HIGH TEMPERATURE CREEP OF Ni-ZOCr-2Th02

SINGLE CRYSTALS

R. W. LUND and W. D. NIX

Department of Materials Science and Engineering, Stanford University, Stanford, CA 94305, U.S..-\.

Abstract-The high temperature creep properties of single crystals of Ni-20Cr-ZThO, have been investi-
gated in the temperature range 6%13OO’C. Single crystal tensile specimens were cut from plates
having a large elongated grain structure and constant stress vacuum creep tests were conducted at
various stresses and temperatures.
By including the temperature dependence of the elastic modulus in the analysis of the data. the
creep activation energy was found to be very nearly equal to that for self diffusion of Ni-2OCr. The
stress dependence of the creep rate was observed to be large and variable, with power law exponents
ranging from 9 to 75 over the temperature range studied. The ductility of these crystals as measured
by percentage reduction of area was very high, typically ranging from 40 to 605,. The percentage
elongation varied inversely with the stress exponent and ranged from 1 to 28”,.
The creep properties of these dispersion strengthened crystals can be described accurately by consider-
ing the creep strength to be given by a simple sum of the creep strength of unthoriated polycrystalline
Ni-2OCr and the Orowan strength, as calculated from the measured ThOz particle distribution. This
simple model describes the measured creep rates to within a factor of three at all stresses and tempera-
t ures.
Resume--On a etudie pour les temperatures comprises entre 650 et 13OO’C.les proprietes de tluage
a haute temperature de monocristaux de Ni-2OCr-ZThO,. On a d&coupe des echantillons de traction
monocristallins dans des plaques presentant de grands grains allonges et on a effectue des essais de
Ruage sous vide a contrainte constante pour diverses contraintes et temperatures.
En introduisant dans l’analyse des resultats la variation du module elastique en fonction de la
temperature, on a trouve que l’energie d’activation de Auage est pratiquement igale a I’inergie d’activa-
tion de l’auto diffusion de Ni-2OCr. La vitesse de Ruage depend fortement et de maniere variable
de la contrainte, les exposants de la loi en puissance allant de 9 a 75 dans le domaine de temperatures
etudiees. La ductiliti de ces cristaux mesuree par le pourcentage de diminution de la section est tres
grande allant typiquement de 40 a 6Oy;. Le pourcentage d’allongement varie comme l’inverse de I’espo-
sant de la contrainte, et il reste compris entre I et 2g”&
Les proprietes au fluage de ces cristaux a durcissement par precipites disperses peuvent etre exacte-
ment d&rites en considtrant que la resistance au fiuage est don&e simplement par la somme de
la resistance au fluage de polycristaux de l’alliage Ni-2OCr (sans thorine) et de la resistance d’Orowan
calculee a partir de la repartition mesuree des particules de ThOl. Le modtle dtcrit les vitesses de
Ruage mesurees a un facteur 3 prts. pour toutes les contraintes et les temperatures.
Zusammenfassung-Das Hochtemperatur-Kriechverhalten von Ni-ZOCr-2Th0, Einkristallen wurde im
Temperaturbereich von 650 bis 1300°C untersucht. Einkristalline Zugproben wurden aus Platten mit
einer groBkornigen. in die Lange gezogcnen Struktur herausgeschnitten; die Kriechversuche wurden
im Vakuum bei konstanter Last durch gefuhrt.
Unter Beriicksichtigung der Temperaturabhlingigkeit des elastischen Moduls bei der Xnalyse der
Daten ergab sich die Kriech-Aktivierungsenergie zu nahezu gleich der Aktivierungsenergie fur Selbstdif-
fusion von Ni-2OCr. Die Spannungsabhlngigkeit der Kriechrate war groB und variierte tiber den unter-
suchten Temperaturbereich mit Potenzgesetz-Exponenten von 9 bis 75. Die Duktilitlt dieser Kristalie,
ermittelt aus der porzentualen Querschnittsverlnderung, war sehr hoch, typischerweise zwischen -to
und 60:,& Die prozentuale Llngenlnderung variierte umgekehrt mit dem Spannungsexponenten und
lag zwischen 1 und ZS?;.
Das Kriechverhalten dieser dispersionsgehlrteten Kristalle kann genau beschrieben werden. indem
die Kriechspannung als eine Summe angesetzt wird aus der Kriechspannung unthorierten, polykristal-
linen Ni-20Cr und der Orowanspannung, berechnet aus der gemessenen Verteilung der ThO,-Teilchen.
Dies einfache Model) beschreibt die gemessenen Kriechraten bis auf einen Faktor drei bei allen Span-
nungen und Temperaturen.

