Increasing Silane Concentration Research Articles

Effect of silane concentration on the properties of crosslinked linear low density polyethylene‐montmorillonite nanocomposite

AbstractIn this study, linear low density polyethylene (LLDPE) was grafted and crosslinked by reactive extrusion melt compounding using different silane concentration with and without the presence of montmorillonite (MMT) nanoclay. The effects of different silane concentration and the addition of nanoclay filler on the degree of crosslinking, mechanical, thermal, rheological, and morphological properties were investigated and reported. Gel content results for all crosslinked samples were found to increase with increasing silane concentration. Tensile strength and Young's modulus of crosslinked LLDPE samples increased with increasing silane concentration compared to neat LLDPE; while the crosslinked LLDPE samples containing nanoclay have achieved higher tensile strength and Young's modulus, indicating strong interfacial interaction between silane grafted LLDPE matrix and nanoclay. However, the decrease of elongation at break for all crosslinked samples were observed compared to neat LLDPE. A reduction in the degree of crystallinity for crosslinked samples, particularly crosslinked samples containing nanoclay, was shown by thermal analysis results; whereas the melting temperature did not change significantly with increased silane concentration and subsequent addition of nanoclay. Thermogravimetric analysis results have revealed significant thermal stability improvement for neat LLDPE with increased silane concentration. Furthermore, crosslinked samples containing nanoclay have achieved better thermal stability compared to crosslinked samples without nanoclay. At lower frequency, it was found that viscosity, and storage modulus of neat LLDPE increased with increased silane concentration due to crosslinking and further addition of nanoclay into crosslinked LLDPE. The transmission electron microscopy results confirmed the intercalated structure of the nanocomposite for the crosslinked samples containing nanoclay.

Improvement of Membrane Distillation Using PVDF Membrane Incorporated with TiO2 Modified by Silane and Optimization of Fabricating Conditions

The objectives in this study are to improve the performance of PVDF membrane by incorporating TiO2 and silane at various dosages and optimize fabricating conditions by using response surface methodology (RSM) for membrane distillation (MD) application. The PVDF membrane was synthesized by phase inversion method using various TiO2, silane and polymer concentrations. Membranes were characterized by performing contact angle measurements, SEM and FTIR observations. Ammonia rejection and permeate flux were measured by operating a direct contact distillation module treating ammonium chloride solution. A PVDF membrane created by adding TiO2 modified by silane improved membrane hydrophobicity. However, the effect of silane on membrane hydrophobicity was less pronounced at higher TiO2 concentrations. Highest ammonium rejection was associated with the highest membrane hydrophobicity. RSM analysis showed that fabricating conditions to achieve highest flux (10.10 L/m2·h) and ammonium rejection (100.0%) could be obtained at 31.3% silane, 2.50% TiO2, and 15.48% polymer concentrations. With a PVDF-TiO2 composite membrane for MD application, the effect of TiO2 was dependent upon silane concentration. Increasing silane concentration improved membrane hydrophobicity and ammonium rejection. RSM analysis was found to bea useful way to explore optimum fabricating conditions of membranes for the permeate flux and ammonium rejection in MD.

Nanocomposite Films of Laponite/PEG-Grafted Polymers and Polymer Brushes with Nonfouling Properties.

We explore the suitability of nanocomposite thin films based on laponite nanomaterial and grafted antiadhesive polymers as transparent nonfouling surfaces. For this purpose, two polymers were chosen: a linear poly(ethylene glycol) (PEG) silane, 2-[methoxy(polyethyleneoxy)propyl]-trimethoxysilane), and thermoresponsive poly(oligo ethylene glycol)-methyl ether-methacrylate (POEGMA) brushes. PEG silane was grafted on the laponite nanoparticles in solution yielding homogeneous and transparent thin films via a dip coating procedure on glass and silicon substrates. POEGMA was grafted on laponite-(3-Aminopropyl)trimethoxysilane (APTMS) nanocomposite films that were processed similarly to PEG-silane using atom transfer radical polymerization (ATRP). Film characterization with, among others, Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), and atomic force microscopy (AFM) attests to successful grafting of the polymers to the laponite nanoparticles. In particular, evidence of basal plane expansion of laponite with increasing silane concentration are obtained using XRD, while patent morphological changes are revealed with AFM. The results are discussed in terms of the different grafting sites on laponite and compared with literature. While LP-PEG-silane is easily applied to a surface from a precursor solution via a dip coating procedure LP-APTMS-OEGMA requires lots more chemicals, a thorough control of reaction parameters, and longer reaction time in order to generate films with the desirable properties. We therefore also addressed the antifouling properties of the films. These were tested together with control samples of bare glass and laponite thin films for 30 days in an algae container. More tests were conducted with fibroblast cell cultures. Our preliminary results show that grafting of PEG containing polymers and polymer brushes alters the properties of the laponite films from fouling to nonfouling surfaces. As a first estimate, the adhesion of particles (diatoms, algae, etc.) to surfaces is reduced by approximately 85% in the case of LP-PEG-silane and up to 92% in the case of LP-APTMS-POEGMA, in comparison to the control surfaces. Furthermore, practically no cell adhesion on such surfaces could be observed.

