Characterization of archeological glasses by micro‐Raman spectroscopy

The method based on the deconvolution of the Raman spectra of glasses, proposed for the investigation of glazed ceramics by Colomban, is applied to archeological samples of glass of two different origins in an attempt to characterize the glass composition and the fictive temperature using a contactless, nondestructive spectroscopic technique. The samples investigated are glassy mosaic tesserae of Roman times from Massa Lubrense, Napoli, Italy, and medieval rosary grains found during the excavations in the church of San Martino di Rivosecco, Parma, Italy. The polymerization index, obtained as the ratio of the bending and stretching band amplitudes, suggests firing temperatures not less than 1000–1100 °C for both Roman and medieval glasses. From the wavenumber shift of some stretching bands at about 1050–1100 cm⁻¹, the content of lead was estimated. The medieval samples show a lower Pb content, a result confirmed by elementary energy dispersive X‐ray spectral data. Copyright © 2010 John Wiley & Sons, Ltd.     

Raman micro‐spectroscopy for quantitative thickness measurement of nanometer thin polymer films

The sensitivity of far‐field Raman micro‐spectroscopy was investigated to determine quantitatively the actual thickness of organic thin films. It is shown that the thickness of organic films can be quantitatively determined down to 3 nm with an error margin of 20% and down to 1.5 nm with an error margin of 100%. Raman imaging of thin‐film surfaces with a far‐field optical microscope establishes the distribution of a polymer with a lateral resolution of ~400 nm and the homogeneity of the film. Raman images are presented for spin‐coated thin films of polysulfone (PSU) with average thicknesses between 3 and 50 nm. In films with an average thickness of 43 nm, the variation in thickness was around 5% for PSU. In films with an average thickness of 3 nm for PSU, the detected thickness variation was 100%. Raman imaging was performed in minutes for a surface area of 900 µm². The results illustrate the ability of far‐field Raman microscopy as a sensitive method to quantitatively determine the thickness of thin films down to the nanometer range. Copyright © 2015 John Wiley & Sons, Ltd.     

Della Robbia blue glaze: micro‐Raman temperature study and X‐ray fluorescence spectroscopy characterization

Micro‐Raman temperature study and X‐ray fluorescence (XRF) spectroscopy were used for characterization of the blue glaze on Saint John the Baptist—majolica terracotta relief attributed to Andrea Della Robbia and Saint John the Baptist with Cross—majolica terracotta statue attributed to Giovanni Della Robbia. Both objects are on permanent exhibition in the John and Mable Ringling Museum of Art in Sarasota, FL. This study proves that the detection of the 548 cm⁻¹ Raman band alone cannot serve as evidence for presence of lazurite crystallites in the pigment in the glaze. It was established that the famous Della Robbia blue is due to the combined effect of Co Ni Cu Zn atoms and S₃⁻ ions embedded in a lead silicate matrix. It is proposed that the Della Robbia family used Co‐containing sulfide ores as a source for manufacturing their blue pigments. Copyright © 2009 John Wiley & Sons, Ltd.     

On the noise limit of stress and temperature measurements with micro‐Raman spectroscopy

We report for the first time on the thorough experimental and theoretical assessment of the noise limit of mechanical stress and temperature measurements with micro‐Raman spectroscopy. A comprehensive study has been performed in which, for different incident laser light intensities and acquisition times, 1000 Raman spectra of mono‐crystalline silicon were acquired per setting. Curve fitting was employed to obtain the peak positions of all the spectra, from which the standard deviations of the measured peak positions were obtained versus the total accumulated amount of laser light incident on the sample during one measurement. It has been found that the noise in the obtained peak position decreases as 1/sqrt(n) over more than three decades of the incident amount of laser light. At very low light conditions, the noise decreases as 1/n. By comparing the experimental results obtained to recent theoretical work, we show that the acquisition is limited by photon shot noise over most of the range and is limited by electronic detector noise at very low light conditions only. Pixelation errors do not play a role. It is concluded that the low electronic noise of typical Raman spectroscope detectors is overkill for the investigation of mechanical stress and temperature in silicon and other materials with comparable peaks, as it has absolutely no influence on the noise level of such an experiment. Maximum Raman signal intensity on the detector and high quantum efficiency detection are more important. Copyright © 2013 John Wiley & Sons, Ltd.     

