Metals Technology

ISSN: 0307-1693 (Print) (Online) Journal homepage: http://www.tandfonline.com/loi/ymst19

Effect of trace impurities on hot ductility of as-cast

cupronickel alloys

S. A. Gavin, J. Billingham, J. P. Chubb & P. Hancock

To cite this article: S. A. Gavin, J. Billingham, J. P. Chubb & P. Hancock (1978) Effect of trace
impurities on hot ductility of as-cast cupronickel alloys, Metals Technology, 5:1, 397-401, DOI:
10.1179/mt.1978.5.1.397

To link to this article: http://dx.doi.org/10.1179/mt.1978.5.1.397

Published online: 19 Jul 2013.

Submit your article to this journal

Article views: 1

View related articles

Citing articles: 5 View citing articles

Full Terms & Conditions of access and use can be found at

http://www.tandfonline.com/action/journalInformation?journalCode=ymst19

Download by: [Universite Laval] Date: 11 May 2016, At: 02:19

 Effect of trace The effect of trace impurity elements on the hot-ductility behaviour of both simple
and complex copper-nickel alloys has been investigated using a modified Gleeble
impurities on hot apparatus. The elements studied were bismuth, lead, selenium, sulphur, and tellurium
added singly and in combination at various levels in the range 1-750 ppm (wt). High
ductility of as-cast strain-rate tensile tests (lOs-I) were carried out on the alloys over a range of
cupronickel alloys temperatures during the cooling part of a simulated TIG welding cycle. Ductility
was found to decrease progressively as the amount of impurity increased, but
recommended safe limits could be specifiedfor simple alloys. Bismuth and tellurium
were particularly harmful whereas sulphur was relatively innocuous even at levels as
high as 750 ppm. When such elements were present in combination, the ductility was
significantly decreased and a simple relationship between ductility and the total
trace impurity content of the alloy is produced. This gives reasonable agreement
with experimentally determined ductilities o/alloys containing two major
impurities and of a commercial-purity Cu-10Ni alloy. With more complex alloys
the relationship is able to rank alloys of various purities in order of increasing
ductility. Significant improvements in ductility in commercial-purity alloys were
achieved by using purer melting charges and better melting and casting procedures.
Moreover, impurity-alloying-element reactions in such alloys resulted in more
severe embrittlement than in simple alloys. MT/514
s. A. Gavin
J. Billingham ©1978 The Metals Society. Manuscript received 21 June 1978. At the time the
work was carried out the authors were in the Department of Materials, Cranfield
J.P.Chubb Institute of Technology, Cranfield, Beds. Mr Gavin is now with British Non-
Downloaded by [Universite Laval] at 02:19 11 May 2016

P.Hancock Ferrous Metals Technology Centre, Wantage,Oxon.

Trace amounts of impurities can play an important role in purity' Cu-10Ni alloy is given in Table 1. The impurity
facilitating fracture processes and reducing ductility,I-3 elements were added to the melt using a specially designed
particularly when these elements are situated at the grain furnace head which allowed additions without disturbing
boundaries. This behaviour is usually countered in com- the argon atmosphere. Bismuth, lead, tellurium, and sel-
mercial practice by utilizing strict control of raw material enium were added in elemental form while sulphur was
purity, and of the melting and casting procedures, but added as cupric sulphide, all materials being wrapped in
despite such precautions, premature failures occur in copper foil before addition, to minimize vaporization
certain alloys. For example, the high-strength copper- losses. Analysis for trace impurities was made using
nickel alloys used in marine applications suffer from limited chemical extraction and atomic absorption, and the figures
hot workability and heat-affected-zone (HAZ) cracking on quoted refer to samples taken from the ingot adjacent to
welding under restraint; previous work has shown these the test specimens.
characteristics to be at least partly owing to the presence of The hot-ductility behaviour of the alloys was assessed by
impurities.4 The tendency to intergranular HAZ cracking testing in tension using a modified Gleeble apparatus. 6
has been associated with the poor intermediate-tempera- This apparatus enabled specimens conforming to BS 18
ture ductility of these alloys. A ductility minimum occurs
in the intermediate-temperature range 850-1100K,4,5 as-
sociated with intergranular fracture~ whereas the fractures
are transgranular at both lower and higher temperatures. Table 1 Mass spectrographic analysis of Cu-10Ni
The alloys therefore exhibit 'ductility trough' behaviour. alloys
Commercial-purity copper-nickel alloys contain numer-
Element, ppm (wt) High purity Commercial purity
ous trace impurities that could reduce ductility; typical
commercial levels, in ppm (wt), are lead < 100, tellurium < Bismuth <0·3 3
100, bismuth < 10, and sulphur 50-100. This study is lead <0·7 13
Tellurium <0·2 14
intended to quantify the effect of common impurity ele- Antimony <0·4 12
ments on the ductility of a Cu-10Ni alloy which forms the Tin <0·2 <1
Silver <0·3 103
basis of many commercially important materials. Selenium <0·3 75
Arsenic 1·4· 36
Zinc 1·0 62
Cobalt 9·4 93
Iron 85·7 133
Experimental Manganese 0·26 26
Sulphur 15 51
Phosphorus <0·5 <14
_High-purity alloys were melted in a resistance-heated Silicon 44 <4
Calcium 0·06 6
furnace under a protective argon atmosphere in an alumina Chlorine 0·55 8
crucible. Porosity was minimized by directional cooling of Aluminium 0'13 4
Oxygen NA NA
the melt and a reproducible grain size, of about 0·5 mm, Nitrogen NA NA
was obtained by stirring the melt just ahead of the sol- Carbon NA NA
idifying interface. The Cu-10Ni alloys were produced from Hydrogen NA NA
pure copper (99'999%) and a Cu-30Ni master alloy ·Possible contamination
(99'9%). A mass spectrographic analysis of the base 'high NA=Not analysed, elements not listed present at <1 ppm (wt)

