The calorimetric investigation of the graphite–HNO3–R system (R=CH3COOH,H2SO4)

The interactions of highly oriented pyrolytic graphite with HNO₃–R (R=CH₃COOH, H₂SO₄) solution were investigated by Calvet type calorimeter at 305.5 K and X-ray diffraction. It was shown that in the graphite–98% HNO₃–100% CH₃COOH system the enthalpy of the formation and the stage number of graphite nitrate depends on HNO₃ percentage in the solution. Calorimetric investigation of the graphite–98% HNO₃–96% H₂SO₄ system demonstrated that the shape of the heat flow curves corroborates the co-intercalation of HNO₃ and H₂SO₄ into graphite. It was established that the formation of the first stage of ternary compounds of variable composition takes place.     

Trace analyses of gaseous products formed during heat treatment of high stage H2SO4-GICs and expanded graphite

H₂SO₄-GICs samples prepared by different methods were heated to 1000 °C under flow of air using heating rates of 2, 10 and 20 K/min Gaseous products of decomposition were analysed using FTIR spectra recorded during the thermal process. It was detected that S–O species started evolving from graphite gallery above 500 °C, not depending on the method of GIC preparation. High expansion of H₂SO₄-GIC was observed when the intercalate evolved from the intercalated graphite before its abrupt oxidation to CO₂. The disordered structure of graphite layers in H₂SO₄-GIC leads to easy release of S–O species without exfoliation effect. It was observed that using 2 K/min heating rate the time needed for intercalate to release from graphite gallery is shorter than that needed for its exfoliation. Therefore, the exfoliation process should be conducted using high heating rate.     

Improvement of the polishing treatment for niobium surfaces of superconducting cavity resonators

For superconducting cavities made from niobium sheet, which are interesting in the field of accelerator applications, smooth and defect free inner surfaces are needed to achieve a high unloadedQ along with high accelerating field strength. These can be obtained using chemical polishing procedures. Whereas normally a mixture of HF, HNO₃, and H₃PO₄ is applied, we chose the known bath containing HF, HNO₃, and H₂SO₄ and worked above 50 °C. The surface quality was judged by visual inspection using a light microscope as well as by microwave measurements of one spherical resonator. The new method gave less grain boundary etching and, with high field levels, an enlarged unloadedQ.     

Proton conductivity of Al(H2PO4)3–H3PO4 composites at intermediate temperature

Composites of Al(H₂PO₄)₃ and H₃PO₄ were synthesised by soft chemical methods with different Al/P ratios. The Al(H₂PO₄)₃ obtained was found to have a hexagonal symmetry with parameter a = 13.687(3)Å, c = 9.1328(1)Å. The conductivity of this material was measured by a.c. impedance spectroscopy between 100 °C and 200 °C in different atmospheres. The conductivity of pure Al(H₂PO₄)₃ in air is in the order of 10^? 6–10^? 7 S/cm between 100 and 200 °C. For samples containing small excess of H₃PO₄, much higher conductivity was observed. The impedance responses of the composites were found to be similar with AlH₂P₃O₁₀·nH₂O under different relative humidity. The conductivity of Al(H₂PO₄)₃–H₃PO₄ composite with Al/P = 1/3.5 reached 6.6 mS/cm at 200 °C in wet 5% H₂. The extra acid is found to play a key role in enhancing the conductivity of Al(H₂PO₄)₃–H₃PO₄ composite at the surface region of the Al(H₂PO₄)₃ in a core shell type behaviour. 0.7% excess of H₃PO₄ can increase the conductivity by three orders of magnitude. These composites might be alternative electrolytes for intermediate temperature fuel cells and other electrochemical devices. Conductivity (9.5 mS/cm) changed little, when the sample was held at 175 °C for over 100 h as the conductivity stabilised.     

Angle-dependent X-ray emission bands of potassium intercalated graphite

The angular dependent X-ray C K-emission bands of C₈K, C₂₄K and pristine graphite were measured at take-off angles 20° and 80°. For the potassium graphite intercalated compounds (GICs) a pronounced peak is observed at 283.2 eV. Numerical decomposition of the emission bands into their constituent π- and σ-subbands gives evidence for non-rigid band behaviour of potassium GICs and shows that the peak has to be attributed to carbon π-like states.     

