Fabrication and evaluation of physical properties and cytotoxicity of zein-based polyurethanes

Polyurethane prepolymer (PUP) was first synthesized from polycaprolactone diol and isophorone diisocyanate; and then a series of zein-based polyurethane (ZEPU) sheets was fabricated from PUP and zein (ZE) using a hot press and moulding process without addition of other additives. Effects of ZE content (W_ZE) on the structure and properties of the resultant ZEPU sheets were investigated by Fourier transform infrared spectroscopy, scanning electron microscopy, dynamic mechanical analysis, tensile testing, and dissolubility testing in alcohol. The results indicated that cross-linking and grafting reactions occurred between ZE and PUP to form new polyurethane showing a higher thermal stability, flexibility, and alcohol-resistance than the neat ZE sheets. For example, the elongation at break of ZEPU with 50 % W_ZE was 211.2 %, which was 47 times higher than that of neat ZE sheet. ZE molecules acted as both cross-linkers and polymer fillers in ZEPU sheets. The cytotoxicity and cytocompatibility of ZEPU sheets were evaluated by cell culture in vitro. The ZEPU sheets showed non- or low-cytotoxicity, and L929 cells grew and expanded well on the surfaces of the sheets with W_ZE over 50 %. Undoubtedly, the fabrication of ZE-based polyurethanes without toxic additives such as catalysts, cross-linkers and chain extenders improved the physical properties and cytocompatibility of zein, thus widening the possible range of applications for zein-based biomaterials.     

Fabrication and ferroelectric properties of sol–gel derived 1–1 intergrowth-superlattice-structured Bi<Subscript>3</Subscript>TiNbO<Subscript>9</Subscript>-Bi<Subscript>4</Subscript>Ti<Subscript>3</Subscript>O<Subscript>12</Subscript> thin films

1–1 intergrowth-superlattice-structured Bi₃TiNbO₉–Bi₄Ti₃O₁₂ (BTN–BIT) ferroelectric thin films have been prepared on p-Si substrates by sol-gel processing. The precursor films are crystallized in the desired intergrown BTN–BIT superlattice structures by optimizing the processing conditions. Synthesized BTN–BIT thin films annealed below 750 °C are polycrystalline, uniform and crack-free, no pyrochlore phase or other second phase, and exhibited good ferroelectric properties. As the annealing temperature increases from 600 to 700 °C, both remanent polarization P _r and coercive electric field E _c of BTN–BIT thin films increase, but the pyrochlore phase in BTN–BIT films annealed above 750 °C will impair the ferroelectric properties. The BTN–BIT thin films annealed at 700 °C have a P _r value ~19.1μC/cm² and an E _c value ~135 kV/cm.     

Mercury volatilization by the most mercury-resistant bacteria from the seawater of Minamata Bay in various physiological conditions

 The volatilization of mercuric chloride (HgCl₂) and methyl mercuric chloride (CH₃HgCl) by the 45 strains (35 Pseudoalteromonas sp., 2 Vibrio sp., 1 Aeromonas sp., and 7 unclassified) of the most mercury-resistant bacteria from Minamata Bay seawater was examined in various physiological conditions. The bacteria could grow and volatilize HgCl₂ in the liquid medium containing 1–10% NaCl. Two Pseudoalteromonas strains could grow and volatilize HgCl₂ at pH levels ranging from 5.0 to 10.0. The resting cells of 43 strains could volatilize HgCl₂ at concentrations ranging from 30 to 68% after 1-h incubation at 30  °C. The resting cells of 41 strains could volatilize CH₃HgCl at concentrations ranging from 13 to 88% after 1-h incubation at 30  °C. Ninety-two percent of mercury was removed from the phosphate buffer containing 0.1 μg/ml by a resting cell of Pseudoalteromonas strain H-4 after 30-min incubation at 30  °C. We were able to screen the special bacteria, which could volatilize mercury compounds at a high rate in various physiological conditions, for the purpose of developing mercury removal methods using bacteria. Received: 26 April 2000 / Accepted: 16 June 2000     

Optical properties and chemical reactivity of hydrogenated amorphous boron thin films

