Laser performance of pyrromethene 567 dye in solid matrices of methyl methacrylate with different comonomers

Laser performance of pyrromethene 567 (PM567) dye dissolved in pure poly(methyl methacrylate) homopolymer and its copolymers with 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 1-vinyl-2-pyrrolidone, 2-phenoxyethyl acrylate, and 2,2,2-trifluoromethyl methacrylate has been investigated. The chosen monomers were selected to mimic solvents used in a previous study on the photophysical and lasing properties of PM567 in liquid solution in order to establish correlations between the lasing properties of PM567 in liquid and solid solutions. The vol/vol proportion of the different comonomers in each copolymer formulation was systematically varied, and the effect of each composition on the lasing properties of PM567 was evaluated. The laser samples were transversely pumped at 534 nm with 5.5-mJ pulses from a frequency-doubled Q-switched Nd:KGW laser. Lasing efficiencies of up to 30% and good photostabilities, with a drop of the initial laser output of 20% after 10000 pump pulses in some of the solid samples, were demonstrated. Received: 2 June 1999 / Revised version: 18 July 1999 / Published online: 3 November 1999     

Atmospheric DBD plasma Deposition of ECO‐Friedly Release Liners for Pressure Sensitive Adhesive Tapes

The presented paper reports on the development of eco‐friendly non‐silicone containing release liners on plastic foils for pressure sensitive adhesive tapes. A solvent free process based on aerosol assisted dielectric barrier discharge (DBD) plasma deposition was used to obtain nano‐sized coatings. Various precursors have been investigated ranging from hydrocarbons and fluorinated hydrocarbons to (meth)acrylates and fluorinated (meth)acrylates. Best results were obtained using 2‐ethylhexyl acrylate. To improved the stability of release properties upon ageing, addition of photo initiators and acrylic cross‐linkers have been evaluated. Tape adhesion tests showed stable release values below 25 cN/20 mm for 2‐ethylhexyl acrylate plasma coatings with acrylic cross‐linkers. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Gold-Containing Nanocomposition Materials on the Basis of Homo- and Copolymers of Methylmethacrylate

Films of polymethyl methacrylate and methyl methacrylate copolymers with ethylhexyl acrylate doped with HAuCl₄ were subjected to UV irradiation followed by thermal treatment at various temperatures. The films were studied by absorption spectroscopy and small-angle X-ray scattering. The photolysis of HAuCl₄ was found to result in the formation of gold nanoparticles, whose size depended on the structure of the polymeric matrix. An increase in the free volume of polymers caused the formation of larger particles.     

Elastoviscous Systems Based on Solutions of Chitosan–Methyl Acrylate and Chitosan Succinamide–Methyl Acrylate Copolymers

Rheological studies of solutions of amphiphilic copolymers based on hydrophilic polysaccharides chitosan (CT) and chitosan succinamide (CTS) sodium salt with methyl acrylate (MA) synthesized by radical copolymerization have been conducted. It has been found that the hydrophobic interaction of poly(methyl acrylate) blocks in solutions of CT–MA and CTS–MA copolymers leads to an increase in the degree of structuring of macromolecules; this feature leads to the formation of an elastoviscous system without introducing of an additional crosslinking agent.     

Preparation and Surface Properties of Fluorinated Acrylates Copolymers

Copolymerization of acrylates and styrene (St) with perfluorooctylacyloxyethyl methacrylate (FA) monomer, prepared from the reaction of perfluorooctanoic acid and hydroxymethyl methacrylate, was carried out by solution polymerization. The fluorinated acrylate and St copolymers (PFA) were examined by GPC, FT-IR, and ¹H NMR. The surface tension of the PFA solution in N-methyl pyrrolidone was tested by the drop volume method. The results showed that the surface tension of the PFA solution decreased in exponential decay with increase of the PFA concentration, and the surface tension of the solution also decreased with increased addition of the FA monomer in the copolymer at the same concentration. Meanwhile, the adsorption of the PFA macromolecules in the air–solution interface increased and enrichment of the fluorinated segments on the solution surface occurred. The studies of the surface free energy, polarity, fluorine content, and morphology of the PFA films illustrated that the surface free energy and polarity of the PFA films were decreased with the augment of the FA monomer in the copolymers, and that the fluorine content and the surface roughness were increased. The surface free energy of the PFA film was as small as 16.6 mN·m^?1. The surface properties of the PFA copolymers obtained by one shot feed during polymerization were superior to those obtained by continuing feed procedure. More fluorine segregation occurred and induced the formation of a fluorine-enriched surface if the PFA copolymer was postheated. The posttreatment was thus beneficial to the improvement of the surface properties of the PFA film.     

