Plasma polymer

The deposition of organic films by plasma polymerization is an important application of non-thennal plasmas 1301. Plasma polymers are fonned at the electrodes and the walls of electrical discharges containing organic vapours. Oily products, soft soluble films as well as hard brittle deposits and powders are fonned. The properties of plasma... 

Photopolymerization and Plasma Polymerization. The use of ultraviolet light alone (14) as well as the use of electrically excited plasmas or glow discharges to generate monomers capable of undergoing VDP have been explored. The products of these two processes, called plasma polymers, continue to receive considerable scientific attention. Interest in these approaches is enhanced by the fact that the feedstock material from which the monomer capable of VDP is generated is often inexpensive and readily available. In spite of these widespread scientific efforts, however, commercial use of the technologies is quite limited. 

When -xylene is used as the monomer feed in a plasma polymer process, PX may play an important role in the formation of the plasma polymer. The plasma polymer from -xylene closely resembles the Gorham process polymer in the infrared, although its spectmm contains evidence for minor amounts of nonlinear, branched, and cross-linked chains as well. Furthermore, its solubiUty and low softening temperature suggest a material of very low molecular weight (15). 

The Auger depth profile obtained from a plasma polymerized acetylene film that was reacted with the same model rubber compound referred to earlier for 65 min is shown in Fig. 39 [45]. The sulfur profile is especially interesting, demonstrating a peak very near the surface, another peak just below the surface, and a third peak near the interface between the primer film and the substrate. Interestingly, the peak at the surface seems to be related to a peak in the zinc concentration while the peak just below the surface seems to be related to a peak in the cobalt concentration. These observations probably indicate the formation of zinc and cobalt complexes that are responsible for the insertion of polysulfidic pendant groups into the model rubber compound and the plasma polymer. Since zinc is located on the surface while cobalt is somewhat below the surface, it is likely that the cobalt complexes were formed first and zinc complexes were mostly formed in the later stages of the reaction, after the cobalt had been consumed. 

The presence of a third peak in the sulfur profile, near the film/substrate interface, indicates that some sulfur diffused through the plasma polymer films and reacted with iron, probably forming FeS at the interface. 

The outer surfaces of these plasma polymers are terminated with hydroxyl groups and have high surface energies. They are readily wet by adhesives and form strong and durable adhesive bonds [51]. 

Ortiz-Magan A.B., Pastor-Bias M.M., Eerrandiz-Gomez T.P., Morant-Zacares C., and Martfn-Martfnez J.M., 2001, Surface modifications produced by N2 and O2 RF-plasma treatment on a synthetic vulcanised rubber. Plasmas Polym., 6(1,2), 81-105. 

Schwerzel, R.E. and Spahr, K.B., Hydrogen Production with Photoactive Semiconductor Catalysts Stabilized by Metallized Plasma Polymer Coatings, Final Report to U.S. Department of Energy, Brookhaven National Laboratory, Battelle, 1989. 

The polymer-substrate (2-3) interface is assumed to be sharp and smooth, but the plasma-polymer (1-2) interface may be diffuse or rough. Unpolarized light of vacuum wavelength A is incident upon the system from region 1 at an angle 0, relative to the normal. 

The full expression for the reflected intensity of a laser interferometer in a plasma/polymer/silicon system can be used to measure the polymer refractive index to within about 3 percent. 

Denes, A.R. and Young, R.A. (1999). Reduction of weathering degradation of wood through plasma-polymer coating. Hol orschung, 53(6), 632-640. 

Glow discharge or "cold" plasmas are gaining increased currency for the deposition of novel and potentially valuable macromolecular coatings. The range of properties attainable by a plasma-polymer is wide, and depends critically on such variables of the plasma deposition process as choice of monomer, substrate temperature (T ), power density (p), the excitation frequency (v), and others incluSing monomer flow rate, reactor geometry, etc... Control over these variables can produce crossllnked, dense deposits which adhere tenaciously to... 

