Hydrophobic properties and color effects of hybrid silica spin-coatings on cellulose matrix

A novel sol–gel derived organic–inorganic hybrid silica sol consisting of organic direct red dye 4BS and inorganic silica (SiO₂) is successfully synthesized by adding coupling agent γ-chloropropyltriethoxysilane (CPTS). Hybrid silica coatings are deposited on cellulose matrix surface via spin-coating approach to introduce effective hydrophobic and color properties. Compared to the dye hybrid silica sol (DHSS), the particle size of CPTS/dye hybrid silica sol (CDHSS) increases from 64.51 to 129.70 nm, while the surface tension reduces from 34.27 × 10⁻³ N m⁻¹ to 31.22 × 10⁻³ N m⁻¹. The hydrostatic pressure of the cellulose matrix coating with CDHSS is 4530.5 Pa, the contact angle is 131.48°, and the wetting time is ~150 min, which attributes to the alkyl chloride aliphatic chain and sharp micro-surface roughness of the hybrid coatings validated directly by AFM and SEM images. The K/S value (5.15) of the cellulose matrix coated with CPTS/dye hybrid silica (CMCCDHS) is 12.44% higher than that of the cellulose matrix coated with dye hybrid silica (CMCDHS), and increased by 30.38% relative to the control coated sample. The maximum absorption wavelengths of the matrixes treated with different processes are the same as the maximum absorption wavelength of the silica sols (510 nm).     

Formation of nanoscale tungsten oxide structures and colouration characteristics

In this work, pH dependent evolution of tungsten oxide (WO₃) nanostructures is being reported along with physical characteristics. The synthesis was carried out via an inexpensive solvothermal cum chemical reduction route, with sodium tungstate (Na₂WO₄) and cetyl trimethyl ammonium bromide (C₁₉H₄₂NBr) as main reactants. The X-ray diffraction, together with transmission electron microscopic studies have revealed formation of regular polyhedral nanocrystalline structures and fractals as one goes from higher pH (= 5·5) to lower pH (= 2) values. The average crystallite size, as calculated through Williamson–Hall plots, was varied within 2·8–6·8 nm for different pH samples. Fourier transform infrared spectroscopy reveals in-plane bending vibration δ (W–OH), observable at ∼1630 cm^− 1 and strong stretching ν (W–O–W) located at ∼814 cm^− 1. Raman spectroscopy has divulged WO₃ Raman active optical phonon modes positioned at ∼717 and 805 cm^− 1. The thermochromic and photochromic properties of the nanoscale WO₃ sample prepared at pH = 5·5, are also highlighted.     

Corrosion behavior in SBF for titania coatings on Mg–Ca alloy

TiO₂ coating was obtained by sol–gel method to improve the corrosion resistance of Mg–Ca alloy in human body environment. The corrosion behavior of Mg–1.0 Ca alloy with TiO₂ coating was investigated by electrochemical tests and immersion tests in simulated body fluid (SBF). Bare Mg–1.0 Ca alloy suffered serious attack after immersed in simulated body fluid only for 48 h. While for the Mg–1.0 Ca alloy with TiO₂ coating, the surface almost maintained intact with only several collapses after immersed in SBF for 168 h. The electrochemical test results showed that the free corrosion current (i _corr) of Mg–1.0 Ca alloy substrate was 3.3275e−2A/cm², while the i _corr of TiO₂ coating was only 1.58549e−5A/cm². Therefore, TiO₂ coating significantly improved the corrosion resistance of Mg–1.0 Ca alloy in SBF. This enhances the potential of Mg–Ca alloy used as biodegradable orthopedic material.     

