Anda di halaman 1dari 14

International

Journal of

Nanoparticles
Volume 3, No.2, 2010

Publishers website: www.inderscience.com


Email: editorial@inderscience.com
ISSN(Online) 1753-2515
ISSN(Print) 1753-2507
Copyright Inderscience Enterprises Ltd
No part of this publication may be reproduced stored or transmitted in
any material form or by any means (including electronic, mechanical,
photocopying, recording or otherwise) without the prior written
permission of the publisher, except in accordance with the provisions of
the Copyright Designs and Patents Act 1988 or under the terms of a
licence issued by the Copyright Licensing Agency Ltd or the Copyright
Clearance Center Inc.
Published and typeset in the UK by Inderscience Enterprises Ltd

Int. J. Nanoparticles, Vol.3, No.2, 2010

Contents
93

Effects of current density on copper nanoparticle prepared by


electrochemical method
Jianlin Xu, Jidong Chen, Shuhua YangLihui Zhang and Jianbang Lu

104

Size-controlled preparation of ruthenium nanoparticles using polyaromatic


amine-containing compounds as hydrogenation nanocatalyst precursors
Katarzyna Morawa Eblagon, Teresa Valdes-Solis, K.M. Kerry Yu,
Anibal J. Ramirez-Cuesta, Shik Chi Tsang

123

Optimal synthesis and nitrate and mercury removal ability of


microemulsion-made iron nanoparticles
M. Shekarriz, S. Taghipoor, F. Haji-Aliakbari, M. Soleymani-Jamarani,
R. Kaveh-Ahangar, M. Eslamian

138

Effects of magnetic field on Rashba spin-orbit interaction in spin dependent


resonant transmission in a ZnSe/Zn1-xMnxSe heterostructure
A. John Peter

149

Temperature dependent thermal conductivity enhancement of copper oxide


nanoparticles dispersed in propylene glycol-water base fluid
M.T. Naik, G. Ranga Janardhana

160

Potential energy curves, permanent and transition dipole moments for


numerous electronic excited states of CaAr
Walid Gaied, Brahim Oujia

173

Structure and magnetic properties of nano-sized HoFe2O4 material


A. Jaafar, A. Al-Saie, M. Bououdina

179

Protein-loaded chitosan nanoparticles modulate uptake and antigen


presentation of hen egg-white lysozyme by murine peritoneal macrophages
S. Madrigal-Carballo, M. Esquivel, M. Sibaja, J. Vega-Baudrit

192

Gelation rate of silica nanoparticles at different supersaturation with and


without ammonium fluoride additive
E.A. Abdel-Aal, M.M. Rashad, R.M. Mohamed

Int. J. Nanoparticles, Vol. 3, No. 2, 2010

Effects of current density on copper nanoparticle


prepared by electrochemical method
Jianlin Xu*
State Key Laboratory of Gansu Advanced Non-Ferrous Metal Materials,
Lanzhou University of Technology,
Lanzhou 730050, China
and
Key Laboratory of Non-Ferrous Metal Alloys and Processing,
The Ministry of Education,
Lanzhou University of Technology,
Lanzhou 730050, China
E-mail: ggdjlxu@sina.com
E-mail: xujl@lut.cn
*Corresponding author

Jidong Chen
ShaoXing Testing Institute of Quality Technical Supervision,
ShaoXing 312017, China
E-mail: chenjd421@163.com

Shuhua Yang and Lihui Zhang


State Key Laboratory of Gansu Advanced Non-Ferrous Metal Materials,
Lanzhou University of Technology,
Lanzhou 730050, China
E-mail: yangshuhua78@163.com E-mail: v208@foxmail.com

Jianbang Lu
Heat Treatment Workshop of Forging Plant,
China National Erzhong Group Co.,
Deyang 618000, China
E-mail: lujianbang2009@163.com
Abstract: Copper nanoparticles are prepared by electrochemical method with
various current density in emulsion containing sodium dodecyl sulfate,
tween80, dodecyl mercaptan, CuSO45H2O. The resulting copper nanoparticles
are investigated by XRD, TEM and FT-IR. The result shows that great changes
have taken place in the size, the dispersibility, and the distribution of particles
size as the current density goes up. According to analysis, it can be found that
the copper nanoparticle can be obtained in smaller size, better dispersibility and
narrower distribution of particle size under the current density of 0.01 A/cm2.
At the same time, current density eventually affects the size of the
nanoparticles as well as overpotential and the size of water droplet.

