Zr2 Zr4

?
o
I
ORNL-3281,
UC-80 Reactor Technology

TID-4500 (17th ed.)
iM
REVIEW OF ZIRCALOY-2 AND ZIRCALOY-4

PROPERTIES RELEVANT TO N.S. SAVANNAH
REACTOR DESIGN
C. L. Whitmarsh
OAK RIDGE NATIONAL LABORATORY

operated by
UNION CARBIDE
for
CORPORATION
the
U.S.
ATOMIC ENERGY
COMMISSION
Printed in USA.
Prico
ULZ5
Available from the
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U. S, Deportment of Commerce Washington 25, D. C.
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Makes
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ORNL-3281
UC-80 - Reactor Technology
TID-4500 (17th ed.)
Contract No. W-7405-eng-26
Reactor Division
REVIEW OP ZIRCALOY-2 AND ZIRCALOY-4 PROPERTIES RELEVANT TO N.S. SAVANNAH REACTOR DESIGN
C.
L.
Whitmarsh
Date
Issued
OAK RIDGE NATIONAL LABORATORY
Oak Ridge, Tennessee

operated "by
UNION CARBIDE CORPORATION
for the
U.
S. ATOMIC ENERGY COMMISSION
CONTENTS
Page
ABSTRACT
1. INTRODUCTION
v
1
2.
DESIGN CONSIDERATIONS
Environment
2
2
Zircaloy-2 Composition
3. CORROSION
Water and Steam Corrosion
Kinetics
4
4
4
5
Factors Affecting Corrosion Fretting

Hydride Effect Hydrogen Solubility Hydrogen Absorption
9 10
12 12 13
Hydrogen Diffusion
Mechanical Properties
14
16
Predicted Pickup of Hydrogen During Reactor Service

4.
5.
18
20
23
PHYSICAL PROPERTIES
MECHANICAL PROPERTIES
Tensile Properties
23
Modulus of Elasticity and Poisson's Ratio

Impact Properties Fatigue Properties Creep Properties
29
30 32 34
Torsional Properties Fabricability

6. NUCLEAR PROPERTIES
38 39
40
7.
RADIATION EFFECTS
41
42
Hydrogen Pickup
Other Effects
In-reactor Failure
47
47
48
in
8.
9.
HAZARDS OF METAL-WATER REACTIONS

OTHER ZIRCONIUM BASE ALLOYS
48
52
53
REFERENCES
APPENDIX
59
IV
ABSTRACT
A literature search covering all available technology on Zircaloy

was conducted with specific emphasis on environmental conditions similar
to those present in the reactor core of the N.S. SAVANNAH. Information
on mechanical properties, corrosion properties, radiation effects, and

other pertinent subjects was collected. Out-of-pile data relevant to Zircaloy-2 structural components in the
N.S. SAVANNAH core show a yield strength of -20 000 psi for annealed ma
terial, a creep rate of <10~5^/hr at 15 000 psi, and corrosion of only a

few mils in 20 years. The principal effects of radiation exposure are
Brittle increased mechanical strength and decreased uniform elongation.
fracture does not occur, however, because reductions in area permit local plastic deformation. The corrosion rate is increased by radiation expo
sure (less than a factor of 5), but even at the increased rate metal loss
is insignificant. The possibility of a violent metal-water reaction, al
though remote, can be significant and must be evaluated for specific cases. Except for hydrogen pickup, Zircaloy-4 exhibits essentially the same
properties as Zircaloy-2, as anticipated from the composition similarity. Excessive hydrogen content, with resulting precipitation of ZrH2, causes
embrittlement of Zircaloy-2. The pickup of hydrogen by Zircaloy-2 is
about three times that of Zircaloy-4.
On the basis of the available information, Zircaloy-4 appears to be

adequate for use as the material of construction for the fuel element con
tainers in the advanced core for the N.S. SAVANNAH.
Zircaloy-4 is recom
Recommenda
mended over Zircaloy-2 because of its lower hydrogen pickup.
tions for 20-year service life cannot be made with complete confidence,
however, because of the necessary extrapolations of data. Creep, corrosion,
and irradiation data must all be extrapolated by factors of 10 to 15 to
obtain 20-year performance predictions.
Existing data give no indication,
however, that any insurmountable problems will be encountered in these

areas for the application of interest.
The possibility of hairline cracks in Zircaloy-2 being propagated to

major defects by long-term radiation exposure deserves special mention.
Hairline cracks sometimes occur during fabrication of the metal that are
not always detected by present inspection methods.
Effects of radiation
on these cracks are unknown, but the possibility of propagation to fail

ure has caused some designers to change from Zircaloy-2 to stainless steel
for fuel element cladding.
Zircaloy-2 is presently being used in various reactors as part of

the fuel matrix, fuel element cladding, and structural components. Zircaloy-4, although not yet in use as a reactor material because of its
newness, has been recommended as the pressure-tube material in the de
sign of the CANDU reactor.
Considerable experimental work pertinent to
reactor applications is being performed at various locations on zirconiumbase alloys.
VI
REVIEW OF ZIRCALOY-2 AND ZIRCALOY-4 PROPERTIES
RELEVANT TO N.S. SAVANNAH REACTOR DESIGN

C. L. Whitmarsh
1.
INTRODUCTION
Preliminary considerations for reducing fuel-cycle costs in reactors
of the N.S. SAVANNAH type1 have indicated the feasibility of replacing

the stainless steel fuel element container with a container of a lower-
neutron-absorption material in order to reduce the required enrichment or to increase the core life or both. Since neutron economy is one of
the more limiting design features, the list of applicable container ma
terials was quickly reduced to magnesium, aluminum, beryllium, and zir

conium or their alloys. Other criteria, such as mechanical strength,
corrosion resistance, fabricability, and available technology, further

reduced the list to Zircaloy-2 or Zircaloy-4. A literature search was
then conducted to collect the available information on the Zircaloys
pertinent to reactor design. in this report.
The information thus collected is presented
Although most of the data reported here were obtained
from tests of Zircaloy-2, it is generally believed that the results, other

than those for hydrogen pickup, pertain equally well to Zircaloy-4 be
cause of the strong composition similarity between these alloys.
Existing reactors that use Zircaloy as fuel cladding or structural
components include the HRE-2, Dresden, Shippingport, submarine thermal

and advanced types, PRTR, NRU, and NRX. Those in advanced design or con
struction stages include the HWCTR, CVTR, NPD, and CANDU.
Experimental
work on Zircaloy is being done primarily at Westinghouse's Bettis Plant,

Chalk River, Savannah River, Hanford, and Knolls Atomic Power Laboratory. The standard reference for zirconium technology is the book, The
Metallurgy of Zirconium, which was published in 1955.2 sented in a Hanford report in 1959.3
Zircaloy-2 pro
perties were reviewed with respect to reactor technology and were pre
Additional data are scattered through
out the classified and unclassified literature.
2.
DESIGN CONSIDERATIONS
Environment
A principal function of the fuel element container in the N.S.
SAVANNAH reactor is to channel cooling water through the core.
The con
tainer, or can, also provides passageways for cruciform control rods, as

shown in Fig. 1. Mechanical and thermal stresses are of concern because
deflection of the container walls might interfere with control-rod move ment. Deflection of the container walls is also dependent on the pres
sure differential of the cooling water between the second- and third-pass
channels and the modulus of elasticity of the material. Since the con
tainer is a structural component of the reactor, long-term usage is speci
fied.
In this case, 20 years is the expected lifetime.
Long-term use
enhances the importance of such factors as corrosion resistance and the
influence of radiation exposure on mechanical properties.
The peak ex
posure to neutrons of energies greater than 1 Mev during a 20-year period
will be ~1023 neutrons/cm2.
UNCLASSIFIED ORNL-LR-DWG 43889R
.'.IM1.'.;
ALUMINA FILLER
ZIRCALOY
' ,' \ , -CONTROL ROD FOLLOWER
PER PHERAL FERRULE
!
0663
',06666**666000 w
-SPACER BAR
(FLOW BLOCK)
FUEL ELEMENT
CONTAINER
}00&Q:
' 1 ){ n a x
SPACER FERRULE
Fig. 1.
Detail of Fuel Cell in the N.S. SAVANNAH Reactor,
A list of pertinent operating conditions is presented below:

Primary loop
Pressure, psig
Water temperature, F
Core inlet
Core outlet Maximum
1750
496
520 546
Water velocity, first pass, ft/sec

Water chemistry
9.66
7.5 to 8.5
3.6 5
pH range
Hydrogen content, ppm Total maximum allowable solids, ppm
Maximum oxygen content

Maximum chlorine content, ppm
0.05
0.1
Zircaloy-2 is a complex alloy of sponge zirconium with the follow
ing major components and impurities specified for reactor-grade material:3

We ight
Element
Major Components
Sn
Fe Cr
1.2-1.7 0.07-0.20
0.05-0.15
Ni
0.03-0.08
Tmpur:ity Maxima
Al
B
0.0075
0.00005
0.0270 0.00005 0.0020

0.0050
Cd
Co
Cu H
0.0025 0.0200
0.0130
Hf Pb
Mg
Mn N
0.0020 0.0050
0.0080
0.0120 0.0020
Si Na
Ti
W
0.0050
0.0100
U (total)
U-235
0.00035
0.0000025
It was developed specifically for nuclear reactor applications in a hightemperature water environment. The alloying agents tin, iron, chro
mium, and nickel were added to sponge zirconium to neutralize the detri
mental effect on corrosion resistance of the impurities nitrogen, alu
minum, and carbon and for their strengthening effect. The low neutron-
absorption cross section of pure zirconium was not increased significantly

by these alloying materials.
Zircaloy-4 was developed from Zircaloy-2 with the principal aim of

reducing the tendency to pick up hydrogen. Thus, the same composition
specifications are applicable, except for nickel, which is limited to
a maximum of 0.007^, and iron, the range of which is reduced to 0.12 to

0.1$fo.
3.
CORROSION
Iodide-grade zirconium has excellent corrosion resistance in high-
temperature, high-pressure water; however, small amounts of impurities,

such as those present in commercially available sponge zirconium, reduce
the corrosion resistance drastically. Since iodide-grade zirconium is
both difficult and expensive to produce and fabricate, Zircaloy with

sponge zirconium as its major constituent represents a practical approach
to the problem.
Water and Steam Corrosion
Corrosion in water or steam produces a protective oxide film on the

surface of Zircaloy-2 by the reaction
Zr + 2H20 -> Zr02 + 2H2
Two distinct corrosion periods have been observed, pretransition and post-
transition.
The pretransition period is characterized by a decreasing
corrosion rate and an adherent, protective film with a shiny black ap
pearance.
The posttransition period is characterized by a constant but
greater corrosion rate and a less protective film that has a white flaky appearance. The time required to reach transition is both temperature
and time dependent.
Kinetics
Pretransition film formation may be represented on a log-log plot
by a straight line:
log W = log k + n log t
where W is the weight gain per unit area, log k is the ordinate inter
cept, n is the slope, and t is the exposure time.
The corrosion rate
during this period is thus seen to be time dependent:
dW = dt
, ,n-x nkt
After transition, the corrosion reduces to a linear function; and, conse
quently, the corrosion rate is constant.

Table 1 and Fig. 2.
Data2^;5 on Zircaloy-2 cor
rosion in water and steam at various temperatures are summarized in
(The tests were made in static, neutral water and
in steam.)
Additional data5 on the temperature dependence of the time

Rate-constant data for the post-
to transition are presented in Fig. 3.
transition period (linear corrosion rate) are presented in Fig. 4.

