Materials Chemistry and Physics 111 (2008) 469474

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Materials Chemistry and Physics

journal homepage: www.elsevier.com/locate/matchemphys

Electrodeposition of nanocrystalline nickel by using rotating

cylindrical electrodes
E. Moti, M.H. Shariat , M.E. Bahrololoom
Department of Materials Science and Engineering, School of Engineering, Shiraz University, Shiraz 7134815939, Iran

a r t i c l e

i n f o

Article history:
Received 27 December 2006
Received in revised form 24 April 2008
Accepted 30 April 2008
Keywords:
Nanocrystalline
Nickel
Electrodeposition
Rotating cylindrical electrode
Hardness

a b s t r a c t
In this research, nanocrystalline nickel (1425 nm) was electrodeposited on rotating cylindrical electrodes
in a modied Watts bath. Saccharin was used as a grain rener. The effect of cathode rotation speed and
saccharin concentration on the grain size was studied by transmission electron microscopy (TEM) and Xray diffraction (XRD) analysis. The preferred orientation of deposits progressively changed from a (2 2 0),
(2 0 0), and (1 1 1) ber texture for a saccharin free bath to a (1 1 1) and (2 0 0) double ber texture for
a bath containing 5 g l1 saccharin. Cathode rotation enhanced the intensity of (1 1 1) peak relative to
(1 0 0). The effect of cathode rotation speed, current density, and saccharin concentration on the coating
microhardness was investigated. The maximum recorded hardness was 620 HV for 14 nm grain size. The
effect of current density and saccharin concentration on morphology was observed by scanning electron
microscopy (SEM). The current efciency changes were studied as a result of saccharin concentration.
2008 Elsevier B.V. All rights reserved.

1. Introduction
Nanostructural materials exhibit different mechanical, physical,
and chemical properties relative to conventional structures [13].
Therefore, in the last two decades much interest has been directed
to them. This group of materials often is identied by a physical
dimension (such as grain size) 1100 nm and a signicant amount
of surfaces and interfaces. Nanostructure materials can be made by
bottom-up approaches like inert gas condensation, chemical methods, and electrodeposition or top-down methods like ball milling,
mechanical alloying, and severe plastic deformation [4]. In contrast with other methods, electrodeposition presents economical
and technological advantages [5]. Accordingly, many efforts have
been made in order to synthesize nanocrystalline Ni [6], Co [7],
Zn [8], NiCo [9], NiB [10], NiZn [11], NiWC [12], and NiSiC
[13].
The investigated properties of nanocrystalline (nc) nickel shows
unique or improved properties as compared to conventional polycrystalline nickel. The hardness of nc nickel has been reported to
be 640 HV at 14 nm grain size [14]. Furthermore, a notable increase
in ultimate tensile stress (1390 MPa) was observed for nc nickel
(40 nm) [15]. The wear rate of nc nickel with an average grain size
13 nm is about half of the wear rate in polycrystalline nickel (90 m)
[16]. Hydrogen transportation rate and storage capacity in nc nickel

Corresponding author.
E-mail address: shariat@shirazu.ac.ir (M.H. Shariat).
0254-0584/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2008.04.051

have been previously shown to be signicantly higher than those

observed in conventional materials [17]. In addition, a higher electro catalytic behavior has been noted with regard to hydrogen
evolution reaction (HER) for alkaline water electrolysis at room
temperature [17]. The improved corrosion and fatigue properties
have also been reported for nc nickel [18,19].
In electrodeposition of nc materials like other bottom-up methods, nucleation and growth are in competition to determine grain
size. Therefore, low growth rate and high nucleation rate for synthesis of nc materials are unavoidable. In some researches grain
reners like saccharin [20], coumarine [21], thiourea [21], and
formic acid [22] have been successfully applied to achieve nc nickel.
These organic additives affect surface diffusion of adion on the
growth surface and decrease growth rate. On the other hand, such
additives increase the cathodic overpotential [23]. Consequently,
based on the classical theories on electrochemical phase formation and growth [24], the nucleation rate is increased. At the same
time problems like hydrogen evolution is probable. For controlling such problems, pulse current [25], rotating electrodes [15],
and anti-pitting agents [15] have been used. Therefore, in all of
the mentioned methods for deposition nanocrystalline materials in
addition to grain rening, deteriorating effects of high overpotential
must be prevented.
The main goal of this work is to combine advantages of saccharin addition as a grain rener and a rotating cylindrical electrode
to produce nc nickel. The effect of saccharin concentration on grain
size, texture, hardness, current efciency, and morphology will be
discussed. The relation between cathode rotation speed and grain

