ISSN 0018-1439 ae Russian Original Vol. 19, No. $, September-October 1985 March, 1986 HIECAP 19(5)309-392 (1985) | HIGH ENERGY CHEMISTRY XAMMA BhICOKMX 3HEPIMA (KHIMIYA VYSOKIKH ENERGII)": TRANSLATES FROM RUSSIAN CONSULTANTS BUREAU, NEW YORKLITERATURE CITED 1. V. D. Rusanov et al., Usp. Fiz., Nauk, 134, No. 2, 185 (1981). 2, L. $. Polak, Nonequilibrium Chemica! Kinetics and their Application [in Russian], Nauka Moscow (1979), pp. 4-240. a , 3. A. Y. Demura et al. in: Phenomena in Ionized Gases. Proceedings of the XVth ICPIG, Part I, Minsk (1981), p. 55. : 4. A.V. Demura et al., in: Fifth International Symposium on Plasma Chesistry. Symposiua Proceedings, Vol. 1, Edinburgh (1961), p. 52. 5. B. B. Nikitin and $1 Ya. Umanskii, in? Plasma Chemistry (in Russian}, No. 1, Atomizdat, Moscow (1974), p. 8. 6. S. 0. Macheret et al., Zh. Tekh. Fiz., 50, No. 4, 705 (1980). 7. G. K. Vasil'ev et al., in: Plasma chemistry (in Russian], No. 9, Energoatomtzdac, Moscow (1982), p. 3. 8. E. A. Andreev and E. £. Nikitin, in: Plasma Ghentstry [4n Russian), No. 3, Atomizdat, Hoscow (1976), p. 28, KINETIC FEATURES OF THE POLYMERIZATION OF PERFLUOROCYCLOBUTANE IN ‘A HIGH-FREQUENCY DISCHARGE G. K. Vinogradov, G. Zh. Imanbaev, Upc 541.64:687. 742 and D. 1. Slovetskii ‘The kinetics of gas-discharge polymerization in an Ar + Freon 318 mixture (the mole percentages were 85 and 15% respectively) on the surfaces of electric probes of various configuration have been investigated. The polymerization rate and the properties of the polymer depend on the fluxes af charged particles onto the surface. The development of probe methods for the investigation of the kinetics and mechanism of the formation of polymers ia electric discharges has made it possible to experimentally Prove the direct participation of positive fons in the formation of polymers in a de glow ‘discharge in mixtures of methane with neon and xenon [1-3], whose possibility was pointed out in [4-6]. In electronegative halogen-containing gases a significant role may be played by the negative ions, and the presence of active radicals, for example, of fluorine atoms, may result in etching of the material of the surface. The role of the charged particles in such systens may be different {7]. In most studies gas-discharge polymerization has been carried out ia hf discharges, which are more stable than de discharges in electronegative, as well as polymerizable gases, and are very widely used in practice. The purpose of the present work was to study the process of the formation of apolymer in an hf capacitive dis~ charge in a mixture of Freon 318 with argon (the mole percentages were 14.5 and 85.52, respectively) with the ald of probe methods, he certificate composition of the Freon was (mole percentages): 92.12% perfluorocyclobutage, 7.76% hexafluoropropylene, 0.12% impurities. The reactor consisted of a channel of rectangular cross section with a width equal to 6 cm, a height equal to 1.9 cm (the electrode gap), and a length equal to 13 cm, which was formed by upper and lower (water-cooled) copper electrode and lateral walls nade from PTFE or glass (Fig. 1). The reactor was placed under the hood of a VUP-4 vacuum exhaust. The gas was supplied in a distributed manner through a collector with 40 holes having 0.1-cm diameters at one end of che channel and freely departed through the other end under the hood. Such a design significantly simplifies the placement and replacement of the probes and does not place strict requirements for the hermetic sealing of the reactor. The source of the hf voltage with a frequency of 40.68 Miz was a modified Ekran-1 generator, which was equipped with devices for the monitoring and regulation of the power. The output power was smoothly regulated in the range from 2 to 100 W. The power supplied to the discharge was determined by a device for measuring the transient power, which was calibrated against a matched active ‘a. V. Topchiev institute of Petrochemical Synthesis, Academy of Sciences of the USSR. Translated from Khintya Vysokikh Energi, Vol. 19, No. 5, pp. 455-460, Septenber-October, 1985, Original article submitted June 26, 1984. 370 0018-1439/85/1905-0370309.50 © 1986 Plenum Publishing CorporationFig. 