<Superscript>29</Superscript>Si, <Superscript>27</Superscript>Al, <Superscript>1</Superscript>H and <Superscript>23</Superscript>Na MAS NMR Study of the Bonding Character in Aluminosilicate Inorganic Polymers

²⁹Si, ²⁷Al, ¹H and ²³Na solid-state magic-angle spinning (MAS) nuclear magnetic resonance (NMR) has been used to relate nominal composition, bonding character and compressive strength properties in aluminosilicate inorganic polymers (AIPs). The ²⁹Si chemical shift varies systematically with Si-to-Al ratio, indicating that the immediate structural environment of Si is altering with nominal composition. Fast ¹H MAS and ²⁹Si T _SiH/T _1ρ relaxation measurements demonstrated that occluded pore H₂O mobility within the disordered cavities is slow in comparison with H₂O mobility characteristics observed within the ordered channel structures of zeolites. The ²⁷Al MAS NMR data show that the Al coordination remains predominantly 4-coordinate. In comparison with the ²⁹Si MAS data, the corresponding ²⁷Al MAS line shapes are relatively narrow, suggesting that the AlO₄ tetrahedral geometry is largely unperturbed and the dominant source of structural disorder is propagated by large distributions of Si–O bond angles and bond lengths. Corresponding ²³Na MAS and multiple-quantum MAS NMR data indicate that Na speciation is dominated by distributions of hydration states; however, more highly resolved ²³Na resonances observed in some preparations supported the existence of short-range order. New structural elements are proposed to account for the existence of these Na resonances and an improved model for the structure of AIPs has also been proposed. Authors' address: John V. Hanna, NMR Facility, Institute of Materials and Engineering Science, Lucas Heights Research Laboratories, Australian Nuclear Science and Technology Organisation, Private Mail Bag 1, Menai, NSW 2234, Australia     

Effect of Sr<Superscript>2+</Superscript> ion substitution with trivalent ions (Sc<Superscript>3+</Superscript>, In<Superscript>3+</Superscript>, La<Superscript>3+</Superscript>, Bi<Superscript>3+</Superscript>) on its ferroelectric instability in SrTiO<Subscript>3</Subscript>

The vibration frequencies of unstable ferroelectric and antiferrodistortion modes and the dependences of the energy on the ion displacement amplitude have been calculated within the generalized Gordon-Kim model for distortions along eigenvectors of these modes in the mixed compounds Sr_{1 − x} A _x Ti_{1 − x} /₄□ _x/4O₃ and Sr_{1 − y} A _2y /₃□ _y/3TiO₃ (A = Sc³⁺, In³⁺, La³⁺, Bi³⁺; □ is the vacancy). To compensate an excess positive charge, vacancies are introduced into the Ti⁴⁺ or Sr²⁺ site. Calculations have been performed in the “daverage” crystal approximation for impurity concentrations of 0.25 and 0.50. To this end, a set of 40 atomic superlattices with various orderings of heterovalent ions Sr²⁺ and impurity A ³⁺ has been considered. It has been found that each impurity type, independently of charge balance, induces ferroelectric instabilities in doped compounds. In the case of doping with In³⁺ and La³⁺ for concentration x = 0.25, the possibility of rotating the polarization vector has been shown.     

Multinuclear MAS NMR Investigation of Sol-Gel and Ball-Milled Nanocrystalline Ga<Subscript>2</Subscript>O<Subscript>3</Subscript>

⁷¹Ga magic-angle spinning (MAS) nuclear magnetic resonance (NMR) has been used to characterize the structural evolution of nanocrystalline Ga₂O₃ samples prepared by sol-gel and ball-milling techniques. ²⁹Si and ²⁷Al MAS NMR have also been used to characterize silica and alumina Zener pinning phases. ⁷¹Ga NMR parameters are reported for the α- and β-Ga₂O₃ phases, and more tentatively for the δ-Ga₂O₃ phase. By simulating the octahedrally coordinated gallium NMR line of β-Ga₂O₃ using Gaussian distributions in χ_Q, the extent of disorder in the Ga₂O₃ crystallites has been quantified. The ball-milled samples contain much more inherent disorder than the sol-gel samples in the nano-phase, which was observed from simulations of the ⁷¹Ga MAS NMR spectra. The silica pinning phase produced highly crystalline and densely aggregated nanocrystalline Ga₂O₃, as well as the smallest nanocrystal sizes. Authors' address: Mark E. Smith, Department of Physics, University of Warwick, Coventry CV4 7AL, UK     

