(Invited) Plasma Technology in Surface Engineering: From Super-Hydrophilic to Super-Hydrophobic Materials
Authors: Nikiforov Anton , Morent Rino , Ma Chuanlong 
Published: November 2022

Materials surface wettability is a fundamental property of a solid. Wettability plays a paramount role in the everyday applications of solid materials in many fields of science and technology. Numerous examples include advanced membranes (from water purification to biopharmaceuticals), energy storage devices, windows, raincoats, roofs, disposable diapers, microfluidics, bandages, tissue scaffolds, and bio-implants. With the continuous development of modern society, the demand for advanced functional materials with the desirable surface wettability is increasing faster than ever before. This is why precise control over surface wettability is expected to provide materials with superior properties for unprecedented applications in diverse fields.
Over the past decade, conventional wet chemistry approaches have been among the most frequently used methods for surface wettability control. However, they are often energy-inefficient, pollute the environment, and rely on harsh synthesis conditions. Recently, low-temperature plasma processing has attracted major attention in surface wettability control. The reason for this particular interest is because plasma processing is highly-selective, environmentally friendly, and low-cost. Plasma processing can uniquely modify both the surface chemistry and surface topography for a wide range of materials. Moreover, it can be operated at very mild conditions such as room temperature, atmospheric pressure, and open-air environments.
Plasma can be used as a controlled reactive physicochemical environment for surface activation, coating deposition, and nanostructuring of diverse materials. The unique plasma-specific conditions and effects allow precise control over microscopic surface chemical composition and surface nanostructures by adjusting the macroscopical energy input. Accordingly, effective control over surface wettability can be achieved for a broad range of hard and soft materials. An environmentally friendly, large scale and low-cost wetting control method that does not result in bulk damage, would result in improvement of industrial applications. A possible solution to this wetting control problem is atmospheric-pressure plasma (APP), especially the plasma generated in open-air due to the benefits of solvent-free treatment, requiring no vacuum systems and suitable for in-line processes. In the current work, we will give a comprehensive overview of different atmospheric pressure plasma processes capable to change the surface properties of the polymers with little or no change of the bulk. Two main approaches: (i) plasma activation introducing oxygen-containing groups into the material surface; (ii) plasma polymerization directed to the change of the surface composition will be highlighted and background will be explained.
Recently our team developed a new approach based on the use of a combination of plasma activation and plasma polymerization, two different plasma techniques in a single process to achieve different surface wetting properties from hydrophilic to hydrophobic, with the high long-term stability of the coatings in water. Such a type of research approach realized in one plasma source was not yet applied for wettability control and has very promising application potential in the industrial processing of polymers. For surface engineering, and easy to scale-up the radio frequency (RF) plasma system was adopted to perform both plasma activation and plasma polymerization on PET substrate in the atmospheric pressure in the open air. Different characterization methods including WCA measurements, Fourier-transform infrared spectroscopy (FT-IR), XPS, and atomic force microscopy (AFM) were applied to get an insight into surface chemistry and morphology and the effect of the combination of the plasma activation with plasma polymerization.
The developed approach has shown the capability of stable coatings deposition with the use of acrylic acid, HMDSO or fluorine-containing precursors PFDA. We demonstrate a single-step, fast, green, cheap, and universal plasma-based approach with potential for large-scale production of oil/water separation membranes, namely aerosol-assisted plasma deposition (AAPD). A hydrophobic polyester membrane is exposed to an in-line atmospheric pressure plasma coupled with an aerosol of a 2-hydroxyethyl methacrylate (HEMA) monomer. A plasma polymerized HEMA thin film is thus successfully coated on the membrane, resulting in an superhydrophilic/underwater superoleophobic surface. With created coating, the water pre-wetted plasma-functionalized polyester membrane shows an ultrahigh separation efficiency above 97.8% towards various oil/water mixtures and a superb water flux above 35.6 L m-2 s-1. Importantly, it also exhibits excellent performance in anti-oil-fouling, recyclability, and durability, indicating its high potential in real-life usage. To further examine the universality of the proposed approach, another hydrophilic monomer (acrylic acid) is also used to functionalize the polyester membranes. The obtained functionalized membranes can also efficiently separate diversified oil/water mixtures. Therefore, this study demonstrates the capability of plasma-based surface engineering methods to manipulate surface properties of materials in a very wide range from superhydrophobic to hydrophilic and even super-hydrophilic which opens new areas of applications.