Reactive plasma free radical reactions

The way in which a plasma polymer is formed has been explained by the rapid step growth polymerization mechanism, which is depicted in Figure 5.3. The essential elementary reactions are stepwise recombination of reactive species (free radicals) and stepwise addition of or intrusion via hydrogen abstraction by impinging free radicals. It is important to recognize that these elementary reactions are essentially oligomerization reactions, which do not form polymers by themselves on each cycle. In order to form a polymeric deposition, a certain number of steps (cycle) must be repeated in gas phase and more importantly at the surface. The number of steps is collectively termed the kinetic pathlength. 

III. Overview and Comments on Free Radical Reactions in Reactive Plasmas. 233... 

To clarify the roles of free radicals in reactive plasmas, it is necessary to measure the products in free radical reactions 1 though 5, which have not been fully understood in the physicochemical studies. 

The reaction mechanisms of plasma polymerization processes are not understood in detail. Poll et al [34] (figure C2.13.6) proposed a possible generic reaction sequence. Plasma-initiated polymerization can lead to the polymerization of a suitable monomer directly at the surface. The reaction is probably triggered by collisions of energetic ions or electrons, energetic photons or interactions of metastables or free radicals produced in the plasma with the surface. Activation processes in the plasma and the film fonnation at the surface may also result in the fonnation of non-reactive products. 

Free radicals are short-lived, highly-reactive transient species that have one or more unpaired electrons. Free radicals are common in a wide range of reactive chemical environments, such as combustion, plasmas, atmosphere, and interstellar environment, and they play important roles in these chemistries. For example, complex atmospheric and combustion chemistries are composed of, and governed by, many elementary processes involving free radicals. Studies of these elementary processes are pivotal to assessing reaction mechanisms in atmospheric and combustion chemistry, and to probing potential energy surfaces (PESs) and chemical reactivity. 

Control of fiber friction is essential to the processing of fibers, and it is sometimes desirable to modify fiber surfaces for particular end-uses. Most fiber friction modifications are accomplished by coating the fibers with lubricants or finishes. In most cases, these are temporary treatments that are removed in final processing steps before sale of the finished good. In some cases, a more permanent treatment is desired, and chemical reactions are performed to attach different species to the fiber surface, e.g. siliconized slick finishes or rubber adhesion promoters. Polyester s lack of chemical bonding sites can be modified by surface treatments that generate free radicals, such as with corrosive chemicals (e.g. acrylic acid) or by ionic bombardment with plasma treatments. The broken molecular bonds produce more polar sites, thus providing increased surface wettability and reactivity. 

During the plasma surface reaction, the plasma and the solid are in physical contact, but electrically isolated. Surfaces in contact with the plasma are bombarded by free radicals, electrons, ions, and photons, as generated by the reactions listed above. The energy transferred to the solid is dissipated within the solid by a variety of chemical and physical processes, as illustrated in Figure 7.95. These processes can change surface wettability (cf. Sections 1.4.6 and 2.2.2.3), alter molecular weight of polymer surfaces or create reactive sites on polymers. These effects are summarized in Table 7.21. 

After a long reaction time, polymers with exceptionally high molecular weight can be synthesized by plasma-induced polymerization. Since only brief contact with luminous gas phase is involved, plasma-induced polymerization is not considered to be LCVD. However, it is important to recognize that the luminous gas phase can produce chemically reactive species that trigger conventional free radical addition polymerization. This mode of material formation could occur in LCVD depending on the processing conditions of LCVD, e.g., if the substrate surface is cooled to the extent that causes the condensation of monomer vapor. 

Free radicals, or radicals, are defined as atomic or molecular species with unpaired electrons on an otherwise open shell configuration. Because a radical has a half-filled orbital, it easily sucks up an electron from another bond, hence exhibiting highly reactive properties and therefore likely to take part in chemical reactions. The first organic free radical is the triphenylmethyl radical, which was identified by Moses Gomberg in 1900 [34], Radicals play an important role in chemical processes such as combustion, atmospheric chemistry, polymerisation, plasma chemistry, biochemistry, etc. [35],... 

Both ionic and free radical mechanisms can be written to explain the foregoing reactions in more detail, but these would be strictly speculative, since no definitive experimental evidence has been obtained. Some sort of benzene ion must form as a result of inelastic collisions between the electrons and benzene molecules in the plasma, but whether these ions or some derivative species are the reactive intermediates is not known. Recently, Potter et al. (11) have shown that styrene, when perfectly dry, does polymerize via an ionic mechanism when irradiated with gamma rays. One can picture a similar mechanism occurring in the electrical discharge. 

A brief survey is given of physicochemical aspects of atomic and molecular processes that are of great importance in reactive plasmas. The processes are composed of the interaction of molecules, in most cases polyatomic molecules, with reactive species such as electrons, ions (both positive and negative), free radicals, and excited atoms and molecules. Topics are chosen from recent studies of some elementary processes in reactive plasmas. Some comments are also given on future problems that call for more work in reactive-plasma research from the viewpoints of physicochemical studies of gas-phase reaction dynamics and kinetics, such as radiation chemistry and photochemistry. 

In the bottom part of Table I, the reactions of free radicals in reactive plasmas are summarized. As described in the preceding sections, there are various reactive or transient species in reactive plasmas. It is generally accepted, however, that free... 

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