In the extrapolation of these data to examine long-term effects,
corrosion during the pretransition period was found to be negligible,
except at the lower temperatures.
For long-term corrosion prediction,

Both sets
linear corrosion data were extrapolated as shown in Fig. 5.
of equations given in Table 1 were plotted for 750, 680, and 600F; data
0^
Table 1.
Corrosion of Zircaloy-2 in Water and in Steam2 >*">5

Transition Posttransition Period Period
Pretransition Period
Temperature
(F)
Corrosion
Corrosion Rate
r, 4- a
Weight
. Gaina
Time
m.
Corrosion8-
Corrosion
Ratea
550
log W=0.50 +0.30 log t |^ =0.95 t-0"70

log W = 0.74 + 0.26 log t = 1.4 t-0-74
34
600
1150
W - 34 = 0.065(t - 1150)
dW
= 0.065
dt
680
log W=0.76 +0.38 log t |^ =2.2 t-0-62
34
112 41
W - 34 = 0.37(t - 112) w - 41 = 1.27(t - 41)

W = 0.02 t + 11
^=0.37
dt
750^
600
log W=1.10 +0.32 log t |H =4.0 t-0-68
dW dt dW
41
1.27
= 0.02
dt
680
= 0.03 t +
15
dt
750
dW
dt
W = 1.4 t + 15
^ = 1.4 dt
dW
572
0.02c
40
2000
dt
0.03
w is in mg/dm2; t in days.
Steam at 1500 psig. "Average rate during pretransition period.
UNCLASSIFIED ORNL-LR-DWG 56352
1000
UNCLASSIFIED
ORNL-LR-DWG 56353
REF 500
REF
TEMPERATURE (F)
/
680 600
//
X
200
/'
E 100
T^
o>
<
t-
"i"
C5
^^ ZK>^^
^>
20
-[r" rT i
6
10
fc
2> 00^
5b0
, nN^>
10
20
50
100
200
500
1000
(xio4)
TIME (days)
</r(R)
Fig. 2.
Steam.
Corrosion of Zircaloy-2 in Water and
Fig. 3. Transition Time for Cor rosion of Zircaloy-2 in Water and

Steam.
<]
03
UNCLASSIFIED
UNCLASSIFIED
ORNL-LR-DWG 56355
ORNL-LR-DWG
56354
8000
TEMPERATURE (F)
900 20
800
680
620
550
10
\' '
\
7000
p EF:
KAPL-2086
CI ASSIFIFr
p 2 Fig 1
STEAM DATA
ABOVE
pbi
E
ID
,LU
Fo> <
a a. 0.5
^-ZIRCALOY- 2
OR 0.2
,_
ZIRCALOY
0.05
\
0.02
I
0.01
I
9
N
10 (xlO*)
3000 4000
Vr (R) Post-Transition Corrosion Rate of Zircaloy - 2 and Zircaloy-4 in Water and Steam.
5000 6000 7000
Fig. 4. Posttransition Corrosion Rate of Zircaloy-2 and Zircaloy-4 in

Water and in Steam.
TIME (days)
Fig. 5. Predicted Long-Term Corrosion of Zircaloy2 and Zircaloy-4 in Water and in Steam.
for 572 and 536F are estimates made at Chalk River5>6 based on extrapola
tion of rate-constant data. It should be noted that data from Lustman2 The assumption
Film thick
were extrapolated from maximum test times of 1000 days.
was made that spalling of the corrosion film does not occur.
ness can be calculated from weight gain by use of the expression
= 0.00252 W
where the film thickness X

pression
is in mils and the weight gain W is in mg/dm2
Metal penetration can be calculated from weight gain by use of the ex
= 0.00158 W
,
'
where the metal penetration X

r m
is in mils.
Factors Affecting Corrosion

The effects of various factors related to corrosion resistance are
summarized below.
Chemical Impurities.
Impurities such as nitrogen, carbon, and alu
minium have a pronounced deleterious effect on the corrosion resistance of Zircaloy-2.

detail in ref.
Specific effects of various impurities are treated in

2.
Cold Work.
Various studies2}7 have indicated that the cold work
effects are minor relative to other factors, for example, fabrication
methods, physical and chemical abnormalities, etc.

Heat Treatment. Cooling rates of greater than 90F/min through the
range 1850 to 1470F are considered necessary to minimize possible seg
regation of phases and a resultant corrosion rate increase.8;9 Annealing

at 1650 to 1850F results in 20 to 80$ higher corrosion rates in 680F
water or 750F steam than annealing at lower temperatures. Work at the
Bureau of Mines3 has indicated that corrosion resistance is relatively
insensitive to heat treating temperatures below approximately 1470F.
Fabrication.
Instances of poor corrosion behavior of Zircaloy-2,
manifest by the appearance of "stringer"-type corrosion, have been traced
to improper arc-melting practice and heat treatment.10

face and increase corrosion in that area.
Two types of
stringers gas void and intermetallic can occur near the metal sur
Contamination.
Contamination which would
affect the water-corrosion
behavior of Zircaloy-2 may result from fabrication and processing, in
spection and corrosion-evaluation testing, and the reactor service en vironment. In particular, fluorides introduced in etching procedures
are know to markedly increase the water-corrosion rate, apparently through
galvanic attack.3
Reactor cooling-water impurities could be important,

Although many investigators have reported
but no specific data are available.
Reactor Environment.
that no significant effects on the corrosion rate of Zircaloy-2 in high-
temperature water have been observed that are attributable to radiation
flux, more recent data14' have indicated otherwise.
Examination of Zircaloy-2
sheaths on irradiated fuel elements at Chalk River gave some evidence that
corrosion rates under irradiation may be higher by, at most, a factor of
5.
Later results5 for Zircaloy-2 coupons tended to confirm an increased
rate, although the difference was much less than the factor of 5.
Water Velocity. No effect of water velocity in the ranges of in
terest on the corrosion rate of Zircaloy-2 in water has been observed.
Fretting
Fretting corrosion has been defined as the attrition of metal be
tween two contacting surfaces, in the absence of a corrosive environment,
as a result of small-amplitude vibrations under small loads.2
Although
few quantitative data are available, several general trends have been
observed. 5 Generally, in fretting, the relative velocity and amplitude

of motion are smaller than in normal wear processes; and the product formed
by fretting normally does not escape, since the two surfaces are never
out of contact.
and wear.
However, there is no sharp dividing line between fretting
Experiments have indicated the more important variables to
be contact pressure, number of cycles, amplitude of relative motion,
10
frequency, material hardness, temperature, coefficient of friction, and

environment. Most of these variables are interdependent, and care should
be used in treating any one as a separate factor.

Fretting of Zircaloy-2 probably occurs by the removal of metallic
particles which subsequently oxidize to form an abrasive powder.
The
abrasive action of the powder is then regarded as being the more severe
cause of wear.
Feng and Rightmire16-'17 assumed that fretting begins with

Later accumulation of trapped wear
ordinary metal transfer and wear.
particles, which cannot escape because of the small amplitude of relative

motion, shifts the wear action gradually into abrasive action until,
finally, the major portion of the damage is due to abrasion.
Results of fretting tests at Bettis15 may be summarized as follows:

1. Fretting weight losses between Zircaloy surfaces were less than
those found between mild steel surfaces.

resistance to fretting corrosion.)
2.
(However, mild steel has poor
Fretting weight losses were less when tests were made in water
than in oxygen or air, particularly in the tests of Zircaloy against

stainless steel.
3.
Fretting weight losses of Zircaloy against stainless steel were
a factor of 10 greater than in the case of Zircaloy-Zircaloy couples. 4. Slip versus fretting weight loss was not a linear function;
weight losses increased rapidly with relative slip of greater than 3 mils.
5. The effect of number of cycles and applied load on fretting was
similar to that found for mild steel; that is, it was nearly linear after
initial periods of greater effect.
Experience at Chalk River in the HRX reactor5 has indicated that

fretting of Zircaloy-2 is of little importance. During three years of
operation, a thick-walled (692 mils) Zircaloy-2 pressure tube was ex

amined internally eight times. The tube was found in very good condition
despite frequent mechanical damage to the surface film caused by the movement of fuel charges. of fretting have occurred. At least two reasonably authenticated instances In all instances the affected regions have
Thin
subsequently been found to be covered with a continuous black film.
samples taken from the inner surface of the tube have a measured corrosion
11
of approximately 0.014 mg/dm2/day.

predicted in Table 1.)
(This is somewhat lower than that
Hydride Effect
The primary source of hydrogen for the formation of ZrH2 is the cor rosion reaction between zirconium and water. Absorbed hydrogen at a
concentration of 1000 ppm appears to have no effect on Zircaloy-2 cor
rosion resistance,18 but 10 to 50 ppm hydrogen is known to affect notch sensitivity.3 Precipitation of the hydride phase in Zircaloy-2 increases
notch sensitivity and reduces ductility to such a degree that reactor
designers are now considering the use of Zircaloy-4 to minimize hydrogen
pickup.
Based on information obtained at Chalk River,19 hydriding will

Failure of two ZIrcaloy-2-clad U02
be the limiting factor for Zircaloy-2 pressure-tube service life in the
D20 moderated NPD and CAEDU reactors.
fuel rods similar to PWR Core 1 blanket fuel elements in a high-pressure

loop in the NRX reactor was attributed to absorption and thermal diffusion
of hydrogen in the Zircaloy-2.20

A comprehensive coverage of the effect of hydrogen on zirconium alloys
is presented in ref. 6.
Hydrogen Solubility
Solubility data6 for hydrogen in the alpha-phase of Zircaloy-2 are

plotted in Fig. 6. A least-squares fit of the data is represented by
C0 = 8.50 X 104 exp (-7600/RT)
where C0 is the terminal solid solubility of hydrogen in ppm by weight,
7600 represents the difference in partial molar heats of solution of

hydrogen in the hydride and alpha phases, R is the universal gas constant
(1.986 cal/mole-K), and T is the absolute temperature in K.

data from other sources are presented graphically in ref. 21.
Solubility
12
UNCLASSIFIED
ORNL-LR-DWG 56356
5000
2000
tooo
\
s
500
CO
z>
\
\
\
200
UJ o
\.
o
ce Q
>
I
100
\
4 5 6 7
N
\
50
(xKT
Vr (R)
Fig. 6.
Hydrogen Solubility in the Alpha-Phase of Zircaloy-2.
Hydrogen Absorption In addition to the hydrogen initially contained in Zircaloy-2
(specification, <25 ppm), the principal sources of hydrogen in the re

actor environment are the radiolytic dissociation of water and the cor
rosion reaction between Zircaloy-2 and water.
Various investigators4>
estimate that approximately 30$ of the hydrogen produced in the corrosion
reaction forms ZrH2, whereas others22 have found that up to 100$ of the corrosion hydrogen is absorbed. Other studies5>23 indicate that a linear
relationship exists between hydrogen pickup and weight gain for a given
alloy (Fig. 7).

Hydrogen absorption in Zircaloy-2 during water corrosion is depend
ent on the hydrogen concentration in the water.6
Although the data are
somewhat scattered, a definite increase in the amount of hydrogen picked
up during corrosion occurs as the concentration of dissolved hydrogen is
increased.
Some reported data24 indicate, however, that the increase in Other results
hydrogen absorption is almost negligible at the N.S. SAVANNAH reactor con
dition of 25 to 35 cm3 of hydrogen per kg of water (-3 ppm).
indicate that hydrogen absorption is sensitive to the pH of the water.25

