ORIG. RUSSIAN: CORROSION RESISTANCE OF ZIRCONIUM AND ITS ALLOYS IN WATER AND STEAM AT HIGH TEMPERATURES

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• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP88-00904R000100100040-6
• Release Decision: RIPPUB
• Original Classification: U
• Document Page Count: 20
• Document Creation Date: December 22, 2016
• Document Release Date: August 12, 2009
• Sequence Number: 40
• Publication Date: May 1, 1964
• Content Type: STUDY

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Zoe
Third United Nations
International Conference
on the Peaceful Uses
of Atomic Energy
Confidential until official release during Conference
A/CONF. 28/P/341
USSR
May 1964
Original; RUSSIAN
CORROSION RESISTANCE OF ZIRCONIUM AND ITS ALLOYS
IN WATER AND STEAM AT HIGH TEMPERATURES
V.S Eme lyanov, A I .Eva ty ukh in, G . B . F ed o rov, G . G . Ryatbva
N. V. Borkov, I . I . Korobkov, P. L. Gruz in
Due to their nuclear, physical, chemical and engineering
properties zirconium and its alloys have a number of advantages
in comparision with other structural materials. However when
zirconium and its alloys are used in reactors cooled by water
or steam these advantages severely decrease due to hydrogen ab-
sorption which leads to deterioration of their corrosive and
mechanical properties.
The mechanism of effect of additions and alloying elements
in zirconium on its corrosion resistance in water and steam has
been studied insufficiently (1,2).
Some investigations on the processes of zirconium and its
alloys corrosion were carried out by the authors earlier. The
paper (3) describes the studies of oxidation kinetics of zirco-
nium and its alloys, of structure and composition of the resul-
ting oxide films. The paper (4) was devoted to studies of zirco-
nium alloying effect on protective properties and critical
thickness of oxide film appearing on it. This paper describes
the results of further investigation carried out for studying
the redistribution of some impurities and alloying elements in
zirconium after the corrosion, in water and steam at high condi-
tions. The oxide film appearing as a result of the corrosion was
also studied with an electron microscope.
Methods and objects of research
The redistribution of additions was studied with the help
of radioactive isotopes. Two methods were used. In the first
case the radioactive isotopes were introduced into zirconium
during the alloying process. The specimens were heat treated
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and then subjected to corrosion Lests. The redistribution of
impurities and alloys in the corrosion process in the inactive
water and steam of high parameters was investigated. In the se-
cond method the inactive alloys of zirconium in water and steam
medium containing tritium were investigated. The specimens were
activated during the corrosion process due to interaction of
tritiwu in water with zirconium.
Using the electron microscope EM-5 the topography of the
surface was studied after corrosion as well as the structure of
the generated films.
In order to investigate the redistribution of elements in
the corrosion process, zirconium alloys with radioactive isotopes
of carbon, nickel and iron(see table I) were smelted.
The cast alloys were heat-forged in air at 900-700?. The
samples were made in the form of I x 8 x 20 mm rectangles. After
heat treatment the samples were studied autoradi ographi c ally and
metal lographically.
Corrosion expei'iments were carried out in static conditions
in microautoclaves filled with distilled water at 370-4000c and
at the pressure corresponding to the elasticity of water vapour
at the given temperature. The time of the experiment was limited
by the appearance of a white oxide film. With some alloys this
white film was not observed, but the experimental time did not
exceed 1000 hours.
After corrosion experiments a series of unparallel cuts
at an angle of about 10 were made in order to investigate the
redistribution of the elements in the oxide film as well as in
the metal. These cuts were made by means of grinding and poli-
shing.
In order to determine the effect of hydrogen on the cor-
rosion resistance of zirconium and its alloys, experiments were
carried in Lhe vapour of tritium water with a radioactivity of
3,curie/m1. Investigations of an iodide zirconium, zirconium alloys
with 0.7% Fe and 0.7% Ni and of zirconium with nitrogen content of
0.025 weight percent were made. The experiments were carried
in static conditions at the temperature of 40000 and under the
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pressure of 220 atm. The maximum time of experiment was 750
hours,
The analysis of the samples after the corrosion experiments
in tritium water was also carried on the unparallel cuts by the
metallographic and autoradiographic methods.
