A General Route to Nanoparticle Thin Films and Coatings

Nanoparticles thin films have wide range of applications such as nanoelectronics, magnetic storage devices, SERS substrate fabrication, optical grating and antireflective coating. Present work describes a method to prepare large area nanoparticles thin film of the order of few square centimeters. Thin film deposition has been done successfully on a wide range of conducting as well as non conducting substrates such as carbon-coated copper grid, silicon, m-plane of alumina, glass and (100) plane of NaCl single crystal. SEM, TEM and AFM studies have been done for microstructural characterization of the thin films. A basic mechanism has been proposed towards the understanding of the deposition process.

Electromagnetic shielding materials and coatings derived from gelation of multiwall carbon nanotubes in an LCST mixture

Thermally induced demixing in an LCST mixture, polystyrene (PS)/polyvinyl methyl ether] (PVME), was used as a template to design materials with high electrical conductivity. This was facilitated by gelation of multiwall carbon nanotubes (MWNTs) in a given phase of the blends. The MWNTs were mixed in the miscible blends and the thermodynamic driven demixing further resulted in selective localization in the PVME phase of the blends. This was further confirmed by atomic force microscopy (AFM). The time dependent gelation of MWNTs at shallow quench depth, evaluated using isochronal temperature sweep by rheology, was studied by monitoring the melt electrical conductivity of the samples in situ by an LCR meter coupled to a rheometer. By varying the composition in the mixture, several intricate shapes like gaskets and also coatings capable of attenuating the EM radiation in the microwave frequency can be derived. For instance, the PVME rich mixtures can be molded in the form of a gasket, O-ring and other intricate shapes while the PS rich mixtures can be coated onto an insulating polymer to enhance the shielding effectiveness (SE) for EM radiation. The SE of the various materials was analyzed using a vector network analyzer in both the X-band (8.2 to 12 GHz) and the K-u-band (12 to 18 GHz) frequency. The improved SE upon gelation of MWNTs in the demixed blends is well evident by comparing the SE before and after demixing. A reflection loss of -35 dB was observed in the blends with 2 wt% MWNTs. Further, by coating a layer of ca. 0.15 mm of PS/PVME/MWNT, a SE of -15 dB at 18 GHz could be obtained.

Epoxy composites containing cobalt(II)-porphine anchored multiwalled carbon nanotubes as thin electromagnetic interference shields, adhesives and coatings

Herein a facile strategy has been adopted to design epoxy based adhesive/coating materials that can shield electromagnetic radiation. Multiwalled carbon nanotubes (MWNTs) were non-covalently modified with an ionic liquid and 5,10,15,20-tetrakis(4-methoxyphenyl)-21H,23H-porphine cobalt(II) (Co-TPP). The dispersion state of modified MWNTs in the composites was assessed using a scanning electron microscope. The electrical conductivity of the composites was improved with the addition of IL and Co-TPP. The shielding effectiveness was studied as a function of thickness and intriguingly, composites with as thin as 0.5 mm thickness were observed to reflect 497% of the incoming radiation. Carbon fibre reinforced polymer substrates were used to demonstrate the adhesive properties of the designed epoxy composites. Although, the shielding effectiveness of epoxy/MWNT composites with or without IL and Co-TPP is nearly the same for 0.5 mm thick samples, the lap shear test under tensile loading revealed an extraordinary adhesive bond strength for the epoxy/IL-MWNT/Co-TPP composites in contrast to neat epoxy. For instance, the lap shear strength of epoxy/IL-MWNT/Co-TPP composites was enhanced by 100% as compared to neat epoxy. Furthermore, the composites were thermally stable for practical utility in electronic applications as inferred from thermogravimetric analysis.

