KfK 4729

Juni 1994
Chemical Interactions between
as-received and pre-oxidized
Zircaloy-4 and Inconel-718 at
High Temperatures
P. Hofmann, M. Markiewicz
Institut fr Materialforschung
Projekt Nukleare Sicherheitsforschung
Kernforschungszentrum Karlsruhe
Kernforschungszentrum Karlsruhe
. Institut fr Materialforschung
Projekt Nukleare Sicherheitsforschung
KfK4729
Chemical interactions between as-received and
pre-oxidized Zircaloy-4 and
Inconel-718 at high temperatures
P. Hofmann, M. Markiewicz*
*Comisi6n Nacional de Energia At6mica
Av. dei Libertador8250, 1429 Buenos Aires
Argentina
Kernforschungszentrum Karlsruhe GmbH, Karlsruhe
Als Manuskript gedruckt
Fr diesen Bericht behalten wir uns alle Rechte vor
Kernforschungszentrum Karlsruhe GmbH
Postfach 3640, 76021 Karlsruhe
ISSN 0303-4003
Abstract
Isothermal reaction experiments were performed in the temperature range of
1000 - 1300 oe in order to determine the chemical interactions between Zircaloy-4
fuel rod c1adding and Inconel-718 spacer grids of Pressurized Water Reactors
(PWR) under severe accident conditions. It was not possible to apply even higher
temperatures since fast and complete Iiquefaction of the components occurred as
a result of eutectic interactions during heatup. The liquid reaction products
formed enhance and accelerate the degradation of the material couples and the
fuel elements, respectively. Only small amounts of Inconel are necessary to Iiq-
uefy large amounts of Zircaloy.
Thin oxide layers on the Zircaloy surface delay the beginning of the chemical in-
teractions with Inconel but cannot prevent them. In this work the reaction kinet-
ics have been determined for the system: as-received and pre-oxidized Zircaloy-
4/lnconel 718. The interactions can be described by parabolic rate laws; the
Arrhenius equations for the various interactions are given.
Chemische Wechselwirkungen von Zircaloy-4 im Anlieferungs- und voroxidier-
ten Zustand mit Inconel718 bei hohen Temperaturen
Zusammenfassung
Zur Bestimmung der chemischen Wechselwirkungen zwischen Zircaloy-4-
Brennstabhllrohren und Inconel 718-Abstandshaltern von Druckwasserreakto-
ren unter schweren Unfallbedingungen wurden isotherme Reaktionsexperimen-
te im Temperaturbereich 1000 - 1300
0
e durchgefhrt. Hhere Temperaturen
konnten nicht angewandt werden, da eine schnelle und vollstndige Verflssi-
gung der Materialien infolge eutektischer Wechselwirkungen schon in der Auf-
heizphase stattfand. Die entstehenden flssigen Phasen beschleunigen die weite-
re Zerstrung der Materialproben bzw. der Brennelemente. Nur geringe Mengen
an Inconel sind notwendig, um groe Mengen an Zircaloy zu verflssigen.
Dnne Oxidschichten auf der Zircaloy- Oberflche verzgern den Beginn der che-
mischen Wechselwirkungen mit Inconel, sie knnen jedoch nicht verhindert wer-
den. Im Rahmen dieser Arbeit wurde die Reaktionskinetik fr die Systeme nicht
oxidiertes Zircaloy/lnconel und voroxidiertes Zircaloy/lnconel bestimmt. Die ver-
schiedenen chemischen Wechselwirkungen knnen durch parabolische Zeitgeset-
ze beschrieben werden; die Arrheniusgleichungen werden angegeben.
Contents
1. Introduction
2. Experimental Details
3. Results
3.1 Chemical behavior
3.2 Reaction kinetics
3.3lnfluence of an oxide layer on Zircaloy/lnconel interaction
4. Discussion
5. Summary and Conclusions
1
1
2
2
5
6
8
9
6. Acknowledgement
7. References
.................................................. 10
10
List of Tables
List of Figures
.........................................................
.........................................................
11
12
- 1-
1.lntroduction
In severe reactor accidents the temperature within the core exceeds 1200C,
which is the maximum tolerable temperature for design-basis accidents. At these
high temperatures the various materials of the fuel-rod bundles interact chemi-
cally with each other and with the steam of the environment. With respect to
core damage initiation and progression, eutectic interactions are of special inter-
est since these interactions result in the formation of liquid phases at low tem-
peratures. Experiments with fuel-rod bundles, which were heated up to 2000C,
c1early showed, by optical observations and temperature measurements, the sig-
nificant impact of Inconel spacer gridson the early melt formation and damage
propagation within the fuel assembly at rather low temperatures [1, 2]. Inconel
spacer grids fail due to Iiquefaction belowtheir melting point (around 1450C), as
a result of eutectic reactions, of nickel and other Inconel alloy components with
zirconium. The resulting liquid reaction products relocate and enhance and accel-
erate the degradation of the fuel rod bundle.
Given this body of evidences, a very important aspect is to study the reaction ki-
netics and the onset of liquid phase formation between Zircaloy c1adding (Zry)
and Inconel718 caused by the chemical interactions.
The Zry c1adding was used in the as-received condition and in the pre-oxidized
(10,20,45, pm oxide layer thicknesses) condition. An oxide layer on the surface of
Zry can initially prevent the interaction with Inconel, but the oxide is rapidly dis-
solved in the Zry at higher temperatures, during an incubation period, ta. The re-
sult of the separate-effects tests are the basis for the description of the material
interactions by models which can be used in computer code systems.
2. Experimental Details
The isothermal annealing experiments were performed with Zircaloy-4 (Zry) cap-
sules into which short cylindrical rods of Inconel718 had been pressed and c10sed
gas-tight by a conical Zry plug. Figure 1shows the components of a compatibility
specimen before being loaded.
The annealing experiments were performed in a tube furnace under flowing
- 2 -
argon. The specimens were heated up to about 900C and then placed into the
pre-heated furnace whieh had the desired annealing temperature. The annealing
time started when the temperature of the specimen was 20 K below the anneal-
ing temperature. The specimens were cooled down to room temperature outside
the furnace.
The temperatures investigated ranged from 1000 to 1300C and the maximum an-
nealing time was 300 minutes. The highest temperature whieh could be examined
was determined by the condition of the reaction couple,with limits imposed by
the failure of the specimen due to the onset of liquid phase formation followed
by a fast and complete Iiquefaction of the Zry crucible at slightly higher tempera-
tures.
After annealing, the specimens were mechanieally cut and then
metallographieally prepared for examinations of the reaction zones with an op-
tieal mieroscope. Some of the specimens were etched to be able to recognize bet-
ter the various phases. The thicknesses of the reaction zones were measured at
four locations of the interface. The maximum thiekness of the reaction zones was