EaRerimental results
The influence of carbon
The distribution of carbon in zirconium depends upon the
heat treatment of the alloys, as our investigations have proved
/'5,6/. In order to investigate the influence of the carbon dis-
tribution upon the corrosion resistance of zirconium, the heat
treatment of the samples before the corrosion experiments was
carried under several conditions (table I). They resulted in a
different distribution of carbon in zirconium samples. This was
observed on the boundaries and subboundaries of the of phase,
which appeared at the A--sot transformation (hardening and
annealing at 1000?); the uniform distribution of carbon in
ol-- solid zirconium solution (annealing at 800?) was also ob-
served.
Corrosion experiments according to the conditions given
in table 3, showed that all the samples, irrespective of the
heat treatment conditions had a low corrosion re:~5istance and
were covered with a white crumbling film after 125 hours.Under
this film there was a dark transitional layer which lay tightly
on the metal.
Pig.I and 2 show autoradiograms of unparallel cuts of the
zirconium-carbon samples, showing the distribution of carbon in
the surface film, the transitional layer and inside the sample.
The carbon distribution in zirconium remained the same after the
experiment as it was before the experiment, provided no corrosion
occurred in the samples. The autoradiogrnms show that corrosion
begins at the boundaries of the grains of the o ..phase and
then spreads along the whole volume (fig.3). In samples which
were subjected to the heat treatment at high temperature in the
region of 9 phase, the corrosion process in observed at first
at the boundaries and subboundaries of the grains. This is caused
by allotropical transformation of P--vot, phases then the pro-
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cess spreads over the grain volume (fig.2). During the corrosion
process a partial decarbonization of zirconium takes place.
Fig.3 shows autoradiograms from the same surface of the
sample annealed at 1000 0 before and after corrosion. It is
apparent that after corrosion the degree of decarbonization and
hence the degree of corrosion is different for various grains.
This can be proved by a different relative darkening of parts
in the autoradiograms, corresponding to single zirconium
grains. This is apparently connectd with different orientation
of the zirconium grains to the surface of the sample. Differently
orientated grains of zirconium corrode at -different rate, which
can probably be explained by the anisotropy of the oxygen dif-
fusion into the lattice of o! -zirconium,
A radiometric analysis of unpara'.lel cuts of zirconium
samples after corrosion has been carried out using the technique
described in the paper (1/98). According to the data of the
radiometric analysis and those measured by a microphotometer the
content of carbon in the surface film is 0.3 compared with that
of the original content in zirconium. This shows that decarbo-
nization of zirconium takes place during the corrosion process
and it may be connected with the generation and removal of car-
bon oxides. Nevertheless a part of carbon still remains in the
oxide film.
The effect of alloying impurities
We have shown that alloying in the range of zirconium solu-
bility with tin increases the energy of self-diffusion activation
(5), increases the sublimation heat (9), decreases the effect of
structural factor on diffusion (10), and attenuates the decrease
of normal elasticity model with temperature rise. Thus tin
alloying improves the strength characteristics at higher tempera-
tures. This may be connected with a sufficient decrease of exces-
sive concentration of vacancies. The effect of niobium resembles
that of tin (5, I0).
In addition tin neutralizes the harmful effect of nitrogen
on corrosion properties of zirconium. The iron, nickel and
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chromium impurities form insoluble intermetalides (Fe2Zr, Zr2Ni
1d Cr2Zr) ; which being microcatode areas anodically polarize
the zirconium matrix and facilitate the formation of a thin
oxide film with a higher strength (II).
The distribution of carbon in zirconium alloys with 0.05
per cent radioactive carbon and I W per cent of tin depends
upon the heat treatment. After hardening and annealing in
-area, one can observe a subboundary and boundary concentra-
tj,on of carbon. The annealing in the of-area leads to a nearly
uniform distribution of carbon in the alloy. After the corrosion
experiments during 580 hours the surface of the samples were
satisfactory. Distribution of carbon in the surface film and
inter the sample was the same and did not change comparing to
the original distribution of carbon in the alloy.
