Properties of nanoporous organosilicate hybrid thin films with a bimodal pore size distribution

Low dielectric poly[methylsilsesquioxane‐ran‐trifluoropropylsilsesquioxane‐ran‐(2,4,6,8‐tetramethyl‐2,4,6,8‐tetraethylenecyclotetrasiloxane)silsesquioxane]s {P[M‐ran‐TFP‐ran‐(TCS)]SSQs} having various compositions were synthesized using trifluoropropyl trimethoxysilane, methyl trimethoxysilane and 2,4,6,8‐tetramethyl‐2,4,6,8‐tetra(trimethoxysilylethyl)cyclotetrasiloxane. The chemical composition of the polymers and the content of SiOH end‐groups were controlled by adjusting the reaction conditions, and they were characterized by ¹H‐NMR. The thermally decomposable trifluoropropyl groups on the P[M‐ran‐TFP‐ran‐(TCS)]SSQ backbone and heptakis(2,3,6‐tri‐O‐methyl)‐β‐cyclodextrin (CD) were employed as pore generators. The dielectric constants of the porous CD/P[M‐ran‐TFP‐ran‐(TCS)]SSQ films were in the range 2.0–2.7 (at 100 kHz) depending on the concentration of the porogens, and showed no change over 4 days under aqueous conditions. The pore size of the films showed a bimodal distribution, with diameters of ca 0.5–1.0 nm for those originating from the trifluoropropyl groups and 1.7 nm from the CD. The elastic modulus and hardness of the 30 vol% CD‐blended film with a dielectric constant of 2.26 were 2.40 and 0.38 GPa, respectively, as determined by a nanoindenter. Copyright © 2005 Society of Chemical Industry     

The reaction of ceria coatings on mica with H2S: An in-situ X-ray diffraction study

Thin layers of ceria were deposited on the surface of mica platelets in solution. The reaction of such particles with hydrogen sulfide yields a red colored special effect pigment. The ceria layer reacts with H₂S to produce a variety of sulfide and oxysulfide phases. The reaction path discovered in situ by time and temperature resolved X-ray diffraction is CeO₂→CeS₂→C-Ce₂S₃→Ce₁₀S₁₄O. The reaction itself is extremely variable depending on gas flow, heating rates and decomposition atmospheres. Effects on the thin film are recorded by scanning electron microscopy (SEM) and revealed a destruction of the layer once red Ce₁₀S₁₄O was formed. The product layer then reveals the typical nonwetting behaviour of a liquid on a surface.     

Effects of Ca and Zr substitution upon structure and properties of Ba5LaTi3Ta7O30 low-loss dielectric ceramics

Effects of Ca and Zr substitution upon the dielectric properties of Ba₅LaTi₃Ta₇O₃₀ ceramics were investigated together with the structural characterization. All the samples of Ba₅La(Zr_xTi_1−x)₃Ta₇O₃₀ formed a filled tungsten-bronze structures, whereas the solid solution limit was determined as x=0.25 in (Ca_xBa_1−x)₅LaTi₃Ta₇O₃₀. Beyond this limit secondary phase of CaTa₂O₆ was detected and it would become the major phase for the Ca-rich compositions. The temperature coefficient of dielectric constant was improved with increasing Zr content while the dielectric constant decreased and the low dielectric loss varied little (in the order of 10⁻⁴). In the case of (Ca_xBa_1−x)₅LaTi₃Ta₇O₃₀, small temperature coefficient of dielectric constant could be obtained with increasing Ca content while the dielectric constant decreased significantly, and a small amount substitution of Ca for Ba induced decrease in dielectric loss.     

A comparative study of the gas sensing behavior of nanostructured nickel ferrite synthesized by hydrothermal and reverse micelle techniques

A comparative study of gas sensing behavior of nanocrystalline nickel ferrite synthesized by micro-emulsion and hydrothermal method to liquefied petroleum gas (LPG) is presented. Nanocrystalline nickel ferrite synthesized by hydrothermal method indicated higher electrical conductivity and gas sensitivity at low operating temperature compared to nanocrystalline nickel ferrite synthesized by reverse micelle technique. This difference in the gas sensing behavior can be attributed to the presence of more oxygen vacancies (i.e. non-stoichiometry) in the hydrothermally synthesized nickel ferrite. Incorporation of palladium had a catalytic effect and the operating temperature was significantly reduced in both the samples. The higher operating temperature of the reverse micelle nickel ferrite material makes the sensor response speed faster (∼10 s) compared to the hydrothermally synthesized material (∼1 min).     

