Investigating the effect of water-mixing nitrogen atmospheric pressure plasma jet on polyether-ether-ketone and time stability under different conditions

Possessing excellent properties including good biocompatibility, high strength, and stiffness, polyether-ether-ketone (PEEK) has significant application values in medical and industrial fields. However, the relatively poor wettability and low adhesion limit its further applications. Atmospheric pressure plasma jet (APPJ) has been utilized for adjusting PEEK properties, but better hydrophilization effect and time stability after treatment are still urgently needed. In this paper, we employ a water-mixing nitrogen (N₂ H₂O) APPJ to process PEEK, and surface wettability can be effectively improved (contact angle ~18° within 2 min, distance between sample and nozzle outlet: 10 mm) without inducing obvious microstructure damages. Additionally, after storing for 40 days, the sample treated by N₂ H₂O APPJ also possessed better wettability (~54°) compared with that treated by N₂ APPJ (~65°). On the basis of this low-damage and high-efficient modification method, we perform aging experiments under different conditions (different temperatures 25, −10°C; and low vacuum condition: 50 kPa) to determine a relatively optimum storing condition for this method. The experiment results indicate that low temperature and vacuum are conducive to retaining the plasma-induced wettability (~34°). The treatment method and storing conditions for PEEK presented here may facilitate the application of PEEK in various fields.     

Effects of surface modification by Ar+ irradiation on wettability of surfaces of poly(ethylene terephthalate) films

Surfaces of poly(ethylene terephthalate); PET, films were irradiated with Ar⁺ at 1 keV using various ion doses (ID) from 10¹⁴ to 10¹⁷ ions/cm² (isc) with and without an O₂ environment. The wettability of the modified surfaces of PET was determined by measuring the contact angle between water droplets and the modified surfaces. The modified surfaces were also characterized by AFM (atomic force microscopy) and XPS (X-ray photoelectron spectroscopy) for changes in the surface morphology, and the chemical composition and molecular structure, respectively. The contact angle decreased from 70° for unmodified surfaces to 45° for modified surface with ID = 10¹⁴ isc without O₂ and remained relatively constant with higher ID. The contact angle, however, reached a minimum value of 8° for modified surfaces with ID = 10¹⁶ isc with O₂. The improved wettability may be due to a combination of the formation of hydrophilic groups, chemical and molecular structural changes, physical structural or morphological changes, and increased roughness of the surface. The wettability of the modified surfaces also depended on the time of exposure to air. The wettability worsened with exposure time to air, but was revived by immersing the films into water. Possible mechanisms for the change of the wettability of the modified surfaces are given.     

Study of nisin adsorption on plasma-treated polymer surfaces for setting up materials with antibacterial properties

Setting up antibacterial materials by nisin adsorption on surfaces depends mainly on the surface properties and the surface treatments allowing the modification of such properties. In order to investigate the factors affecting such adsorption, the native low density polyethylene (LDPE) was modified using Argon/Oxygen (Ar/O₂) plasma, nitrogen (N₂) plasma and plasma-induced grafting of acrylic acid (AA). The films were studied by various characterization techniques. The chemical surface modification was confirmed by X-ray photoelectron spectroscopy (XPS), the wettability of the surfaces was evaluated by contact angle measurements, the surface charge was determined by the zeta potential measurements, and the changes in surface topography and roughness were revealed by atomic force microscopy (AFM). Nisin was adsorbed on the native and the modified surfaces. The antibacterial activity, the nisin adsorbed amount, and the peptide distribution were compared for the four nisin-functionalized films. The highest antibacterial activity was recorded on the Ar/O₂ followed by AA then by N₂ treated films and the lowest activity was on the native film. The observed antibacterial activity was correlated to the type of the surface, hydrophobic and hydrophilic interactions, surface charge, surface topography, nisin adsorbed amount, and nisin distribution on the surfaces.     

