A preliminary assessment of microstructural and compositional characteristics of two variants of precarbonated and postcarbonated concrete mixes

The hydration, precarbonation, and postcarbonation microstructural and compositional attributes of 2 variants of concrete were studied using scanning electron microscope, energy dispersive spectroscopy, and X‐ray diffraction techniques. Results obtained showed presence of large number of diffraction peaks indicative of SiO₂ as major phase. Higher pH, alkalinity, and absence of effects of carbonation were suggested from the presence of portlandite peaks. Evidence of effect of carbonation was studied through the analysis of the experimental diffraction peaks obtained postexposure to accelerated carbonation in a controlled environment. Presence of all the 3 polymorphs of calcium carbonate (CaCO₃) such as aragonite, vaterite, and calcite depending upon the moisture content and the material constituting the concrete sample were envisaged signifying carbonation. Precipitation of these CaCO₃ crystals was responsible for depletion of CH as well as calcium–silicate–hydrate, ettringite with the progress of carbonation as suggested by their absence in the X‐ray diffraction diffractograms of the carbonated samples. The crystal structure of the newly formed minerals in both the variants of concrete sample was highly controlled by the stages of carbonation, with development of amorphous CaCO₃ (amalgamated with that of calcium hydrates) in early stages of carbonation as well as fully developed rhombohedral CaCO₃ crystals in later stages.     

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.     

Structural aspects of two-dimensional polymers: Li4C60, Na4C60 and tetragonal C60. Raman spectroscopy and X-ray diffraction

We present an analysis of three different two-dimensional polymers, tetragonal C₆₀, Li₄C₆₀, and Na₄C₆₀. Based on X-ray diffraction and Raman spectroscopy, we conclude that Li₄C₆₀ forms a tetragonal structure with intermolecular bonds formed by 2+2 cycloaddition, in the same way as for tetragonal C₆₀. Na₄C₆₀, on the other hand, forms a monoclinic structure with single C–C bonds between the molecules. Our Raman spectroscopy results can be interpreted in two ways: either the charge transfer to the C₆₀ molecules is the same in both doped compounds with four electrons/molecule or the electron charge transfer is smaller from the Li ions than from the Na ions.     

In vitro remineralization of acid-etched human enamel with Ca3SiO5

Bioactive and inductive silicate-based bioceramics play an important role in hard tissue prosthetics such as bone and teeth. In the present study, a model was established to study the acid-etched enamel remineralization with tricalcium silicate (Ca₃SiO₅, C₃S) paste in vitro. After soaking in simulated oral fluid (SOF), Ca-P precipitation layer was formed on the enamel surface, with the prolonged soaking time, apatite layer turned into density and uniformity and thickness increasingly from 250 to 350 nm for 1 day to 1.7-1.9 μm for 7 days. Structure of apatite crystals was similar to that of hydroxyapatite (HAp). At the same time, surface smoothness of the remineralized layer is favorable for the oral hygiene. These results suggested that C₃S treated the acid-etched enamel can induce apatite formation, indicating the biomimic mineralization ability, and C₃S could be used as an agent of inductive biomineralization for the enamel prosthesis and protection.     

Synthesis and Raman study on needlelike silicates in ancient Chinese Pb‐Ba glass in Qin and Han dynasties

Two ancient green Chinese Pb‐Ba glass (Qin and Han dynasties) were studied with Raman microspectroscopy, scanning electron microscopy, and energy dispersive X‐ray spectrometry. Some needlelike silicates were found in the samples and inferred as BaSiO₃, BaSi₂O₅, and PbSiO₃ according to the results of energy dispersive X‐ray spectrometry analysis. Then BaSiO₃, BaSi₂O₅, and PbSiO₃ were synthetized in laboratory in order to obtain their Raman spectra. Through comparative study, the needlelike silicates in the ancient Pb‐Ba glass samples were proved to be PbSiO₃, BaSiO₃, and Al₂O₃. According to the ternary phase diagram analysis, a mechanism of local element enrichment was put forward for the barium silicate needlelike silicates (by‐products) formation in the ancient Pb‐Ba glass. Copyright © 2014 John Wiley & Sons, Ltd.     

Charge‐transfer contributions in surface‐enhanced Raman scattering from Ag,Ag2S and Ag2Se substrates

The degree of charge‐transfer in Ag–4‐mercaptopyridine (Mpy) and Ag₂S–4‐Mpy systems is investigated by use of surface‐enhanced Raman spectroscopy (SERS). Ag₂S and Ag₂Se nanoparticles are prepared on the basis of the former formation of Ag nanoparticles to make the SERS analytical objects comparable. We utilize the intensity of the non‐totally symmetric modes (either b₁ or b₂) as compared with the totally symmetric a₁ modes to measure the degree of charge‐transfer. We find ~25% of charge‐transfer contribution for Ag–4‐Mpy, whereas 81 ~ 93% for Ag₂S–4‐Mpy. It means that the charge‐transfer resonance contribution dominates the overall enhancement in SERS of Ag₂S–4‐Mpy. Energy level diagram is applied to discuss the likely charge‐transfer transition between Ag, Ag₂S, Ag₂Se and 4‐Mpy. This article may point out the link among the three main resonance sources and could enable some insights into the electronic pathways available to the metal‐molecule and semiconductor‐molecule systems. Copyright © 2012 John Wiley & Sons, Ltd.     

