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Polymers
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Polymerizations from Surfaces
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Polymerizations from Surfaces

A special issue of Polymers (ISSN 2073-4360).

Deadline for manuscript submissions: closed (28 February 2018) | Viewed by 39563

Special Issue Editor

Prof. Dr. Philipp Vana

E-Mail Website
Guest Editor
Makromolekulare Chemie, Institut für Physikalische Chemie, Georg-August-Universität Göttingen, Tammannstraße 6, D-37077 Göttingen, Germany
Interests: controlled radical RAFT polymerization; synthesis of complex macromolecular architectures and functional polymers; biomimetic polymer design; polymerizations from surfaces; organic–inorganic hybrid materials; kinetics and mechanism of radical polymerizations; mechanical properties of polymers; modeling and simulation of polymerization processes; electrospray ionization (ESI) mass spectrometry; ion-mobility mass spectrometry
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The scope of this Special Issue is to collate reports about recent progress and future perspectives in the field of polymerizations from surfaces.

The tailoring of well-defined polymer structures on the surfaces of solid materials constitutes the molecular basis for advanced functional surfaces. The recent advent of a multitude of controlled radical polymerization methods (also called reversible deactivation radical polymerization according to IUPAC), such as RAFT, ATRP and NMP, which greatly outperform conventional radical polymerization processes with respect to topological control, has had a major impact on this field. These methods allow for the confinement of polymerizations at surfaces, which may lead to polymer brushes and other surface-bound polymer arrangements. They also provide macromolecular architectures of stunning complexity with relative ease, which were far beyond the wildest dreams of polymer chemists just short time ago. These polymers may have tailored functionalities that can be used for controlling the interface regime between the solid material and the soft polymer coverage.

The functionality may also be used to arrange polymer chains and particles in a predetermined manner so that complicated nano-composites emerge. The polymer and its functionality may finally be used to modulate surface functions.

All these benefits are currently fully exploited for new surface structures for applications in energy conversion, e.g., solar cells; nanomedicine, e.g., drug delivery and tagging; and materials science, where they are used for the design of functional, responsive, or high mechanical performance nano-composite materials. It is the intention of the present Special Issue to contribute to this fascinating emerging field in polymer science.

Prof. Dr. Philipp Vana
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-initiated RAFT polymerization

  • surface-initiated ATRP

  • surface-initiated controlled radical polymerization

  • surface-confined polymerization

  • polymer brushes

  • functional polymer surfaces

  • polymer interfaces

  • nano-composites

  • nano-layers

Published Papers (7 papers)

