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…

New Insight on Archaeological Metal Finds, Nails and Lead Sheathings of the Punic Ship from Battle of the Egadi Islands

The wreck of the Punic ship exhibited at the Archaeological Park of Lilybaeum (Marsala, Italy) is a unique example in the world. In this paper, the investigation of some metal finds (30 nails and 3 fragments of sheathings) belonging to the wreck of the Punic ship is reported. Portable X-ray fluorescence and Raman spectroscopy allowed us to identify the elements and compounds constituting them and make some deductions about their composition. X-ray diffractometry, polarised optical microscopy and scanning electron microscopy of the collected micro-samples allowed us to explain the degradation that occurred in the underwater environment.

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

Properties and Structural Studies of Multi-Wall Carbon Nanotubes-Phosphate Ester Hybrids

Long chain phosphate esters bearing at least one or two aryl groups have been synthesized and used for the preparation of stable multi-walled carbon nanotube (MWCNT) hybrids. The non-covalent interaction ester/MWCNT has been investigated by several techniques (SEM, UV-vis, 31P-NMR, RAMAN). The used phosphate ester derivatives demonstrated the ability to produce an excellent dispersion of MWCNT in CHCl3. The obtained dispersions showed a great stability from one to at least three weeks in the range of concentration considered. Thermal analysis showed an increase in the decomposition temperature for the hybrids with respect to pristine MWCNT.

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

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…

Effects of thermal treatment on Eu:YAG nanopowder structure

Polyaminocyclodextrin nanosponges: synthesis, characterization and pH-responsive sequestration abilities

New pH-responsive nanosponges were obtained by reacting four different polyaminocyclodextrins with heptakis-(6-bromo)-(6-deoxy)-β-cyclodextrin. The materials obtained were characterized by various techniques (FT-IR, potentiometric titration, differential scanning calorimetry (DSC), porosimetry (BET), 13C{1H} CP-MAS NMR). Their adsorption abilities at different pH values were verified towards a suitable set of model guests, and seem mainly controlled by electrostatic interactions, as a function of the protonation/charge status of the polymer matrix. By contrast, data positively point out a lesser importance assumed by the induced-fit effect, important in affecting the formation of host–guest…

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

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

Abstract Polycarbonate/silica 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 polycarbonate (PC) was investigated. Clusters of silica nanoparticles were well dispersed in the polycarbonate whose structure remained amorphous. NMR results showed intermolecular interactions involving the carbonyl groups of different polymeric chains which did not affect the intramolecular rotational motions. The presence of the lowest silica content showed a decrease in the storage and loss moduli below the glass transition temperature, pro…

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…

Investigation of archaeological amphorae from the Egadi battles

Abstract Archaeological ceramics are considered one of the most important sources of both technological and chronological information. Here, the investigation of some archaeological underwater amphorae from the Egadi’s Battle, that decided the end of the First Punic War (241 B.C.), is reported. X-ray Diffraction (XRD), X-ray Fluorescence (XRF), petrography, and Thermoluminescence (TL) were used to determine the composition of the amphorae and to evaluate the compatibly of their age with the above Battle. Considering the historical importance of the act and the well-defined historical collocation these amphorae represent an interesting archaeometric case study.

Thermomechanical properties and thermal degradation kinetics of poly(methyl methacrylate) (PMMA) and polycarbonate (PC) filled with cerium-doped yttrium aluminium garnet (Ce:YAG) prepared by melt compounding

This paper reports on the thermomechanical properties and thermal degradation kinetics of poly(methyl methacrylate) (PMMA) and polycarbonate (PC) composites filled with cerium-doped yttrium aluminium garnet (Ce:YAG) at different contents ranging between 0.1 and 5 wt%, and prepared by melt compounding. The interaction between PMMA and the filler was much stronger than that between PC and the filler, and this resulted in a significant improvement in the dynamic mechanical properties of the PMMA composites. The presence of filler did not significantly increase the thermal stability of the PC, while an observable increase in the thermal stability was only observed at higher filler loadings for …

