Sie sind auf Seite 1von 16

JOURNAL OF THE LESS-COMMON METALS r9r

THE DEVELOPMENT OF OXIDATION-RESISTANT NIOBIUM ALLOYS

R. SMITH

The B.S.A. Group Research Centre, Kitts Green, Birmingham (Great Britain)

(Received May rdth, 1960)

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.

THE MECHANISM OF NIOBIUM OXIDATION

When niobium is exposed to an oxidising atmosphere it is believed that, after the


initial dissolution of a small percentage of oxygeni, oxidation probably commences
with the formation of one or all of the lower oxides of niobium2.a (Nb20, NbO and
NbOs) ; but the presence of these oxides has not been conclusively established experi-
mentally under all temperature and pressure conditions of oxidation. Moreover, it is
clear that if present, these lower-oxides exist only as relatively thin layers and prob-
ably play a negligible part in the oxidation process at elevated temperatures.
The next stage is the formation of a preferentially-orientatedlayer of or-Nb205, which
subsequently recrystallises and becomes randomly-orientated. Further holding at the
oxidation temperature results in the transformation of 01to B Nb205, the equilibrium
phase1 at all temperatures above room temperature.
During the growth of the Nb205 layer there is a change in its physical state un-

J. Less-Common Metals, 2 (1960) IgI--206


192 R. SMITH

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.

THE INFLUENCE OF ADDED ELEMENTS ON THE MECHANISM OF NIOBIUM OXIDATION

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.

The formation of oxides other than Nbz05


The improvement in oxidation resistance which results from the addition of sub-
stantial quantities of zirconium 4, chromium5, silicon6, aluminium7 and combinations
of cobalt and iron, cobalt and nickel, chromium and cobalt or chromium and nickel7
is believed to be derived from the formation in the scale of oxides other than Nba05.
However, large additions of these elements have a detrimental effect on the ductility
or refractoriness of niobium. For this reason, attention was concentrated upon small
additions of those elements which exert their effect on oxidation resistance primarily
by their influence on the NbsOs in which they dissolve.
One exception is the systematic improvement in oxidation resistance resulting from
the addition of up to about 25 at. y0 titanium, which produces scales containing
3 Nb205. TiOz beyond about 6 at. y0 titanium in the alloya. In this case, however,
the improvement is not only due to the formation of another phase, as a definite
improvement occurs up to 5 at. o/o titanium and the influence of dissolved titanium
on Nba05 must be significant.

The effect of alloy cation size on the dimensions of Nbs05


In assessing the influence of the alloy cation size on the oxide: metal volume ratio,
its effect on the dimensions of both the oxide and metal lattices must be considered.
Further, since the metal cations occupy a minor part of the oxide volume, any variation
in their dimensions has a proportionally reduced effect on the oxide dimensions.
Although an added element will exert a different dimensional effect in the ionised
state of the oxide to that in the metallic lattice, in general, the relative effects of the
elements which have been studied are about the same in both environments. Because
of these considerations, the oxide:metal volume ratio is hardly affected, unless the
atomic radii of the constituent elements are markedly different and one of them is
appreciably concentrated in the oxide.

J. Less-Common Metals, z (1960) IgI--206


DEVELOPMENT OF OXIDATION-RESISTANT Ni ALLOYS I93

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.

The influetice of addition valency on oxygen diffusion in Nbs05


Nba05 possesses an oxygen-deficient lattice1213 and by virtue of the Wagner
concept13 alloy cations having a higher valency than niobium should, on solid solution
in Nba05, reduce the number of lattice defects and thus the diffusion rate of oxygen
through the adherent compact scale. Elements of lower valency should have the
opposite effect. The relevant experimental findings are therefore the same as those
discussed in the preceding section, but the effects of valency in the two cases are
diametrically opposed, and there is no consistent experimental support for either
mechanism.

Relaxation of internal stresses with& the adherelzt scale


It has been suggested by KLING~ that the creep strength of the Nb205 scale may
be related to ionic mobility, and therefore to the anion deficiency, by analogy with
the state of affairs in metals. Accordingly, if the controlling factor in the influence
of added elements on oxidation is the ease of plastic deformation in the scale, the
effects of valency are opposed to those which were considered in the preceding
section,
However, our knowledge of the deformation processes in oxides is very limited,
and it is probable that the influence of added elements is much more.complex than

J. Less-Common Melds, 2 (1960) IgI--206


194 R.SMITH

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

J. Less-Common Metals, 2 (1960) rgr-206


DEVELOPMENT OF OXIDATION-RESISTANT Ni ALLOYS I95

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%)

Fig. I. Spring balance for high-temperature oxidation-testing.

