X‐ray scattering experiments on sputtered titanium dioxide coatings onto PVDF polymers for self‐cleaning applications

The performance of active polymer substrates used in sensor and actuator or tactile display applications can be hindered by the inevitable soiling of their surface. A possible approach to overcome this problem is to deposit a self‐cleaning coating onto the polymer surface, taking care that the layer underneath withholds its intrinsic properties. In this work, titanium dioxide, TiO₂, was naturally chosen for coating material due to its inherent photocatalytic properties. Thus, TiO₂ thin films were deposited by reactive magnetron sputtering on poly(vinilydene fluoride) ‐ (PVDF) substrates, in its α‐ (nonelectroactive) and β‐ (electroactive) phases. Wide angle x‐ray scattering (WAXS) experiments in a synchrotron were performed to monitor the crystalline structure of the polymer substrates upon thin film deposition and also to assess the crystalline structure of the TiO₂ coating at different temperatures. In the WAXS patterns of the coated α‐PVDF, the TiO₂ polymorph anatase phase can be distinguished. At the same time, no explicit diffraction peaks for anatase were detected in the coated β‐PVDF. Fourier transform infrared spectroscopy evidenced that the chemical structure of PVDF is unaffected by the coating deposition process. These structural results have been correlated with the photocatalytic properties of the TiO₂ coatings. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Atmospheric Pressure Plasma Polymerised Primer to Promote Adhesion of Silicones

By combining a liquid primer and a plasma jet system, a new route to improved adhesion on various substrates has been developed. The liquid primer is introduced as an aerosol into a plasma jet and the resultant active species are deposited as a polymer coating on adjacent surfaces. Careful control of the plasma parameters produced a dry polymerised coating with functional chemistry designed to enhance the adhesion of silicone sealants to two substrates. This paper describes the surface chemistry and adhesion properties of various coatings on both a plastic and a metal substrate. Selected surface analysis techniques were coupled to both wet and dry adhesion testing to characterise the factors that control adhesion within the system. Mechanical testing indicates that adhesion was improved by several orders of magnitude.     

Adhesion between polymer substrates and plasma films from tetramethylsilane and tetramethyltin by glow discharge polymerization

Adhesion between various polymer substrates and plasma films, which had been prepared from either tetramethylsilane or tetramethyltin by glow discharge polymerization and deposited on the surface of the polymer, was evaluated by the Scotch tape test and by lap-shear strength. It was found that the plasma films exhibited fairly good adhesion to the polymer substrates (with the exception of polypropylene). The position where failure occurred was determined by X-ray fluorescence analysis, scanning electron microscopy and energy diffractive X-ray analysis. This position was at an inner layer of the plasma film (cohesive failure of plasma film), within the polymer substrate (material failure of polymer) or at the interface between polymer substrate and plasma film (adhesive failure) depending upon the polymer substrate. These results indicate an important aspect of durability of surface modification by glow discharge polymerization.     

Adhesion of Vacuum Deposited Optical Coatings on PMMA and Polycarbonate

Abstract

The deposition of interference coatings with optical functions (e.g., anti-reflective coatings, beam splitters and filters) on plastic substrates is becoming ever more important. A well-known deposition method for such coatings on polymers is plasma ion-assisted vacuum evaporation (plasma ion-assisted deposition or plasma IAD). However, the industrial production of well-adhering dielectric coatings on unlacquered polymer surfaces has not yet been developed to a satisfactory level. PMMA is known to be extremely difficult to coat with optical layers because of its inadequate adhesion characteristics. Polycarbonate is considered to be less problematic, but in many cases unexpected adhesion failures arise. This paper presents a study of the reasons for the poor adhesion to PMMA of oxide coatings deposited by plasma IAD. We show that in such a coating process it is only the exposure of the substrate to particles and short-wavelength radiation that determines its adhesion to the deposited layer. For polycarbonate, we found a dependence of the adhesion strength of the coating on its porosity. Considering these results, modified plasma IAD processes have been developed that enable the deposition of well-adhering optical coatings on these polymers.     

