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Nb-

.., .., .., .., ..,


..
..., .,
.., ..
, .,

,
-1000

70-75 ./U
6-7 ,

[1,2].
-1000
110 (Zr-1%Nb).
635 1000
.
. 635

(.1,2) [3-8].

2 .0

12

dpa

Z r-4
(S R A )

1 .5

,%

E 110

1 .0

E 635

0 .5

0 .0

0 .0

0 .5

1 .0

1 .5
22

F ,1 0 c m

2 .0

2 .5

3 .0

3 .5

-2

( E > 0 .1 M e V )

.1.
3500, 100 , 8500
,

-1000 ,

.
110

(15-20

(0,01% . 2).

(. 2) [6,9].
635
( 40-50 )
(0,02 .% 2). ,
[7,9].

2 0 ,0 2 % .

50

635
25

2 0 ,0 1 % .

110

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

, / U

)
400
,

75

110

300

200

100
635

10

15

20

25

,,10

30

35

)
.2. ,
-1000
)
)
(max 2,0 /2)

-1000

, ,

.,
.

635 110
.


635


110 .
1.
,
9,137,72 ,
1.

560-5800.
1.

, % .
/

Nb
Sn
Fe
Mo
O
1
635*
0,9-1,1
1,1-1,3
0,3-0,35
0,07-0,09
2
635 1
1,0
0,80
0,30
0,09
3
635 2
0,75
1,25
0,30
0,09
4
635 3
0,75
0,80
0,30
0,09
5
635 4
1,0
1,20
0,30
0,10
0,09
6
635 5
1,25
0,80
0,48
0,09
7
110
0,9-1,1
0,04
8
110 1**
1,0
0,125
0,13
* - [8] 635:

Nb=0,5-1,5; Sn=0,9-1,5; Fe=0,30-0,60; O=0,05-0,15


** - 1101. [10]
2.
, ,
1

.
3.

()
JEM-2000 FXII
200 , ,
(2).
, ,
1, .
, , -
, (L) Zr(Nb,Fe)2 ( (=0,53-0,55
, =0,85-0,88 )) - (Zr,Nb)2Fe (, =1,20 ).
2.

635
635 1
635 2
635 3
635 4

(d, )
(, 1019, -3)
L
T
L
T
Nb
Nb
94
270
4,8
0,3
74
105
230
1,0
6,0
<0,1
84
340
4,0
0,1
100
500
3,5
0,15
-

635 5
110
110 1

46
36

101
80

240
240

16
11

6,5
3,3

0,1
<0,1

Nb Zr(Nb,Fe)2
-; - -.
Nb 1,25 Fe 0,48% .
L- ( 635 5).


3600, 18,6
4000, 10,3 450 .

, -
- ( 635).
450
,
635 635 1, 635 2 635 3,
( 0,75-0,8 % .) Sn Nb,
( 3). ,
635 3,
110.
3.
450
, /

635
635 1
635 2
635 3
635 4
635 5

3600
0,018
0,013
0,015
0,012
0,016
0,017

4000
0,094
0,058
0,056
0,048
0,088
0,065

0
360
4000
8,5
42,0
7,0
27,0
7,0
26,0
6,0
22,5
7,5
40,0
8,0
31,0

110

0,013

0,044

6,0

21,0


,

5000, , Nb,
.
,
NiO+LiO2 5000 [11],
-
. ,
, , ,
.
110
,
, ,
( 4).
4.

( 100 2)

,
-2

110
110 1
635
635 1
635 2
635 3
635 4
635 5

29
37
3
19
20
16
4
31

31,5
36,0
2,0
18,0
19,5
15,0
4,0
27,0

,
%
3,5
0,6
0,022
0,13
0,21
0,44
0,03
0,20

0,30
0,13
0,11
0,11
0,13
0,17
0,11
0,10

1,20
0,45
0,15
0,20
0,30
0,60
0,20
0,50

0,12-0,13% . (
110 1) , .
635 635 4 ( 635 0,1%
)
. 635
110 , 635
635 4.


, ,
,
.