Hydrogenated boron thin films have been deposited at temperatures in the range 50–100 °C with the radiofrequency plasma decomposition of diborane B₂H₆ diluted in hydrogen. The chemical composition of the films has been determined by elastic recoil detection and by the Castaing microprobe techniques. We have found that the as-deposited films contain 10–20 at % H and that they react with the ambient atmosphere within a few days and reach a final composition close to B_0.64H_0.12O_0.12C_0.06N_0.06. The optical properties of the as-deposited films studied by spectroscopic phase-modulated ellipsometry in the range 1.7–5.0 eV are characteristic of the high optical gap semiconductors. The electron diffraction measurements performed onin situ annealed samples show that the films are amorphous up to 950 °C. Infrared spectroscopy investigations performed on the as-deposited films have revealed two hydrogen bonding sites: B-H terminal bonds and B-H-B bridge bonds, along with some B-O-B groups. Upon exposure to the atmosphere, the vanishing of B-H-B and B-O-B bridge bonds and the increase of B-H and B-O-H absorption bands after 1 day, are observed. On leave from Physics Department, CNEA, Avenida Libertador 8250, 1429 Buenos-Aires, Argentina, and CONICET.     

Synthesis and nonlinear optical properties of novel Y-type polyurethanes with high thermal stability of dipole alignment

2,3-Di-(2′-hydroxyethoxy)benzylidenemalononitrile (3) was prepared and condensed with 2,4-toluenediisocyanate and 3,3′-dimethoxy-4,4′-biphenylenediisocyanate to yield novel Y-type polyurethanes 4–5 containing 2,3-dioxy benzylidenemalononitrile group as a nonlinear optical (NLO)-chromophore, which constituted parts of the polymer backbones. Polyurethanes 4–5 were soluble in common organic solvents such as acetone and N,N-dimethylformamide. They showed a thermal stability up to 270 °C in thermogravimetric analysis thermograms and the glass-transition temperatures (T _g) obtained from differential scanning calorimetry thermograms were around 116–135 °C. The second harmonic generation (SHG) coefficients (d ₃₃) of poled polymer films at 106.4 mm⁻¹ fundamental wavelength were around 9.07 × 10⁻¹⁹ C (2.72 × 10⁻⁹ esu). The dipole alignment exhibited high thermal stability up to 10 °C higher than T _g, and there was no SHG decay below 145 °C due to the partial main-chain character of the polymer structure, which was acceptable for nonlinear optical device applications.     

Pb5Ge3O11 ferroelectric films prepared by a modified sol—gel method

Single-crystal Pb₅Ge₃O₁₁ films 5–105 μm thick, adhering well to platinum substrates, were prepared by pyrolysis of metalorganic precursors in combination with in situ sol-gel processing. The best films consisted of densely packed crystallites ranging in size from 200 to 300 μm, with hexagonal habits. A welldefined ferroelectric transition was revealed at 170–180°C. The typical parameters of the films are ɛ₂₀ = 30–40, tan δ ≃0.02, ɛ_max ≃200, P_s = 3.2 μC/cm²,E _c = 16 kV/cm, and ρ = 10⁸-10⁹ Ω cm, in agreement (except for ɛ_max) with those of lead germanate crystals     

Nanosecond electric explosion of thin aluminum films

Pulsed electrodynamic breakage of thin (∼20-nm-thick) aluminum films deposited onto polymer substrates have been experimentally studied. The character of film fracture depends on the level of supplied electric energy W. For 3.5 kJ/g < W < 4.3 kJ/g, discontinuities (striations) are formed in the transverse direction relative to the applied electric field. At high current densities on a level of ∼(1–3) × 10¹² A/m² and explosion times within 50–300 ns, the integral of action to explosion varies within (0.79–1.08) × 10¹⁷ A s/m² depending on the rate of energy supply and differs from published data for relatively massive conductors.     