1. INTRODUCTION characteristics of DS metals are unusual. For

In recent years the high temperature mechanical
properties of dispersion strengthened (DS) metals
have been studied intensively. As a result of these
studies, the creep properties of these materials are
now reasonably well documented. Compared to most
other metals and alloys, the high temperature creep
example, the temperature dependence of the creep
rate (creep activation energy) is often very large and
variable when compared with that for self diffusion.
Wilcox and Clauer found creep activation energies
to be as large as three times that for self diffusion
in two cases [l. 21 and nearly equal to self diffusion
-170 LUND A?iD NIX: CREEP OF Ni-?OCr-2ThOx SmGLE
in others [3-j]. Also, the stress dependence of the
creep rate is sometimes anomalously high and vari-
able. Again, Wilcox and Ctauer [1,&J found stress
exponents ranging from about 6 to 40 for different
DS metals. In addition. the high temperature duct~ity
as represented by either the percentage elongation or
the percentage reduction of area is usually found to
be quite low. often as low as one or two percent [6].
Finally, the creep properties of DS metals are known
to depend very sensitively on grain morphology. Wil-
cox and Clauer [6,7] showed that the creep resistance
of these metals is directly related to the grain aspect
ratio (GAR).
The emergence of ex~rimental facts about DS
metals has stimulated a number of theoretical investi-
gations of dispersion strengthening at high tempera-
tures. Notable among the many theories that have
been proposed are those of Ansell and Weertman [S],
Wilcox and Clauer [9], Ashby [lo] and Malu and
Tien [ll]. Although there are attractive features in
some of these models, they are not capable of giving
a satisfactory description of the creep properties of
DS metals. These models typically fail to predict cor-
rectly the high stress dependence observed and they
predict much faster creep rates than are measured.
The model proposed recently by Malu and Tien [11]
based on the motion of interstitial emitting jogged
screw dislocations is capable of giving creep rates that
are strongly dependent on both stress and tempera-
ture, but its predictions are extremely sensitive to the
jog spacing that one chooses.
When comparing the predictions of existing
theories with experimental results it is important to
remember that the theories invariably deal with the
creep properties of the crystals themselves while
the experiments involve polycrystalline aggregates.
Ordinarily this would not cause a problem since
po[ycrystalline aggregates cannot deform extensively
without requiring the grains to deform as well. How-
ever, the situation may be different for DS metals
because of the very large strength difference between
the grains and the grain boundaries in these metals
and because of their unusual elongated grain struc-
tures. For these metals it is apparent that the grains
simply put1 apart during creep fracture much Iike
fibers do in the faiIure of fiber composites. This is
probably why the percentage reduction of area is less
than the percentage elongation in some cases. Thus
tension creep experiments on polycrystalline DS
metals with elongated grain structures do not provide
unambiguous information about the creep properties
of the grains themselves and, therefore, cannot be
compared directly with the existing theories.
The present work on Ni-ZOCr-ZThO, was under-
taken to determine the high temperature creep
properties of dispersion strengthened single crystals
t Throughout this paper the notation Ni-ZOCr-ZThOl
will refer to the nominal composition of the alloy studied:
20 wt. X Cr and I! vol. 7; Th02.
CRYSTALS
in an effort to avoid the confusing and detrimental
effects of grain boundary sliding and failure. It was
anticipated that the properties of single crystals could
be compared directly with existing theoretical models
of dispersion strengthening and that such a compari-
son would improve our understanding of this impor-
tant phenomenon. Additionally, it was expected that
a study of the properties of single crystals would
establish upper limits of both strength and ductility
for this material for comparison with polycrystalline
properties.
2. ~XPERI~IE~~ PROCEDURE
Four large grained plates of Ni-ZOCr-2ThOzt were
provided by the General Electric Company of Evan-
dale, OH. This material was subjected to their ZAP
process which results in a highly elongated grain
structure. Since our objective was to study single crys-
tals, we planned to cut thin slices parallel to the long
axis of the grains, etch to reveal the grain ~undaries
and spark machine very small single crystal tensile
samples from large grain areas. Fortunate circum-
stances arising from the material characterization
study eventually permitted a simpler procedure to be
adopted.
Thin slices, (0.7-1.0mm thick) were cut from the
plates and smoothed to a uniform finish by lapping
(0.5-0.6 mm thick). Some of the slices were then mac-
roetched (90% HCl, 10YOH,OJ to delineate the grain
boundaries. This was followed by a careful process
of area selection and spark machining of small tensile
coupons from single crystalline areas. After several
single crystal samples were obtained, generally no
more than one per slice, it became evident that a
very Iarge number of slices and, tonsequendy, a very
large amount of material wouid be required to pro-
vide a reasonable number of tensile sampies for the
study. Fortunately, it was revealed by Laue X-ray
photography that all the grains were aligned in the
same crystallographic orientation. The long axis was
aligned with the [IOO] and the normal to the thin
slices was aligned with the [llO], all within three
degrees. In this way the grain boundaries revealed
by the macroetch were determined to be low angle
boundaries. As such, they were not expected to un-
dergo any sliding, nor interfere significantly with high
temperature creep processes. Accordingly, the mac-
roetch and area selection procedures were eliminated
and as many samples as possible (usually 7 or 8) were
cut from each thin slice. This simpler procedure was
used to cut all but three of the test samples for the
data reported. The sampIes without low angle grain
boundaries are noted in Table 1. All of the test
samples were carefully examined after testing to in-
sure that they had deformed in a relatively homo-
geneous manner (no grain boundary shearing or crack-
ing). and many samples were checked for crystallo-
graphic alignment throughout the study. No evidence
 j.,
:+
.‘j
1.1

u-as found in any of the tests to indicate significant
grain boundary involvement or crystallographic mis-
alignment.
Following spark machining. the samples were care-
f&y cleaned and electropolished in 30”, nital to
remove all traces of surfaee damage. The spark
machining tool, one of the thin stices, and a finished
sampie are shown in Fig. f.
The samples were tested in tension under constant
stress, vacuum creep conditions. Details of the creep
machine are reported by Matlock f 123. The tempera-
ture could be held within a ranpc of about 5-C over
a 24 hr period. The vacuum was produced by an oil
diffusion pump and was generally maintained at
6.7 mPa (5 x 10-j Turrj or better. At the highest test
temperatures ft2tOUand i3oO‘Ci a thin PI sheet was

Fig. i. From right to left an uncut plate of iar_ge grained Xi-XK’r-ZThO,. a thin slice t&n from
such a piilK% thz electrical discharge machine tool used to cut the tcnsik coupons. and one oC the
samples are shown. The scale shown is in inches.
17_3 LLXD ~X.VD
NIX: CREEP OF Ni-Xx3-Xhf& SINGLE CRk’STALS

