BARC/2021/E/016

BARC/2021/E/016
EFFECT OF HYDROGEN ON THE ACCELERATED CREEP
PROPERTIES OF Zr-2.5%Nb PRESSURE TUBE MATERIAL
by
Avinash Gopalan1, Vivek Patel1, 2,
Apu Sarkar1, 2 and R. N. Singh1, 2
Mechanical Metallurgy Division1
Homi Bhabha National Institute2

2021
 BARC/2021/E/016
BARC/2021/E/016

GOVERNMENT OF INDIA
DEPARTMENT OF ATOMIC ENERGY

EFFECT OF HYDROGEN ON THE ACCELERATED CREEP

PROPERTIES OF Zr-2.5%Nb PRESSURE TUBE MATERIAL
by
Avinash Gopalan1, Vivek Patel1, 2,
Apu Sarkar1, 2 and R. N. Singh*1, 2
rnsingh@barc.gov.in*
Mechanical Metallurgy Division1
Homi Bhabha National Institute2

BHABHA ATOMIC RESEARCH CENTRE

MUMBAI, INDIA
2021
 BARC/2021/E/016

BIBLIOGRAPHIC DESCRIPTION SHEET FOR TECHNICAL REPORT

(as per IS : 9400 - 1980)

01 Security classification : Unclassified

02 Distribution : External

03 Report status : New

04 Series : BARC External

05 Report type : Technical Report

06 Report No. : BARC/2021/E/016

07 Part No. or Volume No. :

08 Contract No. :

10 Title and subtitle : Effect of hydrogen on the accelerated creep properties of

Zr-2.5Nb pressure tube material

11 Collation : 31 p., 8 figs., 3 tabs.

13 Project No. :

20 Personal author(s) : Avinash Gopalan; Vivek Patel; Apu Sarkar; R.N. Singh

21 Affiliation of author(s) : Mechanical Metallurgy Division, Bhabha Atomic Research Centre,

Mumbai

22 Corporate author(s) : Bhabha Atomic Research Centre, Mumbai - 400 085

23 Originating unit : Mechanical Metallurgy Division,

Bhabha Atomic Research Centre, Mumbai

24 Sponsor(s) Name : Department of Atomic Energy

Type : Government

Contd...
 BARC/2021/E/016

30 Date of submission : July 2021

31 Publication/Issue date : August 2021

40 Publisher/Distributor : Head, Scientific Information Resource Division,

Bhabha Atomic Research Centre, Mumbai

42 Form of distribution : Hard copy

50 Language of text : English

51 Language of summary : English

52 No. of references : 39 refs.

53 Gives data on :
Abstract : Zr-2.5%Nb alloy used as the pressure tube material in the pressurized heavy water
60
reactors undergoes dimensional changes due to creep deformation during service. Hydrogen
formed due to corrosion reaction of Zr–2.5%Nb alloy with water during the operation of the
nuclear ingress into the pressure tube. This absorbed hydrogen plays significant role in governing
the deformation behaviour of the pressure tube. In order to evaluate the effect of hydrogen on
the creep behaviour of the pressure tube material, tensile creep specimens with longitudinal
orientations were hydrided to 200wppm and tested over a range of stress varying from 0.7-
0.9YS at temperatures ranging from 350-450°C. The influence of hydrogen on the creep rate
is evaluated. It is observed that addition of hydrogen decreases the creep rate at 350°C and for
temperature greater than 350°C the addition of hydrogen has minimal effect on the creep rate
of the Zr-2.5Nb pressure tube material.

70 Keywords/Descriptors : ZIRCONIUM ALLOYS; NIOBIUM ALLOYS; CREEP; STRESS

RELAXATION; YOUNG MODULUS; PRESSURE TUBES; DEFORMATION

71 INIS Subject Category : S36

99 Supplementary elements :
 EFFECT OF HYDROGEN ON THE ACCELERATED CREEP
PROPERTIES OF Zr-2.5%Nb PRESSURE TUBE MATERIAL
Avinash Gopalan1, Vivek Patel1, 2, Apu Sarkar1, 2 and R.N. Singh*1, 2
1
Mechanical Metallurgy Division,
Bhabha Atomic Research Centre, Trombay, Mumbai-400085, India
2
Homi Bhabha National Institute, Anushaktinagar, Mumbai-400094, India
rnsingh@barc.gov.in*

Abstract

Zr-2.5%Nb alloy used as the pressure tube material in the pressurized heavy water reactors
undergoes dimensional changes due to creep deformation during service. Hydrogen
formed due to corrosion reaction of Zr–2.5%Nb alloy with water during the operation of
the nuclear ingress into the pressure tube. This absorbed hydrogen plays significant role in
governing the deformation behaviour of the pressure tube. In order to evaluate the effect of
hydrogen on the creep behaviour of the pressure tube material, tensile creep specimens
with longitudinal orientations were hydrided to 200 wppm and tested over a range of stress
varying from 0.7-0.9 YS at temperatures ranging from 350-450°C. The influence of
hydrogen on the creep rate is evaluated. It is observed that addition of hydrogen decreases
the creep rate at 350°Cand for temperature greater than 350°C the addition of hydrogen
has minimal effect on the creep rate of the Zr-2.5Nb pressure tube material.