Membrane distillation of saline with phenolic compound using superhydrophobic PVDF membrane incorporated with TiO2 nanoparticles: Separation, fouling and self-cleaning evaluation

Superhydrophobic polyvinylidene fluoride (PVDF) membrane was used to study membrane distillation of saline with phenolic compound. Besides addition of TiO2 nanoparticles, superhydrophobic surface of PVDF membrane was created by silane grafting after phase inversion. Three types of silane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane, (tridecafluro-1,1,2,2-tetrahydrooctyl) triethoxysilane and (3,3,3-trifluoropropyl) trimethoxysilane were used in this work. All the membranes achieved superhydrophobicity (water contact angle >150°), but pore size and porosity were significantly reduced by increasing silane concentration. Lithium chloride (LiCl, 2wt%) was used to improve superhydrophobic PVDF/TiO2 membranes. Membranes were further evaluated in terms of separation performance, fouling tendency and self-cleaning properties. In membrane distillation, all membranes retained 99.9% of the phenolic content in feed (100g/L of gallic acid). However, superhydrophobic PVDF/TiO2 membranes modified using (tridecafluro-1,1,2,2-tetrahydrooctyl) triethoxysilane (1mL silane: 50mL ethanol) and 2wt% of LiCl was the only membrane that maintained the permeate flux near to 6kg.m−2.h−1 without much flux decline after 8h of operation. It also retained 99.9% of sodium chloride (NaCl) and gallic acid simultaneously at a higher feed temperature of 70°C. Although some of these modified membranes were fouled by gallic acid, they could be easily cleaned under UV radiation.

Role of silane concentration on the structural characteristics and properties of epoxy-/silane-modified montmorillonite clay nanocomposites

In the present work, sodium montmorillonite (MMT) was modified with varying concentrations of (3-amino propyl) triethoxy silane (APS) using water as the dispersing medium. Successful grafting of APS was corroborated using Fourier transform infrared spectroscopy (FT-IR). X-ray diffraction (XRD) studies of silane-modified clay revealed that the average d-spacing values increase at low silane concentration with the almost constant values at higher silane concentration. Total grafting yield of APS calculated using differential thermogravimetric results revealed that grafting yield decreases with increasing silane concentration. Epoxy-based MMT clay nanocomposites were prepared with different loading amounts of pristine (PM0.0) and silylated clay (SM4.4), and its influence on the mechanical, dynamic mechanical, and water uptake properties of the nanocomposites was investigated. The degree of intercalation of pristine or modified clay in the epoxy matrix estimated by XRD experiments exhibits a clear diffraction peak corresponding to the interlayer spacing d001 of 14.8–28 Å. Characterizations of mechanical properties revealed that Young’s modulus and tensile strength increase with increasing concentration of the modified clay, while the fracture toughness shows a maximum at 6 wt% of clay. From the results of dynamic mechanical analysis, it was observed that the nanocomposites filled with silylated clay display higher storage modulus mainly at temperatures above the glass transition temperature. The equilibrium water uptake was reduced significantly on loading 6 wt% of pristine MMT, and this effect is more pronounced on loading silanized MMT in the nanocomposites when compared to the neat epoxy system.

