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R. SMITH
The B.S.A. Group Research Centre, Kitts Green, Birmingham (Great Britain)
SUMMARY
Various mechanisms, whereby the addition of an alloying element to niobium
may influence the oxidation resistance, are examined in the light of previous
experimental work; it is concluded that the effects observed are probably due
to the combination of a number of factors. An account is given of systematic
investigations into the oxidation resistance of an extensive range of ternary
and more complex niobium alloys, containing from g to 25 atomic o/0titanium,
which have succeeded in identifying ductile and refractory alloys showing
oxidation rates at r,~oo’C of about I o/0 of that of pure niobium metal.
INTRODUCTION
Increased attention has recently been paid to niobium as the possible base for a new
series of materials for use at high temperatures. Conventional creep-resisting alloys
are proving inadequate at temperatures above I,o~o’C, but niobium retains a useful
degree of strength in this temperature range. On the other hand, niobium oxidises
so rapidly above r,ooo’C that in the pure or unprotected form it cannot be used in
an oxygen-bearing environment at these temperatures.
It was the purpose of this investigation to examine the effect of alloying on the
oxidation resistance of niobium, in order to develop alloys which could be used for
structural applications under the above conditions. As the resultant materials were
required to be tough and refractory, any alloying development which was found to
be accompanied by a severe lowering of the creep-resistance or ductility was rejected.
connected with the 01to @ transformation, the transformation of the scale from a black
adherent dense phase into a white inadherent porous one.
The primary cause of the high oxidation rate of niobium is probably the large
volume ratio of Nbz05 to the metal from which it is formed. Owing to the dimensional
restraint imposed by the metal, severe compressive stresses develop in the scale as
it grows, causing periodic crackings, which allows the physical penetration of oxygen.
While still sound, the scale is partially protective and if the scale could be modified
by alloying, in order to increase the thickness which it attains before fracture, im-
provements in the oxidation resistance should result. Also, if alloying additions could
be found that would reduce the diffusion rate of oxygen in the compact scale, the
oxidation rate should again be decreased as the scale would take longer to reach the
critical thickness for fracture.
Various factors which may influence oxidation resistance will now be examined in
the light of published experimental findings.
The effects of many added elements vary with temperature; but the following dis-
cussion is primarily concerned with the reported behaviour between about ~,ooo”C
and 1,200°C since this was the main range of interest in the present investigation.
KLOPP et al.9 found that, after exposure to air at 80o”C, the concentrations of
titanium, vanadium, tantalum, tungsten and zirconium in the scale andin theniobium
alloy core differed by only 25% or less. Furthermore, the atomic radii differences are
so small that it can be shown that the total effect on the oxide: metal volume ratio is
insignificant.
The influence of addition valency on oxide stoichiometry and the dimelzsions of Nbz05
The high oxide : metal volume ratio of Nbz05 is due to the large volume of the oxide
occupied by oxygen atoms. The addition of elements with lower effective valencies
than that of niobium should therefore reduce the volume ratio and the tendency to
cracking.
At ~,ooo’C, in those composition ranges where only niobium oxides are formed in
the scale, the following observations are made:
(i) of the quadrivalent elements titanium, zirconium and silicon, titaniuma,9Pio
improves the oxidation resistance of pentavalent niobium, whilst zirconium4S9Si0and
silicone reduce it ;
(ii) vanadium, which can exhibit valencies of both 4 and 3, markedly improves the
oxidation resistance7sgJO;
(iii) molybdenum, with alternative valencies both higher (6) and lower (4) than
niobium, also improves the oxidation resistance7~9~10;
(iv) tungsten, with the same possible valencies as molybdenum, was initially
reported to be detrimental 9J0,i1 but later investigations by MICHAEL7 have shown
that it can have a beneficial effect at I,IOO”C;
(v) chromium, with alternative valencies of 6 and 3, has also been found beneficial%11 ;
There appears, therefore, to be no simple consistent relationship between the in-
fluence of an added element and its valency.
that suggested above. Perhaps both the foreign ions and the defect lattice sites to-
gether introduce internal stresses which help to increase the apparent creep-strength.
