Confocal Raman Spectrometry Research Articles

Was bone used in the glaze of the ancient Qiong kilns for the production of tang dynasty opaque glaze celadon?

Being an important source of primary celadon in ancient China, the Qiong kiln is one of the few kilns that can skillfully produce opaque glaze celadon, which is of great significance in the history of Chinese ceramics. In this study, the chemical composition, microstructure, and crystalline phase of sixteen pieces of opaque glaze celadon excavated from the site of Qiong kiln Shifangtang dated at the Tang Dynasty were investigated by using ultra depth of field microscopy, scanning electron microscopy, energy spectrometry, and micro confocal Raman spectrometry. The findings indicate that Fe is the predominant coloring element in the ceramic glaze, and Cu is sometimes a secondary coloring element. During porcelain firing, washed plant ash was used to increase the phosphorus content of the glaze, while some wares incorporated animal ashes as a flux to improve glaze emulsification.

Quantification of Water Content and Speciation in Synthetic Rhyolitic Glasses: Optimising the Analytical Method of Confocal Raman Spectrometry

Quantification of water content in silicate glasses is of vital significance in understanding magma evolution and metamorphic anataxis. Here we provide a method for the determination of total dissolved water content and water speciation in silicate melts by confocal laser Raman spectrometry based on a set of hydrous rhyolitic glasses. A series of alumino‐silicate glasses with water contents from 0.33 to 9.05% m/m were synthesised in a piston cylinder apparatus. Synchrotron‐FTIR mapping shows that these glasses have relatively homogeneous distributions of dissolved water. Total water contents of the glasses were precisely measured by TC/EA‐MS and FTIR. Both external and internal calibration were established for the quantitative analysis of water content and water speciation in the silicate glasses based on excellent linear correlation between total dissolved water content and integrated area of the water Raman band. Furthermore, by decomposing the total water Raman bands into four Gaussians components, the relative concentration of water speciation (OH groups and molecules H2Om) dissolved in the glasses was determined with a similar trend to water speciation data derived from FTIR. We suggest that the relative concentration of water speciation can be estimated in rhyolitic glasses with 4–8% m/m H2O. Our work provides an accurate method to determine total water content and a potential tool to limit the relative concentration of water speciation dissolved in silicic glasses.

The effect of long-range interactions on the infrared and Raman spectra of aragonite (CaCO3, Pmcn) up to 25 GPa

Long-range interactions are relevant in the physical description of materials, even for those where other stronger bonds give the leading contributions. In this work, we demonstrate this assertion by simulating the infrared and Raman spectra of aragonite, an important calcium carbonate polymorph (space group Pmcn) in geological, biological and materials science fields. To this aim, we used Density Functional Theory methods and two corrections to include long-range interactions (DFT-D2 and DFT-D3). The results were correlated to IR spectroscopy and confocal Raman spectrometry data, finding a very good agreement between theory and experiments. Furthermore, the evolution of the IR/Raman modes up to 25 GPa was described in terms of mode-Grüneisen’s parameters, which are useful for geological and materials science applications of aragonite. Our findings clearly show that weak interactions are of utmost importance when modelling minerals and materials, even when they are not the predominant forces.

Confocal Raman spectroscopy assisted by chemometric tools: A green approach for classification and quantification of octyl p-methoxycinnamate in oil-in-water microemulsions