Effect of ion nitriding on the microstructure and properties of Maraging steel (250 Grade)

In the present investigation, ion nitriding of Maraging steel (250 grade) has been carried out at three different temperatures i.e., at 435 degrees C, 450 degrees C and 465 degrees C for 10 h duration in order to achieve good wear resistance along with high strength required for the slat track component of aircraft. The microstructure of the base material and the nitrided layer was examined by optical and scanning electron microscope, and various phases present were determined by X-ray diffraction. Various properties, such as, hardness, case depth, tensile, impact, fatigue properties and corrosion resistance were investigated for both un-nitrided and ion-nitrided materials. It is observed that the microstructure of the core material remains unaltered and Fe4N is formed in the hardened surface layer after ion nitriding at all the three temperatures employed. Surface hardness increases substantially after ion nitriding. Surface hardness remains almost the same but case depth increases with the increase in ion nitriding temperature due to greater diffusivity at higher temperatures. Tensile strength, fatigue strength and corrosion resistance are improved but ductility and energy absorbed in impact test decrease on ion nitriding. These results are explained on the basis of microstructural observations. The properties obtained after ion nitriding at 450 degrees C for 10 h are found to be optimum when compared to the other two ion nitriding temperatures.

Low-pressure MOCVD of Al2O3 films using aluminium acetylacetonate as precursor: nucleation and growth

A study of the deposition of aluminium oxide films by low-pressure metalorganic chemical vapour deposition from the complex aluminium acetylacetonate, in the absence of an oxidant gas, has been carried out. Depositions on to Si(100), stainless steel, and TiN-coated cemented carbide are found to be smooth, shiny, and blackish. SIMS, XPS and TEM analyses reveal that films deposited at temperatures as low as 600 degreesC contain small crystallites Of kappa-Al2O3, embedded in an amorphous matrix rich in graphitic carbon. Optical and scanning electron microscopy reveal a surface morphology made up of spherulites that suggests that film growth might involve a melting process. A nucleation and growth mechanism, involving the congruent melting clusters of precursor molecules on the hot substrate surface, is therefore invoked to explain these observations. An effort has been made experimentally to verify this proposed mechanism. (C) 2002 Elsevier Science B.V. All rights reserved.

Reactive pulsed laser deposition and characterization of niobium nitride thin films

We present a systematic study to explore the effect of important process variables on the composition and structure of niobium nitride thin films synthesized by Reactive Pulsed Laser Deposition (RPLD) technique through ablation of high purity niobium target in the presence of low pressure nitrogen gas. Secondary Ion Mass Spectrometry has been used in a unique way to study and fix gas pressure, substrate temperature and laser fluence, in order to obtain optimized conditions for one variable in single experimental run. The x-ray diffraction and electron microscopic characterization have been complemented by proton elastic backscattering spectroscopy and x-ray photoelectron spectroscopy to understand the incorporation of oxygen and associated non-stoichiometry in the metal to nitrogen ratio. The present study demonstrates that RPLD can be used for obtaining thin film architectures using non-equilibrium processing. Finally the optimized NbN thin films were characterized for their hardness using nano-indentation technique and found to be similar to 30 GPa at the deposition pressure of 8 Pa. (C) 2011 Elsevier B.V. All rights reserved.

Electrochemical studies on Zn/nano-CeO 2 electrodeposited composite coatings

The Zn-CeO 2 composite coatings through electrodeposition technique were successfully fabricated on mild steel substrate. As a comparison pure zinc coating was also prepared. The concentration of CeO 2 nanoparticles was varied in the electrolytic bath and the composites were electrodeposited both in the presence and absence of cetyltriammonium bromide (CTAB). The performance of the CeO 2 nanoparticles towards the deposition, crystal structure, texture, surface morphology and electrochemical corrosion behavior was studied. For characterizations of the electrodeposits, the techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM) were used. Both the additives ceria and surfactant polarize the reduction processes and thus influence the deposition process, surface nature and the electrochemical properties. The electrochemical experiments like potentiodynamic polarization and electrochemical impedance spectroscopic (EIS) studies carried out in 3.5 wt. NaCl solution explicit higher corrosion resistance by CeO 2 incorporated coating in the presence of surfactant. © 2012 Elsevier B.V. All rights reserved.

