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1.
Characteristic electrochemical transport parameters for an experimental poly(ethylene)terephtalate (PET) track-etched membrane with well-defined structure and low porosity (Θ=0.13%) were determined with the membrane in contact with KCl solutions at different concentrations. Membrane potential, Δφm, measurements were performed to investigate the effective fixed charge concentration, Xf, and transport number of the ions, ti, in the membrane using two different procedures: keeping the concentration ratio constant, or keeping one concentration constant and changing the other one. Results show the membrane presents a weak cation-exchanger character, since the following values were obtained: Xf=−(2.5±0.2)×10−2 M, tK =(0.56±0.06), tCl=(0.44±0.05); taking into account these values, concentration dependence of membrane potential was predicted. Membrane electrical resistance, Rm, was obtained from Impedance Spectroscopy (IS) measurements using equivalent circuits as models, and the membrane porosity Θ=(0.11±0.02)% was also obtained from resistance values, which agrees very well with the value determined from geometrical parameters. From Rm, Δφm and Θ values, the diffusion coefficient of the ions in the membrane pores can be calculated, and the following average values were obtained: DK+=(1.9±0.4)×10−9 m2/s and DCl=(0.8±0.2)×10−9 m2/s, but for an average concentration higher than 0.06 M, their values do not differ practically from solution in agreement with the small negative charge previously indicated.  相似文献   

2.
The hydrodynamic characteristics in aqueous solution at ionic strength I=0.2  of carboxymethylchitins of different degrees of chemical substitution have been determined. Experimental values varied over the following ranges: the translational diffusion coefficient (at 25.0°C), 1.1<107×D<2.9 cm2 s−1; the sedimentation coefficient, 2.4<s<5.0 S; the Gralen coefficient (sedimentation concentration-dependence parameter), 130<ks<680 mL g−1; the intrinsic viscosity, 130<[η]<550 mL g−1. Combination of s with D using the Svedberg equation yielded ‘sedimentation–diffusion' molecular weights in the range 40 000<M<240 000 g mol−1. The corresponding Mark–Houwink–Kuhn–Sakurada (MHKS) relationships between the molecular weight and s, D and [η] were: [η]=5.58×10−3 M0.94; D=1.87×10−4 M−0.60; s=4.10×10−15 M0.39. The equilibrium rigidity and hydrodynamic diameter of the carboxymethylchitin polymer chain is also investigated on the basis of wormlike coil theory without excluded volume effects. The significance of the Gralen ks values for these substances is discussed.  相似文献   

3.
Powders of pure and 5% ytterbium substituted strontium cerate (SrCeO3/SrCe0.95Yb0.05O3−δ) were prepared by spray pyrolysis of nitrate salt solutions. The powders were single phase after calcination in nitrogen atmosphere at 1100 °C (SrCeO3) and 1200 °C (SrCe0.95Yb0.05O3−δ). Dense SrCeO3 and SrCe0.95Yb0.05O3−δ materials were obtained by sintering at 1350–1400 °C in air. Heat treatment at 850 and 1000 °C, respectively, was necessary prior to sintering to obtain high density. The dense materials had homogenous microstructures with grain size in the range 6–10 μm for SrCeO3 and 1–2 μm for SrCe0.95Yb0.05O3−δ. The electrical conductivity of SrCe0.95Yb0.05O3−δ was in good agreement with reported data, showing mixed ionic–electronic conduction. The ionic contribution was dominated by protons below 1000 °C and the proton conductivity reached a maximum of 0.005 S/cm above 900 °C. In oxidizing atmosphere the p-type electronic conduction was dominating above 700 °C, while the contribution from n-type electronic conduction only was significant above 1000 °C in reducing atmosphere.  相似文献   