This work proposes a green analytical method based on confocal Raman spectrometry and chemometrics tools for the qualitative and quantitative analysis of oil in water microemulsions loaded with the UVB filter octyl p-methoxycinnamate (OMC). The method does not use reagents and only 10 µL of sample are needed. The analyzed microemulsion samples were synthetized in the laboratory using decaethylene glycol mono-dodecyl ether (21.9 %) as non-ionic surfactant, ethyl alcohol (7.3 %) as co-surfactant, oleic acid (1.5 %) as oil phase and water (69.3 %). A physicochemical characterization of the samples was carried out obtaining expected values for droplet size (<20 nm), polydispersity index (<0.290) and conductivity (0.04–0.07 mS cm−1), among others. Linear discriminant analysis (LDA) after selection of variables using the successive projections algorithm (SPA) and soft independent modelling of class analogy (SIMCA) were employed to classify microemulsions with different concentrations of OMC (1.0 to 10.0 %). In the case of LDA, seven Raman spectral variables were previously selected by SPA and after this SPA-LDA model resulted in one error in the prediction set achieving an accuracy of 97.8 %. The SIMCA model (α = 0.05) presented an explained variance higher 97 % using four principal components and it allowed the correct classification of 100 % of the samples (N = 15). In the quantitative analysis, partial least squares (PLS) was used to determine OMC in a range according to international legislation. The model presented optimal statistical parameters (R2 = 0.9699; RMSEP = 0.54 %) and the prediction of samples were in close agreement with HPLC method. Moreover, the greenery of the method was estimated using the AGREE metric and an optimal value of 0.85 was obtained demonstrating the proposed analytical method results environmentally friendly.

Structure and Composition of Micro-Manganese Nodules in Deep-Sea Carbonate from the Zhaoshu Plateau, North of the South China Sea

The occurrence of deep-sea ferromanganese nodules and crusts on the seafloor is widespread, providing an important resource for numerous metals such as Ni, Co, and Cu. Although they have been intensively studied in the past, the formation of micro-manganese nodules within carbonate rocks has received less attention, despite the considerable amounts of manganese released from the dissolution of the calcareous framework. The micro-petrographic and geochemical characteristics of reef carbonate rocks recovered from the Zhaoshu plateau in the Xisha uplift, north of the South China Sea, were studied using optical microscopy, scanning electron microscopy, confocal Raman spectrometry, and an electron probe micro-analyzer. The carbonate rocks are composed of biogenic debris, including frameworks of coralline algae and chambers of foraminifer, both of which are suffering strong micritization. Within the calcite micrite, numerous micro-manganese nodules were identified with laminated patterns. Mineral and elemental evidence showed that the Mn oxides in the carbonates are mixed with 10 Å vernadite, 7 Å vernadite and todorokite, both of which are closely associated with the carbonate matrix. The micro-nodules were found to have high Mn/Fe ratios, enriched in Ni and Cu and depleted in Co. We infer that theses nodules are mixed type with early diagenetic growth under oxic–suboxic conditions. The re-distribution of manganite within the rocks is likely influenced by micritization of the calcareous framework. We deduce that microbial-associated reduction of manganite induces the formation of diagenetic todorokite similar to nodules buried in marine sediments.

Characterization of radiochromic films as a micrometer-resolution dosimeter by confocal Raman spectroscopy.

Micrometer spatial resolution dosimetry has become inevitable for advanced radiotherapy techniques. A new approach using radiochromic films was developed to measure a radiation dose at a micrometer spatial resolution by confocal Raman spectroscopy. The commercial radiochromic films (RCF), EBT3 and EBT-XD, were irradiated with known doses using 50, 100, 200, and 300kVp, and 6-MV x rays. The dose levels ranged from 0.3 to 50Gy. The Raman mapping technique developed in our early study was used to readout an area of 100×100µm2 on RCF with improved lateral and depth resolutions with confocal Raman spectrometry. The variation in Raman spectra of C-C-C deformation and C≡C stretching modes of diacetylene polymers around 676 and 2060cm-1 , respectively, as a function of therapeutic x-ray doses, was measured. The single peak (SP) of C≡C and the peak ratio (PR) of C≡C band height to C-C-C band height with a spatial resolution of 10µm on both types of RCF were evaluated, averaged, and plotted as a function of dose. An achievable spatial resolution, clinically useful dose range, dosimetric sensitivity, dose uniformity, and postirradiation stability as well as the orientation, energy, and dose rate dependence, of both types of RCFs, were characterized by the technique developed in this study. A spatial resolution on RCF achieved by SP and PR methods was ~4.5 and ~2.9µm, respectively. Raman spectroscopy data showed dose nonuniformity of ~11% in SP method and <3% in PR method. The SP method provided dose ranges of up to ~10 and ~20Gy for EBT3 and EBT-XD films, respectively while the PR method up to ~30 and ~50Gy. The PR method diminished the orientation effect. The percent difference between landscape and portrait orientations for the EBT3 and the EBT-XD films at 4Gy had an acceptable level of 1.2% and 2.4%, respectively. With both SP and PR methods, the EBT3 and the EBT-XD films showed weak energy (within ~10% and ~3% for SP and PR methods, respectively) and dose rate dependence (within ~5% and ~3% for SP and PR methods, respectively) and had a stable response after 24-h postirradiation. A technique for micrometer-resolution dosimetry was successfully developed by detecting radiation-induced Raman shift on EBT3 and EBT-XD. Both types of RCFs were suitable for micrometer-resolution dosimetry using CRS. With CRS both lateral and depth resolutions on RCF were improved. The PR method provided superior characteristics in dose uniformity, dose ranges, orientation dependence, and laser effect for both types of RCFs. The overall dosimetric characteristics of the RCFs determined by this technique were similar to those known by optical density scanning. The CRS with the PR method is advantageous over other the traditional scanning systems as a spatial resolution of <10µm on RCF can be achieved with less deviations.