Chemometric Tools to Point Out Benchmarks and Chromophores in Pigments through Spectroscopic Data Analyses

Spectral preprocessing data and chemometric tools are analytical methods widely applied in several scientific contexts i.e., in archaeometric applications. A systematic classification of natural powdered pigments of organic and inorganic nature through Principal Component Analysis with a multi-instruments spectroscopic study is presented here. The methodology allows the access to elementary and molecular unique benchmarks to guide and speed up the identification of an unknown pigment and its recipe. This study is conducted on a set of 48 powdered pigments and tested on a real-case sample from the wall painting in S. Maria Delle Palate di Tusa (Messina, Italy). Four spectroscopic techniques …

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…

Non-invasive investigation on pigments of the Aeolian Islands Neolithic pottery

The Neolithic painted pottery, spread all over southern Italy, is considered as an important chronological indicator for the development of VI-V millennium BC prehistoric settlements and cultural traditions. The goal of this work is to contribute to the study of this ceramic class through the chemical characterization of some samples coming from the Aeolian Islands. 16 different sherds have been selected and the pigments preserved in their decorations analyzed via non-invasive techniques: Fiber Optical Reflectance Spectroscopy (FORS), X-ray Fluorescence (XRF), Raman Spectroscopy and Infrared Spectroscopy (FT-IR). The different pigments, some of which no longer clearly visible to the naked e…

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…

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…

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…

Improved chemometric approach for XRF data treatment: application to the reverse glass paintings from the Lipari collection

The Aeolian cultural heritage preserves hundreds of testimonies of the past that have passed through six millennia of history. Among these, the Archeological Park of the Aeolian Islands with the Museum Luigi Bernab`o Brea (Italy) preserves a valuable set of artworks, which are related to a little-known ‘popular’ figurative heritage. It is an assemblage of small glass foils decorated using the technique of reverse painting, datable to between the end of the 17th century and the end of the 18th century, and actually under investigation by historians. Here, an X-ray fluorescence (XRF) spectroscopy study (performed with portable equipment) is combined with a multivariate approach that allows us…

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…

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…

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…

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

Influence of the modification, induced by zirconia nanoparticles, on the structure and properties of polycarbonate

Melt compounding was used to prepare polycarbonate (PC)–zirconia nanocomposites with different amounts of zirconia. The effect of the zirconia loading, in the range of 1–5 wt.%, on the structure, mechanical properties and thermal degradation kinetics was investigated. The zirconia nanoparticle aggregates were well dispersed in the PC matrix and induced the appearance of a local lamellar order in the polycarbonate as inferred by SAXS findings. This order could be a consequence of the intermolecular interactions between zirconia and the polymer, in particular with the quaternary carbon bonded to the methyl groups and the methyl carbon as inferred from the NMR results. The presence of zirconia…

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…

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…

New biocides based on imidazolinium-functionalised hybrid mesoporous silica nanoparticles

Here, we report the development of a new biocide based on hybrid mesoporous silica nanoparticles (MSN). The MSN was synthesized by condensation method in emulsion followed by grafting with two different silylated ionic liquid moieties, namely butyl imidazolinium bromide and imidazolinium propansulfonate betaine. Features of nanoparticles were characterized by Thermogravimetry, Infrared and ss-NMR Spectroscopy, and Transmission Electron Microscopy. The antibacterial properties were tested against a Gram-positive bacterial strain previously isolated from artefacts of interest in the field of Cultural Heritage. Interestingly, the hybrid material presents an antibacterial activity higher than i…

Archaeometric study of execution techniques of white Attic vases: the case of the Perseus crater in Agrigento

