Structural studies of geopolymers by <Superscript>29</Superscript>Si and <Superscript>27</Superscript>Al MAS-NMR

A systematic study of geopolymers by ²⁹Si and ²⁷Al MAS NMR has been carried out in an attempt to understand polymer structural details. ²⁷Al MAS NMR data shows that transient aluminium species are formed during the reaction of metakaolin with NaOH. Interaction of silicate anions with the aluminium sites of metakaolin was evident during the synthesis of geopolymers as observed from low field shift of ²⁹Si MAS NMR resonance lines of silicate centres. As the reaction progresses, the coordination of aluminium (IV, V and VI) in metakaolin changes almost completely to IV. ²⁹Si MAS NMR of selected compositions of the ternary system of sodium silicate, metakaolin and aqueous alkali reveals that geopolymerisation occurs in a distinct compositional region. At high alkalinity [> 30% (mol/mol) overall Na²O content], connectivity of silicate anions is reduced, consistent with poor polymerisation. At low alkalinity [<10% (mol/mol) overall Na²O content], a clear ²⁹Si NMR resonance line due to unconverted metakaolin is observed. NMR spectra were recorded from a series of samples with a fixed Na²O content (20 mol%) and varied SiO²/Al²O³ ratio to observe aluminium substitution in the cross-linked silicon tetrahedra of polymer network. Aluminium insertion into the silicate network is confirmed from the observed ²⁹Si NMR shift as a function of Si/Al ratio. The identification of the presence or absence of metakaolin in the cured geopolymer product is not possible even by ²⁹Si NMR as the signal from metakaolin is indistinguishable from a broad ²⁹Si NMR peak consisting of many resonance lines from the network of cross-linked silicon/aluminium tetrahedra. In an attempt to identify metakaolin signal, we prepared geopolymers with higher SiO²/Al²O³ molar ratios. Since aluminium substitutions in the silicate tetrahedral network are decreased, this results in better-resolved ²⁹Si NMR lines. The ²⁹Si NMR signal due to metakaolin is then distinguishable in the spectra of cured products in a series of samples with 3 to 11 mol% metakaolin. These results indicate that a geopolymer structure is a network of silicon/aluminium tetrahedra with some presence of unreacted metakaolin. The silicon/aluminium tetrahedra might have connectivity ranging from 1 to 4.     

High-purity silicon isotopes <Superscript>28</Superscript>Si, <Superscript>29</Superscript>Si,and <Superscript>30</Superscript>Si

The current status of the problem of obtaining high-purity silicon isotopes ²⁸Si, ²⁹Si, and ³⁰Si is analyzed. The scheme of obtaining monoisotopic silicon includes the stages of isotope separation in the form SiF₄, synthesis and deep purification of isotopically enriched silane, obtaining polycrystalline silicon-28,-29, and-30, and growing monocrystals. The basic problems and methods of their solution in the synthesis and deep purification of silane and obtaining poly-and monocrystals of isotopically enriched silicon are discussed. Data characterizing the achieved level of chemical and isotopic purity of high-purity monocrystals of silicon-28 with a main isotope content of more than 99.99% and silicon-29 and silicon-30 with isotopic purity higher than 99% are presented. In monocrystalline ²⁸Si, the boron content was 4.5 × 10¹³, the phosphorus content was 5 × 10¹¹, the carbon and oxygen contents were <1 × 10¹⁶ at/cm³, and the specific resistance was 800 Ω cm. The results of investigation of heat capacity, heat conduction, photoluminescence, and electron paramagnetic resonance spectra for monoisotopic silicon-28 are presented. The heat conduction of monoisotopic silicon is increased considerably owing to the reduced photon scattering on isotopic inhomogeneities. In the region of 20–30 K, the heat conduction of silicon-28 with an isotopic purity of 99.98% is higher by a factor of 8 than the heat conduction of natural silicon. Investigations of photoluminescence spectra in the magnetic field in the low-temperature region demonstrated the capability of optical detection of nuclear spin states of a phosphorus admixture in high-purity silicon-28. p ]Topical questions for further investigations and possible fields of practical application of high-purity isotopically enriched silicon are discussed.     