Copyright 2010 Inderscience Enterprises Ltd.

93

94

J. Xu et al.
Keywords: current density; copper; nanoparticle; emulsion; electrochemical.
Reference to this paper should be made as follows: Xu, J., Chen, J., Yang, S.,
Zhang, L. and Lu, J. (2010) Effects of current density on copper nanoparticle
prepared by electrochemical method, Int. J. Nanoparticles, Vol. 3, No. 2,
pp.93103.
Biographical notes: Jianlin Xu is a Professor at State Key Lab of Gansu New
Non-Ferrous Metal Materials of Lanzhou University of Technology of China.
His main areas of researching are new metal materials and computer
application in materials. He has accomplished eight research projects planned
by Gansu Province of China. More than 40 research papers have been
published. He is a Technology Committee Member of Chinese Heat Treatment
Society, and was awarded The 555 Innovative Researcher of Science and
Technology by Gansu Province of China.
Jidong Chen is an Engineer at ShaoXing Testing Institute of Quality Technical
Supervision of China. He obtained his Masters degree from Lanzhou
University of Technology of China in 2009. His main area of research is
nano-particles preparation.
Shuhua Yang obtained his BSc from Inner Mongolia University of Technology
in 2008. He is a Master candidate as student under the direction of Dr. Xu. His
current research direction is material science and preparation of nanomaterials.
Lihui Zhang obtained his BSc from Henan University of Science &
Technology in 2006. He is a Master candidate as student under the direction of
Dr. Xu. He is now working mainly on nano-powder preparation.
Jianbang Lu is an Associate Engineer at China National Erzhong Group Co. of
China. He completed his Bachelors degree as a graduate student at Lanzhou
University of Technology of China in 2008. His current research direction is
metal materials engineering.

Introduction

Nanometre metal material performs satisfactorily in the fields of lubrication,


electromagnetism, absorbing material, magneto fluid, catalyse, sensing element, adding
toughness to ceramics, biomedicine, combustion supporting and so on. To grant potential
values of application to the nanometre metal material is a new direction for material
research and chemical engineering research. And great importance is universally attached
to this field by the academic circles of material science, physics, chemistry and industry
(Edelstein et al., 1997; Braos et al., 2003; Takimoto et al., 2004; Andrievski and Glezer,
2001).
With their unique performance, the applications of Cu nanoparticles span over
catalyst, electron conduction slurry, microelectronics, metal alloy, solid lubricant, and so
on. In recent years, the researches on the preparation, the performance and the application
of nanoparticles of Cu are paid great attention both at home and abroad, with the value in
theory and in practice.
Now, the main methods to produce Cu nanoparticles have been categorised as gas
phase evaporation (Huang et al., 2003), plasma (Bica, 1999), machine-chemical (Ding et