Zirconium alloy with 0.1 W per cent of tin was tested at
a higher temperature of water and already after 125 hours it
wao covered with a white film. No visible changes in the distri-
bution of carbon in the film and inside the sample were obser-
'red. Like in the previous alloy the reduction of carbon content
iri the surface film compared to that inside the sample is obser-
ved. According to the radiometric analysis and to the microphoto-
meiering of the autoradiograms the carbon content in the film
compared to that of the original was 0.4.
The zirconium alloys with 0.1 W per cent of carbon and 1 W
per cent of niobium, 0.8 W per cent of iron and 0.8 W per cent
of nickel were tested after annealing at 750? during 1 hour. In
.fl alloys carbon after the heat treatment was distributed in
a-solid solution and in the form of carbides. The distribution
of carbon ii the surface film and inside the metal were alike.
The regions of the autoradiogram over the film are of a lighter
colour than over the inner parts of the sample. Microphotomete-
rd,ng of the autoradiograms of the unparallel cuts of the samples
bowed that the carbon content in the film as compared to the
ib,itial contents in the sample was - 0.5 for zirconium alloyed
wi-0 0.1 W carbon and I W niobium and - 0.6 for zirconium alloyed
wi-h 0.1 W carbon and 0.8 W nickel.
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The redistribution of nickel after corrosion tests L, hot
water was studied in the zirconium alloy with 0.6 W nickel and
in~ triple zirconium alloy with 0.6 W iron and 0.4 W nickel.
The autoradiograms of the unparallel cuts of the samples
annealed before the tests at 10000 show three layers (fig.4).
In the lighter surface layer , separate grains of high temperature
phase of the alloy are present; these differ in the degree of
darkening. Then comes the transitional layer, where the character
of the distribution is the same as inside the sample, but the
intensity of darkening is weaker. In the third layer the charact-
er of the nickel distribution is the same as in the original
sample. The microstructure of the transitional layer (fig.4)
shows a deeper corrosion of the subboundary of n/--phase.
After hardening at 10000 the zirconium alloy with 0.6 W
nickel had a coarse-grained structure. The autoradiograms of the
unparallel cuts of the samples, hardened at 1000? before the
test do not show any nickel redistribution inside the sample.
Selective corrosion in the transitional layer was not observed in
the microstructure.
The autoradiogram of the Lnparallel cut of the zirconium
sample with 0.6 W nickel annealed before the test at 750? does
not show any nickel redistribution in the corrosion process.
But the microstructure of the transitional layer shows selective
corrosion along the subboundaries of the grains, where the nickel
segregations are concentrated (fig-5).
The zirconium alloy with 0.4 W radioactive nickel and 0.6 W
iron was heat treated in c&and 9-regions;this resulted
in different nickel distribution. After annealing at 800? there
appeared a stabilised dphase, which was surrounded at the
grain boundaries with rather coarse segregations of intermetal-
lides Zr2Ni and Fe2Zr. They concentrated all the nickel and iron.
After hardening at 10000 one part of nickel and iron remains in
the solid o4-zirconium solution, while another part is concentra
ted along the boundaries and subboundaries of the oC phase
grains having a needle structure. After annealing at 1000? and
?50? the segregation of nickel and iron are more complete, but
the degree of dispersion of the segregation is high.
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The samples annealed at 8000 before the test were covered
with a thick light film after a test of 250 hours. The micro-
structure of the samples shows a selective corrosion along the
grain boundaries of the o(-phase, where the segregated inter-
metallides are located. Redistribution of nickel either in
the surface film or in the transition. film or inside the sample
was not shown. Samples treated otherwise had a dark tight
surface film after 580 hours test. The autoradiograms of the
unparallel cuts of these samples shoWt4d no redistribution of
nickel in the surface film and inside the sample.
The distribution of iron in zirconium depends upon the heat
treatment of the alloy. When annea1.1g at 800? during 40 hours
the distribution of iron is in the form of coarse intermetallides
along the boundaries of coarse grained c~ -phase. After annealing
at 10000 the iron is distributed along the subboundaries of the
oe -phase. Hardening at 10000 gives a uniform distribution of
iron.
