Metals Technology

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Characterization of phases in a nickel-aluminium

bronze

D. M. Lloyd, G. W. Lorimer & N. Ridley

To cite this article: D. M. Lloyd, G. W. Lorimer & N. Ridley (1980) Characterization of phases in a
nickel-aluminium bronze, Metals Technology, 7:1, 114-119, DOI: 10.1179/030716980803286577

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Characterization of The phases present in an as-cast commercial nickel-aluminium bronze 0/ nominal
composition Cu-10AI-5Ni-5Fe have been characterized by optical and electron-
phases in a optical techniques. Phase distributions andprecipitate morphologies have been
studied by optical microscopy, scanning electron microscopy, and transmission
nickel-aluminium electron microscopy. Analytical electron microscopy, both o/thinfoils and of
bronze extraction replicas, has been used to determine the composition of the various
intermetallic K-phases. MT/633C

©1980 The Metals Society. This paper waspresented at the conference 'Copper 77'
held jointly by the Committee for Metallurgy and Materials Science of the Polish
Academy 0/ Sciences (PAN), the Non-Ferrous Metals Institute, Gliwice, and The
Metals Society in Zakopane, Poland, on 17-20 October 1977. At the time the work
D. M, Lloyd was carried out, the authors were in the University of Manchester/University 0/
Manchester Institute of Science and Technology, Department 0/ Metallurgy,
G,·W, Lorimer Manchester. Dr Lloyd is now with the NCB Research Esta~lishment, Cheltenham,
N. Ridley Gloucestershire.

Nickel-aluminium bronze (NAB), the composition of
which is covered by BS 1400: AB2, is widely used to pro-
duce cast components for marine applications. Under ser-
vice conditions the alloy can show a variable resistance to
corrosion in sea water which has been attributed to micro-
structural features related to the thermal history of the
material. In as-cast components variations in micro-
structure arise because of differences in cooling rate
throughout the section of a casting. A diagram showing
phase relationships for NAB containing 5wt- % Ni and
5wt- % Fe, as determined by Cook et al.,1 is given in Fig. I.
These relationships have been confirmed by McKeown et
a/.2
Under normal rates of cooling, cast NAB usually con-
sists of a fcc Cu-rich solid solution or a-phase, some re-
tained bcc ,B-phase, and numerous intermetallic phases col-
lectively referred to as the K-phases. The work of Cook et
a/.l suggested that the K-phases were based on a Ni-Fe-AI
complex possessing B2-type structures similar to those of
NiAI and FeAI. These precipitates can form with a rosette,
1000
900
spheroidal, or lamellar morphology, the last being the
product of the eutectoidal transformation of the {3-phase,2
{3~a + K ••••••••••••••••••••••••••••••••••••••• (1)
These various morphologies have been designated as dis-
tinct phases, and the categorization established by Weill-
Couly and Arnaud3 is shown in Fig.2. The large particles
which have an irregular or rosette morphology are desig-
nated K1, the smaller cruciform phase is K2, K3 is a lath-
shaped or globular phase, and K4 appears as a fine precipi-
tate in the central regions of a-grains.
The small size and low volume fraction of K2 and K4
particles have made analysis by conventional microprobe
techniques difficult since the activated volume included
some matrix as well as the particle. The previously pub-
lished analyses of the phases present in NAB are included
in Table 1.
A programme of work is being carried out to character-
ize the microstructure of NAB in the as-cast and heat-
treated conditions. In the present paper an investigation of
the cast material is described.
EXPERIMENTAL
The composition of the alloy, which was supplied as a cast
disc 30mm thick, is given in Table 2.

u800
°•.....
w
a::
- :..:",' '.::~~::}; 7r:~:·::.::·:·
~ 700
«
a::
~ ~
..• .. ..'
w
a..
2: 600
w a+~+lt+o
t- ~

500 a.+lt+O
.~~~.
<p ••• ;~/lt3
.... .... l't?~ ~D ~ •• #0.::>4>0:"-

·w
.' t?tlo" (?l>,,??<::ll> 0':>
""

d<!l 0
t? t? c:?1J ,,~<:>
.-'._~,~..-:.: o Q'dC? 0 0 0 t? ,
400 (J' 0 0 0 " 0 DO., •• " , '
~ ~q C1 (:J" .}{4.
8 9 10 11 12 (1 .,' , •••••• :