Primary interest was in the barrier properties obtained from plasma organo-silicones and from inorganic "SIN" coatings. Spectral grade HMDSO was used in the former case, while mixtures of SiH and NH were used to produce the SIN structures. The substrate in much or the work was DuPont Kapton type H polylmide film, 51 pm thick. Substrate temperatures extended to 450 C, as described earlier (6). The thickness of plasma-polymer deposits was about 0.5 pm. Moisture permeation was evaluated by the routine of ASTME-96-53 T (water vapor transmission of materials in sheet form). Additional, more precise data, were obtained with both a Dohrmann Envirotech Polymer Permeation Analyser, modified as previously described (6), and a Mocon "Permatran W" moisture permeation apparatus. 

As stated, the capability of plasma deposits to reduce the access of water to corrosion-sensitive surfaces may be an important motivation for their application in corrosion protection. In order to study this property, Kapton polyimide film was selected as the substrate because of its high inherent permeability to water and its ability to resist elevated temperatures. The response of Kapton film overcoated by PPHMDSO to the permeation of water vapor is shown in Fig. 1. Clearly, the presence of the organo-silicone plasma film greatly reduces water permeation. The magnitude of the effect is much enhanced when plasma polymers are produced at high T and p. 

Rochow, E.G. (1951). An Introduction to the Chemistry of Silane. 2nd, ed.. Chapman Hall. London. Rostami, H., Iskandarni, B. and Kamel, I. (1992). Surface modification of Spectra 900 polyethylene fibers using RE-plasma, Polym. Composites 13, 207-212. 

The observation of these dielectric relaxation processes arising from carbonyl features, has also been reported by Tibbit and co-workers in plasma polytetra-fluoroethylene as well as other plama polymers. In measuring the dielectric loss tangents over a frequency range of 10 -10 Hz at temperatures of — 150 to 100 °C, they have demonstrated that the dielectric loss curves of plasma polymers derived from hydrocarbon and fluorocarbon monomers are very similar, but bear no resemblence to their conventionally polymerized counterparts. 

Plasma polymers are deposited on surfaces in contact with a glow discharge of organic or organometallic monomers, in the form of a thin film and/or as a powder. Such films find applications as surface modifiers and in applications where the bulk properties of extremely thin films are desirable. 

The following are some important characteristics of plasma polymer films 1 2 3 4... 

For most practical coating processes, the monomer flows into a plasma reactor with a continuous glow discharge, and is wholly or partially consumed in the conversion to plasma polymer. In such a setup, gaseous by-products and unconverted monomer are continuously pumped out of the reactor. 

In a plasma polymerization process, the growth of low molecular weight monomer species to a high molecular weight plasma polymer network takes place. In a chemical sense, plasma polymerization is different from conventional polymerizations, such as radical or ionic. The term radical polymerization means that propagating reactions of monomers are initiated by radical species. Ionic polymerization means that chemical reactions are propagated by ionic species in the polymerization step. Plasma polymerization involves an energy source to... 

How the starting molecules are fragmented into activated small fragments depends on the energy level of the plasma and the nature of the monomer molecules. This is a reason why plasma polymers possess different chemical composition when the plasma polymerization is operated at different conditions, such as different monomer flow rate, RF power, and pressure of the reaction chamber, even if the same starting materials are used for the plasma polymerization. 

The hydrodynamic factors that influence the plasma polymerization process pose a complicated problem and are of importance in the application of plasma for thin film coatings. When two reaction chambers with different shapes or sizes are used and when plasma polymerization of the same monomer is operated under the same operational conditions of RF power, monomer flow rate, pressure in the reaction chamber etc., the two plasma polymers formed in the two reaction chambers are never identical because of the differences in the hydrodynamic factors. In this sense, plasma polymerization is a reactor-dependent process. Yasuda and Hirotsu [22] systematically investigated the effects of hydrodynamic factors on the plasma polymerization process. They studied the effect of the monomer flow pattern on the polymer deposition rate in a tubular reactor. The polymer deposition rate is a function of the location in the chamber. The distribution of the polymer deposition rate is mainly determined by the distance from the plasma zone and the... 

In the process of plasma polymerization, a highly crosslinked polymer is deposited on the surface The deposited plasma polymer changes the surface properties of the substrate dramatically. It modifies the surface of powders in terms of surface energy, functional groups, wettability, interaction with polymers, and dispersion... 

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