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1.
Doris Ehrt 《Journal of Non》2008,354(2-9):546-552
Glasses with 55–60 mol% SnO and 40–45 mol% P2O5 have shown extremely large differences in the chemical and thermal properties depending on the temperature at which they were melted. Glasses prepared at low melting temperature, 450–550 °C, had low Tg, 150–200 °C, and low chemical stability. Glasses prepared at high melting temperature, 800–1200 °C, had much higher Tg, 250–300 °C, and much higher chemical stability. No significant differences were found by 119Sn Mössbauer and 31P Nuclear Magnetic Resonance spectroscopy. Large differences in the OH-content could be detected as the reason by infrared absorption spectroscopy, thermal analyses, and 1H Nuclear Magnetic Resonance spectroscopy. In samples with low Tg, a broad OH – vibration band around 3000 nm with an absorption intensity >20 cm?1, bands at 2140 nm with intensity ~5 cm?1, at 2038 nm with intensity ~2.7 cm?1, and at 1564 nm with intensity ~0.4 cm?1 were measured. These samples have shown a mass loss of 3–4 wt% by thermal gravimetric analyses under argon in the temperature range 400–1000 °C. No mass loss and only one broad OH-band with a maximum at 3150 nm and low absorption intensity <4 cm?1 could be detected in samples melted at high temperature, 1000–1200 °C, which have much higher Tg, ~300 °C, and much higher chemical stability.  相似文献   

2.
《Journal of Non》2006,352(26-27):2737-2745
Electrical properties of A2.6+xTi1.4−xCd(PO4)3.4−x (A = Li, K; x = 0.0–1.0) phosphate glasses are investigated over a frequency range from 42 Hz to 1 MHz at different temperatures. Impedance spectroscopy is used to separate the bulk conductivity from electrode effect of electrical conductivity data. The bulk dc conductivity is Arrhenius activated, with activation energies and pre-exponential factors following the Meyer–Neldel rule. The real part of ac conductivity shows universal power law feature. The variation of dielectric constant with frequency is attributed to ion diffusion and polarization occurring in the phosphate glasses. The frequency dependent imaginary part of electric modulus M″(ω) plot shows non-Debye feature in conductivity relaxation. The Kohlrausch–Williams–Watts stretched exponential function was used to describe the modulus spectra and the stretching exponent β is found to be temperature independent. Scaling in M″(ω) shows that the electrical relaxation mechanisms are independent of temperature for given composition at different temperatures.  相似文献   

3.
Photo-induced crystallization of a-Se is investigated by Raman spectroscopy as a function of temperature (250–340 K) and exposure time in thin-film structures used as targets in high-gain avalanche rushing photoconductor (HARP) video cameras. The Stokes-to-Antistokes ratio is monitored to obtain the local temperature Tloc at the laser spot; fluxes (632 nm) of 17 and 10 W/cm2 are used. We find a rich temperature behavior that reflects the competition of changes in viscosity and strain, and defines four distinct regimes. No photo-crystallization is seen for Tloc below 260 K, nor in a 15 K range around Tg  310 K. For Tloc in the regime 260–302 K the initial rate of crystal growth after onset of photo-crystallization is temperature independent, whereas for Tloc > 318 K the growth rate is thermally enhanced. Our results are in qualitative accord with a theory by Stephens treating the effects of local strain on the secondary growth of crystalline nuclei in a-Se. We conclude that the observed growth rate between 260 and 302 K is driven by local strain, and that relaxation of this strain near Tg suppresses crystal growth until thermally assisted processes accelerate the photo-crystallization at higher temperatures.  相似文献   

