Rossella ARLETTI - personale UniMoRe

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Rossella ARLETTI

Professore Associato
Dipartimento di Scienze Chimiche e Geologiche - Sede Dipartimento di Scienze Chimiche e Geologiche

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Pubblicazioni

2024 - An insight into REEs recovery from spent fluorescent lamps: Evaluation of the affinity of an NH4-13X zeolite towards Ce, La, Eu and Y [Articolo su rivista]
Colombo, Francesco; Fantini, Riccardo; Di Renzo, Francesco; Malavasi, Gianluca; Malferrari, Daniele; Arletti, Rossella
abstract

The constantly increasing demand of Rare Earth Elements (REEs) made them to be part of the so-called "critical elements" indispensable for the energy transition. The monopoly of only a few countries, the so-called balance problem between demand and natural abundance, and the need to limit the environmental costs of their mining, stress the necessity of a recycling policy of these elements. Different methods have been tested for REEs recovery. Despite the well-known ion-exchange properties of zeolites, just few preliminary works investigated their application for REEs separation and recycle. In this work we present a double ion exchange experiment on a NH4-13X zeolite, aimed at the recovery of different REEs from solutions mimicking the composition of liquors obtained from the leaching of spent fluorescent lamps. The results showed that the zeolite was able to exchange all the REEs tested, but the exchange capacity was different: despite Y being the more concentrated REE in the solutions, the cation exchange was lower than less concentrated ones (16 atoms p.u.c. vs 21 atoms for Ce and La solutions), suggesting a possible selectivity. In order to recover REEs from the zeolite, a second exchange with an ammonium solution was performed. The analyses of the zeolites show that almost all of Ce and Eu remain in the zeolite, while nearly half of La and Y are released. This, once again, suggests a possible selective release of REEs and open the possibility for a recovery process in which Rare Earths can be effectively separated.

2024 - Reappraisal of red clays in porcelain stoneware production: Compositional and technological characterization [Articolo su rivista]
Fantini, Riccardo; Conte, Sonia; Gualtieri, Alessandro F.; Dondi, Michele; Colombo, Francesco; Sisti, Mattia; Molinari, Chiara; Zanelli, Chiara; Arletti, Rossella
abstract

2023 - Heterogeneity‐driven localization and weakening in scaly clays from a fossil accretionary prism [Articolo su rivista]
Aretusini, S.; Mittempergher, S.; Remitti, F.; Arletti, R.; Polisi, M.; De Paola, N.; Tesei, T.
abstract

2023 - The beneficial role of nano-sized Fe3O4 entrapped in ultra-stable Y zeolite for the complete mineralization of phenol by heterogeneous photo-Fenton under solar light [Articolo su rivista]
Tammaro, Olimpia; Morante, Nicola; Marocco, Antonello; Fontana, Marco; Castellino, Micaela; Barrera, Gabriele; Allia, Paolo; Tiberto, Paola; Arletti, Rossella; Fantini, Riccardo; Vaiano, Vincenzo; Esposito, Serena; Sannino, Diana; Pansini, Michele
abstract

: Highly efficient, separable, and stable magnetic iron-based-photocatalysts produced from ultra-stable Y (USY) zeolite were applied, for the first time, to the photo-Fenton removal of phenol under solar light. USY Zeolite with a Si/Al molar ratio of 385 was impregnated under vacuum with an aqueous solution of Fe2+ ions and thermally treated (500-750 °C) in a reducing atmosphere. Three catalysts, Fe-USY500°C-2h, Fe-USY600°C-2h and Fe-USY750°C-2h, containing different amounts of reduced iron species entrapped in the zeolitic matrix, were obtained. The catalysts were thoroughly characterized by absorption spectrometry, X-ray powder diffraction with synchrotron source, followed by Rietveld analysis, X-ray photoelectron spectroscopy, N2 adsorption/desorption at -196 °C, high-resolution transmission electron microscopy and magnetic measurements at room temperature. The catalytic activity was evaluated in a recirculating batch photoreactor irradiated by solar light with online analysis of evolved CO2. Photo-Fenton results showed that the catalyst obtained by thermal treatment at 500 °C for 2 h under a reducing atmosphere (FeUSY-500°C-2h) was able to completely mineralize phenol in 120 min of irradiation time at pH = 4 owing to the presence of a higher content of entrapped nano-sized magnetite particles. The latter promotes the generation of hydroxyl radicals in a more efficient way than the Fe-USY catalysts prepared at 600 and 750 °C because of the higher Fe3O4 content in ultra-stable Y zeolite treated at 500 °C. The FeUSY-500°C-2h catalyst was recovered from the treated water through magnetic separation and reused five times without any significant worsening of phenol mineralization performances. The characterization of the FeUSY-500°C-2h after the photo-Fenton process demonstrated that it was perfectly stable during the reaction. The optimized catalyst was also effective in the mineralization of phenol in tap water. Finally, a possible photo-Fenton mechanism for phenol mineralization was assessed based on experimental tests carried out in the presence of scavenger molecules, demonstrating that hydroxyl radicals play a major role.

2023 - Unraveling the Molecular Structure of Zeolite–Octyl Methoxycinnamate Hybrid UV Filters: A Combined Spectroscopic and Computational Approach [Articolo su rivista]
Fischer, Michael; Fantini, Riccardo; Arletti, Rossella; Brauer, Jakob; Mino, Lorenzo
abstract

In this contribution, we tried to shed light on the molecular structure of octyl methoxycinnamate (octinoxate, OMC) adsorbed in NaX zeolite, which represents a promising hybrid UV filter system. The combination of infrared spectroscopy and density functional theory modeling was crucial to identify all the complex host-guest interactions and to unveil that, although slightly thermodynamically unfavored, OMC is dominantly present in the trans-form inside the NaX framework. We also showed that the interaction between the zeolite Na cations and the OMC molecule is the key feature that determines the stability and efficacy of these hybrid UV filters. These findings confirm that cationic zeolites are promising materials for the encapsulation of UV filters to decrease their negative impact on the environment and their photochemical instability.

2022 - 5-Hydroxymethylfurfural Oxidation to 2,5-Furandicarboxylic Acid on Noble Metal-Free Nanocrystalline Mixed Oxide Catalysts [Articolo su rivista]
Demet, A. E.; Gimello, O.; Arletti, R.; Tanchoux, N.; Sougrati, M. T.; Stievano, L.; Quignard, F.; Centi, G.; Perathoner, S.; Di Renzo, F.
abstract

Noble metal-free catalysts based on earth-abundant and inexpensive mixed oxides are active catalysts of all steps of the reaction cascade leading from 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA) using tert-butyl hydroperoxide (TBHP) as oxidation agent. Catalysts covering the whole range of composition in the Cu-Mn and Co-Fe series have been prepared and characterised. The nature and composition of the catalyst strongly affect conversion and selectivity. The distribution of products indicates that radical-type oxygen species, deriving from the activation of TBHP, play a determining role in the reaction. The early steps of reaction mainly follow the pattern expected for heterogeneous Fenton catalysts. Mixed oxide catalysts are the most effective in further oxidation steps, leading to the formation of FDCA, both in the Cu-Mn and Co-Fe systems. This behaviour can be related to the distribution of charge in the mixed oxides, suggesting a possible implication of the lattice oxygen in the last reaction steps. The results provide indications on how to optimize the reaction and minimize the formation of byproducts (humins and oligomers).

2022 - Ion exchange capacity of synthetic zeolite L: a promising way for cerium recovery [Articolo su rivista]
Confalonieri, G.; Vezzalini, G.; Maletti, L.; Di Renzo, F.; Gozzoli, V.; Arletti, R.
abstract

The increasing rare earth elements’ (REE) demand to meet the market request and the current political scenario show that it is essential to find good solutions to recover these elements from waste (both industrial and mining). Zeolites are microporous materials with high cation exchange capacity, up to now only little investigated for REE recycle. Here, we propose the use of NH4+-exchanged zeolite L for Ce recovery from a very diluted solution (0.002 M), mimicking the Ce3+ concentration of the liquors deriving from the leaching of spent catalysts. The aim of this work is twofold: (i) to investigate the exploitability of zeolite L as cation exchanger in the Ce recovery; and (ii) to determine the best working conditions. The investigated process consists of a coupled cation exchange: (1) in the first exchange the NH4+ cations — present in the zeolite porosities — are exchanged with the Ce3+ ions in the solution; and (2) in the second experiment, the Ce3+ trapped into the zeolite is recovered through a further exchange with NH4. The best working conditions for Ce3+ exchange of NH4-zeolite L are: batch system, liquid/solid ratio equal to 90 mL/g and 180 mL/g, 24 h of contact at 25 °C. The resulting Ce adsorption capacity (qt) is equal to ~25 mg/g and ~39 mg/g and the removal efficiency 100% and 77% for the two tested liquid/solid ratios, respectively. The kinetics was proved to be fast and consistent with industrial timing; no energy cost for temperature setting is required; and the acid pH (~4) of the solutions does not affect the zeolite structure stability and its exchange performance. It has been demonstrated that the zeolite framework is not affected by the exchange so that the same absorbent material can be employed many times.

2022 - Magnetic clustering of weakly interacting Ni-ions in Ni-exchanged zeolites [Articolo su rivista]
Barrera, Gabriele; Allia, Paolo; Tiberto, Paola; Tammaro, Olimpia; Pansini, Michele; Marocco, Antonello; Manzoli, Maela; Confalonieri, Giorgia; Arletti, Rossella; Esposito, Serena
abstract

Divalent Nickel cations were incorporated in two commercial zeolites (Na-A zeolite and Na-X zeolite) by a process of ionic exchange marginally affecting structure, morphology and porosity of the host materials, as verified by XRD, HRTEM and physisorption measurements. Comparable amounts of magnetic ions were introduced (4.80 wt% in Na-A zeolite and 6.20 wt% in Na-X zeolite), as checked by AAS and TGA. Magnetic measurements were done between 2 and 300 K using a SQUID magnetometer up to 70 kOe. The initial susceptibility follows the Curie-Weiss law with Curie temperatures theta of 10.3 and 11.5 K. The effective magnetic moments on Ni2+ ions suggest almost complete quenching of the angular momentum. No long-range magnetic order is found below theta; however, FC/ZFC magnetization curves indicate the formation of superparamagnetic clusters of magnetic ions with blocking temperature of about 6.5 K in both zeolites. Cluster size, average number of clustered ions, effective anisotropy of clusters are evaluated. A comprehensive picture of all magnetic effects taking place over the whole temperature range is drawn by combining magnetic, structural and morphological data.

2022 - On the chemical condensation of the layers of zeolite precursor MCM-22(P) [Articolo su rivista]
Fabbiani, M; Morsli, A; Confalonieri, G; Cacciaguerra, T; Fajula, F; Haines, J; Bengueddach, A; Arletti, R; Di Renzo, F
abstract

Chemical condensation of layers of silicates has been often proposed as an alternative to thermal condensation, finding limited success. The formation of the industrially relevant MCM-22 zeolite (MWW IZA code) from a mild hydrothermal precursor is the most important example of 2D-3D aluminosilicate condensation. Silanols of opposed layers have been condensed by acid-driven dehydration in concentrated nitric acid, as confirmed by powder XRD and Si-29 NMR spectroscopy, implying interlayer template extraction and corresponding dealumination. Milder acid treatments favour template extraction and shrinkage of interlayer distance, but do not provide significant silanol condensation. Template extraction is further favoured by degradation of the organics in the presence of a Cu2+ homogeneous catalyst.

2022 - Recycling of bottom ash from biomass combustion in porcelain stoneware tiles: Effects on technological properties, phase evolution and microstructure [Articolo su rivista]
Conte, S.; Buonamico, D.; Magni, T.; Arletti, R.; Dondi, M.; Guarini, G.; Zanelli, C.
abstract

This work aims to evaluate the use of bottom biomass ash as an alternative raw material in porcelain stoneware bodies. For this purpose, ash coming from a biomass thermoelectric power plant in Emilia-Romagna (Italy) was selected and its chemical, mineralogical and thermal properties determined. Data indicated its technological role as a flux, so it was introduced in a porcelain stoneware batch in partial replacement of feldspars and experimented at laboratory scale. A bottleneck, relative to the rheological behavior of the slips, was overcome by a slight deflocculant increase. The powder compacts were fired from 1000° to 1220 °C in order to follow the evolution of the technological properties, phase composition (XRPD-Rietveld) and microstructure (SEM). The introduction of ash allowed to lower the firing temperature by 20 °C, while keeping the technological properties comparable with those of the benchmark. Moreover, the mineralogical and microstructural data revealed different sintering kinetics.

2022 - Structural evidence of sunscreen enhanced stability in UV filter-Zeolite hybrids [Articolo su rivista]
Confalonieri, G.; Fantini, R.; Allasia, N.; Vezzalini, G.; Fitch, A. N.; Mino, L.; Arletti, R.
abstract

Organic UV filters are used in many applications (personal-care products, components in packaging, dyes, etc). However, many issues remain related to their safety; their release into the environment is toxic for many organisms and their photodegradation products are possibly dangerous. Encapsulation of these molecules in a zeolitic matrix can avoid their dispersion and promote the enhancement of their properties. In this study, we report the structural characterization of the new LTL/OMC ZEOfilter, produced by encapsulating the organic UV filter octinoxate (OMC, C18H26O3) into synthetic zeolite L. In fact, for the further exploitation and the realization of tailor-made materials, it is fundamental to understand the interactions between the filter and the matrix. X ray powder diffraction, Rietveld structural analysis and Monte Carlo simulations result in a detailed description of the molecules’ setting and configuration. To fit the pores of the zeolite, the conformation of OMC molecules assumes a bent tail, allowing suitable intermolecular distances and host-guest interactions. These results were also corroborated by FT-IR experiments. The host-guest interaction is the key point for the stability and efficacy of LTL/OMC ZEOfilter and may explain why, among different ZEOfilters, the cationic zeolites, and especially zeolite L, display the most promising features.

2021 - Amino acid encapsulation in zeolite MOR: Effect of spatial confinement [Articolo su rivista]
Polisi, M.; Fabbiani, M.; Vezzalini, G.; Di Renzo, F.; Pastero, L.; Quartieri, S.; Arletti, R.
abstract

In this study the absorption of glycine, α-alanine and β-alanine amino acids into the pores of the synthetic zeolite Na-mordenite was investigated with the aim of: (i) evaluating the effectiveness of the MOR framework type in amino acid adsorption (viavapor and aqueous loading); (ii) understanding the host-guest and guest-guest interactions to possibly design a tailor made material and a loading procedure able to maximize the amino acid adsorption; (iii) studying the effect of pressure on the adsorbed amino acids such as, for instance, possible amino acid condensation. The structural characterization, carried out with the combination of diffractometric and infrared spectroscopy analyses, shows that MOR can adsorb amino acids, which are found both in protonated/deprotonated (possibly also generating zwitterions) form. Vapor loading is ineffective for α-alanine, while it is effective in β-alanine and glycine adsorption, even if using different loading degrees. The shape and size of MOR channels make this zeolite suitable to accommodate a peptide. In a glycine loaded sample some molecules condensate to form cyclic dimers, while linear oligomers are detected only in a β-alanine MOR hybrid. The sample loaded with α-l-alanine from aqueous solution does not show the presence of amide bond signals, indicating that the molecules are mostly hosted in zwitterionic form in Na-MOR channels. The application of external baric stimuli does not induce substantial modifications in the structure of the glycine loaded zeolite; this result may be explained by the low number of molecules hosted in the channels. The amino acid amount within the zeolite pores is the most important reactivity parameter and an increased loading could induce chemical modifications.

2021 - Boosting sunscreen stability: New hybrid materials from UV filters encapsulation [Articolo su rivista]
Fantini, Riccardo; Vezzalini, Giovanna; Zambon, Alfonso; Ferrari, Erika; Di Renzo, Francesco; Fabbiani, Marco; Arletti, Rossella
abstract

2021 - Ce-exchange capacity of zeolite L in different cationic forms: a structural investigation [Articolo su rivista]
Confalonieri, G; Vezzalini, G; Quattrini, F; Quartieri, S; Dejoie, C; Arletti, R
abstract

Cerium exchange by microporous materials, such as zeolites, has important applications in different fields, for example, rare earth element recovery from waste or catalytic processes. This work investigated the Ce-exchange capacity of zeolite L in three different cationic forms (the as-synthesized K form and Naand NH4-exchanged ones) from a highly concentrated solution. Chemical analyses and structural investigations allowed determination of the mechanisms involved in the exchanges and give new insights into the interactions occurring between the cations and the zeolite framework. Different cation sites are involved: (i) K present in the original LTL in the cancrinite cage (site KB) cannot be exchanged; (ii) the cations in KD (in the 12-membered ring channel) are always exchanged; while (iii) site KC (in the eight-membered ring channel) is involved only when K+ is substituted by NH4+, thus promoting a higher exchange rate for NH4+ -> K+ than for Na+ -> K+. In the Ce-exchanged samples, a new site occupied by Ce appears in the centre of the main channel, accompanied by an increase in the number of and a rearrangement of H2O molecules. In terms of Ce exchange, the three cationic forms behave similarly, from both the chemical and structural point of view (exchanged Ce ranges from 38 to 42% of the pristine cation amount). Beyond the intrinsic structural properties of the zeolite L framework, the Ce exchange seems thus also governed by the water coordination sphere of the cation. Complete Ce recovery from zeolite pores was achieved.

2021 - High Pressure Behavior of the Hybrid Material AlPO4-5+Azobenzene: An In-situ Synchrotron X-ray Diffraction Study [Relazione in Atti di Convegno]
Polisi, Michelangelo; Malagutti, Fabio; Pastero, Linda; Vezzalini, Maria Giovanna; Arletti, Rossella
abstract

In this paper we present the results of a study aimed at the understanding of the high-pressure behavior of a hybrid composite constituted by azobenzene molecules embedded in 1-D nano-channels of AlPO4-5 porous material. In-situ synchrotron high pressure X-ray powder diffraction experiments have been performed on the hybrid material and the starting porous material AlPO4-5. The “non-penetrating” silicone oil and the “penetrating” methanol:ethanol:water 16:3:1 mixture (m.e.w.) have been used as pressure transmitting media. Using silicone oil, the presence of dye molecules within the zeolite channels affect the pressure behavior of the material increasing its compressibility. In the m.e.w. experiment, the penetration of molecules in the channels influences the elastic behavior of the material, leading to a less compressible material. The reversibility of the unit cell parameters after the pressure treatment and the strong stability showed by the hybrid material suggest the possibility to extend the range of applicability of these composites.

2021 - High-Pressure Synthesis and Gas-Sensing Tests of 1-D Polymer/Aluminophosphate Nanocomposites [Articolo su rivista]
Alabarse, F. G.; Polisi, M.; Fabbiani, M.; Quartieri, S.; Arletti, R.; Joseph, B.; Capitani, F.; Contreras, S.; Konczewicz, L.; Rouquette, J.; Alonso, B.; Di Renzo, F.; Zambotti, G.; Bau, M.; Ferrari, M.; Ferrari, V.; Ponzoni, A.; Santoro, M.; Haines, J.
abstract

Recently, filling zeolites with gaseous hydrocarbons at high pressures in diamond anvil cells has been carried out to synthesize novel polymer-guest/zeolite-host nanocomposites with potential, intriguing applications, although the small amount of materials, 10-7 cm3, severely limited true technological exploitation. Here, liquid phenylacetylene, a much more practical reactant, was polymerized in the 12 Å channels of the aluminophosphate Virginia Polytechnic Institute - Five (VFI) at about 0.8 GPa and 140 °C, with large volumes in the order of 0.6 cm3. The resulting polymer/VFI composite was investigated by synchrotron X-ray diffraction and optical and 1H, 13C, and 27Al nuclear magnetic resonance spectroscopy. The materials, consisting of disordered π-conjugated polyphenylacetylene chains in the pores of VFI, were deposited on quartz crystal microbalances and tested as gas sensors. We obtained promising sensing performances to water and butanol vapors, attributed to the finely tuned nanostructure of the composites. High-pressure synthesis is used here to obtain an otherwise unattainable true technological material.

2021 - New Insights in the Production of Simulated Moon Agglutinates: The Use of Natural Zeolite-Bearing Rocks [Articolo su rivista]
Manzoli, M.; Tammaro, O.; Marocco, A.; Bonelli, B.; Barrera, G.; Tiberto, P.; Allia, P.; Mateo-Velez, J. -C.; Roggero, A.; Dantras, E.; Arletti, R.; Pansini, M.; Esposito, S.
abstract

Two natural zeolite-bearing rocks (one containing clinoptilolite and the other chabazite, phillipsite, and analcime) were Fe-exchanged and thermally treated in a reducing atmosphere at 750 °C for 2 h. Two nanocomposites, formed by the dispersion of Fe nanoparticles in a ceramic matrix, were obtained. The prepared lunar dust simulants also contain Na+, K+, Ca2+, and Mg2+ and other mineral phases originally present in the starting materials. The samples were fully characterized by different techniques such as atomic absorption spectrometry, X-ray powder diffraction, followed by Rietveld analysis, transmission electron microscopy, N2 adsorption/desorption analysis at 77 K, measurements of grain size distribution, magnetic property measurements, broad-band dielectric spectroscopy, and DC conductivity measurements. The results of this characterization showed that the obtained metal-ceramic nanocomposites exhibit a chemical and mineralogical composition and electrical and magnetic properties similar to real moon dust and, thus, appear valid moon dust simulants.

2021 - Steering polymer growth by molding nanochannels: 1,5-hexadiene polymerization in high silica mordenite [Articolo su rivista]
Fabbiani, M.; Confalonieri, G.; Morandi, S.; Arletti, R.; Quartieri, S.; Santoro, M.; Di Renzo, F.; Haines, J.; Fantini, R.; Tabacchi, G.; Fois, E.; Vezzalini, G.; Ricchiardi, G.; Martra, G.
abstract

Zeolites are known as scaffolds for the assembly of molecules via non-covalent interactions yielding organized supramolecular materials. Yet their potential in driving the growth of low-dimensional systems requiring covalent bond formation is still unexplored. We incorporated 1,5-hexadiene in the channels of a high-silica mordenite and analyzed the material by infrared spectroscopy, X-ray powder diffraction, thermogravimetry and modeling techniques. Due to the few zeolite acid sites, 1,5-hexadiene experiences a slow conversion to a polymer mainly formed by cyclopentane units and featuring short side chains that are able to fit the channels. The shape-directing abilities of zeolite frameworks play a two-fold role, involving first the organization of the monomers inside the void-space and then the linear growth of the chain dictated by the channel geometry. These findings highlight the molding action of zeolites in directing transformations of covalent bonds under ambient conditions and may provide insights for obtaining confined polymers with intriguing prospective applications.

