Materials Chemistry and Physics 97 (2006) 371378

Preparation of fine Ni powders from nickel hydrazine complex

Jung Woo Park a, , Eun H. Chae a , Sang H. Kim a , Jong Ho Lee a ,
Jeong Wook Kim a , Seon Mi Yoon b , Jae-Young Choi b
a Materials R&D Group, Passive Component Division, Samsung Electro-Mechanics Co., Ltd., 314, Suwon 443-743, Republic of Korea
b Materials & Devices Research Center, Samsung Advanced Institute of Technology, P.O. Box 111, Suwon 440-600, Republic of Korea

Received 6 May 2005; received in revised form 9 August 2005; accepted 12 August 2005

Abstract

Fine nickel powders with narrow size distribution have been prepared from the reduction of nickel hydrazine complexes in aqueous solution.
The pure nickel hydrazine complexes, [Ni(N2 H4 )3 ]Cl2 were prepared with the molar ratio of N2 H4 /Ni2+ = 4.5, while a mixture of complexes,
such as Ni(N2 H4 )2 Cl2 , [Ni(N2 H4 )3 ]Cl2 , and [Ni(NH3 )6 ]Cl2 were formed with N2 H4 /Ni2+ < 4.5. By the X-ray diffraction (XRD), FT-IR, and
scanning electron microscopy (SEM) analyses, it was found that the reduction of Ni2+ to metallic Ni powder proceeded via the formation of
nickel hydroxide which was reduced by hydrazine liberated from the ligand exchange reaction between the nickel hydrazine complex and
NaOH. The standard deviation of the particle size decreased with the decreasing molar concentration of nickel hydrazine complex while the
mean particle size increased. As the amount of hydrazine increased, the surface roughness of the particles was improved significantly due
to the catalytic decomposition of the excess hydrazine at the surface of the nickel particle. It was found that average particle size could be
controlled from 150 to 380 nm by adjusting the reaction molar ratio and temperature.
2005 Elsevier B.V. All rights reserved.

Keywords: Nickel hydrazine complex; Fine nickel powder; Chemical reduction

1. Introduction layers and thinner electrode layers is inevitable to achieve

There have been extensive studies on the synthesis of
fine nickel powders in the past two decades due to their
potential applications in optical, electronic, catalytic, mag-
netic materials, and so on [13]. Moreover, they have been a
great deal of attention as an internal electrode in multi-layer
ceramic capacitors (MLCCs). MLCCs are one of the most
widely used passive components in electronics, such as com-
puters, wire and wireless communication devices, etc. [4,5].
The continuing development of advanced electronic devices
for high performance with miniaturized dimensions has lead
to the improvements of MLCCs with larger capacitance in
a smaller volume. High volumetric efficient MLCCs (large
capacitance in small volume) can be achieved by control of
the thickness and the lamination number of dielectric layers
[6]. Especially, stacking a larger number of thinner dielectric
Corresponding author. Tel.: +82 31 210 5669; fax: +82 31 300 7900.
E-mail address: jwoo70.park@samsung.com (J.W. Park).
small-size capacitors with larger capacitance. Under these
circumstances, the increasing amount of internal metal elec-
trode has lead to the replacement of Pd or Pd/Ag by Ni as an
electrode material due to its lower cost and lower resistivity
[710]. However, it is more likely to cause not only a short-
circuit between the internal electrode layers but also structural
defects, such as cracks and delamination in the highly inte-
grated MLCCs with thinner dielectric and electrode layers
[11]. Therefore, to circumvent these problems in the fabrica-
tion of the thinner internal electrodes, it is essential for the
use of smaller size and non-agglomerated with the narrow
size distribution Ni powder.
There have been developed various kinds of synthetic
methods, such as chemical vapor deposition, sonochemical
decomposition, microwave-hydrothermal methods, polyol
process, and electrochemical reduction controlled chemical
reduction for the preparation of Ni fine powders [1217].