Metals Technology November 1978· 397

 398 Gavin et al. Effect of trace impurities on cupronickel alloys

Table 2 Levels of trace impurity elements in complex 70

Cu-Ni alloys in ppm (wt)

C Se Te S Pb Bi P As Sb ~o
...50
Commercial complex alloy <200 25 4 60 90 10 40 10 1 z
Complex alloy produced from Q40
high-purity melting stock 50 < 10 2 70 6 1 <10 15 5 I-
<{

~30
• •
g x <0'7ppm Pb •
w 20 ~ 18 ppm Pb 0
with a 25·4 mm gauge length to be subjected to a simulated o
61 ppm Pb
weld cycle by rapid resistance heating to about 0·9Tm in an 10 • 146 ppm Pb
o 565ppm Pb
argon atmosphere, cooling, and then fracturing at a pre- o
selected temperature in the cooling cycle by a pneu- 300 700 900
matically operated crosshead movement. Typical con- TEMPERATURE,
ditions were heating from room temperature to 1320K at a 1 Effect of lead additions on ductility-temperature
rate of lOOKs-I, atmospheric cooling from l320K to the behaviour of a Cu-1 ONi alloy
test temperature, followed by tensile testing at a strain rate
of about lOS-I. The temperature and load were monitored
during the tests using a radiation pyrometer and a pressure
transducer, respectively. Following the tests, ductility was
intermediate-temperature ductility. This was verified in
assessed by measuring both reduction in area and elon-
a simple 10%Ni alloy by comparing melts produc~d
Downloaded by [Universite Laval] at 02:19 11 May 2016

gation of the testpiece. These measurements gave similar

from high- and commercial-purity stock, and also In
results and, consequently, only elongation values are
complex alloys by comparing a remelted commercial a~loy
presented.
with one of the same composition produced from hIgh-
In a complimentary study two further materials were
purity melting stock, FigA. The differences .in trac~ element
produced and examined, namely a commercial-purity Cu-
content between the high- and commercIal-purIty alloys
10Ni alloy and a complex high-strength cupronickel alloy.
are listed in Tables 1 and 2. showing the correlation be-
The binary Cu-lONi alloy was remelted from commercial
tween improved ductility and reduced impurity content. In
material and a mass spectrographic analysis of this alloy
this context, the levels of impurities in the higher purity
after remelting is given in Table 1. The complex precipi-
version of the complex high-strength alloy can be regarded
tation-hardened cupronickel alloy contained 11% nickel,
as safe working limits to ensure good ductility in such
8·5% manganese, 5·6% iron, 1·35% aluminium, 0·2%
materials. The results from similar complex alloys con-
titanium, and 0·1% silicon. Several melts of this alloy were
taining varying levels of bismuth, indicated that the
made. A commercial alloy supplied by AMTE Dockyard
bismuth content was likely to be the most significant factor
Laboratory was remelted in the laboratory and a pure
in controlling ductility. This is illustrated in Fig.5, which
version of the same alloy was prepared using high-purity
also indicates that a much lower level of bismuth was
starting materials. The impurity levels of these two alloys
required to produce a significant decrease in this complex
are compared in Table 2. Additional melts of the same
alloy compared with the levels required in the simple alloys
nominal composition, but with a variable bismuth content,
examined earlier.
were also produced. All alloys were produced by the same
Examination of fracture surfaces from the binary alloys
experimental procedure and had comparable grain sizes to
showed that the fracture mode was ductile at both low and
the simple alloys.
Metallographic examinations were made using optical
and electron microscopy in a Cambridge Instruments S600
scanning electron microscope with a Link Systems energy-
dispersive X-ray analysis attachment to monitor segre-
gation effects. Fractography was performed with the SEM.

