Colloids and Surfaces

A: Physicochemical and Engineering Aspects 202 (2002) 155– 163

www.elsevier.com/locate/colsurfa

Metalcontaining nano-particles within polymeric matrices:

preparation, structure, and properties
S.P. Gubin *
N.S. Kurnako6 Institute of General and Inorganic Chemistry, Russian Academy of Sciences, 31 Leninsky Prospect,
117907 Moscow, Russia
Received 12 July 2000; accepted 16 March 2001

Abstract

A universal method of introduction of metal-containing nano-particles in polymeric matrices has been developed,
which allows for the fabricating of large amounts (kilogram-scale) of polymeric nanoparticles composites. The
encapsulation was done by thermal decomposition of metalcontaining compounds (MRn ; M= Cr, Mo, W, Ti, Zr, Fe,
Co, Ni, Pd, Pt, Cu; R=CO, HCOO, CH3COO, C6H5CH2) in solution melt of polymer (polyethylene, polypropylene,
polytetrafluoroethylene, polyamide, polyarylate, polycarbonate, polysterene, polyethers, polyphenyleneoxide, silox-
ane). Particle size measurement (2–10 nm) and magnetic properties showed that the material really contained the
nanoparticles, which were retaining their unique properties. © 2002 Elsevier Science B.V. All rights reserved.

Keywords: Polymer nanocomposite; Nanoparticles; Magnetic properties

1. Introduction technologies. As is well known, some of the

Nanometer size structures are an intermediate
form of matter, which fills the gap between atoms/
molecules and bulk materials. Often, these types
of structures exhibit exotic physical and chemical
properties different from those observed in bulk
three-dimensional (3-D) materials. The properties
associated with nanoscale particles have been the
subject of a number of recent reviews and publica-
tions [1–4]. This interdisciplinary field of meso-
scopic and nano-scale systems is important to
fundamental physics, as well as for some new
* Tel.: +7-954-71-36; fax: +7-954-12-79.
E-mail address: gubbin@rambler.ru (S.P. Gubin).
metallic nano-particles are thermodynamically un-
stable and chemically very reactive. For many
technological applications, materials with
nanoparticles embedded in a matrix are impor-
tant. In this paper for the stabilization of nano-
particles the matrices of the ‘simplest’ organic
polymers as polyethylene it is used.
The preparation in the kilogramme scale of
uniform polymermetallic nanomaterials using
conventional techniques is rather difficult. The
creation and future utilization of such types of
nano-size systems require the development of new
technological processes.
Colloidal dispersions of inorganic materials in
different polymer media have classically been pre-