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E. Moti et al. / Materials Chemistry and Physics 111 (2008) 469474

Fig. 1. Scanning electron microscopy micrographs (a) 2 A dm2 , 500 rpm, without saccharin addition (b) 2 A dm2 , 500 rpm, saccharin concentration 5 g l1 , (c) 6 A dm2 ,
500 rpm, saccharin concentration 5 g l1 , and (d) microhardness indentation effects (electrodeposition conditions were similar to those of Fig. 1b).

size and hardness is noticed. In addition, the effect of current

density on the hardness and morphology of nc nickel is also
reported.
2. Experimental
Cylindrical copper cathodes each having a surface area of 10 cm2 and 1.9 cm
diameter, were utilized as substrates for electrodeposition of nc nickel (35100 m
thickness) using direct current and 0800 rpm rotation speed. A Watts bath (all
analytical grade chemical) was used containing NiSO4 6H2 O (300 g l1 ), NiCl2 6H2 O
(45 g l1 ), H3 BO3 (45 g l1 ), saccharin (05 g l1 ) as grain rener, and sodium lauryl
sulfate (0.25 g l1 ) as an anti-pitting agent. The bath temperature was adjusted at
60 1 C. Before plating, the substrates were degreased with acetone and then electropolished by dipping into a solution containing 25 vol% phosphoric acid (33 wt%),
25 vol% ethanol alcohol (99 vol%), and 50 vol% distilled water while applying a
1015 A dm2 current density for 1 min. Two nickel sheet (total surface area 25 cm2 )
anodes were xed on two sides of cathode at 2 cm distance. The pH was 2, and it
was kept constant by adding a mixture of H2 SO4 :HCl (7:1). The electrolytes were
replaced after coating ve specimens.
The deposit microstructures were characterized by D8 Bruker X-ray diffraction
(XRD) and the X-ray scan rate was 0.05 s1 /with Cu K radiation ( = 0.15405 nm).
The grain size was determined for X-ray peak broadenings by applying Scherrer formula for (1 0 0) reections [26]. The peak broadenings were measured by integral
width method [26] and corrected for instrumental peak broadening using a fullannealed nickel (at 600 C for 24 h) by Jones equation [26]. To verify the accuracy of
the grain size measurements, some specimens were also examined in a C.M. 200S.E.G. Philips scanning transmission electron microscope (STEM). For making TEM
specimens, the nc nickel deposit were separated from their substrates by immersion in an aqueous solution containing CrO3 (250 g l1 ) and (98 wt%) sulfuric acid
(20 ml l1 ). Then samples were prepared by jet polishing with a 10 vol% perchloric
acid, 15 vol% acetic acid, and 75 vol% methanol electrolyte at 20 C and an applied
voltage of 20 V. The grain size of nanocrystalline nickel was determined directly
from dark-eld and bright-eld transmission electron micrographs by measuring
120 grains.
Morphological studies of deposits were carried out by using an Oxford Instrument Stereoscan 120 scanning electron microscope (SEM). Microhardness of nickel
deposits were measured by using a Wetzier Pietz microhardness tester with a Vickers indenter. The microhardness tests were based on E 384-89 ASTM and the applied
load was 25 g for an indentation time of 15 s. Because of the cylindrical shape of specimens and omitting the effect of substrate on microhardness, all the microhardness

tests were carried out on the cross section of coatings. The current efciency was
calculated from the charges passed and the weight gained by applying Faradays
equation.