Cured melamine systems as thick fire-retardant layers deposited by combination of plasma technology and dip-coating

Melamine and melamine resins are widely used as fire-retardants for polymer building materials. Cured melamine systems are used in heat-sensitive items, such as furniture and window frames and sills. In this work, differently cured methylated poly(melamine-co-formaldehyde) (cmPMF) resins were used as fire-retardant coverage for poly(styrene) (PS) and poly(ethylene) (PE) building materials. Such polymer layers should have several tenths of micrometers thickness to produce sufficient fire retardancy. These thick layers were produced by dip-coating. To promote sufficient adhesion of such thick coating to the polyolefin substrates, also in the case of high temperatures occurring at fire exposure, the polymer substrates were firstly coated with a few hundred nanometer thick adhesion-promoting plasma polymer layer. Such thin plasma polymer layers were deposited by low-pressure plasma polymerization of allyl alcohol (ppAAl). It was assumed that the hydroxyl groups of ppAAl interact with the melamine resin; therefore, ppAAl was well suited as adhesion promoter for thick melamine resin coatings. Chemical structure and composition of polymer films were investigated using infrared-attenuated total reflectance and X-ray photoelectron spectroscopy (XPS). Peel strengths of coatings were measured. After peeling, the peeled polymer surfaces were also investigated using optical microscopy and XPS the layers for identification of the locus of peel front propagation. Thermal properties were analyzed using TGA (thermo-gravimetric analyses). Finally, the fire-retardant properties of such thick coated polymers were evaluated by exposure to flames.     

Seeding of polymer substrates for nanocrystalline diamond film growth

Nanocrystalline diamond (NCD) thin films and structures are grown by microwave plasma CVD technique on SiO₂/Si substrates patterned by polymer. The substrates are seeded by ultra-dispersed diamond (UDD) nanoparticles in polymer, by spin coating of UDD drop and by ultrasonic treatment in solution of UDD.For all samples, the deposited NCD film is strongly related to the primary polymer deposited over the Si/SiO₂ substrate. For a certain concentration of UDD, seeding by polymer composite results in formation of fully closed layer. The drop of UDD requires using of spin coating process and by repeating of this procedure, a NCD layer with clear 3D geometry is achieved. Ultrasonic treatment leads in “implanting” of UDD into the polymer bulk. The primary polymer stripes are damaged during this procedure. In addition, 3D porous like layer is observed after the CVD growth.Optimizing the seeding procedure and the dimension of the primary polymer allow a direct growth of self-standing air bridges suitable for MEMS/NEMS applications.     

Adhesion of glow discharge polymers to metals and polymers

Adhesion of glow discharge polymers to metals and polymers in an adhesive joint was measured by lap-shear test and immersion in hot water of 70°C °C for an extended time. A glow discharge polymer was deposited onto polymers [polyethylene and poly(tetrafluoroethylene)] and metals (aluminum and stainless steel) prior to when the polymer and metal were joined. It is found that the lap-shear strength is enhanced by coating the surfaces of these substrates with plasma film produced from methane, ethylene, and acetylene, and that deterioration of the adhesive bonding part, when immersed in hot water of 70°C, is strongly dependent on the gas used as well as operational conditions where a polymer film is formed. The adhesion of a polymer produced from methane on the polymer and metal is strong enough to apply for durable, adhesive joints.     

Modification of Si(100) surface by plasma-enhanced graft polymerization of allylpentafluorobenzene

Abstract - Hydrophobic fluoropolymer thin films were deposited on Si(100) substrates by plasma polymerization of allylpentafluorobenzene (APFB) under different glow discharge conditions, and in the presence and absence of Ar plasma pre-activation of the substrate surfaces. The FTIR and X-ray photoelectron spectroscopy (XPS) results suggested that the plasma polymerization proceeded mainly through the C=C bond of APFB, and the fluorinated aromatic structure in the deposited polymer films was preserved to different extents, depending on the radio-frequency (RF) power used for plasma polymerization. The use of a low RF power (~5 W) readily resulted in the deposition of thin films having nearly the same fluorinated aromatic structure as that of the APFB homopolymer. For the plasma-polymerized APFB (pp-APFB) films deposited on the Ar plasma-preactivated Si(100) surfaces, solvent extraction results suggested that the pp-APFB films became covalently tethered onto the silicon substrate surfaces. Thermogravimetric (TG) analysis results indicated that the thermal stability of the pp-APFB films had been enhanced substantially after annealing at 270°C in a vacuum oven.     

