Crystallization of mullite from kaolin according to optical spectroscopy of impurity ions

The luminescence spectra of Cr³⁺ and Eu³⁺ ions embedded in mullite ceramic samples are studied. The samples were annealed at temperatures from 600 to 1200°С. Beginning at a temperature of 890°С, the spectra demonstrated the presence of a newly formed crystal phase. At temperatures from 920 to 1200°С, the crystalline form manifested itself as a stable mullite phase. A temperature of 920°С corresponded to a sharp change in the symmetry of the crystal field around Eu³⁺ (phase transition). The parameters of the spectral lines of ions were used to estimate the mullite crystal-lattice disorder and the residual deformations in ceramic samples. The spread of the mullite crystal-lattice parameter is determined as |Δа/а| ≈ 0.028 and is independent of the annealing temperature.     

玻璃基质与纳米颗粒相互影响的光谱学研究

通过低温选择激发玻璃陶瓷中的LaF3:Tm3+的1D2能级,成功地分开了两种局域环境中Tm3+离子的发射谱,使一些频率的发射谱仅来自于晶相,而另一些则仪来自于玻璃相.讨论了玻璃陶瓷中形成玻璃的氧化物和以晶相析出的氟化物之间的相互作用对两种局域环境中Tm3+离子的光学性能的影响.结果表明:晶粒较大时,氧化物玻璃对处于纳米晶体局域环境的稀土离子的影响减弱,纳米晶体对处于氧化物玻璃局域环境的稀土离子的影响增强;晶粒较小时,氧化物玻璃和晶粒接触面的增加会降低处于纳米晶体局域环境的稀土离子的发光效率,但纳米晶体对处于氧化物玻璃局域环境的稀土离子的影响减弱.晶粒越大,氧化物玻璃对处于纳米品体局域环境的稀土离子的发光影响越小,发光性能越好.玻璃基质中SiO2的含量能影响两种局域环境的Tm3+离子发光效率.     

Effect of chloride introduction on the optical properties in Eu~(3+)-doped fluorozirconate glasses

Fluorozirconate glass containing Eu~(3+) ions and chloride ions are prepared by a meltquenching method. The luminescence behavior of Eu~(3+) affected by Cl ions is investigated. With increasing Cl ion concentration, the luminous intensity of Eu~(3+) is significantly enhanced and the quantum efficiency of fluorozirconate glass is improved. Meanwhile, the intensity parameter ?_2 increases according to the Judd–Ofelt calculation, which indicates the decrease of local symmetry. The average lifetime of Eu~(3+) increases by introducing the Cl ions. Moreover, we find two kinds of sites for Eu~(3+)ions in a glass network by analyzing the fluorescence decay. The distribution of Eu~(3+) ions changes with increasing Cl ion concentration.In addition, the excessive Cl ions lead to the separation of the glass phase and the formation of the crystal phase, thus reducing the transmittance dramatically.     

Exciton absorption at the initial stages of the formation of the CuCl phase in a glass

The fundamental absorption spectra of CuCl nanocrystals in glass samples are investigated in the energy range 3–4 eV at a temperature of 300 K with the aim of elucidating the kinetics of the initial stage of the formation of the CuCl phase in the glass. The CuCl phase is grown in the glass under stepwise annealing at temperatures of 500, 615, and 707°C. The kinetics of variation in the intensity and the shift of the maximum in the exciton absorption spectra of CuCl nanocrystals are studied in the course of annealing of the glass samples. It is established that, for all the temperatures under investigation, the formation of the CuCl phase begins with the transient stage that involves the fluctuation formation of supercritical nuclei of the CuCl nanomelt. At a temperature of 500°C, the transient stage gives way to the stage of a rapid increase in the number of supercritical nuclei of the CuCl phase. At temperatures of 615 and 707°C, the transient stage gives way to the stage of an intensive growth of nuclei without a considerable increase in their number. The number of nuclei formed during the transient stage at 707°C is smaller than that observed after the transient stage at 500°C by a factor of 24. However, the sizes of the nuclei formed at 707°C are larger than those observed after the transient stage at 500°C. This difference is explained by the fact that the diffusion length of Cu⁺ ions controlling the formation of the CuCl phase increases with increasing temperature. The experimental data on the kinetics of the formation of the new phase in the glass are in good agreement with the Zel’dovich-Frenkel classical theory of the formation of a new phase, which accounts for the stage of the formation of critical nuclei.     

