Synergetic Effect of Grit-Blasting and Atmospheric Cold Plasma Pretreatments on the Surface Free Energy of a Fibreglass/Epoxy Vinyl Ester Composite

For the first time, the efficiency of different surface pretreatment approaches prior to adhesive bonding of a fibreglass-reinforced epoxy vinyl ester thermoset composite has been investigated. It was found that grit-blasting generally had a negligible effect on the surface free energy (SFE) calculated using the Owens, Wendt, Rabel, and Kaelble method, as well as the Lifshitz–van der Waals/acid-base (LWAB) approach. However, contrary to abrading, grit-blasting has shown its efficiency to flatten sharp surface irregularities and introduce surface roughness features suitable to adhesive bonding processes. With or without a previous grit-blasting step, argon gas atmospheric cold plasma treatment has shown a slight to moderate efficiency in increasing the SFE polar component of the composite. However, it was found that the addition of 0.07% oxygen to the argon plasma readily allows an important gain in the SFE polar component. Indeed, when processed at a speed of 30 m/min on a previously grit-blasted composite surface, the Ar/O₂ atmospheric cold plasma treatment increases the surface free energy to values >73 mJ/m², making the surface condition optimized for structural adhesive bonding. An oxidation mechanism of the composite surface exposed to atmospheric cold plasma was suggested on the basis of correlations established between the polar part of SFE obtained from the Owens et al. method, acid/base components calculated using the LWAB approach, and ATR infrared spectroscopy signatures obtained for a model polyolefin material.     

Surface energy of the plasma treated Si incorporated diamond-like carbon films

Surface energy and surface chemical bonds of the plasma treated Si incorporated diamond-like carbon films (Si-DLC) were investigated. The Si-DLC films were prepared by r.f. plasma assisted chemical vapor deposition using benzene and diluted silane (SiH₄/H₂ = 10:90) as the precursor gases. The Si-DLC films were subjected to plasma treatment using various gases like N₂, O₂, H₂ and CF₄. The plasma treated Si-DLC films showed a wide range of water contact angles from 13.4° to 92.1°. The surface energies of the plasma treated Si-DLC films revealed a high polar component for O₂ plasma treated Si-DLC films and a low polar component for CF₄ plasma treated Si-DLC films. The CF₄ plasma treated Si-DLC films indicated the minimum surface energy. X-ray photoelectron spectroscopy (XPS) revealed that the polarizability of the bonds present on the surface explains the hydrophilicity and hydrophobicity of the plasma treated Si-DLC films. We also suggest that the O₂ plasma treated surface can provide an excellent hemocompatible surface from the estimated interfacial energy between the plasma treated Si-DLC surface and human blood.     

Surface energy of metal containing amorphous carbon films deposited by filtered cathodic vacuum arc

Metal containing amorphous carbon (a-C:Me) films including a-C:Al, a-C:Ti, a-C:Ni, a-C:Si were prepared by the filtered cathodic vacuum arc (FCVA) technique with metal-carbon (5 at.% metal) composite targets. The substrate bias ranging from floating to 1000 V was applied. The wettability of the films was examined using the VCA Optima system from AST Products, Inc. Three types of liquid with different polarities were used to study the surface energy changes of the films. X-ray photoelectron spectroscopy (XPS) was used to analyze the composition and chemical state of the films. Atomic force microscopy (AFM) was employed to characterize the morphology and roughness of the films. The contact angle of the a-C:Me films remains relatively constant with different substrate bias. The Al containing films show the highest contact angle with water, which reaches as high as 101°. The Si containing films show the lowest contact angle approximately 64°. The contact angles of Ni and Ti containing films are approximately 80°, 97°, respectively. The harmonic-mean method was used to calculate the polar and depressive component of the surface energy. The absorption of oxygen on the surface plays an important role on the polar component of the a-C:Me films. The formation of AlO and TiO bonds is responsible for their lower polar component. The metal state Ni results in higher polar component. However, the SiO bond is contributed to the high polar component of a-C:Si films. As all films are atomic scale smooth, the RMS roughness is below 0.5 nm, the roughness does not have obvious effect on the surface energy.     

