Effect of thermal treatments on sputtered silver nanocluster/silica composite coatings on soda-lime glasses: ionic exchange and antibacterial activity

Silver nanocluster/silica composite coatings were deposited on both soda-lime and silica glasses by radio frequency (RF) co-sputtering. The effect of thermal treatments on the microstructure in the range of 150?C450?°C were examined by UV?Cvisible spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Time of Flight-Elastic Recoil Detection Analysis. Sodium/silver ionic exchange was evidenced for coatings sputtered on soda-lime substrates after heating at 450?°C; presence of silver ions and/or silver nanoclusters, nanocluster size and their position inside the sputtered layers will be discussed for as-deposited and heated coatings on both substrates. The antibacterial activity of all coatings was determined against Staphylococcus aureus and Candida albicans by disk diffusion method and colonies forming units count; in agreement with microstructural results, the antibacterial activity present on all coatings was slightly reduced after heating at 450?°C. All coatings have been submitted to humidity plus UV ageing and sterilization by autoclave, gamma ray and ethylene oxide gas. Tape resistance (ASTM D3359-97) tests have been done on each coating before and after ageing and sterilizations, revealing a good adhesion on soda-lime substrates, except for those aged in humidity plus UV and sterilized by autoclave. Scratch tests and nanoindentation tests have been done on each coating, as-deposited and after heating at 450?°C. The coating hardness was improved by heating only when coatings were deposited on silica. The heating of coatings deposited on soda-lime substrates gave opposite effect on their hardness.     

Calcium phosphate coatings deposited by laser ablation at 355 nm under different substrate temperatures and water vapour pressures

Calcium phosphate coatings were deposited on Ti-6Al-4V by laser ablation with a 355 nm Nd:YAG laser at different substrate temperatures. Two series of coatings were deposited at water vapour pressures of 10 and 45 Pa by varying the substrate temperature from 20 to 600 °C. Characterisation of their structure and adhesion has been carried out in order to study the effect of the deposition temperature and the water vapour pressure on the coating properties. It has been found that a high temperature favours the synthesis of crystalline phases. Ca rich phases are synthesised at 10 Pa while hydroxyapatite is obtained at 45 Pa with some alfa tricalcium phosphate. Scratch test measurements have shown, that the coating-substrate adhesion for coatings deposited at 45 Pa is remarkably increased at substrate temperatures higher than 400 °C, but the highest adhesion has been found for amorphous coatings obtained at 10 Pa and 200 °C.     

AlN-TiB2-TiSi2 coatings obtained by pulsed magnetron sputtering

AlN-TiB₂ composite ceramic samples with a TiSi₂ additive are obtained by magnetron sputtering. After deposition, ordered regions in the coatings measure 1 nm across, so that they can be categorized as amorphous-like. Annealing at 900 and 1300°C causes crystallization with grain sizes of 11 and 25 nm, respectively. However, crystallization does not dramatically deteriorate the mechanical properties owing to the formation of high-enthalpy phases (AlB₂ at 900°C and AlB₃ at 1300°C). The hardness of the coatings varies from 15.1 GPa in the as-prepared samples to 11.0 GPa after annealing to 1300°C. This makes it possible to improve the wear resistance of edge tools with these coatings by a factor of 1.32 at a temperature of 1300°C near the contact.     

Peculiarities of structural phase and elastic stress states of superhard TiN-based nanocomposite coatings

A new concept of designing nanocomposite coatings is proposed. The concept consists in microstructural self-organization through simultaneous nucleation of islands of different mutually insoluble or slightly soluble phases at the stage of coating formation. Physical principles on which to select compositions of the coatings were developed and were experimentally verified on multicomponent nanocomposite coatings. With a Sprut magnetron arc plasma complex, superhard (H _μ > 40 GPa) multicomponent nanocomposite coatings of the system Ti-Al-Si-Cr-Ni-Cu-O-C-N were obtained. The peculiarities of structural phase and elastic stress states of the multicomponent coatings before and after annealing at a temperature of up to 1000 °C were studied by transmission electron microscopy, X-ray diffraction analysis, microhardness measurements and scratch tests. The study reveals a wide range of lattice bending-torsion (up to 200° μm^?1) of nanosized (less than 30 nm) coherent scattering regions in the two-level coating structure and of individual (up to 15 nm) TiN nanocrystals. Annealing of the coatings causes the two-level grain structure to relax with the formation of TiN-based nanocrystals of size less than 30–40 nm and with a decrease in lattice bending-torsion down to 40°–50° μm^?1. Comparative analysis of acoustic emission signals and tracks of the multicomponent and TiN coatings in scratch tests points to an increase in fracture ductility in the multicomponent coatings.     