2020 - An in-situ x-ray diffraction and infrared spectroscopic study of the dehydration of AlPO4-54 [Articolo su rivista]
Fabbiani, M.; Polisi, M.; Fraisse, B.; Arletti, R.; Santoro, M.; Alabarse, F.; Haines, J.
abstract

The dehydration of the large pore aluminophosphate AlPO4-54•xH2O was studied in situ as a function of vacuum pressure at room temperature by infrared spectroscopy and x-ray diffraction. On polycrystalline samples, under primary vacuum, the adsorbed water is removed very rapidly. The structural water in the AlO6 octahedra is then removed slowly with the quantity of the fully dehydrated form gradually increasing from 43 to 65% of the total material. This results in a two-phase mixture of fully dehydrated and a distinct partially dehydrated AlPO4-54•1/2H2O phase containing structural water. These phases have almost identical a cell parameters and very close c parameters. Secondary vacuum increases the amount of fully dehydrated material to more than 76%. Prolonged heating under vacuum increases the amount of fully dehydrated material to 90%. On single crystal samples, removal of adsorbed water is slower and results in a reduction in crystal quality, however prolonged exposure to primary vacuum yielded fully dehydrated material without the need for heating. The monoclinic structure of anhydrous AlPO4-54, space group Cm, with a doubled unit cell was confirmed using single crystal synchrotron x-ray diffraction data.

2020 - CO2 adsorption in nanosized RHO zeolites with different chemical compositions and crystallite sizes [Articolo su rivista]
Confalonieri, G.; Grand, J.; Arletti, R.; Barrier, N.; Mintova, S.
abstract

In this work, nanosized RHO zeolite samples with different Si/Al ratios were synthetized and tested for CO2 adsorption by combining in situ IR spectroscopy and in situ X-ray powder diffraction using synchrotron radiation. The structural changes of the RHO nanosized zeolites, subjected to high temperature treatment (350 °C) and CO2 adsorption (1 and 5 bar), studied by high-resolution X ray powder diffraction, indicated the presence of two phases with different cell parameters in both samples. The combination of the X-ray technique with IR allowed evaluation of the CO2 adsorption capacity of the samples and their adsorption dynamic. The results indicated that the CO2 adsorption capacity is mainly related to the sodium content in the nanosized RHO crystals. The performed adsorption experiments showed that 1 bar CO2 is sufficient to saturate the RHO samples at room temperature, and no change in the CO2 adsorption capacity at 5 bar was observed.

2020 - CO2 capture on natural zeolite clinoptilolite: Effect of temperature and role of the adsorption sites [Articolo su rivista]
Davarpanah, E.; Armandi, M.; Hernandez, S.; Fino, D.; Arletti, R.; Bensaid, S.; Piumetti, M.
abstract

In this study, the adsorption capacity of the low-cost zeolite clinoptilolite was investigated for capturing carbon dioxide (CO2) emitted from industrial processes at moderate temperature. The CO2 adsorption capacity of clinoptilolite (a commercial natural zeolite) and ion-exchanged (with Na+ and Ca2+) clinoptilolite were tested under both dynamic (using a fixed-bed reactor operating with 10% vol. CO2 in N2) and equilibrium conditions (measuring single component adsorption isotherms). The dynamic CO2 adsorption capacity of bare clinoptilolite and ion-exchanged clinoptilolite were evaluated in the temperature range from 293 K to 338 K and the obtained breakthrough curves were compared with those of the commercial zeolite 13X (Z13X). Although the adsorption capacity of Z13X exceeded those of bare clinoptilolite and ion-exchanged clinoptilolite at 293 K, the clinoptilolite exhibited the highest CO2 uptake at a moderate temperature of 338 K (i.e. 25 % higher than Z13X). This feature appears in agreement with the lower isosteric heat of CO2 adsorption on clinoptilolite compared to the other samples. The surface species affecting the qiso and adsorption capacity were investigated through the FTIR spectroscopy using CO2 as probe molecule. As a whole, it has been observed that CO2 forms linear adducts onto K+ and Mg2+ cations of the bare clinoptilolite, and carbonate-like species onto its basic sites. With the Na-exchanged clinoptilolite, Na+ ions led to a decrease in surface basicity and to the formation of both single (Na+···O[dbnd]C[dbnd]O) and dual (Na+···O[dbnd]C[dbnd]O⋯Na+) cationic sites available for the formation of linear adducts. As a result of the remarkable adsorption capacity of clinoptilolite at 338 K, this material appears to be a promising adsorbent for the direct CO2 removal from different flue gases sources operating at such temperatures.

2020 - Energetic performance of pure silica zeolites under high-pressure intrusion of LiCl aqueous solutions: An overview [Articolo su rivista]
Confalonieri, G.; Daou, T. J.; Nouali, H.; Arletti, R.; Ryzhikov, A.
abstract

An overview of all the studies on high-pressure intrusion-extrusion of LiCl aqueous solutions in hydrophobic pure silica zeolites (zeosils) for absorption and storage of mechanical energy is presented. Operational principles of heterogeneous lyophobic systems and their possible applications in the domains of mechanical energy storage, absorption, and generation are described. The intrusion of LiCl aqueous solutions instead of water allows to considerably increase energetic performance of zeosil-based systems by a strong rise of intrusion pressure. The intrusion pressure increases with the salt concentration and depends considerably on zeosil framework. In the case of channel-type zeosils, it rises with the decrease of pore opening diameter, whereas for cage-type ones, no clear trend is observed. A relative increase of intrusion pressure in comparison with water is particularly strong for the zeosils with narrow pore openings. The use of highly concentrated LiCl aqueous solutions instead of water can lead to a change of system behavior. This effect seems to be related to a lower formation of silanol defects under intrusion of solvated ions and a weaker interaction of the ions with silanol groups of zeosil framework. The influence of zeosil nanostructure on LiCl aqueous solutions intrusion-extrusion is also discussed.

2020 - High pressure behaviour of tobermorite supergroup minerals: An in situ synchrotron X-ray powder diffraction study [Articolo su rivista]
Polisi, M.; Vezzalini, M. G.; Bonaccorsi, E.; Biagioni, C.; Arletti, R.
abstract

The high-pressure behaviour of two natural samples of kenotobermorite [Ca4Si6O15(OH)2·5H2O] and clinotobermorite [Ca5Si6O17·5H2O] has been studied by in situ synchrotron X-ray powder diffraction. The samples were compressed in silicone oil using a diamond anvil cell. The calculated bulk moduli are as following: kenotobermorite K0 = 83.2 ± 0.4 GPa and clinotobermorite K0 = 93.5 ± 0.8 GPa. The presence of “zeolitic” Ca in clinotobermorite induces a lower compressibility in this sample. The comparison of the current results with previous studies evidenced that experimentally determined bulk moduli are generally higher than those obtained by theoretical calculations and the differences are related to the configuration of the silicate chains as well as to the content of “zeolitic” cations and H2O molecules.

2020 - High-silica mordenite as scaffold for phenylacetylene polymerization: In situ high pressure investigation [Articolo su rivista]
Confalonieri, G.; Fabbiani, M.; Arletti, R.; Quartieri, S.; Di Renzo, F.; Haines, J.; Tabacchi, G.; Fois, E.; Vezzalini, G.; Martra, G.; Santoro, M.
abstract

The joint use of high pressure and regular void-space architectures is a promising route to obtain new nanomaterials with unique properties. We explore herein the pressure-driven injection of aromatic guest species inside zeolite mordenite. Monomeric phenylacetylene (PhA), used as pressure transmitting medium, was inserted in high-silica mordenite at high pressure conditions. In-situ X-ray powder diffraction and IR spectroscopy analyses show that the combined action of high pressure, temperature and zeolite pores accomplish the intrusion of phenylacetylene and its conversion to oligomeric species exhibiting a greater degree of conjugation with respect to the starting monomer. This study may open a new path for the realization of composite materials with interesting optoelectronic properties via pressure-driven intrusion and polymerization of aromatic molecules inside zeolite frameworks.

2020 - Magnetic behavior of Ni nanoparticles and Ni2+ ions in weakly loaded zeolitic structures [Articolo su rivista]
Barrera, G.; Allia, P.; Bonelli, B.; Esposito, S.; Freyria, F. S.; Pansini, M.; Marocco, A.; Confalonieri, G.; Arletti, R.; Tiberto, P.
abstract

2020 - Structural interpretation of the energetic performances of a pure silica LTA-type zeolite [Articolo su rivista]
Confalonieri, Giorgia; Ryzhikov, Andrey; Arletti, Rossella; Quartieri, Simona; Vezzalini, Giovanna; Isaac, Carole; Paillaud, Jean-Louis; Nouali, Habiba; Daou, T. Jean
abstract

2020 - Thermal behavior of high silica mordenite [Articolo su rivista]
Fantini, Riccardo; Arletti, Rossella; Quartieri, Simona; Fabbiani, Marco; Morandi, Sara; Martra, Gianmario; Di Renzo, Francesco; Vezzalini, Maria Giovanna
abstract

This work studies the thermal stability, heat-induced structural deformations, and dehydration/rehydration dynamics of a synthetic high silica mordenite. It is of special interest because this particular phase has proven to be an ideal host for the encapsulation of several kinds of organic molecules making it a promising scaffold for drug delivery. The dehydration process was followed by thermal analysis, infrared spectroscopy in controlled atmosphere, in situ synchrotron XRPD, and structural refinement. Overall, all the results indicate weak interactions of H2O molecules with the silicatic mordenite framework and evidence the presence of hydroxyl groups with different condensation responses at high temperature. Infrared characterization highlighted how the desorption of adsorbed H2O molecules under degassing is already complete at rT. The unit cell parameters exhibit very slow and almost isotropic changes upon heating. Above 550 �C an increase in slope is observed for all parameters. This corresponds to the marked silanol condensation and consequent framework reassessment observed at this temperature by infrared characterization. Overall cell contractions are 0.67%, 1.18%, and 0.81% for a, b, c, respectively and 2.64% for cell volume. HS-MOR undergoes very moderate T induced deformations, indicating a very rigid and stable framework.

2020 - Unusual high-pressure intrusion-extrusion behavior of electrolyte solutions in Mu-26, a pure silica zeolite of topology STF [Articolo su rivista]
Isaac, Carole; Confalonieri, Giorgia; Nouali, Habiba; Paillaud, Jean-Louis; Arletti, Rossella; Daou, T. Jean; Ryzhikov, Andrey
abstract

2019 - CO2 Adsorption/Desorption in FAU Zeolite Nanocrystals: In Situ Synchrotron X-ray Powder Diffraction and in Situ Fourier Transform Infrared Spectroscopic Study [Articolo su rivista]
Polisi, Michelangelo; Grand, Julien; Arletti, Rossella; Barrier, Nicolas; Komaty, Sarah; Zaarour, Moussa; Mintova, Svetlana; Vezzalini, Giovanna
abstract

The host−guest and guest−guest interactions governing the CO2 adsorption/ desorption in two nanosized zeolite samples with FAU framework type and different Si/Al ratios (Na−X Si/Al = 1.24 and Na−Y Si/Al = 2.54) and cation distribution were investigated by in situ synchrotron high-resolution X-ray powder diffraction (XRPD) and in situ Fourier transform infrared (FTIR) spectroscopy. The two complementary techniques allow probing the CO2 adsorption/desorption in the FAU zeolites at different levels, that is, average structure by XRPD versus local structure by FTIR spectroscopy . The presence of physisorbed CO2 molecules in both zeolites was detected by XRPD, whereas only a high amount of chemisorbed CO2 in the Na−X zeolite was found. The presence of unshielded Na cations and H2O molecules in the supercage of the Na−X sample induces the formation of stable bidentate bicarbonate groups. Evacuating CO2-loaded samples resulted in the efficient removal of physisorbed CO2 from both nanosized zeolites; on the contrary, high temperature is required to remove the chemisorbed species from the nanosized Na−X zeolite. Understanding the CO2 sorption behavior and capacity of nanosized zeolites is of great importance in broadening their use in environmental, clinical, and biomedical applications.

2019 - Compressibility behavior and pressure-induced over-hydration of zeolite K-AlSi-L [Articolo su rivista]
Lara, Gigli; Vezzalini, Maria Giovanna; Simona, Quartieri; Rossella, Arletti; Arletti, Rossella
abstract

This paper reports a study, performed by in-situ synchrotron X-ray powder diffraction, of the high-pressure behavior of zeolite L. The experiments were performed using both penetrating (methanol: ethanol: water mixture, m.e.w.) and non-penetrating (silicon oil, s.o.) pressure transmitting media (PTM) to study the compressibility and the possible pressure-induced hydration (PIH) of this synthetic zeolite, technologically relevant as host-guest system exploited in numerous application fields. The experiments were performed from Pamb to 6.2 and 6.3 GPa in s.o. and m.e.w., respectively. The crystal structure refinements were performed up to 6.3 GPa and 3.1 GPa for the patterns collected in m.e.w. and s.o., respectively, while the unit cell parameters were determined in the whole pressure range for both media. A strong PIH effect is evident when zeolite L is compressed in m.e.w. and the over-hydration is essentially ascribable to the filling of most the H2O sites, to the appearance of a new H2O site and to the partially filling of the K sites. The over-hydration starts at a very low pressure (0.5 GPa) and the maximum H2O content can be estimated in 31.1 H2O molecules, against the original value of 18. The PIH is completely reversible upon P release. The main difference between the compression behavior of zeolite L in the two media is the higher compressibility in the non-penetrating one, evidenced by ΔV=− 6.3% and −9.9% in m.e.w. and s.o, respectively. Our data are consistent with the general behavior of zeolites compressed with penetrating media, when the intrusion of H2O molecules hinders the effects of the applied pressure. The results of this work are compared with those obtained on a K-gallosilicate with LTL topology, where PIH induces the formation of H2O nanotubes inside the zeolite channel.

2019 - Differential penetration of ethanol and water in Si-chabazite: high pressure dehydration of azeotrope solution.. [Articolo su rivista]
Confalonieri, Giorgia; Quartieri, Simona; Vezzalini, Maria Giovanna; Tabacchi, Gloria; Fois, Ettore; Daou, Jean; Arletti, Rossella
abstract

This study is aimed to shed light on the mechanisms at the basis of the differential penetration of alcohol and water in hydrophobic zeolites at ambient (Pamb) and non-ambient pressure. Here we report the effects of the penetration of water and alcohol in an all-silica chabazite (Si-CHA) compressed with an ethanol/water azeotrope solution (ethanol: water=95.63 : 4.37 by mass %). We collected in situ synchrotron X-ray Powder Diffraction (XRPD) data in order to monitor the structural modifications induced by the fluid penetration and to investigate the guest-guest and host-guest interactions. First principles molecular dynamics simulations allowed to complete the structural description at high pressure, providing an atomistic level description of the guest-guest hydrogen bond network. For a comprehensive understanding of the processes involving the Si-CHA + azeotrope interactions, both the zeolite and the alcohol/water solution were firstly investigated separately under pressure. The results obtained prove that both H2O and ethanol penetrate Si-CHA porosities even at Pamb. However, while in these conditions the H2O/ethanol ratio adsorbed inside Si-CHA is similar to that of the external azeotrope solution, under pressure the zeolite extra-framework content corresponds to a composition much richer in H2O than the azeotrope one. Hence, our results suggest that a dehydration effect occurred on the azeotrope solution, promoted by pressure. In addition, the experiment performed to test the elastic behavior of Si-CHA with a nonpenetrating pressure transmitting medium interestingly indicates that Si-pure chabazite is the most compressible zeolite among those up to now studied in silicone oil.

2019 - How much is known about glassy materials in Bronze and Iron Age Italy? New data and general overview [Articolo su rivista]
Conte, Sonia; Matarese, I.; Vezzalini, G.; Pacciarelli, M.; Scarano, T.; Vanzetti, A.; Gratuze, B.; Arletti, R.
abstract

Knowledge of glass trading in protohistoric Southern Italy has been limited by a lack of archeometrical data available to date, preventing comparison with the well-known Northern Italian context. The aim of the present work is to help fill the data gap for Southern Bronze-Iron Age vitreous items and enable a general overview of protohistoric Italian glass supply routes. The paper presents physical-chemical data for 61 vitreous items from 11 Southern Italian sites, dated from the beginning of the Bronze Age up to the Archaic period (22nd–6th century BC), ensuring a complete diachronic analysis. SEM-EDS, EMPA, LA-ICPMS, and XRD analyses permitted definition of the raw materials and manufacturing techniques employed, as well as determination of item provenance. The sample set exhibits great variability of glass chemical types, including plant ash glass, mixed alkali, and natron samples. A complex picture emerges, mostly as regards the different natron glass typologies (High-Zr, Low-Zr, Black, etc.) and their rapid technological evolution in the early 1st millennium BC. Taking into account the data reported in this study and those available in literature for both Northern and Southern Italian Bronze-Iron Ages items, this work demonstrates the existence of different trade routes for the first time. This is especially true for the Early/Middle Bronze Age periods, with Northern Italy involved in trade with Central Europe, and South already involved in Mediterranean trade circuits.

2019 - Insertion and Confinement of H2O in Hydrophobic Siliceous Zeolites at High Pressure [Articolo su rivista]
Santoro, Mario; Veremeienko, Vasyl; Polisi, Michelangelo; Fantini, Riccardo; Alabarse, Frederico; Arletti, Rossella; Quatieri, Simona; Svitlyk, Volodymyr; van der Lee, Arie; Rouquette, Jérôme; Alonso, Bruno; Di Renzo, Francesco; Coasne, Benoît; Haines, Julien
abstract

2019 - Quantitative phase analysis using the Rietveld method: Towards a procedure for checking the reliability and quality of the results [Articolo su rivista]
Gualtieri, A.; Gatta, G. D.; Arletti, R.; Artioli, G.; Ballirano, P.; Cruciani, G.; Guagliardi, A.; Malferrari, D.; Masciocchi, N.; Scardi, P.
abstract

The quantitative phase analysis using the Rietveld method is one of the most used analytical protocols for the characterization of several types of natural and synthetic materials, and it can be performed both on fully crystalline multiphase systems and on materials containing even an amorphous fraction. Therefore, there are several applications of this method (e.g., to natural raw materials, traditional ceramics, bricks, glass-ceramics, cementitious binders, etc.). More recently, the application of the Rietveld method has disseminated also in the chemical, pharmaceutical, and other high added-value industrial areas, where it is exploited in the operational planning, formulation analysis, and in patent protection. Nowadays, in consequence of this diffusion, several academic and private laboratories provide phase quantitative analysis using the Rietveld method as customers service, but an accreditation procedure is still pending and lacks a protocol for checking the authenticity and quality of the analytical reports. In this letter, we focus on the principal elements that an analytical report of quantitative phase analysis, based on the Rietveld method, should contain, as well as some best-practice guidelines for sample preparation and data collection procedure.

2019 - Thermal Behavior of Synthetic High-Silica Mordenite [Poster]
Fantini, Riccardo; Arletti, Rossella; Quartieri, Simona; Fabbiani, Marco; Morandi, Sara; Martra, Gianmario; Di Renzo, Francesco; Vezzalini, Giovanna
abstract

2018 - Considering the effects of the Byzantine–Islamic transition: Umayyad glass tesserae and vessels from the qasr of Khirbet al-Mafjar (Jericho, Palestine) [Articolo su rivista]
Fiorentino, Sara; Chinni, Tania; Cirelli, Enrico; Arletti, Rossella; Conte, Sonia; Vandini, Mariangela
abstract

2018 - Dehydration Mechanism of Monastir Ferrierite: a High Resolution In-situ X-ray Powder Diffraction Study [Poster]
Fantini, Riccardo; Arletti, Rossella; Gieré, Reto; Vezzalini, Giovanna; Vigliaturo, Ruggero; Quartieri, Simona
abstract

2018 - Dehydration and high temperature behavior of zeolite ferrierite [Poster]
Fantini, Riccardo; Arletti, Rossella; Quartieri, Simona; Polisi, Michelangelo; Giacobbe, Carlotta; Vezzalini, Giovanna
abstract

2018 - Dehydration mechanism of AlPO4-5: a high-resolution synchrotron X-ray powder diffraction study. [Articolo su rivista]
Polisi, Michelangelo; Rossella, Arletti; Simona, Quartieri; Linda, Pastero; Carlotta, Giacobbe; Vezzalini, Maria Giovanna; Arletti, Rossella
abstract

We present the results of a study on the thermal stability and dehydration dynamics of the porous alumino- phosphate AlPO4-5, from room temperature to 850 °C, carried out by in situ synchrotron X-ray powder dif- fraction experiments. No phase transitions were observed in the investigated T range. Due to the very low interactions among framework and water molecules, dehydration is already complete at 152 °C. It occurs in two main T ranges, one between 60 and 80 °C and the second one between 90 and 120 °C. During these two stages, the cell volume tends to increase to facilitate the water release. Overall, across the full explored T range, the cell volume increase is only 0.84%, indicating that AlPO4-5 is one of the most rigid zeolite frameworks studied to date. Specifically, after complete dehydration at 200 °C, AlPO4-5 undergoes a negative thermal expansion as a consequence of the decrease in both a and c cell parameters. The expansion coefficients for V, a and c cell parameters, in the 152–850 °C range, are αV = −7.12 (10−6/K), αa = −2.5 (10−6/K), αc = −2.2 (10−6/K), respectively.

2018 - Different glassmaking technologies in the production of Iron Age black glass from Italy and Slovakia [Articolo su rivista]
Arletti, Rossella; Henderson, Julian; Degryse, Patrick; Blomme, Annelore; Conte, Sonia
abstract

2018 - High temperature behavior of zeolite ferrierite: in situ synchrotron X-ray powder diffraction study [Poster]
Fantini, Riccardo; Arletti, Rossella; Gieré, Reto; Polisi, Michelangelo; Vezzalini, Giovanna; Vigliaturo, Ruggero; Quartieri, Simona
abstract

2018 - High-temperature behavior of natural ferrierite: In-situ synchrotron X-ray powder diffraction study [Articolo su rivista]
Rossella, Arletti; FANTINI, RICCARDO; Carlotta, Giacobbe; Reto, Gieré; VEZZALINI, Maria Giovanna; Ruggero, Vigliaturo; Simona, Quartieri; ARLETTI, Rossella
abstract

In this paper, we report the results of the first study focused on the thermal stability and dehydration dynamics of the natural zeolite mineral ferrierite. A sample from Monastir, Sardinia [(Na0.56K1.19Mg2.02Ca0.52 Sr0.14) (Al6.89Si29.04)O72∙17.86H2O; a = 19.2241(3) Å; b = 14.1563(2) Å; c = 7.5106(1) Å, V = 2043.95(7) Å3] was investigated by thermogravimetric analysis and in-situ synchrotron X‑ray powder diffraction. Thermogravimetric data show that H2O release begins already in the range 50–100 °C and is complete at ~600 °C. The results of the structure refinements performed in Immm space group by Rietveld analysis with data collected up to 670 °C show that ferrierite belongs to the group of zeolites that do not undergo phase transitions. Upon heating to 670 °C, ferrierite behaves as a non-collapsible structure displaying only a slight contraction of the unit-cell volume (DV = –3%). The unit-cell parameter reductions are anisotropic, more pronounced for a than for b and c (Da = –1.6%; Db = –0.76%; Dc = –0.70%). This anisotropic response to a temperature increase is interpreted as due to the presence in the ferrierite framework of five-membered ring chains of SiO4 tetrahedra, which impart a higher structural rigidity along b and c. Upon dehydration we observe: (1) the gradual H2O loss, beginning with the molecules hosted in the 10MR channel, is almost complete at 670 °C, in good agreement with the TG data; (2) as a consequence of the decreased H2O content, Mg and K migrate from their original positions, moving from the center of the 10MR channel toward the walls to coordinate the framework oxygen atoms. The observation of transmission electron microscopy selected-area electron diffraction patterns revealed defective crystals with an occasional and moderate structural disorder. Beyond providing information on the thermal stability and behavior of natural ferrierite, the results of this work have significant implications for possible technological applications. These data allow for comparison with the dehydration kinetics/mechanisms of the corresponding synthetic phases, clarifying the role played by framework and extra-framework species on the high-temperature behavior of porous materials with ferrierite topology. Moreover, the information on the thermal behavior of natural ferrierite can be used to predict the energetic performances of analogous synthetic Si-pure counterparts, namely “zeosil-electrolyte” systems, under non-ambient conditions. Specifically, the very high thermal stability of ferrierite determined in this study, coupled with the baric behavior determined in other investigations, suggests that the “Si-FER–electrolyte” system may be an excellent candidate for use as an energy reservoir. Indeed, ferrierite exhibits the so-called “spring behavior,” i.e., upon compression in water or in an electrolyte solution, it converts the mechanical energy into interfacial energy, and—when pressure is released—it can completely restore the supplied mechanical energy accumulated during the compression step.