1, Diagram of the reactor: 1) PTFE body; 2) copper electrodes; 3) entrance for gas; 4) collector; 5) distrib- uting holes; 6) thin probe; 7) counterprobe; 8) substrate probe; 9) to hf generator; 10) to probe cireuse, load. ‘The absolute error in the measurement of the power did not exceed 30%, and thé rela- tive error did not exceed 10%, The modulation index of the hE voltage at a frequency of 100 Hz did not exceed 3% owing to the supply af the cathode of the oscillator tube by a stabilized dic source. The pressure in the chamber was measured by a U-shaped oil manometer vith an error of 5 Pa, and the flow rate of the gas was measured by a float-type flow meter with an error no greater than 7%. Besides the parameters indicated, the temperature of the gas in the discharge was evaluated according to the readings of a copper-constantan thermocouple ith a diameter of 0.02 cm. The emission spectra of the discharge in the 200-800-nm wave~ length range were measured on the apparatus with the aid of a KSVU-4 spectroscopic system in various cross sections of the reactor and for various paraneters of the discharge. In this communication we shall present the results of the experiments for only one set of discharge conditions: a pover of 5M, a flow rate of the gas equal to 7.9 cm?/min (under standard conditions), and a pressure of 33.3 Pa. A cylindrical platinum probe with a diameter of 20 » and a length of 2 cm was introduced into the reactor.through a lateral wal}. The nonworking part of the probe was insulated by a quartz capillary with a diameter of 0.03 em. The counter- Probe was an exposed special cylindrical groundvire electrode with an obligue heating f1la~ went (diameter 0.2 cm, length 3.5 em). The counter~probe was located near the exit cross sec- tion of the reactor. Besides the thin cylindrical probe, a flat probe in the space of the dLacharge and a flat substrate probe placed in the plane of the lower grounded electrode were used, The polished end surface of a copper rod with a diameter of 0.23 em, which was in- troduced across the flow to the middie cross section of the reactor, served as the flat Proble in the space of the discharge. The lateral surface of the rod was insulated by PTFE with a thickness of 60. The substrate probe was covered by a shield, which was opened at the tine of the deposition of the nolymer. ‘The polymer was removed from the cylindtial probe by bringing the wire to a temperature of 900-1000°K, and it was removed from the flat probes by etching in an oxygen discharge. The curtent-voltage curves of the probes were recorded point-by-point with the aid of standard instrunentation or with autonatic plotting on an N-305 plotter. The instrumental error in the determination of the current-voltage curves vas 0.52. The kinetics of the growth of the polymer layers were investigated with the aid of the method proposed in [2]. The method makes it possible to obtain a polymer layer at assigned and nonvarying fluxes of the charged particles onto its surface and to continually monitor the rate of growth. The polymer layers were incorporated into the circuit of the current stabilizer during their growth and served as a variable resistance, the voltage drop over which at a constant working current is 9 paraseter related to the thickness. In the general case, the voltage drop is proportional to the product of the resistivity of the polymer layer and its thickness. When the resistivity of the polymer layer is constant, it is directly proportional to the thickness of the polymer layer. Since the resistance of a polymer layer is dependent on the current density (the current-voltage curve is nonlinear), the rate of growth was determined from the variation in the potential drop at one particular neasuring current density in the same direction for all the deposition conditions, which were determined by the value of the working current. ‘The measuring current was periodically passed through the polymer layer (for 1-1.5 sec) during its growth, The thickness of the polymer layer was determined with the aid of an MII-5 microinterferometer with an error no greater than #20 nm. A polymer layer was deposited on the thin probe under stationary dis~ charge conditions from the time when the glow of the probe vanished. The achievenent of stationary discharge conditions was evaluated according to the intensity of the emission in the Ar I line at 750.3 nm. The increase in the intensity ceased after 1.5-2 min. Devia~ tion from the stationary discharge conditions influenced the rate of growth of the polymer layer on the substrate. The sooner the deposition of the polymer began after the activation of the discharge, the greater was the rate of growth. Therefore, the shield on the substrate 371