Production and decay of subcritical nuclei in a solid solution

The decay of “subcritical” nuclei in a solid solution has been revealed in the investigation of the CuCl phase nucleation kinetics in glass. As soon as “supercritical” nuclei with an average radius R = 1.1 nm are created at 500°C, a sharp temperature increase up to 650°C transforms most nuclei created in the first annealing stage into “subcritical” ones, and this results in the decay of 80% of the nuclei in 5 min, while the remaining 20% of the nuclei grow in size to 2.4 nm. Their growth provides a sixfold increase in the CuCl phase growth rate against that in conventional annealing at 650°C. The kinetic dependences of the nucleation parameters—the amount of the phase and the average radius and concentration of the particles—were determined by the intrinsic absorption spectra of the CuCl nanocrystals. The critical radius of the CuCl nanomelt at 650°C has been estimated as 1.3 nm and the evaporation heat of the CuCl phase molecules in glass, as 13 kJ/mol. It is shown that multistage annealing makes it possible not only to control the parameters of the particles of the new phase, but also to determine the critical parameters of the initial nucleation stage.     

Luminescence and scintillation of Eu2+‐doped high silica glass

High silica glass doped with Eu²⁺ ions was prepared as a scintillating material by impregnation of Eu ions into a porous silica glass followed by reduction sintering in CO atmosphere. A dominant emission band of the Eu²⁺ 5d–4f transition peaking around 430 nm was observed in the luminescence spectrum with the excitation peak around 280 nm and no emission from Eu³⁺ was present. Photoluminescence decay kinetics was governed by decay times of a few microseconds. The Eu²⁺‐doped high silica glass exhibited comparable energy resolution and slightly higher photoelectron yield with respect to the Bi₄Ge₃O₁₂ crystal in the pulse height spectra for X‐ray photon energies within 22–60 keV. Furthermore, a factor of 1.2 higher radioluminescence intensity was observed as well. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Tm3+/Yb3+共掺杂玻璃和玻璃陶瓷中蓝色 上转换发光中的能量传递过程

利用高温固相法制备了Tm³⁺/Yb³⁺共掺杂的氟氧化物玻璃和玻璃陶瓷材料,在980 nm的激光激发下,样品发射出明亮的蓝色上转换荧光。通过对玻璃和玻璃陶瓷样品的对比,发现Tm³⁺离子和Yb³⁺离子之间存在着Tm³⁺(³H₄)→Yb³⁺(²F_5/2)的反向能量传输通道,并且与晶场有较强的依赖关系。分析了在玻璃和玻璃陶瓷中蓝色上转换发光过程,随着敏化剂Yb³⁺浓度的增加,在玻璃中正向和反向能量传递的竞争作用使得Tm³⁺离子在Yb³⁺离子的最佳浓度时上转换发光最强;而在玻璃陶瓷中, Tm³⁺离子的上转换发光始终随着Yb³⁺离子的浓度增加而增强。     

Thermal and long-term stability of fast-ion-irradiation-induced refractive index changes in lithium niobate crystals

Irradiation of congruently melting, nominally undoped lithium niobate crystals (LiNbO₃) with high-energy, low-mass ³He ions, which are transmitted through the crystal, causes large and stable changes of the refractive index. In the irradiated regions, the extraordinary index is increased whereas the ordinary index is diminished. The decay of these changes upon annealing treatments up to 400°C is investigated, exhibiting a strongly non-monoexponential decay behaviour. Long-term measurements of the refractive index changes yield no pattern erasure on a timescale of four years.     

Crystallization behaviour of a ferri-silicate α-waste glass concluded from Mössbauer spectroscopy

A reference, ferri-silicate α-waste glass containing 10 mole% Fe₂O₃, was thermally annealed atT _a=620, 700 and 800°C, resulting in the formation of crystalline substances. Standard characterization techniques have revealed that the crystal growth is either three-dimensional or rather two-dimensional depending onT _a. The Mössbauer spectra recorded at 80 and ≈=295 K and fitted with a sum of two ferrous and two ferric doublets, do not show any effect doublet areas are found to be consistent with earlier suggestions that in silicate glasses nearly all of the Fe²⁺ ions have an octahedral coordination. The chemical environment of the Fe³⁺ ions in the parent glass seems to remain essentially unchanged upon crystallization, except for theT _a=800°C sample for which the high degree of crystallinity is reflected in a drastic change of the hyperfine parameters. The nature of the crystalline phase, suggested to be diopside-like from diffraction experiments, is discussed. For that purpose. Mössbauer spectra were collected for a synthetic ferri-diopside sample.     

