Corona-modified polymer surfaces

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. 

The results presented here demonstrate that static SIMS has unique capabilities for the characterization of the surfaces of polymers that have been modified by metal deposition or by plasma or corona techniques. Especially, the introduction of unsaturation and crosslinking are aspects that in some polymers can be observed directly. The formation of low-molecular oxidized material that can be inferred from XPS studies, can also be observed directly. A limitation of the quadrupole-type instrument, which is still the most widely used, is its limited mass range and mass resolution. It can be expected that a considerably more detailed description of modified polymer surfaces can be obtained by application of the more powerful reflectron-type Time-of-Flight SIMS spectrometers, but such studies have, to date, not yet been published. 

Over the years, several methods have been developed in order to modify polymer surfaces for improved adhesion, wettability, printability, dye uptake, etc. These methods include mechanical and wet chemical treatments, and exposure to gas phase processes like corona discharge, flame, UV/ozone, glow discharge plasmas, and particle beams. 

The modification of the chemical composition of polymer surfaces, and thus their wettability with chemical substances, can be realized in different ways electric discharges more commonly called Corona effect, oxidation by a flame, plasma treatment, UV irradiation and also UV irradiation under ozone atmosphere. Numerous studies have been devoted to the effects of these different treatments. More recently, Strobel et al. [204] compared the effects of these treatments on polypropylene and polyethylene terephthalate using analytical methods such as E.S.C.A., F.T.I.R., and contact angle measurements. They demonstrated that a flame oxidizes polymers only superficially (2-3 nm) whereas treatment realized by plasma effect or Corona effect permits one to work deeply in the polymer (10 nm). The combination of UV irradiation with ozone flux modifies the chemical composition of the polymers to a depth much greater than 10 nm, introducing oxygenated functions into the core of the polymer. 

Several techniques including corona discharge [1], plasma treatment [1,3,4], flame treatment [1], and irradiation with UV light in the presence of a UV sensitive gas [5-8] have been developed to modify the polymer surface. The principle of those surface treatment technologies is to introduce polar groups onto the polymer surface. This provides significant improvement of wettability, paintability, biocompatibility and also adhesion to other polymers or metals. 

Plasma vs. Corona Treatment of Polypropylene (PP1. Corona treatments of polyolefins to modify their surfaces are very common in the polymer industry. The chemistry at such surfaces has been widely studied by XPS (4). It is generally assumed that corona treatments create abundant amounts of radicals which react with oxygen to form a hydroperoxide. This reacts further to eventually form crosslinks, oxidized products (ranging from hydroxyls to esters) with and without chain scission. The latter process is believed to lead to low-molecular weight material. There is some controversy over this material. Its role in determining the surface properties of the modified polymer is not completely understood. Its formation cannot be demonstrated directly by XPS, but only by comparing spectra before and after washing. 

In several studies on the adhesion of self-assembled monolayers, Chaudhury modified the surface of a crosslinked PDMS by corona-treatment following self-assembly of monolayers of varying chemistries. In a similar manner, Mangipudi et al. [55] coated thin film of high molecular weight polymer from a solvent on to the oxidized surface of a PDMS cap. These studies are discussed in Section 4.2. 

ABSTRACT. Hiysical and chemical effiects in reactive gases, assisted by corona or by "cold" plasma at low Hcssure, allow one to modify the surface and interfacial properties of various matoials or their combinations, for example of polymers. This, in turn, can gready improve the matnials performance in specific qrplications, such as adhesion. 

Polymer surfaces could be modified both chemically and physically when they are exposed to a physical treatment like plasma, corona discharge, flame treatment, UV irradiation or electron and neutron beam irradiation (41)... 

Most polymeric surfaces are hydrophobic in nature. In order to improve adhesion (adhesion with other surfaces, adhesion with paints or heparin for biomedical appUcations), this trait must be modified [31]. The most common method of doing this is by oxidation of the surface, which can be carried out by either corona discharge, flame treatment, plasma polymerization at the surface, grafting reactions, or blending the polymer with reactive surfactants that enrich at polymer interfaces. It has been shown that benzophenone xmder ultraviolet irradiation can abstract hydrogen from a polymer surface ... 

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. 

The use of static SIMS for the characterization of surfaces of polypropylene (PP), PTFE and a PMDA-ODA type poly-imide is described. Interfaces between evaporated copper or chromium films onto PTFE and polyimide were also analyzed. Some of the polymer substrates were modified by ion beams, corona discharge in air or plasma treatments in air, At and H2. It is demonstrated that SIMS is highly complementary to XPS for the analysis of such modified surfaces, in that effects such as crosslinking, unsaturation and formation of low-molecular weight material at surfaces can be detected. 

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