Plasma polymerization of tetrafluoroethylene. II. Capacitive radio frequency discharge

The plasma polymerization of tetrafluoroethylene (TFE) is studied in a capacitively coupled system with internal electrodes using radio frequency (13.56 MHz) power. The emphasis is on identifying conditions that are compatible with continuous coating of plasma polymer on a substrate moving through the center of the interelectrode gap. At high pressure (500 mTorr), deposition of plasma polymer is primarily on the electrodes rather than on a substrate placed midway between electrodes. Glow is observed in only part of the interelectrode gap at low powers and fills the gap only at high power levels. The use of a magnetic field effects barely discernible changes. Low-pressure (below 100 mTorr) operation is more favorable for deposition of a substantial portion of the plasma polymer on a substrate placed midway between electrodes. The plasma polymer deposited at low pressure is characterized by ESCA and deposition rate data and compared to that deposited in an inductively coupled system. The polymers formed in both systems are broadly similar and completely different from conventional poly(TFE). Subtle system-dependent differences are identified. The known susceptibility of fluorine-containing polymers (including plasma polymer) to a high-power plasma has been used as a probe of plasma power density within the interelectrode gap in the capacitively coupled system. Without magnets the most active zone of the plasma is in the center of the interelectrode gap. The use of a magnetic field moves this active zone closer to the electrodes and leads to a more efficient coupling of energy to a polymerizing glow discharge.     

Ultrathin DLC and SiOx layer deposition on poly(ethylene terephthalate) and restriction of surface dynamics

The hydrophilicity of oxygen plasma‐reated polymer surfaces decays with storing time in air environments. Because they are dense, highly crosslinked, and chemically stable, diamond‐like carbon (DLC) films and silicon oxide films (SiO_x) were deposited on poly(ethylene terephthalate) by plasma‐enhanced chemical vapor deposition to restrict polymer surface dynamics. In this study, the effects of ultrathin films on surface dynamics of these polymers were investigated. The layers were deposited on substrates with thickness below 100 Å. The thickness of films was measured with a scanning analyzer ellipsometer, while ATR‐IR spectroscopy and Raman spectroscopy were performed to observe the chemical structure of the films. Films below 50 Å were also shown to be effective in stabilizing the plasma treated polymer surfaces. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1158–1164, 2000     

Structural Evolution of Thermal-Sprayed Yttria-Stabilized ZrO2 Thermal Barrier Coatings with Annealing—A Neutron Diffraction Study

We studied the influence of the annealing temperature on the atomic structure of yttria-stabilized tetragonal zirconia (YSZ) which was deposited as a 300 μm thick thermal barrier coating (TBC) on nickel superalloy substrates by plasma spraying. To obtain neutron powder diffraction patterns of the barrier coatings we used an experimental technique where the sample is randomly rotated in the neutron beam. The time-averaged neutron diffraction pattern was then analyzed using the Rietveld refinement technique without any need for corrections. This allowed the comparison of the average crystals structures from bulk tetragonal samples obtained via common ceramic routes and those of micrometer thick films deposited on substrates using plasma spray or other nonequilibrium techniques.     

Correlation of morphology and barrier properties of thin microwave plasma polymer films on metal substrate

The barrier properties of thin model organosilicon plasma polymers layers on iron are characterised by means of electrochemical impedance spectroscopy (EIS). Tailored thin plasma polymers of controlled morphology and chemical composition were deposited from a microwave discharge. By the analysis of the obtained impedance diagrams, the evolution of the water uptake ?, coating resistance and polymer capacitance with immersion time were monitored and the diffusion coefficients of the water through the films were calculated. The impedance data correlated well with the chemical structure and morphology of the plasma polymer films with a thickness of less than 100 nm. The composition of the films were determined by means of infrared reflection absorption spectroscopy (IRRAS), X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The morphology of the plasma polymer surface and the interface between the plasma polymer and the metal were characterised using atomic force microscopy (AFM). It could be shown that, at higher pressure, the film roughness increases which is probably due to the adsorption of plasma polymer nanoparticles formed in the plasma bulk and the faster film growth. This leads to voids with a size of a few tens of nanometers at the polymer/metal interface. The film roughness increases from the interface to the outer surface of the film. By lowering the pressure and thereby slowing the deposition rate, the plasma polymers perfectly imitate the substrate topography and lead to an excellent blocking of the metal surface. Moreover, the ratio of siloxane bonds to methyl-silyl groups increases which implies that the crosslink density is higher at lower deposition rate. The EIS data consistently showed higher coating resistance as well as lower interfacial capacitance values and a better stability over time for the film deposited at slower pressure. The diffusion coefficient of water in thin and ultra-thin plasma polymer films could be quantified for the smooth films. The measurements show that the quantitative evaluation of the electrochemical impedance data requires a detailed understanding of the film morphology and chemical composition. In addition, the measured diffusion coefficient of about 1.5×10⁻¹⁴ cm² s⁻¹ shows that plasma polymers can act as corrosion resistant barrier layers at polymer/metal interfaces.     