Fluorescence studies of the Er ↔ Ho and Er ↔ Tm energy transfer in erbium aluminum garnet

We have studied the flourescence characteristics of Ho³⁺ and Tm³⁺ in ErAlG:Ho, Tm and investigated the Er ? Ho and Er ? Tm energy transfer present in this system. In the infrared, the crystal ErAlG:Ho, Tm presents three groups of sharp lines (centered at ～18 000, ～19 300, and ～21 000 Å), whose intensities are strongly temperature-dependent. The first two groups are attributable to the Tm ³H₄ → ³H₆ transition, while the third group represents the Ho ⁵I₇ → ⁵I₈ transition. In YAlG:Er (50%), Ho(2%), only the Ho emission centered at ～21 000 Å is observed in the infrared. Under pulsed excitation, the emissions at ～17 900, ～19 000, and ～21 000 Å in ErAlG:Ho, Tm present a double exponential decay; the time dependences of the decays of the first two emissions are essentially the same; however, the 19 000 and 21 000 Å emissions present different decay patterns. In YAlG:Er (50%), Ho (2%), on the other hand, the decay of the 21 000 Å emission is purely exponential at all temperatures studied. The above results for ErAlG:Ho, Tm are explained by means of a rate-equation model in which the Ho → Er and Tm → Er transfer are treated as activation-type processes which effect a coupling between (1) the Ho and Tm ions, and (2) the Ho or Tm ions and quenching impurities.     

Electron stimulated desorption of carbon monoxide from a (111) niobium surface

Electron stimulated desorption of CO from the (111) face of a Nb single crystal produced both CO⁺ and O⁺ ions after adsorption at 150°K on a clean surface. When the surface was heated to above 250 °K only O⁺ ions were observed, and this current disappeared as the temperature was increased to 700 °K. Readsorption (at 150 °K) was inhibited following the 700 °K heating. These data indicate the formation on heating of a tightly bound surface phase with very low ionic desorption cross section. Threshold energies for CO⁺ and O⁺ ion production were 10.0 ± 0.5 eV and 19.0 ± 0.5 eV, respectively. The cross section for electron stimulated depopulation of the O⁺ producing phase was (4 ± 1) × 10^?18 cm² for 100 eV electrons.     

Electrical and Thermal Properties of NH4BrxCI1-x Single Crystal

The effect of partial replacement of Cl^? ions by Br^? ions in the mixed system of ammonium chloride and ammonium bromide during a set of thermal heating cycles is studied. The study includes electrical measurements (d.c. resistivity, dielectric constant and the spontaneous thermal current), differential thermal analysis (DTA) and dilatometric thermal analysis in the temperature range ?60 °C up to 30°C. The results show a large change in the various measured parameters sensitive to thermal agitation process and to the presence of the bromine ions in the mixed crystal system close to the morphotropic boundary x = 0.5. At this boundary the temperature region of the ordered phase extended by about 28°C. The transformation enthalpy was reduced in such case to 41.3 cal/mol. According to the different experimental data of the system NH₄Br_xCl_1-x, a phase diagram was proposed. This phase diagram predicted that the order-disorder phase transition point changed widely according to the value of x and reached ?2°C when the mixed crystal system contained 50% of Br^? ions.     

Yb3+/Er3+共掺锗碲酸盐玻璃上转换发光增强机理的研究

玻璃的最大声子能量决定稀土离子的上转换发光强度，但本研究发现：Yb^3 ／Er^3 共掺锗碲酸盐玻璃在980nm LD抽运下，上转换荧光强度随着Bi2O3对PbO的取代和碱金属离子半径的增大而明显增强．而Raman光谱显示基质玻璃的最大声子能量并不随Bi2O3对PbO的取代和碱金属离子半径的增大而变化，但玻璃的最大声子密度随着Bi2O3对PbO取代和碱金属离子半径的增大而降低．从玻璃无辐射跃迁概率的角度，通过分析表明，最大声子密度的降低是玻璃上转换发光强度增强的主要原因．     

Yb3+/Er3+共掺锗碲酸盐玻璃上转换发光增强机理的研究

玻璃的最大声子能量决定稀土离子的上转换发光强度，但本研究发现：Yb³⁺/Er ³⁺共掺锗碲酸盐玻璃在980nm LD抽运下，上转换荧光强度随着Bi₂O ₃对PbO的取代和碱 金属离子半径的增大而明显增强.而Raman光谱显示基质玻璃的最大声子能量并不随Bi ₂O₃对PbO的取代和碱金属离子半径的增大而变化，但玻璃的最大声子密 度随着Bi₂O₃对PbO 取代和碱金属离子半径的增大而降低.从玻璃无辐射跃迁概率的角度，通过分析表明，最大 声子密度的降低是玻璃上转换发光强度增强的主要原因.     

Passive Q-switching of erbium glass laser by magnesium aluminosilicate sitall with cobalt ions

We have studied the radiation output parameters for an erbium glass laser, lasing at a wavelength of 1.54 μm, with passive Q-switching by means of a cobalt-containing magnesium aluminosilicate sitall compared with a saturable absorber based on a magnesium aluminum spinel crystal with cobalt ions. We have shown that the output characteristics of the laser emission when using sitall are not inferior to the analogous characteristics of a laser based on a spinel crystal, and are practically independent of the temperature of the saturable absorber in the range 0°C–80°C. The duration (energy) of the output pulses was 70 nsec (∼4 mJ), the energy dispersion of the radiation pulse relative to the average value was no greater than 3%, the beam divergence was 2.8 mrad, the laser beam quality factor was M² = 1.2. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 126–131, January–February, 2007.     