NMR applications to low porosity carbonate stones

The purpose of this paper is to investigate NMR applications to porous materials widely employed in artistic and historical monuments and largely studied in the Cultural Heritage conservation field. Carrara marble, Candoglia marble and travertine samples were studied and data from relaxation times measurements were compared. Very interesting results from treated samples are reported and explained under the structure related spin lattice relaxation time point of view. Images of Carrara marble aged sample (XIX century), coming from the Florence Cathedral obtained for short absorption time of water by capillary rise and for relatively small thickness slices together show the fluid's spatial distribution within the stone. Comparative images showing untreated sample with the treated ones were obtained suggesting very useful applications for the determination of treatment effectiveness.     

Effect of mineralogical and microstructural properties on surface roughness and gloss of some ornamental marbles subjected to polishing process

High surface finish quality of the produced slabs is generally desirable in the stone processing industry. This paper presents the results of an experimental investigation into the effects of mineralogical‐petrographical and chemical variables on the surface roughness and glossiness of some selected ornamental marbles subjected to grinding–polishing processes. For this purpose, a series of grinding–polishing procedures were performed on the slabs of three distinct marble types. Roughness and brightness measurements were carried out on predetermined surfaces of marble samples using a stylus profilometer and a glossmeter, respectively. Thin sections were examined by a polarizing microscope for mineralogical‐petrographical characterization of the studied marbles. Scanning electron microscopy was used to aid in the identification and characterization of the slab surface morphologies at each polishing stage. X‐ray diffraction and scanning electron microscopy with energy‐dispersive X‐ray spectroscopy were used for the determination of mineralogical and chemical compositions of the samples. Mainly because of the differences in textural and chemical compositions, different levels of microroughness and gloss values were observed for the studied marble varieties. The presence of different mineral phases such as the grain (i.e. calcite to calcite) and phase contacts (i.e. calcite to epidote) greatly affected the heterogeneity of the marbles, resulting with different removal mechanisms under the action of abrasive grits. Copyright © 2013 John Wiley & Sons, Ltd.     

Rheological Properties,Morphology, and Thermal Performance of E‐MA‐GMA/PC Blend

Blends of ethylene–methyl acrylate–glycidyl methacrylate terpolymer (E‐MA‐GMA, a random terpolymer) and polycarbonate (PC) were prepared in a Haake torque rheometer and the rheological properties, phase morphology, and thermal behavior were investigated. The graft reactions of PC terminal hydroxyl groups with the epoxy groups of E‐MA‐GMA and the in situ formation of the E‐MA‐GMA‐g‐PC copolymers at the interface were illustrated by the improved mixing torque and melt viscosity in E‐MA‐GMA/PC blends. Typical variation and significant deformation of the dispersed phase was observed in E‐MA‐GMA/PC blends with different composition, where PC was the matrix. With the E‐MA‐GMA content increasing, a complex co‐continuous phase structure with some dispersed E‐MA‐GMA particles wrapped in the continuous PC phase was present, indicating strengthened interfacial adhesion. When the E‐MA‐GMA content was higher than the PC component, fibrous structure of the dispersed PC phase in the E‐MA‐GMA matrix was caused by shear flow and interfacial interaction. DSC studies showed that the melting point of E‐MA‐GMA shifted to lower temperature with the increase of PC content, indicating that the enhanced interaction and graft structure hindered the process of crystallization and crystal growth.     

