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.     

Adhesion promotion of thick fire-retardant melamine polymer dip-coatings at polyolefin surfaces by using plasma polymers

Melamine and melamine resins are widely used as fire retardants for polymer materials used in pharmaceutical, plastic, textile, rubber, and construction industry. Melamine-based flame retardants act by blowing off intumescent layers, char formation, and emission of quenching ammonia gas and diluent molecular nitrogen. Special advantages are: low cost, low smoke density and toxicity, low corrosive activity, safe handling, and environmental friendliness. Methylated poly(melamine-co-formaldehyde) (mPMF) was used as thick (≥40?μm) fire-retardant coating for plasma pretreated polymers. A combined low-pressure plasma pretreatment consisting of oxygen plasma exposure followed by deposition of thin poly(allylamine) (ppAAm) and poly(allyl alcohol) (ppAAl) plasma polymers as adhesion promoters have improved the adhesion of thick mPMF coatings strongly. Chemical structure and composition of deposited polymer films were characterized by infrared-attenuated total reflectance and X-ray photoelectron spectroscopy (XPS). After peeling, the peeled layer surfaces were also investigated for identification of the locus of failure and their topography using optical microscopy and XPS. Often the adhesion promotion was so efficient that the peeling of coating was not possible. Thermal properties of plasma polymers and dip-coating films were analyzed by thermogravimetric analysis. Significant improvement of fire-retardant properties of coated polymers was confirmed by flame tests.     

Polyvinylpyrrolidone adhesion layer for increased uniformity and optical transmittance of silica nanoparticle antireflective coatings

The uniformity of silica nanoparticle antireflective coatings deposited from aqueous solutions on glass substrates is limited by the high surface tension and low evaporation rate of water. In this work, thin films of polyvinylpyrrolidone (PVP) were utilized as an adhesion layer to increase the uniformity and optical transmittance of silica nanoparticle coatings. The increase in adhesive force caused by the presence of the PVP layer was measured using atomic force microscopy (AFM). The micro- and nanoscale uniformities of silica nanoparticle films with and without PVP adhesion layers were characterized using scanning electron microscopy and AFM. It was found that a thin PVP adhesion layer provides the adhesion required to form uniform films of silica nanoparticles. Solar weighted transmittance of 97.6% over a wavelength range of 330–1000 nm was achieved with soda-lime glass substrates coated on both sides.     

Polymer clay self‐assembly complexes on paper

Layer‐by‐layer (LBL) self‐assembly was used to form polymer/clay complexes on paper to enhance its wet strength properties. Initially, alternating layers of poly(allylamine hydrochloride) (PAH) and Kaolin clay were sequentially deposited on quartz substrate and characterized by UV/Vis/NIR spectroscopy as a model system. The same procedure was then applied to a paper test sheet to form multilayered coatings, which were examined with scanning electron microscopy. The wettability of the LBL coated paper test sheet was shown to change from hydrophilic to hydrophobic with increased number of multilayers and if the terminating layer was Kaolin clay. The wet strength of the coated test sheet was improved by more than 270% over the uncoated test sheet with 16 bilayers of PAH/kaolin complex on the surface. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Enhanced adhesion of silica for epoxy molding compounds (EMCs) by plasma polymer coatings

Silica for epoxy molding compounds (EMCs) was coated via plasma polymerization using an RF plasma (13.56 MHz) as a function of the plasma power, gas pressure, and treatment time. The monomers utilized for the plasma polymer coatings were 1,3-diaminopropane, allylamine, pyrrole, 1,2-epoxy-5-hexene, allyl mercaptan, and allyl alcohol. The EMC samples were prepared from biphenyl epoxy resin, phenol novolac, triphenyl phosphine, and plasma polymer-coated silica, and the loading of silica was controlled to 60 wt%. The EMC samples were cured at 175°C for 4 h and subjected to T_g, CTE, and water absorption measurements. The adhesion of silica to epoxy resin was evaluated by measuring the flexural strength of EMC samples and the fracture surfaces were analyzed by SEM. Plasma polymer coatings were also characterized by FT-IR and coating thickness measurements. The plasma polymer coating of silica with 1,3-diaminopropane and allylamine enhanced the flexural strength of EMC samples (167 and 165 MPa), compared with the control sample (140 MPa), and exhibited a higher T_g, a lower CTE, and lower water absorption. The enhanced properties with 1,3-diaminopropane and allylamine plasma polymer coatings can be attributed to the amine functional groups in the plasma polymer coatings.     

