Polymer processing plasma treatment

Before fluorination, the dielectric constant ofpoly(bisbenzocyclobutene) was 2.8, and this value was reduced to 2.1 after plasma treatment. No data were reported in the paper on characterization of structure or properties, except for the dielectric constant of the modified poly(bisbenzocyclobutene). The authors did report that the thermal stability offluorinatedpoly(vinylidenefluoride) was inferior to the original poly(vinylidenefluoride) when treated in a similar way. One of the probable reasons for the low thermal stability is that the NF3 plasma degraded the polymer. According to their results, the thickness of fluorinated poly(bisbenzo-cyclobutene) was reduced by 30%. The same phenomenon was observed for other hydrocarbon polymers subjected to the NF3 plasma process. A remaining question is whether plasma treatment can modify more than a thin surface layer of the cured polymer Additionally, one of the side products generated was hydrogen fluoride, which is a serious drawback to this approach. 

In a previous section, the effect of plasma on PVA surface for pervaporation processes was also mentioned. In fact, plasma treatment is a surface-modification method to control the hydrophilicity-hydrophobicity balance of polymer materials in order to optimize their properties in various domains, such as adhesion, biocompatibility and membrane-separation techniques. Non-porous PVA membranes were prepared by the cast-evaporating method and covered with an allyl alcohol or acrylic acid plasma-polymerized layer the effect of plasma treatment on the increase of PVA membrane surface hydrophobicity was checked [37].The allyl alcohol plasma layer was weakly crosslinked, in contrast to the acrylic acid layer. The best results for the dehydration of ethanol were obtained using allyl alcohol treatment. The selectivity of treated membrane (H20 wt% in the pervaporate in the range 83-92 and a water selectivity, aH2o, of 250 at 25 °C) is higher than that of the non-treated one (aH2o = 19) as well as that of the acrylic acid treated membrane (aH2o = 22). 

Figure 44. A schematic representation of the plasma developed x-ray resist process. Exposure serves to covalenty bind the monomer (m) into the polymer matrix (p). Heating (fixing) drives out (volatilizes) the monomer except where it is "locked in place" by exposure. Plasma treatment converts the silicon to Si02 which retards the etch rate in the exposed areas through formation of a metallic oxide (MO) layer.

Subsequent plasma treatment, modified development processes or lower beam energy during lithography are promising possibilities to produce pores totally free of polymer. Any progress can sensitively be indicated by FTIR spectroscopic imaging. The identification by FTIR imaging spectroscopy of the chemical reasons for the for-... 

There are many different methods for modifying polymer surfaces to improve their adhesion and wetting properties. They include chemical etching and oxidation, ion bombardment, plasma treatments, flame treatment, mechanical abrasion and corona-discharge treatments (1.2). Especially flame and corona treatments are widely used for the modification of polyolefin surfaces to enhance, for instance, their printabilify. Despite the widespread use of such processes in industry, the understanding of the fundamental processes which occur at the polymer surface is very limited. This is undoubtedly due to the shallow depth to which the polymer is modified, typically 5 nm or less. 

In this paper some applications of static SIMS to a variety of modified polymer surfaces are described. They include plasma treatments in reactive and inert gases, corona treatment in air, as well as thermal and ion beam modifications of polymer-metal interfaces. The examples presented and discussed here primarily serve to illustrate the capabilities of static SIMS for the study of such surfaces and interfaces. More detailed discussions of the actual chemical processes that proceed in several of the systems cited will be published elsewhere. 

Another effect, "surface contamination", must also be taken into account This may arise from residual gas and small leaks in the vacuum system, but a further possible source should not be overlooked, namely the following Polymers are capable of entrapping appreciable amounts of gas in their free volume, and these molecules are released under the effect of vacuum and of particle bombardment. In the present experiments the polymers were deliberately not degassed before plasma treatment, as such a pretreatment would not likely be economical in an industrial plasma process. The released molecules, primarily air and water vapor, evidently can participate chemically during plasma treatment by intermixing with the feed gas molecules. 

Low-temperature plasma processes, such as gas plasma treatment and plasma polymerization, have unique advantages in that active (depositing) species strongly interact with the surface of the substrate and modify the surface state. An ultrathin layer of plasma polymer, e.g., thickness less than 50 nm, can be viewed as a new surface state because such a thin layer does not develop a characteristic bulk... 

As far as plasma polymerization and plasma treatment of materials, particularly organic polymers, are concerned, the luminous gas phase (low-pressure plasma) can be divided into three major groups based on the mode of consumption of the gas used to create the plasma (1) chemically nonreactive plasma (2) chemically reactive plasma and (3) polymer-forming plasma. The terms chemically reactive and chemically nonreactive are based strictly on whether the gas used in glow discharge is consumed in chemical processes yielding products in the gas phase or being incorporated into the solid phase by chemical bonds. 

Fluorine contamination has been reported in various environments and applications in the past. It has shown up in plasma processing [10-18], as crosscontamination from storage in contaminated containers or with contaminated samples [14,18], and modification of aluminum deposited on fluoropolymer substrates and other polymers having fluorine-based plasma treatments has also been observed [19-21]. Fluorocarbon lubricants have also been noted to modify the oxide structures on aluminum alloys [22,23], and the degradation of AI2O3 catalytic supports has been associated with fluoride conversion during reactions with fluorocarbons [24]. Alloy oxide modification has also been well noted in the presence of fluorine compounds not of the fluorocarbon family [25]. 

An ultrathin layer of plasma polymer of trimethylsilane (TMS) has been utilized in the corrosion protection of aluminum alloys by means of system approach interface engineering (SAIE) [1 ]. SAIE by means of low-temperature plasmas utilizes low-temperature plasma treatment and the deposition of a nanolilm by luminous chemical vapor deposition (LCVD). This approach does not rely on the electrochemical corrosion-protective agents such as six-valence chromium, and hence the process is totally environmentally benign. 

Considering that the system pressure continues to increase after most of the polymerizable species are exhausted in the gas phase, plasma polymerization of TMS in a closed system can be visualized as a time-delayed, consecutive application of three fundamental processes. The sequence takes the order (1) deposition of Si species, (2) deposition of C species, and (3) H2 plasma treatment of the deposited plasma polymer. 

It should be pointed out that excellent primer adhesion was also obtained with TMS plasma polymers from a (TMS-bAr) mixture in a closed reactor system. This result indicated that, to achieve equally good primer adhesion, TMS polymerization with subsequent Ar plasma treatment could be replaced by one process of cathodic polymerization of a (TMS-bAr) mixture. Since the addition of argon to TMS can help stabilize the gas discharge, plasma polymerization of a (TMS + Ar) mixture is very important in the practical operation of plasma deposition process in conjunction with the industrial IVD process. Plasma polymerization of a mixture of TMS and argon in a closed system also has the advantage of being more... 

DC cathodic polymerization of TMS mixed with argon improved the primer adhesion performance of the closed system TMS plasma polymers. Moreover, the addition of a certain amount of argon into the TMS plasma system further increased the plasma coating quality, reflected in the increase in refractive indices. Based on the higher compatibility with the IVD process, the excellent adhesion performance, and the benefit of one process combining TMS plasma polymerization and the postdeposition plasma treatment, DC cathodic polymerization of TMS mixed with argon in a closed system is being considered as a more realistic and favorable approach in practical applications. 

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