Effects of current density on copper nanoparticle

95

al., 1996), sol-gel (Epifani et al., 2001), inverse microemulsion (Cason et al., 2001),
chemical reduction (Wu and Chen, 2004), microwave irradiation (Tu and Liu, 2000),
supercritical extraction (Ziegler et al., 2001) and so on. But since Cu is relatively low in
redox potential, easy to be oxidised, and bad in outcome dispersibility without a modified
stabiliser, especially when more expensive strong reducing materials like NaBH4 reacted
with cupric salt, in liquid phase reducing method, more cost outcome and more serious
pollution of environment result. At the same time, it is indeed a complicated process to
declutch nanometre particles of Cu from reducing materials. So all the methods
mentioned above are not idealistic.
The preparation of copper nanoparticle by electrochemical deposition is an
environmentally better process. Besides, the as-prepared copper nanoparticle is deposited
on the electrode surface, which is easy to collect. At present, the copper nanoparticle
prepared by the electrochemical method is dendrite, some researches indicate that the
fractal growth is a diffusion limited aggregate and its activity is also weaker than that of
spherical copper nanoparticle (Zhu et al., 2000; Jacob and Garik, 1990). Our team
adjusted the preparing technique after a preliminary research, and spherical copper
nanoparticle are prepared by electrochemical process.
The initial research shows that the current density, the main salt solubility, the value
of pH, and the added organic solvent can affect the shape of the final copper nanoparticle
in the process of the preparation of copper nanoparticle by electrochemical method. In the
paper, spherical copper nanoparticle is prepared by electrochemical method in containing
sodium dodecyl sulfate, tween80, dodecyl mercaptan, CuSO45H2O and various current
density. The effects of current density on final copper nanoparticle, chemical mechanism
of surface dispersant and current density were investigated.

Experimental

2.1 Chemicals
There are some chemicals as follows: bluestone (CuSO45H2O, AR grade), dodecyl
mercaptan (C12SH, 96%, CP grade), sodium dodecyl sulfate, tween80 and absolute
ethanol. All the organic solvents in the experiments were analytically pure and were used
without further purification. Deionised and distilled water was used in the work.

2.2 Preparation of copper nanoparticles


First, Primrose emulsions containing sodium dodecyl sulfate, tween80, dodecyl
mercaptan and CuSO45H2O were mixed into well-proportioned light yellow emulsion by
magnetic stirrer. Then, titrate it to 1.0 of pH by using strong sulphuric acid.
Secondly, using this emulsion as electrolyte, pure copper as anode with its acreage being
2 cm 4 cm and stainless steel net as cathode with its acreage being 3 cm 8 cm, space
between the two patches being about 4550 mm, electrolysis time being 60 min. After
this, cathode is cleaned in an absolute ethanol ultrasonic bath for five minutes. Then some
brown solid powder was collected and repeatedly cleaned with absolute ethanol. Finally,
the solid powder was dried by DZF-6050 vacuum drying cabinet for two hours. Hereto,
spherical copper nanoparticles were obtained. Properties of the copper nanopaticle
prepared in various current densities are presented in Table 1.

96

J. Xu et al.

Table 1

Preparation conditions and properties of the copper nanopaticle


Precursor amount
CuSO4 (mol/L)

Current
density
(A/cm2)

R1

0.05

0.05

R2

0.05

R3

Average
particle
size(nm)

Particle size
distribution(nm)

SDS + Tween80;
1g + 5ml

35

2040

0.075

SDS + Tween80;
1g + 5ml

35

2050

0.05

0.10

SDS + Tween80;
1g + 5ml

25

1540

R4

0.05

0.125

SDS + Tween80;
1g + 5ml

70

40100

R5

0.05

0.15

SDS + Tween80;
1g + 5ml

75

6090

R6

0.05

0.175

SDS + Tween80;
1g + 5ml

110

80150

Sample

Modifier amount

2.3 Sample analysis


Phases of the copper nanoparticle was analysed using Japan Rigaku D8 ADVANCE
X-ray diffraction with Cu-K radiation ( = 0.1540598 nm). The particle size and
morphology were characterised using a HITACHI H-600 transmission electron
microscope (TEM). The process of TEM samples were as follows: First, copper
nanoparticles was dissolved in absolute ethanol with ultrasonic for 20 minutes. Then,
deposit them on a carbon-coated TEM grid. Lastly, the copper nanoparticle was observed
by the TEM when absolute ethanol was volatilised completely. Infrared absorption
spectrum of copper nanoparticles was examined by an infrared spectroscopy of Fourier
transform (NICOLEF FTIR-360 FTIR). Measured sample and KBr powder were evenly
mixed and dried by infrared light, then were pressed into flake. The infrared analysis was
made using pure KBr flake as background.