4.
The theoretical basis and the results of a computer simulation are presented which describe the operational limits of size and concentration for aerosol sizing by laser Doppler spectroscopy LDS,. This analysis suggests that a state of the art LDS system has the capability of sizing 0·03 μm diameter particles when the number concentration is 108 cm−3 or greater and 0·2 μm diameter for coocentrations as low as 100 particles cm−3. An evaluation of the effect on the laser Doppler spectroscopy measurements of a polydisperse aerosol having a log normal size distribution is presented and methods for combining these measurements with other averaged measurements to determine both count median diameter (CMD) and geometric standard deviation (δg) are proposed. For aerosols having log normal distributions with 0·3 < CMD < 3 μm and 1·0 < δg < 2·0, laser Doppler spectroscopy is able to measure the surface area median diameter within ± 15 per cent, independent of polydispersity. Applications of LDS to aerosol sizing are evaluated and its advantages and disadvantages relative to other sizing methods are discussed.  相似文献   

5.
The dielectric and ferroelectric properties of lead indium niobate (Pb(In1/2Nb1/2)O3, PIN) ceramic prepared by an oxide-mixing method via wolframite route were investigated. The 98.5% perovskite fine-grained PIN ceramics with average grain sizes of 1–2 μm were obtained by sintering at 1050 °C for 2 h. The dielectric properties of the PIN were of relaxor ferroelectric behavior with temperature of dielectric maximum (Tm) 53 °C and dielectric constant (r) 4300 (at 1 kHz). The PE hysteresis loop measurements at various temperatures showed that the ferroelectric properties of the PIN ceramic changed gradually from the paraelectric behavior at temperature above Tm to slim-loop type relaxor behavior at temperature below Tm. Moreover, the PE loop became more open at temperatures much lower than Tm. At −25 °C, the maximum polarization is found to be 8 μm/cm2 at a field of 30 kV/cm, with Pr value of 2.5 μm/cm2 and Ec of +7.5 kV/cm.  相似文献   

6.
The sintering behavior and dielectric properties of the monoclinic zirconolite-like structure compound Bi2(Zn1/3Nb2/3)2O7 (BZN) and Bi2(Zn1/3Nb2/3−xVx)2O7 (BZNV, x = 0.001) sintered under air and N2 atmosphere were investigated. The pure phase were obtained between 810 and 990 °C both for BZN and BZNV ceramics. The substitution of V2O5 and N2 atmosphere accelerated the densification of ceramics slightly. The influences on microwave dielectric properties from different atmosphere were discussed in this work. The best microwave properties of BZN ceramics were obtained at 900 °C under N2 atmosphere with r = 76.1, Q = 850 and Qf = 3260 GHz while the best properties of BZNV ceramics were got at 930 °C under air atmosphere with r = 76.7, Q = 890 and Qf = 3580 GHz. The temperature coefficient of resonant frequency τf was not obviously influenced by the different atmospheres. For BZN ceramics the τf was −79.8 ppm/°C while τf is −87.5 ppm/°C for BZNV ceramics.  相似文献   

7.
Maria Andrei  Massimo Soprani 《Polymer》1998,39(26):7041-7047
A new class of polymer electrolytes, based on the interpenetrating polymer network approach, was obtained starting from functionalised macromers, of poly-ether nature, in the presence of a lithium salt (LiBF4, LiClO4, LiCF3SO3) and propylene carbonate (PC) or tetraethyleneglycol dimethylether (TGME), as plasticizers.

The macromers were synthesised by living polymerisation employing a HI/I2 system as the initiator. The macromer has a polymerisable end group, which can undergo radical polymerisation, attached to a monodisperse poly-vinylether, containing suitable ethylene oxide groups for ion coordination. Monomers and macromers were characterised by FTi.r., u.v.–vis, 1H- and 13C-n.m.r.

Self-consistent and easily handled membranes were obtained as thin films by a dry procedure using u.v. radiation to polymerise and crosslink the network precursors, directly on suitable substrates, in the presence of the plasticizer and the lithium salt. The electrolytic membranes were studied by complex impedance and their thermal properties determined by differential scanning calorimetry analysis.