Table 2. Chemical analpis of Ni-XlCr-ZThO, myle crys- crystallographic orientation v;ith the long axis parul-
tals by WY chemical anaikris (wt. “,,i lel to the [loo] and the wide Hat face parallel to the
(I IO). both within 3 deg. Consequently. all of the grain
boundaries defmeated by the macroetch were low
angle boundaries.
The ThO? particle size distribution was determined
using transmission electron microscopy. Extraction
replicas were prepared by carbon coating an electro-
polished surface and then electrolytically dissolving
the matrix material in a -‘0’ 0 perchloric acid-W,
ethyl alcohol solution with a 15 V potential. A typical
found to be beneficial as a diffusion barrier between
photomicrograph of one of the extraction replicas is
the sample and the TZM molybdenum alloy grips.
shown in Fig. 3. Selected area diffraction studies con-
OveraH. the samples were 40mm in Iength and
firmed that all the extracted particles were indeed
5.5 mm in width. The gage section was 19 mm long
ThO,.
and 2 mm wide. The effective gage length was deter-
The ThOz particle size ranged from about 3 to
mined empirically to be 20.3 mm. The thickness
110 nm (30-11OOA) and various aspects of the distri-
varied from about 0.25 to 0.40 mm depending on the
bution are shown in Fig. 4. These data were obtained
initial slice thickness.
from extraction replica measurements of approsi-
Creep strain was monitored during testing by
mately 1000 particles. Transmission electron micro-
measuring the displacement of the grip linkage out-
scope studies of thin foils yielded simiiar results but
side the vacuum furnace system as a function of time
the ease of extraction replica sample preparation
with an LVDT (Linear Variable DiKerential Trans-
made that technique preferabfe.
former) finked to a strip chart recorder. This system
Because our interpretation of the creep properties
was determined to be sensitive to a strain of about
of this material depends sensitively on the precise
3 x lo-‘. Creep strain was calculated by assuming
all of the measured displacement was due to homo-
geneous deformation of the effective gage length of
the sample.
Some of the tests were so fast that the LVDT out-
put and strip chart recorder system did not record
the strain accurately. In these tests the strain was
determined by measuring the overall length change
of the fractured sample under a low power micro-
scope to obtain a value for the total displacement.
The strain was then calculated in the same manner
as for the other samples by assuming homogeneous
strain over the gage length.