Amorphous Li–B–W–O solid-state electrolyte thin film for a solid-state ionic power sources

Li–B–W–O thin film serving as a solid-state electrolyte layer for a solid-state thin film battery has been deposited on a stainless steel (SUS)/Si substrate by thermal evaporation deposition at room temperature. By energy dispersive X-ray spectroscopy and inductively coupled plasma-atomic emission spectrometer measurements, the as-grown thin film showed a stoichiometry of Li_2.99BW_1.8O₉. The as-grown Li–B–W–O solid-state electrolyte thin film possessed an amorphous structure as confirmed by X-ray diffraction. Field emission scanning electron microscopy measurements of the film cross section showed a dense structure that did not have any large defects such as cracks or voids. For a cell structure of SUS/Li–B–W–O/SUS/Si, an impedance measurement conducted at room temperature revealed an ionic conductivity of 2.15 × 10⁻⁷ S cm⁻¹ with activation energy of 0.52 eV, which suggests that Li–B–W–O thin film can possibly be used as an electrolyte in solid-state thin film batteries.     

Crystal structure and negative thermal expansion of solid solution Y<Subscript>2</Subscript>W<Subscript>3−<Emphasis Type="Italic">x</Emphasis></Subscript>Mo<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>12</Subscript>

A new series of solid solutions Y₂W_3−x Mo _x O₁₂ (0.5 ≤ x ≤ 2.5) were successfully synthesized by the solid state method. Their crystal structure and negative thermal expansion properties were studied using high-temperature X-ray powder diffraction and the Rietveld method. All samples of rare earth tungstates and molybdates were found to crystallize in the same orthorhombic structure with space group Pnca, and show the negative thermal expansion phenomena related to transverse vibration of bridging oxygen atoms in the structure. Thermal expansion coefficients (TEC) of Y₂W_3−x Mo _x O₁₂ were determined as −16.2 × 10⁻⁶ K⁻¹ for x = 0.5 and −16.5 × 10⁻⁶ K⁻¹ for x = 2.5 in the identical temperature range of 200–800 °C. High-temperature XRD data and bond length analysis suggest that the difference between W–O and Mo–O bond is responsible for the change of TECs after the element substitution in this series of solid solutions.     

Photoresponse of n -ZnO/ p -Si heterojunction towards ultraviolet/visible lights: thickness dependent behavior

A series of n-ZnO/p-Si thin film heterojunctions have been fabricated by a low cost sol–gel technique for different ZnO film thicknesses and the dark as well as photo current–voltage (I–V) characteristics have been investigated in details. The heterojunction with ZnO thickness of 0.46 μm shows the best diode characteristics in terms of rectification ratio, I _F/I _R = 5.7 × 10³ at 5 V and reverse leakage current density, J _R = 7.6 × 10⁻⁵ A cm⁻² at −5 V. From the photo I–V curves and wavelength dependent photocurrent of the heterojunctions, it is found that the junction with 0.46 μm ZnO thickness shows the highest sensitivity towards both UV and visible lights.     

Structure and electrochemical hydrogen storage properties of Pd/Mg<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Al<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>/Pd thin films prepared by pulsed laser deposition

Three-layered Pd/Mg_1−x Al _x /Pd (x = 0, 0.13, 0.21, 0.39) thin films were prepared by means of pulsed laser deposition. In the present Al concentration range, X-ray diffraction analyses showed that the Mg_1−x Al _x layer was constituted of a single phase Mg(Al) solid solution. The Mg(Al) grains are preferentially orientated along the c-axis and their size decreased (from 18.5 to 10.5 nm) as the Al content increased. Scanning electron microscopy and atomic force microscopy observations indicated that all the films exhibited a globular surface structure. However, the surface roughness of the films decreased as the Al concentration increased. Rutherford backscattering spectroscopy revealed that the Mg–Al layer density (porosity) was strongly dependent on the Al content. Successive hydriding charge/discharge cycles were performed on the different Pd/Mg_1−x Al_x/Pd films in alkaline media. The highest discharge capacity was obtained with the Pd/Mg_0.79Al_0.21/Pd film, namely ~85 μAh cm⁻² μm⁻¹ or 320 mAh g⁻¹, which corresponds to a H/M atomic ratio of ~0.48 in the Mg–Al layer.     

