Reactivity of metal-containing monomers 71.* Synthesis of nanosized quasicrystals and related metallopolymer composites

Article abstract of DOI:10.1007/s11172-011-0282-9

The methods for the preparation of quasicrystalline intermetallic compounds in the protective matrix in the systems Al6₅Cu₂₂Fe ₁₃ and Al₅₄Cu₉Mg3₇ were developed. They are formed both earlie

Full text of DOI:10.1007/s11172-011-0282-9

Russian Chemical Bulletin, International Edition, Vol. 60, No. 9, pp. 1871—1879, September, 2011
1871
Reactivity of metalꢀcontaining monomers
71.* Synthesis of nanosized quasicrystals and related metallopolymer composites
S. M. Aldoshin,a G. I. Dzhardimalieva,a A. D. Pomogailo,a and Yu. A. Abuzinb
aInstitute of Problems of Chemical Physics, Russian Academy of Sciences,
1 prosp. Akad. Semenova, 142432 Chernogolovka, Moscow Region, Russian Federation.
Eꢀmail: adpomog@icp.ac.ru
bNational Research Technological University "MISiS,"
4 Leninsky prosp., 119049 Moscow, Russian Federation
The methods for the preparation of quasicrystalline intermetallic compounds in the protecꢀ
tive matrix in the systems Al65Cu22Fe13 and Al54Cu9Mg37 were developed. They are formed
both earlier and from elements during the formation of a metallopolymer composite material.
Three methods of preparation are optimal: from lowꢀdimensional powders of quasicrystals and
filmꢀforming polymers, by the in situ formation of quasicrystals during the thermal decomposiꢀ
tion of the corresponding precursors, and via the thermal polymerization of metalꢀcontaining
monomers (components of quasicrystals) followed by the controlled pyrolysis of the metalꢀ
lopolymers that formed. The metallopolymer composite obtained by the incorporation of
Al63Cu22Fe13 into the highꢀdensity polyethylene or polyacrylamide matrix affords up to 10 wt.%
cubic phase of βꢀAl50(Cu,Fe)50. The products of thermal decomposition of the lowꢀmolecularꢀ
weight precursors are a mixture of the quasicrystalline (Al65Cu22Fe13) and crystalline (cubic
βꢀAl50(Cu,Fe)50 and tetragonal ωꢀAl7Cu2Fe, Al2Cu) phases. The thermolysis of the metalloꢀ
polymer composition yields a finely dispersed powder, whose main component is an alloy
Al7Cu3Mg6 with an admixture of the Al2CuMg phase.
Key words: quasicrystals, metallopolymer composite, thermolysis, metallopolymers.
Quasicrystals are intermetallic compounds including
metal atoms (including noble and rareꢀearth), whose
atomic structure is characterized by 5ꢀ, 7ꢀ, and higherꢀ
fold symmetry axes. They have been found for the first
time in the rapidly cooled alloy Al86Mn14 with the 5ꢀfold
symmetry axis, which was confirmed by the electron microꢀ
diffraction data.2 The sharp diffraction peaks indicate the
presence of the farꢀrange order in the atomic arrangement
in the structure, which is characteristic of crystals. Howꢀ
ever, the symmetry of the observed diffraction pattern conꢀ
tradicts the fundamental concepts of classical crystalloꢀ
graphy.3 The electron patterns of the new phase contain
distinct quasiperiodical reflections, the distances between
high resistance to corrosion and oxidation. The quasicrysꢀ
tals Al—Cu—Fe have a low density (4—5 g cm–3), a high
hardness (600—1000 kg mm–2), and a high elasticity modꢀ
ulus (70—100 GPa). They are characterized by low heat
conductivity and high specific resistance.4 The high force
of resistance of dislocation movement in quasicrystals
makes them less plastic and, hence, they can be used as
efficient reinforcers in alloys.5 Quasicrystals are classified
as particular unusual solids combining the properties of
both glasses and periodically ordered crystals, whose propꢀ
erties are determined by the aperiodical longꢀrange order
and the local atomic structure.
