Electrochimica Acta 45 (2000) 3389 3396

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Electrodeposition and properties of NiW, FeW and

FeNiW amorphous alloys. A comparative study
Mikol*aj Donten a, Henrikas Cesiulis b, Zbigniew Stojek a,*
a
Department of Chemistry, Uni6ersity of Warsaw, ul. Pasteura 1, PL 02 -093 Warsaw, Poland
b
Department of Physical Chemistry, Vilnius Uni6ersity, Naugarduko 24, Vilnius 2006, Lithuania

Received 5 November 1999; received in revised form 5 January 2000

Abstract

Thin, micrometre-thick layers of a new amorphous alloy, FeNiW, have been obtained by electrodeposition. The
iron mole fraction, [Fe]/([Fe]+[Ni]), can be changed from 0 to 1, however, the best properties under constant current
deposition are obtained for the mole fraction near 0.5. The key, needed properties of the FeW and NiW alloys were
transferred to the FeNiW alloy, while the unwanted properties of the two-component alloys were eliminated. The
new alloy is hard (1040 HV, for equal percentage of Fe and Ni), smooth, of nice appearance, and of good adherence
to both steel and copper. Pulse electroplating further improves the smoothness and uniformity of the electrodeposited
layers and allows one to obtain higher tungsten content of up to 35 at.%. X-ray diffractometry, EDX, and
chronopotentiometry were used to characterise the new material. The influence of pH and the ratio of concentrations
of Fe and Ni in the plating solution was examined. 2000 Elsevier Science Ltd. All rights reserved.

Keywords: Electrodeposition; Amorphous alloys; Tungsten alloys

1. Introduction plication of this kind of alloys as surface coatings will

Electrodeposited alloys of the iron-group metals have
been widely applied in industry, mainly as the materials
for magnetic storage devices and electronics. The NiFe
alloys were the first to be utilised in the production of
magnetic-film memories just because of their desirable
soft magnetic properties, and were widely used later [1].
They also found application in surface micromachining
[2]. The introduction of tungsten to the alloys of this
type improved their durability, hardness and resistance
to high temperatures [3,4]. Due to their hardness, they
can successfully substitute hard chromium coatings,
which are formed in the environmentally hazardous
process based on hexavalent chromium. Thus, the ap-
* Corresponding author. Tel.: +48-22-8220211; fax: + 48-
22-8225996.
E-mail address: stojek@chem.uw.edu.pl (Z. Stojek)
rather expand.
It has been found that the alloys with tungsten can
be deposited in the amorphous form [5]. The presence
of tungsten in the amorphous alloys apparently in-
creased the corrosion resistance of these and other
similar materials [6,7]. Our investigations have shown
that among the three amorphous alloys with tungsten
(FeW, CoW, NiW), NiW is of the best smoothness
and appearance, however, it adheres to steel substrates
poorly, and is of high internal stress what leads to the
formation of microcracks in the alloy layers. The FeW
alloys are much harder and well adhere to the iron/steel
substrates. In our previous work, which reports on the
CoW amorphous alloys [8], we reached a conclusion
that to get a good adhesion of the tungsten alloys to the
substrate an interface between the deposit and substrate
must be formed. Such an interface was formed between
the iron-group metal from the alloy and copper, and

0013-4686/00/$ - see front matter 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 3 - 4 6 8 6 ( 0 0 ) 0 0 4 3 7 - 0
3390 M. Donten et al. / Electrochimica Acta 45 (2000) 33893396

not on the surface of iron/steel. Simply cobalt and
copper have similar crystallographic structures.
The aim of this work was to examine whether the
addition of Fe to the NiW alloy would result in a
better new amorphous alloy, which maintains the good
appearance and smoothness of the NiW alloy, and is
of increased hardness and of better adherence to steel
substrates. FeNiW alloys plated from 1-hydroxy-
ethane-1,1-diphosphonic acid baths could be amor-
phous, only when tungsten content exceeded a critical
value [9]. Our interest in smooth, thin layers of the
amorphous FeNiW alloy was also connected with the
fact that such layers may be a good starting material
for possible formation of the nanocrystalline structures
at electrode surfaces. The electrodeposition of the
amorphous NiFeW alloy films in this work was done
from a citrate-based and environmentally friendly plat-
ing solution.