Results analysis

3.1 XRD analysis


Figure 1 shows the spherical copper nanoparticle X-ray diffraction in different current
density. According to Figure 1, it can be found that diffraction peaks with strong
intensities appear at 2 = 43.3, 50.4 and 74.1 assign to the (111), (200) and (220)
crystal diffractions plane of metal copper (fcc), respectively. Therefore, the as-prepared
nanoparticles are copper powder with face-centred cubic structure. Furthermore, no other
oxide diffraction peaks of copper appear in XRD, which means spherical copper powders
are not oxidised in the air. It is because of the absorption of organic compounds on the
surface of copper powder, so as to improve its stability.

Effects of current density on copper nanoparticle


Figure 1

X-ray diffraction patterns of the copper sample of R1, R2, R3, R4, R5 and R6

Figure 2

TEM images of the copper sample of R1, R2, R3, R4, R5 and R6

97

98

J. Xu et al.

3.2 TEM analysis


Figure 2 shows TEM photos of copper nanoparticle prepared in different current density.
It can be seen from Figure R1 and Figure R2 that distribution of copper nanoparticles are
more even with smaller spherical particles, an average diameter of about 35 nm and no
clear aggregation. In Figure R3, the copper nanoparticles are well-distributed with no
aggregation, the average diameter being about 25 nm. They are better in distribution of
particle size than other samples. In Figure R4, the copper nanoparticles take an average
diameter of about 70 nm, they distributed unevenly. In Figure R5 great aggregation
appears, the grain looks like ball, some take the shape of triangle, stick or polygon. In
Figure R6, the grain is much bigger than those in the other photos and could not be seen
clearly. This may be results from too much coating agent on the surface. From the above
analysis, 0.10 A/cm2 of current density is the best process parameter to prepare copper
nanoparticles.

3.3 Infrared absorption spectrum analysis


Figure 3 is the infrared absorption spectrum of dodecyl mercaptan and samples prepared
under different current density. In Figure 3, curve (1) is the infrared absorption spectrum
of dodecyl mercaptan and curve (2) is the infrared absorption spectrum of R1, R2, R3,
R4, R5, R6, respectively. According to curve (1) of Figure 3(a), it can be found that the
peak at 2,955cm1 is belongs to the CH3 dissymmetry stretching vibration, and peaks at
2,853cm1 and 2,924cm1 of CH2 to symmetric stretching vibration and absorbing
appeared, respectively. The peak at 1,493cm1 is corresponded to the CH2 distortion and
wagging vibration-absorbing and this absorbing peak belongs to CH3 shearing
vibration. The absorption peak at 721 cm1 is belongs to vibration-absorbing peak of
sulphate compound. The curve (2) is the infrared absorption spectrum of R1
sample in the Figure 3(a) when surface dispersant is dodecyl mercaptan and current
density is 0.05 A/cm2. There are several peaks at 2,947 cm1, 2,917 cm1, 2,845 cm1 and
1,469 cm1 of the spectrum. There are several peaks at 2,917 cm1, 2,848 cm1 and
1,498 cm1 of the absorption spectrum of R2 sample with dodecyl mercaptan as surface
dispersant and 0.075 A/cm2 of current density in the Figure 3(b). The characteristic peaks
of R3 sample appears obviously at 2,952 cm1, 2,918 cm1, 2,848 cm1, 1,465 cm1 and
723 cm1 with dodecyl mercaptan as surface dispersant and 0.10 A/cm2 of current
density in the Figure 3(c). When surface dispersant is dodecyl mercaptan and current
density is 0.125 A/cm2, the characteristic peaks of the spectrum line of R4 emergence at
2,914 cms1 and 2,843 cms1 as showed in Figure 3(d). Using the same surface dispersant
with 0.15 A/cm2 and 0.175 A/cm2 of current density, the characteristic peaks of R5
appears at 2,953 cm1, 2,919 cm1, 2,848 cm1, 1,466 cm1 and 719 cm1 and that of R6
appears at 2,919 cm1, 2,850 cm1, 1,465 cm1 and 717 cm1, respectively, as showed in
Figure 3(e) and Figure 3(f). Compared curve (2) of the as-prepared Cu nanoparticles with
curve (1) of pure dodecyl mercaptan in Figure 3, the characteristic peak of coating agent
(namely dodecyl mercaptan) still exists, but can present some excursion due to coating
agent absorption and combination with copper nanoparticle, which is due to of fewer
surface atoms and higher surface energy of copper nanoparticle.

