Surface-Enhanced Vibrational Spectroscopy: SERS and SEIRA

With respect to the origin of single-molecule sensitivity in surface-enhanced Raman scattering, elastic scattering and emission spectra were investigated for Ag particles adsorbed with dye. The scattering peak observed at 600–650 nm was extinguished during the inactivation process of an enormous SERS signal, whereas localized surface plasmon (LSP) peaks located at 520 nm and 730 nm did not change significantly. The scattering peak at 600–650 nm arises from increased electromagnetic coupling between the LSP of adjacent Ag particles through dye molecules. In addition, distinct emission peaks were observed at 550–600 nm and 600–750 nm for hot Ag particles with adsorbates. These bands were attributed to emissive relaxation of metal electrons and fluorescence of molecules, respectively. Furthermore, the shorter wavelength peak showed invariant Stokes shift irrespective of excitation wavelengths, most probably arising from inelastic scattering of excited electrons by adsorbed molecules. The adsorbed state of CO and related species on the Pt film electrode was investigated using attenuated total reflection—surface-enhanced infrared absorption spectroscopy. Intermediate species were found on the bare Pt surface in 1 mM CH₃OH + HClO₄ solutions at +0.2 V ≤ E ≤ +0.6 V that give absorption peaks at 1405 cm⁻¹ and 1300 cm⁻¹. These bands can be attributed to carbonate species or -COH. Water molecules located at the hydrophobic interfaces between CO and electrolyte solutions were evidenced by a quite high OH stretch absorption at 3664–3646 cm⁻¹, as well as a lower broad peak at ca. 3480 cm⁻¹.     

Optical Properties of Energetic Materials: RDX,HMX, AP,NC/NG,and HTPB

Optical properties of RDX, HMX, AP, HTPB/IPDI and a catalyzed NC/NG propellant (N5) were obtained from 2.5 μm to 18 μm using FTIR transmission spectrometry. Scattering-corrected KBr pellet methodology was used for the crystalline materials. Absorption index (k) was measured directly and refractive index (n) was deduced using dispersion theory. At 10.600 μm the absorption coefficients were AP, 190 cm⁻¹ (240 cm⁻¹ at 10.6036 μm); HTPB/IPDI, 360 cm⁻¹; N5, 510 cm⁻¹; RDX, 2800 cm⁻¹; and HMX, 5670 cm⁻¹.     

Contribution of sp3 clusters in films and fibers obtained from camphor

Considerable attention has been focused on the growth of carbon-based films or fibers by various methods. Diamond-like carbon (DLC) films may be of greater importance in some specific electronic applications such as flat panel displays, which represent a very large market. In this study, carbon-based thin films and fibers obtained from doped camphor soot were studied by confocal microRaman spectroscopy at 632.8 nm.Different contributions were identified between 1000 and 1650 cm⁻¹ in the Raman spectra of the as-grown and laser-annealed films and fibers. The contributions were the D-like and G-like peaks of polycrystalline graphite at about 1345 and 1530 cm⁻¹, respectively, with a FWHM value about 5 times larger than in a:C. It is now well established from correlation between Raman signature and grain size measurements that the width of the Raman line is a decreasing function of the graphite grain size. From these results, one can estimate that the grain size of this polycrystalline graphitic phase was small. An additional feature is observed at about 1240 cm⁻¹ which could be due to sp³-bonded carbon clusters.     

Influence of synthesis conditions on the properties of Y2O3–MgO nanopowders and sintered nanocomposites

In this study, a citrate–nitrate combustion method was applied to synthesize composite Y₂O₃–MgO nanopowders. In order to optimize the synthesis condition to support sufficient combustion, the molar ratio of citric acid to nitrate (c/n molar ratio) used in the reaction mixtures was varied between 0.17 and 0.34. Nanopowders with an average particle size of 17 nm were achieved. The properties of these nanopowders indicated that the higher molar ratios decreased the unreacted organic components and increased the amount of carbide on the surface of the oxides, which helped to inhibit the formation of carbonate groups. The amount of carbonate groups was reduced with the increasing c/n molar ratio. Y₂O₃–MgO nanocomposites fabricated through hot-isostatic-pressing sintering showed a uniform distribution of Y₂O₃ and MgO grains, which had an average size of ∼180 nm. In addition, the absorption peaks at 1410 and 1511 cm⁻¹ disappeared until the c/n molar ratio reached 0.28. A high average infrared transmittance of 83% in the range of 4000–1667 cm⁻¹ (2.5–6 μm) was obtained in the nanocomposites.     