Acoustic emission upon spontaneous polarization in triglycine sulfate single crystals

We report on the results of analysis of acoustic emission (AE) under thermal action on a triglycine sulfate (NH₂CH₂COOH)₃ ? H₂SO₄ crystal. The triglycine sulfate single crystals grown from solution and not subjected to mechanical treatment are heated to a temperature above the Curie point (T_C = 49°C). During natural cooling of the crystal, a transition from the paraelectric to ferroelectric phase is accompanied by intense AE. In the temperature range ～28–30°C, an anomalous drop of the mean-square voltage in the AE signal is observed against the background of monotonic accumulation of AE events.     

Silica–zirconium phosphate–phosphoric acid composites: preparation,proton conductivity and use in gas sensors

Mesoporous composites made of silica and α-zirconium phosphate (SiO₂·xZrP) were synthesized starting from mixtures of delaminated ZrP dispersions and tetrapropylammonium oligosilicate solutions. The surface area of the composites reaches a maximum of 700 m²/g for x≈0.02, while the average pore diameter is about 40 Å for x in the range 0.05–0.35. In order to increase proton conductivity at low relative humidity (r.h.), SiO₂·xZrP·yH₃PO₄ composites were prepared and characterised by ²⁹Si and ³¹P MAS NMR and conductivity measurements. At 100 °C and 6% r.h., the conductivity of the composites, with H₃PO₄ loadings of 80% of the pore volume, rises from 5×10⁻⁴ to 2×10⁻² S/cm for x decreasing between 0.35 and 0.05, as a consequence of the concomitant increase of pore volume. For the composite with x=0.18, the dependence of conductivity on H₃PO₄ loading was also investigated at different temperatures and r.h. values. The combined increase of humidity, temperature and H₃PO₄ loading results in an increase of conductivity from 1×10⁻⁷ S/cm (y=0.09, T=25 °C, 0% r.h.) to 4×10⁻² S/cm (y=0.61, T=100 °C, 30% r.h.). SiO₂·0.18ZrP·0.61H₃PO₄ was also tested as a proton electrolyte in an oxygen sensor consisting of a disk of the composite sandwiched between a platinum sensing electrode and a reference electrode based on Ni_1−xO. The sensor is able to detect O₂ at room temperature in a dry environment with a response time of 20–30 s.     

Proton conductivity and phase composition of mixed salts in the systems <Emphasis Type="Italic">M</Emphasis>H<Subscript>2</Subscript>PO<Subscript>4</Subscript>–CsHSO<Subscript>4</Subscript> (<Emphasis Type="Italic">M</Emphasis> = Cs,K)

Phase transformations, electrical transport and thermal properties of the systems K_1?xCs_x(H₂PO₄)_1–x(HSO₄)_x (x = 0.01–0.95) and Cs(H₂PO₄)_1–x(HSO₄)_x (x = 0.01–0.30) have been studied in detail. It has been shown that the mixed compounds Cs(H₂PO₄)_1–x(HSO₄)_x are characterized by an increase in the low-temperature electrical conductivity by one to five orders of magnitude depending on the composition, as well as by the disappearance of the superionic phase transition at x ≥ 0.15. The partial substitution of HSO₄^- ions for the anions in CsH₂PO₄ at x = 0.01–0.10 leads to the formation of Cs(H₂PO₄)_1?x(HSO₄)_x solid solutions isostructural with the CsH₂PO₄ (P2₁/m) phase. For Cs(H₂PO₄)_1–x(HSO₄)_x with x = 0.15–0.30 at room temperature, there is a stabilization of the high-temperature cubic phase isostructural with the CsH₂PO₄ (\(Pm\overline 3 m\)) phase existing in CsH₂PO₄ at temperatures above 230°C. The stability of the \(Pm\overline 3 m\) cubic phase at room temperature has been investigated using X-ray powder diffraction, ¹H NMR spectroscopy, and impedance spectroscopy. In the K_1–xCs_x(H₂PO₄)_1–x(HSO₄) system, there are two regions of compositions with x = 0.05–0.50 and 0.60–0.95, where the proton conductivity and thermal properties are determined respectively by the formation of the CsH₅(PO₄)₂ phase, which is stoichiometrically different from the initial salts, and the potassium-containing phase, which is isostructural with the superionic salt Cs₃(HSO₄)₂(H₂PO₄).     

