Search

The Zaltoprofen/4,4'-Bipyridine system gives rise to two co-crystals of different compositions both endowed - in water and in buffer solution at pH 4.5 - with considerably higher solubility and dissolution rate than the pure drug. The qualitative and quantitative analysis of the DSC measurements, carried out on samples made up of mixtures prepared according to different methodologies, allows us to elaborate and propose an accurate thermodynamic model that fully takes into account the qualitative aspects of the complex experimental framework and which provides quantitative predictions (reaction enthalpies and compositions of the co-crystals) in excellent agreement with the experimental results. Co-crystal formation and cocrystal compositions were confirmed by X-ray diffraction measurements as well as by FT-IR and NMR spectroscopy measurements. The quantitative processing of DSC measurements rationalizes and deepens the scientific aspects underlying the so-called Tammann's triangle and constitutes a model of general validity. The work shows that DSC has enormous potential, which however can be fully exploited only by paying adequate attention to the experimental aspects and the quantitative processing of the measurements.

The conversion-alloying compounds have been identified as promising anode materials for sodium ion batteries (SIBs). One of them, SnO2, with an enormous theoretical capacity of 1558 mAh g−1 is an interesting candidate, also due to its low cost, environmental friendliness and wide availability of tin. However, many drawbacks limit its application in commercial batteries. In this paper, SnO2 has been synthesized from cheap reagents by using simple and easily scalable coprecipitation synthesis routes obtaining nanoparticles with sizes between 2 and 14 nm with almost spherical morphologies. The reasons of the failure of the alloying/de-alloying process were investigated by combining the results obtained from common electrochemical techniques, providing useful examples for the investigation of every material with analogous electrochemical features. Thanks to cyclic voltammetry, different reaction paths were detected for the two samples. The first cycle irreversibility was well characterized with electrochemical impedance spectroscopy, showing interesting trends in the values of the resistance. Galvanostatic cycling with potential limitations was employed to quantify the irreversibility, finding out that the most crystalline sample reached the terminal phase in the Sn-Na system (Na15Sn4), while the least crystalline sample could not achieve such a result (Na3Sn). The crystallinity of SnO2 was determined to be a key parameter, often neglected, for the realization of satisfactory anode compounds.

In the current study, an experimental approach for the further understanding of the LiH hydrolysis reaction for hydrogen production is considered. The experimental work has been undertaken under small scale conditions by utilising fixed bed reactors. The hydrolysis reaction has been studied at several oven temperatures (150 °C, 300 °C and 500 °C). The favourable driving potentials for the hydrolysis reactions were identified by the utilisation of the Gibbs free energy analysis. The main outcome of the study is the deceleration of the reaction pace due to the formation of the by-product layers during the reaction. At the initial stage, due to the contact of steam with the unreacted and fresh LiH surface, the reaction proceeds on a fast pace, while the formation of the layers tends to decelerate the diffusion of steam into the core of material, forcing the production step to be slower. The hydrogen yield was found to be more than 90% of the theoretical value for all the reaction temperatures. Finally, a scenario of a hybrid-electric propulsion system for Unmanned Aerial Vehicles (UAVs) including Li-ion battery, Proton Membrane Fuel Cell (PEMFC) and an on-board hydrogen production system based on LiH hydrolysis is introduced and studied.

The aim of this study was to synthetize cocrystals of nateglinide, an antidiabetic agent of biopharmaceutics classification system Class IIa, as a strategy to improve both the solubility and the dissolution rate of the drug. Benzamide was selected by a screening procedure as a suitable coformer, and binary mixtures with different compositions were prepared and analyzed by differential scanning calorimetry (DSC). An in-depth analysis of DSC data allowed obtaining both the eutectic mixture and cocrystal compositions. The rationale of such an analysis was highlighted and explained. Cocrystals were prepared by kneading and solvent evaporation. Their formation was proved by DSC and confirmed by X-ray powder diffraction, solid-state nuclear magnetic resonance, and Fourier-transform infrared spectroscopy. The functional groups involved in the interaction leading to cocrystals formation were investigated by spectroscopic techniques. The in vitro dissolution profiles show that cocrystals have definite better pharmaceutical performances than the pure drug.