2018 - Intrusion-Extrusion of Electrolyte Aqueous Solutions in Pure Silica Chabazite by in Situ High Pressure Synchrotron X-ray Powder Diffraction [Articolo su rivista]
Confalonieri, Giorgia; Ryzhikov, Andrey; Arletti, Rossella; Nouali, Habiba; Quartieri, Simona; Daou, T. Jean; Patarin, Joël
abstract

2018 - Magnetic metal-ceramic nanocomposites obtained from cation-exchanged zeolite by heat treatment in reducing atmosphere [Articolo su rivista]
Esposito, Serena; Dell’Agli, Gianfranco; Marocco, Antonello; Bonelli, Barbara; Allia, Paolo; Tiberto, Paola; Barrera, Gabriele; Manzoli, Maela; Arletti, Rossella; Pansini, Michele
abstract

2018 - Sasbach Faujasite: structural refinement of natural and NH4-exchanged phase and preliminary results on crystal dealumination [Poster]
Fantini, R.; Arletti, R.; Pastero, L.; Quartieri, S.; Di Renzo, F.; Camara, F.; Vezzalini, G
abstract

2018 - Structure and Host-Guest Interactions of Perylene-Diimide Dyes in Zeolite L Nanochannels [Articolo su rivista]
Gigli, Lara; Arletti, Rossella; Tabacchi, Gloria; Fabbiani, Marco; Vitillo, Jenny G.; Martra, Gianmario; Devaux, Andre; Miletto, Ivana; Quartieri, Simona; Calzaferri, Gion; Fois, Ettore
abstract

2018 - Structure of Natural and NH4-Exchanged Sasbach Faujasite: a single crystal study [Poster]
Fantini, R.; Arletti, R.; Pastero, L.; Quartieri, S.; Di Renzo, F.; Cámara, F.; Vezzalini, G.
abstract

2018 - Structure of natural and NH4-exchanged Sasbach faujasite: a single-crystal study [Articolo su rivista]
Fantini, Riccardo; Rossella, Arletti; Linda, Pastero; Simona, Quartieri; Francesco Di Renzo, ; Fernando, Cámara; Vezzalini, Maria Giovanna; Arletti, Rossella
abstract

The interest for the environmental, industrial and technological applications of Si-rich zeolites is very high. Among the large-pore zeolites, faujasite is one of the most exploited. The aim of this paper is to obtain detailed structural information on natural and NH4-exchanged faujasite before using this zeolite for dealumination tests, targeting the realization of large single crystals of all-silica faujasite. As one of the most Si-rich natural samples, faujasite from Sasbach (Na13.64K0.87Mg10.46Ca8.89Sr0.34(Al51.95Si139.57)O384∙272.29 H2O; space group Fd-3m;a = 24.6906(2) Å) was chosen for study. Single-crystal X-ray diffraction structural refinements of both natural and NH4-exchanged samples are reported and discussed. In the natural faujasite sample, almost all the extraframework species could be located for the first time. In the NH4-exchanged sample the ammonium and water molecule sites were located. Ammonium cations occupy two of the sites occupied by the extraframework species in the original mineral.

2018 - Unravelling the high-pressure behaviour of dye-zeolite L hybrid materials [Articolo su rivista]
Gigli, Lara; Arletti, Rossella; Fois, Ettore; Tabacchi, Gloria; Quartieri, Simona; Dmitriev, Vladimir; Vezzalini, Giovanna
abstract

Self-assembly of chromophores nanoconfined in porous materials such as zeolite L has led to technologically relevant host-guest systems exploited in solar energy harvesting, photonics, nanodiagnostics and information technology. The response of these hybrid materials to compression, which would be crucial to enhance their application range, has never been explored to date. By a joint high-pressure in situ synchrotron X-ray powder diffraction and ab initio molecular dynamics approach, herein we unravel the high-pressure behaviour of hybrid composites of zeolite L with fluorenone dye. High-pressure experiments were performed up to 6 GPa using non-penetrating pressure transmitting media to study the effect of dye loading on the structural properties of the materials under compression. Computational modelling provided molecular-level insight on the response to compression of the confined dye assemblies, evidencing a pressure-induced strengthening of the interaction between the fluorenone carbonyl group and zeolite L potassium cations. Our results reveal an impressive stability of the fluorenone-zeolite L composites at GPa pressures. The remarkable resilience of the supramolecular organization of dye molecules hyperconfined in zeolite L channels may open the way to the realization of optical devices able to maintain their functionality under extreme conditions.

2018 - Zeolite/dye hybrid composites: Organization of photoactive azobenzene molecules inside AlPO4-5 [Articolo su rivista]
Polisi, Michelangelo; Rossella, Arletti; Sara, Morandi; Marco, Fabbiani; Gianmario, Martra; Simona, Quartieri; Linda, Pastero; Vezzalini, Maria Giovanna; Arletti, Rossella
abstract

Organic/inorganic hybrid materials - like zeolites +dyes - are currently used in strategic areas, from sustainable energy technologies to biomedical sciences. In these systems, photoactive molecules are organized in one-dimensional nanostructures inside the zeolite channels. In this paper we present the results of a study aimed to the synthesis and the structural and spectroscopic characterization of azobenzene/AlPO4-5 hybrid composites, performed by a multi-technique approach based on material synthesis, thermal gravimetric analysis, synchrotron X-ray powder diffraction, UV-VIS and IR spectroscopies. The results indicate that azobenzene molecules are hosted in the 12-membered ring channel of AFI framework and the maximum loading is 0.9 molecules per unit cell. The combination of spectroscopic and diffractometric methods point out that, being AlPO4-5 starting material affected by Brönsted acidity, a consistent portion of the azobenzene molecules is protonated and interact with the framework oxygen atoms.

2017 - Irreversible Conversion of a Water-Ethanol Solution into an Organized Two-Dimensional Network of Alternating Supramolecular Units in a Hydrophobic Zeolite under Pressure [Articolo su rivista]
Rossella, Arletti; Ettore, Fois; Lara, Gigli; Vezzalini, Maria Giovanna; Simona, Quartieri; Gloria, Tabacchi; Arletti, Rossella
abstract

Turning disorder into organization is a key issue in science. By making use of X-ray powder diffraction and modeling studies, we show herein that high pressures in combination with the shape and space constraints of the hydrophobic all-silica zeolite ferrierite separate an ethanol-water liquid mixture into ethanol dimer wires and water tetramer squares. The confined supramolecular blocks alternate in a binary two-dimensional (2D) architecture that remains stable upon complete pressure release. These results support the combined use of high pressures and porous networks as a viable strategy for driving the organization of molecules or nano-objects towards complex, pre-defined patterns relevant for the realization of novel functional nanocomposites.

2017 - Preparation and characterization of magnetic and porous metal-ceramic nanocomposites from a zeolite precursor and their application for DNA separation [Articolo su rivista]
Pansini, Michele; Dell'Agli, Gianfranco; Marocco, Antonello; Netti, Paolo Antonio; Battista, Edmondo; Lettera, Vincenzo; Vergara, Paola; Allia, Paolo; Bonelli, Barbara; Tiberto, PAOLA MARIA; Barrera, Gabriele; Alberto, Gabriele; Martra, Gianmario; Arletti, Rossella; Esposito, Serena
abstract

2017 - Pressure-induced penetration of water-ethanol mixtures in all-silica ferrierite [Articolo su rivista]
Arletti, R.; Fois, E.; Tabacchi, G.; Quartieri, S.; Vezzalini, G.
abstract

The all-silica synthetic zeolite Si-FER has been compressed using ethanol/water mixture as pressure transmitting medium (PTM). Analysis of the diffraction data indicates that both components of the PTM penetrate into the zeolite cavities. First-principles molecular dynamics simulations were performed to explore the room-temperature behavior of the Si-FER/ethanol/water system. The results suggest that the organic molecules tend to form hydrogen bonded dimers, which may also be hydrogen bonded to water molecules.

2017 - Pure and Fe-doped CeO2 nanoparticles obtained by microwave assisted combustion synthesis: Physico-chemical properties ruling their catalytic activity towards CO oxidation and soot combustion [Articolo su rivista]
Sahoo, Tapas R.; Armandi, Marco; Arletti, Rossella; Piumetti, Marco; Bensaid, Samir; Manzoli, Maela; Panda, Sirish R.; Bonelli, Barbara
abstract

A sample of pure CeO2 and two samples of Fe-doped CeO2 containing either 3 or 6 at.% Fe were obtained by microwave assisted combustion synthesis. The powders were extensively characterized by several techniques and tested as catalysts for both CO oxidation and soot combustion. As-synthesized CeO2 nanoparticles have a mostly squared shape and size well below 100 nm; they are characterized by the presence of surface Ce³⁺ species likely due to the occurrence of very defective ceria crystalline phases, as revealed by HR-TEM. Oxidation at 400 °C leads to the formation of a hydroxyls-rich surface, with several types of OH groups related to both Ce⁴⁺ and Ce³⁺ species; reduction in H2 at mild temperature (200 °C) leads both to reduction of surface Ce⁴⁺ to Ce³⁺ and formation of new OH groups. With respect to CeO2 nanoparticles, Fe-doped ones have, as a whole, a larger size and less abundant surface OH species. A core-shell structure is inferred where Fe is mostly present in the shell, both in a secondary phase (CeFeO3) and as a dopant, finally lowering the band gap of the material. The presence of Fe improved samples reducibility, as shown by the lowering of the onset of temperature programmed reduction. Catalytic tests of CO oxidation showed that surface Fe species significantly improve the catalytic performance of the samples, by lowering the onset of CO conversion to CO2 especially at low Fe content (i.e. 3 at.%), whereas at 6 at.% Fe loading, the preferential formation of the secondary phase CeFeO3 occurs, finally lowering the CO conversion with respect to the sample containing 3 at.% Fe. Conversely, the soot combustion activity was higher for pure CeO2 nanoparticles, likely due to their smaller size, which increases the amount of solid–solid contact points between soot and the catalyst. However, a positive effect of the presence of surface Fe species on the catalytic activity towards soot combustion was observed, as well.

2017 - The Influence of the Framework and Extraframework Content on the High Pressure Behavior of the GIS Type Zeolites: The Case of Amicite. [Articolo su rivista]
Arletti, Rossella; Giacobbe, Carlotta; Quartieri, Simona; Vezzalini, Maria Giovanna
abstract

This paper reports a study, performed by in-situ synchrotron X-ray Powder Diffraction, of the high pressure behavior of the natural zeolite amicite [K4 Na4 (Al8 Si8 O32 )·10H2 O], the GIS-type phase with ordered (Si, Al) and (Na, K) distribution. The experiments were carried out up to 8.13(5) GPa in methanol:ethanol:water = 16:3:1 (m.e.w.) and 8.68(5) GPa in silicone oil (s.o.). The crystal structure refinements of the patterns collected in m.e.w. were performed up to 4.71(5) GPa, while for the patterns collected in s.o. only the unit cell parameters were determined as a function of pressure. The observed framework deformation mechanism—similar to that reported for the other studied phases with GIS topology—is essentially driven by the distortion of the “double crankshaft” chains and the consequent changed shape of the 8-ring channels. The pressure-induced over-hydration observed in the experiment performed in aqueous medium occurs without unit cell volume expansion, and is substantially reversible. A comparison is made with the high pressure behavior of the other GIS-type phases, and the strong influence on compressibility of the chemical composition of both framework and extraframework species is discussed.

2016 - Evidence for the formation of stable CO2 hydrates in zeolite Na-Y: Structural characterization by synchrotron X-ray powder diffraction [Articolo su rivista]
Arletti, Rossella; Gigli, Lara; Di Renzo, Francesco; Quartieri, Simona
abstract

Preferential adsorption of water is a major problem in the processes of CO2 adsorption on molecular sieves. Adsorption and desorption of CO2 on partially hydrated zeolite Na-Y have been monitored by in situ synchrotron X-ray powder diffraction. The structural refinement of the CO2-saturated diffraction pattern highlighted the formation of tetrameric CO2 clusters connected by water bridges to the sodium cations of two adjacent faujasite supercages. The CO2 desorption was followed by collecting a series of diffraction patterns upon heating from room temperature up to 350 °C. The hydrated CO2 clusters are completely desorbed between 250 °C and 350 °C. This high thermal stability suggests that the formation of hydrated complexes could represent a potentially important mechanism of retention of CO2 during the regeneration of CO2 adsorbents.

2016 - Intrusion-Extrusion Experiments of MgCl2 Aqueous Solution in Pure Silica Ferrierite: Evidence of the Nature of Intruded Liquid by in Situ High Pressure Synchrotron X-Ray Powder Diffraction. [Articolo su rivista]
Arletti, Rossella; Ronchi, Laura; Quartieri, Simona; Vezzalini, Maria Giovanna; Ryzhikov, Andrey; Nouali, Habiba; Daou, T. Jean; Patarin, Joel
abstract

Experimental intrusion-extrusion isotherms of MgCl221H2O solution were recorded at room temperature on pure silica FER-type zeolite (Si-FER). The intrusion occurs at 195 MPa and the phenomenon is completely reversible with a slight hysteresis. The “Si-FER - MgCl2 aqueous solution” system behaves like a spring. The material was deeply characterized before and after intrusion-extrusion experiments and no significant changes were observed. The unit cell parameters were refined e on the basis of the in situ synchrotron X-ray powder diffraction data - up to 1.47 GPa and then at Pamb upon pressure release. The Rietveld refinement of the data collected at 0.28 GPa (280 MPa), a pressure close to the intrusion value, shows that both ions and water molecules present in the MgCl2 aqueous solution were intruded in the porosities. However, the solvation degree of the intruded ions differs from the initial solution, revealing a partial desolvation of both magnesium and chloride ions. As a whole, the nature and amount of the intruded species correspond to a MgCl210H2O composition. Moreover, at a higher pressure (0.68 GPa), a phase transition from the orthorhombic Pmnn to the monoclinic P21/n s.g. is observed in Si-FER. At 1.47 GPa, the zeolite maintains this monoclinic symmetry, while another phase transition, to the monoclinic P21 s g., is argued from the analysis of the pattern of the sample compressed to 2.6 GPa and then collected upon pressure release to ambient conditions.

2016 - Synthesis and structure determination of the novel aluminophosphate TL-1: A new layered compound with corner-sharing AlX6 chains [Articolo su rivista]
Pastero, Linda; Arletti, Rossella; Cámara, Fernando; Gigli, Lara; Cagnoni, Monica
abstract

A novel layered aluminophosphate (TL-1) has been synthesized. Crystals grow as pseudo-hexagonal thin platelets and their whole morphology depends on the synthesis conditions. The structure was solved by single-crystal X-ray diffraction using charge flipping methods. The synthesized layered material, with composition [AlPO4F(H2O)]-(H10C4ON)4, crystallizes in the monoclinic space group P21/a with a=9.2282(5) Å, b=6.9152(4) Å, c=14.4615(9) Å, β=101.57(1)°. The novel compound has corner sharing AlO3F2(H2O) octahedral chains running along [010], where fluorine atoms are at the shared apices, three oxygen atoms are shared with PO4 tetrahedra while the sixth oxygen pertain to an H2O molecule. The stability field of the novel material is enclosed in the HF/Al2O3 ratio ranging between 1 and 4 and the HF/morpholine ratio lower than 3. At temperature lower than 190 °C, the synthesis results is a pure aluminophosphate sample (low alumina/morpholine ratio). A treatment with H2CO3 leads to a complete morpholine removal, as shown by in situ Raman spectroscopy. Powder X-ray diffraction reveals that, after morpholine extraction, the material collapses. The collapse is irreversible.

2016 - Unravelling the Iron Age glass trade in southern Italy: the first trace-element analyses [Articolo su rivista]
Conte, Sonia; Arletti, Rossella; Mermati, Francesca; Gratuze, Bernard
abstract

2015 - Bronze Age vitreous materials from Punta di Zambrone (southern Italy) [Articolo su rivista]
Conte, Sonia; Matarese, Ilaria; Quartieri, Simona; Arletti, Rossella; Jung, Reinhard; Pacciarelli, Marco; Gratuze, Bernard
abstract

2015 - Compressibility and crystal- fluid interactions in all-silica ferrierite at high pressure [Articolo su rivista]
Lotti, Paolo; Arletti, Rossella; Gatta, G. Diego; Quartieri, Simona; Vezzalini, Maria Giovanna; Merlini, Marco; Dmitriev, Vladimir; Hanfland, Michael
abstract

The high-pressure behavior of a synthetic siliceous ferrierite has been studied by in situ single-crystal and powder synchrotron X-ray diffraction with a diamond anvil cell, using four different P-transmitting fluids: the non-penetrating silicone oil and the potentially pore-penetrating methanol:ethanol:H2O ¼ 16:3:1 mixture, ethylene glycol and 2methyl-2propen-1ol. The high-pressure experiment in silicone oil shows a remarkable flexibility of the FER framework. Two displacive phase transitions, following the path Pmnn-to-P121/n1-to-P21/n11 with pressure, were observed. The three polymorphs were found to share a virtually identical bulk compressibility, though showing a different anisotropic pattern. The experiments with potentially penetrating media enhanced the occurrence of a complex scenario, from which the P-induced intrusion of fluid molecules into the FER structural voids can be assumed by the different phase-transition paths and compressibility patterns, by the calculated residual electron density and by the different deformation mechanisms at the atomic scale, observed as a function of the used medium. The starting orthorhombic polymorph was always restored upon decompression in all the experiments. The roles of the different surface area in single crystal and polycrystalline samples, and of the process kinetics on the compressibility and crystalefluid interactions, are discussed.

2015 - Elastic behavior and pressure-induced structural modifications of the microporous Ca(VO)Si4O10 4H2O dimorphs cavansite and pentagonite [Articolo su rivista]
Danisi, Rosa Micaela; Armbruster, Thomas; Arletti, Rossella; Gatta, G. Diego; Vezzalini, Maria Giovanna; Quartieri, Simona; Dmitriev, Vladimir
abstract

The behavior of natural microporous cavansite and pentagonite, orthorhombic dimorphs of Ca(VO) (Si4O10) 4H2O, was studied at high pressure by means of in situ synchrotron X-ray powder diffraction with a diamond anvil cell using two different pressure-transmitting fluids: methanol:ethanol: water = 16:3:1 (m.e.w.) and silicone oil (s.o.). In situ diffraction-data on a cavansite sample were collected up to 8.17(5) GPa in m.e.w, and up to 7.28(5) GPa in s.o. The high-pressure structure evolution was studied on the basis of structural refinements at 1.08(5), 3.27(5) and 6.45(5) GPa. The compressional behavior is strongly anisotropic. When the sample is compressed in s.o. from Pamb to 7.28(5) GPa, the volume contraction is 12.2%, whereas a, b and c decrease by 1.6%, 10.3% and 0.3%, respectively. The main deformation mechanisms at high-pressure are basically driven by variation of the T–O–T angles. Powder diffraction data on a pentagonite sample were collected up to 8.26(5) GPa in m.e.w and 8.35(5) GPa in s.o. Additional single-crystal X-ray diffraction experiments were performed in m.e.w. up to 2.04(5) GPa. In both cases, pressure-induced over-hydration was observed in m.e.w. at high pressure. The penetration of a new H2O molecule leads to a stiffening effect of the whole structure. Moreover, between 2.45(5) and 2.96(5) GPa in m.e.w., a phase transition from an orthorhombic to a triclinic phase was observed. In s.o. pentagonite also transformed to a triclinic phase above 1.71(5) GPa. The overall compressibility of pentagonite and cavansite in s.o. is comparable, with a volume contraction of 11.6% and 12.2%, respectively.

2015 - Molecular wires confined in zeolite L channels for an effective transport of electronic excitation energy: a synchrotron structural study. [Abstract in Atti di Convegno]
Gigli, L.; Arletti, R.; Vitillo, J. G.; Martra, G; Alberto, G.; Tabacchi, G.; Fois, E.; Quartieri, S.; Vezzalini, Maria Giovanna
abstract

2015 - Pressure-induced penetration of guest molecules in high-silica zeolites: the case of mordenite [Articolo su rivista]
Arletti, R.; Leardini, L.; Vezzalini, Maria Giovanna; Quartieri, S.; Gigli, L.; Santoro, M.; Haines, J; Rouquette, J.; Konczewicz, L.
abstract

A synthetic high-silica mordenite (HS-MOR) has been compressed in both non-penetrating (silicone oil, s.o.) and penetrating [methanol : ethanol : water (16 : 3 : 1) (m.e.w.), water : ethanol (3 : 1) (w.e.), and ethylene glycol (e.gl.)] pressure transmitting media (PTM). In situ high-pressure (HP) synchrotron X-ray powder diffraction (XRPD) experiments allowed the unit cell parameters to be followed up to 1.6, 1.8, 8.4, and 6.7 GPa in s.o., w.e., m.e.w., and e.gl., respectively. Moreover, e.gl. was also used as a PTM in in situ HP Raman and ex situ IR experiments. The structural refinement of HS-MOR compressed in e.gl. at 0.1 GPa – the lowest investigated pressure – revealed the presence of 3.5 ethylene glycol molecules per unit cell. The infrared spectrum of the recovered sample, after compression to 1 GPa, is consistent with the insertion of ethylene glycol molecules in the pores. XRPD and Raman spectroscopy experiments performed under pressure indicated the insertion of a small number of guest molecules. Ethylene glycol is partially retained inside mordenite upon pressure release. A symmetry lowering was observed in s.o. above 0.8 GPa, while above 1.6 GPa the patterns indicated a rapid loss of long range order. From ambient pressure (Pamb) to 1.6 GPa, a high cell volume contraction (DV = 9.5%) was determined. The patterns collected with penetrating PTM suggested the penetration of guest molecules into the porous host matrix, starting from a very low P regime. The entrapment of PTM molecules inside micropores contributes to the stiffening of the structure and, as a consequence, to the decrease of the compressibility with respect to that measured in s.o. From the structural point of view, HS-MOR reacts to compression and to the penetration of different guest species with appropriate framework deformations. Interestingly, ethylene glycol is partially retained inside mordenite upon pressure release, which is of importance for potential application of this composite material.

