective properties are partially
lost
40
Zr-2.5Nb voxide properties depends upon the

at 3160C water layer adjacent to the metal oxide
interface
0 200 400 600 800 1000
0
Exposure Time, Days

26
Oxidation Rates
Zircaloy-2
Zircaloys are
Vs immune while
Zr-Nb alloys
Zr-Nb Alloys are Sensitive to
DO
HDO
HDO
LDO
LDO
27
Kiran, Kain, et.al. Nucl. Engg. & Desgn. 2009
Hydrogen Pick-up
Zircaloy-2 Vs Zr-Nb Alloys
Higher DO always led to lower H
pick-up.
28
Kiran Kumar et.al. Nucl. Engg. & Desgn. 2009
Nodular Corrosion of Zr alloys
- Predominant in BWR Cladding tubes

-Oxidizing water chemistry (boiling and radiolysis)
- Enhanced localized oxidation (mostly thick monoclinic)
29
Role of SPPs on oxidation
Cumulative Annealing Parameter (CAP)
åA = åti exp(-Q/RTi)
• SPP size and distribution is
influenced by thermo mechanical
processes taking place during
fabrication of components
• At low end of the precipitate size

range, observed in-reactor corrosion is
enhanced uniform oxide growth
• Nodular corrosion is promoted in

highly oxidizing environments of
BWRs and at higher sized SPPs.
30
Hydrogen Related Damages in Zr alloys
- Hydrogen generated from corrosion reaction is picked up by the alloy.
- When solubility is exceeded hydrogen precipitates as zirconium hydride.
- Zirconium hydride is brittle.
- Hydride orientation depends on texture.
- Diffusion of hydrogen: down the temperature gradient, up the stress gradient and down the concentration gradient.
Degradation modes due to Hydrogen: H H

i) Delayed hydride cracking (DHC) H
ii) Hydride blister
Stress H
H H
DHC
Striations 31
Hydride blister and reorientation of hydrides in PT
Sagged
PT
Hydride blister
Reoriented Hydrides
32
Oxidation in simulated accident condition
900 °C – 12 h
1200 °C - 1h
Isothermal thermogravimetric curves of Zr-2.5Nb in steam in the

range 600-1200 °C
Ananthkrishna, et al. JNM, 2024, 154967 33

Mitigation
i) Oxidation:
* Deaerated condition to be maintained with good water purity
ii) Hydrogen:
* Zr-2.5Nb, Zr-1Nb and Zr-4 has lower hydrogen pickup as compared to Zr-2
iii) Hydride blistering:

* Four garter springs used instead of two used earlier
iv) Accident conditions:

* Development of accident tolerant fuel
34

ØBWR
Conclusions
PHWR:
ØPWSCC of SG tube
MP&CED, BARC
Flow Accelerated Corrosion (FAC):
Flowing conditions
Static conditions
① 3Fe + 4H2O Fe3O4 + 4H2
FAC is different from erosion （3Fe + 6H2O 3Fe(OH)2 + 3H2 Fe3O4 + 2H2O + 4H2）
corrosion!
② Fe3O4 + 6H+ + H2 3Fe2+ + 4H2O or
Fe3O4 + 3(2-b)H+ + H2 3[Fe(OH)b](2-b)+ + (4-3b)H2O
Chemical composition (wt%) of commonly used CS grades
Feed water Feeder FAC resistant grades
A 106 A 333 A 335 A 335

Grade B Grade 6 Grade Grade
P 11 P 22
C 0.30 max 0.30 max 0.05-0.15 0.05-0.15
Mn 0.29-1.06 0.29-1.06 0.30-0.60 0.30-0.60
P 0.035 max 0.025 max 0.025 max 0.025 max
S 0.035 max 0.025 max 0.025 max 0.025 max
Si 0.10 min 0.10 min 0.50 – 1.0 0.50 max
Cr 0.40 max ----- 1.0 – 1.50 1.90-2.60
Cu 0.40 max ----- ---- ----
Mo 0.15 max ----- 0.44-0.65 0.87-1.13
Ni 0.40 max ----- ---- ----
V 0.08 max ----- ---- ----
37
Factors affecting FAC
Hydrodynamic variables – Fluid velocity, pipe configuration, flow disruptions (local turbulence
enhances FAC) – Design considerations
Metallurgical variables – Cr, Mo, Cu enhances FAC resistance (Increase in Cr content reduces FAC
to a great extent).
Environmental variables – Temperature (maxima at ~150OC), pH, dissolved oxygen (Higher oxygen
lower FAC), ionic impurities.
Two phase FAC

