Solubility and adhesion characteristics of plasma polymerized thin films derived from Lavandula angustifolia essential oil

Integration and implementation of organic polymer thin films often require knowledge of the stability when in contact with solvents and the adhesion quality when applied to different substrates. This article describes the solubility and adhesion characteristics of organic polymer thin films produced from Lavandula angustifolia essential oil, using radio frequency plasma polymerization at four RF power levels. Contact angle data was obtained for various solvents and used to determine the surface tension values for the polymer by using three established methods. A relatively strong electron–donor component and a negligible electronic acceptor component for the polymers indicate that they are monopolar in nature. Solubility data derived from interfacial tension values suggest that the polymers would resist solubilization from the solvents explored. The strongest solvophobic response was assigned to water, whereas diiodomethane demonstrated the weakest solvophobic response, with ΔG₁₂₁ > 0 in some instances depending on the surface tension values used. The adhesion tests of the polymers deposited on glass, PET, and PS indicated that the adhesion quality of the thin film improved with RF power, and it was associated with an improvement in interfacial bonding. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electrical and optical properties of plasma polymerized eucalyptus oil films

Electrical and optical properties of the plasma polymerized eucalyptus oil (PPEo) films are discussed in this article. As part of our electrical studies, we have found that the conduction mechanism in the PPEo film is a Schottky type. We have also found that iodine doping can enhance the conductivity of the film. IR studies revealed that PPEo film is a highly crosslinked polymer, and UV‐vis‐NIR studies revealed the information that optical band gap energy of the PPEo film had been reduced as a result of iodine doping. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1102–1107, 2003     

Investigation of plasma polymerized benzene and furan thin films for application in opto‐electronic devices

Conjugated polymers are among the most promising organic materials for opto‐electronic devices. In such applications, the main fabrication problem is to get uniform, defect‐free, and reproducible thin films of these materials. In this investigation, an RF plasma reactor was used to produce cross‐linked organic thin films from benzene and furan precursors. Uniform thin films of desired thickness were fabricated using this plasma polymerization technique. The composition of the plasma‐polymerized films was determined with X‐ray photoelectron spectroscopy. Fourier transform infrared spectra of the monomers and plasma‐polymerized thin films prepared were compared to analyze the chemical structure of the films. Ultraviolet–visible absorption spectroscopy shows a red shift of 45 nm in λ_max for the case of plasma‐polymerized benzene films and 52 nm in the case of plasma‐polymerized furan films when compared to their respective monomer spectra. Photo luminescence spectra of these films show a blue emission with a broad peak at 460 nm for the plasma‐polymerized benzene films and 445 nm for the plasma‐polymerized furan films. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 523–528, 2003     

NH3-TPD and XPS studies of Ru/Al2O3 catalyst and HDS activity

The effects of pretreatment of catalyst on its surface properties and the HDS activity of a 0.49% Ru/Al₂O₃ catalyst were studied in a single-pass, differential microreactor. The surface properties of the catalyst were measured by NH₃-TPD and XPS analysis. The Ru/Al₂O₃ catalyst was pretreated in three ways: reduced in H₂ (Ru-R catalyst), oxidized in air and subsequently reduced in H₂ (Ru-OR catalyst), or sulfided in H₂S/H₂ (Ru-S catalyst). Three types of peaks (low, middle, and high temperatures) were observed in the NH₃-TPD study. The predominant high-temperature peak was observed for both the Ru-OR and Ru-S catalyst, pretreated at 300°C. Mass spectrometry showed that the high-temperature peak in NH₃-TPD consisted of N₂ and H₂ formed from the decomposition of NH₃ on the ruthenium sites. NO adsorption of unsaturated Ru species was related to the low-temperature peak in the NH₃-TPD. The XPS analysis showed that the peaks at 279.9 eV, 280.6 eV, and 282.5 eV were ascribed to metallic ruthenium, RuO₂, and RuO₃, respectively. The low-, middle-, and high-temperature peaks were assigned to RuO₂, acid sites on alumina, and metallic Ru, respectively. Metallic ruthenium was effective in the HDS of thiophene and the decomposition of NH₃.     

