Stress Corrosion Cracking of Zircaloy

By
Aramanda Shanmukha Kiran
MM13M005
(Department of Metallurgical and Materials Engineering, IIT-
Madras)
14/05/20 1
Zircalo
y:
Structural material to clad
fuel pellet in Boiling Water
Reactor and Pressurised Water
Reactor.
Properties – corrosion /
oxidation and irradiation
resistance, neutron economy,
fair strength

Schematic of a fuel rod, comprised of

three components: fuel pellets,
enclosed in a protective cladding and
separated by a small gap

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Chemical
Composition:
Impurities like N, C give pure Zr inconsistent corrosion in
high temperature water and steam
Nuclear grade Zr – virtually free of Hf
α stabilizing element – Sn
β stabilizing element – Nb
Ni gives hydrogen pickup

Alloy Hf Sn Nb Fe Cr Ni
Zircaloy- 0.0 1.20- - 0.07- 0.05- 0.03-
2 1 1.70 0.2 0.15 0.08
Zircaloy- 0.0 1.20- - 0.18- 0.07- -
4
14/05/20 1 1.70 0.24
MM13M005 0.13 3
Corrosion
properties:
Strong affinity to oxygen
Oxide layer – adherent and protective at ambient
temperature
Oxide film – self healing up to 3500C
Repassivation difficult in HF, H2SO4 and organic halides
Prone to pitting and SCC in halide solutions under
oxidising conditions

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 Aqueous
Corrosion Stress Corrosion
WATER Cracking
IASCC
Fractur
e
STRESS

Radiation
Creep

RADIATIO
N
Radiolys
is Radiation
MATERIAL induced
Radiatio segregation
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Corrosio
Mechanism of
ISCC:
ISCC occurs after extended exposure to iodine and after
power ramp
Essential conditions of ISCC
1.Critical strain
2.Critical iodine concentration
3.Minimum time
PCI-SCC model
Stage in
ISCC:
Incubation period
Crack initiation
Crack propagation

Kurt Edsinger et al., Journal of

14/05/20 MM13M005 Materials (2009) 6
Incubation
Period:
No crack like features found on the cladding
Reaction of iodine with the oxide layer weakens bonding
Oxide layer is strong, so dissolution and fracture occurs at
roughness, scratches etc.
Pit formation (length ≫ diameter)
Increases exposure of base metal to iodine bearing
environment
Crack
Initiation:
Crack nucleation occurs on defective regions of base metal
like
1.Grain boundaries
2.Pits
3.Segregation of secondary phases
Zr → HCP crystal structure→ less number of slip systems
Cracking occurs when there is no slip system to relieve
stresses of a dislocation pile-up
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Grain boundaries:

Fracture structure in a grain boundary

fracture zone

Crack nucleation takes

place at GB, when angle
between grain boundary
and direction of tensile
stresses is close to 900

A.B.Rozhnov et. al., Russian Metallurgy (Metally), pp.

14/05/20 984-990 (2009)
MM13M005 8
Pit:

SEM image of pit on Zr cladding tube sample during

SCC test

Regions of stress
concentrations → crack
nucleation
Occurs at site of iodine
adsorption and grows by
metal dissolution
Depression like regions
filled with corrosion
products

A.B.Rozhnov et. al., Russian Metallurgy (Metally), pp.

14/05/20 984-990 (2009)
MM13M005 9
Crack
Propagation:
Iodine diffuses to crack tip and gets adsorbed which
decreases bond strength
Decreases surface energy on basal planes making them
sensitive to cracking
Inter granular cracks transform to transgranular cracks at
critical KISCC
Other mechanism of transgranular crack propagation
1.Trapping of vacancies at crack tip
2.Formation of hydrides at crack tip

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Corrosion
damage on
the surface of
specimens,
transverse
micro
sections, and
ruptures of
zirconium
alloys in SCC
tests in a
methanol –
iodine
medium et.al.,
S.A.Nikulin
Metal Science and
Heat treatment,
pp. 31-39 (2005)
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Effect of External Factors on
ISCC:
External stresses
Iodine concentration
Irradiation
Microstructure
Texture

1.External
Stress:
External stress → SCC of cladding
Due to increase in probability of nucleation and growth of
corrosion cracks by trans-granular mechanism.
Source of stresses:
Change in power during power ramp
Cementation of fuel and cladding by fission products
Coefficient of friction between fuel and cladding
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2.Iodine
Concentration:
Concentration of I its diffusion to crack tip which
accelerates crack propagation
Threshold stresses for SCC this intensifies pit formation

3.Irradiatio
n:
Radiation induced defects causes diffusion, which in turn
causes hardening of cladding
Sets up stress gradient at the crack tip to accelerate SCC
Critical value - 2.1 × 1020n/cm2

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Relationship between crack growth rate (CGR) and
stress intensity factor (KI):

Yu. K. Bibilashvili, A. V. Medvedev, B. I. Nesterov, et al., “Journal of

Nuclear Mateials” Vol. 280, pg. 106 – 110 (2000)

14/05/20 MM13M005 14
4.Microstructure:

Uniform distribution of fine intermetallics in Zr matrix

increases the resistance to SCC
Intermetallics when present at GB increases susceptibility
to transgranular cracks
Fe bearing particles act as catalyst for crack initiation

5.Texture:

ISCC occurs by transgranular cleavage on basal planes of

hexagonal lattice
Basal planes are perpendicular to applied stress → KISCC is
lower and crack growth is faster
Radial texture is resistant to SCC while tangential texture
is prone

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Mitigating ISCC in
Zircaloy:
Reduce crack propagation rate which is accomplished by
different coatings

Graphite
Copper
Zirconium
Advanced barrier coating (TRICLAD™)

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Copper
Coatings:
 Act as metallurgical barrier and reduces crack
propagation rate
 Produced by electroplating
 Cu prevents shear loading of cladding and physical
obstruction to fission products
 Decreased resistance under irradiation due to formation
of brittle intermetallic layer
Zirconium
Coatings:
 Produced by coextruding co-axial cylinders of Zircaloy
and pure Zr
 Pure Zr has superior resistance to PCI in I environment
 Metallurgical bond between coating and cladding tube
reduces strain
 Withstand high strains in I bearing environment
 Increased tendency for the long cracks in failed rods
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Advanced
Barriers:
Cross-section of GE’s Triclad zircaloy-2 lined zirconium-
barrier cladding

Kurt Edsinger et.al., Journal of Materials (2009)

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Features of Advanced
Barrier:
Min. thickness of inner zircaloy-2 layer is 10𝜇m
Cracks propagated through zircaloy-2 are arrested by Zr
barrier layer
Max. thickness of zircaloy-2 depends on length crack
blunted by Zr barrier
C. D.Williams et.al., ASTM STP 1295, pp. 676-694 (1996

Simulated PCI
behaviour of non-
barrier, Zr barrier
and zircaloy -2
(0.0012 in
thickness) lined Zr
barrier

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 Simulated PCI behaviour of zircaloy – 2 lined Zr barrier layer
with different thickness of inner zircaloy -2 layer

Inner liner thickness should be in the range of 15 – 50 µm to

be used to mitigate the PCI failures
C. D.Williams et.al., ASTM STP 1295, pp. 676-694 (1996)
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 THANK
YOU

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