used to evaluate the kinetie data. In addition, some Scanning Electron Mieroscopy
(SEM)/Energy Dispersive X-Ray (EDX) or SEM/Wave Length Dispersive X-Ray
(WDX) examinations were performed to obtain information on the chemical com-
positions of the reaction products and diffusion zones.
The Zry crucibles from the pre-oxidized Zircaloy/lnconel interaction experiments,
were oxidized in an Ar/02 mixture in a tube furnace. The selected temperature
was 1000C and the times needed to produce the oxide layer thieknesses of 20
and 45 11m were 6 and 25 minutes, respectively. Metallographie examinations
were done to check the actual Zr021ayer thieknesses.
3. Results
The chemieal interaction between Zircaloy and Inconel is a diffusion controlled
process and can therefore be described quantitatively by Arrhenius equations.
Besides the identifieation of the reacting species, phases, and the temperature of
onset of liquid phase formation, one of the main results was the determination of
the reaction kineties, whieh may be used in a code system to prediet the material
behavior at high temperatures.
3.1 Chemical behavior
The chemieal interaction between Inconel 718 (chemieal composition of about 53
- 3 -
wt. % Ni, 19 % Cr, 18 % Fe, 6 % Nb+Ti, 3 % Mo) and Zircaloy-4 shows that a liq-
uid reaction zone develops at temperatures as low as 1000C. The melting points
of Inconel718 and Zircaloy-4 are 1335C and 1760C, respeetively [3, 4].
Although many elements are involved in the Zry/lnconel chemical interaction, the
binary phase diagrams offer a reasonable explanation of low temperature liquid
phase formation. The (Ni - Zr), (Fe - Zr) and (Cr - Zr) phase diagrams indicate that
eutectic interactions occur in these binary systems (Figures 2,3) [5, 6]. The (Ni - Zr)
system has four eutectic temperatures, with the lowest eutectie point at about
960C on the Zr-rieh side. The diffusion of approximately 2 wt. % Ni into -Zr re-
sults in the formation of a liquid phase; even at this low temperature (Fig. 2) the
eutectie temperature on the Ni side is about 1170C. The lowest eutectie tempera-
ture exists in the (Fe - Zr) system at about 930C also on the Zr-rieh side, while the
eutectic temperatures in the binary (Cr-Zr) system are 1332 and 1592C, Le. much
higher.
The cross-sections of the Zryllnconel reaction specimens after annealing at 1000,
1100, 1150 and 1200C for various reaction times are shown in Figure 4. The
cross-sections of both as-received and pre-oxidized Zry/lnconel reaction speci-
mens (initial Zr02 layer thiekness: 10 11m) are presented for comparison. The
eutectie interactions, whieh occur at 1000C and higher, result in the formation of
liquid reaction products and voids form as some of the molten material relocates.
Although the specimens were annealed inan upright position, the reaction zones
of the as-received Zry are not symmetrieal around the circumference. Apparently,
very small forces are sufficient to induce asymmetrie reaction zones in the Zry
wall. First interactions have been noticed at 1000C afterannealing times longer
than 5 minutes. In all cases, the reaction in the Zry was much stronger than in
Inconel. This may be explained by phase diagram considerations (Fig. 2, 3). Only
small amounts (> 5 wt. %) of Ni, Fe or Cr are necessary to Iiquefy large quantities
of Zr. Also, since the eutectic temperatures in the (Ni - Zr), (Fe - Zr), and (Cr - Zr)
systems are lowest on the Zr-rieh side, Zr can be Iiquefied at much lower tempera-
tures than Ni, Fe, or Cr. Liquefaction starts as soon as the Iiquidus line of the two
phase field has been reached.
The cross sections of Zry-4/lnconel 718 specimens and typieal microstruetures pro-
duced bythe chemieal interactions are shown in Figures 5through 10.
The solidified reaction zones were examined with SEM/EDX. Besides the deter-
mination of the element distribution, quantitative measurements were
-4-
performed. A typical result of a specimen annealed at 1150C for 1 minute is
shown in Figure 11. As can be recognized, the molten reaction zone consists of
two layers formed due to the eutectic reaction, the morphology of the reaction
zone was observed in the whole range of temperature and time examined. The
element distribution shows Cr enrichment and Ni depletion in the thinner reac-
tion layer I adjacent to the Inconel. In the reaction layer 11, Zr, Ni and Fe are
uniformely distributed, Cr is connected with precipitates in this zone.
The integral chemical analysis of the solidified melt of reaction layer I shows the
following chemical composition: about 56 wt. % Zr, 23 % Cr, 9 % Fe, 5 % Ni, 5 %
MO,2 % Nb. The integral analysis for the reaction layer 11 reveals: 82 wt. % Zr, 12
% Ni, 3 % Fe, 2 % Cr, 1 % Sn, which is very similar to the chemical composition of
the eutectic point on the Zr-rich side in the (Ni - Zr) system (Fig. 2). From the bi-
nary (Ni - Zr) and (Fe - Zr) phase diagrams and the chemical composition of the re-
action zone it is c1ear that the diffusion of Ni and Fe into Zry is initially responsible
for the low-temperature liquefaction of Zircaloy. The further liquefaction of Zry
may then occur faster by dissolution of the Zr in the liquid reaction product.
The metallic (Zr, Ni, Fe, Cr) melts in the two reaction layers decompose into var-
ious phases on cooldown. In Table 1 the results are entered of the quantitative
analysis of the phases in the reaction zone.
A relation between the microstructure observed in the reaction zone and the ter-
nary (Zr - Ni - Fe) and (Zr - Cr - Fe) phase diagrams at 1000C [7] is shown in Figure
11. The integral chemical composition of the reaction zone (dark areas in the
phase diagrams) Iie in the liquid region for the reaction layer 11 and in the Iiq-
uid/solid region for the reaction layer I. The chemical analysis is in agreement
with the microstructure observed in the reaction layers.
During the isothermal interaction the liquid phase formed due to the (Ni - Zr) and
(Fe - Zr) eutectic interactions penetrates along the grain boundaries of the Zr (Cr,
Feh phase, which develops in the reaction layer I (Cr enriched zone) due to the
diffusion of Zr into Inconel. This liquidisolid interaction dissolves to a certain ex-
tent the Zr (Cr, Feh phase; the amount and size of this phase decrease with in-
creasing distance from the Inconei/liquid interface. In the reaction layer 11, which
is liquid at the reaction temperature, the Zr (Cr, Feh phase is present only in a
very limited amount (Fig. 12). During cooldown the liquid alloy of reaction layers
land 11 starts to solidify and decomposes into the -Zr and Zr2 (Ni, Fe)
- 5-
phases. The Cr2 (Zr, Fe) phase was observed only in the reaction layer I at tem-
peratures above 1150C(Fig. 11).
3.2 Reaction kinetics
The behavior of the solid/solid contact interface of Zircaloy/lnconel in the tem-