Effect of MgO calcination temperature on the reaction products and kinetics of MgO–SiO2–H2O system

MgO-based binders have been widely studied for decades. Recently, the MgO–SiO₂–H₂O system was developed as a novel construction material, however, its reaction mechanism remains unclear. This paper investigated the reaction products and kinetics of MgO/silica fume (SF) pastes with MgO calcinated at different temperatures. The results indicate that MgO presented larger grain size after calcination at higher temperature. Mg(OH)₂ and magnesium silicate hydrate (M–S–H) gel were formed when using MgO calcined at 850, 950, and 1050°C. However, only M–S–H gel was formed when using MgO calcined at 1450°C. The reaction kinetics of MgO could be described using α = 1 − e^−k*t. The reaction rate of MgO increased with decreasing calcination temperature, increasing SF dosage, and the addition of sodium hexametaphosphate. Only M–S–H gel was formed when the reaction rate of MgO was below the demarcation line (about 0.250 × 10⁻⁶ s⁻¹), and the corresponding demarcation area was around 14 days.     

A “chain fold band” in the infrared spectra of nylon 6

An absorption band found at 974 cm⁻¹ in the infrared spectra of “amorphous” nylon 6 films has been assigned to CH₂ wagging or twisting vibrations in molecular chain folds. Annealing amorphous films in air at increasing temperatures up to 150°C has been shown to induce a steady increase in the intensity of the absorption band at 974 cm⁻¹. Annealing at higher temperatures resulted in a sharp decrease in intensity up to an annealing temperature of 210°C. This sharp decrease coincided with a sharp increase in the long period determined by low-angle x-ray diffraction studies. Drawing amorphous films has been shown to induce a decrease in the intensity of the band at 974 cm⁻¹. Polarized infrared investigations of amorphous drawn films revealed that the band at 974 cm⁻¹ was strongly perpendicular in character. Treatment of amorphous films in water induced no frequency change in the band at 974 cm⁻¹.     

In-Situ Infrared Study of the Synthesis of Polyaniline Under Acid and Neutral pH

In-situ infrared study of polyaniline (PANI) synthesis showed that the reaction initiated at pH = 1.5 produced a granule PANI microstructure via para-linked dimers of 4-aminodiphenylamine, exhibiting γ(C–H) at 802 cm⁻¹; the reaction initiated at pH = 5.0 and 7.0 produce fiberous, and planar microstructures via ortho-linked dimers of 1,2-aminodiphenylamine and phenazine, exhibiting γ(C–H) at 738 and ν(C=N) at 1446 cm⁻¹. The doped PANI that was produced at pH less than 5.0 showed a feature-less IR background absorption above 1600 cm⁻¹. This absorption could correspond to π-electron delocalization as an indicative of polyaniline conductivity.

     

In situ synthesis of [Ca24Al28O64]4+(4e−) electride ceramic from C12A7 + C3A mixture precursor

Inorganic electride [Ca₂₄Al₂₈O₆₄]⁴⁺(4e⁻) was successfully synthesized via a reaction of Ca₁₂Al₁₄O₃₃ (C12A7), Ca₃Al₂O₄ (C3A), and Al powder at 1050°C for 5 minutes heated by SPS system. The as-prepared polycrystalline C12A7:e⁻ electride exhibits an electron concentration of 2.3 × 10²¹ cm⁻³ and an optical absorption bands at 2.5ev under room temperature. Electron concentration was also determined by thermogravimetry (TG) and differential thermal analysis (DTA). Furthermore, the molecular structure was investigated by Micro Raman measurements; the appearance of the band at 186 cm⁻¹ strongly suggested the formation of C12A7:e⁻ electride. These results not only suggest a novel precursor for fabricating mayenite electrides but also make it possible to produce efficiently the electride in large volume.     