Flexible rGO-SnO2 supercapacitors converted from pastes containing SnCl2 liquid precursor using atmospheric-pressure plasma jet

Reduced graphene oxide (rGO)-SnO₂ nanocomposites are fabricated on carbon cloth from screen-printed pastes containing rGO nanoflakes and SnCl₂ liquid precursor by using a nitrogen atmospheric-pressure plasma jet (APPJ). RGO-SnO₂-coated carbon cloth is then used as the electrode of gel-electrolyte supercapacitors (SCs). Experiments conducted with various APPJ processing times suggest that the optimal APPJ processing time is 300 s. Cyclic voltammetry (CV) measurements indicate that 300-s APPJ processing results in the best areal capacitance of 97.53 mF/cm². The capacitance retention rate is ~85% after a 10,000-cycle CV test. Further, capacitance increases by 11% after a 1000-cycle bending test under a bending radius of 7.5 mm, possibly owing to the better electrolyte/electrode contact and decrease in the charge transport resistance after mechanical bending. This study also characterized APPJ-processed rGO-SnO₂ nanocomposites by scanning electron microscopy with energy dispersive spectroscopy, X-ray photoelectron spectroscopy, X-ray diffractometry, Raman spectroscopy, and water contact angle measurements.     

Surface modification of nanocrystalline diamond/amorphous carbon composite films

The surfaces of nanocrystalline diamond/amorphous carbon (NCD/a-C) nanocomposite films deposited from a 17% CH₄/N₂ mixture have been subjected to a variety of plasma and chemical treatments, namely H₂ and O₂ microwave plasmas, a CHF₃ 13.56 MHz plasma, and a chemical treatment with aqua regia (HCl:HNO₃ 3:1). The resulting surfaces have been studied with respect to their chemical nature by X-ray photoelectron spectroscopy (XPS) and time of flight secondary ion mass spectrometry (TOF-SIMS), concerning their morphology with atomic force microscopy, and by contact angle measurements to study their hydrophobicity and their stability. As-grown surfaces are hydrogen terminated, but the number of C–H bonds can slightly be increased by a H₂ microwave plasma, while treatment with aqua regia considerably lowers the number of C–H bonds at the surface. O₂ and CHF₃ plasmas, on the other hand, lead to a replacement of the terminating C–H bonds by C–O or C–OH and C–F_x groups, respectively. Finally, by contact angle measurements over a period of 150 days it could be shown that the H-terminated surface is very stable whereas the contact angle of the O-treated surface changed considerably with time, probably due to the adsorption of contaminants.     

Surface modification of nylon 6 films treated with an He/O2 atmospheric pressure plasma jet

To investigate the effect of the gas composition of the plasma treatment on the surface modification of an atmospheric pressure plasma jet (APPJ), nylon 6 films were treated with APPJ with pure helium (He), He + 1% oxygen (O₂), and He + 2% O₂, respectively. Atomic force microscopy showed increased surface roughness, whereas X‐ray photoelectron spectroscopy revealed increased oxygen contents after the plasma treatments. The plasma‐treated samples had lower water contact angles and higher T‐peel strengths than the control. The addition of a small amount of O₂ to the He plasma increased the effectiveness of the plasma treatment in the polymer surface modification in terms of surface roughness, surface oxygen content, etching rate, water contact angle, and bonding strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Fabrication of superhydrophobic transparent cyclic olefin copolymer (COC)-SiO2 nanocomposite surfaces

A superhydrophobic cyclic olefin copolymer (COC) nanocomposite coating was produced with a very simple and easy method. Self-cleaning superhydrophobic COC surfaces were obtained by only adding surface hydrophobized SiO₂ nanoparticles by dip coating method. The influence of concentration of SiO₂ and the coating temperatures on the wettability of the surfaces were investigated. The surface wettability of the coatings was examined with the contact angle measurements and the surface roughness and morphology were analyzed by using atomic force microscope and scanning electron microscopy analysis. Surfaces with certain amounts of COC and SiO₂ showed superhydrophobic character with high water contact angle of 169⁰. Also, the obtained superhydrophobic surfaces show superior water repellent, high transparency, and self-cleaning characteristics.     

Synthesis and characteristics of NH<Subscript>2</Subscript>-functionalized polymer films to align and immobilize DNA molecules

We developed a method to use NH₂-functionalized polymer films to align and immobilize DNA molecules on a Si substrate. The plasma-polymerized cyclohexane film was deposited on the Si substrate according to the radio frequency plasma-enhanced chemical vapor deposition method using a single molecular precursor, and it was then treated by the dielectric barrier discharge method in a nitrogen environment under atmospheric pressure. Changes in the chemistry of the surface functional groups were studied using X-ray photoelectron spectroscopy and Fourier transformed infrared spectroscopy. The wettability of the surfaces was examined using dynamic contact angle measurements, and the surface morphology was evaluated using atomic force microscopy.     