Effect of crystal structure on the tribological properties of diamond coatings on hard-alloy cutting tools

Micro- and nanocrystalline uniform diamond coatings with barrier tungsten layers for improved adhesion were deposited in a microwave plasma from methane-hydrogen mixtures on cemented carbide WC–6% Co substrates with high aspect ratios. Dynamic study of cutting forces and sliding friction has shown a significant improvement in the tribological properties of diamond-coated tools in cutting highly abrasive materials, such as A390 silumin and carbon-carbon composites. Confocal Raman spectrometry has been used to examine the features of wear mechanism in nano- and microcrystalline diamond coatings deposited in a microwave plasma.

Use of tourmaline as a potential petrogenetic indicator in the determination of host magma: CRS, XRD and PED-XRF methods

Tourmaline defines a group of complex borosilicate forms as accessory mineral in igneous and metamorphic rocks and they act an important role in the interpretation of the chemical composition changes of the composition of the host fluid of the magma.The variety of tourmaline can be identified by using optical microscopy, X-Ray Diffraction (XRD) and by determining its chemical composition through Polarized Energy Dispersive X-Ray Fluorescence (PED-XRF) methods. However, microscopic investigations and XRD analyses are not quite adequate for detailed determination of tourmaline sub-groups. In addition, the use of chemical composition of tourmaline as a strict indicator of geochemical processes might be a misleading method. In this study, variable tourmaline crystals were collected from three different pegmatitic occurrences in Behrekdag, Yozgat and Karakaya granitic bodies of Central Anatolia to identify their chemical properties through Confocal Raman Spectroscopy (CRS), PED-XRF and XRD analyses.The confocal Raman spectrometry of collected tourmalines from the Behrekdag, Yozgat and Karakaya granites are in the compositions of schorl, schorl and elbaite respectively. The dominant compositional groups of these tourmalines are in the form of schorl. Raman shift values of tourmalines revealed four bands centered at almost 1050, 750, 400 and 300cm−1. The first group of the band arises from SiO stretching, the second from BO stretching and the other two belong to bending modes of OBO and BOAl with symmetrical deformation of SiOSi. The strongest spectra near 360cm−1 should belong to the bonding of AlO. As a result, the confocal Raman studies are more sensitive for identification of tourmaline subgroup compositions and have a quite important in the explaining source of the magma.

Visualization of buried anti‐tank landmines and soil pollution: analyses using ground penetrating radar method with attributes and petrographical methods