Synthesis and characterization of aluminum diboride products using <Superscript>27</Superscript>Al, <Superscript>11</Superscript>B NMR and ab initio studies

Understanding different bonding environments in various metal borides provides insight into their structures and physical properties. Polycrystalline aluminum diboride (AlB₂) samples have been synthesized and compared both with a commercial sample and with the literature. One issue that arose is the relative ease with which boron-rich and aluminum deficient phases of aluminum borides can be presented in AlB₂. Here, we report ²⁷Al, ¹¹B nuclear magnetic resonance (NMR) spectroscopy and first-principles calculations on AlB₂ in order to shed light on these different bonding environments at the atomic level and compare the structural and electronic properties of the products of different preparations. Along with the aforementioned, the present study also takes an in-depth look at the nature of the ¹¹B and ²⁷Al nuclear spin–lattice relaxation recovery data for the AlB₂ and other superhard materials. The nuclear spin–lattice relaxation has been measured for a static sample and with magic-angle spinning. The combination of NMR and band structure calculations highlights the synthetic challenges with superhard materials.     

<Superscript>99</Superscript>Tc NMR Spectroscopy

⁹⁹Tc NMR data for Tc compounds in various oxidation states are summarized.__________Translated from Radiokhimiya, Vol. 47, No. 4, 2005, pp. 291–304.Original Russian Text Copyright © 2005 by Mikhalev.     

Void formation and cracking of Zr<Superscript>41</Superscript>Ti<Superscript>14</Superscript>Cu<Superscript>12.5</Superscript>- Ni<Superscript>10</Superscript>Be<Superscript>22.5</Superscript> bulk metallic glass under planar shock compression

Planar shock compression effects on void formation and cracking in Zr⁴¹Ti¹⁴Cu^12.5Ni¹⁰Be^22.5 bulk metallic glass (BMG) are studied in this paper. Cracking was found to be a result of void linkage in some direction deviation from the maximum shear stress plane. Changing the state of the stress inside the BMG sample led to formation of different void distribution. Nucleation of the microvoids was possibly initiated by release of excess free volume under shock wave compression.     

Phase stabilization and structural studies of nanocrystalline La<Superscript>2</Superscript>O<Superscript>3</Superscript>-ZrO<Superscript>2</Superscript>

La²O³ doped nanocrystalline zirconia (ZrO²) has been prepared by chemical co-precipitation method for various dopant concentrations, varying from 3 to 30 mol%. Structural phases have been characterized by X-ray diffraction technique. All the as-synthesized samples were found to be in monoclinic phase. Annealing of the samples at different temperatures from 400 to 1000∘C stabilized ZrO² either partially or fully the tetragonal/cubic phases. When they were annealed at 1200∘C, the monoclinic phase appeared again with a new cubic pyrochlore structured La²Zr²O⁷ at the expense of stabilized tetragonal phase. Formability of the tetragonal/cubic phase has been influenced by the dopant concentration and the annealing temperature. Sample with 8 mol% La²O³ has been stabilized completely in tetragonal/cubic phase after annealing at 900∘C for 1 h. Smallness of the grain in these nanocrystalline materials may also have assisted in the formation of La²O³-ZrO² solid solution.     

Mechanochemical synthesis of γ-LiAlO<Subscript>2</Subscript> studied by <Superscript>6</Superscript>Li and <Superscript>27</Superscript>Al NMR and synchrotron X-Ray diffraction

The structural transformations accompanying the mechanochemical synthesis of fine-particle γ-LiAlO₂ have been studied by ⁶Li and ²⁷Al NMR and in situ X-ray diffraction. Mechanical activation of a mixture of aluminum hydroxide and lithium carbonate in an AGO-2 planetary mill results not only in size reduction, intermixing, and partial amorphization of the starting materials but also in the mechanochemical synthesis of a carbonate form of aluminum lithium hydroxide. Subsequent heat treatment of the mechanically activated mixture leads to the release of water and carbon dioxide molecules and the formation of an X-ray amorphous phase containing aluminum in octahedral and tetrahedral oxygen coordination. The X-ray amorphous material converts to gamma lithium aluminate through an intermediate phase.     

