Preparation and properties of polysilsesquioxanes: Polysilsesquioxanes and flexible thin films by acid‐catalyzed controlled hydrolytic polycondensation of methyl‐ and vinyltrimethoxysilane

Polymethylsilsesquioxane (PMS) and polyvinylsilsesquioxane (PVS) were prepared by acid‐catalyzed controlled hydrolytic polycondensation of methyl‐ and vinyltrimethoxysilane (MTS and VTS), respectively. The spinnabilities and molecular weights of polysilsesquioxanes were easily controlled by the reaction conditions, such as the molar ratios of water, hydrochloric acid, and methanol to MTS or VTS; nitrogen flow rate; temperature; and stirring rate. PMS and PVS showed spinnability of more than 200 cm when their molecular weights were up to 42,000 (PMS) and 19,000 (PVS) M_w. Transparent, colorless, and flexible films of 0.02–0.10 mm thick were prepared by casting a 20 wt % acetone–methanol (V/V = 1) solution of PMS and PVS on a polymethylpentene shale, followed by heating at 80°C for 3 weeks. The tensile strength of the films, approximately 26 (PMS) and 17 (PVS) MPa, was found to be correlated with the structure of the polysilsesquioxanes. The surface contact angle and electroconductivity of films were also measured. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1017–1026, 1999     

Preparation of polymethylsilsesquioxanes by the base‐catalyzed hydrolytic polycondensation of triisopropoxy(methyl)silane

Base‐catalyzed hydrolytic polycondensation of trialkoxymethylsilane was investigated to synthesize polymethylsilsesquioxanes (PMSs). The reaction of trimethoxy(methyl)silane and triethoxy(methyl)silane with tetramethylammonium hydroxide, tetrabutylammonium hydroxide, and also coline gave insoluble gels. Polymethylsilsesquioxane (PMS‐IP) was obtained by the reaction of triisopropoxy(methyl)silane (MTIPS) with tetrabutylammonium hydroxide as a catalyst. PMS‐IP was composed primarily of T² and T³ units. The percentage of T³ units and the molecular weight of PMS‐IP increased with increases in the molar ratios of catalyst and water to MTIPS and with the reaction time. PMS‐IP was soluble in organic solvents, except for methanol, and was separated by extraction with hexane and methanol into low‐ and high‐molecular‐weight fractions of M_w 2800–4000 and 7300–88,300, respectively. PMS‐IP coating films were prepared by dip coating on the organic, inorganic, and metal substrates, using the acetone–isopropyl alcohol solution of PMS‐IP. Since PMS‐IP solutions prepared with tetrabutylammonium hydroxide were hardly used because of the low content of hydroxy groups in the polymer, they showed low adhesion when compared with those solutions prepared with hydrochloric acid. The dielectric constant of the coating film prepared from the high‐molecular‐weight PMS‐IP was 2.6. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 3623–3630, 2005     

Hydrolytic polycondensation of vinyltrimethoxysilane and formation of vinylpolysiloxane films

Hydrolytic polycondensation of vinyltrimethoxysilane (VTM) was investigated in detail to prepare vinylpolysiloxanes (VPS) having spinnability and tough gel films. VTM was hydrolyzed in various molar ratios r₁ (H₂O/VTM) = 0.5–1.6 (HCl/VTM = 0.105, EtOH/VTM = 1.44) at 70°C under a N₂ stream with stirring at 150 rpm to give vinylpolysiloxanes with =510–2100 ( =1.1–10.4). The controlled hydrolysis in r₁ = 1.40–1.64 formed VPSs having the various degrees of spinnability at N₂ flow rates of 100–500 ml/min. Transparent films of thickness 0.1–0.05 mm and tensile strength 5–16 MPa were prepared when a 20 wt% acetonemethanol (1:1, V/V) solution of VPS (r₁=1.64) was cast at 80°C for several ten days. The reaction was followed by ²⁹Si-NMR spectroscopy to investigate the distribution of unit structures T¹, T² and T³ in VPS depending on r₁.     

CdS和CdSe薄膜的制备及其光电化学性质

本文采用简易的化学水浴沉积法和自牺牲模板法制备CdS、CdSe薄膜,对两种薄膜进行了XRD表征,比较了两种薄膜的紫外吸收光谱并研究了CdS、CdSe薄膜作为太阳能电池中的光阳极时所产生的光电流和光电压,对两种薄膜的电化学性能进行了比较.     

