scholarly journals Non-Equilibrium Plasma Methods for Tailoring Surface Properties of Polyvinylidene Fluoride: Review and Challenges

Polymers ◽  
2021 ◽  
Vol 13 (23) ◽  
pp. 4243
Author(s):  
Alenka Vesel ◽  
Rok Zaplotnik ◽  
Gregor Primc ◽  
Miran Mozetič ◽  
Tadeja Katan ◽  
...  

Modification and functionalization of polymer surface properties is desired in numerous applications, and a standard technique is a treatment with non-equilibrium gaseous plasma. Fluorinated polymers exhibit specific properties and are regarded as difficult to functionalize with polar functional groups. Plasma methods for functionalization of polyvinylidene fluoride (PVDF) are reviewed and different mechanisms involved in the surface modification are presented and explained by the interaction of various reactive species and far ultraviolet radiation. Most authors used argon plasma but reported various results. The discrepancy between the reported results is explained by peculiarities of the experimental systems and illustrated by three mechanisms. More versatile reaction mechanisms were reported by authors who used oxygen plasma for surface modification of PVDF, while plasma sustained in other gases was rarely used. The results reported by various authors are analyzed, and correlations are drawn where feasible. The processing parameters reported by different authors were the gas pressure and purity, the discharge configuration and power, while the surface finish was predominantly determined by X-ray photoelectron spectroscopy (XPS) and static water contact angle (WCA). A reasonably good correlation was found between the surface wettability as probed by WCA and the oxygen concentration as probed by XPS, but there is hardly any correlation between the discharge parameters and the wettability.

Polymers ◽  
2020 ◽  
Vol 12 (5) ◽  
pp. 1136 ◽  
Author(s):  
Rok Zaplotnik ◽  
Alenka Vesel

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.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Andrzej Sikora ◽  
Dariusz Czylkowski ◽  
Bartosz Hrycak ◽  
Magdalena Moczała-Dusanowska ◽  
Marcin Łapiński ◽  
...  

AbstractThis paper presents the results of experimental investigations of the plasma surface modification of a poly(methyl methacrylate) (PMMA) polymer and PMMA composites with a [6,6]-phenyl-C61-butyric acid methyl ester fullerene derivative (PC61BM). An atmospheric pressure microwave (2.45 GHz) argon plasma sheet was used. The experimental parameters were: an argon (Ar) flow rate (up to 20 NL/min), microwave power (up to 530 W), number of plasma scans (up to 3) and, the kind of treated material. In order to assess the plasma effect, the possible changes in the wettability, roughness, chemical composition, and mechanical properties of the plasma-treated samples’ surfaces were evaluated by water contact angle goniometry (WCA), atomic force microscopy (AFM), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS). The best result concerning the water contact angle reduction was from 83° to 29.7° for the PMMA material. The ageing studies of the PMMA plasma-modified surface showed long term (100 h) improved wettability. As a result of plasma treating, changes in the samples surface roughness parameters were observed, however their dependence on the number of plasma scans is irregular. The ATR-FTIR spectra of the PMMA plasma-treated surfaces showed only slight changes in comparison with the spectra of an untreated sample. The more significant differences were demonstrated by XPS measurements indicating the surface chemical composition changes after plasma treatment and revealing the oxygen to carbon ratio increase from 0.1 to 0.4.


Polymers ◽  
2020 ◽  
Vol 12 (9) ◽  
pp. 2008
Author(s):  
Hsiu-Wen Chien ◽  
Hong-Yu Lin ◽  
Chau-Yi Tsai ◽  
Tai-Yu Chen ◽  
Wei-Nian Chen

Superhydrophilic coatings have been widely used for the surface modification of membranes or biomedical devices owing to their excellent antifouling properties. However, simplifying the modification processes of such materials remains challenging. In this study, we developed a simple and rapid one-step co-deposition process using an oxidant trigger to fabricate superhydrophilic surfaces based on dopamine chemistry with sulfobetaine methacrylate (SBMA). We studied the effect of different oxidants and SBMA concentrations on surface modification in detail using UV–VIS spectrophotometry, dynamic light scattering, atomic force microscopy, X-ray photoelectron spectroscopy, and surface plasmon resonance. We found that NaIO4 could trigger the rate of polymerization and the optimum ratio of dopamine to SBMA is 1:25 by weight. This makes the surface superhydrophilic (water contact angle < 10°) and antifouling. The superhydrophilic coating, when introduced to polyester membranes, showed great potential for oil/water separation. Our study provides a complete description of the simple and fast preparation of superhydrophilic coatings for surface modification based on mussel-inspired chemistry.