The present work is a concrete example of how physico-chemical studies, if performed in depth, are crucial to understand the behavior of pharmaceutical solids and constitute a solid basis for the control of the reproducibility of the industrial batches. In particular, a deep study of the thermal behavior of glipizide, a hypoglycemic drug, was carried out with the aim of clarifying whether the recognition of its polymorphic forms can really be done on the basis of the endothermic peak that the literature studies attribute to the melting of the compound. A number of analytical techniques were used: thermal techniques (DSC, TGA), X-ray powder diffraction (XRPD), FT-IR spectroscopy and scanning electron microscopy (SEM). Great attention was paid to the experimental design and to the interpretation of the combined results obtained by all these techniques. We proved that the attribution of the endothermic peak shown by glipizide to its melting was actually wrong. The DSC peak is no doubt triggered by a decomposition process that involves gas evolution (cyclohexanamine and carbon dioxide) and formation of 5-methyl-N-[2-(4-sulphamoylphenyl) ethyl] pyrazine-2-carboxamide, which remains as decomposition residue. Thermal treatments properly designed and the combined use of DSC with FT-IR and XRPD led to identifying a new polymorphic form of 5-methyl-N-[2-(4-sulphamoylphenyl) ethyl] pyrazine-2-carboxamide, which is obtained by crystallization from the melt. Hence, our results put into evidence that the check of the polymorphic form of glipizide cannot be based on the temperature values of the DSC peak, since such a peak is due to a decomposition process whose Tonset value is strongly affected by the particle size. Kinetic studies of the decomposition process show the high stability of solid glipizide at room temperature.

The addition of transition metals to alkali intercalated fullerides proved to enhance their already good hydrogen absorption properties. Herein we present a study based on two different synthetic strategies, allowing the addition of nickel as aggregates with different size to the lithium fulleride Li6C60: the former is based on the metathesis of nickel chloride, while the latter on the thermal decomposition of nickel carbonyl clusters. The hydrogen-storage properties of the obtained materials have been investigated with manometric and calorimetric measurements, which indicated a clear enhancement of the final absorption value and kinetics with respect to pristine Li6C60, as a consequence of nickel surface catalytic activity towards hydrogen molecules dissociation. We found up to 10 % increase of the total H2 weight % absorbed (5.5 wt% H2) in presence of Ni aggregates. Furthermore, the control of the transition metal particles size distribution allowed reducing the hydrogen desorption enthalpy of the systems.

Lanthanum ferrite, LaFeO3 (LF), has raised considerable interest since it can be used in many applications such as solid-oxide fuel cell electrode, sensor material (H2O and ethanol) and catalyst. Since the conventional ceramic route of synthesis has some disadvantages, mainly related to an exaggerated grain growth, LF has been prepared by different methods including combustion synthesis, sol–gel, hydrothermal processes, polymerizable complex method and mechanochemistry. As concerns this last method, a problem occurs due to the moisture sensitivity of La2O3. To overcome the problem, we used lanthanum acetate sesquihydrate [La(CH3COO)3·1.5H2O] and iron (II) oxalate dehydrate [FeC2O4·2H2O] as precursors. The mechanism of the solid-state reactions in the mixtures has been studied by TG–DSC and XRPD. Synthesis of LaFeO3 has been realized by annealing the mechanically activated mixtures for 3 h at temperatures between 500 and 800 °C. While LF prepared at 500 °C

The aim of this work was to search for new polymorphic forms of febantel, an anthelminthic drug of great present interest for the veterinary industry. Solvent-based recrystallization, thermal and mechanical treatments and spray drying were chosen to discover new solid forms. The solids obtained were physicochemically characterized by thermal techniques (DSC and TG), FTIR spectroscopy, laboratory and synchrotron X-ray powder diffraction and scanning electron microscopy. Our work leads to obtain a new solid form never described in the literature. In particular, the new polymorph was obtained by the anti-solvent method and the crystallization from isopropanol. The experimental conditions of crystallization favorable to the formation of the highest amount of the new solid phase were selected. The new phase shows a thermal, spectroscopic and diffractometric behavior unique. Furthermore, the preliminary structure investigation suggests two possible crystal systems: an orthorhombic or a monoclinic one, with really comparable lattice parameters and cell volume. Measurements put into evidence that the new phase is a metastable polymorph that is in monotropic relationship with the stable and known form.

