Surface Modification Of Polytetrafluoroethylene Research Articles

Surface modification of polytetrafluoroethylene (PTFE) fibers through methyl methacrylate (MMA) polymerization for self-lubricating composites

PTFE fibers exhibit strong inertia and possess restricted interfacial compatibility with resin, thereby constraining the application of PTFE self-lubricating composites. To address this issue, PTFE-g-MMA fibers were synthesized by grafting MMA onto the surface of PTFE fibers using high-energy irradiation and chemical grafting techniques, resulting in the enhancement of the tribological properties (the friction coefficient has been reduced by approximately 42.2% and the wear rate has been reduced by about 87.9%) and mechanical properties (the interlaminar shear strength (ILSS) experienced a substantial increase of approximately 45.8%) of the composites. The influence of grafting modification on the formation of PTFE transfer films and the effect of modification time on the tribological properties of composites were investigated systematically. The results indicated that graft modification disrupted the C–F bond of PTFE and promoted the formation of metal-chelated carboxylates, facilitating the formation of PTFE transfer films on the counter surface. This research could provide a general and feasible strategy for large-scale modification of PTFE fibers with exceptional comprehensive properties.

Hydrophilic Nature of Polytetrafluoroethylene through Modification with Perfluorosulfonic Acid-Based Polymers

Polytetrafluoroethylene (PTFE), commercially known as Teflon, is a fluoropolymer with a structure containing (CF2–CF2)n. It has high resistance to acids, alkalis and corrosive chemicals. PTFE is hydrophobic in nature with a water contact angle of 140°. Being hydrophobic in nature is a knotty problem, particularly in electrical applications, as it may lead to short circuits and result in reducing the lifetime of electrical equipment. Herein we describe the surface modification of PTFE from hydrophobic to hydrophilic without altering its bulk property. The surface hydrophilicity is achieved by two different techniques, viz., polymer coating (aquivion and nafion) and plasma treatment. Several characterization techniques including FTIR, Raman, XPS, WCA and SEM were used to analyze the surface of PTFE. It was found that 5% of the polymer solution and N2 plasma treatment for 2 min can produce huge differences in the surface property, as evidenced by the reduction in water contact angle from 140° (neat Teflon) to 80° (surface-modified Teflon). The surface morphology of neat PTFE is completely changed and collapsed as evidenced by the SEM images. The FTIR, Raman and XPS analyses confirm the presence of additional hydrophilic functional groups after the polymer coating and plasma treatment. Hence, this method represents a unique approach to modifying the surface property of Teflon, while maintaining its bulk property.

Super antiwear properties of polytetrafluoroethylene (PTFE) induced by MeV proton irradiation

In this paper, the surface of polytetrafluoroethylene (PTFE) was modified by 1 MeV proton beam at high temperature. The changes of wear resistance and hardness of PTFE before and after irradiation were evaluated by ball/pin disk friction loss tester and nanoindentation tester, respectively. The results showed that the wear resistance of PTFE irradiated by proton at high temperature has been significantly enhanced. The mass wear rate decreases from 2.75 × 10−6 g/Nm to 0.39 × 10−6 g/Nm, and the wear depth decreases from 29.9 μm to 8.2 μm, respectively. Proton irradiation could be a simple and effective method for PTFE surface modification and can significantly improve the wear resistance. The potential chemical reaction mechanism for the improvement of wear resistance of irradiated PTFE in terms of microstructure was discussed. Crosslinking induced by proton irradiation enhanced the interaction force among PTFE molecules, thus the mechanical properties were improved.