. ,

. -
().
,
,
.

4000 . 0,60,9 , .
5.

.
( 635, 635
2).

5.
,
, 4000

110
110 1
635
635 1
635 2
635 3
635 4
635 5

0,60
0,80
0,80
0,80
0,80
0,70
0,80
0,90

,
, 105 .
190,0
175,0
66,0
109,5
53,5
90,5
78,5
78,0



400 0
100 .
3000
.3.

, %

6
5
4
3
2
1
0
110

110 1

635
635 5
635 2
635 4

635 1
635 3

.3.
(4000, 100 , 3000 )

635
1,0-1,7%.
(1,25-1,7%)
0,80% . Sn ( 635 1,
635 3, 635 5).

110 110 1 4,0-4,9%.


. 20 3600.
3600
250330 (.4). 48-54%
635 55-58% 110 110
1.
400

,M a

300

200

100

110

110 1

635 6 35 1 635 4 635 5


635 2 6 35 3

.4.
(=3600)

4.

635 110

1000 .
635
Sn Nb , [8] .
(0,30-0,35% .).
110
0,125% .
Sn 635 -
Sn
-.
Nb Fe, , , ,
Zr-Nb-Fe (L -).
Sn Nb 635
Fe
. Sn Nb
-
( 635 1 635 2).

635 -
, .
Sn Nb
0,80% . ( 635 1, 635 2, 635 3).



635.
110 ( 2).

635
.
. , Sn Nb
(
635 1, 635 2, 635 3) ( 4).
,
, ,
.
,

( 4 5).

.


(.5).
,
635

.
110
Fe (0,12-0,13% .) [10].
.
,
, ,
(). , ,
.
,
.

635 110
635 110

2 .0

200

1 .8

180

1 .6

160

1 10 ( )

1 .4

140

1 .2

120

1 .0

100

6 35 ( )

11 0( )

0 .8

80

0 .6

60

0 .4

40
63 5( )

0 .2
0 .0

0 .0

0 .1

0 .2

0 .3

0 .4

0 .5

0 .6

20
0 .7


5
, 10

(d ),


-1000. 635 1, 635 2,

0 .6

120

0 .5

100

6 3 5 ( )

0 .4

80

0 .3

60

0 .2

40

0 .1

20

0 .0
0 .6

0 .7

0 .8

0 .9

1 .0

1 .1

1 .2

1 .3


, 10 5

(d ),

F e, % .

Sn , % .

.5.

635 3 (.6).
, 635.
Sn
, (.3).

80

60

6 3 5 ( )
1 1 0 ( )

40

20


6 3 5 ( )

0
20

30

40
50
60
, / U

70

80

.6.
(, -1000)

Nb
,
635 110
-1000
.

, Sn, Nb Fe
635 110
.
635 3040% Sn Nb 0,80% .
Sn Nb
110. , Nb
635
. ,
, 0,80% . Sn, 1,0% . Nb 0,30-0,35% .
Fe.

110 0,125% .

.
,
,
. ,
, .


.
.


1. Solonin M.I., Bibilashvilii Yu.K., Lunin Y.A., Golovanov V.N., Panyushkin
A.K., Samoilov O.B., Experience Gained in Operation of Fuel of Water
Cooled Reactors and State of Work in Russia on Fuel Rods and Assemblies
as Applied to High Burnups. Paper submitted to Int.Topical Meeting on
Light Water Reactor Fuel Performance, Portland, 1997.
2. .., .., .. .
. .
: . . .: , 2000, .89-100.
3. Solonin V.I., Bibilashvili Yu.K., Nikulina A.V. et al. Zirconium Alloy for
Fuel Assemblies of New Generation VVER. International Topical Meeting
TopFuel99 [Avignon, France, 13-15 September, 1999], 1999, p.165-177.
4. Solonin V.I., Bibilashvili Yu.K. et al. VVER Fuel Performance and Material
Development for Extended Burn-up in Russia. Second Inter. Symposium
VVER Reactor Fuel Performance [Bulgaria, 1997], p.48.
5. Nikulina A.V. State of the Art and Prospects of Zirconium Materials
Evolution for Fuel Rod Claddings and Other Components of VVER Type
Reactors in Russia, - Topical Conference on Materials and Nuclear Power,
1996, p.157-169.
6. Shebaldov P.V., Peregud M.M., Nikulina A.V. et al. E110 Alloy Cladding
Tube Properties and Condition and Impurity Content, - 12 Inter. Symposium
Zr in the Nuclear Industry ASTM, STP1354, p.545.
7. Nikulina A.V., Markelov V.A., Peregud M.M. et al. Zirconium Alloy E635
as a Material for Fuel Rod Cladding and Other Components of VVER and
RBMK Cores, - 11 Inter. Symposium of Zr in the Nuclear Industry, p.785804.
8. 2141539, 1992.
59307895.0-08, 1998.
5560790, 1996.
9. .., .., .. . ,
- ,

