Localization of n-alcohols and structural effects in aqueous solutions of sodium dodecyl sulfate

Small-angle neutron Mattering measurements OD sodium dodecyl sulfate aqueous solutions have been performed in the presence of n-alcohols, from methanol to octanol, at different alcohol concentrations. By modeling the experimental intensities, it was possible to obtain structural information and to derive simultaneously the distribution of the alcohols between the aqueous and the micellar phases. It was found that short chain alcohols tend to remain in the aqueous phase and, by altering the solvent properties, induce a decrease in the aggregation number of sodium dodecyl sulfate micelles. On the other hand, alcohols with longer hydrocarbon chains were found to be present in both phases thoug…

Sintesi di materiali silicei mesoporosi per catalisi eterogenea

Identification Techniques I

Infrared (IR) and Raman spectroscopy have a high potential for characterisation of material. Extensive series of wet chemical analysis may be substituted by a single spectroscopic measurement followed by detailed chemometric data evaluation. Topics of this chapter are: (i) basics of IR and Raman spectroscopy, (ii) the registration of “correct” spectra, and (iii) spectra evaluation. Dedicated applications in the area of conservation science are collected in separate chapters. The infrared (IR) spectrum is often called the fingerprint of a substance. An IR spectrum identifies a substance like a human fingerprint. Due to their origin the features of an IR spectrum are bands, not peaks. They in…

Mechanical treatment of TiO2 and ZrO2 oxide mixtures

The mixed ZrO2–TiO2 system (5–50 wt% of ZrO2) has been studied to investigate the influence of the mechanical treatment on its physicochemical properties depending on the composition, time of milling (5, 10 and 20 min, r.p.m. 82) and temperature (400, 550 and 700 C). Samples were characterized by Raman spectroscopy, X-ray powder diffraction, Scanning Electron Microscopy coupled with Energy Dispersion X-ray analyzer, High Resolution-Transmission Electron Microscopy and nitrogen adsorption porosimetry. Results show that srilankite (TiZrO4) phase has been produced. No influence of the milling time and temperature on the phase composition is observed. The presence of zirconia increases the ther…

Applicazione di dispersioni idroalcoliche di nanocalce a due casi studio: i Graffiti del carcere dello Steri e un documento d’archivio della Gran Corte Arcivescovile di Palermo

A step forward in disclosing the secret of stradivari's varnish by NMR spectroscopy

It is commonly thought that the varnishes used by the great violin-maker Antonio Stradivari may have a role in determining not only the esthetical features but also the acoustic properties of his instruments, and the idea of a “lost secret” is still widespread among musicians and violin-makers. Previous scientific researches on varnish samples of Stradivari's instruments revealed that they were generally made by a mix of linseed oil with and colophony or metal rosinates in different ratios ranging between 75/25 (oil/resin) and 60/40 (oil/rosinate). However, it is still not clear whether the mixture composition can be related to any structural and/or functional feature of the resulting varni…

Effect of the cerium loading on the HMS structure. Preparation, characterization and catalytic properties

Abstract Ce–HMS mesoporous materials were prepared by incipient wetness method starting from HMS synthesized in acid condition. The effect of cerium quantity, in the range of Ce/Si atomic ratio 0.02–0.3, on its structure and properties was investigated. Results showed that the HMS hexagonal structure was maintained after the cerium adding. Furthermore, the surface area and the pore volume were reduced. The presence of the cerianite nanoparticles located within the HMS channels up to 0.05, thus covering the HMS surface at higher Ce/Si atomic ratio, was observed. The catalytic performances of the materials were tested in ethanol partial oxidation reaction.

The effect of silica nanoparticles on the morphology, mechanical properties and thermal degradation kinetics of PMMA

Abstract Silica–PMMA nanocomposites with different silica quantities were prepared by a melt compounding method. The effect of silica amount, in the range 1–5 wt.%, on the morphology, mechanical properties and thermal degradation kinetics of PMMA was investigated by means of transmission electron microscopy (TEM), X-ray diffractometry (XRD), dynamic mechanical analysis (DMA), thermogravimetric analyses (TGA), Fourier-transform infrared spectroscopy (FTIR), 13 C cross-polarization magic-angle spinning nuclear magnetic resonance spectroscopy ( 13 C{ 1 H} CP-MAS NMR) and measures of proton spin-lattice relaxation time in the rotating frame ( T 1 ρ ( H )), in the laboratory frame ( T 1 ( H )) a…

Microwave Assisted Synthesis of dry CdS Nanoparticles in Water in Oil Microemulsion

Micro-X-Ray Fluorescence and the Old Masters Non-destructive in situ characterisation of the varnish of historical Low Countries stringed musical instruments

Applied Physics A, 107

Newly discovered orichalcum ingots from Mediterranean sea: Further investigation

Abstract In February 2016, 47 ingots were found in the seabed of Contrada Bulala (Gela, CL, Italy) near the site where 40 ingots had previously been recovered. The ingots composition was determined to be a Cu - Zn alloy, dated by the archaeologist to the VI century B.C. This specific alloy was then known as Orichalcum. From an archaeological point of view, the first question raised about the new discovery was whether the ingots of the first and the second excavations belonged to the same shipwreck. Following the previous study, an elemental analysis was performed on the ingots from the second finding by using ICP-OS and ICP-MS techniques. The chemometric treatment of the analytical results …

Sintesi e caratterizzazione di compositi polimetilmetacrilato e nano-SiO2, -TiO2 o -ZrO2

Interaction of Gold with Co-Condensed and Grafted HMS-SH Silica: A 29Si {1H} CP-MAS NMR Spectroscopy, XRD, XPS and Au LIII EXAFS Study

Hexagonal mesoporous silica (HMS) is functionalised with mercaptopropyl groups by adopting two different procedures ; co-condensation and grafting. In both cases tetraethylorthosilicate (TEOS) and 3-mercaptopropyltriethoxysilane (3-MPTES) are used as the silicon and sulfur precursors, respectively. The obtained materials are analysed by several techniques such as N 2 sorption, TG-DTA, XRD, SAXS and-solid state 29 Si { 1 H} CP-MAS NMR spectroscopy. By taking advantage of the chemical interaction between gold and the -SH groups, the effect of the thiol addition procedure on the supporting capability of the functionalised silica is evaluated by depositing gold through the incipient wet impregn…

Loading and release of the complex [Pt(DTBTA)(DMSO)Cl]Cl·CHCl3 with the 2,2′-dithiobis(benzothiazole) ligand into mesoporous silica and studies of antiproliferative activity on MCF-7 cells

Abstract Synthetic delivery systems have great potential for overcoming problems associated with systemic toxicity that accompanies chemotherapy with the use of cisplatin and family of platinum anticancer drugs. Mesoporous silicates have been studied in context of drug delivery and drug targeting. In this paper we report the studies of loading and release of a platinum complex, [Pt(DTBTA)(DMSO)Cl]Cl∙CHCl3 (1) where DTBTA = 2,2′-dithiobis(benzothiazole), that was recently synthesized and structurally characterized. Evaluation in vitro of antitumor activity against a human breast cancer cell line (MCF-7) showed a very potent activity of complex(1). Therefore, we thought to incorporate this co…

Applying the Techniques on Materials I

The knowledge of the composition of the natural dye mixtures gives hints on appropriate procedures for restoration strategies. Identification of the dyes used, the establishment of their biological source, how they have been prepared, how these historical textiles were made, can provide important information. The dyestuffs used up to nineteenth century were either of plant (weld, madder, indigo, etc.) or animal origin (cochineal, shellfish, etc.) and belonged to various chemical types, such as flavonoids (yellow), anthraquinones (red) and indigoids (blue and violet). In this study microsamples (19) were examined from 11 Mevlana’s kaftans, dervishs’ dresses and dated from the thirteenth cent…

Effects of thermal treatment on Eu:YAG nanopowder structure

Analysis of small-angle scattering patterns from a commercial Al-Li alloy by means of a model incorporating a repulsive step potential

Abstract Small-angle X-ray scattering measurements are reported for a commercial Al-8·49%Li-51% Cu (atomic composition) alloy solution treated at 520°C and thermally aged for several times at several temperatures. Data have been analysed by means of a model of ellipsoidal precipitate particles previously proposed by some of us and by a modification of this model where, in the interparticle interference term, allowance is made for interactions between the precipitate particles at longer range than previously. This was achieved by the introduction, in addition to the hard-sphere interaction potential, of a potential step. Our fits indicate that the precipitate particles interact through a rep…

H and 19F NMR Investigation on Mixed Hydrocarbon−Fluorocarbon Micelles

1H and 1 9 F NMR measurements on aqueous solutions of sodium perfluorooctanoate (SPFO) and sodium dodecanoate (SD) mixtures are reported. The surfactant concentration ranged from ∼0.3 to 10 times the critical micelle concentration (cmc ≅ 0.03 mol L - 1 ). The cmc of the SD/SPFO/water mixed system obtained from NMR data was in good agreement with that previously obtained by conductivity measurements. Below the cmc, the experimental chemical shift (δ) was independent of the total concentration for both surfactants. Above the cmc, however, the 6 values for 1 9 F varied linearly with concentration, whereas the values for the hydrogenated surfactant deviated from linearity. These observations in…

PREPARAZIONE E CARATTERIZZAZIONE DI SISTEMI A RILASCIO CONTROLLATO PER APPLICAZIONI SU MANUFATTI DI INTERESSE STORICO-ARTISTICO

Lo scopo di questo studio è la realizzazione e lo studio di sistemi a rilascio controllato costituiti da silice mesoporosa MCM-41 e biocidi commerciali e di nuova generazione. Tali materiali possono essere utilizzati in ambito conservativo per risolvere alcuni problemi di biodeterioramento che interessano i manufatti di interesse storico-artistico e a scopo preventivo per ridurre il numero e la frequenza di interventi conservativi. La MCM-41 è stata preparata in ambiente alcalino mediante il metodo sol-gel utilizzando dei tensioattivi come templanti1. Al fine di creare un’interazione favorevole biocida-superficie, sulla superficie dei pori sono stati ancorati gruppi amminici. L’incapsulamen…

Synthesis and characterization of Nd:YAG nanopowders

Structural effects of macrocyclic compounds and their partition in sodium dodecylsulphate aqueous solutions

The partition of 1,4,7,10,13,16-esaoxacyclooctadecane (18C6), 4,7,13,16-tetraoxa-1,10-diazacyclooctadecane (2.2), 2,5,8,11,14,17-esaoxabicyclo[16.4.0]dicosane (B18C6) and 2,5,8,15,18,21-esoxatricyclo[20.4.0.09.14]esacosane (Cy218C6) in sodium dodecyl sulfate (SDS) aqueous solutions and their effect on the structure of surfactant aggregates has been investigated by small-angle neutron scattering. Results from data analysis have shown that by increasing macrocycle concentration the SDS micelles dimensions reduce for all systems investigated. At the same time information on macrocycles partition between the micellar and the continuous phase have been obtained. It was found that an appreciable …

Il restauro di due delle tavolette “fuori posto” “Abbraccio di due Amanti” e “Drôlerie “ provenienti dal soffitto ligneo dell’Aula Magna dello Steri di Palermo. Indagini sul degrado e sulla tecnica esecutiva a supporto della conservazione.

Le Tavolette fuori posto sono un unicum di quattro dipinti su tavola, oggi di proprietà della Galleria Interdisciplinare Regionale di Palazzo Abatellis di Palermo. Nell’ambito di questo lavoro, eseguito per una tesi di laurea del CdLM in Conservazione e Restauro dei BB.CC. dell’Università di Palermo [1], è stato condotto uno studio approfondito su queste quattro opere sia dal punto di vista storico-artistico che scientifico per conoscere la tecnica esecutiva ed i materiali posti in opera, lo stato di conservazione e per verificare l’ipotesi di appartenenza al soffitto ligneo dell’Aula Magna dello Steri di Palermo. La campagna di diagnostica è stata propedeutica al restauro per indirizzare l…

PROCESSING AND CHARACTERIZATION OF THE POLYMER/CNTs NANCOMPOSITE FIBRES.

PBI-based composite membranes for polymer fuel cells

Abstract In the present study poly(2,2-(2,6-pyridin)-5,5-bibenzimidazole) was used for the preparation of novel MEAs for high-temperature polymer fuel cells (HT-PEMFCs). We prepared hybrid materials with two types of silica fillers in order to increase the MEA performances using this polymer. The membranes were characterized in terms of their microstructure and thermal stability. Cell operation tests and Electrochemical Impedance Spectroscopy were used for the characterization of the MEAs. A maximum power density of about 80 mW cm−2 was obtained at 300 mA cm−2 by using an imidazole-modified silica filler. The EIS technique showed that the fillers chiefly help to reduce the charge transfer r…

Microwave-assisted synthesis of anhydrous CdS nanoparticles in a water-oil microemulsion.

Abstract Microwave irradiation at a frequency of 2.45 GHz and a power ranging between 22 and 30 W was used, in a water–oil microemulsion at 35 ± 2 ° C , to obtain stable, small, crystalline, anhydrous CdS nanoparticles exhibiting enhanced luminescence properties. The process of nanoparticles growth at different irradiation times was followed by UV–vis spectroscopy. It was observed that irradiated nanoparticles grew faster and their size reached a constant value. The final mean nanoparticle diameter was 2.7 nm, smaller than that observed in a non-irradiated sample, in which particle dimensions slowly increased even after 10 h. This finding was confirmed by high resolution transmission electr…

Phase formation in mixed TiO2-ZrO2 oxides prepared by sol-gel method

Pure titania, zirconia, and mixed oxides (3—37 mol.% of ZrO2) are prepared using the sol-gel method and calcined at different temperatures. The calcined samples are characterized by Raman spectroscopy, X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, and nitrogen adsorption porosimetry. Measurements reveal a thermal stability of the titania anatase phase that slightly increases in the presence of 3—13 mol.% of zirconia. Practically, the titania anatase-rutile phase transformation is hindered during the temperature increase above 700 C. The mixed oxide with 37 mol.% of ZrO2 treated at 550 C shows a new single amorphous phase with a surface area of the…

Dispersioni idroalcoliche di nanocalce: sviluppo di nuovi metodi di sintesi e loro caratterizzazione

How Many Secret Details Could a Systematic Multi-Analytical Study Reveal About the Mysterious Fresco Trionfo della Morte?