4.
We measured and collected literature data for the crystal growth rate, u(T), of μ-cordierite (2MgO · 2Al2O3 · 5SiO2) and diopside (CaO · MgO · 2SiO2) in their isochemical glass forming melts. The data cover exceptionally wide temperature ranges, i.e. 800–1350 °C for cordierite and 750–1378 °C for diopside. The maximum of u(T) occurs at about 1250 °C for both systems. A smooth shoulder is observed around 970 °C for μ-cordierite. Based on measured and collected viscosity data, we fitted u(T) using standard crystal growth models. For diopside, the experimental u(T) fits well to the 2D surface nucleation model and also to the screw dislocation growth mechanism. However, the screw dislocation model yields parameters of more significant physical meaning. For cordierite, these two models also describe the experimental growth rates. However, the best fittings of u(T) including the observed shoulder, were attained for a combined mechanism, assuming that the melt/crystal interface growing from screw dislocations is additionally roughened by superimposed 2D surface nucleation at large undercoolings, starting at a temperature around the shoulder. The good fittings indicate that viscosity can be used to assess the transport mechanism that determines crystal growth in these two systems, from the melting point Tm down to about Tg, with no sign of a breakdown of the Stokes–Einstein/Eyring equation.  相似文献   

5.
The processes of charge transport and trapping in amorphous Si1 ? xCx:H films deposited on crystalline p-type Si wafers and annealed in vacuum in the temperature range 300–650 °C have been evaluated. Current–voltage (IV), capacitance–voltage (CV) and admittance–temperature (G–T) characteristics were measured in the temperature range 100–350 K. The spectrum of thermal effusion of hydrogen was measured from room temperature up to 1000 °C.C–V characteristics indicate a slight increase of the dielectric constant k and a large hysteresis after annealing at 450 °C. The hysteresis is believed to be associated with mobile hydrogen effusion from the a-SiC:H film, and it is not seen after a 650 °C anneal. From IV data the maximum rectification ratio is observed after annealing at 450 °C. Variable-range hopping (VRH) conduction at the Fermi level is found to dominate the forward current of the as-deposited structure. After annealing at 450 °C the forward current can be described by space-charge limited (SCL) mechanisms with trapping at shallow levels with energy of about 0.12 eV. After annealing at 650 °C the process of VRH conduction appears again, but the density of hopping sites is much higher than in the as-grown sample. From admittance spectra, the energy position of respective traps in a-SiC:H is at (EV + 0.45) eV for as-deposited material and it decreases slightly after vacuum annealing. On the basis of these results, an energy band diagram of the a-Si1 ? xCx:H/p-Si structure annealed at 450 °C is proposed.  相似文献   

6.
M.R. Sahar  K. Sulhadi  M.S. Rohani 《Journal of Non》2008,354(12-13):1179-1181
Er3+-doped tellurite glasses of the (80 ? x)TeO2–20ZnO–(x)Er2O3 system (0.5 mol% ? x ? 2.5 mol%) have successfully been made by melt-quenching technique and their structure has been investigated by means of DTA and Raman spectroscopy. The DTA results show the thermal parameters; such as the glass transition temperature (Tg) and crystallization temperature (Tc) were determined. It is found that this system provides a stable and wide glass formation range in which the glass stability around 99–140 °C may be obtained. The Raman spectroscopy used the structural studies in the glass system. Two Raman shift peaks were observed around 640–670 cm?1 and 720–740 cm?1, which correspond to the stretching vibration mode of TeO4 tbp and TeO3 tp, respectively. It is found that the spectral shift in Raman spectra is depending on the Er2O3 content. This evolution is an indication of the changes in the basic unit of the glass structure.  相似文献   

7.
《Journal of Non》2007,353(24-25):2328-2332
Chalcogenide glasses based on the cadmium–selenium system, with the selenium composition varying from 0 to 7.5 wt% have been prepared using melt-quenching method i.e., single-roller quenching technique. The X-ray diffraction (XRD) and selected area electron diffraction (SAD) patterns of the CdSe ribbons indicate that the ribbons are amorphous. The transmission electron microscopy (TEM) studies carried out on these ribbons reveal that the constituents are inhomogeneously distributed in these ribbons. The temperature dependence of the electrical resistivity, ρ and thermoelectric power (TEP) of these ribbons has been studied in the temperature range 30–350 °C. The sudden jump in the values of electrical resistivity at a specific temperature for each case in these ribbons has been correlated with the phase transition i.e., the onset of crystallization in these materials during heating. The crystallization temperature, Tc has been found to be a function of Se content of these ribbons. The phase change in these ribbons as a result of heating does not seem to affect the variation of TEP with temperature. However, the slope of TEP versus temperature curves depends on Se content in these ribbons. The differential scanning calorimetry (DSC) of these ribbons indicates that the supercooled region in these ribbons extends from 50 to 70 °C. The composition CdSe ribbon with 0.5 wt% Se has the highest value of Tc and glass forming ability, Kg = 0.7.  相似文献   