Characterization of petroleum using near-infrared spectroscopy: Quantitative modeling for the true boiling point curve and specific gravity

This work describes a new approach to predict the true boiling point (TBP) curve and to estimate the API gravity in order to characterize the petroleum processed in refineries by using the information present in its absorbance spectrum obtained in the near-infrared region (NIR). The absorbance spectra were obtained in the range from 3700 to 10000 cm⁻¹ employing a CaF₂ transmittance cell with a 0.5 mm light path. Three spectral regions were evaluated for modeling purpose: 5000–3900 cm⁻¹, 6000–3700 cm⁻¹, and 9000–700 cm⁻¹. The spectral region corresponding to the combination of C–H vibrations produces absorption spectra with very good quality while the region above 6500 cm⁻¹ is dominated by scattering of the radiation. The absorbance spectra of a total of 122 samples of petroleum and petroleum blends coming from various producing regions in Brazil and abroad were obtained and pre-processed to correct for base line shift and for the integrated area. Two approaches were employed to obtain the models: one using artificial neural networks (ANN) and the other using partial least squares (PLS). The results showed that PLS gives better predictions than ANN for the API gravity and the TBP curve. The best results were obtained using the 5000–3900 cm⁻¹ spectral range. In an external validation, the average RMSEP for the volume of distillate along the TBP curve employing PLS model was 1.13V% while that for API gravity was 0.24. A comparison between the results obtained by a simulator used by the refinery and the PLS model revealed a better performance for the model based on NIR spectrometry.     

The Unimolecular Decomposition of Cyclobutanol: Experimental and Theoretical Study

The thermal decomposition of cyclobutanol has been investigated behind incident and reflected shock waves at temperatures between 950 K and 1450 K in the total density region (1.5 × 10⁻⁶ – 1.5 × 10⁻⁵) mol/cm³. A strong absorption by an intermediate was observed at the wavelength of 193 nm. By comparing the kinetics with that of pyruvic acid, this absorption was identified to be that of vinyl alcohol. The kinetic parameters of vinyl alcohol, both for the production and the decomposition, were determined. The production rate constant was in agreement with that obtained by Back (Can J. Chem. 1982 , 60, 2357), who monitored the ethylene production. The total decomposition mechanism of cyclobutanol was discussed on the basis of MO calculations. It was shown that vinyl alcohol was produced through a biradical before it isomerized to acetaldehyde.     

Optical properties of ultrananocrystalline diamond/amorphous carbon composite films prepared by pulsed laser deposition

Ultrananocrystalline diamond (UNCD)/amorphous carbon (a-C) composite thin films were grown in ambient hydrogen by pulsed laser deposition using a graphite target, and their optical properties were determined by optical absorption spectroscopy and Raman scattering spectroscopy. Three optical bandgaps exist. Two bandgaps are indirect and their values were estimated to be 1.0 eV and 5.4 eV; these bandgaps correspond to the a-C surrounding the UNCDs and the UNCDs respectively. The third bandgap is direct and has a value of 2.2 eV, which significantly contributes to a large absorption coefficient, (10⁶ cm^− 1 at 3.0 eV). Possible origins of the third bandgaps are the grain boundaries (GBs) between the UNCDs and the a-C since they are specific to the UNCD/a-C composite films. The infrared absorption spectrum and the Raman scattering spectrum revealed the incorporation of hydrogen in the GBs. The hydrogen incorporated in the GBs might also have some influence on the appearance of the direct bandgap and its value.     

Signature of lattice defects in far infrared reflectivity of Ba(Mg1/3Ta2/3)O3

Far infrared reflectivity spectra of Ba(Mg_1/3,Ta_2/3)O₃ prepared at several sintering temperatures were measured, and the eigenfrequencies and damping constants of the TO modes were determined. The reflectivity spectra were fitted with the four-parameter semi-quantum model. The variation in the E_u(O_II) at 222 cm⁻¹ and A_2u(O_II) at 238 cm⁻¹ modes in well ordered ceramics was attributed to the variation in the concentration of the B site defects. It was also found that the change in the oxygen partial pressure of the sintering atmosphere causes a change in the seventh (316 cm⁻¹) and eighth (352 cm⁻¹) modes. We attribute these changes to the oxygen site defect although we cannot evaluate the concentration of this defect at this moment. From the behavior of the damping constants it is suggested that the Ba(Mg_1/3Ta_2/3)O₃ (BMT) attains equilibrium defect density at the heat treatment temperature of more than 1630 °C (120 h).     