More than a hundred of quasicrystalꢀforming systems
based on various metals have been found to the present
time. Substantial progress was achieved in the area of deꢀ
velopment of novel methods for their preparation, study of
the structure and properties, and possible practical use.5
Diverse methods are used to obtain monophase quasiꢀ
crystalline alloys: vapor condensation, solidification at
high pressure, devitrification of amorphous substances or
decomposition of oversaturated solid solutions, and meꢀ
chanical activation. "Mechanical smelting" in a ball viꢀ
brating mill is most popular.6 For this purpose, compoꢀ
nents of the Al70Cu20.3Fe9.7 alloy are mixed in an experiꢀ
which are related by the exponents
(the soꢀ
called golden section), and their arrangement confirms
the icosahedral point symmetry group incompatible with
translational symmetry.
Owing to the nonꢀperiodical packing of atoms, quasiꢀ
crystals have a series of properties that are not typical
of usual alloys. They have high hardness, low friction
coefficient (for example, for the quasicrystalline alloy
Al62Cu25.5Fe12.5 the friction coefficient is 0.12—0.14), and
* For Part 70, see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1837—1846, September, 2011.
1066ꢀ5285/11/6009ꢀ1871 © 2011 Springer Science+Business Media, Inc.

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Aldoshin et al.
as follows. A mixture preliminarily homogenized in a porcelain
mortar and consisting of quasicrystals (8 g) with an average parꢀ
ticle size of 0.5 μm and HDPE (5 g) (volume ratio 1 : 2.5) was
placed in a sealed agate 0.5ꢀL beaker. A dark homogeneous
mixture was obtained after stirring for 15 min with an average
rate of 500 rpm. When the monomer was used as a stabilizing
agent at the stage of the preparation of the polymer composite,
the Al65Cu22Fe13 system (17 g) was approved, which representꢀ
ed solid polymerized monomer acrylamide (10 g, volume ratio
1 : 2.5). After mixing and preliminary triturating in a porcelain
mortar, the mixture was placed in a sealed agate beaker of
a Pulversette 6 planetary mill (Fritsch GmbH, Germany) and
stirred for 30 min in the presence of polished agate balls with an
average rotation rate of 550 rpm. The mixture was loaded out
and analyzed.
Quasicrystalline alloy Al7Cu2Fe. The starting mixture of powꢀ
ders (3.26 g of AlH3, 6.12 g of Cu(HCOO)2, and 3.99 g of
Fe(HCOO)3) with a component ratio Al—Cu—Fe (at.%) of
65 : 22 : 13 was stirred according to a stepped scheme: iron and
copper formates in an agate mortar were stirred for 15 min, AlH3
was introduced into the prepared mixture under an inert atmoꢀ
sphere, and then this mixture was mechanically stirred additionꢀ
ally for 15 min in a closed tube. The obtained mixture was subꢀ
jected to thermolysis at 500, 600, and 700 °С for 1 h.
Quasicrystalline alloy Al7Cu3Mg6. The starting mixture of
powders AlH3—Cu(HCOO)2—Mg (finely dispersed powder) was
stirred at a ratio of components Al—Cu—Mg of 54.2 : 9.2 : 36.6
(at.%) or 50 : 20 : 30 (wt.%). All procedures were carried out in
an inert atmosphere. The obtained mixture was subjected to therꢀ
molysis at 500 and 650 °С under the isothermal conditions
in vacuo for 1 h. A dark gray finely dispersed powder was obtained.