Influence of Differently Structured Aluminium–Polypropylene Interfaces on Adhesion

Polar groups were introduced on polypropylene surfaces for increasing the surface energy and the peel strength to evaporated aluminium layers. Three kinds of plasma processes were used for introducing such functional groups to polyolefin surfaces: low-pressure radio-frequency (RF) O₂ plasma exposure, atmospheric-pressure dielectric-barrier discharge (DBD) treatment in air, and the deposition of allylamine plasma polymer. The amino groups of the allylamine plasma polymer were also used as anchoring points for chemical introduction of covalently bonded spacer molecules equipped with reactive endgroups. Thus, silanol endgroups of a covalently bonded spacer were able to interact with the evaporated metal layer. The Al–PP composites achieved a maximal peel strength of 470 N/m by exposing the polymer to the lowpressure O₂ plasma and 500 N/m on exposure to the atmospheric DBD plasma. After allylamine plasma polymerization and grafting of spacers, the peel strength was usually higher than 1500 N/m and the composites could not be peeled.     

Coating of carbon fibers with adhesion-promoting thin poly(acrylic acid) and poly(hydroxyethylmethacrylate) layers using electrospray ionization

Thin coatings of poly(acrylic acid) (PAA) and poly(hydroxyethylmethacrylate) (PHEMA) were deposited onto carbon fibers by means of the electrospray ionization (ESI) technique in ambient air. These high-molecular weight polymer layers were used as adhesion promoters in carbon fiber–epoxy resin composites. Within the ESI process, the carbon fibers were completely enwrapped with polymer in the upper 10 plies of a carbon fiber roving. As identified with scanning electron microscopy also shadowed fibers in a bundle as well as backsides of fiber rovings were pinhole-free coated with polymers (‘electrophoretic effect’). Under the conditions used, the layers have a granular structure. Residual solvent was absent in the deposit. PAA and PHEMA films did not show any changes in composition and structure in comparison with the original polymers as analyzed by X-ray photo-electron spectroscopy and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Single-fiber pullout tests of coated fibers embedded in epoxy resin showed significantly increased interfacial shear strength. It is assumed that chemical bonds between carbon fiber poly(acrylic acid) and epoxy resin contribute significantly to the improved interactions.     

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.     

On the use of CrN/Cr and CrN interlayers in hot filament chemical vapour deposition (HF-CVD) of diamond films onto WC-Co substrates

CrN/Cr-based films were deposited using PVD-arc technique onto Co-cemented tungsten carbide (WC-Co) substrates and, then, seeded with diamond powder suspension or mechanically treated by Fluidized Bed Peening (FBP) of brittle diamond powders. Multilayered coatings were obtained from the superimposition of 4 µm-thick diamond coatings, deposited on the PVD interlayer using hot filament chemical vapour deposition (HFCVD). The effectiveness of fluidized bed peened CrN/Cr interlayers on the adhesion enhancement of diamond on WC-Co substrates was studied and compared to diamond coated WC-Co substrates with unpeened CrN/Cr or CrN interlayers, or pre-treated with two-step chemical etching (Murakami's reagent and Caro's acid, MC-treatment).In particular, growth, morphology, wear endurance and adhesion of the CVD deposited diamond films onto peened CrN/Cr interlayer were looked into. Diamond coatings on peened CrN/Cr interlayers exhibited a rougher surface morphology than as-prepared CrN/Cr films as a result of the surface roughening of the ductile Cr layer produced by the repeated impacts on it of the diamond powders during FBP. FBP was found to be a necessary step in improving the scarce adhesion of CVD diamond onto CrN/Cr-interlayer.However, the use of FB peened CrN/Cr interlayer did not represent the best way to pre-treat WC-Co substrates, as the unpeened single-layer CrN, or the use of MC pretreatment, was found to ensure better adhesion and wear endurance.     