Magnesium oxide synthesized with Alpinia zerumbet leaf extracts as a sustainable alternative to zinc oxide in nitrile rubber compounds: A comparative vulcanization kinetics investigation

Zinc oxide (ZnO) is the most widely used activator in the rubber industry; however, there is growing concern about its use as it can become toxic to the environment, particularly in aquatic systems. This study describes the synthesis of magnesium oxide (MgO) assisted by the Alpinia zerumbet extract, which is then used as an activator in the replacement of ZnO to vulcanize nitrile rubber (NBR) containing 33% and 45% acrylonitrile (ACN). The t₉₀ for NBR-33% and NBR-45% are 20 and 15 min, respectively. This indicates a reduction of 5 min in t₉₀ with an increase in ACN. In comparison, ZnO-activated NBR compounds exhibit the opposite trend, with t₉₀ increasing from 10 for NBR-33% to 19 min for NBR-45%. Furthermore, the decrease in activation energy (E_a) with the increase in conversion for 33%-MgO and 45%-MgO indicates that vulcanization with MgO is a complex process. This behavior is comparable to that of 45%-ZnO, but not for 33%-ZnO because its E_a remains oscillating at 80–90 kJ mol⁻¹ in the entire conversion range. The crosslink densities of 33%-MgO and 45%-MgO are 5.87 and 4.78 mol cm⁻³, respectively. These values are slightly higher than those for 33%-ZnO (5.77 mol cm⁻³) and 45%-ZnO (4.38 mol cm⁻³).     

Effect of isothermal aging on the imidization of PMR-15

The imidization of polymerizable reactive mixtures, PMR-15 has been performed in a vacuum oven at isothermal aging temperatures ranging from 65 to 200°C for aging periods of 0.5 to 2.5 h. The weight loss of the resin and chemical changes that occurred as a result of aging were monitored gravimetrically and by FT-IR spectroscopy. Differential scanning calorimetry was used to determine the temperature at which imidization took place. Imidization was observed to commence at 65°C after long aging times, t ≥ 2.5 h and at ∼95°C at a shorter time, t ∼0.5 h. At higher aging temperatures of 135 to 165°C, extensive imidization occurred. This was shown by the dramatic increase in imide absorption bands at 1780 and 1380 cm⁻¹. Beyond 165°C, there were no significant changes in the imide absorption bands, suggesting that imidization was nearly complete. The activation energy for isothermal aging was determined from the slope of the log of the rate of weight loss vs 1/T curve to be ∼4.5 kJ/mol and is lower than the average activation energy for imidization ∼43 kJ/mol obtained from the plot of the log of the rate of increase of the imide carbonyl peak absorption at 1780 cm⁻¹ vs 1/T.     

On the two-phonon absorption of CVD diamond films

It is well known that the absorption coefficient of diamond in the two-phonon region is constant, for example at 2000 cm^{− 1}, the absorption coefficient is 12.3 cm^{− 1}. This means that the infrared absorbance in the two-phonon region is proportional to the thickness of the samples, which is generally used as standard to normalize the infrared absorption spectra of diamond samples according to their thickness. This is true for natural and HPHT synthetic single crystal diamond. However for polycrystalline or nanocrystalline CVD diamond films, we found that the situation may be different. For high quality thick CVD diamond films of thickness > 150 μm, the infrared absorbance in the two-phonon region is proportional to its thickness. While CVD diamond films of equal thickness but of different quality show variable absorbance in the two-phonon absorption region in terms of thickness. Our investigation on this observation primarily indicates that the grain size of CVD diamond films has influence on the two-phonon absorption. In this work, we present this new result and discuss the mechanism of this phenomenon in the light of the growth mechanism of CVD diamond.     

Chemical copolymerization of aniline with o‐chloroaniline: thermal stability by spectral studies

Poly(aniline‐co‐o‐chloroaniline) salts were synthesized by chemical copolymerization of aniline with o‐chloroaniline using three different acids. The polymer salt samples were heat treated at four different temperatures (150, 200, 275 and 375 °C) and the thermal stability of the polymer salts were studied by conductivity, electron paramagnetic resonance (EPR), infrared (IR) and electronic absorption spectral measurements. The conductivity of the copolymers could be controlled in a broad range from 10 S cm⁻¹ for homopolymer of aniline to 10⁻⁴ S cm⁻¹ for those of o‐chloroaniline. No structural changes took place up to 200 °C and this was confirmed from EPR, IR and electronic absorption spectra. No definite correlation exists between conductivity and spin concentration. © 2000 Society of Chemical Industry     

