Materials Letters 61 (2007) 715 – 718

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Influence of crystallite size on the hardness and fatigue life of steel samples
coated with electrodeposited nanocrystalline Ni–W alloys
K.R. Sriraman 1 , S. Ganesh Sundara Raman ⁎, S.K. Seshadri
Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras, Chennai-600 036, India
Received 6 July 2005; accepted 23 May 2006
Available online 14 June 2006

Abstract

The present work deals with the effect of crystallite size on the hardness and fatigue life of steel samples coated with electrodeposited
nanocrystalline Ni–W alloys. The Ni–W alloys were electrodeposited on steel samples at four different current densities (0.05, 0.10. 0.15 and 0.20 A/
cm2) and at a temperature of 75 °C. The crystallite size of the deposit reduced (from 40 to 13 nm) with an increase in current density (from 0.05 to
0.20 A/cm2) due to an increase in the tungsten content (from 0.72 to 9.33 at.%). Ni–W alloy containing 9.33 at.% W and having a crystallite size of
13 nm exhibited the maximum hardness of 638 HV. The alloys, with the crystallite size in the range 40–13 nm, followed the direct Hall–Petch
relation, i.e. hardness increased with a reduction in the crystallite size. The coated samples exhibited inferior fatigue lives compared to uncoated
samples. This may be attributed to the presence of tensile residual stresses and inherent microcracks in the coatings. Among the specimens coated
with Ni–W alloys, as the crystallite size decreased, the fatigue life of the specimen increased owing to the increase in hardness values.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Deposition; Nanocrystalline coatings; Nanostructure; Nickel–tungsten alloys; Fatigue

1. Introduction reported that the crystal structure of Ni–W alloy is determined by

its tungsten content, which is influenced by the bath composi-
Generally, Ni–W alloys are known to exhibit higher hardness, tion, temperature and current density [10]. Yamasaki has report-
higher heat resistance and also a better corrosion behaviour ed in a study that tungsten content increased from 17.7 at.% to
compared to elemental Ni. Also, there are possibilities of using 22.5 at.% and crystallite size reduced from 7 nm to 2.5 nm when
them in catalytic and magnetic applications. A recent study has the current density was increased from 0.05 to 0.20 A/cm2 [11].
shown that electroplated Ni–W alloys with amorphous/nanocrys- On the other hand, Schuh et al. reported a negligible influence
talline structures can be used in the molding process of the of current density on tungsten content and crystallite size [5].
microfabrication system using the lithographic galvanic deposi- Tungsten content increased slightly from 11.6 at.% to 13.2 at.%
tion technique [1]. Moreover, Ni–W coating may serve in future when the current density was increased from 0.05 to 0.20 A/cm2.
applications as the barrier between copper and silicon in the next The crystallite size was in the range of 6 to 10 nm.
generation of ultra large scale integration circuits and microelec- The hardness of a material, either bulk or coating, becomes a
tromechanical systems [2]. vital parameter governing its mechanical properties. The Hall–
The synthesis of nanocrystalline Ni–W alloys by electrode- Petch mechanism governs the hardening phenomenon in micro-
position was first reported by Yamasaki et al. [3]. Subsequently crystalline materials, i.e. a decrease in crystallite size increases
many researchers have synthesized nanocrystalline Ni–W alloys the hardness values. The same trend is also followed in nickel
for evaluating a variety of properties [4–9]. Younes et al. have and nickel based nanocrystalline alloys until a limiting size
(14 nm in case of nickel deposits) [12]. With sizes lower than this
there is a significant deviation in the Hall–Petch relation and an
⁎ Corresponding author. Tel.: +91 44 2257 4768; fax: +91 44 2257 0509. inverse Hall–Petch relation is observed. Although the exact
E-mail address: [email protected] (S. Ganesh Sundara Raman). mechanism for this phenomenon is unknown, a number of
1
Presently at Tata Motors, Pune, India. contributing factors have been discussed, including the texture
0167-577X/$ - see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.matlet.2006.05.049
716 K.R. Sriraman et al. / Materials Letters 61 (2007) 715–718