Critical properties of thin films of polymer solutions

The critical properties of polymer solutions confined in thin‐film environments is studied with simple scaling arguments and a molecular theory. For purely repulsive surfaces, the critical volume fraction is a universal function of x = N^1/2/L, where N is the chain length and L is the film thickness. The critical volume fraction is nonmonotonic in x and shows a deep minimum at a film thickness several times larger than the chain's radius of gyration. This nonmonotonic behavior results from the interplay between the surface–polymer entropic repulsion and the tendency of the film to avoid large density gradients. The critical temperature is a monotonically increasing function of L, as L goes from the two‐dimensional limit to the three‐dimensional limit. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1849–1853, 2005     

Preparation and Properties of Organic-Inorganic Hybrid Gel Films Based on Polyvinylpolysilsesquioxane Synthesized from Trimethoxy(vinyl)silane

Polyvinylpolysilsesquioxane (PVPS) organic-inorganic hybrid gel films containing polyethylene and siloxane backbone linkages were prepared through the radical polymerization of trimethoxy(vinyl)silane (VTS) followed by the acid-catalyzed hydrolytic polycondensation of trimethoxysilyl groups. The PVPS gel films were transparent and homogeneous. It was found that the mechanical properties of these films correlate both to the degrees of polymerization and to the extent of cross linking.     

Preparation and characterization of mesoporous silica thin films from polyethoxysiloxanes

Tetraethoxysilane (TEOS) and polyethoxysiloxanes (PEOSs; prepared by the acid‐catalyzed hydrolytic polycondensation of TEOS) were subjected to the sol–gel process in the presence of cetyltrimethylammonium bromide (CTAB), respectively. The PEOSs with M_w 700–26,000, as prepared by sol–gel coating of TEOS and PEOS under various conditions, were used. Uniform and crack‐free thin films of thickness 276–613 nm were prepared by spin‐coating of a PEOS solution containing CTAB. When the coating films were sintered at 400 °C, the combustion of ethoxy groups and CTAB took place to provide porous silica thin films. The structure of the thin films was found to be dependent on the molecular weight of PEOS and the molar ratio of CTAB/Si: lamellar or hexagonal phase was observed for M_w less than 15,000 and for CTAB/Si molar ratios greater than 0.10. Honeycomb structures were observed for M_w less than 5000 and for CTAB/Si molar ratios of 0.15. The honeycomb structure was also observed by atomic force microscopy and transmission electron microscope. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2542–2550, 2006     

Preparation and properties of flexible free‐standing films via polyalkoxysiloxanes by acid‐catalyzed controlled hydrolytic polycondensation of tetraethoxysilane and tetramethoxysilane

Acid‐catalyzed controlled hydrolytic polycondensation of tetraethoxysilane (TEOS) and tetramethoxysilane (TMOS) provided polyalkoxysiloxanes PEOS and PMOS, with high molecular weight of 1100–12 000 or 2700–31 000, respectively. They were stable to self‐condensation, soluble in organic solvents, and especially characterized by high silica content of up to 62% (PEOS) and 72% (PMOS). Flexible and transparent free‐standing films with tensile strength of 1.6–5.2 MPa (PEOS) or 3.6–11.8 MPa (PMOS) were prepared by heating polyalkoxysilanes at 80°C for one to several days. They are also regarded to be a potential precursor for coatings and binders. Copyright © 2012 John Wiley & Sons, Ltd.     

Preparation of polyamides derived from 1,6-diamantane dicarboxylic chloride by solution polycondensation and interfacial polycondensation

1,6-Diamantane dicarboxvlic acyl chloride ( I ) was used as a monomer with various aromatic diamines to synthesize polyamides by interfacial polycondensation and solution polycon-densation. The polyamides prepared by interfacial polycondensation had inherent viscosities between 0.38 and 0.15 dL/g. The polyamides prepared by solution polycondensation had inherent viscosities between 0.62 and 0.25 dL/g. The polyamides IIIa prepared by solution polycondensation showed the main melting transition at 380°C by dynamic mechanical analysis. In addition, it was quite temperature-stable and maintained good mechanical properties (G′?10⁸ Pa) up to high temperatures close to the main transition well above 350°C. The polyamide IIIA had a tensile strength of 35 MPa, elongations to break of 10%, and initial modulus of 0.8 GPa. Some of the polyamides were soluble in NMP, DMAc, and DMSO, depending on soft segment moiety of diamine ( II ). The polyamides prepared by interfacial polycondensation have a greater tendency to form crystal than those prepared by solution polycondensation, as evidenced by x-ray diffraction studies. These polyamides had glass transition temperatures in the 270–300°C range, and 5% weight loss temperatures up to 435°C in nitrogen. © 1995 John Wiley & Sons, Inc.     