The &ldquo

Photochemical synthesis of pyrene perfluoroalkyl derivatives and their embedding in a polymethylmethacrylate matrix: a spectroscopic and structural study

A photochemical, alternative and eco-compatible approach to perfluoroalkyl derivatives of pyrene is presented. The perfluoroalkyl chain is regiospecifically introduced at the 1 position of pyrene. The synthesized products have been embedded in a polymethylmethacrylate matrix by photocuring at 365 nm. Both the photochemical reactions can be considered a “green tool” for the synthetic chemist in order to obtain materials with prospective optoelectronic applications. The so-obtained composites have been the object of a study by UV and fluorescence spectroscopy in order to explore their luminescence properties. The small angle X-ray scattering and the transmission electron microscopy techniques…

Physicochemical Characterization Of Ancient Paper And Parchment With Solid State Nuclear Magnetic Resonance

Historical paper and parchment are widely investigated in order to comprehend mechanisms of degradation and to plan proper conservation interventions. NMR spectroscopy is a powerful tool that allows to the changes occurring during the degradation process and to get information on the state of conservation. In this work a Cross Polarization Magic Angle Spinning Nuclear Magnetic Resonance (13C{1H} CP MAS NMR) study of a 16th century book is reported. The physicochemical characterization of paper samples collected from the book was performed through the evaluation of intensity and the changes in line width of signals in the spectra. 13C{1H} CP MAS NMR spectra of paper samples collected from th…

Preparation of Nd:YAG Nanopowder in a Confined Environment

Nanopowder of yttrium aluminum garnet (YAG, Y3Al5O12) doped with neodymium ions (Nd:YAG) was prepared in the water/cetyltrimethylammonium bromide/1-butanol/n-heptane system. Aluminum, yttrium, and neodymium nitrates were used as starting materials, and ammonia was used as a precipitating agent. Coprecipitate hydroxide precursors where thermally treated at 900 degrees C to achieve the garnet phase. The starting system with and without reactants was characterized by means of the small-angle neutron scattering technique. The system, without reactants, is constituted by a bicontinuous structure laying near the borderline with the lamellar phase region. The introduction of nitrates stabilizes th…

Preliminary studies on nanocomposite based on high quality Silicon Carbide nanofibers

Nanocomposites are nowadays the most promising new materials due to their unique properties (such as high mechanical strength, chemical and thermal resistance). The nanocomposite matrix is blended with a nanostructured filler. In this study, Silicon Carbide nanofibers (NFSiC) and their bundles were tested as a reinforcement of two epoxy resins: EPIKOTE 828 and EL 20. PAP-4 (33 phr) and P-900 (40 phr) were used as hardeners in the two cases, respectively. Several samples were prepared in the range between 0.1 and 5 % wt for both types of resins and fillers (NFSiC and NFSiC bundles). Mechanical and electrical properties were tested. The fillers were obtained using a new simple, fast, low-cost…

Impact of the inclusion of hydrotalcite on the morphological and electrical characteristics of an epoxy-based CNT nanocomposite

The experimental results concerning the correlation between morphological and electrical characteristics of a MWCNT/epoxy based composites are presented. The impact of a nanoclay filler is investigated on the DC conductivity of a matrix loaded with different concentrations of MWCNT in order to evaluate the improvements on the dispersion of CNT inside the epoxy matrix. The dispersion is deemed to be very influencing on the electrical conductivity of the nanocomposite. A detailed morphological and structural characterization allows to interpret the electrical behaviour of the nanocomposites. © 2012 IEEE.

Small-Angle Scattering from Phase-Separated Metallic Alloys: From Experiment to Phase Diagrams

In this paper, phase-separated metallic alloys are described in terms of concentration fluctuations. As a consequence, Small Angle Scattering equations which allow to calculate the entire scattering curve by incorporating particle-particle interference effects on the basis of the Percus-Yevick formalism, are obtained. It is shown that, for Aluminium-Lithium alloys, satisfactory fits of the experimental data can be obtained if it is assumed that Li rich elliptical monodisperse precipitate particles approach each other at average distances which are larger than the sum of the hard-sphere particle radii. It is also shown that a possible ambiguity of this model, within the Percus-Yevick formali…

Role of ZrO2 addition on the formation and stabilisation of anatase catalyst: XRD, SAXS and TEM investigation

Sviluppo del metodo urea glass-route per la preparazione di nanoparticelle di Ce:YAG

I materiali a base di yttrium aluminum garnet (YAG) drogato con ioni lantanidi hanno suscitato negli ultimi anni notevole interesse per le loro importanti applicazioni tecnologiche nel campo dei dispositivi optoelettronici quali laser, LED, display e scintillatori per i raggi X. In particolare, lo YAG drogato con ioni Ce(III) è utilizzato, in combinazione ai semiconduttori di nitruro di gallio (GaN) o indio e gallio (GaInN), per la realizzazione di LED a luce bianca1. Il miglioramento delle performance di questi dispositivi è vincolato all’ottimizzazione, in termini di proprietà, dei materiali che lo compongono. Una delle strategie consiste nel preparare nanoparticelle (np) di Ce:YAG con di…

Ce:YAG composites for white LED

Composites and luminescent polymers have been recently found to be potential candidates for the development of white LED, lasers and luminescent concentrators for solar cells. Due to its luminescence properties YAG doped with lanthanides ions is a good candidate as light emitting filler. In a recent our work, the preparation of a polymeric nanocomposite containing Ce:YAG nanoparticles using in situ polymerization has been reported [1]. A good dispersion of Ce:YAG nanoparticles has been obtained maintaining them luminescence properties. In addition, an increase of thermal stability and stiffness of PMMA was observed [2]. Then, the preparation of Ce:YAG-PMMA composite has been performed by us…

Synthesis, characterization and antimicrobial activity of polyaminocyclodextrin-capped Ag Nanoparticles

Biocompatible Ag nanocomposites were prepared by photoreduction of ammoniacal silver acetate in the presence of a polyaminocyclodextrin, namely the poly-{6-[3-(2-(3-aminopropylamino)-ethylamino)-propylamino]}-(6-deoxy)-b-CD (amCD, figure 1). The obtained Ag-amCD systems, which possess an oniontype structure [1] with a metal core surrounded by several layers of the capping agent, were characterized by means of various complementary techniques. In particular, FT-IR spectroscopy confirmed the presence of the amCD scaffold in the composite, and evidenced a partial oxidative degradation of the polyamine branches,due to the fact that these groups function as sacrificial reducing agents in the pho…

Synthesis of yttrium aluminum garnet nanoparticles in confined environment III: Cerium doping effect

Abstract Cerium yttrium aluminum garnet (Ce:YAG, CexY3-xAl5O12) nanoparticles doped with different cerium amount were obtained by calcining the precursors synthesized via co-precipitation in w/o microemulsion for 1 h at 900 °C. The structural and morphological properties were investigated by using X-ray Diffraction (XRD), Infrared Spectroscopy (IR) and Transmission Electron Microscopy (TEM) coupled with Energy Dispersive X-ray Spectroscopy (EDS) in order to investigate the effect of doping level on formation and microstructure of obtained nanoparticles. It was found that the composition of the final products strongly depends on the concentration of cerium. The formation of single YAG phase …

Non-Invasive Investigation of Pigments of Wall Painting in S. Maria Delle Palate di Tusa (Messina, Italy)

The characterization of materials used in the archaeological field needs an experimental approach in order to avoid the destruction or perturbation of artworks. In order to afford this purpose, a multi-analytical spectroscopic approach is regularly used. We combined non-invasive analysis by using handheld spectroscopic instrumentations (mainly XRF and Raman spectrometers) in order to characterize the wall painting preserved in the church of S. Maria delle Palate at Halaesa Arconidea archeological site (Tusa, Messina, Italy). The aim of the work is the characterization of the nature of pigments used for the realization of the wall painting. The wall painting, probably representing St. Franci…

Effect of elongational flow on morphology and properties of Polymer/CNTs nanocomposite fibres

Effectiveness of some protective and self-cleaning treatments: a challenge for the conservation of temple G stone in Selinunte

Abstract The Temple G of the Archaeological Park of Selinunte (Italy), the largest in Europe, is one of the most impressive temples in the Magna Grecia. Today, it is completely destroyed due to a strong earthquake occurred in the Middle Ages. The used stone is a calcarenite coming from the ancient and renowned quarries of Cusa near the acropolis. This work comes from the today’s proposal of Temple G anastylosis. The goal of the work is to provide the results relating the protective effectiveness of three polymer formulations, appropriately selected, on stone samples taken from the “Capitello” quarry, part of “Cusa quarries”. The formulations functionality was deployed by adding TiO2 nanopar…

Applications of transmission electron microscopy in the field of cultural heritage

Co-precipitation synthesis of neodymium-doped yttrium aluminium oxides nanopowders: Quantitative phase investigation as a function of joint isothermal treatment conditions and neodymium content

Abstract Neodymium-doped yttrium aluminium nanopowders with nominal Nd:Y:Al ratio equal to X:3–X:5 (where X = 0, 0.006, 0.012, 0.024, 0.048, 0.081, 0.096, 0.171, 0.192, 0.384, 0.540 and 0.720) were prepared by the co-precipitation method and subjected to five cumulative stages of isothermal treatment in the temperature range from 900 to 1050 °C. The phase evolution of the oxides were investigated quantitatively by the X-ray powder diffraction approach using the Rietveld method of analysis. An almost single phase cubic garnet structure was attained at temperatures as low as 900 °C for specimens with neodymium loading less than ca. 6 at.% with respect to total (Nd + Y) atoms. Isothermal treat…

Synthesis of Nd:YAG nanopowder by microemulsion method

PMMA-titania nanocomposites: Properties and thermal degradation behavior

Titania nanoparticles were prepared using a solegel method and calcination at 200 and 600 � C in order to obtain anatase and rutile phases, respectively. The obtained powders were used to prepare PMMAe titania nanocomposites by a melt compounding method. The effect of the crystalline phase and the amount of titania, in the range 1e5 wt.%, on the morphology, mechanical properties and thermal degradation kinetics of PMMA was investigated by means of X-ray diffractometry (XRD), transmission electron microscopy (TEM), 13 C cross-polarization magic-angle spinning nuclear magnetic resonance spectroscopy ( 13 C{ 1 H}CP-MAS NMR), including the measurement of proton spinelattice relaxation time in t…

Effect of the nanotube aspect ratio and surface functionalization on the morphology and properties of multiwalled carbon nanotube polyamide-based fibers

In this study, the effect of the carbon nanotube (CNT) aspect ratio and surface functionalization on the mechanical behavior and morphological changes of polyamide (PA)-based fibers was investigated. Composites were prepared by the melt blending of CNTs with PA, and at a later time, the fibers were prepared by melt spinning and cold drawing. A reinforcement effect was noticed for all of the CNTs samples, and the increase in the mechanical properties and dimensional stability was more pronounced for highly oriented filaments. When the elongational flow was increased, the orientation of CNTs along the fiber direction was observed, but the nanotube alignment was much more difficult for CNTs wi…

Attività e proposte progettuali sulla conservazione e il trattamento delle opere cartacee

Effects of Thermal Treatment on the Structure of Eu:YAG Nanopowder

Eu:YAG nanopowder precursors were obtained by co-precipitation of aluminium, yttrium and europium nitrates solution with ammonia. The hydroxides precursors were calcined at different temperatures from 900 to 1200°C as a function of holding time (1, 2 and 6 hours). The presence of Eu3+ ions in the matrix was confirmed by Energy Dispersive X-rays analysis. X-Ray Diffraction investigation by the Rietveld method shows that the sample treated at 900°C for 1 hour is essentially the garnet phase with the minor presence of hexagonal and monoclinic metastable phases. The Eu3+ ions are incorporated into the garnet phase, as is suggested by the lattice parameter value being larger than that in literat…

Formation of α-ω(4,7,10,13-pentaoxa-16-azacyclooctadecane) hexadecane micelles in aqueous solution – effect of HCl addition

The structure of aggregates of a new bolaform surfactant [α-ω (4,7,10,13-pentaoxa-16-azacyclooctadecane) hexadecane] in neat aqueous solution has been investigated by small-angle neutron scattering. Preliminary data analysis unequivocally indicates that globular micelles are formed. This finding has been confirmed by the analysis of data obtained upon addition of hydrochloric acid. The observed significant reduction of micelle aggregation number has been attributed to the peculiar complexing ability of the two aza-crown ether units in the surfactant molecule; this is in line with information inferred from the complexation of ions into the non alkylated azacrown ethers. As a consequence of h…

Synthesis of functionalized mesoporous silica assisted by microwave irradiation

Synthesis and characterization of perfluoroalkyl-pyrenes embedded in a polymethylmethacrylate matrix

Effect of the dopant selection (Er, Eu, Nd or Ce) and its quantity on the formation of yttrium aluminum garnet nanopowders

Abstract Hydroxide precursors, synthesized using the co-precipitation method, were calcined for 1 h at the temperatures of 900, 1000 and 1100 °C, respectively, and heated directly to 1500 °C to produce various Y 3 Al 5 O 12 (YAG) nanopowders with different doping quantities of erbium, europium, neodymium and cerium. All samples were investigated using thermo-gravimetry (TG) and differential thermal analysis (DTA), field emission gun-scanning electron microscopy (FEG-SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). TG and DTA experiments were performed from room temperature up to 1500 °C; the weight loss curves combined with the presence of exo- and endo-thermal even…

CARATTERIZZAZIONE E TRATTAMENTO DELLA CARTA DI UN VOLUME A STAMPA DEL 1591

In questo lavoro si riporta l’applicazione di un trattamento innovativo per la deacidificazione e contemporanea riduzione della carta messo a punto per un volume a stampa del XVI sec., contenente i quattro vangeli in arabo e latino, di proprietà della Soprintendenza di Siracusa. È stato studiato lo stato di conservazione della carta mediante tecniche non invasive o microinvasive quali pHmetria, colorimetria, spettroscopia di risonanza magnetica nucleare e spettroscopia infrarossa. Inoltre, l’inchiostro usato per la stampa del testo e delle incisioni è stato identificato mediante la spettroscopia Raman. La carta mostra un degrado di tipo ossidativo e acido. Gli inchiostri presenti contengono…

Determination of the Composition of Mixed Hydrogenated and Fluorinated Micelles by Small Angle Neutron Scattering

Molecular association of cryptand 221D in NaCl-water solutions. A small-angle neutron scattering study

Molecules of 5-Decyl-4,7,13,16,21-pentaoxa-1,10-diaza-bicyclo-[8.8.5.]tricosan (221D) and its sodium complex, with both a hydrophobic and a hydrophilic portion, are expected to form aggregates in water solutions. This was confirmed by surface tension measurements. The aggregation behaviour was studied by small-angle neutron scattering at two different [NaCl]/[221D] molar ratios, such as to obtain, in one case, aggregates entirely made up of ionic monomers, and in the other, mixed micelles constituted by both ionic and non-ionic units. The variation of the aggregation number and number of aggregates indicated that, in the former case, smaller micelles were formed, as a consequence of repulsi…

Pt(II) complex @mesoporous silica: preparation, characterization and study of release

Cisplatin analogs, having cytotoxic activity higher than that exerted by cisplatin, have recently triggered considerable interest by the community. The cis-[PtCl2(DMSO)HL]·2DMSO, where HL = 7-amino-2-(methylthio)[1,2,4]triazolo[1,5-a]pyrimidine-6-carboxylic acid, has shown a potent cytotoxic activity on HepG2 hepatocarcinoma cells, while under identical conditions, it did not affect normal immortalized human liver cells (Chang). In this work, the above complex has been incorporated into MCM41 mesoporous silica, pure and functionalized with amino group, which is considered one of the best host for a drug delivery system for carrying high dosages of a variety of drugs in their mesopores. Sinc…

Partitioning of macrocyclic compounds in a cationic and an anionic micellar solution: a small-angle neutron scattering study.