perature range 1000 - 1200C shows the pronounced damage of Zircaloy, which is
indicated by the extended thickness of the liquid reaction zone resulting from the
chemical interactions. To be able to determine the reaction kinetics between Zry-
4 and Inconel718, the thicknesses ofthe reaction zones were measured as a func-
tion of the reaction time. The isothermal growth of the reaction zone (dissolution
of Zry and Inconel) is a linear function of the square root of time (parabolic rate
law) for all temperatures examined, indicating a diffusion-controlled process. The
maximum thicknesses of the reaction zones in the Zry crucibles and Inconel rods
in the as-received conditions are Iisted in Table2. The squares of the reaction zone
thicknesses in Zry and Inconel are plotted as a function of the annealing times in
Figure 13.
Ni and Fe diffuse into solid Zry and initiate Zry liquefaction as soon as the sol-
idlliquid phase field has been reached. To show the differences in the amount of
dissolved Zry and Inconel, the thicknesses of the reaction zones in Zry and Inconel
are plotted in Figure 14 as a function of temperature for an annealing time of 5
minutes. Small amounts of Inconel dissolve large amounts of Zry. Above about
1250Ccomplete liquefaction of the specimens occurs.
The reaction zone growth rates for the Zry/lnconel interactions are Iisted in Table
~ and plotted as a function of the reciprocal temperature in Figure 15. The experi-
mental data have been fitted by the following equation.
Ix
2
/t = A 'exp (- B/RT) I
where
x (cm): reaction layer thickness, t (s): annealing time, A: pre-exponential factor, B
(J/mol): activation energy, T (K): annealing temperature, R(J/mol'K): 8.314 gas
constant
The growth rate equations determined for the temperature range of 1000 to
1200C are:
-6-
for Zircaloy-4
x
2
/t (cm
2
/s) = 4.435 10
4
exp (-252093/RT)
for Inconel718
x
2
/t (cm
2
/s) = 2.884 '10
5
'exp (-294962/RT)
These equations can be extrapolated to lower temperatures, but not to higher
temperatures since fast and complete liquefaction of the materials takes place at
about 1250C.
3.3lnfluence of an oxide layer on Zircaloy/lnconel interaction
The chemical interaction between pre-oxidized Zircaloy-4 and Inconel718 (initial
Zr02 layer thicknesses: 20 and 45 11m) indicate that the oxide layer delays the be-
ginning of the interaction and reduces the reaction rate, but cannot prevent in-
teraction. The cross section of Zry/lnconel reaction specimens annealed at 1000,
1100, 1150 and 1200C for various reaction times are shown in Figure 4. The cross
section of both as-received and pre-oxidized specimens (initial Zr02 layer thick-
ness 10 11m) are presented for comparison. Inconel does not interact with
stoichiometric Zr02, but the oxide layer will be dissolved by Zry, while forming
oxygen-stabilized a-Zr(O) during a time-dependent incubation period, ta. The de-
lay in interaction (liquid phase formation) is determined by the time which is nec-
essary for the oxygen to diffuse from the Zr021ayer into Zry forming a "metallic"
oxygen-stabilized a-Zry(O) phase which can then interact with Inconel.
The experimental results with the pre-oxidized Zry specimens have shown that
the Iiquefaction of the specimens has shifted to higher temperatures. The chemi-
cal reaction rate was slower when compared with the specimens tested in the as-
received condition. Figures 16 and 17 show the cross sections of pre-oxidized
Zry/lnconel specimens and a detail of the reaction zone produced by the chemical
interaction at 1000 and 1200C. The extent of the reaction in the as-received Zry
condition is presented for comparison. It is c1ear, that the protective character of
the Zr02 layer on the Zry surface, which acts initially as a barrier for the
Zry/lnconel interactions, depends on the temperature, initial oxide layer
-7-
thickness and time. Figures 18 and 19 show the cross sections and typical
microstructures produced by the chemical interaction between pre-oxidized Zry
and Inconel as a function of time. Liquid phase formation starts before the oxide
layer has completely disappeared. Figures 17 and 19 show that a thin porous ox-
ide layer remains in the liquid reaction zone; the same effect was seen in the
chemical interaction between Zry-4 and 1.4919ss (AISI 316) [8]. The oxygen from
the Zr02 layer diffuses into Zry, stabilizing the a-Zry(O) phase, and forms a sub-
stoichiometric Zr02-x oxide layer. In this way, Zr from the oxide layer can interact
with Ni and Fe, producing a liquid phase on the Inconel side which penetrates
through the cracks of the brittle oxide layer reaching the a-Zry (0) phase.
The thicknesses of the reaction zones in Zry and Inconel measured for the pre-
oxidized Zry/lnconel reaction specimens are Iisted in Tables 4 and 5 for an initial
Zr02 thickness of 20 and 45 11m, respectively.The square of the reaction thickness-
es versus the annealing times are plotted in Figures 20 and 21. The differences in
the thicknesses of the liquid reaction zones between Zry and Inconel are smaller
at 1200C and above than at lower temperatures; the same has been found in the
experiments performed with specimens in the as-received condition. The reason
is that at the temperature of about 1170C eutectic interaction develops between
Ni and Zr on the Ni-rich side (phase diagram in Fig. 2); only small amounts of Zr
3 wt. %) are necessary to produce a liquid phase at this temperature by diffu-
sion processes.
The calculated isothermal growth rates are Iisted in Tables 6 and 7 for the initial
Zr02 thicknesses of 20 and 45 11m, respectively, and plotted versus the reciprocal
temperature in Figures 22 and 23. The growth rate equations and 'to' values have
been determined fram the x
2
versus t correlation of the experimental data. In Fig-
ures 24 and 25 a comparison is made of the growth rates of Zry and Inconel, re-
spectively, as a function of the reciprocal temperature for the different condi-
tions of the Zry/lnconel reaction couple. The results indicate that a Zr02 layer de-
lays the chemical interaction between Zry and Inconel. However, the protective
effect of the oxide layer could be inhibited at the contact point of both materials
if the interaction took place in an oxidizing atmosphere. To c1arify this point, a
few experiments were done in steam atmosphere using the configuration sche-
matically represented in Figure 26. The interaction was demonstrated by several
molten zones on the external surface of the Zry tube in the regions of contact. A
cross section of a sampie heated at 1150C for 3 min. is
-8-
shown in Figure 27. Liquid phase formation due to the chemical interactions is
not prevented under conditions of unlimited steam oxidation.
4. Discussion
The main purpose of this work has been to determine the kinetics of reaction be-