Results
~
The as-cast high-purity Cu-lONi alloy exhibited high x~

\
ductility over the entire temperature range of interest Pb
300-1 300 K and was used as a standard material in the
present work. The addition of impurities to this material Te
led to a progressive reduction in intermediate-temperature
ductility, as is indicated, for example, by lead additions in
Fig.1. The extent of this reduction in intermediate-tempera- +~
ture ductility varied with the type and amount of trace
element, as is shown in Fig.2. Of the elements examined,
bismuth caused the most, and sulphur the least, reduction
+----
in ductility. The effect of the impurities was cumulative,
however, as shown in Fig.3, and therefore reducing the
overall impurity content of commercial-purity material 2 Variation of minimum intermediate-temperature
would be expected to result in a significant improvement in ductility with impurity content for a Cu-1 ONi alloy

Metals Technology November 1978

 Gavin et al. Effect of trace impurities on cupronickel alloys 399

70 >-
I-
:::::i
i=
U
x ::::>
o
50 W
0:::
::::>
~
0::: 30
W'""":'
0...2
30 2:0
wi=
1-4:

\
w1(9
Z20
x 60ppm Pb ~O
-...J
Z10 Ow
o • 60ppm Te W 0
~ o 70 ppm Pb,50 ppm Te 2:0-
0:::'-"
<! 70 W
(9
I-
z Z
pure Cu-10Ni alloy
o
-.J
W / *"--
50 high-strength complex alloy (Table 2)
o
o~
30 50 90
Downloaded by [Universite Laval] at 02:19 11 May 2016

BISMUTH CONTENT,
30
~o
5 Effect of bismuth on minimum intermediate-
temperature ductility of two cupronickel alloys
x 60 ppm Pb
• 20 ppm Bi 0
10 0 70 ppm Pb,20ppm Bi
high temperatures. At intermediate temperatures the frac-
400 700 1000 1300 ture became more intergranular and the extent of inter-
TEST TEMPERATURE 1 K granular fracture increased with impurity content or de-
crease in ductility. These intergranular fracture surfaces
3 Ductility-temperature behaviour for selected com-
were largely featureless (Fig.6), except for alloys with high
binations of impurity
levels of particular impurities. Isolated impurity-rich
70 (a)
precipitates were present in alloys with high selenium,
x tellurium, or sulphur, whereas intergranular films were
observed (Fig.7) in alloys with high bismuth and lead
levels. In the ductile alloys precipitates of nickel oxide were
50 observed on the fracture surfaces. As the temperature was
increased above about 1050 K recrystallization was ob-
served, primarily along grain boundaries, thereby blunting
the grain-boundary cracks.
030
The complex alloys showed similar fracture behaviour to
0- the simple alloys but in addition had a heavily cored
z • • dendritic microstructure with precipitates along the grain
o
~ x higher purity
<! 10
(9 • commercial purity
z
o
-.J
W (b)
50

30

10 • •
400 700 1000 1300
TEST TEMPERATURE, K
a Cu-1 ONi; b Cu-11 Ni-8·5Mn-5·6Fe-1·3AI-O·2Ti-O·1 Si
4 Effect of purification on intermediate-temperature 6 Typical intergranular fracture surface of Cu-10Ni
ductility alloy containing 146 ppm Pb tested at 755 K