We report on the preparation of a novel hierarchically-porous super-activated carbon originating from organic waste with specific surface area exceeding 3000 m2/g, obtained starting from biochar derived by the pyrolysis of poultry litter. The chemical activation process proved to be efficient to remove the majority of impurities other than carbon, stabilizing a highly porous hierarchical structure with local graphene-like morphology. The presence of P and S with concentration below 0.1 wt% distinguishes this activated carbon from the usual ones obtained from vegetal sources. Thanks to these features, the obtained porous compound demonstrated to behave as an excellent electrode material for high-performance symmetric supercapacitors, reaching high specific capacitance up to 229 (13) F/g. Remarkably, the devices also supply high current density of 10 A/g without using any conducting additives and display high power density and reliability. Moreover, these optimal performances have been obtained operating by using simple eco-friendly electrolytes, like KOH and Na2SO4 aqueous solutions. The availability, the biocompatibility and the inexpensiveness of the starting materials, together with the low environmental impact of the electrolyte, suggest possible large-scale applications for such devices, for example in the field of transportation or in renewable energy-grids, but also in the field of bio-medicine.

Several different milling parameters (additive content, rotation velocity, ball-to-powder ratio, degree of filling, and time) affect the hydrogen absorption and desorption properties of a reactive hydride composite (RHC). In this paper, these effects were thoroughly tested and analyzed. The milling process investigated in such detail was performed on the 2LiH-MgB2 system doped with TiCl3. Applying an upgraded empirical model, the transfer of energy to the material during the milling process was determined. In this way, it is possible to compare the obtained experimental results with those from processes at different scales. In addition, the different milling parameters were evaluated independently according to their individual effect on the transferred energy. Their influence on the reaction kinetics and hydrogen capacity was discussed and the results were correlated to characteristics like particle and crystallite size, specific surface area, presence of nucleation sites and contaminants. Finally, an optimal value for the transferred energy was determined, above which the powder characteristics do not change and therefore the RHC system properties do not further improve. Fil: Jepsen, Julian. Helmholtz zentrum Geesthacht; Alemania. Helmut Schmidt University; Alemania Fil: Capurso, Giovanni. Helmholtz zentrum Geesthacht; Alemania Fil: Puszkiel, Julián Atilio. Helmholtz zentrum Geesthacht; Alemania. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina Fil: Busch, Nina. Helmholtz zentrum Geesthacht; Alemania Fil: Werner, Tobias. Helmholtz zentrum Geesthacht; Alemania Fil: Milanese, Chiara. Universita Degli Studi Di Pavia; Italia Fil: Girella, Alessandro. Universita Degli Studi Di Pavia; Italia Fil: Von Colbe, José Bellosta. Helmholtz zentrum Geesthacht; Alemania Fil: Dornheim, Martin. Helmholtz zentrum Geesthacht; Alemania Fil: Klassen, Thomas. Helmholtz zentrum Geesthacht; Alemania. Helmut Schmidt University; Alemania

The mechanism of Bi4Ti3O12 formation starting from the two constituent oxides has been studied. Starting from a physical mixture, a solid-state reaction occurs between the two oxides that leads at ≈700 °C to a mixture of the two ternary oxides Bi12TiO20 + Bi4Ti3O12 along with unreacted precursor oxides. At T ≈ 830 °C Bi12TiO20 reacts with TiO2 forming Bi4Ti3O12 and, finally, at T ≈ 850 °C, the residual Bi12TiO20 undergoes the peritectic reaction that produces Bi4Ti3O12 plus a liquid phase. However, the formation of Bi4Ti3O12 is not complete at temperatures as high as 900 °C. Starting from a mechanically activated mixture, the intermediate Bi12TiO20 only forms as a minority phase at a lower temperature (T ≈ 550 °C), and then it rapidly reacts to give Bi4Ti3O12. No trace of the peritectic reaction is found in the case of the activated mixture. The complete formation of Bi4Ti3O12 can be obtained by 3-h annealing of the activated mixture at T ≥ 650 °C. The heat capacity of the product phase Bi4Ti3O12 has also been measured in the temperature range 50–300 °C.