Following a previous investigation on partitioning of some macrocycle compounds in sodium dodecyl sulfate (SDS) and dodecyltrimethylammonium bromide (DTAB) aqueous solutions and their effect on the micellar structure, a small-angle neutron scattering (SANS) study has been performed at fixed surfactant content (0.20 mol/L) and varying macrocycle concentrations from 0.20 up to 1.0 mol/L. Conductivity measurements have been also performed in order to evaluate the effect of the presence of macrocycles on the critical micellar concentration (cmc) of the two surfactants. SANS experimental data were fitted successfully by means of a core-plus-shell monodisperse prolate ellipsoid model. It has been…

Scienza e Arti Perdute: i Segreti degli Antichi Maestri Liutai

Lo scopo di questo lavoro è illustrare agli insegnanti la connessione tra due settori di attività apparentemente lontani: la scelta dei materiali utilizzati nella liuteria artigianale e la chimica. Il ruolo, la composizione e la classificazione delle principali vernici per liuteria sono qui descritte assieme ad una breve sintesi dello stato dell’arte. Nel lavoro, vengono presentati i principali concetti di una tecnica analitica non distruttiva abbastanza semplice (la spettroscopia di fluorescenza da raggi X) ma, probabilmente, non abbastanza nota ai non addetti ai lavori. Un caso di studio a essa correlato è inoltre presentato per evidenziare uno dei possibili contributi del chimico nello s…

On the Role of Extensional Flow in Morphology and Property Modifications of MWCNT/Polyamide-Based Fibers

Unfilled and MWCNT-filled PA fibers are prepared and the effect of the extensional flow on their mechanical performance and morphological variations is investigated. Morphological analyses using SEM, TEM, and SAXS suggest a stronger orientation of the MWCNTs along the fiber direction with increasing extensional flow. A particular MWCNT bundle formation in the PA drawn nanocomposite fibers is observed for the first time, and a pull-out of the central nanotube in some bundles is noted. The maintenance of the "shish-kebab" structure upon extensional flow is responsible for the mechanical improvements and dimensional stability in MWCNT-filled PA fibers.

ART AND TECHNIQUE: ARTISTIC REPRODUCTION OF THE ANCIENT BRONZE IL GUERRIERO DA PETRALIA SOTTANA

The reproduction of artistic objects is useful for museological, teaching, and commercial purposes. In some cases, the reproduction is carried out to replace the originals located in outdoor environments and to prevent the deterioration due to weathering or pollution. This article describes the different phases that led to the reproduction of the Il Guerriero da Petralia Sottana. The observation of stylistic characteristics and the physical-chemical investigation were carried out in order to obtain information about the composition of the alloy and the technological properties of the artifact by using Optical Microscopy and X- ray Fluorescence. The reproduction in wax was performed by using…

Microwave Dehydration Of Water In Oil Microemulsion Containing Nanoparticles Synthesized In Situ

Disidratazione di nanoparticelle sintetizzate in microemulsione w/o

PHYSICO-CHEMICAL CHARACTERIZATION OF THE ACQUALADRONE ROSTRUM

The archaeological discovery of the Acqualadrone rostrum (an offensive naval weapon mounted on the prow at the waterline), off the Italian coast near Messina in 2008, has led to the need for scientific research in order to plan the conservation treatment of this artefact. The discovery is exceptional because of the presence of a wooden section from the original ship. This paper describes the physico-chemical characterization of a metallic and two wooden samples by inductively coupled plasma – optical emission spectroscopy, inductively coupled plasma – mass spectrometry, Fourier transform infrared spectroscopy, 13 C{ 1 H} cross-polarization magic angle spinning NMR spectroscopy, energy-dispe…

Green Synthesis, Molecular Characterization and Associative Behavior of Some Gemini Surfactants without a Spacer Group.

A series of new gemini surfactants without a spacer group, disodium 2,3-dialkyl-1,2,3,4-butanetetracarboxylates, were synthesized in a green chemistry context minimizing the use of organic solvents and applying microwaves (MW) when activation energy was required. Once the desired architecture was confirmed by means of the nuclear magnetic resonance technique (1H-NMR, 1H-1H COSY) for all the studied surfactants, the critical micellization concentration was determined by conductance measurements. The diffusion coefficient of micelles formed by the four compounds was characterized using pulsed field gradient (PFG)-NMR. Diffusion coefficients were found to be dependent on the concentration and …

Suzuki-Miyaura cross-coupling of arenediazonium salts catalyzed by alginate/gellan-stabilized palladium nanoparticles under aerobic conditions in water

The use of palladium nanoparticles stabilized by natural. beads made of an alginate/gellan mixture in the Suzuki-Miyaura cross-coupling reaction of arenediazonium. tetrafluoroborates with potassium aryltrifluoroborates. (1 : 1 molar ratio) with loading as low as 0.01–0.002. mol% under aerobic, phosphine-, and base-free conditions. in water is described. The catalyst system can be reused. several times without significant loss of activity.

Microwave radiation effect on the synthesis of cadmium sulphide nanoparticles in water in oil microemulsion: a preliminary study at different frequencies

AbstractCadmium sulphide nanoparticles have been synthesised in water/sodium bis (2-ethylhexyl) sulfosuccinate (AOT)/n- heptane microemulsions kept at 30 °C by microwave irradiation coupled with water-cooling and in conventional thermostatic conditions at the same temperature. The study has been performed exposing the reaction media to microwave radiation at five different frequencies (2.45, 2.85, 8, 12 and 18 GHz). For each frequency, a suitable microwave exposure set-up has been assembled. During the growth process, the dimensions of the nanoparticles have been characterised by means of UV-Vis spectroscopy. At the end of the growth process, the surface morphology of the nanoparticles has …

Kinetics of particle growth and particle composition of a commercial Al-Li alloy by means of small-angle scattering

Abstract Extending previous work done on a similar alloy, small-angle X-ray scattering measurements are reported for a commercial Al-Cu-Li alloy (2–68% Cu and 1–88% Li by weight). Data have been analysed by means of an ellipsoidal model of precipitate particles using a method previously proposed by some of us which, incorporating interparticle interference effects, reproduces the fuli scattering intensities of the samples studied. Particie dimensions obtained from the fit indicate that the Lifshitz-Slyozov coarsening mechanism holds for ageing at higher temperatures and longer times. The activation energy for volume diffusivity obtained is similar to that of pure binary alloys. The scatteri…

Chromium liquid waste inertization in an inorganic alkali activated matrix: Leaching and NMR multinuclear approach

A class of inorganic binders, also known as geopolymers, can be obtained by alkali activation of aluminosilicate powders at room temperature. The process is affected by many parameters (curing time, curing temperature, relative humidity etc.) and leads to a resistant matrix usable for inertization of hazardous waste. In this study an industrial liquid waste containing a high amount of chromium (≈ 2.3 wt%) in the form of metalorganic salts is inertized into a metakaolin based geopolymer matrix. One of the innovative aspects is the exploitation of the water contained in the waste for the geopolymerization process. This avoided any drying treatment, a common step in the management of liquid ha…

Study of the curing of a DGEBA based system through structural investigation

Improvement of interaction in and properties of PMMA-MWNT nanocomposites through microwave assisted acid treatment of MWNT

Soluble derivatives of multi-walled carbon nanotubes (MWNT) embedded in a poly(methylmethacrylate) (PMMA) matrix forming thick, homogeneous and transparent nanocomposites, were prepared and characterized. A new photo-assisted method using microwaves, to purify the MWNTs from amorphous carbon and synthesis catalyst clusters, was tested in a sulphonitric mix. This method shortened the processing time compared to other methods. Pristine and functionalized MWNTs were introduced into the MMA, then in situ photo-polymerized. Transmission electron microscopy (TEM) and X-ray diffractometry (XRD), as well as Fourier-transform infrared (FTIR), Raman and nuclear magnetic resonance (NMR) spectroscopy w…

Evidence for a Double Doping Regime in Nd:YAG nanopowders

Nanopowders of Yttrium Aluminium Garnet doped with neodymium (Nd:YAG) were investigated by X-Ray Absorption Fine Structure (XAFS) at the Nd LIII-edge in the 1.3 - 20.8 % doping range. XANES spectra appear similar in the full range of the Nd concentration. However, a significant decrease in the white line intensity of XANES is revealed as the quantity of Nd doping ions increases. Plotting the white line intensity as a function of Nd doping ions reveals two linear trends with two different slopes, identifying a threshold value where the neodymium concentration reaches 5 at.% This experimental finding provides support for the existence of a double doping regime in Nd:YAG nanopowders.

A multi-analytical non-invasive and micro-invasive approach to canvas oil paintings. General considerations from a specific case

Abstract The investigation of artwork to understand story, state of conservation and to know about the composing materials is an issue that is getting growing attention in specialized literature. From a methodological point of view the scientific community is trying to reach a common proposal that could contribute to define a Standard Operating Procedure (SOP) for the application of portable non-invasive and microinvasive techniques for in-situ analyses. In this paper the oil painting on canvas “St. Girolamo nello studio” by Nicolo Buttafoco was investigated to known the materials and techniques used by the artist as well as to evaluate its preservation status. The survey has been conducted…

Solid state NMR investigation of the roman Acqualadroni rostrum: tenth year assessment of the consolidation treatment of the wooden part

Abstract: This work follows a previous one dealing with the state of conservation study of the wooden part of the roman Acqualadroni rostrum soon after its finding in the seabed of Acqualadroni (Messina, Italy). The archaeological survey and recovery were particularly relevant since this artefact is one of the two rostrums, nowadays known,found together with its wooden part. Following the recovery, it was consolidated by immersion in a melamine-formaldehyde resin (Kauramin) aqueous solution for eight months at the “Centro di Restauro del Legno Bagnato” (Pisa, Italy). The present investigation is aimed to determine at microscopic scale the wood state of conservation and to highlight interact…

Non-conventional Ce:YAG nanostructures via urea complexes

AbstractCe:YAG nanostructures (Ce:YAG = Cerium in Yttrium Aluminium Garnet), easy to control and shape, have been prepared via templating approach using natural and synthetic materials (i.e. paper, cotton wool and glass wool) previously soaked with a gel-like metals precursor and then thermally treated to achieve the wished morphology. The final material, otherwise difficult to process, can be easily moulded, it is lightweight, portable and forms, at the nanoscale, homogeneous layers of interconnected but not agglomerated nanoparticles (15 ± 5 nm). Using the same synthetic route, called Urea-Glass-Route, but in absence of a template, extremely pure Ce:YAG nanoparticle (45 ± 5 nm) can be als…

Ancient wood of the Acqualadrone rostrum: Materials history through gas chromatography/mass spectrometry and sulfur X-ray absorption spectroscopy

In 2008 the rostrum from an ancient warship was recovered from the Mediterranean near Acqualadrone, Sicily. To establish its provenance and condition, samples of black and brown rostrum wood were examined using sulfur K-edge X-ray absorption spectroscopy (XAS) and gas chromatography/mass spectrometry (GC/MS). GC/MS of pyrolytic volatiles yielded only guaiacyl derivatives, indicating construction from pinewood. A derivatized extract of black wood yielded forms of abietic acid and sandaracopimaric acid consistent with pine pitch waterproofing. Numerical fits to the sulfur K-edge XAS spectra showed that about 65% of the endogenous sulfur consisted of thiols and disulfides. Elemental sulfur was…

Solid state nmr characterization of the waterlogged wooden part of Acqualadrone roman rostrum

The roman rostrum found in the sea of Acqualadrone (ME) was characterized in our previous papers. In the present work solid state NMR spectroscopy was applied on a wooden sample of the same artefact collected by coring and divided in four parts in order to correlate the conservation state to the depth. Results were compared with those obtained for a modern wood of the same species. A structural study was performed by the acquisition of 13C Cross Polarization Magic Angle Spinning (13C CP MAS NMR) spectra. These spectra were acquired to assign the chemical shifts of the species that are present in the wooden matrix. In addition the spectra analysis allowed us to determine the cellulose crysta…

Study of morphology, mechanical properties, and thermal degradation of polycarbonate-titania nanocomposites as function of titania crystalline phase and content

Titania nanoparticles were prepared using a sol–gel method and calcination at 2008C and 6008C to obtain anatase and rutile phases, respectively. The obtained powders were used to prepare polycarbonate (PC)-titania nanocomposites by melt compounding. The effect of different crystalline phases and amounts of titania, in the range 1–5 wt%, on the morphology, mechanical properties, and thermal degradation kinetics of PC was investigated. The results show that the filler modified the plasticity or rigidity of the polymer and influenced the degradation kinetics, in different ways depending on the type and amount of titania. POLYM. COMPOS.,

Synergistic Activity of Silver Nanoparticles and Polyaminocyclodextrins in Nanosponge Architectures

Four new composite materials, formed by silver nanoparticles embedded in polyamino-cyclodextrin nanosponge architectures, were designed exploiting the affinity of polyamino-cyclodextrins towards Ag+ ions. These materials were characterized by means of different techniques (thermogravimetry, FT-IR, solid state NMR, SEM, HR-TEM), and tested as catalysts for the reduction of nitroarenes and the oxidative coupling of anilines. The results obtained showed synergistic activity between the supramolecular binding abilities of the nanosponge matrix and the catalytic properties of the metal nanoparticle, and open the way towards the design of new composite smart nanomaterials with improved catalytic …

Synthesis of Nd:YAG nanopowder using the citrate method with microwave irradiation