Single phase FAC • Flowing fluid - two phase (moist
• Flowing fluid - single phase steam)
• Micropits initiate which grow • Steam with highest moisture causes
and join maximum degradation
• Affected surface: overlapping • Affected surface: tiger striping
horse shoe pits (Scallops) appearance
38
Metallurgical variables affecting FAC
FeCr2O4 film protects against dissolution and damage to film (the dissolution rate of which are
extremely slow in comparison to Fe3O4)
Cr is the most important alloying
• Fe – 1.25Cr - 1Mo (P11)
element in carbon steel!!
• Fe - 2.25Cr - 1Mo (P22)
• Stainless steel (304L/316L type) are highly resistant to FAC
After 500 h at pH 9.75

1300C, 4 m/sec 39
Heitmann & Kastner, 1982
Environmental variables affecting FAC Bignold et al, BNES,1981
O. Jonas, Power, 1985
pH 9.05, Deoxygenated water

Design improvement to minimize flow turbulence/localized flow rates
Dissolution behaviour of magnetite piping layout design and velocity considerations 40
Operating
temperature range pH CONTROL
Carbon steel
Fe + 0.5 Mo
T: 1800C
Fe+Cr+Ni+Mo+Cu
Specific material wear rate, µg/cm2-h

Fe+1Cr+0.5 Mo
Fe+2.2Cr+1Mo
T: 750C
Operating
range
pH
Jonas, Power, 1985
pH 7.0, DO: 40 ppb,

Raising pH to 9.5 – 10.0 reduces FAC rate
Flow rate 35 m/sec, 40 bar
(H.G. Heitmannet et. al. Erosion-corrosion in
water-steam cycles-Causes and counter measures,
VGB-Krafttwerkstecnik 62 No.-3 P-180 March 1982)
41
Surface film: XRD Examination
• Magnetite was found on the sample surface (taken from regions far
away from the failure)
• No oxide was found on the failed regions – Oxide layer is too thin
to be observed by XRD indicating dissolution of surface oxides
Perforation as seen on OD
RAPS # 2 Feeder pipe B12 (S): 2007 PIED Internal report 2007, BARC
Magnetite peaks
Perforation as seen on ID
42
Single phase “Scallops” pattern

ØBWR
Conclusions
PHWR:
ØPWSCC of SG tube
MP&CED, BARC
Primary side corrosion issues: PWSCC of SG tubes
Susceptible
Material (Alloy 600)
• Improper heat
treatment
• Lower grain
boundary carbide
Me
fai cha n
lur nic o sio
e al rr
Co
SCC
Corrosive
Environment
• Primary water
Tensile Stress • High
• Tube bending temperature
• Denting • Lead, hydrogen
Primary side corrosion issues: PWSCC of SG tubes
SG tube
Schematic of a
Location of PWSCC
Secondary water steam generator
Corrosion Products SG tubing – Alloy 600

Primary water
Tube sheet Primary water
Susceptible material:
Environment: Steam generator tube materials
Boric acid, lithium hydroxide, dissolved hydrogen, deaerated condition, high temperature (> 300°C)
Stresses:
Tensile stresses on ID surface of SG tubes at tube sheet, tube support plates and small diameter tube bends
46
Mitigation of PWSCC:
Ø Use better material (Alloy 690, 800)

Ø Controlled microstructure – Thermal
treatment (Alloy 600 TT, Alloy 690 TT)
Susceptible
Material (Alloy 600)
Me
fai cha n
lur nic o sio
r
e al C or
SCC Corrosive
Environment Effect of H2 fugacity (or Corr Potn) on CGR of
• Primary water Ni alloys in high temp water. Magnitude of peak
Tensile Stress • High
• Tube bending temperature varies from ~ 3X for alloy 600,
• Denting • Lead, hydrogen 7X – 9X for alloy 182 weld metal or X-750
Peter Andresen, Corrosion, 64, 707 (2008)
Ø Shot peening of tube inside ØAvoid Pb contamination

Ø Roto peening ØHigher H content in water

ØBWR
Conclusions
PHWR:
ØPWSCC of SG tube
MP&CED, BARC
High temperature • Thermal aging
• Irradiation embrittlement
Irradiation • Environmental Assisted Degradation (EAD)
Loss in fracture toughness, Strain induced corrosion cracking