Our understanding of the factors influencing the fracture strength of oxides is also
limited, and although it is probable that added elements will have an appreciable
effect on this property, the form that this will take cannot easily be predicted. The
possibility of valid experimental assessment of the influence of additions is made
difficult by the need to use specimens which are in the same condition as the thin
compact and adherent scale.
Although sintering of the outer porous scale may in some cases contribute towards
a reduction in the rate of oxidation, it has been observed by previous workers and
during the present investigation that the best alloys are characterised by a dark
adherent underlying scale which is relatively thick compared with that on pure
niobium. Further, during the present investigation it was foundthat thelight-coloured
outer oxide formed much later on the oxidation-resistant alloys than on niobium,
but after a shorter period on alloys containing silicon and zirconium. These obser-
vations suggest that the increased protection afforded by beneficial elements is
primarily associated with their influence on the underlying dark adherent scale.
There are other possible mechanisms of protection, in addition to the general ones
discussed above, which may only operate in the case of a limited number of alloying
elements. Thus, the beneficial effect produced by small percentages of molybdenum
may be due to partial volatilisation of molybdenum as MoOa which is suggested by
the analytical results of KLOPP et ai. 9. Such volatilisation at low molybdenum con-
centrations may reduce the oxide: metal volume ratio, while at higher molybdenum
contents the more marked volatilisation would probably introducede leterious poros-
ity into the scale.
From the foregoing analysis of previous experimental work, it is clear that none
of the proposed mechanisms is capable of explaining the effect of added elements on
niobium oxidation in all cases, and the influence of each addition is probably due to
a complexity of factors. There was, therefore, no theoretical lead as to the direction
the present research should take in the development of ternary and more complex
alloys having improved oxidation resistance. However, from the limited dataraJ4
which were available at the initiation of the project, the indications were that titanium
was the most useful of the binary additions studied. Titanium had been shown to
promote a substantial improvement in oxidation resistance up to temperatures of at
least r,~oo”C, and also to reduce the emb~ttlement produced by interstitial contami-
nants and certain alloying elements in substitutional solid solution, without much
effect on the refractoriness of niobium. Accordingly, this investigation was principally
concerned with examining systematically the effects of further additions to niobium-
titanium alloys.
EXPERIMENTALPROCEDURE
Scope of research
The investigation began with a general survey of the effects of a wide range of
elements, including MO, W, Ta, V, Zr, Cr, Fe, Ni, Co, Mn, B, Re, Ce, Al and Si, on
the oxidation resistance of niobium containing 9, 18 or 25 at. yO titanium. A simple
gravimetric test was used. From the results of the preliminary survey a number of
alloys were selected for more complete investigation by means of a continuously
indicating spring balance.
Intensive oxidation-testing was then carried out in certain promising alloy ranges,
in order to determine the optimum compositions and to assess the influence of tempera-
ture and of still further added elements.
The entire investigation was supported by X-ray and chemical analysis of the
scales, and by m&allographic examination and micro-hardness testing of the metal
base.
Exfierimental methods
The materials used in preparing alloys were as follows:
Niobium: Murex Ltd., Powder, minus 20 mesh (0.30% Ta, 0.03 Fe, less than 0.019/oC,
0.01% N, 0.01% Pb, 0.01% Sn, 0.01% Si and o.o3%Ti)
Titanium: I.C.I.Ltd., sponge (evaluation hardness 135-145 V.P.H.)
Zirconium: Murex Ltd., sponge (evaluation hardness 140-150 V.P.H.)