Bacterial adhesion on silicon-doped diamond-like carbon films

In this paper the surface properties of silicon-doped diamond-like carbon films with various Si contents on 316 stainless steel substrate by a magnetron sputtering technique were investigated. X-ray photoelectron spectroscopy was applied to determine the surface chemical composition of the films. Atomic force microscopy was used for the determination of surface roughness and topography. The sp² contents in the films were determined with Auger electron spectroscopy, which were 67.1%, 34.2% and 25.0% for silicon contents 1%, 2% and 3.8%. The sp³/sp² ratio increases with increasing the silicon contents in the films. Contact angles of three test liquids on the films were obtained with a Dataphysics OCA-20 contact angle analyzer. Surface free energies of the films and their dispersive and polar components were calculated using van Oss acid–base approach. Staphylococcus aureus was used for bacterial adhesion test. The experimental results showed that bacterial adhesion decreased with increasing the silicon content or with increasing sp³/sp² ratio in the films.     

Studies on the surface free energy and surface structure of PTFE film treated with low temperature plasma

The surface free energy and surface structure of poly(tetrafluoroethylene) (PTFE) film treated with low temperature plasma in O₂, Ar, He, H₂, NH₃, and CH₄ gases are studied. The contact angles of the samples were measured, and the critical surface tension γ_c (Zisman) and γ_c (max) were determined on the basis of the Zisman's plots. Furthermore, the values of nonpolar dispersion force γ^a_s, dipole force γ^b_s, and hydrogen bonding force γ^c_s to the surface tensions for the plasma-treated samples were evaluated by the extended Fowkes equation. Mainly because of the contribution of polar force, the surface free energy and surface wettability of PTFE film which was treated with H₂, He, NH₃, Ar, and CH₄ for a short time increased greatly. Electron spectroscopy for chemical analysis (ESCA) shows that the reason was the decrease of fluorine and the increase of oxygen or nitrogen polar functional group on the surface of PTFE. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1733–1739, 1997     

Wettability of poly(ethylene terephthalate) film treated with low‐temperature plasma and their surface analysis by ESCA

The surface of poly(ethylene terephthalate) (PET) film was modified by low‐temperature plasma with O₂, N₂, He, Ar, H₂, and CH₄ gases, respectively. After being treated by low‐temperature plasma, their surface wettability and chemical composition were investigated by means of electron spectroscopy for chemical analysis (ESCA) and contact angle measurement. The result shows that the surface wettability of PET can be improved by low‐temperature plasma, and the effect of the modification is due mainly to the kind of the gases. Mainly because of the contribution of hydrogen bonding force γ[STACK]^c_S[ENDSTACK], the surface wettability of PET treated with O₂, N₂, He, and Ar plasma for a short time (3 min) increase sharply, and the surface wettability is also improved by H₂ plasma treatment; but the CH₄ plasma treatment does not improve the wettability of PET. ESCA shows that the effect of wettability of PET is tightly related to the presence of polar functional groups that reside in the outermost surface layer of PET. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1327–1333, 1999     

Effect of roughness as determined by atomic force microscopy on the wetting properties of PTFE thin films

The influence of film roughness on the wetting properties of vacuum-deposited polytetrafluorethylene (PTFE) thin films has been investigated using atomic force microscopy (AFM) and contact angle goniometry. Surface roughness has been characterized by atomic force microscopy in terms of RMS roughness (R_q) and fractal dimensions. A contact angle correlation with surface roughness, as determined by AFM, is evident from these results, which are discussed on the basis of wetting theory. The results also confirm that the high water contact angles (as high as 150°) recently observed at the surface of a new water repulsive coating material (mixture of PTFE and binder) are because of surface roughness. Such measurements clarify the effect of nanometer-size surface asperities on the wetting properties of hydrophobic coating.     