Preparation and thermoelectric properties of BP films on SOI and sapphire substrates

The chemical vapor deposited (CVD) BP films on Si(100) (190 nm)/SiO _x (370 nm)/Si(100) (625 μm) (SOI) and sapphire (R-plane) (600 μm) substrates were prepared by the thermal decomposition of the B₂H₆–PH₃–H₂ system in the temperature range of 800–1050 °C for the deposition time of 1.5 h. The BP films were epitaxially grown on the SOI substrate, but a two-step growth method, i.e., a buffer layer at lower temperature and sequent CVD process at 1000 °C for 1.5 h was effective for obtaining a smooth film on the sapphire substrate. The electrical conduction types and electrical properties of these films depended on the growth temperature, gases flow rates and substrates. The thermal conductivity of the film could be replaced by the substrate, so that the calculated thermoelectric figure-of-merit (Z) for the BP films on the SOI substrate was 10⁻⁴–10⁻³/K at 700–1000 K. Those on the sapphire substrate were 10⁻⁶–10⁻⁵/K for the direct growth and 10⁻⁵–10⁻⁴/K for the two-step growth at 700–900 K, indicating that the film on a sapphire by two-step growth would reduce the defect concentrations and promote the electrical conductivity.     

Hydrothermal synthesis of ultra-thin LiFePO<Subscript>4</Subscript> platelets for Li-ion batteries

Ultra-thin LiFePO₄ platelets are prepared by a hydrothermal process using tetraethylene glycol as co-solvent. The prepared LiFePO₄ platelets have a very thin thickness of about 50–80 nm, which is beneficial for Li ions to fast transfer in the bulk of the electrode. It is found that the as-synthesized LiFePO₄ cathode material exhibits a quite high reversible capacity of 137 mAh g⁻¹ at 0.2 C. After carbon coating, the obtained LiFePO₄/C composite cathode has the enhanced electronic conductivity, and thus the rate capability has been improved significantly. At 8 and 12 C, the composite has the discharge capacity of 104 and 95 mAh g⁻¹, respectively, which suggests that the ultra-thin LiFePO₄ platelets are a promising candidate for the large-scale Li-ion batteries.     

Nonlinear optical characterization and measurement of optical limiting threshold of CdSe quantum dots prepared by a microemulsion technique

CdSe quantum dots prepared by micro emulsion technique shows quantum confinement effect and broad emission at 532 nm. These quantum dots have about 4.35 nm size, and they exhibit good nonlinear effects which are measured using z-scan technique. The samples have a reverse saturation in the nonlinear absorption as nonlinear optical absorption coefficient β is 2.545 × 10⁻¹⁰ W m⁻¹ and nonlinear optical refraction coefficient n ₂ is −1.77 × 10⁻¹⁰ esu. The third-order nonlinear optical susceptibility is found to be 4.646 × 10⁻¹¹ esu and also the figure of merit is 2.01 × 10⁻¹² esu m. The optical limiting threshold which is found to be 0.346 GW/cm² makes it a good candidate for device fabrication.     

Corrosion resistance evaluation of a Ca- and P-based bioceramic thin coating in Ti-6Al-4V

The objective of this study was to physico/chemically characterize and determine the corrosion resistance of a Calcium–Phosphate (Ca–P) based bioceramic thin coating processed by a sputtering process on titanium alloy (Ti-6Al-4V). The samples utilized in this study were uncoated and coated disks of 10 mm diameter by 3 mm thickness. The coating was characterized by SEM, XPS + ion beam milling (IBM), thin-film mode XRD, and atomic force microscope (AFM) (n = 3). Coated and uncoated Ti-6Al-4V disk surfaces were tested in Phosphate Buffered Saline (PBS) at 25°C through an area of 0.79 cm². A three-electrode cell set-up was used with a saturated calomel electrode (SCE) and a platinum wire as reference and counter electrodes. After 3, 17, and 25 days of immersion, electrochemical impedance spectroscopy (EIS) experiments were performed (n = 3). The EIS tests were carried out in potentiostatic mode at the open circuit potential (OCP). The frequency range considered was from 100 kHz to 10 mHz, using 10 mV root mean square as the amplitude of the perturbation signal. A potentiodynamic polarization scan using a frequency response analyzer potentiostat, was acquired following 3 days of immersion in PBS. The potentiodynamic polarization scans (n = 3) were carried out with a scan rate of 1 mV/s ranging from −0.8V(SCE) to 3.0V(SCE). Results: The physico/chemical characterization showed an amorphous Ca- and P-based coating of ~400–700 nm thickness with Ca–P nanometer size particles embedded in a Ca–P matrix. The Bode phase angle diagrams showed highly capacitive results at low and medium frequencies for both surfaces tested. The polarization curves showed low current densities at the corrosion potential (E _corr), in the order of 10⁻⁸A/cm², typical of passive materials with protective surface films. Coated sample current densities were comparable to the uncoated samples. Conclusion: Coated and uncoated samples were stable in the test solution with a protective film maintained throughout the 25 day immersion test period.     

