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.     

Synthesis of Silica Decorated MWCNTs for Field Emission Property

A novel route to nanocomposites containing surface modified multiwalled carbon nanotubes (MWCNTs) by silica thin film is reported. The effect of chemical oxidation on the surface of MWCNTs by using different acid-treatments is studied.The acidic processes are characterized by Raman spectroscopy, thermogravimetry analysis, scanning electron microscopy, and transmission electron microscopy. MWCNTs can be coated homogeneously with silica film by using tetraethoxysilane (TEOS)as a precursor in a sol-gel process. Varying the shell thickness of amorphous silica coating layers on MWCNTs exhibits excellent thermal stability, reliability, and lifetime of field emission properties, especially down to less than 10 nm.     

Synthesis and characterisation of surface gradient thin conversion films on zinc coated steel

Surface gradient layers on hot-dip galvanised steel were synthesised in order to determine the barrier properties and corrosion resistance of thin amorphous conversion coatings as a function of layer thickness and processing time. For this purpose, a dip coating procedure was established that yields well-defined gradient layers. As a model system for conversion film formation on zinc coated steel, a zirconium based bath chemistry was used. The synthesised zirconium oxyhydroxide gradient films were characterised by localised electrochemical techniques, such as Scanning Kelvin Probe (SKP) and electrochemical impedance spectroscopy using an electrochemical capillary cell. Microscopic infrared reflection absorption spectroscopy (μ-FT-IRRAS) measurements and small-spot X-ray photo electron spectroscopy (XPS) were used as complementary surface analytical techniques. The applied analysing techniques provide a spatial resolution of 100-1600 μm. Thereby, a complete variation of thin film properties, such as thickness, barrier properties, corrosion resistance and chemical composition can be measured as function of the time of film growth on a sample with a length of a few centimetres. This approach allows a precise and accurate determination of structure-to-property relationships of thin conversion films. Moreover, it could be shown that a surface gradient film analysis significantly rationalises experimental time and increases the reliability of the experimental results.     

Effect of metallic seed layers on the properties of nanocrystalline diamond films

Three metallic films (Mo, Ti and W) were sputtered on Si substrates and ultrasonically seeded in diamond powder suspension. Nanocrystalline diamond (NCD) films were deposited using a dc arc plasma jet CVD system on the seeded metallic layers and, for comparison, a seeded Si without any metallic layer. The effect of metallic seed layers on the nucleation, microstructure, composition and mechanical properties of NCD films was investigated by atomic force microscopy (AFM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy and nanoindentation. We found that the metallic seed layers were transformed into metallic carbide or/and metallic silicide during the deposition of NCD films at high temperature. Adding metallic seed layers had no obvious effect on the bonding structure of the NCD films but significantly improved their surface roughness and mechanical properties. The NCD film deposited on W seed layer displays the lowest root-mean-square roughness of 19 nm while that on Ti seed layer has the highest compactness, hardness and elastic modulus.     

Fabrication of a new type of organic-inorganic hybrid superlattice films combined with titanium oxide and polydiacetylene

We fabricated a new organic-inorganic hybrid superlattice film using molecular layer deposition [MLD] combined with atomic layer deposition [ALD]. In the molecular layer deposition process, polydiacetylene [PDA] layers were grown by repeated sequential adsorption of titanium tetrachloride and 2,4-hexadiyne-1,6-diol with ultraviolet polymerization under a substrate temperature of 100°C. Titanium oxide [TiO₂] inorganic layers were deposited at the same temperatures with alternating surface-saturating reactions of titanium tetrachloride and water. Ellipsometry analysis showed a self-limiting surface reaction process and linear growth of the nanohybrid films. The transmission electron microscopy analysis of the titanium oxide cross-linked polydiacetylene [TiOPDA]-TiO₂ thin films confirmed the MLD growth rate and showed that the films are amorphous superlattices. Composition and polymerization of the films were confirmed by infrared spectroscopy. The TiOPDA-TiO₂ nanohybrid superlattice films exhibited good thermal and mechanical stabilities.     

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.     