Corrosion performance of thin hydrogenated amorphous carbon films prepared by magnetron sputtering

Hydrogenated amorphous carbon (a-CH_x) films were prepared by magnetron sputtering at different H₂/Ar gas flow ratios. Several sets of perpendicular magnetic recording disks with a-CH_x overcoats of 5 nm were prepared for accelerated environmental corrosion test. The corrosion spots on the disks and the corrosion products were analyzed using optical surface analyzer and time-of-flight secondary ion mass spectroscopy, respectively. Other techniques, such as Raman spectroscopy, atomic force microscopy nano-scratch and contact angle measurement, were used to characterize the properties of a-CH_x films. Compared to pure carbon overcoat, all the a-CHx overcoats have better corrosion resistance and higher polar component of surface free energy. The a-CH_x film with appropriate H content shows the highest scratching resistance, and the corresponding disk has the lowest corrosion area on the disk surface after the accelerated corrosion.     

Films based on phases in a Si–C–N system. Part II. plasma chemical synthesis of SiC<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>N<Subscript><Emphasis Type="Italic">y</Emphasis></Subscript>:Н films from the mixture of bis(trimethylsilyl)ethylamine and hydrogen

Thin silicon carbonitride SiC_xN_y films are synthesized by means of plasma enhanced chemical vapor deposition using an organosilicon compound such as bis(trimethylsilyl)ethylamine EtN(SiMe₃)₂ as the precursor in a mixture with hydrogen. The chemical composition and properties of the films are characterized by a set of modern research methods such as IR, Raman, and energy dispersive spectroscopy; ellipsometry; scanning electron microscopy; and spectrophotometry. The growth rate, chemical composition, and optical properties of the films have been studied depending on the synthesis temperature in the range from 373 to 1073 K. It is found that the substrate temperature exerts a significant effect on the growth kinetics, surface morphology, physicochemical properties, and functional characteristics of the films. Low temperature SiC_xN_y films have high transparency in the visible and infrared regions of the spectrum. Varying the parameter of synthesis allows one to obtain layers with different values of the refractive index (1.50–2.50).     

Effect of Al content on the electrochemical properties of Mg2−xAlxNi thin film hydride electrodes

Thin films of Mg_2−xAl_xNi alloys have been prepared by magnetron sputtering, and the effects of partial substitution of Al for Mg on the electrochemical properties of the films were studied. EIS results indicate the rate-limiting process for the thin film hydride electrode is the charge transfer reaction during the process of total discharge. A theoretical model has been derived for the impedance of a thin film hydride electrode based upon the assumption that hydrogen diffusion is neglected in the electrode. The charge-transfer reaction rate at the electrode surface and hydrogen diffusivity in the Mg_2−xAl_xNi thin film hydride electrodes were observed to initially decrease then increase with increasing Al content. Results from capacitance measurements indicate n-type semiconductor properties for the corrosion layer during the charge–discharge process. Hydrogen atom and OH⁻ transfer became more difficult with increasing Al content until x = 0.3, after which a significant drop in the barrier resistance was observed.     

Anomalous behavior of the dielectric and electrical properties of polymeric nanodielectric poly(vinyl alcohol)–titanium dioxide films

The complex dielectric permittivity, alternating‐current electrical conductivity, electric modulus, and impedance spectra of polymeric nanocomposite (PNC) films consisting of a poly(vinyl alcohol) (PVA) matrix dispersed with nanosize particles of titanium dioxide (TiO₂); (i.e., PVA–x wt % TiO₂, where x is 0, 1, 3, or 5) were investigated in the frequency range 20 Hz to 1 MHz at ambient temperature. A detailed analysis of the results showed that the values of the dielectric and electrical parameters of these PNC‐based nanodielectric films varied anomalously with increasing TiO₂ concentration. The temperature‐dependent dielectric characterization of the PVA–3 wt % TiO₂ film revealed that the dielectric polarization at a fixed frequency increased nonlinearly with increasing temperature. The temperature‐dependent electric modulus relaxation time values of the nanodielectric film obeyed Arrhenius behavior. The X‐ray diffraction study confirmed that the crystalline phase of the PVA matrix decreased with increasing TiO₂ concentration; this suggested that the interaction of the TiO₂ nanoparticles caused some destruction of the hydroxyl group dipolar ordering in the hydrogen‐bonded crystalline structure of the pristine PVA matrix. The intensities of the diffraction peaks of the TiO₂ nanofiller were enhanced as its concentration increased in these nanodielectrics; this confirmed the existence of TiO₂ nanoparticles inside the crystalline phases of the PVA matrix. The surface morphology of the films was examined by the study of their scanning electron micrographs. The feasibility of using these flexible polymeric nanodielectric films as electrical insulators and dielectric substrates in low‐power microelectronic devices operated at audio‐ and radio‐frequency electric fields was explored. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44568.     