13
UNCLASSIFIED
ORNL-LR-DWG
56357
20
40
60
80
100
WEIGHT GAIN (mg/dm2)
Fig. 7.
Hydrogen Pickup in Zircaloy-2 and Zircaloy-4 during Cor
rosion in Water.
Ammoniated water showed lower values than neutral or lithiated water
(Table 2).
reliably.
Sensitivity to heat treatment has also been shown, but results
are sufficiently scattered and scarce that predictions cannot be made
Alloy composition has a significant effect on hydrogen pickup.
As
the result of several investigations,6>23;26 nickel was determined to
be the principal hydrogen getter in Zircaloy-2.
This led to the develop
ment of Zircaloy-4 (nickel-free Zircaloy-2), which has essentially the

same properties as Zircaloy-2 but a lower tendency to pick up hydrogen.
Hydrogen Diffusion
The diffusivities of hydrogen in alpha-phase zirconium and Zircaloy-2
have been determined by various investigators21'27-'28 and are presented
14
Table 2.
Effect of Water Condition and Heat-Treatment on Hydrogen
Pickup During Corrosion of Zircaloy-2 in 680F Water
Heat Treatment Method Time
Hydrogen Pickup ($ of theoretical)

of
Temperature
(hr)
(c)
775
Cooling
Water at
Ammoniated Water at
Lithiated Water at
pH 7
pH 9.0
23.2 5.49
pH 10.5
31.2 3.62
1/2
24
Furnace cooled
32.8 4.13
800
Furnace
cooled
18.4 3.1
14.4 1.24
21.6 5.00
850
Furnace
cooled
28.8 5.54
32.8 3.72
23.2 3.92
28.0 7.93
36.0 5.46
40.8 6.37
900
Furnace cooled
24
900
Furnace
cooled
38.4 2.53
28.0 7.28
36.0 12.5
950
Furnace cooled
24.8 7.20
37.6 11.98
28.0 8.24
1000
Furnace cooled
32.8 9.26
28.0 6.93
44.0 9.50
850
Mercury quenched
27.2 8.62
18.4 3.39
28.0 14.29
900
Mercury quenched Mercury quenched Mercury
27.2 6.47
20.8 4.84
17.6 8.46
950
21.6 3.65
28.0 4.34
17.6 4.80
1000
21.6 6.57
23.2 7.14
13.6 4.06
quenched
in Fig. 8.
Thermal diffusion occurs when a temperature gradient exists
in a Zircaloy-2 component and hydrogen concentrates in the cooler region. In situations where large thermal gradients are present, diffusion of
hydrogen in Zircaloy-2 becomes a serious problem, as indicated by fuel

rod failures in loop experiments which were attributed to hydrogen embrittlement along the outer surface of the rods. Calculations of con
centration factors based on thermal diffusion theory have been made and
15
UNCLASSIFIED
ORNL-LR-DWG 56358
plotted for various tempera
TEMPERATURE (C)
400
tures and thermal gradients.6

Work at KAPL4 has shown that
irradiation of Zircaloy-2-clad
fuel elements causes a redistri
bution of the hydrogen by dif fusion, with concentration at
the coolest section, but the

redistribution is by no means
5x10'
complete; that is, a hydride

2.0 (x10=)
gradient exists in the cladding
Fig. 8.
in Zircaloy-2.
Diffusivity of Hydrogen
after irradiation. Diffusion
of hydrogen as the result of
stress and activity gradients has also been observed29 and, although not
clearly defined as yet, may make a significant contribution to hydrogen
redistribution in Zircaloy-2.
The primary concern with hydrogen pickup in Zircaloy-2 is its effect
on impact strength, ductility, and, to a lesser degree, tensile strength.

Notched-bar impact properties of zirconium-base alloys are sensitive to hydrogen content in that the transition temperature can be related to the
amount of hydride precipitate present.6
Quenching from above the hydrogen
solubility temperature lowers the transition temperature and increases
the transition range.
Experimental data30 indicating decreased impact
resistance with Increased hydride precipitate are presented In Fig. 9.
Correlation between elongation and hydrogen content31 shows a definite decrease in elongation with increasing hydrogen content (Fig. 10). Ten
sile properties are not so dependent on hydrogen content.
Data31 from
Zircaloy-2 specimens with various heat treatments showed the tensile
strength to be essentially independent of hydrogen concentration up to
approximately 500 ppm; beyond this the strength was severely reduced (Fig.
11).
Screening studies at KAPI34 indicated only small effects of hydrogen
on strain cycling and creep properties, and essentially no effect on
16
100
-200
-100
100
200
300
400
500
TEMPERATURE (C)
Fig. 9.
Hydride Effect on Impact Properties of Zircaloy-2.
UNCLASSIFIED
ORNL-LR-DWG 56360
REF: CRMet-849, p 50, Fig.17

NORMAL ZIRCALOY-2
O AS FABRICATED
NICKEL-BONDED ZIRCALOY-2 a
AS FABRICATED CORROSION TESTED

IRRADIATED
CORROSION TESTED IRRADIATED
"B"
o
fD a
oN
\
-s.
ft
\
B\
~\
10
\
^-u
10
"\
^
-\
10
HYDROGEN CONTENT(ppm)
Fig. 10.
Effect of Hydrogen on Elongation of Zircaloy-2.
17
REF: CRMet -849, p 50 , Fig. 16

NORMAL ZIRCALOY-2
O
a
NICKEL-BONDED ZIRCALOY-2
a a AS FABRICATED
AS
FABRICATED
TESTED
CORROSION
CORROSION TESTED IRRADIATED
IRRADIATED
(X10)
80
xx-roV^fr-
S 70
x 60
Ua
*=L==-=4%=*%-- \
-\
\
V
I 50
Ld
CE
1en
40
^ 30
CO
\ "\
S 20
10 0
10u ^
10'
I02
HYDROGEN CONTENT (ppm)
103
104
Fig. 11.
Effect of Hydrogen on Tensile Strength of Zircaloy-2.
tensile properties at 600F for hydrogen levels up to 500 ppm.
Effects
of simultaneous hydrogen pickup and neutron irradiation have not yet been
clearly assessed, although limited data suggest no significant change In

expected behavior.
These data obviously are not extensive enough to reliably predict
tolerable hydrogen levels for long-term reactor operations.
It appears,
however, that an upper limit of 500 ppm of hydrogen could be suggested
for wrought Zircaloy-2.4
Chalk River designers,5'19 taking a very con
servative approach, established the hydrogen solubility limit in Zircaloy-2
as a maximum tolerance level for the design of pressure tubes for D20-
moderated natural-uranium reactors.
Their contention was that any pre
cipitated hydride would have a deleterious effect on the properties of

Zircaloy-2.
Predicted Pickup of Hydrogen During Reactor Service

Data on hydrogen pickup by Zircaloy-2 is generally in an unsatis
factory state,5 as indicated by the nonreproducibility of experimental

measurements and inadequacy of experimental methods. Investigators still
18
do not have a fundamental understanding of the mechanism of hydrogen pickup.

Any prediction can be no more than an extrapolation of available data,
and one must bear this in mind when evaluating the following information.
Calculated hydrogen pickup data* for Zircaloy-2 and Zircaloy-4

plates under design conditions of the N.S. SAVANNAH reactor are plotted
in Fig. 12. The assumption was made that the plates would be corrosion
^Detailed results are included in the Appendix (Table 2)
700
10
15
20
25
IN-REACTOR SERVICE (yeors)
Fig. 12.
Prediction of Hydrogen Pickup by Zircaloy-2 and Zircaloy-4
Plates in the Core of the N.S. SAVANNAH Reactor.
19
tested prior to use, although this contribution to hydrogen pickup was

almost negligible. The assumed Zircaloy-2 surface temperature of 572F
was somewhat higher than the design temperature of 546F but was one for
which data were available. Cool-region concentration of hydrogen was
neglected because of the very small thermal gradients existing in the
reactor. Corrosion rates of 0.02 mg/dm2/day were used for the pretransi tion period and 0.03 mg/dm2/day for the posttransition period.5
Corrosion was considered to occur on both sides of the plates which make up the fuel element container. Hydrogen pickup was estimated to be
30$ of the theoretical amount produced in the corrosion reaction during

corrosion testing and 100$ during exposure in the reactor. Out-of-pile
This
corrosion-rate data were used to calculate available hydrogen.
method gives values in agreement with measured values of hydrogen content
in fuel sheathing.14 Zircaloy-4 data were calculated on the basis that its hydrogen pickup5 was one-third that of Zircaloy-2.5
4. PHYSICAL PROPERTIES
Hot-rolled, vacuum-annealed Zircaloy has a density32 of 6.570 0.0006
g/cm3 at 20C and a melting point of 3360F.

(see also Table 1 of Appendix).
from the expression
Data33 on the coefficient of
thermal expansion as a function of temperature are presented in Fig. 13
The thermal expansion may be calculated
L = L0[0.99983 + (5.628 X 106)T + (l.58l X 10"9)T2]
and then the coefficient of expansion corresponding to a particular tem

perature T can be obtained from the following equation:
L0 &P
L0 dT
dL
(5.62 X 10-6) + (3.162 X 10"9)T ,
where T is in C.
The constants in these expressions were obtained for
25$ cold-rolled and annealed Zircaloy-2 plate.
No anisotropy was de
tected, although work on zirconium34 had indicated otherwise.
20
UNCLASSIFIED
ORNL-LR-DWG
56363
< 'o
o
CO
4.0
3.9
<
Q. X
w
<
3.8
5
en
FLi_
3.7
O
F-
z
LU O Li_ Li_ LU
3.6
3.5
3.4
3.3
100
200
300
400
500
600
700
800
900
1000
TEMPERATURE (F)
Fig. 13.
of Temperature.
Coefficient of Thermal Expansion of Zircaloy-2 as a Function
Data on electrical resistivity are sensitive to specimen history. The electrical resistivity of Zircaloy-2 at room temperature has been
reported2'4 as 29 X 10"6 ohm-in. and as 25 X 10"6 ohm-in.

Data on thermal conductivity are presented in Fig. 14. variation exists in the data from the sources cited.2,3^33
Temperature,
Considerable
cold work, and impurity effects have not been well established.
No data on the specific heat of Zircaloy-2 were found; however, the

small alloy content would not be expected to effect a large deviation from the values for zirconium.
Fig. 15.
The data for zirconium are presented in
Two allotropic forms occur in Zircaloy-2:
an alpha phase (close-
packed hexagonal) up to approximately 1480F and a beta phase (bodycentered cubic) which is stable above approximately 1770F to the melt
ing point, 3360F. These transition temperatures are sensitive to heat
Although
ing and cooling rates, and thus may vary as much as 50 to 100F.
data are meager, there are reports of dimensional instability resulting
from thermal cycling through the transition range.2-*35
21
9.2
8,8
REF
A REF 3
O REF 33
t 8-4
---
*^
>-
,^-A-A
1
o ^
|7.6
o z> Q
I 72
<
S
cr
w
F-
6.8
'^\
0 100 200 300 400 500 600 700 800 900 1000
TEMPERATURE (F)
Fig. 14.
perature .
Thermal Conductivity of Zircaloy-2 as a Function of Tem
UNCLASSIFIED
ORNL-LR-DWG 56365
0.088
"s^
0.084
u_
-
0.080
s
<r
0.076
LJ
0_
0.072
/
!
200
400
600
800
1000
1200
1400
TEMPERATURE (F )
Fig. 15.
Specific Heat of Zirconium as a Function of Temperature.
22
5.
MECHANICAL PROPERTIES
The mechanical properties of Zircaloy-2 are considered reasonably good in a high-temperature water environment. ever, quite sensitive to specimen history. These properties, are, how
Even small variations in the
exact details of the fabrication procedure can affect the preferred ori
entation and the resulting mechanical properties.36
Impurities oxygen,
Radiation effects
nitrogen, and hydrogen also significantly affect mechanical properties,

although the mechanism and degree are not always known. on mechanical properties are discussed in Section 7.
Tensile Properties
Zircaloy-2 shows the typical stress-strain relationship of nonferrous
metals (Fig. 16).
Since tensile properties are dependent on specimen
history, a so-called "base-annealed" condition (annealed at 1382F in

vacuum for approximately 20 hr, and furnace cooled in vacuum) is used here
as a reference condition.
(xlCT)
100
/
80
'^
50 7o COLD WORK
60
/
^ __ ANNEALED
1
40
20
0.10
0.15
0.20
0.25
STRAIN (in./in.)
Fig. 16.
Typical Stress-Strain Relationship for Zircaloy-2,
23
Averaged data showing the effect of temperature on tensile prop
erties36-42 and elongation are plotted in Figs. 17 and 18.
Anisotropy
is clearly shown, with yield strength and ultimate strength generally

being affected in opposite direction.
A statistical study42 was performed on tensile-strength data from

a large number of samples of more than 100 different ingots. The spread of the data, which was reported as a standard deviation, was attributed
primarily to measurement errors, heat treatment effects, and specimen heating time. As-welded data were also reported because of their im The data from this study are presented in
portance in stress analysis.