Fig. 1. SEM image of surface of NiW alloy (A) and FeNiW alloy (B) deposited on copper; ratio of concentrations of Fe and
Ni in plating solution, 1:1.
 M. Donten et al. / Electrochimica Acta 45 (2000) 33893396 3391

Deionized water of Milli-Q (Austria) quality was used

for preparation of the solutions. Temperature was kept
at 65C using a water bath.
Current density was controlled by an EG&G PAR
173 galvanostat/potentiostat. Two values of current
density were applied: 35 mA/cm2 (optimal for FeW
alloy deposition), and 70 mA/cm2 (optimal for NiW
alloy deposition). Deposition time was fixed at 120 min,
which resulted in 6 8-mm thick layers. pH of the bath
was adjusted by appropriate additions of either 25%
ammonia solution or citric acid, and was examined at
room temperature using a pH meter before and after
each deposition. For details regarding pH of the bath,
see Section 3.2. A 1000-ml plating cell, with two anode
compartments separated from the cathode compart-
ment by glass frits, was used. The volume of the plating
solution was 500 ml, and the solution was gently stirred
with a mechanical stirrer during the platings. The an-
odes were two plain platinum sheets of area 8 cm2
each. Pure copper- and mild steel foils (40 5 0.1-
Fig. 2. Influence of pH of plating bath solution on contents of mm pieces) were used as the supports for the alloy
Fe, Ni and W in electrodeposited alloys. Depositions were layers. They were located at the centre of the cell. The
done in solution containing equal concentrations of Ni and Fe,
foils were degreased and slightly etched/activated with
and at current density of 35 mA/cm2.
5% sulfuric acid just before plating. The current effi-
ciency for constant current deposition was estimated as
2. Experimental procedure
approximately 15%. In pulse depositions, a PC com-
puter and home-written software were used to control
Thin, micrometre-thick films of NiFeW alloys were
electrodeposited from a plating bath solution, contain-
ing sodium tungstenate (78 g/l), sodium citrate (Na2Cit,
59 g/l), phosphoric acid (85%, 7.69 ml/l), and boric acid
(10.25 g/l). Butindiol 1,4 (50mg/l) and detergent
Rokafenol N-10 (100 ml/l) were used as the brightener
and the wetting agent, respectively. The solution of this
composition was successfully applied for the electrode-
position of high-tungsten content alloys of Ni and Co
[10,11]. Ni(II) was added in the form of NiSO4 and the
source of Fe(II) was FeSO4. The sum of the nickel and
iron concentrations in the plating solution was kept
constant and equal to 0.02 M. All chemicals were of
reagent grade purity. Butindiol was purchased from
Fluka; Rokafenol N-10, phenol ethoxylate, a nonionic
detergent, was purchased from Rokita, Poland, and all
the other chemicals were received from POCh, Poland.

Table 1
Composition of alloy layer (in at.%) at different distances from
the substrate surfacea