Laser surface cladding of MRI 153M magnesium alloy with (Al+Al2O3)

Laser surface cladding was carried out on a creep-resistant MRI 153M magnesium alloy with a mixture of Al and Al2O3 powders using a pulsed Nd:YAG laser at scan speeds of 21, 42, 63 and 84 mm/s. The Al2O3 particles partially or completely melted during laser irradiation and re-solidified with irregular shapes in the size range of 5–60 µm along with a few islands as large as 500 µm, within the grain-refined Mg-rich dendritic matrix. More than an order of magnitude improvement in wear resistance after cladding was attributed to the presence of ultra-hard Al2O3 particles, increased solid solubility of Al and other alloying elements, and a very fine dendritic microstructure as a result of rapid solidification in the cladded layer. However, corrosion resistance of the laser cladded alloy was reduced by almost an order of magnitude compared to that of the as-cast alloy mainly due to the presence of cracks and pores in the cladded layer.

Study of fracture behaviour of bond coats on nickel superalloy by three-point bending of microbeams

A microbeam testing geometry is designed to study the variation in fracture toughness across a compositionally graded NiAl coating on a superalloy substrate. A bi-material analytical model of fracture is used to evaluate toughness by deconvoluting load-displacement data generated in a three-point bending test. It is shown that the surface layers of a diffusion bond coat can be much more brittle than the interior despite the fact that elastic modulus and hardness do not display significant variations. Such a gradient in toughness allows stable crack propagation in a test that would normally lead to unstable fracture in a homogeneous, brittle material. As the crack approaches the interface, plasticity due to the presence of Ni3Al leads to gross bending and crack bifurcation.

Effect of substrate roughness on growth of diamond by hot filament CVD

Polycrystalline diamond coatings are grown on Si (100) substrate by hot filament CVD technique. We investigate here the effect of substrate roughening on the substrate temperature and methane concentration required to maintain high quality, high growth rate and faceted morphology of the diamond coatings. It has been shown that as we increase the substrate roughness from 0.05 mu m to 0.91 mu m (centre line average or CLA) there is enhancement in deposited film quality (Raman peak intensity ratio of sp (3) to non-sp (3) content increases from 1.65 to 7.13) and the substrate temperature can be brought down to 640A degrees C without any additional substrate heating. The coatings grown at adverse conditions for sp (3) deposition has cauliflower morphology with nanocrystalline grains and coatings grown under favourable sp (3) condition gives clear faceted grains.

Precursor Dependent Microstructure Evolution and Nonstoichiometry in Nanostructured Cerium Oxide Coatings Using the Solution Precursor Plasma Spray Technique

A solution precursor plasma spray (SPPS) technique has been used for direct deposition of cerium oxide nanoparticles (CNPs) from various cerium salt solutions as precursors. Solution precursors were injected into the hot zone of a plasma plume to deposit CNP coatings. A numerical study of the droplet injection model has been employed for microstructure development during SPPS. The decomposition of each precursor to cerium oxide was analyzed by thermogravimetric-differential thermal analysis and validated by thermodynamic calculations. The presence of the cerium oxide phase in the coatings was confirmed by X-ray diffraction studies. Transmission electron microscopy studies confirmed nanocrystalline (grain size <14 nm) characteristic of the coatings. X-ray photoelectron spectroscopy studies indicated the presence of a high concentration of Ce3+ (up to 0.32) in the coating prepared by SPPS. The processing and microstructure evolution of cerium oxide coatings with high nonstoichiometry are reported.

Microwave Irradiation Assisted Method for the Rapid Synthesis of fine Particles of alpha Al2O3 And alpha (Al1-XCrx)(2)O-3 And Their Coatings on Si(100)

Chromium substituted beta diketonate complexes of aluminium have been synthesized and employed as precursors for a novel soft chemistry process wherein microwave irradiation of a solution of the complex yields within minutes well crystallized needles of alpha (Al1 XCrx)(2)O-3 measuring 20 30 nm in diameter and 50 nm long By varying the microwave irradiation parameters and using a surfactant such as polyvinyl pyrrolidone the crystallite size and shape can be controlled and their agglomeration prevented These microstructural parameters as well as the polymorph of the Cr substituted Al2O3 formed may also be controlled by employing a different complex Samples of alpha (Al1 XCrx)(2)O-3 have been characterized by XRD FTIR and TEM The technique results in material of homogeneous metal composition, as shown by EDAX and can be adjusted as desired The technique has been extended to obtain coatings of alpha (Al1 XCrx)(2)O-3 on Si(100)