Hybrid composite made of glauconite and polyaniline was prepared in aqueous solution of citric acid. Scanning electron microscopy combined with energy dispersive X-ray analysis shows uniform aggregates made of glauconite microparticles and polyaniline matrix. The results of X-ray powder diffraction suggest that: (1) citric acid used for the polymerisation of aniline causes formation of emeraldine salt where macromolecular ordering in the amorphous polymer takes place; (2) no chemical interaction between glauconite and emeraldine takes place in the prepared composite. FT-IR spectra of the prepared polymer and composite show features indicating all the functional groups that are present in the diiminoquinone–diaminobenzene state of polyaniline. Thermal stability of the composite was higher than the prepared polymer suggesting the occurrence of an interphase interaction between glauconite and emeraldine. After pyrolysis in purified nitrogen the composite still remained glauconite, and e-Fe3N together with amorphous and graphitic carbon were found as reaction products. The values of electrical conductivity and magnetization of the composite suggest that optimization of these values might be achieved based upon the relationship between glauconite and polyaniline.

This paper deals with the preparation of new poly(High Internal Phase Emulsion) [polyHIPE] materials, templated by varying different preparation parameters. The obtained systems are based on acrylic monomers, polymerized by free radical polymerization initiated by potassium persulfate and the redox initiator N,N,N′,N′-tetramethylethylenediamine (TEMED) to gain a crosslinked system at room temperature. To get a functional material, glycidyl methacrylate (GMA) has been introduced in the polymeric structure. The HIPE system was effectively stabilized by a co-polymer surfactant, while a polysorbate surfactant did not stabilize the emulsion. Water as the internal phase with its content ranging from 80 to 90% was explored. A deep characterization of the materials, including SEM, DSC, TGA, BET, swelling and weight loss was carried out. The developed systems are promising and can find successful applications for analytical and biomedical purposes.

In this work, the polymorphic α-magnesium borohydride form was infiltrated by wet impregnation using tetrahydrofuran (THF) as solvent and subcritical carbon dioxide as innovative drying process. Pressure infiltration at high temperature was also tested as another promising method for confinement. After infiltration, onset decomposition temperature was reduced from 280 °C into 220 °C using high pressure infiltration and down to 100 °C using wet impregnation followed by CO2 drying. Faster kinetics were obtained in both cases due the possible particle size reduction in the precipitation process of the complex hydride and the presence of silica, which could behave as an additive. It is the first time that this complex borohydride is 6.1 wt% H2 reversible performing the rehydrogenation at moderate conditions of 390 °C and 120 bar H2 using silica as support. Different values were obtained after infiltration method due to the different intermediates that were obtained after the first dehydrogenation.

Reaction kinetic behaviour and cycling stability of the 2LiBH4-MgH2 reactive hydride composite (Li-RHC) are experimentally determined and analysed as a basis for the design and development of hydrogen storage tanks. In addition to the determination and discussion about the properties; different measurement methods are applied and compared. The activation energies for both hydrogenation and dehydrogenation are determined by the Kissinger method and via the fitting of solid-state reaction kinetic models to isothermal volumetric measurements. Furthermore, the hydrogen absorption-desorption cycling stability is assessed by titration measurements. Finally, the kinetic behaviour and the reversible hydrogen storage capacity of the Li-RHC are discussed. Fil: Jepsen, Julian. Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung; Alemania Fil: Milanese, Chiara. Università degli Studi di Pavia; Italia Fil: Puszkiel, Julián Atilio. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Patagonia Norte; Argentina Fil: Girella, Alessandro. Università degli Studi di Pavia; Italia Fil: Schiavo, Benedetto. Università degli Studi di Palermo; Italia Fil: Lozano, Gustavo A.. Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung; Alemania Fil: Capurso, Giovanni. Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung; Alemania Fil: Von Colbe, José M. Bellosta. Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung; Alemania Fil: Marini, Amedeo. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina Fil: Kabelac, Stephan. Leibniz Universität Hannover; Alemania Fil: Dornheim, Martin. Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung; Alemania Fil: Klassen, Thomas. Helmholtz-Zentrum Geesthacht Zentrum für Material- und Küstenforschung; Alemania

