Gelled Na<Subscript>2</Subscript>HPO<Subscript>4</Subscript> · 12H<Subscript>2</Subscript>O with amylose-g-sodium acrylate: heat storage performance,heat capacity and heat of fusion

A novel gelling method was studied to stabilize phase change material Na₂HPO₄ · 12H₂O with amylose grafted sodium acrylate. Gelled Na₂HPO₄ · 12H₂O shows stable heat storage performance prepared at optimized conditions: 2.7mass/mass% sodium acrylate, 0.4 mass/mass% amylose, 0.05–0.09 mass/mass% N, N′-methylenebisacrylamide, 0.05–0.09 mass/mass% K₂S₂O₈ and Na₂SO₃ (mass ratio 1:1), at 50 °C. Na₂HPO₄ · 12H₂O was dispersed in gel network as tiny crystals less than 0.1 mm. Melting points were in the range 35.4 ± 2 °C. Short-term thermal cycling proves the effectiveness of the novel method for eliminating phase separation in the gelled salt. Adiabatic calorimetric measurement of heat capacities shows two phase transitions, which correspond to melting of Na₂HPO₄ · 12H₂O and freezable bond water in gel, respectively. Heat of fusion of pure Na₂HPO₄ · 12H₂O was determined as 260.9 J g⁻¹. Distribution of extra water is: free water:freezable water:nonfreezing water = 0:0.85:0.15.     

Chemical analysis of rain and snow samples from Chernogolovk/Russia by IC, TXRF and ICP–MS

 Data are reported for a first measurement campaign for a great number of cations (the range of concentrations for main components is given in ng/mL: Na:<70–880; Mg: 12–160; Al:<7–120; K: 200–1600; NH₄ ⁺: 2500–9000; Ca: 300–2500; Fe:<140–1200; Zn: 20–320) and anions (HCOO^-: 100–1800; CH₃COO^-: 400–14500; C₂O^2- ₄: <100–460; NO^- ₂: <20–55; NO^- ₃: 660–9900; SO^2- ₃:<100–1150; SO₄ ^2-: 450–19700; Cl^-: 170–3200) in rain and snow samples of the Chernogolovka region 80 km northeast of the centre of Moscow. These data serve as a first assessment of the situation of the atmosphere in this region. For the determination of fluoride, formate, acetate, nitrite, bromide, nitrate, sulfite, and sulfate by IC, a relevant development of the method was carried out. For some metallic cations, a critical quality control was achieved by parallel measurements with ICP-MS, TXRF, and IC. Furthermore, time resolved measurements were performed for a rain event. Filtration experiments were undertaken to differentiate between the presence of a series of elements and species in liquid or solid state in the collected aqueous samples. Received: 25 July 1996 / Revised: 26 September 1996 / Accepted: 13 October 1996     

Experimental determination and prediction of the vapor pressure of some binary and quaternary aqueous solutions of alkaline nitrites and nitrates

Vapor pressure of H₂O + NaNO₃ and H₂O + NaNO₂ solutions were measured with static method from 298.1 to 353.1 K in a range of salt mass fractions between 0.05 and 0.50. As well, the vapor pressure was determined for quaternary mixtures LiNO₃ + NaNO₃ + KNO₃ + H₂O (salt mass ratio 53:5:42) and LiNO₃ + KNO₃ + NaNO₂ + H₂O (salt mass ratio 53:35:12) from 313.1 to 353.1 K and total salt mass fraction of 0.30, 0.40 and 0.50. The experimental vapor pressure data of binary systems were correlated with the temperature and the liquid-phase composition using an analytical polynomial equation. The capability of the electrolyte non-random two liquid model (Electrolyte-NRTL) to predict the vapor–liquid equilibrium was evaluated by comparing predicted and experimental data of the mixtures studied in this work.     

State of atoms and interatomic interactions in complex perovskite-like oxides: XXXI. Influence of magnesium concentration on chromium atoms state and interatomic interactions in lanthanum gallate doped with chromium and magnesium

Magnetic susceptibility of LaCr _x Ga_1−1.2x Mg_0.2x O_3−δ and LaCr _x Ga_1−1.5x Mg_0.5x O_3−δ solid solutions with the ratios [Cr]:[Mg] = 5:1 and 2:1 was studied. Fractions of clusters and single chromium atoms were calculated for the series of solid solutions with [Cr]:[Mg] = 5:1. The relation of the systems with [Cr]:[Mg] = 5:1 and [Cr]:[Sr]:[Mg] = 5:1:1 was revealed. For the system with [Cr]:[Mg] = 2:1 a temperature dependence of effective magnetic moment was found, which suggests that the exchange parameter is temperature dependent.     

