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Polymers
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Surface Chemistry of Polymers
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Surface Chemistry of Polymers

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

Deadline for manuscript submissions: closed (30 September 2020) | Viewed by 34344

Special Issue Editor

Dr. Alenka Vesel

E-Mail Website
Guest Editor
Department of Surface Engineering and Optoelectronics, Jozef Stefan Institute, Jamova cesta 39, 1000 Ljubljana, Slovenia
Interests: plasma surface engineering; surface modification; plasma surface functionalization and etching; plasma nanoscience; plasma technologies; biointerfaces; surface analysis by XPS

Special Issue Information

Dear Colleagues,

Polymers and polymer blends have been widely investigated in recent decades. The bulk properties are governed by thermodynamics of polymers, while surface chemistry is by far more complicated, because it involves numerous reactions with rate coefficients that are not always known or determined precisely. In addition, surface impurities influence the surface chemistry of polymers. Furthermore, surface chemistry depends on the orientation of surface molecules, and an important factor is the morphology. The complexity of polymer surface chemistry is particularly imperative upon incubation of polymeric products with complex organic materials, such as body fluids. The response of polymers to biological matter is still poorly understood despite huge efforts from both the scientific community and relevant industries. Unlike bulk chemistry, which is often regarded marginal at room temperature, the surfaces retain their activity well after the appropriate finish has been achieved. Aging effects are often detrimental for many surface finishes of polymers and polymer blends and often represent an unsolved problem in mass application of polymer products with a tailored surface chemistry.

It is my pleasure to invite you to submit a manuscript for this Special Issue on Surface Chemistry of Polymers. Suitable topics include the surface chemistry involved upon grafting of different molecules, in particular, biomolecules for improved biological response, tailoring surface chemistry by functionalization with new functional groups, methods for increasing the surface area such as nanostructuring, and basic phenomena of surface chemistry of polymers. Papers on surface chemistry of polymers or polymer blends containing nanocarbon are also welcome. The papers should include results on monitoring the surface reactions and finish by at least one method for surface characterization. Critical reviews are also welcome—though, in the case of review papers, it is desirable to draw correlations between treatment parameters used by different authors and resultant surface finish.

Dr. Alenka Vesel
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

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. Polymers 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

  • surface chemistry
  • tailoring surface properties by plasmas
  • polymers
  • polymer blends
  • polymers with nanocarbon
  • surface characterization
  • biological response

Published Papers (11 papers)

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Editorial

Jump to: Research, Review

4 pages, 167 KiB  
Editorial
Surface Chemistry of Polymers
by Alenka Vesel
Polymers 2020, 12(11), 2757; https://doi.org/10.3390/polym12112757 - 23 Nov 2020
Cited by 1 | Viewed by 1855
Abstract
Surface chemistry plays a key role in modern applications of polymer materials [...] Full article
(This article belongs to the Special Issue Surface Chemistry of Polymers)

Research

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13 pages, 2608 KiB  
Article
Extracellular Vesicle Isolation Yields Increased by Low-Temperature Gaseous Plasma Treatment of Polypropylene Tubes
by Matic Resnik, Janez Kovač, Roman Štukelj, Veronika Kralj-Iglič, Petr Humpolíček and Ita Junkar
Polymers 2020, 12(10), 2363; https://doi.org/10.3390/polym12102363 - 15 Oct 2020
Cited by 4 | Viewed by 1961
Abstract
Novel Extracellular Vesicles (EVs) based diagnostic techniques are promising non-invasive procedures for early stage disease detection which are gaining importance in the medical field. EVs are cell derived particles found in body liquids, especially blood, from which they are isolated for further analysis. [...] Read more.
Novel Extracellular Vesicles (EVs) based diagnostic techniques are promising non-invasive procedures for early stage disease detection which are gaining importance in the medical field. EVs are cell derived particles found in body liquids, especially blood, from which they are isolated for further analysis. However, techniques for their isolation are not fully standardized and require further improvement. Herein modification of polypropylene (PP) tubes by cold Atmospheric Pressure Plasma Jet (APPJ) is suggested to minimize the EVs to surface binding and thus increase EVs isolation yields. The influence of gaseous plasma treatment on surface morphology was studied by Atomic Force Microscopy (AFM), changes in surface wettability by measuring the Water Contact Angle (WCA), while surface chemical changes were analyzed by X-Ray Photoelectron Spectroscopy (XPS). Moreover, PP tubes from different manufacturers were compared. The final isolation yields of EVs were evaluated by flow cytometry. The results of this study suggest that gaseous plasma treatment is an intriguing technique to uniformly alter surface properties of PP tubes and improve EVs isolation yields up to 42%. Full article
(This article belongs to the Special Issue Surface Chemistry of Polymers)
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Graphical abstract