Preparation and characterization of thin organosilicon films deposited on SPR chip

The paper reports on the preparation and characterization of organosilicon thin polymer films deposited on glass slides coated with 5 nm adhesion layer of titanium and 50 nm of gold. The polymer was obtained by the decomposition of 1,1,3,3-tetramethyldisiloxane precursor (TMDSO) premixed with oxygen induced in a N₂ plasma afterglow using remote plasma-enhanced chemical vapor deposition (PECVD) technique. The film thickness was controlled by laser interferometry and was 9 nm. The chemical stability of the gold substrate coated with the organosilicon polymer film (p-TMDSO) was studied in different acidic and basic solutions (pH 1-14). While the gold/polymer interface showed a high stability in acidic media, the film was almost completely removed in basic solutions. The resulting surfaces were characterized using atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), water contact angle measurements, cyclic voltammetry, and surface plasmon resonance (SPR).     

Chemical solution deposition of pure and Gd-doped ceria thin films: Structural,morphological and optical properties

High quality smooth, uniform and crack-free ceria and gadolinium doped ceria (GDC) thin films were prepared on Si and Si/YSZ substrates by chemical solution deposition. The thermal behavior of Gd-Ce-O precursor was investigated by TG-DSC measurements. The phase purity and structure of deposited films were evaluated using X-ray diffraction (XRD) analysis and Raman spectroscopy. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were employed for the estimation of surface morphological features. Oxidation state of Ce ions in fabricated films was analyzed by X-ray photoelectron spectroscopy (XPS). Optical properties were evaluated by diffuse reflectance UV–vis spectrometry. Thickness of the films can be controlled by applying a certain number of spin coating cycles. A linear relation between the thickness of the films and the number of deposited layers was observed. The single-layer thickness was determined to be approximately 20 nm. The influence of annealing temperature and Gd content on the film structure, morphology and optical properties was studied and discussed. The dependence of an optical band gap as a function of grain size was demonstrated.     

Characterization of thermally aged AlPO<Subscript>4</Subscript>-coated LiCoO<Subscript>2</Subscript> thin films

The electrochemical properties and stability during storage of pristine and AlPO₄-coated LiCoO₂ thin films were characterized. The wide and smooth surface of the thin film electrode might provide an opportunity for one to observe surface reactions with an electrolyte. The rate capability and cyclic performance of the LiCoO₂ thin film were enhanced by AlPO₄ surface coating. Based on secondary ion mass spectrometry analysis and scanning electron microscopy images of the surface, it was confirmed that the coating layer was successfully protected from the reactive electrolyte during storage at 90°C. In contrast, the surface of the pristine sample was severely damaged after storage.     

XPS and IR analysis of thin barrier films polymerized from C2H4/CHF3 ECR-plasmas

Thin fluorocarbon polymer films are prepared on PE-foils in low-pressure electron cyclotron resonance plasmas using ethylene (C₂H₄) and trifluoromethane (CHF₃) as monomers. The thin fluorinated hydrocarbon layers strongly reduces the permeability of polyethylene to alkanes. For example, the permeation of toluene was decreased by a factor of about 100 by a single, thin fluorocarbon layer. A further reduction of the permeation down to a factor of 1600 can be obtained by a multilayer coating. X-ray photoelectron spectroscopy and Fourier transform IR spectroscopy are used to characterize the plasma polymerized films. It is shown that the addition of CHF₃ to a C₂H₄ plasma leads to an increase of CF₃—, CF₂—, and CF— groups and to a decrease of CH₃— and CH₂— groups in the film. The chemical composition of the polymer layers and their toluene permeabilities are discussed. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 717–722, 1997     

Polyacrylic acid macromolecule—complexed zinc phosphate crystal conversion coatings