Structural characterisation of aluminium layered double hydroxides by Al solid-state NMR

²⁷Al solid-state NMR has been applied to study the local structure of pristine and chemically modified aluminium layered double hydroxides (LDH). The pristine LDH only shows six-fold coordinated, octahedral, aluminium, while the calcined and subsequently surfactant treated LDH sample shows a significant fraction of four-fold coordinated tetrahedral aluminium. The co-existence of two types of octahedral sites with different quadrupolar parameters is clearly observed in both samples. Quadrupolar coupling constants and isotropic chemical shifts have been measured from the ²⁷Al triple-quantum MAS NMR allowing to fit the ²⁷Al MAS spectra and quantify the different species in the samples. The quantitative analysis reveals that 30% of the aluminium is in four-fold coordination in the surfactant-modified LDH. We show that this chemical modification retains the two types of AlO₆ sites with a decreased intensity of the site showing the lowest quadrupolar coupling constant.     

<Superscript>29</Superscript>Si MAS-NMR study of oxide conductors derived from the apatite-type La<Subscript>9.33</Subscript>Si<Subscript>6</Subscript>O<Subscript>26</Subscript> compound

The preparation of (La_9.33−2x/3Sr _x □_0.67−x/3)Si₆O₂₄O₂ (0 ≤ x ≤ 2) samples with different amounts of cation vacancies is reported. Structure and unit-cell parameters were deduced by Rietveld analysis of XRD patterns. Structural features that enhance oxygen conductivity in Sr-doped apatites are discussed. Up to three components were detected in ²⁹Si MAS-NMR spectra which change with the amount and distribution of cation vacancies. In general, oxygen conductivity increases with the amount of vacancies at La1 (6h) sites, passing through a maximum for x = 0.4. In the case of activation energy, a minimum is detected near x = 1.2, indicating that entropic and enthalpic change in different ways. The presence of cation vacancies should enhance oxygen hopping along c-axis; however, the analysis of the frequency dependence of conductivity suggests that oxygen motions are produced along three axes.     

<Superscript>27</Superscript>Al NMR Study of the Structure and Dynamics of Natrolite

The temperature dependences of nuclear magnetic resonance and magic angle spinning nuclear magnetic resonance spectra of ²⁷Al nuclei in natrolite (Na₂Al₂Si₃O₁₀· 2H₂O) have been studied. The influence of water molecules and sodium ions mobility on the shape of the ²⁷Al NMR spectrum and framework dynamics have been discussed The temperature dependences of the spin–lattice relaxation times T₁ of ²⁷Al nuclei in natrolite have also been studied. It has been shown that the spin–lattice relaxation of the ²⁷Al is governed by the electric quadrupole interaction with the crystal electric field gradients modulated by translational motion of H₂O molecules in the natrolite pores. The dipolar interactions with paramagnetic impurities become significant as a relaxation mechanism of the ²⁷Al nuclei only at low temperatures (<270 K).     

Broadband infrared luminescence from transparent glass–ceramics containing Ni<Superscript>2+</Superscript>-doped <Emphasis Type="BoldItalic">β</Emphasis> -Ga<Subscript>2</Subscript>O<Subscript>3</Subscript> nanocrystals

Transparent Ni²⁺-doped β-Ga₂O₃ glass–ceramics were synthesized. The nanocrystal phase in the glass–ceramics was identified to be β-Ga₂O₃ and its size was about 3.6 nm. It was confirmed from the absorption spectra that the ligand environment of Ni²⁺ ions changed from the trigonal bi-pyramid fivefold sites in the as-cast glass to the octahedral sites in the glass–ceramics. The broadband infrared emission centering at 1270 nm with full width at half maximum (FWHM) of more than 250 nm was observed. The fluorescence lifetime was about 1.1 μs at room temperature. The observed infrared emission could be attributed to the ³ T _2g (³ F )→³ A _2g (³ F ) transition of octahedral Ni²⁺ ions. It is suggested that the Ni²⁺-doped transparent β-Ga₂O₃ glass–ceramics with broad bandwidth and long lifetime have a potential as a broadband amplification medium. PACS 42.70.-a; 42.70.Ce; 81.40.Tv     