Large negative magnetoresistance and metal-insulator transition observed in MnO/C composite coatings grown on ceramic alumina by metalorganic chemical vapor deposition

MnO/C composite coatings were grown by the metalorganic chemical vapor deposition process on ceramic alumina in argon ambient. Characterization by various techniques confirms that these coatings are homogeneous composites comprising nanometer-sized MnO particles embedded in a matrix of nanometer-sized graphite. Components of the MnO/C composite coating crystalline disordered, but are electrically quite conductive. Resistance vs. temperature measurements show that coating resistance increases exponentially from a few hundred ohms at room temperature to a few megaohms at 30 K. Logarithmic plots of reduced activation energy vs. temperature show that the coating material undergoes a metal-insulator transition. The reduced activation energy exponent for the film under zero magnetic field was 2.1, which is unusually high, implying that conduction is suppressed at much faster rate than the Mott or the Efros-Shklovskii hopping mechanism. Magnetoconductance us. magnetic field plots obtained at various temperatures show a high magnetoconductance (similar to 28.8%) at 100 K, which is unusually large for a disordered system, wherein magnetoresistance is attributed typically to weak localization. A plausible explanation for the unusual behavior observed in the carbonaceous disordered composite material is proposed. (C) 2010 Elsevier Ltd. All rights reserved.

Thermodynamic modeling to analyse composition of carbonaceous coatings of MnO and other oxides of manganese grown by MOCVD

Equilibrium thermodynamic analysis has been applied to the low-pressure MOCVD process using manganese acetylacetonate as the precursor. ``CVD phase stability diagrams'' have been constructed separately for the processes carried out in argon and oxygen ambient, depicting the compositions of the resulting films as functions of CVD parameters. For the process conduced in argon ambient, the analysis predicts the simultaneous deposition of MnO and elemental carbon in 1: 3 molar proportion, over a range of temperatures. The analysis predicts also that, if CVD is carried out in oxygen ambient, even a very low flow of oxygen leads to the complete absence of carbon in the film deposited oxygen, with greater oxygen flow resulting in the simultaneous deposition of two different manganese oxides under certain conditions. The results of thermodynamic modeling have been verified quantitatively for low-pressure CVD conducted in argon ambient. Indeed, the large excess of carbon in the deposit is found to constitute a MnO/C nanocomposite, the associated cauliflower-like morphology making it a promising candidate for electrode material in supercapacitors. CVD carried out in oxygen flow, under specific conditions, leads to the deposition of more than one manganese oxide, as expected from thermodynamic analysis ( and forming an oxide-oxide nanocomposite). These results together demonstrate that thermodynamic analysis of the MOCVD process can be employed to synthesize thin films in a predictive manner, thus avoiding the inefficient trial-and-error method usually associated with MOCVD process development. The prospect of developing thin films of novel compositions and characteristics in a predictive manner, through the appropriate choice of CVD precursors and process conditions, emerges from the present work.

Quasicrystalline Coatings Through Laser Processing: A Study on Process Optimisation and Microstructure Evolution

Composite coatings containing quasicrystalline (QC) phases in Al-Cu-Fe alloys were prepared by laser cladding using a mixture of the elemental powders. Two substrates, namely pure aluminum and an Al-Si alloy were used. The clad layers were remelted at different scanning velocities to alter the growth conditions of different phases. The process parameters were optimized to produce quasicrystalline phases. The evolution of the microstructure in the coating layer was characterized by detailed microstructural investigation. The results indicate presence of quasicrystals in the aluminum substrate. However, only approximant phase could be observed in the substrate of Al-Si alloys. It is shown that there is a significant transport of Si atoms from the substrate to the clad layer during the cladding and remelting process. The hardness profiles of coatings on aluminum substrate indicate a very high hardness. The coating on Al-Si alloy, on the other hand, is ductile and soft. The fracture toughness of the hard coating on aluminum was obtained by nano-indentation technique. The K1C value was found to be 1.33 MPa m1/2 which is typical of brittle materials.