The white ground crater by the Phiale Painter (450–440 BC) exhibited in the “Pietro Griffo” Archaeological Museum in Agrigento (Italy) depicts two scenes from Perseus myth. The vase is of utmost importance to archaeologists because the figures are drawn on a white background with remarkable daintiness and attention to detail. Notwithstanding the white ground ceramics being well documented from an archaeological and historical point of view, doubts concerning the compositions of pigments and binders and the production technique are still unsolved. This kind of vase is a valuable rarity, the use of which is documented in elitist funeral rituals. The study aims to investigate the constituent m…

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…

The Church of S. Maria Delle Palate in Tusa (Messina, Italy): Digitization and Diagnostics for a New Model of Enjoyment

Cultural places represent the tangible part of the identity and historical heritage of a civilization as well as an extraordinary driving force for the economic development of a country. Within its huge asset, Italy counts a wide number of archaeological sites and monuments which, despite their cultural value, are totally cut off from the most important cultural routes. This paper aims to demonstrate how specific actions of digitization can contribute to valorize (restoring a cultural value) ‘marginal’ landmarks, promoting their knowledge and inclusion. The case study described is represented by the Church of “Santa Maria delle Palate”, located inside the well-known …

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

Graphene coating obtained in a cold-wall CVD process on the Co-Cr Alloy (L-605) for medical applications

Graphene coating on the cobalt-chromium alloy was optimized and successfully carried out by a cold-wall chemical vapor deposition (CW-CVD) method. A uniform layer of graphene for a large area of the Co-Cr alloy (discs of 10 mm diameter) was confirmed by Raman mapping coated area and analyzing specific G and 2D bands

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…

Identifying the Unknown Content of an Ancient Egyptian Sealed Alabaster Vase from Kha and Merit’s Tomb Using Multiple Techniques and Multicomponent Sample Analysis in an Interdisciplinary Applied Chemistry Course

This article highlights the multianalytical study of exuded liquid from an ancient Egyptian sealed alabaster vase by Master's students in an applied chemistry for cultural heritage course. Master students are introduced to the field of Archaeometry that see the collaboration of experts in different areas of research such as conservators, curators of museums, physicists, chemists, etc. The sample is a residue exuded on the linen strip sealing an ancient Egyptian alabaster vase (inventory number S.8448) from the collection of the Museo Egizio in Turin (Italy). The students start to plan the noninvasive investigation by X-ray fluorescence (XRF), transmission electron microscopy (TEM), and ener…

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.

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…

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…

Effect of Ce3+ concentration on persistent luminescence of YAGG:Ce3+,Cr3+,Nd3+ nanophosphors obtained by the co-precipitation method

Abstract Synthesis of Y3Al2Ga3O12 garnet (YAGG) nanophosphors co-doped with Ce3+, Cr3+, and Nd3+ ions by co-precipitation is reported. The effect of Ce3+ concentration on the structure of garnet and on optical properties including persistent luminescence was investigated. The X-ray diffraction measurements showed that single garnet phase was obtained. The contraction of the crystallites size was observed with increasing the cerium concentration. The combined emission of three used co-dopants together allows to extend persistent luminescence spectral range. The photoluminescence, excitation and persistent luminescence spectra were collected and the optimal Ce3+ concentration for the highest …

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…

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.,

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.

Investigation on a low environmental impact solvent mixture applied to a wooden painted slab

Cleaning is one of the most complex and delicate step in a restoration project, often due to the manufacturing techniques of the artifacts and their advanced state of decay. Eco-friendly solvents can permit to execute the cleaning operations with a reduced health impact for the restorers and for the environment. In this work, the performance of the 1,3- dioxolane/methylal (DIOX-MET) solvent mixture is evaluated over a wooden painted slab that had been covered with a thin layer of a protective varnish, probably during a previous conservation work performed in the Sixties. Removal of this varnish has been considered on behalf of its yellowing degradation process, which caused chromatic change…

Formulation of Mesoporous Silica Nanoparticles for Controlled Release of Antimicrobials for Stone Preventive Conservation

The biotic deterioration of artifacts of archaeological and artistic interest mostly relies on the action of microorganisms capable of thriving under the most disparate environmental conditions. Thus, to attenuate biodeterioration phenomena, biocides can be used by the restorers to prevent or slow down the microbial growth. However, several factors such as biocide half-life, its wash-out because of environmental conditions, and its limited time of action make necessary its application repeatedly, leading to negative economic implications. Sound and successful treatments are represented by controlled release systems (CRSs) based on porous materials. Here, we report on the design and developm…

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…

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…

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.