20 pages, 7450 KiB  
Article
Investigation of Surfactant-Polymer Interactions Using Rheology and Surface Tension Measurements
by Jia Yang and Rajinder Pal
Polymers 2020, 12(10), 2302; https://doi.org/10.3390/polym12102302 - 08 Oct 2020
Cited by 35 | Viewed by 5273
Abstract
The interactions between surfactants and a drag-reducing polymer were investigated at a low polymer concentration of 500 ppm, using measurements of the rheology and surface activity of surfactant-polymer solutions. A well-known drag-reducing polymer (anionic sodium carboxymethyl cellulose) and five different surfactants (two anionic, [...] Read more.
The interactions between surfactants and a drag-reducing polymer were investigated at a low polymer concentration of 500 ppm, using measurements of the rheology and surface activity of surfactant-polymer solutions. A well-known drag-reducing polymer (anionic sodium carboxymethyl cellulose) and five different surfactants (two anionic, two non-ionic, and one zwitterionic) were selected for the interaction studies. The surfactant-polymer solutions were shear thinning in nature, and they followed the power law model. The interaction between the surfactant and polymer had a strong effect on the consistency index of the solution and a marginal effect on the flow behavior index. The surface tension versus surfactant concentration plots were interpreted in terms of the interactions between surfactant and polymer. The critical aggregation concentration (CAC) of the surfactant was estimated based on the surface tension and rheological data. The CAC values of the same charge surfactants as that of the polymer were found to be significantly higher than other combinations of surfactant and polymer, such as non-ionic surfactant/anionic polymer, and zwitterionic surfactant/anionic polymer. Full article
(This article belongs to the Special Issue Surface Chemistry of Polymers)
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20 pages, 2664 KiB  
Article
Two-Layer Functional Coatings of Chitosan Particles with Embedded Catechin and Pomegranate Extracts for Potential Active Packaging
by Sanja Potrč, Tjaša Kraševac Glaser, Alenka Vesel, Nataša Poklar Ulrih and Lidija Fras Zemljič
Polymers 2020, 12(9), 1855; https://doi.org/10.3390/polym12091855 - 19 Aug 2020
Cited by 20 | Viewed by 2756
Abstract
Two-layer functional coatings for polyethylene (PE) and polypropylene (PP) films were developed for the active packaging concept. Prior to coating, the polymer films were activated by O2 and NH3 plasma to increase their surface free energy and to improve the binding [...] Read more.
Two-layer functional coatings for polyethylene (PE) and polypropylene (PP) films were developed for the active packaging concept. Prior to coating, the polymer films were activated by O2 and NH3 plasma to increase their surface free energy and to improve the binding capacity and stability of the coatings. The first layer was prepared from a macromolecular chitosan solution, while the second (upper) layer contained chitosan particles with embedded catechin or pomegranate extract. Functionalized films were analyzed physico-chemically to elemental composition using ATR-FTIR spectroscopy and XPS. Further, oxygen permeability and wettability (Contact Angle) were examined. The antimicrobial properties were analyzed by the standard ISO 22196 method, while the antioxidative properties were determined with an ABTS assay. Functionalized films show excellent antioxidative and antimicrobial efficacy. A huge decrease in oxygen permeability was achieved in addition. Moreover, a desorption experiment was also performed, confirming that the migration profile of a compound from the surfaces was in accordance with the required overall migration limit. All these properties indicate the great potential of the developed active films/foils for end-uses in food packaging. Full article
(This article belongs to the Special Issue Surface Chemistry of Polymers)
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12 pages, 3399 KiB  
Article
Degradable Poly(ethylene oxide)-Like Plasma Polymer Films Used for the Controlled Release of Nisin
by Jaroslav Kousal, Jana Sedlaříková, Zuzana Kolářová-Rašková, Zdeněk Krtouš, Liliana Kučerová, Anna Hurajová, Mykhailo Vaidulych, Jan Hanuš and Marián Lehocký
Polymers 2020, 12(6), 1263; https://doi.org/10.3390/polym12061263 - 01 Jun 2020
Cited by 3 | Viewed by 2308
Abstract
Poly(ethylene oxide) (PEO)-like thin films were successfully prepared by plasma-assisted vapor thermal deposition (PAVTD). PEO powders with a molar weight (Mw) between 1500 g/mol and 600,000 g/mol were used as bulk precursors. The effect of Mw on the structural and surface properties was [...] Read more.