Abstract Nd:YAG nanopowders were prepared using the Pechini process with microwave irradiation ( MWs ). A reference sample was also prepared using conventional heating. XRD pattern analysis showed that nanopowder obtained by means of conventional heating and calcination for 1 h at 900 °C has a structure made up of the garnet phase together with the hexagonal phase that disappeared after two additional hours of thermal treatment. The MWs powder calcined for 1 h consists of the single garnet phase. SAXS data analysis indicated that nanoparticles are characterized by a sharp interface. TEM investigation showed crystalline particles with remarkable agglomeration in both samples, although a more…

Microwave applications in the synthesis of nanostructured materials and in organic extractions

Preparation and characterisation of Ce:YAG -polycarbonate composites for white LED

Ce:YAG-polycarbonate composites were prepared with several amounts of Ce:YAG in the range 0.1-5 wt.% by using melt compounding. The structure and morphology of the composites were investigated by means of X-ray diffractometry and transmission electron microscopy. The optical properties of the composites were studied by using photoluminescence spectroscopy. The intermolecular interaction between the polymer and the filler surface was investigated using 13C cross-polarization magic-angle spinning NMR spectroscopy (13C {1H} CP-MAS NMR). The results showed that the dispersion of the particles in the polymer, and the optical properties, depend on the Ce:YAG amount. The composites were combined w…

Conservation state of two paintings in the Santa Margherita cliff cave: role of the environment and of the microbial community

Abstract The conservation of ancient paintings sited in humid environments is an actual challenge for restorers, because it needs the knowledge of the materials the paintings are made up and of their interaction with a peculiar surrounding environment; thus, tailored procedures and strategies aimed at restoring and preserving paintings are necessary. The Santa Margherita’s cave in Castellammare del Golfo (Trapani, Italy) is a natural cave, containing the remains of paintings, in a poor state of conservation, belonging to an ancient church dated back to the Middle Age. The present manuscript reports the monitoring of environmental conditions (i.e., temperature and humidity) in a full year as…

Structural and spectroscopic characterization of a hierarchical material made of MCM41 and CdS nanoparticles

Structural Characterization of Zirconia Nanoparticles Prepared by Microwave-Hydrothermal Synthesis

Nanocrystalline zirconia powders have been prepared by microwave-hydrothermal synthesis starting from aqueous solution of ZrOCl2·8H2O. Results of investigations on the aqueous suspension stability of the washed zirconia nanopowders by dynamic light scattering showed that the suspension, constituted by superaggregates of nanoparticles (131 ± 10 nm), was stable up to 15 days. Nanopowders were investigated by means of transmission electron microscopy and small angle x-ray scattering measurements which proved that the zirconia nanopowder is constituted by small primary nanoparticles of ca. 8 nm that agglomerate forming bigger aggregates of 50 ± 1 nm.

X-ray Fluorescence Spectroscopy applied to the study of three sicilian painted artworks

This paper reports on three X-Ray Fluorescence (XRF) studies of ancient Sicilian painted materials: a 13th century canvas from Cerami (Enna, Italy), the Muqarnas wood ceiling of the 12th century Palatine Chapel (Palermo, Italy) and a delicate early 20th century viola d’amore, the property of the Conservatorio di Musica “Vincenzo Bellini” in Palermo. Information about the pigments and preparation layer mixtures used as well as inferences regarding various past painting techniques emerged from the interpretation of spectra and data analyses.

Graphene nanoplatelets (GNPs): new preparation methods and their structural characterization

Graphene is one of the allotropes of elemental carbon with a planar monolayer of carbon atoms arranged into a two-dimensional honey-comb lattice [1]. It has demonstrated a variety of intriguing properties as new material for future applications and composite industry [2-3]. In particular the interesting electrical properties candidate the graphene to be an excellent successor to silicon in electronic applications. Since its preparation is rather difficult and complex, graphene nanoplatelets (GNPs) are also intensively studied. GNPs are more easily to obtain, have similar properties and can be used in the same applications [4]. The aim of the current research is the development of new prepar…

Synthesis, size control, and passivation of CdS nanoparticles in water/AOT/n-heptane microemulsions

Abstract CdS nanoparticles have been synthesised by adding tetrabutylammonium hydrogen sulphide to water/sodium bis(2-ethylhexyl) sulfosuccinate/ n -heptane microemulsions containing CdSO 4 . Analysis of UV–Vis absorption spectra recorded at various times indicates that an initial rapid formation of CdS nanoparticles is followed by a very slow growth process which can be well described by a power law. The growth process is totally inhibited by the addition of an appropriate amount of bis(2-ethylhexyl)amine (BEA) leading to the formation of stable nanosized CdS particles coated by an oriented monolayer of chemically bonded BEA molecules. Depending on the BEA addition time, the growth inhibit…

Oxidized graphene in ionic liquids for assembling chemically modified electrodes: a structural and electrochemical characterization study

Dispersions of graphene oxide (GO) nanoribbons in ionic liquids, ILs (either 1-butyl-3-methylimidazolium chloride (BMIM-Cl-) or 1-butylpyridinium chloride (-Bupy-Cl-)) have been used to assemble modified screen printed electrodes (SPEs). The graphene oxide/ionic liquid dispersions have been morphologically and structurally characterized by the use of several techniques: X-ray photoelectron spectroscopy (XPS), Fourier transform-infrared (FT-IR) spectroscopy, high-resolution-transmission electron microscopy (HR-TEM). The assembled modified SPEs have then been challenged with various compounds and compared to several electro-active targets. In all cases high peak currents were detected, as wel…

As the filler influences morphology, mechanical properties and thermal degradation of a polymer

Characterization of Nd-MCM41 obtained by impregnation

Synthesis and antibacterial activity of iron-hexacyanocobaltate nanoparticles.

This paper deals with the synthesis and characterization of iron-hexacyanocobaltate (FeHCC) and its antibacterial properties. The nanoparticles were prepared by a facile co-precipitation technique. Crystal structure, particle morphology, and elemental composition were determined using X-ray Powder Diffraction, X-ray fluorescence spectroscopy, Transmission Electron Microscopy (TEM), and Infrared Spectroscopy (IR). The antibacterial activity of the FeHCC nanoparticles was tested against Escherichia coli and Staphylococcus aureus as models for Gram-negative and Gram-positive bacteria, respectively, by bacterial counting method and microscopic visualization (TEM, FEG-SEM, and fluorescence micro…

Application of the small-angle neutron scattering technique to the study of solubilization mechanisms of organic molecules by micellar systems

Abstract We present the possible contribution of the small-angle neutron scattering (SANS) technique to the molecular interpretation of the solubilization phenomena in simple micellar systems. We show for a few ternary micellar systems, that an appropriate analysis of SANS experimental data can provide information on modifications induced on micellar dimension, shape, number of monomer, and charge and on the partition coefficient of the additive and its localization inside the micellar aggregate. The influence of n -alcohols on the thermodynamics and on the structure of sodium dodecyl sulphate (SDS) aqueous solution has been extensively investigated, so the agreement between the results obt…

Graphene and ionic liquids new gel paste electrodes for caffeic acid quantification

Abstract Graphene/ionic liquids nanocomposite gels were synthesized by an electrochemical etching approach and fully characterized under a morphological and structural point of view. For this purpose, several analytical techniques were applied, as HR-TEM/EDX (High Resolution-Transmission Electron Microscopy/Energy Dispersive X-Ray Analysis); FE-SEM/EDX (Field Emission-Scanning Electron Microscopy/Energy Dispersive X-Ray Analysis); XPS (X-Ray Photoelectron Spectroscopy); FT-IR (Fourier Transform-Infrared Spectroscopy) and electrochemical techniques. After the characterization study, nanocomposite-gel paste electrodes were assembled, exhibiting a selective and specific detection toward the ca…

Morphology and properties of poly(methyl methacrylate) (PMMA) filled with mesoporous silica (MCM-41) prepared by melt compounding

This paper reports on the morphologies of poly(methyl methacrylate) (PMMA)/mesoporous silica (MCM-41) composites prepared by melt compounding with various MCM-41 contents in the range of 0.1–5 wt%, the interactions between the polymer and filler in these composites, and their thermomechanical, mechanical and thermal degradation properties. The composites formed transparent films at low filler loadings (\0.5 wt%) because of well-dispersed, unagglomerated particles. The presence of polymer did not alter the pore dimensions in the MCM-41 structure and it maintained its hexagonal structure, even though the polymer chains partially penetrated the pores during composite preparation. The PMMA inte…

Polyamide-Based Fibers Containing Microwave-Exfoliated Graphite Nanoplatelets

Exfoliated Graphite NanoPlatelets (GNP) have been obtained from Graphite Intercalation Compounds (GIC) subjected to thermal and microwave treatments. Accurate morphological and structural characterization of obtained GNP, performed to compare the degree of exfoliation, show that microwave-treated GNP, exhibit well-exfoliated structure, without any reduction in dimensions compared with the native GIC, differently to the thermal-treated ones. Microwave-treated GNP have been introduced in polyamide (PA) through melt-mixing to obtain nanocomposite that has been subjected to elongational flow, with the aim to improve the nanofiller dispersion and induce GNP orientation along the fiber direction.…

I ‘vasi di Centuripe’: per un approccio integrato

Il contributo intende evidenziare le prospettive di un approccio interdisciplinare integrato allo studio della ceramica policroma “di Centuripe”. Dagli inizi del XX secolo, tale classe ha riscosso ampio apprezzamento per le sue delicate pitture e la ricchezza di ornamenti a rilievo applicati (dipinti e dorati) che abbelliscono i vasi, rendendoli pressoché inutilizzabili nella pratica per scopi funzionali, ma altamente efficaci come doni funerari in antico, e oggi come pezzi di grande impatto per commercianti di antichità e collezionisti moderni. Data la piaga, diffusa fino a tempi recenti, degli scavi clandestini, dei “restauri” arbitrari e delle falsificazioni, i vasi di Centuripe necessit…

Composizione per la deacidificazione e la riduzione della carta e relativo metodo per il restauro della carta

La presente invenzione si riferisce al campo della chimica e più precisamente al settore del restauro e conservazione della carta. Essa consiste in una composizione basica e riducente da utilizzare in un relativo metodo per il restauro di carta antica soggetta a degrado acido e ossidativo.

Structure of Urea Clusters Confined in AOT Reversed Micelles

The structure of sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and that of urea containing AOT reversed micelles has been investigated by small-angle neutron scattering (SANS) and Fourier transform infrared (FT-IR) spectroscopy at different AOT concentrations and urea/AOT molar ratios. For the AOT/n-heptane system, SANS data analysis indicates that AOT molecules form prolate ellipsoidal aggregates, which grow asymmetrically along the major axis upon increasing the surfactant concentration. For the urea/AOT/n-heptane system, the SANS results are consistent with the hypothesis that urea is encapsulated as small-sized ellipsoidal hydrogen-bonded clusters within the hydrophilic micellar core of …

Consolidation tests on the graffiti of the Steri’s prison with nanotechnological Ca(OH)2 dispersed in iso-propanol

The combination of weathering and human activities often induce pyhisicochemical alteration on the surface of wall paintings. One of the most still largely used restoration techniques for these works of art, is based on the application of organic polymers. Due to their ability to stick detached and powdered pigments,these products provide an immediate consolidating effects. Unfortunately, both their aging and their pyhisicochemical incompatibility with the inorganic support can have serious consequences also causing further damage to the work of art. In this paper a new technological approach is presented based on the use of Ca(OH)2 nanoparticles dispersed in isopropanol. Some applicative t…

Viscosity studies of solutions of water inn-aliphatic alcohols at various temperatures

Viscosity measurements have been made at 25°C on solutions of water inn-propanol, and at 15, 25, 35, and 45°C on solutions of water inn-butanol,n-pentanol, andn-hexanol over the respective solubility ranges. For most of the systems, water decreases the viscosity of the dry alcohols, while for the lower members of the series literature data report an increase in viscosity on addition of water. These results are rationalized in terms of two kinds of interaction between water molecules and alcohols: participation of water molecules in chain formation for the lower alcohols and formation of water-centered complexes for butanol and higher alcohols.

Microstructure and phase composition of bronze Montefortino helmets discovered Mediterranean seabed to explain an unusual corrosion

AbstractTwo Monterfortino helmets, recovered in the Mediterranean seabed, show unusual features with respect to the more common helmets of the same period and found in underwater environments. Hence, they were investigated by a multi-analytical approach, which allowed us to identify the compounds constituting the helmets and to make some considerations about their metallurgy, although all the metal was converted to degradation products. The helmets, originally made in bronze, have maintained their original shape because of copper sulphides formation. The observed differences in composition between the two helmets were attributed to the position modification, of one of them, into the seabed …

Molecular Association of a Nonionic and an Ionic-Induced Surfactant:  Cryptand (221D) NaCl in Water

The cryptand 5-decyl-4,7,13,16,21-pentaoxa-1,10-diazabicyclo-[8.8.5] tricosane [221D] strongly resembles a surfactant in its characteristics:  it contains a hydrophilic headgroup, the cryptand unit, and a hydrophobic unit, the decyl chain. It is insoluble in water, but in the presence of an appropriate amount of NaCl, as a consequence of the complex formation between 221D and Na+, it becomes soluble and forms aggregates. The aggregates, depending on the NaCl-221D molar ratio, can be considered as mixed ionic nonionic micelles or ionic micelles. The evolution of the aggregate dimensions and their shape has already been studied at two NaCl-221D molar ratios as a function of the 221D concentra…

An Iranian booklet: non destructive examination by Energy Dispersive X-Ray Diffractometry and Micro-Raman Spectroscopy

Energy Dispersive X-Ray Diffractometry was used in combination with micro-Raman Spectroscopy to study an undated illuminated Iranian booklet. In both cases, no preliminary preparation of the samples was needed: the data were acquired in a non-destructive way in a natural environment. The book is of particular interest because of the unusual presence of miniatures on some pages. The two techniques were used to collect data from small areas of the pages and in different regions of the miniature in order to identify inks and pigments and to attempt chronological assignment. Raman spectra were affected by strong background fluorescence. In spite of this, different peaks were detected and identi…

Investigation on four centuripe vases (late 3rd-2nd cent. B.C.) by portable X-ray fluorescence and total reflectance-FTIR

Abstract Four Centuripe vases dated back to the late 3rd-2nd centuries B.C. were analysed using imaging under visible and ultra-violet illumination as well as complementary non-invasive and non-destructive portable X-Ray Fluorescence (XRF) and Total Reflectance – Fourier Transform InfraRed (TR-FTIR) spectroscopies. The vases are of great importance since they represent a rare expression of the Hellenistic vase painting. Four specimens, a “pyxis”, a “lebes gamikos” and two “lekanides” decorated with figures of different type, are exhibited in the Antonino Salinas Archaeological Museum in Palermo-Italy. The investigation was aimed to identify the used pigments and the painting technique, to r…

La spettroscopia di risonanza magnetica nucleare in stato solido per lo studio dello stato di conservazione di materiali cellulosici

This work shows the potentiality of the solid state nuclear magnetic resonance (ss-NMR) technique applied to characterize cellulosic materials and the possibility of analyze small amounts of starting material within reasonable experimental time using a modern equipment. The NMR analyses were performed to assess the conservation state of a material in order to plan appropriate conservative and restorative interventions. 13C {1H} Cross Polarization (CP) Magic Angle Spinning (MAS) NMR was used to identify the paper and wood components and the crystalline degree of the cellulose. Besides, in wood holocellulose/lignin ratio and the condensation degree of the lignin were determined.