Surface coating protective against oxidative plasma etching of polypropylene

Polypropylene (PP) sheets were coated with the ultrathin polymer layers by plasma polymerization of hexamethyldisiloxane and two other Si-containing monomers, and the protection effects from oxidative plasma etching were investigated. Etching was evaluated by the weight loss of PP sheets after the exposure to an oxidative plasma of O₂ or air. The effects of plasma polymer coating on the etching resistance were investigated with respect to the type of plasma polymer, thickness of a coating layer, oxidative plasma etching conditions, etc. Weight of the coated PP sheets was less changed and the substrates remained stable after a certain period of oxidative plasma treatments, during which time the original PP film had prominently lost weight. The importance of the crosslinked network with —Si— MPO components in plasma polymers on the etching resistance was suggested from the results. Infrared spectra were taken and analyzed with the plasma polymers after O₂-plasma treatments, and the increase in the Si—O structure was indicated by the increase in the peak intensity at 1023 cm⁻¹. Stabilization against oxidative etching was attributed to the crosslinked Si—O structure on the surface layer. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1049–1057, 1997     

Synthesis and characterization of boron carbide films by plasma-enhanced chemical vapor deposition

The plasma-enhanced chemical vapor deposition of boron carbide was investigated on quartz glass and alumina substrates from a gas mixture of BCl 3 , H 2 , and CH 4 in an inductively coupled plasma (ICP) medium produced by a radio frequency (RF) discharged onto the gases passing through a tubular reactor under atmospheric pressure. A thin solid boron carbide coating with a gray color was deposited on both substrates. The results of XRD revealed that the major solid phase formed in the coating material was β-rhombohedral B 4 C. The SEM analysis showed that the surface homogeneity increased with an increase in the exposure time, and different boron carbide structures were formed at different RF powers and exposure times.     

Surface modification of coil coatings with thin plasma polymer films structure and stability

Plasma deposition of a thin top layer with tailored properties is an effective strategy of modification of the organic coating surface. Thin plasma polymer layers are candidates and can provide superior hardness, scratch resistance, modified surface hydrophobicity and easy to clean properties.The present work studies the stability of thin plasma polymer films deposited as top layer on polyurethane coil coating systems. Microwave, hollow cathode and radio frequency plasma polymerization reactors were employed in order to deposit a thin SiO_x based plasma polymer layer.The plasma film stability was studied using surface analysis techniques, ex situ and in situ atomic force microscopy and scanning electron microscopy. Energy dispersive spectroscopy, FTIR spectroscopy and optical measurements confirm the composition and plasma layer properties. The structure of the plasma layers was investigated by means of transmission electron microscopy.The surface morphology together with composition evolution allows the study of the stability of the different coatings. The structure examination of the formed plasma polymer film offers good clarification for coating failure. Decrease of the operating pressure during plasma polymerization and oxygen concentration in precursor mixture lead to formation of compacter layer with higher stability. Introduction of fluorine-containing precursor also increases the anti-weathering performance of the plasma polymer films.     

SYNTHESIS AND CHARACTERIZATION OF BORON CARBIDE FILMS BY PLASMA-ENHANCED CHEMICAL VAPOR DEPOSITION

The plasma-enhanced chemical vapor deposition of boron carbide was investigated on quartz glass and alumina substrates from a gas mixture of BCl 3 , H 2 , and CH 4 in an inductively coupled plasma (ICP) medium produced by a radio frequency (RF) discharged onto the gases passing through a tubular reactor under atmospheric pressure. A thin solid boron carbide coating with a gray color was deposited on both substrates. The results of XRD revealed that the major solid phase formed in the coating material was β-rhombohedral B 4 C. The SEM analysis showed that the surface homogeneity increased with an increase in the exposure time, and different boron carbide structures were formed at different RF powers and exposure times.     