Nitrogenated amorphous carbon films synthesized by electron cyclotron resonance plasma enhanced chemical vapor deposition

Nitrogenated amorphous carbon (a-CN_x:H) films were investigated as protective overcoats for industrial applications. Thin a-CN_x:H films have been deposited on silicon by electron cyclotron resonance plasma-enhanced chemical vapor deposition. The substrate bias was found to play an important role in determining the chemical compositions and mechanical properties of the films. The surface roughness and hardness of the films can reach 1.4 Å and 20 GPa, respectively. The influence of mechanical properties by hydrogen was studied. A correlation exists between the background slope of Raman spectra and the hydrogen content as determined by elastic recoil detection analysis.     

A comparative study of the interaction between the dried ink layer and PLA film used for packaging purposes

This research aims at comparing the interactions between the water-based printing ink and polylactide (PLA) printing base. As a reference base, a polyethylene terephthalate (PET) film was chosen. The wettability of both films was investigated. The Owens–Wendt method was applied to calculate the surface free energy (SFE). The values of SFE and its polar and dispersive components were compared with the surface tension (ST) of the ink and the polar and dispersive components of ST. The wetting envelopes of the investigated PLA and PET films are presented. Finally, the bonding strength between the dried ink layer and the printing base was analyzed. The PET film exhibited higher values of SFE. However, the bonding strength between the dried ink layer and the printing base was higher for PLA films. Our results reveal that PLA films can be an excellent choice as packaging materials, with comparable or even better print quality than conventional fossil-based plastics.     

Hydrophobicity and transparency of Al2O3-based poly-tetra-fluoro-ethylene composite thin films using aerosol deposition

Alumina and polytetrafluoroethylene (Al₂O₃-PTFE) composite films were fabricated by a simple aerosol deposition (AD) process, to confirm its applicability for various display screens requiring water resistant, anti-smudge and easy-to-clean properties. The surface morphologies, hydrophobic properties, and transparencies of the composite films with different PTFE contents, varying from 0.01 to 1?wt% were investigated. As a result, the composite films with over 0.3?wt% PTFE showed a sudden rise in surface roughness and low transmittance, despite having the highest contact angle of 128° at a PTFE content of 0.3?wt%. From the energy dispersive spectrometer analysis, the crash-cushioning effect of PTFE and agglomerated PTFE particles were determined to be major causes of surface roughness and opacity. In contrast, the transmittance showed a tendency to be enhanced, with an increasing PTFE content in the range of 0.01, 0.05, and 0.1?wt% PTFE, respectively. Especially, the film with 0.1?wt% of PTFE had contact angle of 111° and exhibited a high transmittance of over 75%, which was inferred to be an appropriate amount of PTFE, with a high elongation filling up the surface and the internal defects, leading to an enhancement of transparency. Consequently, these results implied that the AD-prepared Al₂O₃-PTFE composite coatings are promising candidates for various display applications.     

Calendar of events

This review reports the successful synthesis of novel oligomeric silanes having end-capped fluoroalkyl groups. Glass surface was effectively modified by these oligomeric silanes. In particular, oligomeric silanes were more reactive and effective in the surface fluoroalkylation than monomeric silanes. From contact angle measurements, surface free energies were reduced to 15–20 and 1–3 mJ/m² for the dispersive and the polar components, respectively, and the surfaces were shown to be both highly water- and oil-repellent. Modified glass surface was analyzed using XPS. A linear correlation was observed between the dispersive component of surface free energy γ_S ^d and the area ratio of the F1s peak to the Si2p peak. The structure of the siloxane layer on the modified glass surface is discussed in terms of a network interphase model.     