Luminescence and thermally stimulated recombination processes in Li<Subscript>6</Subscript>Gd(BO<Subscript>3</Subscript>)<Subscript>3</Subscript>:Ce<Superscript>3+</Superscript> crystals

The luminescence and thermally stimulated recombination processes in lithium borate crystals Li₆Gd(BO₃)₃ and Li₆Gd(BO₃)₃:Ce have been studied. The steady-state luminescence spectra under X-ray excitation (X-ray luminescence), temperature dependences of the intensity of steady-state X-ray luminescence (XL), and thermally stimulated luminescence (TSL) spectra of these compounds have been investigated in the temperature range of 90–500 K. The intrinsic-luminescence 312-nm band, which is due to the ⁶ P _J → ⁸ S _7/2 transitions in Gd³⁺ matrix ions, dominates in the X-ray luminescence spectra of these crystals; in addition, there is a wide complex band at 400–420 nm, which is due to the d → f transitions in Ce³⁺ impurity ions. It is found that the steady-state XL intensity in these bands increases several times upon heating from 100 to 400 K. The possible mechanisms of the observed temperature dependence of the steady-state XL intensity and their correlation with the features of electronic-excitation energy transfer in these crystals are discussed. The main complex TSL peak at 110–160 K and a number of minor peaks, whose composition and structure depend on the crystal type, have been found in all crystals studied. The nature of the shallow traps that are responsible for TSL at temperatures below room temperature and their relation with defects in the lithium cation sublattice are discussed.     

Physical and Spectral Investigations of Cu<Superscript>2+</Superscript>-Doped Alkali Zinc Borate Glasses

Physical and spectral studies on 20ZnO + xLi₂O + (30-x)Na₂O + 50B₂O₃ (5 ≤ x ≥ 25) doped with 0.1 mol% of paramagnetic CuO impurity are carried out. Powder X-ray diffraction patterns of the glass samples confirm the amorphous nature. The physical parameters of all the glasses were also evaluated with respect to the composition. The electron paramagnetic resonance spectra of all these glasses exhibit resonance signals that are characteristic of Cu²⁺ ions. The optical absorption spectra also confirm the Cu²⁺ ion in tetragonally elongated octahedral site. Various crystal field, spin-Hamiltonian and bonding parameters are evaluated. It is observed that the mixed alkali effect is significant.     

NMR Study of a Rare-Earth Aluminoborosilicate Glass with Varying CaO-to-Na<Subscript>2</Subscript>O Ratio

The effect of substituting two Na⁺ by one Ca²⁺ in a rare-earth aluminoborosilicate glass is investigated by multinuclear magic-angle spinning (MAS) and multiple-quantum (MQ)MAS nuclear magnetic resonance (NMR) spectroscopy. Quantitative analysis of the ²³Na and ²⁷Al MAS/MQMAS data along with the ¹¹B MAS NMR data provides complementary information enabling to cast light on different structural key points. A strong decrease of the N ₄ = BO₄/(BO₃ + BO₄) ratio is observed consecutively to this substitution, indicating that sodium is more favorable than calcium to the formation of BO₄ units. The experimental N ₄ ratio is compared to the Dell and Bray model prediction and it is shown that several adjustments, due to the presence in our glass of Nd and Zr, are necessary to obtain acceptable agreement with experimental data. ²⁹Si MAS NMR data also put in evidence an effect of the substitution on the polymerization degree. Glass in glass phase separation is clearly detected when the ratio of CaO to Na₂O is greater than 1 and a different evolution of NMR parameters is observed for the ratio of CaO to Na₂O being less than or equal to 1. Concerning aluminum charge compensation, it is demonstrated that, as long as no phase separation is detected, the negative charge of AlO₄ ⁻ entities is almost exclusively balanced by sodium cations. Finally, changes of the sodium ions organization within the glass network are also evidenced by spin–lattice relaxation and spin echo decay measurements. Authors' address: Thibault Charpentier, Laboratoire Claude Fréjacques, Service de Chimie Moléculaire, Commissariat à l'Energie Atomique Saclay, 91191 Gif-sur-Yvette cedex, France     

<Superscript>4</Superscript>He<Superscript>3</Superscript>H<Superscript>2</Superscript>H three-body model of the <Superscript>9</Superscript>Be nucleus

Within the framework of the single-channel approximation, an {αtd} model of the ⁹ Be nucleus is presented. A comparative analysis of the t ⁶ Li wave functions describing relative motion of bound states constructed in {ααn} and {αtd} cluster representations is carried out on the example of calculations of the ⁹ Be(γ,t₀)⁶ Li process characteristics. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 85–89, January, 2008.     

