D

Journal of Materials Science and Engineering A 2 (5) (2012) 385-390

DAVID

PUBLISHING

Polymeric Composite Materials with the Strengthened

Superficial Properties
Fakhrutdinova Venera Hafizovna, Islamov Anvar Makhmutovich, Ilyukhin Dmitry Genadevich and
Abdrahmanova Lyailya Abdullovna
Kazan State University of Architecture and Engineering, Kazan City 420066, Russia
Received: March 21, 2012 / Accepted: April 18, 2012 / Published: May 10, 2012.
Abstract: Polymer composite materials are one of the most important and widely used modern polymeric materials. Surface diffusive
processing of the polymer by the nanomodifying components can receive the gradient materials with high physical and mechanical
properties. In the case of using silica sol as a low-molecular-weight diffusant it is possible to obtain a strengthened gradient layer in the
matrix of the base polymer due to a structuring effect of the modifier and enhancement of the polymer macromolecular bonds. As a
result, use of silica sol leads to increased surface microhardness up to 2 times and the flex modulus up to 1.2 times and high resistance
to chemical reagents.
Key words: Polyvinylchloride, nanomodifier, diffusion, swelling, grade.

1. Introduction
Analysis of trends in fundamental studies and new
technologies for the production polymer and composite
materials, including nanosystems, with a set of positive
physical and chemical properties shows that traditional
methods of polymers synthesis, polymerization and
polycondensation, largely exhausted themselves and
the probability of occurrence polymers with
characteristics significantly exceeding the achieved
certain level decreased significantly. During the
operation the polymer products surface is exposed to
various aggressive factors, which are distributed
unevenly in the product volume and concentrated
largely on the surface, containing an increased amount
of local stresses and defects associated with the
processing technology. These factors accelerate the
destruction of the surface layer of the real body and
thereby reduce the durability of finished products
during the operation [1-3].
Modification of the polymeric materials and
Corresponding author: Fakhrutdinova Venera Hafizovna,
Ph.D., research field: nanomodification of polymers. E-mail:
venerushka07@mail.ru.

products surface develops rapidly in recent years. It is a

promising area, which allows on the basis of known
polymers to develop technology for the production of
high quality new materials with the set of improved
physical-chemical and performance properties.
The surface modification of polymers is carried out
traditionally by mechanical [2, 3], energy [4, 5] and
diffusion [6-10] exposure on the material superficial
layers in the finished product without modifying the
structure and composition of the inner layers. The most
effective way of modification is the surface treatment
by different liquid reagents. As a result of the liquid
diffusion in polymeric material is formed a modified
surface layer with variable structure and properties
over the thickness, that is the gradient layer. This
creates not so much a protective coating as a new layer
of the modified polymer with decreasing concentration
of the modifier into the depth of the base material
volume. By varying the temperature and time
parameters of diffusion impregnation, the depth of
penetration and thus the thickness of surface gradient
layer can be adjusted. The efficiency of the diffusion
method to fill the pores in the structure of the polymer

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Polymeric Composite Materials with the Strengthened Superficial Properties

by low-molecular substance is undeniable [1].

Fundamentals of strengthening the surface of the
polymer products by creating gradient structures are
caused by the initial heterogeneity of the polymer on
the supermolecular level. Amorphous polymers, in
particular, the linear PVC, are distinguished by local
heterogeneity of molecular packing and the presence of
dense globular structures. Interglobular regions have a
lower packing density of molecules, large defects,
including defective parts of macromolecules and
impurities. This is a weakened region of the polymer
block; it has a lower strength and hardness than the
closely packed globular or domains, less resistant to
thermal degradation and to attack by corrosive media.
There are real microdefects in the polymer due to
localized overtensions that are common to polymer
with spherilitic structure [11-14].
Exactly these weak areas of polymer material should
be strengthened. And because they are more available
to diffusion swelling, it predetermines the modification
of polymers by monomers and oligomers.
When reactive oligomers are used as a diffusant, it is
possible to create gradient interpenetrating networks
(IPNs) in the matrix of base polymer after the curing of
oligomers. Gradient IPNs are a mixture of
three-dimensional polymers, the concentration of the
components of which varies along section of the
sample. This type of systems can be obtained by the
method of successive curing. The pre-formed first
polymer swelling in the monomers is stopped at a
certain stage, not reach the equilibrium, and
polymerization is carried out to produce second
polymer, which concentration in the matrix polymer
changes from the surface to its depths. The result is a
formation of the systems whose properties differ from
the properties of individual polymers and of IPNs,
obtained in the traditional way. If the matrix polymer is
linear, then semi-IPNs type structures are formed [11].
The method of successive curing in the obtaining of
composite materials is a fundamentally new method of
polymer modification in the products, allowing to solve