DFT and QSAR studies of PTFE/ZnO/SiO2 nanocomposite

Polytetrafluoroethylene (PTFE) is one of the most significant fluoropolymers, and one of the most recent initiatives is to increase its performance by using metal oxides (MOs). Consequently, the surface modifications of PTFE with two metal oxides (MOs), SiO2 and ZnO, individually and as a mixture of the two MOs, were modeled using density functional theory (DFT). The B3LYPL/LANL2DZ model was used in the studies conducted to follow up the changes in electronic properties. The total dipole moment (TDM) and HOMO/LUMO band gap energy (∆E) of PTFE, which were 0.000 Debye and 8.517 eV respectively, were enhanced to 13.008 Debye and 0.690 eV in the case of PTFE/4ZnO/4SiO2. Moreover, with increasing nano filler (PTFE/8ZnO/8SiO2), TDM changed to 10.605 Debye and ∆E decreased to 0.273 eV leading to further improvement in the electronic properties. The molecular electrostatic potential (MESP) and quantitative structure activity relationship (QSAR) studies revealed that surface modification of PTFE with ZnO and SiO2 increased its electrical and thermal stability. The improved PTFE/ZnO/SiO2 composite can, therefore, be used as a self-cleaning layer for astronaut suits based on the findings of relatively high mobility, minimal reactivity to the surrounding environment, and thermal stability.

Surface Modification of Polytetrafluoroethylene and Polycaprolactone Promoting Cell-Selective Adhesion and Growth of Valvular Interstitial Cells.

Tissue engineering concepts, which are concerned with the attachment and growth of specific cell types, frequently employ immobilized ligands that interact preferentially with cell types of interest. Creating multicellular grafts such as heart valves calls for scaffolds with spatial control over the different cells involved. Cardiac heart valves are mainly constituted out of two cell types, endothelial cells and valvular interstitial cells. To have control over where which cell type can be attracted would enable targeted cell settlement and growth contributing to the first step of an engineered construct. For endothelial cells, constituting the outer lining of the valve tissue, several specific peptide ligands have been described. Valvular interstitial cells, representing the bulk of the leaflet, have not been investigated in this regard. Two receptors, the integrin α9β1 and CD44, are known to be highly expressed on valvular interstitial cells. Here, we demonstrate that by covalently grafting the corresponding peptide and polysaccharide ligand onto an erodible, polycaprolactone (PCL), and a non-degradable, polytetrafluoroethylene (PTFE), polymer, surfaces were generated that strongly support valvular interstitial cell colonization with minimal endothelial cell and reduced platelet adhesion. The technology for covalent binding of corresponding ligands is a key element towards tissue engineered cardiac valves for in vitro applications, but also towards future in vivo application, especially in combination with degradable scaffold material.

Dopamine-Induced Surface Zwitterionization of Expanded Poly(tetrafluoroethylene) for Constructing Thermostable Bioinert Materials.

Although energy-demanding, the surface modification of polytetrafluoroethylene (PTFE) for biomedical applications is mandatory to mitigate irreversible biofouling that occurs whenever PTFE comes into contact with biological fluids. Here, we propose to take advantage of the adhesive properties of dopamine (DA) and of the antifouling ability of various zwitterionic monomers (sulfobetaine methacrylate (SBMA), sulfobetaine methacrylamide (SBAA), sulfobetaine acrylamide (SBAA'), and 4-vinylpyridine propylsulfobetaine (4VPPS)) and form antifouling coatings by copolymerization on the surface of expanded PTFE membranes. This simple, low-energy, and one-step coating procedure arises in significant biofouling mitigation. All zwitterionic coatings led to important reduction of biofouling by red blood cell conentrate (88-94%), platelet conentrate (70-90%), whole blood (40-66%), or bacteria (83-96%). Also, it is shown that the interactions of polydopamine with ePTFE are stable even at high temperatures. However, the zwitterionic monomers are differently affected. While the performance of SBMA coatings decreased (as SBMA is prone to hydrolysis), those of SBAA, SBAA', and 4VPPS coatings were generally maintained. All in all, this study illustrates that efficient and stable antifouling zwitterionic coatings can be generated onto PTFE membranes for biomedical applications, without the use of conventional high-energy-demanding surface modification processes.