Vibrational spectroscopy of the seselin crystal

Seselin, C₁₄H₁₂O₃, is a coumarin which crystallizes in a monoclinic structure P2₁/b(C_2h⁵) with four molecules per unit cell. In a Fourier‐transform Raman spectroscopic study performed at room temperature, several normal modes were observed. Vibrational wavenumber and wave vector calculations using density functional theory were compared with experiment, which allowed the assignment of a number of normal modes of the crystal. Temperature‐dependent Raman spectra were recorded between 10 and 300 K. No anomalies were observed in the phonon spectra, indicating that the monoclinic structure remains stable. Copyright © 2007 John Wiley & Sons, Ltd.     

Molecular Structures of H2X and D2X(X=0, S,Se, Te)

There are two possible configurations for H₂O, linear(D_∞h) or bent(C_2v). For a C_2v′, the three bands ν_1′ ν₂ and ν₃ should appear in both Raman and infrared. For a D_∞h. however, the ν₁, band should appear in only Raman and the ν₂ and ν₃ bands, in only infrared, that is, a principle of mutual exclusion of Raman and infrared should hold. The present author concludes that H₂X and D₂X(X=O, S, Se, Te) have a linear D_∞h. structure, since the obtained spectra show mutual exclusion of Raman and infrared.     

Correlations between Raman parameters and elemental composition in lead and lead alkali silicate glasses

This article examines the influence of the composition on the Raman spectra of lead silicate glass. Modern and historic lead alkali glasses and high‐lead glazed ceramics were analysed complementarily by Raman spectrometry and elemental techniques, either electron microprobe, proton induced X‐ray emission (PIXE) or scanning electron microscope with energy dispersive spectrometry (SEM‐EDS). The results showed that lead alkali silicate and high‐lead silicate glasses can be easily distinguished from their Raman spectra profile. In lead alkali silicate glasses, continuous variations were observed in the spectra with the compositional change. In particular, the position of the intense peak around 1070 cm⁻¹ was linearly correlated to the lead content in the glass. A unique decomposition model was developed for the spectra of lead alkali silicate glasses. From the combination of the Raman and elemental analyses, correlations were established between the spectral components and the composition. These correlations permitted to interpret the spectra and access additional compositional information, such as the lead content from area ratio A₉₉₀/A_900–1150, the total alkali + alkaline‐earth content from the area ratio A₁₁₀₀/A_900–1150 or the silica content from the area ratio A₁₁₅₀/A_900–1150. In lead silicate glass containing over 25 mol% PbO, the compositional variation induced no variation in the SiO₄ network region of the Raman spectra [150–1350 cm⁻¹], therefore no correlations and compositional information could be gained from the glass spectra in this range of composition. This new development of Raman spectroscopy for the analyses of glass will be very valuable for museums to not only access compositional information non‐destructively but also to understand the structural changes involved with their alteration. Copyright © 2008 John Wiley & Sons, Ltd.     

Theoretical and experimental studies on the adsorption behavior of thiophenol on gold nanoparticles

FT‐Raman spectra were obtained for thiophenol (TP) and TP on gold nanoparticles. All vibrational fundamentals for the TP molecule are assigned on the basis of the scaled quantum force field procedure. Three model systems are studied and compared for the interactions of TP with the Au atom: (1) TP with a Au atom, C₆H₅SH Au; (2) TP anion with a Au atom, C₆H₅S⁻ Au; and (3) TP with a Au atom and subsequent formation of thiophenylate, C₆H₅SAu. The equilibrium structures and Raman spectra were calculated for the model systems using density functional theory (DFT) with the B3LYP functionals and the mixed basis set 6‐311 + G** (for C, S, H) and LANL2DZ (for Au), and theoretical Raman wavenumbers of C₆H₅SAu and C₆H₅S⁻ Au were assigned according to potential energy distributions. The third model system is shown to be preferred over the other two. The calculated binding energies are also shown to support the third model system. It is suggested that a simple model, such as the one used in the present study, is reasonable to describe surface‐enhanced Raman spectroscopy of thiophenol adsorbed on gold nanoparticles. Copyright © 2007 John Wiley & Sons, Ltd.     