Among those methods, the chemical reduction of nickel salts,
such as NiCl2 and NiSO4 by a strong reducing agent in

0254-0584/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2005.08.028
372 J.W. Park et al. / Materials Chemistry and Physics 97 (2006) 371378
aqueous solution has been researched intensively due to not
only economical and mass-productive aspects but also tech-
nological aspects, such as better structural control on the
microscopic level, low reaction temperature, and the sim-
ple procedure [1823]. In this chemical reduction method,
hydrazine and alkali metal borohydride have been gener-
ally used as an external reducing agent. But in the case
of alkali metal borohydride, borohydride ions are known
to reduce metal cations to metal borides, particularly in
aqueous systems [2426]. On the other hand, hydrazine has
more widely been used as reducing agent for preparation of
metal nanoparticles because pH and temperature dependent
reducing ability of hydrazine make controllability of reduc-
tion rate easy. Hydrazine is basic and the chemically active
free ion is hydrazium cation, N2 H5 + . The standard reduc-
tion potential for the hydrazinium ion, N2 H5 + is 0.23 V
(N2 + 5H+ + 4e = N2 H5 + ) in acidic solution. But in basic
solution, the standard reduction potential of hydrazine N2 H4
is 1.16 V (N2 H4 + 4OH = N2 + 4H2 O + 4e ) [19,27]. On
the other hand, standard reduction potentials of Ni2+ and
Ni(OH)2 are 0.25 and 0.72 V for Ni2+ + 2e = Ni and
Ni(OH)2 + 2e = Ni + 2OH , respectively. Therefore, it is
necessary to maintain enough alkalinity of solution and
avoid precipitation of agglomerated nickel hydroxide dur-
ing the reduction process for inducing an efficient control
of reduction rate, size, and morphology of metal particle. In
this respect, nickel hydrazine complex is attractive starting
material for preparation of fine nickel powder by chemi-
cal reduction method. The stabilization of nickel cation by
hydrazine ligand may retard and prevent an abrupt formation
and agglomeration of nickel hydroxide. Also, highly uniform
distribution of hydrazine molecule around the nickel cation
by liberation in high pH can induce homogeneous reduction
process.
Although considerable efforts have been made to study
the change in the size and shape, there are no reports in the
literature regarding the preparation of fine nickel powder by
the controlled reduction of nickel hydrazine complexes in
aqueous solution.
In this paper, we report on the preparation of fine nickel
powders from the nickel hydrazine complex and their reduc-
tion pathway. We have also investigated on the effect of nickel
hydrazine complexes, reaction molar ratio and reaction tem-
perature on the phase composition, and morphology of nickel
powders.
2. Experimental
2.1. Materials
All chemicals used in this experiment were reagent grade
and used without further purification. Nickel chloride hex-
ahydrate (NiCl2 6H2 O) was received from Incheon Chemi-
cals. 80 wt.% hydrazine monohydrate (N2 H4 H2 O) solution
and 50 wt.% sodium hydroxide (NaOH) solution were pur-
chased from Daejung chemicals & Metals. The water used
throughout this work was deionized with Human Power I+
water purification system (Human Co., Korea).
2.2. Synthesis of nickel hydrazine complex
Typically, an appropriate amount of nickel chloride solu-
tion dissolved in deionized water was slowly added dropwise
over 30 min to an appropriate amount of hydrazine mono-
hydrate at 60 C. During the addition, blue, blueviolet, or
pink precipitates depending on the reaction molar ratio of
N2 H4 /Ni2+ were formed, and the resulting mixtures were
stirred for 12 h. The crude products obtained by filtration
were washed three times with 30 mL of deionized water and
finally dried at 30 C for 24 h in a vacuum dry oven. The
products were characterized by X-ray diffraction (XRD) and
FT-IR.
2.3. Preparation of ne nickel powder
To a nickel hydrazine complex solution prepared by above
procedure, an appropriate amount of NaOH was poured at
corresponding reaction temperature and the resulting mix-
ture was stirred for 1 h. As the reduction reaction proceeded,
the blue, blueviolet, or pink solution turned to black within
15 min, indicating a formation of metallic nickel. The result-
ing black slurry was carefully decanted and washed repeat-
edly with deionized water to remove by-products, such as
NaCl and unreacted hydrazine or NaOH. The metallic pow-
der, thus obtained was filtered and dried in a vacuum dry oven
at 80 C for 24 h.