ABSTRACTThis paper presents an approximation to display buried anti‐tank landmines with ground‐penetrating radar method, including physical data attributes by measuring data in a special military field and determination of soil pollution using mineralogical and chemical features of the soil obtained by confocal Raman spectrometry and polarized energy dispersive X‐ray fluorescence, which are petro‐graphical methods, before and after bursting the mine. Two‐dimensional ground penetrating radar data were acquired on parallel profiles using 800‐MHz shielded antenna on unexploded anti‐tank landmines buried approximately 10 cm–15 cm in depth. After general processing in the time domain, we employed migration, a frequency‐wavenumber (F‐K) filter, and ground‐penetrating radar data attributes with an amplitude envelope, spectral whitening, and first‐time derivative to activate anti‐tank landmine visualization. Finally, we obtained three‐dimensional half bird ‘s eye view of the processed volume with each separate attribute. We also derived the transparent three dimensional volumes by assigning opacity to the amplitude‐colour range. The results showed that the depth slices including attributes and the transparent three‐dimensional depth‐volumes could clearly image the anti‐tank landmine. In addition, migration and F‐K filter during special processing were very important in removing data noise. Ground‐penetrating radar data atthbutes—particularly amplitude enveloping— could suppress small phase shifts in the neighbouhng traces of the landmine amplitude anomalies and helped to obtain more complete results showing location and depth in the three‐dimensional volume.The results of the analyses of the major oxide elements and heavy metal elements, such as Fe2O3 Pb, Zn, As, Mn, Mo, Co, Ni, Sb, and Sn, in the test area revealed that there were almost no major differences before and after blasting the anti‐tank landmines. This indicates that one‐time bursting of the anti‐tank landmines in the field has not polluted the soil in this area.

The origin and determination of silica types in the silica occurrences from Altintaş region (Uşak–Western Anatolia) using multianalytical techniques

The studied area is located in Western Anatolia and situated on the NE–SW directed Uşak–Güre cross-graben that developed under a crustal extensional regime during the Late Miocene–Pliocene. Silica occurrences have been mostly found as mushroom-shaped big caps. They also show sedimentary structures such as stratification. Silica occurrences are milky white, yellowish white, yellow to chocolate brown and rarely pale blue, bluish gray in color and have no crystal forms in hand specimen. Some of the silica samples show conchoidal fracture. Silica minerals are mostly chalcedony, low-quartz (α-quartz) and sporadically opal-CT in spectras, according to confocal Raman spectrometry. The silica samples have enrichment of Fe (1000–24,600ppm), Ca (100–10,200ppm), P (4–3950ppm) and Mn (8–3020ppm). Other striking elements in fewer amounts are Ba (0.9–609.6ppm), Ni (15.7–182.3ppm) and Co (18.6–343.1ppm). In chondrite-normalized spider diagram, silica samples display partial enrichment in LIL elements (Rb, Ba, Th). The δ18O (‰ V-SMOW) values for silica samples vary from 18.4‰ to 22.8‰ and are similar to low temperature hydrothermal silica. Confocal Raman spectrometry and oxygen isotope indicate that the silica minerals may precipitate from host fluid which is relatively has low temperatures hydrothermal solutions derived from the residual melt of basaltic magma.

Structure–property relationship in aliphatic polyamide/polyaniline surface layered composites

Conducting polymer composite films based on different aliphatic polyamides (PA) (PA-6, PA-11 and PA-12) have been synthesized by in situ aniline polymerization inside a surface layer of the PA host matrix. Dielectric permittivity and dielectric loss of these films are explained in terms of the interfacial polarization. The real part of permittivity is found to be higher in the PA/polyaniline (PANI) composite films than in the virgin PA polymer matrix. Such behaviour is attributed to the interaction between PA and PANI molecular chains and to the conductivity increase after the aniline polymerization. The performed confocal Raman spectrometry and X-ray diffraction studies also confirmed the presence of interactions between PA and PANI molecular chains.

XRF and Raman Characterization of Antimonite

Two type Antimonite (stibnite) ore samples were analyzed by polarized energy dispersive X-ray fluorescence (PEDXRF) spectrometry and by confocal Raman spectrometry (CRS) in this study. The samples were collected from two different localities (İzmir-Ödemiş and Bursa-Uludağ zones from Turkey) according to the sampling methods. The first locality hosted within the metamorphic basement and the second locality hosted within the felsic intrusive rock units. The goal of this paper is to compare two different stibnite samples from various regions through PEDXRF and CRS with the optical characteristic features under the ore microscope. Ore microscopy studies reveal that the İzmir-Ödemiş stibnite is associated mainly with calcite and the Bursa-Uludağ stibnite is associated with celestite and quartz as gangue minerals. Two different colored species were observed in the stibnite of the studied samples. Ore microscopy results, CRS with the PEDXRF results show that the stibnites from the two different localities have different mineral associations, different chemical compositions, and different physical properties.