Keywords: Zr-2.5Nb alloy, creep rate, hydride, Norton (stress) exponent, activation energy.
CONTENT
1. INTRODUCTION ............................................................................................................... 1
2. MATERIALS AND EXPERIMENTAL WORK ................................................................. 2
2.1. Material ................................................................................................................................ 2
2.2. Tensile Test.................................................................................................................... ...... . 2
2.3. Creep Test....................................................................................................................... ..... 2
3. RESULTS............................................................................................................................. 3
4. DISCUSSION………………………………………………………………………….. .... 4
4.1. Mechanisms of Creep Deformation in Zr-Alloys…………………………………….. ...... 4
4.2. Effect of Hydrogen on the Minimum Creep Rates and Creep Parameters
of Zr-2.5Nb Material………………………………………………………………….. ...... 5
4.3. Role of Dissolved Hydrogen during Creep Deformation…………………………….. ...... 6
4.4. Role of Hydrides during Creep Deformation…………………………………………....... 7
5. SUMMARY AND CONCLUSIONS…………………………………………………. ..... 7
ACKNOWLEDGEMENT…………………………………………………………………….. ..... 8
REFERENCES………………………………………………………………………………… .... 9
 List of Figures

Fig. No. Title Page

Fig.1 Fabrication route of the Zr-2.5Nb pressure tubes used in 220 MWe 13
IPHWR.
Fig.2 Back Scattered SEM images at different magnifications of Radial- 13
Axial plane of as-received pressure tube.
Fig.3 Drawing of the (a) tensile and (b) creep sample, t- represents the 14
thickness of the tube (~3.6 mm in this study).
Fig.4 Plot of Terminal Solid Solubility for Dissolution (TSSD) of hydrogen 15
in Zr-2.5Nb material [23] and hydrided microstructure of Zr-2.5Nb
pressure tube material charged with 200 wppm. Circumferential (C)
and Radial (R) directions are marked.
Fig.5 (a) Plot of Engg. stress vs. Engg. plastic strain obtained for all the 15
tensile tests. (b) Plot of 0.2%YS and UTS values at different
temperatures for as-received and 200 wppm hydrogen charged
specimens of Zr-2.5Nb pressure tube.
Fig.6 Creep strain vs. time and strain rate vs. time plots of the Zr-2.5%Nb 20
pressure tube material obtained using creep specimens tested at
different temperatures and stress fractions of YS: (a) 350°C, 0.7YS,
(b) 350°C, 0.8YS, (c) 350°C, 0.9YS, (d) 400°C, 0.7YS, (e) 400°C,
0.8YS, (f) 400°C, 0.9YS, (g) 450°C, 0.7YS, (h) 450°C, 0.8YS, (i)
450°C, 0.9YS
Fig.7 Plot of the minimum creep rate vs. stress for Zr-2.5Nb pressure tube 21
material in AR and charged with 200 wppm condition at different
temperatures to determine the stress exponent, n.
Fig.8 Creep activation energy, Q determination using the plots of ln  22
vs. 1⁄ for Zr-2.5Nb pressure tube material in AR and charged with
200 wppm condition at constant stress levels of 0.7, 0.8 and 0.9 times
of YS.

List of Tables

Table No. Title Page

Table.1 Composition of Zr-2.5Nb pressure tube material used in 220 MWe 23
IPHWR.
Table.2 Stress exponent values obtained at different temperatures for AR and 23
200 wppm Zr-2.5Nb pressure tube.
Table.3 Activation energy values obtained for Zr-2.5Nb pressure tube material 23
in AR and charged with 200 wppm conditionat different stress levels.
 NOMENCLATURE
AR As Received

ASTM American Society for Testing and Materials

E Young’s modulus

Minimum strain rate

IPHWR Indian Pressurized Heavy Water Reactor

n stress exponent (Norton exponent)

PT Pressure tube

Q activation energy

R Gas constant

Stress

T Temperature

TSS Terminal solid solubility

TSSD Terminal solid solubility in dissolution

UTS Ultimate tensile strength

YS Yield Strength

wppm Part per million in weight

1. INTRODUCTION
Zirconium based alloys are the only materials, which satisfy many unique requirements (such
as low thermal neutron absorption cross section and high strength) for the use in thermal
nuclear power reactors. Zr–2.5%Nb alloy is widely used as the pressure tube material in the
pressurized heavy water reactors because of their superior mechanical properties and
corrosion resistance. During normal operation of the reactor, the pressure tubes typically
experience temperature of about ~ 300°C and an operating pressure of about ~10 MPa. The
internal pressure of 10 MPa results in an axial stress at pressure tube wall of about 65 MPa
and hoop stress of about 130 MPa [1 & 2]. Due to the simultaneous effect of stress,
temperature and irradiation, the pressure tube undergoes deformation during normal
operation of the reactor. The deformation leads to dimensional variations in the pressure
tube-elongation in the axial direction, diametric expansion, sag and wall thinning. The
mechanisms responsible for these dimensional changes are: (a) irradiation growth – stress
free deformation at constant volume due to the effect of neutron flux, (b) thermal
creep – deformation due to the effect of stress and temperature, and (c) irradiation
creep – deformation due to the effect of stress and neutron flux [3]. The thermal creep is the
major contributor to deformation at both the ends of the pressure tube, where the effect of
irradiation is relatively low [4]. The thermal creep is dependent on parameters like texture,
chemical composition and micro-structure (grain size, distribution of the second phase and
the volume fraction of the second phase). During the operation of the reactor, the zirconium
alloys pick up hydrogen, which is available as a by-product of the corrosion reaction. The
hydrogen is sparingly soluble in zirconium at room temperature (<1 wppm). But as the
temperature increases the solubility increases. At 300°C the solubility of hydrogen in
zirconium alloy is about 60 wppm and at 400°C it is about 240 wppm [5]. The hydrogen
remains in solution till it reaches Terminal Solid Solubility (TSS) (maximum concentration of
hydrogen that can be contained in zirconium alloy solid solution). Beyond TSS, the hydrogen
precipitates as zirconium hydride phase. Hydrogen, either in the solution or in the hydride
form is known to affect creep properties in zirconium alloys [6]. Hence it is important to
determine the role of hydrogen in creep performance of Zr-2.5Nb alloys.