(0) u
3. MATERIALS CHARACTERIZATION 20j.m

A chemical analysis of the material studied is given

in Table 2. The thoria was analyzed as thorium and
is assumed to be combined completely with oxygen.
The calculated value for the vol. yri of thoria is also
given in the table and is 2.14?&
Opticat photomicrographs of the material are
shown in Fig. 2. These micrographs reveal a single
phase material containing oxide stringers which are
most likely chromium oxide. These inclusions appear
to have been broken up during the mechanical work-
ing and they give an indication of the degree of work-
ing during processing. These inclusions are of such
a size and shape that they do not play a significant
rofe in the creep behaviour of this material. _The
grain boundaries revealed by the macroetch
(90HCl-10H102) could not be detected with optical
Fig. 2. OpticA photomicropaphs of sections parallel to
microscopy usin_p any of the common etchants. the rolled face of X-ZOCr-2Th02 showing: iai chromium
As previously stated in Section 2. it was determined oxide inclusions in an unetched sample and (bi an overall
that all of the material studied had virtually the same view of the sample etched with modified Keller’s etch.
 LCND ASL) NIX: CREEP OF Xi-XCr-2Th02
Fig. 3. Electron micrograph of an extraction replica taken
from Ni-20Cr-2Th02 showing the spatial distribution of
Th02 particles. Clustering of some of the Th02 particles
is evident. The ThOz particles that are well separated from
each other are considered as free particles.
value of the Orowan stress, very careful consideration
was given to the determination of the sizes and spac-
ings of the particles that act as obstacles to disloca-
tion motion.
As discussed in the Appendix. the average planar
particle spacing (center-to-center) must be taken as:
I This figure shows that the stress exponent.
i = -. . . (1)
, -k,
where S, is the number of particles per unit area.
However, the sample extraction replica shown in Fig.
3 indicates that many of the particles are clustered
together. As such, use of the total particle count in
equation (1) would result in an anomalously small
value for L. Thus, “clusters” and “free” particles were
counted and sized separately to provide a more realir-
to-? 103
I modulus. following Barrett. Ardell and Sherby [ 131.
Fig. 4. Characteristics of the distribution of sizes of ThOz
particles in Xi-ZOCr-?ThO, single crystals. Each labeled
particle size (abscissa) corresponds to a size class.
SISGLE CRYST.-\LS 4’3
tic particle spacing. First an overall particle count
and size distribution was made in order to obtain
a base distribution. The “free” particle volume frac-
tion and cumulative weight fraction were then deter-
mined by relating the “free” particle count to this
overall base distribution. This analysis gal-e the fol-
lowing results:
1. center-to-center planar particle spacing (includ-
ing clusters as single obstacles)
;. = 100nm (1OOOA):
7. mean obstacic diameter (clusters and free par-
ticles)
Z,,,,, = 17.0nm (1iO.A);
3. mean free particle diameter (excluding clusters)
;i.,_, = 10.6 nm (106 A).
4. EXPERIMENTAL RESULTS
Creep tests were conducted at temperatures ranging
from 65O’C to 13OO’C(055-0.95 T,). All of the tests
exhibited normal creep behavior, that is. a decelerat-
ing creep rate in primary. an extended secondary. and
an accelerating creep rate in tertiary. A typical family
of creep curves is shown in Fig. 5. The minimum
or steady state creep rates were of primary interest
in this study. These creep rates are given in Table
1 and illustrated in Fig. 6 as a function of stress,
‘d&,
II =
( dln(; ! T‘
varies from about 9 to 75 over the temperature range
studied. There appears to be a transition in behavior
at 8OO’Cand 9OOC and a trend toward higher stress
exponents at higher temperatures.
By normalizing the measured creep rates with re-
spect to the self diffusion coefficient for I+I!OCr and
the applied stresses with respect to the elastic
all of the data can be brought onto a single master
curve as shown in Fig. 7. The success of this normaii-
zation is evidence that self diffusion is the controlling
Fig. 5. .-\ family of typical creep curves of Xi-ZOCr-ZThO,
single crystals. These represent all tests conducted at
13OO’C.
47-t LUND .AhD NIX:
Fig. 6. The minimum strain rate for Ni-2OCr-2Th02 sin-
gle crystals as a function of creep stress at various
temperatures.
creep mechanism. In a previous paper [I41 we were
able to show a similar result for Ni-ZThO, using the
data of Wilcox and Clauer [l, 21. In that paper it was
shown that by using the temperature dependent elas-
tic modulus to normalize the applied stress, normali-
zation of the strain rate involved an activation energy
equal to that for self diffusion.
Stress dependence
An interpretation of the present results has been
developed which provides a very simple explanation
10’3,
1 $ = constant
IO’2i
r
IO”
10’0
102: 1 ! ,! !
6 6 ,o-’ 2 9 6 6 ,0.3 2 4
o-//E
Fig. 7. The diffusion compensated minimum creep rate of
Ni-20Cr-2Th02 single crystals as a function of the
modulus compensated applied stress. Also shown are the
calculated Orowan stress, the creep law for polycrystalline
Ni-1OCr and the predicted creep behavior for
Ni-20Cr-2Th0, single crystals following the additive rule
of equation (1). The test labeled No. 12 was heated in-sitar
for 7f hr at l3COC before testing at 12OO’Cand its pos-
ition indicates a dissolution of some Th02 particles.
+Creep strength is used to describe the modulus norma-
lized Row stress under steady state creep conditions.
CREEP OF Ni-XCr-3Th0, SINGLE CRYSTALS
of the large and variable stress dependence of the
creep rate. In essence we have discovered that the
master curve representing all of the creep data
approaches asymptotically the Orowan stress at high
temperatures and low stresses. This is shown in Fig.
7. The Orowan stress, as calculated from the Th02
particle distribution (see Appendix) and as repre-
sented by the vertical line, coincides closely with the
asymptotic behavior of the creep data. This indicates
that measurable creep does not occur below the
Orowan stress for this material. Above the Orowan
stress the creep rate is apparently controlled by the
same processes that control creep of Xi-2OCr. At
these low temperatures and high stresses the master
curve for Ni-20Cr-2Th03 single crystals approaches
the creep law for polycrystalline Ni-2OCr taken from
the literature. These asymptotic relations suggest a
very simple rule for describing the creep properties
of the single crystals of Ni-20Cr-2Th01. It is that
the creep strengtht of the dispersion strengthened
crystals be given as a simple sum of the creep strength
of the single crystals of Xi-ZOCr-2ThO:. It is that
Orowan strength. The curved line which coincides
with most of the creep data is a graphical represen-
tation of that rule. This additive rule. which can be
expressed as
,’ 7
(2)
describes the measured creep rates to within a factor
i
I of three at all temperatures and stresses.
i The additive rule represented by equation (2) can
be interpreted in terms of an effective stress as follows.
The Orowan stress can be regarded as a critical stress
that must be exceeded for creep to occur. When the
applied stress exceeds the Orowan stress. the crystal
creeps in response to the ditference between the
applied stress and the Orowan stress (ie, the effective
stress), following the creep law for the Ni-200
matrix. Thus the effective stress that drives the matrix
creep process appears to be simply the difference
between the applied stress and the Orowan back
stress.
i A question may be raised about the validity of
i comparing unthoriated polycrystalline Xi-20Cr with
single crystals of Ni-20Cr-ZThO,. In defense of this
comparison we note that grain boundaries are not
expected to contribute significantly to the creep pro-
cesses in polycrystalline Ni-20Cr. Because of this the
polycrystalline creep properties provide a good
approximation of the single crystal behavior of
Ni-20Cr and the comparison we have made is prob-
ably justified.
Another approximation we have made involves the
use of Young’s modulus in normalizing the applied
stress as opposed to the shear modulus for the active
slip system. One reason for this approximation is that
 LUXD A+D SIX: CREEP OF Ni-ZOCr-XhO,
the elastic constants of Ni-2OCr are not available up
to the temperatures of interest. Furthermore, the
dynamic Young’s modulus of Xi-ZOCr-2Th0, is
available only up to about IOOO’C and had to be
extrapolated to 13OO’C.The extrapolation is shown
in Fig. 8. The elastic constants of pure nickel are
known up to 500°C [i 51 and these were used to cal-
culate the ratio E/p (I 11)[TlO] up to that tempera-
ture. This ratio was found to be nearly constant with
temperature, indicating that the temperature depen-
dence of E and p (111) [ilO] for pure Ni are virtually
