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Plasma Polymers for Advanced Material Design

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Materials Chemistry".

Deadline for manuscript submissions: closed (31 May 2021) | Viewed by 19222

Special Issue Editors


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Guest Editor
Flinders Institute for Nanoscale Science & Technology, Flinders University, Bedford Park, SA 5042, Australia
Interests: effects of surface chemistry and nanotopography on the interaction between (bio) materials; proteins and cells primarily to address challenges faced by the biomedical device and energy industry

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Guest Editor
Queensland University of Technology QUT, Brisbane, Australia
Interests: Polymer thin films; Biomaterials; Antibacterial surfaces; Organic electronics; Biodegradable materials; Green chemistry; Non-equilibrium reactive chemistry; Plasma nanoscience; Nanobioscience; Material characterisation; In vitro material testing

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Guest Editor
University of South Australia, Adelaide, Australia
Interests: Mechanical Testing; Mass Spectrometry; Material Characterization; Mechanical Properties; Coating; Thin Films and Nanotechnology; Stem cell Therapy; Biomaterials; Cancer research

Special Issue Information

Dear Colleagues,

The fast-paced progress of modern nanotechnologies is inspiring the development of a rich diversity of functional materials. The utilization of plasma processes for the fabrication of advanced organic coatings and thin films, referred to as plasma polymers, has led to exciting breakthroughs over the last decade. Examples include antimicrobial coatings, stimuli-responsive membrane, breathable textiles, and more. Some of these materials cannot be achieved by conventional means, and have unique plasma-induced properties. The design of material surface properties using plasma polymerisation hold great promise to revolutionize a spectrum of fields, ranging from electronics to biology and medicine.

This Issue is themed around the need to improve both our understanding and control of plasma polymer design for targeted applications in fields ranging from energy storage and conversion and advanced manufacturing, to biomedical devices. This Issue further aims to highlight the current challenges and obstacles that lie on the path of bridging the gap between plasma polymer research and their use in applied technologies. Overall, this Issue will bring together outstanding innovative work from the fields of chemistry, physics, biology, engineering, and material science with the common goal of providing guidance and future directions to other researchers in the field.

We invite investigators to contribute original research articles and review articles that will inspire the next generation of functional plasma polymers for applications in a wide range of technologies. Potential topics include, but are not limited to, the following:

  • nanotextured plasma polymers
  • plasma synthesis of novel nanoscale coatings
  • electrical properties of plasma polymers
  • nature-inspired plasma polymers
  • atmospheric pressure plasma polymers
  • coatings for medical devices
  • antibacterial plasma polymer coatings
  • functional plasma polymers for (bio)sensing platforms
  • stimuli responsive materials generated via plasma processes.

Dr. Melanie MacGregor
Prof. Dr. Kateryna Bazaka
Dr. Hanieh Safizadeh Shiraz
Guest Editor

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Plasma polymers
  • Plasma deposition
  • CVD
  • Glow discharge polymerization

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Published Papers (6 papers)