Surface modification of polytetrafluoroethylene (PTFE) with a heparin-immobilized extracellular matrix (ECM) coating for small-diameter vascular grafts applications

Intimal hyperplasia, thrombosis formation, and delayed endothelium regeneration are the main causes that restrict the clinical applications of PTFE small-diameter vascular grafts (inner diameter < 6 mm). An ideal strategy to solve such problems is to facilitate in situ endothelialization. Since the natural vascular endothelium adheres onto the basement membrane, which is a specialized form of extracellular matrix (ECM) secreted by endothelial cells (ECs) and smooth muscle cells (SMCs), functionalizing PTFE with an ECM coating was proposed. However, besides ECs, the ECM-modified PTFE improved SMC growth as well, thereby increasing the risk of intimal hyperplasia. In the present study, heparin was immobilized on the ECM coating at different densities (4.89 ± 1.02 μg/cm2, 7.24 ± 1.56 μg/cm2, 15.63 ± 2.45 μg/cm2, and 26.59 ± 3.48 μg/cm2), aiming to develop a bio-favorable environment that possessed excellent hemocompatibility and selectively inhibited SMC growth while promoting endothelialization. The results indicated that a low heparin density (4.89 ± 1.02 μg/cm2) was not enough to restrict platelet adhesion, whereas a high heparin density (26.59 ± 3.48 μg/cm2) resulted in decreased EC growth and enhanced SMC proliferation. Therefore, a heparin density at 7.24 ± 1.56 μg/cm2 was the optimal level in terms of antithrombogenicity, endothelialization, and SMC inhibition. Collectively, this study proposed a heparin-immobilized ECM coating to modify PTFE, offering a promising means to functionalize biomaterials for developing small-diameter vascular grafts.

Surface Modification of Polytetrafluoroethylene by Atmospheric Pressure Plasma-Grafted Polymerization

The aim of this study was to observe the atmospheric pressure plasma for polytetrafluoroethylene (PTFE) surface modification. The hydrophilicity of the effectively-anchored acrylic acid polymerization on the PTFE surfaces through atmospheric pressure plasma-grafted polymerization was examined using surface chemical composition analysis. The hydrophilic acrylic acid coating was created, via graft polymerization, onto a PTFE surface that was activated by the atmospheric pressure plasma. The photoemission plasma species in this plasma were identified by optical emission spectroscopy. The influences of atmospheric pressure plasma on the PTFE surface properties were also studied. We observed a significant increase in the surface free energy of the PTFE due to the atmospheric pressure plasma treatments. In this study, the changes in the chemical composition of this plasma-grafted, polymerized PTFE surfaces were also determined using FTIR, ESR, and XPS. It suggests that a specific level of surface wettability can be attained by tailor-designing the characteristics of the atmospheric pressure plasma-grafted, acrylic acid polymerization on the PTFE surface by adjusting the chemical composition and surface morphology, which are organized by the plasma surface activation and monomer concentration.

Ion-Implantation Modification of Surface Flashover Properties in Vacuum of Polytetrafluoroethylene

Surface modification of polytetrafluoroethylene (PTFE) is performed by nitrogen ion implantation for improving the PTFE surface flashover voltage in vacuum. In this paper, nitrogen ions are produced by an electron cyclotron resonance ion source. The properties of the samples are investigated with X-ray photoelectron spectroscopy, electrometer, microhardness tester, surface potential measurement, and surface flashover system. The Stopping and Range of Ions in Matter software is used to simulate the ion implantation. Experimental results show that the surface flashover voltage of treated samples improves remarkably and increases with the injection energy. After ion implantation, the content of fluorine in the treated samples decreases, and the content of oxygen increases. The surface conductivity increases from $1.15\times 10^{{-15}}$ to 1.36 10−13 S/m, the surface potential decreases faster, and the trap density and energy increase with the implantation energy. The process of electron avalanche and the accumulation of surface charges have been suppressed, thus hindering the development of flashover and improving the surface flashover voltage.

Surface functionalization of polytetrafluoroethylene substrate with hybrid processes comprising plasma treatment and chemical reactions.