Al,wt-o/o o /1 0 0 <&J • " -:'<.':;'~"';

1 Vertical section of Cu-AI-5Ni-5Fe equilibrium 2 Schematic representation of K-phases present in
diagram, after Cook et al.1 cast NAB, after Weill-Couly and Arnaud3

114 MetalsTechnology March 1980

 Lloyd et al. Nickel-aluminium bronze phases 115

Table 1 Analysis (wt-%) of various precipitates in cast NAB obtained from present investigation and previous
work3

Precipitate and analysis techniques·

K1 l D D K3 S C C Globular
EPMA K2 K3 K3 K3 EPMA K4 K4 K4 phase
Elements (Ref.3) SEM XEMMA XEMMA FEMMA (Ref.3) XEMMA XEMMA FEMMA SEM

AI 10 14'7±0'4 15-3 28-7±2'4 31'6±1'8 24·00 18-20 6'2±0'8 9'2±0'7 14·1 0'3±0'1
Si 3'3±0'3 3·0 0'9±0'6 1'8±0'7 0·8 3·1 ±0'7 3·1 ±0'6 2·6 0'4±0'1
Mn .. 2'3±0'6 2·5 2'0±0'3 2'2±1'3 1·9 2'9±0'9 3·1 ±0'6 2·0 4·3±0·5
Fe 69 40'0±8'5 52·0 18'0±3'8 19'3±5'8 15·00 26-43 81'0±2'1 77'6±2'1 57·5 90'6±1'2
Ni 8 8·9±1·4 9·2 38'4±2'2 33'0±3'9 30·5 23-34 2'7±0'6 3·1 ±0'8 8·2 1'6±0'1
Cu 13 31'9±9'1 18·0 12'0±1'8 12'1±1'8 27·7 13-20 . 4'1±1'6 3'9±0'6 15'6 2'8±0'8

Numberof Not known 5 Particle with 50 10 Not known 8 51 4

analyses lowest Cu
content

·EPMA=electron probe microanalysis; SEM=scanning electron microscopy; X EMMA=particie analysed on an extraction replica using the electron micro-
scope microanalyser; F EM MA = particle analysed on a thin foil using the electron microscope microanalyser; l = lamellar K3; D=degenerate K3; C= cruciform K4 ;
S=spheroidal K4•

Sections for optical microscopy were cut from the casting where lOA and lOB are X-ray intensities from infinitely thin
and ground and polished following conventional pro-
cedures. Specimens were either etched with 10% solution specimens, (~) A and (~) B are the mass-a'Jsorp-
P SPEC P SPEC
of ferric nitrate or ferric chloride in alcohol, or ion etched tion coefficients of the characteristic radiation from elements
at 6kV in an Edwards IBM lA Ion Thinning Apparatus. A and B, resp~ctively, in a specimen (SPEC) of density P and
Samples for examination in the scanning electron micro- thickness t. It is assumed for ease of calculation that the
scope were prepared as for optical metallography and ion average X-ray travels a distance in the specimen equal to
etched. Electron microscopy of both thin foils and surface half the thickness.
replicas was carried out in a Philips EM 301 operating at When the ratio of characteristic X-ray intensities is
100kV. The foils were prepared by ion thinning while measured (equation (2)), it can be seen by combining
carbon extraction replicas of polished and etched speci- equations (3) and (4) thus:
mens were prepared using standard techniques.
Microprobe analysis of large features (> 2fLm dia.) was
carried out on a Cambridge S 180 scanning electron micro- llA = 1IoAexp{-
B 0B
[(I!) A P SPEC
_ (!!:)P B
SPEC
]p-2 t
} (5)

scope, operating at 30kV, fitted with an energy-dispersive
detector. Standard bulk-correction procedures were applied
to the analysis data. Smaller precipitates were analysed on
extraction replicas or in thin foils using an EMMA-4
analytical electron microscope, operating at lOOkV, fitted
with an energy-dispersive X-ray detector.
that the difference in X-ray absorption coefficients is the
important factor. If two characteristic X-rays have similar
values of mass-absorption coefficient, their intensity ratios
will be unaffected.
Results