8.
Glass samples have been prepared in the NaPO3–KHSO4 binary system with the classical melting, casting and annealing steps. Electrical and dielectrical properties of glass samples were studied. Measurements of DC and AC conductivity and complex electrical permittivity of xNaPO3–(100 ? x)KHSO4 glass system were carried out at temperatures ranging from room temperature to temperature located 15 °C below glass transition temperature Tg. Results showed that changes of NaPO3 concentration considerably affect values of observed parameters. DC conductivity of glass increases as NaPO3 concentration grows until concentration x = 60. However, beyond this value a sharp decrease of DC conductivity was observed. In addition relaxation times showed abrupt changes at concentration x = 60, corresponding to the lowest relaxation times at the temperature 90 °C.  相似文献   

9.
《Journal of Non》2007,353(13-15):1437-1440
Surface morphology and roughness of amorphous spin-coated As–S–Se chalcogenide thin films were determined using atomic force microscopy. Prepared films were coated from butylamine solutions with thicknesses d  100 nm and then annealed in a vacuum furnace at 45 °C and 90 °C for 1 h for their stabilization. The root mean square surface roughness analysis of surfaces of as-deposited spin-coated As–S–Se films indicated a very smooth film surface (with Rq values 0.42–0.45 ± 0.2 nm depending on composition). The nanoscale images of as-deposited films confirmed that surface of the films is created by domains with dimensions 20–40 nm, which corresponds to diameters of clusters found in solutions. The domain character of film surfaces gradually disappeared with increasing annealing temperature while the solvent was removed from the films. Middle-infrared transmission spectra recorded a decrease of intensities of vibration bands connected to N–H (at 3367 and 3292 cm−1) and C–H (at 2965, 2935 and 2880 cm−1) stretching vibrations. Temperature regions of solvent evaporation T = 60–90 °C and glass transformation temperatures Tg = 135–150 °C of spin-coated As–S–Se thin films were determined using a modulated differential scanning calorimetry.  相似文献   

10.
A new melting enthalpy ΔHm criterion for the prediction of glass forming ability (GFA) of alloys is proposed and five Zr–Al–Ni–Cu bulk metallic glasses (BMG) with critical dimension Zmax up to ? 7.5 mm are also developed by us in the light of the optimum ΔHm of Zr–Al–Ni–Cu alloy system. And then, we researched the relationships between ΔHm and two GFA parameters (critical cooling rate Rc and Zmax) of five bulk metallic glass (BMG) systems, such as Mg–Ni–Nd, Pd–Cu–Si, La–Al–Ni–Cu, Zr–Al–Ni–Cu and Zr–Ti–Ni–Cu–Be, respectively. The results show that the relationships between ΔHm and Rc are all concave upward parabolas, and the optimum ΔHms for Mg–Ni–Nd, Pd–Cu–Si, Zr–Al–Ni–Cu, Zr–Ti–Ni–Cu–Be and La–Al–Ni–Cu are 10.3960 kJ mol?1, 21.2202 kJ mol?1, 19.7146 kJ mol?1, 18.1455 kJ mol?1 and 13.1558 kJ mol?1, respectively. On the contrary, the relationships between ΔHm and Zmax are all concave downward parabolas, and the optimum ΔHms for Mg–Ni–Nd, Pd–Cu–Si, Zr–Al–Ni–Cu, Zr–Ti–Ni–Cu–Be and La–Al–Ni–Cu are 10.5530 kJ mol?1, 21.0830 kJ mol?1, 19.6603 kJ mol?1, 19.7231 kJ mol?1 and 13.1173 kJ mol?1, respectively. Furthermore, other BMGs’ Rcs or Zmaxs predicted by above-mentioned relationships satisfactorily agree with the tested results, which indicates that these relationships are reliable. However, the predicted results are reliable only if the main components are similar with the fitted BMGs or the additive is sparkle enough that the alloy’s character does not change. On the whole, the ΔHm can act as a criterion for quickly predicting the alloy’s GFA and be helpful for the development of new BMGs.  相似文献   