the problem of strengthening their surface, in a wide

range to adjust the properties, in particular surface
hardness, wear resistance, resistance to hydroabrasive
wear and diffusion penetration of chemically
aggressive media. The method is much more efficient
and more economical than bulk modification
(consumption of a reactive modifier is reduced in 3-10
times).
Principles for creating the gradient IPNs with high
mechanical and other properties were implemented on
the example of two amorphous polymers, polyvinyl
chloride (PVC) and polymethylmethacrylate (PMMA)
by means of diffusion modification; specific features of
gradient layers formation were found; their structural
models that take into account the heterogeneity of the
supermolecular structure of the base polymers were
proposed [15-20].
Polymeric systems by Ivanchev definition [21] are
natural nanostructured systems, they have a complex
supramolecular internal structure (coil, pack, globule
and crystallite) with a different arrangement of the
constituent elements in space and the different nature
of the interaction between them. Note, size of the
polymer crystallite is 10-20 nm (macromolecule may
include a few of the crystallites, because its length is
400
nm).
These
arguments
suggest
that
macromolecular formation and polymer systems due
to the peculiarities of their structure are always
nanostructural formations [21].
Surface modification of polymeric products, in
accordance with modern concepts of nanostructured
and nanoreactor formations can be represented as a
surface nanomodification (still the question of the
formation of nanostructured and nanoreactor
elements in the surface diffusion modification of
polymers by monomers and oligomers was not
considered in broad terms).

2. Experiment
Following materials were used in the research: block
samples of PVC size 20 mm 20 mm 4 mm, silica sol

Polymeric Composite Materials with the Strengthened Superficial Properties

387

Table 1 The main characteristics of silica sol.

Characteristic
Density (kg/m3)
Weight concentration of SiO2 (g/L)
Weight concentration of Na2O (g/L)
Viscosity (cSt max)
Micelle diameter (nm)

Value
1,200
330-340
34
20.0
5-9.5
10.3

were used as a low molecular weight diffusant. Silica

sol was a lyophilized colloidal system with nanoscale
particles usually spherical (Table 1). To characterize
the particle size distribution of silica sol used laser
particle size analyzer (HORIBA LA950), (Fig. 1). The
surface of the nucleus of the colloidal particle
consisting of silicon dioxide SiO2 is covered by silanol
groups SiOH, which dissociation causes the emergence
of the double electric layer and the negative charge of
the sol particles:
SiOH + OSi OH + Si O Si
SiOH + OSi H2O + SiO.
Samples of PVC were subjected to surface treatment
in a dispersed system of silica sol at 60 C until the
equilibrium degree of swelling.
To analyze the structure of the gradient polymer
used the following methods:
(1) High-resolution scanning electron microscopy
(HR-SEM);
(2) Dynamic mechanical method (DMA);
(3) Microhardness test (HVS-1000).

3. Results and Discussion

Use of nanostructure-forming inorganic modifier
silica sol as the diffusant allows to adjust the character
of nanostructured formations and hence the strength
properties of PVC materials. It should be noted that
only small doses of the sorbed low molecular weight
diffusant (up to 0.5 wt.%) are required to realize this
method of modification.
The first stage of the modification process is the
swelling of PVC in nanomodifying component, silica
sol. Kinetic curves are typical saturation curves (Fig. 2).
An increase in temperature leads to a decrease in time

Fig. 1 The silica sol particles distribution in sizes.

Fig. 2 Kinetic curves of swelling of PVC in silica sol at

room temperature (1) and at 60 C (2).

required to reach an appropriate degree of swelling.