Microcrystalline testing used in combination with Raman micro‐spectroscopy for absolute identification of novel psychoactive substances

Two new psychoactive substances, namely 4‐methylmethcathinone (mephedrone) and 5,6‐methylenedioxy‐2‐aminoindane (MDAI) were analysed with a novel combination of microcrystalline tests followed by Raman micro‐spectroscopy to facilitate their absolute identification. The discrimination power of the proposed combination was successfully demonstrated through the analysis of the positional isomers 2‐ and 3‐methylmethcathinone. The addition of mercury dichloride as a microcrystalline test reagent produced specific microcrystals of each tested analyte. The robustness of the method was evaluated in the presence of common cutting agents (caffeine and benzocaine) as well as on street samples. The crystal lattice structures of mephedrone, 2‐methylmethcathinone and MDAI mercury dichloride microcrystals were determined by single crystal X‐ray diffraction. This confirmed the presence of both drug and reagent together in the lattice and accounts for the distinct habit of the observed microcrystals. Raman spectra of the formed microcrystals differed from those obtained from their standard salt form by loss and/or gain of some vibrational modes. Particularly important was the appearance of the mercury chloride link to each tested drug molecule which showed as strong bands at low wavenumbers. Its presence was corroborated by its detection in the crystal lattice. It was therefore concluded that microcrystalline testing followed by Raman micro‐spectroscopy satisfies the technique combination requirement for psychoactive substances recommended by the Scientific Working Group for the Analysis of Seized Drugs (SWGDRUG) and provides a rapid and cheap analysis route. The proposed technique combination also aids the development of new microcrystalline tests as it allows for confirmation of the uniqueness of the developed microcrystals almost in‐situ rather than growing single crystals for often long periods of time needed for single crystal X‐ray diffraction analysis. Copyright © 2016 John Wiley & Sons, Ltd.     

Raman spectroscopy to probe residual stress in ZnO nanowire

Raman spectroscopic studies are performed to probe the stress along the length of a bent ZnO nanowire. The zone‐centre E₂^high optical phonon shows a systematic red shift as the junction point of the two arms of the nanowire is approached. The mechanism of the red shift is discussed on the basis of the tensile strain. From the red shift of the phonon peak position, the strain at different regions on the nanowire is estimated. Stress in the bent nanowire is also investigated using photoluminescence (PL) spectroscopy. Results of both Raman and PL study confirm that the bent nanowire is under tensile strain. Copyright © 2011 John Wiley & Sons, Ltd.     

Use of micro‐Raman spectroscopy to study reaction kinetics in blended white cement pastes containing metakaolin

Curing temperature is known to play an important role in the formation, development, and stability of the hydrated phases appearing during pozzolanic reactions (chemical reaction between puzzolanic addition, metakaolin (MK), and calcium hydroxide from cement hydration). A typical example of this important reaction is to be found in metakaolin‐bearing cement pastes, characterized by hexagonal phases whose thermodynamic stability declines with rising temperature. These phases cannot be exhaustively researched with traditional techniques (such as X‐ray diffraction) due to their poor crystallinity. Consequently, micro‐Raman spectroscopy was used in the present study to explore the behavior of white cement paste blends containing 0, 10, and 25% MK at two curing temperatures (20 and 60 °C). This led to the identification, for the first time using Raman spectroscopy, of phases C₂ASH₈¹ (stratlingite) and C₃ASH₆, which appear in the MK–white cement reaction. The C S H gel formed was characterized by Q¹ dimers and a C/S ratio of 1.3–1.5. Raising the curing temperature favored the formation of C₄AH₁₃. Copyright © 2009 John Wiley & Sons, Ltd.     