Table 3.
Table 3.
Tensile Strength of Zircaloy-2
Longitudinal Specimen
At Room
Transverse
Specimen
As-Welded
Specimen
At Room
At Room
Temperature
At 600F
Temperature
56 200
At 600P
Temperature
59 600
Ax, 600CP
'iield strength at 0.2%

offset, psi Standard deviation, psi
Ultimate Strength, psi
38 900
15 000
19 800
24 800
5 600
68 400
4 600
1 300 33 100 2 100
5 400 65 400
4 700
2 300
5 700
2 600
36 000 3 000
29 400
1 300
78 400
6 000
Standard deviation, psi
The tensile strength of Zircaloy-2 is increased (with consequent

reduction in ductility) when the material is cold worked, as shown in
Figs. 19 and 20.
The da.ta39 A3~A5 were, in general, obtained from speci

Ratios were also calculated3 from averaged
mens with similar histories.
data to show tne trend of tensile and ductility properties as a function
of cold work and temperature (Figs. 21 and 22).
One study37 indicated
that a temperature of approximately 800F was necessary before any signifi
cant loss of strength induced by cold work occurred with time (up to
500 hr). Initial cold working tended to reduce anisotropy in Zircaloy-2
plate and tubes.5
Hot-rolled plates were shown to have isotropic tensile

Further cold working increased anisotropy
properties at 20fo cold work.
24
UNCLASSIFIED
ORNL-LR-DWG 56367
90,000
90,000
Ref: Zr DATA FILE, BULLETIN NO. 5,

80,000
CARBORUNDUM METALS CO.
70,000
70,000
60,000
60,000
w
S 50,000
^
CO
50,000
50
ft
40,000
40,000
30,000
30,000
20,000
20,000
YIELD
STRENGTH^
10,000
10,000
200
400
600
800
1000
1200
200
400
600
800
1000
1200
TEMPERATURE (F)
TEMPERATURE (F)
Fig. 17. Effect of Temperature on Longitudinal Tensile Properties of Annealed Zircaloy-2.
Fig. 18.
Effect of Temperature
on Transverse Tensile Properties of Annealed Zircaloy-2.
UNCLASSIFIED
ORNL-LR-DWG 56369
2.0
REF: HW-60908 ,p.63,Fig. 4
or
lu z
or h
1
<
YIELD
2
o
o
Q
z
u
< LU 0^ Q
Ll
16 I-"
-I
<
c/> lu
/?
//
^
0
.-,
STRENGTH
t
ULTIMATE STRENGTH
</> lu
<
CD
1.4
1.2 10
20
30
40
50
60
70
COLD WORK (%)
Fig. 19.
Effect of Cold Work on the Ultimate and Yield Strength of
Zircaloy-2 at Room Temperature.
1.2
REF: HW-60908, p. 63, Fig. 14 A
REDUCTION OF AREA
lu z or o
or r_
or o
0.6
TOTAL . ELONGATION
or
\
0.4
6
O
0.2 20
30
40
50
60
70
COLD WORK (%)
Fig. 20.
Effect of Cold Work on the Elongation and Reduction of Area
of Zircaloy-2 at Room Temperature.
26
H P c+
p ^
tl) fjq
CD CO
F3 cd *xj 0 HW OQ
DUCTILITY (FRACTION RE
FERRED TO BASE-ANNEAL ED CONDITION AT SAME
4
CD
ro
i-i p c+ ro H
F3
CD
o
TENSILE STRESS (FRACTION REFERREDTO BASEANNEALED CONDITION AT SAME TEMPERATURE)
TEMPERATURE)
o
O O
o
CO
den H-
ro
in
H-
H
CD
TO WOR O
/
/
y
CD o
O O
H)
/
4
c+
H-
N
HO
> /
r~
CD
en
m
-1-
m /
-1
1
5
u
m
-k C) o
H O
VI
I
c
3[
3|
N
(T) o
|CWOLRKD AOREDUCFT,1I0No Hj
33 > -1
o
cTl m
0
!V>
> 1 -H 1
4
O
P
tn
O\
C
5 \
n V
\
O
P H O
c3
4^
'
<D
p
o
CO
\
\
ro
o o
c+
C
O O C
r
r
p
(73
H-
P
O
7K
^rJ
P
o
o
o
c+
H-
O H P^
P
O Hd
o
IM
o o
tv P p p*
O H
P"
ro
F3
n>
i
s:
o 4 fV
but in the opposite direction; that is, the longitudinal yield strength
became greater than the transverse yield strength.
Heating of both hot-rolled and annealed Zircaloy-2 in the beta region
(>1770F) causes roughly a 10% loss in tensile strength, a 20$ increase in yield strength, a 40$ loss in elongation, and a 50% loss in reduction in area.46 Heating within the alpha-beta range (-1480 to -1770F) is
reported to have no effect on strength, although the ductility decreases
with increasing temperature. Quenching from the beta region, which is
typical of welding, provides increased yield strength.

sulting strength increase and ductility decrease.
There is some
indication that Zircaloy-2 is susceptible to age hardening,3 with re

Oxygen, nitrogen, and hydrogen have an influence on tensile properties
of Zircaloy-2. Hydrogen effects were discussed in Section 3. Both oxygen
and nitrogen cause increased strength and decreased ductility 7 (Fig. 23).
In fact, variations in tensile test results from several investigators
are often due to oxygen contamination of the test specimens.
Modulus of Elasticity and Poisson's Ratio
Modulus of elasticity data from several sources (refs. 3, 33, 37,
-41, 48, 4-9) are presented in Fig. 24. Reasonably good linearity with temperature was established; the scatter was attributed to effects of specimen history. Anisotropy of the elastic properties was evident. The
few data available on Poisson's ratio for Zircaloy-2 are presented in
Table 4.
Table 4.
Elastic Properties of Zircaloy-2
Specimen
Condition
Test
Modulus
Temperature
Poisson's
of
(C)
Elasticity
Ratio
X 106
Annealed
27
150
13.9-14.3
0.368-0.380
0.425-0.460
13.3-13.8
14.5 13.9-14.2
Cold worked
27
150
0.382-0.406 0.392-0.432
28
UNCLASSIFIED
ORNL-LR-DWG 56373
NITROGEN CONTENT (wt%)

0.02 0.04 0.06 0.08
0.12
or
LU LU
or
<
o
CC 0.
S
o
or
<
-120
0.2
0.3
0.4
0.6
OXYGEN CONTENT (wt%)
Fig. 23.
Zirconium.
Effect of Oyxgen and Nitrogen on the Tensile Properties of
Impact Properties
Impact properties are of particular importance because of the pos

sibility of rapid crack propagation similar to that observed in ferritic
steels.
Various studies5 have indicated that catastrophic crack propaga

Further
tion will not occur in Zircaloy-2 at room temperature or above.
more, indications are that the decrease in energy to fracture with de

creasing temperature in impact tests is associated with the nucleation of small cracks within the material rather than the rapid propagation of one
crack.
29
UNCLASSIFIED
ORNL-LR-DWG 56374
12
REF
49 48
CONDITION
0
A
STATIC LONGITUDINAL
33
33
10 3 3
37
A V
TRANSVERSE
LONGITUDINAL TRANSVERSE
ANNEALED
37
41
COLD WORKED TRANSVERSE LONGITUDINAL
41
100
200
300
400
500
600
700
800
900
1000
1100
TEMPERATURE (F)
Fig. 24.
perature .
Modulus of Elasticity of Zircaloy-2 as a Function of Tem
Data on hardness and impact strength41'50'51 of Zircaloy-2 are listed

in Table 5 and plotted on Figs. 25 and 26. Beta quenching tends to im
prove the impact strength of Charpy V-notch specimens of Zircaloy-2.
Table 5.
Impact Data on Zircaloy-2
Temperature
Specimen
Condition
Hardness
(F)
Room As
(DPH*)
161
Charpy V-Notch Impact Energy
(ft-lb)
cast
Room Room 392
Beta quenched Beta quenched Beta quenched
180.4
22.5
51
DPH = Diamond-Pyramid Hardness,
30
240
200
160
120
200
400
600
800
1000
1200
1400
1600
1800
TEMPERATURE (F)
Fig. 25.
perature.
Diamond Point Hardness of Zircaloy-2 as a Function of Tem
UNCLASSIFIED
ORNL-LR- DWG 56376
Ref: Zr DATA FILE, BULLETIN NO. 5,

CARBORUNDUM METALS CO. :
LONGITUDINAL SPECIMEN VERTICAL NOTCH
TRANSVERSE SPECIMEN
HORIZONTAL NOTCH
100
200
300
400
TESTING TEMPERATURE PC)
Fig. 26.
Charpy Impact Data on Zircaloy-2.
31
Both oxygen and nitrogen would be expected to cause embrittlement, al
though quantitative data are not available.

tent was discussed in Section 3.
The effect of hydrogen con
Fatigue Properties
Fatigue-test data32>A0>52~54 show that Zircaloy-2 is notch sensitive.

This effect is illustrated in Fig. 27, which also indicates the similarity
between the fatigue strengths of Zircaloy-2 and Zircaloy-4.
Modification
of notch geometry in the range Kip = 3 to 9 does not affect fatigue strength
for lifetimes less than 106 cycles as shown in Fig. 28; KT is the theo
retical stress concentration factor. The strain-fatigue properties of
Zircaloy-2 are relatively insensitive to temperature, orientation, and stress concentration magnitude, as shown in Fig. 29.
UNCLASSIFIED
(xlCT
40
ORNL-LR-DWG
56377
Ref
WAPD-
ZH-23, p. 5, Fig.1
II
30
~~
A A 20
ZIF CALOY-2, UNNOTCF

ZIF)CAL0Y-2, notche:
ZIF CALOY-4, UNNOTCF1ED,

ZIFJCALOY-4, NOTCHEC),
ED, KT = 1 KT = 1 , /fr = 3
A>=3
*-
^^
10
f^r___
Kr
IS THEOR ETICAL
STRESS
CONCENTRATION
Ft \CT0R
10D
2
CYCLES TO
5
FAILURE
10
10'
Fig. 27. Reverse-Bend Stress-Fatigue Data for Base-Annealed Zircaloy-2 and Zircaloy-4 Tested at 600F.
32
UNCLASSIFIED
(X 10)
ORNL-LR-DWG 56378
10J
10
CYCLES TO FAILURE
Fig. 28.
Results of Reverse-Bend Fatigue Tests at 600F and Zero
Mean Stress on Base-Annealed Zircaloy-2.
UNCLASSIFIED
ORNL-LR-DWG 56379
O HOLE R.T.
KT= 2.5
HOLE R.T. HOLE 600F TRANSVERSE TO ROLLING DIRECTION
KT = 2.5
HOLE 600F
KT=2.5
D "U" NOTCH R.T. "U" NOTCH 600F
KT=4.0 K?= 4.0
"U" NOTCH R.T. "U" NOTCH 600F "V" NOTCH R.T.
KT = 2.5 KT = 4.0
KT = 4.4
KT = > 6.0
PARALLEL TO
ROLLING Dl RECTION
0 "V" NOTCH R.T. KT=>6.0 ^ "V" NOTCH 600F KT=>6.0

10'
"V" NOTCH 600F
Kr = > 6.0
HEE
-T-t+H-^r=R-IIHH
-NOTE- DATA BASED ON V4 in I , GAGE LENGTH _,_
ZIRCALOY-2-ROLLED (BASE ANN. CONDITION)