3. Results and discussion

Fig. 1a shows the morphology of nickel deposited at 2 A dm2
and 500 rpm without saccharin addition. Such morphology was
related to structures with grain size in micrometer range [27]. This
deposit exhibits a relatively large surface roughness. Consequently,
diffuse light reection gives it a dull appearance [28]. Saccharin
addition (5 g l1 ) changed the morphology of deposit (Fig. 1b). In
addition to inhibition of pyramidal growth because of saccharin
addition [29], the uniform current distribution in rotating cylindrical electrode [30] promoted the leveling. As a result of leveling a
very smooth surface was observed. For this reason as also reported
elsewhere [28], the appearance of nc nickel was mirror-like. Such
results were also observed by Qu et al. [31], Erb and El-Sherik [7].
In contrast to Fig. 1b, the destructive effects of increasing current
density from 2 to 6 A dm2 is shown in Fig. 1c. Clearly, blisters
are observed and they can be as a result of adsorbed hydrogen.
Because of hydrogen adsorption or hydrogen evolution, pH can
locally increase. Therefore, black areas in Fig. 1c may be nickel
hydroxide. Fig. 1d shows the Vickers microindentation effect on
the cross section of copper substrate (the greater lozenge in the
lower part of Fig. 1d) and nc nickel coating (the smaller lozenge in
upper part of Fig. 1d). The measured microhardness for copper is
90 8 HV and for nc nickel is 620 25 HV.
The effect of saccharin concentration on the preferred orientation of nickel deposits is shown in Fig. 2. For microcrystalline
nickel the orientation with signicant (2 2 0), (2 0 0), and (1 1 1)
reection are exhibited in Fig. 2a. In accord with this random
grain orientation, the surface morphology of microcrystalline nickel
(Fig. 1a) does not exhibit the regular symmetry. However, the pre-

E. Moti et al. / Materials Chemistry and Physics 111 (2008) 469474

Fig. 2. X-ray diffraction pattern for nickel at different saccharin concentration (a) 0,
(b) 0.25, (c) 1, (d) 3 and (e) 5 g l1 , 500 rpm, 2 A dm2 .

ferred orientated in the (1 1 1) plate direction was reported for

microcrystalline nickel [32]. This difference can be a result of
cathode rotation in this research. Increasing saccharin concentration changes the preferred orientation from a (2 2 0), (2 0 0),
and (1 1 1) to (1 1 1) (2 0 0) double ber texture (Fig. 2be).
This is consistent with ndings reported by El-Sherik and
Erb [6]. Some researchers related this phenomenon to the decrease
in grain size, crystallographically anisotropy, surface energy, and
nucleation rate [33]. In addition, as a result of thinner coating
(32 m) X-ray reection, marked S, originating from substrate, can
also be seen in Fig. 2e. The effect of saccharin concentration on
the line broadening of (1 1 1) reection was presented in Fig. 3.
The average grain size value of nickel deposited at saccharin concentration 1, 3, and 5 g l1 calculated from the (1 1 1) lines of f.c.c.
nickel according to Scherrer formula were 28, 18, and 14 nm. The
results of calculation are invalid for (1 1 1) lines broadening in saccharin concentration 0 and 0.25 g l1 , because the measured line
broadenings approximately are equal to the instrumental error
(0.0043188 rad).
X-ray diffractograms measured at different cathode rotation
speed for 2 A dm2 and 5 g l1 saccharin are shown in Fig. 4.
Textural changes were observed in Fig. 4. The intensity ratio
RI = I(200)/I(1 1 1) is decreased by increasing the cathode rotation

471

Fig. 3. (1 1 1) X-ray diffraction peaks of nickel at different saccharin concentration,

(a) 0, (b) 0.25, (c) 1, (d) 3 and (e) 5 g l1 , 500 rpm, 2 A dm2 .