Synthesis and characterization of Ln3+ (Ln3+=Nd3+, Eu3+, Ce3+) doped YAG nanocrystalline

Correlation spectroscopy in molten and supercooled antimony trichloride.

Correlation spectroscopy measurements performed on molten and supercooled antimony trichloride with the homodyne technique show correlation functions that have a nonexponential behavior. Two well-defined distributions of correlation times can be observed in different temporal regions. This behavior is discussed in terms of a structural relaxation of clusters dynamically formed by intermolecular and interchain bonds. The Arrhenius plot of these correlation times shows a linear behavior with the same activation energy for both. In contrast, the activation energy of shear viscosity has a different value, showing that the processes determining the temperature behavior of \ensuremath{\tau} and $…

The static dielectric constant of solutions of water inn-alcohols at 15, 25, 35, and 45°C

Dielectric constants (measured at 1 MHz) are reported for solutions of water (concentration range 0 to 0.2 mole fraction) in 1-propanol at 25°C, and in 1-butanol, 1-pentanol, and 1-hexanol at 15, 25, 35, and 45°C. These results, together with literature values for solutions of water in methanol, ethanol, 1-heptanol, and 1-octanol, show that water interacts with alcohols in at least two ways: (1) it can participate in the formation of dynamic hydrogen-bonded chains, thereby raising the polarizability; (2) it can form relatively stable structures such as H2O(ROH)4 which have zero net dipole moment and consequently diminish volume polarizability. For C n H 2n+1 OH alcohols,n≥4, most of the ini…

Cobalt hexacyanoferrate–poly(methyl methacrylate) composite: Synthesis and characterization

Abstract The preparation of cobalt hexacyanoferrate nanoparticles–poly(methyl methacrylate) (CoHCF–PMMA) composites are described together with their characterization and thermochromic properties. CoHCF nanoparticles – investigated by dynamic light scattering – were prepared by optimizing solvent composition and temperature to obtain nanoparticles with a reduced degree of aggregation. The nanoparticles were embedded in a PMMA matrix to obtain a transparent coloured composite which was studied by transmission electron microscopy. The nanoparticle chromic features, enhanced by their reduced sizes, were investigated by UV–vis and FT-IR spectroscopy.

Mass spectrometry coupled to chromatography systems and cultural heritage: a case study on the content of an ancient jar

In this chapter an introduction to mass spectrometry will be given, with particular reference to mass spectrometry coupled to chromatography systems. Further some mass spectrometry applications in the field of cultural heritage will be briefly reported and discussed. Finally a experimental investigation on the content of an ancient jar will be reported. Together with experimental details a description of the techniques adopted, results obtained and forthcoming experiments will be also given.

Assessment of protection treatments for carbonatic stone using nanocomposite coatings

In this paper the effect of the application of four kinds of polymer dispersions containing nanoparticles, used as protectives, on two type of carbonatic lithotypes, White Noto and Comiso stone, is reported. The study was conducted by analysing the contribution of each component of the system. After the structural characterization of the coating itself, the performance of those colloidal systems has been studied upon application on the calcarenites, preferring non-invasive techniques and microdestructive techniques. Effect of the nanoparticles presence on hydrorepellency and roughness of the stone surface and on chromatic changes has also been considered. The tests conducted have proven tha…

Incorporation of Pt(II) complex with [amino-2(methylthio)(1,2,4)triazole-(1,5-a)pyrimidine-6-carboxylic-acid] ligand in MCM41 for controlled release

Drug carriers play a critical role for the loading and the release of the drug. A promising frontier is represented by a new class of innovative medicines that represents directional transport vehicles "drug delivery" and consist of assembled structures carrier (nano)-drug. Silica-based materials, nontoxic, biocompatible, have been used as adjuvant and excipient in pharmaceutical technology. In this class of compounds, the mesoporous materials, such as MCM41, SBA-15 and hexagonal mesoporous silica, have been investigated for medication and drug delivery due to their properties. In fact, these materials show a large specific pore volume made up of regular pores having a diameter in the nanom…

Development of controlled release systems of biocides for the conservation of cultural heritage

Abstract The presence of microorganisms is one of the main causes of monument deterioration. Biocides are usually applied after or before restoration in order to prevent or slow down microbial growth. Frequent applications are necessary leading to increased costs and high risks to humans and the environment. The aim of this study is the design of novel controlled release systems comprising a biocide loaded into a mesoporous silica. Pristine MCM41 as well as MCM41 functionalised with carboxy- (MCM41-COOH) and amino-groups (MCM41-NH2) were used. Biotin T and New Des 50, two commercial formulations, were chosen as biocides. The biocide encapsulation was performed adding the mesoporous silica t…

Simultaneous structural and elemental analysis by Energy Dispersive X-ray Diffraction: its potentiality in the field of Cultural Heritage

Synthesis and characterization of mesoporous Mn-MCM-41 materials

Si { 1 H} CP-MAS NMR X-ray photo-emission spectroscopy a b s t r a c t MCM-41 has been synthesized at two different pH using cetyl-trimethylammonium bromide (CTAB) surfactant as template and adding the silica precursor to aqueous solutions containing CTAB. The obtained solids were calcined at 600 ◦ C for 4 h. Mn-MCM-41 powders with different Mn/Si molar ratios were prepared using the incipient wetness method, followed by calcination at 550 ◦C for 5 h. At the end of the impregnation process the powders colour changed from white to brown whose intensity depends on manganese quantity. The materials characterization was performed by X-ray diffraction, N2 adsorption, 29 Si Cross Polarization–Mag…

Structure of isotactic polypropylene/ hydrogenated oligo(cyclopentadiene) blends: 1. Polypropylene-rich blends

Blends of isotactic polypropylene (iPP) and hydrogenated oligo(cyclopentadiene) (HOCP) containing 30% or less HOCP have been studied by small-angle X-ray scattering in the temperature range 25 to 160°C. The structure of blends has been analysed in terms of a pseudo two-phase model consisting of stacks of lamellae whose thickness is a function of temperature and composition. Structural parameters of the model have been derived and their temperature and composition dependences have been interpreted in the light of existing theories.

Influence of Temperature on Calcium Hydroxyapatite Nanopowders

The aim of this work is to investigate the effects of thermal treatment, in the range of temperature between 80°C - 900°C, on crystallinity, morphology and particles size of calcium hydroxylapatite nanopowders (HAp). A complete study was carried out applying 31P Magic Angle Spinning NMR, X-ray diffraction, nitrogen porosimetry and Transmis- sion Electron Microscopy techniques. HAp specimens were prepared by chemical precipitation in an aqueous solution of calcium nitrate and ammonium hydrogen phosphate. The thermal treatment performed, showed the formation of crystals whose appearance has three main morphologies and different particles size. HAp treated up to 500°C showed a set of needle-li…

Synthesis and Characterization of Nanostructured Cobalt Hexacyanoferrate

Cobalt hexacyanoferrate (CoHCF) nanoparticles have been synthesized by mixing aqueous solutions of K3Fe(CN)6 and CoCl2 under vigorous stirring at different temperatures and following two different procedures, drop-by-drop or immediate mixing. The resulting CoHCF nanoparticles, with dimensions of several tens of nanometers, were characterized using TEM, SEM-EDX, IR, and XRD. Their electrochemical behavior was investigated in comparison with the CoHCF powder bulk compound. The CoHCF nanoparticles exhibit an electrochemically driven conversion to the bulk one that has been investigated by a chemometric approach in order to establish the best synthetic parameters. The rate and the degree of con…

Synthesis of yttrium aluminum garnet nanoparticles in confined environment, and their characterization

Abstract Nanopowders of yttrium aluminum garnet (YAG, Y3Al5O12) have been prepared by thermal treatment of hydroxides obtained by synthesis in a confined environment constituted by water/Cetyltrimethylammonium bromide (CTAB)/1-butanol/n-heptane. The phase behavior of the above system has been investigated on varying the water/CTAB molar ratio (R) at constant 1-butanol/CTAB and heptane/CTAB molar ratio. The dispersed aqueous phases were constituted by solutions of ammonia and of yttrium and aluminum nitrates, respectively. Measures of Kinematic Viscosity, Electrical Conductivity and Small Angle X-ray Scattering have been carried out. It was found that, on increasing the ammonia solution cont…

Effect of methaacrylic acid on the structure of Eu:YAG-PMMA composites

Polymeric composites of lanthanide-doped materials were recently considered as potential candidates for the development of light emitting diodes, lasers and luminescent concentrators for solar cells. In particular, nanoparticles of yttrium aluminum garnet (YAG) doped with cerium ions embedded in polymetylmetacrylate (PMMA) have been valuable for white LED devices [1,2]. Different structures and micromechanical properties have been observed when the methacrylic acid (MAA) is present in the composite. With the aim to understand the effect of MAA on the composite structure, a series of Eu:YAG composites prepared by in situ polymerization starting from mixtures of MAA and methylmetacrylate (MMA…

Macro-micro relationship in nanostructured functional composites

This paper examines the results of the characterization of two functional composites: Poly(methyl methacrylate) (PMMA)-Ce:YAG (yttrium aluminium garnet doped with cerium) and PMMA-cobalt hexacyanoferrate (CoHCF). The composites were prepared as possible emitters in the fields of lighting thermal sensors. The prepared composites were char- acterized using transmission electron microscopy (TEM), nuclear magnetic resonance (NMR) spectroscopy, thermogravi- metric analysis (TGA), differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) analyses to study the correlation between micro and macro characteristics. We found that the molecular interactions of the two different fill…

Ce:YAG nanoparticles embedded in a PMMA matrix: preparation and characterization

A Ce:YAG-poly(methyl methacrylate) composite was prepared using in situ polymerization by embedding the Ce:YAG nanopowder in a blend of methyl methacrylate (MMA) and 2-methacrylic acid (MAA) monomers and activating the photopolymerization using a radical initiator. The obtained nanocomposite was yellow and transparent. Its characterization was performed using transmission electron microscopy, small angle X-ray scattering, (13)C cross-polarization magic-angle spinning nuclear magnetic resonance, and photoluminescence spectroscopy. Results showed that Ce:YAG nanoparticles are well dispersed in the polymeric matrix whose structure is organized in a lamellar shape. The luminescence properties o…

Micelles in Mixtures of Sodium Dodecyl Sulfate and a Bolaform Surfactant

Mixtures composed of water, sodium dodecyl sulfate (SDS), and a bolaform surfactant with two aza-crown ethers as polar headgroups (termed Bola C-16) were investigated by modulating the mole ratios between the components. The two surfactants have ionic and nonionic, but ionizable, headgroups, respectively. The ionization is due to the complexation of alkali ions by the aza-crown ether unit(s). Structural, thermodynamic, and transport properties of the above mixtures were investigated. Results from surface tension, translational self-diffusion, and small angle neutron scattering ( SANS) are reported and discussed. Interactions between the two surfactants to form mixed micelles result in a com…

First discovery of orichalcum ingots from the remains of a 6th century BC shipwreck near Gela (Sicily) seabed

Ingots recently recovered from the seabed near Gela, a major harbour of Sicily, reveal an unexpected side of ancient metallurgy. The ingots were found near remains of a ship and earthenware dated around the end of the VI century BC and probably coming from the eastern Mediterranean and the Aegean sea. The ingots were analysed by means of X-Ray Fluorescence spectroscopy via a portable spectrometer. Results indicate that they are mostly consist of copper and zinc although many of them have a significant amount of lead. This alloy is nowday called brass, but in ancient time it was know as orichalcum, one of the rarest and most precious alloy along with gold and silver. Only small items of oric…

A multivariate statistical approach of X-ray fluorescence characterization of a large collection of reverse glass paintings

We present an X-ray fluorescence spectroscopy (XRF) study combined with a multivariate approach that allow to detect compositional differences and similarities among the glass supports of a large set of reverse glass paintings belonging to the collection of the Mistretta museum. Reverse painting on glass is an old decorative technique used since the Roman time consisting in applying a cold paint layer on the reverse side of a glass support. The collection shows a large spreading of provenience and dating of the items. In consideration of the current classification solely based on stylistic criteria, we applied a multivariate analysis on the XRF measurements data set to find a more objective…

Physico-chemical characterization of the Acqualadrone rostrum

The archaeological discovery of the Acqualadrone rostrum (an offensive naval weapon mounted on the prow at the waterline), off the Italian coast near Messina in 2008, has led to the need for scientific research in order to plan the conservation treatment of this artefact. The discovery is exceptional because of the presence of a wooden section from the original ship. This paper describes the physico-chemical characterization of a metallic and two wooden samples by inductively coupled plasma – optical emission spectroscopy, inductively coupled plasma – mass spectrometry, Fourier transform infrared spectroscopy, 13C {1H} crosspolarization magic angle spinning NMR spectroscopy, energy-dispersi…

FT-IR and dielectric study of water/AOT liquid crystals

Abstract In order to explore the influence of microwave radiation on highly viscous microheterogeneous systems, the evolution of structural and dynamical properties of the water/sodium bis(2-ethylhexyl) sulfosuccinate (AOT) liquid crystals as a function of the molar ratio R (R=[water]/[AOT]) has been investigated by FT-IR spectroscopy and time domain reflectometry. The study emphasises how the progressive hydration of the surfactant head groups is mainly responsible for the structural and dynamical evolution of water/AOT liquid crystals. In particular, it has been found that the state of water at lower R values is strongly perturbed, bulk-like water appears only at R>23 and the water/AOT in…

Thermal Properties, Raman Spectroscopy and Tem Images of Neutron-Bombarded Graphite