the same between room temperature and 500°C.
Without other evidence it seems reasonable to assume
that E and g (111) [llO] have a similar temperature
dependence in Ni-2OCr as well.
The success of the simple additive rule for describ-
ing the creep properties of Ni-ZOCr-2ThOl in terms
of the creep properties of Ni-2OCr and of the Orowan
stress depends very sensitively on the magnitude of
the calculated Orowan stress. The Orowan equation
we have used in this analysis is developed in the
Appendix and is expressed in final form as
- Shahinian and Achter data. The data we have used
0.93 i R b
4 V”
0 z orowln = 4rr(COSocoS~)(1 + v)(l - v)“‘(j. - 67)
. (3)
In fi
0 10
All of the terms in this equation are very well known
except i. and 2, the planar particle spacing and the
average particle size, respectively, and R and ro, the
outer and inner cut-off radius for the dislocation
energy calculation. Each of these terms is considered
in detail in the Appendix and the resulting range of
possible values of the Orowan stress is discussed. For
the present analysis we have taken
n=:4.,..~.=4band(r_a,=~~-a,,,.).
It is evident that other values could dk chosen for
these constants and they would lead to alternate in-
terpretations of the creep data. However, the form
of the master curve representing all of the creep
Fig. 8. Young’s modulus for polycrystalline Ni-ZOCr-
ZThO, as a function of temperature [25] extrapolated to
13OO’Cusing a fourth order polynomial function.
SINGLE CRYSTALS 475
properties strongly suggests the existence of a critical
stress and this in turn lends credence to our calcula-
tion of the Orowan stress. Furthermore. there is little
fundamental agreement on the exact form term by
term of the Orowan equation and even less agree-
ment on the numerical values of these terms. In view
of this we regard the correlation between the critical
stress for creep and the calculated Orowan stress as
being quite good.
In addition to uncertainties about the value of the
Orowan stress. there is some disagreement over the
creep properties of polycrystalline Ni-2OCr. Data
from three separate studies are shown in Fig. 9. If
the data of Shahinian and Achter [16] is considered.
agreement with the proposed model is good only at
high temperatures and low stresses. At low tempera-
tures and high stresses the additive rule would predict
creep rates that are about an order of magnitude too
slow. Furthermore. the Ni-20Cr-2ThOz single crys-
tals creep faster than the unthoriated Ni-2OCr of Sha-
hinian and Achter at these high stresses. Since this
is highly improbable, we have chosen not to use the
was taken from Monma, Suto and Oikawa [ 173, and
Sidey a,nd Wilshire [18]. These results are in good
agreement with each other and can be represented
by a single line as shown in Fig. 9. The extrapolation
of their data is unfortunate but is not considered inva-
lid.
With the Orowan stress set by the values defined
above, it is evident that some of the data points at
the lowest stresses, as well as the point labeled No.
42 are out of agreement with the rest of the data
Fig. 9. The diffusion compensated minimum creep rate for
Ni-tOCr-2ThOz single crystals and Ni-ZOCr polycrystals
as a function of the modulus compensated applied stress.
The additive rule predictions using each of the data lines
is shown, indicating that the data line of hlonma, Suto
and Oikawa [17] and Sidey and Wilshire [18] gives the
best prediction.
476 LUND AND NIX: CREEP OF Ni-2OCr-2ThOt
and with the additive rule. These deviations are even
more clearly shown in Fig. 6. The deviate behavior
of the tests at high temperatures and low stresses is
believed to have been caused by some form of degra-
dation of the oxide dispersion at the test temperatures
of 1200 and 1300°C. Several possible explanations
were considered. including the onset of a new high
temperature creep mechanism having a lower stress
dependence. The test labeled No. 42 was designed to
determine whether oxide degradation or the interven-
tion of an alternate creep mechanism causes the devi-
ations at high temperatures. The sample was held at
1300’C for 7* hr prior to creep testing at 1200’C. The
increase in creep rate by nearly four orders of magni-
tudet is convincing evidence that oxide degradation
is responsible for the deviate behavior of the long
time tests at the highest temperatures. In terms of
the additive rule we have proposed, the oxide degra-
dation apparently causes the Orowan stress to de-
crease.
Particle coarsening and dissolution of the thoria
particles (small particles first) have been considered
as possible mechanisms for the oxide degradation and
subsequent shift in the Orowan stress. Particle coar-
sening was discounted on the grounds that Dalal and
Grant [19] observed only a 3% increase in the aver-
age Th02 particle diameter in Ni-ZOCr-2ThOL and
100 hr at 1300°C. This leaves dissolution of thoria
particles into the Ni-200 matrix as the most likely
mode of oxide degradation. After careful consider-
ation of the magnitude of the effect on creep, there
appears to be evidence to support this form of degra-
dation.
It was observed that the extraction replicas of
sample No. 42 exhibited a much higher population
density of very small particles than did the untested
material. This observation was originally discounted
as being an artifact, but after repeatedly obtaining
the same distribution with extra care and different
methods of replica preparation, it was accepted as
fact. It strongly suggests the dissolution of small par-
ticles at the high temperature and reprecipitation on
cooling.
Work by Alcock and Brown [20] and Footner and
Alcock [21] has shown that such reactions are feas-
ible at these temperatures. They determined the solu-
bility of thorium in Ni and Ni-2OCr to be in the
range of 0.03-0.05 wt % at 1300 and 1350°C under
a controlled oxygen partial pressure of l.OmPa
(lo-* atm). This is the approximate oxygen partial
pressure that existed in the vacuum test chamber.
This solubility can be used to calculate the expected
effect of particle dissolution on the Orowan stress.
The curves in Fig. 10 indicate how the Orowan stress
would be expected to vary with weight percent of
t This test was very fast, requiring approximately I set
to complete. Consequently the creep curve was not
recorded. However, the elongation to failure of ISoi, indi-
cated a valid creep test so that our estimate of the creep
rate is probably correct to within a factor of about three.
SINGLE CRYSTALS
Fig. 10. Variation in the calculated Orowan stress of
Ni-ZOCr-2Th02 single crystals as each thoria particle size
class starting with the smallest is removed by dissolution.
This figure provides an explanation for the test labeled
No. 42. An Orowan stress for this test is calculated using
the additive rule and is shown as a horizontal line. This
agrees reasonably well with the reduced Orowan stress
(based on varying only E.)at the solubility range for thor-
ium at these temperatures.
thorium dissolved in the NC2OCr matrix assuming
that the smallest Th02 particles dissolve first. The
upper curve represents the variation in Orowan stress
if all of the terms in the Orowan equation are permit-
ted to vary as the small particles dissolve. The lower
curve shows the changes in Orowan stress if only the
particle spacing is assumed to change. The range of
thorium solubility as measured by Alcock is also
shown. The size classes of the distribution shown in
Fig. 4 are also indicated in the figure.
The upper curve in Fig. 10 is unusual in the sense
that the Orowan stress is insensitive to the dissolution
of the smallest particles. This is caused by the compet-
ing effects of particle size and particle spacing. Even
though the particle size appears in the logarithmic
term in the Orowan equation and as a modification
of the spacing it has a large effect when the smallest
particles are assumed to dissolve. Because of this
effect, the Orowan stress is predicted to decrease by
only 11% when Alcock’s solubility limit is reached.
By comparison, the Orowan stress for sample No.
42 was determined to be 50% less than for the
remainder of the data. This reduced Orowan stress
is shown as a horizontal line in Fig. 10. The curve
representing the variation in Orowan stress when
only the particle spacing is assumed to change pre-
dicts a reduction of about 40% at the Alcock solubi-
lity limit. This compares favorably with the observed
reduction.
The assumption that only the particle spacing
changes when small particles dissolve is probably
reasonable considering the uncertainty of our know-
ledge of the various factors in the Orowan equation.
Clearly the upper curve in Fig. 10 is unreasonable
and cannot be taken seriously. We conclude, there-
fore, that the Orowan stress reduction is best repre-
 LCXD AND NIX: CREEP OF Ni-JOG-2Th0, SINGLE CRYSTALS 477