Study of sulphation of Candoglia marble by means of micro X-ray diffraction experiments

This research is aimed at assessing the particular kind of damage caused by the interaction between atmospheric pollution and the marble surface of a magnificent late gothic church, Milan Cathedral, restored in the early 1970s. On the basis of visual inspections and diagnostic investigations the facade appears to be seriously damaged by surface erosion and thick black crusts; biological crusts, micro-fractures and detachments are widely present.This paper reports on SR-μXRD data collected at the Synchrotron Radiation Source (SRS), Daresbury Laboratory, and at the European Synchrotron Radiation Source (ESRF) from selected samples, covered with black crusts, originating from the Milan Cathedral facade. Mineralogical maps of the deterioration layers have been recorded by two spatial resolutions (5–100 μm), from the bulk of the stone material to the outer layer of the black surface. These maps help in elucidating the mechanism of formation of the black crusts. PACS 33.20.Rm; 61.10.Eq; 61.10.Nz; 78.70.Ck     

Mössbauer studies of acrylonitrile/alkyl methacrylate copolymers doped with ferric chloride

Acrylonitrile/methyl methacrylate (A/M), acrylonitrile/ethyl methacrylate (A/E) and acrylonitrile/n-butyl methacrylate (A/B) copolymers containing ferric chloride were prepared by free radical bulk polymerization. TGA studies show that the addition of ferric chloride increases the thermal stability of these copolymers. Mössbauer studies of the copolymers showed the presence of Fe³⁺ species only. Mössbauer spectra of the copolymer heated at 200°C, 350°C and 500°C did not show a reduction of the Fe³⁺ species, and α-Fe₂O₃ was the final product formed.     

The use of electron spin resonance spectroscopy for determining the provenance of classical marbles

The possibility of identifying the provenance of classical marbles and solving related questions, such as the joining fragments problem, via electron spin resonance spectroscopy has been reexamined. The method is based on characterization of the Mn²⁺ impurity ubiquitously present in marbles. Six different, although correlated, spectroscopic variables, such as intensity, linewidth, metal hyperfine splitting and others have been measured, together with some petrographic properties, for over 500 samples belonging to 14 different Italian, Greek and Turkish quarrying sites. The work, still in progress, is aimed to establish a marble database including all the historically relevant sites within the Mediterranean basin. The experimental data matrix has been analyzed with the aid of multivariate statistical techniques, primarily linear and quadratic discriminant analysis, and the ability of the method to classify correctly unknown samples has been estimated through standard techniques (resubstitution, jackknife), but also employing control “unknown” samples. The essential result is that, although the all-variables approach may describe the data set very accurately, the predictive power is due to four variables only, which are a suitable combination of spectroscopic and petrographic information. In this way 82.4% of the control samples could be assigned correctly, whereas inclusion of additional variables in the classification rule may result in substantially poorer performance. The conclusion is that ESR spectroscopy, although not providing a complete and general solution for the marble provenance problems, is probably, at the moment, the most developed methodology for identifying marbles. Its results, coupled with artistic historical information, deal correctly with a number of relevant archaeometric problems.     

Anti-graffiti nanocomposite materials for surface protection of a very porous stone

The preservation of stone substrates from defacement induced by graffiti represents a very challenging task, which can be faced by applying suitable protective agents on the surface. Although different anti-graffiti materials have been developed, it is often found that their effectiveness is unsatisfactory, most of all when applied on very porous stones, e.g. Lecce stone. The aim of this work was to study the anti-graffiti behaviour of new nanocomposite materials obtained by dispersing montmorillonite nanoparticles (layered aluminosilicates with a high-aspect ratio) into a fluorinated polymer matrix (a fluorinated polyurethane based on perfluoropolyether blocks). Polymeric structure was modified by inducing a cross-linking process, in order to produce a durable anti-graffiti coating with enhanced barrier properties. Several composites were prepared using a naturally occurring and an organically modified montmorillonite clay (1, 3, and 5 % w/w concentrations). Materials were applied on Lecce stone specimens, and then their treated surfaces were soiled by a black ink permanent marker or by a black acrylic spray paint. Several repeated staining/cleaning cycles were performed in order to evaluate anti-graffiti effectiveness. Colorimetric measurements were selected to assess the anti-graffiti performance. It was found that the presence of 3 % w/w organically modified montmorillonite in the polymer coating is enough to induce a durable anti-graffiti effect when the stone surface is stained by acrylic paint. Less promising results are obtained when staining by permanent marker is considered as all the investigated treatments afford a reasonable protection from ink only for the first staining/cleaning cycle.     