Silver delafossite nitride, AgTaN2?

A new silver nitride, AgTaN₂, was synthesized from NaTaN₂ by a cation-exchange reaction, using a AgNO₃-NH₄NO₃ flux at 175 °C. Its crystal structure type is delafossite (R3¯m) with hexagonal lattice parameters of a=3.141(3) Å, c=18.81(2) Å, in which silver is linearly coordinated to nitrogen. Energy dispersive X-ray analysis and combustion nitrogen/oxygen analysis gave a composition with atomic ratios of Ag:Ta:N:O as 1.0:1.2(1):2.1(1):0.77(4), which is somewhat Ta rich and indicates some oxide formation. The X-ray photoelectron spectroscopy analysis showed a Ta- and O-rich surface and transmission electron microscope observation exhibited aggregates of ca. 4-5 nm-sized particles on the surface, which are probably related to the composition deviation from a AgTaN₂. The lattice parameters of stoichiometric AgTaN₂ calculated by density functional theory agree with the experimental ones, but the possibility of some oxygen incorporation and/or silver deficiency is not precluded.     

Chemical analysis of rain and snow samples from Chernogolovk/Russia by IC, TXRF and ICP–MS

 Data are reported for a first measurement campaign for a great number of cations (the range of concentrations for main components is given in ng/mL: Na:<70–880; Mg: 12–160; Al:<7–120; K: 200–1600; NH₄ ⁺: 2500–9000; Ca: 300–2500; Fe:<140–1200; Zn: 20–320) and anions (HCOO^-: 100–1800; CH₃COO^-: 400–14500; C₂O^2- ₄: <100–460; NO^- ₂: <20–55; NO^- ₃: 660–9900; SO^2- ₃:<100–1150; SO₄ ^2-: 450–19700; Cl^-: 170–3200) in rain and snow samples of the Chernogolovka region 80 km northeast of the centre of Moscow. These data serve as a first assessment of the situation of the atmosphere in this region. For the determination of fluoride, formate, acetate, nitrite, bromide, nitrate, sulfite, and sulfate by IC, a relevant development of the method was carried out. For some metallic cations, a critical quality control was achieved by parallel measurements with ICP-MS, TXRF, and IC. Furthermore, time resolved measurements were performed for a rain event. Filtration experiments were undertaken to differentiate between the presence of a series of elements and species in liquid or solid state in the collected aqueous samples. Received: 25 July 1996 / Revised: 26 September 1996 / Accepted: 13 October 1996     

Effect of iron acetylacetonate on physico-chemical properties of waterglass based aerogels by ambient pressure drying

The effect of iron acetylacetonate on the physico-chemical properties of waterglass based silica aerogels by ambient pressure drying has been investigated. Doping the gels with iron acetylacetonat (FeAA) facilitates in the diminution of the density of the aerogels. The well established silica network provides effective confinement of FeAA nanoparticles which resists the collapse of silica network during ambient pressure drying. Therefore, in the present paper, the effects of FeAA on the physico-chemical properties of the aerogels have been studied by varying the FeAA:Na₂SiO₃ molar ratio from 3 × 10⁻⁴ to 6 × 10⁻⁴. The aerogels were prepared via ambient pressure drying and characterized by the bulk density, thermal conductivity and water contact angle. The aerogel’s surface morphology, elemental analysis and pore structure were characterized by means of EDAX and FTIR, TEM and N₂ adsorption- desorption analyzer. The high temperature hydrophobicity of these aerogels was checked by heating them in temperature controlled furnace. Silica aerogels with low density ~0.050 g/cc have been obtained using the molar ratio of Na₂SiO₃:H₂O:FeAA:Citric acid:TMCS at 1:146.67:3 × 10⁻⁴:0.54:9.46, respectively. EDAX and FTIR studies show that the iron species are entrapped in the mesoporous framework and not took part in the bonding with silica.     