Quasicrystal Al68Cu21Fe11. A mixture of Al(NO3)3•9H2O
(10 g), 2.13 г Cu(NO3)2•3H2O (2.13 g), and Fe(NO3)3•9H2O
(2.1 g) was triturated with acrylamide (13 g). The reaction acꢀ
companied by the evolution of water of crystallization and forꢀ
mation of a light green pasteꢀlike substance. After the end of the
reaction, the product was washed with benzene and ether to
remove an excess of acrylamide and water and the resulting
mixture of acrylamide complexes was dried in vacuo. At the
initiation temperature 50 °С in vacuo, the monomeric mixture
underwent frontal polymerization in the condensed phase to form
metallopolymer as a finely dispersed dark brown powder, which
was subjected to thermolysis in vacuo at 500, 600, and 700 °С.
Quasicrystalline sample Al54Cu9Mg37 was obtained by the
combination of polymerization of the acrylamide complex
of MgII nitrate with the assembling method. The complex
Mg(NO3)2(СH2=CHCONH2)4•2H2O was synthesized by the
substitution of water of crystallization in crystalline hydrate
Mg(NO3)2•6H2O for molecules of the acrylamide ligand.
Found (wt.%): С, 31.71; H, 5.46; N, 18.09; Mg, 5.8. Calculatꢀ
ed (%): С, 30.75; H, 5.16; N, 17.93; Mg, 5.19. The acrylamide
complex of MgII nitrate was mixed in an agate mortar with other
metalꢀcontaining components of the synthesized alloy: AlH3 and
Cu(HCOO)2 with the ratio of components Al : Cu : Mg equal to
54.2 : 9.2 : 36.6 (at.%) or 50 : 20 : 30 (wt.%). The obtained mixꢀ
ture was subjected to thermolysis at 500 °С under the isothermal
conditions in vacuo for 2 h to form the product as a homogeꢀ
neous dark gray finely dispersed powder. The composition and
morphology of the obtained alloys were studied by chemical
analysis and scanning electron microscopy on a Tescan Vega
TS5130MM scanning electron microscope with an INCA Enerꢀ
mentally selected ratio, and after dividing for may hours
the obtained mixture is heated to 800 °С in an argon atꢀ
mosphere and stored for 10—20 min. One of the most
abundant methods for the preparation of metastable and
stable quasicrystalline phases of the fast quenching of liquid
melts with cooling rates of 104—106 K s–1. The methods
for sputtering and controlled thermolysis of the amorꢀ
phous phase were developed. The methods of cold gasoꢀ
dynamic sputtering with surging of a supersound flow of a
matrix material mixture on the metal surface,7 mechaniꢀ
cal smelting, and others are used for the production of
composite materials with tribological properties. For inꢀ
stance, stable decagonal quasicrystals of Al70Ni15Co15 were
grown from the melt using the Czochralski technique.8
Decagonal quasicrystals of Al72.5Ni7.5Co20 were obtained
after prolong annealing (20 days at 950 °С) and standard
quenching of an alloy.9 Monophase decagonal quasicrysꢀ
tals of Al72Ni12Co16 were grown using a special levitation
setup by the crystallization of overcooled melts10 and laser
treatment of alloys.11
Methods of solidꢀphase syntheses,12,13 in particular,
selfꢀpropagating highꢀtemperature synthesis,14 are promꢀ
ising from the technological point of view. The approach
based on the preparation of nanometer quasicrystals by
sol—gel reactions seems interesting.15 Nanoparticles of
the Al65Cu20Fe15 quasicrystal 15 1.8 nm in size dispersed
in the silica gel matrix were thus synthesized.
However, the products obtained by these methods conꢀ
tain a considerable amount of other compounds along
with the quasicrystalline phase. Therefore, additional anꢀ
nealing is used for the preparation of a material with
a perfect structure (for instance, for the monophase alloy
Al—Cu—Fe, annealing at 730 °С for 24 h is carried out).16
Investigation of quasicrystals is an intensively develꢀ
oped field of science: our concepts about their preparation
are extended, new types of compositions are revealed, their
structure is refined, and new areas of application are
searched for.
The purpose of the present work is the synthesis of
metallopolymer composites from nanosized quasicrystalꢀ
line intermetallic compounds and the study of diverse variꢀ
ants of their formation.