2015 - Thermal behaviour of siliceous faujasite: further structural interpretation of negative thermal expansion [Articolo su rivista]
Leardini, L.; Quartieri, S.; Vezzalini, Maria Giovanna; Arletti, R.
abstract

The high-temperature behaviour of siliceous faujasite (Si-Y) was investigated by in situ synchrotron Xray powder diffraction from room temperature up to 1123 K. This porous phase is remarkably stable when heated, and no phase transitions or changes in symmetry are observed. A marked negative thermal expansion (NTE), already reported in literature for a heating range from 25 to 573 K, was confirmed up to about 923 K. Above this temperature a positive thermal expansion was observed. Si-Y’s thermal behaviour was interpreted on the basis of the transverse thermal vibrations of the oxygen atoms involved in the T–O–T linkages and a series of other structural features characterizing the faujasite structure, namely the T–T distances between adjacent tetrahedral sites, the thickness of the double 6-membered rings, and the ditrigonal index of the 6-membered rings. Moreover, the thermal behaviour of several other anhydrous porous materials with NTE behaviour is discussed and compared to that of Si-Y.

2015 - Thionine Dye Confined in Zeolite L: Synthesis Location and Optical Properties [Articolo su rivista]
Gigli, Lara; Arletti, Rossella; Vitillo, Jenny G.; Alberto, Gabriele; Martra, Gianmario; Devaux, André; Vezzalini, Maria Giovanna
abstract

The process of light conversion is at present deeply investigated to develop more efficient devices for artificial photosynthesis, water splitting, photovoltaic applications, and targeting therapeutic agents. This process is induced by nanostructured functional materials, such as zeolites light sensitized by dye molecules adsorbed into their pores. Here a detailed study of the organization of the cationic dye thionine (Th) inserted into the linear 12MR channels of zeolite L is carried out by XRPD, FT-IR spectroscopy for the determination of the host−guest interactionsand UV−vis absorption and photoluminescence spectroscopies for the investigation of the electronic states of the guest. Two composites with different Th loading (labeled ZL/0.15Th and ZL/0.27Th) were obtained through ion exchange. TGA spectra and IR-ATR spectroscopy clearly indicated penetration of Th molecules into the ZL channels. Rietveld structural refinement showed that Th molecules in both composites are aligned parallel to the 12MR channel axis and located on the mirror planes parallel to the c-axis. Water molecules interact strongly with the dye and form a kind of solvent−matrix tube shaped around the Th molecule, favoring the upright arrangement of the molecules. DR−UV−vis spectra of the ZL/Th composites indicated that Th molecules are hosted in the ZL channels in a monomeric form. Photoluminescence spectroscopy demonstrated that photoluminescent dyes correspond to ca. 5% of the total amount of Th molecules in the zeolite porosities. While most of the photoluminescent Th molecules exhibit a lifetime equivalent to Th in solutions, the complementary fraction of photoluminescent Th exhibit significantly longer lifetimes, resulting from an entrapment in defects of the zeolite structure, inducing strong rotational constraints to the molecules.

2015 - Toward molecular wires confined in zeolite channels for an effective transport of electronic excitation energy. [Abstract in Atti di Convegno]
Gigli, L.; Arletti, R.; Vitillo, J. G.; Martra, G; Alberto, G.; Tabacchi, G.; Fois, E. .; Quartieri, S.; Vezzalini, Maria Giovanna
abstract

Sunlight is the fundamental energy source sustaining life on Earth. Green plants are provided of very sophisticated and highly efficient tools to exploit light, they are able to harvest sunlight and to transport electronic excitation energy by means of a particular “antenna system” to reaction centres (natural photosynthesis). The antenna consists of regular arrangements of chlorophyll molecules held at fixed positions by means of proteins. Light absorbed by any of these molecules is transported - by radiationless energy transfer (FRET) - to reaction centres, providing the energy necessary for the chemical processes to be initiated. A green leaf consists of millions of such well-organized antenna devices. A long-standing challenge has been the development of an artificial system able to mimic the photosynthetic system. Artificial antenna systems can be realized once several organized chromophores are able to absorb the incident light and to channel the excitation energy to a common acceptor component1-3. Artificial antenna can be built by incorporating dyes into the one-dimensional channels of zeolite L (ZL). ZL crystals feature strictly parallel nano sized channels arranged in hexagonal symmetry. These channels can be filled with high concentration of suitable guests. The geometric constraints imposed by the host structure allow achieving supramolecular organization of photoactive guests1. It has been shown2,that the properties of the dye-ZL systems depend on the molecular packing inside the channels, controlling the intermolecular and the dyes/framework interactions In this work we presents a study on the optical properties of a two –dyes antenna system in which fluorenone molecules (donor molecule) and thionine(acceptor molecule) are organized in Zeolite L porosities. To interpret the optical properties of the hybrids a detailed structural study at atomistic level was mandatory. Due to the impossibility of studying from the structural point of view a two –dyes systems, two “one-dye” hybrids (ZL/fluorenone and ZL/thionine) were firstly synthesized and characterized to investigate the intermolecular and the dyes/framework interactions4. The results of thermogravimetric, IR, and X-ray structural refinements carried out for the one-dye system ZL/FL established that 1.5 molecules per unit cell is the maximum FL loading , in contrast with the data reported previously in literature5 and that the FL carbonyl group strong interact with a K+ of the ZL. The FL distribution at maximum loading can be consider as a self-assembly of planar dye molecules into a noncovalent nanoladder. FL molecules organized in such a single, continuous nanostructure of dye molecules did not exhibit significant electronic interactions. Indeed, both absorption (recorded in the diffuse reflectance mode) and photoemission electronic spectra of ZL/FL systems with different FL loading scaled almost linearly in intensity with the amount dye hosted in the unit cell (ranging from 0.5 to 1.5), without significant changes of the spectral profiles. Noticeably, the combination and steady state and time resolved photoluminescence data indicated that even at the maximum loading ca. 90% of FL molecules are photoluminescent, with significant increase in the average quantum yield with respect to FL molecules in solution. Such a finding clearly indicates that excited states coupling (Davydov splitting) is not contributing to the optical properties of the material. The structural study of the ZL/TH system revealed that the maximum possible loading of TH is equal to 0.3 molecules per unit cell in agreement with the TGA and literature data6. Short distances between the carbon, sulfur and nitrogen atoms and two water molecule sites , in turn at bond distance from the oxygen atoms of the main channel, suggested a water-mediated Th-ZL interactions7. Moreover, IR spectroscopy provided evidence of the interaction of

2015 - WO3 nanorolls self-assembled as thin films by hydrothermal synthesis [Articolo su rivista]
Vankova, S; Zanarini, S; Amici, J; Cámara, F; Arletti, R; Bodoardo, S; Penazzi, N
abstract

We report a novel type of WO3 nanostructure, i.e. nanorolls obtained as a self-assembled thin film on a transparent conductive substrate. The mild conditions of preparation, avoiding the use of HCl, result in an eco-friendly hydrothermal method with reduced crystallization time. FESEM and HR-TEM show that WO3 nanocrystals are made of rolled nanoflakes with a telescope-like appearance at their tip. For their nano-porosity, electrochemical accessibility, good adhesion to substrates and the envisaged presence of nanocavities between the WO3 layers, these materials hold tremendous promise in nano-electronics, electrochromic devices, water photo-splitting cells, Li-ion batteries and nano-templated filters for UV radiation.

2014 - A novel layered aluminophosphate with corner-sharing AlO₆ chains [Poster]
Camara, F.; Pastero, Linda; Arletti, R.; Cagnoni, M
abstract

2014 - Butrint (Albania) between eastern and western Mediterranean glass production: EMPA and LA-ICP-MS of late antique and early medieval finds [Articolo su rivista]
S., Conte; T., Chinni; Arletti, Rossella; M., Vandini
abstract

2014 - Close-Packed Dye Molecules in Zeolite Channels Self-Assemble into Supramolecular Nanoladders. [Articolo su rivista]
Gigli, L.; Arletti, R.; Tabacchi, G.; Fois, E.; Vitillo, J. G.; Martra, G.; Agostini, G.; Quartieri, S.; Vezzalini, Maria Giovanna
abstract

A tough challenge in nanomaterials chemistry is the determination of the structure of multicomponent nanosystems. Dye−zeolite L composites are building blocks of hierarchically organized multifunctional materials for technological applications. Supramolecular organization inside zeolite L nanochannels, which governs electronic properties, is barely understood. This is especially true for confined close-packed dye molecules, a regime not investigated in applications yet and that might have great potential for future development in this field. Here we realize for the first time composites of zeolite L with maximally packed fluorenone molecules and elucidate their structure by integrated multitechnique analyses. By IR spectroscopy, thermogravimetric analysis, and X-ray diffraction, we establish the maximum degree of dye loading obtained (1.5 molecules per unit cell), and by modeling we reveal that at these conditions fluorenone molecules form quasi 1-D supramolecular nanoladders running along the zeolite channels. Spatial and morphological control provided by the nanoporous matrix combined with a complex blend of strong dye−zeolite and weaker dye−dye van der Waals interactions lie at the origin of this unique architecture, which is also stabilized by the hydrogen bond network of coadsorbed water molecules surrounding the dye nanoladder and penetrating between its rungs.

2014 - First Archaeometrical data of glass from Sarno necropoleis (9th 6th century BC) [Relazione in Atti di Convegno]
Conte, S.; Arletti, R.; Mermati, F
abstract

2014 - HP-induced confinement and polymerization of ethylene glycol in high-Si mordenite [Poster]
Leardini, L.; Quartieri, S.; Arletti, R.; Vezzalini, G
abstract

2014 - HP-induced intrusion and supramolecular organization of guest molecules in zeolites [Relazione in Atti di Convegno]
Arletti, R
abstract

2014 - HP-induced penetration of guest molecules in high-Si mordenite [Poster]
Quartieri, S.; Leardini, L.; Arletti, R.; Vezzalini, G.
abstract

2014 - HP-induced supra-molecular organization of guest molecules in FER-type zeolites [Abstract in Rivista]
Arletti, R.; Quartieri, S; Vezzalini, G.; Fois, E.; Tabacchi, G.
abstract

2014 - High-Si mordenite: compressibility, P-induced amorphization and guest molecules penetration [Poster]
Leardini, ; Quartieri, ; Arletti, Rossella; Vezzalini, G
abstract

2014 - High-pressure-induced structural changes, amorphization and molecule penetration in MFI microporous materials: a review [Articolo su rivista]
Vezzalini, Maria Giovanna; Rossella, Arletti; Simona, Quartieri; Arletti, Rossella
abstract

This is a comparative study on the high-pressure behavior of microporous materials with an MFI framework type (i.e. natural mutinaite, ZSM-5 and the all-silica phase silicalite-1), based on in-situ experiments in which penetrating and nonpenetrating pressure-transmitting media were used. Different pressure-induced phenomena and deformation mechanisms (e.g. pressure-induced over-hydration, pressure-induced amorphization) are discussed. The influence of framework and extra-framework composition and of the presence of silanol defects on the response to the high pressure of MFI-type zeolites is discussed.

2014 - Impose Pressure and Change Technology: Pressure-induced intrusion and organized nanostructures in zeolites [Relazione in Atti di Convegno]
Arletti, R
abstract

2014 - MZ-35, a new layered pentasil borosilicate synthesized in the presence of large alkali cations [Articolo su rivista]
Arletti, R.; Mugnaioli, E.; Kolb, U.; Di Renzo, F.
abstract

2014 - Pressure-induced amorphization and guest-molecule penetration in high-Si mordenite, [Poster]
Quartieri, S.; Leardini, L.; Arletti, R.; Vezzalini, G.
abstract

2014 - Pressure-induced intrusion and supra-molecular organization of guest molecules in FER-type zeolites: a combined experimental and theoretical study [Relazione in Atti di Convegno]
Arletti, R.; Quartieri, S; Vezzalini, G.; Fois, ; Tabacchi, ; G,
abstract

2014 - Pressure-induced intrusion, supra-molecular organization and polymerization of guest molecules in all-silica zeolites, [Relazione in Atti di Convegno]
Arletti, R.; Leardini, L.; Vezzalini, G.; Di Renzo, F.; Dmitriev, V.; Quartieri, S
abstract

2014 - Pressure-induced supramolecular organization in microporous materials: the case of all-silica ferrierite zeolite [Poster]
Arletti, R.; Vezzalini, G.; Quartieri, S.
abstract

2014 - Pressure-induced water intrusion in FER-type zeolites and the influence of extraframework species on structural deformations. [Articolo su rivista]
Arletti, R.; Vezzalini, Maria Giovanna; Quartieri, S.; Di Renzo, F.; Dmitriev, V.
abstract

The response to pressure of a natural ferrierite from Monastir (Sardinia, Italy) (Mon-FER) and of the synthetic all-silica phase (Si-FER) was investigated by means of in situ synchrotron X-ray powder diffraction in the presence of penetrating (methanol:ethanol:water 16:3:1, m.e.w.) and non-penetrating (silicone oil, s.o.) pressure transmitting media (PTM). The following aspects are discussed: (i) the penetration of extra- H2O molecules into the all-silica phase and the related structural aspects involving both framework and extraframework systems; (ii) the influence of the zeolite composition and of the different PTM used in the compression experiments on the overall elastic parameters of the two investigated samples; (iii) the elastic parameters and the unit cell P-induced deformations of the mineral phase; (iv) the reversibility extents of the observed phenomena. Evidence of H2O molecules penetration during compression of Si-FER in m.e.w. was found. The refinement performed at 0.2 GPa enabled location of 15 H2O molecules forming bulk-like and monodimensional H2O clusters. No methanol or ethanol penetration was observed. The results demonstrate that the free volume of the porous material is not the only parameter influencing water condensation since applied pressure is an additional fundamental factor. The bulk modulus value calculated from Pamb to 4.9 GPa for Mon-FER (K0 = 44 GPa, Kp = 0.2) is intermediate between the lowest (about 14 GPa) and the highest (about 72 GPa) values determined to date for zeolites compressed in non-penetrating PTM. The highest P-induced deformations are observed for Si-FER compressed in s.o. In general, higher rigidity for the natural sample was found in both media.

2014 - Thermal behavior of Si-faujasite: new insights from in situ synchrotron X-ray powder diffraction study [Poster]
Leardini, L.; Arletti, R.; Vezzalini, G.; Quartieri, S.
abstract

2014 - Thermal expansion in bafertisite, International Mineralogical Association conference [Relazione in Atti di Convegno]
CAMARA ARTIGAS, Fernando; Arletti, R.; Sokolova, ; E, ; Hawthorne F., C
abstract

2013 - A Study of Glass Tesserae from Mosaics in the Monasteries of Daphni and Hosios Loukas [Capitolo/Saggio]
Arletti, Rossella
abstract

2013 - A XANES study of chromophores in archaeological glass [Articolo su rivista]
Arletti, R; Quartieri, S.; Freestone, I
abstract

We applied X-ray absorption near edge spectroscopy (XANES) to obtain information on the origin of glass colour of several archaeological samples and on the oxidation conditions employed during their production. We studied a series of selected glass fragments—mainly from excavated primary and secondary production centres and dated to the first millennium AD—containing iron and manganese in a wide compositional range. In most of the studied samples iron is rather oxidised, while Mn K-edge XANES data show that, in all the studied glasses, Mn is mainly present in its reduced form (predominantly 2+), with the possible subordinate presence of Mn3+. The most oxidised samples are the HIMT (high iron manganese titanium) glasses, while the less oxidised ones belong to the primary natron glass series from the early Islamic tank furnaces at Bet Eliezer (Israel), and to the series coming from a Roman glass workshop excavated in Basinghall Street, London. In these glasses, iron is approximately equally distributed over the 2+ and 3+ oxidation states. The XANES analyses of two glasses which had been deliberately decolourized using Sb- and Mn-based decolourizers demonstrate that Sb is more effective than Mn as oxidant.

2013 - A new framework topology in the dehydrated form of zeolite levyne. [Articolo su rivista]
Arletti, R.; Vezzalini, Maria Giovanna; Quartieri, S.; Cámara, F.; Alvaro, M.
abstract

0003-004X/13/1112–2063$05.00/DOI: http://dx.doi.org/10.2138/am.2013.4583 2063 A new framework topology in the dehydrated form of zeolite levyne Rossella Arletti1, Giovanna Vezzalini2, Simona Quartieri3, Fernando Cámara1 and Matteo Alvaro4,* 1Dipartimento di Scienze della Terra, Università di Torino, via Valperga Caluso n. 35, 10125 Torino, Italy 2Dipartimento di Scienze Chimiche e Geologiche, Università di Modena e Reggio Emilia, via Giuseppe Campi, 183, 41125 Modena, Italy 3Dipartimento di Fisica e Scienze della Terra, Università di Messina, Viale F. Stagno D’Alcontres, 31, 98122 Messina, Italy 4Dipartimento di Scienze della Terra e dell’Ambiente, Università degli Studi di Pavia, Italy; and International Research School of Planetary Sciences, Università G. d’Annunzio, Chieti, Italy A bstract The thermoelastic behavior and structural evolution of a natural levyne-Ca [(Ca7.8 Na2.2K1.1)Σ11.1 Al20.0Si34.2O108⋅51.5H2O; R3m; a = 13.377(4) Å, c = 22.870(1) Å, V = 3544.1(3) Å3] were studied by both T-resolved synchrotron X‑ray powder diffraction (SR-XRPD) between room temperature and 800 °C, and by conventional-source high-temperature single-crystal X‑ray diffraction (SC-XRD). Above 230 °C, water loss and reallocation of extraframework cations induce the straining and consequent breaking of T-O-T bridges in the D6R, with resulting migration of tetrahedral cations to new tetrahedral sites. The new tetrahedra share an edge with the previously occupied tetrahedra. This phenomenon gives rise to a new topology, which coexists to about 40%, with the original one. The new framework consists of a sequence of a novel zeolitic cage (described as a 20-hedron formed by fourteen 6mR and six 4mR) and two consecutive cancrinite cages along [0001]. This topology, which is reported in the database of the hypothetical zeolite structures as 166_2_293, belongs to the ABC-6 family and can be described by the following sequence of 6-rings: ABCBCACAB, to be compared with that of levyne AABCCABBC. In the new topology the extraframework cations are distributed over 3 new sites: one at the center of the 6mR ⊥ [0001] shared by the two cancrinite cages, one near the center of the 6mR ⊥ [0001] at the base of the new cage, and a last one in a 6mR window of the new cage. The 8mR bidimensional channel system originally present in levyne is therefore absent in the new topology and hence molecular diffusion is likely to be partially hindered in the dehydrated form. The phase transition is not completely reversible, at least in the short term, as only partial rehydration was demonstrated.

2013 - Dehydration dynamics of levyne: evidence for a new zeolite topology [Poster]
Arletti, R; Quartieri, S; Vezzalini, G; Cámara, F
abstract

The thermal induced structural modifications of a natural levyne were studied by both time-resolved synchrotron X-ray powder diffraction between room-T and 800°C, and by conventional-source high- T single crystal X-ray diffraction. Above 230°C, a new topology rises, coexisting in a percentage of about 50% with the original one. The new framework consists of a sequence of a new zeolitic cage (described as a 20-hedron formed by fourteen 6mR and by six 4mR) and two cancrinite cages along [0001]. The new topology – reported in the database of the hypothetical zeolite structures as 166_2_293 – belongs to the ABC-6 family and can be described with the sequence ABABABCBC, to be compared with that of levyne AABCCABBC.

2013 - Dehydration dynamics of levyne: evidence of a new zeolite topology [Abstract in Atti di Convegno]
Arletti, R.; Quartieri, S.; Vezzalini, Maria Giovanna; Camara, F.
abstract

The high temperature behaviour of natural zeolite levyne was studied by in situ SR-XRPD. Water loss induces the cation migration toward the framework to obtain a better coordination, forcing the breaking of some T-O-T bridges and the consequent formation of new bonds and of a new structure. The 8mR bidimensional channel system of levyne is absent in the new topology and hence the molecular diffusion should be partially hindered in the dehydrated form.

2013 - Dye Loading influence on performances of Fluorenone/zeoliteL Light Harvester [Abstract in Atti di Convegno]
Gigli, L.; Arletti, R.; Fois, E.; Tabacchi, G.; Quartieri, S.; Vezzalini, Maria Giovanna; Agostini, G. Alberto G.; Martra, G.; Vitillo, J. G.
abstract

Zeolite L (LTL), is an appealing and excellent host for the supramolecular organization of different kinds of molecules and complexes. However, relatively few experimental structural information is available about the orientation and alignment of the dye molecules in the zeolite pores. Hence, a detailed structural characterization is of great importance for understanding the functionality of these host-guest systems. Between all the possible guests, neutral dye fluorenone (C13H8O) (FL) has received a considerable attention [1,2] because of its ability to form a host-guest complex with LTL, stable if exposed at the atmosphere. Moreover, the fluorescent nature of fluorenone makes this complex interesting as a component of the energy relay system in artificial antennas. Although a detailed structural characterization is still lacking, theoretical studies have shown as the orientation of fluorenone is especially interesting as it is directly related to the light harvesting properties of fluorenone [3]. Moreover, it has shown as the presence of water can influence on the electronic spectra of this host-guest complex and then affect its performances as light harvester [3]. In this study, three different FL/K-LTL materials characterized by an increasing loading of FL have been synthesized by mixing in inert atmosphere the dehydrated K-LTL and FL powder in ratio of 0.5, 1.0, 1.5 and 2.0 molecules/unit cell, and then heating the samples at 120°C in air for 24 h. The vials were maintained under continuous rotation during the heating in order to optimize the contact between the zeolite and the dye. The samples so obtained were characterized by means of X-ray powder diffraction, thermo-gravimetric analysis, IR and UV-vis spectroscopies, fluorescence and nitrogen adsorption. The incorporation of FL into the K-LTL channels was confirmed by a significant change of the unit cell parameters and by drastic decrease in the K-LTL surface area also at low FL loading. The strong interaction between FL carbonyl group and the extraframework potassium cation predicted by theoretical modelling [1] was confirmed by the short bond distances (2.77 Å), evidenced in the Rietveld refined structure, and by the shift of the C=O stretching frequency evidenced in the IR spectra. Such an interaction explains why FL is not displaced by water molecules when FL/K-LTL hybrid is re-exposed to the air [1]. Interestingly, although the UV-vis absorption spectrum was almost unaffected by the FL loading, the corresponding emission spectrum evidenced a strong influence: the optimum FL/K-LTL ratio was then determined in order to optimize the performances of the device as light harvester. The structural information obtained theoretically and from XRD allowed also to explain the loading dependence of the optical properties of the material and to correlate it with the relative orientation of the fluorenone molecules in the zeolite channels.