Polytetrafluoroethylene (PTFE) exhibits excellent mechanical properties and chemical stability and has been widely used in medical fields for the preparation of implantable medical devices. However, the implantation of PTFE in living systems results in inflammation reactions and infections at the surface thus limits its long-term applications. For PTFE surface modification, we examined the effects of mussel-inspired polydopamine (PDA) coating and the further introduction of functional groups. During PDA coating, the plasma pretreatment on PTFE enhanced the stability of the PDA coating layer. Furthermore, the introduction of functional groups on the PDA layer was carried out using reactive functional groups for the photoinduced graft polymerization of methacrylate. For instance, 2-methacryloyloxyethyl phosphorylcholine (MPC) could be polymerized from the surface of the substrate. These chemical modifications were confirmed step by step using spectroscopes to obtain the hydrophilic surface of the poly(MPC)-modified PTFE. The protein adsorption behaviors on PTFE and poly(MPC)-modified PTFE were compared to understand biocompatibility characteristics of these substrates. The surface of PTFE was immediately covered with albumin and the contact between the substrate and the serum resulted in an increase in the fibrinogen composition with time. On the other hand, fewer proteins were adsorbed on the poly(MPC)-modified PTFE substrate. Thus, this modification procedure would serve as a strategy for safer alterations in PTFE surfaces to expand the life span of the PTFE-carrying medical devices in living systems.

Modification of Polymer Substrates with Extreme Ultraviolet - Potential Application in Cancer Cell Identification

During the last two decades, the development of laboratory scale extreme ultraviolet sources has been intensified due to growing interest in use of extreme ultraviolet sources photons for various applications in science and technology. In this study, we present a potential application of extreme ultraviolet sources surface modification of polymers to be used as substrates for cancer cell identification. The surface modification of polytetrafluoroethylene (PTFE) polymer samples was performed by a lab scale compact laser-plasma extreme ultraviolet sources source based on a double-stream gas-puff target. The gas target was irradiated with a 3 ns/0.8 J Nd:YAG laser pulse at 10 Hz with 50 and 300 pulses. HCV29 non-malignant transitional epithelium and T24 bladder cells adhesion and proliferation studies on pure and extreme ultraviolet sources modified PTFE surfaces were performed. The extreme ultraviolet sources modified surfaces demonstrated regular increase in cancer cell proliferation comparing to pristine sample. Initial results indicate that extreme ultraviolet sources treated substrates can facilitate the identification of cancer cells

Water tank triboelectric nanogenerator for efficient harvesting of water wave energy over a broad frequency range

A water tank triboelectric nanogenerator based on polytetrafluoroethylene (PTFE) is fabricated for harvesting water wave energy. The impacts of contact frequency over a broad frequency range including the frequency range of ocean waves and output characteristics under resistive and capacitive loads for different liquid types are investigated in order to identify the optimal contact frequency and load conditions for maximizing the power density and energy conversion efficiency. In addition, surface modification of PTFE with different patterns for enhancing its hydrophobicity is implemented in order to reduce charge screening. Furthermore, the impact of contact frequency on the output characteristics for the surface modified PTFE is also studied. It is observed that the open-circuit voltage and short-circuit current exhibited opposite trends with increasing contact frequency. The highest power density of 9.62W/m2 and energy conversion efficiency of 63.2% are achieved using saline water and rhombic pattern surface modified PTFE at contact frequency of 0.1Hz, representing 8 fold improvement compared to the reported water tank based triboelectric nanogenerator based on fluorinated ethylene propylene. The results demonstrate that the nanogenerator has promising potential in scavenging water kinetic energy.

Extreme ultraviolet (EUV) surface modification of polytetrafluoroethylene (PTFE) for control of biocompatibility

Extreme ultraviolet (EUV) surface modification of polytetrafluoroethylene (PTFE) was performed in order to enhance the degree of biocompatibility. Polymer samples were irradiated by different number of EUV shots using a laser–plasma based EUV source in the presence of nitrogen gas. The physical and chemical properties of EUV modified PTFE samples were studied using Atomic Force Microscopy, X-ray photoelectron spectroscopy and water contact angle (WCA) methods. Pronounced wall type micro and nano-structures appeared on the EUV treated polymer surfaces resulting in increased surface roughness and hydrophobicity. Stronger cell adhesion and good cell morphology were observed on EUV modified surfaces by in-vitro cell culture studies performed using L929 fibroblasts.