Experimental
The following reagents were used: aluminum nitrate
Al(NO3)3•9H2O (pure, Khimmed, Russia), iron nitrate nonꢀ
ahydrate (98%) (PANREAC, Spain), copper(II) formate (pure,
Vekton, Russia); magnesium nitrate (pure), Mg(NO3)2•6H2O,
iron formate Fe(HCOO)3, acrylamide 98.5 (Acros Organics,
New Jersey, US); polyethylene with high density (965 kg m–3
,
HDPE), melt flow index MFI = 4.5 g/(10 min) with a specific
surface of 10 m2 g–1 and the degree of crystallinity 64%.
The starting powders Al65Cu22Fe13 (0.01 μm < d < 3 μm, disꢀ
tribution maximum 0.5 μm) were presented by the FGUP VIAM
(Russia). The metallopolymer composite material was prepared

Synthesis of nanosized quasicrystals
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 9, September, 2011
1873
gy 350 energyꢀdispersive Xꢀray spectral analyzer. Xꢀray phase
analysis was carried out on a DRONꢀUM2 diffractometer in the
reflection mode of detection of diffraction patterns using an Xꢀray
tube with a BSVꢀ27 copper anode (voltage U = 30 kV, current
I = 25 mA) and a 1,3BSVꢀ29 chromium anode (U = 35 kV,
I = 35 mA) and on a D8 Advance Xꢀray setup (Bruker AXS) in
the copper radiation detection mode (U = 40 kV, I = 40 mA).
The qualitative Xꢀray phase analysis of the obtained diffraction
patterns was performed using the DIFFRACplus BASIC EVA
10.0 software. Quantitative phase analysis was carried out by
the Rietveld method using the Topaz 3.0 program. IR spectra
were recorded on a Specord Mꢀ80 instrument (Carl Zeiss Jena,
Germany).
ysis mode). The rate of the processes is monitored by both
the amount of evolved gaseous products and the change in
the weight of the initial or accumulated product using the
spectral or other characteristics of the reacting systems.
Assembling of quasicrystals from metalꢀcontaining preꢀ
cursors. The thermal transformations of carboxylates, in
particular, metal formates, are accompanied by the forꢀ
mation of highly dispersed (for example, the average Cu0
particle size is 60 nm) metals stabilized by the hydroꢀ
carbon matrix.17,18
Quasicrystalline alloys Al65Cu22Fe13 and Al7Cu2Fe were
obtained from the lowꢀmolecularꢀweight metalꢀcontainꢀ
ing precursors: AlH3 and iron Fe(HCOO)3 and copper
Cu(HCOO)2 formates. The thermolysis results in a finely
dispersed powdered substance. According to the Xꢀray
phase analysis, at 500 °С the thermolysis product conꢀ
tains Al65Cu22Fe13 and crystalline phases of cubic
βꢀAl50(Cu,Fe)50 and tetragonal ωꢀAl7Cu2Fe (Fig. 1) alꢀ
loys. An increase in the thermolysis temperature to 600
and 700 °С decreases the content of ωꢀAl7Cu2Fe and the
growth of the cubic phase βꢀAl50(Cu,Fe)50. At 700 °С the
content of the quasicrystalline phase in the thermolysis
product reaches 30 wt.%.
Results and Discussion
Three different methods were developed for the synꢀ
thesis of metallopolymer composites. The methods are
based on the formation of a polymer stabilizing matrix
around quasicrystals or their precursors followed by the
controlled thermolysis of the obtained materials leading
to the formation of the quasicrystal phase stabilized by the
polymer shell. The variants of the synthesis used can be
classified as environmentally appropriate "dry" methods,
because solvents are used at none of the stages of this
multistage process. These approaches can be described as
follows.