2013 - Elastic behavior of All-Silica Ferrierite: P-induced hydration of a “hydrophobic” zeolite [Relazione in Atti di Convegno]
Arletti, R.; Quartieri, S.; Vezzalini, G.
abstract

2013 - Elastic behavior of all-silica Ferrierite: HP-induced hydration of a “hydrophobic” zeolite [Abstract in Atti di Convegno]
Arletti, R.; Quartieri, S.; Vezzalini, Maria Giovanna
abstract

The HP structural investigations of an all-silica ferrierite showed that, in both experiments, the penetration of water and alcohols is achieved at very low pressure. All the species entering the pores are arranged in chains running along the central axes of the channels. The interactions among the extraframework molecular species and the framework oxygen atoms are very weak, due to the hydrophobicity of the framework walls.

2013 - Fluorenone dye-Zeolite L hybrid: a novel optical material [Abstract in Atti di Convegno]
Gigli, Lara; Arletti, R.; Quartieri, S.; Vezzalini, Maria Giovanna
abstract

A major challenge facing humanity is developing renewable source of energy. Following the biological blueprint of the natural photosynthesis is possible design synthetic systems for converting light into stored energy: the so called artificial antenna systems. The encapsulation of ordered chromophore molecules into one dimensional zeolite channel systems results in host-guest compounds suitable for the development of novel optical materials such as lenses, infrared light-emitting diodes (used in telecommunications) or dye nanostructured materials for optical data storage [1]. X-ray powder diffraction study of zeolite K-L loaded with 0.5, 1, 1.5, 2 fluorenone-dye (FL) molecules per unit cell (ZL/FL hybrid) [2], was carried out to understand the functionality of these host-guest systems from the structural point of view. These data evidenced a significant change of the unit cell parameters due to the embedding of FL into the ZL 12-membered channels. The Rietveld refinements revealed that the maximum loading is 1.5 FL molecules per unit cell. A strong interaction between FL carbonyl group and two extraframework potassium cations is proved by the short bond distances which make this composite very stable.

2013 - MZ-35, a new layered pentasil borosilicate synthesized in the presence of large alkali cation, [Poster]
Arletti, R.; Mugnaioli, E.; Kolb, U.; Di Renzo, F.
abstract

2013 - Microporosity of amorphous aluminosilicate precursors of zeolites [Poster]
Mosly, A.; Arletti, R.; Bengueddach, A.; Quignard, F.; Di Renzo, F.
abstract

2013 - ORGANOPHILIC ZEOLITE Y USED IN PRB TECHNOLOGY: REGENERATION AFTER SULFONAMIDE ANTIBIOTICS REMOVAL FROM WATER [Abstract in Atti di Convegno]
Leardini, L.; Martucci, A.; Braschi, I.; Blasioli, S.; Arletti, R.; Quartieri, S.
abstract

2013 - REGENERATION OF AN ORGANOPHILIC ZSM-5 AFTER SULFAMETHOXAZOLE ANTIBIOTIC ADSORPTION: AN IN SITU HIGH-TEMPERATURE SYNCHROTRON POWDER DIFFRACTION STUDY [Abstract in Atti di Convegno]
Leardini, L.; Martucci, A.; Braschi, I.; Blasioli, S.; Arletti, R.; Quartieri, S.
abstract

2013 - REGENERATION OF ORGANOPHILIC ZEOLITES AFTER SULFAMETHOXAZOLE ANTIBIOTIC ADSORPTION [Abstract in Atti di Convegno]
Leardini, L.; Martucci, A.; Braschi, I.; Blasioli, S.; Arletti, R.; Quartieri, S.
abstract

2013 - Structural characterization of Fluorenone dye in Zeolite L [Abstract in Atti di Convegno]
Gigli, . L.; Agostini, G.; Arletti, R.; Fois, E.; Lamberti, C.; Tabacchi, G.; Quartieri, S.; Vezzalini, Maria Giovanna
abstract

The structural refinement of FL-ZL hybrid allowed to localize 1.7 FL molecules in the 12-ring channels. The strong interaction of FL carbonyl oxygen with K atoms is in line with the stability of this material under ambient conditions.

2013 - The high thermal stabilility of the zeolite K-L: dehydration mechanism by in situ SR XRPD experiments [Abstract in Atti di Convegno]
Gigli, L.; Arletti, R.; Quartieri, S.; Renzo, F. Di; Vezzalini, Maria Giovanna
abstract

Zeolite L has a very high thermal stability, maintains a good crystallinity up to 814 °C and can be classified as inflexible [4]. In particular, it is noteworthy that zeolite L undergoes a slight thermal expansion, which is very unusual for an alumino-silicate microporous material. Actually, while most of zeolites show the so-called negative thermal expansion [see 5 for a review], the positive one is observed in a number of neutral siliceous zeolites, like CIT-5, AlPO4-31and the one-dimensional 12MR system ITQ-4. In these materials the expansion is mainly realized along the direction of the main and large 12- or 14-ring channel [6], as observed in the zeolite L here investigated. Usually, in zeolites, most of the extraframework cations are coordinated by water molecules. Upon dehydration these cations move closer to the framework to form new bonds inducing strains on the framework, resulting in a structural deformation or even in bond breaking. Zeolite L represents an exception, because only one of the three cation sites (KD) is bonded to a water molecule, while the coordination spheres of the other cations are formed by only framework oxygen atoms. Moreover, among the five water sites, only two are at coordination distance from the framework oxygen atoms, while the others are involved only in water-water hydrogen bonds. These structural features explain why the dehydration process does not induce substantial structural modifications in the framework and why zeolite L even undergoes a small unit cell volume increase upon heating.

2013 - The high thermal stability of the synthetic zeolite K-L: dehydration mechanism by in-situ SR-XRPD experiments [Articolo su rivista]
Gigli, Lara; Arletti, R.; Quartieri, S.; Di Renzo, F.; Vezzalini, Maria Giovanna
abstract

Thermally induced structural modifications of a synthetic zeolite L [K8.46 (Al8.35 Si27.53) O7217.91H2O, framework type LTL, s.g. P6/mmm, a = 18.3367(1) and c = 7.5176(1) Å] were studied by temperatureresolved synchrotron X-ray powder diffraction. In the investigated temperature range (RT-814 C), neither structure breakdown nor phase transitions occurred. The largest unit cell deformation was observed between 100 and 240 C, accompanied by an increase and decrease of the a and c cell parameters, respectively. After complete water release, an inversion of the a and c parameter behavior was observed, while the cell volume continued to increase, although following a more flattened curve. Overall, in the investigated T range, a small cell volume increase of 0.7% was observed. The release of the five water molecules present in zeolite L started with the most weakly bonded one and occurred between 80 and 240 C. During dehydration the framework underwent minor rearrangements, which facilitated water release: the apertures of the main 12-ring and the 8-ring channels became more circular and the 6-membered rings became more hexagonal. The thermal expansion of zeolite L, very unusual for a non-siliceous zeolite, was interpreted and compared with previous data reported in literature for this porous material, and with the behavior of the synthetic phases ITQ-4 and CIT-5.

2013 - The high thermal stability of the zeolite K-L:dehydration mechanism by in-situ SR-XRPD experiments [Abstract in Atti di Convegno]
Gigli, Lara; Arletti, Rossella; Quartieri, Simona; Di Renzo, Francesco; Vezzalini, Maria Giovanna
abstract

2013 - The use of X-ray absorption spectroscopy in historical glass research [Capitolo/Saggio]
Quartieri, ; Arletti, Rossella
abstract

2013 - “ImPACT” FIRB Futuro in Ricerca: Pressure-induced supermolecular organization of water and ethanol in all-silica zeolites. [Abstract in Atti di Convegno]
Arletti, R.; Vezzalini, Maria Giovanna; Quartieri, S.
abstract

In situ LS-XRPD experiments in high pressure using the pressure transmitting media methanol:ethanol:water 16:3:1 and ethanol:water 3:1. Penetration of water and ethanol molecules and formation of water and ethanol chains.

2013 - “ImPACT” FIRB Futuro in Ricerca: Structural characterization of fluorenone-zeolite L host-guest complex [Abstract in Atti di Convegno]
Gigli, Lara; Arletti, R.; Fois, E.; Martra, G.; Tabacchi, G.; Vitillo, J. G.; Vezzalini, Maria Giovanna; Quartieri, S.
abstract

The HP structural investigations of an all-silica ferrierite showed that, in both experiments, the penetration of water and other species is achieved at very low pressure. All the species entering the channels are arranged in chains running in the middle of the channels. The interaction among the extraframework species and the framework oxygen atoms is very weak, probably as a consequence of the hydrophobicity of the framework.

2012 - A new zeolite topology deriving from levyne dehydration. [Abstract in Atti di Convegno]
Arletti, R.; Quartieri, S.; Vezzalini, Maria Giovanna; Alvaro, M.; Càmara, F.
abstract

Knowledge of the structural modifications induced by temperature in zeolites and of their stability fields is of prime importance to assess zeolite persistence and effectiveness in their technological applications. Some porous materials, when completely dehydrated, undergo irreversible changes in the framework topology. In general, these changes are due to the strain induced by migration of cations - initially located in the channels and surrounded by water molecules - to achieve a better coordination with framework anions after the water release. Notwithstanding the spread interest for porous materials with levyne topology (LEV), their thermal behavior and stability have not been studied in detail up to now. In this work, the thermal induced structural modifications of a natural levyne from Fagridalur (Iceland) (Ca7.8 Na2.2K1.1Al19.8Si31.2O10851H2O, a= 13.3619(4) Å, c= 22.8820(1) Å, V = 3538.0(3) Å3, s.g. R-3m) were studied by both temperature-resolved synchrotron X-ray powder diffraction experiments (SR-XRPD), and by conventional-source high-temperature single crystal X-ray diffraction (SC-XRD). LEV framework consists of stacking 6-rings perpendicular to [0001] (6mR) in the sequence AABCCABBC (Merlino et al. 1975). Levyne cage is confined by two pairs of 6mR (D6R building units), and contains the non-framework cations and water molecules. A three-dimensional channel system, confined by 8-membered rings, lies perpendicular to [0001]. The SR-XRPD patterns were collected in continuum from room-T to 800°C, while SC-XRD experiments were performed at room-T, 30, 100 and 250°C. Below 100°C a lattice parameter increases, while c decreases, accounting for a very low volume reduction and few water molecule loss. Between 100 and 200 °C, the release of more than 23 water molecules induces the cations migration toward the framework oxygen atoms, so to achieve a better coordination. Above 230°C, a further water loss induces the breaking of the oxygen bridges in the D6R, the edge-sharing tetrahedral phenomenon and the rising of a new topology. The two phases coexist in a percentage about 50% up to the highest investigated temperature. The new framework consists of a sequence of a new zeolitic cage (Fig.1) and two cancrinite cages along [0001]. The structure – reported in the database of the hypothetical zeolite structure as 166_2_293 [2] –belongs to the ABC-6 family [3] and can be described with the following sequence: ABACACBCBA. The new cage can be described as a 20-hedron formed by fourteen 6mR and by six 4mR. The cations are distributed over 3 new sites: one at the center of the six membered ring shared by the two cancrinite cages, one near the center of the base of the new cage and one in a 6mR window of the new cage.

2012 - Adsorption mechanism of 1,2-dichloroethane into an organophilic zeolite mordenite: A combined diffractometric and gas chromatographic study [Articolo su rivista]
Martucci, A.; Pasti, L.; Nassi, M.; Alberti, A.; Arletti, R.; Bagatin, R.; Vignola, R.; Sticca, R.
abstract

2012 - Archaeometrical analyses of early egyptian glass from Thebe area. [Abstract in Atti di Convegno]
Arletti, R.; Lusetti, A.; Ferrari, D.; Vezzalini, Maria Giovanna
abstract

In this work a series of fragments of Egyptian unguentaria are characterized from the chemical and physical point of view. The analysed samples were produced in the first step of the Egyptian glass production, during the new Kingdom of Egypt. The glass production in Egypt started under Thumosis III kingdom and developed until it reached its maximum during the kingdom of Amenhotep III (XVIII dinasty, 1390-1352 BC.) e Amenhotep IV/Akhenaton (XVIII dinasty, 1352-1338 BC). In this period, different glass shapes and typologies appears, and also the variety of decorations and colours increased. The analysed samples pertain to six vessels (amphoriskoi and krateriskoi) coming from Thebes area and now stored at the Egyptian Museum of Turin (Italy) after the excavation carried out at the Valley of the Queens. All these vessels, are blue with yellow, white and turquoise decorations and were produced with the core forming technique. The chemical analyses of major and minor elements were performed by Electron Microprobe (EMPA). The nature of the opacifying and colouring agents was determined by X-ray powder diffraction. Since only micro volumes were sampled from the artefacts (less than 1 mm3), the diffraction experiments were successfully carried out using a single crystal diffractometer equipped with a CCD camera. The chemical data obtained show that all the samples contain high levels of Na2O. However, along with a number of glass containing rather high level of both MgO and K2O - thus classified as plant ash based glass - some of them show rather low levels of K2O along with high MgO percentages. Most of these low-potassium high-magnesium samples are Al- rich Co-bearing blue glass: this seems to indicate they were probably coloured with the addition of Co-bearing alum. This is also consistent with the high level of MnO present in these samples. This situation suggests the use of two different kinds of flux for the production of these glass: an organic source (for the production of most of yellow, white and turquoise glass) and an inorganic one (leading to lower levels of K and Mg) used for the production of the Co-bearing samples. Yellow opaque decorations are rich in Pb and Sb, while only Sb is present in the white and light blue ones. This is consistent with the results of the X-ray powder diffraction analyses, that confirmed the presence of lead antimonates in the yellow decorations and of calcium antimonates in white and light blue ones. No crystalline phases were detected in dark blue, black and violet bulk glass.

2012 - Confinement of dye molecules in nanopores: structural characterization of fluorenone in zeolite L by synchrotron X-ray powder diffraction [Abstract in Atti di Convegno]
Gigli, L.; Agostini, G.; Arletti, R.; Fois, E.; Lamberti, C.; Tabacchi, G.; Quartieri, S.; Vezzalini, Maria Giovanna
abstract

The understanding of the behavior of molecules inside porous materials under the combined effects of applied pressure, spatial confinement and constraints in morphology at the nanoscale is a challenge which has never been endeavored so far. One of the purposes of “ImPact” Project (financed by Italian MIUR, FIRB- Futuro in Ricerca 2013-2016) is to understand at atomistic level the supramolecular organization of different molecules in zeolites frameworks. In particular, the pressure-induced modifications of functional properties of hybrid materials (e.g. Zeolite L + organic colorants), currently applied in strategic areas, from sustainable energy technologies to biomedical sciences, are studied. Neutral dye fluorenone (FL) is able to form a stable host-guest complex with Zeolite L(ZL) - an appealing and excellent host for the supramolecular organization- and has received a considerable attention since it is a component of the energy relay system in artificial antennas [1,2]. Nevertheless, relatively few structural information, even at Pamb, is available about the orientation and alignment of the dye molecules in the zeolite pores. On the other hand, theoretical studies have shown that the orientation of fluorenone and the presence of water are parameters that strongly influence the light harvesting properties of this host-guest complex [3]. Hence, a detailed structural characterization is of great importance for understanding the functionality of these host-guest systems. In this study, three different FL/K-ZL materials have been synthesized by an increasing loading of FL in ratio of 0.5, 1.0, 1.5 and 2.0 molecules/unit cell. The samples obtained were characterized by means of X-ray powder diffraction, thermo-gravimetric analysis, IR and UV-vis spectroscopies at P amb. The incorporation of FL into the zeolite channels was confirmed by a significant change of the unit cell parameters and by drastic decrease in the ZL surface area also at low FL loading (Figure 1). The strong interaction between FL carbonyl group and the extraframework potassium cation, predicted by theoretical modelling [1], was confirmed by the short bond distances (2.77 Å), evidenced in the Rietveld refined structure, and by the shift of the C=O stretching frequency evidenced in the IR spectra. Such an interaction explains why FL is not displaced by water molecules when FL/ZL hybrid is re-exposed to the air [1]. Interestingly, although the UV-vis absorption spectrum was almost unaffected by the FL loading, the corresponding emission spectrum evidenced a strong influence: the optimum FL/K-LTL ratio was then determined in order to optimize the performances of the device as light harvester. The structural information obtained theoretically and from XRD allowed also to explain the loading dependence of the optical properties of the material and to correlate it with the relative orientation of the fluorenone molecules in the zeolite channels.

2012 - Dehydration dynamics of levyne: a combined synchrotron XRPD and single crystal diffraction study [Abstract in Atti di Convegno]
Arletti, R; Quartieri, S; Vezzalini, Maria Giovanna; Alvaro, M; Càmara, F.
abstract

Zeolite dehydration has been widely studied because of the potential use of these porous phases as molecular sieves, sorbents, and catalysts. Knowledge of the structural modifications induced by temperature and of the stability field of these materials is of prime importance to assess their persistence and effectiveness in technological applications. The reversibility of dehydration process, which is considered one of the most remarkable properties of zeolites, is in general - but not always - completely fulfilled, at least in the short term. Some porous materials, when completely dehydrated, undergo irreversible changes in the framework topology. In general, these changes are due to the strain induced by migration of cations - initially located in the channels and surrounded by water molecules - to achieve a better coordination with framework anions after the water release. Notwithstanding the geological and technological interest for porous materials with levyne topology (LEV), its thermal behavior and stability has not been studied in detail up to now. In this work, the thermal induced structural modifications of a natural levyne (Ca7:8 Na2:2K1:1Al19:8Si31:2O108 51H2O, a= 13.3619(4) Å, c= 22.8820(1) Å, V = 3538.0(3) Å3, s.g. R?3m) were studied by both temperature-resolved synchrotron X-ray powder diffraction experiments (SR-XRPD), and by conventional-source high-temperature single crystal X-ray diffraction (SC-XRD). LEV framework consists of stacking 6-rings perpendicular to [0001] (6mRs?[0001]) in the sequence AABCCABBC.. . (Merlino et al. 1975). The repeat distance of this long sequence is about 22.90 Å. Between pairs of 6mRs?[0001] (d6R building units) are two levyne cages (LEV), which contain the non-framework cations and water molecules. One d6R and two LEV cages built up channels along [0001]. Moreover three equivalent channels, perpendicular to the threefold axis, confined by eight-membered rings are present in LEV-type framework. The SR-XRPD patterns were collected in continuum from room-T to 800°C, while single crystal experiments were performed at room-T, 30, 100 and 250°C. Below 100°C a lattice parameter increases, while c decreases, accounting for a very low volume decrease and only few water molecules are lost. Between 100 and 200 °C the release of more than 23 water molecules induces the cations migration toward the framework oxygen atoms, so to achieve a better coordination. Above 230°C, a further water loss induces the migration of Ca cations - previously hosted in the channels- inside the d6R building units, which are empty before the thermal treatment. This induces an abrupt cell volume reduction accompanied by symmetry reduction. No complete amorphization is observed up to the highest T studied. The X-ray structure refinement performed on the pattern collected upon reverse to room-T after transformation revealed that structural modifications are not reversible and the room-T cell parameters are not regained. Some aspects of levyne dehydration dynamics are similar to those found by Zema et al. (2008) for zeolite chabazite.

2012 - Dye molecules confined in nanopores: structural characterization of fluorenone in zeolite L [Abstract in Atti di Convegno]
Gigli, L.; Agostini, G.; Arletti, R.; Fois, F.; Lamberti, C.; Tabacchi, G.; Quartieri, S.; Vezzalini, Maria Giovanna
abstract

Zeolite L (ZL) framework - characterized by one-dimensional 12-ring channels - is a versatile host material for the supramolecular organization of cromophore molecules. The inclusion of dyes molecules into the channels is particularly intriguing, as the resulting host-guest compounds may exhibit unique properties, such as efficient energy transfer [1-3]. The lack of detailed structural information about the orientation and alignment of the neutral dye fluorenone (FL) in the ZL pores suggested this study, aimed to understanding the functionality of these host-guest systems from the structural point of view. The ZL/FL hybrid complex was investigated by synchrotron X-ray powder diffraction experiments (Fig. 1) at GILDA beamline (ESRF, Grenoble). The loading of the dye on previously dehydrating the zeolite L was carried out by using gas-phase adsorption under vacuum, so to assure that water molecules did not block the pathway for molecule entering [4]. The diffraction data evidenced the embedding of FL into the channels, as well as the minor presence (7.4 %) of fluorenone molecules on the zeolite surface. As a consequence, the structure of FL-ZL hybrid was determined by a two-phases Rietveld refinement, in the hexagonal space group P6/mmm [5]. The relevant incorporation of FL into the channels of the dehydrated ZL was confirmed by a significant change of the unit cell parameters. 1.8 FL molecules per unit cell were located near the walls of the large 12-membered ring channel (Fig. 2). A strong interaction between FL carbonyl group and the extraframework potassium cation is suggested by the short bond distances, and explains why FL is not displaced by water molecules when the FL-ZL hybrid is re-exposed to the air. Our experimental results are in good agreement with those obtained by molecular dynamics simulations on a less loaded hybrid [6] and will be compared with new computational data presently in progress.

2012 - ELASTIC BEHAVIOR OF MFI-TYPE ZEOLITES: 3- COMPRESSIBILITY OF SILICALITE AND MUTINAITE [Articolo su rivista]
Quartieri, S.; Arletti, R.; Vezzalini, Maria Giovanna; Di Renzo, F.; Dmitriev, V.
abstract

We report the results of an in-situ synchrotron X-ray powderdiffra ction study–performedusing silicone oil as‘‘non-penetrating’’ pressure transmitting medium– of the elastic behavior of three zeolites with MFI-type framework: the natural zeolite mutinaite and two silicalites (labeledAandB) synthesized under different conditions. While in mutinaite no symmetry change is observed as a function of pressure, a phase transition from monoclinic (P21/n) to orthorhombic (Pnma) symmetry occurs at about 1.0GPa in the silicalite samples. This phase transition is irreversible upon decompression. The second order bulk moduli of silicalite A and silicalite B, calculated after the fulfillment of thephase transition, are: K0=18.2(2)and K0=14.3 (2)GPa, respectively. These values make silicalite the most compressible zeolite among those up to now studied in silicone oil. The structural deformations induced by HP in silicalite A were investigated by means of complete Rietveld structural refinements, before and after the phase transition,at Pamb and 0.9GPa,respectively.The elastic behaviors of thethree MFI- type zeolites here investigated were compared with those of Na-ZSM-5 and H-ZSM-5, studied in similar experimental conditions: the two silicalites–which are the phases with the highestSi/Al ratios and hence the lowest extraframework contents–show the highest compressibility. On the contrary, the most rigid material is mutinaite, which has a very complex extraframework composition characterized by a high number of cations and wate rmolecules.