NOTCHED SPECIMENS (FLAT) .
.NO
HC2 528
p. B-22,
1SSIFIED
10u
Tl
F TESTS, UNNOTCHED
M-TEMPERATURE TESTS, UNNOTCHED
10 '
103
105
CYCLES TO FAILURE
107
Fig. 29.
Strain-Fatigue Properties of Zircaloy-2.
33
Effects of heat treatment on fatigue properties are indicated in
Table 6.
The strain-fatigue properties of welded Zircaloy-2 are unaf
fected by base annealing in comparison with as-welded unnotched speci mens at 600F; however, stress-fatigue data for the same specimens show
somewhat better properties for the as-welded specimens.53

ture tests
Room-tempera
indicate no difference between as-welded and base-annealed
specimens.
Table 6.
Fatigue Properties of Zircaloy-2 at 600F
Specimen
Condltion
Beta quenched and
alpha annealed Base annealed
Endurance Limit (psi)
^T
Ratl
0.80
0.87
,.
Notch-Sensitivity
Index At
Unnotched
X 103
Notched
X 103
108 Cycles^
0.60
0.85
27.5
28.0
11.0
9.0
Fatigue ratio is the ratio of the unnotched fatigue strength to

the tensile strength.
Notch-sensitivity index = (Kf - l)/(Kt - l), where Kf = ratio of

unnotched fatigue strength to notched fatigue strength and K-p, = ratio of
theoretical maximum stress at notch to nominal stress.
Combined static and alternating stresses tend to decrease the over
all life of Zircaloy-2.
This effect is shown on a modified Goodman dia
gram for a notched specimen with K^ = 9 in Fig. 30.
Creep Properties
The creep characteristics of Zircaloy-2 tend to be sensitive to ther-
mal, mechanical, and chemical factors in the specimen history,

as shown in Figs. 31 and 32.
o/;
>'.>
Tr7
*^Q
>
^ ^
(In the figures in this section the parameters
high and low oxygen content refer to material derived from atmosphericmelted ingots and from vacuum-melted ingots, respectively. Typical
atmospheric-melted Zircaloy contains 1100 to 1200 ppm of oxygen.)

good summary of experimental results is available in ref. 3.
34
UNCLASSIFIED
(x103)
Ref:WAPD-MRK-3, p.B-24, B-3, Classified
ORNL-LR-DWG 56380
ZIRCALOY-2 BASE-ANNEALED
"V"-N0TCHED SPECIMENS, KT =
BENDING FATIGUE TESTS AT 600F,
HEAT 0M-160
25 4 = m
10
15
20
25
30
(x103)
MEAN STRESS (psi
Fig. 30.
Modified Goodman Diagram Showing the Combined Static and
Bending Fatigue Test Results at 600F for Zircaloy-2.
UNCLASSIFIED
5
ORNL-LR-DWG
56381
Z LONGITUDINAL TO ROLLING DIRECTIO N -A TRANSVERSE TO ROLLING DIRECTION

6
1
'
7 5F
A
.
1
1
4
.
u-
_400"F-J
^?-*'
-600F
i^:
^_^î
700F-
A^-
^kZZ^"
900 F
A'
4
"l'^"*
10"' CREEP RATE (%/hr)
10
Fig. 31.
Secondary Creep Rate of Zircaloy-2.
Primary creep strain in annealed Zircaloy-2 is almost entirely
stress sensitive, whereas secondary creep rates appear to be mainly tem perature sensitive. The major mode of deformation in creep is apparently
by slip.
In the case of 15$ cold-worked Zircaloy-2, the primary creep
strain is both stress and temperature sensitive, as shown in Fig. 33.
35
UNCLASSIFIED
ORNL-LR-DWG 58521 ON
500
REF: HW-60908, p. 80, FIG
21
200
V O
ANNEALED, 450F, LOW 0 ANNEALED, 550 F, LOW 0 ANNEALED, 650F, LOW 0
UNCLASSIFIED
ORNL-LR-DWG
56382
100
A
J
15 7 CW, 550 F, LOW 0

15% CW, 650 F, LOW 0 ANNEALED, 700 F, HIGH 0
15% CW. 482F. HIGH 0
Ref: HW-60908, p. 82, Fig. 23

50
60
15% CW
fifi?F
HIGH 0
.COLD WORKED (10- 25%), LOW

OXYGEN CONTENT
50
i 20
1
< or
7 i
10
'5
40
/
LU
'
30
or o >or
<
20
*i
i
/ *1 /
^ j-
10
-/r.
/
400 500 600 700 800 900
..
SO*
a P
rf
1000
0.5
_i,-A_A l-A kr^ yf V
.'
/
/2
/
TEMPERATURE (F)
Fig. 32. Effect of Oxygen on An nealed and Cold-Worked Zircaloy-2 at a
J x -//
*>' y ''"
*
'
Creep Rate of 1 X 10-4 $/hr.
0.2
/
10 20
y
30 40
60
0.1
(x 103)
STRESS (psi)
Fig. 33.
Primary Creep Strain of Zircaloy-2.
Considerable work on creep testing of cold-worked Zircaloy-2 has been
performed in conjunction with reactor development at Chalk River5 and
Battelle37 which indicates that, at temperatures less than 650F, cold

work of up to 25% essentially doubles the creep strength of Zircaloy-2.
Within the range 13 to 25%, the degree of cold working appears to have
very little effect on the creep rate of the cold-worked Zircaloy.
For long-term operation, it is necessary to know the time for onset
of the third stage of creep ($3). cannot be confidently done.3
On the basis of present data, this
Available information indicates a linear
relation between log 03 and stress for a given stress and test material,
as shown in Fig. 34. Impurity content and temperature are major variables.
Other data5 indicate that third-stage creep in 13 to 25%o cold worked

Zircaloy-2 at 300C and 16 500 psi occurs at approximately 2%> total plastic
strain and that first-stage creep represents approximately
Ref: HW-60908, p. 84, Fig. 24
0.08$ total plastic strain.
GROUP AÂNNEALED> HIGH OXYGEN CONTENT 10M
[O ANNEALED
'
-0- B{-^ -- --) LOW OXYGEN CONTENT *> ^ !& COLD ^S H'GH *YGEN C0NT
[a ANNEALEDj
Thus, for a secondary creep
rate of 5 X 10"6$/hr (typical

for N.S. SAVANNAH design con
ditions), approximately 47 years

would be required to reach third-stage creep.
10
Even though not considered
completely reliable, long-term
creep predictions3 have been

made that are based on experi
10'
mental data (Fig. 35).
The
principal uncertainties are the previously mentioned third-
stage creep and the possibility

of recurrence of primary creep
10
50
(X103)
under cyclic temperature, stress,

and radiation conditions of inreactor service. Data have
Fig. 34. Time for Onset of ThirdStage Creep in Zircaloy-2.
37
UNCLASSIFIED
ORNL-LR-DWG 56384
(xlO3
Ref: HW-60908, p.85, Fig. 25
O 15 7o COLD WORK, HIGH OXYGEN CONTENT

50
157o COLD WORK, LOW OXYGEN CONTENT
T ANNEALED,LOW OXYGEN CONTENT
40
co
30
20
10
>10 years
400
500
600
700
800
900
TEMPERATURE (F)
Fig. 35.
Long-Term Creep Predictions for Zircaloy-2,
been obtained in relaxation tests36 that indicate a 15 to 50% increase in

creep rate at 900F.
Torsional Properties
Data obtained on the torsional properties56 of Zircaloy-2 are pre

sented in Table 7. One effect not evident is the lower hydrogen content
of the base-annealed material.
(Base-annealing removes hydrogen from
the material; for example, 50 ppm in a hot-rolled specimen would be re
duced to 10 ppm.)
38
Table 7.
Torsional Properties of Zircaloy-2
Specimen
Condition
Torsional
Elastic Modulus
Torsional
Torsional Yield
Proportional
Limit (psi)
Stress at 0.2$ Offset (psi)
X 106
Base annealed
Base annealed
5.24
5.29
17 850
19 450 13 550
29 000 32 100 29 500
Hot rolled
Hot rolled
5.22
5.22
13 700
28 300
Fabricability
Zircaloy-2 has been fabricated by almost all the known metal-working
operations, although those operations requiring elevated temperatures

must be performed in an inert atmosphere to prevent oxygen and nitrogen
contamination.
Extrusion, drawing, casting, and welding have been suc
cessfully done with Zircaloy-2.
Welding techniques have been developed57

Obtaining a good weld
that do not require expensive gas-chamber setups.
between Zircaloy-2 and stainless steel is difficult, however, because

of the large difference between the respective coefficients of thermal
expansion.
Riveting is apparently a feasible joining method, but it has
the possible disadvantage of creating a more susceptible corrosion area.
The principal defect resulting from fabrication is the occlusion of

a gas void or intermetallic compound near the metal surface; such a region
is susceptible to excessive corrosion.

defect.
This is usually called a "stringer"
The practice of vacuum-melting ingots has greatly reduced the
incidence of "stringers."
Cracks have been observed in the cladding of newly fabricated fuel
elements, but the exact source of the trouble has not been determined.58
Occurrence of such defects is not always detected by the eddy-current
method of Inspection, and in certain cases the use of the more expensive ultrasonic inspection procedure is being considered. No completely sat
isfactory nondestructive inspection method has been developed for detecting
defects less than 5 mils deep.
In some cases,59 the cladding material is
39
being changed from Zircaloy-2 to stainless steel because of the possi
bility of major defects propagating from long-term radiation exposure of

these undetected hairline cracks.
During the latter phases of fabrication of the Shippingport reactor
fuel tubes,60 the over-all yield from ingot to finished mill product was
45$, and acceptability of the tubes was 98$.

6. NUCLEAR PROPERTIES
An important feature of Zircaloy-2 is its low thermal-neutron-
absorption microscopic cross section, which is reported to be 0.22 to 0.24

barn.32'41 Pure zirconium has a 0.l8-barn cross section; 0.015 to 0.02
barn is contributed by the alloying agents, and the remainder comes from
impurities in the metal.

in ref. 61.
Cross-section dependence on energy is discussed
Natural zirconium has an atomic number of 40 and is composed of five
isotopes, the average atomic weight being 91.22 (Table 8).
For neutron
energies less than 2 Mev, all reactions are (n,5) reactions, whereas at
higher energies, (n,p) reactions can occur.62 Neutron absorption yields the stable isotopes Zr91 and Zr92 and the unstable isotopes Zr93, Zr95, and Zr97, which undergo beta decay accompanied by gamma emission (Table 9).63 A few data are available on capture gamma rays64 which indicate
Table 8.
Isotopic Com
position of Natural
Zirconium
Isotope
Abundance
($)
Zr90 Zr91
Zr92 Zr94 Zr96
51.5
11.2
17.1
17.4 2.80
40
Table 9.
T , Decay
Mode
P,7
p,y
Decay Data on Zirconium Isotopes63

TT , T._ Radiation and Energy8(Mev)
/.. -,
Isotope
,, -,
Half-Life
Zr93 Zr95 Zr97
9 X 105 years
65 days
p"(0.063)
P~(0.37,0.84), 7(0.72,0.23) P"(1.91), 7(0.75)
P,7
17 hours
Beta energies are maximum values; the average energy
is approximately 40$ of the maximum energy.
that in approximately 18$ of the neutron captures in natural zirconium,

a gamma ray with an energy of 6 to 8 Mev is emitted.
7.
RADIATION EFFECTS
Mechanical property changes have been the principal effects observed
upon neutron irradiation of Zircaloy.
Although data are not available
for reliable predictions for a fast-neutron* dose of 1023 neutrons/cm2,

trends have been indicated by tests at lower exposures. Irradiations to
fast-neutron doses of up to 6 X 1021 neutrons/cm2 have caused an increase

in strength and a decrease in ductility. The data are scattered, how
ever, and consequently precise correlations with integrated flux are not
possible. Existing data have indicated saturation effects only on the
properties of hardness and electrical resistivity.
Most of the mechanical property data presented in this section were
obtained in pressurized-water reactors60;65 with a water temperature of
approximately 475F and a fast flux of 0.75 to 5.11 X 1014 neutrons/cm2-sec,

When available, fast-flux values are reported, because thermal-neutron
effects in metals are insignificant in comparison with those caused by
fast neutrons.
Thus far, all in-reactor experience has been with Zircaloy
as fuel cladding.
*In this report, fast neutrons are defined as those having an energy
of 0.65 Mev or greater.
41
The stress-strain characteristics of Zircaloy-2 are altered by fast
neutrons in a manner similar to the effect of cold-work (Fig. 36).
The
yield strength increases faster than the ultimate strength; the total
elongation is reduced; and the uniform elongation is reduced to almost
zero, as shown in Figs. 37 through 40.
At an integrated flux level of
approximately 1021 neutrons/cm2, the yield strength and ultimate strength

are essentially equal. The data show, however, that sizeable reductions
in area (~20 to 40$) can still occur after a dose of 6 X 1021 neutrons/cm2
(Fig. 41). Thus, Zircaloy-2 appears to retain the ability to deform
in spite of locally in a plastic manner rather than by brittle fracture,
the reduction in uniform elongation.
Other postirradiation mechanical tests65 have shown hardness to be
dependent on total flux level (Fig. 42).
Strain-fatigue tests60 showed
UNCLASSIFIED
ORNL-LR-DWG 56385
-l^l
Ref: WA PD-TM-184, p.15,F
g. 2, Classified
i \ IRRADIATED (6.0 x102' neutrons/cm2)

80
70
^^\
-^NONIRRAC
IATED
60
/f'4 r
/
50
" ~
'
40
SPECIMENS TESTED AT
ROOM TEMPERATURE
1
12
16
20
24
28
32
NOMINAL STRAIN (7.)
Fig. 36.
Typical Stress-Strain Curve for Irradiated Zircaloy-2.
42
a reduction of only about 15$ in the bending stress of notched and un notched 0.100-in.-thick plates after a fast-neutron exposure of 5.0 X 1021
neutrons/cm2.
Data on the fatigue properties of irradiated Zircaloy-2
are presented in Table 10.
Table 10.
Fatigue Properties of Irradiated Zircaloy-2
Unirradiated Specimens
tt
Irradiated Specimens6
Unnotched
TT , , , Notched
Unnotched
4. i_ j
Notched
Kt - 3
15 500
Tr
Kt = 3
13 000
Failure stress at 106 cycles, psi

Kf, strength reduction factor0
24 000
21 500
1.55
1.60
q, notch sensitivity
0.275
0.30
factord Fast-neutron exposure of approximately 5.0 X 1021 neutrons/cm2.