Table 1
Plating bath formulation and for Ni–W alloy
Chemicals mol/l Purpose
Nickel sulfate (NiSO4·7H2O) 0.06 Ni source
Sodium tungstate (Na2WO4·2H2O) 0.15 W source
Trisodium citrate dihydrate 0.30 Complexer for Ni and W
(Na3C6H5O7·2H2O)
Ammonium chloride (NH4Cl) 0.50 To increase current
efficiency
Boric acid (HBO3) 1.00 Buffer
Sodium bromide (NaBr) 0.15 Conductivity
Sodium saccharin 0.08 Stress reliever
(COC6H4SO2NNa·2H2O)
Sodium laurel sulfate (CH3)(CH2) 0.0867 Surfactant
10CH2OSO3Na

changes, diffusion creep, triple junctions, formation and pile up

of dislocation network, etc. [13–15].
Hanlon et al. have shown that fully dense nanocrystalline
Fig. 1. Effect of current density on the deposition rate and current efficiency of
(13 nm) and ultra fine crystalline (100 nm) Ni produced by Ni–W alloys.
electrodeposition exhibited longer stress-controlled fatigue lives
compared to conventional microcrystalline Ni (1 μm) [16]. How-
ever, based on fatigue crack growth test results they have indi- before plating. In all cases the plating was carried out for sufficient
cated that grain refinement in the nanocrystalline regime can have duration so as to obtain a coating thickness of about 100 μm.
a deleterious effect on the resistance to subcritical fatigue fracture. Chemical compositions of the foils were determined employ-
The present investigation was undertaken to study the influ- ing energy dispersive analysis using X-rays attached with a
ence of crystallite size of electrodeposited Ni–W alloys on the scanning electron microscope. Free standing foils were ob-
hardness and fatigue life of steel samples coated with these served under a transmission electron microscope (TEM) operat-
alloys. Electroplating of Ni–W alloys was carried out at four ed at 100 kV in dark field imaging mode and photographs were
different current density levels (0.05, 0.10, 0.15 and 0.20 A/cm2) taken. The average crystallite size was determined with the help
from a bath maintained at 75 °C. Further, evaluation of the of an image analysis software.
mechanical properties in terms of hardness and fatigue life of Microhardness measurements were carried out using a micro-
these plated samples was carried out. hardness tester with a diamond pyramid indentor at a load of 100 g.
An average of ten readings was taken to obtain the hardness values
2. Experimental details of the coatings. Load-controlled fatigue tests were carried out at a
load ratio of 0.1 on low carbon steel specimens (both uncoated and
Two substrate materials were used for plating: a) copper coated) using a servo hydraulic testing machine at a constant
(99.9%) to get free standing foils for the purpose of characteri- maximum stress of 325 MPa.
zation and b) low carbon low alloy steel (0.17% C, 0.70% Mn,
0.15% Si, traces of Mo, Ni, Cr, Cu and rest Fe) for the evaluation
of hardness and fatigue life.
Alkaline sodium citrate based bath was chosen to obtain Ni–W
deposits. The plating bath composition used, given in Table 1, was
similar to that used by Yamasaki et al. with slight modifications
[3]. The pH of the bath was maintained at 8.5. Commercially pure
Ni (99.1%) was used as the anode material. Plating was carried
out at a temperature of 75 °C employing four different current
densities (0.05, 0.10. 0.15 and 0.20 A/cm2). Copper sheet cou-
pons of the size 5 mm length and 4 mm width were degreased with
dilute nitric acid before plating and were treated with chromic acid
solution containing 250 g/l of Cr2O3 after plating to dissolve
copper and obtain free standing foils. These free standing foils
were used for characterization purposes. Steel discs of 30 mm
diameter and 5 mm thickness were plated with Ni–W alloy for
evaluation of microhardness. Steel specimens of 10 mm gauge
width, 65 mm gauge length and 5 mm thickness were used for
fatigue tests. All samples were degreased with saturated solution Fig. 2. Effect of current density on W incorporation and crystallite size of Ni–W
of NaOH in ethanol and then activated with dilute sulphuric acid alloys.
 K.R. Sriraman et al. / Materials Letters 61 (2007) 715–718 717