Two-Photon Absorption in Nanoheterostructures with <Emphasis Type="Italic">D</Emphasis><Superscript>(−)</Superscript>-Centers

A two-photon impurity absorption coefficient of the “quantum dot — D⁽⁻⁾-center” complexes synthesized in a transparent dielectric matrix is calculated within the model of zero-radius potential. The evolution of spectral dependence of the absorption coefficient of the nanoheterostructure based on semiconductor CdS _x Se _1−x glasses is studied versus the average quantum-dot radius. It is shown that the contribution of the two-photon impurity absorption to the exited two-photon luminescence is fairly significant at a reasonable quantum-dot concentration. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 46–50, July, 2005.     

Magnetic properties of LiNi<Subscript>0.5</Subscript>Mn<Subscript>0.47</Subscript>Al<Subscript>0.03</Subscript>O<Subscript>2</Subscript> as positive electrode for Li-ion batteries

The layered LiNi_0.5Mn_0.47Al_0.03O₂ was synthesized by wet chemical method and characterized by X-ray diffraction and analysis of magnetic measurements. The powders adopted the α-NaFeO₂ structure. This substitution of Al for Mn promotes the formation of Li(Ni_0.47²⁺Ni_0.03³⁺Mn_0.47⁴⁺Al_0.03³⁺)O₂ structures and induces an increase in the average oxidation state of Ni, thereby leading to the shrinkage of the lattice unit cell. The concentration of antisite defects in which Ni²⁺ occupies the (3a) Li lattice sites in the Wyckoff notation has been estimated from the ferromagnetic Ni²⁺(3a)–Mn⁴⁺(3b) pairing observed below 140 K. The substitution of 3% Al for Mn reduces the amount of antisite defects from 7% to 6.4–6.5%. The analysis of the magnetic properties in the paramagnetic phase in the framework of the Curie–Weiss law agrees well with the combination of Ni²⁺ (S = 1), Ni³⁺ (S = 1/2) and Mn⁴⁺ (S = 3/2) spin-only values. Delithiation has been made by the use of K₂S₂O₈. According to this process, known to be softer than the electrochemical one, the nickel ions in the (3b) sites are converted into Ni⁴⁺ in the high spin configuration, while Ni²⁺(3a)–Mn⁴⁺(3b) ferromagnetic pairs remain, as the Li⁺(3b) ions linked to the Ni²⁺(3a) ions in the antisite defects are not removed. The results show that the antisite defect is surrounded by Mn⁴⁺ ions, implying the nonuniform distribution of the cations in agreement with previous NMR and neutron experiments.     

The effect of temperature and pressure on the heat conductivity of TlSbC<Stack><Subscript>2</Subscript><Superscript>VI</Superscript></Stack> (<Emphasis Type="Italic">C</Emphasis><Superscript>VI</Superscript> → S,Se, Te)

The effect of temperature and pressure on heat conductivity of ternary compounds TiSbC ₂^VI (C ^VI → S, Se, Te) in the solid and liquid states in a temperature range of 300–800 K, as well as under the pressure up to 0.35 GPa in a temperature range of 275–450 K, is studied. The dependence of heat conductivity on average atomic weight under the S → Se → Te transition is found. Analysis of the experimental data makes it possible to attribute TlSbS₂ to the class of substances exhibiting semiconductor-semiconductor melting behavior.     

Quadrupole and paramagnetic interactions of 27Al nuclei in mixed yttrium-dysprosium-aluminum garnets Y3−x DyxAl5O12

An ²⁷Al NMR study of mixed yttrium-dysprosium-aluminum garnets Y_3−x Dy _x Al₅O₁₂ is reported for x=0, 0.15, 0.50, 0.64, and 1.00. The quadrupole coupling parameters for the a and d aluminum sites have been determined. The spectra have been theoretically calculated with inclusion of the paramagnetic shift induced by Dy³⁺ ions. An analysis of the NMR line shape has permitted a conclusion that there is no substitutional order in the mixed crystals under study. Fiz. Tverd. Tela (St. Petersburg) 40, 1047–1051 (June 1998)     