2.4. Characterization
The nickel hydrazine complexes and nickel powders were
characterized by X-ray diffraction (Rigaku, RINT2200HF+ )
using Cu K radiation with graphite monochromator. The Ni
particle size and morphology analyses were performed using
scanning electron microscopy (SEM, JEOL, JSM-6700F with
accelerating voltage of 10 kV). FT-IR spectra were recorded
with a Nicolet Magna-IR 760 spectrometer.
3. Results and discussion
3.1. Synthesis of nickel hydrazine complexes
It has been known that the reaction between hydrazine and
NiCl2 with the molar ratio of hydrazine: Ni2+ = 1:2 or 1:3 in
dilute ethanol solution yields bis(hydrazine) nickel(II) chlo-
ride (Ni(N2 H4 )2 Cl2 ) or tris(hydrazine) nickel(II) chloride
([Ni(N2 H4 )3 ]Cl2 ), respectively [2830]. However, accord-
ing to our preliminary experiments in concentrated aque-
ous solution, the resulting complexes exist as the mixtures
of Ni(N2 H4 )2 Cl2 , [Ni(N2 H4 )3 ]Cl2 , and [Ni(NH3 )6 ]Cl2 of
which compositions are highly dependent on the reaction
 J.W. Park et al. / Materials Chemistry and Physics 97 (2006) 371378
Fig. 1. XRD patterns and FT-IR spectra of as-prepared nickel hydrazine complexes. The molar ratio of the hydrazine/Ni2+ are (a) 2, (b) 3, and (c) 4.5.
condition, such as the reaction temperature and the molar
ratio of hydrazine/Ni2+ . When the reaction temperature was
below 60 C, the product existed as mixture of three com-
plexes, Ni(N2 H4 )2 Cl2 , [Ni(N2 H4 )3 ]Cl2 , and [Ni(NH3 )6 ]Cl2
regardless of the molar ratio of hydrazine/Ni2+ . On the
other hand, at a reaction temperature of 60 C, the color
change of the solution and the reaction products are quite
different with the molar ratio of hydrazine/Ni2+ . The com-
positions of the products from the reaction molar ratio of
hydrazine/Ni2+ = 2, 3, and 4.5 in aqueous solution at 60 C
were determined by XRD and FT-IR (Fig. 1) analyses. When
the molar ratio of hydrazine/Ni2+ = 2 and 3, the green color of
the nickel chloride solution turned to purple upon the addition
of hydrazine monohydrate. As the reaction proceeded, blue
and blueviolet precipitates were formed. However, the ini-
tial green color of the nickel chloride solution turned to purple
and finally pink precipitates were formed in the case of the
reaction molar ratio of hydrazine/Ni2+ = 4.5. The XRD pat-
terns in Fig. 1 shows that the reaction products have different
compositions with the reaction molar ratio of hydrazine/Ni2+ .
The diffraction peaks marked with (
) and (
) of the blue pre-
cipitates from the reaction molar ratio of hydrazine/Ni2+ = 2
are attributed to the Ni(N2 H4 )2 Cl2 (JCDPS no. 28-065) and
[Ni(NH3 )6 ]Cl2 (JCDPS no. 76-1842), respectively, in Fig. 1a.
Also, the FT-IR spectra in Fig. 1a shows the vibrational peaks
arising from the Ni(N2 H4 )2 Cl2 and [Ni(NH3 )6 ]Cl2 com-
plexes. The stretching vibrational mode (NN) of hydrazine
ligands at the frequency of 980 cm1 and other vibrational
peaks except the peaks in the region of 1458, 1398, 650, and
613 cm1 are consistent with the values in the Ni(N2 H4 )2 Cl2
complex reported in the earlier literature [28,30,31].