tween Zircaloy and Inconel with a view of understanding and describing analyti-
cally the chemical interactions between the Zircaloy-4 fuel rod c1adding tubes and
Inconel 718 spacer grids in integral experiments Iike the CORA tests [9]. Although
some interaction experiments have been described in the literature [10, 11], no
Arrhenius equation had been previously been developed from the data. In all
cases, the maximum thickness of the reaction zone was used in the evaluation of
the kinetic data to obtain conservative results.
In the Zry/lnconel system, a considerable amount of liquid phase is formed
around 1000C; the amount of liquefied material increases with increasing tem-
perature and time. The nickel-zirconium and iron-zirconium phase diagrams
(Figs. 2, 3) show that due to eutectic interactions early melt generation has to be
expected which initiates melt progression within the fuel assembly at low tem-
peratures.
The results of the present single-effect tests are in agreement with results of in-
tegral tests (CORA experiments) where fuel rod bundles were heated to tempera-
tures of about 2000C [9]. In all cases, damage to the bundle was initiated by
Zircaloyllnconel and Zircaloy/stainless steel interactions. Localized Iiquefaction of
these components started at around 1200C. The low-temperature melt forma-
tion initiates bundle damage and causes the chemical attack of the fuel rods dis-
solving the Zry c1adding tubes and part of the U02 fue!. By this process, molten
fuel formation and relocation as weil as early fission product release can take
place even weil below the melting point of Zry. The melts relocate towards cooler
regions of the core where they may cause coolant channel blockages upon solidi-
fication.
Thin oxide layers on the Zry surface can delay the chemical interactions with
Inconel, but cannot prevent them. Zr02 interacts with metallic Zr while forming
oxygen-stabilized a-Zr(O) resulting in a sub-stoichiometric Zr02. a-Zr (0) is capa-
ble of interacting with the Inconel alloy components. The oxygen dissolved in the
Zry lattice exerts an influence on the diffusion and/or dissolution processes; the
reaction rates are slower. In all other cases, the reaction of Zry with oxygen or
steam is more favorable thermodynamically than the reactions with
-9-
Inconel, but as the integral bundle meltdown experiments [9] show, a steam envi-
ronment cannot prevent the chemical interaction between Zry and Inconel.
The chemical analysis of the reaction zone in the single-effect tests showed a
great similarity in the chemical composition of some phases (developed during
the chemical interactions) compared with the analysis of integral CORA experi-
ments [9] and chemical analysis on selected sampies from the TMI-2 reactor core
[7], for example the phases Zr2 (Ni, Fe) and -Zr.
The chemical interactions which take place during the integral fuel bundle tests
could be explained only by the single-effects test results. The complexity of a se-
vere reactor accident scenario with the resulting multitude of materials interac-
tions make a complete interpretation of the many possible chemical interactions
extremely difficult and in some cases even impossible.
5. Summary and Conclusions
- Inconel 718 in contact with Zircaloy gives rise to chemical interactions which
can be described bya parabolic rate law.
- As a result of eutectic interactions at temperatures as low as 1000C, the liquid
phase causes a fast and complete Iiquefaction of both components of the reac-
tion couple at about 1250C.
- Onlya small amount of Inconel is necessary to Iiquefy large amounts of Zry.
- Thin Zr02 layers on the Zircaloy surface delay liquid phase formation and re-
duce the rates of reaction, but cannot prevent the chemical interaction.
In experiments of short durations, the Zr02 layers shift the Iiquefaction tem-
perature to higher values; the required incubation period depends on the ini-
tial oxide layer thickness and on the temperature.
Liquid phase formation due to the chemical interactions at low temperatures
is not prevented under unlimited steam oxidation conditions.
- 10-
6. Acknowledgement
The authors wish to thank Dr. T. Haste (AEA Technology, Winfrith) for his thor-
ough and critical review of this paper.
This work was partially funded by the Commission of the European Communities
under the Reinforced Concerted Action Project "Core Degradation", Contract
Number FI3S-CT92-0001.
7. References
[1] S. Hagen, P. Hofmann, G. Schanz, L. Sepold; Interaction in Zircaloy/U02
Fuel Rod Bundles with Inconel Spacer at Temperatures above 1200C; Re-
sults of the Experiments CORA-2 and CORA-3, KfK Report 4378,1990.
[2] P. Hofmann et al.; Low-Temperature Liquefaction of LWR Core Compo-
nents, Severe Accident Research Program Review Meeting, Brookhaven Na-
tional Laboratory, Upton, NewVork, April 30 - May 4,1990.
[3] Metals handbook, Vol. 1, 10th edition, 1990, ASM International, Materials
Park, OH, USA.
[4] G. Miller; Zirconium; Academic Press Inc., Publishers 111, N. V., 1986
[5] T. B. Massaiski; Binary alloy phase diagrams, Vois. 1,2, American Society for
Metals, Ohio, 1986.
[6] D. Arias, J. P. Abriata; The Fe-Zr system, Bulletin of Alloy Phase Diagrams,
Vol. 9, No. 5, 597 - 604,1988.
[7] H. Kleykamp, R. Pejsa; Chemical and X-Ray Diffraction Analysis on Selected
Sampies from the TMI-2 Reactor Core, KfK 4872; May 1991.
[8] P. Hofmann, M. Markiewicz; Chemical interaction between as-received
and pre-oxidized Zircaloy-4 and stainless steel at high temperatures;
KfK 5106,1994.
[9] S. Hagen, P. Hofmann, G. Schanz, L. Sepold; Results of the severe CORA
fuel damage experiments CORA-2 and CORA-3; KfK 4376, 1989.
[10] B. Daniel, A. Nichols, J. Simpson; The Iiquefaction of alloys identified with
structural materials in a PWR core; AEEW-M 2250, Dec. 1985.
[11] F. Nagase, T. Otomo, H. Uetsuka; Interaction between Zircaloy tube and
Inconel spacer grid at high temperature; JAERI-M 90 -165,1990.
- 11 -
List of Tables
Table 1: Quantitative analysis of phases in the Zircaloy-4/lnconel 718 reaction
zone (Fig. 12).
Table 2: Measured total thicknesses of reaction zones in Zircaloy and Inconel for
the as-received Zircaloy-4/lnconel 718 diffusion couple as a function of
temperature and time (Fig. 13).
Table 3: Reaction zone growth rates in Zircaloy and Inconel for the as-received
Zircaloy-4/lnconeI718 diffusion couple (Fig. 15).
Table 4: Measured total thicknesses of reaction zones in Zircaloy and Inconel for
the pre-oxidized Zircaloy-4/lnconeI718 diffusion couple; initial Zr02 ox-
ide layer thickness: 20 11m (Fig. 20).
Table 5: Measured total thicknesses of reaction zones in Zircaloy and Inconel for
the pre-oxidized Zircaloy-4/lnconeI718 diffusion couple; initial Zr02 ox-
ide layer thickness: 45 11m (Fig. 21).
Table 6: Reaction zone growth rates in Zircaloy and Inconel for the pre-oxidized