Surface structural changes, surface energy and antiwear properties of polytetrafluoroethylene induced by proton irradiation

Abstract In this work, the polytetrafluoroethylene (PTFE) surface was modified with 25 keV proton beam irradiation in vacuum condition. Multiple characterization techniques including X-ray photoelectron spectroscopy, Raman spectroscopy and infrared spectroscopy were employed for research on microstructure changes in the PTFE surface. The changes in the surface energy and antiwear properties of PTFE were evaluated using contact angle analysis and a ball-on-disk tribometer, respectively. Experimental results showed that the surface energy of PTFE obviously increased from 13.17 mJ/m 2 to 33.73 mJ/m 2 and the wear rate decreased from 8.9 × 10 − 3 mm 3 /Nm to 5.8 × 10 − 4 mm 3 /Nm after proton irradiation for 15 min. Moreover, TRIM simulation indicated that the H + ions cannot penetrate through the PTFE block and only stop at a depth of about 730 nm from the material surface. Proton irradiation has been proved to be a simple, rapid and effective measure for the surface modification of PTFE with distinctly improved surface energy and antiwear properties, and the possible reaction mechanism taking place in PTFE was also discussed in this paper.

The Effect of Surface Modification of Polytetrafluoroethylene (PTFE) on the Properties of POM/PTFE Fiber Composites

Surface modification of polytetrafluoroethylene (PTFE) fiber by plasma grafting polymerization with acrylamide (AAm) was studied to improve the compatibility between polyacetal (POM) and PTFE. The best modified PTFE manufactured by self-designed plasma polymerization was investigated and denoted as AAm (20wt%)-g (plasma 30min)-PTFE. The grafting polymerization is successful and shown by ESCA spectra of modified PTFE fibers. It is also proved by SEM photographs and the improvement of properties of the POM/PTFE composites. As a result, the friction coefficients, Taber wear factors, and impact strengths of composites with 85wt% of POM and 15wt% of a variety of PTFEs were investigated. The frictional coefficient of POM/ AAm (20wt%)-g (plasma 30min)-PTFE deceased to 0.162; while that of POM/PTFE was 0.174. Taber wear factor of the composite significantly decreased from 5.2 to 1.5 when the PTFE was replaced by AAm-g (plasma)-PTFE. Meanwhile, the impact strength increased from 6.1 kg-cm/cm (POM/PTFE) to 9.3kg-cm/cm (POM/ AAm-g (plasma)-PTFE). Besides, the multi-yield behaviors were found in the Stress-Strain curves of composites with modified PTFE fibers.

Application of photo-etching of polytetrafluoroethylene induced by high energy synchrotron radiation to LIGA

Polytetrafluoroethylene (PTFE) microstructures’ processing characteristics using X-ray photo decomposition and desorption are studied in the highest energy region (2–12 keV). While the exposed surface states are seen melting and boiling from the remaining bubble structure of the irradiated surface, basic photochemistry of PTFE is also same as previous reports. Surface modification of PTFE from hydrophobic to hydrophilic was investigated in order to bond PTFE sheets to a brass substrate. Then, we have a successfully fabricated Ni microstructure by LIGA process using PTFE photo-etching using high energy X-ray. Proposed LIGA using SR-photo-etching of PTFE can simplify the total process, and it can ensure that dimensional errors remain small due to swelling in developer and electroplating bath.

Surface modification of PTFE using an atmospheric pressure plasma jet in argon and argon + CO 2