Polarized Raman mapping study of the microheterogeneity in 0.67PbMg1/3 Nb2/3O3‐0.33PbTiO3 single crystal

Polarized micro‐Raman spectroscopy was carried out on the (001) face of a 0.67PbMg_1/3Nb_2/3O₃‐33%PbTiO₃ (PMN‐33%PT) single crystal. The Raman images revealed the spatial variations of the intensity of the Raman bands, suggesting that the structure in the PMN‐33%PT single crystal varied from one micro‐area to another. When changing the polarization direction of the incident light with respect to the selected crystalline axes, the intensities of the Raman modes varied periodically. According to the Raman selection rules (RSRs), the angular dependences of the Raman modes indicated that the PMN‐33%PT single crystal is in the monoclinic phase. Furthermore, the color patterns in the Raman images were associated with the coexistence of the M_A‐ and M_C‐type monoclinic phases in the PMN‐33%PT single crystal. Our results provide useful information for understanding the microheterogeneity of the relaxor PMN‐xPT single crystals with compositions near the morphotropic phase boundary region. Copyright © 2010 John Wiley & Sons, Ltd.     

Shedding light onto the spectra of lime: Raman and luminescence bands of CaO,Ca(OH)2 and CaCO3

In microscopy studies of 19^th‐century cement stone, we found free lime in the form of darkened spherical structures, as they were described in the literature already. When trying to determine their phase composition by Raman spectroscopy, we encountered contradictive assignments in literature spectra of the lime phases CaO, Ca(OH)₂ and CaCO₃ and observed strong spectral features that have been ignored or erroneously assigned so far. In this study we present Raman spectra of pure lime phases and of a naturally grown calcite crystal, burnt limestone (quick lime, mainly CaO), aged slaked lime putty (mainly Ca(OH)₂), and carbonated lime putty (mainly CaCO₃). Based on the results, we shed light mainly onto these two questions: (1) Does CaO have a Raman spectrum? (2) Which features in the spectra are luminescence bands that could be (and already have been) misinterpreted as Raman bands? We proof our assignment of luminescence bands in lime phases by using three different laser wavelengths for excitation, and give hypotheses on the origin of the luminescence as well as practical advices on how to identify these misleading features in Raman spectra. This article is mainly addressed to users of Raman spectroscopy in different fields of material analysis who might not be aware of the presence of interfering bands in their spectra. Copyright © 2014 John Wiley & Sons, Ltd.     

Raman spectra and phase composition of MnGeO3 crystals

MnGeO₃ single‐crystal samples have been synthesized by optical zonal melting and spontaneous crystallization. X‐ray crystal analysis showed the first sample to be a two‐phase one with phase ratio as follows: 17% – monoclinic C2/c, and 83% – orthorhombic Pbca; the phase ratio of the second sample was unknown. Raman spectra have been produced for these samples. Lattice dynamics has been simulated and polarization dependencies of lines' intensities have been analyzed to interpret experimental Raman spectra and to attribute lines to the spectra of monoclinic and orthorhombic phases. Copyright © 2015 John Wiley & Sons, Ltd.     

Structural study of Mg‐bearing sodosilicate glasses by Raman spectroscopy

The presence of magnesium in glasses of geological, medical, and technological interests influences their physicochemical and durability properties. However, the understanding of the role of magnesium is dependent on the combined knowledge of the structural environment of magnesium in the glass or melt and of the silicate network connectivity of the studied systems. In this article, we present a Raman spectroscopic study of the network connectivity of 10 ternary silicate glasses in the system Na₂O MgO SiO₂ and one Mg‐free binary silicate glass Na₂O SiO₂. Results obtained at constant polymerization suggest the existence of various Qⁿ units according to the nature of the modifying cation. As polymerization decreases for Na₂O MgO αSiO₂ glasses (labeled as NMSα with α decreasing from 10 to 2), the band associated with Si O Si bending in fully polymerized region disappears being gradually replaced by a band attributed to Si O Si bending in region containing mainly Q² and Q³ species. For highly polymerized glasses (NMS10‐NMS4), the coexistence of these two bands suggests the presence of two interconnected networks. Concomitantly, the signal associated with Q³ species first increases. For a further decrease of the polymerization, the high wavenumber part of the signal associated with Q³ species decreases, while the intensity of the high wavenumber part of the band related to Q² species increases. This result strongly suggests that magnesium charge‐balances preferentially Q² species rather than Q³ species. Copyright © 2010 John Wiley & Sons, Ltd.     

Single‐molecule surface‐enhanced Raman scattering of fullerene C60

We achieved single‐molecule surface‐enhanced Raman scattering (SM‐SERS) spectra from ultralow concentrations (10⁻¹⁵ M) of fullerene C₆₀ on uniformly assembled Au nanoparticles. It was found that resonant excitation at 785 nm is a powerful tool to probe SM‐SERS in this system. The appearance of additional bands and splitting of some vibrational modes were observed because of the symmetry reduction of the adsorbed molecule and a relaxation in the surface selection rules. Time‐evolved spectral fluctuation and ‘hot spot’ dependence in the SM‐SERS spectra were demonstrated to result from the single‐molecule Raman behavior of the spherical C₆₀ on Au nanoparticles. Copyright © 2010 John Wiley & Sons, Ltd.     