J. Less-Common Metals, 2 (1960) 191-206


196 R. SMITH

The alloys were melted in a tungsten-electrode arc furnace containing an atmosphere


of purified argon, after evacuation of the furnace chamber to 2.10-2 mm Hg.
The preliminary survey was mainly conducted upon small specimens, approxi-
mately 4 mm cube and weighing about I g, machined from 5 g alloy buttons and the
faces ground, polished on fine emery paper and degreased. A number of long-term
tests were conducted on z g rectangular specimens and these are identified later. The
specimens were placed in an alumina boat, introduced into a tube furnace open to
the atmosphere, and the original dimensions and increase in weight after exposure
used to calculate the degree of oxidation in terms of weight increase per unit area.
In order to cover an extensive composition range a standard comparative test of I h
at I,IOO’C was adopted for nearly all the alloys, but additional treatments of varied
duration at I,IOO”C and other temperatures have also been applied to individual
alloys.
Information on the progress of oxidation in certain selected alloys was obtained by
testing in the apparatus illustrated in Fig. I, using undried air flowing at a rate of
0.5 ljmin. Specimens about 3 mm square and I mm thick, weighing about 0.4 g were
placed in a small platinum thimble, which was suspended by a platinum/r3 yOrhodium
wire in a vertical tube furnace from a calibrated Pyrex glass spring. The deflection
of the spring, which measured the weight of the wire, thimble and contents, was
followed by means of a travelling microscope. The static gravimetric test in a modified
form was reverted to in the final series of tests, since its simplicity enabled the exami-
nation of a wider range of alloy compositions in a given time.
During the preliminary survey small rectangular test specimens were used, but
these were susceptible to the considerably accelerated oxidation noted at edges and

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).

J. Less-Common Metals, 2 (1960) xgI-ao6


DEVELOPMENToF OXIDATION-RESISTANTNi ALLOYS 197

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

(Total weight gain in mg/cmz on I g and 2* g rectangular specimens)

Pure niobium 45.8


Nb-18Ti 7.7
-r8Ti- 3Mo 22.0
-rSTi- 6Mo 19.0
- 18Ti- gMo 4.2 63.2
- r8Ti-18Mo 18.0
-r8Ti- gW 3.3 11.0 244,9*
-r8Ti-I8W 2.0 X6.8 27.0 ( 5 h)
- qTi-x8W 5.1
-r8Ti-IzW x49.0*
- 18Ti- gTa 5.0
- 18 Ti - 18 Ta 7.4 29.2
-18Ti- 3V 17.0
- 18Ti- 6V 16.8
-r8Ti- gV 14.0
-18Ti-18V 52.0 C.O. C.O. ( 5 h)
- gTi- 6Cr IO.8
- 9 Ti - g Cr 12.0
- QTi-18Cr II.0
-r8Ti- 6Cr 5.8 123.0 (25 h)
-r8Ti-IoCr I.4 7.0 29.9 ( 5 h)
- 18 Ti - 12 Cr 0.7 47.2 ( 5 h)
- 18Ti-18Cr 6.0
- 25Ti- gCr 2.0 270.2* C.O. (18 h)
- gTi- 6% 32.0
- QTi- gZr 22.0 C.O.
-r8Ti- 6Zr 101.8 ( 5 h)
-18Ti- gZr 7.0 31.0
-r8Ti-18Zr IQ.0

--. ---

J. Less-Commqn Metals, 2 (1960) rgr-206


198 R. SMITH

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)

-ISTi- 9Fc 8.; Mean


7.7 1 8.0
-ISTi- 6Co 9.0
- I8Ti- 6Mn 10.0

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

(Total weight gain in mg/cm2 on 2 g and I g* rectangular sfkcimens)

Nb - 18 Ti 13.1 320 (hf)


- z5Ti- 9W 4.7 98.9
-zzTi- 9W 3.0 79.3
- 22Ti - 18 W 12.1 148.7
- ISTi- 9W -3Cr 1.4’
-ISTi- 9 W -6Cr 1.5’
- 25 Ti - 9 W - 6 Cr 16.4 321.6(M)
- ISTi-IoCr -2Ce 16.2 281.9(M)
-3oTi-I2 Cr 22. I
- ISTi- 9W -6Ni 0.8’
- xSTi- 9W -3Ni 161.8(M)
- ISTi- 9W -3V Ij.0 C.O.
-ISTi- 9W -6V 15.3 219.7
-ISTi- 9W -3Ta II.2 66.6
-ISTi- 9W -6Ta 17.5 1’3.7
_ ISTi- 6Ce co:
-I8Ti- 6Al 6.6*
-ISTi- 6Si 13.6’
-ISTi- 6Re 8.0.
-ISTi- I B I8.5*
- rSTi- 2B 2I.O
- xSTi-IjW -2Ce 14.6 213.8(M)
- 33 Ti - 33 Cr 0.6. 20 (20 h)+
- 50 Ti - IO Zr 23.0*

I g specimens denoted by l.
(M) = The mean of the original and final surface areas used.
C.O. = complete oxidation.

J. Less-Common Metals. 2 (1960) 191-206


DEVELOPMENT OF OXIDATION-RESISTANT Ni ALLOYS ‘99

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.