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Research

12 pages, 38268 KiB  
Article
Polyethylene-Grafted Gold and Silver Nanoparticles Using Catalyzed Chain Growth (CCG)
by Jannik Wagner, Wentao Peng and Philipp Vana
Polymers 2018, 10(4), 407; https://doi.org/10.3390/polym10040407 - 06 Apr 2018
Cited by 8 | Viewed by 6333
Abstract
We report an efficient synthesis route for the formation of gold/silver-core–PE-shell nanohybrids in a simple self-assembly approach using PE with strong aurophilicity and argentophilicity, via thiol- and trithiocarbonate terminated moieties. This united the unique properties of polyethylene (PE) with gold and silver nanoparticles, [...] Read more.
We report an efficient synthesis route for the formation of gold/silver-core–PE-shell nanohybrids in a simple self-assembly approach using PE with strong aurophilicity and argentophilicity, via thiol- and trithiocarbonate terminated moieties. This united the unique properties of polyethylene (PE) with gold and silver nanoparticles, using the well-defined end-group design of PE. These nanocomposites showed a similar solubility as PE, as confirmed by dynamic light scattering, and could be fully incorporated into a polyethylene matrix with different particle contents, as visualized by transmission electron microscopy. Using UV/vis-spectroscopy, we observed reversible, thermoresponsive aggregation/deaggregation properties in the nanohybrids, validating the strong and effective anchoring of PE on gold/silver surfaces. Full article
(This article belongs to the Special Issue Polymerizations from Surfaces)
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16 pages, 3306 KiB  
Article
Surface Modification of Wood Flour via ARGET ATRP and Its Application as Filler in Thermoplastics
by Martin Kaßel, Julia Gerke, Adrian Ley and Philipp Vana
Polymers 2018, 10(4), 354; https://doi.org/10.3390/polym10040354 - 22 Mar 2018
Cited by 7 | Viewed by 7267
Abstract
Wood flour is particularly suitable as a filler in thermoplastics because it is environmentally friendly, readily available, and offers a high strength-to-density ratio. To overcome the insufficient interfacial adhesion between hydrophilic wood and a hydrophobic matrix, a thermoplastic polymer was grafted from wood [...] Read more.
Wood flour is particularly suitable as a filler in thermoplastics because it is environmentally friendly, readily available, and offers a high strength-to-density ratio. To overcome the insufficient interfacial adhesion between hydrophilic wood and a hydrophobic matrix, a thermoplastic polymer was grafted from wood flour via surface-initiated activators regenerated by electron transfer-atom transfer radical polymerization (SI-ARGET ATRP). Wood particles were modified with an ATRP initiator and subsequently grafted with methyl acrylate for different polymerization times in the absence of a sacrificial initiator. The successful grafting of poly(methyl acrylate) (PMA) was demonstrated using attenuated total reflection Fourier transform infrared (ATR-FTIR) spectroscopy, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and water contact angle (WCA) measurements. To confirm the control over the polymerization, a cleavable ATRP initiator was immobilized on the particles, allowing the detachment of the grafted polymer under mild conditions. The grafted particles were incorporated into a PMA matrix using solvent casting and their influence on the mechanical properties (Young’s modulus, yield strength, and toughness) of the composite was investigated. Tensile testing showed that the mechanical properties improved with increasing polymerization time and increasing ratio of incorporated grafted particles. Full article
(This article belongs to the Special Issue Polymerizations from Surfaces)
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11 pages, 2498 KiB  
Article
The Effect of Polyaniline (PANI) Coating via Dielectric-Barrier Discharge (DBD) Plasma on Conductivity and Air Drag of Polyethylene Terephthalate (PET) Yarn
by Shuai Liu, Deqi Liu and Zhijuan Pan
Polymers 2018, 10(4), 351; https://doi.org/10.3390/polym10040351 - 22 Mar 2018
Cited by 30 | Viewed by 5214
Abstract
In this paper, a simple method to prepare PANI-coated conductive PET yarn is reported, which involves pre-applying aniline and HCl vapors on PET surface and subsequent dielectric-barrier discharge (DBD) plasma treatment of the coated yarn under atmospheric pressure. The volume resistivity of the [...] Read more.
In this paper, a simple method to prepare PANI-coated conductive PET yarn is reported, which involves pre-applying aniline and HCl vapors on PET surface and subsequent dielectric-barrier discharge (DBD) plasma treatment of the coated yarn under atmospheric pressure. The volume resistivity of the optimal sample was about 1.8 × 105 times lower than that of the control. Moreover, with the increase of coating amount of PANI, the air drag of PET yarns improved gradually. The surface chemistry of the treated yarn was analyzed by Fourier transform-infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS), while the morphology was observed by scanning electron microscopy (SEM) and atomic force microscopy (AFM). This study offers a new method to prepare conductive fabric via air-jet loom and is expected to increase the weaving efficiency of air-jet loom. Full article
(This article belongs to the Special Issue Polymerizations from Surfaces)
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13 pages, 3776 KiB  
Article
Modification of Polyamide-Urethane (PAUt) Thin Film Composite Membrane for Improving the Reverse Osmosis Performance
by Li-Fen Liu, Xing-Ling Gu, Sa-Ren Qi, Xin Xie, Rui-Han Li, Ke Li, Chun-Yang Yu and Cong-Jie Gao
Polymers 2018, 10(4), 346; https://doi.org/10.3390/polym10040346 - 21 Mar 2018
Cited by 8 | Viewed by 5499
Abstract
In the current study, the poly (amide-urethane) (PAUt) membranes were successfully fabricated by interfacial polymerization of m-phenylenediamine (MPD) and 5-choroformyloxyisophaloyl chloride (CFIC) on the polysulfone substrates. Two modification methods based on layer-by-layer assembly were applied to modify the PAUt membrane surface to achieve [...] Read more.