Possibility of fabricating an inductive high-speed detector for electromagnetic radiation using thin YBa2Cu3O7−δ films

It is shown that an inductive high-speed nonequilibrium detector for electromagnetic radiation can be fabricated using thin YBaCuO films. An electronic detection regime has been obtained for the first time using a low-temperature inductive YBaCuO detector in the measuring frequency band Δf=1–50 MHz and it has been shown that no bolometric detection regime exists at operating temperatures far below the superconducting transition. The time constant of the low-temperature inductive YBaCuO detector in the electronic regime is determined only by the electron-phonon interaction time in the nodal regions τ _e-ph ^d . The detector has the following limiting characteristics: when the operating temperature is reduced from 10 to 1K, the time constant τ _D varies between 10 and 100 ps and the sensitivity D* improves substantially from 10⁹ to 4×10¹² W⁻¹ cm Hz^1/2. Pis’ma Zh. Tekh. Fiz. 25, 14–19 (January 26, 1999)     

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.     

Synthesis, elaboration and characterization of the new material CuIn3S5 thin films

CuIn₃S₅ compound was prepared by direct reaction of high-purity elemental copper, indium and sulphur. CuIn₃S₅ thin films were prepared from powder by thermal evaporation under vacuum (10⁻⁶ mbar) onto glass substrates. The glass substrates were heated from 30 to 200 °C. The powder was characterized for their structural and compositional properties by using X-ray diffraction (XRD) and energy dispersive X-ray (EDAX). The XRD studies revealed that the powder exhibiting P-chalcopyrite structure. From the XRD data, we calculated the lattice parameters a and c. Then, the cation–anion bond lengths l _AC and l _BC are deduced. The films were characterized for their structural, compositional, morphological and optical properties by using XRD, EDAX, atomic force microscopy and optical measurement techniques (transmittance and reflectance). XRD analysis revealed that the films deposited at a room temperature (30 °C) are amorphous in nature, whereas those deposited on heated substrates (≥75 °C) were polycrystalline with a preferred orientation along (112) of the chalcopyrite phase. The surface morphological analysis revealed that the films grown at different substrate temperature had an average roughness between 1.1 and 4.8 nm. From the analysis of the transmission and reflection data, the values of direct and indirect band gap of the films were determined. We found that the optical band gap decreases when the substrate temperature increases.     

The effect of repeated annealing temperature on the structural,optical, and electrical properties of TiO<Subscript>2</Subscript> thin films prepared by dip-coating sol–gel method

In this study, we have studied the effect of repeated annealing temperatures on TiO₂ thin films prepared by dip-coating sol–gel method onto the glasses and silicon substrates. The TiO₂ thin films coated samples were repeatedly annealed in the air at temperatures 100, 200, and 300 °C for 5 min period. The dipping processes were repeated 5 to 10 times in order to increase the thickness of the films and then the TiO₂ thin films were annealed at a fixed temperature of 500 °C for 1 h period. The effect of repeated annealing temperature on the TiO₂ thin films prepared on glass substrate were investigated by means of UV–VIS spectroscopy, X-ray diffraction (XRD), and atomic force microscopy (AFM). It was observed that the thickness, average crystallite size, and average grain size of TiO₂ samples decreased with increasing pre-heating temperature. On the other hand, thickness, average crystallite size, and average grain size of TiO₂ films were increased with increasing number of the layer. Al/TiO₂/p-Si metal–insulator–semiconductor (MIS) structures were obtained from the films prepared on p-type single silicon wafer substrate. Capacitance–voltage (C–V) and conductance–voltage (G/ω–V) measurements of the prepared MIS structures were conducted at room temperature. Series resistance (R _s) and oxide capacitance (C _ox) of each structures were determined by means of the C–V curves.     

Studies on thick films of photoconducting cadmium sulphide

Highly photosensitive films of CdS have been prepared using the thick film technique. The films obtained from the composition containing CdS-100, CdCl₂−10 and CuCl₂−0·05 parts by weight (reacted at 500° C) are found to give the best photosensitivity on firing at 600° C. The ratio of light to dark current ∼10⁸–10⁹ which is considerably higher than what is reported for thin films, single crystals and sintered layers. A strong chemisorption of oxygen is found to be responsible for high photosensitivity. The spectral response for doped CdS film is similar to that obtained for thin films, single crystals and sintered layers and also shows a red shift with increasing Cu concentration. However, the undoped CdS has a broad spectral response at room temperature ranging fromλ=550 to 690 nm; unlike the thin films and single crystals which give a sharp peak atλ=510 to 520 nm. A probable explanation has been suggested for this type of behaviour. NCL Communication No. 2502.     