2012 - Location of MTBE and toluene in the channel system of the zeolitemordenite:Adsorption and host–guest interactions [Articolo su rivista]
Arletti, Rossella; Martucci, Annalisa; Lberti, AlbertoA; Pasti, Luisa; Nassi, Marianna; Bagatin, Roberto
abstract

2012 - Pre-Roman glass from Mozia (Sicily-Italy): the first archaeometrical data [Articolo su rivista]
Arletti, R.; Ferrari, D.; Vezzalini, Maria Giovanna
abstract

This study present the results of an archaeometrical investigation performed on a series of opaque pre-Roman glass (vessels and ornaments) dated from the 6th to 4th century BC coming from Sicily. Sixteen core formed vessels, twelve beads, three pendants and one spindle-whorl recovered in the Phoenician-Punic sites of Mozia and Birgi were analysed thought a micro destructive approach. The complete chemical analyses and X-Ray diffraction analyses were performed on small fragments of glass. The aims of this work are: 1) to obtain a chemical characterization of these samples in order to understand the raw materials employed for their production; 2) to obtain information regarding the opacifying phases dispersed in the glass; 3) to make a comparison with the results recently obtained on coeval and similar finds recovered in other cultural context, in particular in Northern Italian Etruscan contexts in order to understand whether they could belong to the same Greek-Eastern production. The chemical data of these samples confirm they are silica soda lime glass produced with natron. The opaque decorations of the samples were done by using Sb based opacifiers. The major and minor analyses of the majority of the samples seem to suggest a common origin with the coeval material found in Northern Italian context. On the contrary, for some artifacts, in particular the pendants, a Phoenician-Punic origin is supposed.

2012 - Structural characterization of fluorenone in zeolite L by synchrotron X-ray powder diffraction. [Abstract in Atti di Convegno]
Gigli, L.; Agostini, G.; Arletti, R.; Fois, E.; Lamberti, C.; Tabacchi, G.; Quartieri, S.; Vezzalini, Maria Giovanna
abstract

Zeolite L (ZL) framework  characterized by one-dimensional 12-ring channels is a versatile host material for the supramolecular organization of cromophore molecoles. The inclusion of dyes compounds into the channels is particularly intriguing, as the resulting host-guest compounds may exhibit unique properties, such as efficient energy transfer [1-3]. The lack of detailed structural informations about the orientation and alignment of the neutral dye fluorenone (FL) in the ZL pores suggested this study, aimed to understanding the functionality of these host-guest systems from the structural point of view. The ZL/FL hybrid complex was investigated by synchrotron X-ray powder diffraction experiments at GILDA beamline (ESRF, Grenoble). The loading of the dye on previously dehydrating the zeolite L was carried out by using gas-phase adsorption under vacuum, so to assure that water molecules did not block the pathway for molecule entering [4]. The diffraction data evidenced the embedding of FL into the channels, as well as the minor presence (7.4 %) of fluorenone molecules on the zeolite surface. As a consequence, the structure of FL-ZL hybrid was determined by a two-phases Rietveld refinement, in the hexagonal space group P6/mmm [5]. The relevant incorporation of FL into the channels of the dehydrated ZL was confirmed by a significant change of the unit cell parameters. 1.8 FL molecules per unit cell were located near the walls of the large 12-membered ring channel. A strong interaction between FL carbonyl group and the extraframework potassium cation is suggested by the short bond distances, and explains why FL is not displaced by water molecules when the FL-ZL hybrid is re-exposed to the air. Our experimental results are in good agreement with those obtained by molecular dynamics simulations on a less loaded hybrid [6].

2011 - Archaeometrical Analyses of Early Egyptian Glass [Relazione in Atti di Convegno]
Arletti, R.; Lusetti, A.; Ferrari, D.; Vezzalini, G.
abstract

2011 - Borosilicate and aluminosilicate pollucite nanocrystals for the storage of radionuclides [Articolo su rivista]
Montagna, G.; Arletti, R.; Vezzalini, Maria Giovanna; Di Renzo, F.
abstract

Cesium can be encapsulated in crystalline aluminosilicates or borosilicates of ANA framework type byhydrothermal synthesis from alkaline solutions at a temperature as low as 115 °C. No miscibility gap isobserved in the borosilicate–aluminosilicate solid solution. The presence of cesium in the synthesis batchslightly decreases the yield of incorporation of boron in the silicate framework. Nanocrystals from 25 to50 nm are formed in most of the synthesis conditions.

2011 - Compressibility behaviour of as-synthesized high-silica Ferrierite. [Abstract in Atti di Convegno]
Arletti, R.; Quartieri, S; Vezzalini, Maria Giovanna
abstract

Ferrierite (FER framework topology) is a well-known aluminosilicate zeolite mineral. An understanding of the structure and properties of FER remains important because of its role as a catalyst in commercial reactions. For example, it is important in the petrochemical industry, where it has been used as a shape selective catalyst for the production of isobutene. The thermal behavior of this phase (in its high silica form) was recently studied by Bull et al [1], while its compressibilty has never been investigated before. The high pressure (HP) behavior of synthetic high silica zeolite ferrierite (FER) was investigated by means of in-situ synchrotron X-ray powder diffraction, with the aim to understand the P-induced deformation mechanism. The microporous material was synthesized starting from pure silica and pyridine and propyl-amine as structure directing agents. Here we report the preliminary results on the compressibility of the as-synthesized phase. The study of the compressibility of the calcinated one will be carried out in the following steps of the project. The crystal structure of ferrierite is built up of rings of fivecorner-shared SiO4 tetrahedra (known as five-membered ringsor 5MRs) building units, which form layers in the ab plane. The layers are connected to form a matrix of 10MR channels running parallel to the c axis, which are intersected by 8MR channels running parallel to the b axis. Six-membered rings connect the 10MRs alongthe c axis direction. The HP diffraction experiments were performed at BM01a beamline (ESRF), at the fixed wavelength of 0.71 Å, using a modified Merril-Basset DAC and a mixture of methanol:ethanol:water (16:3:1) as P-transmitting medium. The powder patterns were collected from Pamb to 6.2 GPa. Some patterns were also measured upon pressure release up to Pamb, to check the reversibility of the compression effects. The unit cell parameters were refined by means of Rietveld method. The main results of this study are: 1) No complete X-ray amorphization is observed up to about 6.6 GPa; 2) No abrupt change of the elastic behavior is observed in the whole pressure range. Between Pamb and 6.2 GPa the reduction of the cell parameter are 4%, 5% and 6% for a, b and c respectively, accounting for a volume reduction of about 14 %. 3) The P-induced effects on the as-synthesized Si-ferrierite cell parameters are completely reversible. 4) The bulk modulus obtained using a second order Birch-Murnaghan equation of state and data weighted by the uncertainties in P and V was K0 = 30.1(3) GPa. This compressibility is one of the highest when compared with the other natural and synthetic zeolites studied with “penetrating” aqueous media [2, 3] and is very similar to that of SAPO-34 [4], another microporous material studied at HP in its as-synthesized form containing the organic template.

2011 - Elastic behavior of MFI-type zeolites: 1-Compressibility of Na-ZSM-5in penetrating and non-penetrating media [Articolo su rivista]
Arletti, R.; Vezzalini, Maria Giovanna; Morsli, A.; Di Renzo, F.; Dmitriev, V.; Quartieri, S.
abstract

Na-ZSM-5, performed using both silicone oil (s.o.) and (16:3:1) methanol:ethanol:water (m.e.w.), as ‘‘non-penetrating’’ and ‘‘penetrating’’ pressure transmitting media, respectively. In the range from ambient pressure (Pamb) to 6.2 GPa, the reductions of a, b, c, and V observed in s.o. are: 6.4, 6.3, 6.9 and 18.5%,respectively. From Pamb to 7.4 GPa, a unit-cell volume reduction of about 14.6% is observed for Na-ZSM-5 compressed in m.e.w., and the corresponding reductions of a, b, and c cell parameters are 6.3, 4.6, and 4.5%, respectively. In both cases no phase transitions are observed and the unit cell parameters of ambientconditions are recovered upon decompression. The complete structural refinements relative to the experiments performed in m.e.w. up to 1.6 GPa reveal a strong increase in the extra-framework content – with the penetration of additional water/alcohols molecules in the partially occupied extra-framework sites of as-synthesized Na-ZSM-5. This P-induced penetration, which does not induce any cell volumeexpansion, is only partially reversible, since a fraction of the extra-molecules remains in the channels upon decompression. Our results show that Na-ZSM-5 is the softest microporous material among those so far compressed in s.o. Moreover, its compressibility is higher in s.o. than in m.e.w. (K0 = 18.2(6) GPa,K0 = 4 (fixed) and 28.9(5) GPa, K0 = 4 (fixed), respectively). This can be ascribed to the penetration of the extra-water/alcohol molecules, which contribute to stiffen the structure and to contrast the channel deformations.

2011 - Elastic behavior of MFI-type zeolites: Compressibility of H-ZSM-5 in penetrating and non-penetrating media. [Articolo su rivista]
Quartieri, S.; Montagna, G.; Arletti, R.; Vezzalini, Maria Giovanna
abstract

The elastic behavior of H-ZSM-5was investigated by in-situ synchrotron X-ray powder diffraction, using both silicone oil (s.o.) and (16:3:1) methanol:ethanol:water (m.e.w.) as ‘‘non-penetrating’’ and ‘‘penetrating’’ pressure transmitting media, respectively. From Pamb to 6.2GP the volumereductionobserved in s.o. is 16.6%. This testifies that H-ZSM-5 is one of the most flexible microporous materials up to now compressed in s.o. Volume reduction observed in m.e.w. up to 7.6GPa is 14.6%. Astrong increase in the total electron number of the extraframeworks ystem, due to the penetration of water/alcohol molecules in the pores, is observed in m.e.w. This effect is the largest up to now observed inzeolites undergoing this phenomenon without cell volume expansion. The higher compressibility ins.o.than in m.e.w.can be ascribed to the penetration of the extra-water/alcohol molecules, which stiffenthe structure and contrast the channel deformations.

2011 - Florence Baptistery: chemical and Mineralogical Investigation of glass mosaic tesserae [Articolo su rivista]
Arletti, R.; Conte, S.; Vandini, M.; Fiori, C.; Bracci, S.; Bacci, M.; Porcinai, S.
abstract

2011 - Glass beads from Villanovian excavations in Bologna (Italy): an archaeometrical investigation [Articolo su rivista]
Arletti, R.; Bertoni, E.; Vezzalini, Maria Giovanna; Mengoli, D.
abstract

Excavations performed in the 1970s in the present-day trade fair zone of Bologna brought to light remains of civilisationsof the 8–7th century B.C. Archaeological studies identified a large number of objects which clearly indicated the existence of anextensive Villanovian village. Fifteen blue, turquoise, and dark green glass beads were selected and analysed in the present study.Chemical analyses of major and minor elements were obtained by EMPA, whereas trace elements were determined on selectedsamples by LA-ICP-MS. The occurrence of eventual opacifying agents dispersed in the matrix was attested by SEM observations.The chemical data allow identification of a group of four beads characterised by a mixed alkali composition, typical of FrattesinaFinal Bronze Age production. All the other samples have low levels of K2O (,2 wt%) and relatively high Na2O (.15 wt%). Among these last samples, which can be classified as natron-based glass, a number of blue beads show a high quantity of MgO (about 3 wt%), in combination with a low K2O amount. These low-K, high-Mg glasses also exhibit extremely high amounts of Al2O3, possibly due to the use of Co-bearing alum as colouring compound. Also the trace-element data confirm the division of the natron-based samples into two different sub-groups on the basis of the concentration of V, Cr, Ti and Zr. This suggests that the glass found at this site derivesfrom three different melts. Regarding the opacity of the samples, in most of the cases this effect is due to the dark colour of the glass (i.e., blue, dark green) which hinders the transmission of light. Crystalline particles of calcium antimonate were found only in the turquoise-colour samples.

2011 - High-pressure behavior of high silica ferrierite [Abstract in Rivista]
Arletti, R.; Quartieri, ; S, .; Vezzalini, Maria Giovanna
abstract

Ferrierite (FER framework topology) is a well-known aluminosilicate zeolite mineral. An understanding of the structure and properties of FER remains important because of its role as a catalyst in commercial reactions. For example, it is important in the petrochemical industry, where it has been used as a shape selective catalyst for the production of isobutene. The thermal behavior of this phase (in its high silica form) was recently studied by Bull et al [1], while its compressibilty has never been investigated before. The high pressure (HP) behavior of synthetic high silica zeolite ferrierite (FER) was investigated by means of in-situ synchrotron X-ray powder diffraction, with the aim to understand the P-induced deformation mechanism. The microporous material was sinthesized starting from pure silica and pyridine and propyl-amine as structure directing agents. Here we report the preliminary results on the compressibility of the as synthesized phase. The study of the compressibility of the calcined one will be carried out in the following steps of the project.The crystal structure of ferrierite is built up of rings of fivecornershared SiO4 tetrahedra (known as five-membered ringsor 5MRs) building units, which form layers in the ab plane.The layers are connected to form a matrix of 10MR channels running parallel to the c axis, which are intersected by 8MR channels running parallel to the b axis. Six-membered rings connect the 10MRs alongthe c axis direction. The HP diffraction experiments were performed at BM01a beamline (ESRF), at the fixed wavelength of 0.71 Å, using a modified Merril- Basset DAC and a mixture of methanol- ethanol and water (16:3:1) as penetrating P-transmitting medium. The powder patterns were collected from Pamb to 6.2 GPa. Some patterns were also measured upon pressure release up to Pamb, to check the reversibility of the compression effects. The unit cell parameters were refined by means of Rietveld method. The main results of this study are: 1) No complete X-ray amorphization is observed up to about 6.6 GPa; 2) No abrupt change of the elastic behavior is observed in the whole pressure range. Between Pamb and 6.2 GPa the reduction of the cell parameter are 4%, 5% and 6% for a, b and c respectively, accounting for a volume reduction of about 14 %. 3) The bulk modulus obtained using a second order Birch-Murnaghan equation of state and data weighted by the uncertainties in P and V was K0 = 30.1(3) GPa. This compressibility determined in m.e.w. is one of the highest when compared with other natural and synthetic zeolites studied with “penetrating” aqueous media [2], [3]. 4) The P-induced effects on as-syntehsized ferrierite structure are completely reversible.

2011 - MOSAIC GLASS FROM ST PETER’S, ROME:MANUFACTURING TECHNIQUES AND RAW MATERIALSEMPLOYED IN LATE 16TH-CENTURY ITALIANOPAQUE GLASS [Articolo su rivista]
Rossella, Arletti; Vezzalini, Maria Giovanna; Cesare, Fiori; Mariangela, Vandini; Arletti, Rossella
abstract

A recent restoration of late 16th-century mosaics in one of the vaults beneath the dome of St Peter’s Basilica in Rome allowed sampling and analysis of a group of glass tesserae. The aimof this work is the characterization of opaque coloured glasses possibly produced in Rome.The characteristics of the glass from St Peter’s were compared with those of Venetian and Tuscan production, in order to assess possible common origins. Chemical analysis of 30 samples was carried out by electron microprobe, while the nature and morphology of opacifiers were determined by X-ray diffraction and scanning electron microscopy. Almost all the opaque samples were characterized by the presence of SnO2 crystals. In addition, depending on the colour of the glass, other crystalline phases were identified: lead-tin oxide (PbSnO3) in yellow glass, cuprite (Cu2O) in orange glass and two calcium-tin silicates with differentstoichiometry (CaSnSiO5 and Ca3SnSi2O9) in the green-yellow variety. A frame of reference for identifying raw materials and glass-making techniques is provided by textual sources, hereexamined in comparison with the compositional characteristics of the tesserae from St Peter’s.

2011 - Opacity in Mosaic: crystals make technological History [Poster]
Arletti, R.; Vandini, M.
abstract

2011 - THE MEDITERRANEAN GROUP II: ANALYSES OF VESSELS FROM ETRUSCAN CONTEXTS IN NORTHERN ITALY [Articolo su rivista]
Arletti, R.; Rivi, L.; Ferrari, D.; Vezzalini, Maria Giovanna
abstract

A large sample set of transparent and opaque glass artefacts recovered from Etruscan contexts innorthern Italy (Bologna and Spina (FE) necropoleis) and dated to a period between the 6th and 4thcentury BC are analysed in this paper. Samples of highly decorated beads, spindle whorls and vessels ofthe ‘Mediterranean Group I’ (Alabastron, Oinochoes, Amphoriskos) were selected in order to determinewhether these different glass artefacts were produced at the same manufacturing site. While the vesselsalmost certainly originate from Greece, the beads could derive from a more ancient local productionascertained at the site of Frattesina (Rovigo, Italy) and dated to the Bronze Age.The aims of this study are: (i) to characterise a set of Iron Age glass artefacts, thus providing newquantitative chemical data; and (ii) to identify possible differences between finds recovered fromdifferent localities and between glass vessels and beads, in order to establish whether different manufactureswere active contemporaneously.The chemical analyses of major and minor elements were performed with an electron microprobe. Thenature of the opacifying and colouring agents was determined by X-ray diffraction. The sample set isrelatively homogeneous and most of the samples can be classified as low magnesium glass. The yellowopaque decorations are rich in Pb and Sb, while only Sb is present in the white and light blue samples.The XRD analyses confirmed the presence of lead antimonates in the yellow decorations and of calciumantimonates in the white and light blue decorations.

2011 - XANES, UV-VIS and luminescence spectroscopic studyof chromophores in ancient HIMT glass [Articolo su rivista]
DE FERRI, Lavinia; Arletti, Rossella; Ponterini, Glauco; Quartieri, Simona
abstract

This work is aimed to the study of a series of Late Roman glass fragments belonging to the peculiar group called HIMT (High Iron Magnesium Titanium glass), characterized by different color nuances, and previously chemically characterized by our group. XANES, UV-VIS and luminescence spectroscopies are exploited for determining the distribution of the oxidation states ofthe two chromophores Fe and Mn. In all the ancient glass samples, Fe results to be mostly in its oxidate state 3+. The prevalent Mn oxidation state is 2+, however the presence of minor amounts of Mn3+ has been proved. The different spectroscopic techniques, used in a combined approach, areable to interpret the apparent anomalous colour of some of the ancient glass samples.

2010 - A study of glass tesserae fom mosaic in the monasteries of Daphni and Hosios Loukas (Greece) [Articolo su rivista]
Arletti, R.; Fiori, C.; Vandini, M.
abstract

2010 - ARCHAEOMETRICAL INVESTIGATION OF SICILIANEARLY BYZANTINE GLASS: CHEMICAL ANDSPECTROSCOPIC DATA [Articolo su rivista]
Arletti, R.; Giacobbe, C.; Quartieri, S.; Sabatino, G.; Tigano, G.; Triscari, M.; Vezzalini, Maria Giovanna
abstract

A series of early Byzantine glasses, recovered in Ganzirri (Sicily, Italy), was analysed formajor, minor and trace elements. All the analysed fragments were found to be natron-basedsilica–lime glass. Concerning minor and trace elements, the samples can be divided into twogroups: glass with high Fe, Ti and Mn contents (HIMT glass) and glass with low levels ofFe, Ti and Mn. These results, strictly in agreement with literature data for glass of theMediterranean region, can be interpreted as a consequence of the wide trade networkestablished in this region and of the intense circulation of raw glass and artefacts fromdifferent Mediterranean areas. X-ray absorption spectroscopy studies at Fe and Mn K-edges,performed on HIMT glass, indicate that Fe is in the oxidized form while Mn is in the reducedform.

2010 - ARCHAEOMETRICAL INVESTIGATIONS ON SAN SEVERO MOSAIC TESSERAE(CLASSE, RAVENNA): THE USE OF DIFFERENT RAW MATERIALS FOR THE PRODUCTION OF OPAQUE GLASS IN VI CENTURY AD [Abstract in Atti di Convegno]
Arletti, R.; Vandini, M.; Palazzi, V.
abstract

2010 - Boggsite under high pressure: a case of zeolite over-hydration [Relazione in Atti di Convegno]
Quartieri, S.; Arletti, R; Vezzalini, G; Dmitriev, V.
abstract

2010 - Characterization of Glass Mosaic Tesserae from Florence Baptistery: a Multitechnique approach [Poster]
Arletti, R.; S., Conte; Vandini, M.; Fiori, C.; Bacci, M.; Bracci, S.; Bogi, T.; Porcinai, S.
abstract

2010 - ELASTIC BEHAVIOR OF ZEOLITE BOGGSITE IN SILICON OIL AND AQUEOUS MEDIUM: A CASE OF HP-INDUCED OVER-HYDRATION [Articolo su rivista]
Arletti, R.; Quartieri, S.; Vezzalini, Maria Giovanna
abstract

This paper reports the results of an in situ high-pressure synchrotron X-ray powder diffraction investigation on the natural zeolite boggsite [(K0.06Na0.36Sr0.01Ca7.00Mg1.20)(Al17.52Si78.62Fe0.05O192)·82.3 H2O]. The study was performed using both a (16:3:1) methanol:ethanol:water mixture (m.e.w.) as a nominally “penetrating” hydrostatic P-transmitting medium and silicon oil (s.o.) as a “non-penetrating” medium. The studied pressure ranges are: Pamb–7.6 and Pamb–5.9 GPa in m.e.w and s.o., respectively. No complete X-ray amorphization is observed up to the highest investigated pressures, and the original unit-cell parameters are almost completely recovered upon decompression in both media. The reductionsof a, b, c, and V, within the pressure-ranges investigated, are 5.3, 4.2, 4.0, and 13.0% in s.o. and 4.1, 4.1, 3.8, and 11.5% in m.e.w. The Rietveld structural refinements of the powder patterns of the experiments in m.e.w. converged successfully up to 3.6 GPa and demonstrated the penetration of 13 additional water molecules between 0.3 and 2.9 GPa. This over-hydration occurs without any unit-cell volume expansion and can be explained by the fact that no new extraframework sites arise during compression and that water penetration is the only factor to increase the occupancy of already existing sites. Boggsite compressibility is higher in s.o. than in m.e.w. In particular, compressibility in m.e.w. is lower below 3 GPa, whereas above this pressure, the P-V trend becomes similar in the two media. This can be ascribed to the fact that, during water molecule penetration (0.3 < P < 3 GPa), the effect of the P-transmitting medium is directed to compress the system as well as to penetrate the channels.