The samples annealed at 800? were covered with a white film
after 125 hours. The samples after the heat treatment had a good
surface condition during a test for 250 hours. No distribution
of iron was observed on the surface film and in it during the
corrosion process in samples annealed at 7500 and 10000 and
hardened at 10000 (fig.6). The microstructure of the transition
layer of the samples does not show the selective corrosion of the
alloy. In samples annealed at 8000 a deeper corrosion of the
grain boundaries in o'-phase was observed. The segregated
intermetallides were located along the boundaries (fig. ?a). The
autoradiogram and the microstructure of the surface film are
shown in fig. 7b. The iron is seem, to be present in the oxide
film.
Fig.8 shows autoradiograms of unparallel cuts of the samples
of pure zirconium ("a"), of the zi,reon.ium alloy with nickel and
iron ("b" and tie") and zirconium alloy with nitrogen ("d") after
corrosion tests in tritium water. In all the cases we see that
as a result of the corrosion of samples hydride inclusions are
found.
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In zirconium, containing 0.025%of nitrogen, the quantity of
the hydride phase is much greater than in other two alloys,
i.e. the presence of nitrogen in zirconium makes the metal more
susceptible to hydrogen absorption during the corrosion process.
In the alloy with nitrogen the hydrides are distributed along
the boundaries and subboundaries of grains and form a characte-
ristic grid.
In pure zirconium and in its alloy with iron and nickel
after an equal length of test the quantity of hydrides and the
character of their distribution are nearly the same and the hyd-
rides are located as separate accumulations.
On the boundary between the metal and the oxide film there
is no preferential location of hydrides i.e. there is no hydride
sublayer under the oxide film. This was determined for all the
investigated alloys under different test exposures.
The regions of the sample surfaces which on unparallel cuts
are interstitial between the metal and oxide film were investiga-
ted. During the preparation of the unparallel cuts the oxide
film could not be cut under the given angle (about 2?), but
being brittle, cleaved, forming steps. Besides the oxide film
itself had a certain relief. Therefore the boundary of the cleave
of the oxide film was not straight. Some of the protruded places
of the film cleaved forming closed areas, free of oxide film,
and surrounded by the undestroyed film.
The left part of fig.IO shows one of such areas under side
illumination; the right part of fig.IO shows the autoradiogram
of the same area. One can clearly see that hydride formations
are located in the centre of the area.
It is known that the volume increases about 20%o with the
formation of the zirconium hydride (13). If such a large increase
of the volume takes place directly under the oxide film it causes
a local swelling of the film and this in its turn causes con-
siderable stresses in it. When the stresses reach some critical
value the film may crack in places of swelling. Thus the forma-
tion of hydride parts under the oxide film causes the :I' creasing
of its protecting properties and promotes the increa.~:L ng of the
corrosion process in the water-vapour media. Such conclusion
agrees with results of the work (14).
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Electron microscopic investigations of the oxide film on
zirconium and its alloys after corrosion
The electron microscopic investigation of the oxide film for-
med on zirconium and its alloys with tin, iron, nickel, niobium
and chromium during the corrosion process was carried out for
studying its structure.Fig.I0 shows some typical electron micro-
photoes of the surface of zirconium samples and those of its alloys
after their long corrosion in water-vapour media at 370 and 4000
(a,b) and after a short time (3 sec.) oxidation in oxygen at 120 inn
Hg and IIO0?C (c). On these samples the film has a clearly visible
structure of oxide grains and the substructure resembling a system
of parallel lines. The size and the form of the oxide grains remain
such as were those of the alloy crystals. The appearance of. linear
substructure in the grains of the oxide film is probably due to
the plastic flows in the film induced by clamping stresses. These
stresses appear in the film due to a great difference in metal and
oxide volumes (the volume ratio of Zr02 and Zr is I.6) and due to
a very tight cohesion between the film and the metal.
The space between the lines in the substructure of single
grains is approximately equal, but the direction of the lines is
different in various grains; there are such grains where the linear
substructure is absent. This proves that the generation of sub-
structure lines is connected with the orientation of crystals of
the oxide in the film.
The linear substructure of the oxide film on zirconium and
its alloys is formed after a long corrosion in the steam-water
media and after a short-time oxidation in oxygen at high tempe-
ratures (Fig. IOb).
The investigation of cross sections of the oxide films on zir-
conium and its alloys after a long corrosion proved the appearance
of longitudinal fractures and lamination of the film observed in
the paper (15). It was found that the appearance of longitudinal
fractures is followed by the appearance of cross fractures, which
pass not along the gain boundaries but across the grains themsel-
ves.