Preparation and characterization of poly(lactic acid)/recycled polypropylene blends with and without the coupling agent, n-(6-aminohexyl)aminomethyltriethoxysilane

Blends of polylactide (PLA) and recycled polypropylene (rPP) were prepared by melt-processing using a corotating twin-screw extruder and subsequent pelletizing of the extrudates for injection molding. The PLA/rPP blends were characterized by Thermogravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA), rheometer (MCR-102), scanning electron microscopy(SEM), tensile tests, and impact measurements. The results indicate that the PLA/rPP blend is immiscible and has a two-phase structure. TGA revealed enhancement of the thermal stability of the blends upon addition of rPP. The storage modulus, loss modulus, and complex viscosity of the blends increased with rPP concentration. Mechanical studies showed that introduction of rPP results in a decrease in tensile strength and modulus and enhancement of the impact strength of PLA in the blends. The effects of a silane coupling agent on the morphology and on the tensile and impact properties of the rPP blends of silane-modified PLA were also examined. SEM studies suggest that silane is an effective interfacial modifier. Thus, better interfacial adhesion was observed with silane-modified blends as compared with unmodified blends. Silane also improved the mechanical properties of the modified blends. The blends reached maximum tensile strength at 1.5 wt.% silane (relative to modified PLA content), and impact strength increased with increasing silane concentration. These results confirm the enhancing effect of silane on modified PLA/rPP blends.

Photoluminescence of Si-vacancy color centers in diamond films grown in microwave plasma in methane-hydrogen-silane mixtures

The processes of the synthesis of silicon-doped microcrystalline diamond films on AlN and Si substrates in microwave plasma in “methane-hydrogen-silane” mixtures were studied. It is shown that the dependence of the photoluminescence (PL) line intensity of silicon-vacancy centers in diamond (λ = 738 nm) on the silane concentration in a gas mixture passes through a maximum at SiH4/CH4 concentrations of 0.1% for Si substrates and 0.6% SiH4/CH4 for aluminum nitride substrates. It was found that such nonmonotonic variation of the PL intensity with increasing silane concentration occurs despite the unchanged growth rate of the diamond film, its structure, and phase composition in the studied silane concentration SiH4/CH4 range of 0–0.9%.

Improve silane utilization for silicon thin film deposition at high rate

In order to investigate the silane utilization during silicon thin film deposition, one quadrupole mass spectrometer was used to monitor the partial pressure of silane during high pressure and high power deposition process. Relationship of silane consumption with silane concentration, excitation power and reaction pressure was investigated. The results show that increasing silane concentration leads to lower silane consumption. Increasing excitation power can improve the silane utilization, which is proved by higher deposition rate. However, when the power is higher than a certain value, much more power will consume by the transmission line and matching network. The power coupled into the plasma saturates to a certain value and then no more silane decomposes any more. In addition, the silane consumption decreased and then increased with increasing reaction pressure, which is related with the voltage of electrodes. These results could help to improve silane utilization for low cost production and better quality of film.

The microstructure and optical properties of crystallized hydrogenated silicon films prepared by very high frequency glow discharge

A series of nc-Si:H films with different crystalline volume fractions have been deposited by very high frequency glow discharge in a plasma with a silane concentration [SiH 4]/([SiH 4] + [H 2]) varying from 2% to 10%. The nc-Si:H films have been characterized by Raman spectroscopy, XRD diffraction, and UV–vis–near infrared spectrophotometer. The deposition rate increases nearly linear with increasing the silane concentration while the crystalline volume fraction decrease from 58% to 12%. The refractive index and the absorption of the samples were obtained through a modified four-layer-medium transmission model based on the envelope method. It was found that the refractive indices and absorption coefficient increase with increasing silane concentration. Compared to the films deposited using conventional RF-PECVD with excitation frequency of 13.56 MHz, the samples prepared by very high frequency glow discharge have higher absorption coefficients, which is due to its better compactness and lower defect density.