Interfacial interaction of solid cobalt with liquid Pb-free Sn–Bi–In–Zn–Sb soldering alloys

Dissolution kinetics of cobalt in liquid 87.5%Sn–7.5%Bi–3%In–1%Zn–1%Sb and 80%Sn–15%Bi–3%In–1%Zn–1%Sb soldering alloys and phase formation at the cobalt–solder interface have been investigated in the temperature range of 250–450 °C. The temperature dependence of the cobalt solubility in soldering alloys was found to obey a relation of the Arrhenius type c _s = 4.06 × 10² exp (−46300/RT) mass% for the former alloy and c _s = 5.46 × 10² exp (−49200/RT) mass% for the latter, where R is in J mol⁻¹ K⁻¹ and T in K. For tin, the appropriate equation is c _s = 4.08 × 10² exp (−45200/RT) mass%. The dissolution rate constants are rather close for these soldering alloys and vary in the range (1–9) × 10⁻⁵ m s⁻¹ at disc rotational speeds of 6.45–82.4 rad s⁻¹. For both alloys, the CoSn₃ intermetallic layer is formed at the interface of cobalt and the saturated or undersaturated solder melt at 250 °C and dipping times up to 1800 s, whereas the CoSn₂ intermetallic layer occurs at higher temperatures of 300–450 °C. Formation of an additional intermetallic layer (around 1.5 μm thick) of the CoSn compound was only observed at 450 °C and a dipping time of 1800 s. A simple mathematical equation is proposed to evaluate the intermetallic-layer thickness in the case of undersaturated melts. The tensile strength of the cobalt-to-solder joints is 95–107 MPa, with the relative elongation being 2.0–2.6%.     

Fabrication and characterization of bioactive composite coatings on Mg–Zn–Ca alloy by MAO/sol–gel

High corrosion rate and accumulation of hydrogen gas upon degradation impede magnesium alloys’ clinical application as implants. In this work, micro-arc oxidation (MAO) was used to fabricate a porous coating on magnesium alloys as an intermediate layer to enhance the bonding strength of propolis layer. Then the composite coatings were fabricated using sol–gel method by dipping sample into the solution containing propolis and polylactic acid at 40°C. The corrosion resistance of the samples was determined based on potentiodynamic polarization experiments and immersion tests. Biocompatibility was designed by observing the attachment and growth of wharton’s jelly-derived mesenchymal stem cells (WJCs) on substrates with MAO coating and substrates with composite coatings. The results showed that, compared with that of Mg–Zn–Ca alloy, the corrosion current density of the samples with composite coatings decreased from 5.37 × 10⁻⁵ to 1.10 × 10⁻⁶ A/cm² and the corrosion potential increased by 240 mV. Composite coatings exhibit homogeneous corrosion behavior and can promote WJCs cell adhesion and proliferation. In the meantime, pH value was relatively stable during the immersion tests, which may be significant for cellular survival. In conclusion, our results indicate that composite coatings on Mg–Zn–Ca alloy fabricated by MAO/sol–gel method provide a new type bioactive material.     