Determining the long term creep properties of the material is a highly cost intensive and time
taking process. It can take about 1,50,000 – 2,00,000 hours to complete a creep test at actual
component working conditions. An alternative approach is to extrapolate the creep properties
obtained from accelerated creep tests. Several methods have been proposed for prediction of
the creep properties of a material at service conditions using the data obtained from
accelerated creep tests [7]. In this study, to determine the effect of hydrogen on the creep rate
of the Zr-2.5Nb pressure tube material both tensile and creep tensile specimens from the
longitudinal orientation were machined. These specimens were hydrided with 200 wppm of
hydrogen. Accelerated creep tests were performed at stresses ranging from 0.7-0.9 YS and
temperatures ranging from 350-450°C.

1
2. MATERIALS AND EXPERIMENTAL WORK
2.1. Material
Zr–2.5%Nb Pressure tubes used in the 220 MWe IPHWR (Indian pressurized heavy water
reactor) was received in the form of cold pilgered and stress relieved condition to investigate
the creep properties of the material. The pressure tubes were fabricated using the fabrication
route shown in (Fig.1) from the quadruple melted ingots. (Fig.2) shows the back scattered
SEM images at different magnifications of radial-axial plane of as-received pressure tube.
The tube dimensions were: length 5.4 m, outer diameter 90 mm and thickness ~3.5 mm. The
nominal composition of the Zr–2.5Nb material used in this investigation is shown in
(Table.1). Spools of length 135 mm were cut from the tube and the oxide layers from the
inner and outer surfaces were removed. These polished tubes were charged with hydrogen
gaseously using the modified Sieverts apparatus. The details of the method of hydriding has
been described elsewhere [8]. The tubes were charged with 200 wppm of hydrogen. The
actual hydrogen concentration of the specimen measured using hot vacuum extraction
technique was 199±1 wppm. Hereafter in this report, the samples charged with 200 wppm
hydrogen will be designated as 200 wppm samples.

2.2. Tensile Test

The tensile specimens were fabricated with its axis oriented along the longitudinal direction
of the tube for performing uniaxial tensile tests at elevated temperatures as per ASTM E21-20
[9]. The dimensions of the specimen machined are shown in (Fig.3(a)). The tensile tests were
carried out at temperatures of 350, 400 and 450C at a nominal strain rate of 1 10 s-1.
Three K-type thermocouples were attached in the top, middle and bottom region of the gage
length to control and monitor the temperature of the specimen. The specimen was soaked at
the test temperature for 30 mins before deformation. The tensile tests were carried out using a
100 kN electromechanical Universal Testing Machine. The desired test temperature was
controlled within the range of 1°C.

2.3. Creep Test

The creep specimens were fabricated with its axis oriented along the longitudinal direction of
the tubes for performing uniaxial creep test as per the ASTM E139-11 [10]. The uniaxial
stress rupture tests were carried out under tension using a dead load creep testing machine
(Make – Star Testing Systems) having automatic lever levelling system having a lever arm
ratio of 20:1. The dimensions of the creep specimen are shown in the (Fig.3(b)). The creep
test machine is fitted with a three-zone furnace and a temperature controller for achieving the
desired test temperature. The test temperature was maintained and controlled within range of
1°C. The temperature of the specimen was measured using a K-type thermocouple mounted
at the parallel length section. The creep strain of the test specimen was measured using a high
temperature extensometer cage (tube-in-tube type) with LVDT arrangement. The error in the
displacement measurement was within 1 µm. The stress rupture tests were carried out at
three temperatures (350, 400 and 450°C) under three different loads, (corresponding to
0.7YS, 0.8YS and 0.9YS). YS stands for yield strength of the material at the test temperature.

2
3. RESULTS
The creep behaviour of Zr-2.5%Nb pressure tube material reported here is for the as received
(AR) and 200 wppm hydrogen charged conditions. The composition of the Zr-2.5Nb in the
AR condition is shown in the (Table.1). The AR specimens contains about 4 wppm hydrogen
as seen in the (Table.1). The microstructure of the spool charged with 200 wppm is shown in
the (Fig.4). All the hydride plates are oriented along the circumferential direction. The plots
of engg. stress vs engg. plastic strain is shown in the (Fig.5(a)) for all the tensile tests and the
results of the tensile tests are shown in the (Fig.5(b)). The Yield Stress (YS) and Ultimate
Tensile Stress (UTS) are plotted with temperature between 350 to 450°C. In all the cases the
strength (both YS and UTS) decreases with increase in the test temperature. At all
temperatures between 350 to 450°C the specimens containing hydrogen had ~10% lower
strength as compared to the AR specimens.

The creep-rupture tests were conducted at temperatures of 350, 400 and 450°C for the stress
levels of 0.7 YS, 0.8 YS and 0.9 YS. The plots of creep strain vs. time obtained for the AR
and 200 wppm specimens are shown in the (Fig.6) for the various combinations of stresses
and temperatures. The creep curves for all the tests performed exhibited typical three stage
behaviour comprising of distinct primary, secondary and tertiary regimes. Very short primary
creep regime was observed at all the test conditions. As observed from the (Fig.6(a-c)), the
rupture life of the specimen with 200 wppm hydrogen at 350°C was~3 times higher at
0.7 YS, 0.8 YS and 0.9 YS. This implies that at 350°C, addition of hydrogen increases rupture
life. The rupture life of the specimen with 200 wppm hydrogen at 400°C was observed to be
approximately similar to the AR specimens 0.7 YS, 0.8 YS and 0.9 YS (Fig.6(d-f)). At 450°C
(Fig.6(g-i)) the rupture life was ~1.5 times lower for the AR specimens when compared to the
hydrided samples for a stress level of 0.7 YS. The rupture life was approximately same for
the AR specimens when compared to the hydrided samples for a stress level of 0.8 YS and
0.9 YS. From these observations it can be concluded that since specimens with enhanced
hydrogen levels have greater creep life at lower temperature (i.e 350°C), the presence hydride
phase enhances the rupture life in Zr-2.5Nb pressure tube material as compared with
hydrogen in solution.