Zircaloy-4/lnconel 718 diffusion couple; initial Zr02 oxide layer thick-
ness: 20 11m (Fig. 22).
Table 7: Reaction zone growth rates in Zircaloy and Inconel for the pre-oxidized
Zircaloy-4/lnconel 718 diffusion couple; initial Zr02 oxide layer thick-
ness: 45 11m (Fig. 23).
- 12 -
List of Figures
Fig.9:
Fig.4:
Fig.5:
Fig.8:
Setup of the reaction couples.
Binary phase diagram of the Ni-Zr system [5].
Binary phase diagrams of the Fe-Zr and Cr-Zr systems [5, 6].
Chemical interactions between Zircaloy-4 and Inconel 718 at different
temperatures; influence of a thin Zr02 layer on the reaction behavior
(right column of pictures).
Chemical interactions between Zircaloy-4 and Inconel718;
annealing conditions: 1000C/5 min.
Chemical interactions between Zircaloy-4 and Inconel718;
annealing conditions: 1000C/15 min.
Chemical interactions between Zircaloy-4 and Inconel718;
annealing conditions: 1100C/2 min.
Chemical interactions between Zircaloy-4 and Inconel718;
annealing conditions: 1100C/10 min.
Chemical interactions between Zircaloy-4 and Inconel718;
annealing conditions: 1150C 1 min.
Fig.10: Chemical interactions between Zircaloy-4 and Inconel718;
annealing conditions: 1150C 12min.
Fig.7:
Fig.6:
Fig.1:
Fig.2:
Fig.3:
Fig. 11: Chemical composition ofthe Zircaloy-4/lnconel718 reaction zone after
1 min at 1150C.
Fig. 12: Isothermal section of the Fe-Zr-Ni and Fe-Zr-Cr system at 1000C [7]. Rela-
tion between the observed microstructures and the phase diagrams (Ta-
ble 1).
Fig.13: Maximum reaction zone thicknesses in Zircaloy and Inconel for the
Zircaloy-4/lnconel718 system between 1000 and 1200C (Table 2).
Fig.14: Comparison of the reaction zone thicknesses in Zircaloy and Inconel for
the Zircaloy-4/lnconel718 system versus temperature;
annealing time: 5 min.
Fig.15: Reaction zone growth rates for the Zircaloy-4/1nconel 718 reaction sys-
tem (Table 3).
Fig.16: Chemical interactions between Zircaloy-4 and Inconel 718; 1000C/30
min. Influence of a 20 11m thick Zr02layer.
Fig.17: Chemical interactions between Zircaloy-4 and Inconel718; 1200C/5 min.
Influence of Zr021ayers of different thicknesses.
Fig.18: Chemical interactions between pre-oxidized Zircaloy-4 and Inconel 718
as a function of time.
- 13 -
Fig.19: Chemical interactions between pre-oxidized Zircaloy-4 and Inconel 718
as a function of time.
Fig.20: Maximum reaction zone thicknesses in Zircaloy and Inconel for the pre-
oxidized Zircaloy-4/lnconel 718 systems; initial Zr02 layer thickness: 20
p.m (Table 4).
Fig. 21: Maximum reaction zone thicknesses in Zircaloy and Inconel for the pre-
oxidized Zircaloy-4/lnconel 718 system; initial Zr02 layer thickness: 45
p.m (Table 5).
Fig.22: Reaction zone growth rates for the pre-oxidized Zircaloy-4l1nconel 718
system; initial Zr021ayer thickness: 20 p.m (Table 6).
Fig.23:
Fig.24:
Reaction zone growth rates for the pre-oxidized Zircaloy-4/lnconel 718
system; initial Zr021ayer thickness: 45 p.m (Table 7).
Reaction zone growth rates in Zircaloy for the as-received and pre-
oxidized Zircaloy-4/lnconel-718 system; influence of Zr02 layer thickness
on reaction rate.
Fig.25: Reaction zone growth rates in Inconel for the as-received and pre-
oxidized Zircaloy-4/lnconel-718 system; influence of Zr02 layer thickness
on reaction rate.
Fig.26: Schematic of the Zircaloy-4 tubellnconel 718 grid system spacer used in
experiments under oxidizing conditions (steam).
Fig.27: Chemical interactions between Zircaloy-4 tube and Inconel 718 after 3
min at 1150C in steam atmosphere.
-14-
Table 1: Quantitative analysis of phases in the Zircaloy-4/
Inconel718 reaction zone (Fig. 12).
Reaction layer
Element Cone. in at. % Phase
(see Fig. 12)
Zr 95
I, 11 Sn 2 -Zry
Ni, Fe, Cr 3
Zr 68
1,11 Ni 22 Zr2 (Ni, Feh
Fe 7
Cr 3
Cr 48
I, 11 Zr 34
Fe 11 Zr (Cr, Feh
Mo 4
Ni 3
Cr 65
1 Zr 12
Fe 11 Cr2 (Zr, Fe)
Mo 7
Ni, Nb 5
-15-
Table 2: Measured total thicknesses of reaction zones in Zircaloy and Inconel
for the as-received Zircaloy-4/1nconel718 diffusion couple as a
function oftemperature and time (Fig. 13).
Temperature Time
Reaction zone thickness, 11m
Specimen
oe
min
Zircaloy-4 Inconel718
29 1000 30 675 230
30 " 60 790 255
28 " 120 1290 550
31 1100 10 720 200
32 " 15 975 275
36 1200 3 995 507
35 " 5 1315 700
-16-
Table 3: Reaction zone growth rates in Zircaloy and Inconel
forthe as-received Zircaloy-4/lnconeI718 diffusion
couple(Fig. 15 ).
Reaction zone growth rate, x
2
/t
Temperature
cm
2
/s
oe
Zircaloy-4 Inconel718
1000 2.1710-6 3.2510-7
1100 9.40.10-
6
7.7410-7
1200 5.6610-5 1.5510-5
Rate equations:
For Zircaloy-4
x
2
/t (cm
2
/s) = 4.43510
4
exp (-252093/RT)
For Inconel718
Ix
2
/t (cm
2
/s) = 2.884lO
S
exp (-294962/RT)
R = 8.314 J/mol'K
- 17 -
Table 4: Measured total thicknesses of reaction zones in Zircaloy and Inconel for
the pre-oxidized Zircaloy-4/lnconeI718 diffusion couple; initial Zr02
oxide layer thickness: 20 llm (Fig. 20).
Time
Reaction zone thickness, llm
Specimen Temperature
min
Zircaloy-4 Inconel
009 1100 120 240 140
037 " 180 1890 514
011 1200 5 400 255
010 " 10 840 975
012 " 15 1440
041 1300 1 740 856
049 " 1.5 1008 1130
-18-
Table 5: Measured total thicknesses of reaction zones in Zircaloy and Inconel for
the pre-oxidized Zircaloy-4/lnconeI718 diffusion couple; initial Zr02
oxide layer thickness: 45 11m (Fig. 21).
Time
Reaction zone thickness, 11m
Specimen Temperature
min
Zircaloy-4 Inconel
043 1100 180 290 110
044 " 300 1095 306
023 1200 5 190 105
022 " 10 595 485
024 " 15 850 930
047 1300 1 440 290
048 " 2 1040 1255
- 19-
Table 6: Reaction zone growth rates in Zircaloy and Inconel
forthe pre-oxidized Zircaloy-4/lnconeI718
diffusion couple; initial Zr021ayer thickness: 20 11m
(Fig.22).
Reaction zone growth rate, x
2
/t
Temperature
cm
2
/s
oe
Zircaloy-4 Inconel718
1100 9.76-10-6 6.79-10-7
1200 3.18-10-5 2.95-10-5
1300 1.51-10-
4
1.80-10-
4
Rate equations:
For Zircaloy-4
x
2
/(t-to) (cm
2
/s) = 20952exp (-246427/RT)
For Inconel718
x
2
/(t - to)(cm
2
/s) = 1.72710
13
exp (-507395/RT)
R= 8.314 J/mol'K
to values, s
oe
Zry-4 Inconel
1100 7175 6912
1200 314 339
1300 24 20
- 20-
Table 7: Reaction zone growth rates in Zircaloy and Inconel
forthe pre-oxidized Zircaloy-4/lnconeI718
diffusion couple; initial Zr021ayer thickness: 45 11m
(Fig.23).
Reaction zone growth rate, x
2
/t
Temperature
cm
2
/s
oe
Zircaloy-4 Inconel718
1100 1.5510-6 1.1210-7
1200 1.1410-5 1.4210-5
1300 1.48.10-
4
2.49.10-
4
Rate equations:
For Zircaloy-4
x
2
/(t-to) (cm
2
/s) = 5.441 09'exp (-41 0306/RT)
For Inconel718
x
2
/(t - to) (cm
2
/s) = 5.410
19
exp (-699018/RT)
R = 8.314 J/mol'K
to values, s
oe
Zry-4 Inconel
1100 12900 9741
1200 276 340
1300 68 40
-21-
L..-__ conical plug
rod of Inconel 718
Zircaloy - 4 crucible
Fig. 1: Setup of the reaction couples.
Atomic Percent Zirconium
0 10 20 30 40 50 60 70 80 90 100
,1""1" .. ,1'1' " .. ,I .... , I!
;, ,
I
, !,. , , 1 I ,!
l
I; ,
I 1