(1) Assembling method: the in situ formation of quasiꢀ
crystals during the thermal decomposition of the correꢀ
sponding precursors taken in stoichiometric amounts. This
method often results in the formation of nanosized partiꢀ
cles, which are stabilized by the stabilizing polymer matrix
appeared due to polymerization transformations of the
ligand fragments of the precursors.
(2) Introduction of lowꢀdimensional powders of quaꢀ
sicrystals in a composition with the matrix of filmꢀformꢀ
ing polymers (both from the ingredients and by the comꢀ
bined dispersion of powders of quasicrystals and polymers
on highꢀperformance planetary matrices).
(3) Thermal polymerization of metalꢀcontaining monoꢀ
mers (components of quasicrystals) followed by the conꢀ
trolled pyrolysis of the metallopolymers than formed. In
this case, nanocrystals stabilized by the polymer shell are
always formed. The properties of such multicomponent
systems are controlled by the synthesis and thermolysis
conditions. The polymer matrix formed in the synthesis
prevents the formation of large particles, and the stabilizꢀ
ing shell is the product of thermal destruction of the polyꢀ
mer fragments.
Particles of the thermolysis products are densely packed
agglomerates consisting of cut crystals with an average
diameter of 10 μm and particular pentagonal prisms formed
at different angles (Fig. 2).
Quasicrystals Al—Cu—Mg. Magnesiumꢀcontaining
quasicrystalline systems are interesting from the viewpoint
of preparation of materials that efficiently absorb dihydroꢀ
gen.19 For the preparation of the quasicrystalline alloy
Al—Cu—Mg, we used the solidꢀphase synthesis from the
metalꢀcontaining precursors. The Xꢀray phase analyꢀ
sis data indicate that the main component of the prodꢀ
uct is the alloy Al7Cu3Mg6 and also admixtures of the
Al2CuMg phase (Fig. 3, Table 1). An increase in the
thermolysis temperature to 650 °С results in the disꢀ
appearance of the Al7Cu3Mg6 phase and the appearance
of phases of metallic aluminum, magnesium, and magneꢀ
sium oxide (Fig. 4).
Introduction and stabilization of polymetallic quasicrysꢀ
tals Al65Cu22Fe13 in polymer matrices. The polymer shell
separates metallic particles from each other and from the
external medium and thus performs functions of the stabiꢀ
lizing agents and improves the properties of the metalꢀ
lopolymer composite. The methods of coacervation,
precipitation with a nonꢀsolvent or evaporation of the
solvent, physical adsorption, extrusion (the particles of
covered with the shell upon forcing of the quasicrystalꢀ
line intermediate compound through the filmꢀformꢀ
ing material), sputtering in the fluidized bed, vapor conꢀ
densation, polymerization on the particle surface, and
others. The results of studies of the starting powder by
the Xꢀray phase method are presented in Fig. 5 and
in Table 2.
Solidꢀphase thermolysis (both in vacuo and in a mediꢀ
um of gaseous transformation products: selfꢀgenerated atꢀ
mosphere)16 possesses the most potent possibilities for the
formation of metallopolymer composites. The temperaꢀ
ture of thermal transformation can be maintained conꢀ
stant (isothermal conditions) or subjected to programꢀ
mable changes (nonꢀisothermal conditions, thermal analꢀ

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Aldoshin et al.
I (arb. units)
a
2000
Al65Cu22F13
Al7Cu2Fe
AlFe
1000
30
40
50
60
70
80
2θ/deg
I (arb. units)
b
1000
0
30
40
50
60
70
80
2θ/deg
Fig. 1. Xꢀray diffraction pattern of the products of thermal transformations of a mixture of the metalꢀcontaining precursors
AlH3—Cu(HCOO)2—Fe(HCOO)3 at 500 (а) and 700 °С (b).
The preliminary studies on the formation of the proꢀ
tective shell on quasicrystals from polystyrene (PS) soluꢀ
tions with various concentrations in aromatic solvents
showed that this way is not promising. This is because of
the surface properties of the polymer that are not optimal
for this application, namely, poor wettability at the interꢀ
face, a low energy of the quasicrystal—PS interaction, etc.