Quantitative analysis of thin specimens

If a sample satisfies the thin-film criterion (X-ray absorption
and fluorescence are sufficiently small that they can be neg-
lected) the ratio of two characteristic X-ray intensities
I A/I B can be converted simply into a weight-fraction ratio
CAl CB using the equation
CA/CB=kAB/AjIB .•.•........................
where kAB is a constant at a given voltage, 'which is in-
dependent of specimen thickness and composition, and can
be either determined experimentally4 or calculated.5 A
normalization procedure, e.g. ~Cn = 1, must be used to con-
vert the weight-fraction ratios into weight percentages.
When the sample thickness is increased, or if soft X-rays
from elements such as Al and Si are emitted, the observed
X-ray intensities are modified by absorption. Quantitative-
ly such a situation may be expressed for elements A and B
by equations
MORPHOLOGY
Figure 3 shows optical micrographs of the as-cast alloy.
The large white areas are the a-phase, most of which has a
Widmanstatten morphology; there also appears to be
some primary dendritic a-phase (Fig.3a). The small areas
of {3-phase have etched black. The Kl-phase (Fig.2), re-
ported by other authors,1-3 was not detected. The K2-
(2)
phase, light grey etching cruciform particles less than 10;um
dia., was observed throughout the structure, with the
highest density occurring in regions which had undergone
the eutectoid transformation. The Ka-phase etched dark
grey and appeared in a lamellar form and as a degenerate
globular. structure. f\ fine dispersion of K4 precipitates was
seen within the a-phase and there was a zone free of
precipitates at the periphery of the a-phase (Fig.3b). A
number of globular precipitates were also observed.
Scanning electron micrographs of the cast alloy are
shown in Fig.4a and b. Figure 4a provides a useful link be-
tween the optical and electron micrographs: the Kalamellae

IA=/oAexp[-(~)A
p SPEC
p!.-]2 (3)
Table 2 Chemical analysis of alloy, wt-%

and Element Cu AI Ni Fe Mn Zn Pb Sn Si Mg

IB=IoBexp[-(!!:)BP SPEC
p!]2 (4) Amount 80·02 9·37 4·84 4·38 1·18 0·08 0·03 0·01 0·07 < 0·01

Metals Technology March 1980

 116 Lloyd et al. Nickel-aluminium bronze phases

b
a WidmansHitten and dendritic a-phase; b K2-, K3-, and K.-phases
3 Optical micrographs of as-cast NAB

are clearly resolved, as are the K2- and the K4-phases.

Figure 4b is a scanning electron micrograph of one of the
large globular particles, which has an internal structure.
Figure 4c shows a K2 particle.
Electron micrographs of the lamellar and degenerate
morphologies of the K3-phase were obtained from extrac-
tion replicas (Fig.5a) and thin-foil specimens (Fig.5b and c).
Figure 6 illustrates the spheroidal and cruciform morphol-
ogies of precipitates which are believed to be K4. As can be
seen from Fig.6c, some of the particles are internally
twinned. The large K4 particles have a similar morphology a general distribution of phases; b globular particle; C K2 particle
to the K2-phase (Figs.3b and 4c). 4 Scanning electron micrographs of cast NAB

CHEMICAL ANALYSIS
The integrated peak intensities of X-ray spectra from theK2-
phase and the large globular particles, as obtained from
bulk specimens, were converted into weight fractions using
conventional microprobe analysis procedures.6 The globu-
lar precipitates were found to be iron-rich (see Table 1) and
contained significant amounts of manganese. The 'halo' of
small particles surrounding them contained sulphur.
The composition of the cruciform K2-phasewas observed
to vary significantly from particle to particle; this was
particularly true of the copper concentration. The small
size of these particles, typically 3ftm dia., combined with.
their convoluted shape invariably resulted in the inclusion
of some of the matrix in the activated volume for X-ray
production. The average microprobe-analysis data for five
K2 particles, as well as that for the K2 particle which ~as
found to have the lowest copper concentration (whIch,
presumably, included the smallest amount of the matrix
in the analysis) are given in Table 1. The error limits quoted
correspond to one standard deviation.
The X-ray analysis 'fingerprints' typical of lamellar K3
and cruciform K4 precipitates taken from carbon extraction
replicas supported on gold grids are shown in Fig. 7. The Ti
peaks originate from the circlip of the specimen holde~.
Both phases contain significant amounts of low atomIc
number elements Al and Si as well as medium atomic
number elements Cu, Ni, and Fe; as discussed above, sig-
nificant absorption of the Al and Si K radiation would be
expected. .
An approximate estimate of the extent of Al K X-ray
absorption in the K3 and K4 precipitates can be made by
assuming that they are based on NiAI and Fe3AI, respec-
tively. The X-ray mass-absorption coefficient of Al in
NiAI,
(!!:)Al
P NiAl
=3413cm2g-1