When water-soluble polyacrylic acid (PAA) macromolecules are introduced into zinc phosphating liquids, significant improvements in the yield of conventional zinc phosphate conversion films deposited on carbon steel surfaces are obtained. The improvements include controllability of crystal dimensions, degree of crystallinity, and coating weight. The conversion layer formed is a composite microstructure consisting of a bulk PAA polymer and complexed PAA continuously overlaying a uniform array of fine dense zinc phosphate crystals. Interfacial studies of the composite layer using infrared spectroscopy, energy-dispersive X-ray spectrometry associated with scanning electron microscopy, and X-ray photoelectron spectroscopy indicated that the functional carboxylic acid groups in the PAA molecules were strongly chemisorbed by the Zn atoms at the outermost surface sites of the crystal layers. The intermolecular bridging action of the surface Zn atoms which connect the PAA and the zinc phosphate crystal layers results in good adhesion at the PAA–crystal interfaces. In addition, the plasticized complex formation plays an essential role in increasing the stiffness and the ductility of the normally conventional crystal films. The flexibility of the complex coating surface and the thickness and surface roughness of the thin PAA overlayer all affect the adhesive force at the interface between the organic polymer topcoat and the complexed coating.     

不同旋涂方式对铜锌锡硫硒薄膜及相应器件性能的影响

晶体质量是决定铜锌锡硫硒(Cu₂ZnSn(S,Se)₄, CZTSSe)吸收层薄膜吸收效率的关键,旋涂是溶液法制备CZTSSe吸收层的第一步,因此旋涂方式的选择至关重要。为了探究不同旋涂方式对CZTSSe吸收层薄膜质量和相应器件性能的影响,分别采用三组不同的旋涂方式制备铜锌锡硫(Cu₂ZnSnS₄, CZTS)前驱体薄膜及CZTSSe吸收层薄膜,并利用X射线衍射仪(XRD)、能谱仪(EDS)、显微拉曼光谱仪(Raman)、场发射扫描电子显微镜(FE-SEM)分析了不同旋涂方式对所制备的CZTSSe吸收层薄膜晶体结构、元素成分、相纯度、表面形貌的影响。同时,采用电流密度-电压(J-V)测试和外量子效率(EQE)测试对CZTSSe吸收层薄膜太阳电池的光电特性进行了表征。结果表明:旋涂7周期,且第一周期烘烤之前旋涂2次的效果最好,所制备的CZTS前驱体薄膜均匀,无裂纹,CZTSSe吸收层薄膜结晶度更高,薄膜表面更平整致密,晶粒大小更均匀,实现了9.63%的光电转换效率。通过对采用不同旋涂方式制备的器件的性能参数进行统计分析,得出新的旋涂方式可以提高CZTSSe薄膜太阳电池的可重复性,为将来可能的大规模商业化应用做铺垫。     

Preparation of polybenzimidazole/functionalized carbon nanotube nanocomposite films for use as protective coatings

Functionalized multi‐walled carbon nanotubes (MWCNTs) via microwave‐induced polymerization modification route, and polybenzimidazole (PBI) nanocomposite films containing 0.1‐5 wt% functionalized MWCNTs were successfully synthesized. The functionalized MWCNTs were characterized by field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and X‐ray photoelectron spectroscopy (XPS). The results verify that the polymer was successfully grafted to the MWCNTs with a polymer layer that was several nanometers thick. The TGA results showed that the quantity of the attached polymer reached approximately 9.4 wt%. The mechanical properties of the nanocomposite films were measured by tensile test and dynamic mechanical analysis (DMA). The tensile test results indicated that the Young's modulus increased by about 43.9% at 2 wt% CNT loading, and further modulus growth was observed at higher filler loading. The DMA studies indicated that the nanocomposite films had a higher storage modulus than pure PBI film in the temperature range of 30‐300°C, and the storage modulus was maintained above 0.82 GPa. Simulation results confirmed that the PBI nanocomposite films had desirable mechanical properties for use as a protective coating. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers.     