Atmospheric-pressure plasma treatment of polyamide 6 composites for bonding with polyurethane

An atmospheric-pressure plasma jet (APPJ)-based surface treatment process was investigated for the structural (τ_B > 15 MPa) adhesive bonding of polyamide 6 (PA6) composites. The treated surfaces were examined by contact angle measurement, X-ray photoelectron spectroscopy, and atomic force microscopy (AFM). Additionally, the shear strengths of single lap specimens were determined as a function of different plasma intensities and polyurethane adhesives. Our results show that APPJ leads to an increase of the surface free energy, oxygen concentration, and number of functional groups. Furthermore, the topography of the surface was significantly modified by exposure to APPJ. AFM measurements show that special attention has to be paid to the intensity of the plasma treatment to avoid melting and flattening of the PA6 surface on the nanometer scale. With optimized multiple APPJ treatments, lap shear strength of 20 MPa was achieved for the first time for this material system, allowing the material system to be employed in future automobile applications.     

Contact angle and vacuum floatability of ultrafine size particles

The contact angle of ultrafine size particles has been evaluated using 1 µm monosize SiO₂ particles of various degrees of wettability. The contact angle was determined by film flotation and Zisman plots. Chlorotrimethylsilane (CTS) was used to methylate the SiO₂ particle surface and establish the level of surface wettability. Also, the vacuum floatability of the methylated ultrafine SiO₂ particles was assessed to correlate it to the contact angle. This vacuum floatability was very low below 40º and increased monotonically above this contact angle value because of favorable bubble nucleation and a greater stability of the bubbles on the hydrophobic surface. Free energy of bubble nucleation on the hydrophobic surfaces has been estimated and correlated to the vacuum floatability of the ultrafine particles.     

Proliferation rate of fibroblast cells on polyethylene surfaces with wettability gradient

Surface wettability on anchorage‐dependent cells has an important role in cell growth rate. In our previous studies, we prepared a wettability gradient on polyethylene (PE) surfaces using corona discharge treatment from a knife‐type electrode whose power increased gradually along the sample length. The PE surfaces were oxidized gradually with increasing power and characterized by Fourier transform infrared spectroscopy, contact angle goniometry, and electron spectroscopy for chemical analysis. The purpose of this study is to determine the rate of proliferation on polymer surfaces with different wettability. The behavior of cell growth for NIH/3T3 fibroblast cells attached on the polymer surfaces with different hydrophilicity was investigated using wettability gradient PE surfaces prepared by corona discharge treatment. They were investigated for the number of grown cells from 24 to 60 h in terms of surface wettability. From the slope of cell number on PE gradient surface versus culture time, the proliferation rates (number of cell/cm² · h) were calculated. It was observed that the proliferation rate was increased more on positions with moderate hydrophilicity of the wettability gradient surface than on the more hydrophobic or hydrophilic positions, i.e., 1111 (number of cell/cm² · h) of 57° of water contact angle at the 2.5‐cm position (P < 0.05). This result seems closely related to the serum protein adsorption on the surface: the serum proteins were also adsorbed more on the moderately hydrophilic surface. In conclusion, surface wettability plays an important role in cell adhesion, spreading, and proliferation on the polymer surfaces. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 599–606, 2004     

Effect of nitrogen and oxygen incorporated into TMSAA plasma coating on surface‐bound heparin activity

To investigate the influence of nitrogen and oxygen incorporated into N‐trimethylsilylallyamine (TMSAA) plasma coating on heparin binding to the surfaces, four types of monomer combinations were utilized. Those combinations include TMSAA alone, TMSAA mixed with nitrogen (TMSAA + N₂), with air (TMSAA + air), and with oxygen (TMSAA + O₂). Fourier transform infrared (FTIR) spectroscopy was employed to study the coating of the bulk structure. The thickness and surface morphology of the coatings were measured using atomic force microscopy (AFM). Electron spectroscopy for chemical analysis (ESCA) and the contact angle were used to investigate the surface elemental composition and hydrophilicity, respectively. It was found that the incorporation of oxygen into the coating formation significantly increased the deposition rate of the TMSAA + O₂ coating, but the heparin activity was the least even though it made the coating surface more hydrophilic. This is considered to have resulted from the loss of nitrogen in the coating structure due to the oxygen replacement to nitrogen. The nitrogen incorporated into the coating had no noticeable effect on the heparin surface‐binding ability. The TMSAA + air plasma grafting process exhibited the best heparin attachment to the surface, which could be largely attributed to its highest surface roughness, although the nitrogen composition was decreased to some extent compared to the pure TMSAA plasma coating. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1875–1883, 2003     