Sodium montmorillonite silylation: Unexpected effect of the aminosilane chain length

In this work, the silylation of sodium montmorillonite (Na-MMT) was performed in glycerol using 3-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane and 3-[2-(2-aminoethylamino)ethylamino]-propyl-trimethoxysilane. The effects on the d-spacing of sodium montmorillonite (Na-MMT) upon reaction with three aminosilanes of different chain length were studied in details by combining experimental and computational techniques. Infrared spectroscopy was used to monitor the grafting process, while the degree of grafting was calculated using thermogravimetric analysis. X-ray diffraction experiments were carried out to evaluate the shift of the (0 0 1) basal spacing. It was found that the degree of silylation of Na-MMT increases with increasing the length of the aminosilane organic moieties, the overall aminosilane concentration, and temperature. The same beneficial effects were observed on the silicate d-spacing, as its value increases with increasing silane concentration and reaction temperature. Remarkably, however, increasing the length of the organic chains in the silane modifiers resulted in decreasing values of the Na-MMT interlayer distance. A rationale for this behavior is proposed on the basis of atomistic molecular dynamics simulation evidences.

Computational Modeling of Silicon Nanoparticle Synthesis: II. A Two-Dimensional Bivariate Model for Silicon Nanoparticle Synthesis in a Laser-Driven Reactor Including Finite-Rate Coalescence

In this work, a two-dimensional model was developed for silicon nanoparticle synthesis by silane thermal decomposition in a six-way cross laser-driven aerosol reactor. This two-dimensional model incorporates fluid dynamics, laser heating, gas phase and surface phase chemical reactions, and aerosol dynamics, with particle transport and evolution by convection, diffusion, thermophoresis, nucleation, surface growth, coagulation, and coalescence processes. Because of the complexity of the problem at hand, the simulation was carried out via several sub-models. First, the chemically reacting flow inside the reactor was simulated in three dimensions in full geometric detail, but with no aerosol dynamics and with highly simplified chemistry. Second, the reaction zone was simulated using an axisymmetric two-dimensional CFD model, whose boundary conditions were obtained from the first step. Last, a two-dimensional aerosol dynamics model was used to study the silicon nanoparticle formation using more complete silane decomposition chemistry, together with the temperature and velocities extracted from the reaction zone CFD simulation. A bivariate model was used to describe the evolution of particle size and morphology. The aggregates were modeled by a moment method, assuming a lognormal distribution in particle volume. This was augmented by a single balance equation for primary particles that assumed locally equal number of primary particles per aggregate and fractal dimension. The model predicted the position and size at which the primary particle size is frozen in, and showed that increasing the peak temperature was a more effective means of improving particle yield than increasing silane concentration or flowrate.

Structural Analysis of Nanocrystalline Silicon Prepared by Hot-wire Chemical Vapor Deposition on Polymer Substrates

AbstractNanocrystalline silicon (nc-Si:H) films were deposited by hot-wire chemical vapor deposition (HWCVD) directly onto Corning glass and polyimide (Kapton E) substrates. The effect of silane concentration (in hydrogen carrier gas) on film crystallinity and conductivity were studied for a constant substrate growth temperature of 220°C. Raman spectroscopy, X-ray diffraction and cross-sectional transmission electron microscopy (XTEM) showed that nc-Si:H (grain-size 20-65 nm) was observed for silane concentrations below 5.8 %. Similar to previous reports, closer inspection using XTEM found that there was an initial growth of an amorphous interfacial layer which then crystallized into a randomly-oriented polycrystalline material after 10 - 100 nm of growth.. However, unlike previous reports, there was no detectable difference in the structure or conductivity for films grown on the two types of substrates. In both cases, the dark conductivity decreased with increasing silane concentration while the photo-conductivity was uniform for all films at values between 2 and 4×10-5 S/cm.