Ionic conductivities (σ) were measured for PC and TGME-based membranes at various plasticizer and salt contents as a function of T (60 to −20°C). LiClO4/PC/PE electrolytes, with 3.8% (w/w) salt and 63% PC, have the highest σ (1.15×10−3 and 3.54×10−4 S cm−1 at 20°C and −20°C, respectively). One order of magnitude lower conductivities are achieved with TGME; samples with 6% (w/w) LiClO4 and 45% (w/w) TGME exhibit σ values of 2.7×10−4 and 2.45×10−5 S cm−1 at 20°C and −20°C.  相似文献   


8.
Ammonium polyacrylate (NH4PA) was introduced into powdered mixtures consisting of anatase-structured TiO2 nanoparticles and silicon alkoxide precursors at the sol level, and the rheological behavior of the mixtures was examined under various solid loadings (φ=0.05–0.13 in volumetric ratios), shear rates (  s−1) and NH4PA concentrations. The alkoxide precursors were mixtures of tetraethyl orthosilicate (TEOS, Si(OC2H5)4), ethyl alcohol (C2H5OH), H2O and HCl in a constant [H2O]/[TEOS] ratio of 11. The nanoparticle–sol mixtures generally exhibited a pseudoplastic flow behavior over the shear-rate regime examined. The NH4PA appeared to serve as an effective surfactant which facilitates the suspension flow by reducing the flow resistance at low NH4PA concentrations. At φ=0.10, a viscosity reduction ca. 85% was found at  s−1 when the NH4PA concentration was held at 2.5 wt.% of the solids. As the NH4PA exceeded a critical level, e.g., [NH4PA]≥3.0 wt.%, the NH4PA acted as a catalyst which quickly turned the TiO2–silica sol mixtures (φ=0.10) into a gelled structure, resulted in a pronounced increase of mixture viscosity. The maximum solids concentration (φm) of the mixtures was experimentally determined from a derivative of relative viscosity, i.e., (1−ηr−1/2)–φ dependence. The estimated φm increased from 0.127 to 0.165 when NH4PA of 0.5 wt.% was introduced into the TiO2–silica sol mixtures.  相似文献   

9.
Surface dynamics during latex film formation   总被引:3,自引:0,他引:3  
Surface dynamics during latex film formation has been investigated theoretically and experimentally by atomic force microscopy. The peak-to-valley distance, y(t), of the latex particles in the surface plane of the latex film decayed exponentially with time during film formation. A theoretical relationship between y(t) and time, t, is given by y(t)=y(0) exp[−t/τ], where y(0) is the value of y(t) when t is zero. τ is a characteristic constant related to the nature of polymer, the particle radius, the surface diffusion coefficient and the temperature. The relationship between the surface diffusion coefficient, Ds, y(0), the radius of the latex particles, R, temperature, T, and τ is given approximately by Ds=1.2×10−20y(0)2[2Ry(0)]2T/τ (cm2/s), where the units are manometers for y(0) and R, kelvin for temperature, and seconds for τ. By measuring the decay of y(t) with time, the surface diffusion coefficient can be obtained. The surface diffusion coefficient for a poly(methyl methacrylate-co-butylacrylate) (50:50) copolymer latex film was found to be A×10−13 cm2/s, A is temperature-dependent.  相似文献   

10.
Layered -titanate materials, NaxMx/2Ti1−x/2O2 (M=Co, Ni and Fe, x=0.2–0.4), were synthesized by flux reactions, and electrical properties of polycrystalline products were measured at 300–800 °C. After sintering at 1250 °C in Ar, all products show n-type thermoelectric behavior. The values of both d.c. conductivity and Seebeck coefficient of polycrystalline Na0.4Ni0.2Ti0.8O2 were ca. 7×103 S/m and ca. −193 μV/K around 700 °C, respectively. The measured thermal conductivity of layered -titanate materials has lower value than conductive oxide materials. It was ca. 1.5 Wm−1 K−1 at 800 °C. The estimated thermoelectric figure-of-merit, Z, of Na0.4Ni0.2Ti0.8O2 and Na0.4Co0.2Ti0.8O2 was about 1.9×10−4 and 1.2×10−4 K−1 around 700 °C, respectively.  相似文献   