Point location Fe Ni W

Substrate side 38.39 37.24 24.37

Inside layer 35.17 37.84 26.99 Fig. 3. Chronopotentiograms corrected for ohmic drop for
Solution side 31.19 43.92 24.89 deposition of FeW, NiW and FeNiW alloys onto Cu and
Fe. pH 8.5, j =35 mA/cm2. FeNiW alloy deposition were
a
Substrate, copper; ratio of concentrations of Fe and Ni in done in the solution with [Fe]/{[Fe]+[Ni]}= 0.2. Substrate,
plating solution, 3:7. ( ) iron; ( ) copper. Reference electrode, SCE.
3392 M. Donten et al. / Electrochimica Acta 45 (2000) 33893396
Fig. 4. Changes in composition of electrodeposited FeNiW
amorphous alloys caused by changes in concentrations of Ni
and Fe in plating bath solution. (A) Amount of nickel and
iron in deposited alloy plotted versus mole fraction of Fe,
[Fe]/([Fe]+ [Ni]), in the bath. (B) Amount of tungsten in
deposited alloy plotted versus mole fraction of Fe in the bath.
Current density, 70 mA/cm2, open symbols; 35 mA/cm2, filled
symbols.
the galvanostat. Two current waveforms were employed
in these depositions. Waveform 1 consisted of the re-
duction and rest (zero current) pulses, Tred and Trest, of
the same duration. In waveform 2, the reduction and
rest pulses were separated by a short oxidation pulse of
magnitude identical to that of the reduction pulse and
of duration, Tox, equal to 7% of Tred. For waveform 2,
the relation between the duration of the pulses was the
following, Tred = Tox + Trest.
Chronopotentiometric experiments were done with
the three electrode system using a Lithuanian poten-
tiostat/galvanostat model PI-50-1.1 and a function gen-
erator model PR-8. A platinum sheet served as the
counter electrode and a SCE was the reference elec-
trode. Ohmic drop was evaluated in separate experi-
ments by switching off the galvanostatic pulse after 30
s of electrolysis and measuring the immediate resulting
potential drop with the use of an oscilloscope.
Surface topography and composition of the deposits
were examined using a scanning electron microscope
LEO 435 VP supplied with a Roentec, model M1, EDX
analyser. The XRD patterns of the alloys were obtained
using a DRON X-ray diffractometer equipped with a
Fe lamp. Microhardness of the deposits was determined
with a Vickers diamond pyramid. The load used in the
hardness measurements was 2 and 5 g, and the penetra-
tion depth was never bigger than 1.5 mm. Each sample
was probed in 10 places and the result is given as the
mean value.
3. Results
3.1. Deposit appearance
High internal stress of tungsten alloy coatings was
observed for both cobalt- and nickel based amorphous
alloys. The stress was more profound for the NiW
alloy. As a result, a rather dense net of microcrackes
appeared at the surface. Peeling of the alloy off the
substrate surface could be seen also. The microcracks
on the NiW surface are shown in Fig. 1A. The effect
is more intensive when either iron- or steel sheets are
the substrates for the electrodeposition of the NiW
alloy. In the case of Ni, it is possible to remove a
significant fraction of the coverage from the substrate
using a piece of regular office adhesive tape. The poor
adhesion observed for the layers of NiW and also
CoW amorphous alloys electrodeposited on iron and
steel substrates, is at least partially connected with
significant differences between the internal structures of
the substrate and the major components (Ni or Fe) of
the alloys. If the similarity between the crystal structure
is really important, as was shown in the literature, for
example, for CoW alloy [8], then adhesion to steel
substrate of the amorphous WNi alloy should be
significantly improved by the addition of iron to the
alloy.
Fig. 1B presents micrographs of the new three-com-
ponent alloy. It is seen in the figure that the introduc-
tion of iron to the NiW alloy eliminates the cracks on
the surface. The FeNiW alloy is also less brittle than
the NiW alloy. Apparently, the addition of Fe to the
NiW alloy effectively reduces the tensile stress in the
 M. Donten et al. / Electrochimica Acta 45 (2000) 33893396
electrodeposited layers. At the same time, the surface of
the coverage remains mirror-like and shine, what is
typical for the NiW alloys. Adhesion of the three-com-
ponent alloy layers to steel substrate is also much better
now, since the removal of the deposit from the sub-
strate surface is much more difficult. Regarding the