Preparation and characterization of grafting polyacrylamide from PET films by SI‐ATRP via water‐borne system

The grafted homopolymer and comb‐shaped copolymer of polyacrylamide were prepared by combining the self‐assembly of initiator and water‐borne surface‐initiated atom transfer radical polymerization (SI‐ATRP). The structures, composition, properties, and surface morphology of the modified PET films were characterized by FTIR/ATR, X‐ray photoelectron spectroscopy (XPS), contact angle measurement, and scanning electronic microscopy (SEM). The results show that the surface of PET films was covered by equable grafting polymer layer after grafted polyacrylamide (PAM). The amount of grafting polymer increased linearly with the polymerization time added. The GPC date show that the polymerization in the water‐borne medium at lower temperature (50°C) shows better “living” and control. After modified by comb‐shaped copolymer brushes, the modified PET film was completely covered with the second polymer layer (PAM) and water contact angle decreased to 13.6°. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Electrochemical behaviour of thin films deposited by plasma DBD torch on copper: An O2-diffusion barrier

In the field of corrosion protection, the research of environmentally friendly coating processes is one of the research topics. The use of gaseous atmospheric plasma, especially dielectric barrier discharge (DBD) plasma is an interesting way to rapidly form a thin protective coating. The aim of this work is to characterize the electrochemical behaviour of a SiO_xC_yN_z film, formed from different organosilicon precursors, in neutral corrosive environment on copper. The film morphology and composition were determined by transmission electron microscopy (TEM) observations and X-ray photoelectron spectroscopy (XPS). The electrochemical behaviour of the different treated copper was studied by stationary techniques and electrochemical impedance spectroscopy (EIS). With the same plasma parameter, the kind of organosilicon precursor determines the chemical stability of the coatings in water, then their protective properties. When the SiO₂-like structure contains a low carbon level, the SiO_xC_yN_z films present a good stability in water, and acts clearly as an O₂ barrier membrane.     

Ultra thin layers as new concepts for corrosion inhibition and adhesion promotion

The adsorption and self-organization process as well as the surface reactions of several bifunctional adhesion promoters on different oxide surfaces have been investigated. The aim was to improve the adhesion between metal oxides and different organic coatings. We developed a large number of bifunctional compounds, which are able to adsorb spontaneously on different pre-treated metal (oxide) surfaces. The second group can be designed for grafting different otherwise incompatible layers.

Therefore, a special two-step procedure has been developed: (1) adsorption of the designed bifunctional molecules on the substrate and (2) surface reaction of the terminal reactive group with a polymeric top coating or with further monomers resulting in a strongly bond composite.

For this purpose substances were chosen having a surface reactive group, an aliphatic spacer and a reactive group for a suitable top layer. Phosphonic acids forming strong bonds with several metal surfaces were chosen as surface-active groups on metal oxide substrates.

The termination of these compounds with further reactive groups opened a wide range of possible applications. Functionalities like amino or carboxylic groups allowed reactions with commercial lacquers (e.g., polyurethane) for improving adhesion promotion and corrosion inhibition of the metal substrates. By using polymerizable groups like thiophene and pyrrole an in situ surface polymerization with further monomers is possible directly on the substrate.

The adsorbed films of bifunctional phosphonic acids on metal (oxide) substrates were characterized by contact angle measurements, X-ray photoelectron spectroscopy (XPS), the surface polymerized films were investigated by atomic force microscopy (AFM), scanning electron microscopy (SEM), cyclovoltammetry (CV), and electrochemical impedance spectroscopy (EIS). The results showed that monolayers were formed, which were correctly oriented on the surfaces: the phosphonic acid group was attached to the substrate whereas the terminal group was free standing for further reactions. Surface polymerization with additional monomer was possible either chemically or electrochemically resulting in smooth polymer layers of adjustable thickness. The conducting polymers were found to be p-conductive with a doping level of about 30%. Conductivity measurements revealed a conductivity of about 0.13 S/cm for the best films.

Based on this principle two possible applications are given: firstly, a corrosion protecting system for steel, and secondly, a model release system for protecting steel after damage of the coating.     