Ultra-Thin Polymer Layer Deposition by Aerosol–Dielectric Barrier Discharge (DBD) and Electrospray Ionization (ESI) at Atmospheric Pressure

Polyolefins are chemically inert and do not adhere well to metals, polymers or inorganics. To overcome this problem, polyolefin surfaces were modified thermally, plasmachemically, or by flame treatment with different oxygen-containing groups, however, unfortunately, such treatments were accompanied by undesired, adhesion lowering polymer degradation. To solve this dilemma, solutions of synthetic polymers and copolymers were prepared, sprayed into the barrier discharge or electrosprayed without discharge and deposited as thin adhesion-promoting layers. The deposited polymer layers from poly(vinylamine), poly(ethylene glycol)–poly(vinyl alcohol) copolymers and poly(acrylic acid) were endowed with monotype functional groups. Using the aerosol — dielectric barrier discharge only a fraction of functional groups survived the deposition process in contrast to the electrospray in which all functional groups were retained.     

The effect of plasma‐polymerised silicon hydride‐rich polyhydrogenmethylsiloxane on the adhesion of silicone elastomers

BACKGROUND: Silicone elastomers have outstanding material properties including good thermal stability, low electrical conductivity, biocompatibility and resilient physical and chemical properties. These elastomers, however, exhibit relatively poor adhesion to stainless steel, and the use of a nanometre thick plasma‐polymerised primer layer as a means of enhancing this adhesion was investigated in this study. The primer coatings studied consisted of polyhydrogenmethylsiloxane (PHMS), tetraethyl orthosilicate (TEOS) and mixtures of these two liquid precursors. RESULTS: The plasma‐polymerised primer coatings were deposited onto stainless steel substrates using a PlasmaStream^? atmospheric pressure plasma jet system. Deposited coatings were examined using ellipsometry, contact angle measurements, optical profilometry, Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy and scanning electron microscopy. The adhesion of silicone elastomers bonded to the primed and bare stainless steel surfaces was assessed using 45° adhesion strength measurements. Elastomer adhesion was correlated with surface energy, thickness and roughness. CONCLUSION: An up to 15‐fold increase in adhesive fracture energy was observed for silicone elastomers bonded to the primed versus untreated stainless steel. The highest adhesion was observed for a coating deposited from a PHMS‐to‐TEOS precursor molar ratio of 3 to 1. Copyright © 2009 Society of Chemical Industry     

Adhesion of calcium phosphate coatings on polyethylene (PE), polystyrene (PS), poly(tetrafluoroethylene) (PTFE), poly(dimethylsiloxane) (PDMS) and poly-L-lactic acid (PLLA)

Calcium phosphate (CaP) coatings can be applied to improve the biological performance of polymeric medical implants. For clinical applications, a strong adhesion of the coating to the polymeric substrate is important. Therefore, the adhesion of rf magnetron-sputter-deposited CaP coatings on five polymers was studied: polyethylene (PE), polystyrene (PS), poly(tetrafluoroethylene) (PTFE), poly-L-lactic acid (PLLA) and poly(dimethylsiloxane) (PDMS). To influence the adhesion, the interface was varied in six different ways, e. g. by a plasma or ion-beam pretreatment, or by using a Ti interlayer. The adhesion was determined by using scratch, tensile and 180^° bend tests. Especially the polymers PE and PS needed a bombardment by energetic particles prior to or during coating deposition, to enable the formation of chemical bonds between the coating and the polymer, which gave adhesion. On PLLA and PDMS, being oxygen containing polymers, it was easier to establish a strong interface. An overtreatment of the polymeric substrates gave worse adhesion, probably due to the formation of weak low molecular weight (LMW) layers on the polymer. On PTFE, the use of a Ti interlayer was necessary to prevent the PTFE from UV degradation during coating deposition, as this caused cohesive failure within the PTFE. The results showed that each polymer requires a different approach for obtaining optimal adhesion. The observed adhesion could often be explained in the terms of processes occurred during the pretreatment of the polymers or the deposition of the coating.     

Plasma deposition of adhesion-promoting polymer layers onto polypropylene for subsequent covering with thick fire retardant coatings

Melamine resins were used as 50-μm-thick fire retardant coatings for polypropylene (PP). Preceding deposition, low-pressure plasma polymer films of allyl alcohol were coated onto PP to improve the adhesion between PP and melamine resin coatings. The efficiency of such fire retardant coatings was confirmed by flame tests. The plasma-deposited polymer and the dip-coated melamine resin films were characterized by Fourier transform infrared-attenuated total reflectance spectroscopy and X-ray photoelectron spectroscopy (XPS). The adhesion of coatings was measured using a 90° peel test with a doubled-faced adhesive tape. To detect the locus of failure, the peeled layer surfaces were inspected using optical microscopy and XPS. Thermal properties of PP thick melamine resin-coated films were analyzed by thermogravimetric analysis.     

