GAS PRODUCTS OF ARGON PLASMA INTERACTION WITH POLYARAMID AND POLY(ETHYLENE TEREPHTHALATE)
Authors: Titov Valeriy A. , Shikova Tatyana G. , Smirnov Sergey A. , Ovtsyn Alexander A. , Kuzmicheva Lyudmila A. , Khlustova Anna V. 
Published: July 2018

Non-equilibrium plasma is widely used for surface modification of polymer materials. Reactions of plasma active species with polymers lead not only to the surface modification, but to the formation of gaseous products, which change the plasma composition and internal plasma parameters. It results in the dependence of surface etching and modification kinetics on the quantity of material been treated (on sample sizes in a reactor). These phenomena are known as so called “loading effect” and have been studied for the treatment of polypropylene and polyimide films, poly(ethylene terephthalate) films and fabrics in oxygen and air plasma. It can be expected that gas products of noble gas plasma action on polymers will change strongly plasma parameters and modification results. In this paper, experimental data are represented on composition of gas products and their evolution rates at the treatment of polyaramid films, fibers and poly(ethylene terephthalate) fabric in low-pressure argon plasma. Poly(ethylene terephthalate) textile fabric (PET) made of monofilament yarns (SAATI, S.p.A., Italy) and polyaramide (PA) films and complex yarns “Rusar®” (Termotex, Russia) were used in experiments. Direct current discharge was excited in a flow of argon (technical grade) in a glass tube reactor with 3 cm inner diameter. Fabric samples were placed as cylinders on the reactor wall in the discharge positive column. Square of PET samples was varied from 18 to 111 cm2. The PA yarns with the total length of 550 or 1020 cm were placed in the reactor on special holder with the length of 20 cm. Total gas pressure in reactor was varied from 30 to 300 Pa at discharge current of 20 – 110 mA. Gas flow rate in the reactor was kept constant and equal to 30 cm´s-1. Gas phase analysis was carried out by the methods of plasma emission spectroscopy and mass-spectrometry. Plasma emission spectra and mass-spectra show evolution of H2, CO and H2O molecules at the treatment of PA and PET in argon plasma. Evolution rates for different gas products and their mole fractions have been obtained as functions of total gas pressure. Increase in polymer sample square has been shown to result in changing the ratios between evolution rates for different gas products. Sum of CO, H2 and H2O mole fractions increases with polymer sample square and decreases with gas pressure. Dissociation of molecular gas products results in the changing plasma active species. Oxygen and hydrogen atom lines and OH emission bands are observed in plasma emission spectra. Alteration of intensity ratio for О(3p3P ® 3s3S0) and Ar (4p3D3 ® 4s3P2) lines (IO/IAr) versus time after discharge starting shows the possible participation of oxygen atoms in heterogeneous reactions with polymers. Evolution of molecular gas products of heterogeneous reactions influences plasma properties and rates of plasma chemical reactions. The data obtained will be used for the further analysis of mechanisms of heterogeneous reactions of plasma active species with polymers.