Preparation of titanium-dioxide films by heating titanium/silicon-dioxide structures on silicon in oxygen

 When titanium/silicon-dioxide (Ti/SiO₂) structures prepared by depositing titanium (Ti) on thermally oxidized silicon in vacuum were heated to temperatures of 800–1000°C in flowing oxygen gas, silicon surfaces were covered with a mixture films containing preferentially (110)-oriented Ti0₂ instead of the SiO₂ films. The thickness of the mixture films could be determined by that of the deposited Ti films. Titanium silicide grew only in the region near between the grown mixture film and the silicon substrate. The dielectric constants of the grown mixture films increased exponentially with increasing oxidation temperature and increased slowly with increasing the Ti film thickness, while the breakdown field strength increased slowly with increasing oxidation temperature and increased exponentially with increasing the Ti film thickness. The oxide films prepared at 1000°C had dielectric constants of (15–25)ɛ_o resistivities of 10¹⁰–10¹¹ Ω cm, and breakdown field strengths of about 10⁶ V/cm. Received: 10 February 1998 / Accepted: 10 March 1998     

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.     

Spectroscopic characterization of tungstated zirconia prepared by equilibrium adsorption from hydrogen peroxide solutions of tungsten(VI) precursors

Two series of WO _x /ZrO₂ samples are prepared by equilibrium adsorption from H₂O₂ solutions at pH 1.8 containing two different precursor anions, [W₂O₃(O₂)₄(H₂O)₂]²⁻ and [H₂W₁₂O₄₀]⁶⁻. The starting material is amorphous zirconium oxyhydroxide. The maximum W densities obtained are larger than that reported in the literature for systems synthesized by the same method using aqueous non-peroxide solutions. In the case of the metatungstate precursor, this increase is attributed to the generation of additional anchoring sites by interaction between the amorphous support and H₂O₂. The high uptake achieved when the peroxo complex is used as a precursor is a result of both the ZrO _x (OH)_4-2x –H₂O₂ interaction and low nuclearity of the adsorbing anion. The materials are characterized by XRD, DR–UV–vis, Micro-Raman and FT-IR spectroscopy. The surface acidities of samples with identical W loading prepared by equilibrium adsorption from the [H₂W₁₂O₄₀]⁶⁻–H₂O₂ system and by impregnation with aqueous solution of ammonium metatungstate are investigated by FT-IR spectroscopy of CO adsorbed at 80 K.     

Enhancement of the generating power in Cu/Bi–Te/Cu composite thermoelectric devices

The voltage ΔV and electric current ΔI of the p- and n-type Cu/Bi–Te/Cu composite thermoelectric devices were measured as a function of ΔT for four regions of the intrinsic Bi–Te compound, Cu/Bi–Te and Bi–Te/Cu interfaces and Cu/Bi–Te/Cu composite using thermocouples set at intervals of s = 2 and 6 mm, where the lengths of Bi–Te compound and copper are 4 and 5 mm, respectively. ΔV and ΔI of all regions tended to increase linearly with an increase of ΔT. The resultant α was obtained from the relation ΔV/ΔT. The resultant α values of regions including the interface are much higher in absolute value than those of the intrinsic Bi–Te compounds, so that the barrier thermo-emf is found to occur in the forward-bias direction. It indicates that the barrier thermo-emf appears even in the semiconductor-metal junction, as in the case of the p–n junctions. The resultant α of Cu(T _H)/Bi–Te interface rich in the heat flow increases with an increase of ΔT, while that of Bi–Te/Cu(T _C ) interface poor in the heat flow decreases with an increase of ΔT. The ΔT-dependence of α of the interfaces is entirely opposite at the hot and cold sides. As a result, the resultant α of the p- and n-type Cu/Bi–Te/Cu composites remained little varied with changes of ΔT, so that the present composites have a thermal stability superior to the intrinsic Bi–Te compounds.The generating powers ΔW _Bi-Te and ΔW _Cu/Bi-Te/Cu for the p- and n-type intrinsic Bi–Te compounds and Cu/Bi–Te/Cu composites increased parabolalically with an increase of ΔT, and the ratios of ΔW _{Cu/Bi–Te/Cu} to ΔW _Bi–Te reached great values of 1.41 and 1.45 for the p- and n-type composites, respectively. It was thus found that the enhancement in the resultant α of the composite materials results in a significant improvement in the conversion efficiency for generators.     