The obtained samples by diffusion impregnation
during different periods of time with varying degrees of
swelling (mass and volume) change the actual
concentration of modifier in the surface layer. The
maximum degree of impregnation (up to 1.4 wt.%)
corresponds the modifier concentration more than 6%.
The modifier concentration gradient in the surface
layers causes the changes in the properties over the
thickness of the samples. There is a definite relation
[15-18] between the concentration of the diffusant and
parameters such as the microhardness of the sample. So
the change in microhardness can indirectly determine
the nature of the modifier distribution in the surface
layer of the polymer sample. Fig. 3 shows the curves of
the distribution of microhardness over the thickness of
the flat sample (plate 4 mm thick). In studying the
processes of surface nanomodification, the authors are
dealing with a complex system, which involves several
components: the dissolved nanomodifier, the solvent

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Polymeric Composite Materials with the Strengthened Superficial Properties

deepening into the sample was estimated by the content

of Si and O, whose presence is due to not only its
content in silica sol, but the presence in the content of
ketogroups of PVC macromolecules. Chemical state of
the raw PVC surface was almost identical to the
characteristic of gradient PVC at a depth of 250 m
(Figs. 4-6).

Fig. 3 Distribution of microhardness over the thickness of

the PVC samples containing (1) 0%, (2) 1.4%, (3) 1.4%
silica sol (2) before and (3) after solvent removal.

(water) and the surface layer of the polymer block. The

penetration diffusion layer of the solvent in the
polymer block is always greater than of nanomodifier.
Diffusion modification is not only loading of
modifying component in the most critical surface layer,
but also improving the structure and physical state of
the surface layers of polymer products, firstly, due to
the formation of hydrogen bonds and the ordering of
water structure in the polar groups of PVC [22, 23];
secondly, due to the structuring effect of free d-orbitals
of silicon and unshared electron pairs of chlorine and
oxygen of the polymer; thirdly, due to the formation of
bonds of the donor-acceptor character. After removal
of physically bound water (free) there is a further
increase in the microhardness on the surface because of
structural changes that lead to transformation of both
the molecular and supramolecular nature. The most
thermodynamically equilibrium structure is formed.
The chemical compositions of gradient layers at
different depths were analyzed by high-resolution
scanning electron microscopy to estimate the changes
in the silica sol concentration in the surface layers. The
content of the modifier was identified by the lines of
the spectra of Si and O. Quantitative surface analysis
based on the proportionality of the intensity of spectral
lines of atomic concentration of the test element.
Decreased the silica sol concentration with the

Fig. 4 The chemical composition of the modified PVC at a

depth of 50 m.

Fig. 5 The chemical composition of the modified PVC at a

depth of 150 m.

Polymeric Composite Materials with the Strengthened Superficial Properties

389

4. Conclusions

Fig. 6 The chemical composition of the modified PVC at a

depth of 250 m.

Specifics of the formation of specific nanostructures

in the polymer and the realization of their
nanostructural
characteristics
were
observed.
Improving the complex of physical and mechanical
characteristics and changes in the structure was
achieved with the loading of fine nanoscale inorganic
particles into the surface layer of polymer block, and to
implement the desired effect only small amounts of
additives (0.5 wt.%) are required. Polymer system in
the surface layers is transformed into organic-inorganic
polymer composite material by means of the formation
of nanoscale structured zones, a hybrid system based
on the incompatible by nature components [21].
The
principles
of
nanochemistry
and
nanotechnology in the polymer materials can greatly
increase the efficiency of polymer systems, to improve
their properties and operational characteristics.

References
[1]
[2]
[3]

[4]

Fig. 7 Temperature dependence of the elastic modulus for

(1) pure and (2) the modified PVC.

The state of the surface layer affects the

macro-properties of polymer material which
significantly altered by changing the packing density.
For example, the elastic modulus of surface-modified
samples were higher (Fig. 7). This can be explained by
the fact that the action of nanomodifier causes the
unique physical crosslinking of the polymer which
leads to its compaction and, consequently, to an
increase in strength and elastic modulus of the polymer
system.