Effects of current density on copper nanoparticle


Figure 3

99

Fourier transformation infrared absorption spectra of dodecyl mercaptan solution and


the nanoparticle R1, R2, R3, R4, R5 and R6 under different current density (see online
version for colours)

100

J. Xu et al.

Discussion

4.1 Analysis of the current density on copper nanoparticles


According to the electrolysis principle, as to certain electrolyte, an upper and lower limits
range of current density is often allowed to use. If this range is exceeded, crystallisation
layer, not particulate matter will be formed. The current density exerts a great influence
on thickness of the crystallisation. When the current density is lower than that of the
lower limit of the current density, the crystallisation is thicker; this is because of low
current density and small overpotential and slow formation of crystal nucleus, so that
only a few crystals grow up. With the increase of the current density, and the
overpotential, when the upper limit of the current density is reached, the formation of
crystal nucleus speeds up notably, the crystallisation is relatively thin. When the current
density exceeds the upper limit of the current density, because there is few discharging
ion near the cathode, usually discharging occurs in the raised angle and salient part, and
nodulation or dendrite as well. If the current density continues rising, because hydrogen
evolution makes cathode region pH value rise, the basic salt or the hydroxide will form,
these materials will be absorbed or mixed with near the cathode and inhibitory coating, so
as to form the spongy precipitate.

4.2 Function of emulsion in preparing nanometre copper powder


The copper nanoparticles prepared by the simple sulphate system has accumulated a large
number of positive and negative electric charges on its surface because after the getting
thinning order of magnitude of nanometre of particle. The particle shape is extremely
irregular, the surface energy is with not energy stable state, and acting force between
particles like Van der Waals force makes it easy for them to aggregate and reach stable
state, so as to cause the aggregation of large number of nanoparticle. To this situation, we
substitute electrolytic emulsion for the single electrolytic liquid to carry out the reaction.
Before or at the beginning of reduction of particles, surfactant in the form of micelles in
the emulsion can makes the better separation of participles thus, prevents their
aggregation effectively (lipophilic group assembles within the micelles, and hydrophilic
group base moves towards water). Mechanism can be seen Figure 4, among which:
a

is electrolytic emulsion before reaction, it reaches temporary balance under the


repulsion of electric charges and Van der Waals force

is the ultra thin powder particles surrounded by emulsion drops when the reaction
happens; when in order to reflect that happens, the ultra thin powder body particle
produced is surrounded by the emulsification drop

Because of the relative instability of thermodynamics of the emulsion, in order to


reduce the free energy in the system, the emulsion drops collide with the ultra thin
powder body each other and cause the subsiding flocculation adsorption and
aggregation of emulsion, in the course of core shape and, crystallisation of the
powder, the poor conductor coatings formed on the metal crystal nucleus.

Because the spherical surface area is minimum, and the interface tension is relatively
lower, the powder membrane changes from (c) to (d) in form, up to now, the metal
crystal nucleus stop further growing and aggregating because of prevention of covering