Metals Technology March 1980

 Lloyd et al. Nickel-aluminium bronze phases 117

a a

b b

c
c
a spheroidal and cruciform precipitates in extraction replica; b spheroidal
a lamellar and globular K3-phase in carbon extraction replica; b lamellar K3- precipitates in thin foil; c cruciform precipitate in thin foil
phase in thin foil; c globular K3 particle in thin foil: sample has been
coated with gold 6 Spheroidal and cruciform morphologies of precipi-
tates believed to be K4
5 Electron micrographs of lamellar and degenerate
morphologies of K3-phase

and
while p=6·68gcm-3.

(e)
P
Ni
NiAI
=59' 5cm2g-1 In an Fe3AI precipitate 0·3fLm thick, 28 % of the Al Ka.
radiation generated at the. centre of the particle will be ab-
and sorbed, but only 1% of the Fe Ka,.
p=6·5gcm-3. Hence, the absorption of Al Ka" and of Si Ka" radiation
in the K3 and K 4 particles will be significant and the analyses
A NiAI particle 0·2fLm dia. will absorb 20% of the Al Ka, were corrected as follows. The apparent compositions were
radiation generated at the centre of the particle but only calculated from X-ray intensities using equation (1) (no
0·1 % of the Ni Ka,. For Fe3AI absorption) and the kAB va1ues published by Cliff and Lori-
fL) Al
=3357cm2g-1
mer.4 These values of the uncorrected weight fractions
(p Fe3AI
were used to estimate the X-ray mass-absorption coeffi-
cients in the particular' phase for Al Ka, and Si Ka, radiations.
(p-)Fe =74'5cm2g-1 The K3-phase was assumed to have the same density as
p Fe3AI NiAI, i.e. 6·5gcm -3 (Ref. 7), and a theoretical density of

Metals Technology March 1980

118 Lloyd et al. Nickel-aluminium bronze phases

Table 3 Data used to correct X-ray' intensities from degenerate K3 particle for absorption*

Uncorrected (~)element (I::) element (~) element

Element weight fraction P specimen 1st iteration specimen 2nd iteration P specimen 3rd iter~tion Wt-%

AI 0,1650 4026 0·2480 3675 0·2400 3702 0·2400 24·00

Si 0·0057 3158 0·0077 3198 0·0077 3198 0·0077 0·77
Mn 0·0210 112 0·0190 112 0·0190 112 0·0190 1·90
Fe 0·1660 90 0·1500 90 0·1500 90 0·1500 15·00
Ni 0·3340 120 0·3020 120 0·3050 120 0·3050 30·50
Cu 0·3030 98 I 0·2740 98 0·2770 98 0·2770 27·70

"Half particle thickness (t/2) =0'2~m; p=6'5g cm-3•

6·7gcm-S was calculated for K4,assuming that itwas FesAI.
Absorption-corrected weight fractions were determined
using equations (2)-(4), and an average particle thickness as
measured from electron micrographs. These were then
normalized by setting ~Cn = 1. New X-ray mass-absorption
coefficients were calculated and weight-fraction ratios were
again determined using equations (3) and (4). Three iterations
were usually found to be sufficient to give convergence.
The data produced at each stage of the calculation for a
KSprecipitate held in a thin foil are summarized in Table 3.
The absorption-corrected compositions (wt- %) of the KS-
and K4-phases, determined from analysis of thin foils and
carbon extraction replicas, are included in Table 1. The
chemical analyses of the KS-and K4-phases taken from thin
foils are richer in Cu than those determined from extraction
replicas. This disparity in analyses is likely to be the result
of Cu K X-ray contributions arising from the matrix in the
thin foils, and greater confidence is placed in the chemical
analyses obtained from extraction replicas. The compo-
sition of selected phases is given in at.- % in Table 4.
manganese, and copper may partially replace iron, and
silicon may partially replace aluminium. It is tempting to
propose that K4 is a second-generation precipitate of the
K2-phase, since the phases have similar morphologies and
are both Fe-rich. Because of the small size of the K2-phase,
chemical analysis of such precipitates in bulk (see Tables 2
and 4), is unreliable owing to interference effects from the
matrix. However, more recent analyses of K2 precipitates
extracted from an alloy of slightly different composition to
that examined in the present work, gave figures close to
those recorded in Table 4 for the K4 particles.
The lamellar and globular KSmorphologies are similar to
those reported previously.3 Chemical analysis (see Tables 1
and 4) suggests that the phase is based on an equi-atomic
aluminide which is lower in iron and richer in nickel than
was reported by Weill-Couly and Arnaud3 for the lamellar
Ks-phase. The origin of this difference is not immediately
obvious.