, - --, , 1999., IAEANECDOC-1128, 1999, .103-113.


10. 214539, 1999.
PCT/RU99/00368, 1999.
11. .., ..

, - 2026465.

INTRRELATION OF Nb CONTAINING ZIRCONIUM ALLOY


COMPOSITION WITH CORROSION AND TENSILE PROPERTIES
A.V. Nikulina , V.F.Konkov, V.N.Shishov, M.M.Peregud,
T.N.Khokhunova, N.Yu.Gorskaya
FSUE RF A.A.Bochvar All-Russia Research Institute of Inorganic
Materials (VNIINM), Moscow, Russia
L.P.Sinelnikov, O.A.Golosov
GUDP SF RDIPE, Zarechny, Russia

Introdution
The program of the work under way in Russia to improve nuclear fuel of
novel generation VVER-1000 and further increase the operation reliability of
fuel rods at the fuel burnup up to 70-75 MW .day/kg U in 6 to 7 year cycles is
strongly focused on increasing the life-time of zirconium clad fuel rods and fuel
assembly components [1,2].
Zr-alloy E110 (Zr-1%Nb) is in successful operation as cladding of fuel in
VVER-1000. Another Zr-alloy E635 is in successful operation in VVER-1000
as tubes of guide thimbles and rigid angles and currently is under test in those
reactors as fuel rod claddings. Both the alloys belong to high corrosion
resistance materials. E635 alloy also features a high strain resistance under
conditions of neutron field and stresses (fig.1,2) [3-8].

2 .0

12

dpa

Z r-4
(S R A )

1 .5

,%

E 110

1 .0

E 635

0 .5

0 .0

0 .0

0 .5

1 .0

1 .5
22

F ,1 0 c m

2 .0

2 .5

3 .0

3 .5

-2

( E > 0 .1 M e V )

Fig.1. Creep strain of cladding tubes at 3500, 100 MPa, 8500 h


Among the major characteristics of zirconium materials that might limit
the life time of fuel cladding and fuel assembly components at the scheduled
loads in new generation VVER-1000 there are:

aqueous corrosion and hydrogenation

strain induced dimensional changes of items.


Under the conditions of the reactors now in operation E110 alloy is
subject to corrosion to form very thin oxide coats (15-20 m) at the
insignificant hydrogen pick-up (0.01% mass. 2). Upon boiling the items made
of this alloy develop nodular corrosion (fig. 2b) [6,9].
Under the same conditions E635 alloy is subject to corrosion to form
thicker (up to 40-50 m) oxide coats and higher hydrogen uptake (0.02 mass.%
2). However, this alloy is immune to nodular corrosion under boiling
condition [7,9].

60
2 0 .0 2 % m ass.

40

E 635

20

2 0 .0 1 % m ass.