11.
An organic precursor synthesis of 8 mol% yttria stabilized zirconia (YSZ) powder from Zr–Y composite nitrate solution and sucrose has been studied. Oxidation of sucrose in Zr–Y composite nitrate solution containing excess nitric acid in situ generates hydroxy carboxylic acids that forms a white sol which showed peaks at 1640 cm−1 and 1363 cm−1 in IR spectrum corresponding to hydroxy carboxylic acid complexes of Zr and Y. Precursor mass obtained by drying the sol on calcinations at 600 °C produced loosely agglomerated particles of cubic YSZ. Deagglomerated YSZ contain submicron particles with D50 value of 0.5 μm and the particles are aggregates of nanocrystallites of nearly 10 nm size. Compacts prepared by pressing the YSZ powder sintered to 96.7% TD at 1450 °C. The sintered YSZ ceramic showed an average grain size of 2.2 μm.  相似文献   

12.
The single gas H2 and N2 permeability of a 4 μm thick dense fcc-Pd66Cu34 layer has been studied between room temperature and 510 °C and at pressure differences up to 400 kPa. Above 50 °C the H2 flux exhibits an Arrhenius-type temperature dependence with JH2=(5.2±0.3) mol m−2 s−1 exp[(−21.3 ± 0.2) kJ mol−1/(R·T)]. The hydrogen transport rate is controlled by the bulk diffusion although the pressure dependence of the H2 flux deviates slightly from Sieverts’ law. A sudden increase of the H2 flux below 50 °C is attributed to embrittlement.  相似文献   

13.
Nanometer perovskite-type oxides La1−xSrxMO3−δ (M = Co, Mn; x = 0, 0.4) have been prepared using the citric acid complexing-hydrothermal-coupled method and characterized by means of techniques, such as X-ray diffraction (XRD), BET, high-resolution scanning electron microscopy (HRSEM), X-ray photoelectron spectroscopy (XPS), temperature-programmed desorption (TPD), and temperature-programmed reduction (TPR). The catalytic performance of these nanoperovskites in the combustion of ethylacetate (EA) has also been evaluated. The XRD results indicate that all the samples possessed single-phase rhombohedral crystal structures. The surface areas of these nanomaterials ranged from 20 to 33 m2 g−1, the achievement of such high surface areas are due to the uniform morphology with the typical particle size of 40–80 nm (as can be clearly seen in their HRSEM images) that were derived with the citric acid complexing-hydrothermally coupled strategy. The XPS results demonstrate the presence of Mn4+ and Mn3+ in La1−xSrxMnO3−δ and Co3+ and Co2+ in La1−xSrxCoO3−δ, Sr substitution induced the rises in Mn4+ and Co3+ concentrations; adsorbed oxygen species (O, O2, or O22−) were detected on the catalyst surfaces. The O2-TPD profiles indicate that Sr doping increased desorption of the adsorbed oxygen and lattice oxygen species at low temperatures. The H2-TPR results reveal that the nanoperovskite catalysts could be reduced at much lower temperatures (<240 °C) after Sr doping. It is observed that under the conditions of EA concentration = 1000 ppm, EA/oxygen molar ratio = 1/400, and space velocity = 20,000 h−1, the catalytic activity (as reflected by the temperature (T100%) for EA complete conversion) increased in the order of LaCoO2.91 (T100% = 230 °C) ≈ LaMnO3.12 (T100% = 235 °C) < La0.6Sr0.4MnO3.02 (T100% = 190 °C) < La0.6Sr0.4CoO2.78 (T100% = 175 °C); furthermore, there were no formation of partially oxidized by-products over these catalysts. Based on the above results, we conclude that the excellent catalytic performance is associated with the high surface areas, good redox properties (derived from higher Mn4+/Mn3+ and Co3+/Co2+ ratios), and rich lattice defects of the nanostructured La1−xSrxMO3−δ materials.  相似文献   