Surface modification of Kevlar 149 fibers by gas plasma treatment

Kevlar 149 fibers have been surface treated with NH₃-, 0₂-, or H₂O-plasm to modify the fiber surfaces. SEM (scanning electron microscopy) is used to characterize the surface topography of fibers etched by gas plasmas. The chemical compositions and functional groups of the fiber surfaces are identified by ESCA (electron spectroscopy for chemical analysis) and SSIMS (static secondary ion mass spectroscopy), respectively. The contact angle of water on modified PPTA [poly(p-phenylene terepbthalamide)] film prepared from using Kevlar 149 fibers is also used to investigate the wettability. The results show that the etching abilities of gas plasmas are dependent on the type of gas used for plasma treatments. The contact angle data indicate that all the three gas plasma treatments are effective in rendering the surface of PPTA more hydrophilic. The ESCA analysis results show that the surface compositions of plasma-treated fibers are highly dependent on the type of gas used and treatment time. Changes in surface compositions of fibers treated by NH₃-, O₂-, and H₂O-plasma are observed. Increasing nitrogen and oxygen contents are observed for the NH₃-plasma treatment, and the O₂- and H₂O-plasma treatments, respectively. Furthermore, the incorporation of amino groups into fiber surfaces by NH₃-plasma treatment and the extensive damage of the aromatic ring and the polymer backbone by H₂O-plasma and O₂-piasma are evidenced by SSIMS.     

Effect of low-pressure O2 and Ar plasma treatments on the wettability and morphology of biaxial-oriented polypropylene (BOPP) film

Low-pressure plasma treatments in an rf discharge of O₂ and Ar were employed to introduce polar functional groups onto the biaxial-oriented polypropylene (BOPP) surfaces to enhance the wettability and activation. The effects of plasma treatment on the morphology and wettability of the BOPP films were characterized using static contact angle measurements, attenuated total reflection (ATR)–FTIR spectroscopy, scanning electron microscopy (SEM) and atomic force microscopy (AFM).     

In vitro blood compatibility of modified PDMS surfaces as superhydrophobic and superhydrophilic materials

The surface of polydimethylsiloxane rubber (PDMS) was irradiated by a CO₂‐pulsed laser. The irradiated surfaces were grafted by hydroxyethylmethacrylate phosphatidylcholine (HEMAPC) by using the preirradiation method. The laser‐treated surfaces and HEMAPC‐grafted PDMS surfaces were characterized by using a variety of techniques including ATR‐FTIR spectroscopy, scanning electron microscopy (SEM), and wettability, which was measured by a water‐drop contact angle. Different surfaces with different wettability were prepared. These surfaces, including untreated PDMS (hydrophobic), laser‐treated PDMS (superhydrophobic), and HEMAPC‐grafted surfaces (superhydrophilic), were used for a platelet adhesion study. Results from in vitro testing indicated that chemical structures, such as negative‐charge polar groups and wettability, are important factors in blood compatibility of these surfaces and the superhydrophilic (the most wettable) and the superhydrophobic (the most unwettable) of modified PDMS surfaces have excellent blood compatibility compared to the unmodified PDMS. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91:2042–2047, 2004     

Degradation properties of PLA and PHBV films treated with CO2-plasma

The objectives of this study are to investigate the effects of an inductively coupled CO₂-plasma treatment on two biodegradable PLA and PHBV films and to confirm the possibility of improving the degradation properties in variety of solutions. X-ray photoelectron spectroscopy and contact angle measurement were employed to analyze the surface chemical states and to observe specific chemical changes on the surfaces. To study biodegradation, three acidic, neutral, and basic solutions were prepared, respectively. After the plasma treatment and the degradation test, scanning electron microscopy was also employed to observe the surface morphologies of the films. In conclusion, the exposure of the polymer surfaces to CO₂-plasma could encourage the formation of polar groups and oxidation on the surfaces, thereby increasing the roughness, wettability, and degradability of the surfaces.     