Fabrication of coaxial nanowire heterostructures: SiO x nanowires with conformal TiO2 coatings

Silica nanowires, grown via the active oxidation of a silicon substrate, have been coated with TiO₂ using two coating methods: solution-based deposition of Ti-alkoxides and atomic layer deposition. Analysis of as-deposited and annealed films shows that it is possible to produce stable conformal coatings of either the anatase or rutile phases of TiO₂ on nanowires with diameters greater than 100 nm when annealed between 500–600°C and 800–900°C, respectively, with annealing at higher temperatures (1050°C) producing coatings with a highly facetted rutile morphology. The efficacy of the process is shown to depend on nanowire diameter, with nanowires having diameters less than about 100 nm fusing together during solution-based coating and decomposing during TiO₂ atomic layer deposition. The use of a suitable buffer layer is shown to be an effective means of minimizing nanowire decomposition. Finally, annealing coated nanowires under active oxidation conditions (1100°C) is shown to be an effective technique for depositing additional conformal SiO _x coatings, thereby providing a means of fabricating multi-layered coaxial nanostructures.     

Using Zn as target to fabricate ZnO coating by thermal oxidation in air on quartz substrate

In this work, ZnO coatings were fabricated by the RF-sputtering method on quartz substrates in an inert gas ambient of Ar followed by a thermal oxidation process in air at different temperatures. The effect of thermal oxidation temperatures on the structures and photoluminescence (PL) properties of the coatings were studied. The structural characteristics of the samples were analyzed by X-ray diffraction (XRD) and atomic force microscope (AFM). The PL spectra were obtained by using a Xe laser as a light source with an excitation wavelength of 325 nm at room temperature. The force-curves were obtained by AFM. The results show that all the prepared ZnO coatings have a compact hexagonal wurtzite structure. With the increasing annealing temperature from 400 °C to 600 °C, the particle size, surface RMS roughness, photoluminescence intensity and adhesion force of the prepared ZnO coatings were increased as well.     

Comparative study of hydroxyapatite and octacalcium phosphate coatings deposited on metallic implants by PLD method

The aim of the presented study was an analysis of two apatite coatings: hydroxyapatite (HA) and octacalcium phosphate (OCP) as coatings materials for metallic implants. Both layers were deposited by means of the PLD method. As a target material, synthetic, powdered and pressed hydroxyapatite was used. HA was deposited on 316L steel substrate in two temperature ranges for obtaining different coatings: 150±30°C and 430±30°C for OCP and HA, respectively. As an intermediate layer, the nanocrystalline diamond layer (NCD) was deposited. Examined calcium phosphate layers were tested for adhesion of osteoblast cell culture (MG-63). Analytical methods (AFM, FTIR) showed the usefulness of the PLD method for deposition of the apatite layers on metallic implants. Both examined layers showed biocompatibility with human osteoblast cells and presented favorable conditions for their proliferation.     

Polymer-precursor-derived (am-) SiC/TiC composites for resistive heaters in large volume multi-anvil high pressure/high-temperature apparatus

(Amorphous-)SiC/TiC composites for resistive tubular heaters in HP/HT experiments were obtained via a polymer-precursor process. A slurry consisting of a commercial SiC-precursor polymer (allylhydridopolycarbosilane, AHPCS) and TiC powder as conductive filler was applied to the inner walls of zirconia insulation tubes, using a centrifugation-casting method. Resistive coatings with homogeneous thickness of ～200 μm were obtained. The heaters were tested in octahedral multi-anvil assemblies at ～10 GPa with simultaneous recording of heating voltage and current. Up to a maximum temperature of ～1800°C they showed temperature vs. power characteristics reproducible from batch to batch, with resistance decreasing from 0.08 to 0.02 Ω during heating. Microstructural characterization using SEM/EDX was carried out on the recovered SiC/TiC composite material, as well as on pristine resistive heaters directly after coating and curing to 230°C, and after additional pyrolysis at 900°C in argon. In all cases, a stable composite microstructure of an interpenetrating network of TiC particles with either silicon carbide polymer precursor or an amorphous SiC phase were found. The composites were characterized by XRD and thermogravimetry. Further improvement of coating procedure and materials combination (precursor/filler/insulator substrate) may result in advanced coatings, operational well beyond 2000°C.     