Preparation and photoluminescence properties of RE:Na3La9O3(BO3)8 (RE=Er, Yb) crystals

Using Na₂CO₃-H₃BO₃-NaF as fluxes, transparent RE:Na₃La₉O₃(BO₃)₈ (abbr. RE:NLBO, RE=Er, Yb) crystals have been grown by the top seed solution growth (TSSG) method. The X-ray powder diffraction analysis shows that the RE:NLBO crystals have the same structure with NLBO. The element contents were determined by molar to be 0.64% Er³⁺ in Er:NLBO, 2.70% Yb³⁺ in Yb:NLBO, respectively. The polarized absorption spectra of RE:NLBO have been measured at room temperature and show that both Er:NLBO and Yb:NLBO have a strong absorption bands near 980 nm with wide FWHM (Full Wave at Half Maximum) (21 nm for Er:NLBO and 25 nm for Yb:NLBO). Fluorescence spectra have been recorded. Yb:NLBO has the emission peaks at 985 nm, 1028 nm and 1079 nm and the emission peak of Er:NLBO is at 1536 nm. Spectral parameters have been calculated by the Judd-Ofelt theory for Er:NLBO and the reciprocity method for Yb:NLBO, respectively. The calculated values show that Er:NLBO is a candidate of 1.55 μm laser crystals and Yb:NLBO is a candidate for self-frequency doubling crystal.     

Flux syntheses of La-doped NaTaO3 and its photocatalytic activity

The La-doped (2%) NaTaO₃ perovskite-type solid was synthesized in high purity and homogeneity within a molten Na₂SO₄/K₂SO₄ (1:1 molar ratio) flux in much shortened reaction times, 0.5-1.0 h, compared to conventional solid-state techniques. The particle morphologies were investigated by scanning electron microscopy and were irregular block-shaped with dimensions of 500-100 nm and smaller surface features. The bulk particle sizes were found to decrease with increasing amounts of flux used in the synthesis, from 1:1 (NaTaO₃:flux), 1:2 to 1:3 for a reaction duration of 1 h. Photocatalytic activities of the NaTaO₃ products were measured in an aqueous methanol solution to be 535-1115 μmol H₂ h⁻¹ g⁻¹, and which increased with increasing particle sizes and decreasing amounts of flux used in the synthesis. These rates were up to ×2 greater than that measured for a conventionally prepared La-doped (2%) NaTaO₃ sample, which is currently one of the most efficient UV-photocatalysts known.     

Anodic oxidation of 2-aminofluorene in CH2Cl2 + 0.2 M Bu4NBF4: electrochemical behaviour of the derived oxidation products

The physicochemical properties and electrochemical behaviour of products obtained by anodic oxidation of 2-aminofluorene in CH₂Cl₂ + 0.2 M Bu₄NBF₄ are presented together with the oxidation conditions. Received: 8 January 1998 / Accepted: 21 September 1998     

Synthesis of transparent mixed vanadia/niobia gels and their decomposition to a new metastable VNb9O25 phase

Controlled hydrolysis and condensation of a mixture of vanadyl-tris-n-propoxide, VO(OPr)₃, and niobium pentaethoxide, [Nb(OEt)₅]₂, at 5 °C in propanol yields clear and transparent gels in which the ratio of V:Nb is 1:1, 1:4.5 or 1:9. Oxalic acid and low temperatures are used to slow down the rate of condensation processes. At 800 °C, the thermal decomposition of a gel with the composition 1:9 forms a thermodynamically metastable, new phase of the composition VNb₉O₂₅. At lower temperatures, metastable solid solutions with TT-Nb₂O₅ structure (600 °C) and M-Nb₂O₅ structure (700 °C) are formed from the amorphous xerogel. The new VNb₉O₂₅ phase is structurally related to M-Nb₂O₅. The solid solution with M-Nb₂O₅ structure acts structure directing, leading preferentially to a monoclinic low-temperature form of VNb₉O₂₅. The full transformation of this metastable phase to the well known tetragonal VNb₉O₂₅ requires a annealing temperature of about 1000 °C.     