In situ chemical analysis of modern organic tattooing inks and pigments by micro‐Raman spectroscopy

The chemical composition of tattooing pigments has varied greatly over time according to available technologies and materials. Beginning with naturally derived plant and animal extracts, to coloured inorganic oxides and salts, through to the modern industrial organic pigments favoured in today's tattooing studios. The demand for tattooing is steadily growing as it gains cultural popularity and acceptance in today's society, but ironically, increasing numbers of individuals are seeking laser removal of their tattoos for a variety of reasons. Organic pigments are favoured for tattooing because of their high tinting strength, light fastness, enzymatic resistance, dispersion and relatively inexpensive production costs. Adverse reactions have been reported for some organic inks, as well as potential complications, during laser removal procedures stemming from the unintentional creation of toxic by‐products. Currently, regulatory bodies such as the US Food and Drug Administration have not approved any coloured inks to be injected into the skin, and tattoo ink manufacturers often do not disclose the ingredients in their products to maintain proprietary knowledge of their creations. A methodology was established using micro‐Raman spectroscopy on an animal model to correctly identify the constituents of a selection of modern, organic tattoo inks in situ or post procedure, within the skin. This may serve as a preliminary tool prior to engaging in Q‐switched laser removals to assess the risks of producing potentially hazardous compounds. Likewise, the pigments responsible for causing adverse reactions in some patients may be quickly identified to hasten any corresponding treatment. Copyright © 2008 John Wiley & Sons, Ltd.     

Study of carrier concentration profiles in Al‐implanted Ge by micro‐Raman spectroscopy under different excitation wavelengths

The distribution profile of Al implanted in crystalline Ge has been investigated by micro‐Raman spectroscopy. Using different excitation laser lines, corresponding to different optical penetration depths, the Al concentration at different depths beneath the sample surface has been studied. We have found a strong correlation between the intensity of the Al–Ge Raman peak at ~370 cm⁻¹, which is due to the local vibrational mode of substitutional Al atoms, and the carrier concentration profile, obtained by the spreading resistance profiling analysis. A similar connection has been also observed for both shape and position of the Ge–Ge Raman peak at ~300 cm⁻¹. According to these experimental findings, we propose here a fast and nondestructive method, based on micro‐Raman spectroscopy under different excitation wavelengths, to estimate the carrier concentration profiles in Al‐implanted Ge. Copyright © 2013 John Wiley & Sons, Ltd.     

Microfocus X‐ray scattering and micro‐Raman spectroscopy: Transcrystallinity in isotactic polypropylene

Microfocus X‐ray scattering and micro Raman spectroscopy have been applied to study the β‐transcrystalline morphology in isotactic polypropylene. The transformation from the α‐ to the β‐form through the so‐called bifurcation of growth mechanism has been investigated with high spatial resolution. We found that the mixed α–β region does not present spatial correlation along the shearing direction, implying that there is no cooperative crystallization from the different β‐nucleation centres. In addition, a strong change in the lamellar orientation of the α‐form thin layer that induces the growth of the β‐crystallites has been observed for the first time. Finally, changes in the relative intensities of some selected Raman bands allowed the observation of the α–β transformation process at the molecular level.

     

Effect of Al content on the structure of Al‐substituted goethite: a micro‐Raman spectroscopic study

The characterization of X‐ray diffraction, X‐ray fluorescence, and field emission scanning electron microscope were used to confirm the successful preparation of Al‐substituted goethite with different Al content. The micro‐Raman spectroscopy was utilized to investigate the effect of Al content on the goethite lattice. The results show that all the feature bands of goethite shifted to high wavenumbers after the occurrence of Al substitution for Fe in the structure of goethite. The shift of wavenumber shows a good linear relationship as a function of increasing Al content especially for the band at 299 cm⁻¹ (R² = 0.9992). The in situ Raman spectroscopy of thermally treated goethite indicated that the Al substitution not only hinders the transformation of goethite, but also retarded the crystallization of thermally formed hematite. All the results indicated that Raman spectrum displayed an excellent performance in characterizing Al‐substituted goethite, which implied the promising application in other substituted metal oxides or hydroxides. Copyright © 2013 John Wiley & Sons, Ltd.     