This results in the low stabilizing effect in this case. For
instance, for the composite based on the quasicrystal
Al65Cu22Fe13 with an average particle size of 0.5 μm and
PS, the efficiency of stabilization of the polymetallic parꢀ
ticles turned out fairly low.
The methods of mechanochemical mixing of quasicꢀ
rystals with the polymer matrix or its precursor are more
attractive from the technological point of view. Dependꢀ
ing on the character of motion of the ball loading (polꢀ
ished agate balls), there are three modes of dividing of the
polymer matrix: sliding (abrasion), rolling (impact), and

Synthesis of nanosized quasicrystals
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 9, September, 2011
a
1875
100 μm
b
10 μm
c
20 μm
Fig. 2. Images of particles of the products of thermolysis at 500 °С of a mixture of the metalꢀcontaining precursors AlH3—Cu(HCOO)2—
Fe(HCOO)3: general view (a) and pentagonal crystals (b, c).

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Russ.Chem.Bull., Int.Ed., Vol. 60, No. 9, September, 2011
Aldoshin et al.
I (arb. units)
38.05
38.75
750
44.25
44.85
42.8
36.55
35.0
19.1
500
250
45.4
27.2
21.1
22.85
25.0
64.4
77.45
51.3
40.85
62.4
52.2
46.65
70.65
66.85
68.85
15.2
72.95
75.3
53.75
78.9
81.15
31.6
49.4
55.3
83.4
20
40
60
80
2θ/deg
Fig. 3. Xꢀray diffraction pattern of the product of thermolysis at 500 °С of a mixture of the metalꢀcontaining precursors
AlH3—Cu(HCOO)2—Mg.
I (arb. units)
38.45
1750
1500
38.95
40.1
41.05
1250
1000
750
42.05
42.6
43.0
44.7
45.35
47.3
20.7
37.9
65.05
19.2
47.8
500
78.15
66.2
67.0
69.1
29.4
27.25
82.35
62.3
35.0
77.25
73.4
80.95
57.15
250
20
40
60
80
2θ/deg
Fig. 4. Xꢀray diffraction pattern of the product of thermolysis at 650 °С of a mixture of the metalꢀcontaining precursors
AlH3—Cu(HCOO)2—Mg.

Synthesis of nanosized quasicrystals
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 9, September, 2011
1877
Table 1. Xꢀray phase data for the product of thermolysis at 500 °С of a mixture of the metalꢀ
containing precursors AlH3—Cu(HCOO)2—Mg
2θ/deg
d/nm
Irel (%)
Phase
000—
2θ/deg
d/nm
Irel (%)
Phase
15.20
19.10
25.00
27.20
31.60
35.00
36.55
38.05
38.75
40.85
42.80
44.25
44.85
45.40
46.65
5.829
4.647
3.562
3.278
2.831
2.564
2.458
2.365
2.324
2.209
2.113
2.047
2.021
1.998
1.947
5
20
16
26
7
37
45
100
90
16
47
43
49
34
13
49.40
51.30
53.75
55.30
62.40
64.40
66.85
68.85
70.65
72.95
75.30
77.45
78.90
81.15
1.845
1.781
1.705
1.661
1.488
1.447
1.399
1.364
1.333
1.297
1.262
1.232
1.213
1.185
5
15
11
5
14
26
6
5
7
4
5
Al7Cu3Mg6
Al2CuMg
Al2CuMg
—
Al2CuMg
Al7Cu3Mg6
—
Al7Cu3Mg6
Al7Cu3Mg6
Al7Cu3Mg6
—
Al2CuMg
Al2CuMg
Al2CuMg
Al2CuMg
Al2CuMg
Al7Cu3Mg6
Al7Cu3Mg6
Al2CuMg
Al2CuMg
Al2CuMg
000—
23
6
6
—
Al7Cu3Mg6
Al2CuMg
Al2CuMg
Al7Cu3Mg6
Al2CuMg
vortical (predominantly impact). Impact and shift loads
result in dispersion and efficient rolling of quasicrystals
into the polymer matrix of HDPE. The combined milling
also affects the structure of the polymer matrix. For inꢀ
stance, HDPE undergoes partial destruction and crossꢀ
linking, insignificant amorphization of the crystalline
phase occurs, and the crystalline phase of extended PE
appears (d = 3.55 and 2.55 Å) (Fig. 6, Table 3). It should
be mentioned that, according to the Xꢀray phase analysis
data, the introduction of Al63Cu22Fe13 into the HDPE
matrix results in the appearance of up to 10 wt.% of the
cubic phase βꢀAl50(Cu,Fe)50. The necessary ratio between
the phases of the quasicrystal and polymer matrix is monꢀ
itored both at the stage of charge preparation and during
the subsequent controlled thermolysis of the obtained
product.