1800
1 A
r
t
1600-1
L
/
t
oU
/
l.uoC
Il
1400K

t..
Q)
0.

-
\ ________ J \ I \
"
/ Ir
Q)
I\)
E-
I\)
1000 -I 1\Ni) I
,
I I
IIW
lrnDC V I
\/ ILJ 980C
73.4-
e
6

'-

_ N
".
:z: :z i3
Z
t2
-
Z -
z
:z: z
cr.Zr)
800
0 10 20 30 40 50 60 70 80 90 100
Ni
Weight Percent Zirconium Zr
Fig.2: Binary phase diagram ofthe Ni-Zr system [5].
-23-
100
100
Fe
91l.lIZ 91Z'C
(o:Fe)
90
90
920'C
L. _. _._. _. _. _. _. _. _._.. _. _. _._.
: lIa,nalle Trllndormlllion
1

,
, 470'C
"\
\
'. 1462'C

,
,
I
1673'
55.1.

,
I

I
1
,
Alomic Percenl Iron
50 60 70
I I t I 'I
30
,
L
20
I
o:Zr)
600
400
200
u
o
2000 1
0
Ip

1600- "
", '
, '
1600 \ '\
I ,
, ,
, ,
, ,
1400 \ ""
" ,
" ,
*(pZr)\ /
, , ,
1200 \ \ I
::l \
-J , \,
1000 1 " ' 974'C
L-. _-&.' 926C \ ... _-----------
<lJ
0.. 8113'C
E 600 \: 730'C : 'L _
<lJ I
"
"
I
' 1 I
I
'
"
1 I
:i :
tl : . .._._._._._. . .. _._._._._
fa. ... : : : )lllgnellc Trlln.rormllllon
L..' I I
N:: :
:: I
o ...............
o 10 20 30 40 50 60 70 80
Zr Weighl Percenl Iron
o 10 20 30
1900 "
1655
0
C
90
N
..
u
..
N

Alomic Percenl Chromium

40 50 60 70 BO
, , ......., , ....... ....
I
I
I
')'ZrCr
2
53.3%,1673
0
C i
'. I
______ ...... 159?oC :
156?OCA,;
--------p-Z-C- -;
r r
2
: u: ,
i 0 I
Nil
I (I) I I
: (Cr)-t
II
l
900
1700
1500
U
0
<lJ
r..
::l
-'
(\l 1300
r..
<lJ
0..
E
<lJ

