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Advances in Plasma Processes for Polymers II

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A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Processing and Engineering".

Deadline for manuscript submissions: closed (28 April 2023) | Viewed by 25243

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Dr. Choon-Sang Park

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Electrical Engineering, College of Engineering, Milligan University, Johnson City, TN 37682, USA
Interests: atmospheric pressure plasma; microplasma jet device; plasma polymerization; solution plasma; bio applications; microdischarge; Dielectric Barrier Discharge (DBD); high-pressure plasma; plasma thruster; ion propulsion; flexible microplasma thruster; plasma cancer therapy; plasma endodontics; Polymer Light-Emitting Diodes (PLEDs); short-time and long-time (life time) discharge characteristics of plasma display panel and plasma devices
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Dear Colleagues,

Polymerized nanoparticles and nanofibers can be prepared using various processes, such as chemical synthesis, the electrochemical method, electrospinning, ultrasonic irradiation, hard and soft templates, seeding polymerization, interfacial polymerization, and plasma polymerization. Among these processes, plasma polymerization and aerosol-through-plasma (A-t-P) processes have versatile advantages, especially due to having a “dry” process, for the deposition of plasma polymer films and carbon-based materials with functional properties suitable for a wide range of applications, such as electronic and optical devices, protective coatings, and biomedical materials. Furthermore, it is well known that plasma polymers are highly cross-linked, pinhole-free, branched, insoluble, and adhere well to most substrates. In order to synthesize polymer films using plasma processes, therefore, it is very important to increase the density and electron temperature of plasma during plasma polymerization.

This Special Issue aims to compile original and cutting-edge research works in the fields of plasma process, polymerization, synthesis, characterization, treatment, modification, manufacturing, and applications of functional plasma-processed polymers.

Dr. Choon-Sang Park
Guest Editor

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Keywords

low-pressure plasma
atmospheric pressure plasma
plasma process
plasma polymerization
plasma synthesis
plasma deposition
dielectric barrier discharge
fragmentation
recombination
polymer
conductive polymer
copolymer
plasma treatment
surface modification
large area treatment and deposition

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Published Papers (11 papers)

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Research

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14 pages, 5685 KiB

Open AccessArticle

Study of a Conical Plasma Jet with a Cloth-Covered Nozzle for Polymer Treatment

by Felipe Vicente de Paula Kodaira, Ana Carla de Paula Leite Almeida, Thayna Fernandes Tavares, Antje Quade, Luis Rogério de Oliveira Hein and Konstantin Georgiev Kostov

Polymers 2023, 15(16), 3344; https://doi.org/10.3390/polym15163344 - 9 Aug 2023

Viewed by 1162

Abstract

Although atmospheric pressure plasma jets (APPJs) have been widely employed for materials modification, they have some drawbacks, such as the small treatment area (couple of cm²). To overcome this limitation, a funnel-like APPJ with a wide exit has been proposed. In this work, a gas-permeable cotton cloth covered the nozzle of the device to improve the gas flow dynamics and increase its range of operation. The funnel jet was flushed with Ar, and the plasma was ignited in a wide range of gas flow rates and the gap distances between the exit nozzle and the sample holder. The device characterization included electric measurements and optical emission spectroscopy (OES). To evaluate the size of the treatment and the degree of surface modification, large samples of high-density polyethylene (PE) were exposed to plasma for 5 min. Afterward, the samples were analyzed via water contact angle WCA measurements, scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS). It was found that surface modification occurs simultaneously on the top and bottom faces of the samples. However, the treatment incorporated different functional groups on each side. Full article

(This article belongs to the Special Issue Advances in Plasma Processes for Polymers II)

