Aggregation and precipitation stages in NaCl:Pb2+ studied by UV absorption

UV absorption measurements during isochronal annealing of homogenised and as-grown single crystals show two distinct stages in NaCl:Pb²⁺ where number density of free impurities reduce. With the help of our earlier light scattering results the low temperature stage has been attributed to aggregation of impurity-vacancy dipoles whereas the stage appearing at the higher temperature is assigned to the precipitation process.     

Metastable precipitation kinetics in NaCl:Pb2+ crystals at room temperature

The RT precipitation kinetics have been studied for the metastable phase in NaCl:Pb²⁺ crystals by precise density measurements. The results obtained seem to be unaccountable in terms of the diffusion-controlled growth of constant or increasing number of particles. The observed process is concluded to be a coalescence (Ostwald ripening). At the late stage the experimental data fit the $\text{t}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>3</mtext>}}$ law for solute depletion predicted by the asymptotic coalescence theory of Lifshitz and Slezov. A diffusion coefficient of Pb²⁺ in the NaCl lattice and the particle size have been estimated by using the theory.     

Effect of M+2 ions on the luminescence of Pb+2 in NaCl

The effect of additional doping with M⁺² ions on the luminescence of NaCl:Pb⁺² has been systematically investigated. The data show that the same two emissions at 310 and 380 nm are observed for mixed Pb⁺²-M⁺² clusters as for Pb⁺² aggregates. Moreover, the presence of a M⁺² ion associated to a Pb⁺² ion in a mixed cluster shifts the 310 nm emission (predominantly observed for free Pb⁺²-vacancy dipoles) to 380 nm. The results are consistent with the Fukuda's model, involving an emission at 310 nm from tetragonal (T) minima in the adiabatic potential energy surface (APES) and another one from less symmetry (X) minima at 380 nm. The data for NaCl:Pb⁺²:Mn⁺², show that an excitation transfer is taking place from the X minima of the ³T_1u state of Pb⁺² to Mn⁺².     

Absorption spectra of NaCl: Pb2+ at the A-band region

The origin of the absorption spectrum of NaCl:Pb²⁺ at the A-band region has been investigated. Main peaks are observed at 265, 273 and 290mμ in an untreated sample. In addition to the effect of lead concentration and thermal treatments, the luminescence and excitation spectra associated to the various bands have been determined. It is concluded that the 290 mμ band should be a composition of a number of bands corresponding to different types of simple dipole aggregates. The 265 mμ band, as well as the structure appearing in the region 220–260 mμ, is consistent with the existence of PbCl₂ precipitates.     

Calcium precipitation in NaCl monitored by the Eu2+ -fluorescence

Taking into account that the optical spectroscopy of the Eu²⁺ ion is quite sensitive to the crystalline environment in which this ion is located, in the present investigation the fluorescence of a small concentration (8 ppmm) of divalent europium incorporated into a NaCl crystal which was also doped with ≈4500 ppmm of Ca²⁺ has been systematically investigated as a function of different thermal treatments in order to study the calcium-precipitation processes in the host NaCl. The data presented in this paper strongly suggest that the annealing of quenched samples at 200°C produces the incorporation of Eu²⁺ into the stable dihalide phase CaCl₂, as well as into the metastable precipitated CaCl₂-like plate zones parallel to the {111} planes of the NaCl matrix. This fact is associated with the increase in intensity of two overlapping emission bands peaking at 430 and 432 nm. On the other hand, the aging of quenched samples at room temperature produces the growth of three emission bands peaking at 400, 414, and 447 nm. The former two emission bands have been associated with Eu²⁺ embedded into calcium precipitates, the structures of these precipitates being different from that of CaCl₂, while the band at 447 nm has been ascribed to europium ions incorporated into the metastable precipitated CaCl₂-like plate zones parallel to the {310} planes of the NaCl matrix. Some of the characteristics of the different calcium second phase precipitates have been obtained by measuring the crystal field splitting (10 Dq) of the 4f⁶5d configuration of the divalent europium ions when they were located inside them. Values for the 10 Dq splitting were determined from the excitation spectrum of each of the emission bands associated with the different calcium-precipitated phases.     

An interpretation of the optical absorption spectra of Pb3+: KCl and Zn+: NaCl

The low energy optical absorption (O.A.) spectrum of a nsion placed in a local O_h symmetry is discussed within the molecular orbital (M.O.) picture. Such model predicts two dipole allowed charge-transfert transitions and one band, arising from the atomic ns np excitation, which qualitatively explains the experimental O.A. spectra of Pb³⁺ : KCl and Zn⁺ : NaCl. Each of the three observed bands in these cases is reasonably assigned and the possible effects - of the spin-orbit coupling on the ns np transition discussed. Suggestions concerning the interpretation of the O.A. spectrum - of X-irradiated Cd: NaCl are also reported.     