Other constituents: Ta, V, W, MO, Fe, Ni, Co and Cr. Johnson Matthey & Co Ltd.,
spectrographically pure (99.99%)
25 d %Ti
Fig. 2. Degree of oxidation in air of ternary niobium alloys containing 9. 18 or 25 at. yO titanium,
after r h at I, IOO“C (I g rectangular specimens).
sharp projections on niobium alloys. This irregular surface oxidation was considered
undesirable and was largely avoided in the second extensive survey, by carrying out
the tests on approximately spherical I g specimens. A standard comparative test of
20 h at I,IOO’% was established for all alloys, but a considerable amount of testing
was carried out at other temperatures and also for periods of I, 2,40,50 and IOOhours.
As oxidation proceeds the surface area of the unoxidised metal decreases and there-
fore the oxidation data reported in the first survey, which was calculated on original
area, is too low. In the second survey, using spherical specimens, the mean of the
original and final surface area was used to calculate an oxidation rate which is a closer
approximation to the true one.
EXPERIMENTAL RESULTS
~r~~~~~~~r~ survey alathe effect of ad~~t~o~sto ~iob~z~~-tita~~~~ alloys
The results of oxidation tests on rectangular ternary niobium-alloy specimens
containing 9~8 or 25 at. yOtitanium are given in Table I. The results of the x-h tests
at r,~oo”C and certain other tests are also presented graphically in Fig. 2.
TABLE I
DEGREE OF OXIDATION OF TERNARY NIOBIUM ALLOYS
--. ---
TABLE I (continued)
-.. ..-. ._-
Time and temper&we of eg3osurc
Nmimzl doy ._
composirion
1 hl 5 hl IOO hl
c-k %! I,ddC
I,IGdC IJdC I,IdC
.._
-ISTi- 3?;i 5.5 17.6
-xSTi- 6?ii I.8
-ISTi- 9Ni 8.5 22.5
-ISTi- 3Fc 6.0
-ISTi- 6Pe
C.O. (25 h)
z g specimens denoted by *
C.O. = complete oxidation.
Certain ternary alloys containing Cr, Fe, Ni, MO, W or Ta were found to be superior
to niobium-18 at. yO titanium and on the basis of the one hour tests at I,IOO”C it
appeared that controlled additions of tungsten, nickel, iron and chromium might
reduce the oxidation rate to less than 10% of that of niobium. The limited number
of tests which were carried out at ~,zoo’C and for longer times at I,IOO’C generally
confirmed these findings.
TABI,E II
DEGREE OF OXlDATION OF TERNARY AND QUATERNARY ALLOYS
I g specimens denoted by l.
(M) = The mean of the original and final surface areas used.
C.O. = complete oxidation.
Tests were next conducted on some other ternary alloys and niobium-titanium-
tungsten alloys containing quaternary additions of nickel, chromium, vanadium and
tantalum. The results, presented in Table II, indicated that nickel and chromium
additions improved the oxidation resistance of niobium 18 at. y0 titanium-g at. y0
tungsten but that vanadium and tantalum additions were detrimental.
These tests also suggested that higher percentages of titanium would not lead to
a marked improvement in oxidation resistance. Also, titanium, together with iron,
nickel and chromium, was expected to decrease, and tungsten to increase, the re-
fractoriness. This was confirmed during a programme of high-temperature creep-
testing, subsequently carried out on a wide range of niobium alloys. It was therefore
decided generally to adopt a titanium level of 20 at. y0 in later tests as a compromise
between the requirements of oxidation resistance and ductility on the one hand and
hot strength on the other.
Additional specimens were also prepared from each alloy in Tables I and II, for
a workability assessment, conducted at room temperature. Most of the alloys with
the notable exception of those containing chromium, were quite ductile and many
withstood 60% deformation by pressing, with only slight edge cracking. The addition
of 2 at. o/o cerium to niobium-18 at. o/o titanium-10 at. o/o chromium was found not
to improve the ductility significantly. Although chromium was established to be a
beneficial addition, the presence of titanium did not sufficiently reduce its embrittling
effect: and thus chromium was rejected as a basic ternary addition for immediate
study.