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10 pages, 6625 KiB

Open AccessArticle

Antibacterial Effects of a Carbon Nitride (CN) Layer Formed on Non-Woven Polypropylene Fabrics Using the Modified DC-Pulsed Sputtering Method

by Young-Soo Sohn, Sang Kooun Jung, Sung-Youp Lee and Hong Tak Kim

Polymers 2023, 15(12), 2641; https://doi.org/10.3390/polym15122641 - 10 Jun 2023

Cited by 3 | Viewed by 1217

Abstract

In the present study, the surface of non-woven polypropylene (NW-PP) fabric was modified to form CN layers using a modified DC-pulsed (frequency: 60 kHz, pulse shape: square) sputtering with a roll-to-roll system. After plasma modification, structural damage in the NW-PP fabric was not observed, and the C–C/C–H bonds on the surface of the NW-PP fabric converted into C–C/C–H, C–N(CN), and C=O bonds. The CN-formed NW-PP fabrics showed strong hydrophobicity for H₂O (polar liquid) and full-wetting characteristics for CH₂I₂ (non-polar liquid). In addition, the CN-formed NW-PP exhibited an enhanced antibacterial characteristic compared to NW-PP fabric. The reduction rate of the CN-formed NW-PP fabric was 89.0% and 91.6% for Staphylococcus aureus (ATCC 6538, Gram-positive) and Klebsiella pneumoniae (ATCC4352, Gram-negative), respectively. It was confirmed that the CN layer showed antibacterial characteristics against both Gram-positive and Gram-negative bacteria. The reason for the antibacterial effect of CN-formed NW-PP fabrics can be explained as the strong hydrophobicity due to the CH₃ bond of the fabric, enhanced wetting property due to CN bonds, and antibacterial activity due to C=O bonds. Our study presents a one-step, damage-free, mass-productive, and eco-friendly method that can be applied to most weak substrates, allowing the mass production of antibacterial fabrics. Full article

(This article belongs to the Special Issue Advances in Plasma Processes for Polymers II)

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14 pages, 28219 KiB

Open AccessArticle

Sputtering Plasma Effect on Zinc Oxide Thin Films Produced on Photopolymer Substrates

by Juan Jesus Rocha-Cuervo, Esmeralda Uribe-Lam, Cecilia Daniela Treviño-Quintanilla and Dulce Viridiana Melo-Maximo

Polymers 2023, 15(10), 2283; https://doi.org/10.3390/polym15102283 - 12 May 2023

Cited by 5 | Viewed by 2193

Abstract

This work presents a post-cured treatment alternative for photopolymer substrates considering the plasma produced via the sputtering process. The sputtering plasma effect was discussed, analyzing the properties of zinc/zinc oxide (Zn/ZnO) thin films deposited on photopolymer substrates, with and without ultraviolet (UV) treatment as a post-treatment process, after manufacturing. The polymer substrates were produced from a standard Industrial Blend resin and manufactured using stereolithography (SLA) technology. After that, the UV treatment followed the manufacturer’s instructions. The influence of the sputtering plasma as an extra treatment during the deposition of the films was analyzed. Characterization was performed to determine the microstructural and adhesion properties of the films. The results showed the effect of plasma as a post-cured treatment alternative: fractures were found in thin films deposited on polymers with previous UV treatment. In the same way, the films showed a repetitive printing pattern due to the phenomenon of polymer shrinkage caused by the sputtering plasma. The plasma treatment also showed an effect on the thicknesses and roughness values of the films. Finally, according to VDI–3198 standards, coatings with acceptable adhesion failures were found. The results provide attractive properties of Zn/ZnO coatings on polymeric substrates produced by additive manufacturing. Full article

(This article belongs to the Special Issue Advances in Plasma Processes for Polymers II)

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15 pages, 5489 KiB

Open AccessArticle

Nanostructured Polyaniline Films Functionalized through Auxiliary Nitrogen Addition in Atmospheric Pressure Plasma Polymerization

by Jae Young Kim, Hyojun Jang, Ye Rin Lee, Kangmin Kim, Habeeb Olaitan Suleiman, Choon-Sang Park, Bhum Jae Shin, Eun Young Jung and Heung-Sik Tae