Adhesion of extrusion‐coated polymer sealing layers to a fiber‐based packaging material with an atomic layer deposited aluminum oxide surface coating

Adhesion of extrusion‐coated polymer sealing layers on an atomic layer deposited (ALD) aluminum oxide (Al₂O₃) surface coating was investigated with a view to gain information on the applicability of ALD deposited barrier layers in fiber‐based packaging materials. The polymers used for the sealing layer were low density polyethylene (LDPE), polyethylene terephthalate (PET), and polylactide (PLA). They were extrusion‐coated onto the ceramic side of paper/PET/Al₂O₃ substrates, where the Al₂O₃ layer was a few tens of nanometers thick. According to the results, good adhesion was obtained for LDPE coating, whereas the other coatings showed a considerable lack of adhesion. Presumably, the oxidation faced by LDPE in the air gap of the extrusion‐coating process was able to create an extensive number of reactive sites that strongly bonded with the hydroxyl groups on the oxide surface of the substrate. With the PET and PLA coatings, such oxidation did not occur and the adhesion obtained remained at a relatively poor level. With all of the coatings, the adhesion levels were improved using corona discharge equipment as a pretreatment prior to the extrusion‐coating process. POLYM. ENG. SCI., 52:1985–1990, 2012. © 2012 Society of Plastics Engineers     

Evaluation of Osseointegration of Titanium Alloyed Implants Modified by Plasma Polymerization

By means of plasma polymerization, positively charged, nanometre-thin coatings can be applied to implant surfaces. The aim of the present study was to quantify the adhesion of human bone cells in vitro and to evaluate the bone ongrowth in vivo, on titanium surfaces modified by plasma polymer coatings. Different implant surface configurations were examined: titanium alloy (Ti6Al4V) coated with plasma-polymerized allylamine (PPAAm) and plasma-polymerized ethylenediamine (PPEDA) versus uncoated. Shear stress on human osteoblast-like MG-63 cells was investigated in vitro using a spinning disc device. Furthermore, bone-to-implant contact (BIC) was evaluated in vivo. Custom-made conical titanium implants were inserted at the medial tibia of female Sprague-Dawley rats. After a follow-up of six weeks, the BIC was determined by means of histomorphometry. The quantification of cell adhesion showed a significantly higher shear stress for MG-63 cells on PPAAm and PPEDA compared to uncoated Ti6Al4V. Uncoated titanium alloyed implants showed the lowest BIC (40.4%). Implants with PPAAm coating revealed a clear but not significant increase of the BIC (58.5%) and implants with PPEDA a significantly increased BIC (63.7%). In conclusion, plasma polymer coatings demonstrate enhanced cell adhesion and bone ongrowth compared to uncoated titanium surfaces.     

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     

Effect of electroless nickel interlayer on the electrochemical behavior of single layer CrN, TiN, TiAlN coatings and nanolayered TiAlN/CrN multilayer coatings prepared by reactive dc magnetron sputtering

The electrochemical behavior of single layer TiN, CrN, TiAlN and multilayer TiAlN/CrN coatings, deposited on steel substrates using a multi-target reactive direct current (dc) magnetron sputtering process, was studied in 3.5% NaCl solution. The total thickness of the coatings was about 1.5 μm. About 0.5 μm thick chromium interlayer was used to improve adhesion of the coatings. With an aim to improve the corrosion resistance, an additional interlayer of approximately 5 μm thick electroless nickel (EN) was deposited on the substrate. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) were used to study the corrosion behavior of the coatings. Scanning electron microscopy and energy dispersive X-ray analysis were used to characterize the corroded samples. The potentiodynamic polarization tests showed lower corrosion current density and higher polarization resistance (R_p) for the coatings with EN interlayer. For example, the corrosion current density of TiN coated steel was decreased by a factor of 10 by incorporating 5 μm thick EN interlayer. Similarly, multilayer coatings of TiAlN/CrN with EN interlayer showed about 30 times improved corrosion resistance as compared to the multilayers without EN interlayer. The porosity values were calculated from the potentiodynamic polarization data. The Nyquist and the Bode plots obtained from the EIS data were fitted by appropriate equivalent circuits. The pore resistance (R_pore), the charge transfer resistance (R_ct), the coating capacitance (Q_coat) and the double layer capacitance (Q_dl) of the coatings were obtained from the equivalent circuit. Multilayer coatings showed higher R_pore and R_ct values as compared to the single layer coatings. Similarly, the Q_coat and Q_dl values decreased from uncoated substrate to the multilayer coatings, indicating a decrease in the defect density by the addition of EN interlayer. These studies were confirmed by examining the corroded samples under scanning electron microscopy.     