polymer matrix is formed from the adsorbed monomer
directly on the quasicrystal surface.20 In this case, the
degree of conversion of the monomer into polymer deꢀ
pends on the dispersion intensity. Freshly formed juvenile
metal surface serve as initiators of polymerization: an elecꢀ
tron is transferred by the surface metal atoms to the monoꢀ
mer to form initiating particles of the radical ion type. The
solid monomer acrylamide and quasicrystal Al65Cu22Fe13
were approved as media at the stage of formation of the
polymer matrix for the preparation of the polymer matrix.
Unreacted acrylamide in the obtained composite was
washed off with benzene in which the polymer product is
insoluble. According to the data of IR spectroscopy,
the spectrum of the metallopolymer composite retains abꢀ
sorption bands in the region of stretching (νs(NH) and
νas(NH)) and outꢀofꢀplane bending (δ(NH)) NH vibraꢀ
tions at 3198, 3350, and 1613 cm–1, as well as bending and
stretching vibrations of СН2 and СН (1428 and 1280 cm–1).
The absence of the δ(=СН) absorption bands at 962 cm–1
confirms the conversion of the С=С bonds during polyꢀ
merization. The optimization of the concentration ratios
quasicrystal : monomer and the conditions of the conꢀ
version of the latter to polymer require further studies, as
well as the molecular weight characteristics of the polyꢀ
mers formed.
Variants of the preparation of metallopolymer comꢀ
posites are especially interesting in the cases where the
I (arb. units)
45.25
42.9
1000
76.9
Table 2. Xꢀray phase data for the quasicrystalline alloy
23.75
26.15
27.6
64.1
65.85
Al65Cu22Fe13
2θ/deg
d/nm
Irel (%)
2θ/deg
d/nm Irel (%)
23.75
26.15
27.60
42.90
3.746
3.408
3.232
2.108
13
14
8
45.25
64.10
65.85
76.90
2.004
1.453
1.418
1.240
100
12
7
0
20
40
60
80
2θ/deg
Fig. 5. Xꢀray diffraction pattern of the quasicrystalline alloy
Al65Cu22Fe13.
95
27

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Russ.Chem.Bull., Int.Ed., Vol. 60, No. 9, September, 2011
Aldoshin et al.
I (arb. units)
Table 3. Xꢀray phase data for the quasicrystalline alloy
Al—Cu—Fe in the composite on the polyethylene matrix
a
69.6
65.75
2θ/deg
d/nm
Irel (%)
Phase
29.15
31.90
35.55
41.45
55.50
65.75
69.90
83.30
104.00
108.00
4.552
4.168
3.752
3.237
2.460
2.110
2.007
1.724
1.454
1.416
13
27
13
10
9
91
100
6
PE
PE
PE
31.9
29.15
100
Al13Cu4Fe3
Al13Cu4Fe3
Al13Cu4Fe3
Al13Cu4Fe3
Al13Cu4Fe3
Al13Cu4Fe3
Al13Cu4Fe3
35.55
39.15
41.45
103.95
108.0
55.5
83.3
18
9
20
I (arb. units)
40
60
80
100
2θ/deg
transformations of the acrylamide complexes with a specꢀ
ified ratio of the components result in the formation of
nanosized particles of the alloys uniformly distributed in
the polymer matrix. The elongation of the annealing duraꢀ
tion (to 5 h) leads to a more structured nanocomposite.