Preparation and optical characterization of hydroxyapatite and ceramic systems with titanium and zirconium formed by dry high-energy mechanical alloying

Calcium phosphate-based bioceramics, mainly in the form of hydroxyapatite, Ca₁₀(PO₄)₆(OH)₂—HAP, is the main mineral constituent of teeth and bones with excellent biocompatibility with hard and muscle tissues. These materials exhibit several problems of handling and fabrication, which can be overcome by mixing them with a suitable binder. The dry milling process of fabrication of HAP presents the advantage that melting is not necessary and the powder obtained is nanocrystalline. The high efficiency of the dry milling process opens a new way to produce commercial amount of nanocrystalline HAP and others bioceramic. In this work dry mechanical alloying has been used to produce nanocrystalline powders of HAP using three different experimental procedures (HAPA: Ca(H₂PO₄)₂ + Ca(OH)₂; HAPB: Ca(H₂PO₄)₂ + CaCO₃; and HAPC: CaHPO₄ + CaCO₃). HAP was obtained after 5, 10 and 15 h of milling in the reactions HAPA and HAPB, but it is necessary 15 h of milling in the reaction HAPC to obtain HAP. In order to improve the mechanical properties of HAP calcium phosphate ceramics, with titanium (CaP-Ti) and zirconium (CaP-Zr), have been prepared by dry ball milling using two different experimental procedures: CaP-Ti1: Ca(H₂PO₄)₂ + TiO₂; CaP-Ti2: CaHPO₄ + TiO₂; and CaP-Zr1: Ca(H₂PO₄)₂ + ZrO₂, CaP-Zr2: CaHPO₄ + ZrO₂. The calcium titanium phosphate phase, CaTi₄P₆O₂₄, was obtained in the reaction CaP-Ti1. In the reactions CaP-Ti2, CaP-Zr1 and CaP-Zr2, it was not observed the formation of any calcium phosphate phase even after 15 h of dry mechanical alloying. The milled HAP and the ceramics systems obtained were characterized by X-ray powder diffraction, infrared and Raman scattering spectroscopy.     

Versatility of an intramolecularly hydrogen-bonded 4-(N,N-dimethylamino)benzoate group as a signaling subunit for anion recognition

The versatility of the 4-(N,N-dimethylamino)benzoate (DMAB) group embedded in host 1 as a signaling subunit for anion recognition was elucidated in terms of ¹H NMR, CD, and fluorescence studies. Host 1 showed 1:1 complexation with monovalent anions and stepwise 1:1 and 2:1 (host 1: anion) complexation with divalent phosphate anions. The binding constants between host 1 and anions were determined by means of ¹H NMR titrations in CD₃CN (HPO₄²⁻: log K_1:1=6.2, log K_2:1=4.9; H₂P₂O₇²⁻: log K_1:1=4.4, log K_2:1=1.8; AMP²⁻: log K_1:1>7, log K_2:1>5) and the affinity of host 1 toward divalent anions, HPO₄²⁻, H₂P₂O₇²⁻, and AMP²⁻, is stronger than that toward monovalent anions, NO₃⁻, BF₄⁻, ClO₄⁻, HSO₄⁻, and PF₆⁻. The CD exciton chirality studies of host 1 with divalent anions, HPO₄²⁻ and AMP²⁻, revealed that the two DMAB groups in the 2:1 complexes were arranged with negative chirality (counterclockwise). The dual fluorescence behavior of the DMAB group demonstrated not only the complexation stoichiometry but also the role(s) of the lipophilic countercation such as tetrabutylammonium and/or the hydrophilic residue in AMP during anion recognition.     

New 18-l process-scale counter-current chromatography centrifuge

A new Dynamic Extractions Maxi-counter-current chromatography (CCC) centrifuge with a column volume of 18-l has been installed in the Advanced Bioprocessing Centre at Brunel. This instrument has four times the capacity of the 4.6-l Maxi-CCC centrifuge which has been operating robustly for 3 years. Tests using the model sample system benzyl alcohol and p-cresol with a heptane:ethyl acetate:methanol:water (HEMWat) phase system (1.4:0.1:0.5:1.0) show that resolution is almost double with this new high capacity device. Commissioning tests with a mixture of caffeine, K_D = 0.21; ferulic acid, K_D = 0.82; umbelliferone, K_D = 1.2 and vanillin, K_D = 1.49 using a HEMWat phase system of 1:1.5:1:1.5 on the 9-l column show that resolutions equivalent to analytical instruments will be possible using the full 18-l capacity. They also show that predictable scale-up from simple test tube tests is feasible with knowledge of the stationary phase retention for the planned process scale run.     