The plot of creep strain rate vs. time is shown in the (Fig.6). The curves display three
different creep regimes viz. (i) primary creep regime having decreasing creep rate,
(ii) secondary creep regime showing mildly decreasing, minimum and mildly increasing
creep rate, and (iii) tertiary creep regime showing sharply increasing creep rate. The
minimum creep rate increases as the temperature increases for all the specimens at all stress
levels. At 350°C (Fig.6(a-c)), the minimum creep rate obtained for the 200 wppm specimens
was observed to be approximately 2 to 3 times lower than the minimum creep rate obtained
for the AR specimen. This implies that on addition of hydrogen the minimum creep rate
decreases at 350°C. At 400°C (Fig.6(d-f)), the minimum creep rate obtained for the
200 wppm specimens was observed to be approximately 1 to 2 times higher than the
minimum creep rate obtained for the AR specimens. At 450°C (Fig.6(g-i)), the minimum
creep rate obtained for the 200 wppm specimens was observed to be approximately
1 to 1.5 times higher than the minimum creep rate obtained for the AR specimens. This

3
implies that on addition of hydrogen, at higher temperatures where the hydrogen is in
solution form, minimum creep rate increases marginally. From the above discussion it is
observed that the addition of 200 wppm of hydrogen decreases the creep rate of the Zr-2.5Nb
pressure tubes for temperatures below 400°C and increases the creep rate for temperatures
above 400°C.

The minimum creep rate is related to the applied stress () by the Norton creep equation:

̇ ⁄ Eq.(1)

where is the minimum or steady state creep rate,  the applied stress, n the stress exponent,
A is a constant, Q the activation energy for creep.

The value of the stress exponent at a particular temperature is determined from the slope of
the plot of  vs in log-log scale. The plots of minimum creep rate with stress are shown in
the (Fig.7) at temperatures of 350, 400 and 450°C for AR and 200 wppm specimens. The
stress exponent for the AR specimens was 5.8, 5.2 and 5.2 at temperatures of 350, 400 and
450°C, respectively. The stress exponent for the 200 wppm specimens was 7.9, 6.4 and 5.5 at
temperatures of 350, 400 and 450°C, respectively. This shows that the addition of 200 wppm
hydrogen increased the stress exponent of Zr-2.5Nb alloy.

The creep activation energy, Q, was determined from the plot of ln  vs. 1⁄ at constant
stress. (Fig.8) shows the plots of ln  vs. 1⁄ at constant stress levels of 0.7, 0.8 and 0.9
times of YS for AR and 200 wppm specimens. The activation energy for the AR specimens
was 130, 112 and 123 kJ/mol at stress level of 0.7, 0.8 and 0.9 times of YS, respectively. The
activation energy for the 200 wppm specimens was 160, 138 and 147 kJ/mol at stress level of
0.7, 0.8 and 0.9 times of YS, respectively. This shows that the addition of 200 wppm
hydrogen increased the activation energy of Zr-2.5Nb alloy. The values of n and Q obtained
from the creep tests conducted in this study is tabulated in the (Table.2 & 3), respectively. As
observed from the table, the values of n and Q slightly increased with the addition of
hydrogen in Zr-2.5Nb alloy.

4. DISCUSSION
4.1. Mechanisms of Creep Deformation in Zr-Alloys
Creep is a time dependent deformation process at elevated temperature under constant load
below the YS of the material. In general, for metals and alloys creep is dominant at
temperatures > 0.3-0.4 Tm, Tm being the melting point of the alloy. Zr alloys possess high
melting point ~ 1850C. Thus, they are not believed to undergo creep during a service
condition with temperature ~300C. However, since Zr alloys exhibit a α (hcp) to β (bcc)
phase transformation at a temperature ~ 890C [11], they are amenable to creep at
temperatures < 0.3Tm. Due to the technical importance of in-service creep of nuclear
structural components, several studies have been carried out on pure Zr and different Zr
based alloys (Zircaloy, Zirlo, Zr-2.5Nb) to investigate the creep behavior of the alloys in
wide range of temperatures and stresses. There is now a reasonable understanding on the
underlying creep mechanism of Zr alloys. Hayes and Kassner compiled creep data of various