1100
90 60 30 40 50 60 70
Weighl Percenl Chromium
20 10

o
Zr
Fig.3:
Binary phase diagrams of the Fe-Zr and er-Zr systems [5, 6].
-24-
1000
0
(/15min
-----Zry - 4--
Inconel 718 --
1100
0
(/2min
reaction zone
(liquid... at temperature)
1150
0
(/2min
ZrO 2
layeron 1.0.
Fig.4: Chemical interactions between Zircaloy-4 and Inconel 718 at different
temperatures; influence of a thin Zr02 layer on the reaction behavior
(right column of pictures).
-25-
3
1
2
reaetion zone (liquid ~
at temperature )
Zircaloy - 4 e ,.'
Zry
reaetion
zone
Inconel
11000O(/5minI
Fig.5: Chemical interactions between Zircaloy-4 and Inconel718;
annealing conditions: 1000C/5 min.
2
1
-26-
Zry - 4
reaction zone
(liquid at temperature)
Inconel 718
2mrn
'>-----1
Inconel
11000 (/15minI
Fig.6: Chemical interactions between Zircaloy-4 and Inconel718;
annealing conditions: 1000C/15 min.
-27-
i ': e,"rj
Zircaloy - 4 .
1
2
Zircaloy-4
3
, 1 0 0 ~ m ,
once molten reaetion zone
Inconel
I
Zry
interface
Fig.7: Chemical interactions between Zircaloy-4 and Inconel718;
annealing conditions: 1100(/2 min.
once malten reaction zone
1
localized melting of the
Zircaloy crudble
-28-
3
2
Inconel
interface
reaction
zone
Zry
1100
0
(/10min
Inconel718
." .
-j
. '
-I
interface
Fig.8: Chemical interactions between Zircaloy-4 and Inconel718;
annealing conditions: 1100(/10 min.
2
-29-
penetration of the Inconel rod
into Zifca!oy crucib!e
Zry-4
Ineone! 718
[TI
I
Ineonel
reaetion
zone
Zry
I
1150
0
(/lmin
interface
- Zry
Fig.9: Chemical interactions between Zircaloy-4 and Inconel718;
annealing conditions: 1150C 1 min.
-30-
2
3
1
2mm
t-------I
L ~ o o ~ m : j
once mol ten rn "\t"t'.nn zone
readion
zone
Ineonel
Zry
. readion
zone
Ineonel
1150
0
(/2min
interface
Fig.10: Chemical interactions between Zircaloy-4 and Inconel718;
annealing conditions: 1150C / 2 min.
-31-
Inconel 718
Zr
Ni
r--Zr:49, Cr:26, Fe:12, Mo:6, Ni:4, Nb:3wt.%
Ni:9, Cr:5, Fe:4, (Mo+Nbl:4 wt.%
][-- Cr: 55, Zr: 18, Fe: 11, Mo: 10, (Ni+Nbl: 5wt.%
Cr
Fe
r--Zr:95, Sn:3, (Ni+(r+Fel:2wt.%
Ni:13, (Fe+(rl:S wt.%
/1150
0
U1min I
fig. 11: Chemical composition of the Zircaloy-4/1nconel718 reaction zone after
1 min at 1150C.
-32-
reaction layer I /
reaetion zone ----
1000C/15min
\
T-Fe
solid at
temperature
....'
()
Z,Ftl Z,Ftl FtZr
1
20 40 60
-- al.%Zr -
p-Zr
1000
0
(
l-Fe
n-Zr
lAI: integral analysis of reaction layer I (BI: integral analysis of reaction layer 11
Fig. 12: Isothermal section of the Fe-Zr-Ni and Fe-Zr-Cr system at 1000C [7]. Rela-
tion between the observed microstructures and the phase diagrams (Ta-
ble 1).
VJ
VJ
I
no Zr0
2
layer,as-received
__ reaction zone in Inconel
_ reaction zone in Zircaloy
1000
0
(
I::..
1200
0
(
112000(
I
1100
0
(
" "1100
0
(
,,"
,,"
,,"
"
,," I::..
0
0"-'; _----------10000(
0" _-1::..-- I::..

1 2 3
4 5 I
,
,
.,
,
,
I
I
I
Hili
'0
If/
I.
2
QJ
C
o
N
C
o
...
u
ro
QJ
Cl::
N
X
l/)
l/)
QJ
C
~
u
.c
...
N
E
E
Annealing time t , h
fig.13: Maximum reaction zone thicknesses in Zircaloy and Inconel for the
Zircaloy-4/lnconeI718 system between 1000 and 1200C (lable 2).
-34-
1500
e
::L
QJ
c:
o
N
c:
o
:z:
'-'
,."
QJ
c::::
1000
500
1000
Zircaloy- 4/Inconel 718
annealing time: Smin
reaction zone in Zry
\
1100
Liquefaction
of the
speclmens
above 1250
0
(
\
reaction zone in Inconel
1200
Temperature, oe
Fig.14: Comparison of the reaction zone thicknesses in Zircaloy and Inconel for
the Zircaloy-4/lnconeI718 system versus temperature;
annealing time: 5 min.
-35-
Temperature,O(
1200 1100 1000
no
_ reaetion rate in Zircaloy
__ reaetion rate in Inconel
V)
........
.....
E
Ix
2
/t=44354 exp (-252092/RT) I
'-'
..0-
10-
4
........
/
.....
><
A
QJ
..0-
n:I
c...
..r::::.
..0-
0

10-
5
0
"
c...
c:n
"
QJ
c::
/"
0
N
c::
0
"
A
:+=
x
2
/t=288455 exp (-294962/RT)
"
'-'
" n:I
10-
6
"
QJ
c::
"
0
"
"
J/ mol KI
"
" 0
,
,
10-
7
7 8
Reciprocal temperature , 1fT , 10
4
/K
Fig. 15: Reaction zone growth rates for the Zircaloy-4/lnconel 718 reaction sys-
tem (Table 3).
as-received Zry
pre:'oxidized Zry
initial Zr0
2
layer: 2 0 ~ m
-36-
void
due to
melt
relocation
loconel/lry eutecti.cinteractions
Inconel
Inconel/pre-oxidized Zry
1000C/30min
lX-ZriOI
Fig.16: Chemical interactions between Zircaloy-4 and Inconel 718; 1000C/30
min. Influence of a 20 11m thick Zr02layer.
-37-
as-received Zry
no Zr0
2
layer
Inconel/Zircaloy eutectic interadions
1mm
t----I
pre-oxidized Zry
initial Zr0
2
layer: 2 0 ~ m
pre-oxidized Zry
initial Zr0
2
layer: 4 5 ~ m
2mm
t---l
In(l}nel
\--
reaction
zone
1200C/Smin
5 0 ~ m
I------i
Fig.17: Chemical interactions between Zircaloy-4and Inconel718; 1200C/5 min.
Influence of Zr021ayers of different thicknesses.
-38-
1200
0
( / 5min
2mm
1----1
Uquefied
material
1200
0
( / 10min
liquefied
material
1200
0
( / 15min
Initial Zr0
2
layer thickness: 4 5 ~ m
Fig.18: Chemical interactions between pre-oxidized Zircaloy-4 and Inconel 718
as a function of time.
-39-
gap
Inconel --+---..
1200
0
[ / 5min
reaetion
zone In -i--........
Inconel
1200
0
( / 10min
.o4----i-- Zircaloy
initial interface
initial interface
reaetion
zone In
Inconel
20llffi
I-------l
1200
0
( / lSmin
Initial Zr0
2
layer thickness: 4 5 ~ m
Fig.19: Chemical interactions between pre-oxidized Zircaloy-4 and Inconel 718
as a function of time.
1300
0
(
N
JU
2OOO
(
initial Zr0
2
thickness : 20 ~ m
E
/1100
0
(
__ reaction zone in Inconel
E
2 :1
_ reaction zone in Zircaloy
N
x
A
V)
I
V)
I QJ
c:
I
u
.c. I
~
QJ
I
c:
1
I;
0