alloys plated on copper, an addition of Fe to the alloy
does not decrease its adhesion to the copper substrate.
3.2. Influence of pH
The FeNiW amorphous alloy can be deposited
from the citrate bath in a relatively wide range of pH.
The limitation at low pH is the formation of poly-
tungstates followed by the precipitation of tungstic
acid. These processes can start at pH lower than 5. At
pH higher than 10 another limitation appears, it is the
formation of iron hydroxides. Therefore, the pH range
potentially suitable for the electrodeposition of the
alloy layers is 510. All deposits obtained in this pH
range had the (quasi) amorphous structure, since the
X-ray diffractograms were appropriately wide. How-
ever, the compositions of the alloys electrodeposited at
various pH change; they are shown in Fig. 2. These
results have been obtained in solutions containing equal
concentrations of Ni and Fe. Since, over the pH range
from 7 to 8.5, the composition of the FeNiW alloy is
roughly constant and the content of tungsten is the
highest, this pH range was taken as the optimal and
was used in further depositions. The initial pH in
further platings was always 8. The final pH never
departed from this value by more than 0.5. The ratio of
concentrations of Ni and Fe in the deposited alloys
differed from that of the plating bath solution, and this
may be surprising. However, this effect appeared also in
the simultaneous depositions of the iron-group pairs of
metals and was discussed in the literature [12,13]. The
anomalous preferential deposition of iron during the
codeposition with more noble nickel was shown in the
literature to be a result of the formation of hydroxides
in the solution. Talbot et al. [12,14] and Hessami and
Tobias [15] claimed that the metal hydroxides are the
Table 2
Influence of FeNiW alloy composition on position of X-ray diffraction signal and alloy hardnessa
Fe content/at.% Ni content/at.% W content/at.%
0 81 19
9 72 19
21 58 21
39 33 28
55 16 29
69 0 31
a
Thickness of alloy layer, 8 mm.
b
Alloy layer thickness, 50 mm.
3393
charge-transfer species. Because, it was found that the
equilibrium for the formation of the monohydroxide/
hydroxide of less noble iron is favoured, the concentra-
tion of iron should be higher in the Ni/Fe deposit.
Sasaki and Talbot [12] have found that the ratio of Fe
and Ni contents in the deposit is 2.3:1. This ratio fits
well the data in Fig. 2 obtained for the amorphous
NiFeW alloy electroplated in the solution of optimal
pH range and of equal Fe and Ni concentrations. In
fact, in the case of the ternary tungsten alloys plated on
copper, this effect is even enhanced during the initial
step of the electrodeposition. This is presented in Table
1, where the content of Ni and Fe in the alloys versus
the distance from the substrate surface is given. Please,
note that the data in Table 1 were obtained for the
ratio of concentrations of Fe and Ni in the solution,
equal to 3:7.
3.3. Chronopotentiometry
Since, the electrodeposition is done in the alkaline
solution, and under the conditions of excessive hydro-
gen evolution, pH can increase substantially near the
cathode surface. This favours the formation of iron
hydroxy complexes and yields higher weight fraction of
iron in the alloy at the beginning of the electrodeposi-
tion (at the substrate surface). As it is shown in Fig. 3,
for very short deposition times, the values of the
cathode potential are very similar for both substrates
and the alloys containing iron. Since, the deposition
process is of very low current efficiency (15%) and is
accompanied by intensive hydrogen evolution, and
therefore the cathode potential is rather determined by
hydrogen evolution, we attribute the closeness of the
cathode potentials to similar reaction mechanisms and
dominating deposition of iron on the surface of both
substrates. As the deposition time prolongs to tens of
seconds, the potentials stabilise, and the following rela-
tion is seen, the more Ni on the surface, the lower the
hydrogen evolution is. Now the distinct difference be-
tween the potentials for the NiW alloy deposited on
steel and copper can be attributed to preferential depo-
sition of Ni on copper.
Diffraction signal position, 2u/ Hardness/HV
56.1 810 (960)b
56.1 820
56.4 910
54.8 1040
54.6 1070
53.8 1140 (1380)b
3394 M. Donten et al. / Electrochimica Acta 45 (2000) 33893396