Blue-light-excitable broadband yellow-emitting CaGd2HfSc(AlO4)3:Ce3+ garnet phosphors for white light-emitting diode devices with improved color rendering index

The current commercial white light-emitting diodes (LEDs) are generally based on the combination of blue LED chips and Y₃Al₅O₁₂:Ce³⁺ yellow phosphors. However, because of the lack of red component, such white LED devices exhibit cool white-light emissions with low color rendering index (Ra < 75, R9 < 0). Therefore, it is urgent to discover new blue-light-excitable yellow-emitting phosphors with enhanced red emissions for fabricating high color-quality white LEDs. In the present work, we demonstrate a novel broadband yellow-emitting CaGd₂HfScAl₃O₁₂:Ce³⁺ garnet phosphor for blue-light-excited white LEDs with improved color rendering index. The as-prepared CaGd₂HfScAl₃O₁₂:Ce³⁺ garnet phosphor possesses a cubic structure with Ia$\overline{3}$d space group, and the unit cell parameters of the representative CaGd₂HfScAl₃O₁₂:2%Ce³⁺ phosphor are a = b = c = 12.450 Å, α = β = γ = 90°, and V = 1,929.59(4) ų. Impressively, we find that the CaGd₂HfScAl₃O₁₂:Ce³⁺ garnet phosphor shows an intense absorption band in the 300–500 nm wavelength range with a maximum at 452 nm owing to the 4f→5d transition of Ce³⁺ ions. On 452 nm excitation, the optimal CaGd₂HfScAl₃O₁₂:2%Ce³⁺ sample exhibits a broad asymmetric yellow emission band in the wavelength range of 470–750 nm with peak at 564 nm and full width at half maximum of 151 nm. The Commission Internationale de l’Eclairage chromaticity coordinates and internal quantum efficiency of the CaGd₂HfScAl₃O₁₂:2%Ce³⁺ sample are (0.4485, 0.5157) and 30.4%, respectively. Finally, a white LED device is fabricated by combing a 450 nm blue LED chip with commercial Y₃Al₅O₁₂:Ce³⁺ yellow-emitting phosphor, which generates white light with low color rendering index (CRI; Ra = 74.7, R9 = ?12.7) and high correlated color temperature (CCT = 6,554 K) under the 60 mA driving current. In sharp contrast, another white LED device, which is made by coating our as-prepared CaGd₂HfScAl₃O₁₂:2%Ce³⁺ yellow-emitting phosphors onto the surface of a 450 nm blue LED chip, produces white-light emission with high CRI value (Ra = 84.5, R9 = 26.3) and relatively low CCT of 5,649 K. This work reveals that the newly discovered broadband yellow-emitting CaGd₂HfScAl₃O₁₂:Ce³⁺ phosphors can serve as a potential color converter in high-color-quality phosphor-converted white LEDs.     

Catalytic dehydrogenation of cyclooctane with titanium, zirconium and hafnium metallocene complexes

Metallocene complexes in combination with cocatalysts like methylalumoxane (MAO) are not only excellent catalysts for olefin polymerization but also appropriate catalysts for the activation of alkanes in homogeneous (autoclave) and heterogeneous (fixed bed reactor) reactions. The activities of the catalysts depend on the temperature, the cocatalysts, additives, the central metal and the ligand structure. Generally, complexes with low steric demands and MAO as cocatalyst gave the highest activities. The comparison of different π-ligands resulted in the following activity order: cyclopentadienyl > indenyl > fluorenyl. The influence of σ-ligands and n-donor ligands gave the following activity order: -Cl > -PMe₃ > -CH₂Ph > -(CH₂)₄CH₃ > -NPh₃. The activities depended on the nature of the cocatalyst and decreased in the following order: MAO ? AlMe₃ > AlEt₃. The addition of aluminum powder and the Lewis base NPh₃ increased the activity of the Cp₂ZrCl₂/MAO catalyst. The Cp₂ZrCl₂/MAO/NPh₃ catalyst showed the highest activity in homogeneous reactions with 458 turnovers in 16 h at 300 °C. The Cp₂ZrCl₂/MAO/NPh₃/SI1102 catalyst gave the highest activity in heterogeneous catalysis with 206 turnovers in 5 h at 350 °C. None of the catalysts required a hydrogen acceptor like an external olefin.     