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156 S.P. Gubin / Colloids and Surfaces A: Physicochem. Eng. Aspects 202 (2002) 155–163
pared by attrition, milling and precipitation from
nonsolvents or from supersaturation solutions [5–
7]. The role of macromolecules in these processes
has been that of a dispersing and stabilizing
agent. But these methods are not applicable for
fabrication of the particles with diameter as small
as 1–10 nm.
We have recently found that it is possible to
introduce nanoparticles into ordinary polymers
like polyethylene. As a rule such nanoencapsula-
tion is done using solution/melt of polymer in
hydrocarbon oil. For introduction of nano-parti-
cles in polymeric matrixes these were used for
their formation in situ as a result of high velocity
thermodestruction of metalcontaining (including
organometallic) compounds (MCC). The opti-
mum conditions are developed for the decomposi-
tion of MCC in order to introduce complicated
and highly reactive nanoparticles into the poly-
meric matrix. For the subsequent characterization
we have used small-angle X-ray scattering
(SAXS), X-ray RED, EXAFS, X-ray emission
spectroscopy and Mossbauer effect measurements
in combination.
In some case the physical properties of the
obtained material are nontrivial.
Generally, the electrical and magnetic behavior
of nano-structured systems is governed by both
the intrinsic properties of the nano-structures and
their interactions with the matrix. Thus, the mag-
netic behavior of the system can be controlled by
the size, shape, chemical composition and struc-
ture of the nano-particles and/or by the nature of
the matrix in which they are embedded.
Magnetic particles in the nano-meter range
form single magnetic domains in which the mag-
netic moment performs fast fluctuation near an
easy direction (collective magnetic excitations), as
well as, slower fluctuation between different easy
directions (superparamagnetic relaxation).
In this article, we report briefly on the magnetic
properties of these nanocomposite materials.
2. Materials and methods
All chemicals and solvents used for the prepara-
tion of samples were reagent grade. Carbonyls,
acetates, formiates and some other classes of co-
ordination compounds, including organometallics
(M= Cr, Mo, W, Ti, Zr, Fe, Co, Ni, Pd, Pt, Cu)
have been used as MCC. The polymer matrix
used in this study is a commercial polymer manu-
factured by Russian Companies and marketed
under the following trade names, PE (low density)
277-020; PE(high density) 153-020 and 108-020;
PP 21012 and 21030; PA 6-120/310 and PA 6-210.
In the typical experiment the solution of MCC
in the volatile organic solvent under on inert
atmosphere has been dropped under strong stir-
ring to solution/melt of the polymer in hydrocar-
bon oil. The temperature of the reaction was
connected with the nature of the polymer and has
been fixed in the interval 200– 260 °C. The sol-
vent and the volatile products of MCC decompo-
sition have been condensed in the cooled
collector. The solid product has been isolated
from the excess of oil after cooling of the reaction
mixture. The residual amounts of oil have been
separated by extraction.
The samples, obtained as dark-colored pow-
ders, was assigned for further structural and phys-
ical investigations. The material were produced in
the form of tablets 1– 4 mm thick and 15–20 mm
in diameter. The samples have been fabricated
with the metal weight concentration in the range
2 –50%, in 2% step.
For the preparation of heterometallic nanopar-
ticles we used as a rule available heterometallic
MCC; in some case labile heterometallic MCC
were prepared in solution immediately before
adding in reaction mixture. For example, the first
samples of polymer-nano-ferrites, PE+ 5%
BaFe2O4 and PE + 5% BaFe12O19 were produced
[8] by the above method.
Elemental analyses were performed in the ana-
lytical laboratory of our institute. The powder
X-ray diffraction patterns of samples were
recorded with CuKa, radiation in the 2q range of
0–35° using a standard X-ray unit.
Our diffraction experiments were performed
with the small-angle camera ‘Frax’, used in a
small-angular version. The X-ray synchrotron ra-
diation (u=1115 A, ) from VEPP-4 (Novosibirsk)
was reflected by monochromator and high-order
reflections were eliminated by means of an X-ray
 S.P. Gubin / Colloids and Surfaces A: Physicochem. Eng. Aspects 202 (2002) 155–163
mirror (Pt-coated melt quartz). All DC magne-
tization measurements were performed on a vi-
brating sample magnetometer PARC-155. The
morphology, particle size and distribution were
investigated using a high-resolution electron mi-
croscope (JEM-100B-1). For the preparation of
samples the powders of nanometallopolymer were
dispersed in water in an ultrasonic bath for 20
min and then a drop of this suspension was
deposited onto a carbon mesh on a copper grid.
3. Results and discussion
3.1. Preparation
Our goal was the creation of large-scale materi-
als, where metalcontaining nanoparticles (d =1 –
10 nm) retained their unique physical properties
and were uniformly distributed. Many properties
of nano-particles are very sensitive to their vol-
ume, therefore, it is vital to have a material with
narrow particle size distribution.
All above-mentioned polymers are semicrys-
talline. Their fine texture is determined by the
size, shape, and orientation of crystallites, and
their distribution, as well as by the structure of
the amorphous regions. The structure of such
polymers is loose, they contain many nano-voids,
which is natural in any polymers. These voids
(nanoreactors) are connected with polymer
molecules packing and located both within and
between crystalline and amorphous parts of mi-
cro-volumes [9,10]. The access of MCC in these
nanoreactors has been achieved because of ‘part-
ing’ of the polymeric chains (lamels) with the
labile short molecules of hydrocarbon oil under
high temperatures and intensive stirring. The pro-
cesses are chematically shown at the Fig. 1.
Nanoparticles were generated by the following
method. MCCs were dissolved in a volatile sol-
vent; the solution droplets were then passed into a
reaction vessel where a chemical reaction took
place to convert the reactants to nanoparticles
having the required composition. Average resi-
dence times were typically few seconds with tem-
peratures of 200– 260 °C. The liquid droplets are
deposited into a heated solution/melt of polymer.
157
The process of forming nanoparticles by droplet
decomposition can be viewed in the simplest case
as the drying of droplets followed by solid and
liquid phase chemical reactions in a nanoreactor-
polymer cavity; the typical examples of MCC
thermal decomposition are:
Cu(HCOO)2 “ Cu + H2O+ CO2 + CO
Ti(C6H5CH2)4 “ Ti +C6H5CH3 + (C6H5CH2)
Fe(CO)5 “ Fe +Fe3C+ CO2 + CO
The process has been organized in such a way,
that thermodestruction of MCC was only in the
polymer volume (a separate metal phase was ab-
sent) and every new drop of MCC solution
reached its own nanoreactor. At high supersatura-
tion, particle formation occurs by homogeneous
nucleation. Nucleation is followed by particle
growth and, for sufficiently high particle concen-
trations, by coagulation and agglomeration. How-
ever, the actual behavior of the system is in many
cases more complicated.
Experiments on kinetic have shown that the
growth of particles occurs simultaneously in many
cavities in all the polymer volume; the number
and the sizes of such cavities are specific to each
polymeric matrix. The semicrystalline polymers
used in this investigation had heterogeneous struc-
tures with lamellar, cylindrical or spherical nano-
domains of different sizes that could serve as
nano-reactors; inside them a variety of nanoparti-
cles could be synthesised in a controlled manner.
Fig. 1. The model of transformation of MCC solution by
dropping of nano-particle.
158 S.P. Gubin / Colloids and Surfaces A: Physicochem. Eng. Aspects 202 (2002) 155–163