Effects of current density on copper nanoparticle

101

coat. As a result, little and steady nanoparticles are available. The surface dispersant is
not a simple physical absorption on the surface of copper nanoparticle, but there is strong
adsorptive action between them due to some bridge oxygen chemical bond of c-o-c, c-o
and s = o in the surface dispersant and copper nanoparticles. The absorption can be
verified by infrared absorption spectra diagram. For example, when copper adsorbed
nanoparticle dodecyl mercaptan, its characteristic peaks take place some excursion as
showed in Figure 3(a). The peak at 2,955 cm1 of CH3 shifts to 2,947 cm1, the peak of
CH2 changes from 2,924 cm1 and 2,853 cm1 to 2,917 cm1 and 2,845 cm1, respectively.
And the distortion and wagging vibration-absorbing peak of CH2 removes to
1,469 cm1.The peak at 721 cm1 of sulphate compound also changes. Same phenomenon
also appear in infrared absorption spectra diagram of other samples, as shown in
Figure 3(b), Figure 3(c), Figure 3(d), Figure 3(e) and Figure 3(f). Therefore, the result of
the strong adsorption is forming a coating of dodecyl mercaptan on the surface of copper
nanoparticles. The surface coating not only can obstruct oxidation, but also can repress
the growth of copper nanoparticles. The structure of absorbed dodecyl mercaptan do not
changed, which is validate by Figure 3. All long carbon chain alkenes part and relevant
absorption of functional group of samples still exist with no obvious variation, which
showed that all the prepared samples include ligands, and have no variation in structure.
Besides, the table taking appeared in 1,150 cm11,400 cm1 is belongs to the curve and
shake-vibration of the dodecyl mercaptan, and in the area bands is often used as an
effective evidence that the alkyl chain rule is exactly arranged of the dodecyl mercaptan.
Figure 4

Schematic diagram of coating mechanism of powder particle

(a)

(b)

(c)

(d)

4.3 effect of current density on nano-copper prepared by the emulsion


Emulsion is composed of surfactants, aid-surfactants, oil (usually hydrocarbons), water
(or electrolyte solution) ordinarily. Small puddle in emulsion is surrounded by
monolayer of surfactants and aid-surfactants, so as to form emulsion particles, which are
sphericity or polygon, the size of which is between dozens and hundreds of nano.
Emulsion particles are in continuous Brownian motion, taking advantage of
self-dissociation and absorption makes particle itself electrically charged. In a collision
with other particles, the hydrocarbon chain of surfactant and aid-surfactant forming
interface get to another particle infiltrate each other, at the same time, materials in puddle
can pass through the interface, and so that the reaction happens. As the reaction occurred
in tiny water nuclear, and the growth of reaction product is restricted by radius of water
nuclear, therefore, the size of water nuclear directly determines the size of the
nano-powder.

102

J. Xu et al.

When DC current passes into the emulsion prepared, dissociation will take place in
emulsion itself, so will the copper anode under the reaction of electrolyte solution and
electric current. As the time goes by, there will be a large number of ionising Cu2+ and
free electrons in solution, and the water in the solution will be electrolysed so as to
produce H+ and OH, as well as free electrons. Thus, a large number of free electrons,
emulsion surfactant ion in the emulsion are adsorbed on the interface; the hydrophobic
part is inserted into Oil phase, polarity in phase of water, forming pervasion dual-layer
with Cu2+. As some of the charged particles get together to, form a certain electrical
energy barrier, or large number of potential difference, result in all the system so that
surfactant ion adsorption is greatly enhanced. With enhance absorption, the surface
molecules movement can be easily carried out from lower surface tension to higher one.
Therefore, the nuclear membrane coating of water is pressed and thickened under larger
surface tension so as to make the size of puddle relatively smaller, which supply a
nano-size environment for nano-copper formation. The variational trend of average
particle size with changing current density reflected the circumstance in Table 1. The
average particle size minishes from 35 nm to 25 nm as current density increases from
0.05 A/cm2 to 0.10 A/cm2; But when the current is too strong and exceeds a certain limit,
the influence of over the potential impact will be dominant, surfactant activity in
emulsion will be greatly decreased, and the goal of restraining copper particles growth is
beyond expectation. In Table 1, beyond 0.10 A/cm2 of current density, the average
particle size shows an increasing trend with increasing current density. The morphology
of resulting copper nanoparticles are shown in Figure 3.
From the analysis above we can learn that the influence of current density to an
average electrolyte process is more obvious and direct. With the help of inter-reaction of
surfactant and dispersant agents, emulsion plays an important role in the electrochemical
preparation of nano-copper powder, coating nanoparticle and prevention of their
aggregation. Also, the influence of current density on water nucleus size indirectly affects
the particle size of powder.