Structure and morphology control in thin films of regioregular poly(3‐hexylthiophene)

This review focuses on the structural control in thin films of regioregular poly(3‐hexylthiophene) (P3HT), a workhorse among conjugated semiconducting polymers. It highlights the correlation existing between processing conditions and the resulting structures formed in thin films and in solution. Particular emphasis is put on the control of nucleation, crystallinity and orientation. P3HT can generate a large palette of morphologies in thin films including crystalline nanofibrils, spherulites, interconnected semicrystalline morphologies and nanostructured fibers, depending on the elaboration method and on the macromolecular parameters of the polymer. Effective means developed in the recent literature to control orientation of crystalline domains in thin films, especially by using epitaxial crystallization and controlled nucleation conditions are emphasized. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1218–1233, 2011     

Antibacterial and physicochemical properties of co‐sputtered CuSn thin films

Copper‐tin thin films (CT TFs) were deposited on p‐type Si(100) by radio frequency (RF) magnetron co‐sputtering method. The atomic ratio of Cu and Sn showed complementary tendency with various RF powers on metal targets. Antibacterial test was conducted with Gram‐negative Escherichia coli. The ratio of Cu and Sn ions and the contact time with E. coli affected the antibacterial efficiency. Increasing the ratio of Cu ions and contact time showed higher antibacterial activity. Cu₂₀Sn₆ called as bronze structure, metallic Cu, and copper oxide phases were identified from X‐ray diffraction data after sterilization. The lattice strain that was changed due to the substitution of Cu and Sn was also calculated. The surface morphology of CT TFs was entirely grown to round shape when the dominant element was Sn. But, as the content of Cu increased, the surface morphology was changed from ball shape to sharp column shape. When fixed contact time, the intensities of Cu 2p increased but the intensities of Sn 3d decreased as increasing the atomic ratio of Cu. The oxidation of Cu was more sharply progressed as the RF power on Cu target increased. When fixed CT TFs, the intensities of Cu 2p were consistent but the intensities of Sn 3d_3/2 decreased as increasing contact time between CT TF and E. coli.     

Analysis of thin solid films and surfaces by infrared spectroscopy

Thin solid films and surfaces are characterized by IR spectroscopy, based on reflectance and transmittance measurements, in particular with polarized light at oblique incidence. Thus two independent data sets fors- andp-polarization are available. Atp-polarization additional absorption lines at the zeros of the dielectric function are observed (Berreman-mode). The interpretation of the measured spectra is carried out by a fit procedure to simulate the observed spectra. As a result the specimens are characterized in terms of vibronic resonances and their oscillator strengths or concentration, thicknesses of various films in a stack of layers, profiles of depth depending chemical composition, or concentration and mobility of conduction electrons.All examples are relevant for application in technology, as microelectronics, thin film technology, catalysis, e.g. The results of the IR analysis are compared with those of other analytical methods as SIMS, RBS, and AES. The agreement is very good. One important advantage of the IR analysis, however, is the fact that it is a non-destructive method.     

Chain orientation and anisotropies in optical and dielectric properties in thin films of stiff polyimides