The characteristic peaks, such as the rocking vibration
(650 and 613 cm1 ) and the symmetric distortion of the NH3
ligands in the [Ni(NH3 )6 ]Cl2 complex can be also found in
Fig. 1a and are accordant with the reported values [32]. In
the case of the reaction molar ratio of hydrazine/Ni2+ = 3,
diffraction peaks and FT-IR spectra of the blueviolet
precipitates show the reaction products are the mixture
373
of [Ni(N2 H4 )3 ]Cl2 , Ni(N2 H4 )2 Cl2 , and [Ni(NH3 )6 ]Cl2 as
shown in Fig. 1b. In contrast, [Ni(N2 H4 )3 ]Cl2 are formed
exclusively (with the negligible amount of Ni(N2 H4 )2 Cl2
and [Ni(NH3 )6 ]Cl2 ) from the reaction with the molar ratio
of hydrazine/Ni2+ = 4.5. The diffraction peaks marked with
() and the vibrational peaks including (NN) of hydrazine
ligands at the frequency of 974 cm1 in Fig. 1c are compa-
rable to the values in the [Ni(N2 H4 )3 ]Cl2 complex reported
in the earlier literature [28,30]. Because the concentration
of hydrazine monohydrate is always higher than that of
the nickel chloride during the dropwise addition, the pur-
ple [Ni(N2 H4 )3 ]Cl2 complex was initially formed regardless
of the molar ratio of hydrazine/Ni2+ . While the subsequent
addition of the nickel chloride solution, the disproportiona-
tion reaction between initially formed [Ni(N2 H4 )3 ]Cl2 and
nickel chloride would induce a formation of Ni(N2 H4 )2 Cl2
complex in the case of lower molar ratio hydrazine/Ni2+ = 2
and 3. In addition to this disproportionation, the decompo-
sition reaction between Ni(N2 H4 )2 Cl2 and free hydrazine
would proceed to form [Ni(NH3 )6 ]Cl2 complex. The hex-
akis(ammonia) nickel chloride complex formation from the
decomposition reaction between Ni(N2 H4 )2 Cl2 and free
hydrazine was reported by the Guo et al. in their synthesis of
[Ni(NH3 )6 ]Cl2 nanotube [33]. As the increasing molar ratio
of hydrazine/Ni2+ , [Ni(N2 H4 )3 ]Cl2 complex can be formed
by the reaction of Ni(N2 H4 )2 Cl2 or [Ni(NH3 )6 ]Cl2 with addi-
tional excess hydrazine. In fact, the XRD patterns and FT-IR
spectra in Fig. 1 shows that the portion of the Ni(N2 H4 )2 Cl2
or [Ni(NH3 )6 ]Cl2 complexes decrease and the portion of
the [Ni(N2 H4 )3 ]Cl2 complex increases as the molar ratio of
hydrazine/Ni2+ is raised from 2 to 4.5.
It is notable that the different products are formed with the
reaction condition. As the reduction reaction will proceed via
these hydrazine complex precursors and the reduction poten-
tials and chemical reactivity of the complexes are supposed to
be different, respectively, synthesis of pure nickel hydrazine
complex should be required to induce a homogeneous reduc-
tion reaction.
374 J.W. Park et al. / Materials Chemistry and Physics 97 (2006) 371378
Fig. 2. The solution temperature profile with reaction time. [Ni2+ ] =
1.585 M, molar ratio for N2 H4 /Ni2+ = 4.5, and NaOH/Ni2+ = 2.66.
3.2. Formation of Ni particles and their reduction
pathway
In conventional process, the reduction reaction of nickel
ion with the hydrazine as a reducing agent in aqueous solution
could be expressed as Eq. (1)
2Ni2+ + N2 H4 + 4OH 2Ni + N2 + 4H2 O
However, in the case of [Ni(N2 H4 )3 ]Cl2 complex, it has
not been known the reduction pathway upon the addition of
NaOH to the [Ni(N2 H4 )3 ]Cl2 complex solution. The tem-
perature profile of the solution with the reaction time upon
the addition of NaOH was represented in Fig. 2. When
the NaOH (molar ratio for NaOH/Ni2+ = 2.66) was poured
into the [Ni(N2 H4 )3 ]Cl2 complex solution (prepared with
molar ratio for N2 H4 /Ni2+ = 4.5), the pink solution turned
to sky blue immediately within 30 s (step I). As the reaction
proceeded, the sky blue solution initially formed gradually
changed to dark cyan, and finally gray blue in 2 min. The
Fig. 3. XRD patterns and FT-IR spectra of the samples at each reaction time. The samples were obtained at (a) 30 s, (b) 2 min, (c) 4 min, and (d) 6 min.