Oxidation testiq of selected alloys by meaw of the therm,al s@ing bala+we


The results of the preliminary survey, which indicated the beneficial effect of W,
Ni, Fe and Cr additions, were derived from a limited number of tests of fixed duration
and did not elucidate the mode of oxidation. Accordingly, a limited number of alloys
were selected for examination on the spring balance and some oxidation curves typical
of those obtained are presented in Fig. 3. It was found in all cases that the oxidation

T-----------l

TIME (twm)

Fig. 3. Oxidation of some niobium alloys in air at I,IOOT .Weight increase continuously recorded
by Pyrex spring balance.

f. Less-Common Met&, 2 (1960) 191-206


200 R. SMITH

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.

Influence on oxidation-resistance of small variations in the level of tungstert, nickel, iron


and cobalt additions
Variatiolz of tungstert in 20 at. y. titanium alloys (Fig. 4). The results from tests

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.

J. Less-Common Metals, 2 (1960) IgI--206


DEVELOPMENTOFOXIDATION-RESISTANT Ni ALLOYS 201

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.

J. Less-Common Metals, 2 (1960) IgI--206


202 R. SMITH

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

Fig. 6. Oxidation rates of niobium-titanium-tungsten-nickel alloys in air at ~,ooo~C, r,~ooT


and 1,140T.

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

J. Less-Common Metals, YZ(1960) 191-206


DEVELOPMENT OF Ni ALLOY’S 203

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.

Metallografihic and X-ray examilaations


A representative programme of metallographic and X-ray examinations was con-
ducted simultaneously with the oxidation testing, but this did little to elucidate the
mechanism of protection by alloying. Generally two layers of oxide-scale, porous and
compact, were observed; together with a hardened and differentially-etching metallic
surface zone. The more oxidation-resistant alloys were found to possess a thicker
underlying layer of dark scale.
The additions of tungsten, nickel, molybdenum, iron, chromium and cobalt exam-
ined produced only slight modifications to the 3 NbsO 5. TiOz scale formed on
niobium-zo at. y. titanium but the effects of other elements were more complex.

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.

J. Less-Common Metals, z (1960) IgI--206


204 Ii. SMITH

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

(Weight gained in mg/cm2/h on I g spherical specimens)

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.

A more practical indication of the potential of the oxidation-resistant alloys was


obtained from a number of IOO h oxidation tests which were conducted. For example,
on exposure at I,IOO”C, approximately I g spherical specimens of unalloyed niobium
and niobium-20 at. y0 titanium-10 at. y. tungsten-2 at. y0 nickel oxidised by
g7 mg/cma in I hour and 70 mg/cms in IOO h, respectively, indicating more than a
hundredfold increase in oxidation resistance.
This order of improvement is inadequate for most applications involving oxidising
atmospheres above ~,ooo’C ; but if a satisfactory protective coating could be applied,
the refractory oxidation-resistant alloys could be used for the component core, thus
reducing the seriousness of any localised coating failure. Further, the range of possible
additions to the niobium-titanium-tungsten and niobium-titanium-tungsten-
nickel alloys has by no means been exhausted, and some new addition or a variation
in the relative levels of additions already examined will possibly lead to some further
improvement in oxidation resistance without a marked deterioration in other de-
sirable properties.

Meclzanism of @otection
Since tungsten, nickel, iron and cobalt additions introduced no additional oxides

J. Less-Common Metals, 2 (1960) rgr-206


DEVELOPMENTOF OXIDATION-RESISTANT Ni ALLOYS 205

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

J. Less-Common Metals, 2 (1960) IgI--206


206 R. SMITH

temperatures, in B. W. GONSER AND E. M. SHERWOOD, Technology of Columbium, John Wiley,


New York; Chapman and Hall, London, 1958.
H. J. GOLDSCHMIDT, J. Iron and Steel Inst. (London), 194 (1960) 169.
A. B. MICHAEL, The oxidation of columbium-base and tantalum-base alloys. Regional A.Z.M.E.
Conf. Reactive Metals, Buffalo, 1958.
R. S. ROTH AND L. W. COUGHANOUR, J. Research Natl. Standards, 55 (1955) zag.
C. T. SIMS, W. D. KLOPP AND R. I. JAFFEE, Trans. Am. Sot. Metals, 51 (1957) 263.
S. J. PAPROCKI AND J. T. STACY, Investigation of some niobium-base alloys, Battelle Mem. Inst.
Rep. No. rr43 (October 1956).
F. J. CLAUSS AND C. A. BARRETT, Preliminary study of the effect of binary alloy additions on
the oxidation resistance of columbium, in B. W. GONSER AND E. M. SHERWOOD, Technology of
Columbium, John Wiley, New York; Chapman and Hall, London, 1958.
0. KUBASCHEWSKI AND B. E. HOPKINS, Oxidation of Metals and Alloys, Butterworths Sci.
Publ., London, 1953.
C. WAGNER, Z. physik. Chem., B. 22 (1938) 181.
H. A. SALLER, J. T. STACY AND S. W. POREMBHA, Initial investigation of niobium-base alloys.
Battelle Mem. Inst. Rep. No. 1003 (May 1955).

J. Less-Common Metals, 2 (1960) 19x-206