T-----------l
TIME (twm)
Fig. 3. Oxidation of some niobium alloys in air at I,IOOT .Weight increase continuously recorded
by Pyrex spring balance.
decreased in a parabolic fashion during the first one or two hours, after which the
specimen oxidised in an approximately linear manner during the next few hours. After
a period of exposure dependent on the size and oxidation resistance of the specimen,
the oxidation rate, calculated on the original surface area, deviated progressively from
linearity as the effective surface area of the residual metal core decreased. It was
concluded that with the size and type of specimen and form of apparatus used the
oxidation rate could only be recorded reliably on tests of up to about 8 hours. For this
reason the curves presented are only for 8 hours although three of the specimens
were tested for over 45 hours. Tests of over zoo hours have been conducted on
Nb-18 at. y0 Ti-9 at. y0 W,-6 at. y0 Ni; Nb-18 at. y0 Ti-9 at. y0 W-3 at. y0 Ni;
and Nb- 18 at. o/oTi-15 at. o/oW; which confirmed the regular nature of the oxidation
process for these alloys during the longer exposure periods, although the later oxi-
dation rates had no absolute significance due to the consumption of much of the
specimen.
The tests carried out on the spring balance confirmed that the alloy combinations
selected during the preliminary survey had considerable oxidation resistance relative
to niobium and that they appeared to remain effective for long periods (up to 300 h)
and over the temperature range 1,ooo~-1,2oo~C.~
At this stage it was decided to determine the optimum alloy compositions more
precisely and to assess the inter-related effect of the beneficial added elements.
I I 4 6 8 10 12 id 16 18 10
ATmK % TUNGSTEN
Fig. 4. Oxidation rates of niobium-20 at. y0 titanium-tungsten alloys in air at ~,ooo’C, I,IOO’C
and 1,140°C.
conducted at I,OOO’, 1,100’ and 1,140’C all indicated that the influence of tungsten
additions up to about 4 at. o/o is complex. There is evidence of an initial decrease in
oxidation resistance at I at. o/o tungsten followed by a general but fluctuating im-
provement up to 6 at. y. tungsten. Further additions of tungsten up to about 16 at. y0
do not produce any significant variation in oxidation resistance at I,IOO’C, but larger
additions result in a pronounced deterioration.
The rate of oxidation of Nb-2o at. y. Ti-20 at. y0 W at I,IOO”C was greater than
that at 1,140’C; but generally, the effect of tungsten follows the same trend at I,OOO’,
1,100~ and 1,14o’C, with a progressive increase in the oxidation rate with temperature.
It was noted that the beneficial effect of tungsten additions was less pronounced at
I,OOO’%than at I,IOO’C. Oxidation rates determined from x-h tests at 1,200'C were
found to be 2 to 3 times greater than those at I,IOO”C.
Reduction in the titanium content from 20 at. y. to 15 at. y. did not have any
significant effect on the oxidation resistance of niobium alloys containing from 6 to
rg at. o/0 tungsten.
A wide range of tungsten additions therefore double the oxidation resistance of
niobium-20 at. y. titanium but as the tungsten content is increased the ductility
gradually deteriorates and the practical limit is probably about 12 at. %.
Variation of nickel, iron and cobalt in 20 at. y. titanium alloys (Fig. 5). The addition
of up to 8 at. o/0 nickel leads to a progressive increase in the oxidation resistance of
niobium-20 at. o/o Ti alloys, and an increase in the titanium level to 25 at. y0 only
produced a significant improvement in the case of the 5 at. y. nickel alloy.
Fig. 5. Oxidationratesin air at I,IOO%of Nb--20 at. y0 Ti or Nb-25 at. yO Ti alloys containing
ternary additions of iron, nickel or cobalt.
Iron appears to differ from nickel in that only small additions produce an improve-
ment in oxidation resistance; and 20 at. yOtitanium alloys containing 6 and 8 at. yO
iron are inferior to the iron-free alloy. The r-h oxidation rates are also noticeably high.