11.
The grain boundary groove shapes for equilibrated solid neopentylglycol (NPG) solution (NPG–3 mol% D-camphor) in equilibrium with the NPG–DC eutectic liquid (NPG–36.1 mol% D-camphor) have been directly observed using a horizontal linear temperature gradient apparatus. From the observed grain boundary groove shapes, the Gibbs–Thomson coefficient (Г), solid–liquid interfacial energy (σSL) of NPG solid solution have been determined to be (7.5±0.7)×10?8 K m and (8.1±1.2)×10?3 J m?2, respectively. The Gibbs–Thomson coefficient versus TmΩ1/3, where Ω is the volume per atom was also plotted by linear regression for some organic transparent materials and the average value of coefficient (τ) for nonmetallic materials was obtained to be 0.32 from graph of the Gibbs–Thomson coefficient versus TmΩ1/3. The grain boundary energy of solid NPG solution phase has been determined to be (14.6±2.3)×10?3 J m?2 from the observed grain boundary groove shapes. The ratio of thermal conductivity of equilibrated eutectic liquid to thermal conductivity of solid NPG solution was also measured to be 0.80.  相似文献   

12.
《Journal of Non》2005,351(43-45):3503-3507
Lead-free glasses in the SiO2–B2O3–Bi2O3–ZnO quaternary system were studied. The glass formation region, as determined by XRD patterns of bulk samples, was limited to glasses having more than 40 mol% of the glass-forming oxides SiO2 and B2O3. Crystalline phases of Zn2SiO4 (willemite) were detected in compositions of 30SiO2 · 10B2O3 · 20Bi2O3 · 40ZnO and 20SiO2 · 10B2O3 · 25Bi2O3 · 45ZnO. Glass transition temperatures (Tg), dilatometric softening points (Td) and linear coefficients of expansion in the temperatures range of 25–300 °C (α25–300) were measured for subsystems along the B2O3 join of 10, 20 and 30 mol%. For these subsystems, Tg ranged from 411 to 522 °C, and Td ranged from 453 to 563 °C, both decreasing with increasing Bi2O3 content. The measured α25–300 ranged from 53 to 95 × 10−7 °C−1, with values increasing with increasing Bi2O3 content. The ZnO content had the opposite effect to the Bi2O3 content. It appears that Bi3+ acts as a glass-modifier in this quaternary system.  相似文献   

13.
We report structural and magnetic properties of fine particles embedded in an amorphous magnetic matrix. As-quenched amorphous Fe73.5Nb3CuSi13.5B9 ribbons (FINEMET) were submitted to the thermal treatments of several times (1 ? t ? 240 min) at 570 °C using a conventional furnace. The analyses of the X-ray diffraction patterns at room temperature reveal that our samples consist of single phase Fe3Si nanocrystals embedded in a residual amorphous phase. Magnetic measurements show that the saturation moment at T = 450 °C increases as a function of annealing time. This behavior is attributed to an increase of the fraction of nanocrystallites in the residual amorphous phase.  相似文献   

14.
The elastic properties of alkali germanate glasses, xR2O?(100 ? x)GeO2 (R = Li, Na, K, Rb, Cs ; x = 14, 28), have been studied by Brillouin scattering in the wide temperature range up to 1200 °C. The remarkable aging effect of Brillouin shift ΔνL has been observed below a glass transition temperature Tg  500 °C. The temperature dependence of longitudinal sound velocity VL of well annealed glasses shows the gradual decrease below Tg, while on further heating the remarkable decrease is observed above Tg. The scaled temperature dependence of VL is nearly independent on alkali metals below the melting temperature Tm. While on further heating above Tm, the drastic decrease of VL and increase of αL show the remarkable alkali dependence. It may be attributed to the appearance of dynamic process related to ionic hopping of alkali metals released from glass network above Tm.  相似文献   