NMR investigations of silane-coated nano-sized ZnO particles

29Si, 129Xe and 13C NMR is used to investigate a porous material consisting of nano-sized ZnO particles coated by silane molecules. These materials are synthesized by a novel sol–gel procedure where the nanoscale ZnO particles are formed in the presence of the coating material 3-methacryloxypropyl-trimethoxysilane (“silane”). The BET specific surface of the uncoated particles, synthesized by the same process in the absence of silane, is 43 m 2/g. As a function of the silane concentration the BET specific surface area of the coated particles first increases with silane concentration, then reaches the maximum of 100 m 2/g at a silane concentration of 1–2 mol.% and finally decreases to almost zero at 10 mol.% silane. This surface area behavior is very different when the same material is UV-irradiated directly after the synthesis. The BET value of the UV irradiated material continually increases with increasing silane concentration till it levels off at 130 m 2/g at 10 mol.% silane. Also the properties of the material have changed significantly upon UV irradiation, a wool-like structure is produced and by the UV irradiation the material changed from being hydrophobic to hydrophilic. From the spectroscopic results we conclude that the non-irradiated material consists of ZnO particles separated by a silicate network bonded to the ZnO surface. Above silane concentrations of 5 mol.% the organic parts of the silane form organic domains with sizes of several tens of nanometers. In that concentration range the material with hydrophobic properties contains nanometer-size ZnO particles and nanometer-size organic domains, separated and bound together by a silicate network. UV irradiation destroys the organic domains and the material becomes highly porous with a high BET surface and hydrophilic properties.

Effects of HWCVD-deposited Seed Layers on Hydrogenated Microcrystalline Silicon Films on Glass Substrates

AbstractMicrocrystalline silicon was deposited by hot-wire chemical vapor deposition (HWCVD) using a graphite filament with and without a thin 50 nm microcrystalline silicon seed layer. Increasing silane concentration diluted in H2 led to a decrease in crystalline fraction as well in a decrease in dark conductivity and photo-conductivity. In addition, films deposited with a seed layer were found to have higher dark conductivity and photo-conductivity than those without a seed layer but deposited at slower growth rates. However, Raman spectroscopy showed that use of a seed layer resulted in only a small increase in crystalline fraction at the surface of the films which had thicknesses between 250-400nm. TEM measurements confirmed the crystalline nature of deposited films showing average grain sizes of 25 nm.

Deposition of microcrystalline silicon prepared by hot-wire chemical-vapor deposition: The influence of the deposition parameters on the material properties and solar cell performance

Microcrystalline silicon (μc-Si:H) of superior quality can be prepared using the hot-wire chemical-vapor deposition method (HWCVD). At a low substrate temperature (TS) of 185 °C excellent material properties and solar cell performance were obtained with spin densities of 6×1015cm−3 and solar cell efficiencies up to 9.4%, respectively. In this study we have systematically investigated the influence of various deposition parameters on the deposition rate and the material properties. For this purpose, thin films and solar cells were prepared at specific substrate and filament temperatures and deposition pressures (pD), covering the complete range from amorphous to highly crystalline material by adjusting the silane concentration. The influence of these deposition parameters on the chemical reactions at the filament and in the gas phase qualitatively explains the behavior of the structural composition and the formation of defects. In particular, we propose that the deposition rate is determined by the production of reactive species at the filament and a particular atomic-hydrogen-to-silicon ratio is found at the microcrystalline/amorphous transition. The structural, optical, and electronic properties were studied using Raman and infrared spectroscopies, optical-absorption measurements, electron-spin resonance, and dark and photoconductivities. These experiments show that higher TS and pD lead to a deterioration of the material quality, i.e., much higher defect densities, oxygen contaminations, and SiH absorption at 2100cm−1. Similar to plasma enhanced chemical-vapor deposition material, μc-Si:H solar cells prepared with HW i layers show increasing open circuit voltages (Voc) with increasing silane concentration and best performance is achieved near the transition to amorphous growth. Such solar cells prepared at low TS exhibit very high Voc up to 600 mV and fill factors above 70% with i layers prepared by HWCVD.

Effects of Fibre Surface Treatment on Dynamic Tensile Properties of Glass Woven Fabric Reinforced Vinylester Composites

Glass fibre has been recognized as a strain rate dependent material. Its failure behaviour changes from brittle to ductile as the strain rate increases. As a consequence, the strength of the glass fibre increases, but the fibres within a composite become more prone to debond from the matrix because of the brittleness of the matrix material, promoted by the high strain rate. In the present study, the tensile responses of glass woven fabric reinforced vinyl ester composites with various fibre surface treatments are examined under static and dynamic loading conditions. The results show that both the ductility and the strength of the composites increased with increasing strain rate. The tensile strength was lower and the failure strain was higher in the weft direction than in the warp direction, because of excessive crimping in the former direction. The tensile strength in general increased with increasing silane concentration, for the majority of strain rates studied. The influence of fibre surface treatment on the impact tensile strength and modulus of composites were functionally similar, confirming the influence of fibre-matrix interphase properties on composite fracture behaviour at high strain rates.