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Research

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17 pages, 39537 KiB  
Article
Decontamination-Induced Modification of Bioactivity in Essential Oil-Based Plasma Polymer Coatings
by Olha Bazaka, Karthika Prasad, Igor Levchenko, Mohan V. Jacob, Kateryna Bazaka, Peter Kingshott, Russell J. Crawford and Elena P. Ivanova
Molecules 2021, 26(23), 7133; https://doi.org/10.3390/molecules26237133 - 25 Nov 2021
Cited by 5 | Viewed by 2209
Abstract
Plasma polymer coatings fabricated from Melaleuca alternifolia essential oil and its derivatives have been previously shown to reduce the extent of microbial adhesion on titanium, polymers, and other implantable materials used in dentistry. Previous studies have shown these coatings to maintain their performance [...] Read more.
Plasma polymer coatings fabricated from Melaleuca alternifolia essential oil and its derivatives have been previously shown to reduce the extent of microbial adhesion on titanium, polymers, and other implantable materials used in dentistry. Previous studies have shown these coatings to maintain their performance under standard operating conditions; however, when used in e.g., a dental implant, these coatings may inadvertently become subject to in situ cleaning treatments, such as those using an atmospheric pressure plasma jet, a promising tool for the effective in situ removal of biofilms from tissues and implant surfaces. Here, we investigated the effect of such an exposure on the antimicrobial performance of the Melaleuca alternifolia polymer coating. It was found that direct exposure of the polymer coating surface to the jet for periods less than 60 s was sufficient to induce changes in its surface chemistry and topography, affecting its ability to retard subsequent microbial attachment. The exact effect of the jet exposure depended on the chemistry of the polymer coating, the length of plasma treatment, cell type, and incubation conditions. The change in the antimicrobial activity for polymer coatings fabricated at powers of 20–30 W was not statistically significant due to their limited baseline bioactivity. Interestingly, the bioactivity of polymer coatings fabricated at 10 and 15 W against Staphylococcus aureus cells was temporarily improved after the treatment, which could be attributed to the generation of loosely attached bioactive fragments on the treated surface, resulting in an increase in the dose of the bioactive agents being eluted by the surface. Attachment and proliferation of Pseudomonas aeruginosa cells and mixed cultures were less affected by changes in the bioactivity profile of the surface. The sensitivity of the cells to the change imparted by the jet treatment was also found to be dependent on their origin culture, with mature biofilm-derived P. aeruginosa bacterial cells showing a greater ability to colonize the surface when compared to its planktonic broth-grown counterpart. The presence of plasma-generated reactive oxygen and nitrogen species in the culture media was also found to enhance the bioactivity of polymer coatings fabricated at power levels of 10 and 15 W, due to a synergistic effect arising from simultaneous exposure of cells to reactive oxygen and nitrogen species (RONS) and eluted bioactive fragments. These results suggest that it is important to consider the possible implications of inadvertent changes in the properties and performance of plasma polymer coatings as a result of exposure to in situ decontamination, to both prevent suboptimal performance and to exploit possible synergies that may arise for some polymer coating-surface treatment combinations. Full article
(This article belongs to the Special Issue Plasma Polymers for Advanced Material Design)
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17 pages, 1597 KiB  
Article
Characterising a Custom-Built Radio Frequency PECVD Reactor to Vary the Mechanical Properties of TMDSO Films
by Racim Radjef, Karyn L. Jarvis, Colin Hall, Andrew Ang, Bronwyn L. Fox and Sally L. McArthur
Molecules 2021, 26(18), 5621; https://doi.org/10.3390/molecules26185621 - 16 Sep 2021
Viewed by 2099
Abstract
Plasma-polymerised tetramethyldisiloxane (TMDSO) films are frequently applied as coatings for their abrasion resistance and barrier properties. By manipulating the deposition parameters, the chemical structure and thus mechanical properties of the films can also be controlled. These mechanical properties make them attractive as energy [...] Read more.
Plasma-polymerised tetramethyldisiloxane (TMDSO) films are frequently applied as coatings for their abrasion resistance and barrier properties. By manipulating the deposition parameters, the chemical structure and thus mechanical properties of the films can also be controlled. These mechanical properties make them attractive as energy adsorbing layers for a range of applications, including carbon fibre composites. In this study, a new radio frequency (RF) plasma-enhanced chemical vapour deposition (PECVD) plasma reactor was designed with the capability to coat fibres with an energy adsorbing film. A key characterisation step for the system was establishing how the properties of the TMDSO films could be modified and compared with those deposited using a well-characterized microwave (MW) PECVD reactor. Film thickness and chemistry were determined with ellipsometry and X-ray photoelectron spectroscopy, respectively. The mechanical properties were investigated by nanoindentation and atomic force microscopy with peak-force quantitative nanomechanical mapping. The RF PECVD films had a greater range of Young’s modulus and hardness values than the MW PECVD films, with values as high as 56.4 GPa and 7.5 GPa, respectively. These results demonstrated the varied properties of TMDSO films that could in turn be deposited onto carbon fibres using a custom-built RF PECVD reactor. Full article
(This article belongs to the Special Issue Plasma Polymers for Advanced Material Design)
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14 pages, 1892 KiB  
Article
Comparative Study of Natural Terpenoid Precursors in Reactive Plasmas for Thin Film Deposition
by Daniel S. Grant, Jakaria Ahmed, Jason D. Whittle, Andrew Michelmore, Krasimir Vasilev, Kateryna Bazaka and Mohan V. Jacob
Molecules 2021, 26(16), 4762; https://doi.org/10.3390/molecules26164762 - 6 Aug 2021
Cited by 5 | Viewed by 1980
Abstract
If plasma polymer thin films are to be synthesised from sustainable and natural precursors of chemically heterogeneous composition, it is important to understand the extent to which this composition influences the mechanism of polymerisation. To this end, a well-studied monoterpene alcohol, terpinen-4-ol, has [...] Read more.
If plasma polymer thin films are to be synthesised from sustainable and natural precursors of chemically heterogeneous composition, it is important to understand the extent to which this composition influences the mechanism of polymerisation. To this end, a well-studied monoterpene alcohol, terpinen-4-ol, has been targeted for a comparative study with the naturally occurring mix of terpenes (viz. Melaleuca alternifolia oil) from which it is commonly distilled. Positive ion mode mass spectra of both terpinen-4-ol and M. alternifolia oil showed a decrease in disparities between the type and abundance of cationic species formed in their respective plasma environments as applied plasma power was increased. Supplementary biological assay revealed the antibacterial action of both terpinen-4-ol and M. alternifolia derived coatings with respect to S. aureus bacteria, whilst cytocompatibility was demonstrated by comparable eukaryotic cell adhesion to both coatings. Elucidating the processes occurring within the reactive plasmas can enhance the economics of plasma polymer deposition by permitting use of the minimum power, time and precursor pre-processing required to control the extent of monomer fragmentation and fabricate a film of the desired thickness and functionality. Full article
(This article belongs to the Special Issue Plasma Polymers for Advanced Material Design)
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23 pages, 28203 KiB  
Article
Plasma Processing of Low Vapor Pressure Liquids to Generate Functional Surfaces
by Sandra Gaiser, Urs Schütz, Patrick Rupper and Dirk Hegemann
Molecules 2020, 25(24), 6024; https://doi.org/10.3390/molecules25246024 - 19 Dec 2020
Cited by 3 | Viewed by 2825
Abstract
The concept of depositing solid films on low-vapor pressure liquids is introduced and developed into a top-down approach to functionalize surfaces by attaching liquid polyethylene glycol (PEG). Solid-liquid gradients were formed by low-pressure plasma treatment yielding cross-linking and/or deposition of a plasma polymer [...] Read more.
The concept of depositing solid films on low-vapor pressure liquids is introduced and developed into a top-down approach to functionalize surfaces by attaching liquid polyethylene glycol (PEG). Solid-liquid gradients were formed by low-pressure plasma treatment yielding cross-linking and/or deposition of a plasma polymer film subsequently bound to a flexible polydimethylsiloxane (PDMS) backing. The analysis via optical transmission spectroscopy (OTS), optical, confocal laser scanning (CLSM) and scanning electron microscopy (SEM), Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) as well as by water contact angle (WCA) measurements revealed correlations between optical appearance, chemical composition and surface properties of the resulting water absorbing, covalently bound PEG-functionalized surfaces. Requirements for plasma polymer film deposition on low-vapor pressure liquids and effective surface functionalization are defined. Namely, the thickness of the liquid PEG substrate was a crucial parameter for successful film growth and covalent attachment of PEG. The presented method is a practicable approach for the production of functional surfaces featuring long-lasting strong hydrophilic properties, making them predestined for non-fouling or low-friction applications. Full article
(This article belongs to the Special Issue Plasma Polymers for Advanced Material Design)
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26 pages, 10874 KiB  
Article
Influence of Low-Pressure RF Plasma Treatment on Aramid Yarns Properties
by Alicja Nejman, Irena Kamińska, Izabela Jasińska, Grzegorz Celichowski and Małgorzata Cieślak
Molecules 2020, 25(15), 3476; https://doi.org/10.3390/molecules25153476 - 30 Jul 2020
Cited by 14 | Viewed by 3183
Abstract
The aim of the study was to modify the surface free energy (SFE) of meta- (mAr) and para-aramid (pAr) yarns by their activation in low-pressure air radio frequency (RF) (40 kHz) plasma and assessment of its impact on the properties of the yarns. [...] Read more.
The aim of the study was to modify the surface free energy (SFE) of meta- (mAr) and para-aramid (pAr) yarns by their activation in low-pressure air radio frequency (RF) (40 kHz) plasma and assessment of its impact on the properties of the yarns. After 10 and 90 min of activation, the SFE value increased, respectively, by 14% and 37% for mAr, and by 10% and 37% for pAr. The value of the polar component increased, respectively by 22% and 57% for mAr and 20% and 62% for pAr. The value of the dispersion component for mAr and pAr increased respectively by 9% and 25%. The weight loss decreased from 49% to 46% for mAr and 62% to 50% for pAr after 90 min of activation. After 90 min, the specific strength for mAr did not change and for pAr it decreased by 40%. For both yarns, the 10 min activation in plasma is sufficient to prepare their surface for planned nanomodification. Full article
(This article belongs to the Special Issue Plasma Polymers for Advanced Material Design)
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Review