Ferroelectric Q and antiferroelectric P phases' coexistence and local phase transitions in oxygen‐deficient NaNbO3 single crystal: micro‐Raman,dielectric and dilatometric studies

Micro‐Raman studies of oxygen‐deficient gray‐colored NaNbO₃ single crystals have shown that at room temperature both antiferroelectric P and ferroelectric Q phases are present simultaneously as separate regions tens of micrometers in size. Phase transitions in P and Q regions have been elucidated by dielectric, dilatometric and micro‐Raman studies. For the first time, the sequence of phase transitions between antiferroelectric phase P and ferroelectric Q and N phases has been revealed. Copyright © 2012 John Wiley & Sons, Ltd.     

Identification of chemical modification in single human keratinocyte cells exposed to low doses of chlorpyriphos by Raman micro‐spectroscopy

Raman micro‐spectroscopy can be used to investigate biological single cells exposed to different chemicals. Since chronic exposure at low doses of pesticides can promote several diseases, the investigation of cellular changes induced by exposure to non‐cytotoxic doses of pesticides is of increasing interest. The efficiency of Raman micro‐spectroscopy to detect chemical modification in normal human keratinocytes induced by exposure to non‐cytotoxic doses of chlorpyriphos, an organophosphate pesticide present in many plant‐protection products, was investigated. Such modification affects mainly proteineous components (both single amino acids and amide linkages between amino acids) of the nucleus, cellular membranes and cytoplasm as well as the nucleic acid component of the nucleus. Chemical modifications are already detectable after 24 h exposure of keratinocytes at a chlorpyriphos concentration of 10⁻⁶ M , which is three orders of magnitude lower than the cytotoxic concentration (10⁻³ M ). Heavy damage to the lipid component occurs after exposure to the nearly cytotoxic concentration (10⁻⁴ M ). Atomic force microscopy images of keratinocyte cells exposed for 24 h to various chlorpyriphos concentrations show a progressive deterioration of the morphology of cellular membrane as the chlorpyriphos concentration increases. The results of this work may have wide applications in the monitoring of molecular changes in single human cells exposed to toxic agents. Copyright © 2010 John Wiley & Sons, Ltd.     

Evaluation of crystalline perfection degree of multi‐walled carbon nanotubes: correlations between thermal kinetic analysis and micro‐Raman spectroscopy

Commercially available and laboratory‐prepared multi‐walled carbon nanotubes (MWCNTs) are systematically investigated by the use of micro‐Raman spectroscopy (MRS), thermogravimetric analysis (TGA) and complementary techniques (scanning electron microscopy (SEM) and transmission electron microscopy (TEM)) with the aim of establishing a standardised post‐growth diagnostic protocol for the assessment of their overall crystalline quality. By studying a set of ‘reference’ samples, clear correlations are evidenced between the Raman graphitisation indexes (D/G, G′/G and G′/D intensity ratios) commonly adopted to describe the crystalline arrangement of nanotubes, and their reactivity towards oxygen, as measured by the apparent activation energy needed for their oxidation, inferred from the kinetic analysis in quasi‐isothermal conditions. The higher the crystalline perfection degree, the higher the energy needed for oxidising them. The efficacy of the found correlations in indirectly assessing the reactivity of nanotubes prepared under different conditions is successfully demonstrated by the use of a second set of samples. The physical meaning and range of validity of the shown correlations are further discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Ageing of calcium silicate cements for endodontic use in simulated body fluids: a micro‐Raman study