Similarly, only small additions of cobalt (3 and 4 at. %) were found beneficial and
larger additions drastically reduced oxidation resistance.
Variatiort of lzickel irt titanium-turtgstela alloys (Fig. 6). At I,IOO”C, a significant
decrease in oxidation resistance was observed on the addition of I at. ‘$! nickel to
niobium-20 at. yOtitanium-10 at. oh tungsten; but further additiens of 2 and 3 at. yO
nickel lead to a progressive improvement. Alloys containing between 3 and 7 at. yO
nickel showed some scatter, but the oxidation resistance remained approximately
constant.
0I I 2 3 ‘I 5 6 7 8 9 IO
AmM!c % NICKEL
The effects of increasing nickel contents at 1~40°C and I,IOO’C are similar, with
I at. o/Onickel probably having a detrimental effect; but at ~,ooo”C, a progressive
improvement was recorded up to 4 at. o/Onickel. It appears that, on increasing the
temperature from 1,000’ to 1,140%, the oxidation rateof niobium-20 at. yOtitanium-
IO at. yOtungsten- I at. y, nickel increases more rapidly than that of alloys containing
larger nickel additions, so that only the higher contents are beneficial at the higher
temperatures.
Increasing the titanium content of the IO at. yO tungsten-6 at. yO nickel alloy to
25 at. o/o resulted in an appreciable decrease in oxidation resistance, whilst the effect
of a decrease to 15 at. y. was insignificant. The effect of a reduction in the tungsten
content of the niobium-20 at. y. titanium-10 at. y. tungsten-3 at. y. nickel alloy
alloy to 6 at. o/o tungsten was also insignificant.
Variatiolz of cobalt irt titanium-tungsten alloys (Fig. 7). The effects of cobalt on
niobium-20 at. o/Otitanium-10 at. o/o tungsten and niobium-20 at. y. titanium are
similar, in that additions of 2, 3 and 4 at. o/0 cobalt slightly improve the oxidation
resistance, whilst 6 and 8 at. o/o cobalt markedly reduce it.
70 -
L
P
= .
: 6.0 El
8
e 5.0 -
ki
6 40.
3.0 -
Zo(.b--.. *
--o- * ” . ” 20
0 Nb-2Ool=bT~~6ol%w~co 1
IO- e . . . . . 2c
8 2 3 4 5 6 7 8
*TOMlC 9.2COBALT
Fig. 7. Oxidation rates of niobium-20 at. y0 titanium-tungsten-cobalt alloys in air at I,IOO’C.
DISCUSSION OF RESULTS
Review of findings
The outcome of the investigation was that niobium alloys containing 15-25 at. y.
titanium and 6-10 at. y. tungsten provided the most promising base for the develop-
ment of high-temperature high-strength alloys, since the oxidation resistance was
superior to the other ductile alloys studied, and subsequent testing had shown that
their creep strength was of the same order as that of niobium.
Nickel was found to be an effective beneficial addition to the niobium-titanium-
tungsten base and an alloy of niobium-zo at. ‘=J&titanium-10 at. y. tungsten-4 at. y.
nickel had the maximum oxidation resistance over the temperature range from 1,000~
to 1,140’C. A reduction in the tungsten content to 6 at. y0 improves the ductility
without any significant effect on oxidation resistance, but the creep-strength is re-
duced. On the other hand, a reduction in the nickel content to 2 at. y0 improves to
some extent the ductility and creep-strength but reduces the oxidation resistance.
Other modifications of the more promising compositions were examined (Table III),
but no further significant improvement was noted.
TABLE III
OXIDATION RATE OF SOME COMPLEX NIOBIUM ALLOYS
Nb-zoTi- 6W I.5
- zoTi- 6W-I Zr 2.4
- 20T - SW 2.8
-zoTi- 6W-3Cr 3.3
- 20 Ti - 6 W - 4 Co 4.6
-zoTi- 6W-4Co-3Cr 3.’