Neutron-irradiated graphite to a total dose of 3.6 × 1016 n cm−2 was studied by DSC, Raman spectroscopy and transmission electron microscopy (TEM). The Wigner energy of neutron-irradiated graphite was 9.5 J/g as measured by DSC; it was released with an exothermal peak at 220°C. The Raman spectroscopy has confirmed the expected effect caused by neutron irradiation of the graphite substrate. The TEM imaging has shown that neutron-irradiated graphite can be effectively exfoliated by sonication in comparison to pristine graphite, which under similar conditions does not exfoliate at all. The interstitial Frenkel defects in neutron-irradiated graphite are intercalated between the graphene layers …

Preparazione assistita da microonde di nanoplacchette di grafene in miscela acqua/liquido ionico

Synthesis and characterization of CdS nanoparticles embedded in a polymethylmethacrylate matrix

CdS nanopowder capped with sodium bis(2-ethylhexyl)sulfosuccinate was synthesized by using water-in-oil microemulsions. The CdS nanoparticles of about 5 nm obtained were embedded in polymethylmethacrylate matrix by a photocuring process. The transparent yellow solid compound was characterized by optical absorption and emission spectroscopy, high-resolution transmission electron microscopy, and energy-dispersive X-ray spectroscopy. The properties of this compound were compared with those of the nanopowder dispersed in heptane and in methylmethacrylate. The results obtained indicate that the nanoparticles are homogeneously dispersed in the matrix and do not change in size during the embedding…

A new preparation method of nanolime dispersion for the conservation of artworks

Microwave-assisted synthesis of semiconductor nanoparticles in water/oil microemulsion

Stable CdS and ZnS nanoparticles with exalted luminescence properties have been obtained in water/sodium bis (2-ethylhexyl) sulfosuccinate (AOT)/n-heptane microemulsion using microwave in order to take away selectively water molecules from microemulsion system. The nanoparticles synthesis was performed using a microwave exposure set-up opportunely assembled that allows irradiating the reactor with microwave of 2.45 GHz maintaining constant the temperature. The nanoparticles growth kinetics, as a function of irradiation time, was performed by means of UV-Vis spectroscopy. Information about the structural changes that microemulsion undergoes when irradiated with microwave was obtained by mean…

Nanoparticles of AlTiZr mixed oxides as support of hydrodesulfurizaton catalysts: Synthesis and characterisation

Abstract TiAlZr mixed oxides, synthesized using sol–gel method, were characterized and used as supports of hydrodesulfurization catalysts (12 wt% Mo) prepared by impregnation either with molybdenum heteropolyacid H3PMo12O40 or its cobalt salt Co1.5PMo12O40. Structure, morphology and textural properties of oxides and catalysts were characterized using X-ray powder diffraction (XRD), Raman spectroscopy, Nitrogen adsorption porosimetry, TEM-EDS, temperature-programmed desorption (TPD) and temperature-programmed reduction (TPR) techniques. Activity of the catalytic systems was tested in thiophene hydrodesulfurization (HDS). No formation of a new oxide phase was revealed in the synthesized mixed…

Co-precipitation synthesis of YAG:Nd nano-powders: the effect of joint thermal and mechanical treatment

Polyamide/carbonaceous particles nanocomposites fibers: Morphology and performances

In this work, the influence of carbonaceous particles with different sizes and shapes on the morphology and mechanical performances of polyamide (PA)-based fibers was investigated. Graphene nanoplatelets (GNP) are compared with spherical and rod-like carbon fillers such as carbon black (CB) and multiwall carbon nanotubes (CNTs). The increments of the complex viscosity as well as elastic and loss moduli, in the melt state, assessed by rheological analysis, are reduced by modifying polyamide (PA) matrix with nanofillers in a following order: CNTs > GNP > CB. All the nanocomposites, however, show viscosity and moduli higher than those of neat PA. The CB loading causes a mere increase of the vi…

Ion pair association in isodielectric mixtures at 25�C

Conductance measurements of potassium perchlorate and iodide have been carried out on the following mixtures: methanol-ethylene carbonate, acetone-ethylene carbonate, acetonitrile-ethylene carbonate, sulfolane-ethylene carbonate, isodielectric with water; and in benzene-sulfolane, benzene-acetonitrile, ethanol-sulfolane, isodielectric with methanol. The extent of ionic association at a given concentration in two solvents of the same dielectric constant is greater in the aprotic solvent.

Miniatures of Iranian booklet: in situ examination with Micro-Raman Spectroscopy and Energy Dispersive X-Ray Diffractometry

Investigation on the stability of dispersion of zirconia nanoparticles prepared by microwave- hydrothermal synthesis

Difficulties in reproducing the performances of nanoparticles dispersions are obstructive for the progress of the nanotechnology. A plausible reason for this variability is the lack of the control of the stability as well as the dimensions of the nanoparticles in the dispersions. In this work we report results of investigations on the stability of zirconia nanoparticles in aqueous medium, monitoring nanoparticles sizes by means of Transmission Electron Microscopy (TEM), Dynamic Light Scattering (DLS). Nanocrystalline zirconia powders, prepared by microwave-hydrothermal synthesis, were determined to be 6-8 nm in size by TEM observations. By using DLS technique the as-prepared dispersions wit…

Consolidation and protection by nanolime: recent advances for the conservation of the graffiti, Carceri dello Steri Palermo and of the 18th century lunettes, SS. Giuda e Simone Cloister, Corniola (Empoli)

Abstract Nanolime dispersed in 2-propanol was extensively used for the consolidation of wall paintings. The knowledge of the advances of this methodology dealing with all the possible effects associated with the nanolime new material in conservation is fundamental to assess and improve the technique. In this paper, four different dispersions of Ca(OH) 2 nanoparticles were characterised by Small Angle X-rays Scattering technique (SAXS) and Transmission Electron Microscopy (TEM) in order to achieve information on size, shape, polydispersity, agglomeration, and crystal structure (by SAED patterns) of the particles. Once characterised, the dispersions were tested in two different case studies, …

Coprecipitation synthesis of Nd:YAG nanopowders II: the effect of Nd dopant addition the on Luminescence Properties

Abstract Nanopowders of Yttrium Aluminium Garnet (Y3Al5O12, YAG) doped with neodymium (Nd:YAG, 0.2–24.0 at.%) were prepared using the co-precipitation method followed by an annealing treatment up to 950 °C. For a concentration of neodymium lower than 3.2 at.% the materials were found constituted by the garnet phase according to X-ray diffraction investigations. However, at higher neodymium loading the hexagonal and monoclinic forms of yttrium aluminium oxides were found together with the garnet phase. For Nd quantity lower than 0.8% the luminescence emission spectra appear to be nearly the same, indicating that in the examined range of composition the immediate surrounding of the emitting N…

More insight into characterization of the waterlogged wooden part of Acqualadroni Roman Rostrum by solid-state NMR

Abstract Solid-state NMR spectroscopy was applied to characterize the wooden part of a roman Rostrum recovered in the Tyrrhenian Sea in the Acqualadroni area (Messina, Italy). The Acqualadroni Rostrum has been, in the recent past, investigated to establish its provenance and conservation. In this paper, solid-state NMR was used to obtain information on the conservation state of the wood as a preliminary step for the conservation process. A wooden sample of this artifact, collected by coring, was divided in four parts in order to correlate the conservation state to the depth. Results were compared with those obtained for a modern wood of the same species. A structural study was performed by …

Micro-analytical identification of the components of varnishes from South Italian historical musical instruments by PLM, ESEM-EDX, microFTIR, GC-MS, and Py-GC-MS

Abstract A multi-analytical investigation was carried out to study varnish micro-samples from historical stringed musical instruments from the collection of the “Vincenzo Bellini” Conservatory in Palermo (Italy). This paper reports on the results of the application of five micro-destructive techniques: optical microscopy analysis of cross-sections, micro-Fourier transform infrared spectroscopy, gas chromatography coupled with mass spectrometry, pyrolysis gas chromatography coupled with mass spectrometry with thermochemolysis, and environmental scanning electron microscopy with X-ray microanalysis. The study provides microchemical information about the composition of the varnishes of the ins…

Characterization of Nd-MCM41 obtained by impregnation

Abstract Silica mesoporous molecular sieves (MCM-41), prepared by using micelles as template, were functionalized by means of incipient wetness method. Evidence for the neodymium presence in the silica matrix was obtained by means of EDX. SEM micrographs showed that impregnation does not change significantly MCM-41 morphology. The maintenance of the hexagonal structure was confirmed by XRD pattern analysis. However, the observed loss of long-range ordering, the cell parameter increase and the surface area decrease, observed by gas adsorption technique, were attributed to the introduction of neodymium oxide inside the MCM-41 mesochannels. By FT-IR and Raman spectra it was found that the main…

Study of morphology, mechanical properties and thermal degradation of titania-polycarbonate nanocomposites as function of crystalline phase and amount

Titania nanoparticles were prepared using a sol–gel method and calcination at 2008C and 6008C to obtain anatase and rutile phases, respectively. The obtained powders were used to prepare polycarbonate (PC)-titania nanocomposites by melt compounding. The effect of different crystalline phases and amounts of titania, in the range 1–5 wt%, on the morphology, mechanical properties, and thermal degradation kinetics of PC was investigated. The results show that the filler modified the plasticity or rigidity of the polymer and influenced the degradation kinetics, in different ways depending on the type and amount of titania.

Small Angle Neutron Scattering from Systems of Interacting Particles. Modelling High Density Micellar Fluids

The need for analytical solutions of the scattering equation for complex situations (polydisperse samples, scattering from non centrosymmetrical particles, etc.) has somehow escaped the attention of the workers in the Small Angle Scattering field, although it is clear that, at the level of sophistication today available for the experiments, a more rigorous approach is necessary. For quite a few years our group has been actively engaged in SANS research and has occasionally devoted its attention to develop alternative ways of data analysis based on more rigorous solutions of the scattering equation.

Morphology, mechanical properties and thermal degradation kinetics of PMMA-zirconia nanocomposites prepared by melt compounding

Zirconia nanoparticles were synthesized by means of a sol-gel method and embedded in poly(methyl methacrylate) (PMMA) by melt compounding. The zirconia was well dispersed in the PMMA matrix, with only a few clusters, especially for the highest investigated zirconia content. NMR results showed heteronuclear dipolar interactions involving the carbons and the surrounding hydrogen nuclei. The effect of the amount of zirconia, in the range of 1–5!wt%, on the thermomechanical properties and thermal degradation kinetics of PMMA was also investigated by means of dynamic mechanical analysis (DMA), thermogravimetric analyses (TGA), and Fourier-transform infrared spectroscopy (FTIR). The presenc…

Synthesis of nanosized powders Nd-doped YAG by coprecipitation and microemulsion methods

Micellization in Model Surfactant Systems

Formation of micelles in model lattice surfactant systems was studied by a novel methodology based on grand-canonical Monte Carlo simulations. The methodology involves combining free-energy information from a series of simulations in small systems by histogram reweighting. The solution osmotic pressure as a function of overall volume fraction of surfactant shows a sharp break at the critical micelle concentration (cmc) at sufficiently low temperatures. Studies in larger systems at appropriate values of the surfactant chemical potential are used to investigate the size distribution of micellar aggregates. The methodology allows for a clear distiction between micellization and macroscopic pha…

Study of the Curing Process of DGEBA Epoxy Resin Through Structural Investigation

In this work, a multi-scale approach with different analytical methods is applied to study the curing process and the structural properties of a diglycidyl ether of bisphenol A (DGEBA) epoxy resin. This monomer, thermally cured using 4,4′-diaminodiphenilsulfone (DDS) as hardener, is analyzed after 10, 45, 90, and 120 min of reaction time at 180 °C to obtain information on samples with different cross-linking densities. Samples are also characterized after extraction in acetone in order to obtain structural information on the insoluble parts. For this purpose, differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), solid-state nuclear magnetic resonance (ss-NMR),…

Il cratere attico a fondo bianco del Pittore della Phiale al Museo Archeologico di Agrigento: primi dati da un’indagine composizionale sui pigmenti

Il cratere attico a fondo bianco del pittore Phiale (440 a.C.), esposto al Museo Archeologico "Pietro Griffo" di Agrigento è un manufatto di grande raffinatezza. Raffigura il mito di Perseo e Andromeda ed è molto interessante sia per l'iconografia che per la tecnica pittorica generalmente documentata su lekythoi e vasi più piccoli. La presente ricerca interdisciplinare si è concentrata sulla tecnica pittorica di questo cratere ed è stata condotta direttamente al Museo mediante tecniche spettroscopiche non invasive e non distruttive (fluorescenza a raggi X e TRFTIR). Lo studio, di cui presentiamo qui i risultati preliminari, intende definire la natura del terreno bianco e pigmenti (secondo b…

Luminescence properties of neodymium-doped yttrium aluminium garnet obtained by the co-precipitation method combined with the mechanical process

Nanopowders of yttrium aluminium garnet Y3Al5O12 (YAG) doped with neodymium ions were obtained by the co-precipitation method from the reaction of aluminium and yttrium nitrate and neodymium oxide with ammonia. After washing and drying the hydroxide precursors were calcined at 500, 700, 800 and 900 °C for 1 hour and at 1000 °C for 3 hours. This product was treated by ball milling in a zirconia vial for 0.5, 1.5 and 10 h in order to achieve smaller nanoparticles. The structure, microstructure, morphology and optical properties were investigated by means of diffractometric, microscopic and spectroscopic techniques. The course of the amorphous-to-crystalline transformation was complete after c…

Interazioni non covalenti tra esteri fosforici e nanotubi di carbonio a parete multipla

Fin dal 1991, quando Iijima li osservò per la prima volta, i nanotubi di carbonio (CNT) sono diventati oggetto d'interesse scientifico, in virtù delle loro proprietà fisiche, chimiche e meccaniche. Un impiego molto interessante riguarda l'aumento di stabilità di matrici polimeriche. I nanocompositi polimerici, in cui sono presenti percentuali molto basse di CNT (2.5%), presentano enormi miglioramenti nelle caratteristiche termomeccaniche, nella resistenza al calore e nella conduttività elettrica. C'è, però, un impedimento fondamentale a tutte le applicazioni che riguarda l'insolubilità intrinseca dei CNT nei solventi. La funzionalizzazione sia essa covalente che non è un espediente per ovvi…

Sicilian Byzantine Icons through the Use of Non-Invasive Imaging Techniques and Optical Spectroscopy: The Case of the Madonna dell’Elemosina

The iconographic heritage is one of the treasures of Byzantine art that have enriched the south of Italy, and Sicily in particular, since the early 16th century. In this work, the investigations of a Sicilian Icon of Greek-Byzantine origin, the Madonna dell’Elemosina, is reported for the first time. The study was carried out using mainly non-invasive imaging techniques (photography in reflectance and grazing visible light, UV fluorescence, infrared reflectography, radiography, and computed tomography) and spectroscopic techniques (X-ray fluorescence and infrared spectroscopy). The identification of the constituent materials provides a decisive contribution to the correct historical and arti…

Corrigendum to “The effect of silica nanoparticles on the morphology, mechanical properties and thermal degradation kinetics of PMMA [Pol. Degrad. Stab. 97 (2012) 452-459]. Polymer Degradation and Stability 97 (2012) 2477

The Small Angle Scattering technique: an effective tool in the structural investigation of archaeologically relevant specimens

An overview of application of Small Angle X-ray Scattering (SAXS) techniques to topics of interest in the field of Cultural Heritage is presented. The basic concepts of the technique, a description of sources and laboratory instrumentation and some models and methods for data analysis are discussed. Applications of SAXS to various kinds of materials are reported to obtain information on the structure useful to shed light in some subjects such as preparation, physical treatment, traceability and degradation of materials.