K,
c
theoretical stress-concentration factor.
Ratio of unnotched stress to notched stress.
(Kf - l)/(Kt - 1).
UNCLASSIFIED
ORNL-LR-DWG 56386
(xtO
60
TEMPERATURE OF TESTS ROOM TEMPERATURE
O 400F
A 600F
WAPD-TM-184, p. 22
. 19, Classified
2 3 4 5
(x102<)
TOTAL INTEGRATED FAST FLUX (neutrons/cm2)
Fig. 37.
Effect of Fast-Neutron Exposure on the 0.2$ Offset Yield
Strength of Zircaloy-2.
43
UNCLASSIFIED
(X10~
100
ORNL-LR- DWG 56387
(X10
Fig. 38.
Effect of Fast-Neutron Exposure on the Ultimate Tensile
Strength of Zircaloy-2.
UNCLASSIFIED
ORNL-LR-DWG 56388
40
1
TEMPERATURE OF TEST
<
ROOM TEMPERATURE
400 F
pi 30
2
_i
A 600F
O
F-
<
20
3
LU
[
<
Fi
400 AND 600 F
R 10
REF:
|
WAPD-TM-184
-*- IEMPERATURE
r-i
"
< )
, p 23, FIG. 21 , CLASSIFIED
!
2 3 4
1
5
(X10'
Fig. 39.
of Zircaloy-2.
Effect of Fast-Neutron Exposure on the Total Elongation
Preliminary in-pi]e creep data4 indicate that the creep rate may
be somewhat reduced during neutron exposure. No effect has been observed
up to a fast-neutron exposure of 6 X 1021 neutrons/cm2 on the modulus of elasticity.65 Impact properties are apparently dependent on a combina
tion of hydrogen content and flux exposure, although Charpy V-notch tests showed no change in the brittle-to-ductile fracture behavior of Zircaloy-2
specimens containing 8 ppm of hydrogen that were irradiated to a fast-
neutron exposure of 1.9 X 1019 neutrons/cm2 in water at 150 to 200C.
44
20
REF
WAPD-TM-184, p 23 , Fig. 22 , CLASSIFIED
E is'
2
O
<
O
'
TEMPERATURE
O 400 F
OF TEST
ROOM TEMPE RATURE
A 600 F
0
_J LU
10
\\ \
5
cr
0
Li.
i
3
\\oA^8
0
ROOM TEMPERATURE
*
3
400 AND 600" F

4 5
J5A
( X10'
Fig. 40.
of Zircaloy-4.
Effect of Fast-Neutron Exposure on the Uniform Elongation
UNCLASSIFIED ORNL-LR-DWG 56390 70 r
TEMPERATURE
OF TEST
ROOM TEMPERATURE 400F
600F
TOTAL INTEGRATED FAST FLUX (neutrons /cm')
Fig. 41.
of Zircaloy-2.
Effect of Fast-Neutron Exposure on the Reduction in Area
transition temperature increase of 54 to 63F over that for the unirra

diated control specimen was found for a specimen with 130 ppm of hydro
gen. 66>67
More recent data5 indicate, however, that irradiation to doses
of up to 6 X 1021 neutrons/cm2 have no significant effect on the impact

properties of Zircaloy-2.
45
(4)
(6)
_,1
"(6)
fe^.
ROOM-TEMPERATURE TESTS
I
0
INDICATES THE RANGE OF VALUES

INDICATES THE NUMBER OF VALUES REPRESENTED
Ref: WAPD-TM-184, p. 22, Fig.18, CLASSIFIED

1
I 2 I 3 I 4 L_ 5
(X10
TOTAL INTEGRATED FAST FLUX ( neutrons / cm 2 )
Fig. 42.
Zircaloy-2.
Effect of Total Fast-Neutron Exposure on the Hardness of
Work at Chalk River5 has shown that (l) irradiation at temperatures
up to 716F does not increase the rate of recovery of cold-worked
Zircaloy-2, (2) although the ductility of annealed Zircaloy-2 is consid

erably greater than that of the cold-worked material prior to irradiation,
there is little difference after irradiation, and (3) irradiation at 716F

gives a small increase in mechanical properties in comparison with those
of material held at 716F without irradiation. Additional data suggest
that Zircaloy-2 can be used at temperatures up to 752F before thermal softening becomes the dominant factor with respect to mechanical strength.
Postirradiation annealing has indicated that irradiation-induced
effects on hardness and tensile properties can be reduced considerably
by annealing, the annealing temperature and time being dependent on ir
radiation conditions.65
Recovery of properties by annealing appeared

The dependence of strength on exposure tem
to be insignificant at temperatures below 536F, whereas the recovery was
quite pronounced at 716F.
perature3 indicates that nominal effects occur in the temperature range 240 to 450F at ~3 X 1020 neutrons/cm2 (Fig. 43).
Reliable comparison of test data obtained by different investigators
is difficult because of the strong influence of specimen history on
mechanical properties.
In addition, flux and energy-spectra data are
hard to obtain, and generally several experimental conditions differ in
46
UNCLASSIFIED
ORNL-LR-DWG 56392
100
TOTAL INTEGRATED FAST FLUX =~3>
1020 neutrons/cm2
Ref: HW-60908, p. 89, Fig. 26
YIELD STRENGTH 60
40
100
200
300
400
500
600
700
EXPOSURE TEMPERATURE (F)
Fig. 43.
Effect of Irradiation Temperature on the Room-Temperature
Tensile Properties of Zircaloy-2.
the various studies.
A theoretical treatment of radiation-damage models
and considerable experimental information are presented in ref. 68.
Hydrogen Pickup
The effect on hydrogen pickup represents an indirect effect of ir
radiation exposure on mechanical properties, since the resulting hydrogen

embrittlement decreases the ductility and increases the notch sensitivity of Zircaloy-2. This was discussed previously in Section 3. Zircaloy-2-
clad UO2 fuel rods have shown greater hydrogen pickup during reactor ser
vice than would be expected from out-of-pile experiments.25

gen in the water has not been determined.
Whether this
is attributable to irradiation, increased corrosion, or dissolved hydro
Other Effects
In-pile exposure of Zircaloy-2 components in water-moderated reactors
is usually accompanied by the formation of a surface layer consisting
primarily of iron oxide and water, with lesser amounts of other corrosion
products, usually referred to as crud.
In-pile corrosion of the Zircaloy-2
and crud formation are definitely interrelated, although most of the iron
comes from corrosion of steel components in the reactor. Crud settles
out in low-velocity regions in the reactor's primary system and causes
47
objectionable situations by fouling heat transfer surfaces and creating
high activity levels. Long-lived crud activity is primarily due to Co58

and Co60, which are formed by activation of Ni58 and Co59, respectively.
Although these materials are present in the Zircaloys, the principal source
in existing reactors is usually stainless steel, Stellite, or Haynes No.
25 alloy components in the reactor.
The corrosion rate of Zircaloy-2 has not been observed to be signifi
cantly affected by irradiation by some investigators,11-13'24 but more

recent information5;14 has indicated a one- to fivefold increase in the
corrosion rate (see Sec. 3). Buildup of fission products will occur in the primary system cool
ing water of a reactor as the result of uranium impurity in the Zircaloy
(nominal, 1.6 ppm; maximum, 3.5 ppm). Absorption of neutrons by U238

results in the formation of fissionable Pu239 and Pu241. The activity
levels are not high enough, however, to restrict reactor operation.
In-reactor Failure
Fuel elements consisting of UO2 pellets clad with Zircaloy-2 have

been observed to have defects in the cladding after irradiation. Three
failures occurred in 1000 fuel segments irradiated in the VBWR and GETR
as part of a test program.
The segments that failed had longitudinal

Postirradiation
cracks along the high heat-flux portion of the cladding.
examination revealed severe hydride formation in the vicinity of the
cracks and heavy oxidation of the cladding internal surface.
The possi
bility exists that defects of this type might rapidly self-propagate and
eventually lead to disintegration of the fuel element.
Several explanations for these failures have been proposed; for ex
ample, undetected fabrication defects, such as stringers, fission-product

damage, stress-corrosion cracking, hydrogen embrittlement, etc.
8.
HAZARDS OF METAL-WATER REACTIONS
Although the probability of occurrence is very remote during re
actor operation, under certain conditions zirconium can react with water
48
(or steam) with explosive violence.
Such conditions could occur if the

The rate
core overheated as the result of a loss-of-coolant accident.
of heat generation from the Zr-H20 reaction is dependent on the heat of
reaction, rate of reaction, specific area of metal, mixing reactants,

total quantity of metal, and subsidiary heat, such as from combustion of
product hydrogen.
From the standpoint of reactor environment, the most

Heat release from massive
important variable is the metal-particle size.
metal reaction (ordinary corrosion in water) is insignificant, whereas

vaporized metal can react explosively. Core meltdown could produce par
ticles of sizes in the dangerous range, and, depending on core geometry and heat transfer characteristics, the reaction could be self-propagating.
The problem has been studied by several investigators69"71 and all seem
to agree that, although the possibility of a Zr-H20 reaction is very re

mote, the extent of possible damage resulting therefrom warrants a care
ful study of each reactor.
Thermodynamic data72 on the reaction
Zr(liquid) + 2H20(steam) > Zr02 + 2H2

are given in Table 11 and Fig. 44. This reaction can be represented by73
AW =k(T) tn(T) ,
k(T) = A exp (-Q/RT)
where
AW = oxygen weight gain, g/cm2, k(T) = rate constant,

t = time,
n(T) = temperature dependent exponent,

A = constant,
Q = activation energy, cal/mole, R = gas constant, cal/K-mole,

T = absolute temperature, K.
Calculated values of corrosion are presented in Fig. 45.
49
UNCLASSIFIED
(X 10^
40
ORNL-LR-DWG 56394
/
/
/ /
OXYGEN WEIGHT GAIN, ISW =k (r)/"m,