Coatings ◽  
2019 ◽  
Vol 9 (6) ◽  
pp. 397 ◽  
Author(s):  
Jinguang Wei ◽  
Qiuqin Lin ◽  
Yahui Zhang ◽  
Wenji Yu ◽  
Chung-Yun Hse ◽  
...  

Coating quality for scrimber products against exterior conditions is largely dependent on the surface properties. The wettability, morphology, and chemical composition of pine scrimber surfaces were investigated to better understand the surface properties. The scrimber was found to be a hydrophilic material because the water contact angles were less than 90°. The panels with a density of 1.20 g/cm3 had the largest angle change rate (k = 0.212). As the panel density increased, the instantaneous contact angle of each test liquid (i.e., water, formamide, and diiodomethane) on the panels decreased, and so did surface free energy. Panels with higher density showed lower surface roughness. Surface roughness across the wood grain was greater than that along the grain. SEM observations showed the high-density panels had a smoother surface with fewer irregular grooves in comparison with the low-density panels. X-ray photoelectron spectroscopy (XPS) analysis indicated that more unoxygenated groups appeared on the surface of high-density panels.


1995 ◽  
Vol 383 ◽  
Author(s):  
M. R. Houston ◽  
R. T. Howe ◽  
K Komvopoulos ◽  
R. Maboudian

ABSTRACTThe surface properties of diamond-like carbon (DLC) films deposited by a vacuum arc technique on smooth silicon wafers are presented with specific emphasis given to stiction reduction in microelectromechanical systems (MEMS). The low deposition temperatures afforded by the vacuum arc technique should allow for easy integration of the DLC films into the current fabrication process of typical surface micromachines by means of a standard lift-off processing technique. Using X-ray photoelectron spectroscopy (XPS), contact angle analysis, and atomic force microscopy (AFM), the surface chemistry, microroughness, hydrophobicity, and adhesion forces of DLC-coated Si(100) surfaces were measured and correlated to the measured water contact angles. DLC films were found to be extremely smooth and possess a water contact angle of 87°, which roughly corresponds to a surface energy of 22 mJ/m2. It is shown that the pull-off forces measured by AFM correlate well with the predicted capillary forces. Pull-off forces are reduced on DLC surfaces by about a factor of five compared to 10 nN pull-off forces measured on the RCA-cleaned silicon surfaces. In the absence of meniscus forces, the overall adhesion force is expected to decrease by over an order of magnitude to the van der Waals attractive force present between two DLC-coated surfaces- To further improve the surface properties of DLC, films were exposed to a fluorine plasma which increased the contact angle to 99° and lowered the pull-off force by approximately 20% over that obtained with as-deposited DLC. The significance of these results is discussed with respect to stiction reduction in micromachines.


Polymers ◽  
2020 ◽  
Vol 12 (10) ◽  
pp. 2181
Author(s):  
Sumita Swar ◽  
Veronika Máková ◽  
Ivan Stibor

Different forms of unmodified and modified Poly(ethylene glycols) (PEGs) are widely used as antifouling and antibacterial agents for biomedical industries and Nylon 6 is one of the polymers used for biomedical textiles. Our recent study focused on an efficient approach to PEG immobilization on a reduced Nylon 6 surface via N,N′–disuccinimidyl carbonate (DSC) conjugation. The conversion of amide functional groups to secondary amines on the Nylon 6 polymer surface was achieved by the reducing agent borane-tetrahydrofuran (BH3–THF) complex, before binding the PEG. Various techniques, including water contact angle and free surface energy measurements, atomic force microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and Fourier-transform infrared spectroscopy, were used to confirm the desired surface immobilization. Our findings indicated that PEG may be efficiently tethered to the Nylon 6 surface via DSC, having an enormous future potential for antifouling biomedical materials. The bacterial adhesion performances against S. aureus and P. aeruginosa were examined. In vitro cytocompatibility was successfully tested on pure, reduced, and PEG immobilized samples.