Microstructure and upconversion luminescence of Yb<Superscript>3+</Superscript> and Ho<Superscript>3+</Superscript> co-doped BST thick films

Ba_0.8Sr_0.2TiO₃ (BST) thick films co-doped with Yb³⁺ and Ho³⁺ were fabricated by the screen printing techniques on alumina substrates. The structure and morphology of the BST thick films were studied by XRD and SEM, respectively. After sintered at 1240 °C for 100 min the BST thick films are polycrystalline with a perovskite structure. The upconversion luminescence properties of the RE-doped BST thick films under 800 nm excitation at room temperature were investigated. The upconversion emission bands centered at 470 and 534 nm corresponding to ⁵F₁ → ⁵I₈ and ⁵F₄ → ⁵I₈ transition, respectively were observed, and the upconversion mechanisms were discussed. The dependence of the upconversion emission intensity upon the Ho³⁺ ions concentration was also examined; the emission intensity reaches a maximum value in the sample with 2 mol% Yb³⁺ and 0.250 mol% Ho³⁺ ions. All the results show that the BST thick films co-doped with Yb³⁺ and Ho³⁺ may have potential use for photoelectric devices.     

Isolation of <Superscript>58</Superscript>Co, <Superscript>54</Superscript>Mn,and <Superscript>86</Superscript>Rb from <Superscript>89</Superscript>Sr production wastes

Procedures for isolation of ⁵⁸Co, ⁵⁴Mn, and ⁸⁶Rb from ⁸⁹Sr production wastes are described. The production of ⁸⁹Sr was based on irradiation of natural Y in the form of oxide, placed in 1Cr18Ni10Ti stainless steel ampules, on a BR-10 fast reactor. ⁵⁸Co and ⁵⁴Mn were isolated from the casings of stainless steel ampules, and ⁸⁶Rb, from the tail solution after the isolation of ⁸⁹Sr.     

Intense frequency upconversion luminescence in Yb<Superscript>3+</Superscript>/Tm<Superscript>3+</Superscript>-codoped oxychloride germanate glasses

Yb³⁺/Tm³⁺-codoped oxychloride germanate glasses for developing potential upconversion lasers have been fabricated and characterized. Structural properties were obtained based on the Raman spectra analysis, indicating that PbCl₂ plays an important role in the formation of glass network and has an important influence on the maximum phonon energies of host glasses. Intense blue and weak red emissions centered at 477 and 650 nm, corresponding to the transitions ¹G₄ → ³H₆ and ¹G₄ → ³H₄, respectively, were observed at room temperature. With increasing PbCl₂ content, the intensity of blue (477 nm) emission increases significantly, while the red (650 nm) emission increases slowly. The results indicate that PbCl₂ has more influence on the blue emissions than the red emission in oxychloride germanate glasses. The possible upconversion mechanisms are discussed and estimated. Intense blue upconversion luminescence indicates that these oxychloride germanate glasses can be used as potential host material for upconversion lasers.     

Ce<Superscript>3+</Superscript> and Eu<Superscript>2+</Superscript> luminescence in calcium and strontium aluminates

Compound CaAl₄O₇ (CA4), SrAl₄O₇ (SA4), CaAl₁₂O₁₉ (CA12) and SrAl₁₂O₁₉ (SA12) have been synthesized by using single step combustion method. The phosphors have been characterized by XRD, SEM and PL techniques. Both CA4 and SA4 possess monoclinic crystal structure whereas CA12 and SA12 possess hexagonal structure. Effects of crystal symmetry on the emission spectrum have been studied by doping the samples with Ce³⁺ and Eu²⁺ ions. The luminescence properties of Ce³⁺ and Eu²⁺ in these hosts is discussed on the basis of their covalent character and the crystal field splitting of the d-orbital of dopant ions. The spectroscopic properties, crystal field splitting, centroid shift, red shift and stokes shift have been studied. Spectroscopic properties of Eu²⁺ ions have been accurately predicted from those of Ce³⁺ ions in the same host. Most importantly experimental results were matched excellently with the calculated results. The preferential substitution of Ce³⁺ and Eu²⁺ at different Ca²⁺, Sr²⁺ crystallographic sites have been discussed. The dependence of emission wavelengths of Ce³⁺ and Eu²⁺ on the local symmetry of different crystallographic sites was also studied by using Van Uitert’s empirical relation. Differences in the emission spectrum of these samples have been observed despite their similar crystal structures and space group. Possible reasons have been discussed.     