Polymers 2023, 15(7), 1626; https://doi.org/10.3390/polym15071626 - 24 Mar 2023

Cited by 4 | Viewed by 1814

Abstract

Polyaniline (PANI) was synthesized from liquid aniline, a nitrogen-containing aromatic compound, through the atmospheric pressure (AP) plasma process using a newly designed plasma jet array with wide spacing between plasma jets. To expand the area of the polymerized film, the newly proposed plasma jet array comprises three AP plasma jet devices spaced 7 mm apart in a triangular configuration and an electrodeless quartz tube capable of applying auxiliary gas in the center of the triangular plasma jets. The vaporized aniline monomer was synthesized into a PANI film using the proposed plasma array device. The effects of nitrogen gas addition on the morphological, chemical, and electrical properties of PANI films in AP argon plasma polymerization were examined. The iodine-doped PANI film was isolated from the atmosphere through encapsulation. The constant electrical resistance of the PANI film indicates that the conductive PANI film can achieve the desired resistance by controlling the atmospheric exposure time through encapsulation. Full article

(This article belongs to the Special Issue Advances in Plasma Processes for Polymers II)

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14 pages, 1662 KiB

Open AccessArticle

Simultaneous Treatment of Both Sides of the Polymer with a Conical-Shaped Atmospheric Pressure Plasma Jet

by Felipe Vicente de Paula Kodaira, Bruno Henrique Silva Leal, Thayna Fernandes Tavares, Antje Quade, Luis Rogerio de Oliveira Hein, William Chiappim and Konstantin Georgiev Kostov

Polymers 2023, 15(2), 461; https://doi.org/10.3390/polym15020461 - 16 Jan 2023

Cited by 3 | Viewed by 2152

Abstract

A conical-shaped atmospheric pressure plasma jet (CS-APPJ) was developed to overcome a standard limitation of APPJs, which is their small treatment area. The CS-APPJs increase the treatment area but use the same gas flow. In the present work, polypropylene samples were treated by CS-APPJ and characterized by scanning electron microscope (SEM), the contact angle, Fourier-transformed infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). It was observed that the treatment co-occurs on the face directly in contact with the plasma and on the opposite face (OF) of the samples, i.e., no contact. However, the treatment changed the chemical composition on each side; the OF is rougher than the direct contact face (DCF), probably due to the oxygen groups in excess at the DCF and nitrogen in quantity at the OF. Although simultaneous treatment of both sides of the sample occurs for most atmospheric plasma treatments, this phenomenon is not explored in the literature. Full article

(This article belongs to the Special Issue Advances in Plasma Processes for Polymers II)

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15 pages, 2615 KiB

Open AccessArticle

Atmospheric Pressure Plasma Polymerisation of D-Limonene and Its Antimicrobial Activity

by Asad Masood, Naeem Ahmed, M. F. Mohd Razip Wee, Anuttam Patra, Ebrahim Mahmoudi and Kim S. Siow

Polymers 2023, 15(2), 307; https://doi.org/10.3390/polym15020307 - 6 Jan 2023

Cited by 10 | Viewed by 2404

Abstract

Antibacterial coating is necessary to prevent biofilm-forming bacteria from colonising medical tools causing infection and sepsis in patients. The recent coating strategies such as immobilisation of antimicrobial materials and low-pressure plasma polymerisation may require multiple processing steps involving a high-vacuum system and time-consuming process. Some of those have limited efficacy and durability. Here, we report a rapid and one-step atmospheric pressure plasma polymerisation (APPP) of D-limonene to produce nano-thin films with hydrophobic-like properties for antibacterial applications. The influence of plasma polymerisation time on the thickness, surface characteristic, and chemical composition of the plasma-polymerised films was systematically investigated. Results showed that the nano-thin films deposited at 1 min on glass substrate are optically transparent and homogenous, with a thickness of 44.3 ± 4.8 nm, a smooth surface with an average roughness of 0.23 ± 0.02 nm. For its antimicrobial activity, the biofilm assay evaluation revealed a significant 94% decrease in the number of Escherichia coli (E. coli) compared to the control sample. More importantly, the resultant nano-thin films exhibited a potent bactericidal effect that can distort and rupture the membrane of the treated bacteria. These findings provide important insights into the development of bacteria-resistant and biocompatible coatings on the arbitrary substrate in a straightforward and cost-effective route at atmospheric pressure. Full article

(This article belongs to the Special Issue Advances in Plasma Processes for Polymers II)