Influence of electrolyte temperature on properties and infrared emissivity of MAO ceramic coating on 6061 aluminum alloy

6061 aluminum alloy was treated by MAO at various temperatures of the alkali silicate electrolyte using pulsed bipolar current mode for ten minutes. The surface microstructures and properties were studied using SEM, EDX, and XRD. The infrared emissivities of the MAO ceramic coatings were measured at the 70 °C using FTIR spectrometer. The electrolyte temperature strongly affected all the surface properties. The MAO alumina ceramics prepared in cold electrolytes have volcano-like and accumulated particles microstructures, while those prepared in hot electrolytes were: rougher, thinner and contained grainy spherical hollow bulgy microstructures with more pore density and more sillimanite and cristobalite phases which enhanced the IR emissivity. Also, the increment of sillimanite and cristobalite phases moved the apparent peaks toward longer wavelengths, and broadened the opaque region of the IR spectra. As a result, the increment of electrolyte temperature from 12.3 °C to 90.5 °C increased the average of LWIR emissivity from 80.4% to 94.4%, respectively, for the MAO ceramic coatings.     

Variable-Temperature and High-Pressure Micro-Raman Spectra of Inorganic Artists' Pigments: Crystalline Wulfenite,Lead(II) Molybdate(VI), PbMoO4

Variable-temperature (?150°C to 600°C) and high-pressure (up to ～5 GPa) micro-Raman spectra have been obtained for the mineral wulfenite [lead(II) molybdate(VI), PbMoO₄], a main constituent of the artists' pigment, orange molybdate. The spectra were quite similar in both the temperature and the pressure studies, except for broadening and shifting of some peaks. No phase changes were detected, although there is possibly some amorphization beginning at ～600°C. The photoacoustic IR spectrum in the 1950–450 cm^?1 region is reported for characterization purposes. The long-term stability of PbMoO₄ with respect to extreme changes in both temperature and pressure illustrates the importance of orange molybdate in artwork and protective coatings.     

Microstructure — Electrical properties relationship of YSZ thin films reactively sputter-deposited at different pressures

In order to decrease the operating temperature of Solid Oxide Fuel Cells (SOFC) from about 1000 °C to around 700 °C, the thickness of commonly used electrolytes such as Yttria Stabilised Zirconia (YSZ) must be decreased for about one order of magnitude in the range 1–10 μm. In this paper, we investigate the suitability of reactive magnetron sputtering for deposition of about 1 μm-thick YSZ films dedicated to SOFC. The coatings are synthesised by sputtering a metallic Zr-16 at.%Y target in the presence of a reactive argon-oxygen discharge. The deposition stage is controlled by Optical Transmission Interferometry (OTI) in order to guarantee the film transparency and its thickness. The influence of the deposition pressure on the chemical, structural and morphological properties of the coatings is studied in order to establish relationships with their ionic conductivity, determined by impedance spectroscopy. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Photoluminescence study of native defects in annealed GaAs

Low temperature (6°K) photoluminescence measurements have been performed on GaAs annealed under various conditions, to study defects generated by outdiffusion of the constituent atoms. Several defect-related luminescence peaks have been observed and associated with Ga and As outdiffusion. The outdiffusion of these elements during annealing to 850°C in vacuum and with Ga or As overpressure and SiO₂ coatings is studied by monitoring the intensities of these peaks.     

Influence of the thickness of sputter-deposited platinum films on the electrochemical promotion of propane combustion

8 to 120 nm-thick Pt coatings were sputter-deposited on Yttria-Stabilised Zirconia (YSZ) membranes, 17 mm in diameter, by magnetron sputtering of a Pt target at low pressure (0.3 Pa). The catalytic activity of propane combustion under open-circuit conditions is first measured near to the stoichiometry (0.2%C₃H₈/1%O₂) and shows that the coatings present a rather high catalytic activity. Close-circuit measurements were finally performed at 337 °C and 400 °C. They show that rather high faradaic efficiencies in the range 10⁶ can be reached as soon as the Pt film is thick enough to allow a bias of its whole area. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

Surface oxidation phenomena of boride coatings grown on iron

Single phase and polyphase boride coatings were grown on iron using B₄C-base powder mixures, oxidized for 1 h in gascous oxygen at temperatures up to 850°C and then studied by means of surface Mössbauer measurements, X-ray diffraction analyses and metallographic observations.     

Competitive reactivity of iron towards boron and silicon in surface treatments with powder mixtures

The processes occurring at the surface of iron in contact with fluoride-activated B₄C-base powder mixtures at 850°C were investigated by substituting the diluent SiC with different silicon compounds. The coatings were analyzed by X-ray diffraction, surface Mössbauer spectroscopy and metallographic techniques. The possibility of passing from iron boriding to iron siliciding was shown, and a mechanism proposed for the process.     