sented by the lower curve and that the reduced
Orowan stress for sample No. 42 is due to particle
dissolution.
Temperclaire dependence
It is common practice to describe high temperature
creep using the familiar phenomenological equation,
correction term is small and can be neglected. How-
ever, when the temperature dependence of the elastic
modulus is ~rticularly large or when the creep stress
exponent is large, the correction must be made. For
example, in a previous paper we showed that the un-
usually large creep activation energies reported by
Wilcox and Clauer for Ni-2Th02 can be reduced to

i,= ( 1
AC;” exp - 6
0
RI
.
that for self diffusion by making this correction.
Following these previous studies, we have norma-
lized the stress by dividing by the temperature depen-
This kads to the welt known relation for the creep dent elastic modulus. UnfortunateIy no elastic pro-
activation energy. perty data for this material could be found above
about 1000°C. Thus an extrapolation of existing
(3 data [25,26] was required. The extrapolation shown
in Fig, 8 was made by fitting the data to a fourth
order polynomial relation between Young’s modulus
Using these relations Dorn and Sherby and others and temperature.
have shown that the activation energy for creep in The difi’usion coefficient for seff diffusion of
pure metals and alloys is equal to that for self diffu- Ni-200 has been determined by several investiga-
sion [ZZ. 233. In addition, Sherby [24] proposed that tors. The results of these studies, as summarized by
the creep equation be modified to account for the Monma et al. [27], give activation energies that range
effect of the elastic modulus on creep. His modified from about 272 to 305 kJ/mole (65-73 kcal/mol).
creep equation is written as: These are presented in Table 3. Finding no basis for
choosing one set of data over another, we have used
all of the available results to arrive at an activation
energy (285 kJ/moie. 68 kcallmoie) and pre-exponen-
where E represents the temperature dependent Young’s tial constant (1.5cm’/sec) for seif diffusion. It is im-
modulus. Using this equation the activation energy for portant to note that the diffusion coefficient for Cr
creep is expressed as: in Ni-2OCr has very nearly the same activation
energy and pre-exponential constant as Ni [27,28].
,lR T?
dE (7) Consequently, no weighted average or **effective”
E a7
value of D is necessary for this solid solution.
Use of both the self diffusion coefficient and the
where the first term on the right is the apparent creep elastic modulus as normalizing factors results in near
activation energy and the second is a correction term complete convergence of the data (Fig. 7). Such con-
accounting for the temperature dependence of the vergence is evidence that self diffusion is the controll-
elastic modulus. Barrett, Ardell and Sherby 113-J ing creep mechanism, just as for pure metals and solid
showed that the creep activation energy for cadmium solutions. The convergence method is perhaps less
corresponds to that for self diffusion only if the cor- attractive than a direct determination of the acti-
rection term is included in the analysis. For many vation energy using the Arrhenius relation with u,lE
pure metals and solid solutions the elastic modulus held constant, but it is much more convenient in our