speed. It can be related to more adsorption of saccharin ion or

atomic hydrogen on the cathode surface during electrodeposition.
The textural organization of deposits has been attributed to the
existence or formation of different chemical species on the cathode surface during the cathodic process. It was reported that nickel
deposits in the presence of organic additives denoted (1 1 1) texture or an apparently random orientation [34]. In addition, it was
reported that by using the rotating electrode hydrogen adsorption on the cathode is increased and it in turn inhibits growth
for (2 0 0) direction [35]. Both of these results have a good consistency with the XRD results in this work. The calculated grain
sizes of deposits are mentioned in Fig. 4. Grain sizes of deposit
produced by the rotating electrode are smaller than that of the
deposit of stationary electrode. It can be related to the better saccharin adsorption on the rotating electrode. On the other hand,
grain size at 800 rpm is larger than grain size at 500 rpm. This may
be a result of small hydrogen ion adsorption instead of large saccharin ion adsorption in high shear force on the cathode surface
at high cathode rotation speed. Similar conclusions deduced from
the literatures [6,35], although hydrogen adsorption can noticeably
change the texture, it does not affect the grain size like saccharin.
Fig. 5ac shows planer bright-eld and dark-eld STEM micrographs for a nickel deposit, which was produced from a bath

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E. Moti et al. / Materials Chemistry and Physics 111 (2008) 469474

aspect and mechanism of grain rening deserve further investigation.

Elements like grain size, internal stress, and porosity [36] affect
the hardness. In general, without considering factors like internal
stress and porosity, the hardness of a polycrystalline metal can be
represented by well-known HallPetch equation.
H = H0 + kd1/2

Fig. 4. X-ray diffraction pattern for nickel at different cathode rotation speed (a)
stationary cathode, (b) 500 and (c) 800 rpm at 5 g l1 saccharin concentration and
2 A dm2 .

containing 5 g l1 saccharin, 2 A dm2 current density and 500 rpm

rotation speed. The grain size distribution was shown in Fig. 5d. The
grain size distribution is in the range 825 nm, and the determined
average grain size was 13.5 nm, which was in good agreement with
XRD results. This consistency implies that the XRD technique is
a suitable method to characterize the grain size of nc nickel in
this study. Like the planer micrographs of nc nickel, which was
electrodeposited by DC current technique [14] the equiaxed grain
structure were observed, as shown in the TEM micrographs of
Fig. 5. Such microstructures have been reported by El-Sherik and
Erb [6].
Fig. 6 shows the effect of cathode rotation speed on microhardness and the grain size of nickel coatings at 2 A dm2 and
5 g l1 saccharin concentration. The increase in microhardness
was observed with increase in cathode rotation speed from 0
to 500 rpm. On the other hand, in the cathode rotation speed
more than 500 rpm the decrease in microhardness was shown.
An inverse relation was noticed for grain size and cathode rotation speed. This phenomenon can be related to grain rening
mechanism. Large organic molecule (like saccharin) can produce
transient chemical or physical barrier layers to transport of adions
and adatoms on the cathode surface [8]. In rotation speeds higher
than 500 rpm the saccharin adsorption on the cathode surface
maybe was disrupted. These preliminary results on nc nickel was
prepared by rotating cylindrical electrodes and its electrochemical

(1)

where H0 is hardness constant, k a constant, and d grain size.