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29 pages, 7129 KiB  
Review
Plasma and Polymers: Recent Progress and Trends
by Igor Levchenko, Shuyan Xu, Oleg Baranov, Olha Bazaka, Elena P. Ivanova and Kateryna Bazaka
Molecules 2021, 26(13), 4091; https://doi.org/10.3390/molecules26134091 - 5 Jul 2021
Cited by 52 | Viewed by 6150
Abstract
Plasma-enhanced synthesis and modification of polymers is a field that continues to expand and become increasingly more sophisticated. The highly reactive processing environments afforded by the inherently dynamic nature of plasma media are often superior to ambient or thermal environments, offering substantial advantages [...] Read more.
Plasma-enhanced synthesis and modification of polymers is a field that continues to expand and become increasingly more sophisticated. The highly reactive processing environments afforded by the inherently dynamic nature of plasma media are often superior to ambient or thermal environments, offering substantial advantages over other processing methods. The fluxes of energy and matter toward the surface enable rapid and efficient processing, whereas the charged nature of plasma-generated particles provides a means for their control. The range of materials that can be treated by plasmas is incredibly broad, spanning pure polymers, polymer-metal, polymer-wood, polymer-nanocarbon composites, and others. In this review, we briefly outline some of the recent examples of the state-of-the-art in the plasma-based polymer treatment and functionalization techniques. Full article
(This article belongs to the Special Issue Plasma Polymers for Advanced Material Design)
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