Poly(ethylene oxide) (PEO)-like thin films were successfully prepared by plasma-assisted vapor thermal deposition (PAVTD). PEO powders with a molar weight (Mw) between 1500 g/mol and 600,000 g/mol were used as bulk precursors. The effect of Mw on the structural and surface properties was analyzed for PEO films prepared at a lower plasma power. Fourier transform (FTIR-ATR) spectroscopy showed that the molecular structure was well preserved regardless of the Mw of the precursors. The stronger impact of the process conditions (the presence/absence of plasma) was proved. Molecular weight polydispersity, as well as wettability, increased in the samples prepared at 5 W. The influence of deposition plasma power (0–30 W) on solubility and permeation properties was evaluated for a bulk precursor of Mw 1500 g/mol. The rate of thickness loss after immersion in water was found to be tunable in this way, with the films prepared at the highest plasma power showing higher stability. The effect of plasma power deposition conditions was also shown during the permeability study. Prepared PEO films were used as a cover, and permeation layers for biologically active nisin molecule and a controlled release of this bacteriocin into water was achieved. Full article
(This article belongs to the Special Issue Surface Chemistry of Polymers)
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12 pages, 3580 KiB  
Article
Effect of VUV Radiation on Surface Modification of Polystyrene Exposed to Atmospheric Pressure Plasma Jet
by Rok Zaplotnik and Alenka Vesel
Polymers 2020, 12(5), 1136; https://doi.org/10.3390/polym12051136 - 15 May 2020
Cited by 24 | Viewed by 2802
Abstract
Precise tailoring of surface properties by gaseous plasma treatments remains a key scientific challenge, especially when adequate surface wettability should be laterally distributed, and sharp interfaces between hydrophobic and hydrophilic areas are desirable. The evolution of surface wettability and functional groups on polystyrene [...] Read more.
Precise tailoring of surface properties by gaseous plasma treatments remains a key scientific challenge, especially when adequate surface wettability should be laterally distributed, and sharp interfaces between hydrophobic and hydrophilic areas are desirable. The evolution of surface wettability and functional groups on polystyrene (PS) upon treatment with argon plasma jet was monitored by water contact angles and X-ray photoelectron spectroscopy (XPS). An array of water droplets was deposited on PS samples treated either directly by the plasma jet or only VUV radiation arising from the plasma. Rather sharp interfaces between the activated and not-affected regions were observed in both cases. The functionalization with highly-oxidized carbon functional groups, as determined by high-resolution C1s XPS spectra, was by far more efficient using the VUV radiation only. In contrast, the optimal wettability was achieved using direct plasma treatment. The results were explained by different mechanisms involved in the interaction of radiation and reactive plasma species with the polymer surface. Full article
(This article belongs to the Special Issue Surface Chemistry of Polymers)
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13 pages, 3215 KiB  
Article
Low-Temperature Plasma Modification of Styrene–Butadiene Block Copolymer Surfaces for Improved Adhesion—A Kinetic Approach
by Jacek Tyczkowski, Hanna Kierzkowska-Pawlak, Jan Sielski and Iwona Krawczyk-Kłys
Polymers 2020, 12(4), 935; https://doi.org/10.3390/polym12040935 - 17 Apr 2020
Cited by 12 | Viewed by 2533
Abstract
This paper proposed a kinetic model that can describe the changes in the adhesion properties of styrene–butadiene (SBS) block copolymer surfaces under the influence of low-temperature plasma treatment. As a measure of these changes, the peel strength of joints formed between the copolymer [...] Read more.
This paper proposed a kinetic model that can describe the changes in the adhesion properties of styrene–butadiene (SBS) block copolymer surfaces under the influence of low-temperature plasma treatment. As a measure of these changes, the peel strength of joints formed between the copolymer surface and the polyurethane adhesive was chosen. Five types of low-temperature low-pressure RF plasma, two inert plasmas (Ar and He), and three reactive plasmas (O2, CO2, and CCl4) were tested. It was found that for all these types of plasma, the peel strength with the plasma treatment time first increases rapidly reaching a maximum value, and then there is a visible decrease in peel strength, after which the peel strength increases again. This dependence of the peel strength on the plasma treatment time is very well described by the proposed model, which considers three processes: (1) the generation of radical states followed by the creation of functional groups involved in the adhesive bonding process, (2) the surface cross-linking that decreases the concentration of these functional groups, and (3) the formation of nano-roughness. The model analysis revealed differences between the action of reactive and inert plasmas in the SBS surface cross-linking mechanism and preferential etching process, as well as differences in the generation of radical states between the O2 plasma (electron process) and other plasmas tested (ionic processes). Full article