formation of nickel hydroxide during steps I and II was iden-
tified by XRD (Fig. 4a and b) and FT-IR (Fig. 5a and b). The
rapid color change of the solution upon the addition of the
NaOH was due to the formation of nickel hydroxide by the
ligand exchange of Cl ion by OH as following equation:
[Ni(N2 H4 )3 ]Cl2 + 2NaOH Ni(OH)2 + 3N2 H4 + 2NaCl
(2)
The diffraction peaks marked with () in Fig. 3a and
b can be indexed as hexagonal phase of Ni(OH)2 (JCDPS
no. 14-0117). In FT-IR spectra shown in Fig. 3a and b, the
sharp absorption peaks in the region of around 3600 cm1
due to non-hydrogen bonded OH groups and the broad
absorption band centered around 460 cm1 due to the Ni O
stretching vibration can be assigned to vibrational peaks
of Ni(OH)2 . The broad absorption band centered around
3400 and 16001650 cm1 are corresponding to the hydro-
gen bonded OH stretching and H O H bending vibrational
mode of water. In the region of steps III and IV in Fig. 2,
the color of the solution gradually changed to gray (step III)
and black (step IV) with the appreciable evolution of nitrogen
gases due to the reduction of Ni2+ as expressed in Eq. (1). The
formation of metallic nickel particle in steps III and IV was
evidenced by the diffraction peaks marked with () in Fig. 3c
which are characteristic XRD patterns of face centered cubic
(1) metallic Ni phases (JCDPS no. 04-0850). The XRD patterns
of the samples obtained at 8 min. Fig. 3d shows only metallic
Ni phases. Also, there are no absorption peaks correspond-
ing to Ni(OH)2 in the FT-IR spectra of this sample (Fig. 3d).
Therefore, it can be thought that the reduction reaction was
completed in the region IV. The SEM micrographs of the
samples at each reaction time are represented in Fig. 4. The
nanosized nickel hydroxide particles were formed upon the
addition of NaOH as shown in Fig. 4b and c. According to the
Scherrers equation [34], the mean particle sizes of Ni(OH)2
in Fig. 3ac are calculated to be around 4 nm. The dissolu-
tion of these nanosized nickel hydroxides into the solution,
and subsequent reduction by hydrazine would be occurred
 J.W. Park et al. / Materials Chemistry and Physics 97 (2006) 371378
Fig. 4. SEM micrographs of the samples at each reaction time. The samples were obtained at (a) 0 min ([Ni(N2 H4 )3 ]Cl2 complex), (b) 30 s, (c) 2 min, (d) 4 min,
(e) 6 min, and (f) 1 h.
in the next steps. Although the metallic nickel particle can-
not be distinguished from nickel hydroxide in Fig. 4d, the
XRD patterns (Fig. 3c) of this sample shows the formation
of metallic nickel phases in step III. Eventually, fine nickel
powders as shown in Fig. 4e were formed by way of nucle-
ation and growth steps. The crystallite sizes of metallic Ni
powders in Fig. 4d and e are calculated to be about 20 nm.
The particle size, the crystallite size, and the size distribu-
tion between the samples obtained at 6 min and 1 h are nearly
identical. No difference in mean particle size and crystallite
size between those two samples indicates that the growth of
the nickel particles is completed within 6 min.