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16 pages, 2585 KiB

Open AccessArticle

Influence of Dielectric Barrier Discharge Cold Plasma Treatment on Starch, Gelatin, and Bacterial Cellulose Biodegradable Polymeric Films

by Mayara Lima Goiana, Adriano Lincoln Albuquerque Mattos, Henriette Monteiro Cordeiro de Azeredo, Morsyleide de Freitas Rosa and Fabiano André Narciso Fernandes

Polymers 2022, 14(23), 5215; https://doi.org/10.3390/polym14235215 - 30 Nov 2022

Cited by 10 | Viewed by 2019

Abstract

The environmental damage caused by plastic packaging and the need to reduce pollution requires actions to substitute plastic materials for more sustainable and biodegradable materials. Starch, gelatin, and bacterial cellulose films are three potential biodegradable polymeric films for use in packaging. However, these materials need improvements in their physical, chemical, and mechanical properties to be used in packaging. In this work, these films were treated with cold plasma to evaluate the effects of treatment conditions on several physical, chemical, and mechanical properties. The dielectric barrier discharge plasma technology was applied with varying treatment times (0 to 20 min) and excitation frequencies (50 to 900 Hz) at 20 kV. The optimal excitation frequency for starch films (50 Hz) was different from the optimal frequency for gelatin and bacterial cellulose films (900 Hz), indicating a high dependency on the treatment in this variable that is often neglected. Plasma treatment improved the hydrophobicity, surface morphology, water resistance, and mechanical properties of all three films, with the advantage of not recurring to chemical or biological additives. Full article

(This article belongs to the Special Issue Advances in Plasma Processes for Polymers II)

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14 pages, 4584 KiB

Open AccessArticle

Development of an Atmospheric Pressure Plasma Jet Device Using Four-Bore Tubing and Its Applications of In-Liquid Material Decomposition and Solution Plasma Polymerization

by Gyu Tae Bae, Hyo Jun Jang, Eun Young Jung, Ye Rin Lee, Choon-Sang Park, Jae Young Kim and Heung-Sik Tae

Polymers 2022, 14(22), 4917; https://doi.org/10.3390/polym14224917 - 14 Nov 2022

Cited by 4 | Viewed by 2648

Abstract

In this study, we describe an atmospheric pressure plasma jet (APPJ) device made of four-bore tubing operable in inhospitable humid environments and introduce two potential applications of liquid material processing: decomposition of aqueous phosphorus compounds and solution-plasma polymerization. A four-bore tube was used as the plasma transfer conduit and two diagonal bores contained metal wires. In the proposed APPJ device, the metal wires serving as electrodes are completely enclosed inside the holes of the multi-bore glass tube. This feature allows the APPJ device to operate both safely and reliably in humid environments or even underwater. Thus, we demonstrate that the proposed electrode-embedded APPJ device can effectively decompose aqueous phosphorus compounds into their phosphate form by directly processing the solution sample. As another application of the proposed APPJ device, we also present the successful synthesis of polypyrrole nanoparticles by solution plasma polymerization in liquid pyrrole. Full article

(This article belongs to the Special Issue Advances in Plasma Processes for Polymers II)

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19 pages, 5626 KiB

Open AccessArticle

Novel Dextran Coated Cerium Doped Hydroxyapatite Thin Films

by Carmen Steluta Ciobanu, Ionela Cristina Nica, Anca Dinischiotu, Simona Liliana Iconaru, Patrick Chapon, Bogdan Bita, Roxana Trusca, Andreea Groza and Daniela Predoi

