Semi-crystalline poly(ethylene terephthalate) (PET) film surfaces were modified with argon and oxygen plasmas by radio-frequency (RF) glow discharge at 240 mTorr/40 W; the changes in topography and surface structure were investigated by atomic force microscopy (AFM) in conjunction with specular reflectance of infrared microspectroscopy (IMS). Under our operating conditions, analysis of the AFM images revealed that longer plasma treatment results in significant ablation on the film surface with increasing roughness, regardless of the kind of plasma used. The basic topographies, however, were different depending upon the kind of gas used. The specular reflectance analysis showed that the ablative mechanisms of the argon and oxygen plasma treatments are entirely different with one another. For the Ar-plasma-treated PET surface, no observable difference in the chemical structure was observed before and after plasma treatment. On the other hand, the oxygen-plasma-treated PET surface displays a significant decrease in the number of aliphatic C-H groups. We conclude that a constant removal of material from the PET surface occurs when using the Ar-plasma, whereas preferential etching of aliphatic C-H groups, with respect to, e.g., carbonyl and ether groups, occurs upon oxygen plasma.

Atomic force microscopy(AFM) was used to study the polyethylene(PE) surfaces grafted and immobilized with acrylic acid by Ar plasma treatment. The topographical images and parameters including RMS roughness and Rp-v value provided an appropriate means to characterize the surfaces. The plasma grafting and immobilization method were a useful tool for the preparation of surfaces with carboxyl group. However, the plasma immobilization method turned out to have a limitation to use as a means of preparation of PE surface with specific functionalities, due to ablation effect during the Ar plasma treatment process.

Isotactic polypropylene (PP) surfaces were modified with argon and oxygen plasmas using a radiofrequency (RF) glow discharge at 240 mTorr and 40 W. The changes in topography and surface structure were investigated by atomic force microscopy (AFM) in conjunction with specular reflectance of infrared (IR) microspectroscopy. Under our operating conditions, the AFM image analysis revealed that longer plasma treatment resulted in significant ablation on the PP surface, regardless of the kind of plasma employed, but the topography was dependent on the nature of the gases. Specular reflectance IR spectroscopic analysis indicated that the constant removal of surface material was an important ablative aspect when using either plasma, but the nature of the ablative behavior and the resultant aging effects were clearly dependent on the choice of plasma. The use of argon plasma resulted in a negligible aging effect; in contrast, the use of oxygen plasma caused a noticeable aging effect, which was due to reactions of trapped or isolated radicals with oxygen in air, and was partly responsible for the increased surface area caused by ablation. The use of oxygen plasma is believed to be an advantageous approach to modifying polymeric materials with functionalized surfaces, e.g., for surface grafting of unsaturated monomers and incorporating oxygen-containing groups onto PP.

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