Conclusion
1. In the carbon alloys of zirconium during the corrosion
process decarbonization of the oxide film takes place that pro-
bably is connected with the formation of carbon oxides and.their
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Alloying a
itions,
per cent
N?
Alloy
base
C
Sn
Fe
Ni
Nb
I.
Zr
0.3
2.
Zr
0.05*)
1.0
3.
Zr
0.3
1.0
4.
Zr
0.3
0.8
5.
Zr
0.3*)
0.8
6.
Zr
0.3*)
1.0
7
Zr
0.6 )
8.
Zr
0.6
0.4*)
Zr
0.5*)
Radioactive impurity
Annealing 750?-1 hr
Annealing 800?- 0 hr
Annealing 10000-2 hr
hardening at 10000 (after
exposure for 2 hr)
annealing 750-; hr
annealing 1000 -2hr
annealing 750?-$r
annealing 750--ihr
annealing 750?-IYir
gnneali.ng 750-1hr
annealing 750--Ihr
annealing 1000?-2$r
hardening at I000 (after
exposure for 2 hr)
annealing 750?
I
hr
annealing 800?d1
annealing 1000 -2$r
hardening at 1000 (after
exposure for 2 hr)
annealing 750 1hr
annealing 800
annealing 1000 -2}
hardening at I0000 (after
the exposure for 2 hr)
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T a b l e I
Test
Time
temBerature,
C
hours
370
T-25
370
580
400
125
400
958
400
836
400
1045
370
125
250
580
3(0
250
580
580
400
250
125
250
250
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REFER E N C E S
I. The Metallurgy of Zirconium. Edited by B.Lustman and F.Kerze.
N.4., Tor., I (1955).
2. Thomas. The corrosion of zirconium and its alloys in water at
higher temperatures. Proceedings of the International Conference
on Peaceful Uses of Atomic Energy (Geneva, 1955) v.9,p. 407.
3. V.S.Emelyanov, A.I.Evstyukhin,I.I.Korobkov and D.V.Ignatov.
Electrongraphic and kinetic investigations of the oxidation
of zirconium and its alloys at high temperatures. Proceedings
of the Second International Conference on Peaceful Uses of
Atomic Energy (Geneve,1958) v. 5,p.60.
4. A.I.Evstyukhin , I . I. Korobkov. The effect of alloying on the
protective properties and critical thickness of the oxide film
on zirconium.In the book "Metallurgy and Metallography of Pure
Metals'; Moscow, Atomizdat, issue 2, p. 93 (1960).
5. P.L.Grusin,A.I.Evstyukhin,V.S.Emelyanov, G.G.Ryabovap.B.Fedorov.
The Study of Diffusion and Distribution of Elements in Alloys
on zirconium and titanium base using the radioactive isotopes.
Proceedings of the Second International Conference on Peaceful
Uses of Atomic Energy (Geneve,1958) v.19, P. 187.
6. G.G.Ryabova , P.L. Grusin. The study of the Distribution of Ele-
ments in Zirconium and its Alloys by Autoradiography.In the
book "Metallurgy and Metallography of Pure Metals". Moscow,
Atomizdat, issue 3, p. 96 (1962)
7. P.L. Grusin, G. B. Fedorov, G.G.Ryabova , E. V. Danilkin. The Study of
metal and alloy corrosion by tracer techniques, In the book
"Metallurgy of pure metals" Moscow ,Atomizdat,issue 4,p.196(1963)
8. E. V. Danilkin, G. B. Fedorov,G.G.Ryabova . About quantitative ra-
diography technique. Ditto, p.207.
9. G.V.Fedorov,E.A.Smirnov.Thermodynamic properties of zirconium
and its tin alloys. Thermodynamics of the Nuclear Materials.
Proceedings of the Symposium of the IAEA,Vienna,p.285 (1962).
10. G. B. Fedorov. Some peculiarities of strength and diffusion
properties of zirconiurt.The studies on heat-resistant alloys.,
v.X.Publishing of AS of USSR, Moscow,p.46 (1963).
i1. V.I.Mikheeva.The Hydrides of Transitional Metals. Publishing of
AS USSR,p. 169 (1963).