Table 3. A summary of activation energies and pre~xponential factors for diffusion of Ni and Cr in Ni,
Ni-2OCr and Ni-2OCr-ZThO,
4% LUND AND NIX: CREEP OF Ni-30Cr-?Th02
case. At the highest temperatures studied the stress
exponent becomes very large (n o 75) with the conse-
quence that the creep rate is extremely sensitive to
both the applied stress and the elastic modulus. Very
smal1 errors in estimating the high temperature elastic
modulus produce large variations in the creep rate.
In some cases these can be so large that the resulting
creep rate cannot be measured accurately (creep rate
is either too slow or too fast). For these reasons we
have chosen to hold the applied stress constant, com-
pensate for the temperature dependence of the elastic
modulus and use data convergence to determine the
creep activation energy.
It should be noted that the value of Q, that results
in the best convergence of the present data is 33.5kJ/
mole (SOkcal/mole) instead of the value for self diffu-
sion, 285 kJ/mole (68 kcal/mole). Such a ditference,
when compared with the large values reported by pre-
vious workers, is relatively insignificant. However,
even this slight difference is somewhat puzzling and
it may suggest the involvement of a secondary
m~hanism such as solute drag.
As expected, the ductility of these single crystals
was observed to be much greater than that for poly-
crystalline material. The percentage reduction of area
typically ranges between 40 and 60”4 while the elon-
gation varies between 1 and 28% depending on the
stress and temperature. The samples evidently fail by
plastic instability. They show very severe local neck-
ing at the point of failure.
Recent work by Hart [29] and Burke and Nix [30]
has shown that steady state creep in tension is for-
mally unstable. Under these circumstances shape per-
turbations in the gage section are expected to grow
and to lead to localized necking. Burke and Nix stud-
ied the initial rate of growth of such ~rtur~tions
and found, as expected, that the necks develop
quickly in metals with high stress exponents. Frost
and Ashby[31] observed that the numerical results
of Burke and Nix could be integrated to give the
percentage elongation to failure as a function of the
creep stress exponent. They found that a simple rela-
tion of the form
where K 2 2 - 3. describes the numerical results
reasonably well. Since the present experiments involve
stress exponents that range from 9 to 75 we have
an opportunity to examine the experimental validity
of this relation. The percentage eiongation to failure
is shown in Fig. II as a function of the normalized
creep rate, (k/O). The prediction of equation (S) is also
shown in the figure for K = 2. The predicted curve
is constructed by referring to Fig. 7 to obtain the
creep stress exponent as a function of (+D). The equa-
tion evidently describes the data reasonably well. We
SINGLE CRYSTALS
Fig. 1I. Strain to failure (percentage elongation) as a func-
tion of diffusion compensated minimum strain rate from
Fig. 7. This figure provides a comparison of the measured
strain to failure with predictions based on plastic instabi-
lity and necking [30,31 J.
therefore conctude that these samples fail by plastic
instabiIity and necking.
5. DISCUSSION
The present experiments provide a basis for under-
standing the unusual creep properties that have long
been associated with DS metals. We have shown that
the activation energy for creep is not anomalously
large as previously reported. Provided that the tem-
perature dependence of the elastic modulus is taken
into account, the measured creep activ-ation energy
is near that for self diffusion, just as it is for pure
metals and solid solutions.
On the basis of the present work it is suggested
that the various and large creep stress esponents that
have been reported in the literature arise naturaIly
from the effects of the Orowan stress. -4s shown in
Fig. 7, the observed stress exponent can vary between
9 and 75 depending on how close the applied stress
is to the Orowan stress. It is evident that virtually
any stress exponent can be found if the applied stress
is judiciously chosen. For polycrystalline DS metals
creep appears to occur well below the Growan stress.
This is shown in Fig. 12 where the present data for
single crystais are compared with the data for poly-
crystalline samples with elongated grains reported by
Wilcox, Clatter and Hutchinson [6J. It is likely that
the creep properties of the polycrystallinc samples are
the result of inhomogeneous creep deformation.
Given the properties of the single crystals it seems
likely that creep in elongated polcrystais occurs by
grain boundary sliding and the development of stress
concentrations at grain boundary junctions. The high
stresses in these regions evidently exceed the Orowan
stress thereby causing creep to occur in some parts
of the sample and not others. Grain boundary separ-
ation and ultimate failure probably occur before the
grains are fully plastic. If creep flow occurs in this
way it is easy to see how it could occur at stresses
 LU4D ASD NIX: CREEP OF Ni-ZOCr-?ThO,
U/E
Fig. 12. Diffusion compensated strain rate as a function
of modulus compensated stress showing a comparison of
the properties of single crystals with those for polycrkstal-
line samples [6].
well below the Orowan stress. It is also apparent that
such a process is extremely complex because of the
inhomogeneity and that the properties of polycrystals
cannot be related to single crystal properties in a sim-
ple way. The relationship observed for single crystals
is apparently obscured in the polycrystalline exper-
iments.
Although we have shown that the simple additive
rule describes the creep properties of Ni-ZOCr-2ThOz
rather well, several important fundamental questions
have been left unanswered. First, we still do not un-
derstand the creep process well enough to know how
the Orowan bowing process should influence the kin-
etics of creep. If one assumes that dislocations cannot
climb over particles at any appreciable rate then it
is easy to see how the Orowan stress would represent
a threshold stress below which creep could not be
observed. However, in view of the complexities in-
volved, it is somewhat surprising that a simple addi-
tion of the matrix creep strength and the Orowan
strength so accurately describes the creep properties.
A related question involves the absence of measure-
able creep below the Orowan stress. Virtually all
existing theories of dislocation climb over particles
predict creep rates below the Orowan stress that
would have been observed in our experiments. That
creep is not observed indicates that our present know-
ledge of the alternate passing mechanisms is incom-
plete. This problem is currently being investigated by
Holbrook [32] and will be reported in a future paper.
6. COXCLUSIONS
1. The present work supports the contention that
the high temperature creep properties of dispersion
SINGLE CRYSTALS 479
strengthened metals are controlled by self diffusion,
just as for thz case of pure metals and solid solutions.
2. A simple additive rule involving the creep
strength of Xi-1OCr and the Orowan strength can
be used to describe the creep properties of these single
crystals:
i = constant.
A corrollary of this conclusion is that creep is not
observable below the Orowan stress.
3. At very high temperatures (2 1200X) the solubi-
lity of thorium in Ni-2OCr is sufficient to cause a
significant decrease in the Orowan stress and concur-
rent decrease in the creep resistance.
1. The ductility of these single crystals is much
greater than that for polycrystals. The reduction of
area typically ranges between 40 and 60”, Lvhile the
percentage elongation varies between 1 and 28””
depending on the stress and temperature.
5. The samples fail by plastic instability and neck-
ing in accordance with recent theoretical treatments
of this phenomenon.
,~cknowletlyrmu,lrs-The authors wish to acknowledge the
contributions made to this work by their colleagues at
Stanford University. In particular we express our-thanks
to C. R. Barrett. P. P. Pizzo and J. H. Holbrook for their
helpful criticisms and suggestions. Special thanks are also
due to D. S. Lund and P. S. Gilman who helped us accom-
plish this work.
The work was supported by the Air Force O&e of
Scientific Research under Grant No. AFOSR-73-1434.
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215. 838 (1959).
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.-ll/o~s, p. 50% ASM (1970).
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sity. August 1971.
480 LUND AND NIX: CREEP OF Ni-ZOCr-2ThOt
13. Barrett C. R.. Ardell A. J. and Sherby 0. D., Trans.
A1,W.E 230, 200 (1964,.
14. Lund R. W. and Nix W. D., Met. Trans. (A) 6, 1329
(1975).
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sfanfs and Calculated Aggregure Properties: A Hcmd-
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(1959).
17. Monma K., Suto H. and Oikawa H.. J. Japan Inst.
Metals 28, 253 (1964).
18. Sidey D. and Wilshire B. Metal Sci. J. 3, 56 (1969).
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21. Footner P. K. and Alcock C. B., Mer. Fans. 3, 2633
(1972).
22. Bird J. E., Mukherjee A. K. and Dotn J. E., Quantifa-
rice Relations Between Properties and Microstructures
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24. Sherby 0. D., Act& Met. f0, 135 (1962).
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APPENDIX
Calculation of the Orowun Stress
Because the Orowan stress plays such an important part
in our description of the creep properties of
Ni-ZOCr-ZThO,, it is necessary for us to describe the
equation we have used in some detail and to indicate the
SINGLE CRYSTALS
way each term in the equation has been evaluated. In its
simplest form the Orowan bowing relation [33] is
expressed as
27-
r = -. (A-l)
bi.
where T is the line tension of the dislocation, assumed
to be constant, b is the Burger’s vector and i is the spacing
between point obstacles in the slip plane. If we wish to
account for the fact that the line energy of a dislocation
depends on its character, the bowing problem must be con-
sidered in more detail. Following Ashby [3-t] we take the
line energy to be
E
d
=K~@lnfl (A-11
4n 0 rO’
where K is l/l+ and 1 for edge and screw dislocations.,
respectively, p is the shear modulus (elastic isotropy is
assumed) and R and r,, represent the outer and inner cut-
write separate critical bowing stresses for edge and screw
dislocations as:
and
r.c,uv b R
-=-[n -. fA-4)
P (1 - v)hE. 0 ro
As suggested by Ashby 1351 we take the overall passing
stress to be the geometric mean of equations (A-3) and
(A-41, which results in the following relation:
h R
0
T
In -. (A-51
r( = 2n(l - v)’ ‘i. r.
This equation would be expected to apply to certain per-
fectly regular distributions of infinitesimally small particles.
For randomly distributed particles of finite size other fac-
tors must be considered.
In the development of equation (A-5) it is implicitly
assumed that the shear stress required to cause critical
bowing at one point in the slip plane is the same for all
other points. This would be the case. for example, if the
particles were in a square array and if the expanding dislo-
cation loops were square also, so that both edge and screw
dislocations would always encounter the obstacle spacing
l/, N,. For randomly distributed particles the dislocations
are confronted by a distribution of spacings with the conse-
quence that the focal shear strength and the average shear
strength are not the same. Kocks [36] has shown that an
additional factor is needed to account for this difference.
By taking the Orowan stress to be the critical applied shear
stress at which dislocations move indefinitely over slip
planes containing randomly distributed. impenetrable
point obstacles, he found that an additional factor of
0.95,.(d4) should be included on the right hand side of
equation (A-5).
The above analysis is for point obstacles. For particles
of finite size, it would seem that an effective separation
distance of 1 - 8 should be used in place of 2. Here a
is the arithmetic mean particle diameter defined by
(A-61
where ni is the number of particles having the diameter
dti
 LUND *SD SIX: CREEP OF Ni-2OCr-2Th02 SINGLE CRYSTALS 481