Influence of precipitation processes on the optical spectra of Pb2+ in alkali halides

The influence of the aggregation and precipitation processes of lead ions on optical (absorption and luminescence) spectra have been studied for KBr, KI and RbCl. Bands presumably associated with aggregates and precipitates have been identified and compared with those observed for NaCl and KCl. The thermal annihilation behavior of precipitate bands as well as the effect of precipitation on yield-stress have also been determined. As a consequence, a more complete scheme of the influence of aging processes on optical spectra of lead-doped alkali halides has now become available.     

巯基化、钠化和酸化膨润土对Cu2+，Pb2+和Zn2+的吸附性能研究

基于改性膨润土可能存在的优异吸附能力,利用傅里叶变换红外光谱仪和场发射扫描电镜研究分析了巯基化、钠化及酸化三种改性膨润土对Cu2+,Pb2+和Zn2+的等温吸附与竞争吸附实验结果。研究结果表明,在单一重金属离子的等温吸附环境下,巯基化膨润土对Cu2+,Pb2+和Zn2+的吸附能力明显优于其他两种材料,且对Pb2+具有一定的吸附选择性,吸附率达到近100%;在竞争吸附环境下,三种改性膨润土对Cu2+,Pb2+和Zn2+的吸附率都有所下降,但巯基化膨润土仍旧能够保持较好的吸附能力,较其他膨润土的吸附率大约高出10%～40%;三种重金属离子的吸附量均表现为Cu2+＞Pb2+＞Zn2+,这与三种重金属离子的竞争能力、化学亲和力等大小有关;膨润土的巯基改性,步骤简单且吸附重金属的效果好,对膨润土改性及其应用具有重要意义。     

EPR spectra of NaCl:V2+ and KCl:V2+ above room temperature

Measurements above 300 K of the temperature variation of EPR spectra in NaCl and KCl, doped with divalent vanadium, are analysed. A new isotropic spectrum in KCl:V²⁺, which appears above 500 K, due to vanadium in cubic surroundings, is reported.     

ESR detection of pressure-induced structural change around Pb2+ and Cd2+ in soda borate glasses

The pressure-induced changes in the coordination structure of Cd²⁺ and Pb²⁺ were examined by measuring the ESR spectra of γ-ray-induced Cd⁺ and Pb³⁺ centers. The s-character of the magnetic electron in the centers increased on densification and was estimated from the analysis of the hyperfine absorption due to a ²⁰⁷Pb³⁺ and ¹¹¹Cd⁺ and ¹¹³Cd⁺. The increase in the s-character means that the strength of both Pb²⁺O and Cd²⁺O bonds was reduced upon densification and that the coordination number of Cd²⁺ and Pb²⁺ increased. The coordination sphere of Cd²⁺, which responds more sensitively than that of Pb²⁺ to the change in chemical environments, was more heavily compressed than that of Pb²⁺.     

Positron annihilation in Pb2+ doped KCl single crystals

The angular distribution of annihilation photons (ADAP) has been measured in a pure KCl single crystal and in one doped with Pb²⁺ impurities to concentrations of 100 ppm, 550 ppm and 1050 ppm. In unannealed, impurity doped, crystals the intensity of the narrow component increases with increase of impurity concentration. The narrowing of the ADAP curves is explained by assuming trapping of positrons at impurity induced positive ion vacancies. On annealing, the result on the 550 ppm impurity doped crystal shows that there is a dissolution of impurity-vacancy complexes at nominal concentrations of impurity, and the result on the 1050 ppm crystal shows that there is precipitation of impurity for very high concentrations.     

Neutron scattering in Ag+ and Na+ β-aluminas

Na⁺ and Ag⁺ β-alumina for various stoichiometries and for various hydration states have been studied by neutron scattering using incident energy of 0.8 meV with a resolution of 20 μeV in the 200–325° C temperature range. From the weak quasielastic signal (QES) observed for the non- stoichiometric (NS) Ag⁺ β-alumina a translational diffusion constant D_t has been estimated at about 10^-5 cm² s^-1 at 200°C. No such QES has been observed for stoichiometric Ag⁺ and Na⁺ compounds. The dehydration of Na⁺ β-alumina has been evidenced by the disappearance of the broad QES above 300°C; correlatively the low frequency inelastic spectrum of Na⁺ of β-alumina is changed.     

Effect of hyperfine interaction on the luminiscence of Pb2+ and Bi3+ centers in alkaline-earth chalcogenides

Emission spectra of MgS, CaO, CaS, CaSe and SrS phosphors activated with a Pb²⁺ or a Bi³⁺ ion are measured at 4.2 K. By the analysis of the phonon structure of the ³A_1u → ¹A₁g emission band, it is found that the hyperfine interaction provokes the zero-phonon line on the emission band for the alkaline-earth chalcogenide phosphors activated with a Pb²⁺ or a Bi³⁺ ion.     

