ISSN 1070-4272, Russian Journal of Applied Chemistry, 2007, Vol. 80, No. 8, pp. 1413!1418. + Pleiades Publishing, Ltd., 2007.
Original Russian Text + S.A. Trifonov, E.A. Sosnov, Yu.S. Belova, A.A. Malygin, N.G. Razinkova, G.G. Savkin, 2007, published in Zhurnal Prikladnoi
Khimii, 2007, Vol. 80, No. 8, pp. 1374!1379.
AND POLYMERIC MATERIALS
Influence of Chemical Modification of the Surface
of Polyethylene with Phosphorus, Boron, Titanium,
Vanadium, and Silicon Halides on Its Vapor Permeability
S. A. Trifonov, E. A. Sosnov, Yu. S. Belova, A. A. Malygin,
N. G. Razinkova, and G. G. Savkin
St. Petersburg State Technological Institute (Technical University), St. Petersburg, Russia
Russian Research Institute of Experimental Physics, Russian Federal Nuclear Center,
Federal State Unitary Enterprise, Sarov, Nizhni Novgorod oblast, Russia
Received March 15, 2007
Abstract-The influence of a gas-phase chemical modification of low-density polyethylene with volatile
halides of various elements [PCl
, and Si(CH
] on the surface layer morphology
and vapor permeability of polymeric formulations was examined by atomic-force microscopy, chemical
analysis, and adsorption method.
In this study, we examined how the chemical com-
position and the surface morphology of low-density
polyethylene (LDPE) modified with vapor of volatile
, and Si(CH
correlate with the vapor permeability of the resulting
As polymeric matrices served LDPE films with ad-
dition of a thermostabilizer (Fenozan 1010, 0.4 wt %)
and a photostabilizer (carbon black, 2 wt %), de-
posited by vortex-induced vibration sputtering .
The average film thickness was 0.48 + 0.04 mm.
The LDPE was modified with a series of highly
volatile halides (phosphorus and titanium chlorides,
vanadium oxychloride, boron bromide, and dimethyl-
dichlorosilane). To select appropriate modifiers for
elucidating their influence on the vapor permeability
of the polyethylene (PE) coatings, we analyzed
the following factors: (1) formation on the polymeric
matrix surface of element-containing structures pos-
sessing hydrophilic (in the case of PCl
hydrophobic [in the case of Si(CH
and (2) influence of the chemical nature of the mod-
ifier on the redox transformations of the polymer
is an oxidant, and PCl
It should be noted that the halides we used in this
study readily enter into exchange, addition, and ox-
idation reactions .
Gas-phase modification of LDPE was carried out
in a flow reactor at 50oC in a stream of dried air
saturated with a modifier vapor. The halide ions in
the new grafted functional groups were replaced
with hydroxy groups via vapor-phase hydrolysis of
the samples. The completion of the hydrolysis was
ascertained by termination of release of halogen-
containing products at the reactor outlet.
The condition of the surface of the initial poly-
ethylene and the changes of its topography, caused
by the gas-phase treatment, were examined on a Sol-
ver P47 Pro (NT-MDT, Russia)
microscope by the method of atomic-force microscopy
(AFM) in the tapping mode in air. The specimens
were scanned in two modes: topographic and phase-
The AFM examinations were carried out at the Collective
Use Center Chemical Assembling of Nanomaterials, St. Pe-
tersburg State Technological Institute (Technical University).