Water
tearing resistance due to (SICC) / Corrosion Fatigue (CF)
hydrogen
20 MnMoNi 5 5 (A 508 Cl3) steel in HTHP water

For low extension rates JR plots reported to shift down:
Hydrogen formation at crack tip due to dissolution of sulphide inclusions in steel, A508-2 steel in HTHP water
For higher extension rates more
(L.A. James severe
et al., 1999) pop-ins: Related DSA 49
additional possible hydrogen sources like corrosion/oxidation (Schellenberger et al., 1994) and possible hydrogen pickup
Hydrogen damage in RPV
Cladding HAZ Aggressive chemistry in cracks
MnSH
HH
H 3 Fe + 4 H2O → Fe3O4 + 8H
Primary H
H RPV
Water
MnS
H H
3 Fe + 4 H2O → Fe3O4 + 8H
(dissolved H) SS
MnS
H HH
3 Fe + 4 H2O → Fe3O4 + 8H
H
• Weld microstructure: inhomogeneous

• Prone to EAC Clad
• High residual stresses due to welding
• Presence of brittle phases
• Hydrogen also picked up at unclad regions!
• Hydrogen concentration can reach RPV
equilibrium concentration at 300 C easily. Kondo et al, NED (1971)
RPV steel has never shown any cracking in actual service, however, laboratory experiments have shown that50 fast
crack growth can occur under simulated BWR operating conditions.
History:
• 2012 – Flaws discovered in RPV (SA508 Cl.3 ) of Doel 3 (operational since 1982) & Tihange 2
(operational since 1983) PWR, UT of RPV revealed ~8000 linear indications in Doel 3 and ~
2000 linear indications in Tihange 2 – attributed to hydrogen flakes developed during
fabrication before service, missed due to inadequate quality control during fabrication.
• No under clad cracks detected.
• Reactor restarted after one year after safety analysis found the indications to be benign.
~ 9 mm flaw size
51
52
S. Roychowdhury, et al., JNM 2016
SCC resistance of RPV steel:
• High residual stresses are generated during SS cladding of RPV steel due to
the difference in thermal expansion of SS and LAS
• High residual stresses in RPV are eliminated by post weld heat treatment
• PWHT reduces residual stresses in the LAS and tempers the LAS HAZ
eliminating hard phases (without PWHT, in case of repair welding residual stresses in the
RPV base material may remain)
• PWHT temperature is not sufficient to eliminate residual stresses in the

stainless steel weld deposit and may retain residual stresses of the order of
the YS. The peak stress appears sub-surface.
53
• Cladding SCC is a possibility but of little concern as SCC will not propagate into
the LAS.
• SCC has never been reported in RPV after proper PWHT, reported only in
cases of improper PWHT
• RPV attachment welds (such as core shroud support attachment weld etc.)
have high residual stresses and do not undergo PWHT – possible location of
SCC and may be of concern.
54
Strain induced corrosion cracking (SICC)
• Crack propagation due to slow dynamic straining with localized plastic deformation
• No cyclic loading OR infrequent cycles such as during plant start-up and shut-down
• Combination of SCC (static load) and corrosion fatigue (cyclic load) (Low cycle fatigue)
• Tested in laboratory using SSRT test using smooth/C(T) specimens
• Cracking in CS/LAS piping reported in isolated cases in German BWR/PWR – hard weld
HAZ, H-induced SCC/SICC exacerbated by stress concentration
H-induced SCC/cracking in hard weld HAZ of LAS pipelines in German BWR/PWR

exacerbated by stress concentration Hickling 1986 55
Factors affecting SICC:
• Oxidising environment (due to oxygen), severe dynamic straining (thermal gradient,
pressurisation cycle during plant transients), high local stresses (weld defects)
• Corrosion (pitting) during shutdown may also contribute
• SICC – local stress concentration has a predominant role to play as compared to material
or environmental aspects
• Cracking in properly manufactured and heat treated LAS components were not observed
• SICC never observed in LAS RPV steel
Based on laboratory testing severe SICC may occur under following conditions:
• Corrosion potential > -200 mVSHE (ECPcrit)
• A critical strain rate @ 10-3 /s
• Local plastic strain
• Temperature > 150 °C
• Sulphur content in carbon steel/low alloy steel > 0.003 wt.%
• All the factors needs to be simultaneously satisfied