This method allows to change the sizes and the

form of obtained nanoparticles in various limits
by different polymeric matrices.
A more homogenous nucleation and growth of
a particles and as a result monotonic distribution
of the particles in the whole volume of the mate-
rial (independent from the concentration of intro-
duced metal) and narrow distribution of the
particles in sizes have been achieved.
It was shown that this method allowed varying
the size from 2 to 10 nm (in some case— bimodal
distribution) and inter-particle distance from 15
down to 9 nm. The particles have a width of size
distribution not more than 30%. In principle, the
method permits to create just as homometal parti-
cles (Fe, Co, Mn, Cr, rare earth) and binary ones
(Fe –Co, Fe –Nd, Co – Sm, Gd – Mn etc.) and
more complex compounds, including oxides
(Mx Oy, M=Fe, Co, Mn), borides, nitrides etc. It
is possible to diversify the type of polymer matrix
too, using polyethylene, polypropylene, polyte- Fig. 2. Diffractogram of samples of PE + Fe, (1) pure PE; (2)
trafluoroethylene, polyamide, polyarylate, poly- 3% Fe; (3) 10% Fe; (4) 30% Fe.
carbonate, polysterene, polyethers, polyphenyl-
eneoxide, siloxane etc. means of diffraction of high-intensity synchrotron
The possibility of the fabrication of nanoparti- radiation. The high-intensity radiation provides a
cles of complex composition, as Nd– Fe –B, possibility to register very fine diffracted features
SmCo5, ferrites, also has been studied. related to minor variations in the chemical com-
Nanoparticles of ferrites have been generated position of metalcontaining polymers. On the ex-
by the thermodestruction of a solution a variety ample Fe-containing polymers it was shown that
of precursors in solution/melt of polymer. They the diffraction patterns of the above samples were
include oxalates, acetates, alkoxides and formi- essentially the same (a shoulder in the second
ates. The composition of the produced nanoparti- reflection from the larger scattering angles) as
cles was exactly corresponded the composition of known for amorphous Fe [11].
the initial solution [9,10]. Let us consider the structure of nanoparticles,
polymeric matrices and their interaction in
3.2. Structure detail.