High‐Temperature Stable Zirconia Particles Doped with Yttrium,Lanthanum, and Gadolinium

Zirconia microspheres synthesized by a wet‐chemical sol–gel process are promising building blocks for various photonic applications considered for heat management and energy systems, including highly efficient reflective thermal barrier coatings and absorbers/emitters used in thermophotovoltaic systems. As previously shown, pure zirconia microparticles deteriorate at working temperatures of ≥1000 °C. While the addition of yttrium as a dopant has been shown to improve their phase stability, pronounced grain growth at temperatures of ≥1000 °C compromises the photonic structure of the assembled microspheres. Here, a new approach for the fabrication of highly stable ceramic microparticles by doping with lanthanum, gadolinium, and a combination of those with yttrium is introduced. The morphological changes of the particles are monitored by scanning electron microscopy, ex situ X‐ray diffraction (XRD), and in situ high‐energy XRD as a function of dopant concentration up to 1500 °C. While the addition of lanthanum or gadolinium has a strong grain growth attenuating effect, it alone is insufficient to avoid a destructive tetragonal‐to‐monoclinic phase transformation occurring after heating to >850 °C. However, combining lanthanum or gadolinium with yttrium leads to particles with both efficient phase stabilization and attenuated grain growth. Thus, ceramic microspheres are yielded that remain extremely stable after heating to 1200 °C.     

Borosiliciding of Fe–Ni alloys and evaluation of their resistance to abrasive wear

X-ray diffraction analysis, Mössbauer measurements and metallographic observations were performed on borosilicide coatings grown at 850°C on Armco iron and the Fe₆₄Ni₃₆ binary alloy using a KBF₄-activated powder mixture of B₄C and Si₃N₄. The phase composition of the coatings was determined, a result allowing to show that the thermochemical treatment gives rise to iron boriding and iron siliciding reactions of different strength, depending on the treated material. The presence of Ni in the base metal allows iron-free nickel silicides to form as important components of the coating. The resistance of borosilicide coatings to abrasive wear is evaluated and discussed.     

Beobachtungen von Diffusionsprozessen im Schichtensystem Silber-Zinksulfid mit dem Photoemissions-Elektronenmikroskop

By means of the photoemission electron microscope Balzers Metioscope KE 3 the diffusion processes were investigated which occur at elevated temperatures in a system of silver and zincsulfide coatings. At 150 °C the formation of Ag₂S at the surface of the silver film can be seen (high emitting round spots on bright background) and at 240 °C one can observe the diffusion of silver through the zincsulfide film (high emitting small spots on dark background). On heating coagulation process of the silver particles takes place in the boundary zone near the silver layer. With increasing temperatures the mobility of these particles becames high enough to allow them to migrate into the silver layer.     

Dependence of infrared radiation on microstructure of polymer derived ceramic coating on steel

High infrared emissivity ceramic coatings were prepared on 304 steel by pyrolyzing reactions with poly(hydridomethylsiloxane) (PHMS) and Al/Cr₂O₃ based mixing powders. The effects of pyrolysis temperature, testing temperature and surface roughness on infrared radiation of polymer derived ceramic coating were systematically investigated. The results indicated that the coating pyrolyzed at 800 °C exhibited a slightly higher infrared emissivity value than that of the coating pyrolyzed at 600 °C, which was attributed to the enhancing photon emission caused by the complete conversion of Al to Al₂O₃ and PHMS pyrolysis into SiO₂, together with the introduction of Cr₂O₃ based mixing powders. The emissivity value in 3–8 μm waveband of the coating was lower about 0.03 at 600 °C compared with 800 °C testing temperature, while the emissivity value was almost the same in 8–20 μm waveband. The high surface roughness of the coating led to a slightly increasing emissivity due to the enhancing infrared absorbance.     

Composite coatings of polyamide/graphene: microstructure,mechanical, thermal,and barrier properties

This effort reports on novel fluorinated polyamide (FPA) and polyamide 1010 (PA1010)-based blends and graphene reinforced nanocomposite. PA1010/FPA (80:20) blend was opted as matrix material on the basis of molecular weight, thermal, and shear stress performance. Graphene was obtained through in situ chemical method of graphene oxide reduction. PA1010/FPA/Graphene nanocomposites was developed using various graphene loadings (up to 5 wt.%). Thin film coatings were prepared on glass substrate. Consequently, the PA1010/FPA/Graphene attained regular spongy morphological pattern. PA1010/FPA/Graphene 3 also showed improved T₀ and T_max of 534 and 591 °C relative to the neat blend (T₁₀ 423 °C; T_max 551 °C). Limiting oxygen index measurement indicated better non-flammability of PA1010/FPA/Graphene 1–3 nanocomposite series (57–60%) relative to the blend series (28–31%). UL94 tests also showed V-0 rating for nanocomposites. Furthermore, PA1010/FPA/Graphene 3 nanocomposite revealed significantly high tensile strength (62 MPa), flexural modulus (1690 MPa), and adhesive properties to be utilized as coating materials. The nanocomposite coatings also displayed outstanding barrier properties against O₂ and H₂O compared with neat blends.