Polytetrafluoroethylene (PTFE) has many successful engineering applications due to its great chemical stability. However, for some industrial applications, the poor adhesion of PTFE to other materials is a disadvantage. To extend the PTFE application range, several methods have been developed to modify its surface properties. Among these different techniques, plasma surface modification is the most promising one and therefore, an atmospheric pressure plasma jet (APPJ) will be used in this work to modify PTFE samples. Two different discharge gasses have been used: pure argon and an argon/CO 2 mixture and both plasma jets have been examined with optical emission spectroscopy to identify the plasma species present in the discharge. From these results, it was found that the discharge in argon contains argon atoms, nitrogen molecules and metastables, atomic oxygen and OH radicals, while the argon/CO 2 discharge contains also radicals containing CO groups. In a second part of the work, the chemical and physical changes induced by both discharges on PTFE surfaces have been investigated using contact angle measurements, SEM, AFM and XPS. From these results, it was found that exposure times below 20 s lead to a small contact angle decrease due to the introduction of a small amount of oxygen. In contrast, at higher treatment times, the contact angle starts to increase again due to advanced chain scissions leading to a high amount of oligomeric segments on the PTFE surface. As a result of these surface degradation processes, the wettability of PTFE could not be greatly enhanced, however, in the near future, it will be investigated whether these degradation reactions can be eliminated.

PTFE surface modification by Ar plasma and its characterization

Polytetrafluoroethylene (PTFE) samples were exposed to argon plasma discharge and the changes of the PTFE surface properties were studied by different methods. Surface wettability and aging of the plasma modified PTFE were derived from the contact angle measured by standard goniometry. Electrokinetical potential (ζ-potential) was determined by SurPASS Instrument. The ζ-potential and the contact angle characterize “chemistry” of the PTFE surface and also make possible to follow the aging of the PTFE surface after the plasma treatment. The surface morphology and roughness were examined by Atomic Force Microscopy (AFM). Surface concentrations of elements were determined by X-ray photoelectron spectroscopy (ARXPS). The contact angle of the modified PTFE decreases with increasing time of the plasma treatment. During the aging of the plasma modified PTFE the contact angle increases. After the plasma treatment dramatic changes in the PTFE surface morphology and roughness were observed. Also a significant increase of ζ-potential is observed, which indicates more hydrophilic surface of the modified PTFE in comparison with pristine one. With increasing time of the plasma treatment the total oxygen content in the polymer surface layer increases.

Dependence of Ion Energy on PTFE Surface Modification Effect by Nitrogen Ion Irradiation

PTFE (Poly-tetra-fluoro-ethylene) has superior characteristic. But, it has low adhesion force. In order to improve adhesion force, we have studied on surface modification of PTFE by using discharge under high E/n (E:electric field, n:particle density) condition in nitrogen. From the results, it was deduced that ion energy around 40 eV is effective for polar groups introduction. In addition, treated surface unevenness did not increase compared with the untreated one. Then, we performed nitrogen ion irradiation by changing ion energy. From the results, it is shown that low ion energy is effective for polar groups introduction. It is also shown that high energy ion suppresses surface roughness.Thus, we measured surface energy and composition of samples irradiated by high and low energy ions. When ion with 30 eV was irradiated for 5 minute and following it ion with 1060 eV was irradiated for 10 second, many polar groups were introduced and surface unevenness was kept at the untreatment level. From the results by XPS (X-ray Photoelectron Spectroscopy) analysis and FT-IR (Fourier transform Infrared Spectroscopy) analysis by using the ATR (Attenuated Total Reflection) method, it was confirmed that polar groups of oxygen component and cross-linked structure via nitrogen or carbon was introduced at the surface.

Polytetrafluoroethylene surface modification by filamentary and homogeneous dielectric barrier discharges in air

In this paper, polytetrafluoroethylene (PTFE) films are modified using non-equilibrium plasma generated by homogeneous DBD in air at medium pressure, and the results are compared to those treated by using filamentary DBD in air at atmospheric pressure. The surface properties of PTFE films before and after the treatments are studied using contact angle and surface energy measurement, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). It is found that the plasma treatments modify the PTFE surface in both morphology and composition. The PTFE films modified in both treatments show a remarkable decrease in water contact and a remarkable increase in surface energy. XPS analysis reveals that oxygen-containing polar groups are introduced onto the PTFE surface, and SEM analysis shows that the surfaces of the films are etched after both the treatments. It is found that homogeneous DBD is more effective in PTFE surface modification than filamentary DBD as it can make the contact angle decline to a lower level by introducing more oxygen-containing groups, and the possible reason for this effect is discussed.