It is notable that the catalytic decomposition reaction of
remaining hydrazine at the surface of nickel particles cannot
be ruled out in the (bd) steps in Fig. 4. The decomposition
of hydrazine at the surface of nickel nanoparticle is reported
by Wu and Chen [16] as following equation:
N2 H5 OH 2H2 + N2 + H2 O
375
In fact, the generation of hydrogen gas in the course of our
reduction reaction was evidenced by GCMS analysis. The
surface of nickel might be refreshed by this catalytic decom-
position of hydrazine, which can induce surface smoothing
of nickel particles.
3.3. The effect of nickel hydrazine complex
concentration
The effects of nickel hydrazine complex concentration
on the formation of nickel powders were investigated. The
reduction reactions were carried out with molar ratio for
Ni2+ :N2 H4 :NaOH = 1:4.5:2.66 at 60 C for 1 h. The mean
particle size with standard deviation and SEM micrographs
are shown in Figs. 5 and 6.
It was found that the standard deviation of the parti-
cle size decreased with the decreasing molar concentration
of nickel hydrazine complex. Also, the mean particle size
(3) increased as the concentration of Ni2+ decreased from 1.585
376 J.W. Park et al. / Materials Chemistry and Physics 97 (2006) 371378
Fig. 5. The particle size and size standard deviation of nickel powders from
the various nickel hydrazine complex concentration.
to 1.057 M but almost unchanged between [Ni2+ ] = 0.528 and
1.585 M.
These results can be explained by the reaction rate on the
nucleation. It is known that the average particle size decreases
with increasing the nuclei concentration in the solution due
to suppressing the growth of particles by the formation of
many nuclei in the period of nucleation step. Additionally,
when most nuclei are formed at the same time and grow
at the same rate, the size distribution of resulting particles
will be in the narrow range. In this work, the induction time
for reduction decreased from 10 to 4 min with increasing
the concentration of Ni2+ from 1.107 to 1.585 M. In com-
parison with the rapid solution temperature rising due to
the exothermic redox reaction for [Ni2+ ] = 1.585 M (78 C
Fig. 6. SEM micrographs and XRD patterns of nickel powders prepared from (a) [Ni2+ ] = 0.528 M, (b) [Ni2+ ] = 1.057 M, and (c) [Ni2+ ] = 1.585 M.
in 8 min), the solution temperature gradually rose to 68 C in
18 min for [Ni2+ ]=1.107 M. In these cases, the formation of
smaller number of nuclei in the lower concentration due to
the low solution temperature and low nucleation rate would
induce growth of particles with broad size distribution. How-
ever, in the very low concentration, such as [Ni2+ ] = 0.528 M,
the particle size decreased again with broad size distribution.
Because the solution temperature maintained at 60 C over
the reaction time, the reduction rate might be too low, and
thus considerable amount of unreduced nickel species might
be remained in the solution. Eventually, the final particle size
decreased and the surface roughness increased due to the con-
tamination of unreduced nickel hydroxide as shown in Fig. 6a.
The contamination of unreduced nickel hydroxide in the case
of [Ni2+ ] = 0.528 M can be found in XRD patterns in Fig. 6a.
3.4. The effect of hydrazine concentration and reaction
temperature
To find the effect of the hydrazine concentration on
the morphology of resultant nickel powders, the reduc-
tion reactions were carried out at 60 C for 1 h with the
molar ratio for N2 H4 /Ni2+ = 2, 6, and 8 while maintain-
ing NaOH/Ni2+ = 2.66. The SEM micrographs of resulting
nickel powders are represented in Fig. 7. As the amount of
hydrazine increased, the surface smoothness of the particles
was improved significantly. The smoothening of the surface
roughness with increasing the amount of hydrazine are proba-
bly due to the catalytic decomposition of the excess hydrazine
at the surface of the nickel particle as mentioned in Section
3.2. However, the particle size was not changed apparently
with increasing the amount of hydrazine as shown in Fig. 7.
When the molar ratio of hydrazine to nickel chloride and the
 J.W. Park et al. / Materials Chemistry and Physics 97 (2006) 371378 377

Fig. 7. SEM micrographs of nickel powder from various hydrazine concentrations. [Ni2+ ] = 1.585 M, NaOH/Ni2+ molar ratio is 2.66. N2 H4 /Ni2+ molar ratio
is (a) 2, (b) 6, and (c) 8.