Separation of Carrier-Free <Superscript>115<Emphasis Type="Italic">m</Emphasis></Superscript>In from Its Parent <Superscript>115</Superscript>Cd Using the Synthesized TODGA-Impregnated Silica Gel

A radiotracer technique has been used to achieve the carrier-free separation of ^115mIn from its parent ¹¹⁵Cd in hydrochloric acid medium on a chromatographic column packed with TODGA-impregnated silica gel. At 8 M HCl, both cations are bound at the chelating site, which results in maximum adsorption. When the column is treated with 2 M HCl, the daughter complex gets desorbed and is eluted from the column, whereas the parent remains undisturbed. Pure silica gel does not adsorb radioactivity under these conditions. The radiochemical purity of daughter was checked by its half-life (4.49 h).     

Near-infrared downconversion in Ce<Superscript>3+</Superscript>–Yb<Superscript>3+</Superscript> co-doped YAG

The phosphors YAG co-doped with Ce³⁺–Yb³⁺ ion pair were successfully synthesized by solid state reaction method varying the concentration of Yb³⁺ ions from 1 to 15 % mol. The phosphors were characterized by powder X-ray powder diffraction and surface morphology was studied by scanning electronic microscope. The photoluminescence (PL) properties were studied by spectrophotometers in near infra red (NIR) and ultra violet visible region. The synthesized phosphors can convert a photon of blue region (469 nm) into photons of NIR region (979 and 992 nm). The co-operative energy transfer was studied by time decay curve and PL spectra. The theoretical value of quantum efficiency was calculated from steady time decay measurement and the maximum efficiency approached up to 145.19 %. Hence this phosphor could be used as a downconversion luminescent convertor in front of crystalline silicon solar cell (c-Si) panels to reduce thermalization loss due to spectral mismatch of the solar cells.     

Green synthesis of white-light-emitting ZnSe:Eu<Superscript>2+</Superscript>, Mn<Superscript>2+</Superscript> quantum dots in an aqueous solution

High-quality ZnSe:Eu, Mn quantum dots (QDs) with white light emitting were synthesized via a green preparation method in an aqueous solution using thioglycolic acid as a stabilizing agent. The composition of the QDs could be flexibly controlled by varying the amount of Eu or Mn cation. The effects of reflux time and Eu²⁺ ion dopant concentration on the luminescence properties were systematically investigated. The obtained QDs were characterized by photoluminescence spectrometry, X-ray powder diffraction, and high-resolution transmission electron microscopy. The proposed method formed cubic ZnSe:Mn²⁺, Eu²⁺ QDs with the maximum emission peak at 460 and 580 nm. In the optimal condition, the quantum yields of ZnSe:Mn²⁺, Eu²⁺ QDs could reach 27.68%. The CIE color coordinates were (0.328, 0.334), which agreed with those of pure white light (0.33, 0.33). The results verified that the ZnSe:Mn²⁺, Eu²⁺ QDs exhibited potential in light-emitting diode applications.     

Color tunable luminescence from LaAlO<Subscript>3</Subscript>:Bi<Superscript>3+</Superscript>, Ho<Superscript>3+</Superscript> doped phosphors for field emission displays

Bi³⁺-activated LaAlO₃:Ho³⁺ Phosphor, was prepared by Polyol method, and its photoluminescent properties were investigated under (UV) light excitation. Luminescence studies indicated that optimum concentration of Bi³⁺ and Ho³⁺ in LaAlO₃ was found to be 1 and 1.5 at.%. The luminescent intensity of Ho³⁺ emission lines was remarkably enhanced on exciting with 272 nm, which suggested that efficient energy transfer from Bi³⁺ ions to Ho³⁺ ions takes place. There is significant energy overlap between the emission band of Bi³⁺ ions and the excitation band of Ho³⁺ ions.The ET efficiency has been calculated and found to be 69%. The critical ET distance has been calculated by the concentration–quenching method. The enhanced intensity and tuned luminous color of LaAlO₃: Bi³⁺/Ho³⁺ phosphors from blue to cyan provides a promising material for field emission display devices.     