The results of the microhardness experiments in different saccharin concentration are summarized as a function of grain size in
HallPetch plot of Fig. 7. For comparison the hardness data of other
researches were shown [37,38]. The deviation form HallPetch
equation is not presented in this research, whereas such behavior
is shown by Erb [37], Nieh and Wang [38]. The possible explanation
for this discrepancy is such behavior which can be seen in grain
size less than 14 nm in nc nickel. Furthermore, the maximum hardness measured in this investigation was 620 HV for grain size 14 nm,
which is slightly smaller (about 20 HV) than other results. The difference can be related to the existence of internal stress or micro
porosity, both of them affect hardness [36].
The HallPetch plot of hardness versus reciprocal square root
of grain size, were calculated for different cathode rotation speed,
is shown in Fig. 8. Clearly, the microhardness of nc nickel deposits
was prepared by using rotating electrodes satised the HallPetch
equation. But in the stationary cathode condition hardness did not
obey the HallPetch equation. Therefore, in addition to grain size,
defects in the coating affect the microhardness in stationary cathode condition. From electrochemical aspect, the low rotation speed
should indicate that the metal deposition being examined is under
metal ion transport control [39]. Therefore, reduction of hydrogen
ion is possible in stationary cathode condition in nickel deposition. Hydrogen evolution makes defects in the nickel coating and
decrease microhardness in low rotation speed. Furthermore, gas
bubbles on the stationary cathode during electrodeposition were
observed that could locally disrupt saccharin adsorption, so grain
size distribution can be wider in this condition. Totally, wider grain
size distribution and defect can deleteriously inuence the hardness of deposit.
The microhardness of nc nickel versus current density at
500 rpm and 5 g l1 saccharin concentration, as the best liner trendline is shown in Fig. 9. Clearly, the deleterious effect of increasing
current density on microhardness is proved. The microhardness
decrease for this coating can be explained as a result of blisters
which were shown in Fig. 1c. Such behavior was reported for nickel
deposition [40].
Fig. 10 exhibits the current efciency of nickel deposit as a function of saccharin concentration at 2 A dm2 . The current efciency
for additive-free solution has been determined 95% which is consistent with Brugger [23]. The decrease in current efciency is
presented by increase of saccharin concentration, and the minimum current efciency is 87% at 5 g l1 saccharine concentration.
A decrease in current efciency was reported for nc and amorphous
NiP electrodeposition by McMahan and Erb and it was related
to the adsorbed hydrogen in deposits [41]. Saccharin addition to
Watts bath increase the cathodic overpotential [23] and it augment
the possibility of phenomena like hydrogen evolution and hydrogen adsorbtion. In addition, the reduction of unsaturated bands in
saccharin was reported in nickel deposition [42]. Therefore, by saccharin addition in the Watts solution, the total current density is
the sum of the current densities for nickel deposition, hydrogen
evolution, hydrogen adsorbtion, and additive reduction. pH rise
in the bath (at higher saccharin concentration) is a reason that is
consistent with the decrease of efciency.

E. Moti et al. / Materials Chemistry and Physics 111 (2008) 469474

473

Fig. 5. Scanning transmission electron micrographs of nc-Ni, electrodeposited with bath containing 5 g l1 saccharin, 2 A dm2 , 500 rpm including (a and c) bright-eld view
in the plane of the foil and (b) dark-eld image. (d) Relative grain distribution.

Fig. 6. Effect of cathode rotation speed on microhardness (--) and grain size (--).
Fig. 8. HallPetch plot of hardness (HV) vs. reciprocal square-root grain size (d1/2 )
for nc-Ni. Results from (--) rotating electrodes and (--) stationary cathode.

Fig. 7. HallPetch plot of hardness (HV) vs. reciprocal square-root grain size (d1/2 )
for nc-Ni (() this research), compared with data from literatures (() T.G. Nieh) and
(() U. Erb) [36,37].

Fig. 9. Effect of current density on microhardness.

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E. Moti et al. / Materials Chemistry and Physics 111 (2008) 469474

References

Fig. 10. Effect of saccharin concentration on current efciency (2 A dm2 , 500 rpm).

4. Conclusions
Nanocrystalline nickel was electrodeposited from a watts bath
with rotating cylindrical electrode. Mirror-like nc nickel without blisters and micro pits was electrodeposited at 2 A dm2 ,
500 rpm, and 5 g l1 saccharin concentration. Saccharin concentration increase changed orientation and rened the grain
size to 14 nm. As a result of better saccharin and hydrogen
adsorption, cathode rotation reinforced the (1 1 1) peak relative
to (1 0 0). We nd that nickel exhibits HallPetch strengthening to grain sizes near 14 nm. The maximum hardness was
620 HV and hardness drop was observed with increase of current density. The grain size and microhardness were controlled
by changing cathode rotation speed. A decrease in current
efciency was observed as a result of increase saccharin concentration.
Acknowledgements
The authors wish to extend thanks to Shiraz University Research
Council for their nancial support through the grant number
84-GR-ENG-8. The valuable help of the laboratories staff of the
Material Science and Engineering Department in Shiraz University is highly appreciated. The authors wish to express thanks to
Prof. K. Janghorban for his valuable comments on XRD and TEM
micrographs.

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