With these corrections the Orowan relation may be the critical passing condition. The segments on either side
expressed a3 of the particle form a kind of dipole in which the stress
- field of each segment falls off rapidly at about half the
particle diameter. We use the mean free particle diameter.
0.95 ; b
a,,,,. instead of the mean particle diameter, a,,.,,,. to prevent
(A-7) the cluster diameters from dominating our estimate of the
-1’ = ‘~(1 - v)‘ ‘(;. - (1)
cut-off. Transmission electron microscopy indicates that
For comparison with our experimental results it is con- the dislocations are held up mainly by the free particles.
venient to write this in terms of the tensile stress and We have taken r,, = 4b. in part because this particluar
choice makes the Orowan stress coincide exactly- with the
Young’s modulus. For this we use*
asymptotic behavior of the creep data. As noted above,
p = E/2(1 i V) previous estimates of r0 range from about b 2 to 56. If
and the smallest estimate of r0 were used the Orowan stress
r = 0 cos 4 cos 0 (Schmid’s Law), would be about twice what we have predicted. If the largest
value were used. the predicted Orowan stress would have
where 4 and 6 are the respective angles between the slip been about 15:; lower. Not having precise knowledge of
direction and slip plane normal and the tensile axis. With this cut-off radius therefore introduces some uncertainty
these conversions we have in the present calculation.
I; For the present calculation we have taken
0.95 ,b b = 0.25 nm (2.5A). case = 11, 3, coso = I, 2.
I7 J (I + v) (1 - \.)i’? = 1.086, i. = 100 nm (looUr\) and
In 5 (A-g)
E=4?r(cos$wos0)(I +I!)(1 -!+“(;.-b 0 ro nfrec = 10.6 nm (106 A). The values lead to

There is always some debate about the values that

should be taken for the inner and outer cut-off radii for
the dislocation energy calculation. Estimates of r0 range
from b/2 to 5b [37.38]. while the choice of R depends on
the configuration of the dislocation in question. In the f Reference to the elevated temperature elastic constants
present work we have taken R to be +a,,,, on the grounds for Ni[lj] indicates that httt,C1,~, = EaSusS’31 - vb to a
that the dislocation segments nearest the particle determine very good approximation.