Dissolution patterns caused by chemical etching of Al–Co–Cu and Al–Co–Ni decagonal quasicrystals with a HF–HNO3–H2O solution

Dissolution patterns essential for Al–Co–Cu and Al–Co–Ni decagonal quasicrystals (d-QCs) have been investigated in detail by chemical etching using a HF–HNO₃–H₂O solution followed by scanning electron microscopy (SEM) observations. The chemical etching of definite surface areas of the samples, which are either normal or parallel to the tenfold axes, using a solution with HF–HNO₃–H₂O (1?:?5?:?4 in volume ratio; 0°C; 5–10?min), produces a large number of microfacet pits of decagonal prismatic shape. In addition, the same etching test in combination with SEM observations was carried out on a deformed sample of the Al–Co–Ni d-QC, which had been subjected to concentrated mechanical stress at an elevated temperature of 850°C by means of the Vickers indentation technique. The morphological features of the resulting micropits and their possible origins are discussed on the basis of results obtained by SEM observations.     

Effect of cation substitution in Cs<Subscript>1–2<Emphasis Type="Italic">x</Emphasis></Subscript>Ba<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>H<Subscript>2</Subscript>PO<Subscript>4</Subscript> on structural properties and proton conductivity

We synthesized compounds with partial substitution of Cs⁺ cations in CsH₂PO₄ by Ba²⁺ cations. The structural, electron transport and thermodynamic properties of Cs_1–2x Ba _x H₂PO₄ (x = 0–0.15) were studied for the first time with the help of a set of physicochemical methods: infrared and impedance spectroscopy, X-ray diffraction and synchronous thermal analysis. The proton conductivity of Cs_1–2x Ba _x H₂PO₄ at 50–230°C was investigated in detail by impedance measurements. The formation of solid substitution solutions isostructural with CsH₂PO₄ (P2₁/m) is observed in the range of substitution degrees of x = 0–0.1, with a slight decrease in the unit cell parameters and some salt amorphization. The conductivity of disordered Cs_1–2x Ba _x H₂PO₄ in the low-temperature region increases by two orders of magnitude at x = 0.02 and increases with an increasing fraction of barium cations by three or four orders of magnitude at x = 0.05–0.1; the superionic phase transition practically disappears. At x = 0.15, heterophase systems based on salts are formed, showing high conductivity and a further decrease in the activation energy of conductivity to 0.63 eV. The conductivity of the high-temperature phase of Cs_1–2x Ba _x H₂PO₄ does not change with increasing fraction of the substituent.     

Reactions of chlorine and related molecules with graphite intercalation compounds

K-graphite intercalation compounds (GICs), metal chloride-GICs and reduced products of CuCl₂-GICs were allowed to react with chlorine. Decomposition of K-GICs took place through the reaction with chlorine. The extent of the decomposition was found to be dependent not on the gas pressure of the chlorine but on the stage number of the starting GIC. Metal chloride-GICs were unreactive with chlorine, whereas chlorine could react with copper particles generated in the interlayer of graphite through the reduction of CuCl₂-GICs. The reaction products were CuCl and CuCl₂; the former exists as crystals in the interlayer, and the latter can form CuCl₂-GICs. Also reported on are reactions of GICs with chlorobenzene, benzoyl bromide and iodine monochloride.     