The X-ray diffraction study showed that all 3.2.1. Nano-particles

samples are X-ray amorphous. This means that
the size of the nano-particles is less than 10 nm.
As it is seen from the Fig. 2, the routine diffrac-
tograms are poor in information and besides the
peaks of initial polymer did not contain other
peaks, which were known for the crystallites of
the corresponding metal and its simplest
derivatives.
The short-range order structures in metalcon-
taining polymers have been investigated now by
Transmission electron microscopy (TEM) car-
ried out in different imaging modes allows one to
check the sample morphology, i.e. the size and
shape distributions of nano-particles, and to eval-
uate their separation. In the morphological study
of the metalcontaining specimens, it was impor-
tant to check first that the observed objects were
really nano-particles and also to locate precisely
the boundary of each particle to determine accu-
rately the particle size and shape distribution [12].
 S.P. Gubin / Colloids and Surfaces A: Physicochem. Eng. Aspects 202 (2002) 155–163
On Fig. 3, one can see the area of polymeric
lamella, which has the structure of parallel de-
posited polymer chains; they are also separated
enough regular dark inclusions. The estimation of
media sizes of the particles gives the value 3.69 1
nm. The TEM analyses show that the present
matrix synthesis, under the condition described
above, favors the formation of nonequiaxial parti-
cles with ellipsoid shape. On the other photo-
graphs a few larger particles with a media size
892 nm are noticed alongside with the basic
particles. The observable picture is not in opposite
to the preliminary results, obtained by SAXS.
The SAXS studies evidenced particles regularly
dispersed in the polymer matrix with narrow log-
normal size bimodal distribution centered around
3.290.3 nm (more than 80% particles from total
quantity) and 8 nm (91 nm) (see Fig. 4).
Fig. 3. (a) The TEM micrograph of Co particles into
polyethylene matrix (1 cm = 10 nm). (b). The log-normal
distribution function fit to the particle diameter histogram
(standard deviation (S.D.) | = 1.3).
159
Fig. 4. Size distribution of Fe-particles in PE matrix.
Mossbauer spectroscopy for Fe, containing
samples makes it possible to determine and to
control the ‘phase’ constitution of the composites,
and also to evaluate the size of the particles [13].
Initially the samples of the PE with FeCl3 and
Fe2O3 nano-particles were used as a model. The
Mossbauer spectra of these samples are rather
simple. Thus, in the case of iron chloride the
spectrum represents a doublet on the parameters
applicable to anhydrous FeCl3 (l=0.36 mm s − 1).
In the case of iron oxide, the asymmetric doublet,
which is the superposition of two doublets, is an
adequately nano-sized g-modification of oxide
(III) and possibly a small content of Fe3O4, with
the parameters l =0.23 mm s − 1, Q= 0.84 mm
s − 1 and l= 0.52 mm s − 1, and Q=0.87 mm s − 1,
according to what was observed. Samples of
PE +Fe (0.20, 4.54 and 7.92% w) were studied by
Mossbauer spectroscopy (Fig. 5). It is to be noted
that the investigated samples contained several
forms of iron. This was purely metallic iron, and
its parameters, which can be quite precisely deter-
mined from the spectra data, namely chemical
shift and magnetic field, correspond to the so-
called a-Fe. Further, a-Fe2O3, corresponding to
an intensive doublet (l= 0.35 mm s − 1) was ob-
served in the central part (the absence of magnetic
hyperfine cleavage testifies that the size of the
particles does not exceed 6 nm). The remaining
fraction was made up of iron carbide, probably
Fe5C2. Thus, the observed spectra for the ‘iron in
160 S.P. Gubin / Colloids and Surfaces A: Physicochem. Eng. Aspects 202 (2002) 155–163

Fig. 5. Model of the described Mossbauer spectrum PE + 4.5% Fe (composition, C 81.22%; H 12.7%; Fe 4.54%).

