Polymerization plasma

Plasma polymerization is a typical dry process for the preparation of thin solid films. In the plasma polymerization starting from thiophene and 3-methyl-thiophene, the glow discharge was carried out at 7.3 kHz audio frequency (AF) and 13.56 MHz radio frequency (RF) and Ar was employed as the carrier gas [600,601]. The electrical conductivity of iodine-doped AF-PT and RF-PT is 2.2X 10 Scm and 4.3 x 10 Scm (1.8x 10 S cm [600]), respectively, and of iodine-doped AF-PMT and RF-PMT is 1.0 x 10 S cm and 2.8 X 10 S cm respectively [601]. Plasma-polymerized poly(3-bromo-thiophene) shows high electrical conductivity [602]. 

Besides grafting or functionalization, both etching and crosslinking may occur simultaneously on a polymer surface exposed to plasma. The gas used primarily determines which process is dominant. When oxidizing gases like O2, carbon monoxide, carbon dioxide, or water are used, etching and functionalization of the surface dominate. 

The term plasma polymerization is widely used to denote a specific type of plasma chemistry process resulting in the deposition of polymer films by a passage of an organic gas or vapor through the plasma. From the early 1960s, plasma polymerization has 

Plasma polymerization is usually a simpler and more versatile process than the traditional methods of polymer film production, since fewer fabrication steps are necessary. In addition, the plasma process can be used to produce polymeric films (calledplasmapolymers) that do not polymerize under normal chemical polymerization conditions.  

Plasma polymerization involves reactions between plasma species, between plasma and surface species, and between surface species. Usually a free radical mechanism is considered and two cases are distinguished  

The plasma polymerization process takes place through several reaction steps initiation, propagation, termination, and re-initiation. While in conventional polymerization the termination step finishes the process, in plasma polymerization neutral products formed in the termination steps can undergo re-initiation and propagation reactions. 

The series Macromolecular Chemistry issues biennial reviews of the literature concerning particular fields of polymer science. This article is such a review of the field embraced by the title Plasma Polymerization (PP) through 1979 and 1980. The information is drawn from Chemical Abstracts, whose publication time scale means that 1980 is not wholly covered by this work. 

Since this is the first review of PP to appear in this series it is appropriate to begin with a brief description of the technique and the characteristic features of its products. The remainder of the review is divided into four sections kinetic and mechanistic studies of plasma polymerization, product and plasma characterization, applications of plasma polymerization to achieve technological goals (including patents), and finally plasma-induced polymerization of liquid monomers. 

This division is not perfect and there will obviously be some overlap between sections. Studies have been classified according to the general flavour as perceived by the reviewer. 

The mechanisms by which the conversion of low-molecular-weight species into high-molecular-weight species takes place under plasma conditions are very complex and not entirely understood. It is possible, however, to provide a generalized picture of what is likely to be taking place and to outline the conditions necessary to promote PP in an efficient manner. 

A plasma is a partially ionized gas composed of ions, electrons, and neutral species, with electron densities of approximately 10 —10 cm, and is a copious P. de wade, Chem. Ber., 1874,7, 352. 

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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... 

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. 

An important and well studied example is the deposition of plasma-polymerized fluorinated monomer films [35], Monomers are fluoroalkyls, fluorohydroalkyls, cyclo-fluoroalkyls, as well as unsaturated species. The actual... 

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. 

Solution polymerization of VDE in fluorinated and fluorochlorinated hydrocarbons such as CEC-113 and initiated with organic peroxides (99), especially bis(perfluoropropionyl) peroxide (100), has been claimed. Radiation-induced polymerization of VDE has also been investigated (101,102). Alkylboron compounds activated by oxygen initiate VDE polymerization in water or organic solvents (103,104). Microwave-stimulated, low pressure plasma polymerization of VDE gives polymer film that is <10 pm thick (105). Highly regular PVDE polymer with minimized defect stmcture was synthesized and claimed (106). Perdeuterated PVDE has also been prepared and described (107). 

Surface Modification. Plasma surface modification can include surface cleaning, surface activation, heat treatments, and plasma polymerization. Surface cleaning and surface activation are usually performed for enhanced joining of materials (see Metal SURFACE TREATMENTS). Plasma heat treatments are not, however, limited to high temperature equiUbrium plasmas on metals. Heat treatments of organic materials are also possible. Plasma polymerization crosses the boundaries between surface modification and materials production by producing materials often not available by any other method. In many cases these new materials can be appHed directly to a substrate, thus modifying the substrate in a novel way. 