Thermal Dehydration and Vibrational Studies of ZnK4(P3O9)2 · 6H2O

The thermal dehydration of ZnK₄(P₃O₉)₂ · 6H₂O was studied in the range 25–500°C by thermogravimetric analysis (TGA and DSC) and X‐ray diffraction. We found, based on the TGA and DSC scans, the dehydration of this salt takes place in three stages with a loss of the six water molecules. The infrared and Raman spectra of ZnK₄(P₃O₉)₂ · 6H₂O have been recorded and interpreted using a factor group analysis. The internal modes are assigned in terms of POP and PO₂ structural units using experimental and theoretical IR and Raman frequencies.     

High temperature phase transition in NH4H2PO4

NH₄H₂PO₄ (ADP) has been investigated by infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis and d.c. conductivity in the temperature range of 25–180° C. Sharp reversible changes were observed in the region from 400 to 500 cm^?1 of the infrared spectra in the temperature range of 138–174° C. Similar and supportive data were obtained with DSC, TGA and DC conductivity measurements. The results clearly suggest a high temperature phase transition for ADP before its melting point.     

NMR Investigations of the Protonic Transport Mechanism in Composed Materials on the Basis of Cesium Acid Sulfates and Phosphates

The composite materials Cs(HSO₄)_1?x (H₂PO₄) _x were investigated by X-ray phase analysis, differential scanning calorimetry, nuclear magnetic resonance (NMR) relaxation, pulsed field gradient NMR (PFG-NMR) and impedance spectroscopy. Three composite materials types x = 0.1 ÷ 0.3 mixture CsHSO₄, α-Cs₃(HSO₄)₂(H₂PO₄), β-Cs₃(HSO₄)_2.5(H₂PO₄)_0.5—compositions of area I; x = 0.4 ÷ 0.5 mixture α-Cs₃(HSO₄)₂(H₂PO₄) and Cs₂(HSO₄)(H₂PO₄)—compositions of area II; x = 0.6 ÷ 0.9 mixture Cs₂(HSO₄)(H₂PO₄) and CsH₂PO₄—compositions of area III, were synthesized. The phase transition temperature from the low-to-high conductive phase for obtained composite materials is notably below (about 100 °C) than that for the individual components. The proton self-diffusion coefficients measured by PFG-NMR are lower than the diffusion coefficients calculated from proton conductivities data. The correlation times τ _d controlling the ³¹P–¹H magnetic dipole–dipole interaction were calculated according to data of the spin–lattice relaxation on ³¹P nuclei. The self-diffusion coefficients estimated from the Einstein equation are in good agreement with the experimental self-diffusion coefficients measured by PFG-NMR. It confirms the fact that the proton mobility is caused by the rotation of PO₄ anion tetrahedra.     

Crystal growth and characterization of a novel inorganic–organic hybrid NLO crystal: (NH4)[Cd(NCS)3]·C12H24O6

It is reported here, for the first time, that high-quality bulk size (18 × 5 × 4 mm³) single crystals of a new nonlinear optical crystal, [(NH₄)[Cd(NCS)₃]·C₁₂H₂₄O₆] [Ammonium (18-crown-6-ether) Cadmium(II) tri-thiocyanate; ACCTC], have been grown from aqueous solution via slow evaporation technique. Solubility of ACCTC has been determined for various temperatures. The grown crystals were characterized by single crystal X-ray diffraction, FT-IR, FT-Raman, and UV–Vis–NIR studies. ACCTC crystallizes in orthorhombic system with cell parameters a = 14.7568 ?, b = 15.4378 ?, and c = 10.6383 ? with space group Cmc2₁. The optical second-harmonic generation effect has been measured by using the Kurtz powder technique and is found to be 2 times higher than that of KDP (KH₂PO₄). The sample possesses wide optical transparency range from 200 to 2,500 nm. The TG-DSC thermal analysis revealed that the sample is thermally stable up to 237.92 °C, which is comparatively far better than the thermal stability of [(18C6)Li][Cd(SCN)₃]; CLTC (170 °C).     