PE’ samples shows the superposition of three or Experimental EXAFS data on r and Z for
more phases and are satisfactorily described by a PE + 5%Mo show (Fig. 6) that the sample con-
model that include the superposition of four sex- tains metallic Mo (interatomic distances A well
tets and two doublets. It should be noted that coincide with the metallic ones). The peak with
with the change of the iron content in the PE, the
spectra also change.
According to our experimental data, nano-par-
ticles have a complex composition and structure
that depend on the concentration of metal in the
polymeric matrix. All particles are multiphase,
they contain metal, metal carbide and metal ox-
ides. This seems to a general conclusion valid for
most samples, not only for Fe-containing ones.
The phase analysis of samples with M= Mo
has been carried out by two methods, by con-
struction of radial electronic density distribution
functions obtained from the curve of intensity of
X-ray scattering (X-ray RED) [14,15] and EX-
AFS-spectroscopy [16]. Both methods give values
of interatomic distances (r) and coordination
numbers (Z), which can be compared with those
calculated from structural data for a certain
phase. Thus, X-ray RED and EXAFS methods Fig. 6. EXAFS of nano-composite PE +5% Mo (composition,
inspect and supplement each other. C 80.65%; H 12.4%; Mo 4,93%).
 S.P. Gubin / Colloids and Surfaces A: Physicochem. Eng. Aspects 202 (2002) 155–163
r =1.97A can be assigned to the distance Mo– C/
O and indicates either at interaction of metal with
a matrix or oxidation; probably, the both cases
took place. X-ray RED analysis showed that both
metal and oxide phases were observed.
The bonding of metal with surrounding atoms
and the density of unpaired 3-D electrons local-
ized on the metal atoms has been investigated
using the X-ray emission spectra. These spectra
are useful in solving some structural problems and
provide information on atomic orbitals of nearest
neighbor atoms or molecular orbitals of matrix-
pseudoligand. In all materials Mossbauer and X-
ray spectroscopic investigations point to three
essential results:
1. nano-particles are multiphase, irrespective
of the concentration of metal in the poly-
meric matrix;
2. the phase composition of the nano-particles
differs sharply in the materials with low and
high concentration of metal in the matrix;
3. there are the direct metalC bonds with
matrix.
3.2.2. Matrices
It was demonstrated that the matrix inside that
the nano-particles were synthesized played an ac-
tive role in determining their composition and
chemical and physical properties in addition to
providing the means for particle dispersion. The
macroscopic properties of the nano-composites
reflected the combined action of the interfaces
between the nano-particles and the matrix, the
matrix properties, the quantum-size effects and
the morphologies of the nano-structure.
It was shown that using the same MCC and
under the same conditions (concentrations, solu-
tion temperature, time for addition of the MCC,
stirring velocity, etc.), the nature of the polymeric
matrix had an impact on, (a) the size of the
particles; (b) the mean distances between the
nano-particles; (c) the composition of the parti-
cles. The methods that were developed made it
possible to control these processes and to direct
them to obtain materials with predetermined
structural parameters.
We showed, that it was possible to change the
chemical structure of an external surface of a
161
nano-particle by interaction with polymer matrix
with in certain limits. The presence on the surface
of Fe-particles of a phase that corresponded in
general to the phase FeF2-high spin iron ions
(Kb5-spectra) was established by X-ray emission
and Mossbauer spectroscopy [17,18]. It can take
place only owing to defluorination of polyte-
trafluoroethylene by highly reactive iron nano-
particles. This result is not only novel, but also
very important because, in practice, polyte-
trafluoroethylene is considered to be one of the
most inert polymers and its defluorination is a
very complicated task. Analogous result was ob-
tained with more reactive polymers, such as
polyvinyl chloride (Fe–Cl phase), polyethyleneg-
lycol (Fe –O phase), polyamine (Fe–N phase),
polysilane (Fe–Si phase) [19] etc. Thus, the role of
a polymeric matrix is not reduced only to a role of
environment for retaining of nano-particles. As it
was shown the surface atoms of nano-particles
effectively interacted with environmental poly-
meric circuits. The nanoparticle, growing in these
matrixes, will partially destroy environmental
polymer chains by bond breaking involving the
atoms F, Cl, O, N or C. The last ones are the
potential ligands for creation on a surface of
particles appropriate metal-ion subphase
(environment).
For the determination of modifications to the
structure of a polymeric matrix we used 1H Wide-
Line NMR-spectra with success [20].
The temperature dependence of the width of the
proton resonance line arising from bulk samples
of polymers (wide-line spectra) provided an infor-
mation on the molecular motion of hydrocarbon
chains. A study of the second moment of (S2) and
various relaxation times (T1, T2) of the resonance
line as a function of the content of metallic parti-
cles yields important data on the variation of
degree of crystallinity, chain axis orientation, and
degree of molecular motion. For example, the
narrow component of a spectrum attributed to
the noncrystalline (amorphous) regions disap-
peared in a PE–Fe system with Fe content above
3%, whereas in the PE–Ni system, this occurred
only when the Ni content was higher than 8%.
However, the wide component of a spectrum
could be written down to 30% Ni in the PE, but
for Fe, only up to 8%.
162 S.P. Gubin / Colloids and Surfaces A: Physicochem. Eng. Aspects 202 (2002) 155–163

Probably the very small metal particles are

deposited initially in the amorphous, looser re-
gions of the PE sample, where they suppress the
molecular motions by decreasing of free volume
and by forming chemical bonds with the matrix.
This process, that increases the thermal stability,
should be accompanied by changes in spin-lattice
relaxation time, specific heat, and the mechanical
properties at ordinary temperatures. All of these
phenomena we noticed in the variety of investi-
gated samples.