2010 - Elastic behaviour and HP-induced phase transitions in MFI-type zeolites [Relazione in Atti di Convegno]
Quartieri, S; Montagna, G; Arletti, R; Vezzalini, G
abstract

2010 - Elastic behaviour of MFI-type zeolites: HP-induced phase transitions and over-hydration [Relazione in Atti di Convegno]
Quartieri, S.; Arletti, R.; Montagna, G.; Di Renzo, F; Vezzalini, G.
abstract

2010 - HP-induced deformations and phase transitions in MFI-type zeolites [Relazione in Atti di Convegno]
Montagna, G.; Vezzalini, G.; Quartieri, S.; Arletti, R.; Di Renzo, F.
abstract

2010 - High pressure behavior of boggsite in non-penetrating and aqueous media: a case of over-hydration [Relazione in Atti di Convegno]
Arletti, R.; Quartieri, S.; Vezzalini, G.
abstract

2010 - High pressure induced over Hydration of Boggsite [Poster]
Arletti, R.; Quartieri, S.; Vezzalini, G.
abstract

2010 - IRON OXIDATION STATE IN ARCHAEOLOGICAL SILICATIC GLASS: A COMPARISON BETWEEN XANES AND MÖSSBAUER DATA [Relazione in Atti di Convegno]
Arletti, R.; Quartieri, S.; De Ferri, L.; Freestone, I. C.; Wagner, F.
abstract

2010 - Non-invasive chemical and phase analysis of Roman bronze artefacts from Thamusida (Morocco) [Articolo su rivista]
Gliozz, E.; Arletti, R.; Cartechini, L.; Imberti, S.; Kockelmann, W. A Memmi I.; Rinaldi, R.; Tykot, R. H.
abstract

2010 - Polychrome Mediterranean vessels and beads: exchanges in western Mediterraneran area during Iron Age [Relazione in Atti di Convegno]
Arletti, R.
abstract

2010 - REMOVAL OF HYDROCARBONS FROM WATER BY ZEOLITE MORDENITE [Relazione in Atti di Convegno]
Arletti, R.; Martucci, A.; Alberti, A.; Pasti, L.; Nassi, M.; Vignola, R.
abstract

2010 - ROMAN WINDOW GLASS: A COMPARISON AMONG FINDINGS FROM THREE DIFFERENT ITALIAN SITES [Articolo su rivista]
Arletti, R.; Vezzalini, Maria Giovanna; Benati, S.; Mazzeo Saracino, L.; Gamberini, A.
abstract

Thirty-three samples of window glass and five glass lumps coming from three Italian archaeological sites - Suasa excavations (AN- Italy, settled from the 3rd century BC to the 5th - 6th cen AD), the Roman town Mevaniola (Forlì- Cesena, Italy) settled from the Imperial Age up to the 4th cen. AD) and heodoricVilla of Galeata (Forlì-Cesena- Italy, settled from the 6th cen. AD onwards) -were analysed to track the changes in the chemical composition and manufacturing technology of window glass through the centuries. Aims of this study are: i) to establish the origin of the raw materials; ii) to verify the chemicalhomogeneity among samples coming from different sites and/or produced with different techniques; iii) to sort the samples into the compositional groups of ancient glass. The analysis of all the chemical variables allowed two groups to be distinguished: a) finds from Mevaniola and Suasa and b) finds from Galeata. Allthe samples have the composition of the silica-soda-lime glass but, the analysis of minor elements, in particular of Fe, Mn, and Ti, makes it possible to split the samples into two groups, with the higher levels of these elements always found in the Galeata samples (HIMT glass). In conclusion, it can be asserted that the main differences between the samples are related to their chronology.

2010 - The first archaeometric data on polychrome Iron Age glass from sites located in northern Italy [Articolo su rivista]
Arletti, R.; Maiorano, C.; Ferrari, D.; Vezzalini, Maria Giovanna; Quartieri, S.
abstract

2010 - Unusual zeolite morphologies from oriented aggregation of nanoparticles [Relazione in Atti di Convegno]
Benabdallah, R.; Hamidi, F; Arletti, R.; Bengueddach, A.; Di Renzo, F.
abstract

2010 - VILLANOVIAN EXCAVATIONS IN BOLOGNA: FIRST DATA ON GLASS BEADS [Relazione in Atti di Convegno]
Arletti, R; Bertoni, E.; Vezzalini, G; Mengoli, D.
abstract

2009 - Characterization of glass mosac tesserae from Florence Baptistery: the use of materials coming from different ateliers [Abstract in Atti di Convegno]
Arletti, R.; Conte, S.; Vandini, M.; Fiori, C.; Griffo, A.; Cagnini, A.; Bogi, T.; Porcinai, S.
abstract

2009 - First results on Alumino- Boro- silicates with framework-type ANA: possible traps for radioactive waste [Relazione in Atti di Convegno]
Montagna, G.; Arletti, R.; Vezzalini, G.; Di Renzo, F.
abstract

2009 - High pressure response of MFI zeolites with different extraframework content [Relazione in Atti di Convegno]
Montagna, G.; Arletti, R.; Vezzalini, G.; Quartieri, S.
abstract

2009 - Polichrome glass of VII VI century BC: Etruscan and Phoenician context in comparison [Abstract in Atti di Convegno]
Arletti, Rossella; Vezzalini, Maria Giovanna; S., Quartieri; D., Ferrari
abstract

2009 - Polychrome glass from etruscan contexts in Northern Italy: chimica and mineralogical data [Abstract in Atti di Convegno]
Arletti, Rossella; Vezzalini, Maria Giovanna; S., Quartieri; D., Ferrari
abstract

2009 - Polycrome beads and vessels from etruscan and Phoenician context in comparison [Poster]
Arletti, R.; Vezzalini, G.; Maiorano, C.; Ferrari, D.
abstract

2009 - Sicilian early Bizantine glass finds: from analytical data to trade informations. [Capitolo/Saggio]
Arletti, R; Quartieri, S; Sabatino, G; Triscari, M; Vezzalini, Maria Giovanna; Giacobbe, C; Tigano, G.
abstract

The Ganzirri glass finds can be classified, on the basis of the CaO/Al2O3 ratio, as Levantine I. Moreover, both minor and trace element data allows us to discriminate two distinct groups, one of which is composed of typical HIMT glass. The co-presence of these two glass types is reported for several localities of the Mediterranean area in Byzantine times, and, in particular, the REE and trace elements patterns of the Ganzirri samples are extremely similar to those found for Cyprus finds. Our results confirm that the glass artefacts found in both localities were produced with different glass batches, made with distinct coastal sands. This conclusion is not surprising when considering the strategic position of both sites for trading in the Mediterranean region.

2009 - The Pre-Roman glass from Mozia (Italy) [Relazione in Atti di Convegno]
Arletti, R.; Ferrari, D.; Acquaro, E.; Vezzalini, G.
abstract

2009 - The role played by the B/Si ratio in B-analcime structural modifications: first results on a potential trap for radioactive waste [Abstract in Atti di Convegno]
Montagna, G.; Arletti, R.; Vezzalini, G.; Di Renzo, F.
abstract

2008 - ARCHAEOMETRICAL ANALYSES OF GLASS CAKES AND VITREOUS MOSAIC TESSERAE FROM MESSINA (SICILY, ITALY) [Articolo su rivista]
Arletti, R.; Quartieri, S.; Vezzalini, Maria Giovanna; Sabatino, G.; Triscari, M.; Mastelloni, M. A.
abstract

We report the results of a study performed on several glass samples recovered after the destructioncaused in Messina by the earthquake of 1908, and stored in the ‘Fiore’ deposit of the Regional Museumof Messina (Italy). The samples, still lacking a reliable classification, are glass cakes, some spare mosaictesserae, and fragments of a well-dated mosaic (Mosaico dell’Angelo, XIII–XIV century A.D.). EPMA,SEM-EDS, XRPD and XAS were employed to provide a detailed chemical, mineralogical and spectroscopiccharacterization of the samples. The chemical analyses of major elements show high levels of K2O andMgO, as a result of the prevalent use of plant ashes as flux. The cakes are characterized by a large dispersionof Si, Al and Ca contents, suggesting the use of different starting raw materials. The most commoncrystalline phases used as opacifiers and colorants are quartz and wollastonite. Crystalline aggregates ofSnO2 are present in the gray cakes, whereas PbSnO3 crystals are found in two green mosaic tesserae. Allthe red samples contain small clusters of metallic copper. On the basis of the chemical composition, it ispossible to confirm that most of the samples were produced in the XIII–XIV century, while no specificconclusions were reached on the possible use of the glass cakes as raw glass materials for the productionof the investigated mosaic tesserae.

2008 - ARCHAEOMETRICAL STUDIES OF ROMAN IMPERIAL AGE GLASS FROM CANTON TICINO. [Articolo su rivista]
Arletti, R.; Vezzalini, Maria Giovanna; BIAGGIO SIMONA, S.; MASELLI SCOTTI, F.
abstract

An archaeometrical study of Roman glass finds recovered in the Canton Ticino area was performed after the finding of traces of possible glass-working at Muralto near Locarno. The aim of this work is to provide chemical characterization of these glass varieties—never analysed before—and to compare the results obtained with those for glass of the same period coming from other sites (Aquileia, Augusta Praetoria and Modena). The chemical data shows that the composition of Canton Ticino glass remained the same from the first to the fourth century AD. Moreover, the large amounts of Sb used as a decolouring agent in these samples represents a peculiar trait.

2008 - Analisi archeometrica di tessere musive in pasta vitrea da un pavimento di Lipari. [Capitolo/Saggio]
Triscari, M.; Quartieri, S.; Sabatino, G.; Vezzalini, Maria Giovanna; Arletti, R.; Mastelloni, M. A.
abstract

2008 - Dehydration dynamics of synthetic zeolite ECR-1: in situ X-ray Powder diffraction experiment [Relazione in Atti di Convegno]
Arletti, R.; DI RENZO F, GUALTIERI A. F.
abstract

2008 - Eleventh century Byzantine mosaic tesserae from the Greek monasteries of Daphni and Hosios Loukas [Abstract in Atti di Convegno]
Arletti, Rossella; M., Vandini; C., Fiori; Vezzalini, Maria Giovanna
abstract

2008 - HP- induced deformation effects in MFI-type zeolite [Abstract in Atti di Convegno]
Montagna, Gabriele; Arletti, Rossella; Vezzalini, Maria Giovanna; Quartieri, S.
abstract

2008 - High pressure deformation mechanism of Li-ABW: sinchrotron XRPD study and ab initio molecular dynamics simulations. [Articolo su rivista]
Fois, E.; Gamba, A.; Medici, C.; Tabacchi, G.; Quartieri, S.; Mazzucato, E.; Arletti, R.; Vezzalini, Maria Giovanna
abstract

The response to compression of the synthetic zeolite Li-ABW (LiAlSiO4 H2O, Z = 4, s.g. Pna21) was explored by synchrotron X-ray powder diffraction experiments, using silicone oil as non-penetrating pressure transmitting medium, and Car Parrinello Molecular Dynamics simulations. In the range Pamb – 8.9 GPa, a nearly isotropic compression for the axial parameters and a cell volume decrease of approximately 12% are observed. A discontinuity in the cell parameters vs P behaviour can be detected between 5 and 6 GPa. As a consequence, the bulk modulus was calculated separately in the Pamb – 4.9 GPa and 5.6–8.9 GPa pressure ranges. The corresponding values (72(2) GPa and 80(2) GPa, respectively) are among the highest found up to now for zeolites studied with non-penetrating P-transmittingmedia. Molecular Dynamics simulations were performed at volumes corresponding to Pamb, 1.5, 5.6, and 7.6 GPa, respectively.At 1.5 GPa the channel system is already elliptically deformed, and the zig-zag trend of the 4-ring tetrahedral chains is enhanced. Moreover, the water molecule chain running along the channel becomes interrupted and the water molecules are more strongly connected to the framework oxygen atoms. The four-fold coordination of Li cation is maintained up to the highest pressure and only a slight bond distance decrease is observed above 1.5 GPa. In the Pamb – 5.6 GPa range, all T–O–T angles decrease with pressure, and hence the Li-ABW structure can be defined as collapsible. Otherwise, at higher compression, average T–O–T angles increase slightly. Overall, the deformation of the Li-ABW upon compression resembles that achieved by anhydrous Li-ABW in the high temperature regimes.

2008 - High pressure deformation mechanism of Li-ABW: synchrotron XRPD study and ab-initio molecular dynamic simulations [Articolo su rivista]
Fois, E; Medici, C; GAMBA A, TABACCHI G.; Arletti, R.; Mazzucato, E; Quartieri, S; Vezzalini., G; Dmitriev, V
abstract

2008 - In situ study of dehydration of ECR1: Na-as synthesized and NH4-exchanged in comparison [Relazione in Atti di Convegno]
Arletti, R.; Gualtieri, A. F.; Di Renzo, F.
abstract

The thermal behavior of Na-as synthesized and NH4 exchanged samples of ECR-1 has been studied by synchrotron radiation powder diffraction. The temperature resolved experiments were performed in capillary using a translating imaging plate system. The aim of this study is to follow in situ the dehydration mechanism of the zeolite ECR1, in its as-synthesized and NH4-exchanged form in order to determine its thermal stability and whether the structure undergoes phase transition during dehydration. The as-synthesized sample is stable up to 715°C, whereas the NH4-exchanged one is stable up to 925°C. Cell parameter refinements show a total volume decrease of 0.95% for the as-synthesized phase and of 3.82% for the NH4 form. © 2008 Elsevier B.V. All rights reserved.

2008 - In situ study of the dehydration of ECR-1: Na-as synthesized and NH4-exchanged in comparison [Relazione in Atti di Convegno]
Arletti, R.; Gualtieri, Alessandro; Di Renzo, F.
abstract

The thermal behavior of Na-as synthesized and NH4 exchanged samples of ECR-1 has been studied by synchrotron radiation powder diffraction. The temperature resolved experìments were performed in capillary using a translating imaging piate System. The aim of this study is to follow in sifu thè dehydratìon mechanism of thè zeolite ECR-1, in its as-synthesized and NH4-exchanged forni in order to determine its thermal stability and whether thè structure undergoes phase transition during dehydration. The as-synthesized sample is stable up to 715 °C, whereas the NH4-exchanged one is stable up to 925 °C. Cell parameter refinements show a total volume decrease of 0.95% for thè as-synthesized phase and of 3.82 % for thè NH4 form.

2008 - Neutron diffraction applications to the study of Roman Army bronze artifact from Thamusida (Morocco) [Relazione in Atti di Convegno]
Arletti, R.; L, Cartechini; E, Gliozzo; R, Rinaldi; S, Imberti; W, Kockelmann; I, Memmi
abstract

2008 - Neutron scattering material analysis of Bronze Age metal artefacts [Articolo su rivista]
L, Cartechini; Arletti, R.; R, Rinaldi; W, Kockelmann; S, Giovannini; A, Cardarelli
abstract

2008 - Polychrome etruscan glass: FIRST NON-DESTRUCTIVE CHARACTERISATION WITH SYNCHROTRON mXRF, mXANES and XRPD. [Articolo su rivista]
Arletti, R; Vezzalini, Maria Giovanna; Quartieri, S; Ferrari, D; Merlini, M; AND COTTE, M.
abstract

This work is devoted to the characterization ofa suite of very rare, highly decorated and coloured glass vesselsand beads from the VII to the IV century BC. The most seriousdifficulty in developing this study was that any sampling –even micro-sampling – was absolutely forbidden. As a consequence,themineralogical and chemical nature of chromophoresand opacifiers present in these Iron Age finds were identifiedby means of the following synchrotron-based, strictly nondestructive,techniques: micro X-ray fluorescence (μ-XRF),FeK-edge micro X-ray absorption near edge spectroscopy (μ-XANES) and X-ray powder diffraction (XRPD). The μ-XRFmapping evidenced high levels of Pb and Sb in the yellow decorationsand the presence of only Sb in the white and light-blueones. Purple and black glass show high amounts of Mn andFe, respectively. The XRPD analyses confirmed the presenceof lead and calcium antimonates in yellow, turquoise and whitedecorations. FeK-edge μ-XANES spectra were collected in differentcoloured parts of the finds, thus enabling the mapping ofthe oxidation state of these elements across the samples. In mostof the samples iron is present in the reduced form Fe2+ in thebulk glass of the vessels, and in the oxidized form Fe3+ in thedecorations, indicating that these glass artefacts were producedin at least two distinct processing steps under different furnaceconditions.

2008 - Roman and late-roman window glass from three Italian sites: chemical and morphological data in comparison [Abstract in Atti di Convegno]
Arletti, Rossella; Vezzalini, Maria Giovanna; MAZZEO SARACINO M., L; Gamberini, A.
abstract

2008 - Texture analysis of Bronze Age axes by neutron diffraction [Articolo su rivista]
Arletti, R.; L, Cartechini; S, Giovannini; R, Rinaldi; W, Kockelmann; A, Cardarelli
abstract

2008 - Vetro musivo romano della fine del XVI secolo. [Articolo su rivista]
Fiori, C.; Vandini, M.; Arletti, R.; De Giorgi, R.; Vezzalini, Maria Giovanna
abstract

2007 - Archaeometric studies at the GILDA beamline at the European Synchrotron Radiation Facility [Articolo su rivista]
F, Dacapito; C, Maurizio; B, Brunetti; L, Cartechini; A, Sgamellotti; Arletti, R.
abstract

2007 - Colouring and opacifying agents in polycrome etruscan glass: archaeometric data from synchrotron μXRF, μXANES and XRPD. [Abstract in Atti di Convegno]
Arletti, Rossella; Vezzalini, Maria Giovanna; Quartieri, S.; Malnati, L.; Ferrari, D.; Dacapito, F.; Merlini, M. COTTE M.
abstract

2007 - Do you need an organic template? A comparison of man-made and natural synthesis of zeolites [Relazione in Atti di Convegno]
Arletti, R.
abstract

2007 - I colori di Piazza Armerina; caratterizzazione chimico-fisica di tessere in pasta vitrea. [Abstract in Atti di Convegno]
Sabatino, M.; Vezzalini, Maria Giovanna; Arletti, R; Mastelloni, M. A. QUARTIERI S.; Santalucia, F.; Triscari, M.
abstract

2007 - In situ study of dehydration of ECR-1: Na- as synthesized and NH4 exchanged in comparison [Relazione in Atti di Convegno]
Arletti, R.; GUALTIERI A., F; DI RENZO, F
abstract

2007 - Microporosity of the amorphous aluminosilicate precursors of zeolites: the case of the gels of synthesis of mordenite [Articolo su rivista]
A, Morsli; F, DRIOLE M.; T, Cacciaguerra; Arletti, R.; B, Chiche; F, Hamidi; A, Bengueddach; F, Quignard; F, DI RENZO
abstract

2007 - Mosaic glass from San Pietro (Rome-Italy): characterisation of late 15th century glass [Relazione in Atti di Convegno]
DE GIORGI, R; Arletti, R.; Fiori, C.; Vandini, M; Vezzalini, G
abstract

2007 - Neutron diffraction study of Bronze Age tools from second millennium BC dwellings in Italy [Articolo su rivista]
Arletti, R.; Cartechini, L.; Giovannini, S.; Rinaldi, R.; Kockelmann, W.; Cardarelli, A.
abstract

Neutron diffraction was utilized to characterise XX to XIII century BC bronze axes (Ancient to Late Bronze Age) from "Terramare" and other Bronze Age settlements near Modena, Italy. Archaeometric metallurgy issues have been addressed by means of phase and texture analysis from measurements carried out at the ROTAX and GEM beam lines of the neutron spallation source ISIS of the Rutherford Appleton Laboratory (UK), Neutron data provide accurate composition and structural information from the bulk of the alloy, with good grain statistics, without limitations due to surface alterations and with few limitations as to sample size. Bronze composition results are in good agreement with data obtained by micro-sampling and traditional analytical techniques thus confirming the validity of the method used for a totally non-destructive determination of the alloy composition from precise lattice parameter measurements. Phase analysis from diffraction profiles provides identification and quantification of surface alteration and corrosion products, free of interference with the analysis of the bulk alloy. Furthermore, texture analysis techniques may yield information on the ancient production methods of the artefacts. © Società Italians di Fisica.

2007 - Polychrome Etruscan glass: a non destructive study by mu XRF, mu XANES and XRPD [Abstract in Rivista]
Arletti, R; Vezzalini, Maria Giovanna; Quartieri, S; Ferrari, D; Merlini, M; Cotte, M.
abstract

2007 - Polychrome etruscan glass: first non destructive data from synchrotron μ-XRF, μ-XAS and XRDP [Relazione in Atti di Convegno]
Arletti, R.; QUARTIERI S, VEZZALINI G.; D, Ferrari; M, Cotte; M, Merlini
abstract

2007 - Produzione di vetro colorato per mosaico nella prima e tarda epoca bizantina. [Abstract in Atti di Convegno]
Fiori, C.; Vandini, M.; Arletti, Rossella; Vezzalini, Maria Giovanna
abstract

2007 - STABILIZATION OF A MICROPOROUS AMORPHOUS PRECURSOR OF MORDENITE BY CO2-INDUCED CHEMICAL CONDENSATION OF SILANOLS [Relazione in Atti di Convegno]
A, Mosli; F, DRIOLE M.; T, Cacciaguerra; Arletti, R.; B, Chiche; F, Hamidi; A, Bengueddach; DI RENZO F, QUIGNARD F.
abstract

2007 - Smalti Musivi dei Monasteri di Dafni e Hosios Lukas [Articolo su rivista]
C, Fiori; M, Vandini; Arletti, R.
abstract

2007 - Tecniche invasive, micro-invasive e non invasiva nello studio dei beni culturali [Relazione in Atti di Convegno]
Arletti, R.
abstract

2007 - Windows glass from I to V century A.D.: three Italian sites in comparison [Relazione in Atti di Convegno]
Arletti, R.; Benati, S; MAZZEO SARACINO, M; Vezzalini, G; Gamberini, A
abstract

2006 - Analisi Archeometriche di Pani di vetro e tessere musive siciliane di epoca bizantina [Abstract in Atti di Convegno]
Arletti, Rossella; Mastelloni, M. A.; Quartieri, S.; Sabatino, G.; Triscari, M.; Vezzalini, Maria Giovanna
abstract

2006 - Analisi Archeometriche di vetri musivi tardo-bizantini dal monastero di Dafni (Grecia) [Abstract in Atti di Convegno]
Fiori, C.; Vandini, M.; Arletti, Rossella; Vezzalini, Maria Giovanna
abstract

2006 - Analisi Archeometriche di vetri musivi trado-bizantini dal monastero di Dafni (Grecia) [Relazione in Atti di Convegno]
Fiori, C; Vandini, M; Arletti, R.; Vezzalini, G
abstract

2006 - Applications of neutron diffraction to the study of Archaic to Late Bronze age artefacts, [Relazione in Atti di Convegno]
Arletti, R.; R, Rinaldi; W, Kockelmann; S, Giovannini; A, Cardarelli
abstract

2006 - Archaeometric analyses of game counters from Pompeii [Capitolo/Saggio]
Arletti, R.; Ciarallo, A.; Quartieri, S.; Sabatino, G.; Vezzalini, G.
abstract

Among the glass finds of the Pompeii excavations, numerous objects of opaque and transparent glassy material of different colours were recovered and classified as game counters. The main aims of this work were to characterize these samples so as to identify the materials used as colorants and opacifying agents, and subsequently to deduce the technology used for their production. The results of the chemical and mineralogical analyses obtained for game counters were also compared with those obtained for transparent and opaque glass artefacts. The chemical analyses were carried out, using only 300 mg of sample, by both wavelength-dispersive electron microprobe and X-ray fluorescence analysis. The crystalline phases present in the opaque glass were identified using both an automatic X-ray powder diffractometer and a Gandolfi camera. Secondary and backscattered electron images were obtained to study the distribution and morphology of the opacifier particles, and qualitative chemical analyses were obtained with an energy-dispersive system. All the game counters analysed can be classified as silica-soda-lime glass. Two calcium antimonates (CaSb2O6 and Ca2Sb2 O7) were identified in the opaque white, green and blue glass, and Pb2Sb2O7 particles were detected in the opaque yellow glass. Particles of metallic copper were detected by both energy-dispersive system and X-ray powder diffraction. These results support the hypothesis that transparent game counters were obtained by remelting of fragments of common transparent artefacts. In contrast, opaque finds were probably produced using the glassy paste employed in the production of mosaic tesserae. © The Geological Society of London 2006.