E 110

10

15

20

25

30

40

35

45

50

55

60

65

70

75

80

B u r n u p , M W d a y /k g U
)
400

T h ic k n e s s o f o x id e c o a t, m

T h ic k n e s s o f o x id e c o a t, m

80

E 110
n o d u la r
c o r r o s io n

300

200

100

E 635
u n ifo r m
c o r r o s io n

10

15

20

25

T im e, h ou r , 10

30

35

b)
Fig.2. Corrosion of fuel cladding under conditions typical of VVER-1000
a) no boiling
b) surface boiling (max linear heat flux 2.0 MW/m2)

Under the conditions of the scheduled for the new generation VVER-1000
the fuel claddings shall withstand more intensive processes that would enhance
corrosion and hydrogenation, plastic strain build-up at the expense of creep,
irradiation induced growth etc which might shorten the life-time of zirconium
claddings.
This paper presents the results of investigating the interrelation of the
alloying compositions of the alloys of the E635 and E110 types with corrosion
and tensile properties.
The investigations were aimed at improving those alloys to further
increase the resistance to uniform corrosion of E635 alloy while retaining the
achieved high resistance to nodular corrosion under boiling conditions and the
strain resistance under neutron irradiation as well as the resistance of E110 alloy
to nodular corrosion upon boiling.
1. Materials Investigated
The compositions of the investigated alloys from which cladding tubes
9.137.72 mm were produced under the plant conditions are tabulated in table 1.
The tubes were as recrystallized after the anneal at 560-5800.
Table 1.
Alloying Composition of Alloys

Content, % mass.
Alloy
Nb
Sn
Fe
Mo
O
1
E635*
0.9-1.1
1.1-1.3
0.3-0.35
0.07-0.09
2
E635 1
1.0
0.80
0.30
0.09
3
E635 2
0.75
1.25
0.30
0.09
4
E635 3
0.75
0.80
0.30
0.09
5
E635 4
1.0
1.20
0.30
0.10
0.09
6
E635 5
1.25
0.80
0.48
0.09
7
E110
0.9-1.1
0.04
8
E110 1**
1.0
0.125
0.13
* - According to the patent [8] E635 alloy contains:
Nb=0.5-1.5; Sn=0.9-1.5; Fe=0.30-0.60; O=0.05-0.15
** - E1101. Patent RF [10]

2. Test and Investigation Methods


Using tubes the composition of which is described in Table 1 the
following was studied:

electron microscope examined microstructure

corrosion resistance in autoclaves

propensity of alloys for nodular corrosion evolution and protective


properties of oxide coats

tensile properties under tension and internal pressure

creep under internal pressure.


1. Results of studies
Microstructure of tubes
By the method of transmission electron microscopy using the microscope
JEM-2000 FXII at the acceleration voltage up to 200 kV the phase composition,
crystal structure as well as average sizes and concentrations of precipitates were
determined (table 2).
The structures of the tubes fabricated from the alloys the compositions of
which are given in table 1 differ in the composition and crystal structure of the
phases. Aside from the -solid solution, the main phase available in the
structures of the alloys is Laves phase (L) of Zr(Nb,Fe) 2 composition (HCP
lattice (=0.53-0.55 nm, =0.85-0.88 nm)) with small quantity of the -phase
(Zr,Nb)2Fe (FCC lattice, =1.20 nm).
Table 2.
Main Structural Features of Tubes
Alloy
E635
E635 1
E635 2
E635 3
E635 4
E635 5
E110
E110 1

Precipitates
Average size (d, nm)
Concentration (, 1019, m-3)
L
T
L
T
Nb
Nb
94
270
4.8
0.3
74
105
230
1.0
6.0
<0.1
84
340
4.0
0.1
100
500
3.5
0.15
101
240
6.5
0.1
46
16
36
80
240
11
3.3
<0.1