Discussion

The distribution of the phases observed during the present

work is similar to that reported by other workers,l-s (see
Fig.2), except for the absence of the Kl-phase and the
presence of a globular phase .-,,20fLm dia. It is possible
that the formation of Kl.is very sensitive to alloy content (a)
and/or cooling rate, and that one or both of these .criteria
were not satisfied in the material examined. Alternatively,
the Kl-phase may be merely a larger type of K2 particle
presumably formed from the melt, although, as may be
seen from Table 2, there is a significant difference between
the composition of Kl, as given by Weill-Couly and
Arnaud,3 and that found for K2 during the present investiga-
tion.
AL
The K4-phaseis observed to possess either a spheroidal or
a cruciform morphology, the latter structure being similar
to, but smaller than, the K2 cruciforms. The absorption-
corrected' chemical analyses of both forms of K4, given in Ni Ka.
Table 1, are found to correspond to the (FeNiMnCu)s
(AISi) complex based on FesAI (Table 4), where nickel,

(b) NiK~

Table 4 Composition of selected phases, at.-%

K21amellar K4 cruciform
Element XEMMA XEMMA

AI 27·1 46·3 17·0

Si 5·1 1·4 5·5
Mn 2·2 1·6 2·8 a K4-phase; b degenerate K3-phase
Fe 44·5 14·0 69·1
Ni 7·5 28·5 2·6 7 X-ray analysis fingerprints typical of lamellar K3 and
Cu 13·6 8·2 3·0 cruciform K4 precipitates taken from carbon ex-
traction replicas supported on gold grids

Metals Tech'nology March 1980

 Lloyd et al. Nickel-aluminium bronze phases 119

The large globular phase is surrounded by small sulphur- helpful discussions. EMMA-4 was purchased with a grant
containing particles and may be a feature produced in the from the Science Research Council.
melt.
References
Summary
1. M. COOK, W. F. FENTIMAN, and E. DAVIS: J. Inst. Met., 1951-52,80,
419.
The morphology and distribution of the intermetallic 2. J. MCKEOWN, D. N. MENDS, E. S. BALE, and A. D. MICHAEL: ibid.,
phases present in nickel-aluminium bronze have· been 1954-55,83,69.
studied using optical, scanning electron, and transmission 3. P. WEILL-COULY and D. ARNAUD: Fonderie, 1973, (322),123.
4. G. CLIFF and G. w. LORIMER: J. Microsc., 1975,103,203.
electron microscopy techniques. The compositions of the 5. J. I. GOLDSTEIN, J. L. COSTLEY, G. W. LORIMER, and S. J. B. REED:
K2-, K3-, and K4-phases, as well as the large globular phase, 'Proc. of the workshop on analytical electron miscroscopy, SEM
have been examined by microprobe analysis of bulk and 1977', Vol.l, 315; 1977, Chicago, lIT Research Institute.
thin specimens. 6. M. J. NASIR:J. Microsc., 1976, 108,7"9.
7. A. J. BRADLEY and A. TAYLOR: Proc. R. Soc., 1937,159,56.
8. E. A. CULPAN and G. ROSE: J. Mater. Sci., 1978, 1647.

Acknowledgments
The investigation was supported by the Procurement
Executive of the Ministry of Defence. The authors are
grateful to Dr A. Thorpe of the Admiralty Materials
Laboratory for arranging the supply of material and for
Addendum
Since the preparation of this paper, analyses of NAB alloys
which broadly support the results presented here have been
published.8

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