4
Zr alloys for a wide range of stresses and temperatures [12 & 13]. It has been reported that
the creep parameters (stress exponent and activation energy) vary over a range of temperature
and stresses [14] for Zr alloys. The variations in the parameters are due to the fact that the
different creep mechanisms operate for a particular range of stresses and temperatures. The
creep mechanisms are broadly classified into (a) diffusion based mechanism and
(b) dislocation based mechanisms. The diffusion based creep mechanisms are pre-dominantly
classified into two: Nabarro-Herring creep [15] and Coble creep [16]. These mechanisms
have stress exponent n close to 1. The Nabarro-Herring creep is based on vacancy movement
within the grain to cause the creep. Whereas in Coble creep, the vacancy movement is
through the grain boundaries to cause creep. It is reported that for zirconium at low stresses
(<20 MPa) the mechanism operative are Nabarro-Herring creep or Coble creep; the stress
exponent n was reported close to unity [12]. However, for the Zr alloys at the reactor
operating conditions the creep is controlled by dislocation-based creep mechanisms [12]. Li
et al. [11] tested Fuel Sheathing (FS) capsules and Miniature Pressure Tubes (MPTs) of
Zr-2.5Nb alloy for finding out stress exponent under bi-axial state of stress. FS capsules were
tested under transverse stress range of 100 MPa to 325 MPa at 350oC and from 100 MPa to
200 MPa at 400oC. The value of n obtained for stresses below 250 MPa was 2.88 and 3.02 for
350oC and 400oC, respectively. For stress range of 250-325 MPa the stress exponent
increased to 7. For MPTs, under transverse stress range of 275-325 MPa at 350°C, the
stress exponent value for both the transverse and axial direction varies in range of
3.9-7.3 with an average value of 6.4. Christodoulou et al. [17] conducted creep tests on the
uniaxial tensile specimen in the stress range of 200-500 MPa for both the axial and transverse
direction at temperature range of 100- 250C, and found the value of ‘n’ to be in the range of
3.8-4.5. Shewfelt et al. [18] tested the uniaxial creep specimens of CANDU Zr-2.5Nb
pressure tubes in both the axial and transverse orientation at temperature ranging from
450-700C and different stresses. It was observed that at 450 and 500oC the stress exponent
was ~ 9, and it remained constant over the entire stress range of the experiment.
Guguloth et al. [19] reported the stress exponent values to be 6.6, 5.2 and 3.6 at temperature
of 350oC, 400oC and 450oC, respectively, in the stress range of 82-283 MPa by testing
uniaxial creep specimens in the longitudinal orientation of Zr-2.5Nb alloy. Above mentioned
studies indicated that the values of n lie between 3 to 9 for Zr-2.5Nb alloy in the temperature
range of 350-450C. It was concluded that for Zr alloys, the dominating or rate controlling
creep mechanism is the dislocation based creep mechanism where the dislocation glide is the
strain producing mechanism and the dislocation climb is the rate controlling mechanism [20].

The stress exponent in this study for the AR specimens ranged from 5.2 to 5.8 for
temperatures ranging from 350-450°C. These values of n corroborate with that reported in the
literature.

4.2. Effect of Hydrogen on the Minimum Creep Rates and Creep Parameters of
Zr-2.5Nb Material
As mentioned earlier, the Zr alloys used in the reactor pick up hydrogen during service. The
picked-up hydrogen, can be either in solid solution or precipitated form in the Zr alloy
component depending upon the temperature and the amount of hydrogen. Both forms of

5
hydrogen are reported to affect the creep performance of Zr alloys [6]. Several studies have
been conducted to investigate the role of hydrogen on the creep behaviour of zirconium
alloys [21-24]. Previous studies indicated that the hydrogen in solution form increases the
creep rate and hydrogen in precipitate form decreases the creep rate in Zr alloys [21-24].

Pan et. al. [25] have studied the terminal solid solubility of hydrogen in Zr-2.5Nb as a
function of temperature. The plot of Terminal Solid Solubility of Hydrogen in Dissolution
(TSSD) as a function of temperature in Zr-2.5Nb alloy is shown in the (Fig.3). It can be seen
from (Fig.3) that the solubility of hydrogen in the Zr-2.5Nb alloy increases exponentially
with temperature. The content of hydrogen used in the present study was 200 wppm. On
comparing with the TSSD plot in (Fig.4), it indicates that the complete dissolution
temperature for 200 wppm hydrogen in Zr-2.5Nb alloy is ~409C. Therefore, for the test
temperature of 450°C, the hydrogen present in the Zr-2.5Nb specimens were completely in
dissolved state. The TSSD of hydrogen for the test temperatures of 350 and 400°Care
112 and 184 wppm, respectively. Therefore, at 400°C, nearly all the hydrogen was in solid
solution. At 350°C, the hydrogen present in the Zr-2.5Nb specimens was both in solution and
hydride precipitate form.

As observed in the result section of this study, at 350°C the minimum creep rates for the
200 wppm hydrided specimens of Zr-2.5Nb was lower than that of the AR specimens. At test
temperatures of 400 and 450°C, the minimum creep rates for the 200 wppm hydrided
specimens were marginally higher than the AR specimens. At 350C, substantial amount of
hydrogen was present in the hydride precipitate form during the creep of the Zr-2.5Nb alloy
samples. On the contrary, at 400 and 450C the hydrogen in the samples were in the solution
during creep deformation. Thus, the decrease in the creep rate at 350C and marginal increase
of the creep rate at 400 and 450C indicates that the hydride precipitates present during creep
results in the decreases creep rate and hydrogen in solution marginally increases the creep
rate of the Zr-2.5Nb alloy. These observations corroborate with the results reported for other
Zr alloys [21-24].

The values of the stress exponent for the 200 wppm hydrided samples were in the range of
5.5 to 7.9. Though there is slight increase in the value of n in the hydrided samples, however
the high values of n indicate that the dislocation-based creep mechanisms are operative at this
stress and temperature range for both the AR and hydrided specimens of Zr-2.5Nb PT.

4.3. Role of Dissolved Hydrogen during Creep Deformation

In this study, it is observed that the hydrogen in the solution increased the creep rates
marginally for the Zr-2.5Nb alloys. A similar observation was made on the zirconium
polycrystalline material [26], zircaloy-4 [27], HANA-4 cladding [24 & 28] and Zr-2.5Nb PT
alloy [29 & 30]. It has been argued that the increase in creep rate of hydrogenated zirconium
is due to the reduction in its Young's modulus in presence of solute hydrogen due to increase
in lattice parameters [26, 28 & 30]. An alternative explanation on the increase in creep rate
during experiments is based on the interaction of hydrogen with dislocations. Investigations
carried out in some other materials with similar crystal structure indicated that the influence

6
of hydrogen on dislocation mobility in metals is a complex phenomenon [31-33]. Usually, the
dissolved atom interacts with dislocation core, relaxes the stress field around the dislocation
and fixes it. However, given the quite high mobility of hydrogen atoms compared with
dislocation, it is believed that solute hydrogen mitigates the stress field and in turn accelerates
the dislocation movement. Atomic scale ab initio study showed that solute hydrogen may get
trapped by the core of dislocations in zirconium alloys, causing a decrease in lattice friction
and propelling planar glide of dislocations [34-36] resulting in increase in the creep rate.