Nb and Zr(Nb,Fe)2 phases are uniformly distributed within and along


boundaries of the -grains; the T-phase is primarily located along the -grain
boundaries.
The contents of Nb and Fe in the alloys increased to 1.25 and 0.48%
mass., respectively, are attendant with the growth of the concentration of the Lphases precipitates (E635 5 alloys).
Corrosion of tubes
The corrosion of the tubes was investigated in autoclaves containing
deionized water at the temperature of 3600 and the pressure of 18.6 MPa as
well as in steam at the temperature of 400 0 and the pressure of 10.3 MPa for
450 days.
The tubes fabricated from all the modified alloys were subject to
corrosion to form dense strongly bonded oxide coats dark-grey in water and
grey-brown in steam (E635 alloy types).
At the post-transition stage of corrosion after 450 days testing the lowest
corrosion rate (compared to E635 alloy) was demonstrated by the alloys E635
1, E635 2 and E635 3 having reduced (to 0.75-0.8 % mass.) content of
Sn or Nb or both (table 3). The thickness of an oxide on the tubes of the above
modifications, particularly on E635 3, and their corrosion rates are
comparable to those of E110 alloy tubes.
Table 3.
Corrosion of Tubes 450 day Tested in Autoclaves
Corrosion rate, m/day

Calculated thickness of oxide,

Alloy

m
0

635
635 1
635 2
635 3
635 4
635 5
110

Water 360
0.018
0.013
0.015
0.012
0.016
0.017
0.013

Steam 400
0.094
0.058
0.056
0.048
0.088
0.065
0.044

Water 360
8.5
7.0
7.0
6.0
7.5
8.0
6.0

Steam 4000
42.0
27.0
26.0
22.5
40.0
31.0
21.0

Resistance of alloys to nodular corrosion


As distinct from the alien alloys of the Zry type the propensity for
nodular corrosion of which is assessed in autoclaves with steam at 5000,
Nb-containing alloys needed developments of some other method to assess their
corrosion.
Using the procedure developed by SF RDIPE and employing solid
electrolyte - NiO+LiO2 powder for oxidation at 5000C express-tests were carried
out for the susceptibility of the alloys to nodular corrosion [11]. As parameters
characterizing the tendency of the alloys to nodular corrosion use was made of
the quantity, density, specific surface and nodule dimensions at the surface of an
oxidized specimen.
Under the conditions of the experiment the E110 alloy revealed a
noticeable susceptibility to the evolution of nodular corrosion which
manifested itself as a surface area occupied by nodules, nodule sizes and density
(table 4).
Table 4.
Characterization of Nodular Corrosion
(the analyzed area is 100 mm2)
Alloy

E110
E110 1
E635
E635 1
E635 2
E635 3
E635 4
E635 5

Quantity
of
nodules
29
37
3
19
20
16
4
31

Nodule
density,
cm-2
31.5
36.0
2.0
18.0
19.5
15.0
4.0
27.0

Specific
surface of
nodules, %
3.5
0.6
0.022
0.13
0.21
0.44
0.03
0.20

Nodules sizes, mm
Average
Maximal
0.30
0.13
0.11
0.11
0.13
0.17
0.11
0.10

1.20
0.45
0.15
0.20
0.30
0.60
0.20
0.50

The alloying with iron in the quantity of 0.12-0.13% mass (E110 1


alloy) substantially reduced the specific surface occupied by nodules.

The E635 alloy and its modification E635 4 (containing 0.1% ) feature a
very low propensity for the evolution of nodular corrosion. The other
modifications of the E635 alloy as compared to the E110 alloy, also have a low
susceptibility, however, they are inferior to both the E635 and E635 4 alloys.
Protective properties of oxide coats
An oxide coat available at the surface of zirconium tubes plays a
protective role if it governs the processes taking place in a metal adjoining layer
that prevent oxygen from penetrating this layer.
Pores or cracks as well as higher conductivity areas available in an oxide
lead to a decrease of the impedance modulus. In this case the metal-oxide coat
liquid electrolyte capacitor is the one having an effective electrical resistance
(eff).
One of the methods used to assess the protective properties of oxide coats
formed on the tubes from the alloys under study was the method of determining
the effective specific electrical resistance.
The protective properties of oxide coats were studied using the alloys
oxidized at 4000. The thickness of the oxide coats on the specimens was 0.60.9 m which was in line with the pre-transition stage of corrosion. The
measured specific resistance of the coats is presented in table 5.
Essentially all alloying elements promote a decrease in the specific
resistance of an oxide coat. The most prominent influence on the decrease of the
resistance is effected by the content of tin (E635, E635 2 alloys).