Fig. 8. SEM micrographs of nickel powders from reaction temperature for (a) 55 C (Dmean = 378 98.3 nm), (b) 52 C (Dmean = 304 73.9 nm) (c) 45 C
(Dmean = 201 32.8 nm), and (d) 40 C (Dmean = 148 19.7 nm). [Ni2+ ] = 1.585 M and reaction molar ratio for Ni2+ :N2 H4 :NaOH = 1:6.4:5.1.
378 J.W. Park et al. / Materials Chemistry and Physics 97 (2006) 371378
nickel ion concentration was large enough, the nucleation rate
cannot be further raised, and the number of nuclei held almost
constant with further increasing of hydrazine concentration.
Therefore, the size of the resulting particles was kept at nearly
constant value with the molar ratio of N2 H4 /Ni2+ = 2, 6, and
8. However, the concentration of hydrazine was too high
(molar ratio for N2 H4 /Ni2+ = 8), the non-spherical in shape
and hard agglomerated powders with broad size distribution
were observed as in Fig. 7c.
The effects of the reaction temperature on the resulting Ni
powder were also investigated. As the reaction temperature
was raised, the mean particle size of the Ni powder increased.
This is probably due to the increasing growth rate at the higher
reaction temperature. Eventually, 150, 200, 300, and 400 nm
grade fine nickel powders with narrow size distribution and
low surface roughness could be prepared with the different
reaction temperatures as shown in Fig. 8.
4. Conclusion
Fine nickel powders with narrow size distribution have
been prepared from the reduction of hydrazine complexes in
aqueous solution at 60 C. It was found that the phase and
composition of hydrazine complex used as a precursor in
this work were highly dependent on the synthetic condition.
The pure hydrazine complexes, [Ni(N2 H4 )3 ]Cl2 were pre-
pared with the molar ratio of N2 H4 /Ni2+ = 4.5, while a mix-
ture of complexes, such as Ni(N2 H4 )2 Cl2 , [Ni(N2 H4 )3 ]Cl2 ,
and [Ni(NH3 )6 ]Cl2 were formed with N2 H4 /Ni2+ < 4.5. It
was found that the reduction of Ni2+ to metallic Ni pow-
der proceeded via the formation of nickel hydroxide upon
the addition of NaOH to nickel hydrazine complex solution.
The resulting nickel hydroxide was reduced by hydrazine
liberated from reaction between the nickel hydrazine com-
plex and NaOH. The standard deviation of the particle size
decreased with the decreasing molar concentration of nickel
hydrazine complex while the mean particle size increased.
However, when the concentration of nickel hydrazine com-
plex was too low, the particle size decreased again with the
broad size distribution due to the slow reduction rate. As
the amount of hydrazine increased, the surface roughness
of the particles was improved significantly due to the cat-
alytic decomposition of the excess hydrazine at the surface
of the nickel particle. The particle size was not changed
apparently with increasing amount of hydrazine because
the high concentration of Ni2+ ion in the reaction con-
dition of this work made the number of nuclei to hold
constant.
The advantages of this work for preparing the metallic
powders lie in the narrow size distribution of the resulting
powders, the high yield, and mild reaction conditions. There-
fore, it offers an attractive and convenient process for mass
production.
Acknowledgments
We thank Dr. Hyun Chul Lee and Yong Gyun Lee (Sam-
sung Advanced Institute of Technology) for fruitful discus-
sions.
References
[1] W.J. Tseng, S.Y. Lin, Mater. Sci. Eng. A362 (2003) 160.
[2] D.H. Chen, S.H. Wu, Chem. Mater. 12 (2000) 1354.
[3] S.H. Park, C.H. Kim, Y.C. Kang, Y.H. Kim, J. Mater. Sci. Lett. 22
(2003) 1537.
[4] H. Kishi, Y. Mizuno, H. Chazono, Jpn. J. Appl. Phys. 42 (2003) 1.
[5] Y. Sakabe, Am. Ceram. Soc. Bull. 81 (2002) 24.