4.4. Role of Hydrides during Creep Deformation

Hydrogen beyond the solubility limit precipitates as brittle hydride phases in zirconium
alloys' metal matrix. Observations from this study indicated that hydride precipitate increase
the hardening of zirconium alloys, which causes decrease in creep rate. Hydride precipitate
acts as an obstacle to dislocation glide and improves the creep resistance. Another hypothesis
to explain this creep behaviour is based on the different elastic properties of the zirconium
metal matrix and hydride precipitates. Nano-indentation studies by [37] as well as [38]
reported significant difference in mechanical properties between zirconium metal matrix and
precipitates of hydride in it. Hydride precipitates have lower value of elastic modulus than the
zirconium matrix. Singh et al. [39] computed the stress field of hydride and reported that the
stress field in matrix surrounding a dissolving hydride plate is compressive. This compressive
stress might result reduction in the creep rate.

5. SUMMARY AND CONCLUSIONS

Accelerated creep behaviour was studied on the Zr-2.5Nb pressure tubes for the as received
material (~5 wppm) and 200 wppm hydrogen charged material for a stress varying from
0.7-0.9 YS at temperatures ranging from 350-450°C. The conclusions are as follows:

(a) The minimum creep rate at 350°C decreased by the factor of 2 to 3 for the material
containing 200 wppm hydrogen as compared to the as-received material. Whereas, the
minimum creep rate increased by the factor of 1 to 2 and 1 to 1.5 with addition of
200 wppm hydrogen at temperatures of 400 and 450°C, respectively. This means
hydrogen in solid solution form increases minimum creep rate, whereas, in hydride
precipitate form it decreases the minimum creep rate.

(b) The rupture life increased by the factor of 3 at 350°C, approximately same at 400°C and
450°C with addition of 200 wppm hydrogen. This means hydrogen in solid solution form
decreases rupture life, whereas, in hydride precipitate form it increases the rupture life.
The effect of hydrogen on creep behaviour was more dominant at lower temperature and
lower stress.

(c) The stress exponent and activation energy increased slightly with addition of hydrogen
in the Zr-2.5Nb pressure tube material. But, the addition of hydrogen in the Zr-2.5Nb
alloy did not the change the creep mechanism as observed in the AR Zr-2.5Nb alloy.

7
ACKNOWLEDGEMENT
Constant encouragement provided by Dr. S. Banerjee and Dr. R. K. Sinha former
AEC chairman, Mr. S. A. Bhardwaj former AERB Chairman, Dr. G. K. Dey and
Dr. Madangopal Krishnan, former Director, Materials Group and Mr. A. K.
Balasubramanian, former Director (T), NPCIL is acknowledged. Technical assistance
provided by Shri Sandeep A. Chandanshive and Shri Pramod N. Mandavkarare thankfully
acknowledged.

8
REFERENCES
[1] Bajaj, S.S. and Gore, A.R. “The Indian PHWR”, Nuclear Engineering and Design,
236(7-8):701–722, 2006.
https://doi.org/10.1016/j.nucengdes.2005.09.028.

[2] Shewfelt, R.S.W. and Lyall, L.W. “A high-temperature longitudinal strain rate
equation for Zr-2.5 wt% Nb pressure tubes”, Journal of Nuclear Materials,
132(1):41–46, 1985.
https://doi.org/10.1016/0022-3115(85)90391-5.

[3] Christodoulou, N. et al. “Modeling in-reactor deformation of Zr-2.5Nb pressure tubes

in CANDU power reactors”, In: Zirconium in the Nuclear Industry: Eleventh
International Symposium (Garmisch-Partenkirchen, Germany: The Eleventh
International Symposium on Zirconium in the Nuclear Industry, September 11-14,
1995), edited by E.R. Bradley and G.P. Sabol, (Series: ASTM STP, 1295), West
Conshohocken, PA: American Society for Testing and Materials, 518–537, 1996.
https://doi.org/10.1520/STP16188S.

[4] Holt, R.A. “In-reactor deformation of cold-worked Zr-2.5Nb pressure tubes”,

Journal of Nuclear Materials, 372(2-3):182–214, 2008.
https://doi.org/10.1016/j.jnucmat.2007.02.017.

[5] Motta, A.T. et al. “Hydrogen in zirconium alloys: A review”, Journal of Nuclear
Materials, 518:440–460, 2019.
https://doi.org/10.1016/j.jnucmat.2019.02.042.

[6] Sarkar, A. et al. “Creep behavior of hydrogenated zirconium alloys”, Journal of

Materials Engineering and Performance, 23(10):3649–3656, 2014.
https://doi.org/10.1007/s11665-014-1129-y.

[7] Wilshire, B. and Battenbough, A.J. “Creep and creep fracture of polycrystalline
copper”, Materials Science and Engineering A, 443(1-2):156–166, 2007.
https://doi.org/10.1016/j.msea.2006.08.094

[8] Singh, R.N. et al. “Hydrogen charging, hydrogen content analysis and metallographic
examination of hydride in zirconium alloys”, BARC/2003/E/34, Bhabha Atomic
Research Centre, 2003.