Preparation and XPS surface chemical analysis of PS/PU nanocomposites

Aqueous emulsions of anionic polyurethane ionomers, based on polypropylene glycol as soft segment, isophorone diisocyanate as diisocyanate, dimethylolpropionic acid as chain extender and potential ionic center, and triethylamine as neutralizer, were synthesized. They were mixed with styrene monomers to prepare polystyrene–polyurethane (PS/PU) nanocomposites by an evocator. The sizes and distributions of the particles were measured by dynamic light scattering, and the microstructure of the nanocomposites was observed by transmission electron microscope. X‐ray photoelectron spectroscopy (XPS) was used to study the surface characterization of anionic PU and PS/PU nanocomposites. It could be found that the nanoparticles of PU could encapsulate the styrene monomers effectively and the leakage type of every element in PU was not affected by the introduction of Ps. There were more hard segments on the surface of crosslinking PS/PU nanocomposites because of the formation of crosslinking structure and interpenetrating polymer network between PU and PS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3889–3894, 2006     

Surface and Interfacial Studies of Plasma-Modified Composite Surfaces

Model epoxy and bismaleimide compounds in thin film form were used to simulate epoxy and bismaleimide composite surfaces, in order to study compositional changes and interfacial reactions induced by oxygen plasma treatment. X-ray photoelectron spectroscopy (XPS) and infrared reflection-absorption spectroscopy (IR-RAS) were used to probe chemical changes which occurred. XPS and IR-RAS were found to be complementary techniques in determining the nature of functional groups incorporated into surfaces by plasma treatment. IR-RAS analysis of the model surfaces following exposure to a liquid epoxy resin revealed that while adsorption of the liquid epoxy occurred on both plasma-treated and nonplasma-treated surfaces, the oxygen plasma-treated surface alone was capable of initiating ring-opening reactions in the epoxy. However, this effect was not observed unless immediate contact was made between the plasma-treated surface and the liquid epoxy resin, illustrating the short-lived reactivity of the functional groups on the plasma-treated surface.     

Derivatization of discharge-treated LDPE: an extension of XPS analysis and a probe of specific interactions in adhesion

Specific reactions for the derivatization of oxygen-containing functional groups in polymer surfaces have been developed in order to improve the precision of analysis by X-ray photoelectron spectroscopy (xps). These have been used to probe the chemical composition of low density polyethylene (ldpe) surface-modified by electrical discharge treatment. Simultaneously the effect of derivatizing particular groups on the auto-adhesive behaviour of these surfaces has been examined. Two independent specific interaction mechanisms have been identified.     

Preparation and characteristics of thin film with wear-resistant behavior on HDPE surface polymerized by C2H2–H2–SiH4 plasma

Plasma-polymerized deposition of an acetylene–hydrogen–silane mixture (C₂H₂–H₂–SiH₄) to obtain thin film with good wear behavior on a high-density polyethylene (HDPE) surface was present in this work. It was found that the bond between thin film and HDPE substrate was excellent and H₂ gas in system led the deposited thin film to better adhesive properties, but slower thin film deposition rate. Surface wear-resistant properties of modified HDPE were improved with the input of SiH₄. Infrared and X-ray photoelectron spectroscopy spectra suggested that there be large quantities of >CO, O H, C Si, and Si O groups in thin film and that the ratio of C to Si was increased due to the addition of SiH₄ and H₂, which inferred that the thin film structure and components lie between organic and inorganic materials. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1561–1566, 1998     

Optical characterization of plasma‐polymerized pyrrole‐N,N,3,5‐tetramethylaniline bilayer thin films