N
~ c:
I
0 v
I
~
~
..
0
u
I
ru
tJ
I "",,,1100
0
( QJ
0:::
,,"'"
."'"
v
,

I ,,"
OIY
i
*,,"-
1 2 3 4 5
Annealing time t , h
Fig.20: Maximum reaction zone thicknesses in Zircaloy and Inconel for the pre-
oxidized Zircaloy-4/1nconel 718 systems; initial Zr02 layer thickness: 20
11m (Table 4).
~
.....
I
,/1100
0
(
initial Zr0
2
thickness : 45 11m
__ reaction zone in Inconel
_ reaction zone in Zircaloy
K
_------- _&--1100
0
(
345
Annealing time t , h
1300
0
(
N
E
,1200
0
(
E
2
',1200
0
(
N
x
,
VJ
,
VJ
QJ
I
c::
~
,
u
-
~
'1
QJ
~
c::
0
1
N
c::
0
~
I;
u
rtJ
QJ
0:::
v
,
t
ou--
1 2
Fig. 21: Maximum reaction zone thicknesses in Zircaloy and Inconel for the pre-
oxidized Zircaloy-4/1nconel 718 system; initial Zr02 layer thickness: 45
p.m (Table 5).
-42-
Temperature, oe
1300 1200 1.100
VI
"
I"'0oI
E
1...1
-c::.
.......
I
.......
10-
4
-
"
I"'0oI
><
Q.j
.......
rc
r...
..r:::::
......
=-
10-
5
<:)
r...
c::l'"
Q.j
c::
<:)
N
c::
<:)
:.;:::
1...1
rc
Q.j
10-
6
e::::
initial. Zr0
2
thickness : 20 Hm
........... reaction rate in Zircaloy
__ reaction rate in Inconel
to values, 5
oe. Zry4 Inconel
1100 7175 6912
1200 314 339
1300 24 20
\
~
/,
xZ/lt-t.l: 20952 exp(-2464271RTl ,
\
/ ' ~
..... xZ-/I-t.-t.-I:-1.7-27-X-l0- 0-ex-p-( -5-07-39-S/-R
'
Tl \
R=8J14 J/ mol, K
10-
7
..1--------...-----------;
7 8
Reciprocal temperature , 1fT , 10
4
/K
Fig.22: Reaction zone growth rates for the pre-oxidized Zircaloy-4/lnconel 718
system; initial Zr021ayer thickness: 20 11m (Table 6).
-43-
Temperature,O(
1300 1200 1100
to values. 5
initial ZrOz thickness : 45
_ reaction rate in Zircaloy
__ reaction rate in Inconel
oe
Zry-4 Inconel
1100 12900 9741
1200 276 340
1300 68 40

\
\
\
\
'\ x
2
/{t-t
o
l=5.4 10
9
exp (-410306/RTI
\
\
\
\
\
..----_--/---,>.\ ""
10
19
exp 1-699018/RTI \ I I
\ . R-:8.314 J/ mol K.
7 0\
10- ___I
7 8
QJ
-
",
e-
.J::
-
E 10-
5
c:::n
QJ
c:::
o
......
c:::
o
:.;::
'-'
10-
6
Reciprocal temperature , 1/T , 10
4
/K
Fig.23: Reaction zone growth rates for the pre-oxidized Zircaloy-4/1nconel 718
system; initial Zr021ayer thickness: 45 11m (Table 7).
-44-
Temperature,O(
1300 1200 1100 1000
cu
--
t"O
c...
..c
--
10-
5
c:::n
cu
c
o
N
c:
o
:z:
"-'
t"O
~ 10-
6
reaction rate in Zirca[oy
- - no Zr0
2
layer,as-received (t 0=0)
_. _ initial Zr0
2
thickness : 20 pm
__ initial Zr0
2
thickness : 45 pm
10.
7
...1.---------,--------.....;
7
Reciprocal temperature I 1/T , 10
4
/K
Fig.24: Reaction zone growth rates in Zircaloy for the as-received and pre-
oxidized Zircaloy-4/lnconel-718 system; influence of Zr021ayer thickness
on reaction rate.
8
-45-
Temperature,O(
1300 1200 1100 1000
reaction rate in Inconel
-- no Zr0
2
layer,as-received (t0=0)
_ ._ initial Zr0
2
thickness : 20 ~ m
_ initial Zr0
2
thickness : 45 ~ m
G.I
-
",
'-
.c
-
10-
5
cn
G.I
c:
o
N
c:
o
:z:
~
",
~ 10-
6
10-
7
....1.--------,-----=----------1
7
Reciprocal temperature , 1fT , 10
4
/K
8
Fig.25: Reaction zone growth rates in Inconel for the as-received and pre-
oxidized Zircaloy-4/1nconel-718 system; influence of Zr021ayer thickness
on reaction rate.
-46-
' ~ - welding
Inconel 718
end cup
Inconel grid
/
Zry -4 tube
\
....--
y
..-
,
\
---
\
I---
...
gas suppl
Fig.26: Schematic of the Zircaloy-4 tubellnconel 718 grid system spacer used in
experiments under oxidizing conditions (steam).
-47-
1.0.
0.0.
Zry - Inconel --tP-I
contad region
1--------
once malten readion zone
1
readion
zone
Zry
I
liquid at
temperature
interface
11150
0
(/3min I
steam environment
Fig.27: Chemical interactions between Zircaloy-4 tube and Inconel 718 after 3
min at 1150C in steam atmosphere.