[9] American Society for Testing and Materials. ASTM E21-20. “Standard Test Methods
for Elevated Temperature Tension Tests of Metallic Materials”, West Conshohocken,
PA: ASTM, 2020.
https://doi.org/10.1520/E0021-20

[10] American Society for Testing and Materials. ASTM E139–11. “Standard Test
Methods for Conducting Creep, Creep-Rupture, and Stress-Rupture Tests of Metallic
Materials”, West Conshohocken, PA: ASTM, 2018.
https://doi.org/10.1520/E0139-11R18

9
[11] Li, W. and Holt, R.A. “Anisotropic thermal creep of internally pressurized Zr-2.5Nb
tubes”, Journal of Nuclear Materials, 401(1-3):25–37, 2010.
https://doi.org/10.1016/j.jnucmat.2010.03.015.

[12] Hayes, T.A. and Kassner, M.E. “Creep of zirconium and zirconium alloys”,
In: Mechanical and Creep Behavior of Advanced Materials, edited by I. Charit et al.,
(Series: The Minerals, Metals & Materials Series), Cham: Springer, 2017.
https://doi.org/10.1007/978-3-319-51097-2_9.

[13] Hayes, T.A. and Kassner, M.E. “Creep of zirconium and zirconium alloys”,
Metallurgical and Materials Transactions A, 37(8):2389–2396, 2006.
https://doi.org/10.1007/BF02586213.

[14] Franklin, D., Lucas, G. and Bement, A.L. “Creep of zirconium alloys in nuclear
reactors”, (Series: ASTM STP, 815), Philadelphia, PA: American Society for Testing
and Materials, 1983.
https://doi.org/10.1520/STP815-EB

[15] Herring, C. “Diffusional viscosity of a polycrystalline solid”, Journal of Applied

Physics, 21(5):437–445, 1950.
https://doi.org/10.1063/1.1699681

[16] Coble, R.L. “A model for boundary diffusion controlled creep in polycrystalline
materials”, Journal of Applied Physics, 34(6):1679–1682, 1963.
https://doi.org/10.1063/1.1702656

[17] Christodoulou, N. et al. “Analysis of steady-state thermal creep of Zr-2.5Nb pressure

tube material”, Metallurgical and Materials Transactions A, 33(4):1103–1115, 2002.
https://doi.org/10.1007/s11661-002-0212-4.

[18] Shewfelt, R.S.W. “The anisotropic deformation of Zr-2.5 wt% Nb Candu pressure
tubes between 20 and 700°C”, Canadian Metallurgical Quarterly, 23(4):441–445,
1984.
https://doi.org/10.1179/cmq.1984.23.4.441.

[19] Guguloth, K. et al. “Mechanism of creep deformation with evolution of microstructure

and texture”, Materials Science and Engineering A, 721:286–302, 2018.
https://doi.org/10.1016/j.msea.2018.02.035.

[20] Kassner, M.E. and Pérez-Prado, M.T. “Five-power-law creep in single phase metals
and alloys”, Progress in Materials Science, 45(1):1–102, 2000.
https://doi.org/10.1016/S0079-6425(99)00006-7.

[21] Setoyama, D. and Yamanaka, S. “Indentation creep study of zirconium hydrogen solid
solution”, Journal of Alloys and Compounds, 379(1-2):193-197, 2004.
https://doi.org/10.1016/j.jallcom.2004.02.035.

10
[22] Bouffioux, P. and Rupa, N. “Impact of hydrogen on plasticity and creep of
unirradiated zircaloy-4 cladding tubes”, In: Zirconium in the Nuclear Industry:
Twelfth International Symposium (Toronto, Canada: The Twelfth International
Symposium on Zirconium in the Nuclear Industry, June 15-18, 1998), edited by G.
Sabol and G. Moan, (Series: ASTM STP, 1354), West Conshohocken, PA: American
Society for Testing and Materials, 399-422, 2000.
https://doi.org/10.1520/stp14310s.

[23] Kishore, R. “Effect of hydrogen on the creep behavior of Zr-2.5%Nb alloy at 723 K”,
Journal of Nuclear Materials, 385(3):591-594, 2009.
https://doi.org/10.1016/j.jnucmat.2009.01.034.

[24] Kombaiah, B., Sarkar, A. and Murty, K.L. “Effect of hydriding on the creep behavior
of HANA-4 zirconium alloy”, Materials Science and Engineering A, 767:138435,
2019.
https://doi.org/10.1016/j.msea.2019.138435

[25] Pan, Z.L., Ritchie, I.G. and Puls, M.P. “The terminal solid solubility of hydrogen and
deuterium in Zr-2.5 Nb alloys”, Journal of Nuclear Materials, 228(2):227–237, 1996.
https://doi.org/10.1016/S0022-3115(95)00217-0

[26] Setoyama, D. and Yamanaka, S. “Indentation creep study of zirconium hydrogen solid
solution”, Journal of Alloys and Compounds, 379(1-2):193–197, 2004.
https://doi.org/10.1016/j.jallcom.2004.02.035.

[27] Rupa, N. et al. “About the mechanisms governing the hydrogen effect on
viscoplasticity of unirradiated fully annealed zircaloy-4 sheet”, In: Zirconium in the
Nuclear Industry: Thirteenth International Symposium (Annecy, France: The
Thirteenth International Symposium on Zirconium in the Nuclear Industry, June10-14,
2001), edited by G. Moan and P. Rudling, (Series: ASTM STP, 1423), Pennsylvania:
American Society for Testing and Materials, 811-836, 2002.
https://doi.org/10.1520/stp11418s.

[28] Yamanaka, S. et al. “Thermal and mechanical properties of zirconium hydride”,

Journal of Alloys and Compounds, 293-295:23–29, 1999.
https://doi.org/10.1016/S0925-8388(99)00389-8

[29] Kishore, R., Banerjee, S. and Rao, P. Rama “First report on observation of abnormal
creep in a Zr-2.5wt.%Nb alloy at low stresses”, Journal of Materials Science,
44(9):2247–2256, 2009.
https://doi.org/10.1007/s10853-008-2962-x.