Conclusions

Copper nanoparticles were prepared by electrochemical method and different current


density in emulsion mixed with sodium dodecyl sulphate, tween80, dodecyl mercaptan
and certain concentration of CuSO45H2O. It can be concluded by analysis of XRD, TEM
and FT-IR.
1

on condition that there is no technique change, current density is about 0.1 A/cm2,
spherical nanoparticles are available with small size, distribution of particles size and
good separation.

current density works in potential and water nucleus size respectively, finally affects
particle size of nano-copper.

Acknowledgements
The work was supported by Doctor Research Fund of Lanzhou University of
Technology.

Effects of current density on copper nanoparticle

103

References
Andrievski, R.A. and Glezer, A.M. (2001) Size effects in properties of nanomaterials, Scripta
Materials, Vol. 44, Nos. 89, pp.16211642.
Bica, I. (1999) Nanoparticle production by plasma, Mater. Sci. Eng. B, Vol. 68, No. B, pp.59.
Braos, G.P., Mairelles, T.P., Rodriguez, C.E. and Jimenez, L.A. (2003) Gas-phase hydrogenation
of acetonitrile on zirconium-doped mesoporous silica-supported nickel catalysts, Journal of
Molecular Catalysis A: Chemical, Vol. 193, Nos. 1/2, pp.185181.
Cason, J.P., Miller, M.E., Thompson, J.B., et al. (2001) Solvent effects on copper nanoparticle
growth behavior in AOT reverse micelle systems, Journal of Physics and Chemistry B,
Vol. 105, No. 12, pp.22972302.
Ding, J., Tsuzuki, T., McCormick, P.G., et al. (1996) Ultrafine Cu particles prepared by
mechanochemical process, Journal of Alloys and Compounds, Vol. 234, No. 2, pp.L1L3.
Edelstein, A.S., Murday, J.S. and Rath, B.B. (1997) Challenges in nanomaterials design, Progress
in Materials Science, Vol. 42, Nos. 14, pp.521.
Epifani, M., De, G. and Licciulli, A. (2001) Preparation of uniformly dispersed copper nanocluster
doped silica glasses by the sol-gel process, Journal of Materials Chemistry, Vol. 11,
pp.33263332.
Huang, J., Ren, S. and Xie, C. (2003) Nanocrystalline powder copper prepared by reduction in
aqueous solution, Journal of Materials Science & Engineering, Vol. 21, No. 1, pp.5759.
Jacob, B. and Garik, P. (1990) The formation of patterns in non-equilibrium growth, Nature,
Vol. 348, pp.523528.
Takimoto, M., Nakamura, Y., Kimura, K. and Mori, M. (2004) Highly enantioselective catalytic
carbon dioxide incorporation reaction: nickel-catalyzed asymmetric carboxylative cyclization
of bis-1,3-dienes, Journal of the American Chemical Society, Vol. 126, No. 129,
pp.59565957.
Tu, W. and Liu, H. (2000) Continuous synthesis of colloidal metal nanoclusters by microwave
irradiation, Chemical Materials, Vol. 12, No. 2, pp.564567.
Wu, S.H. and Chen, D.H. (2004) Synthesis of high concentration Cu nanoparticles in aqueous
CTAB solutions, Journal of Colloid and Interface Science, Vol. 273, No. 1, pp.165169.
Zhu, J.J., Liu, S., Gedanken, A., et al. (2000) Shape-controlled synthesis of silver nanoparticles by
pulse sonoelect rochemical methods, Langmuir, Vol. 16, No. 16, pp.63966399.
Ziegler, K.J., Doty, R.C., Johnston, K.P., et al. (2001) Synthesis of organic monolayer stabilized
copper nanocrystals in supercritical water, Journal of the American Chemical Society,
Vol. 123, No. 32, pp.77977803.