2006 - COLOURING AND OPACIFYING AGENT IN POLICROME ETRUSCAN GLASS: ARCHAEOMETRIC DATA FROM SYNCHROTRON μ XRF, μ XAS AND μ XRD [Relazione in Atti di Convegno]
Arletti, R.; Vezzalini, G; Quartieri, S; Malnati, L; Ferrari, D; Dacapito, F; Merlini, M; Cotte, M
abstract

2006 - Diffrazione neutronica a tempo di volo applicata allo studio di utensili in bronzo del II millennio A.C. dalle Terramare [Relazione in Atti di Convegno]
R, Rinaldi; Arletti, R.; L, Cartechini; S, Giovannini; CARDARELLI A, KOCKELMANN W.
abstract

2006 - Glass cakes and mosaic tesserae from Messina (Sicily): an archaeometrical study. [Abstract in Atti di Convegno]
Arletti, Rossella; Quartieri, S.; Sabatino, G.; Triscari, M.; Vezzalini, Maria Giovanna; Mastelloni, M. A.
abstract

2006 - Glass mosaic tesserae from Pompei: an archeometrical investigation [Articolo su rivista]
Arletti, R.; Quartieri, S.; Vezzalini, Maria Giovanna
abstract

This work reports the results of an archaeometrical investigation performed, through a multitechniqueapproach, on a series of Roman glass mosaic tesserae found in Pompeii excavations.Chemical and mineralogical analyses of mosaic tesserae of different colours were performed inorder to single out the colouring and opacifying agents employed in Roman times. Moreover, dueto the paucity of information on the production technology of mosaic tesserae, the chemical dataare compared with that of common transparent glass found at the same site, in order to evaluatewhether vessels and mosaic tiles could have been prepared with the same recipes and startingfrom the same glass batch. The chemical analyses were performed by Electron Microprobe,whereas the mineralogical investigation on the opaque samples were carried out by couplingScanning Electron Microscopy and X-ray Powder Diffraction. The results obtained show that allthe analysed samples have the typical composition of natron-based glass. The similarities with thechemical composition - at least in terms of major elements - of common translucent glass couldsuggest the use of the same raw materials for the preparation of the batch. All opaque blue andgreen tesserae contain crystalline aggregates respectively of calcium and lead antimonates, exceptone blue tessera, which contains traces of cuprorivaite and quartz (Egyptian blue pigment). Thered sample shows the presence of cuprite aggregates dispersed in a lead-rich matrix.This paper is dedicated to the memory of friend and colleague Filippo Olmi, who prematurelypassed away few months ago.

2006 - Influence of dehydration kinetics on T-O-T bridge breaking in zeolites with framework type STI: the case of stellerite. [Articolo su rivista]
Arletti, R.; Mazzucato, E.; Vezzalini, Maria Giovanna
abstract

The thermally induced structural modifications of the natural zeolite stellerite [Ca8Al16Si56O144·58H2O, a = 13.5947(4), b = 18.1823(6), and c = 17.8335(6) Å, V = 4408.1(3) Å3, space group Fmmm, framework type STI] were studied in a temperature-resolved X-ray powder diffraction experiment, usingsynchrotron radiation, in the temperature range RT-976 K. In the initial stage of heating (below 430 K) Stellerite Phase A (space group Fmmm) is stable, and the cell volume decreases only 0.6% to thistemperature. Between 430 and 490 K most of the water is released, the symmetry lowers, and a phase transition to the collapsed so-called Phase B (space group Amma) is observed. In this phase rotation of the 4254 Secondary Building Units causes cell volume contraction and deformation of the channelsystem. This new phase, at 530 K, shows the statistical breaking of T-O-T bridges in the four-rings and the migration of tetrahedral atoms to new “face-sharing” tetrahedra, which partially occlude boththe channels parallel to [100] and to [001]. This framework deformation is interpreted as due to the strain induced by calcium atoms on the framework to achieve better coordination after the release of water. The new structure is stable up to 750 K and the total volume decrease is about 8%. The dehydration process causes a similar framework deformation and the transition to a collapsed phase characterized by the statistical breaking of T-O-T bridges in all zeolites with STI-type frameworks.However, comparing the results obtained with different thermal kinetics, it is possible to assume that the experimental conditions play a primary role in the mechanisms of dehydration and of framework bridge breaking.

2006 - PRODUZIONE DI VETRO COLORATO PER MOSAICO NELLA PRIMA E TARDA EPOCA BIZANTINA, CONGRESSO AIAR, COLORE E ARTE, STORIA E TECNOLOGIA DEL COLORE NEI SECOLI, [Relazione in Atti di Convegno]
C, Fiori; M, Vandini; Arletti, R.; Vezzalini, ; G,
abstract

2006 - Polycrome Etruscan glass: first archaeometric data from synchrotron mXRF, mXANES and XRPD [Abstract in Atti di Convegno]
Arletti, Rossella; Vezzalini, Maria Giovanna; Quartieri, S.; Malnati, L.; Ferrari, D.; Dacapito, F.; Merlini, M.; Cotte, M.
abstract

2006 - Polycrome Etruscan glass: first archaeometric data from synchrotron μXRF, μXANES and XRPD, [Relazione in Atti di Convegno]
Arletti, R.; Vezzalini, G; Quartieri, S; Malnati, L; Ferrari, D; Dacapito, F; Merlini, M; Cotte, M
abstract

2006 - Roman coloured and opaque glass: a chemical and spectroscopic study [Articolo su rivista]
Arletti, R.; Dalconi, M. C.; Quartieri, S.; Triscari, M; Vezzalini, Maria Giovanna
abstract

This work reports the results of an archaeometrical investigation of opaque Roman glass and is mainly focussed on the role of configuration and oxidation state of copper on the colour and opacity of red and green opaque finds (mosaic tesserae, game counters, and glass artefacts) from Sicily and Pompeii excavations. The glass fragments were characterisedby EMPA, SEM-EDS, TEM, and XRPD analyses and the copper local environment was investigated using X-ray absorption spectroscopy. The analyses of high-resolution Cu-K edge XANES and EXAFS spectra suggest that, in red samples, copper is present as monovalent cations coordinated to the oxygen atoms of the glass framework, accompanied by metallic clusters. In green samples all the copper cations are incorporated in the glass matrix.

2006 - Sicilian Early Bizantine glass finds: from analytical data to production and trade information [Abstract in Atti di Convegno]
Arletti, Rossella; Quartieri, S.; Sabatino, G.; Tigano, G.; Triscari, M.; Vezzalini, Maria Giovanna; Giacobbe, C.
abstract

2005 - Arcaeometrical analyses of glass cake and mosaic tesserae from Sicily [Abstract in Rivista]
Arletti, R.; Mastelloni, M. A.; Quartieri, S.; Sabatino, G.; Triscari, M.; Vezzalini, Maria Giovanna
abstract

2005 - Archaeometrical analyses of glass cake and mosaic tesserae from Sicily [Relazione in Atti di Convegno]
Arletti, R.; A, MASTELLONI M.; S, Quartieri; G, Sabatino; M, Triscari; G, Vezzalin
abstract

2005 - Archaeometrical analysis of glass of western Emilia Romagna (Italy) from the Imperial Age [Capitolo/Saggio]
Arletti, R.; Giordani, N; Tarpini, R; Vezzalini, G
abstract

2005 - Archeometrical analysis of glass of western Emilia Romagna (Italy) from the imperial age. [Capitolo/Saggio]
Arletti, Rossella; Giordani, N.; Tarpini, R.; Vezzalini, Maria Giovanna
abstract

Recent studies have allowed a typological and chronological characterization of Roman glass dated from the 1st to the 4th century AD. The samples have beenwere recovered from several archaeological sites during a surface survey on the plain South south of the river Po, which was a crucial transit area both via land and river. The chemical composition of 79 glass fragments of different typology was obtained by WDS-XRF and EMPA. The results were treated with hierarchical agglomerative cluster analysis. All the analysed samples resulted Silica-Soda-Lime glass. The differences in the chemical composition were mainly related to the colour and the age of the samples, whereas no relation was found with artefact typology or site of the find. The chemical composition of Padana plain glass was compared with literature data for samples of the same period coming from Aosta and Aquileia.

2005 - Bronze axes from pile dwellings of the second millennium BC, Italy. A neutron diffraction study [Relazione in Atti di Convegno]
R, Rinaldi; Arletti, R.; L, Cartechini; W, Kockelmann; S, Giovannini; A, Cardarelli
abstract

2005 - Colouring and opacifying agents in Roman glass: a multi-technique analytical approach [Abstract in Atti di Convegno]
Arletti, Rossella; Quartieri, S.; Sabatino, G.; Triscari, M.; Vezzalini, Maria Giovanna
abstract

2005 - Copper bearing Roman Glass: XAFS investigations. [Abstract in Atti di Convegno]
Arletti, Rossella; Dalconi, M. C.; Quartieri, S.; Triscari, M.; Vezzalini, Maria Giovanna
abstract

2005 - Dehydration dynamics of Stellerite: a synchrotron radiation XRPD study [Relazione in Atti di Convegno]
Arletti, R.; Mazzucato, E; Vezzalini, G
abstract

2005 - High-pressure behaviour of yugawaralite at different water content: an ab initio study. [Capitolo/Saggio]
Fois, E.; Gamba, A.; Tabacchi, G.; Quartieri, S.; Arletti, R.; Vezzalini, Maria Giovanna
abstract

The influence of the water content in a partially occupied water site in yugawaralite on the pressure-induced structural modifications of this zeolite has been studied by means of ab initio molecular dynamics simulations. The effect of the water site occupancy has been singled out by comparing results from simulations, performed with the cell parameters determined via XRPD at rP and 8.8 GPa, on two model systems whose cell stoichiometry differs only by the presence of a water molecule in such a site. Our results show that the global P-induced changes of the framework structure upon compression are mainly attributable to the template effect of Ca extra-framework cations, while the presence or absence of water in a partially occupied site affects the framework structure only at short range distances from the site. However, the overall water content plays a fundamental role in stabilizing/destabilizing the zeolite structure as a function of pressure.

2005 - Il vetro musivo dell XI secolo del monastero di Dafni (Atene, Grecia) [Abstract in Atti di Convegno]
Fiori, C.; Vandini, M.; Arletti, Rossella; Vezzalini, Maria Giovanna
abstract

2005 - Il vetro opaco in epoca romana: studi spettroscopici in luce di sincrotrone su reperti da Pompei e siti siciliani [Relazione in Atti di Convegno]
Arletti, R.; Quartieri, S; Sabatino, G; Triscari, M; Vezzalini, G
abstract

2005 - Indagini archeometriche su vetri pompeiani: il caso delle pedine da gioco. [Capitolo/Saggio]
Arletti, R.; Ciarallo, A.; Quartieri, S.; Sabatino, G.; Vezzalini, Maria Giovanna
abstract

Tra i reperti vitrei rinvenuti negli scavi di Pompei si riconoscono piccoli oggetti di pasta vitrea classificati come pedine da gioco. Essi presentano un’ampia gamma di colorazioni e sono quindi di grande interesse per indagini di carattere archeometrico essenzialmente rivolte allo studio dei coloranti e degli opacizzanti utilizzati in epoca romana. A questo scopo sono state eseguite analisi morfologiche, chimiche e mineralogiche su 8 campioni opachi e 2 trasparenti. Le analisi chimiche sono state ottenute utilizzando microsonda elettronica, fluorescenza a raggi X e spettrometria EDS. Per identificare la natura delle fasi cristalline presenti all’interno delle paste vitree sono stati raccolti spettri di diffrazione a raggi X. I risultati ottenuti hanno permesso di individuare la presenza di agenti opacizzanti all’interno delle 8 pedine opache, quali antimoniati di calcio e piombo e particelle metalliche di rame. Al contrario, all’interno delle pedine trasparenti non sono state rinvenute particelle cristalline.

2005 - Ipotesi di una produzione primaria di vetro in epoca romana nelle terre dell’attuale Canton Ticino [Abstract in Atti di Convegno]
Arletti, Rossella; BIAGGIO SIMONA, S.; CARDANI VERGANI, R.; Vezzalini, Maria Giovanna
abstract

2005 - Ipotesi di una produzione primaria di vetro in epoca romana nelle terre dell’attuale Canton Ticino, XI giornate di Studio del comitato nazionale Italiano AIHV, Bologna,Italy December,16-18 2005 [Relazione in Atti di Convegno]
Arletti, R.; BIAGGIO SIMONA, S; CARDANI VERGANI, R; Vezzalini, G
abstract

2005 - LA –ICP-MS study of trace elements in Bizantine glass finds from Ganzirri (Messina, I) [Abstract in Rivista]
Sabatino, G.; Arletti, R.; Quartieri, S.; Tigano, G.; Triscari, M.; Vezzalini, Maria Giovanna; Giacobbe, C.
abstract

2005 - Mazzite-Na, a new zeolite from Boron, California: Its description and crystal structure [Articolo su rivista]
Arletti, R.; Galli, Ermanno; Vezzalini, Maria Giovanna; Wise, W. S.
abstract

Mazzite-Na, Na(8)Al(8)Si(28)O(72)center dot 30H(2)O, is a new zeolite mineral species occurring in basalt at the bottom of the open pit of the U.S. Borax mine at Boron, California. It crystallizes as white, very thin, flexible fibers up to 2 mm in length, and commonly fills small cavities as satiny mats. The luster is vitreous, and the streak is white. The fineness of the fibers precludes the determination of the hardness and the observation of any cleavage. The observed and calculated densities are 2.16 and 2.18 g/cm(3), respectively. The mineral is uniaxial positive with n(epsilon) = 1.472(3) and n(omega) = 1.471(3). Electron-microprobe analyses yielded (in wt%) SiO2 57.65, Al2O3 14.35, Fe2O3 0.65, MgO 0.22, CaO 0.18, BaO 0.14, Na2O 8.07, K2O 0.03, and H2O 18.70 (TG analysis), which gives the empirical cell contents (Na7.52K0.02Mg0.16Ca0.09Ba0.03)[Fe0.24Al8.13Si27.71O72]center dot 29.98H(2)O. Mazzite-Na is hexagonal, P6(3)/mmc, a = 18.2343(7), c = 7.6371(2) angstrom, Z = 1. The strongest seven measured X-ray lines [d in angstrom(I)(hkl)] are: 9.08(100)(110), 6.86(70)(101), 5.95(70)(210), 4.681(40)(211), 3.787(80)(002), 3.511(40)(112), and 3.150(70)(500). The framework consists of columns of gmelinite cages parallel to c, cross-linked to form two types of channels; one has an elliptical 8-ring cross section and the other has a circular 12-ring cross section. The extra-framework Na cations are located at three different sites. NaI is at the center of the 6-ring between adjacent gmelinite cages and is coordinated by six framework oxygen atoms and two H2O molecules. NaII lies on the centerline of the 8-ring channel and is coordinated by four framework oxygen atoms and two H2O molecules. NaIII occupies sites along the walls of the 12-ring channel and is coordinated with two framework oxygen atom and four H2O molecules. With the naming of this mineral for its Na dominant composition the original mineral is renamed mazzite-Mg, and the name mazzite is raised to series status.

2005 - Microanalysis and cultural heritage: microdestructive analyses on archaeological finds [Relazione in Atti di Convegno]
Arletti, R.; S, Bigi; S, Giovannini
abstract

2005 - SR-XRD for the structural characterization of zeolites at ambient and non- ambient conditions [Relazione in Atti di Convegno]
Arletti, R.; Galli, E; Vezzalini, G; Mazzucato, E; WISE W., S
abstract

2005 - The Ancient Glass Production: XAFS study on Roman opaque glass [Relazione in Atti di Convegno]
Arletti, R.; DALCONI M., C; Quartieri, S; Sabatino, G; Triscari, M; Vezzalini, G
abstract

2005 - The opaque Roman Glass: synchrotron radiation studies on tesserae from Pompeii and Sicily [Relazione in Atti di Convegno]
Arletti, R.; DALCONI M., C; Quartieri, S; Sabatino, G; Triscari, M; Vezzalini, G
abstract

2005 - The “template” effect of the extra-framework content on zeolite compression: The case of yugawaralite. [Articolo su rivista]
Fois, E.; Gamba, A.; Tabacchi, G.; Arletti, R.; Quartieri, S.; Vezzalini, Maria Giovanna
abstract

The microscopic behavior of the Ca-zeolite yugawaralite has been studied by ab initio moleculardynamics simulations adopting experimental cell parameters obtained at pressures up to ∼9 GPa.Pressure-induced volume contraction occurs via rotations of quasi-rigid TO4 tetrahedra that reducethe size of the channels in which the extra-framework species are located. Such rotations are governedby deformation of the coordination polyhedron of Ca, which is made up of water and framework Oatoms. Contraction of the Ca-H2O distances is favored at moderate pressure; at higher pressure theshortening of Ca-framework O atom distances becomes prevalent. The hydrogen bond network playsa fundamental role in the overall response to pressure. Our results indicate that the high-P-induceddeformation of the framework structure is strictly correlated to the extra-framework species that actas templates in the compression process.

2005 - Vetri di epoca romana dal Canton Ticino: una produzione locale? [Relazione in Atti di Convegno]
Arletti, R.; BIAGGIO SIMONA, S; CARDANI VERGANI, R; Vezzalini, G
abstract

2004 - Archaeometrical analyses of game counters of Pompei [Relazione in Atti di Convegno]
Arletti, R.; Ciarallo, A; Quartieri, S; Sabatino, G; Vezzalini, G
abstract

2004 - Archaeometrical analyses of game counters of glass from Pompeii: the case of game counters [Relazione in Atti di Convegno]
Arletti, R.; Ciarallo, A; Quartieri, S; Sabatino, G; Vezzalini, G
abstract

2004 - Atomistic interpretation of the high-pressure behavior of the zeolite yugawaralite [Relazione in Atti di Convegno]
Fois, E; Gamba, A; Tabacchi, G; Quartieri, S; Arletti, R.; Vezzalini, G
abstract

2004 - Dehydration dynamics of Stellerite : a synchrotron XRPD study [Relazione in Atti di Convegno]
Arletti, R.; Mazzucato, E; Vezzalini, G
abstract

2004 - Il contributo delle analisi archeometriche alla ricostruzione del quadro della circolazione dei manufatti vitrei lungo l’asse padano: materiali dal Modenese e da Aquileia a confronto, [Relazione in Atti di Convegno]
Arletti, R.; N, Giordani; F, MASELLI SCOTTI; R, Tarpini
abstract

2004 - Indagini archeometiche di pedine da gioco provenienti da Pompei [Relazione in Atti di Convegno]
Arletti, R.; Ciarallo, A; Quartieri, S; Sabatino, G; Vezzalini, G
abstract

2004 - Indagini archeometriche su vetri pompeiani: il caso delle pedine da gioco [Capitolo/Saggio]
Arletti, Rossella; Ciarallo, A.; Quartieri, S.; Sabatino, G.; Vezzalini, Maria Giovanna
abstract

2004 - Opacizzanti e cromofori in tessere vitree romano: esempi da Pompei e siti siciliani [Relazione in Atti di Convegno]
Arletti, R.; CIARALLO A., M; MASTELLONI M., A; Quartieri, S; Sabatino, G; Triscari, M; Vezzalini, G
abstract

2004 - The contribution of archaeometrical analyses in the reconstruction of the circulation of glass artifacts across the Po plain: materials from the Modena area and Aquileia compared [Relazione in Atti di Convegno]
Arletti, R.; N, Giordani; F, MASELLI SCOTTI; R, Tarpini
abstract

2003 - Structural deformation mechanisms of zeolites under pressure [Articolo su rivista]
Arletti, R; Ferro, O; Quartieri, S; Sani, A; Tabacchi, G; Vezzalini, Maria Giovanna
abstract

The HP behavior of the natural zeolite yugawaralite and of the synthetic zeolite Na-A was studiedby in situ synchrotron X-ray powder diffraction, using a non-penetrating P-transmitting medium. Theunit-cell parameters of yugawaralite were refined up to the pressure of 10 GPa, at which reductionswere found of about 7, 2.4, 7, 1.3, and 15% for a, b, c, b, and V, respectively. Contractions of 6.5 and18.4% were found for a and V, respectively, for zeolite Na-A in the range 10–4 to 6.8 GPa. Diffractionpatterns collected during decompression show that the effects induced by high pressure on both samplesare almost completely reversible. These results are compared with those obtained under similar experimentalconditions for other natural zeolites, with the aim of rationalizing the deformation mechanismsof these porous materials and comparing their flexibility under high-pressure and high-temperatureconditions.

2001 - Gelatin microspheres crosslinked with D,L-glyceraldehyde as a potential drug delivery system: preparation, characterisation, in vitro and in vivo studies [Articolo su rivista]
Vandelli, Maria Angela; Rivasi, Francesco; Guerra, P.; Forni, Flavio; Arletti, R.
abstract

To overcome the restriction in using crosslinked gelatin in the pharmaceutical field, D,L-glyceraldehyde (GAL), a non-toxic crosslinking agent, was proposed. Gelatin microspheres crosslinked with different concentrations of GAL (0.5, 1 or 2%, w/v) and for different time periods (1 or 24 h) were prepared. The effect of the preparation variables was evaluated analysing the extent of crosslinking, the morphological aspect, the particle size and the swelling behaviour. To evaluate the pharmaceutical properties, an antihypertensive drug, clonidine hydrochloride, was chosen as drug model and loaded into the microspheres. Either the increase of the crosslinker concentration or of the crosslinking time period decreased both the swelling and the in vitro drug release processes of the microspheres. After the subcutaneous injection, the loaded microspheres crosslinked with the lowest GAL concentration (0.5%. w/v) or for the shortest time period (1 h) showed a reduction of systolic blood pressure (SBP) similar to that recorded with a clonidine hydrochloride solution having the same drug concentration. Instead, the microspheres crosslinked for 24 h with concentrations of GAL higher than 0.5% (w/v) produced a more gradual and sustained SEP reduction and the antihypertensive effect was maintained until 52-72 h. The biocompatibility studies showed that the microspheres crosslinked with GAL are well tolerated in vivo. These results suggest the potential application of gelatin microspheres crosslinked with GAL as a suitable drug delivery system for the subcutaneous administration. (C) 2001 Elsevier Science B.V. All rights reserved.

Università degli studi di Modena e Reggio Emilia

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