Polymer surfaces: plasma treatment

The RO2 peroxide radicals formed on the polymer surface by treatment in non-thermal plasma systems are able to initiate different important chemical surface processes. The... 

Bismarck A et al (2008) Effects of surface plasma treatment on trihology of thermoplastic polymers. Polym Eng Sci 48(10) 1971-1976... 

Surface modification refers to the modification that occurs only on the surface of a polymer material without further internal modification. Surface modifications of polymeric materials include surface chemical oxidation, corona surface treatment, surface flame treatment, surface heat treatment, surface plasma treatment, surface metallization processing, ion implantation, and surface grafting polymerization. Because surface modification occurs only on the surface of materials, the performance does not change uniformly. 

An important newer use of fluorine is in the preparation of a polymer surface for adhesives (qv) or coatings (qv). In this apphcation the surfaces of a variety of polymers, eg, EPDM mbber, polyethylene—vinyl acetate foams, and mbber tine scrap, that are difficult or impossible to prepare by other methods are easily and quickly treated. Fluorine surface preparation, unlike wet-chemical surface treatment, does not generate large amounts of hazardous wastes and has been demonstrated to be much more effective than plasma or corona surface treatments. Figure 5 details the commercially available equipment for surface treating plastic components. Equipment to continuously treat fabrics, films, sheet foams, and other web materials is also available. 

While polymeric surfaces with relatively high surface energies (e.g. polyimides, ABS, polycarbonate, polyamides) can be adhered to readily without surface treatment, low surface energy polymers such as olefins, silicones, and fluoropolymers require surface treatments to increase the surface energy. Various oxidation techniques (such as flame, corona, plasma treatment, or chromic acid etching) allow strong bonds to be obtained to such polymers. 

The relatively high volatility of Tg[CH = CH2]8 has enabled it to be used as a CVD precursor for the preparation of thin films that can be converted by either argon or nitrogen plasma into amorphous siloxane polymer films having useful dielectric propertiesThe high volatility also allows deposition of Tg[CH = CH2]g onto surfaces for use as an electron resist and the thin solid films formed by evaporation may also be converted into amorphous siloxane dielectric films via plasma treatment. ... 

Some physical techniques can be classified into flame treatments, corona treatments, cold plasma treatments, ultraviolet (UV) treatment, laser treatments, x-ray treatments, electron-beam treatments, ion-beam treatments, and metallization and sputtering, in which corona, plasma, and laser treatments are the most commonly used methods to modify silicone polymers. In the presence of oxygen, high-energy-photon treatment induces the formation of radical sites at surfaces these sites then react with atmospheric oxygen forming oxygenated functions. 

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. 

Apart from modifications in the bulk, also surface modification of PHAs has been reported. Poly(3HB-co-3HV) film surfaces have been subjected to plasma treatments, using various (mixtures of) gases, water or allyl alcohol [112-114]. Compared to the non-treated polymer samples, the wettability of the surface modified poly(3HB-co-3HV) was increased significantly [112-114]. This yielded a material with improved biocompatibility, which is imperative in the development of biomedical devices. 

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. 

To determine the number of equivalent Ti monolayers (1 equivalent Ti monolayer = 2 x 1015 Ti atoms/cm2) needed on the polymer surface to protect the underlying organic film during 02 RIE, several PMMA films were treated with TiCLt under different processing conditions. After treatment with TiCLt the films were etched in an 02 plasma for different lengths of time and the etching rates were determined. The Ti concentration in the samples was measured both before and after etching (Table II). 

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). 

The surface analytical techniques mentioned above provide wealth information on the composition and structure of polymer surfaee and changes resulting from modification by plasma discharge. It should be however stressed that, despite of broad spectrum of analytical techniques available, the information is not sufficient to understand all imderlying proeesses in their eomplexity. Espeeially, it is the case of plasma treatment when the interaetions of many plasma eonstituents with polymer surface may play a role. Existing theoretical models are restricted to some specific cases and they usually deseribe only some part of the proeess. 

The parameters of treatment were chosen since these led to the most pronounced changes of polymer surface in our previous experiments [70-74]. It was observed elsewhere that plasma treatment of polymer macromolecules results in their cleavage, ablation, alterations of chemical structure and thus affects surface properties e g. solubility [75]. The chemical structure of modified polyethylene (PE) was characterized by FTIR and XPS spectroscopy. Exposition to discharge leads to cleavage of polymeric chains and C-H bonds followed by generation of free radicals which easily oxidize [10,76]. By FTIR spectroscopy the presence of new oxidized structures within whole specimen volume can be detected. IR spectra in the 1710-1745 cm" interval [71,77] from PE, exposed to... 

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