Thermodynamic and heat transfer properties of the 2LiBH4-MgH2 composite (Li-RHC) system are experimentally determined and studied as a basis for the design and development of hydrogen storage tanks. Besides the determination and discussion of the properties, different measurement methods are applied and compared to each other. Regarding thermodynamics, reaction enthalpy and entropy are determined by pressure-concentration-isotherms and coupled manometric-calorimetric measurements. For thermal diffusivity calculation, the specific heat capacity is measured by high-pressure differential scanning calorimetry and the effective thermal conductivity is determined by the transient plane source technique and in situ thermocell. Based on the results obtained from the thermodynamics and the assessment of the heat transfer properties, the reaction mechanism of the Li-RHC and the issues related to the scale-up for larger hydrogen storage systems are discussed in detail. Fil: Jepsen, Julian. Helmholtz-Zentrum Geesthacht; Alemania Fil: Milanese, Chiara. University of Pavia; Italia Fil: Puszkiel, Julián Atilio. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Comisión Nacional de Energía Atómica. Centro Atómico Bariloche; Argentina. Helmholtz-Zentrum Geesthacht; Alemania Fil: Girella, Alessandro. University of Pavia; Italia Fil: Schiavo, Benedetto. Universidad de Palermo; Argentina. Istituto per le Tecnologie Avanzate; Italia Fil: Lozano, Gustavo A.. Helmholtz-Zentrum Geesthacht; Alemania. BASF; Alemania Fil: Capurso, Giovanni. Helmholtz-Zentrum Geesthacht; Alemania Fil: Von Colbe, José M. Bellosta. Helmholtz-Zentrum Geesthacht; Alemania Fil: Marini, Amedeo. University of Pavia; Italia Fil: Kabelac, Stephan. Leibniz Universität Hannover; Alemania Fil: Dornheim, Martin. Helmholtz-Zentrum Geesthacht; Alemania Fil: Klassen, Thomas. Helmholtz-Zentrum Geesthacht; Alemania

We herein report on the synthesis of mixed alkali cluster intercalated fullerides NaxLiy−xC60 (y = 12; x = 1–6) by a two-steps mechanochemical reaction of fullerene with sodium and lithium. These compounds crystallize in the cubic lattice of C60 displaying a contracted lattice parameter with respect to the Na6C60 parent structure. The analysis of the hydrogen sorption behaviour shows a slight decrease in the dehydrogenation enthalpy for y = 12 with respect to the sodium free member. Raman spectroscopy highlighted a partial electron transfer from alkali metals to C60, suggesting the presence of charged sodium/lithium clusters. Finally, we applied muon spectroscopy to understand the different hydrogenation mechanisms in NaxLi6−xC60 and NaxLi12−xC60 and explain their different performance.

Magnesium has been studied as a potential hydrogen storage material for several decades because of its relatively high hydrogen storage capacity, fast sorption kinetics (when doped with transition metal based additives), and abundance. This research aims to study the possibility to use waste magnesium alloys to produce good quality MgH2. The production costs of hydrogen storage materials is still one of the major barriers disabling scale up for mobile or stationary application. The recycling of magnesium-based waste to produce magnesium hydride will significantly contribute to the cost reduction of this material. This study focuses on the effect of different parameters such as the addition of graphite and/or Nb2O5 as well as the effect of milling time on the material hydrogenation/de-hydrogenation performances. In addition, morphology and microstructural features are also evaluated for all the investigated materials.

Gold and gold–palladium nanodeposits were obtained by pulse electrolysis in dimethylformamide with 4×10−3 M HAuCl4 and in dimethyl sulfoxide solution with a mixture of 4×10−3 M HAuCl4 and 4×10−3 M PdCl2, respectively. Isolated gold nanoparticles of about 15 nm in diameter were found by SEM observation after 6 ms of electrochemical deposition. Three pulse and pause periods with duration of 6 ms and 300 ms respectively led to an increase in the particle size approximately two times. In case of gold-palladium deposition, no particles were detected after 10 electrochemical cycles while after 50 cycles 10–35 nm nanoparticles were found. Detailed SEM analysis of electrode surface suggested that at the beginning of electrochemical deposition the growth of gold/nucleation of gold–palladium NPs is a preference for mono-Au/bimetallic Au–Pd system.