MCM-41 silica effect on gel polymer electrolytes based on thermoplastic polyurethane

Abstract Polymer electrolytes were prepared from thermoplastic polyurethane with addition of mixture of N-ethyl(methylether)-N-methylpyrrolidinium trifluoromethanesulfonimide (PYRA12O1TFSI) ionic liquid, lithium bis(trifluoromethanesulfoneimide) salt and propylene carbonate. MCM-41 mesoporous silica was added in proportions ranging from 5 to 20 wt.% with respect to TPU. The electrolytes were characterized by thermogravimetric analysis, differential scanning calorimetry, linear voltammetry and impedance spectroscopy. The MCM-41 addition to the system was found to improve the electrochemical stability of the membranes and to reduce the gel electrolyte/metallic Li interfacial resistance. The f…

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…

Multimetallic Oxynitrides Nanoparticles for a New Generation of Photocatalysts

A versatile synthetic strategy for the preparation of multimetallic oxynitrides has been designed and here exemplarily discussed considering the preparation of nanoscaled zinc-gallium oxynitrides and zinc-gallium-indium oxynitrides, two important photocatalysts of new generation, which proved to be active in key energy related processes from pollutant decomposition to overall water splitting. The synthesis presented here allows the preparation of small nanoparticles (less than 20 nm in average diameter), well-defined in size and shape, yet highly crystalline and with the highest surface area reported so far (up to 80 m2  g-1 ). X-ray diffraction studies show that the final material is not a…

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 …

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…

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

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.

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…

Effect of hydrothermal time on the forming specific morphology of YPO4:Eu3+ nanoparticles for dedicated luminescent applications as optical markers

A way to control the desired shape and microstructure of YPO4:Eu3+ nanoparticles through the precipitation method followed by a hydrothermal treatment is reported. This method is useful for achieving very high control over the YPO4:Eu3+ formation process with the selection of appropriate synthesis parameters. In detail, the autoclave processing time allows control of the shape and size of nano-needle-shaped particles independently in both directions, as confirmed by X-ray powder diffraction, FT-IR Spectroscopy and Electron Transmission Microscopy. In order to analyse the effect of the nanoparticles’ surroundings on the excitation and relaxation processes of luminescent ions, Eu3+ ion was us…

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…

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…

Graphene Oxide Carboxymethylcellulose Nanocomposite for Dressing Materials.

Sore, infected wounds are a major clinical issue, and there is thus an urgent need for novel biomaterials as multifunctional constituents for dressings. A set of biocomposites was prepared by solvent casting using different concentrations of carboxymethylcellulose (CMC) and exfoliated graphene oxide (Exf-GO) as a filler. Exf-GO was first obtained by the strong oxidation and exfoliation of graphite. The structural, morphological and mechanical properties of the composites (CMCx/Exf-GO) were evaluated, and the obtained composites were homogenous, transparent and brownish in color. The results confirmed that Exf-GO may be homogeneously dispersed in CMC. It was found that the composite has an i…

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…

IBRIDI FORMATI DA NANOTUBI DI CARBONIO A PARETE MULTIPLA E ESTERI FOSFORICI: PROPRIETA’ E STUDI STRUTTURALI

Nel corso degli ultimi anni i nanotubi di carbonio in virtù delle loro proprietà fisiche, chimiche e meccaniche sono diventati tra i più promettenti materiali per la realizzazione di congegni a livello nanometrico. I CNT trovano numerose applicazioni nel campo, della nanoelettronica, nella costruzione di materiali ad elevata conducibilità elettrica ed elevata resistenza meccanica,2 e vengono, anche, impiegati come agenti di rinforzo dispersi in una matrice polimerica.3 Problema principale di questi materiali è che essi risultano scarsamente solubili in ambiente acquoso e in solventi organici, a causa delle forti forze attrattive di van der Waals che esistono tra le superfici dei CNT, che li…