• Even if one of the condition is not satisfied then SICC is extremely unlikely 56

ØBWR
Conclusions
PHWR:
ØPWSCC of SG tube
MP&CED, BARC
PWR RPV – concentrated boric acid at high temperature
Excessive thinning of RPV material
4” x 5” cavity
Down to 3/8” SS
None of 68 PWRs
in USA had any
similar boric
acid wastage
Wastage Rate:
4800 mpy
At 212 °C
Leakage of borated water
due to SCC in CRDM
IAEA report 58
US-NRC report
59

ØBWR
Conclusions
PHWR:
ØPWSCC of SG tube
MP&CED, BARC
Weld pool
IG crack
SCC at H3 Weld Line

of BWR Core Shroud
Ref. : TEPCO/GE data
IG crack
Weld deposit
IGSCC observed in austenitic stainless steels grades:
- SS 304
- SS 304L
- SS316 NG
- SS321 SCC on type 316NG Piping System
- SS347 Ref. : Ulla Ehrnsten et. al;"Tenth International Conference on
Environmental Degradation of Materials in Nuclear Power Systems
Water Reactors"
61
IGSCC of non-sensitized SS 321/SS347 in IGSCC of sensitized SS 321 in German IGSCC of non-sensitized SS316NG in
German BWR IAEA Tecdoc 1522 BWR Spiedel et al. 1999, 9th Env Deg conf BWR Kilian et al. 2002, 10th Env Deg conf
IGSCC in BWR in Austenitic SS growing into the

weld and stopping, Andresen et al.
IGSCC of sensitized SS 321/SS347

IGSCC of non-sensitized SS 321/SS347 steam steam line (downcomer) in RBMK 62
line (downcomer) in RBMK IAEA-EBP-IGSCC IAEA-EBP-IGSCC
Ulla Ehrnsten et al., 17th Env Deg conf, 2015
• IGSCC reported in steam line of SS304 in BWR in Finland after 30 years of operation, crack filled with oxide.
• Crack was away from the weld fusion line – away from the location of peak sensitisation and strained material (adjacent to
the weld)
• Cause – Sensitisation/LTS occurred due to a repair weld leading to IGCCC in a steam line
63
• Peak in residual stress is a more important factor in deciding the location of IGSCC than peak in sensitisation
Factors affecting SCC in BWR
Susceptible
Material
•Sensitization, LTS IGSCC
•Strain (10 – 20%)
• Surface condition
•RIS (Cr depletion) IASCC Neutron fluence effect on IASCC
Me Andresen et al.
fai cha n
lur nic o sio
r
e al C or
SCC
Corrosive
Environment
Tensile Stress •Oxidizing water
•Operational •Temperature
•Thermal •ECP
•Vibrational •Impurities
•Residual
Andresen et al.
64
Dependence of IASCC on fast neutron fluence
A) SusceptibleSensitization
material – of Stainless SteelsLTS
i) Sensitization,
• Precipitation of Cr23C6 at the grain boundary Cr depletion
• Precipitation and growth – 500-850 °C – Sensitisation
• Temperature range: 500-8500C. • Growth of existing carbides < 500 °C - LTS
• At Cr concentration < 12%, passive film becomes weak and prone to

attack in aggressive environment.
• Sensitisation – welding, LTS – Long term operation
Location of IGSCC of sensitized SS 304 pipeline in BWR

65
P. Aaltonen et al. 1987, 3rd Env Deg conf
Marginal reduction in grain boundary Cr concentration Bruemmer et al., 6th Env Deg conf, 1993
affects SCC susceptibility in HTHP water 66
A) Susceptible material – ii) Strain (non-sensitized)
Non - Sensitised strain hardened

Strain (%)
Distance from fusion line (mm)

IGSCC of non-sensitized SS316NG in
Residual strain as a function
BWR Kilian et al. 2002, 10th Env Deg conf
of distance from weld fusion line
IGSCC of non-sensitized SS316NG in
BWR Shoji et al.
67
A) Susceptible material – ii) Strain (contd.)
Location of IGSCC in non-sensitised stainless steel
Stresses arising from

solidification of weld pool Region of heavy plastic deformation
Weld pool leading to increase in strength and
IGSCC susceptibility
Surface deformed layer due to