Reduced state correlations of the enskog modulus for gases and liquids

The Enskog modulus, bρ x, has been subjected to a generalized treatment to develop reduced state correlations for nonpolar and polar substances that exhibit hydrogen bonding. These correlations present relationships between 1 + bρx and ρ_R, the reduced density. For nonpolar substances, the PVT data of argon, nitrogen, methane, ethane, and carbon dioxide were used for the development of these relationships, which were found to depend on z_c, the critical compressibility factor. PVT data for ammonia, methyl alcohol, and water yielded a different correlation, which is applicable to polar substances which exhibit hydrogen bonding. These relationships were found to depend on the parameter, β = (T_b-T_m)/M, which quantitatively describes the extent of hydrogen bonding for polar compounds.     

Surface modification of polyester films by RF plasma

Plasma treatment of PET films was carried out under argon, followed by exposure to an oxygen atmosphere. The films underwent considerable changes in surface composition and morphology, as demonstrated by contact angle measurements, FTIR‐ATR, AFM, and XPS. It was found that the surface acquired oxygen containing polar functional groups such as —C=O, —OH, and —OOH, which increased in number as the plasma treatment time increased. During storage, the treated films underwent significant surface reorganization, and both the time and temperature contributed to the increase in the contact angle. As revealed by AFM measurements, these changes were accompanied by an increase in roughness in the form of ridges. The ridges were observed to grow in height with increasing treatment time, although their spacing showed little evolution. A correlation among the observations obtained from various techniques was established, giving a comprehensive picture of the structure and dynamics of plasma‐treated PET surfaces. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1083–1091, 2000     

Surface modification of low‐density polyethylene (LDPE) film and improvement of adhesion between evaporated copper metal film and LDPE

To improve the interfacial adhesion between evaporated copper film and low‐density polyethylene (LDPE) film, the surface of LDPE films was modified by treating with chromic acid [K₂Cr₂O₇/H₂O/H₂SO₄ (4.4/7.1/88.5)]/oxygen plasma. Chromic‐acid‐etched LDPE was exposed to oxygen plasma to achieve a higher content of polar groups on the LDPE surface. We investigated the effect of the treatment time of chromic acid in the range of 1–60 min at 70°C and oxygen plasma in the range of 30–90 sec on the extent of polar groups created on the LDPE. We also investigated the surface topography of and water contact angle on the LDPE film surface, mechanical properties of the LDPE film, and adhesion strength of the evaporated copper metal film to the LDPE film surface. IR and electron spectroscopy for chemical analysis revealed the introduction of polar groups on the modified LDPE film surface, which exhibited an improved contact angle and copper/LDPE adhesion. The number of polar groups and the surface roughness increased with increasing treatment time of chromic acid/plasma. Water contact angle significantly decreased with increasing treatment time of chromic acid/plasma. Combination treatment of oxygen plasma with chromic acid drastically decreased the contact angle. When the treatment times of chromic acid and oxygen plasma were greater than 10 min and 30 sec, respectively, the contact angle was below 20°. With an increasing treatment time of chromic acid, the tensile strength of the LDPE film decreased, and the film color changed after about 10 min and then became blackened after 30 min. With the scratch test, the adhesion between copper and LDPE was found to increase with an increasing treatment time of chromic acid/oxygen plasma. From these results, we found that the optimum treatment times with chromic acid and oxygen plasma were near 30 min and 30 sec, respectively. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1677–1690, 2001     

The Effect of Lowering the Surface Free Energy of Water on the Thermodynamic Work of Adhesion

The dispersive and polar force components of surface free energy have been measured for water left in contact with films dried from various emulsion adhesives. The polar component was lowered but the dispersive components were about 28 mJ m^?2 in each case. From these measurements of thermodynamic work of adhesion in the presence of contaminated water have been calculated for adhesive-polystyrene interfaces. An equation has been derived giving the dependence of thermodynamic work of adhesion upon the total surface free energy of water. It shows that the thermodynamic work of adhesion decreases as the surface free energy of water is lowered, but it eventually reaches a minimum and then may increase slightly.