Preparation and characterization of Ce:YAG-PMMA and Ce:YAG-PC composites for white LED

Polymeric composites of lanthanide-doped materials were considered as potential candidates for the development of white LED. Ce:YAG-PMMA and Ce:YAG-PC composites were prepared by melt compounding. The characterization was performed using transmission electron microscopy, X-ray diffractometry, thermogravimetry and photoluminescence spectroscopy. The effect of filler quantity, in the range 0.1-5 wt.%, on the morphology, optical and thermal properties was investigated.

Synthesis and characterization of neodimium doped yttrium aluminum garnet (Nd-YAG) nanoparticles.

High Resolution-magic Angle Spinning NMR Study of Olive Leaves

In recent years HR-MAS 1H NMR spectroscopy has proven to be a useful tool for the rapid determination of the metabolic profile of several solid and semisolid foods, such as fruits and vegetables, cheese and meat. Olive leaves are today recognized as direct sources of bioactive compounds and natural antioxidants (flavonoids, secoiridoids) suitable as food additives, and their extracts form the basis of beauty care products and pharmaceutical supplements. Thus, olive leaves are emerging as a new and potentially important product for olive tree growing regions. In this report we present the application of 1H and 13C HR-MAS 1D and 2D NMR spectroscopy for the characterization and analysis of tri…

Ce:Y3Al5O12−Poly(methyl methacrylate) Composite for White-Light-Emitting Diodes

A Ce:YAG-poly(methyl methacrylate) (PMMA) composite was prepared by using the melt compounding method. The structure and morphology were investigated by X-ray diffractometry, transmission electron microscopy, and small-angle X-ray scattering. The optical properties (emission, excitation, and fluorescence decay rate) of the composite were studied by using photoluminescence spectroscopy. The polymer–filler interactions were studied using 13C cross-polarization magic-angle spinning NMR spectroscopy (13C{1H} CP-MAS NMR). The results indicated that Ce:YAG particles are well-dispersed in the PMMA matrix without loss of their luminescence properties or significant spectral shift, thus suggesting t…

Quasi-elastic light scattering in polymer-containing microemulsion

Abstract Quasi-elastic light scattering (QELS) was performed in dilute water in oil microemulsion stabilized by AOT surfactant. The water-soluble polyethylene oxide (PEO) with low molecular weight (8000) added to the microemulsion seems to be confined within the aqueous microphase, since PEO is insoluble in oil (n-heptane). The measurements by QELS of diffusion coefficient, at dilute concentrations, allow determination of the size of the droplets. The phase diagram of the microemulsion undergoes remarkable changes on addition of the polymer. The results show that at fixed R ( water surfactant ratio) the droplets decrease their size as the concentration of polymer increases. This occurrence …

A combination of portable non-invasive techniques to study on reverse glass paintings at Mistretta museum

Abstract Reverse painting on glass is an old decorative technique used since the Roman time consisting in applying a cold paint layer on the reverse side. The Sicilian Regional Museum of forestry and pastoral traditions in Mistretta (Messina, Italy) houses the largest collection of reverse glass paintings in Italy with a total of 195 artworks. The artworks are attributed to the different Italian geographic area from north to south Italy. A combination of non-invasive analysis by using complementary portable spectroscopic instrumentations (mainly XRF and Raman Spectrometers) was applied on some selection of reverse glass paintings. The goal of the work is the characterization of the nature o…

Indagine composizionale sulle pitture di due vasi di Centuripe

Due vasi Centuripe a Palermo sono stati analizzati utilizzando XRF portatile complementare e FTIR a riflessione totale spettroscopie. Le analisi consentono di chiarire la tavolozza e la tecnica della decorazione (pittura a tempera con un legante organico), e mostrano la presenza di pigmenti sia antichi che moderni (a causa di qualche recente riverniciatura). Uno dei risultati più interessanti è stata l'identificazione di due fasi del solfato di calcio nello strato sottostante i dipinti: a causa delle condizioni che trasformano il gesso in bassanite, la presenza di il gesso o, in alternativa, la bassanite in ciascuna parte analizzata possono rappresentare un criterio per distinguere l'origin…

Corrigendum to “The effect of silica nanoparticles on the morphology, mechanical properties and thermal degradation kinetics of PMMA” [Polym Degrad Stab 97 (2012) 452–459]

Fractal approach in petrology: Small-angle neutron scattering experiments with volcanic rocks.

Following Mandelbrot's pioneering work in 1977, we attempt to use the concept of fractal dimension in petrology. Fractal dimension is an intensive property of matter which offers a quantitative measure of the degree of surface roughness. Neutron scattering experiments have been performed on 18 volcanic rocks from different localities. The scattered intensity as a function of the momentum transfer obeys a power law whose exponent varies, for the rock samples presented, between -3 and -4. We conclude that, at the molecular level, our volcanic rocks are not fractal volumes. With regard to the particle-matrix interface, it is not possible to provide a determination at the present stage of resea…

MCM-41-CdS nanoparticle composite material: Preparation and characterization

The preparation and characterization of a hierarchical material constituted by a mesoporous silica MCM-41 whose mesochannels contain CdS nanoparticles capped with both bis(2-ethylhexyl) amine and bis(2-ethylhexyl) sodium sulfosuccinate is reported. MCM-41 powder was synthesized by using the LCT methodology. CdS nanoparticles were obtained within the inversed micelle core of a water/ AOT/n-heptane microemulsion. Nanoparticles growth was followed by means of UV–Vis spectroscopy and was inhibited by BEA addition. The CdS-capped nanoparticles were separated by centrifugation, washed with water and ethanol and finally dispersed in n-heptane. The insertion of CdS nanoparticles into MCM-41 mesocha…

Effect of elongational flow on morphology and properties of polymer/CNTs nanocomposite fibers

Carbon nanotubes (CNTs) have been attracting increasing interest for the fabrication of polymer-based nanocomposites because of their excellent properties. Traditional methods for the preparation of polymer/CNTs nanocomposites are in situ polymerization, solution blending, and melt mixing. The achievement of a good CNT dispersion and a percolation network is important in order to obtain better mechanical and electrical properties. However, the rheological behavior of polymer/CNTs systems, in particular regarding the extensional flow, has not been much investigated so far. In this work we present, for the first time, rheological data in non-isothermal extensional flow and an investigation on…

A multi-disciplinary investigation of the "Tavolette fuori posto" of the "Hall of Barons" wooden ceiling of the "Steri" (Palermo, Italy)

Abstract Four painted slabs, called “Tavolette fuori posto” (Slabs out of place), of Galleria Interdisciplinare Regionale della Sicilia — Palazzo Abatellis (Palermo, Italy) were investigated with multi-techniques approach by using noninvasive and micro-destructive techniques. The slabs presumably belong to the decoration of the wooden ceiling of the “Hall of Barons” of the Palazzo Chiaramonte, said Steri, in Palermo (Italy). The aim of this study was to investigate the kind of materials used by the artist, the executive technique and the state of conservation. Pigments, binders and trace of previous restorations were identified. The results were used to properly plan the restoration interve…

A multivariate approach to the study of orichalcum ingots from the underwater Gela's archaeological site

Abstract In this work a careful ICP-OES and ICP-MS investigation of 38 ancient ingots has been performed to determine both major components and trace elements content to find a correlation between the observed different features and the composition. The ingots, recovered in an underwater archaeological site of various finds near Gela (CL, Italy), were previously investigated by X-Ray Fluorescence (XRF) spectroscopy to know the composition of the alloy and it was found that the major elements were copper and zinc, in a ratio compatible with the famous orichalcum similar to the contemporary brass that was considered a precious metal in ancient times. The discovery of huge amount this alloy is…

Solid State NMR Spectroscopy Investigation of the Molecular Structure of Epoxy Based Materials Cured in Different Conditions

In this work two epoxy resin model systems, whose monomers are typically used in structural composites, were thermally cured in different cure conditions in order to obtain different cross-linking densities. Their molecular structures were investigated through solid state NMR spectroscopy in order to correlate them to the cure process conditions used and the results were discussed in the light of the dynamical mechanical thermal analysis (DMTA) performed.

On the role of extensional flow in morphology and property modifications of MWCNT/polyamide-based fibres

Unfilled and MWCNT-filled PA fibers are prepared and the effect of the extensional flow on their mechanical performance and morphological variations is investigated. Morphological analyses using SEM, TEM, and SAXS suggest a stronger orientation of the MWCNTs along the fiber direction with increasing extensional flow. A particular MWCNT bundle formation in the PA drawn nanocomposite fibers is observed for the first time, and a pull-out of the central nanotube in some bundles is noted. The maintenance of the “shish-kebab” structure upon extensional flow is responsible for the mechanical improvements and dimensional stability in MWCNT-filled PA fibers.

Nanometric semiconductor particles in mesoporous silica: synthesis and characterization

Solid state NMR applications in the field of cultural heritage

Solid State NMR characterization of the waterlogged wooden part of Acqualadrone roman rostrum

Study on the stability of dispertions of zirconia nanoparticles

La diagnostica chimico-fisica a supporto della conservazione e del restauro delle opere cartacee

Questo contributo è stato prodotto a seguito dell’intervento del Prof. Caponetti e della sessione laboratoriale guidata dalla Dott.ssa Saladino in collaborazione con il Dott. Renda e la Dott.ssa Chirco in cui è stata realizzata una dimostrazione pratica di come si possano eseguire le indagini di materiale cartaceo con strumentazione portatile. Nel presente contributo sono presentate e illustrate alcune delle tecniche di indagine idonee per l’analisi di opere cartacee, ed in particolare alcune di quelle che possono essere applicate mediante strumentazione portatile. Queste tecniche forniscono informazioni complementari e consentono la conoscenza dell’opera stessa (tipologia di carta, tecnica…

A study on the essential oil of Ferulago campestris : How much does extraction method influence the oil composition?

The essential oil of different parts of Ferulago campestris (Bess.) collected in Sicily has been extracted by microwave-assisted hydrodistillation (MAHD) and by classic hydrodistillation (HD). A comparative qualitative-quantitative study on the composition of the oils was carried out. A total of 100 compounds were identified in the oils obtained by MAHD, whereas 88 compounds characterized the HD oils. The most prominent components were, in all different parts of F. campestris and in both extraction methods, 2,4,5-trimethylbenzaldehyde and 2,4,6-trimethylbenzaldehyde isomers; the latter was not previously found. The attempt to evaluate where the oil components are located in all parts of the…

Convenient Photochemical Synthesis of Silver-Polyaminocyclodextrin Nanocomposites: The Role of the Light Source from a Mechanistic Viewpoint

An investigation on the light-driven reduction of the [Ag(NH3)2]+complex in the presence of polyaminocyclodextrins was carried out, in order to clarify the mechanism of the process. The role of the organic auxiliary as both the sacrificial reductant and the capping agent was positively assessed. Moreover, particular attention was paid to the role of the irradiation source. Experimental results indicate that a complex mechanism is involved in the formation of the nanocomposite, with a primary photoinduced single-electron-transfer process promoted by irradiation with green light, followed by a secondary chemical reduction process activated by NIR. Representative composites were characterized …

Synthesis of yttrium aluminum garnet nanoparticles in confined environment II: Role of the thermal treatment on the composition and microstructural evolution

Abstract Nanoparticles of yttrium aluminum garnet (YAG, Y 3 Al 5 O 12 ) have been obtained by thermal treatments, at several temperature in the range 400–950 °C, of the precursors synthetized via co-precipitation in water in oil microemulsion. The obtained nanoparticles have been characterized by means of X-ray Diffraction and Transmission Electron Microscopy coupled with Energy Dispersive X-ray Spectroscopy (EDS) and Select Area Electron Diffraction (SAED). Results show the phase evolution occurring to obtain not aggregated nanoparticles of YAG phase. A possible growth mechanism of YAG nanoparticles is discussed on the basis of observed particle microstructure and morphology. The results i…

Co-precipitation synthesis of Nd:YAG nano-powders: the effect of Nd dopant addition with thermal treatment

Nanopowders of Yttrium Aluminium Garnet doped with neodymium ions were obtained by the co-precipitation method from the reaction of aluminium, yttrium and neodymium nitrate with ammonia. The amount of neodymium was selected in order to produce samples of nominal stoichiometry NdXY (3-X)Al5O12 (where X = 0.006, 0.012, 0.024, 0.048, 0.081, 0.096, 0.17, 0.19, 0.38, 0.54, and 0.72, respectively). After washing and drying, the hydroxide precursors were subjected to Thermo-Gravimetry and Differential Thermal Analysis experiments from room temperature up to 1500 °C, which showed the presence of exothermal events accompanying phase transformation phenomena. X-ray diffraction investigations conducte…

Determination of selected polyaromatic hydrocarbons by gas chromatography–mass spectrometry for the analysis of wood to establish the cause of sinking of an old vessel (Scauri wreck) by fire

Abstract The aim of this paper was to establish the cause of sinking of an old wooden vessel by polycyclic aromatic hydrocarbon (PAH) analyses because wood combustion is a source of PAHs. In particular, the molecular PAH patterns generated by each source are like fingerprints and it is possible to determine the processes that generate PAHs by studying their distribution in wood samples. The relative abundance of high molecular weight PAHs, together with the PAH compound ratios and with total index (proposed by us) has demonstrated that samples owe their PAHs in wood archaeological material to a predominant single mode of origin, i.e. combustion processes, therefore we can say that the sinki…

A New Methodological Approach to Correlate Protective and Microscopic Properties by Soft X-ray Microscopy and Solid State NMR Spectroscopy: The Case of Cusa’s Stone

Hydrophobic treatment is one of the most important interventions usually carried out for the conservation of stone artefacts and monuments. The study here reported aims to answer a general question about how two polymers confer different protective performance. Two fluorinated-based polymer formulates applied on samples of Cusa’s stone confer a different level of water repellence and water vapour permeability. The observed protection action is here explained on the basis of chemico-physical interactions. The distribution of the polymer in the pore network was investigated using scanning electron microscopy and X-ray microscopy. The interactions between the stone substrate and the protective…

Structure of a quaternary microemulsion by changing its composition

ENERGY DISPERSIVE X-RAY DIFFRACTION IN CULTURAL HERITAGE SCIENCE: THE WINNING DUO OF STRUCTURAL AND ELEMENTAL ANALYSIS

The capabilities of Energy-Dispersive X-ray Diffraction (EDXD) in the field of Cultural Heritage are disccussed. EDXD diffractometer, equipped with a white source, is particularly suited for the structural and elemental analysis of items having different nature. Given its compact and versatile design, the instrument allows to collect data from samples without tearing down of any portion and with no specific preparation. In the wide energy range sampled during the measurements, both X-ray fluorescence and diffraction features appear. In all cases, data are acquired in air and in a non-destructive way, and their collection is fast.