[30] Yamanaka, S., Kuroda, M. and Setoyama, D. “Mechanical properties of zirconium

hydride an hydrogen solid solution”, Nippon Genshiryoku Gakkai Wabun Ronbunshi,
1(4):323–327, 2002.
https://inis.iaea.org/search/search.aspx?orig_q=RN:34021736

11
[31] Birnbaum, H.K. and Sofronis, P. “Hydrogen-enhanced localized plasticity—A
mechanism for hydrogen-related fracture”, Materials Science and Engineering A,
176(1-2):191–202, 1994.
https://doi.org/10.1016/0921-5093(94)90975-X

[32] Robertson, I.M. “The effect of hydrogen on dislocation dynamics”, Engineering

Fracture Mechanics, 68(6):671–692, 2001.
https://doi.org/10.1016/S0013-7944(01)00011-X.

[33] Teter, D.F., Robertson, I.M. and Birnbaum, H.K. “The effects of hydrogen on the
deformation and fracture of β-titanium”, Acta Materialia, 49(20):4313–4323, 2001.
https://doi.org/10.1016/S1359-6454(01)00301-9

[34] Domain, C., Besson, R. and Legris, A. “Atomic-scale Ab-initio study of the Zr-H
system: I. Bulk properties”, Acta Materialia, 50(13):3513-3526, 2002.
https://doi.org/10.1016/S1359-6454(02)00173-8

[35] Domain, C., Besson, R. and Legris, A. “Atomic-scale ab initio study of the Zr–H
system: II. Interaction of H with plane defects and mechanical properties”, Acta
Materialia, 52(6):1495–1502, 2004.
https://doi.org/10.1016/j.actamat.2003.11.031

[36] Udagawa, Y. et al. “Ab initio study on plane defects in zirconium–hydrogen solid
solution and zirconium hydride”, Acta Materialia, 58(11):3927–3938, 2010.
https://doi.org/10.1016/j.actamat.2010.03.034

[37] Xu, Jiujun and Shi, San-Qiang “Investigation of mechanical properties of ε-zirconium
hydride using micro-and nano-indentation techniques”, Journal of Nuclear Materials,
327(2-3):165–170, 2004.
https://doi.org/10.1016/j.jnucmat.2004.02.004

[38] Kuroda, M. et al. “Nano indentation studies of zirconium hydride”, Journal of Alloys
and Compounds, 368(1-2):211–214, 2004.
https://doi.org/10.1016/j.jallcom.2003.08.094

[39] Singh, R.N. et al. “Influence of stress field of expanding and contracting plate shaped
precipitate on hydride embrittlement of Zr-alloys”, Materials Science and Engineering
A, 579:157–163, 2013.
https://doi.org/10.1016/j.msea.2013.04.117

12
 Fig.1. Fabrication route for
f the Zr-22.5Nb presssure tubes used
u in 2200 MWe IPH
HWR.

Fig.2. B
Back Scatttered SEM images at different
d magnificatio
m ons of Radiial-Axial pllane of
as-received
d pressure tube.

13
 a

Fig.3. Drawing of the (a) tensile and (b) creep sample, t- represents the thickness of the
tube (~3.6 mm in this study).

14
Fig.4. Plot of Terminal Solid Solubility for Dissolution (TSSD) of hydrogen in Zr-2.5Nb
material [23] and hydrided microstructure of Zr-2.5Nb pressure tube material
charged with 200 wppm. Circumferential (C) and Radial (R) directions are
marked.

Fig.5. (a) Plot of Engg. stress vs. Engg. plastic strain obtained for all the tensile tests.
(b) Plot of 0.2% YS and UTS values at different temperatures for as-received
and 200 wppm hydrogen charged specimens of Zr-2.5Nb pressure tube.

15
16
17
18
19
Fig.6. Creep strain vs. time and strain rate vs. time plots of the Zr-2.5%Nb pressure
tube material obtained using creep specimens tested at different temperatures
and stress fractions of YS: (a) 350°C, 0.7 YS, (b) 350°C, 0.8 YS,
(c) 350°C, 0.9 YS, (d) 400°C, 0.7 YS, (e) 400°C, 0.8 YS, (f) 400°C, 0.9 YS,
(g) 450°C, 0.7 YS, (h) 450°C, 0.8 YS, (i) 450°C, 0.9 YS

20
Fig.7. Plot of the minimum creep rate vs. stress for Zr-2.5Nb pressure tube material in
AR and charged with 200 wppm condition at different temperatures to
determine the stress exponent, n.

21
Fig.8. Creep activation energy, Q determination using the plots of   vs. ⁄ for
Zr-2.5Nb pressure tube material in AR and charged with 200 wppm condition at
constant stress levels of 0.7, 0.8 and 0.9 times of YS.

22
 Table.1. Composition of Zr-2.5Nb pressure tube used in 220 MWe IPHWR.

Sr. Tube Ingot Elemental composition

no. Id condition
Nb O Fe H N C Cl P
(wt%) (ppm) (ppm) (ppm)
(ppm) (ppm) (ppm) (ppm)

Quadruple
1 D 2.58 1051 580 4 28 13 0.19 8.9
melted

Table.2. Stress exponent values obtained at different temperatures for AR and

200 wppm Zr-2.5Nb pressure tube.

n, stress exponent

Temperature→
350°C 400°C 450°C
H Content↓
AR (~5 wppm) 5.8 5.2 5.2
200 wppm 7.9 6.4 5.5

Table.3. Activation energy values obtained for Zr-2.5Nb pressure tube material in AR
and charged with 200 wppm condition at different stress levels.

Q (kJ/mol), activation energy

Stress Level→
0.7 YS 0.8 YS 0.9 YS
H Content↓

AR (~5 wppm) 130 112 123

200 wppm 160 138 147

23