- zoTi-row 2.0
- 20 Ti - IO W - I Zr 4.4
2.8
-zoTi-row-4Ni I.4
- zoTi-row-4Ni-5Al I.7
- 20 Ti - IO W - 3 Ni - 3 Cr 11.8
- 2oTi-row-3Ni-2Cu 1.6
-zoTi-row-3Ni-2Mn I.9
Spherical I g specimens used, and oxidation rate calculated from the mean
of original and final surface area.
Meclzanism of @otection
Since tungsten, nickel, iron and cobalt additions introduced no additional oxides
into the scale on niobium-zo at. o/o titanium alloys their beneficial effect probably
derives from their influence on 3 Nbz05. TiOn by minor solid solution.
No structure determination of 3 Nb205 .TiOs is available; but it is clear from the
X-ray diffraction pattern that the structures of @ Nbz05 and 3 NbzOs.TiOz are closely
allied. However, additional elements do not always influence the protective qualities
of the two oxides in the same way. For example, 9 at. o/ozirconium was found to have
a slightly beneficial effect on niobium-18 at. % titanium compared with its established
detrimental effect on niobium itself, while 9 at. y. vanadium had a detrimental effect
compared with its known beneficial effect on pure niobium.
The inter-related effects of the principal beneficial elements on the performance of
the niobium-20 at. y. titanium base can be assessed from Figs. 4 to 7. The effect of
cobalt variations in the niobium-zo at. o/otitanium-10 at. o/0tungsten-cobalt alloys
is similar to that observed for niobium-zo at. o/otitanium-cobalt alloys, with a rapid
decrease in oxidation resistance at 6 and 8 at. y0 cobalt. On the other hand, in the
niobium-zo at. o/otitanium-10 at. o/otungsten-nickel alloys a high level of oxidation
resistance is maintained throughout the range 4-8 at. o/onickel, as in the niobium-20
at. o/o titanium-nickel alloys. Furthermore, a variation in the tungsten content of
both the niobium-20 at. y. titanium and niobium-eo at. y. titanium-3 at. y0 nickel
alloys from 6 to IO at. o/o tungsten produces no significant effect on the oxidation
resistance. Since the effects of nickel and cobalt are additive to, and probably un-
related to, that of tungsten, it is possible that the mechanisms by which they produce
a protective scale are different.
CONCLUSIONS
A decrease in the oxidation of niobium by a factor of one hundred has been accom-
plished by alloying with about 20 at. y0 titanium, IO at. y0 tungsten and 3-4 at. y.
nickel.
Modification of the above composition within the limits IS-25 at. y0 titanium,
6-14 at. y. tungsten, o-4 at. y. nickel produces other levels of ductility and creep-
strength which are suitable for many applications, but some reduction in oxidation
resistance also occurs.
ACKNOWLEDGEMENTS
The author gladly takes the opportunity of thanking Mr. D. A. OLIVER,Director of
Research, The B.S.A. Group Research Centre for his sustained encouragement, also
Dr. H. J. GOLDSCHMIDT and Mr. J. A. BRAND for their X-ray crystallographic work
on oxides.
REFERENCES
1 H. J. GOLDSCHMIDT, J. Inst. Metals, 87 (1958-59)235.
2 W. D. KLOPP, C. T. SIMS PND R. I. JAPFEE, High-temperature oxidation and contamination
of niobium, Battelle Mem. Inst. Rep. Nr. 1170 (January 1957).
3 H. P. KLING, The development of oxidation-resistant niobium alloys, in B. W. GONSER AND
E. M. SHERWOOD, Technology of Columbium. John Wiley, New York; Chapman and Hall,
London, 1958.
4 R. SPEISER, Development of an oxidation-resistant columbium alloy Report No. 17, RF Project
467, The Ohio State University Research Foundation (August 1958).
5 C. A. BARRETT AND F. J. CLAUSS, Oxidation of columbium-chromium alloys at elevated