14.
Effect of electrical ageing (EA) on the field emission parameters of thin multiwall carbon nanotube composite (t-MWCNTs-composite) was studied. Initially, t-MWCNTs were mixed with -terpineol and ethyl cellulose and subjected to three roll milling process to obtain t-MWCNTs-composite. Following this, the composite was screen printed on a conducting substrate, annealed for 10 min and employed to the electrical ageing process for a period of 6 h. The ageing, on each cathode layer, was repeated for five times and JE characteristics have been collected before and after each ageing attempt. The analysis revealed that, the magnitude of threshold turn-on-field gradually increased from its virgin value of 1.223 to 1.968 V µm− 1 and corresponding mean field enhancement factor, γm, gradually decreased from 2700 ± 210 to 1940 ± 30 with a sequential increase in the ageing attempts. The degradation rate, δJt, estimated for untreated and EA samples, indicated that the magnitude of δJt reached to an equilibrium value of ~ 0.785 μA cm− 2 min− 1, which shows a stable emission state of the emitters. To investigate the effect of EA on the physical state of the emitters, a few virgin and all EA samples were subjected to scanning electron microscopy, micro Raman spectroscopy and X-ray photoelectron spectroscopy. The details of the analysis are presented.  相似文献   

15.
The processing conditions, reaction mechanism, fine structure of the powders, microstructure, and dielectric properties of SrBiNb2O9 (SBN) were systematically studied. A relative density of >80% was obtained using a two-step sintering process at moderate pressure. XRD showed that a single phase with the layered perovskite structure of SrBi2Nb2O9 (SBN) was formed after calcining at 600 °C. No intermediate phase was found during heat treatment at and above 600 °C. The crystallite size (D) and the effective strain (η) were found to be 38.8 nm and 0.01475, respectively, while the particle size obtained from TEM was laid between 25 and 36 nm. SEM revealed that the average grain size after sintering at 900 °C for 4 h was 0.67 μm. Dielectric constant and corresponding tangent loss were measured in the frequency range from 1 kHz to 1 MHz from which the Curie temperature (Tc) was found to be at 450 °C.  相似文献   

16.
Ten weight percent BBZS (Bi2O3, B2O3, ZnO and SiO2) glass was added to x(Ba4Nd9.333Ti18O54) − (1 − x)(BaLa4Ti4O15) (BNLT, 0 ≤ x ≤ 1) composite dielectric ceramics to lower their sintering temperature whilst retaining microwave properties useful for low temperature co-fired ceramic and antenna core technology. With the addition of 10 wt% BBZS glass, dense BNLT composite ceramics were produced at temperatures between 950 and 1140 °C, depending on composition (x), an average reduction of sintering temperature by 350 °C. X-ray diffraction, scanning and transmission electron microscopy and Raman spectroscopy studies revealed that there was limited inter-reaction between BLT/BNT and the BBZS glass. Microwave property measurement showed that the addition of BBZS glass to BNLT ceramics had a negligible effect on r and τf, although deterioration in the measured quality factor (Qf) was observed. The optimised composition (xBNT − (1 − x)BLT)/0.1BBZS (x = 0.75) had r  61, τf  38 ppm/°C and Qf  2305 GHz.  相似文献   