Fragmentation of sputtered Si<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>O<Stack><Subscript><Emphasis Type="Italic">m</Emphasis></Subscript><Superscript>+</Superscript></Stack> clusters: Release kinetic and dissociation energies

The spectra of kinetic energies of positive Si _n O _m ⁺ cluster ions (n = 2–5, m = 2–7) have been measured using a double focusing ion microanalyzer with reverse geometry at instants 10⁻⁵ to 10⁻⁴ s after emission. The dissociation energies have been determined within the evaporative ensemble model and the theory of unimolecular decay reactions. The results obtained are compared with the binding energies of neutral Si _n O _m clusters.     

A Definitive Example of Aluminum-27 Chemical Shielding Anisotropy

Solid-state²⁷Al NMR spectra have been obtained for a crystalline 1:1 complex of AlCl₃and OPCl₃. Aluminum chloride phosphoryl chloride, AlCl₃· OPCl₃(1), is unusual in that the Al–O–P bond angle is close to 180°. From analysis of the²⁷Al MAS NMR spectra, it was determined that the²⁷Al nuclear quadrupole coupling constant is 6.0(1) MHz, the asymmetry in the electric field gradient (efg) tensor is 0.15(2), and the isotropic chemical shift, δ_iso(²⁷Al), is 88(1) ppm. Solid-state²⁷Al NMR of a stationary sample reveals a line shape affected by a combination of anisotropic chemical shielding and second-order quadrupolar interactions. Analysis of this spectrum yields a chemical shift anisotropy of 60(1) ppm and orientations of the chemical shift and electric field gradient tensors in the molecular frame. Experimental results are compared with those calculated usingab initioHartree–Fock and density functional theory.     

Investigation of the Mn-doped compound CuGaTe<Subscript>2</Subscript> by <Superscript>63</Superscript>Cu AND <Superscript>69</Superscript>Ga nuclear magnetic resonance techniques

The synthesized base compound CuGaTe₂ and the Mn-doped compounds Cu_0.97Ga_0.97Mn_0.06Te₂ and Cu_0.93Ga_0.93Mn_0.14Te₂ have been investigated by using ⁶³Cu and ⁶⁹Ga NMR spectroscopy. The NMR spectra obtained testify to substantial structural distortions near the cationic positions in the crystal lattice of Mndoped samples. The constants of quadrupole coupling between ⁶³Cu and ⁶⁹Ga nuclei in the compounds investigated have been estimated.     

Crystal structure and magnetic properties of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> nanoparticles by <Superscript>27</Superscript>Al NMR data

The magnetization of a series of Al₂O₃ with different particle sizes and their ²⁷Al NMR spectra have been studied at room temperature. The field dependence of the magnetization demonstrated the existence of a long-range ferromagnetic order in a small part of the sample at room temperature; however, the relative volume of this contribution was very small (less than 1%), and this seems likely due to an impurity phase. The NMR spectra did not contain any lines of metallic aluminum the existence of which in these nanooxides was assumed before in a surface layer of the nanoparticles, according to the data of other techniques. The data on the phase composition and the charge distribution in different phases of the Al₂O₃ nanoparticles have been obtained. The change in the mean particle size (by a factor of almost three) only insignificantly changed their phase composition.     

High-frequency EPR of Tb<Superscript>3+</Superscript>-doped KPb<Subscript>2</Subscript>Cl<Subscript>5</Subscript> crystal

High-frequency electron paramagnetic resonance (EPR) spectra of the KPb₂Cl₅:Tb³⁺ crystal have been investigated. Three types of spectra were observed in the frequency range of 74–200 GHz. The most intensive spectrum with the resolved hyperfine structure corresponded to transitions between sublevels of the¹⁵⁹Tb³⁺ ground quasi-doublet with the zero-field splitting (ZFS) close to 48 GHz. Experimental results were analyzed by the exchange charge model of the crystal field affecting terbium ions in low-symmetry Pb²⁺ positions with the chlorine sevenfold coordination and the charge compensating vacancy in the nearest potassium site. The calculated values ofg-factors and ZFS were in agreement with the experimental data. The nature of a broad EPR line with ZFS of about 180 GHz and of additional weak EPR lines observed as satellites of the main Tb³⁺ lines was discussed.