In situ Raman and photoluminescence study on pressure‐induced phase transition in C60 nanotubes

Single crystalline C₆₀ nanotubes having face‐centered‐cubic structure with diameters in the nanometer range were synthesized by a solution method. In situ Raman and photoluminescence spectroscopy under high pressure were employed to study the structural stabilities and transitions of the pristine C₆₀ nanotubes. A phase transition, probably because of the orientational ordering of C₆₀ molecules, from face‐centered‐cubic structure to simple cubic structure occurred at the pressure between 1.46 and 2.26 GPa. At above 20.41 GPa, the Raman spectrum became very diffuse and lost its fine structure in all wavenumber regions, and only two broad and asymmetry peaks initially centered at 1469 and 1570 cm^–1 were observed, indicating an occurrence of amorphization. This amorphous phase remained to be reversible until 31.1 GPa, and it became irreversible to the ambient pressure after the pressure cycle of 34.3 GPa was applied. Copyright © 2012 John Wiley & Sons, Ltd.     

Phonon anomalies and structural transition in spin ice Dy2Ti2O7: a simultaneous pressure‐dependent and temperature‐dependent Raman study

We revisit the assignment of Raman phonons of rare‐earth titanates by performing Raman measurements on single crystals of O¹⁸ isotope‐rich spin ice and nonmagnetic pyrochlores and compare the results with their O¹⁶ counterparts. We show that the low‐wavenumber Raman modes below 250 cm⁻¹ are not due to oxygen vibrations. A mode near 200 cm⁻¹, commonly assigned as F_2g phonon, which shows highly anomalous temperature dependence, is now assigned to a disorder‐induced Raman active mode involving Ti⁴⁺ vibrations. Moreover, we address here the origin of the ‘new’ Raman mode, observed below T_C ~ 110 K in Dy₂Ti₂O₇, through a simultaneous pressure‐dependent and temperature‐dependent Raman study. Our study confirms the ‘new’ mode to be a phonon mode. We find that dT_C/dP = + 5.9 K/GPa. Temperature dependence of other phonons has also been studied at various pressures up to ~8 GPa. We find that pressure suppresses the anomalous temperature dependence. The role of the inherent vacant sites present in the pyrochlore structure in the anomalous temperature dependence is also discussed. Copyright © 2012 John Wiley & Sons, Ltd.     

Beryllium Silicate,Be2SiO4 (phenakite) – a Novel Trigonal SRS‐Active Crystal

In single crystals of the beryllium silicate Be₂SiO₄ with trigonal symmetry , known also as the mineral phenakite, χ⁽³⁾‐nonlinear lasing by stimulated Raman scattering (SRS) is investigated. All observed Stokes and anti‐Stokes lasing components are identified and ascribed to a single SRS‐promoting vibration mode with ω_SRS ≈876 cm⁻¹. With picosecond single‐wavelength pumping at one micrometer the generation of an octave‐spanning Stokes and anti‐Stokes comb is observed.     

Approximate chemical analysis of volcanic glasses using Raman spectroscopy

The effect of chemical composition on the Raman spectra of a series of natural calcalkaline silicate glasses has been quantified by performing electron microprobe analyses and obtaining Raman spectra on glassy filaments (~450 µm) derived from a magma mingling experiment. The results provide a robust compositionally‐dependent database for the Raman spectra of natural silicate glasses along the calcalkaline series. An empirical model based on both the acquired Raman spectra and an ideal mixing equation between calcalkaline basaltic and rhyolitic end‐members is constructed enabling the estimation of the chemical composition and degree of polymerization of silicate glasses using Raman spectra. The model is relatively insensitive to acquisition conditions and has been validated using the MPI‐DING geochemical standard glasses 1 as well as further samples. The methods and model developed here offer several advantages compared with other analytical and spectroscopic methods such as infrared spectroscopy, X‐ray fluorescence spectroscopy, electron and ion microprobe analyses, inasmuch as Raman spectroscopy can be performed with a high spatial resolution (1 µm²) without the need for any sample preparation as a nondestructive technique. This study represents an advance in efforts to provide the first database of Raman spectra for natural silicate glasses and yields a new approach for the treatment of Raman spectra, which allows us to extract approximate information about the chemical composition of natural silicate glasses using Raman spectroscopy. We anticipate its application in handheld in situ terrestrial field studies of silicate glasses under extreme conditions (e.g. extraterrestrial and submarine environments). © 2015 The Authors Journal of Raman Spectroscopy Published by John Wiley & Sons Ltd