Polymers ◽  
2020 ◽  
Vol 12 (11) ◽  
pp. 2736
Author(s):  
Sho Hirai ◽  
Patchiya Phanthong ◽  
Hikaru Okubo ◽  
Shigeru Yao

The consumption of polypropylene (PP) has significantly increased over that of other materials because of its light weight, easy molding, and high mechanical strength. However, the applications of PP are limited, owing to the lack of surface properties, especially with respect to adhesive properties and hydrophilicity. In this study, we developed a surface modification method for enhancing the adhesive properties and hydrophilicity on the PP surface using a side-chain crystalline block copolymer (SCCBC). This method was simple and involved the dipping of a PP film in a diluted SCCBC solution. The optimized modification conditions for enhancing the adhesive properties of PP were investigated. The results revealed that the adhesion strength of PP modified with the SCCBC of behenyl acrylate and 2-(tert-butylamino)ethyl methacrylate was enhanced to 2.00 N/mm (T-peel test) and 1.05 N/mm2 (tensile shear test). In addition, the hydrophilicity of PP modified with the SCCBC of behenyl acrylate and di(ethylene glycol)ethyl ether acrylate was enhanced to a water contact angle of 69 ± 4°. Surface analysis was also performed to elucidate a plausible mechanism for PP modification by the SCCBCs. This surface modification method is facile and enhances desirable properties for the wide application of PP.


2002 ◽  
Vol 68 (8) ◽  
pp. 3855-3858 ◽  
Author(s):  
Karola Waar ◽  
Henny C. van der Mei ◽  
Hermie J. M. Harmsen ◽  
John E. Degener ◽  
Henk J. Busscher

ABSTRACT The aim of this study is to determine whether growth in the presence of bile influences the surface properties and adhesion to hydrophobic bile drain materials of Enterococcus faecalis strains expressing aggregation substance (Agg) or enterococcal surface protein (Esp), two surface proteins that are associated with infections. After growth in the presence of bile, the strains were generally more hydrophobic by water contact angles and the zeta potentials were more negative than when the strains were grown in the absence of bile. Nitrogen was found in lower surface concentrations upon growth in the presence of bile, whereas higher surface concentrations of oxygen were measured by X-ray photoelectron spectroscopy. Moreover, an up to twofold-higher number of bacteria adhered after growth in bile for E. faecalis not expressing Agg or Esp and E. faecalis with Esp on its surface. E. faecalis expressing Agg did not adhere in higher numbers after growth in bile, possibly because they mainly adhere through positive cooperativity and less through direct interactions with a substratum surface. Since adhesion of bacteria is the first step in biomaterial-centered infection, it can be concluded that growth in bile increases the virulence of E. faecalis.


2012 ◽  
Vol 1403 ◽  
Author(s):  
Wei Gao ◽  
Yakai Feng ◽  
Jian Lu ◽  
Jintang Guo

ABSTRACTPhosphorylcholine glyceraldehyde (PCGA) was used as a phosphorylcholine (PC) group containing compound to graft onto the surface of polycarbonateurethane (PCU) film using 1,6-hexanediamine (HDA) or α,ω-diamino-poly(ethylene glycol) (APEG, Mn = 200) as a spacer, in order to introduce biomimetic structure onto the polymer surface. X-ray photoelectron spectroscopy (XPS) analysis shows that PCGA has been covalently linked to the PCU surface. Water contact angle test suggests that the surface hydrophilicity has been improved after PCGA is grafted onto the surface of PCU film. Scanning electron microscope (SEM) observation of the modified PCU films after contacting with plasma-rich plasma demonstrates that platelets rarely adhere but a large number of platelets adhere to the original PCU surface. The hemocompatibility of the PC modified PCU film has been improved obviously after grafting with PCGA with PEG spacer.


Polymers ◽  
2021 ◽  
Vol 13 (11) ◽  
pp. 1849
Author(s):  
Martin Schmidt ◽  
Stefan Zahn ◽  
Florian Gehlhaar ◽  
Andrea Prager ◽  
Jan Griebel ◽  
...  

Radiation-induced graft immobilization (RIGI) is a novel method for the covalent binding of substances on polymeric materials without the use of additional chemicals. In contrast to the well-known radiation-induced graft polymerization (RIGP), RIGI can use non-vinyl compounds such as small and large functional molecules, hydrophilic polymers, or even enzymes. In a one-step electron-beam-based process, immobilization can be performed in a clean, fast, and continuous operation mode, as required for industrial applications. This study proposes a reaction mechanism using polyvinylidene fluoride (PVDF) and two small model molecules, glycine and taurine, in aqueous solution. Covalent coupling of single molecules is achieved by radical recombination and alkene addition reactions, with water radiolysis playing a crucial role in the formation of reactive solute species. Hydroxyl radicals contribute mainly to the immobilization, while solvated electrons and hydrogen radicals play a minor role. Release of fluoride is mainly induced by direct ionization of the polymer and supported by water. Hydrophobic chains attached to cations appear to enhance the covalent attachment of solutes to the polymer surface. Computational work is complemented by experimental studies, including X-ray photoelectron spectroscopy (XPS) and fluoride high-performance ion chromatography (HPIC).


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