Magnetoelectric performance of cylindrical Ni–lead zirconate titanate–Ni laminated composite synthesized by electroless deposition

The cylindrical Ni–lead zirconate titanate (PZT)–Ni laminated composites with various magnetostrictive–piezoelectric phase thickness ratios were synthesized by electroless deposition. The influences of the bias magnetic field (H _dc) and the ac magnetic field frequency (f) on magnetoelectric (ME) effect are discussed. It is seen that the ME voltage coefficient depends strongly on H _dc and f. The ME voltage coefficient and electromechanical resonance frequency increase as the magnetostrictive–piezoelectric phase thickness ratio increases. The calculated resonant frequency increases with the magnetostrictive–piezoelectric phase thickness ratio, which agrees well with the experimental results. The maximum ME voltage coefficient of the cylindrical Ni–PZT–Ni laminated composite is 3.256 V cm⁻¹ Oe⁻¹, which is much higher than that of the plate laminated composite with the same magnetostrictive–piezoelectric phase thickness ratio. Electroless deposition is an efficient method to prepare ME laminated composites with complex structures. Proper resonant frequency and stronger ME effect can be obtained by optimizing the structure.     

Photoluminescence and thermal stability of yellow-emitting Sr-α-SiAlON:Eu<Superscript>2+</Superscript> phosphor

Novel α-SiAlON:Eu²⁺-based yellow oxynitride phosphors with the formula Sr_0.375−x Eu _x ²⁺Si_12−m−n Al _m+n O _n N_16−n (m = 0.75, n = x = 0.004–0.04) have been prepared by firing the powder mixture of SrSi₂, α-Si₃N₄, AlN, and Eu₂O₃ at 2,000 °C for 2 h under 1 MPa nitrogen atmosphere. The luminescence properties, the dependence of the activator concentration of Eu²⁺ and the thermal stability of Sr-α-SiAlON:Eu²⁺ phosphor have been investigated in comparison with Ca-α-SiAlON:Eu²⁺ phosphor. Similar to Ca-α-SiAlON:Eu²⁺ phosphor, Sr-α-SiAlON:Eu²⁺ phosphor has the excitation wavelength ranging from the ultraviolet region to 500 nm, and exhibit intense yellow light. The strongest luminescence was achieved at about x = 0.02 with the emission peak at 578 nm, slightly shorter than that of Ca-α-SiAlON:Eu²⁺ phosphor at 581 nm. Temperature-dependent emission intensity of Sr-α-SiAlON:Eu²⁺ phosphor is comparable to that of Ca-α-SiAlON:Eu²⁺ phosphor. The results suggest that the different position of the emission peak for Sr- and Ca-α-SiAlON:Eu²⁺ depends on the composition and the Stokes shift, and the thermal stability is nearly independent of Sr and Ca or fixed by the network of (Si, Al)–(O, N) in α-SiAlON at the same Eu²⁺ concentration.     

Copper coating on coir fibres

Conditions for obtaining continuous coatings of copper (thickness range 1.5 to 5μm) on coir fibres have been reported. Activation of the surface of coir fibres was achieved by treating the surface of the fibres with NaOH-HCHO/ammoniacal AgNO₃ solution. Copper was deposited on the activated surface of coir fibres from Fehling-formaldehyde solution. The effects of variation in formaldehyde and sodium hydroxide concentrations and pressures inside the coating vessel on deposition rates were determined. The minimum concentrations of NaOH and HCHO required for maintaining a maximum rate of deposition of copper from a solution contaning 10g l⁻¹ copper sulphate were found to be 6.6 g l⁻¹ and 2.5 to 3.5 g l⁻¹, respectively. Optical and scanning electron microscope studies show that relatively more uniform and non-porous copper coatings were obtained when deposition was carried out under reduced pressures. A 5μm thick copper coating on coir fibre prevents the propagation of flame as was shown by flammability tests. Copper coating on coir fibre decreases its electrical resistivity from 2.55×10⁶Ωcm to 4.68×10⁻³Ωcm with 1.5μm thick coating and 3.76×10⁻⁵Ωcm with 5μm thick coating. Reinforcement of polyester with copper-coated coir fibre leads to an increase of about 25% in tensile strength and flexural strength as compared to polyester reinforced with plain coir fibre.     