WHERE / IS
30
TIME
BOSTROM'S DATA
~~ EXTRAPOLATIONS
Ref. 72
// // //
-
1.00
0.80
20
-
0.60 5
/
/ /
/
y
/
10
X
X
0.40 ~ /
/
s
>
--"'
0.20
800
1200
1600
2000
TEMPERATURE (K)
Fig. 44.
High-Temperature Metal-Water Reaction Curves for Zircaloy.
Table 11.
Thermodynamic Data of the Liquid Zirconium-
Steam Reaction69^72
Temperature
K
AHy,
k(T) x 104
C F
n(T)
cal/mole
-144 320
ca
il/g of Zr
6.31
1400
1500 1227
0.462
0.552 0.66
2241 2421 2601
1600 1700
1327
1424
1527
-143 970 -143 660
-1582 -1578
-1575
-1571
9.6*
15.2
1800
1900
2781
2961
1627 1727
-143 280 -142 990
-1568
-1564
-1561
2000a
2100 2200
3141
3321
-142 680
-142 352
25.0 43.6
0.784
0.945
1827
1927
3501
-142 024
-1557
aFor temperatures above 2000K, the data are extrapolated on the basis that AEL decreases uniformly by 3.28 cal/mole-"K.
50
UNCLASSIFIED ORNL- LR- DWG 56393
17, 300
1730
173
17.3
o
_l
1.73
<
<
0.173
0.0173
CORROSION TIME (sec)
Fig . 45.
Oxidation Constants for Zirconium.
For precise evaluation of hazards associated with Zr-H20 reaction,

the present state of knowledge is inadequate. The principal deficiencies
are in the determination of the metal particle size and the understanding
of the heat transfer mechanism.69
However, calculations based on assumed
models for pressurized-water reactor accidents have been performed.70'7

In no case did the added heat of the metal-water reaction significantly
alter the over-all situation.
Even if core meltdown occurred, the prob
ability of an extensive Zr-H20 reaction would be very low because heat trans
fer out of the core would be sufficient to inhibit the reaction. In a test
at Chalk River74 a Zircaloy-2-clad U02 fuel element was intentionally melted

in a pressurized-water loop and only a limited reaction was observed.
51
9.
OTHER ZLRCONIUM-BASE ALLOYS
Development work on zirconium-base alloys is being performed by
many investigators.19;5 j75
The primary aim of most work to date has

Although still in the devel
been to increase mechanical strength while maintaining corrosion resist ance and low-neutron-absorption properties.
opment stage, the binary zirconium-niobium and the ternary zirconium-tinniobium alloys appear to be the most promising. For the application con
sidered here, however, the limited technology available on these alloys

prohibits their use.
Zircaloy-4 was developed to provide an alloy with greater resistance

to hydride formation and its resulting embrittlement. Information pre
sently available5'40 indicates no significant differences between the

properties of Zircaloy-4 and Zircaloy-2 at temperatures up to 572F, ex
cept with respect to hydride pickup. The hydrogen pickup of Zircaloy-4
is substantially lower than that of Zircaloy-2 (Fig. 6).
Kass and
Kirk23'26'76 report only 10 to 15$ corrosion hydrogen pickup by Zircaloy-4

as compared with 40 to 55$ by Zircaloy-2. Elimination of nickel (deter
mined to be a hydrogen getter) from Zircaloy-2 produced the desired ef
fects.
Thus, Zircaloy-4 contains 1.2 to 1.7$ Sn, 0.12 to 0.18$ Fe, 0.05
Since
to 0.15$ Cr, and the balance Zr, with a maximum of 0.007$ Ni.
nickel is insoluble in alpha zirconium, this change would be expected to

cause no effect on mechanical properties; and this has been found to be
true.
52
REFERENCES
1.
G. E. Kulynych, Nuclear Merchant Ship Reactor, Final Safeguards Report, Volume I, Description of the N.S. SAVANNAH, BAW-1164
(June 1960).
2.
3.
B. Lustman and F. Kerze, The Metallurgy of Zirconium, McGraw-Hill,

New York, 1955.
G. E. Zima, A Review of the Properties of Zircaloy-2, HW-60908
(Oct. 14, 1959). 4.

5.
R. J. Alllo, Behavior of Zirconium-Base Alloys and Hafnium in LongLived Cores, KAPL-2088 (May 5, 1960). Classified E. C. W. Perryman, A Review of Zircaloy-2 and Zircaloy-4 Properties
Relating to the Design Stress of CANDU Pressure Tubes, CRMet-937
(June 1960).
6.
G. J. Biefer, L. M. Howe, and A. Sawatsky, Hydrogen Pick-Up In

Zirconium Alloys, A Review of Data up to June 1, 1959, CRMet-849
(September 1959).
7.
8.
Quarterly Progress Report - Fuels Development Operation for January,

February, and March, 1957, HW-49803 (Apr. 15, 1957). Classified
S. H. Bush, Properties of Zirconium and Zircaloy-2 and Alternate
Reactor Structural Materials for the DPR, HW-33248 RD (Sept. 30, 1954).
9. Bettis Technical Review, Reactor Metallurgy, WAPD-BT-2 (July 1957).
-^^ - f
10.
11.
Bettis Technical Review, Reactor Metallurgy, WAPD-BT-10 (October 1958).

G. E. Galonian et al., Effect of Radiation on the Corrosion of
Metallic Materials in 580F Water, KAPL-M-GEG-4 (Nov. 11, 1955).

12. B. Cox, The Effect of Solution Composition and Radiation on the High
Temperature Aqueous Corrosion of Zirconium and its Alloys, HARD(C)P 44

(July 1957).
13.
J. K. Dawson, B. Cox, R. Murdock, and R. G. Sowden, "Some Chemical Problems of Homogeneous Aqueous Reactors," Proceedings of Second United
Nations International Conference on the Peaceful Uses of Atomic Energy,
Geneva, 1958, Vol. 7, p. 234, United Nations, New York, 1958. 14. W. Evans and F. H. Krenz, The X-2 (t) Test, Examination of Hydrogen
Pick-Up in Specimen LR, Exp-NRX-2904 (February 1960).
53
15.
Bettis Technical Review, Reactor Metallurgy, WAPD-BT-15 (September

1959).
16.
I-Ming Feng and B. G. Rightmire, "An Experimental Study of Fretting,"
Proc. Inst. Mech. Eng. 170, 1055 (1956).

17. I-Ming Feng and B. G. Rightmire, "The Mechanism of Fretting,"
Lubrication Eng. 9, 134 (1953). 18. F. H. Krenz, G. J. Biefer, and N. A. Graham, "Chalk River Experience
with Zircaloy-2 and Aluminum-Nickel-Iron Alloys in High-Temperature
Water," Proceedings of Second United Nations International Conference

on the Peaceful Uses of Atomic Energy, Geneva, 1958, Vol 5, p 2418,
United Nations New York, 1958.
19. AECL Industrial Symposium on Equipment Manufacturing and Development
Problems for Nuclear Power Systems, Chalk River, Ontario, April 19
and 20, 1960, AECL-990.
20.
D. A. Vaughan and J. R. Bridge, "High Temperature X-Ray Diffraction
Investigation of the Zr-H System," J. Metals, 528-31 (May 1956).

21. A. Sawatzky, The Diffusion and Solubility of Hydrogen in the a
Phase of Zircaloy-2, CRMet-826 (February 1959).

22. K. M. Goldman and D. E. Thomas, Hydrogen Pick-Up during Corrosion
Testing of Zirconium and Zircaloy-2, WAPD-MM-184 (Feb. 19, 1953).

23. W. W. Kirk, "Corrosion and Hydrogen Pick-Up of Zircaloy-2 and Zircaloy-4,"
1959).
24. J. D. Eichenberg, R. M. Lieberman, and F. P. Mrazik, Irradiation of
pp 814 in Zirconium Highlights, WAPD-ZH-21 (December
U02 Fuel Rods - The X-l-L Experiment, WAPD-208 (April 1960).

25. S. Kass, Report of October 1954 Meeting of the Zirconium Alloy
Corrosion Committee, WAPD-MM-713 (Nov. 30, 1954). 26. S. Kass and W. W. Kirk, "Corrosion and Hydrogen Evaluation of Nickel-
Free Zircaloy-2," pp 1-A- in Zirconium Highlights, WAPD-ZH-15 (March

1959).
27.
C. M. Schwartz and M. W. Mallett, "Observations on The Behavior of
Hydrogen in Zirconium," Trans. A.S.M. 46, 640 (1954).

28. M. W. Mallett and W. M. Albrecht, "Low-Pressure Solubility and Diffu
sion of Hydrogen in Zirconium," J. Eleetrochem. Soc. 104, 142 (1957).
54
29.
J. M. Markowitz, Hydrogen Redistribution in Zircaloy-2 under Thermal and Mechanical Stress Gradients, WAPD-TM-171 (January 1959).
30.
31.
B. Lustman and J. G. Goodwin, "Zirconium and its Alloys," Reactor

Handbook, 2nd ed., Vol. I, pp 708-38 (i960).
W. Yenlscavich, R. A. Wolfe, and R. M. Lieberman, IrradiationInduced Hydrogen Absorption of Nickel-Enriched Zircaloy-2: The WAPD-
29-14 Experiment, WAPD-T-912 (November 1958).
32.
33.
L. S. Rubenstein, "Properties of Zircaloy-2," Nucleonics 17 (3), 72

(March 1959).
Reactor Technology Report No. 8 - Metallurgy, KAPL-2000-5 (March 1959).
34.
35.
36.
R. K. McGeary and B. Lustman, "Preferred Orientation in Zirconium,"

Trans. AIMME 191, 994-1002 (1951).
Pressurized Water Reactor (PWR) Project Technical Progress Report

for the Period February 24, 1958 to April 23, 1958, WAPD-MRP-73. Metallurgy Division Annual Progress Report for Period Ending July 1, 1960, 0RNL-2988.
37.
F. R. Shober et al., The Mechanical Properties of Zirconium and
Zircaloy-2, BMI-1168 (Feb. 18, 1957).

38. J. Weinberg, "Summary of Mechanical Property Data on Vacuum Melted
Zircaloy-2," pp 12-14 in Zirconium Highlights, WAPD-ZH-12 (November

1958).
39. W. D. McMullen, Interim Report on Creep Behavior of Zircaloy-2 and
Zircaloy-3, WAPD-TM-132 (April 1958). 40. J. G. Goodwin and F. L. Shubert, "The Effects of Primary Processes
on the Properties of Zircaloy-4," pp 1-6 in Zirconium Highlights,

WAPD-ZH-23 (March 1960).
41.
42.
Zirconium Data File, The Carborundum Metals Company, Akron, New York.
J. G. Goodwin and F. L. Schubert, "The Tensile Properties of
Zircaloy-2," pp 1-14 in Zirconium Highlights, WAPD-ZH-25 (October 1960)

43. R. S. Kemper and D. L. Zimmerman, Neutron Irradiation Effects on the
Tensile Properties of Zircaloy-2, HW-52323 (Aug. 22, 1957).

44. A. B. Burgess and W. S. Kelly, The Effect of Neutron Irradiation at 100 C and 200 C on the Mechanical Properties of Cold-Worked Zircaloy-2,
HW-52004 (Aug. 21, 1957).
Classified
45.
A. B. Burgess and T. G. Edwards, Elevated Temperature Tensile
Properties of Zircaloy-2, HW-51722 (August 1957).

46. J. G. Goodwin et al., Progress Report on Metallurgical Studies of
Zirconium Alloys, November 15, 1957 to February 15, 1958, WAPD-NCE-
7532 (Feb. 15, 1958). 47. C. Tyzack, "Zirconium and its Alloys," Nuclear Engineering 3 (24), 102
(March 1958). 48. R. L. Mehan, Modulus of Elasticity of Zircaloy-2 Between Room
Temperature and 1000F, KAPL-M-RLM-16 (July 3, 1958).

49. H. A. Sailer, R. F. Dickerson, and E. L. Foster, Induction-Melted
Zirconium and Zirconium Alloys, BMI-908 (March 18, 1954).

50. H. Loevenstein and H. L. Gilbert, Zirconium; A Review and Summary
of Published Data, AECU-3818 (October 1958).

51. J. A. De-Mastry, F. R. Shober, and R. F. Dickerson, Development of
High-Strength Corrosion-Resistant Zirconium Alloys, BMI-1418 (Feb. 22, 1960). 52. J. Hino, "Metallurgy of Zirconium and Hafnium, Zircaloy Evaluation,"
p B-36, Sec. I03b44 of Technical Progress Report Materials Depart-
ment - for the Period December 16, 1958 to March 31, 1959, WAPD-MRK-1.
Classified.
53.
J. Hino, "Metallurgy of Zirconium and Hafnium," p B-20, Sec. 111B44

of Technical Progress Report Materials Department for the Period
June 26, 1959 to September 25, 1959, WAPD-MRK-3.
Classified.
54.
K. M. Goldman and J. Hino, "Metallurgy of Zirconium and Hafnium,"

p B-21, Sec. Illb44 of Technical Progress Report Materials Depart
ment for the Period September 26, 1959 to December 25, 1959,
WAPD-MRK-4. Classified.
55.
P. J. Pankaskie, Interim Report on Creep Characteristics of Zircaloy-2,
HW-59383 (Mar. 25, 1959).