[6] Y. Sakabe, Curr. Opin. Solid Mater. Sci. 2 (1997) 584.
[7] I. Burn, G.H. Maher, J. Mater. Sci. 10 (1975) 633.
[8] T.R. Armstrong, K.A. Young, R.C. Buchanan, J. Am. Ceram. Soc.
73 (1990) 700.
[9] H. Kishi, Y. Okino, M. Honda, Y. Iguchi, M. Imaeda, Y. Ohsato, T.
Okuda, Jpn. J. Appl. Phys. 36 (1997) 5954.
[10] D.F.K. Henning, J. Eur. Cream. Soc. 21 (2001) 1637.
[11] J.H. Jean, C.R. Chang, Z.C. Chen, J. Am. Ceram. Soc. 80 (1997)
2401.
[12] K. Yurij, F. Asuncion, R.T. Cristina, C. Juan, P. Pilar, P. ruslan, G.
Aharon, Chem. Mater. 11 (1999) 1331.
[13] S. Illy, O. Tillement, F. Machizaud, J.M. Dubois, Philos. Magn. A
79 (1978) 1021.
[14] S. Komarneni, R. Pidugu, Q.H. Li, R. Roy, J. Mater. Res. 10 (1995)
1687.
[15] B. Xia, I.W. Lenggro, K. Okuyama, J. Am. Ceram. Soc. 84 (2001)
1425.
[16] S.H. Wu, D.H. Chen, J. Colloid Interface Sci. 259 (2003) 282.
[17] S.H. Wu, D.H. Chen, J. Chem. Lett. 33 (2004) 406.
[18] K.H. Kim, Y.B. Lee, S.G. Lee, H.C. Park, S.S. Park, Mater. Sci.
Eng. A 381 (2004) 337.
[19] K. Yu, D.J. Kim, H.S. Chung, H. Liang, Mater. Lett. 57 (2003) 3992.
[20] J. Gao, F. Guan, Y. Zhao, W. Yang, Y. Ma, X. Lu, J. Hou, J. Kang,
Mater. Chem. Phys. 71 (2001) 215.
[21] J. Zhang, S. Yang, Q. Xue, J. Mater. Res. 15 (2000) 541.
[22] Y.D. Li, C.W. Li, H.R. Wang, L.Q. Li, Y.T. Qian, Mater. Chem.
Phys. 59 (1999) 88.
[23] D.H. Chen, C.H. Hsieh, J. Mater. Chem. 12 (2002) 2412.
[24] G.N. Glavee, K.J. Klabunde, C.M. Sorensen, G.C. Hadjipanayis,
Langmuir 9 (1993) 162.
[25] G.N. Glavee, K.J. Klabunde, C.M. Sorensen, G.C. Hadjipanayis,
Langmuir 10 (1993) 4726.
[26] G.N. Glavee, K.J. Klabunde, C.M. Sorensen, G.C. Hadjipanayis,
Inorg. Chem. 34 (1995) 28.
[27] B.L. Cushing, V.L. Kolesnichenko, C.J. OConnor, Chem. Rev. 104
(2004) 3893.
[28] D. Nicholls, R. Swindells, J. Inorg. Nucl. Chem. 30 (1968) 2211.
[29] C. Battistoni, G. Mattogno, A. Monaci, F. Tarli, J. Inorg. Nucl. Chem.
32 (1970) 2313.
[30] G.A. Konin, A.M. Bolshakov, L.V. Khmelevskaya, Russ. J. Coord.
Chem. 22 (1996) 928.
[31] A. Braibanti, F. Dallavalle, M.A. Pellinghelli, E. Leporati, Inorg.
Chem. 7 (1968) 1430.
[32] K.H. Schmidt, A. Muller, Coord. Chem. Rev. 19 (1976) 41.
[33] L. Guo, C. Liu, R. Wang, H. Xu, Z. Wu, S. Yang, J. Am. Chem.
Soc. 126 (2004) 4530.
[34] H.P. Klug, E.A. Leory, X-ray Diffraction Procedure, Wiley, New
York, 1974, p. 656.