Plasma interface engineered coating systems for magnesium alloys

In this study, a dc low-temperature plasma technique, including plasma treatment and plasma polymerization, was used to create interface engineered coating systems with a structure of Mg/plasma interlayer/cathodic electrocoating (E-coat) for machined AZ31B magnesium (Mg) alloy panels. The plasma interlayer deposited from trimethylsilane (TMS) precursor had a nano-scale thickness of ∼65 nm and well-controlled surface properties through subsequent plasma treatments in order to achieve different level of interfacial adhesion between the E-coat and the Mg substrates. The surface wettability of the plasma interlayer was monitored by water surface contact angle measurement. The interface adhesion of the coating system was evaluated using N-methylpyrrolidinone (NMP) paint removal test and ASTM tape test conducted under dry and wet conditions. Electrochemical impedance spectroscopy (EIS) was employed to investigate the effects of plasma interlayer properties including surface wettability and adhesion enhancement on corrosion protection properties of the coating systems. It was found that a more wettable interface enhanced the electrolyte penetration through the coating and thus reduced the corrosion resistance of the coating system. On the other hands, the improved interface adhesion had little effects on EIS results mainly due to the high chemical reactivity of the Mg alloy substrates.     

Influence of water addition on the structure of plasma-deposited allyl alcohol polymer films

One hundred and fifty nanometre thick polymer films made of allyl alcohol and H₂O addition were deposited onto aluminium substrates using the radio-frequency (rf) pulsed plasma mode. The structure–property relationships of polymer films were studied in dependence on the precursor ratio allyl alcohol-water. Both the regularity of structure and composition of such thin films in comparison to chemically polymerized allyl alcohol were investigated using by bulk-sensitive Fourier transform infrared spectroscopy (FTIR) in the spectral range of 4000–500 cm^?1 as well as surface-sensitive X-ray photoelectron spectroscopy (XPS). The intention of this work was to increase the yield in OH groups by addition of water to the allyl alcohol precursor. For an unambiguous identification of the functionality of the deposited films, the OH groups were labelled with trifluoroacetic anhydride and subsequently measured by XPS as well as quantitatively by FTIR. As expected, the O/C ratio grew with increasing water admixture by oxidation of both the plasma polymerized allyl alcohol layer to preferably aldehyde and/or carboxylic acid groups. In contrary, the concentration of OH groups in the deposited polymer film decreases dramatically with increasing admixture of water to the allyl alcohol plasma. It has been shown that the additional water has produced preferably higher oxidized C-O_x species with two or three C–O bonds. This fits also very well with the observation that almost no deuterium is introduced into the surface of plasma polymer if D₂O was added instead of H₂O.     

Synthesis and Tribological Behavior of Silicon Oxycarbonitride Thin Films Derived from Poly(Urea)Methyl Vinyl Silazane

A process for deposition of silicon oxycarbonitride films from poly(urea)methyl vinyl silazane (PUMVS) by spin coating precursor solutions onto a substrate, followed by polymerization, cross-linking and pyrolysis has been developed. The cross-linked polymer films (350 nm thick), deposited on variety substrates (e.g., silicon, sapphire, zirconia), were pyrolyzed in nitrogen or ammonia environments either in a hot isostatic press or in a tube furnace. Their microstructure was characterized using infrared and Raman spectroscopy. The tribological (friction and wear) behavior was evaluated in dry nitrogen and air with 50% relative humidity using a unidirectional linear wear tester in a ball-on-disk configuration. Wear surfaces, transfer films and wear debris were analyzed by scanning electron micrograph (SEM)/energy dispersive spectroscopy (EDS).     

Influence of plasma nitriding treatment on the adhesion of DLC films deposited on AISI 4140 steel by PVD magnetron sputtering

Duplex surface treatments composed of diamond like carbon (DLC) coating followed by plasma nitriding have drawn attention for a while. In this study, AISI 4140 steel substrates were plasma nitrided at different treatment temperatures and times. Then, DLC films were deposited on both untreated and plasma nitrided samples using PVD magnetron sputtering. The effect of different plasma nitriding temperatures and times on the structural, mechanical and adhesion properties of DLC coatings was investigated by XRD, SEM, microhardness tester and scratch tester, respectively. It was found that surface hardness, intrinsic stresses, layer thickness values and phase distribution in modified layers and DLC coating were the main factors on adhesion properties of duplex coating system. The surface hardness and residual stress values of AISI 4140 steel substrates significantly increased with both DLC coating and duplex surface treatment (plasma nitriding + DLC coating). Increasing plasma nitriding temperature and time also increased the diffusion depth and the thickness of modified layers. Hard surface layers led to a significant improvement on load bearing capacity of the substrate material. However, it was also determined that the process parameters, which provided lower intrinsic stresses, improved the adhesion properties of the duplex coating system.