To evaluate bioactivity properties, a calcium silicate experimental cement (wTC) and a phosphate‐doped wTC cement (wTC‐TCP) were aged for different times (1–180 days) at 37 °C in two simulated body fluids, i.e. Dulbecco's phosphate buffered saline (DPBS) and Hank's balanced salt solution (HBSS). The cements were analyzed by micro‐Raman spectroscopy to investigate the presence of calcium phosphate deposits and the composition changes as a function of the storage time (hydration of anhydrite/gypsum and formation of ettringite; hydration of belite/alite and formation of hydrated silicates). After 1 day of ageing in DPBS, the two cements already showed a different behavior: only the surface of wTC‐TCP cement showed the band at 965 cm⁻¹, suggesting the formation of a detectably thick calcium phosphate deposit. The trend of the I₉₆₅/I₉₉₀ Raman intensity ratio indicated the formation of a meanly thicker apatite deposit on the wTC‐TCP cement until 90 days. After 60 days of ageing in DPBS, the thickness of the apatite deposit on wTC and wTC‐TCP was about 200 and 500 µm, respectively, whereas at 180 days, the two cements did not appear significantly different (thickness of about 900 µm). The bioactivity of both cements in HBSS was less pronounced than in DPBS, according to the lower phosphate concentration of HBSS; at the same time, higher amounts of calcite were found on the surface of both cements. The wTC‐TCP cement showed a higher bioactivity in this medium also; after 180 days, the thickness of the apatite deposit on wTC and wTC‐TCP was < 50 µm and about 100 µm, respectively. Copyright © 2009 John Wiley & Sons, Ltd.     

UV‐resonance Raman micro‐spectroscopy to assess residual chromophores in cellulosic pulps

Ultraviolet‐resonance Raman (UV‐RR) micro‐spectroscopy is an appropriate and sensitive tool to assess the chromophore structures in bleached cellulosic pulps used for papermaking. The particular selectivity in detection and identification of chromophores in pulps is achieved by acquiring the UV‐RR spectra in the solid state with laser excitation at 325 nm. This wavelength corresponds to absorption of poly‐unsaturated chromophore structures in partially bleached/fully bleached pulps, and linearly correlated with the signal at ca 1600 cm⁻¹ in the UV‐RR spectra. The characteristic vibrations from particular pulp chromophore structures have been assigned from experiments with model compounds, thus allowing the establishment of a UV‐RR database. Among the components of bleached pulp, the xylan–lignin complex was suggested to be an important source of chromophores. The monitoring of pulp bleaching by UV‐RR allowed us to suggest that it is the formation of new polysaccharide‐derived chromophores upon bleaching that hinders development of further brightness and is co‐responsible for the brightness reversion of fully bleached pulps. Copyright © 2010 John Wiley & Sons, Ltd.     

Polarized Raman and photoluminescence studies of a sub‐micron sized hexagonal AlGaN crystallite for structural and optical properties

The polarized Raman spectroscopy is capable of giving confirmation regarding the crystalline phase as well as the crystallographic orientation of the sample. In this context, apart from crystallographic X‐ray and electron diffraction tools, polarized Raman spectroscopy and corresponding spectral imaging can be a promising crystallographic tool for determining both crystalline phase and orientation. Sub‐micron sized hexagonal AlGaN crystallites are grown by a simple atmospheric pressure chemical vapor deposition technique using the self catalytic vapor–solid process under N‐rich condition. The crystallites are used for the polarized Raman spectra in different crystalline orientations along with spectral imaging studies. The results obtained from the polarized Raman spectral studies show single crystalline nature of sub‐micron sized hexagonal AlGaN crystallites. Optical properties of the crystallites for different crystalline orientations are also studied using polarized photoluminescence measurements. The influence of internal crystal field to the photoluminescence spectra is proposed to explain the distinctive observation of splitting of emission intensity reported, for the first time, in case of c‐plane oriented single crystalline AlGaN crystallite as compared with that of m‐plane oriented crystallite. Copyright © 2016 John Wiley & Sons, Ltd.     

Investigation of some Chinese jade artifacts (5000 BC to 771 BC) by confocal laser micro‐Raman spectroscopy and other techniques

The study on material properties of ancient stone or jade artifacts is essential to trace the trade routes of raw materials, the tools used to making them, and moreover the social function of the artifacts. In present research, we focused on 23 intact samples that were made of versatile rocks. These samples dated from 5000 bc to 771 bc were unearthed from the Yellow River and Yangtze River basins in China. Based on the analytical results of confocal laser micro‐Raman spectroscopy, 14 minerals consisted of these rocks such as muscovite, antigorite, calcite, quartz, diopside, turquoise, corundum, and sillimanite were identified. The obtained scientific information about their primary material properties helps us to better understand their social functions and technologically related issues. Copyright © 2015 John Wiley & Sons, Ltd.