Effects of silane coupling agents on the vulcanization characteristics of natural rubber

AbstractThe vulcanization characteristics of silica‐filled natural rubber (NR) were studied in the presence of silane coupling agents, 3‐octanoylthio‐1‐propyltriethoxysilane (NXT) and bis [(3‐triethoxysilylpropyl) tetra sulfide] (TESPT, or Si‐69). The scorch time, cure rate index, and the rate constant of NR were measured using an Oscillating Disk Rheometer in the temperature range of 140–170°C. The scorch time of NR decreases with increasing TESPT and NXT concentrations, and the scorch time of NR compound with NXT is longer than that with TESPT. The apparent activation energies of vulcanization for the compounds with NXT and TESPT both decrease with increasing silane concentration. The apparent activation energy of vulcanization of NR compound with NXT is lower than that with TESPT at various concentrations. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 1511–1518, 2004

Intrinsic microcrystalline silicon prepared by hot-wire chemical vapour deposition for thin film solar cells

Microcrystalline silicon (μc-Si:H) prepared by hot-wire chemical vapour deposition (HWCVD) at low substrate temperature T S and low deposition pressure exhibits excellent material quality and performance in solar cells. Prepared at T S below 250 °C, μc-Si:H has very low spin densities, low optical absorption below the band gap, high photosensitivities, high hydrogen content and a compact structure, as evidenced by the low oxygen content and the weak 2100 cm −1 IR absorption mode. Similar to PECVD material, solar cells prepared with HWCVD i-layers show increasing open circuit voltages V oc with increasing silane concentration. The best performance is achieved near the transition to amorphous growth, and such solar cells exhibit very high V oc up to 600 mV. The structural analysis by Raman spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM) shows considerable amorphous volume fractions in the cells with high V oc. Raman spectra show a continuously increasing amorphous peak with increasing V oc. Crystalline fractions X C ranging from 50% for the highest V oc to 95% for the lowest V oc were obtained by XRD. XRD-measurements with different incident beam angles, TEM images and electron diffraction patterns indicate a homogeneous distribution of the amorphous material across the i-layer. Nearly no light induced degradation was observed in the cell with the highest X C, but solar cells with high amorphous volume fractions exhibit up to 10% degradation of the cell efficiency.

A comparison of microcrystalline silicon prepared by plasma-enhanced chemical vapor deposition and hot-wire chemical vapor deposition: electronic and device properties

The optoelectronic properties of undoped μc-Si : H have been investigated, with emphasis on the states close to the edges of the band gap. The usefulness of the constant photocurrent method (CPM) for the determination of the absorption coefficient, α(E), is critically described. Combined with carefully evaluated photothermal deflection spectroscopy data, CPM spectra yield valuable information on the transport and dynamics of photo-generated carriers. By comparing photoluminescence and Raman spectra on high-quality samples prepared by plasma-enhanced and hot-wire chemical vapor deposition, with different silane concentrations in the gas stream, a correlation between the microstructure and photoluminescence energy is obtained. It is proposed that the density of band tail states is reduced with increasing silane concentration, leading to an increase in the photoluminescence energy and in the open-circuit voltages of solar cells.

Deposition of Si-DLC films with high hardness, low stress and high deposition rates

In this work silicon-incorporated diamond-like carbon (Si-DLC) films were produced by plasma enhanced chemical vapor deposition (PECVD) from gaseous mixtures of CH 4 and SiH 4. A study of the influence of self-bias and gas composition on the mechanical and structural properties of the films was carried out. Results show that films deposited at high self-bias present high deposition rates, low stress and surprisingly high hardness. Increasing silane concentration in the gas phase leads to an enhancement of the observed effects. Compositional and structural characterization show that deposition at high bias leads to increased sp 2 character and rather low silicon contents. Increasing the silane content in the plasma leads to an increase in the sp 3 fraction of the films, and yields a further reduction of stress with almost no effect upon hardness. In this way, the possibility of producing films with high hardness (>20 GPa), low stress (∼0.5 GPa) and high deposition rates (>40 nm/min) has been demonstrated. This result is thought to be very important from the point of view of technological applications.