17.
A relation was obtained between electro-chemical properties of sodium salts (NaCl, NaBr, and Na2SO4), and the thermodynamic property of permeability in symmetrical cellulose acetate membranes, the distribution coefficient K and the kinetic property, the overall diffusion coefficients D. K and D were obtained by the method we proposed using measured unsteady- and steady-state dialysis data. The K values increase with the increase of water content and are in the range of 10−2 for sodium halides and 10−3 for Na2SO4. D is found to increase with the increase of the solute concentration, and the extrapolated values of D to zero concentration D(0) are obtained as 0.015–0.03 μm2/s and increase with the increase of water content in the membrane. D can be divided into the concentration independent diffusion coefficients in the dense part of the membrane Dd and in the porous Dp, applying a two-part (perfect or dense and imperfect or porous) model of the membrane. Contrary to Dd, Dp increases with the increase of Ww and can be correlated as Dp,c = d exp (γ × Ww). It is shown that the averaged Dd, D increases with the increase of the quantity of the ionic mobility u of the solutes at infinite dilution divided by valence, and that the parameter γ increases with the increase of the ionic mobility u. The value of K increases slightly with the increase of water content and decreases with the increase of the Flory—Huggins parameter χ. The Flory—Huggins parameter χ is calculated from the measured values of distribution coefficients and data obtained from the literature. And it was found that the gradient of linear decrease of χ (λcation) depends on equivalent ionic conductivity of anion of salt, λan.  相似文献   

18.
Fully dense composites of 0–30 wt% discrete TiN particles distributed in a ß-sialon matrix of overall composition Si5·5Al0·5O0·5N7·5 have been prepared by hot isostatic pressing at 1650 and 1750°C. Pressureless sintering at 1775°C gave materials with an open porosity. Typical sizes of the TiN particles were 1–3 μm, and no intergranular glassy phase was observed in the prepared materials. The grain size of ß-sialon was below 1 μm in the materials HIPed at 1650°C, and 1–2 μm at 1750°C. The Vickers hardness was fairly constant for the TiN-ß-sialon composites with up to 15 wt% TiN added: Hv10 around 17·5 GPa for materials HIPed at 1650° and around 17 GPa at 1750°C, whereas at higher TiN contents the hardness decreased to around 16 GPa. The indentation fracture toughness of the ß-sialon ceramic increased approximatively from 3 to 4 MPam1/2 at an addition of 15 wt% TiN particulates. The fracture toughness could be further increased to 5 MPam1/2 by addition of small amounts of Y2O3 and A1N to a ß-sialon composite with 30 wt% TiN.  相似文献   

19.
Bearing in mind the excellent dielectric properties at high frequency of some niobates like ZnNb2O6, Zn3Nb2O8, BaNb2O6, Ba5Nb4O15 (r 20–45, tan δ < 10 × 10−4 and ρi > 1010 Ω cm), synthesis, sintering and properties of these oxides are reported. The lowering of their sintering temperature has been investigated for these four ceramics using sintering aids. Using appropriate additive, it is possible to densify these ceramics at a temperature for which base metal electrodes, e.g. Cu and Ag can be employed. Two formulations were found to be sinterable at 1000 °C (lower than the copper melting point) whereas a third formulation is co-sinterable with silver electrodes. For this later, the dielectric properties are globally maintained in comparison with the pure compound sintered at 1200 °C. This result makes this formulation suitable for silver based passive components devices manufacturing.  相似文献   

20.
(Mg1−xZnx)2SiO4 ceramics were prepared and characterized. The densification temperatures of the present ceramics are much lower than those for Mg2SiO4 and Zn2SiO4 end-members. Small solid solution limits of Zn in Mg2SiO4 and Mg in Zn2SiO4 are observed, and the bi-phase structure is confirmed in (Mg1−xZnx)2SiO4 ceramics with x = 0.1–0.9. Even though, it is clear that the Qf value of Zn2SiO4 ceramics can be significantly improved together with a suppressed temperature coefficient of resonant frequency τf by substituting Mg for Zn. (Mg0.4Zn0.6)2SiO4 ceramics indicate a good combination of microwave dielectric characteristics: r = 6.6 Qf = 95,650 GHz, and τf = −60 ppm/°C.  相似文献   

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