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…

Effects of solvent-free microwave extraction on the chemical composition of essential oil of Calamintha nepeta (L.) Savi compared with the conventional production method

The essential oil of Calamintha nepeta has been obtained by solvent-free microwave extraction (SFME) and by classical hydrodistillation (HD). A comparative qualitative-quantitative study on the composition of the oils was carried out. A total of 38 compounds, constituting 97.6% of the oil, were identified in the oil obtained by SFME, whereas 46 compounds, representing 95.4% of the oil, were characterized in the HD oil. SFME-distilled oil is richer in lightly oxygenated monoterpenes (LOM) than HD oil. It also has a higher amount of sesquiterpenes and a lower quantity of hydrocarbon monoterpenes. HD oil seems to be affected by chemical changes more than SFME oil.

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…

Polymeric Ce:YAG nanocomposites: synthesis and characterization

These last years, the development of hybrid polymer-inorganic nanocomposites has been attracted much attention. In particular, composites containing lanthanide-doped materials as filler are candidates for the development of light emitting diodes, lasers and solar cells. Polymers such as polymethylmethacrylate (PMMA), polycarbonate (PC) and polyurethane (PU) are adequate matrices because their good transmission over the visible spectral range, excellent mechanical properties of plasticity, lightness, easiness of fabrication and low cost of mass production. Yttrium aluminum garnet (YAG) doped with Ce(III) ions is one of the yellow phosphor used in the major commercial white LED combined with …

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…

Role of the thermal treatment on the microstructure of YAGG nanopowders prepared by urea glass route

Yttrium aluminium gallium garnet (YAGG, Y3Al2Ga3O12) doped with rare-earth ions has drawn large attention owing to its optical properties with applications ranging from persistent luminescent phosphors to nanothermometers. Herein, three different YAGG materials were synthesized via the urea glass route followed by thermal treatment, relatively undoped; doped with Ce3+, Cr3+, and Nd3+; and doped with Ce3+, Cr3+, and Yb3+. The garnet formation was studied in situ upon thermal treatment from 300 to 1000 ◦C using synchrotron powder diffraction. Our results show that with this method, the onset of formation of the garnet is about 860 ◦C, with comparable cell parameters for both undoped and doped…

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

Influence of the Ce: YAG amount on structure and optical properties of Ce:YAG-PMMA composites for white LED

Ce:YAG-poly(methyl methacrylate) (PMMA) composites were prepared by using a melt compounding method, adding several amounts of Ce:YAG in the range 0.1–5wt.%. The optical properties of the obtained composites and of the composites combined with a blue LED were measured to investigate the effect of the amount of Ce:YAG on the resulting emitted light in view of possible application in white LED manufacture. An increase in Ce:YAG amount caused an increase in the emission and a shift of 15 nm, influencing the white LED performance. The structure and morphology of the composites were studied. The results show that the interaction between the two components, observed by using solid state NMR exper…

Catalytic and photocatalytic epoxidation of limonene: Using mesoporous silica nanoparticles as functional support for a Janus-like approach

Abstract Mesoporous silica nanoparticles (MSN) were used as a platform to design novel active materials for the catalytic and photocatalytic epoxidation of limonene. Binary systems comprised of TiO2 and MSN were used for the catalytic reaction when doped with manganese, and for the photocatalytic reaction when functionalised with hexadecyl chains or imidazolinyl groups. All of the MSN based systems were synthesized by condensation in emulsion. A thorough characterization of the powders has been performed by means of Inductively Coupled Plasma – Optical Emission Spectroscopy (ICP-OES), X-ray diffraction (XRD), FT-IR, Raman and EPR Spectroscopy, Fluorescence and diffuse reflectance UV–vis (DR…

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…

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.