Sugaring marble in the Monumental Cemetery in Bologna (Italy): characterization of naturally and artificially weathered samples and first results of consolidation by hydroxyapatite

The so-called sugaring of marble is a very common degradation phenomenon, affecting both historical monuments and modern buildings, which is originated by environmental temperature fluctuations. Thermal cycles are indeed responsible for micro-cracks formation at the boundaries between calcite grains, so that marble is subjected to granular disintegration and can be reduced to a sugar-like powder of isolated calcite grains by just the pressure of a finger. Since no effective, compatible and durable treatment for sugaring marble consolidation is currently available, in this paper a novel consolidating treatment recently proposed for limestone, based on the formation of hydroxyapatite inside the stone, was investigated for weathered marble. To test the new treatment on suitably decayed marble samples, some naturally sugaring marbles from the Monumental Cemetery in Bologna (Italy, nineteenth century) were firstly characterized by scanning electron microscope (SEM), mercury intrusion porosimetry (MIP) and ultrasonic pulse velocity (UPV) measurement. Then, artificially weathered samples were produced by heating fresh Carrara marble samples at 400 °C for 1 h. The effects of artificial weathering were characterized using the same techniques as above, and a very good agreement was found between microstructure and mechanical features of naturally and artificially weathered samples. Then, the hydroxyapatite-based treatment was tested on the so-obtained artificially weathered samples, and the treatment effects were characterized by UPV, MIP and SEM equipped with energy dispersive spectrometry and Fourier transform infrared spectroscopy. The hydroxyapatite-based treatment exhibited a remarkable ability of restoring marble cohesion and a good compatibility in terms of modifications in pore size distribution, which leads to regard this treatment as a very promising consolidant for weathered marble.     

Laser induced micro-photoluminescence of marble and application to authenticity testing of ancient objects

For the last 70 years, the authenticity of disputable marble objects has been tested by using a black light lamp. According to empirical observations “fresh marbles are purple while ancient ones are blue under the lamp”. This discrimination lacks scientific basis but is very popular because sculptured stone dating is impossible. This work aims to test the reliability of the “UV method” by studying the laser excited photoluminescence (PL) of marble surfaces. An argon ion laser beam was focused through a microscope objective onto the sample, offering a PL spatial resolution of 3 μm. Newly-cut marbles show an intense emission at 610 nm ascribed to Mn²⁺ and a less intense one at 390 nm. Excavated surfaces show the 610 nm emission and a broadband (380–530 nm) one. Similar broadband emissions due to humic (HAs) and fulvic acids (FAs) are typical in soil PL spectra and were observed in the spectra of samples taken from the soil surrounding the excavated surfaces. Additionally, electron paramagnetic resonance (EPR) spectra of excavated surfaces show a peak at g=2.0045, typical in calcite doped with humic acids. We presume that the 380–550 nm emission originates from HA and FA salts existing in the infiltrated soil or the recrystallised calcite developed in marble patinas. Finally, the application of the “UV method” on twelve ancient and modern surfaces proved that the technique is only partly reliable and should be used together with other analytical techniques. PACS 78.55.-m; 78.55.Hx; 81.70.Fy; 87.64.Hd     

Surface properties of ionomers based on styrene-b-acrylic acid copolymers obtained by copolymerization in emulsion

Surface properties of styrene-b-acrylic acid copolymers obtained in emulsion and suitable ionomers before and after UV-irradiation were studied by measurements of contact angles and FTIR-ATR spectroscopy.The research focused on the influence of different content of carboxylic acid groups in copolymers, of various types and contents of alkali metal salts in ionomers and of cesium acrylate or methacrylate in ionomers on hydrophilicity of the surfaces of these samples and the course of photodegradation in them.Hydrophilicity of initial copolymer surfaces was higher than this of polystyrene as a result of presence of carboxylic acid groups, which also made the surfaces of these copolymers more sensitive to UV-irradiation.Hydrophilicity of the surfaces of ionomers containing cesium acrylates depended on the content of cesium salt in the samples. The course of ionomer photooxidation was also dependent on the content of this salt.The surface of ionomer containing cesium methacrylate was more polar than this of ionomer containing cesium acrylate.Styrene-based ionomers containing 3.7 mol% of various alkali metal acrylates had less polar surfaces than initial copolymer and they were also more resistant to UV-irradiation in comparison to the initial copolymer.Copolymers obtained in emulsion and suitable ionomers had more polar surfaces and they were more sensitive to UV-light compared to copolymers obtained in bulk and their ionomers.     