A capacitively coupled parallel‐plate reactor has been used to deposit plasma‐polymerized pyrrole (PPPy), plasma‐polymerized N,N,3,5‐tetramethylaniline (PPTMA), and plasma‐polymerized pyrrole‐N,N,3,5‐tetramethylaniline (PPPy‐PPTMA) bilayer thin films on to glass substrates at room temperature. To deposit the bilayer films, pyrrole monomer has been used as the mother material and N,N,3,5‐tetramethylaniline monomer has been deposited in different deposition time ratios after the pyrrole films were formed. Fourier transform infrared (FTIR) and ultraviolet–visible (UV–vis) spectroscopy techniques have been used to characterize the as‐grown thin films of about 500‐nm thick. The structural analyses by FTIR spectroscopy have indicated that the monomer has undergone the reorganization and the ring structure is retained during the plasma polymerization. From the UV–vis absorption spectra, allowed direct transition (E_qd) and allowed indirect transition (E_qi) energy gaps were determined. The E_qd for PPPy, PPTMA, and PPPy‐PPTMA bilayer films are found to be 3.30, 2.85, and 3.65 eV respectively. On the other hand, the E_qi for the same series are 2.25, 1.80, and 2.35 eV, respectively. From these results, it is seen that the energy gaps of the PPPy‐PPTMA bilayer films have been increased compared with the PPPy and PPTMA films. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

NTP转化C3H6/NO/N2气氛中NO及发射光谱分析

利用介质阻挡放电产生低温等离子体转化C₃H₆/NO/N₂气氛中NO,结合发射光谱诊断法研究了碳氢化合物C₃H₆对NO转化的影响。研究结果表明,随着放电功率的升高,NO转化率先升高后逐渐趋于平缓,NO₂浓度持续降低,N₂O浓度呈先升高后降低趋势,NO主要被还原为N₂;相同放电功率下,随着C₃H₆初始浓度升高,NO_x转化率和N₂O浓度升高、NO₂浓度降低;添加C₃H₆会降低N₂第二正带系和NO-γ带的发射光谱强度,产生CN自由基的激发跃迁谱线,影响NO的化学反应机制,同时生成了棕黄色的聚合物。     

Preparation of oxygen gas barrier polypropylene films by deposition of SiOx films plasma‐polymerized from mixture of tetramethoxysilane and oxygen

Silicon oxide (SiOx) film deposition on the surface of oriented poly(propylene) (OPP) films was done to form a new oxygen gas barrier material using plasma polymerization of the tetramethoxysilane (TMOS)/O₂ mixture. The SiOx film deposition on OPP films never improved oxygen gas barrier properties. The inefficacy of the SiOx deposition was due to poor adhesion at the interface between the deposited SiOx and OPP films and also to the formation of cracks in the deposited SiOx film. If prior to the SiOx film deposition surface modification of OPP films was done by a combination of the argon plasma treatment and TMOS coupling treatment, this contributed effectively to strong adhesion leading to success in the SiOx deposition on the OPP film surface, and then the oxygen gas barrier ability was improved. The oxygen permeation rate through the SiOx‐deposited OPP film was decreased from 2230 to 37–52 cm³/m²/day/atm, which was comparable to that of poly(vinylidene chloride), 55 cm³/m²/day/atm at a film thickness of 11 μm. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 2389–2397, 2000     

Characterization of non-stoichiometric Ga2O3-x thin films grown by radio-frequency powder sputtering

We report the synthesis and characterization of non-stoichiometric Ga₂O_3-x thin films deposited on sapphire (0001) substrates by radio-frequency powder sputtering. The chemical and electronic states of the non-stoichiometric Ga₂O_3-x thin films were investigated. By sputtering in an Ar atmosphere, the as-grown thin films become non-stoichiometric Ga₂O_2.7, due to the difference in sputtering yield between Ga and O species of the Ga₂O₃ target. The electronic states of the thin films consist of ~85% Ga³⁺ and ~15% Ga¹⁺, corresponding to Ga₂O₃ and Ga₂O, respectively. The films have the electrical characteristics of a semiconductor, with electrical conductivity of approximately 5.0 × 10^-4 S cm^-1 and a carrier concentration of 4.5 × 10¹⁴ cm^-3 at 300 K.     