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

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

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.

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…

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]

Particle size-related limitations of persistent phosphors based on the doped Y3Al2Ga3O12 system

AbstractCo-doped Ce3+, Cr3+ and Pr3+ yttrium–aluminium–gallium garnet powders of various sizes were obtained by co-precipitation method. The microstructure and morphology were investigated by XRPD, TEM and gas porosimetry. The luminescence properties were studied by excitation and emission spectra, quantum yield and decay times. Thermoluminescence measurements were performed to evaluate the activation energy, traps redistribution and frequency factor. Limitation in the energy transfer between dopant ions in the small particles, traps depth and surface defects were considered and investigated as responsible for the quenching of persistent luminescence. The phosphors annealed at 1100 °C show …

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…

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…

Effect of annealing temperature on persistent luminescence of Y3Al2Ga3O12:Cr3+ co-doped with Ce3+ and Pr3+

Abstract Y3(Al,Ga)5O12 (YAGG) materials doped with Ce3+, Cr3+ and Pr3+ were synthesized by using a modified Pechini method and subsequently annealed in air at selected temperatures between 900 and 1500 °C. According to X-ray powder diffraction (XRPD) and transmission electron microscopy (TEM) analyses, the particles and size distributions become large and broad, respectively, due to sintering and agglomeration at high annealing temperatures. Based on infrared (FTIR) spectra and calculation of multi-phonon de-excitation probabilities, the high energy O–H vibrations are not causing significant multi-phonon de-excitation of the emitting 5d level of Ce3+ if the annealing temperature is above 90…

Nanometric semiconductor particles in mesoporous silica: synthesis and characterization

The colours of Segesta. Searching for the traces of the lost pigments

Many monuments and objects of the ancient civilizations were painted, but unfortunately the pigments are not still present and sometimes only small traces are evident. The analysis of the traces requires a multianalytical approach through the use of non-invasive techniques and only if necessary of a microsampling. Here, the study of the traces of colours found in some architectural elements and findings belonging to the Archeological Park of Segesta (Trapani, Italy) is reported. The traces are identified and characterised via several techniques such as Optical Microscopy, UV-Fluorescence Imaging, Fiber Optical Reflectance Spectroscopy (FORS), X-ray Fluorescence (XRF) and FT-IR Spectroscopy.…

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…

Effect of surface impurities on downconversion luminescence of Pr3+, Yb3+ activated SrF2 nanoparticles

Abstract Pr3+,Yb3+ activated SrF2 nanoparticles synthesized by low-temperature hydrothermal method were studied. The composition and size of nanoparticles were intentionally changed by controlling synthesis conditions. After structural and morphological characterization, the spectroscopic properties of the nanoparticles were analyzed in the visible and near infrared spectra ranges. The results show correlation between the gradual change of the amount of carboxylate and hydroxyl moieties on the nanoparticle surface, varied by the size nanoparticles and the quenching of the luminescence. The size-related amount of surface quenchers is strongly connected to the decrease of the downconversion e…

Functionalization of mesoporous silica nanoparticles through one-pot co-condensation in w/o emulsion

In this work, three different functionalized mesoporous silica nanoparticles (MSNs) were synthesized through the co-condensation synthesis in oil/water emulsion. Hexadecyltrimethoxysilane, triethoxy-3-(2-imidazolin-1-yl)propylsilane and (3-mercaptopropyl)triethoxysilane were used as organo-substituted silica precursors with variable molar ratio with respect to tetraethylorthosilicate (TEOS, 1:4, 1:9, 1:19). The occurred functionalization was investigated by Infrared Spectroscopy and FT-Raman and 29Si {1H} CP-MAS-NMR spectroscopy. Results show that the three materials were successfully functionalized. The influence of the different pendant groups and their concentration on the mesostructured…