56. R. E. Johnson, "Torsional Properties of Zircaloy-2 and Zircaloy-3,"
pp 49-56 Bettis Technical Review Reactor Metallurgy, WAPD-BT-10
(October 1958).
56
57.
C. N. Spalaris, "Fabrication of Zircaloy-2 Channels for Vallecltos
Boiling Water Reactor Fuel Assemblies," Nuclear Sci. and Eng. 6,
37--43 (1959).
58.
59.
"Dresden Down Till January; Zircaloy Tube Fault Sought," Nucleonics

18 (l), 18 (January 1960).
"Dresden To Get Stainless Steel Core," Nucleonics 18 (9), 25

(September 1960).
60.
61.
B. Lustman et al., "Zircaloy Cladding Performs Well in PWR,"

19 (l), 58-63 (January 1961).
Nucleonics
D. J. Hughes and R. B. Schwartz, Neutron Cross Sections, BNL-325,
2nd ed. (July 1, 1958).

62. N. Tralli, Neutron Cross Sections for Zirconium and Yttrium, APEX-466
(June 30, 1958). 63.

64.
H. Etherington (ed.), Nuclear Engineering Handbook, McGraw-Hill, New York (1958), pp 7-9.
B. B. Kinsey and G. A. Bartholomew, "Neutron Capture Gamma Rays
from Heavy Even-Charge Nuclei," Can. J. Phys. 31, 1051 (1953).

65. G. J. Salvaggio, R. E. Johnson, and S. W. Porembka, Mechanical
Properties of Irradiated S1W Core 3 Zircaloy-2, WAPD-TM-184
(November 1959).
66.
Classified.
Quarterly Progress Report, Metallurgy Research Sub-Section, for July,
August, September 1955, HW-39495 (Nov. 1, 1955).

67. R. G. Wheeler and W. S. Kelly, Irradiation of Zircaloy-2 Impact
Specimens Containing Hydrogen, HW-39805 (Nov. 2, 1955).

68. W. J. Leonard, A Compilation of Effects of Radiation Damage on the
Mechanical Properties of Zirconium and Zircaloy-2, ORNL-CF-60-11-117
(Nov. 7, 1960).
69.
Classified.
VII. Reactor Safety Aspects
L. F. Epstein, Metal-Water Reactions;
of Metal-Water Reactions, GEAP-3335 (Jan. 31, 1960).

70. J. I. Owens, R. W. Lockhart, D. R. litis, and K. Hikido, Metal-Water
Reactions; VIII. Preliminary Considerations of the Effects of a
Zircaloy-Water Reaction during a Loss of Coolant Accident in a
Nuclear Reactor, GEAP-3279 (Sept. 30, 1959).
71.
L. M. Swartz, PWR Loss-of-Coolant Accident Core Meltdown Calculations,
WAPD-SC-544 (May 1957).

72. W. A. Bostrum, The High Temperature Oxidation of Zircaloy in Water,
WAPD-104 (March 19, 1954).

73.
74.
B. Lustman, Zirconium-Water Reactions, WAPD-137 (Dec. 1, 1955).

The Canadian Study for a Full-Scale Nuclear Power Plant, AECL-557
(January 1958).
75. Properties of Reactor Materials, Part I, Proceedings of the Second
United Nations International Conference on the Peaceful Uses of Atomic
Energy, Geneva, 1958, Vol. 5, pp 1310, United Nations, New York,

1958.
76.
S. Kass and W. W. Kirk, "The Effect of Iron and Oxygen Variation on

Corrosion and Hydrogen Uptake Behavior of Zircaloy-4," pp 1-4- in
Zirconium Highlights, WAPD-ZH-24 (May 1960).
58
APPENDIX
Table 1.
Coefficient of Thermal Expansion

for Zircaloy-2a
Instantaneous
Temperature
3F)
Avfê Coefficient
of Expansion from
)F to Indicated
Coefficient of
(in./in./F)
' '
X 10"6
Expansion
Temperature
X 10"6
3.24
3.33
(in./in./F)
212
3.30
392
3.48
3.65
572 752
932
1112
a
3.42
3.50 3.59
3.82 4.00
4.18 34.
3.67
From ref.
59
ON o
Table 2.
Predicted Hydrogen Pickup rjy Zircaloy-2 Plates8,

Hydrogen Pickup
Total
Plat.e
Thickn.ess
Zircaloy-2
Surface
Hydrogen from
Corrosion
Total Hydrogisn
10 yr
yr 20 ;
Initial
Test
Density
mils
Hydrogen
ppm
30 yr
ppm
(ppm)
ppm
(mg/dm2)
cm
mg/dm2
(ppm)
Mg/dm2
ppm
Mg/dm2
Mg/dm2
10 yr
20 yr
30 yr
X 106
75
100
0.919 0.254
0.126 0.167
0.375 0.375 0.375 0.375 0.375
3
2 2 2
1
28
27
22.3
177 134 107

95
22.3
22.3 22.3
22.3
49.8 49.8
395
77 77 77 77 77 77
611
205
161
423
325 265 240
639
298
238
213
461 368
329
488
395 356
333
125 140
150 163
0.318
0.356
0.209 0.234
0.251 0.273
27
27
26
0.382 0.415
89 82
0.375
26
22.3
49.8 49.8 49.8 49.8
134 122 115
198 182
307 282
224
108
208
308
Both surfaces of plate are exposed to water; Zircaloy-2 surface temperature = 572Pj Zircaloy-2 corrosion rate
(per surface) = 0.02 mg/dm2/day (pretransition); Zircaloy-2 corrosion rate (per surface = 0.03 mg/dm2/day (posttransition);
corrosion transition time = 2000 days; initial hydrogen content of 25 ppm; water pH of 6.57.5 and hydrogen content of 3.6 ppm.
ORNL-3281
UC-80 Reactor Technology TID-4500 (17th ed.)

Internal Distribution
1. 2.
T. M. R. R.
D.
D.
Anderson
35.
36. 37.
H. W. H. H.
G.
MacPherson
Bender G. E. S.
P. L. G. J. B. R. D.
3.
4.
5. 6.
7.
Berggren Biggers Billington

Blizard
D. Manly C. McCurdy
F. McDuffie
38.
39.
A.
S. K. M.
J.
E.
Miller
Moore
E. A. E.
40.
41.
Boch
Bohlmann Borkowski
Z. Morgan
L. Nelson
8.
9. 10.
11.
42. 43. 44. 45.

46.
C.
R. F.
A.
D. M. M.
Briggs
Bruce
M. Perry Phillips
L. Picklesimer
12.
13.
C.
T. B.
Cagle
Cole Colston
Corum Cox
E. Ramsey
W. Rosenthal
E.
W. M.
47. 48. 49.

50.
M.
H. A. L. L.
14.
15. 16. 17.
W. Savage
W. Savolainen
J.
J.
A. L. E.
K.
D.
R.
Schaffer
Shobe
F. J.
W.
R.
Culler
51. 52.
53.
18.
19. 20. 21.
Cunningham Ergen
Evans
0.
M.
Sisman J. H. Skinner Snell
B. P.
54.
55.
A. I.
J.
A. J. W.
B. W.
Fraas
Spiewak
A. C. Swartout Thurber
22.
23.
H.
R. L. R.
Frye,
Gall
Jr.
56. 57.
W.
D. J. A.
24.
25.
26.
Greenstreet
58.
59.
B. Trauger
W. Ullmann
Grimes
V.
N.
0.
E.
Haynes
Hinkle Jenks Jordan
60.
61. 62.
M. Weinberg
L. L. Whitmarsh Winton
27.
C. M.
28.
29.
30. 31.
G.
W.
s. 0.
H.
H.
I.
H.
63-64.
65-67.
Central Research Library

OREL - Y-12 Technical Library
Document Reference Section
Kaplan
KLepper
Lane
32. 33.
J. c.
A. E. N.
68-89.
90.
Laboratory Records Department
Larson (K-25)
Lyon
Laboratory Records, RC
34.
R.
External Distribution
91.
Ira Adler, New York Operations Office, AEC
92.
93.
W. R. Congdon, Babcock & Wilcox Company, Atomic Energy Division,

Lynchburg, Virginia
J. G. Gallagher, Alco Products, Inc.
94.
95.
W. C. Gribble, Division of Reactor Development (Army Reactors),

AEC, Washington
J. F. O'Brien, Martin Company, Nuclear Division

61
96.
9799.
M. M. Mann, New York Shipbuilding Corporation, Camden, New

Jersey
R. 0. Mehann, States Marine Lines, Inc.
100103.
104.
R. T. Schomer, Babcock &. Wilcox Company, Atomic Energy Division,

Lynchburg, Virginia
W. C. Stamm, Ebasco Services, Inc., New York
105108.
109. 110111. 112.
E. K. Sullivan, Division of Reactor Development (Maritime Re actors), AEC, Washington

B. W. Winchell, Todd Shipyards Corporation, Nuclear Division Reactor Division, AEC, 0R0 Division of Research and Development, AEC, 0R0
113713.
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UC-80 Reactor Technology

REVIEW OF ZIRCALOY-2 AND ZIRCALOY-4

OAK RIDGE NATIONAL LABORATORY

Available from the

Office of Technical Services

U. S, Deportment of Commerce Washington 25, D. C.

This report was prepared os an account of Government sponsored work.

Neither the United States,

any warranty or representation, express or implied, with respect to the accuracy,

privately owned rights; or

UC-80 - Reactor Technology

TID-4500 (17th ed.)

Contract No. W-7405-eng-26

OAK RIDGE NATIONAL LABORATORY

Oak Ridge, Tennessee

S. ATOMIC ENERGY COMMISSION

Factors Affecting Corrosion Fretting

Predicted Pickup of Hydrogen During Reactor Service

Modulus of Elasticity and Poisson's Ratio

Torsional Properties Fabricability

HAZARDS OF METAL-WATER REACTIONS

A literature search covering all available technology on Zircaloy

on mechanical properties, corrosion properties, radiation effects, and

terial, a creep rate of <10~5^/hr at 15 000 psi, and corrosion of only a

about three times that of Zircaloy-4.

On the basis of the available information, Zircaloy-4 appears to be

tainers in the advanced core for the N.S. SAVANNAH.

mended over Zircaloy-2 because of its lower hydrogen pickup.

and irradiation data must all be extrapolated by factors of 10 to 15 to

obtain 20-year performance predictions.

Existing data give no indication,

however, that any insurmountable problems will be encountered in these

The possibility of hairline cracks in Zircaloy-2 being propagated to

not always detected by present inspection methods.

on these cracks are unknown, but the possibility of propagation to fail

Zircaloy-2 is presently being used in various reactors as part of

sign of the CANDU reactor.

Considerable experimental work pertinent to

reactor applications is being performed at various locations on zirconiumbase alloys.

REVIEW OF ZIRCALOY-2 AND ZIRCALOY-4 PROPERTIES

RELEVANT TO N.S. SAVANNAH REACTOR DESIGN

Preliminary considerations for reducing fuel-cycle costs in reactors

of the N.S. SAVANNAH type1 have indicated the feasibility of replacing

the more limiting design features, the list of applicable container ma

terials was quickly reduced to magnesium, aluminum, beryllium, and zir

corrosion resistance, fabricability, and available technology, further

then conducted to collect the available information on the Zircaloys

pertinent to reactor design. in this report.

The information thus collected is presented

Although most of the data reported here were obtained

from tests of Zircaloy-2, it is generally believed that the results, other

components include the HRE-2, Dresden, Shippingport, submarine thermal

struction stages include the HWCTR, CVTR, NPD, and CANDU.

work on Zircaloy is being done primarily at Westinghouse's Bettis Plant,

Additional data are scattered through

out the classified and unclassified literature.

A principal function of the fuel element container in the N.S.

SAVANNAH reactor is to channel cooling water through the core.