Effect of plasma pretreatment on durability of sol-gel superhydrophobic coatings on laser modified stainless steel substrates

Superhydrophobic surfaces were generated on stainless steel SS 304 substrates, using a combination of physical as well as chemical modification of the surface and tested for use in biomedical applications. Nanosecond pulsed laser was used for physical modification, i.e. creating nanoscaled roughness on the substrates. An additional chemical modification was performed using fluorosilane-based sol-gel nanocomposite coatings to further improve the hydrophobicity. Presently, the key challenge that such surfaces face, is to possess a substantial durability. In this study, a surface activation technique such as plasma pre-treatment was adopted to improve the adhesion of coatings on the laser treated substrates. The coatings deposited using dip coating technique were cured at 150 °C. The surface morphology and the roughness of the processed substrates and the coated samples were characterized using Atomic Force Microscope and Scanning Electron Microscope. The wettability of the surface was monitored and evaluated throughout the study using water contact angle measurements. Weathering tests and scratch resistance measurements using a crockmeter were carried out to evaluate the durability, which revealed that the adhesion could be improved with plasma treatment of the laser textured substrates, prior to coating deposition. Maximum anti-bacterial activity of up to 90% towards the bacterial species Escherichia coli was found on the substrates coated with the fluorosilane-based superhydrophobic coatings for an exposure time of 30 min, without any addition of external anti-bacterial agents. Thus, the preliminary results obtained from the present investigation were found to be promising and were indicative of use of these surfaces for biomedical applications.     

Electrochemical approach to evaluate the interlayer adhesion of organic coatings

In this work we used the electrochemical impedance spectroscopy (EIS) to quantify the interlayer adhesion of coatings. Different automotive basecoat/clearcoat systems were tested on their interlayer adhesion with EIS. For EIS measurements, two thin electrode stripes of an electroconductive ink were applied between two coating layers. The impedance measurements were conducted to find out the effect of moisture on the interlayer adhesion. The data obtained show a strong sensitivity of the interlayer impedance on the outer air humidity and point out at the possibility of following the water accumulation in the interlayer and the formation of the conductive paths. Such phenomena lead to the adhesion loss and delamination between the coating layers. We found that the interlayer adhesion loss follows the same trend as the changes of the activation energy of the ion mobility, which can be derived from the interlayer resistance, measured with EIS.

For the verification of EIS measurements blister test measurements were carried out. With this method, it is possible to evaluate directly the interlayer adhesion of coatings. A good correlation was found between EIS and blister test data.     

Characterization of a plasma polymer coating from an organophosphorus silane deposited at atmospheric pressure for fire-retardant purposes

Protective coatings from diethylphosphatoethyltriethoxysilane (DEPETS) have been deposited on different polymer substrates in a plasma discharge operated at atmospheric pressure. Plasma polymer chemistry and structure were characterized by means of Fourier transform infrared spectroscopy (FTIR), laser desorption ionization-mass spectrometry (LDI-MS), nuclear magnetic resonance (NMR) and scanning electron microscopy (SEM). A chemical structure of the plasma polymer has been proposed based on the coating molecular characterization. Coatings were deposited on polycarbonate (PC) and polyamide 6 (PA6) substrates. The flame retardant properties of coated substrate samples were assessed using cone calorimetry and compared to those of bare substrates. A significant increase in the time to ignition (TTI), up to +143%, was recorded after coating deposition due to the formation of a high-performance barrier layer at the surface of both polymer substrates.