Influence of the precipitated phases of Pb++ and Sr++ on the f-coloring behavior of NaCl

The F-coloring efficiencies of NaCl:Pb⁺⁺ and NaCl:Sr⁺⁺ have been measured during stage I as a function of lead and strontium precipitation into the metastable and stable phases, the optical absorption spectrum of the doped crystals was analyzed after each annealing treatment. On the other hand, strontium precipitation was monitored using Eu⁺⁺ as an optical probe taking advantage of the fact that this ion can be incorporated into the Sr-precipitates producing emission bands characteristic of each type of precipitate in which it is embedded. The results indicate that the metastable and stable second phase precipitates of these ions contribute in a quite different manner to the coloring processes.     

White light generation of glass ceramics containing Ba_2LaF_7：Eu~（2＋）,Tb~（3＋） and Sm~（3＋） nanocrystals

The Eu 2＋ /Tb 3＋ /Sm 3＋ co-doped oxyfluoride glass ceramics containing Ba2LaF7 nanocrystals are prepared in the reducing atmosphere.The X-ray difiraction results show that Eu 2＋ ,Tb 3＋ and Sm 3＋ ions are enriched into the precipitated Ba2LaF7 nanophase after the annealing process.It deduces efficient energy transfers from Eu 2＋ to Tb 3＋ and Sm 3＋ and intenses warm white luminescence of the glass ceramics. Comparing with the glass,the luminescence quantum yield of the glass ceramics is also enlarged by about 3 times.This demonstrates the potential white light-emitting diode application of the glass ceramics produced in this letter.     

Phonon scattering by Ni3+ ions in Al2O3

Previous thermal conductivity measurements on Al₂O₃ + Ni single crystals have been extended down to 80 mK. The quantitative analysis shows that the lineshape of the low temperature resonant is determineded by random strains in the crystal, and gives a possible value for the ‘tunneling splitting’ 3Γ of 0.54 cm^?1.     

原子吸收光谱法研究巯基改性膨润土对Pb2+的吸附解吸

通过红外光谱(FTIR)法和扫描电镜(SEM)对钙基和巯基改性膨润土的官能团和表面结构进行了比较分析,以火焰原子吸收光谱法(FAAS)为检测手段,研究了巯基改性膨润土对Pb2+吸附的影响因素并优化了吸附条件,讨论了模拟酸雨解吸Pb2+的条件。比较了钙基和巯基改性膨润土作为吸附剂对水溶液中Pb2+的吸附、固定能力。研究表明：25 ℃下,吸附时间为60 min、离子强度为0.1 mol·L-1的KNO₃、pH 6.0时,5.0 g·L-1巯基改性膨润土对100 mg·L-1的Pb2+的吸附率达到98%以上,平衡吸附量达到67.27 mg·g-1,吸附能力明显优于钙基膨润土(9.667 mg·g-1),吸附过程符合Langmuir和Freundlich等温线方程。用pH 3.50的极限酸度模拟酸雨进行解吸,解吸率为0。表明该巯基改性膨润土对Pb2+具有很强的吸附、固定能力,适于重金属铅污染土壤中铅的吸附固定修复之用。     

利用偏振喇曼谱研究KBr:Pb2+单晶中的HD色心

本文报道掺铅溴化钾单晶在液氮温度下经大剂量X射线辐照后的偏振喇曼测量结果。利用几年前才发展起来的所谓“表现型”分析方法,确认喇曼谱中频移为186cm^-1的信号具有点群C_1k(010),它起因于H_D色心的A模振动。 关键词：     

Time resolved spectroscopy of KCl:Pb2+ excited in the A absorption band

By using a single photon-time correlation technique, time resolved emission spectra of the three time components are investigated in KCl:Pb excited in the A absorption band. The results, obtained in the temperature range 80–300 K, are discussed on the basis of the available theoretical models and of the effect of the charge compensating vacancy.     

Transition moment variation in the A2Σ+ → X2Πi transition of HCl+, DCl+ and HBr+

Relative emission intensities of sixteen bands of HCl⁺ (A²Σ⁺ - X²Π_i), four bands of DCl⁺ (A²Σ⁺ - X²Π_i), and 5 bands of HBr⁺ (A²Σ - X²Π_i) have been made using both ion-beam excitation and microwave discharge sources. Intensities were determined by comparison with computer-generated spectra. Treatment of the data within the r-centroid approximation shows that in HCl⁺ the electronic transition moment decreases strongly at large $\text{r}{}_{\mathrm{v\prime v″}}$ [$\text{Re}\text{α}\text{exp}\text{(?3.6}\text{r}{}_{\mathrm{v\prime v″}}\text{)}\text{for 1.44}\text{A}\text{?}\text{< r}{}_{\mathrm{v\prime v″}}\text{< 1.82}\text{A}\text{?}$] but levels off at shorter $\text{r}{}_{\mathrm{v\prime v″}}$. DCl⁺ data agree quantitatively with HCl⁺. The variation in the HBr⁺ moment is similar, with $\text{R}\text{e}\text{α}\text{exp}\text{[?4.5}\text{r}{}_{\mathrm{v\prime v″}}\text{]}\text{for 1.58}\text{A}\text{?}\text{<}\text{r}{}_{\mathrm{v\prime v″}}\text{< 1.78}\text{A}\text{?}$.