Photoelectrochemical properties of brush plated Cd x Zn1−x Se films

Cd _x Zn_1−x Se films(0 ≤ x ≤ 1) were deposited for the first time by the brushplating technique at room temperature from an aqueous bath containing zincsulphate, cadmium sulphate and selenium oxide. The deposition current densitywas varied in the range of 50–250 mA cm⁻². The as deposited films exhibitedcubic structure. Composition of the films was estimated by EDAX studies. XPSstudies indicated the binding energies corresponding to Zn(2p_3/2), Cd(3d_5/2 and 3d_3/2) and Se(3d_5/2 and 3d_3/2). Optical band gap of the films varied from 1.72 to 2.70 eV as the composition varied from CdSe to ZnSe side. Atomic forcestudies indicated grain size in the range of 20–150 nm. Photoelectrochemical cells were made with polysulphide as the redox electrolyte. The output was maximum for the photoelectrodes of composition Cd_0.9Zn_0.1Se.     

Comparative microscopic and spectroscopic analysis of temperature-dependent growth of WO3 and W0.95Ti0.05O3 thin films

We present a comparative microscopic and spectroscopic study of the morphology and composition of WO₃ and W_0.95Ti_0.05O₃ thin films, grown by radio-frequency magnetron reactive sputtering at substrate temperatures varied from room temperature to 500 °C, using atomic force microscopy (AFM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). With increasing growth temperature, the AFM results show increase in the average crystallite size and in the surface roughness for both undoped and doped samples. The AFM data, along with the Raman results, clearly indicate that for the given set of experimental conditions, higher growth temperatures are required to obtain crystalline Ti-doped WO₃ films than for WO₃ films. Also, the Raman results suggest a potential phase transformation from a monoclinic WO₃ structure to an orthorhombic, but more probably a tetragonal, configuration in the W_0.95Ti_0.05O₃ thin films. This remark is based on the observed shifting, with Ti doping, to lower frequencies of the Raman peaks corresponding to W–O–W stretching modes of WO₃ at 806 and 711 cm⁻¹ to 793 and 690 cm⁻¹, respectively. XPS data indicate that the doped material has a reduced WO_3−x stoichiometry at the surface, with the presence of W⁶⁺ and W⁵⁺ oxidation states; this observation could also be related to the existence of a different structural phase of this material, corroborating with the Raman measurements.     

Nanotechnology-associated coatings for aircrafts

Polymeric epoxy-based composites are modified with nanopowders of silicon oxide (∼ 100 nm). By the method of spraying, these composites are applied to specimens of 2024-T3 aluminum alloy preliminary treated with molybdate solutions to get conversion layers. Three types of polymeric coatings are considered: reference, treated by silica, and with additional polyurethane coatings. The aim of modification of polymeric coatings is to absorb and/or block unwanted ions/molecules (Cl⁻, O₂, OH⁻, H₂O, etc.) and improve the protective properties of the films. The tests carried out by the method of electrochemical impedance spectroscopy, in a salt-fog chamber, and by immersion in a 0.5 M NaCl solution reveal high anticorrosion characteristics of the coating. New coatings are promising for the corrosion protection in the aircraft industry. Published in Fizyko-Khimichna Mekhanika Materialiv, Vol. 43, No. 3, pp. 103–108, May–June, 2007.     

Synthesis and microwave absorption studies of ferrite paint

A new hexaferrite composition, BaCo _x Si _x+y Fe_12−2x−y O₁₉ (x=0·90;y=0·05), in fine (∼μ size) powder form, is prepared. Ferrite paint formulations are made by dispersing this powder in different weight proportions in an epoxy resin. X-band (8–12 GHz) microwave absorption behaviour of the paint coatings of different thicknesses is studied. Remarkably high value, ≥10 dB, of signal absorption at 9·5 GHz is observed for a coating thickness of 0·60 mm with a ferrite fill factor of 57 wt%. Most of this work, in a poster form, was presented at the 8th AGM of MRSI, BARC, Mumbai, February 10–12, 1997. The paper was adjudged the best for poster paper award