A DFT study on the mechanism of the gas phase reaction of ground-state Y (4d5s,D) with 2-butyne

The reaction of ground-state Y with 2-butyne has been investigated in detail using B3LYP method. Four pathways for elimination of H₂ were identified. Two isomers, Y(HCCC)CH₃ and Y(H₂CCCCH₂) were assigned to the observed product, YC₄H₄. The calculated PESs suggest that the concerted H₂-elimination leading to Y(H₂CCCCH₂) + H₂ product is the most favorable pathway. For the elimination of CH₃, combining the results of this work with our previous study on Y + propyne reaction, a general mechanism for the reactions of Y with 2-alkynes bearing RCCCH₃ structure was established: Y + RCCCH₃ → π-complex → TS(H-migration) → HY(CH₂CC)R → TS (CC insertion) → (CH₂)HYCCR → TS(H-migration) → H₃CYCCR → CH₃ + YC₂R. Such mechanism was found to be always energetically more favorable than the direct sp–sp³ CC bond insertion mechanism. Further, such mechanism can also be applied to the elimination of CH₄ and it can be described as: Y + CH₃CCCH₃ → π-complex → TS (H-migration) → HY(H₂CCC)CH₃ → TS(CC insertion) → (H₂CCC)HYCH₃ → TS(H-migration) → CH₄ + YC₃H₂.     

Transfer of polyantimony units

Transfer reagents are useful tools in chemistry to access metastable compounds. The reaction of [Cp′′₂ZrCl₂] with KSb(SiMe₃)₂ leads to the formation of the novel polyantimony triple decker complex [(Cp′′Zr)₂(μ,η^1:1:1:1:1:1-Sb₆)] (1, Cp′′ = 1,3-di-tertbutyl-cyclopentadienyl), containing a chair-like Sb₆⁶⁻ ligand. Compound 1 represents a valuable transfer reagent to form novel antimony ligand complexes. Thus, the reaction of 1 with Cp^R-substituted transition metal halides of nickel, cobalt and iron leads to the formation of a variety of novel Sb_n ligand complexes, such as the cubane-like compounds [(Cp′′′Ni)₄(μ₃-Sb)₄] (2) and [(Cp′′′Co)₄(μ₃-Sb₄)] (3a) or the complexes [(Cp^BnCo)₃(μ₃-Sb)₂] (4) and [(Cp′′′Fe)₃(μ₃-Sb)₂] (5), representing a trigonal bipyramidal structure. Moreover, beside the transfer of Sb₁ units, also the complete entity can be transferred as seen in the iron complex [(Cp′′′Fe)₃(μ_3,η^4:4:4-Sb₆)] (6). DFT calculations shed light on the bonding situation of the products.

The synthesis and characterization of the unique polyantimony complex [(Cp′′Zr)₂(μ,η^1:1:1:1:1:1-Sb₆)] (1) is described. Compound 1 was used as antimony source to transfer Sb_n units to late transition metal fragments [Cp^RM] (M = Fe, Co, Ni).     

SN2-Selective allylic substitution of chiral γ-aryl substituted allylic picolinates with alkynylcopper reagents

Substitution of γ-aryl secondary allylic picolinates with alkynyl copper reagents was studied. The copper reagent, prepared from TMSCCMgBr and CuBr·Me₂S in 2:1, was subjected to substitution of the picolinate derived from (E)-3-phenyl-1-methyl-2-propenyl alcohol at 0 °C for 1 h in THF to produce a mixture of α- and γ-products and the alcohol in 67:20:13, while the reagent in 3 or 4:1 ratio gave the α-product with 90-91% selectivity. On the contrary, reaction in CH₂Cl₂-THF (6-8:1) at 0 °C for 1 h furnished the α-product with 99% regioselectivity. The effect of CH₂Cl₂ was also demonstrated with eight more examples. Furthermore, 99% inversion was determined by transformation to the literature compound and by chiral HPLC.