Fabrication and properties of ZnO/GaN heterostructure nanocolumnar thin film on Si (111) substrate

Zinc oxide thin films have been obtained on bare and GaN buffer layer decorated Si (111) substrates by pulsed laser deposition (PLD), respectively. GaN buffer layer was achieved by a two-step method. The structure, surface morphology, composition, and optical properties of these thin films were investigated by X-ray diffraction, field emission scanning electron microscopy, infrared absorption spectra, and photoluminiscence (PL) spectra, respectively. Scanning electron microscopy images indicate that the flower-like grains were presented on the surface of ZnO thin films grown on GaN/Si (111) substrate, while the ZnO thin films grown on Si (111) substrate show the morphology of inclination column. PL spectrum reveals that the ultraviolet emission efficiency of ZnO thin film on GaN buffer layer is high, and the defect emission of ZnO thin film derived from Zn_i and V_o is low. The results demonstrate that the existence of GaN buffer layer can greatly improve the ZnO thin film on the Si (111) substrate by PLD techniques.     

Formation of nanocrystalline and amorphous carbon by high fluence swift heavy ion irradiation of a plasma polymerized polyterpenol thin film precursor

This study aimed to produce graphitic‐polymer nanocomposite thin films via the swift heavy ion irradiation of polyterpenol thin films synthesized from an environmentally sustainable precursor by radio‐frequency plasma enhanced chemical vapor deposition. Atomic force microscopy and scanning electron microscopy revealed fluence‐dependent surface restructuring of the thin films leading to the formation of interconnected island structures, with no discernible delamination from the underlying aluminum substrate. Raman spectroscopy confirmed the development of D and G peaks associated with graphitic materials, whilst Fourier transform infrared spectroscopy indicated retention of the plasma polymer's chemical functionalities (including hydroxyl groups) within the material after irradiation. Graphitic‐polymer nanocomposite films prepared by this dry and solvent‐free process have numerous potential applications in biological assay, organic electronics, and membrane technology. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46498.     

Temperature dependence of surface composition and morphology in polymer blend film

Thin films of poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN) blend can phase separate upon heating to above its critical temperature. Temperature dependence of the surface composition and morphology in the blend thin film upon thermal treatment was studied using in situ X-ray photoelectron spectroscopy (XPS) and in situ atomic force microscopy (AFM). It was found that in addition to phase separation, the blend component preferentially diffused to and aggregated at the surface of the blend film, leading to the variation of surface composition with temperature. At 185 °C, above the critical temperature, the amounts of PMMA and SAN phases were comparable. At lower temperatures PMMA migrated to the surface, leading to a much higher PMMA surface content than in the bulk. The migration and preferential segregation of a blend component in thin films demonstrated here are responsible for the great difference between in situ and ex situ experimental (not real quenching or annealing) results of polymer blend films, and help explain the slow kinetics of surface phase separation at early stage for blend thin films reported in literature. This is significant for the control of surface properties of polymer materials.     

Waterborne acrylic–polyaniline nanocomposite as antistatic coating: preparation and characterization

An antistatic and electrically conductive acrylic–polyaniline nanocomposite coating was successfully synthesized by interfacial polymerization of aniline in the presence of acrylic latex. The acrylic latex was prepared through emulsion polymerization, and aniline was polymerized by in situ interfacial polymerization at the interface of acrylic latex/chloroform phase. Fourier transform infrared spectroscopy (FTIR), UV–Vis spectroscopy and CHNS elemental analysis revealed the existence of 6.24 wt% emeraldine salt of polyaniline (PAni) in the dried film of the nanocomposite. Scanning electron microscopy (SEM) confirmed the presence of colloidal polymer particles in the aqueous phase which was confirmed to have some advantages, including prevention of aggregation of particles, dispersibility improvement and enhancement of the PAni nanofibers aspect ratio in the acrylic polymer matrix. According to SEM results, PAni fibers with the length ranging from 12 to 67 µm and diameters between 0.078 and 1 µm, highly dispersed in the acrylic polymer matrix, were successfully synthesized. Thermal, electrical and mechanical properties of the acrylic copolymer were significantly affected by PAni incorporation. The onset degradation temperature in thermogravimetric analysis revealed that the thermal stability of the nanocomposite was improved compared to that of the pure acrylic copolymer. The nanocomposite film showed electrical conductivity of about 0.025 S/cm at room temperature, along with satisfactory mechanical properties, attractive as an antistatic material in coating applications.