Electrical conductivity and gas sensitivity of Zn-Sb-O thick films

The thick film of Zn-Sb-O was prepared by coating the paste of nanoparticles mixture (Sb₂O₃:ZnO=1:3) on the alumina substrate, followed by sintering at 500-900 °C for 2 h in air. The electrical resistance and gas-sensing properties to benzene, alcohol and acetone of Zn-Sb-O films were found to be dependent on the change of phase structure caused by sintering temperature.     

Effect of hot pressing on processing and properties of BBN ceramics

BBN (BaBi₂Nb₂O₉) is very interesting and promising lead free material with relaxor properties in capacitors, sensors and actuators.     

Structural study of cubic pyrochlores based on quantum mechanical simulation

In the ideal A₂B₂O₆O′ pyrochlore structure, the x-value of O atom position is a variable parameter. In Bi_1.5ZnNb_1.5−xTa_xO₇ (BZNT) cubic pyrochlores, the x-values alter with the different compositions of Nb/Ta. In this work, a series of initial models for BZNT were established by analyzing X-ray diffraction data. Then three structure modifying methods, including Rietveld refinement, Rietveld refinement with energy and geometry optimization based on quantum mechanics, were employed to obtain the precise models using Materials Studio. Moreover, the reflectivities of BZNT were computed by quantum mechanical simulation based on the refined models. Comparing the simulation results from different modifying models with the experimental results, it is found that Rietveld refinement with energy optimization is the most accurate method for BZNT pyrochlores. According to the simulation results, the different reflectivities correspond well with various x-values of O atom positions in BZNT pyrochlores.     

Novel electro-optic properties of epitaxially grown (Pb, La)(Zr, Ti)O3 (PLZT) thin films derived by advanced sol–gel methods

Advanced sol–gel methods using a secondary solvent addition into (Pb, La)(Zr, Ti)O₃ (PLZT) sol–gel solution and a methanol pre-treatment of sapphire substrates are demonstrated. For the secondary solvent addition, the additive affected the crystallinity and electro-optic (EO) property of PLZT films and only methanol addition can improve them. In addition, the methanol pre-treatment is also appeared to be effective to improve film characteristics.

Through these optimizations, epitaxially grown PLZT thin films on r-cut sapphire are obtained and a high Pockels coefficient which is comparable to those of bulk PLZTs is achieved. It is believed that these PLZT thin films are applicable for integrated EO devices and open the door for the future data communication systems.     

Inorganic–organic hybrid materials with zirconium oxoclusters as protective coatings on aluminium alloys

Inorganic–organic hybrid materials are attracting a strong scientific interest mainly for their outstanding inherent mechanical and thermal properties, which can be traced back to the intimate coupling of both inorganic and organic components. By carefully choosing the experimental parameters used for their synthesis, chemically and thermally stable acrylate-based hybrid material embedding the zirconium oxocluster Zr₄O₄(OMc)₁₂, where OMcCH₂C(CH₃)C(O)O, can be deposited as UV-cured films on aluminium alloys.

In particular, the molar ratios between the oxocluster and the monomer, the polymerisation time, the amount of photo-initiator and the deposition conditions, by using an home-made spray-coating equipment, were optimised in order to obtain the best performing layers in terms of transparency and hardness to coat aluminium alloy (AA1050, AA6060 and AA2024) sheets. Furthermore, it was also evaluated whether the hybrid coatings behave as barrier to corrosion.

Several coated samples were prepared and characterised. Environmental scanning electronic microscopy (ESEM) and scratch test were used to investigate the morphology of the films and to evaluate their scratch resistance, respectively. Electrochemical impedance spectroscopy (EIS) was performed in order to evaluate if the coatings actually protect the metallic substrate from corrosion.

In order to measure shear storage modulus (G′) and loss modulus (G″) of the materials used for coatings, bulk samples were also obtained by UV-curing of the precursors solution. Dynamical mechanical thermal analysis (DMTA) was performed in shear mode on cured disks of both the hybrid materials and pristine polymer for comparison. The values of T_g were read off as the temperatures of peak of loss modulus. The length and mass of all the samples were measured before and after the DMTA analysis, so that the shrinkage of the materials in that temperature range was exactly evaluated.