In the current study, the poly (amide-urethane) (PAUt) membranes were successfully fabricated by interfacial polymerization of m-phenylenediamine (MPD) and 5-choroformyloxyisophaloyl chloride (CFIC) on the polysulfone substrates. Two modification methods based on layer-by-layer assembly were applied to modify the PAUt membrane surface to achieve antifouling property: 1. Chitosan (CS) was directly self-assembled on the PAUt membrane (i.e., PAUt-CS); and 2. polydimethyl diallyl ammonium chloride (PDDA), polystyrene sulfonate (PSS), and CS were successively self-assembled on the membrane surface (i.e., PAUt-PDDA/PSS/CS). The resultant membranes were symmetrically characterized by Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR), X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM) and Contact Angle Meter (CAM), respectively. The results indicated that the modified membranes had much smoother and more hydrophilic surfaces as compared to the nascent PAUt membrane. Meanwhile, the modified membranes exhibited better reverse osmosis performance in terms of water permeability and salt rejection. After the modified membranes were fouled by lake water, the PAUt-PDDA/PSS/CS membrane presented the best antifouling performance among the three types of membranes. Combining the reverse osmosis performance with the anti-fouling property obviously, the PAUt-PDDA/PSS/CS membrane behaved as a promising candidate to be used in real applications. Full article
(This article belongs to the Special Issue Polymerizations from Surfaces)
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16 pages, 1075 KiB  
Article
Surface Segregation of Cyclic Chains in Binary Melts of Thin Polymer Films: The Influence of Constituent Concentration
by Francis M. Gaitho, Mesfin Tsige, Genene T. Mola and Giuseppe Pellicane
Polymers 2018, 10(3), 324; https://doi.org/10.3390/polym10030324 - 15 Mar 2018
Cited by 6 | Viewed by 3679
Abstract
We carry out extensive molecular dynamics simulations of thin films of bead-spring models of binary mixtures composed of cyclic and linear polymer chains. We study the equilibrium behavior of the polymer chains for two very different chain lengths, which resemble short (10-mers) and [...] Read more.
We carry out extensive molecular dynamics simulations of thin films of bead-spring models of binary mixtures composed of cyclic and linear polymer chains. We study the equilibrium behavior of the polymer chains for two very different chain lengths, which resemble short (10-mers) and long (100-mers) chains, at different concentrations of the binary mixture. We clearly show how the concentration variable affects the enrichment of either of the two polymer species at the interface, and also how the chain length influences this process. Full article
(This article belongs to the Special Issue Polymerizations from Surfaces)
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9 pages, 7320 KiB  
Article
Self-Sensitization and Photo-Polymerization of Diacetylene Molecules Self-Assembled on a Hexagonal-Boron Nitride Nanosheet
by Elisseos Verveniotis, Yuji Okawa, Kenji Watanabe, Takashi Taniguchi, Takaaki Taniguchi, Minoru Osada, Christian Joachim and Masakazu Aono
Polymers 2018, 10(2), 206; https://doi.org/10.3390/polym10020206 - 19 Feb 2018
Cited by 5 | Viewed by 5788
Abstract
Long poly-diacetylene chains are excellent candidates for planar, on-surface synthesized molecular electronic wires. Since hexagonal-Boron Nitride (h-BN) was identified as the best available atomically flat insulator for the deposition of poly-diacetylene precursors, we demonstrate the polymerization patterns and rate on it under UV-light [...] Read more.
Long poly-diacetylene chains are excellent candidates for planar, on-surface synthesized molecular electronic wires. Since hexagonal-Boron Nitride (h-BN) was identified as the best available atomically flat insulator for the deposition of poly-diacetylene precursors, we demonstrate the polymerization patterns and rate on it under UV-light irradiation, with subsequent polymer identification by atomic force microscopy. The results on h-BN indicate self-sensitization which yields blocks comprised of several polymers, unlike on the well-studied graphite/diacetylene system, where the polymers are always isolated. In addition, the photo-polymerization proceeds at least 170 times faster on h-BN, where it also results in longer polymers. Both effects are explained by the h-BN bandgap, which is larger than the diacetylene electronic excitation energy, thus allowing the transfer of excess energy absorbed by polymerized wires to adjacent monomers, triggering their polymerization. This work sets the stage for conductance measurements of single molecular poly-diacetylene wires on h-BN. Full article
(This article belongs to the Special Issue Polymerizations from Surfaces)
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8680 KiB  
Article
Microstructure and Performance of a Porous Polymer Membrane with a Copper Nano-Layer Using Vapor-Induced Phase Separation Combined with Magnetron Sputtering
by Nana Li, Yuanjing Fu, Qingchen Lu and Changfa Xiao
Polymers 2017, 9(10), 524; https://doi.org/10.3390/polym9100524 - 18 Oct 2017
Cited by 12 | Viewed by 4935
Abstract
Antibacterial metalized poly(vinylidene fluoride) (PVDF) porous membranes with a nano-layer were obtained via the method of vapor-induced phase separation combined with magnetron sputtering of copper. Magnetron sputtering has such advantages as high deposition rates, low substrate temperatures, and good adhesion of films on [...] Read more.
Antibacterial metalized poly(vinylidene fluoride) (PVDF) porous membranes with a nano-layer were obtained via the method of vapor-induced phase separation combined with magnetron sputtering of copper. Magnetron sputtering has such advantages as high deposition rates, low substrate temperatures, and good adhesion of films on substrates. The influence brought by deposition time on the microstructure, hydrophobic property, copper distribution state, anti-biofouling, and permeation separation performance was investigated via atomic force microscopy (AFM), field emission scanning electron microscopy (FESEM), energy-dispersive X-ray (EDX) spectrometry, contact angle measurements, and capillary flow porometry, along with the porosity, water flux, protein solution flux, rejection rate, water flux recovery rate, and antibacterial property. The results showed that copper particles formed island-type deposits on the membrane surface and were embedded into cross-section pores near the surface owning to the interconnection of pores. Subsequently, the water flux and protein solution flux declined, but the rejection rate and water flux recovery rate increased. Meanwhile, Cu-coated PVDF membranes exhibited an excellent antibacterial ability. Full article
(This article belongs to the Special Issue Polymerizations from Surfaces)
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