Welding of
grinding reducing initiation time
thick plate for IGSCC
Stresses arising from constraintment 15 – 20 % strain

of the structure preventing weld shrinkage in regions
adjacent to the
weld
Strain (%)
Distance from fusion line (mm)
Residual strain as a function

of distance from weld pool
68 68
CGR for sensitised
and non-sensitised
strain hardened SS
are of the same
order!
Effect of YS on CGR due to IGSCC

Andresen et al. 69
A) Susceptible material – iii) Surface condition
Stress concentration
Annesha Das, PhD, HBNI
IGSCC of non-sensitized SS 321/SS347 steam line

(downcomer) in RBMK IAEA-EBP-IGSCC 70
A) Susceptible material – iv) Radiation induced segregration (RIS)
Cr (wt%)
RIS :
• Depletion of Cr at grain
Fe (wt%)
boundaries and
• Segregation of Ni at
grain boundaries
and
Ni (wt%)
• Segregation of Si and P
at grain boundaries
Si (wt%)
Effect of irradiation on IASCC
Distance from grain boundary, nm Irradiation also increases strength of material

Radiation Induced Segregation (RIS) in 71
high purity stainless steel
B) Corrosive environment
i) Oxidising water chemistry Radiolysis of water in BWR
H2 O → e-aq , H+ , H· , H2 , OH· , OH- , HO2· , O2 , H2O2 Short life radicals
Generation of oxidising species due to radiolysis
e-aq + H2O = H+ + OH- H2O2 , O2 retained in water
e-aq + H+ = H
H2 partitioned into steam
2OH = H2O2
Mixed potential developed
H + O2 = HO2
due to oxidation and reduction.
HO2 +OH = O2 + H2 O
The two reactions (oxidation and
HO2 + HO2 = O2 + H2O2
reduction) determine the
H + e-aq + H2O = H2 + OH- Electrochemical Potential
72
Dissolved
oxidising
Potential developed species of 200-
300ppb
Corrosion Potential, VSHE
produced due
to radiolysis is
sufficient to
serve as a
200 ppb 300 ppb driving force
Negligible IGSCC for IGSCC of SS
crack growth rate
73
Sensitized 304 Stainless
Steel Effect of corrosion
2000 ppb O2
500 ppb O2
200 ppb O2
30MPaÖm, 288C Water
0.06-0.4µS/cm, 0-25ppb SO4 potential on crack growth
rate for sensitized,
annealed, and cold worked
Crack Growth Rate, mm/sec
stainless steel.
1.0E-07
CGR of 10-7 mm/s – 3 mm / year
10-8 mm/s – 0.3 mm/year
10-9 mm/s – 0.03 mm/year
1.0E-08
Oxidising species in BWR operating

water is the main corrosive species
to cause IGSCC in austenitic stainless
1.0E-09 steel
Corrosion Potential, VSHE
74
ii) Ionic species
Effect of water purity on IGSCC

occurrences in Alloy 600 in BWR-NWC
Brown, Gordon, 1987, 3rd Env Deg Conf
Effect of Cl concentration and DO on

Sulphate and chloride are the most detrimental anions!
IGSCC susceptibility 75
Crack tip solution chemistry
Experimental conditions
Crack tip water chemistry
• Increased concentration of Chloride at crack tip from 5 ppb to

~1000 ppb
• Sulphate concentration increases from 3-4 ppb to 500-1000 ppb
Q. Peng et al., 2003 76

C) Stress
• IGSCC grows adjacent to the welds where the weld residual stress (due to weld shrinkage of
constrained welds) is very high
• Higher residual stress will be present in strain hardened material
• Fit up stress, operational stresses also increase IGSCC susceptibility
• Flaws, stress raisers increase local stresses
• Fabrication (machining marks)/ welding defects / surface imperfections are preferred sites
for SCC initiation
•Abusive surface grinding result in surface cold work and high residual stresses
77
SCC mitigation
A) Material aspects
• All grades of stainless steels (sensitized and non-sensitised) are prone to IGSCC in oxidizing
BWR environment. IGSCC is generic in nature. IGSCC cannot be avoided. Can only be delayed.
•L-grade stainless steels (C < 0.03wt.%), Nuclear grade stainless steel (C < 0.02wt.%, N – 0.06
– 0.12 wt.%, C+N < 0.13 wt.%) – High resistance to weld induced sensitisation and LTS
(change SS 304 to SS304L/SS316L/SS316NG)
• Avoid abusive grinding and fabrication procedures which result in work hardened layer at
the top surface and cause IGSCC in non-sensitised grades
• SS 321 replaced by SS 347 in German BWRs, SS347 has better resistance to KLA than SS321
78
B) Environmental control
§ Hydrogen water chemistry (HWC) – maintaining a level of hydrogen to suppress hydrolysis,

brings ECP (ECP < - 230 mVSHE) to levels where crack growth rate is very slow
§ Hydrogen chosen: (a) No effect on pH, (b) Minimum system impact & (c) Not corrosive or
toxic, H addition ~2 ppm
Problem with HWC