Photoluminescence of a silver-doped glass

The absorption, emission and excitation spectra of Ag⁺ ions in a soda lime glass doped with two different concentration of silver are investigated. Absorption spectra exhibit a main broad band peaked at about 260 nm (4.77 eV) with a shoulder at about 227 nm (5.46 eV). The relative height of the shoulder depends on silver concentration in the glass. Emission spectra of Ag⁺ are dominated by an ultraviolet broad band at about 330 nm (3.76 eV). The excitation spectra for this emission show a preponderant broad band peaked at about 227 nm (5.46 eV) which coincides with peak position of the shoulder displayed in the optical absorption spectra. A weak broad featureless emission band centred at about 550 nm (2.25 eV) with an excitation peak at about 242 nm (5.12 eV) is tentatively related to an impurity from the host silica glass rather than originated in silver-type centres. Comparison of the luminescence decay curves for both emissions show substantial differences between them. Consequently, the emissions in the time-resolved spectra can easily be discriminated.     

EPR/FMR, FTIR, X-Ray and Raman Investigations of Fe-Doped SiCN Ceramics

SiCN magnetic ceramics doped with Fe ions were synthesized at different pyrolysis temperatures in the range from 600 to 1600°C. Several phases of ceramics were detected using the techniques of electron paramagnetic resonance/ferromagnetic resonance, Raman, Fourier-transform infrared and X-ray diffractometry, listed as follows: (a) transformation to the ceramic state from the polymer state, where the Fe ions are in the paramagnetic state, as the temperature is increased from 600 to 800°C; (b) formation of two different Fe species in the range of 950–1150°C: nanocrystalline particles in the ferromagnetic state and Fe ions incorporated into the free-carbon state in the superparamagnetic state; (c) diminution of the free-carbon content above 1150°C, and, as a consequence, diminution of the intensity of the broad Fe signal related to this phase; (d) appearance of a new Fe phase at about 1200°C; (e) disappearance of the ferromagnetic phase at about 1400°C; (f) disappearance of all Fe ions above 1530°C. The samples exhibiting superparamagnetic behavior are potentially useful in developing high-temperature magnetic sensor devices.     

Swift heavy ion irradiation induced modification of BiFeO3 thin films prepared by sol-gel method

We report the preparation of multiferroic BiFeO₃ thin films on ITO coated glass substrates through sol-gel spin coating method followed by thermal annealing and their modification by swift heavy ion (SHI) irradiation. X-ray diffraction and Raman spectroscopy studies revealed amorphous nature of the as deposited films. Rhombohedral crystalline phase of BiFeO₃ evolved on annealing the films at 550°C. Both XRD and Raman studies indicated that SHI irradiation by 200 MeV Au ions result in fragmentation of particles and progressive amorphization with increasing irradiation fluence. The average crystallite size estimated from the XRD line width decreased from 38 nm in pristine sample annealed at 550°C to 29 nm on irradiating these films by 200 MeV Au ions at 1 × 10¹¹ ions cm⁻². Complete amorphization of the rhombohedral BiFeO₃ phase occurs at a fluence of 1 × 10¹² ions.cm⁻². Irradiation by another ion (200 MeV Ag) had the similar effect. For both the ions, the electronic energy loss exceeds the threshold electronic energy loss for creation of amorphized latent tracks in BiFeO₃.     

Features of the local structure of rare-earth dodecaborides RB12 (R = Ho, Er, Tm, Yb, Lu)

The parameters of the local crystal structure of dodecaborides RB₁₂ (R = Ho, Er, Tm, Yb, Lu) have been determined by extended X-ray absorption fine structure (EXAFS) spectroscopy. It has been shown that the vibrations of the rare-earth ion with respect to the boron cage are well described in the harmonic approximation. At the same time, the displacement of rare-earth ions from equilibrium positions of the crystal structure should be taken into account to determine the length of the R-B bond. The analysis of EXAFS spectra has revealed the displacement of 1–6% of rare-earth ions by about 0.2–0.3 Å in all compounds under investigation; this displacement at low temperatures results in the formation of a cage glass phase.     

Raman scattering study of crystal dynamics and order-disorder transitions in alkali hydrosulfides

Raman spectra have been measured for NaSH, CsSH and RbSH over a range of temperatures from 85 to 400°K. The results show that the order-disorder phase transitions in these solids are associated with significant changes in the details of their crystal dynamics. In addition the Raman spectra provide clear evidence for the existence of previously unobserved low-temperature phases in each compound, which apparently involve total ordering of the SH^? ions.