The work deals with the synthesis of multiferroic BiFeO3 starting from mixture of Bi citrate and Fe(II) oxalate dihydrate. By combined TG-DSC and XRPD experiments it is put into evidence that the mechanically activated mixture absorbs an extra enthalpy (+235 kJ) that is due to the reaction between the forming oxides. Furthermore it is shown that mechanical activation of the starting mixture sensibly enhances the formation of Bi ferrite. Indeed BiFeO3 is obtained by annealing the activated mixture at temperatures as low as 750 °C while this does not happen by annealing the physical mixture at temperatures up to 800 °C. Finally by MTDSC (Modulated Temperature Differential Scanning Calorimetry) we measured the thermal capacity of BiFeO3 obtained from the annealed activated mixture.

Magnesium borohydride Mg(BH4)2 is a promising hydrogen storage material as it releases high hydrogen storage capacity at mild desorption temperatures, but it is still limited by slow hydrogen release kinetics and by the harsh conditions required to re-hydrogenate this compound. In this work, composites made of commercial Mg(BH4)2 and synthesized silica aerogel microparticles were prepared by thermal treatment in hydrogen under 120 bar and 200ºC. As a result, the sorption properties of the hydride are improved: calorimetric measurements show that decomposition temperature is reduced by 60ºC, and the typical 3-step decomposition mechanism of Mg(BH4)2 changes to a single-step mechanism in range of 220-400°C. The kinetics of the first dehydrogenation at 300ºC was two times faster in Mg(BH4)2-SiO2 composites than in the case of bulk γ-Mg(BH4)2. Additionally, the re-hydrogenation of this material at comparatively moderate conditions of 390ºC and 110 bar is presented for the first time, achieving cyclability with a reversible release of hydrogen up to 6wt%. Different amounts of hydrogen were exchanged depending on the temperature of desorption (300ºC or 400ºC) and the presence or absence of silica aerogel. This result indicates that silica aerogel chemically interacts with Mg(BH4)2, acting as an additive, which can result in different hydrogenation-dehydrogenation routes in which different amounts and types of intermediates are formed, influencing the kinetics and the cyclability., 2018-07-27, Spanish Ministry of Economy and Competitiveness project ENE2014-53459-R

The synthesis of Li2SnO3 starting from high energy milled SnC2O4–Li2CO3 has been studied by coupled thermogravimetric and heat-flux differential scanning calorimetry (TG–DSC). The course of the reaction has been assessed. The product obtained has been characterized both as concerns its water absorption and its thermal capacity.

Simultaneous TG–DSC measurements have been used to study the solid state reaction in the system SnC2O4–4MgCO3·Mg(OH)2·xH2O (Sn:Mg = 0.5). The results obtained with physically prepared mixture and with mixture mechanically activated by high-energy milling are compared. Synthesis of the compound Mg2SnO4 has been attempted starting from both type of mixture: Mg2SnO4 forms by annealing the activated mixture at temperatures between 850 and 1,000 °C while it can hardly be obtained from physical mixtures even by thermal treatment at temperature as high as 1,300–1,350 °C. Mg2SnO4 prepared by annealing the activated mixture has been characterized by diffuse reflectance FT-IR spectroscopy, modulated temperature differential scanning calorimetry, scanning electron microscopy, and specific surface area measurements (B.E.T. method).

The effect of mesoporous Co3O4, NiCo2O4 and NiO on the hydrogen sorption performance of MgH2 was investigated. These oxides were synthesized by multi-step nanocasting and introduced during the high-energy ball milling of MgH2 powder to act as catalysts. Hydrogen desorption on the as-milled powders was assessed upon heating the samples from room temperature to 400 °C. In all cases, the onset temperature for desorption was lowered by taking advantage of the introduced additives. The NiO-doped sample displayed the best response, the desorption rate being 7 times faster than in pure MgH2. Complementary kinetic studies on this particular sample revealed that the sorption activation energies were much lower (50 kJ/mol for absorption and 335 kJ/mol for desorption) than the corresponding ones for undoped MgH2 (57 kJ/mol for absorption and 345 kJ/mol for desorption), thus proving the catalytic activity of the mesoporous NiO oxide. Significantly, the X-ray powder diffraction (XRPD) patterns taken on the NiO-doped sample after discharging/charging cycles revealed that Mg could fully hydrogenate at the end of the charging process, while Mg metal was still detected in the undoped (pure) sample. Favored conditions for dissociative chemisorption of hydrogen could be ascribed to the formation of metallic Ni arising from complete or partial reduction of NiO, as observed in the XRPD patterns.