Table 5.
Effective Specific Resistance of Oxide Coats Formed on Alloys Oxidized in Air
at 4000
Alloy

Oxide coat thickness,


m

E110
E110 1
E635
E635 1
E635 2
E635 3
E635 4
E635 5

0.60
0.80
0.80
0.80
0.80
0.70
0.80
0.90

Specific electric
resistance ,
eff, 105 hm.m
190.0
175.0
66.0
109.5
53.5
90.5
78.5
78.0

Creep of internally pressurized tubes


The creep resistance of the internally pressurized tubes fabricated from
the modified alloys has been studied at 4000C and the stress of 100 Pa.
The thermal creep strain of the tubes after 3000 h testing is illustrated in
fig.3.
6

C r e e p s tr a in , %

5
4
3
2
1
0
E 110

E 110 1

E 635
E 635 5
E 635 2
E 635 4

E 635 1
E 635 3

Fig. 3. Thermal creep strain over tube diameter


(4000, 100 MPa, 3000 h)

Under the above conditions the tubes produced from all other
modifications of E635 alloy have the creep strain in the range of 1.0-1.7%. The
higher creep strain (1.25-1.7%) was demonstrated by the tubes from the
modified alloys having tin lowered down to 0.80% mass. (E635 1, E635 3,
E635 5 alloys).
Under the same testing conditions the creep strain of the tubes made from
E110 and E110 1 alloys was within 4.0-4.9%.
Strength of internally pressurized tubes
The strength and ductility were assessed via testing internally pressurized
tubes up to the burst. The tests were carried out at 20 and 3600.
At 3600 the strength of the tubes from the modifications studied was
within 250330 MPa (fig.4). In this case the ductility was in the range of 4854% for E635 and its modifications and 55-58% for E110 and E110 1.
400

200

,M Pa

300

100

E 110

E 11 0 1

E 6 35 E 635 1 E 63 5 4 E 6 35 5
E 63 5 2 E6 35 3

Fig.4. Strength of internally pressurized tubes


(test=3600)

2. Discussion of Results
Out-of pile tests and investigations of tubes from E635 and E110 Zr aloys
and their modifications aimed at having higher corrosion resistant fuel claddings
and fuel assembly components under loads scheduled for new generation
VVER-1000 reactors have demonstrated that the target is feasible.
The investigated modifications of the E635 alloy basically differed in the
contents of Sn and Nb within the limits contemplated by the patent for the alloy
[8] . The iron content of the alloy was kept constant (0.30-0.35% mass.).
The modified E110 alloy contained iron in the quantity of 0.125% mass.
Sn available in the E635 alloy and its modifications is in the -solid
solution that is why a variation in the content of Sn might only affect its content
in the -solution.
Aside from a low amount of Nb and Fe in the -solid solution they are
also available in the structure of tubes as ternary intermetallics Zr-Nb-Fe (L- and
-phases).
The variation in the contents of Sn and Nb in the E635 modifications at
the unchanged content of Fe affected the concentration and sizes of intermetallic
particles. As the contents of Sn and Nb decrease the concentration of the Lphase becomes lower while the concentration of the -phase increases (E635
1 and E635 2 alloys).
The carried out investigations reveal that it is the composition of the solid solution and not the intermetallic particles that primarily influences the
corrosion of the E635 alloy. The result of the reduced content of Sn or Nb to
0.80% mass. (E635 1, E635 2, E635 3 alloys) is favorable in terms of
the uniform corrosion.
In comparison to the E635 alloy, the alloys having that content of the
indicated elements demonstrate a substantially higher resistance to uniform
corrosion under autoclave conditions and form appreciably thinner oxide coats.
The results acquired on the uniform corrosion of the particular alloys are close
to those of the E110 alloy (table 3).
The E635 alloy features a high resistance to nodular corrosion. Its
studied modifications have preserved that property. However, it is noted that