Drug release from cast films of ethylene vinyl acetate (EVA) copolymer: Stability of drugs by <Superscript>1</Superscript>H NMR and solid state <Superscript>13</Superscript>C CP/MAS NMR

The study utilizes an oral biocompatible material based on ethylene vinyl acetate copolymer (EVA) designed to release drugs in vitro at therapeutic levels over several days. We examined the drug stability during film casting process using proton and solid state NMR techniques. The drug-loaded EVA films were prepared from the dry sheet obtained by solvent (dichloromethane) evaporation of polymer casting solutions. Drugs tested include chlorhexidine diacetate (CDA), doxycycline hydrochloride (DOH), tetracycline hydrochloride (TTH) and nystatin (NST). Drug release from the films was examined for at least 14 days in 10 ml ddH₂O (NST in water/ethanol (4:1)) which was replaced daily. Changes in optical density were followed spectraphotometrically. Effect of temperature on rate measurements was studied and the energies of activation (E^∗) were calculated using Arrhenius plots. Effect of EVA copolymer composition on CDA release rate was also investigated. The enhanced rates with temperature increase may be attributed to the formation of channels with increased geometry in the polymer. The highest E^∗ observed for CDA compared to DOH and TTH may be related to their average molecular weights. Spectral analyses for CDA and NST revealed that the chemical and physical structures of the drugs remained unaffected during the film casting process.     

Microwave synthesis and luminescence properties of YVO<Subscript>4</Subscript>:Eu<Superscript>3+</Superscript>

Europium-doped YVO₄ phosphors have been synthesized using microwave radiation of 700 W power. The uniformity and high rate of microwave heating, as well as “nonthermal” effects of microwave radiation, considerably accelerate the decomposition of precursors and YVO₄:Eu³⁺ synthesis. The europium concentration was varied from 1 to 8 at %. The luminescence intensity of YVO₄:Eu³⁺ was shown to depend on Eu³⁺ concentration, with a maximum at 8 at % Eu³⁺. According to transmission electron microscopy data, the synthesized phosphors consist of nanoparticles 6 to 8 nm in size, with an appreciable degree of agglomeration.     

Labeling and biological evaluation of <Superscript>99<Emphasis Type="Italic">m</Emphasis></Superscript>Tc-tricarbonyl-chenodiol for hepatobiliary imaging

^99m Tc-tricarbonyl-labeled chenodiol (chenodeoxycholic acid, CDCA) intended for hepatobiliary imaging was prepared by 30-min heating at 100°C with a radiochemical yield of >98%. The radiolabeling yield and stability of the complex were evaluated using different chromatographic techniques. Biodistribution studies in Albino Swiss mice at different time intervals after administration of the complexes showed that the maximum uptake of the complexes in the liver was 35.5 ± 0.25% ID/g at 30 min post injection. ^99m Tc-tricarbonyl- CDCA shows promise for hepatobiliary imaging.     

Hydrothermal synthesis of blue-emitting YPO<Subscript>4</Subscript>:Yb<Superscript>3+</Superscript> nanophosphor

The blue-emitting YPO₄ phosphors doped with Yb³⁺ were prepared by a simple hydrothermal method. All the products were characterized by XRD and TEM, which revealed that they were zircon structure with leaf-like morphology. According to the analysis of photoluminescence spectra, upon ultraviolet (275 nm) excitation, the Yb³⁺ doped YPO₄ phosphor showed an intense blue emission composed of two main bands at 420 and 620 nm assigned to charge transfer state (CTS) → ²F_5/2 and CTS → ²F_7/2, respectively. Moreover, the optimum doping concentration of Yb³⁺ in YPO₄ phosphor was 1%, which exhibited the maximum emission intensity. The possible physical mechanism of concentration quenching was discussed, and the critical transfer distance determined to be 23.889 Å. In particular, the color purity of the as-synthesized Yb³⁺ doped YPO₄ phosphor was as high as 83%, which made it an excellent candidate for blue-emitting materials.     

Upconversion emissions in Yb<Superscript>3+</Superscript>–Tm<Superscript>3+</Superscript>-doped tellurite glasses excited at 976 nm

Intense Tm³⁺ blue upconversion emission has been observed in Tm³⁺–Yb³⁺ codoped oxyfluoride tellurite glass under excitation with a diode laser at 976 nm. Three emission bands centered at 475, 650 and 796 nm corresponding to the transitions ¹G₄→ ³H₆, ¹G₄→ ³H₄ and ³F₄→ ³H₆, respectively, simultaneously occur. The dependence of upconversion intensities on Tm³⁺ ions concentration and excitation power are investigated. For fixed Yb₂O₃ concentrations of 5.0 mol%, the maximum upconversion intensity was obtained with Tm₂O₃ concentration of about 0.1 mol%. The blue upconversion luminescence lifetimes of the Tm³⁺ transitions ¹G₄→ ³H₆ are measured. The results are evaluated by the possible upconversion mechanisms.