In this work, thermoanalytical, diffractometry, and microscopy measurements have been performed in order to characterize the effect of high energy milling on a drug active in the migraine prophylaxis and smoke cessation. We can assert that the mechanical treatment induces only a partial amorphisation of the solid phase, in particular it reduces the crystal order by producing lattice defects which propagate from the surface to the bulk crystal. For this reason, the DSC is able to detect the presence of ordered solid, while the powder X-ray diffractometry, because of its low penetration depth, does not reach the crystalline core of the particles.

Due to its thermodynamic properties and high reversibility, Ti doped sodium alanate is considered as a prototype hydrogen storage material. In this work we show how sodium alanate can be synthesized by reactive ball milling using aluminum particles obtained from recycled waste incineration slag. The synthesis was monitored with an in situ milling vial and characterized stepwise by PXD and DTA analyses. The sorption properties of the material were investigated using in situ synchrotron radiation PXD and volumetric analyses. A complete conversion of the starting reactants was obtained.

The investigations based on kinetic improvement and reaction mechanisms during melt infiltration, dehydrogenation, and rehydrogenation of nanoconfined 2LiBH4-MgH2-0.13TiCl4 in carbon aerogel scaffold (CAS) are proposed. It is found that TiCl4 and LiBH4 are successfully nanoconfined in CAS, while MgH2 proceeds partially. In the same temperature (25-500ºC) and time (0?5 h at constant temperature) ranges nanoconfined 2LiBH4-MgH2-0.13TiCl4 dehydrogenates completely 99% of theoretical H2 storage capacity, while that of nanoconfined 2LiBH4?MgH2 is only 94%. Nanoconfined 2LiBH4-MgH2-0.13TiCl4 performs three-step dehydrogenation at 140, 240, and 380ºC. Onset (the first-step) dehydrogenation temperature (140ºC), significantly lower than those of nanoconfined sample of 2LiBH4-MgH2 and 2LiBH4-MgH2-TiCl3 (DT = 140 and 110ºC, respectively) is in agreement with the decomposition of eutectic LiBH4-Mg(BH4)2 and lithium?titanium borohydride. For the second and third steps (240 and 380ºC),decompositions of LiBH4 destabilized by LiCl solvation and MgH2 are accomplished, respectively. In conclusion, dehydrogenation products are B, Mg, LiH, and TiH. Reversibility of nanoconfined 2LiBH4-MgH2-0.13TiCl4 sample is confirmed by the recovery of LiBH4 after rehydrogenation together with the formation of [B12H12] derivatives. The superior kinetics during the 2nd, 3rd, and 4th cycles of nanoconfined2LiBH4-MgH2-0.13TiCl4 to the nanoconfined 2LiBH4-MgH2 can be due to the formations of Ti-MgH2 alloys (Mg0.25Ti0.75H2 and Mg6TiH2) during the 1st rehydrogenation. Fil: Gosalawit Utke, Rapee. Institute of Materials Research; Alemania. Suranaree University of Technology; Tailandia Fil: Milanese, Chiara. University of Pavia; Italia Fil: Javadian, Payam. University of Aarhus; Dinamarca Fil: Girella, Alessandro. University of Pavia; Italia Fil: Laipple, Daniel. Institute of Materials Research; Alemania Fil: Puszkiel, Julián Atilio. Institute of Materials Research; Alemania. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina Fil: Cattaneo, Alice S.. University of Aarhus; Dinamarca Fil: Ferrara, Chiara. University of Aarhus; Dinamarca Fil: Wittayakhun, Jatuporn. Suranaree University of Technology; Tailandia Fil: Skibsted, Jørgen. University of Aarhus; Dinamarca Fil: Jensen, Torben R.. University of Aarhus; Dinamarca Fil: Marini, Amedeo. University of Pavia; Italia Fil: Klassen, Thomas. Institute of Materials Research; Alemania Fil: Dornheim, Martin. Institute of Materials Research; Alemania