Study of the orientation of HNO3 molecules intercalated in graphite using nuclear techniques

Nuclear resonance scattering of photons from ¹⁵N has been used to study the orientation of the HNO₃ intercalant molecule with respect to the graphite planes. In the second-stage compound C₁₀(HNO₃) and the temperature range T = 15°K ? 300°, no orientational phase transition was observed and the NO₃ molecular plane was found to be oriented at an angle θ ∽ 82 ± 8° with respect to the graphite planes.     

Synthesis and physical properties of alkaline earth metal graphite compounds

We report synthesis and search for superconductivity of Ba, Sr, Ca and Mg-GIC. We adopted conventional vapor phase reaction in order to prepare high quality GICs. No superconducting transition was found for Ba and Mg-GIC. As for Sr, Sr-GIC showed a sharp superconducting transition at T_c=1.65 K. Sr graphite compound SrC_x prepared from powder graphite by thermal treatment at higher temperature showed ferromagnetic character.     

A new story in the structural chemistry of cerium(IV) phosphate

Two different cerium(IV) phosphates have been prepared by ageing at 95 °C an aqueous solution made from Ce(NO₃)₆(NH₄)₂, nitric acid, and phosphoric acid with the following conditions: P/Ce=2, [HNO₃]=5.8 M and [Ce⁴⁺]=0.1 M. The control over the formed solid was achieved through the ageing time. After 18 h, a metastable compound (A), corresponding to Ce(PO₄)_1.5(H₂O)(H₃O)_0.5(H₂O)_0.5, is obtained, while after 5 days a stable one (B), corresponding to Ce(PO₄)(HPO₄)_0.5(H₂O)_0.5, is recovered. Both solids exhibit a P/Ce ratio of 1.5. Their structures, ³¹P solid state NMR, and thermal behaviors are compared.     

A single step ultrasound-assisted nitrocellulose synthesis from microcrystalline cellulose

Nitrocellulose is a nitrated cellulose polymer with a broad application in industry. Depending on the nitrogen content, this polymer can be used for manufacturing explosives, varnishes, clothes, and films, being considered a product of high value-added. In this work, the use of ultrasound was investigated for the intensification of nitrocellulose synthesis from microcrystalline cellulose. The ultrasound-assisted nitrocellulose synthesis (UANS) was carried out using several ultrasound systems, such as baths and cup horns, allowing the evaluation of the frequency (from 20 to 130 kHz) and delivered power (from 23 to 134 W dm⁻³) to the reaction medium. The following parameters were evaluated: acid mixture (H₂SO₄, H₃PO₄, CH₂O₂ or CH₃COOH with HNO₃, 2 to 14.4 mol L⁻¹), ultrasound amplitude (10 to 70%) and reaction time (5 to 50 min). Better nitrocellulose yield (nitrogen content of 12.5% was obtained from 1 g of microcrystalline cellulose employing a cup horn system operating at 20 kHz, 750 W of nominal power with 60% of amplitude, 25 mL of acid solution (13.6 mL of 18.4 mol L⁻¹ H₂SO₄ + 9.2 mL of 14.4 mol L⁻¹ HNO₃ + 2.2 mL H₂O), at 30 °C for 30 min. At silent conditions (mechanical stirring ranging from 100 to 500 rpm), the nitrogen content was lower than 11.8% which demonstrate the ultrasound effects for nitrocellulose synthesis.     

Rubidium-cation conductivity of Rb<Subscript>3–2<Emphasis Type="Italic">x</Emphasis></Subscript>Pb<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>PO<Subscript>4</Subscript> solid solutions

New Rb₃PO₄-based ceramic materials with high rubidium-cation conductivity in the Rb_3–2x Pb _x PO₄ system have been synthesized and studied. Introduction of Pb²⁺ cations leads to a sharp increase in the conductivity of rubidium orthophosphate due to formation of cation vacancies and, at temperatures 350–550°C, also due to the stabilization of high-temperature cubic modification Rb₃PO₄. At high temperatures, the electrolytes prepared have very high ion conductivity higher than 10^–1 S cm^–1 at 700°C, which is higher than the values previously obtained in similar systems with additions of tin and cadmium ions. The factors influencing the transport properties of the materials under study are discussed.