§ 16N formed due to (n, p) reaction with 16O. NWC – Soluble nitrates
HWC – volatile compounds – ammonia, nitrous oxide – spreads radiation
§ HWC alters nature of surface oxide leading to entrapment of 60Co. Higher
radiation buildup
79
ØNoble Metal Chemical Addition (NMCA)/OLNC
• NMCA - Pt/Rh compounds added to reactor water during outage
• OLNC – Online addition of chemicals during plant operation Noble metal
addition catalyses hydrogen – oxygen recombination, brings down local
oxygen levels at surface, augments HWC.
IAEA Tecdoc P1522 80

q Problems with NMCA
§ Particles are typically of size 20-50 nm and are held onto the oxide surface
by weak Van de Waal’s forces and can get washed away with time due to
flow
§Particles may not penetrate into small cracks or crevices
§Minimum levels of hydrogen necessary for effectiveness.
q Better water chemistry control
C) Controlling stresses
• Surface compressive stresses on surface in contact with environment will prevent/delay
IGSCC initiation
•Induce compressive stresses on the inner side of tubes indirectly – heat sink welding,
mechanical stress improvement, last pass heat sink welding, induction heat stress
improvement, weld overlay
• Directly induce surface compressive stresses (advanced techniques) – surface peening, Low
plasticity burnishing 81

ØBWR
Conclusions
PHWR:
ØPWSCC of SG tube
MP&CED, BARC
• A failure occurred in the carbon steel (A 106 Grade B of ASTM) 10% feedewater pipeline at KAPS #
2 (9th February 2006)
•Operating temperature - 1710C and pressure of feed water 57 Kg/cm2, flow rate 35 m3 / h (2.33 m/sec)
[pH: 8.8 – 9.5, sp. Conductivity: 10 µS/cm at 250C, DO: < 5 ppb, Ammonia: < 300 ppb, Hydrazine: 50 – 200 ppb]
• Failure occurred after 10.11 hot years of operation

• Thickness at fracture reduced to 0.4 mm from original thickness of 7.11 mm
(design thickness 7.64 mm, 80 NB)
Minimum thickness required for

continuous operation was 2.89 mm
9 cm 90 cm
83
10% Feedwater
Line to SG
at KAPS # 2
84
Affected ID surface Least Affected ID surface
Affected ID surface The OD surface 85

86
Control measures:
• A comprehensive pipeline inspection programme:
* Periodic inspection and replace thinned parts.
• Material replacement:
* Local replacement by more resistant material containing Cr and Mo ~1.9-2.6 wt% and 0.87-1.13
wt%, respectively (ASTM 335 Grade P22).
* Design changes like one schedule higher thicknesses and design for lower disturbance in flow,
elbows
•Controlled water chemistry: pH control.
•Developing predictive capabilities – Optimize locations for inspection and refine based on actual
plant observations.
87

ØBWR
Conclusions
PHWR:
ØPWSCC of SG tube
MP&CED, BARC
89
Corrosion problems in secondary side of SG
90
D. Feron, R.W. Staehle
Denting, Pitting
Ø Localized reduction in diameter of SG tubes

ØCorrosion of carbon steel TSP – ~3x volume expansion
Ø High chloride, copper concentration in plugged regions TSP design
ØMitigation – Use of SS TSP, egg-crate design, better
chemistry control, eliminating Cu alloys in the circuit, no
91
condenser tube leakage D. Feron, R.W. Staehle
Wastage, ODSCC IGC, IGSCC, IGA
IGSCC
IGC
IGA
Ø Localized thinning of SG tubes
Mitigation – Prevent sludge buildup, AVT, better water chemistry control