decreased content of Sn and Nb of the alloy degrade to some extent its resistance
to nodular corrosion (E635 1, E635 2, E635 3 alloys) (table 4).
It is evident from the results of the investigations that the thinner is the
corrosion effected oxide coat the more is the oxide prone to evolution of
nodules.
The investigations have demonstrated that the lower growth rate of an
oxide upon interacting with water or steam is in line with the higher electrical
resistance of an oxide (tables 4 and 5). However, alloys having a higher
electrical resistance are more prone to nodular corrosion. The interrelation
between the specific electrical resistance of oxide coats and nodular corrosion
resistance is attested by the analogy in dependence on alloying (fig.5). It is
likely that there has to be some optimum in the quest of E635 alloy for retaining
the high resistance to nodular corrosion and reducing the thickness of an oxide
upon uniform corrosion.
In terms of the nodular corrosion of E110 alloy the availability of Fe
(0.12-0.13% mass.) is favorable [10].

In this case its high resistance to

0 .2

40

0 .1

20

0 .0
0 .6

0 .7

0 .8

0 .9

1 .0

1 .1

1 .2

Sn , % .

1 .3


, 10 5

(d ),

uniform corrosion is retained.


Among the factors that influence the protective properties of oxide coats
there might be macrostresses of an oxide layer adjoining the metal (substrate).
The results are available that point to the role of this factor. They indicate that
there exists some optimal magnitude of macrostresses that provides for the
protection of the substrate against the penetration of oxygen and does not induce
the break-down of an oxide coat.
The results of out-of-pile investigations into E635 and E110 alloys with
modified alloying compositions and the data available on the behavior and
properties of E635 and E110 alloys allow some forecast of the corrosion
0 . 6and deformation stability of fuel claddings
1 2 0 under the scheduled loads
resistance
of the VVER-1000
reactors. Such a forecast 1 has
0 .5
0 0 been implemented for
6 3 5 ( )
theE635M1, E635M2, E635M3 modifications (fig. 6). Similarly to the E635
alloy the0 . 4above mentioned modifications retain 8a0 high creep resistance and
strength.0 The
reduced content of Sn in the alloy degrades
its creep resistance,
.3
60
however, in this case too it remains adequately high (fig.3).

200

1 .8

180

1 .6

160

E 1 1 0 ( )

1 .4

140

1 .2

120

1 .0

100

E 6 3 5 ( )

E 1 1 0 ( )

0 .8

80

0 .6

60

0 .4

40
E 6 3 5 ( )

0 .2
0 .0

0 .0

0 .1

0 .2

0 .3

0 .4

0 .5

0 .6

E ffe c tiv e s p e c ific e le c tr ic a l r e s is ta n c e


o f o x id e , 1 0 5 O h m m

M a x im a l s iz e o f n o d u le s (d ), m m

2 .0

20
0 .7

0 .6

120

0 .5

100

E 6 3 5 ( )

0 .4

80

0 .3

60

0 .2

40

0 .1

20

0 .0

0 .6

0 .7

0 .8

0 .9

1 .0

1 .1

1 .2

1 .3

E ffe c tiv e s p e c ific e le c tr ic a l


r e s is ta n c e o f o x id e , 1 0 5 O h m m

M a x im a l s iz e o f n o d u le s (d ), m m

C o n te n t F e , % m a s s.

C o n te n t S n , % m a s s .
Fig.5. Influence of alloying on maximal size of nodules and effective
specific electrical resistance

M a x im a l th ic k n e s s o f o x id e c o a t, m

80

60

E 6 3 5 (M I R r e a c to r )
E 1 1 0 (M I R r e a c to r )
M R re a c to r
B a la k o v o N P P

40

20

N e w m o d if i c a ti o n s o f E 6 3 5
u n d e r d e v e lo p m e n t ( f o r e c a s t )

0
20

30

40

50
M a x im a l b u r n -u p , G W /tU

60

70

80

Fig.6. Oxide coat on fuel claddings


(conditions characteristic of VVER-1000 )