Fig. 5. SEM images of cross-brakes of FeNiW alloys plated on copper substrate from the same plating bath solution (A) constant
current method, current density 35 mA/cm2, (B) pulse current method (waveform 1); deposition pulse time 40 ms at current density
of 70 mA/cm2; rest pulse time 40 ms at current density of 0 mA/cm2. Deposition time, 90 min for both methods. Ratio of
concentrations of Fe and Ni in plating solution, 1:1.

3.4. Influence of [Fe] /([Fe]+[Ni ]) mole fraction
In the next experiments, the influence of variation of
the concentration ratio CFe/CNi in the plating solution
on composition of the deposit, and deposits physical
properties was examined. For those investigations, two
series of depositions for two current densities were
done. The current densities chosen for the examination
were 35 mA/cm2 (optimal for FeW alloy deposition)
and 70 mA/cm2 (optimal for NiW alloy deposition).
For both series of experiments, the compositions of the
plating bath solution were changed in nine steps from
the pure NiW bath solution to the pure FeW bath
solution. The results of those experiments are shown in
 M. Donten et al. / Electrochimica Acta 45 (2000) 33893396
Fig. 4. The Ni and Fe content curves in Fig. 4A
confirm the chronopotentiometric findings that the
preferential deposition of iron in a wide range of Ni/Fe
ratio takes place in the solution. An analysis of the
curve of tungsten content shown in Fig. 4B indicates
that tungsten concentration is roughly constant ( 20
at.%) for lower concentrations of Fe. Next, the W
content increases to reach a plateau ( 26 at.%) for the
[Fe]/([Fe]+ [Ni]) ratio equal approximately to 0.6. For
higher than 0.8 values of this ratio, the W content
increases again and is maximal for the pure FeW
alloy. A probable explanation of this effect can be given
after examining the internal structure of the tungsten
based alloys. It was documented previously that NiW
and FeW amorphous alloys have different internal
organisation. The structure of NiW alloy is similar to
the highly deformed nickel structure, Fm3m, and the
structure of FeW alloy is closer to the iron structure,
Im3m [16]. The X-ray diffraction experiments confi-
rmed the amorphous structure of all examined deposits.
An analysis of the position of the maximal intensity of
the broad diffraction signals indicates that a reorganisa-
tion of the internal structure of the deposited alloys
takes place while the iron content in the NiW alloy
increases. The appropriate quantitative data are pre-
sented in Table 2. It is seen from Table 2 that the most
intensive changes in the position of the peaks in the
diffractograms appear when the [Fe]:[Ni] ratio in the
alloy approaches 1. For the value of this ratio smaller
than 1, the dominating structure in the FeNiW alloy
is apparently that of deformed nickel. The structure of
deformed iron can be obtained for high molar fraction
of iron only. The XRD pattern changes described cor-
relate well with the changes in tungsten content in the
examined alloys.
The increase in Fe content, which is paralleled by
appropriate increase in W content, leads also to appar-
ent increase in hardness of the alloy. This is shown in
Table 2. The values of microhardness measured for
very thin layers (8 mm) may be slightly affected by the
substrate which is much softer, however, the trend seen
Table 3
Composition of FeNiW alloys, in at.%, deposited by pulse
current methodsa
Frequency/Hz Waveform 1 Waveform 2
Fe Ni W Fe Ni W alloys that are satisfactorily smooth, hard, uniform, of
1 40.6 28.1 31.1 20.0 70.6 9.4
2.5 41.4 26.5 32.1 30.2 48.1 21.7
12.5 44.8 20.4 34.8 37.5 35.5 26.5
50 46.4 18.7 33.8 44.8 20.2 35.0
a
Ratio of concentrations of Fe and Ni in plating solution,
1:1.
3395
must be real. The values of microhardness obtained for
much thicker alloy layers are rather more accurate and
are also given in Table 2.
3.5. Pulse deposition of the alloys
Application of pulse electrodeposition usually im-
proves the quality of the metallic deposits. This was
also true for the two-component reach-in-tungsten
amorphous alloys [11]. In the case of three-component
NiFeW alloy, pulse deposition also improved the
quality of the deposits.
The positive effect for pulse deposition was not so
evident when simple optical inspection of the samples
was done. The three-component alloys obtained with
constant current had already smooth surfaces and low-
ered internal stress. The first advantage of the pulse
methods was that the edges of the plated samples were
smoother and more compact, when the pulse plating
was applied. Closer observations of broken alloy layers
allowed us to detect an improvement in the homogene-
ity of the internal structure and smoothness of the
surface of the deposits obtained by pulse plating. The
structure of the constant-current plated alloy is some-
what more grainy, which made the surface of the crack
non-uniform and generated many small pieces of the
alloy during the breaking. This is shown in Fig. 5,
where the cross-brakes of the layers of the FeNiW
alloys deposited on the same substrate are compared.
The formation of amorphous grain structure is interest-
ing. This indicates that the growth rate of the alloy
layers is not identical at the substrate surface. Strong
hydrogen evolution may stand behind this
phenomenon.
The frequency of the current waveform has an appar-
ent influence on the alloy stoichiometry. An increase in
waveform frequency leads to an increase in both iron
and tungsten content. At 12.5 and 50 Hz, the tungsten
content reaches the maximum value of 35 at.% for
waveforms 1 and 2, respectively. The situation is illus-
trated in Table 3.
4. Conclusions
Electrodeposition under constant current conditions
from a citrate-based environmental-friendly bath allows
to obtain the three-component, amorphous FeNiW
good look, and of good adherence to both copper and
steel. The alloys with the Fe mole fraction, [Fe]/([Fe]+
[Ni]), approaching 1 have the best properties, however,
the properties for the other stoichiometries do not
depart far from these. SEM micrographs reveal that the
internal structure and the surface smoothness of the
alloys obtained under constant current conditions are
3396 M. Donten et al. / Electrochimica Acta 45 (2000) 33893396
still not ideal. The pulse deposition brings further im-
provements, especially in the texture of the alloy bulk
which is somewhat grainy in the constant-current al-
loys, and in the surface smoothness. Also, the pulse
deposition allows one, by changing the current wave-
form frequency, to obtain higher tungsten content of up
to 35 at.%. This increase is achieved at the cost of
nickel content. The disadvantages of using the pulse
plating are the use of more complex instrumental set-up
and further drop in current efficiency to 11%.
Acknowledgements
This work was supported in part by grant BST-623/5
from the University of Warsaw. One of us (H. Cesiulis)
thanks the Department of High Education and Science
of the Ministry of Education and Science of Lithuania
for a research fellowship during which a part of this
work was carried out.
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