I2.I.N.Wanklyn.3-e Colloque de Metallurgie sur la Corrosion.
North Holland Publishing CY(1960) pp. 127-135.
13. B.Cox and T.Jonston. AERE,R-3881.
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Re f e r e n c e s
I. B.JIacTUeH,O.Kepu,/peA/ McT&JinyprxH 1;xpxoH14H,M.143A-Bo MHOCTp.
JIHT./I959/.
2.Touac,KopposMR uxpxoHxR x ero CnJ1aBOB B BoAe npx nOBb[weHHb1X Tel
nepaTypax.AoIJIa U 1HOCTpaHHbIX ygeHHX Ha Me2KAyHapoAHOLI KoH0epeHu14x no
MMPHOM MCrIOJ1b30BaHIIO aTOMHO2 3Heprwi (}XeHeBa,I955).MeTaJinyprxH HAep-
Hog 3HepreTHKH H AeJACTBxe o6JlytIeHMH H8 uaTepLannM.M.roCTeXH3AaT,I956,
CTp.376.
3.B.C.EMenbaHOB,A.K.iCTIOX H,YI.M.Kopo6KOB H A.B.UIrHaTOB.BneHTpoa-
Ho-rpaepMgecxxe z xI4HeTH4ecKHe xccxeAoBaHIH oKxCJIeHHR 9TPICOH1H x ero
CnnaBOB npH BUCOXXX Te)nepaTypax.B KH."TpyAei 2-9 McXAyHapoAHO9 KoHCpe--
peHuHH no MMPHOUy !CrOJIb3OB8HHIO BTOMHOA 3HeprxH.AOKJiaAbl COBeTCKHX yMe-
HUX".ToM 3, M.ATOMN3A8T /1959/ CTp.474.
4.A.H.EBCTI0xiR, YI.H.Kopo61COB.BJHHHHe JierxpOBaxxR Ha 3aIMTHbie
CBO CTB8 H KPHTilgeCKyIO TOJIU(HHy OKHCHOA nJlexxx Ha uxpKOH}H.B c6."MeTan-
JlyprHR H ueT8XJI0BeAeHHe 'IHCTWX McTaJInoB".M.ATOUH3AaT,BHn.2/I960/cTp. 9"-
5.II.JI.rpy3xH,A.N.EBCTmxxx,B.C.EmenbRHOB,r.P.P>6oBar.B.TeAOPOB.
iaygexxe An ya i x pacnpeAeJieHww 3JiemeHTOB B CiIJI8Bax Ha OCHOBe uxpxo-
HHfi X T?LTaHa ueTOAOM paAK08KT}BHb1X H30TO11OB.B KH."TpyAu 2-M MeatAJHapo;
Hog KOH iepeHuHH no MHpHOM MCfOJIb3OB8HHIO 8TOMHOA 3Heprxx.AoKJIaAbi CO-
BeTCKHX ygeHUx".Tou 6,M.ATOmx3AaT /I959/, CTp.I89.
6.P.P.PadoBa,n.JI.rpy3HH.H;JygeHHe pacnpeueJieHHH 3JIeMeHTOB B uxpxo-
HHYI H ero cnJiaBaX McTOAOB aBTopaAHorpa~xk.B c6.'"MeTaJIJiyprxfi H McTaJIJio-
BeAenxe tIMCTUX xeTa3lnoB" M.ATOM HdA8T,Bun.3 /1962/, cTp.96.
7.H.JI.I'py3xH,I'.B.(DeAopoB,I'.i'.PR6oBa,E.B.A8HKXRXH.Yl3ygeHHe Koppo3Hb
McT8JIJIOB H U28BOB M@TOAaMH P8AHOaKTHBHJ X HHAHKaTOpoB.B c6."MeTaJIJryp-
rHR H ldeTaJIJIOBeAeHxe uMCTUX McTaJIJIOB".M.ATOUx3A8T,Bbin.4/I963A,e p.i98.
8.E.B.)IaHHnxMH,r.B.OeAopoB,l'.r.PR6oBa, K McTOUHKe KoWIxgeCTBeHH0A
paAHorpacxH.Tau ixe cTp.2U7.