3. Results and discussion

The results of the synthesis and characterization are available in

another paper by the same authors [17]. The deposition rates of the
coatings increased with an increase in current density as shown in Fig. 1.
The current efficiency of the deposition process decreased with an in-
crease in current density. The current efficiency was found to be low
(maximum value was about 35%) due to the larger difference between
the static potentials of Ni and W. This may also be attributed to a large
amount of hydrogen evolution during the plating process [18]. Brenner
reported that an increase in the current density increased the tungsten
incorporation but decreased the current efficiency [19]. The amount of
tungsten codeposition increased with an increase in the plating current
density (Fig. 2). This was due to the reduction in the static potential of
the alloy compared to the parent metals as suggested by Ma et al. [9].
The transmission electron micrographs in dark field imaging mode
showed nanocrystals distributed in an amorphous matrix (for example,
see Fig. 3). Using an image analysis software the average crystallite size
was determined. Higher current density resulted in a smaller crystallite
size (see Fig. 2). Increase in the applied current densities resulted in the
Fig. 4. Dependence of hardness and fatigue life on crystallite size of Ni–W
incorporation of larger amount of tungsten. alloys.
Fig. 4 shows the variation of microhardness with (crystallite size)− 0.5.
The best fit line is also shown by a continuous line. The hardness of the
alloy coatings was found to be in the range of 575–638 HV. As the than the intrinsic hardness of nickel and much smaller than the grain size
tungsten content increased in the deposit, an increase in the microhard- contribution [5]. The alloy coatings followed the direct Hall–Petch
ness was obtained. The alloy containing 9.33 at.% tungsten and having a relation, i.e. hardness increased as the crystallite size reduced.
crystallite size of 13 nm exhibited the maximum hardness of 638 HV. It The uncoated specimens tested at a maximum stress of 325 MPa did
should be noted that the crystallite size decreased as the tungsten content not fail even after 2.5 × 106 cycles. On the other hand, the coated
increased. In the case of nanocrystalline alloys two different factors may samples failed within 3.5 × 105 cycles. The inferior fatigue lives of the
be responsible for strengthening namely solid solution strengthening and coated specimens may be attributed to the presence of tensile residual
grain boundary hardening. It has been shown that the solid solution stresses and inherent microcracks in the coatings causing an early
strengthening effect of tungsten is about an order of magnitude smaller nucleation of fatigue cracks in the substrate, as reported by Pertuz et al.
for electroless Ni–P coated steels [20]. The fatigue crack was initiated
at the surface of the deposit and subsequently extended to the substrate
with the assistance of the metallic bonding established at the deposit–
substrate interface thereby reducing the crack nucleation stage as has
been reported for the Ni–P coated steels [21,22]. Moreover the rough-
ness of the coatings also might have contributed to the reduction in life.
Crack propagation rate was enhanced due to the effective bonding
between the coating and the substrate [23].
Among the coated specimens the sample coated with a deposit
having a crystallite size of 13 nm (plated at the highest current density of
0.2 A/cm2) exhibited the longest life (see Fig. 4; the best fit line is shown
as a dotted line). As explained earlier, the increase in plating current
density increased the tungsten content in the deposit and decreased the
size of the grains of the deposit. Crystallite size plays an important role
in the fatigue life of the electroplated components. Hanlon et al. in-
vestigated the effect of crystallite size on the fatigue properties of
electrodeposited nanocrystalline Ni thin foils [16]. They have reported
that fully dense nanocrystalline nickel foils showed superior resistance
to stress-controlled fatigue compared to the microcrystalline counter-
parts owing to their superior hardness. In the present study all deposits
were in the direct Hall–Petch regime and the increased tungsten content
due to increased current density led to more refined grains which
increased the strength of the coating resulting in longer life.

4. Conclusions

Based on the results obtained in the present investigation on

Fig. 3. Transmission electron micrograph of Ni–W alloy deposited at a current electrodeposited nanocrystalline Ni–W alloys plated at 75 °C
density of 0.10 A/cm2. the following conclusions have been drawn.
718 K.R. Sriraman et al. / Materials Letters 61 (2007) 715–718

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