According to the energyꢀdispersive Xꢀray spectral analysis
data, the quasicrystalline phase has the composition
Al68Cu21Fe11.
b
32.2
250
35.85
Synthesis of quasicrystalline Al54Cu9Mg37 was carꢀ
ried out in several stages. At the first of them, the acrylꢀ
amide complex of magnesium nitrate Mg(NO3)2ꢀ
(СH2=CHCONH2)4•2H2O was obtained by the substituꢀ
tion of water of crystallization in the crystalline hydrate
Mg(NO3)2•6H2O for acrylamide molecules. At the secꢀ
ond stage, the complex was mixed with the calculated
amount of other metalꢀcontaining components of the alloy
(AlH3 or Cu(HCOO)2) followed by thermolysis at 500 °С.
The composition of the obtained alloy was examined by
Xꢀray phase analysis.
Thus, in the present work, we approved for the first
time different variants of the preparation of the metalꢀ
containing composites using the lowꢀdimensional powꢀ
ders of quasicrystals and filmꢀforming polymers: adsorpꢀ
tion of polymers from their solutions and combined disꢀ
persion of powders of quasicrystals and polymers, as well
as their monomeric precursors. It was shown that particles
of quasicrystals Al65Cu22Fe13 and Al54Cu9Mg37 can be staꢀ
bilized by the polymer matrix during polymer composite
formation. The quasicrystals are stabilized in all cases studꢀ
ied; however, the most promising direction of preparation
of materials of this type seems to be the polymerization of
monomers and formation of polymer composites from the
calculated amounts of the ingredients of quasicrystals
capable of further polymerizing. This method requires no
use of beforehand prepared quasicrystals, whose synthesis
is a laborꢀconsuming process.
0
20
40
60
80
100
2θ/deg
Fig. 6. Xꢀray diffraction patterns of the quasicrystalline alloy
Al—Cu—Fe in the composite on the polyethylene matrix (a) and
the initial polyethylene (b).
Preparation of quasicrystalline alloys by the polymerꢀ
ization of metalꢀcontaining monomers. Metal complexes,
whose ligand environment contains a substituents with
the multiple bond capable of polymerization transforming
are named metalꢀcontaining monomers.21 These precurꢀ
sors are rather frequently used for the synthesis of polyꢀ
metallic alloys (for instance, YCuBa— or BiCaSrPbCu—
HTSC ceramic22). It could be assumed that they would be
convenient precursors for the polymerꢀassisted synthesis
of quasicrystals: assembling of quasicrystals from elements
with the simultaneous formation of the stabilizing polyꢀ
mer shell.
Quasicrystalline alloy Al68Cu21Fe11. The typical experiꢀ
ment included the in situ solidꢀphase synthesis of the acrylꢀ
amide complexes Al—Cu—Fe at the ratio of components
65 : 22 : 13 (at.%) or 45.23 : 36.05 : 18.72 (wt.%). The
composition and morphology of the thermolyzed prodꢀ
ucts were studied by scanning electron microscopy with
an energyꢀdispersive Xꢀray spectral analyzer. The scanꢀ
ning electron spectroscopic data indicate that the thermal
The authors are grateful to A. M. Kolesnikova and
D. S. Shaitura for Xꢀray phase analyses of the samples.

Synthesis of nanosized quasicrystals
Russ.Chem.Bull., Int.Ed., Vol. 60, No. 9, September, 2011
1879
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Received March 4, 2011;
in revised form June 14, 2011