Structural investigation of e-beam cured epoxy resins through solid state NMR

Abstract In this paper the network structure of e-beam cured DGEBF based epoxy resins is investigated. Two epoxy systems, having different reactivity and cured in different process conditions, were analyzed through solid state NMR spectroscopy. The analysis shows that the more reactive system has higher cross-linking density and higher uniformity of network distribution. Similar information were obtained, in a previous work, on the same systems through dynamic mechanical thermal analysis. It is worth noting that unlike DMTA tests, which interfere with the molecular structure of the analyzed material, due to the heating during the analysis itself, more reliable information, without any artef…

Ce:YAG-PMMA nanocomposite for white LED

Ce:YAG-PMMA composite was prepared by a melt compounding method. The characterization was performed using transmission electron microscopy, X-ray diffractometry, and photoluminescence spectroscopy. Results showed that Ce:YAG particles are well dispersed in the polymeric matrix. The luminescence properties of the nanocomposite do not show quenching or significant spectral shift indicating that the nanocomposite can be useful for advanced applications such as white LED construction.

Sensor Properties of Pristine and Functionalized Carbon Nanohorns

Nanodispersions of pristine single-wall carbon nanohorns (i.e., p-SWCNHs) and oxidized-SWCNHs (i.e.; o-SWCNHs) were used to modify screen printed electrode (SPE). p-SWCNHs and o-SWCNHs were fully characterized by using several analytical techniques, as: HR-TEM (High Resolution-Transmission Electron Microscopy), FE-SEM/EDX (Field Emission-Scanning Electron Microscopy/Energy Dispersive X-ray Analysis), Raman spectroscopy, thermogravimetric analysis, differential thermal analysis (DTA), and the Brunauer-Emmett-Teller (BET) method. The chemically modified SPEs were also characterized with Cyclic Voltammetry (CV), using several different electro-active targets. In all cases, p-SWCNHs showed bett…

Physicochemical characterization of metal hexacyanometallate–TiO2composite materials

The paper describes the synthesis and characterization of novel TiO2–metal hexacyanometallates (MHCMs) composite materials. The starting material, TiO2, was modified by addition of cobalt-hexacyanoferrate (CoHCF) or iron-hexacyanocobaltate (FeHCC) at various concentrations. The resulting composites were characterized as follows: cyclic voltammetry (CV) followed the formation of TiO2–MHCM clusters, TEM micrographs studied their morphology, XAS and XPS data indicated that MHCM bonds to TiO2 through the nitrogen atom of its –CN group and modifies the environment of Ti compared to that of pure anatase. As expected, and confirmed by UV-Vis and XP-valence band data, the electronic properties of T…

A novel radiation exposure control apparatus for microwave assisted chemical reactions

AbstractA radiation exposure control apparatus is used for microwave (2.45 GHz) treatment of chemical reactions in controlled and reproducible conditions. A spectrophotometer has been interfaced with the microwave set-up in order to monitor the reaction evolution in situ. Both numerical and experimental dosimetries are carried out in order to evaluate the field distribution within the sample. Finally, particular working conditions are suggested.

The Acqualadrone Rostrum: a physical-chemical investigation to understand the Material History

The aim of this work is to define the conservation state and to ascertain the provenance of raw materials used in the construction of the Acqualadrone Rostrum. In 2008 the rostrum (an offensive naval weapon mounted on the prow at the waterline), from an ancient warship was recovered from the Mediterranean near Acqualadrone, Messina, Sicily. The archaeological discovery has led to the need for scientific research in order to plan the conservation treatment of this artefact. The discovery is exceptional because of the presence of a wooden section from the original ship. The physical-chemical investigation, by using some complementary spectroscopic techniques, was focused on the characterizati…

Portable non invasive analyses for Cultural Heritage

The requirements that the scientific analyses for Cultural Heritage must have are: nondestructive and noninvasive, multielemental, sensitive, reliable and sufficiently rapid, able to carry out measurements in situ on objects of all types, and to deduce information practically on-line. Among the techniques that fulfill these requirements we find: multispectral imaging, portable EDXRF, Raman and UV-VIS-NIR spectrometry. In this paper we are going to show some cases in which it will appear clear the necessity of the correct order with which applying the non invasive techniques and what data of each of them it is necessary to understand in situ to obtain the maximum of the subsequent scientific…

Organic-inorganic nanocomposites prepared by reactive suspension method: investigation on filler/matrix interactions and their effect on the nanoparticles dispersion

Epoxy resin/TiO2 nanocomposites prepared by both reactive suspension method, based on in situ synthesis, and conventional mechanical mixing are analysed by solid-state nuclear magnetic resonance and transmission electron microscopy in order to have a deeper insight into the nature of interactions at the polymer/particle interface and their effect on the nanoparticles dispersion. Specifically, solid-state nuclear magnetic resonance experiments showed that the nanoparticles, synthesized by reactive suspension method, can efficiently link the matrix by hydrogen bonds forming a hybrid organic-inorganic 3D network. Such evidences strongly supports our previously reported theory, in which the nan…

Luminescence properties of neodymium-doped yttrium aluminium garnet obtained by the co-precipitation method combined with the mechanical process.

Nanopowders of yttrium aluminium garnet Y3Al5O12 (YAG) doped with neodymium ions were obtained by the co-precipitation method from the reaction of aluminium and yttrium nitrate and neodymium oxide with ammonia. After washing and drying the hydroxide precursors were calcined at 500, 700, 800 and 900 °C for 1 hour and at 1000 °C for 3 hours. This product was treated by ball milling in a zirconia vial for 0.5, 1.5 and 10 h in order to achieve smaller nanoparticles. The structure, microstructure, morphology and optical properties were investigated by means of diffractometric, microscopic and spectroscopic techniques. The course of the amorphous-to-crystalline transformation was complete after c…

Application of Gas Chromatography coupled with Mass Spectroscopy (GC/MS) to the analysis of archaeological ceramic amphorae belonging to the Carthaginian fleet that was defeated in the Egadi battle (241 B.C.)

<p class="Abstract"><span lang="EN-US">The aim of this preliminary work was to identify characteristic compounds in 7 underwater marine ceramic amphorae sherds dating from the period of the battle of the Egadi Islands that decided the end of the First Punic War (241 B.C.) by Gas Chromatography coupled with Mass Spectroscopy (GC/MS).</span></p>

Morphology, interfacial interaction, and thermal degradation of polycarbonate/MCM-41 (nano)composites

ABSTRACTThis article reports on the morphology, interfacial interaction, thermal stability, and thermal degradation kinetics of polycarbonate (PC)/mesoporous silica (MCM-41) composites with various MCM-41 contents, prepared by melt compounding. The composites with low filler loadings (<0.3 wt%) maintained their transparency because of the well dispersed MCM-41 particles, but at higher filler loadings the composites lost their transparency due to the presence of agglomerates. The presence of agglomerates decreased the thermal stability of PC due to the reduced effectiveness of the particles to immobilize the polymer chains, free radicals, and volatile degradation products.

Effect of nanoparticles on the morphology, mechanical properties and thermal degradation kinetics of polymetylmetacrylate and polycarbonate

Cisplatin derivative loaded in mesoporous MCM-41: preparation and characterization

The aim of this study is to design and investigate a new material constituted by mesoporous silica MCM-41 and a new cisplatin derivative, cis-PtCl2(DMSO)HL]•2DMSO, where HL = 7-amino-2-(methylthio)[1,2,4]triazolo[1,5-a]pyrimidine-6-carboxylic acid, having biological activity.[1] The high surface area and the tunable pore size of MCM-41 allow it for loading vast amounts of bioactive molecules, including biocides and drugs. Mesoporous silica MCM-41 was prepared in alkaline environment from tetraethoxysilane as Si source and cetyltrimethylammonium bromide (CTAB) as template. [2] Amino groups have been successfully grafted onto the pore surface with 3-aminopropyl triethoxysilane (APTES) in orde…

On the nature of phase separation in a commercial aluminium-lithium alloy

Abstract The formation of lithium-rich precipitate particles, known as δ′ phase, is responsible for the particularly desirable mechanical properties which make aluminium-lithium alloys interesting for different industrial applications. The structure and the kinetics of the phase separation process are conveniently studied by small-angle X-ray scattering, though uncertainties remain on the actual shape of the phase diagram of the system, particularly in the region of interest. In this paper are reported small-angle X-ray scattering measurements on a commercial AlLi (8.49% Li atoms) both in the region of formation of the precipitate and during its successive growth. Modelling of the experime…

Application of small angle neutron scattering to micellar fluids

Abstract In this paper we present a short overview of the application of small angle neutron scattering (SANS) to micellar fluids. In the first part of the paper a general expression of the scattering equation is derived, with particular emphasis on the approximations involved and on their practical consequences. In the second part of the paper we present six selected test cases (such as mono- and polydisperse fluids, critical fluids, shapes other than spherical, etc.) taken from our own work, to demonstrate the kind of analysis performed in each case to extract the information from SANS data.

Alcoholic nanolime dispersion obtained by the insolubilisation-precipitation method and its application for the deacidification of ancient paper

Abstract Nanolime dispersions for the deacidification of ancient paper constitute a valid alternative to the lime traditional ones. Their efficacy depends on particles size, polydispersity and agglomeration that can be controlled depending on the preparation method. In this work, nanolime preparation by insolubilisation-precipitation method is reported. Nanoparticles dispersed in a water-isopropanol mixture were obtained without any manipulation of the dispersion. The stability of the dispersion together with particle size and morphology were found to be dependent on water to isopropanol molar ratio and on the synthesis temperature. One of the dispersion was applied on a manuscript to asses…

Synthesis, Characterization and Catalytic Activity of mesoporous Mn-MCM-41 materials

MCM-41 has been synthesized at two different pH using cetyl-trimethylammonium bromide (CTAB) surfactant as template and adding the silica precursor to aqueous solutions containing CTAB. The obtained solids were calcined at 600 ◦C for 4 h. Mn-MCM-41 powders with different Mn/Si molar ratios were prepared using the incipient wetness method, followed by calcination at 550 ◦C for 5 h. At the end of the impregnation process the powders colour changed from white to brown whose intensity depends on manganese quantity. The materials characterization was performed by X-ray diffraction, N2 adsorption, 29Si Cross Polarization–Magic Angle Spinning NMR, and X-ray Photoelectron Spectroscopy. The effects …

H3PW12O40 supported on mesoporous MCM-41 and Al-MCM-41 materials: preparation and characterisation

MCM-41 and Al–MCM-41 has been synthesized using cetyl-trimethylammonium bromide (CTAB) surfactant as template and adding the silica precursor to aqueous solutions containing CTAB. The obtained solids were calcined at 600 °C for 4 h. HPW heteropolyacid supported on the mesoporous were prepared using the incipient wetness method. The characterization of materials was performed by X-ray diffraction, Transmission Electron Microscopy, N2 adsorption, 29Si Cross Polarization–Magic Angle Spinning and 27Al MAS NMR. Results showed that the hexagonal structure is obtained in both cases. The Aluminium species are located inside an extra-framework. The impregnation reduces the surface area of the mesopo…

Energy dispersive X-ray diffraction potentiality in the field of cultural heritage: simultaneous structural and elemental analysis of various artefacts.

The applicability of an Energy Dispersive X-ray Diffractometer to some technical questions in the field of Cultural Heritage is presented. This diffractometer, equipped with a white source, has been utilized for the structural and elemental analysis of some items having different nature. Given its design, the instrument allows to collect data from samples as big as a book or a little more. Samples, without collection of any portion and without any preliminary preparation, have been placed in the instrument and spectra have been collected in a wide energy range that contains X-ray fluorescence and diffraction features. In all cases, data acquired in air and in a non destructive way were reli…

Influence of cerium content and heat treatment on Ce:YAG@glass wool nanostructures

The paper reports the influence of cerium content and heat treatment on composition, structural features and optical properties of nanostructures constituted by a layer of Ce:YAG nanoparticles on glass wool (Ce:YAG@GW). The Ce:YAG@GW nanostructures were obtained embedding the glass wool (GW) in a gel-like precursor and calcining at 800 and 900 °C. Gel-like precursor of urea glass route (UGR) method has been used to prepare both nanostructures and Ce:YAG nanoparticles prepared as references. Structural properties were investigated by using X-ray diffraction (XRD) and infrared spectroscopy (IR). Results showed that the composition of the final products strongly depends both on the cerium cont…

Small angle scattering study of the structure of isotactic polypropylene-hydrogenated oligo(cyclopentadiene) blends

Abstract Blends of isotactic polypropylene ( i PP) and hydrogenated oligo cyclopentadiene (HOCP) have been studied by means of small angle X-ray scattering in the temperature range 70–160°C. The structure of blends containing less than 25% HOCP is very similar to the one of plain i PP, i.e. lamellae whose thickness increases by increasing the temperature. Blends containing more than 25% HOCP are characterized by two kinds of lamellae formed by layers of i PP and amorphous material rich in i PP and in HOCP, respectively. The crystallizable i PP present in both phases crystallizes from the melt, in analogy to what happens in HDPE/HOCP blends and in agreement with the values of the crystallini…

Tungsten -catalysts supported on ZrO2 nanopowder