Growth and characterization of fluorocarbon thin films grown from trifluoromethane (CHF3) using pulsed‐plasma enhanced CVD

Trifluoromethane (CHF₃) was used as a precursor gas in pulsed‐plasma enhanced CVD to deposit fluorocarbon films onto Si substrates. The film composition, as measured by X‐ray photoelectron spectroscopy (XPS) of the C1s peak, was observed to change as the plasma duty cycle was changed by varying the plasma off‐time; this offers a route to control the molecular architecture of deposited films. FTIR results indicate that the film is primarily composed of CF_x components, with little or no C H incorporation into the film. The rms roughness of the films is extremely low, approaching that of the Si substrate; the low growth rate and consequent high‐power input/thickness is believed to be partly responsible. CHF₃ produces films with higher % CF₂ compared to other hydrofluorocompound (HFC) monomers (CH₂F₂ and C₂H₂F₄). However, the deposition kinetics for all three HFC gases display similar trends. In particular, at a fixed on‐time of 10 ms, the deposition rate per pulse cycle reaches a maximum at an off‐time of approximately 100 ms. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 842–849, 2000     

Dielectric and ferroelectric properties of multilayer BaTiO3/NiFe2O4 thin films prepared by solution deposition technique

In this work different lead-free multilayered structures, composed of perovskite BaTiO₃ and spinel NiFe₂O₄ thin layers, were obtained by solution deposition method. Structural characterization of the sintered thin films confirmed the well-defined layered structure with overall thickness from 160 to 600 nm, crystalline nature of perovskite BaTiO₃ and spinel NiFe₂O₄ phases without secondary phases (after sintering below 900 °C) and grains on nanometer scale. Dielectric properties of the multiferroic multilayer BaTiO₃/NiFe₂O₄ thin films were analyzed in temperature and frequency range from 30 °C to 200 °C and 100 Hz to 1 MHz, respectively. In comparison to the pure BaTiO₃ films, the introduction of ferrite layer reduces dielectric response and increases low frequency permittivity dispersion of the multilayer thin films. The multilayer samples have shown relatively low dielectric loss with stronger contribution of conductivity at higher temperatures, and characteristic broad peak representing “relaxation” of the interface charge accumulation.     

A Kinetic study of Tb3+ and Dy3+ co-substituted CoFe2O4 spinel ferrites using temperature dependent XRD,XPS and SQUID measurements

In this research work, we have investigated the structural development of Tb³⁺ and Dy³⁺ co-substituted CoFe₂O₄ ferrites using temperature and time dependent XRD measurements. Sol-gel auto combustion technique was used to synthesized Tb³⁺ and Dy³⁺ co-substituted spinel ferrites with composition CoFe_2-x-y Tb_xDy_yO₄ (x + y = 0.0–0.25). Various characterization techniques such as High temperature XRD, XPS and SQUID were used to observe the Kinetics mechanism as well as the impact of co-substitution on the structural and magnetic properties. Room temperature XRD scans showed that the synthesized materials having single phase and were crystalline in nature. The crystallite size was lied in nano regime ranging from 26.07 to 21.92 nm and lattice parameters were found to be decreased with increasing rare earth metal ions contents. Temperature and time dependent XRD data suggested that structure of investigated samples not degrade even at temperature 900 °C which was maintained for 2 h. The ionic states of Co²⁺, Tb³⁺, Dy³⁺ and Fe³⁺ were confirmed by X-ray Photoelectron spectrometry measurements along with the binding energies of Co2p, Tb 2p, Dy 2p, Fe 2p which confirmed the tetrahedral and octahedral sites for substituted ions. Room temperature magnetic measurements of annealed nanoferrites were carried out by operating the SQUID magnetometer in VSM mode. The data demonstrated that increasing concentrations of substituent (Tb³⁺and Dy³⁺) resulted in the reduction of various magnetic parameters such as remanence, saturation magnetization and Coercivity. The calculated values of saturation magnetization and coercivities were found in the range of 78.1–45.15emu/g and 742–543Oe respectively. This study concluded that cation distribution and crystallite size is effective in controlling the structural, morphological and magnetic properties.     

Modification of Polydimethylsiloxane Coatings by H2 RF Plasma,Xe2* Excimer VUV Radiation,and Low‐Energy Electron Beams

The crosslinking of thin liquid PDMS layers by three different technically relevant processes, H₂ radio‐frequency plasma treatment, Xe₂* excimer VUV irradiation, and low‐energy electron beam processing is investigated. The modifications to the layers due to the processing are monitored by means of RAIRS. Plasma processing of liquid PDMS leads to a direct conversion to a SiO_x‐like material of the topmost layers, whereas a gradual transition from PDMS to the same product is observed upon VUV irradiation. Electron exposure does not induce oxidation. The initiating steps of the conversion induced by the interaction with VUV photons, low‐energy electrons, or their combined effect with ions and H atoms in the plasma are discussed. The latter creates a high density of damage sites.