92
D. Feron, R.W. Staehle

ØBWR
Conclusions
PHWR:
ØPWSCC of SG tube
MP&CED, BARC
Corrosion in Fire water line Dousing Water Fill Line 1.5’’ CS pipe
(Non acidic, high pressure process water pipeline)
ERW Pipes of CS
Mitigation –
• Prevented suspended matter in water

• Periodic flushing to prevent buildup of
deposits
Heavy deposits on ID Leakage seen from OD
• Weld at 12 o’clock position (weld at 6 o’clock
helps in accumulation of deposits)
Gradual thinning leading to perforation 94

Initiation of corrosion from ID
Corrosion under insulation
Crack on OD side of SS pipeline (high temperature water line) Cl content in unacceptable range (ASTM 795-08)
Mitigation –
• Insulation material should be as per ASTM
standard
Crack depth ~4 mm • Replace SS line with CS
• Prevent ingress of water
95

ØBWR
Conclusions
PHWR:
ØPWSCC of SG tube
MP&CED, BARC
Conclusions
• Corrosion degradation of nuclear materials is a natural phenomena
• A proper understanding of the corrosion problem helps in devising mitigation strategies
Understanding mechanism
Environmental control
Surface modification
Improving design
Material selection
Periodic inspection 97
98

13

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

13

Uploaded by

Copyright:

Available Formats

Corrosion degradation of nuclear structural materials

Structural Integrity: Corrosion assisted degradations / failures

A) Introduction to corrosion in NPPs:

v Materials behave differently when exposed to a corrosive environment:

Subcritical crack growth mechanisms..

A) Introduction to corrosion in NPPs:

2) Galvanic corrosion 3) Crevice corrosion

Cross-section of pits Pit

•SS, Al more prone to pitting in presence of Cl 304 17.5-20.8

Sensitisation due to carbon pickup

Dezincification of Brass (Cu-Zn)

Crack initiation: Thin cracks with crack tip

conductivity at 250C, µS cm-1 On the average about 60

Dissolved Oxygen, (ppb) <5

Chloride, (ppm) < 0.2

Hydrazine, (ppm) 5. begin with and < 0.2 at the end

A) Introduction to corrosion in NPPs:

Pressure tube - Zr-2.5Nb

Fuel cladding – Zr-2

A) Introduction to corrosion in NPPs:

Assure integrity Assure fuel Minimize out of

Cost of repair >> cost of maintaining water chemistry!! 15

TAPS 3&4 KKNP TAPS 1&2

Primary coolant: D2O Primary coolant: H2O Primary coolant: H2O

Water Chemistry: D2O (97% min) Water Chemistry: Water Chemistry:

Minimize Ensure Maintain heat

Cost of repair >> cost of maintaining water chemistry!! 17

• Similar water chemistry for PWR and PHWR

Parameter Value Chemical/Source Remarks

Ammonia £300 (µg/l) Decomposition of Higher value of ammonia is deleterious

Parameter Value Chemical/Source Remarks

Sodium £100 (µg/l) Higher value indicates the condenser

A) Introduction to corrosion in NPPs:

Oxidation and hydrogen related

Fuel side corrosion

Elements Zircaloy-2 Zircaloy-4 Zr-2.5%Nb Zr-1%Nb

Zircaloy-2: Fuel clad in BWR & was earlier used as

Zircaloy-4: Fuel clad in PHWR, PWR, Calandria Tube &

Zr-2.5%Nb: Pressure Tube in PHWRs

Zr-1%Nb: Fuel clad in VVERs

Zr-2.5%Nb-0.5Cu: Garter Spring in PHWR

Linear – Porous or cracked oxide, no diffusion barrier, not

vBlack ® grey ® white

Zr-2 at 3160C During Post-Transition

Zr-2.5Nb voxide properties depends upon the

Exposure Time, Days

- Predominant in BWR Cladding tubes

• At low end of the precipitate size

• Nodular corrosion is promoted in

Degradation modes due to Hydrogen: H H

ii) Hydride blister

Isothermal thermogravimetric curves of Zr-2.5Nb in steam in the

Ananthkrishna, et al. JNM, 2024, 154967 33

iii) Hydride blistering:

iv) Accident conditions:

A) Introduction to corrosion in NPPs:

Feed water Feeder FAC resistant grades

A 106 A 333 A 335 A 335

Two phase FAC

After 500 h at pH 9.75

pH 9.05, Deoxygenated water

Specific material wear rate, µg/cm2-h

pH 7.0, DO: 40 ppb,

A) Introduction to corrosion in NPPs: