Patrick Rupper

Suppression of Hydrophobic Recovery by Plasma Polymer Films with Vertical Chemical Gradients

Vertical chemical gradients extending over a few nanometers were explored. The gradients are based on plasma-polymerized oxygen-containing ethylene (ppOEt) films. Using plasma conditions with low CO2/C2H4 ratio and high energy input, cross-linked films were deposited as base layer, while increasing CO2 and lowering energy input resulted in less cross-linked yet highly functional films as applied as top layer. Aging studies indicate that, in particular, for very thin gradient structures, the cross-linked subsurface zone effectively hinders reorientation of the surface functional groups, thus restricting hydrophobic recovery and oxidation effects.

Composition and Stability of Plasma Polymer Films Exhibiting Vertical Chemical Gradients

Controlling the balance between stability and functional group density in grown plasma polymer films is the key to diverse applications such as drug release, tissue-engineered implants, filtration, contact lenses, microfluidics, electrodes, sensors, etc. Highly functional plasma polymer films typically show a limited stability in air or aqueous environments due to mechanisms like molecular reorganization, oxidation, and hydrolysis. Stabilization is achieved by enhancing cross-linking at the cost of the terminal functional groups such as -OH and -COOH, but also -NH2, etc. To overcome such limitations, a structural and chemical gradient was introduced perpendicular to the surface plane; this vertical gradient structure is composed of a highly cross-linked base layer, gradually changing into a more functional nanoscaled surface termination layer. This was achieved using CO2/C2H4 discharges with decreasing power input and increasing gas ratio during plasma polymer deposition. The aging behavior and stability of such oxygen-functional vertical gradient nanostructures were studied in air and in different aqueous environments (acidic pH 4, neutral pH ≈ 6.2, and basic pH 10). Complementary characterization methods were used, including angle-resolved X-ray photoelectron spectroscopy (ARXPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS) as well as water contact angle (WCA) measurements. It was found that in air, the vertical gradient films are stabilized over a period of months. The same gradients also appear to be stable in neutral water over a period of at least 1 week. Changes in the oxygen depth profiles have been observed at pH 4 and pH 10 showing structural and chemical aging effects on different time scales. The use of vertical gradient plasma polymer nanofilms thus represents a novel approach providing enhanced stability, thus opening the possibility for new applications.

Improving the Stability of Amino-Containing Plasma Polymer Films in Aqueous Environments

Plasma polymer films that contain amine groups (NH2-PPFs) are known to degrade over time, particularly in aqueousxa0environments. To reduce such aging effects, a vertical chemical gradient regarding the amine group density was explored ranging over a few nanometers at the coating surface. The gradient-containing nanofilms were formed in low-pressure plasma by tuning plasma conditions while keeping the plasma switched on. The coating process started with a more cross-linked NH2-PPF (70 W, 4:7 NH3/C2H4), followed by the deposition of a few nanometers of a less cross-linked yet more functional NH2-PPF (50 W, 7:7 NH3/C2H4). Characterization of the prepared gradient coatings showed that the chemical composition depends on the NH3/C2H4 gas flow ratio, as observed by different analytical methods: plasma diagnostics during deposition and depth profiling analyses of the deposited coating. Finally, surface chemistry was analyzed during air and water aging, showing a similar aging process of the NH2-PPF single layer and NH2-PPF with a vertical chemical gradient in air, while the stability of the gradient coating was found to be enhanced under aqueous conditions maintaining an [NH2]/[C] amount of ∼1%.

Plasma polymer film designs through the eyes of ToF-SIMS

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is increasingly used for the detailed chemical characterization of complex organic materials. Of particular interest in biointerface materials, it provides the accurate molecular information on their surface, a prerequisite for the understanding of subsequent interaction with biomaterials. Plasma polymer films are promising biointerface materials, as tuning the deposition parameters allows the control over film stability and density of surface functional groups. However, the optimization of these film properties not only requires a detailed characterization of the film chemistry, but also that of the deposition mechanisms. Here, ToF-SIMS is used within its different operation modes to investigate those on several plasma polymer film designs. The detailed information on surface molecular chemistry, interface conformation, vertical and lateral chemical and cross-linking gradients is gathered and linked to the underlying deposition mechanisms. In combination with other techniques, the interpretation and understanding of the final functional property of the films in terms of protein adsorption and site-specific binding is achieved.