Conclusion
The interrelation has been studied of alloying composition of zirconium Nbcontaining alloys with corrosion and tensile properties aimed at further
improving the E635 and E110 alloys in terms of their performance under
operating conditions of new generation VVER-1000.
It has been demonstrated that the contents of the alloying elements Sn, Nb
and Fe available in alloys of the E635 and E110 types influence
appreciably their corrosion properties.
The resistance of E635 alloy to uniform corrosion is 30-40% increased with
the contents of Sn and Nb reduced to 0.80% mass. The oxide coat
thickness for the alloys having that content of Sn and Nb is similar to that
of E110 alloy. However, at a reduced content of Nb in E635 alloy its
resistance to nodular corrosion degrades a little. That is why, the

modified alloy containing 0.80% mass. Sn, 1.0% mass. Nb and 0.300.35% mass. Fe is more preferable. This alloy retains high tensile
properties and strain resistance.

Iron in the quantity of 0.125% mass. available in E110 alloy improves its
resistance to nodular corrosion with all the other properties being
retained.
The interrelation has been revealed of the thickness of corrosion induced
oxide coats on the alloys with the protective properties of coats and the
nodular corrosion evolution. The alloys that corrode to form thin oxide
coats are more sensitive to nodular corrosion.
Based on the results of out-of-pile tests and examinations new modifications
of the above alloys have been designed that demonstrate improved
corrosion properties. Cladding tubes produced from the novel
modifications are in the process of in-pile testing.

List of References
1. Solonin M.I., Bibilashvilii Yu.K., Lunin Y.A., Golovanov V.N., Panyushkin
A.K., Samoilov O.B., Experience Gained in Operation of Fuel of Water
Cooled Reactors and State of Work in Russia on Fuel Rods and Assemblies
as Applied to High Burnups. Paper submitted to Int.Topical Meeting on
Light Water Reactor Fuel Performance, Portland, 1997.
2. Konovalov V.F., Molchanov V.L., Solonin M.I. et al. Nuclear Fuel Power
Reactors. State of the Art and Prospects. Nuclear Fuel Cycle: Collection
of Papers. M. MinAtom, RF, 2000, pp.89-100.
3. Solonin V.I., Bibilashvili Yu.K., Nikulina A.V. et al. Zirconium Alloy for
Fuel Assemblies of New Generation VVER. International Topical Meeting
TopFuel99 [Avignon, France, 13-15 September, 1999], 1999, p.165-177.
4. Solonin V.I., Bibilashvili Yu.K. et al. VVER Fuel Performance and Material
Development for Extended Burn-up in Russia. Second Inter. Symposium
VVER Reactor Fuel Performance [Bulgaria, 1997], p.48.
5. Nikulina A.V. State of the Art and Prospects of Zirconium Materials
Evolution for Fuel Rod Claddings and Other Components of VVER Type
Reactors in Russia, - Topical Conference on Materials and Nuclear Power,
1996, p.157-169.
6. Shebaldov P.V., Peregud M.M., Nikulina A.V. et al. E110 Alloy Cladding
Tube Properties and Condition and Impurity Content, - 12 Inter. Symposium
Zr in the Nuclear Industry ASTM, STP1354, p.545.
7. Nikulina A.V., Markelov V.A., Peregud M.M. et al. Zirconium Alloy E635
as a Material for Fuel Rod Cladding and Other Components of VVER and
RBMK Cores, - 11 Inter. Symposium of Zr in the Nuclear Industry, p.785804.
8. Patent RF Zirconium Base Alloy 2141539, 1992.
Europatent 59307895.0-08, 1998.
Patent, USA 5560790, 1996.
9. Konkov V.F., Nikulina A.V., Peregud M.M. et al. Factors Influencing outof and in-Pile Corrosion of Zr Cladding of Fuels. Int. Work Meeting on

Water Chemistry and in-Pile Corrosion Hluboka nad Vltavou, Czech


Republic, 1999, IAEA-NECDOC-1128, 1999, pp.103-113.
10.Patent RF Zirconium Base Alloy 214539, 1999.
International Application PCT/RU99/00368, 1999.
11.Perekhodzev V.I., Sudnik A.G., Way of Determining Zr-alloy Propensity
for Nodular Corrosion, - Patent RF 2026465.

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