Polymers 2022, 14(9), 1826; https://doi.org/10.3390/polym14091826 - 29 Apr 2022

Cited by 5 | Viewed by 2375

Abstract

Dextran coated cerium doped hydroxyapatite (Ca_10-xCex(PO₄)₆(OH)₂), with x = 0.05 (5CeHAp-D) and x = 0.1 (10CeHAp-D) were deposited on Si substrates by radio frequency magnetron sputtering technique for the first time. The morphology, composition, and structure of the resulting coatings were examined by scanning electron microscopy (SEM), energy-dispersive x-ray spectroscopy (EDX), atomic force microscopy (AFM), metallographic microscopy (MM), Fourier transform infrared spectroscopy (FTIR), and glow discharge optical emission spectroscopy (GDOES), respectively. The obtained information on the surface morphologies, composition and structure was discussed. The surface morphologies of the CeHAp-D composite thin films are smooth with no granular structures. The constituent elements of the CeHAp-D target were identified. The results of the FTIR measurements highlighted the presence of peaks related to the presence of ν₁, ν₃, and ν₄ vibration modes of (PO₄³⁻) groups from the hydroxyapatite (HAp) structure, together with those specific to the dextran structure. The biocompatibility assessment of 5CeHAp-D and 10CeHAp-D composite coatings was also discussed. The human cells maintained their specific elongated morphology after 24 h of incubation, which confirmed that the behavior of gingival fibroblasts and their proliferative capacity were not disturbed in the presence of 5CeHAp-D and 10CeHAp-D composite coatings. The 5CeHAp-D and 10CeHAp-D coatings’ surfaces were harmless to the human gingival fibroblasts, proving good biocompatibility. Full article

(This article belongs to the Special Issue Advances in Plasma Processes for Polymers II)

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Review

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18 pages, 3425 KiB

Open AccessReview

Review of Plasma Processing for Polymers and Bio-Materials Using a Commercial Frequency (50/60 Hz)-Generated Discharge

by Hong Tak Kim, Cheol Min Jung, Se Hyun Kim and Sung-Youp Lee

Polymers 2023, 15(13), 2850; https://doi.org/10.3390/polym15132850 - 28 Jun 2023

Cited by 5 | Viewed by 2267

Abstract

This manuscript introduces the properties and diverse applications of plasma generated using commercial frequencies of 50/60 Hz. Commercial frequency (CF) derived plasma exhibits characteristics similar to DC discharge but with an electrical polarity and a non-continuous discharge. Due to the low-frequency nature, the reactor configurations usually are capacitively coupled plasma type. The advantages of this method include its simple power structure, low-reaction temperature, and low substrate damage. The electrical polarity can prevent charge buildup on the substrates and deposited films, thereby reducing substrate damage. The simple, low-cost, and easy-to-operate power structure makes it suitable for laboratory-scale usage. Additionally, the various applications, including plasma-enhanced vapor deposition, sputtering, dielectric barrier discharge, and surface modification, and their outcomes in the CF-derived plasma processes are summarized. The conclusion drawn is that the CF-derived plasma process is useful for laboratory-scale utilization due to its simplicity, and the results of the plasma process are also outstanding. Full article

(This article belongs to the Special Issue Advances in Plasma Processes for Polymers II)

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11 pages, 1882 KiB

Open AccessReview

Strategies for Improved Wettability of Polyetheretherketone (PEEK) Polymers by Non-Equilibrium Plasma Treatment

by Gregor Primc

Polymers 2022, 14(23), 5319; https://doi.org/10.3390/polym14235319 - 5 Dec 2022

Cited by 8 | Viewed by 3586

Abstract

Polyetheretherketone (PEEK) is the material of choice in several applications ranging from the automotive industry to medicine, but the surface properties are usually not adequate. A standard method for tailoring surface properties is the application of gaseous plasma. The surface finish depends enormously on the processing parameters. This article presents a review of strategies adapted for improved wettability and adhesion of PEEK. The kinetics of positively charged ions, neutral reactive plasma species, and vacuum ultraviolet radiation on the surface finish are analyzed, and synergies are stressed where appropriate. The reviewed articles are critically assessed regarding the plasma and surface kinetics, and the surface mechanisms are illustrated. The directions for obtaining optimal surface finish are provided together with the scientific explanation of the limitations of various approaches. Super-hydrophilic surface finish is achievable by treatment with a large dose of vacuum ultraviolet radiation in the presence of oxidizing gas. Bombardment with positively charged ions of kinetic energy between about 100 and 1000 eV also enable high wettability, but one should be aware of excessive heating when using the ions. Full article

(This article belongs to the Special Issue Advances in Plasma Processes for Polymers II)

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