(This article belongs to the Special Issue Surface Chemistry of Polymers)
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17 pages, 3159 KiB  
Article
Insights into Adsorption Characterization of Sulfated Xylans onto Poly(ethylene terephthalate)
by Lidija Fras Zemljič, Nena Dimitrušev, Rok Zaplotnik and Simona Strnad
Polymers 2020, 12(4), 825; https://doi.org/10.3390/polym12040825 - 05 Apr 2020
Cited by 4 | Viewed by 2006
Abstract
The main aim of this investigation was to study the interaction of sulfated xylans as antithrombotic substances with poly(ethylene terephthalate) (PET) model films as a model for blood contacting surfaces. The adsorption of sulfated xylans onto PET model films was studied as a [...] Read more.
The main aim of this investigation was to study the interaction of sulfated xylans as antithrombotic substances with poly(ethylene terephthalate) (PET) model films as a model for blood contacting surfaces. The adsorption of sulfated xylans onto PET model films was studied as a function of pH and ionic strength using the quartz crystal microbalance with dissipation (QCM-D) technique. The application of positively charged polyethyleneimine (PEI) as an anchoring polymer was done to improve the adsorption. The hydrophilic/hydrophobic properties of functionalized PET surfaces were monitored by goniometry, whilst their elemental composition was determined by X-ray photoelectron spectroscopy. Sulfated xylans adsorbed favorably at pH 5 by physical interactions and by entropy gain driven adsorption. Higher ionic strengths of solutions improved adsorption, due to the reduction of electrostatic repulsive forces between PET surfaces and anionic xylans’ macromolecules. The intermediate PEI layer caused more extensive and stable adsorption due to Coulomb interactions. The surface modifications presented in this work provided important information regarding the adsorption/desorption phenomena between antithrombotic sulfated xylans and PET surfaces. The latter is of great interest when preparing advanced polymer composite material such as functional antithrombotic PET surfaces for blood-contacting medical devices and presents an extremely challenging research field. Full article
(This article belongs to the Special Issue Surface Chemistry of Polymers)
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11 pages, 2255 KiB  
Article
Yarrowia lipolytica Adhesion and Immobilization onto Residual Plastics
by Alanna Botelho, Adrian Penha, Jully Fraga, Ana Barros-Timmons, Maria Alice Coelho, Marian Lehocky, Kateřina Štěpánková and Priscilla Amaral
Polymers 2020, 12(3), 649; https://doi.org/10.3390/polym12030649 - 12 Mar 2020
Cited by 8 | Viewed by 2636
Abstract
Research in cell adhesion has important implications in various areas, such as food processing, medicine, environmental engineering, biotechnological processes. Cell surface characterization and immobilization of microorganisms on solid surfaces can be performed by promoting cell adhesion, in a relatively simple, inexpensive, and quick [...] Read more.
Research in cell adhesion has important implications in various areas, such as food processing, medicine, environmental engineering, biotechnological processes. Cell surface characterization and immobilization of microorganisms on solid surfaces can be performed by promoting cell adhesion, in a relatively simple, inexpensive, and quick manner. The adhesion of Yarrowia lipolytica IMUFRJ 50682 to different surfaces, especially potential residual plastics (polystyrene, poly(ethylene terephthalate), and poly(tetrafluoroethylene)), and its use as an immobilized biocatalyst were tested. Y. lipolytica IMUFRJ 50682 presented high adhesion to different surfaces such as poly(tetrafluoroethylene) (Teflon), polystyrene, and glass, independent of pH, and low adhesion to poly(ethylene terephthalate) (PET). The adhesion of the cells to polystyrene was probably due to hydrophobic interactions involving proteins or protein complexes. The adhesion of the cells to Teflon might be the result not only of hydrophobic interactions but also of acid–basic forces. Additionally, the present work shows that Y. lipolytica cell extracts previously treated by ultrasound waves (cell debris) maintained their enzymatic activity (lipase) and could be attached to polystyrene and PET and used successfully as immobilized biocatalysts in hydrolysis reactions. Full article
(This article belongs to the Special Issue Surface Chemistry of Polymers)
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Review