15.
We report the results of a systematic study of the thermal and optical properties of a new family of tellurite glasses, TeO2–ZnO–BaO (TZBa), as a function of the barium oxide mole fraction and compare them with those of TeO2–ZnO–Na2O (TZN). The characteristic temperatures of this new glass family (glass transition, Tg, crystallization, Tx, and melting, Tm) increase significantly with BaO content and the glasses are more thermally stable (greater ΔT = Tx ? Tg) than TZN glasses. Relative to these, Raman gain coefficient of the TZBa glasses also increases by approximately 40% as well as the Raman shift from ~ 680 cm? 1 to ~ 770 cm? 1. The latter shift is due to the modification of the glass with the creation of non-bridging oxygen ions in the glass network. Raman spectroscopy allows us to monitor the changes in the glass network resulting from the introduction of BaO.  相似文献   

16.
V.I. Mikla  V.V. Mikla 《Journal of Non》2011,357(22-23):3675-3688
One of the most important parameters which determine the performance of many modern devices based on amorphous semiconductors is the drift mobility-lifetime product, μτ. There has been much interest in determination of charge-carrier ranges in amorphous semiconductors by various measurement techniques. Although the mobility, μ, can be measured by the conventional time-of-flight transient photoconductivity technique, the determination of the lifetime, τ, is often complicated by both experimental and theoretical limitations. The present article provides an overview of xerographic measurements as a tool for studying the electrical properties of amorphous semiconductors. First, details of the experimental set-up are discussed. Thereafter, the analysis and interpretation of dark discharge, the first cycle residual potential, cycled-up saturated residual potential are considered. It is shown that from such measurements the charge-carrier lifetime, τ, the range of the carriers, μτ, and the integrated concentration of deep traps in the mobility gap can be readily and accurately determined. Xerographic measurements on Se-rich amorphous photoconductors have indicated the presence of relatively narrow distribution of deep hole traps with integrated density of about 1013 cm? 3. These states are located at ~ 0.85 eV from the valence band. A good correlation was observed between residual potential and the hole range, in agreement with the simple Warter expression. The capture radius is estimated to be rc = 2–3 Å. Since rc for pure a-Se and a-AsxSe1 ? x is comparable to the Se–Se interatomic bond length in a-Se, it can be suggested that deep hole trapping centers in these chalcogenide semiconductors are neutral-looking defects, possibly of intimate valence-alternation pair (IVAP) in nature. The absence of any electron spin resonance signal (ESR) at room temperature seemed to be a strong argument in favor of this suggestion. Finally, photoinduced effects on xerographic parameters are discussed. It has been shown that photoexcitation of a-AsxSe1 ? x amorphous films with band-gap light alters deep hole and electron states. During room-temperature annealing photosensitized states relax to equilibrium. Recovery process becomes slower with increasing As content. Qualitative explanation of the observed behavior may be based on associating the deep states with C3+ and C1?intimate-valence-alternation–pair (IVAP) centers.  相似文献   

17.
Li Chen  Chunlei Yu  Dongbing He  Lili Hu  Wei Chen 《Journal of Non》2011,357(11-13):2286-2289
Transparent glass-ceramics were synthesized by heat-treatment of glass with a composition of 5La2O3–13.2MgO–28.8Al2O3–46SiO2–4.5TiO2–2.5ZrO2–0.15CoO (LMAS) (wt.%). The activation energy of crystallization and the Avrami parameter for the LMAS glass were determined from the DTA curves at different heating rates. The most two intense bands of Raman spectrum of initial glass at ~ 810 cm?1 and ~ 900 cm?1 were connected with the presence of [SiO4] and [TiO4] tetrahedral, respectively. After heat-treated at 700 °C/10 h+820 °C/8 h, the intensity of the band for [TiO4] tetrahedral weakened, while an intensive band at ~ 800 cm?1 for the Ti–O bond appeared. Other bands were characteristics of high-silicate network and x(MgTi2O5y(Al2TiO5) polycrystals. The changes reflected phase separation after heat-treatment of the initial glass. The strong absorption band of glass-ceramics centered at 580 nm can be assigned to 4A2(4F)→4T1(4P) and the broad absorption band at 1100–1700 nm to 4A2(4F)→4T1(4F) transitions of tetrahedral coordinated Co2+ ion. Two broad emission bands, one was around 660 nm, the other was from 800 nm to 1050 nm, of glass-ceramics correspond to the 4T1(4P)→4A2(4F) and 4T1(4P)→4T2(4F) transitions of tetrahedral coordinated Co2+ ions. The absorption and emission features clearly demonstrated that Co2+ ions were incorporated into nanocrystals and located in tetrahedral sites.  相似文献   