     

IR reflectance characterization of glass-ceramic films obtained by high pressure impregnation of SnO2 nanopowders on float glass

Glass-ceramic thin films of tin dioxide on float glass surfaces were obtained using a method based on high pressures and temperatures below the glass transition temperature. SnO₂ thin films were confirmed using XRD, SEM and XRF techniques. These thin films were identified using IR reflectance due to a shift induced by Sn ion content of about ∼100 cm⁻¹ in the main maximum peak position which is typical of stretching vibration intensities of a ν_Si−O-Si bridging bonds, or a νSi-O⁻ nonbridging bonds.     

Evidence of redox interactions between polypyrrole and Fe3O4 in polypyrrole-Fe3O4 composite films

The electrical properties of conducting polymers make them useful materials in a wide number of technological applications. In the last decade, an important effect on the properties of the conducting polymer when iron oxides particles are incorporated into the conductive matrix was shown. In the present study, films of polypyrrole were synthesized in the presence of magnetite particles. The effect of the magnetite particles on the structure of the polymer matrix was determined using Raman spectroscopy. Mass variations at different concentrations of Fe₃O₄ incorporated into the conducting matrix were also measured by means of quartz crystal microbalance. Additionally, the changes in the resistance of the films were evaluated over time by electrochemical impedance spectroscopy in solid state. These results show that the magnetite incorporation decreases polymeric film resistance and Raman experiments have evidenced that the incorporation of magnetite into polymeric matrix not only stabilizes the polaronic form of the polypyrrole, but also preserves the polymer from further oxidation.     

Enhanced one-step purification of C2H4 from C2H2/C2H4/C2H6 mixtures by fluorinated Zr-MOF

The extraction of C₂H₄ from C₂H₆/C₂H₄/C₂H₂ mixtures is of great significance in the chemical industry for C₂H₄ production but the process remains challenging due to the similarity of these C₂ hydrocarbon species in their molecular size and physical properties. Here, we report the fluorination of a stable Zr-MOF, UiO-66, to fine-tune the pore dimensions and pore functionality. In particular, UiO-66-CF₃ shows notably preferential adsorption of C₂H₆ and C₂H₂ over C₂H₄, with C₂H₂/C₂H₄ and C₂H₆/C₂H₄ selectivities of 1.4 and 1.9, respectively. Theoretical calculations provide insight into the binding sites of UiO-66-CF₃ for C₂ hydrocarbon adsorption. Breakthrough experiments further confirmed the capability of the material for purification of C₂H₄ from C₂H₂/C₂H₄/C₂H₆ ternary mixtures, evidenced by the high purity C₂H₄ (99.9%+) obtained directly from outlet gas.     

Variable‐energy positron lifetime study of silicon‐oxide films plasma deposited from hexamethyldisiloxane and oxygen mixtures

Mixtures of hexamethyldisiloxane [HMDSiO, (CH₃)₃SiOSi(CH₃)₃] and oxygen are plasma polymerized at different oxygen pressures (P = 1.3–11.4 Pa) and a fixed monomer pressure (P_m = 2.6 Pa). The discharge power is kept at 100 W throughout the work. Nanometer‐size holes in the deposited films are characterized by variable‐energy positron annihilation lifetime spectroscopy (PALS). Additional information on the film composition and structure is obtained by X‐ray photoelectron spectroscopy and IR absorption spectroscopy. The ortho‐positronium lifetime τ₃ and intensity I₃ increase with the P up to 6.2 Pa and then decrease with the P. PALS measurements after annealing at 400°C show that films prepared at high oxygen pressure have a less stable structure than a film deposited at a lower oxygen pressure. These results are discussed in comparison with plasma deposition of pure HMDSiO, as are the possible effects of oxygen radicals on the film structure. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 974–980, 2001