Optical and electrical properties of SnO2 films prepared by chemical vapour deposition

Transparent and conducting SnO₂ films are prepared at 500°C on quartz substrates by chemical vapour deposition technique, involving oxidation of SnCl₂. The effect of oxygen gas flow rate on the properties of SnO₂ films is reported. Oxygen with a flow rate from 0·8–1·35 lmin⁻¹ was used as both carrier and oxidizing gas. Electrical and optical properties are studied for 150 nm thick films. The films obtained have a resistivity between 1·72 × 10⁻³ and 4·95 × 10⁻³ ohm cm and the average transmission in the visible region ranges 86–90%. The performance of these films was checked and the maximum figure of merit value of 2·03 × 10⁻³ ohm⁻¹ was obtained with the films deposited at the flow rate of 1·16 lmin⁻¹.     

Grain growth of copper films prepared by chemical vapour deposition

Copper films having thickness 600 nm were prepared on TiN using chemical vapour deposition (CVD). The deposited films were annealed at various temperatures (350–550°C) in Ar and H₂(10%)-Ar ambients. The changes in the grain size of the films upon annealing were investigated. Annealing in an H₂(10%)-Ar ambient produced normal grain growth; annealing in an Ar ambient caused grain growth to stop at 550°C. The grain size followed a monomodal distribution and the mean size increased in proportion to the square root of the annealing time, indicating the curvature of the grain is the main driving force for grain growth. Upon annealing at 450°C for 30 min in an H₂(10%)-Ar ambient, the average grain size of the film increased from 122 nm to 219 nm, and the resistivity decreased from 2.35 μΩ cm to 2.12 μΩ cm at a film thickness of 600 nm. This revised version was published online in July 2006 with corrections to the Cover Date.     

Studies on tin oxide films prepared by electron beam evaporation and spray pyrolysis methods

Transparent conducting tin oxide thin films have been prepared by electron beam evaporation and spray pyrolysis methods. Structural, optical and electrical properties were studied under different preparation conditions like substrate temperature, solution flow rate and rate of deposition. Resistivity of undoped evaporated films varied from 2.65 × 10⁻² ω-cm to 3.57 × 10⁻³ ω-cm in the temperature range 150–200°C. For undoped spray pyrolyzed films, the resistivity was observed to be in the range 1.2 × 10⁻¹ to 1.69 × 10⁻² ω-cm in the temperature range 250–370° C. Hall effect measurements indicated that the mobility as well as carrier concentration of evaporated films were greater than that of spray deposited films. The lowest resistivity for antimony doped tin oxide film was found to be 7.74 × 10⁻⁴ ω-cm, which was deposited at 350°C with 0.26 g of SbCl₃ and 4 g of SnCl₄ (SbCl₃/SnCl₄ = 0.065). Evaporated films were found to be amorphous in the temperature range up to 200°C, whereas spray pyrolyzed films prepared at substrate temperature of 300– 370°C were poly crystalline. The morphology of tin oxide films was studied using SEM.     

Au–Sapphire (0001) solid–solid interfacial energy

This work presents an experimental methodology for the measurement of interfacial energy (γ_SP) and work of adhesion (W _ad) of a metal–ceramic interface. A thin Au film was dewetted on the basal surface of sapphire substrates to form submicron-sized particles, which were analyzed using the Winterbottom method to determine the equilibrated particle–substrate solid–solid interfacial energy. Electron microscopy showed that a large portion of the particles contained grain boundaries, while all of the single crystalline particles had three distinct morphologies and orientations with the substrate. Two orientation relationships were determined from transmission electron microscopy, for which the interfacial energy in air at 1000 °C was determined: Au (111)–sapphire (0001): γ_SP = 2.15 ± 0.04 J/m², W _ad = 0.49 ± 0.04 J/m²; Au (100)–sapphire (0001): 2.18 ± 0.06 J/m², W _ad = 0.55 ± 0.07 J/m².