Metals Technology November 1978

 400 Gavin et al. Effect of trace impurities on cupronickel
7 Low melting point films on the intergranular facets
of Cu-10Ni alloy containing 565 ppm Pb tested at
755K
Downloaded by [Universite Laval] at 02:19 11 May 2016
boundaries. In the commercial-purity complex alloy a
needle-like phosphorus-rich precipitate was also seen
along the grain boundaries, Fig.8.
Discussion
The test results indicated that the ductility-trough effect
became more pronounced as the amount of impurity
increased and that certain impurities were much more
effective in reducing ductility than others. When impurities
were present in isolation, the following limits (in ppm (wt))
should ensure adequate ductility in simple alloys (assessed
as 20~~ elongation in the Gleeble test), bismuth < 20,
tellurium < 45, lead < 120, and selenium < 150 (see Fig.2).
Sulphur was relatively innocuous and could be tolerated at
levels as high as 750 ppm (wt).
The deformation behaviour was characterized by a
ductility-trough effect with predominantly intergranular
failure in the temperature range of low ductility. At both
lower and higher temperatures, fracture surfaces were of
the ductile dimple type with fracture occurring mainly by
microvoid coalescence. A probable mechanism for this
behaviour is the segregation of impurities to the grain
boundaries where they lower the cohesive strength of the
boundary eventually causing intergranular failure as the
temperature increases. At temperatures above about
1050 K recovery processes such as dynamic recrystalliz-
ation will occur, 7 which could result in a relief of stress
concentrations at grain boundaries thereby favouring
transgranular fracture processes. Evidence for segregation
of impurities to grain boundaries has been obtained:
Auger electron spectroscopy carried out on an inter-
granular fracture surface from a bismuth-containing alloy
indicated significant segregation of bismuth to the grain
boundaries giving an effective bismuth concentration of
about 30 at.-%. 8 In addition, low melting point, grain-
boundary films were observed in the SEM on fracture
surfaces from alloys containing large amounts of single
additions of lead or bismuth (Fig.7).
Tramp impurities play an important detrimental role in
the hot-ductility behaviour of copper-nickel alloys and
therefore should be kept at the lowest possible levels in
Metals Technology November 1978
alloys
8 Needle-like phosphorus-rich precipitate close to
intergranular crack
order to optimize mechanical properties. Although limits
for isolated impurities can be specified in simple alloys,
these are insufficient when two or more potentially danger-
ous elements are present simultaneously in moderate
amounts. The combined effects of two or more elements on
ductility can be estimated by a comparison of the relative
gradients of the ductility-composition curves (Fig.2), assum-
ing straight-line relationships at low concentrations. If, for
example, the impurity contents which correspond to a 25%
reduction in ductility are measured from Fig.2, then the
following relative values are obtained: Bi/8, Te/12, Pbj19,
Se/38, 8j105. A simple relationship can be calculated from
these results which will enable an estimate to be made of the
ductility of an alloy containing several impurities by refer-
ence to a bismuth equivalent composition (BiE). Such an
equation can be written as:
BiE= Bi + 0·7Te+ 0·4Pb+ 0·2Se+ 0·1S
where the composition of each element is given in ppm
(wt). The minimum ductility of the alloy can be read
directly from Fig.2 using the calculated bismuth equivalent
concentration. The equation can predict approximately
ductility in simple eu-l0Ni alloys and will also rank other
cupronickel alloys in respect of their impurity-related
ductility behaviour. At high impurity concentrations, par-
ticularly with respect to sulphur, the differences between
predicted and actual minimum ductility will increase be-
cause of differences in the form of the ductility-eom-
position curves for the various impurities. However, this
does not lead to significant differences within the range of
compositions usually encountered. The equation would
predict, for instance, that an alloy containing 70 ppm (wt)
lead and 50 ppm (wt) tellurium would have a bismuth
equivalent of 63 which (from Fig.2) should reduce the
ductility of the alloy to 6%, in reasonable agreement with
the 10% obtained by experiment (Fig.3). Similarly, the
minimum ductility observed for the commercial-purity·
binary alloy (19%), Fig.4, and the alloy containing lead and
bismuth in combination (16%), Fig.3, can be predicted
from the BiE relationship as 110;0and 8%, respectively. It
should be noted that in the current work the impurity
additions appeared to act independently and, in par-
ticular, no compounds were formed between the impurity
additions. The BiE equation would not be expected to
apply in systems where compounds are formed or where
large additional impurity-impurity interactions occurred.
 Gavin et al.
In more complex precipitation-hardened cupronickel