Surface modification of a contact lens can be grouped into physical and chemical types of treatment. Physical treatments include plasma treatments with water vapor (siUcone lens) and oxygen (176) and plasma polymerization for which the material surface is exposed to the plasma in the presence of a reactive monomer (177). Surfaces are also altered with exposure to uv radiation (178) or bombardment with oxides of nitrogen (179). Ion implantation (qv) of RGP plastics (180) can greatiy increase the surface hardness and hence the scratch resistance without seriously affecting the transmission of light. 

Tsai et al. have used RAIR extensively in investigations of plasma polymerized acetylene films as primers for rubber-to-metal bonding [12]. Fig. 12 shows RAIR spectra of films having a thickness between about 5.7 and 90.0 nm. A strong band... 

Tsai et al. have also used RAIR to investigate reactions occurring between rubber compounds and plasma polymerized acetylene primers deposited onto steel substrates [12J. Because of the complexities involved in using actual rubber formulations, RAIR was used to examine primed steel substrates after reaction with a model rubber compound consisting of squalene (100 parts per hundred or phr), zinc oxide (10 phr), carbon black (10 phr), sulfur (5 phr), stearic acid (2 phr). 

Polished steel substrates primed with plasma polymerized acetylene films were immersed into a stirred mixture of these materials at a temperature of 155 5°C to simulate the curing of rubber against a primed steel substrate. During the reaction, the mixture was continuously purged with nitrogen to reduce oxidation. At appropriate times between 1 and 100 min, substrates were removed from the mixture, rinsed with hexane ultrasonically for 5 min to remove materials that had not reacted, dried, and examined using RAIR. The RAIR spectra obtained after reaction times of 0, 15, 30, and 45 min are shown in Fig. 13. 

When a plasma polymerized acetylene film on a steel substrate was reacted with the squalene-containing model rubber compound at 155°C for 15 min, a new band assigned to zinc stearate appeared near 1539 cm in the RAIR spectra... 

Fig. 13. RAIR spectra of model rubber compound reacted with plasma polymerized acetylene films on steel substrates for (A) 0, (B) 15, (C) 0 and (D) 45 min. Adapted by permission of Gordon and Breach Science Publishers from Ref. [12].

Another illustrative example of the application of FTIR spectroscopy to problems of interest in adhesion science is provided by the work of Taylor and Boerio on plasma polymerized silica-like films as primers for structural adhesive bonding [15]. Mostly these films have been deposited in a microwave reactor using hexamethyldisiloxane (HMDSO) as monomer and oxygen as the carrier gas. Transmission FTIR spectra of HMDSO monomer were characterized by strong... 

Many applications of XPS to problems in adhesion science have been reported in the literature. One interesting example is provided by the work of Tsai et al. on the use of XPS to investigate reactions between model rubber compound and plasma polymerized acetylene films that was discussed above [22,23], Consideration of that system permits some interesting comparisons to be made regarding the type of information that can be obtained from RAIR and XPS. 

The XPS survey spectrum of a 75 nm thick film of plasma polymerized acetylene that was deposited onto a polished steel substrate is shown in Fig. 18 [22]. This film consisted mostly of carbon and a small amount of oxygen. Thus, the main peaks in the spectrum were attributed to C(ls) electrons near 284.6 eV and 0(ls) electrons near 533.2 eV. Additional weak peaks due to X-ray-induced O(KVV) and C(KLL) Auger electrons were also observed. High-resolution C(ls) and 0(ls) spectra are shown in Fig. 19. The C(ls) peak was highly symmetric. 

Fig. 18. XPS survey spectrum of a plasma-polymerized acetylene film with a thickness of 75 nm that was deposited onto a polished steel substrate. Reproduced by ptermission of John Wiley and Sons from Ref. [22].

Fig. 39. Auger depth protile obtained from a plasma-polymerized film on a polished steel substrate after the film was reacted with a model rubber compound for 65 min. Reproduced by permission of Gordon and Breach Science Publishers from Ref [45].

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. 

Positive SIMS spectra obtained from plasma polymerized acetylene films on polished steel substrates after reaction with the model rubber compound for times between zero and 65 min are shown in Fig. 44. The positive spectrum obtained after zero reaction time was characteristic of an as-deposited film of plasma polymerized acetylene. However, as reaction time increased, new peaks appeared in the positive SIMS spectrum, including m/z = 59, 64, and 182. The peaks at 59 and 64 were attributed to Co+ and Zn, respectively, while the peak at 182 was assigned to NH,J(C6Hn)2, a fragment from the DCBS accelerator. The peak at 59 was much stronger than that at 64 for a reaction time of 15 min. However,... 

Negative SIMS spectra obtained from plasma polymerized acetylene films on polished steel substrates as a function of reaction time with the model rubber compound are shown in Fig. 45. The most important changes observed in the... 

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