18.
《Journal of Non》2007,353(32-40):3338-3341
A series of glass forming alloys (Ti33Zr33Hf33)100−xy(Ni50Cu50)xAly (x = 20–70 at.% and y = 0–30 at.%) have been developed by equiatomic substitution of similar elements. Of these alloys (Ti33Zr33Hf33)50(Ni50Cu50)40Al10 was chosen in this study to investigate the structural relaxation and glass transition behavior. The as-quenched (Ti33Zr33Hf33)50(Ni50Cu50)40Al10 alloy was fully amorphous and had a wide supercooled liquid region ΔT = Tx(503 °C)  Tg(433 °C) = 70 °C, where Tg and Tx are the glass transition and crystallization temperatures, respectively. Low temperature pre-heat treatments of the (Ti33Zr33Hf33)50(Ni50Cu50)40Al10 alloy for 10 min at 310 °C, 370 °C and 390 °C caused structural relaxation accompanied by the formation of very fine scale lattice ordering. After these heat treatments, the glass transition became hard to observe in the (Ti33Zr33Hf33)50(Ni50Cu50)40Al10 alloy. Increasing the pre-heat treatment temperatures and holding times caused the glass transition to become more clearly detectable with increasing endothermic heat release.  相似文献   

19.
B. Kościelska  A. Winiarski 《Journal of Non》2008,354(35-39):4349-4353
Sol–gel derived xNb2O5–(100 ? x)SiO2 films (where x = 100, 80, 60, 50, 40, 20, 0 mol%) were nitrided at various temperatures (800 °C, 900 °C, 1000 °C, 1100 °C and 1200 °C). The structural transformations occurring in the films as a result of ammonolysis were studied using X-ray diffraction (XRD), atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The XRD results have shown that the temperatures below 1100 °C were too low to obtain a pure NbN phase in the samples. The AFM observations indicate that the formation of the NbN phase and the size of NbN grains are related to the silica content in the layer. NbN grains become more regular and larger as the niobium content increases. The maximum grain size of about 100 nm was observed for x = 100. Preparation of the Nb2O5–SiO2 sol–gel derived layers and the subsequent nitridation is a promising method of inducing crystalline NbN in amorphous matrices. It follows from the XPS results that a small amount of Nb2O5 remains in the films after nitridation at 1200 °C and that nitrogen reacted not only with Nb2O5 but also with SiO2.  相似文献   

20.
J. Ozdanova  H. Ticha  L. Tichy 《Journal of Non》2009,355(45-47):2318-2322
The glasses representing (Bi2O3)x(WO3)y(TeO2)100?x?y and (PbO)x(WO3)y(TeO2)100?x?y systems were prepared. The dilatometric glass-transition temperatures of examined glass samples were found in the region 383–434 °C, the coefficient of thermal expansion varied from 12 to 16 ppm/°C and the density ranged from 6.302 to 6.808 g/cm3. From the optical transmission measurements of thin glassy bulk samples prepared by a glass blowing, the optical gap values were found in the narrow region 3.21–3.36 eV. For the temperature interval 300–480 K, the values of the temperature coefficient of the optical band gap varied from 3.7 × 10?4 to 5.24 × 10?4 eV/K. It is suggested that Raman feature observed at around 350 cm?1 can be assigned to an overlap of Raman bands attributed to WO6 corner shared octahedra and to the following three atomic linkages: Bi–O–Te, Pb–O–Te and W–O–Te.  相似文献   

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