ESR spectroscopy as a tool for identifying joining fragments of antique marbles: the example of a pulpit by Donatello and Michelozzo

ESR spectroscopy is one of the physicochemical techniques used to characterize archaeological white marbles and obtain information about their quarries of provenance. This is done by measuring selected spectral features of the Mn(2+) impurity ubiquitously present in marbles and developing a statistical classification rule from the variable vectors measured for a significant number of samples of known provenance (the quarry database). Now we show that the overall variability exhibited by the same spectroscopic features decreases rapidly with the linear dimensions of the sampled block and can be used to distinguish fragments belonging to the same piece of stone from those simply originating from the same quarry. Application of the method to the seven marble panels of the Donatello pulpit in Prato (Tuscany) shows that they have all been cut from the same single block and their different degradation must be ascribed to differential weathering and to the different conservation treatments undergone in the past. The limits and possible drawbacks of the method are also discussed.     

Characterisation of solid-state dyes and their use as tunable laser amplifiers

This paper reports on the spectroscopic and photo physical characteristics of solid-state dyes and their use as tunable high-gain laser amplifiers. A comparison of the absorption and fluorescence spectra is made for the dyes pyrromethene 567, pyrromethene 597, pyrromethene 650, rhodamine 6G in the solid hosts, polymethyl methacrylate, polycom and ormosil, and compared to the case of the dyes in the solvent methanol. Results show a reduced Stokes shift and an increased fluorescence lifetime for dyes in the solid hosts compared to the solvent. The use of pyrromethene 650 in polymethyl methacrylate as a tunable laser amplifier was investigated. The dye amplifier was shown to exhibit photo-induced birefringence, and the fluorescence polarisation and intensity dependent anisotropy effects of gain and refractive index was characterised. The molecular reorientation time for pyrromethene 650 in the solid host was calculated to be 6.8 ns. The solid-state dye exhibited a single pass gain of 500at 616 nm. The saturation behaviour was investigated and values of emission cross-section determined. Operation of the solid-state dye in a laser oscillator showed effects of strong shift in the lasing wavelength as a function of the cavity Q due to the small Stokes shift of the dye in the solid host. PACS 42.55.Mv; 42.50.Lh; 42.70.Jk     

Isotope-geochemical and mineralogical-petrographic characteristics of the pergamon altar marble

Abstract We report preliminary results of our provenance study of marble from the Telephos Frieze of the Pergamon altar. The emphasis here is on the stable isotope geochemistry of marble. The obtained δ(13)C values (2.4 to 3.5‰) vary insignificantly. However, the δ(18)O values give two clusters. The isotopically light marbles (close to -9.5‰) derive from panels 1-8 and the heavy marbles (-3.5 to -1.0‰) derive from panels 11-50. Mineralogical, petrographic and geochemical investigations (accessory minerals, grain size distribution, rare earth elements) further refined the marble characteristics. In spite of certain differences observed (grain size distributions, isotopy and contents of certain elements) for the two marble groups, the present data support a common provenance. So far, east Aegean islands and the Marmara region are favored.     

异戊二烯与甲基丙烯酸甲酯交替共聚物及其嵌段共聚物的13C-NMR研究

本文以¹³C-NMR方法研究了异戊二烯(IP)和甲基丙烯酸甲酯(MMA)的交替共聚物Poly (IP-a-MMA)及其与苯乙烯(ST)和丙烯酸甲酯(MA)交替共聚物Poly (ST-a-MA)的嵌段共聚物Poly[(ST-a-MA)-b-(IP-a-MMA)-b-(ST-a-MA)]的微观结构,结果表明在完全交替的共聚物中,IP单元主要以反-1,4-结构存在。IP和MMA以"头-头"和"头-尾"两种方式共聚,而以前者为主。     

Composition,Luminescence, and Color of a Natural Blue Calcium Carbonate from Madagascar

Concerning the transparent blue calcite crystals of blue marble from Madagascar, this work suggests that their cavities, accessorial quartz, and marble stress textures do not provide unambiguous characterization of the blue color compared to other white marbles. It is suggested that the presence of stronium (～850 ppm), barium (～18 ppm), vanadium (～10 ppm), and nickel (～2 ppm) might be considered influential chromophores for the blue color. Blue marble aliquots were characterized to determine their mineralogical, textural, and chemical composition to elucidate luminescence spectra and the causes of the blue color by use of different techniques.