[5]

[6]
[7]

[8]

A.N. Machulis, E.E. Tornau, Diffusion Stabilization of

Polymers, MINTIS, Vilnius, 1974, p. 256.
A.S. Hoffman, Surface modification of polymers, Chinese
Journal of Polymer Science 13 (1995) 105-203.
T.J. Carry, Organic chemistry at chemically resistant
polymer surfaces: Modification of surface reactivity
and surface properties, Chemia. 44 (90) (1990)
316-318.
M. Dror, M.L. Elsable, G.C. Berry, Gradient
interprenetrating polymer networks, 1 Pbly (ether urethane)
and polyacrylamide IPN, J. Appl. Polym. Sci. 26 (1981)
1741-1757.
G. Akovali, A. Labban, Gradient polymers: Some futher
studies with systems of hard matrices contania hard
gradients, In: IUPAC morco, Florence 1980, Int. Symp.
Macromol, Preprints Pisa, 1980, pp. 264-267.
A.E. Chalyh, Diffusion in the polymer systems, .,
Chemistry, 1987, p. 312.
A.A. Tager, L.V. Adamova, N.T. Herush, The influence
of pre-swelling in methanol on the sorption and diffusion
of water in cross-linked copolymers of methyl
methacrylate, Highmolecular Comp. (1991) 176-179.
I.I. Zlotnikov, V.V. Lisovskiy, V.G. Savkin, Methods of
diffusion modification of phenolic, STC abstracts:
Modification of polymeric materials during their
processing and modification of the molded products from

390

[9]
[10]
[11]
[12]

[13]

[14]

[15]

[16]

Polymeric Composite Materials with the Strengthened Superficial Properties

them, Izhevsk, 1988, p. 42.
A.A. Shturman, Strengthening of details from the
secondary plastic, Plast. Masses (1991) 53-54.
V.G. Nazarov, Surface modification of polymers:
Monograph, ., Msuee, 2008, p. 474.
U.S. Lipatov, Physical chemistry of multicomponent
polymer systems, Nauk. Dumka, Kiev, 1988, p. 384.
L.R. Strelkova, G.T. Fedoseeva, K.S. Minsker,
Photochemical ageing of rigid PVC, Plast. Masses7 (1976)
2-73.
L.R. Strelkova, G.T. Fedoseeva, K.S. Minsker,
Photochemical degradation of PVC, Highmolec. Comp.
(1976) 2064-2066.
G.T. Fedoseeva, L.R. Strelkova, E.O. Krats,
Photo-oxidative degradation of polyvinylchloride under
atmospheric ageing, Plast. Masses 7 (1980) 28-29.
L.A. Abdrahmanova, V.H. Fakhrutdinova, V.G. Khozin,
Surface modifications of products of PVC by furan
oligomers, Plast. Masses 1 (1993) 17-18.
L.A. Abdrahmanova, V.H. Fakhrutdinova, V.G. Khozin,
Processing of PVC-products by reactive oligomers, Plast.
Masses 4 (1995) 30-31.

[17] L.A. Abdrahmanova, V.G. Khozin, Thermodynamics of

binary systems of PVC-furan plasticizer, Journal of
Applied Chemistry 69 (1996) 486-489.
[18] L.A. Abdrahmanova, V.H. Fakhrutdinova, V.G. Khozin,
Chemical transformations of furan compounds in the
matrix of PVC, Journal of Applied Chemistry 72 (1998)
1003-1006.
[19] L.A. Abdrahmanova, V.H. Fakhrutdinova, V.G. Khozin,
Prospects for enhancing the surface of polymeric building
materials using the diffusion modification, Building
Materials 11 (2005) 11-14.
[20] L.A. Abdrahmanova, V.H. Fakhrutdinova, V.G. Khozin,
Diffusion modification of polymethylmethacrylate
oligoester akrilates, Journal of Applied Chemistry 76
(2003) 1883-1885.
[21] S.S. Ivanchev, A.N. Ozerin, Nanostructures in polymer
materials, Highmolec. Comp. B 48 (2006) 1531-1544.
[22] I.V. Kozlov, S.P. Papkov, Physico-chemical basis of
plasticization of polymers, . Chemistry (1982) 223.
[23] V.N. Gud, B.S. Kolupaev, IR spectroscopic study of
adsorbed by polymers water of different polarity, Plast.
Masses 3 (2011) 44-47.