Thin films of poly(p-phenylene biphenyltetracarboximide) (BPDA-PDA), prepared by thermal imidization of the precursor poly(amic acid) on substrates, have been investigated by optical waveguide, ultraviolet-visible (UV-VIS), infrared (IR), and dielectric spectroscopies. The polyimide films exhibit an extraordinarily large anisotropy in the refractive indices with the in-plane index n_∥ = 1.806 and the out-of-plane index n_⊥ = 1.589 at 1064 nm wavelength. No discernible effect of the film thickness on this optical anisotropy is found between films of ca. 2.1 and ca. 7.8 μm thickness. This large birefringence is attributed to the preferential orientation of the biphenyltetracarboximide moieties with their planes parallel to the film surface, coupled with the strong preference of BPDA-PDA chains to align along the film plane. The frequency dispersion of the in-plane refractive index n_∥ is consistent with the results calculated by the Lorentz–Lorenz equation from the UV-visible spectrum exhibiting several absorption bands in the 170–500 nm region. The contribution from the IR absorption in the range 7000–400 cm,^?1 computed by the Spitzer-Kleinmann dispersion relations from the measured spectra, adds ca. 0.046 to the in-plane refractive index n_∥. Tilt-angle–dependent polarized IR results indicate nearly the same increase for the out-of-plane index n_⊥. Application of the Maxwell relation then leads to the out-of-plane dielectric constant ε^⊥ ? 2.7 at 1.2 × 10¹³ Hz, as compared with the measured value of ca. 3.0 at 10⁶ Hz. Assuming this small difference to remain the same for the in-plane dielectric constants ε_∥, we obtain a very large anisotropy in the dielectric properties of these polyimide films with the estimated in-plane dielectric constant ε_∥ ? 3.4 at 1.2 × 10¹³ Hz, and ε_∥ ? 3.7 at 10⁶ Hz. © 1992 John Wiley & Sons, Inc.     

Investigation of thin surface films by microprobe analysis

The electron microprobe has been applied to study thin films on metallic substrates. The intensities of the characteristic X-rays emitted by thin films of various elements and thicknesses on sublayers of different materials were measured. Two different theoretical approaches (Bishop and Poole, as well as Yakowitz and Newbury) were applied to interpet the X-ray intensities and to determine the film thickness from the intensity measurements. The effect of backscattering from the substrate, resulting in an increase of the intensity of characteristic X-rays of the film, is being described on the basis of a theory given by Hutchins. The corresponding equation for the backscattering factor has been modified to take into account the transmission of the electrons through the film, depending on the mass thickness of the film and the electron energy. The results obtained from theory and experiment are in good agreement for the different experimental parameters applied, except for very thick layers of high atomic numbers measured at low energies where the absorption of electrons in the film plays a dominant role.     

Preparation and characterization of nanostructured thin films of Au and Ag nanoparticles synthesized by ascorbic acid on modified glass surface

Immobilization of Ag and Au nanoparticles (NPs) synthesized by ascorbic acid on chemically modified glass surface has been studied. 3‐[2‐(2‐Aminoethylamino)ethylamino]propyl‐trimethoxysilane (AMPTS), N‐(2‐aminoethyl)‐3‐aminopropyltrimethoxysilan, and 3‐trimethoxysilyl‐1‐propanethiol (MSPT) were used as surface modifying agents. To improve immobilization efficiency, the ammonia solution has been used along with the silane reagents, which assisted to adsorb the metal NPs on glass surface. It was found that AMPTS and MSPT have considerable effect on deposition of Ag and AuNPs on glass substrate. The fabricated thin films were characterized by using UV‐Vis spectroscopy, atomic force microscopy, energy‐dispersive X‐ray spectroscopy and subjected to antimicrobial resistance test. The UV–Vis spectra show a distinctive plasmon resonance absorbance peak for thin films of Au and AgNPs prepared with MSPT and AMPTS, respectively. Atomic force microscopy images indicate that formation of Au and AgNPs with spherical morphology after immobilization on the glass substrate and also the dimensions of NPs on the surface appear larger than those observed in the parent colloidal solution. Energy‐dispersive X‐ray spectroscopy measurements confirmed the presence of silver and gold on the modified glass surface, and elemental composition was measured. The Au and AgNPs thin films show antibacterial activity against gram negative (Escherichia coli) and gram positive (Staphylococcus aureus) bacteria in comparison with a blank sample. Copyright © 2015 John Wiley & Sons, Ltd.     