3.3. Properties

The obtained materials have many interesting

properties, high thermal stability, increased me-
chanical characteristics in comparison to the ini-
tial polymer, semiconductive conductivity, etc.
[21,22]. In this work, we briefly consider only
magnetic characteristics, as an evidence of nano-
size of particles. Fig. 7. Zero field cooling and field cooling magnetization for
sample PE +5% Fe.

3.4. Magnetic properties The DC magnetic measurement of sets of sam-

A small magnetic nano-particle forms a single
magnetic domains in which a magnetic moment
performs fast fluctuation near an easy direction
(collective magnetic excitations), as well as, slower
fluctuation between different easy directions (su-
perparamagnetic relaxation) [23]. It is connected
with the changes in the magnetic and electronic
structure under decreasing size and with quantum
effects when the scale of structures becomes com-
parable with coherence length and other charac-
teristic parameters.
In accordance with decreasing of size the parti-
cle finally contains only one domain. This particle
is characterized by large coercive force [24,25]
because the rotation of the magnetization of the
entire particle is in general associated with a large
change in energy (depending on the anisotropy
energy of the particle). The state of the particle is
not in equilibrium and it is known [26] as ‘stable’
or ‘blocking’. It is supposed, that all magnetic
nano-particles of transition (3d, 4f) elements with
D smaller than 20 nm should be of a single
domain.
ples with different Fe, Co, Ni concentrations in
above mentioned matrices was carried out. Tem-
perature-dependent DC magnetic susceptibility
data for the sample is shown in Fig. 7. At high
temperatures, the field-cooled (FC) and zero-field-
cooled (ZFC) magnetization data exhibit the same
trend, but at low temperatures they significantly
diverge. This picture is typical for single domain
magnetic nanomaterials. The position of maxi-
mum is a blocking temperature. It was observed
that the value of the blocking temperature in the
samples being studied grew as the metal concen-
tration increased. For example, it was found that
the position determined to be the maximum ZFC
curve value of blocking temperature Tb ranged
from less than 4.2–77 K in the case of the
PTFE + 1 wt.%Fe and PTFE +30 wt.% Fe sam-
ples, correspondingly. Also, the temperature of
the magnetic phase transition decreases from ap-
proximately 100 K (for 24 wt.% Fe) to less than
30 K (for 8 wt.% Fe), matrix-PE. At this stage of
the research we assume that two types of nano-
particles with different blocking temperatures are
contained in the volume of some of the samples.
 S.P. Gubin / Colloids and Surfaces A: Physicochem. Eng. Aspects 202 (2002) 155–163
From above it is evident, that the implemented
technology is a method for synthesis of magnetic
single domain particles embedded in polymer ma-
trix. Our estimations show that the magnetic an-
isotropy of Fe nano-particles exceeds the value for
bulk a-Fe at 20 °C by a factor ten [27]. This fact
instills confidence that high-anisotropic nano-par-
ticles of other compositions will also hold large
magnetic anisotropy important for materials for
magnetic memory devices.
4. Conclusions
Our experiments demonstrated that we were
able to stabilize, isolate and characterize nanopar-
ticles of various composition using a polymer
matrix. The matrix, inside which nanoparticles are
synthesized, plays an active role in determining