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…

The silver collection of San Gennaro treasure (Neaples): A multivariate statistic approach applied to X-ray fluorescence data

Abstract In this work we report an X-ray fluorescence spectroscopy (XRF) study combined with a multivariate approach allowing to detect compositional differences and similarities among the alloys used in realization of silver collection of San Gennaro items collection. The San Gennaro treasure in Naples (Italy) represents, in fact, one of the most important silver collections in the world. The classification of the collection items is very complex, not only for the large number of objects, but also in consideration that between 1600 and 1700, in Naples, more than 350 laboratories were active, most of them specialized in specific art of work. As a consequence, a given collection object could…

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.

Effect of annealing treatment on the persistent luminescence of Y3Al2Ga3O12:Ce3+,Cr3+,Pr3+ ceramics

Abstract The Y3Al2Ga3O12:Ce3+,Cr3+,Pr3+ (YAGG) persistent luminescent ceramics were sintered in static air (without airflow) and followed by hot isostatic pressing (HIP) treatment. The low aggregated and relatively narrow particle-size distributed starting powders, with the particle size of about 50 nm, were synthesized by using Pechini method and then annealed at 900 °C for 16 h in static air. Compared to nano-phosphors, the ceramics exhibited more intense and longer persistent luminescence (PersL). The photoluminescence and PersL spectra were found to have a similar shape, indicating that the emitting centers for photoluminescence and PersL processes were same. The intense Ce3+ and Cr3+ b…

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.

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…

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…

Luminescent YPO4:Eu@PVA dispersions for anti-counterfeiting ink applications

A method was developed to obtain YPO4:Eu dispersions of PVA as a luminescent inks. YPO4:Eu nanoparticles were prepared by precipitation followed by hydrothermal treatment. The dispersion preparation included systematic studies to prepare a stable colloidal system and to investigate the role of parameters affecting its stability and UV-excited YPO4:Eu emission intensity. The effect of PVA concentration was studied in detail for two different PVAs to determine the optimal parameters for its use as ink with specific luminescent properties. The type of interactions responsible for the dispersion stability was also investigated.

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

Optical studies of Y3(Al,Ga)5O12:Ce3+,Cr3+,Nd3+ nano-phosphors obtained by the Pechini method

The Y-3(Al,Ga)(5)O-12:Ce3+,Cr3+,Nd3+ (YAGG) nano-phosphors with homogeneous particle-size distribution, low aggregation and average crystalline size of about 65 nm were obtained using a modified Pechini method. Only slight aggregation of the crystallites occurs after post-annealing at 1100 degrees C. The intense Ce3+ bands in the excitation spectra of the Ce3+,Cr3+,Nd3+ co-doped materials monitoring the Cr3+ emission at 690 nm indicate energy transfer from Ce(3+ )to Cr3+. Weak Nd3+ lines are observed, as well. In addition, the emission of Nd3+ at 1060 nm with excitation of Ce3+ and Cr3+ confirms the Ce3+/Cr3+ to Nd3+ energy transfer. The short average luminescence decay times for the Ce3+ e…

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…

Urea Glass Route as a Way to Optimize YAGG:Ce3+,Cr3+,Pr3+ Nanocrystals for Persistent Luminescence Applications

A new approach for the synthesis of Y3Al2Ga3O12 (YAGG) nanophosphors allowing the preparation of crystallites with sizes starting from 45 nm is presented. The controllability of the energy and trap density of the resulting material samples by annealing temperature was confirmed by thermoluminescence (TL) measurements. It has been shown that the annealing of samples at temperatures up to 1300 degrees C does not cause any substantial growth of crystallites, still remaining below 100 nm, but leads to changes in the activation energy of the persistent luminescence (PersL) process. On the other hand, annealing above 1400 degrees C results in grain growth on the submicron scale, which was confirm…

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…

Tungsten -catalysts supported on ZrO2 nanopowder