Preparation and photochromism of Keggin-type molybdphosphoric acid/silica mesoporous composite thin films

Using tetraethoxysilane and 3-aminopropyltriethoxysilane as the silica sources, amino-functionalized organic/inorganic hybrid mesoporous silica thin films with 2-dimensional hexagonal structure have been synthesized by evaporation induced self-assembly process in the presence of cetyltrimethyl ammonium bromide templates under acid conditions. The Keggin-type molybdphosphoric acid (PMo) is incorporated into the mesoporous silica thin films with amino-groups by wetness impregnation, and the PMo/silica mesoporous composite thin films are obtained. The results of X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), and Fourier transform infrared (FTIR) spectra indicate the PMo molecules maintain Keggin structure and are homogeneously distributed inside mesopores. The composite thin films possess excellent reversible photochromic properties, and change from colorless to blue under ultraviolet irradiation. The photochromic mechanism of the composite thin films is studied by ultraviolet-visible (UV-vis), electron spin resonance (ESR) and X-ray photoelectron spectroscopy (XPS) spectra. It is shown that intervalence charge transfer (IVCT) and ligand-to-metal charge transfer (LMCT) are the main reasons of photochromism. PMo anions interact strongly with amino-groups of the mesoporous suface via hydrogen bond and electrostatic force. After ultraviolet irradiation, the charge transfer occurs by reduction of heteropolyanions accompanying the formation of heteropolyblues with multivalence Mo(VI, V), and the bleaching process of composite thin films is closely related to the presence of oxygen.     

The synthesis and properties of CaCu3Ti4O12 thin films

The CaCu₃Ti₄O₁₂ (CCTO) thin films were synthesized via a metal‐organic solution containing stoichiometric amounts of the metal cations at 700 °C for 1 h. The stable metal‐organic solution was prepared by dissolving calcium nitrate, copper nitrate, and tetrabuty titanate in grain alcohol. The phases, microstructures, and electric properties of CCTO thin films were characterized by X‐ray diffraction, scanning electron microscopy, atomic force microscope, and electric measurements. The results show that the CCTO thin films have homogeneous microstructure, smooth surface, low leakage current, and high values of dielectric constant. The low leakage current can be attributed to the small surface roughness. The high value of dielectric constant can be attributed to the internal barrier layer capacitor mechanism and metal‐insulator‐semiconductor junction of CCTO thin films. Copyright © 2013 John Wiley & Sons, Ltd.     

Structural and magnetic properties of nano-crystalline FeCoNiN thin films

Iron cobalt nickel nitride (FeCoNiN) thin films are prepared by sol-gel spin coating route. The structural, magnetic and surface properties of the thin films are evaluated. The crystalline nature of thin films was enhanced upon annealing, leading to increased crystallite size. The X-ray diffraction shows mixed phases with crystallite size in the range of 20–26.93 nm. Thin films show ferromagnetism at room temperature. Coercivity and saturation magnetization are in the range of 642–716 Oe and 2.5–7.5 emu/cm³ respectively. Both coercivity and saturation magnetization increased with annealing of thin films. Magnetic properties are related to the crystallinity of thin films. The increase in crystallite size results into an increase of magnetic properties. Rectangular shaped particles are seen on the surface of thin films. The same type of grains can be seen on the surface of thin films which confirmed the formation of FeCoNiN as predicted by XRD. These novel thin films might be used in memory devices and optoelectronic applications.     

Effect of post-metallization annealing on the ferroelectric properties of sol-gel derived PZT thin films

A series of monolithic Pt-PZT-Pt capacitors was prepared based on sol-gel derived PZT 53/47 films fired to 700 C. After deposition of top Pt electrodes, the capacitors were subjected to post-metallization annealing (PMA) temperatures of 100 C to 700 C. Dielectric and ferroelectric (FE) characterizations were performed. Increasing the PMA temperature produced lower values of spontaneous and remanent polarizations, dielectric constant and leakage currents. The observations are correlated with a proposed FE capacitor model.     

Improvement in Tensile Strength and Water Repellency of Paper after Treatment with Methyltrimethoxysilane Oligomer Using Titanium Butoxide as a Catalyst

The improvement in the tensile strength and water repellency of paper after treatment with a 2-propanol solution of a methyltrimethoxysilane (MTMS) oligomer was studied using filter paper. Titanium butoxide introduced in the solution as a catalyst effectively reacted with the MTMS oligomer, and a Si–O–Ti bond was generated inside the paper. The tensile strength of the paper was remarkably improved by this treatment of impregnation and polymerization of the MTMS oligomer. It was speculated that the reaction proceeded by consuming water that existed among the cellulose fibers by hydrogen bonding, because there was little difference in the tensile strength between the paper treated in air and the paper treated in a dry box. The methoxy groups in the MTMS oligomer demonstrated their good ability of making a three-dimensional network, and at the same time, the methyl groups in the oligomer showed their excellent water repellency. As a result, the treated paper had a good tensile strength even under wet conditions.