Confocal Raman spectroscopic mapping studies on a single CuO nanowire

In this study we are able, using a copper grid substrate, to successfully grow separate nanowires with a high level of crystallinity, for a length of up to 10 μm. They were synthesized under various temperatures. We compare and contrast three types of geometries (micron-, nano-scale, and tip-like single CuO nanowires), to identify their potential for monitoring the size effects of quantum confinements. The confocal Raman spectrometry results confirm the expected outcome, that reducing of the diameter of a cylindrical cross-section of a single nanowire results in Raman frequency downshifts. The results can be explained by the bond polarizability model. The applicability of investigating the size effects of the quantum confinement of the tip-like geometry of a single nanowire without any preparation for different sizes of nanoparticles is possible because the detection is relatively straightforward and the reproduced Raman signals can be observed.

Quantitative Detection of Immunoreaction using Magnetite Nanoparticles and Raman Scattering Spectroscopy

We developed a new quantitative detection method for an immunoreaction combining magnetite (Fe3O4) nanoparticle labeling with confocal Raman spectrometry. Magnetite nanoparticles are transparent, Raman active, and easily can be controlled easily by magnets in bimolecular reactions. Human Chorionic Gonadtropin (hCG) was selected as a target molecule for this investigation. Sandwich immunoreaction was performed on a dot-patterned substrate using two anti-hCG antibodies, which were the antibody immobilized on the substrate and the biotinylated antibody. The immunoreaction was microscopically visualized by reacting streptavidin-modified magnetite nanoparticles with the biotinylated antibody on the substrate. The adsorbed magnetite nanoparticles on the dot pattern were detected by Raman intensity imaging. A good linear relation between the integrated Raman intensity spectra at 220 cm-1 and hCG concentration was gained. This method may be applied toward the detection of other target molecules in the fields of biotechnology and biomedicine. [DOI: 10.1380/ejssnt.2008.142]

Reasons of different colors in the ignimbrite lithology: Micro-XRF and confocal Raman spectrometry method

Medium to large volume ignimbrites usually show vertical changes in terms of color, mineral components, texture and geochemistry. Determination of vertical changes in single extensive ignimbrite flow unit is difficult and requires careful studies. Color changes in ignimbrite flow units are very important for earth scientists. This may cause to identify the same ignimbrite series with different definition. Incesu ignimbrite has a wide distribution in the Central Anatolian Volcanic Province (CAVP). It is classified into three levels as lower, middle and upper according to color and welding degree. There is a sharp contact between the lower and middle level. The lower level is dark brown to black in color and the middle level has pinkish red to red color. The present paper focuses on the investigation of color changes between the ignimbrite levels by using micro-XRF and confocal Raman spectrometry. Micro-XRF and Raman spectrometry studies were performed on the polished thin sections of the lower and middle levels with different compositions. These differences were because of the compositional changes of K and slightly Fe elements distribution within the matrix. The dark brown to black color of the lower level was related to the high concentration of the K and Fe relatively to the middle level. Confocal Raman spectrometry investigations exhibited the matrix of the lower level mainly composed of anorthoclase, supporting the results of the micro-XRF.

Intracellularly grown gold nanoparticles as potential surface-enhanced Raman scattering probes

Gold nanoparticles grown within the intracellular confines of living cells are introduced as potential surface-enhanced Raman scattering (SERS) substrates for confocal Raman spectrometry. Electron microscopy and a silver-enhanced reflectance laser scanning confocal microscopic approach were used to visualize the size, shape, and distribution of intracellularly grown gold nanoparticles (IGAuN) as small as 1 nm. Passive uptake as the conventional approach for delivering nanoparticles inside cells faces the insurmountable challenge of escaping the endosomal/lysosomal pathway. In contrast, IGAuN provides an unprecedented advantage of providing access to cytoplasm and nucleus.