alloys it has been shown that alloying additions usually
reduce ductility9,lO and therefore it is not possible to
predict accurately the minimum ductility by using the
bismuth equivalent relationship but this is still useful to
give a ductility ranking for alloys of different purity. If the
higher purity and commercial-purity complex alloys (Fig.5)
are considered, the simple relatiQi.1ship gives bismuth
equivalent values of about 15 and 6t:>,'ppm(wt) indicating
ductilities of 280/0 and 8%, respectively, whereas the
experimentally observed values were 17~!c> and 1·5%, the
differences being caused by the reduction in ductility
caused by the alloying additions.9 The presence of these
alloying elements could well account for the difference
between observed and calculated ductility for the higher
purity alloy but this difference is enlarged in the com-
mercial-purity alloy. Thus, it is suggested that impurity-
alloying-element interaction could playa part in producing
the excessively low ductility in the commercial alloy. For
example, needle-like phosphorus-rich precipitates were
observed along the grain boundaries of the alloy (Fig.8).
Such precipitates could act as stress raisers and encourage
premature intergranular behaviour, thus enhancing the
Downloaded by [Universite Laval] at 02:19 11 May 2016
tendency of the alloy to mid-temperature brittleness. Al-
though the equation does not give accurate ductility
results for such complex alloys, it does enable an estimate
to be made of the change in ductility that results from a
change in the total impurity content. The effect of indi-
vidual elements in complex alloys is different from that in
simple alloys as indicated by the results for bismuth shown
in Fig.5. These differences could be caused by differences in
grain-boundary structure, or diffusion properties, or by
impurity-alloying-element interactions.
It is recommended, therefore, that to obtain the best
ductility, the total impurity level should be reduced to the
lowest possible value within the industrial economic con-
straints associated with the cost of the melting charge and
the melting and casting process. It has been demonstrated
that the poor ductility of high-strength commercial-
purity alloys can be improved by a reduction in the total
impurity level of the alloy such as might be achieved in
practice by a vacuum remelting process or by using a purer
melt charge. This would reduce HAZ cracking problems
and should result in increased application for this type of
alloy.
Conclusions
1. Low intermediate-temPerature ductility in copper-
nickel alloys has been associated with the presence of
tramp impurity elements. The ductility decreases as the
Effect of trace impurities on cupronickel alloys 401
amount of impurity increases, the effect varying with
element, with bismuth showing the most severe effect.
Safe limits of single impurities to ensure good ductility in a
Cu-l0Ni alloy have been determined in ppm (wt) as:
bismuth < 20, tellurium <45, lead < 120, and selenium <
150. Sulphur is relatively innocuous in amounts up to at
least 750 ppm (wt).
~.! .. :When present in combination, the effect of impurities
ori:"citictility is cumulative, which means that the highest
melt cleanliness is necessary to ensure good ductility, and
that selective impurity removal is unlikely to eliminate all
risks of reduced ductility. An estimate of the total effect of
trace impurities can be made by calculating the bismuth
equivalent concentration using the equation
BiE = Bi + O·7Te +0·4Pb + O·2Se + 0·1S
and relating this to ductility from the experimentally
determined ductility-bismuth-concentration curve.
3. Complex high-strength precipitation-hardened cupro-
nickel alloys often have poor intermediate ductility. By
reducing the tramp impurities to low levels, for example, by
vacuum remelting or using purer melt charges, adequate
ductility can be produced. Improved ductility could lead to
the increased application of such materials.
Acknowledgments
The authors would like to thank Dr C. Dimbylow and G.
Newcombe of the Admiralty Materials Technology Est-
ablishment Dockyard Laboratory, Portsmouth, for pro-
vision of materials and helpful discussion, and Dr H. M.
Southworth and D. Hall of the University of Birmingham,
for the Auger work. One of us (SAG) would like to thank
the Science Research Council for financial support.
References
1. E. D. HONDROS and D. MCLEAN: Phi/os. Mag., 1974,29,771.
2. J. R. LOW, JR: Trans AIME, 1969,245,2481.
3. R. J. JACKSON, D. A. EDGE, and D. C. MOORE: J. Inst. Met., 1970,98,
193-198.
4. M. H. SCOTT: Met. Constr., 1972,4,292.
5. P. w. HOLSBERG: Weld.J., 1970,49, 554s.
6. E. F. NIPPES,w. F. SAVAGE, B. J. BASTIAN, H. F. MANSON, and R. M.
CURRAN: ibid., 1960,39, 411s.
7. J. P. CHUBB and J. BILLINGHAM: Met. Technol., 1978,5,100-103.
8. D. HALL and H. M. SOUTHWORTH: University of Birmingham,
personal communication, 1977.
9. J. P. CHUBB, J. BILLINGHAM, P. HANCOCK, C. DlMBYLOW, and G.
NEWCOMBE:J. Met., 1978,30, (3), 20.
10. D. F. LUPTON and J. R. THOMPSON: J. Inst. Met., 1972, 100,
352-356.
Metals Technology November 1978