ISSN 1070-4272, Russian Journal of Applied Chemistry, 2015, Vol. 88, No. 1, pp. 110−117. © Pleiades Publishing, Ltd., 2015.
Original Russian Text © A.S. Kochetkova, N.Yu. Eﬁ mov, E.A. Sosnov, A.A. Malygin, 2015, published in Zhurnal Prikladnoi Khimii, 2015, Vol. 88, No. 1, pp. 115−123.
Effect of the Chemical Modiﬁ cation of the Filler Surface
on the Structure and Permeability of a Composite Film
Based on Polyvinyl Chloride
A. S. Kochetkova, N. Yu. Eﬁ mov, E. A. Sosnov, and A. A. Malygin
St. Petersburg State Institute of Technology (Technical University), Moskovskii pr. 26, St. Petersburg, 190013 Russia
Received May 27, 2014
Abstract—Composite ﬁ lms based on polyvinyl chloride and nanodispersed Al
[initial and modiﬁ ed by suc-
cessive treatment with POCl
O vapors] were synthesized. As shown by AFM examination,
the ﬁ ller in the course of the ﬁ lm preparation is mainly distributed in near-surface zones of the polymer. The
permeability of the composite ﬁ lm to water vapor varies depending on the chemical composition of the aluminum
oxide surface. The diffusion characteristics of the synthesized polyvinyl chloride composite were evaluated from
the standpoint of the diffusion–sorption permeability theory within the framework of the two-phase model of
the polymer structure.
Wide use of polyvinyl chloride (PVC) ﬁ lms as a
packing material makes it necessary to ensure control of
the ﬁ lm permeability to various gases (O
water vapor, and other components of the environment
in the required direction, depending on the kind of the
product being protected. One of the efﬁ cient ways to
decrease the water vapor permeability of polymer ﬁ lms
is introduction of inorganic ﬁ llers [1, 2]. The properties
of the ﬁ lled ﬁ lms, including the barrier properties, can
be controlled by varying the shape and size of ﬁ ller
particles, their concentration in the composite ﬁ lm, and
the character of their interaction with the matrix.
The decrease in the water vapor permeability of ﬁ lled
ﬁ lms is determined by the geometric factor: deceleration
of the diffusion of molecules by impermeable inorganic
particles present on the diffusion path. On the other
hand, the local structure of the polymer can change upon
interaction with the ﬁ ller particles, largely determined
by the chemical afﬁ nity of the ﬁ ller particle surface.
Therefore, chemical modiﬁ cation of the ﬁ ller surface
can inﬂ uence the conformational state of the polymer
surrounding the ﬁ ller, which, in turn, can lead to changes
in the rate and mechanism of physical processes such as
Among known methods for constructing the surface
of solids, a particular place is occupied by the molecular
layering (ML) method allowing construction of the
surface functional groups with the atomic and molecular
level of accuracy in presetting their composition
and structure. This is particularly important in using
nanosized matrices [4–6]. The ML possibilities allow
synthesis on the nanoparticle surface of structures that
will not appreciably increase the particle size, so that
the geometric parameters of the ﬁ ller can be preserved.
This study was aimed at revealing the relationship
between the chemical composition of the surface of
nanodispersed aluminum oxide and the structure and
water vapor permeability of the composite polyvinyl
chloride ﬁ lm with low content of this ﬁ ller.
Taking into account the results of previous studies,
we prepared the composite material by homogenization
of the dispersed ﬁ ller (2.0 wt %) in a melt of PVC of