Jump to: Editorial, Research

15 pages, 1614 KiB  
Review
Plasma-Stimulated Super-Hydrophilic Surface Finish of Polymers
by Miran Mozetič
Polymers 2020, 12(11), 2498; https://doi.org/10.3390/polym12112498 - 27 Oct 2020
Cited by 30 | Viewed by 4237
Abstract
Super-hydrophilicity is a desired but rarely reported surface finish of polymer materials, so the methods for achieving such a property represent a great scientific and technological challenge. The methods reported by various authors are reviewed and discussed in this paper. The super-hydrophilic surface [...] Read more.
Super-hydrophilicity is a desired but rarely reported surface finish of polymer materials, so the methods for achieving such a property represent a great scientific and technological challenge. The methods reported by various authors are reviewed and discussed in this paper. The super-hydrophilic surface finish has been reported for polymers functionalized with oxygen-rich surface functional groups and of rich morphology on the sub-micrometer scale. The oxygen concentration as probed by X-ray photoelectron spectroscopy should be above 30 atomic % and the roughness as determined by atomic force microscopy over a few nm, although most authors reported the roughness was close to 100 nm. A simple one-step oxygen plasma treatment assures for super-hydrophilicity of few polymers only, but the technology enables such a surface finish of almost any fluorine-free polymer providing a capacitively coupled oxygen plasma that enables deposition of minute quantities of inorganic material is applied. More complex methods include deposition of at least one coating, followed by surface activation with oxygen plasma. Fluorinated polymers require treatment with plasma rich in hydrogen to achieve the super-hydrophilic surface finish. The stability upon aging depends largely on the technique used for super-hydrophilization. Full article
(This article belongs to the Special Issue Surface Chemistry of Polymers)
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17 pages, 2135 KiB  
Review
Recent Advances in Surface Activation of Polytetrafluoroethylene (PTFE) by Gaseous Plasma Treatments
by Gregor Primc
Polymers 2020, 12(10), 2295; https://doi.org/10.3390/polym12102295 - 07 Oct 2020
Cited by 52 | Viewed by 5071
Abstract
Fluorinated polymers are renowned for their chemical inertness and thus poor wettability and adhesion of various coatings. Apart from chemical methods employing somewhat toxic primers, gaseous plasma treatment is a popular method for the modification of surface properties. Different authors have used different [...] Read more.
Fluorinated polymers are renowned for their chemical inertness and thus poor wettability and adhesion of various coatings. Apart from chemical methods employing somewhat toxic primers, gaseous plasma treatment is a popular method for the modification of surface properties. Different authors have used different plasmas, and the resultant surface finish spans between super-hydrophobic and super-hydrophilic character. Some authors also reported the hydrophobic recovery. The review of recent papers is presented and discussed. Correlations between plasma and/or discharge parameters and the surface finish are drawn and the most important conclusions are summarized. The concentration of oxygen in the surface film as probed by X-ray photoelectron spectroscopy is inversely dependent on the concentration of oxygen in gaseous plasma. The predominant mechanism leading to hydrophilic surface finish is bond scission by deep ultraviolet radiation rather than functionalization with reactive oxygen species. Full article
(This article belongs to the Special Issue Surface Chemistry of Polymers)
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