their composition and physical properties in addi-
tion to providing a means of particle dispersion.
This research demonstrates the significant poten-
tial of MCC thermodestruction processing for the
synthesis of appreciable quantity of nanoparticle
containing polymer materials.
Acknowledgements
Dr I.D. Kosobudskii and G.Yu. Yurkov have
contributed substantially to the synthesis and in-
vestigation of nano-materials. I wish to thank Dr
A.V. Kozinkin and Dr D.A. Pankratov for com-
munication of their EXAFS and Mossbauer re-
sults on Fe-particles prior to publication. The
experimental and theoretical analysis of magnetic
properties of nano-particles is the result of a close
collaboration with Professor A.M. Tishin and Dr
Yu.A. Koksharov. The author would like to ac-
knowledge all of them.
References
[1] Y. Voloktin, Nature (London) 384 (1996) 621.
[2] M. Antometti, C. Goltner, Angew. Chem. Int. Ed. Engl.
36 (1997) 910.
163
[3] J.L. Dorman, D. Fiorani (Eds.), Magnetic Properties of
Fine Particles, Elsevier, Amsterdam, 1992.
[4] S. Gandopadhyay, et al., Phys. Rev. B 45 (1992) 9778.
[5] G. Schmid (Ed.), Clusters and Colloids, From Theory to
Applications, VCH, Wenheim, 1994.
[6] G. Shon, U. Simon, Colloid Polym. Sci. 273 (1995) 101.
[7] I.P. Suzdalev, et al., Colloids Surf. A108 (1996) 315.
[8] Y.A. Koksharov, D.A. Pankratov, S.P. Gubin, et al., J.
Appl. Phys. 89 (2001) 2293.
[9] H. Tadokoro, Structure of Crystalline Polymers, Wiley,
New York, 1979.
[10] Methods of Experimental Physics, L. Marton, C. Marton
(Eds.), New York, 1980.
[11] G.S. Yurjev, M.A. Sheromov, Nucl. Instrum. Methods
Phys. Res. A 359 (1995) 181.
[12] G.G. Cocks, in: P.J. Elving, E.J. Meehan, I.M. Kolthoff
(Eds.), Electron Microscopy in Treatise on Analytical
Chemistry, vol. 8, Wiley, New York, 1986, p. 493.
[13] S. Morup, in: G.J. Long (Ed.), Mössbauer Effect Studies
of Microcristalline Materials in Mössbauer Spectroscopy
Applied to Inorganic Chemistry, vol. 2, Plenum Press,
New York, 1984, p. 89.
[14] E.M. Moroz, Usp. Khim. 61 (1992) 188.
[15] E.M. Moroz, Russ. Chem. Rev. 61 (1992) 356].
[16] D.J. Koshubey, EXAFS Spectroskopiya Katalizatorov
(EXAFS Spectroskopy of catalysts), Nauka, Novosibirsk,
1992 (in Russia).
[17] A.V. Kozinkin, V.G. Vlasenko, S.P. Gubin, A.T. Shu-
vaev, I.A. Dubovtsev, Neorg. Mater. 32 (1996) 422.
[18] A.V. Kozinkin, V.G. Vlasenko, S.P. Gubin, A.T. Shu-
vaev, I.A. Dubovtsev, Inorg. Mater. 32 (1996) 376 (Engl.
Transl.).
[19] S.P. Gubin, A.V. Kozinkin, M.I. Afanasov, N.A. Popova,
O.V. Sever, A.T. Shuvaev, A.M. Tsirlin, Neorg. Mater.
35 (1999) 237 (in Russia).
[20] J.R. Lyerla, in: L. Marton, C. Marton (Eds.), High-reso-
lution Nuclear Magnetic Resonance Spectroscopy in
Methods of Experimental Physics, vol. 16, Vead. Press,
New York, 1980, p. 241.
[21] S.P. Gubin, I.D. Kosobudskii, Usp. Khim. 52 (1983)
1350.
[22] S.P. Gubin, I.D. Kosobudskii, Russ. Chem. Rev. 52
(1983) 766.
[23] B.D. Cullity, Introduction to Magnet Materials, Addison-
Wesley, Reading, MA, 1972.
[24] M.E. McGenry, S.A. Majetich, J.O. Artman, M. DeGrae,
S.W. Stanley, Phys. Rev. B 49 (1994) 11358.
[25] E.M. Brunsman, R. Sutton, E. Bortz, S. Kirkpartick, K.
Midelford, J. Williams, P. Smith, M.E. McGenry, S.E.A.
Majetich, J.O. Artman, M. DeGraef, S.W. Stanley, J.
Appl. Phys. 75 (1994) 5882.
[26] C. Petit, P. Linox, M.P. Pileni, J. Chem. Phys. 94 (1990)
1598.
[27] Y.A. Koksharov, S.P. Gubin, I.D. Kosobudsky, M. Bel-
tran, Y. Khodorkovsky, A.M. Tishin, J. App. Phy. 88
(2000) 1587.