9.I'.B.,TeAOpOB,E.A.UmxpHOB,TepuoAHHaupiqecxxe CBO kCTBa i.HPKOHMH i4
ero Cnn8Bo3i c OJIOBOM, Thermodynamics of the Nuclear Materials.Procee-
dings of the Symposium, International Atomic Energy Agency.Vienna
(1962) p.285.
IO.r.b.zeAopoB.HeKOTOpNe oe06eHHOCTK npOgHOCTH JX H AZg4y3MOHHb1X xa-
p8KTepHCTMK uxpKOHHHI, C6. "NccJIeAOBaHHft no zaponpougbar cnvIaBaM". TOM X,
13A.AH CCCP,9./I963/, CTp.46.
II.B.K.MxxeeBa,rMApx,lpU nepexoAHUx McT8JIJ1oB.R3A-Bo AH CCCP 19609
CTp.I63.
12. Wanklyn J.N. 3-e Colloque de metallurgie sur la corrosion.
North Holland publishing CY (1960) pp.I27-135.
13. Cox B. and Jonston T. Chemistry Division-Atomic Energy
Research Establishment Harwall, Berkshire (1962) AERE-R-3881.
-I3-
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Fig. 1 (a)
Fig. 1 (b)
Fig. I. Autoradiogram of an unparallel cut and the microstructure of
the transit laywr of the zirconium alloy with 0.1% carbon
annealed before the corrosion tests at 8000.
Fig.2. Autoradioram of an unparallel cut of the zirconium alloy with
0.1% carbon annealed before corrosion tests at 10000.
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 Approved For Release 2009/08/17: CIA-RDP88-00904R000100100040-6
after the corrosion tests of the zirconium alloys with 0.I
Fig-3. Auboradiogram of the surface of the sample a) before and b)
carbon hardened at 10000
.
.
annealed before corrosion tests at 10000
Fig.4. Autoradiogram a) of the unparallel cut and b) microstructure
of the transit layer of the zirconium alloy with 0.6;% nickel
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 Approved For Release 2009/08/17: CIA-RDP88-00904R000100100040-6
Fig. 5 (a)
Fig. 5 (b)
Fig.5, Autoradioi3ram a) of the unparallel cut and b) the microstruc-
ture of the transit layer of the zirconium alloy with 0.6o
nickel annealed before the corrosion tests at 7500.
FiS.6. Autoradiogram of an unparallel cut of the zirconium alloy with
0.5% iron,annealed before the corrosion tests at 1000?.
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 Approved For Release 2009/08/17: CIA-RDP88-00904R000100100040-6
X1.,,7 . ~. ., . ? - ..1 ~~.'". . C
Fig. 7 (a)
Fig. 7 (b)
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Fig.7. Autoradiograms (left) and microstructures (right) of the
surface film (b) and transitional layer (a) of the zirconium
alloy with 0.5% iron annealed before corrosion tests at 1000?
 Approved For Release 2009/08/17: CIA-RDP88-00904R000100100040-6
Pig. 8 (a)
Fig. 8 (b)
Fig. 8 (o)
Fig. 8 (d)
Fig.8. Autoradiograrns of an unparall?el cut of samples after tests
in the vapour of tritium water:a) of pure zirconium after
corrosion tests for 300 hours.b) of zirconium alloy with 0.7570
iron and 0.7%o nickel after corrosion tests for 300 hours.
c) the same as given in b) after corrosion tests for 750 hours
d) of zirconium with 0.025% nitrofen after corrosion tests
for 300 hours.
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 Approved For Release 2009/08/17: CIA-RDP88-00904R000100100040-6
,~? ?i: j? tvt
Fig.9 .Microstructure (left) and autoradiog;ram (right) of the region
under the oxide film taken away, :where hydrides of zirconium
are seen (600).
Fig. 10 (a)
Fig. 10 (a)
Fig. 10 (b)
Fig.10,Electronic microphotoes of the surfaces of the samples after
corrosion in water vapour medium at 370?C for 3400 hours
(x8000) : a) idodide zirconium. ?b) zirconium alloy with 1%
niobium. c) zirconium alloy with 0.6% tin, 0.6% iron, 0.6%
nickel, I% niobium. d) zirconium alloy with 1% tin, 0.11.,
chromium. e)zirconiu.m oxidised in oxigen at 3300?C for 3 c.
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