Surface degradation and hydrophobic recovery of polyolefins treated by air corona and nitrogen atmospheric pressure glow discharge

The surface degradation and production of low molecular weight oxidized materials (LMWOM) on biaxially oriented polypropylene (BOPP) and low‐density polyethylene (LDPE) films was investigated and compared for two different dielectric barrier discharge (DBD) treatment types, namely air corona and nitrogen atmospheric pressure glow discharge (N₂ APGD). Contact angle measurements, X‐ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM) analyses were performed in conjunction with rinsing the treated films in water. It is shown that N₂ APGD treatments of both polyolefins result in much less surface degradation, therefore, allowing for a significantly higher degree of functionalization and better wettability. Hydrophobic recovery of the treated films has also been studied by monitoring their surface energy (γ_s) over a period of time extending up to several months after treatment. Following both surface modification techniques, the treated polyolefin films were both found to undergo hydrophobic recovery; however, for N₂ APGD modified surfaces, γ_s ceases to decrease after a few days and attains a higher stable value than in the case of air corona treated films. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1291–1303, 2004     

Adhesion Properties and Structure of Ion-Beam Modified Polyimide Films

Polyimide (PI) surface modification was carried out by an ion beam treatment to improve the adhesion between the polyimide film and copper. The PI film surface was treated with an ion-beam source at ion doses ranging from 1.96 × 10¹³ to 2.38 × 10¹³ ions/cm² using a mixture of nitrogen (N₂) and hydrogen (H₂). Contact angle measurement, atomic force microscopy and X-ray photoelectron spectroscopy, respectively revealed an increase in the surface roughness, a decrease in contact angle, and the formation of oxygen complexes and functional groups on the treated PI surfaces. Adhesion between the copper and PI film treated with the beam was superior to that of the untreated PI film. The 90° peel test revealed the highest peel strength of 7.8 N/cm.     

Surface modification of polytetrafluoroethylene films by plasma pretreatment and graft copolymerization to improve their adhesion to bismaleimide

BACKGROUND: Polytetrafluoroethylene (PTFE) is utilized in many engineering applications, but its poor wettability and adhesion properties with other materials have limited its use. The study reported was aimed at achieving surface modification of PTFE films by radiofrequency NH₃ and N₂ plasma treatment, followed by graft copolymerization, in order to improve the interfacial adhesion of PTFE and bismaleimide. RESULTS: X‐ray photoelectron spectroscopy results showed that a short‐time plasma treatment had a distinct defluorination effect and led to nitrogen functional group formation. The nitrogen chemical bonding form was different for NH₃ and N₂ plasma treatments. Under the same experimental conditions, the NH₃ plasma exhibited a better etching effect than did the N₂ plasma. Contact angle measurement showed an improvement in both surface energy and wettabliity by short‐time plasma treatment. The concentration of the surface‐grafted bismaleimide on PTFE increased after the plasma pretreatment. The lap shear strength between PTFE and bismaleimide increased significantly after surface modification. CONCLUSION: This study found that plasma treatment caused changes in surface chemistry, thus leading to an increase of the wettability of PTFE surfaces. Hence, the adhesion properties of PTFE with bismaleimide were significantly improved. Copyright © 2008 Society of Chemical Industry     

Control of wettability of polymers using organic surface chemistry

The analytical technique of contact angle analysis has been used both to monitor organic transformations on the surfaces of fluoropolymer films and also to help correlate surface structure with wettability. This paper describes the preparation and characterization, particularly with regard to wettability, of several series of surface-modified derivatives of chemically resistant polymers. A series of esters prepared with acid chlorides and alcohol-functionalized poly(chlorotrifluoroethylene) (PCTFE-OH) displays expected water contact angle trends and indicates that wettability can be controlled using organic surface chemistry. The identification of carboxylic acids on the surface of poly(vinylidene fluoride) (PVF₂-CO₂H) by the pH dependence of the water contact angle is discussed. Also described and compared with X-ray photoelectron spectroscopy is the use of contact angle for observing polymer surface reconstruction.