Electrical properties of thick boron and nitrogen contained CVD diamond films

The acceptor and donor defects of thick (approx. 0.4 mm) free-standing boron and nitrogen containing microwave plasma CVD polycrystalline diamond films were investigated. Charge-based deep level transient spectroscopy (Q-DLTS) was applied to study impurity-induced defects, their density and energy distribution in the energy range of 0.01 eV≤E−E_v≤1.1 eV above the valence band. It was shown, that differential capacitance–voltage, and Hall effect measurements combined with DLTS data can be used to determine the degree of compensation, and the concentration of compensating donors (mostly the positively charged single-substitutional nitrogen (N⁺)) in p-type CVD polycrystalline diamond films. It was found, that incorporated boron atoms induce three levels of electrically active defects. Two of them with concentration (2–3)×10¹⁶ cm⁻³ each have activation energies of 0.36 and 0.25 eV with capture cross-sections of 1.3×10⁻¹³ and 4.5×10⁻¹⁹ cm², respectively. The third type of defect has an activation energy of 0.02 eV, capture cross-section 3×10⁻²⁰ cm² and concentration 10¹⁵ cm⁻³, this shallow trap being a probable general caterer of holes in low-doped films. The total concentration of electrically active uncompensated acceptors in all p-type diamond samples was approximately 2×10¹⁷ cm⁻³ with hole concentration of approximately 1.5×10¹⁴ cm⁻³ and hole mobility in the range of 30–40 cm² V⁻¹ s⁻¹ at room temperature. If assumed that compensating donors are mostly nitrogen, the films contained no less than 3×10¹⁶ cm⁻³ of N⁺.     

The role of nitrogen in the deposition of polycrystalline diamond films

The role of nitrogen in the formation of polycrystalline diamond films prepared using a microwave plasma CVD system has been studied using micro-Raman spectroscopy, X-ray diffraction and X-ray photoelectron spectroscopy (XPS). Although the nitrogen concentration in the films was too low to be detected by XPS, the Raman spectrum was found to be significantly affected by the nitrogen flow ratio. The intensity of the Raman peak at 1480 cm⁻¹ significantly decreases, whereas that of 1190 cm⁻¹ peak remains almost unchanged in comparison with the 1350 and 1550 cm⁻¹ peaks with increasing nitrogen flow ratio. In contrast, the preferentially (111)-orientated growth and the growth rate were little influenced by the nitrogen flow ratio. These results indicate that nitrogen plays a special role in the formation and structure of the polycrystalline diamond films studied in this report.     

Enhanced thermoelectric figure of merit in indium and ytterbium double-filled skutterudite bulk materials through simultaneously optimising power factor and reducing thermal conductivity

In this study, Yb_xCo₄Sb₁₂ and In_xYb_0.3Co₄Sb₁₂ bulk materials were fabricated via microwave synthesis combined with spark plasma sintering. Based on ytterbium single filling, indium was further filled into the voids of CoSb₃. Carrier concentration and mobility were regulated as 1.6–1.8 × 10²⁰ cm^-³ and ∼30 cm²V⁻¹S⁻¹, respectively, resulting in an improved power factor of ∼4900 μWm⁻¹K⁻². The phonon-resonant scattering, caused by indium and ytterbium double filling, was combined with other phonon scattering mechanisms such as nano-inclusion, dislocation, and grain boundary segregation, which resulted in a significantly decreased lattice thermal conductivity of 0.72–2.08 Wm⁻¹K⁻¹. Owing to the improvements in carrier concentration and phonon transport, excellent thermoelectric performance, reflected by ZT = 1.38 at 773 K, was achieved in In_0.4Yb_0.3Co₄Sb₁₂.     

Third-order nonlinear optical properties and two-photon absorption in polymers doped with p-phenyl sydnone

We report the measurements of the third-order susceptibilities and two-photon absorption in three different polymers doped with p-phenyl sydnone moiety viz., 2-benzylhydrazono-5-(3-p-tolylsydnone-4-yl)1,3,4,-thiadiazine, which is recently synthesized and characterized, with the prospective of reaching a good compromise between processability and high nonlinear optical properties. The measurements were done using nano second Z-scan at 532nm. The Z-scan spectra reveal a large negative nonlinear refraction coefficient n₂ of the order 10⁻¹⁴ cm²/W and a two-photon absorption β, which is determined to be the order of cm/GW. The absorption cross section is 10⁻⁴⁶ cm⁴ s/photon. The molecular second-order hyperpolarizability in PMMA matrix was calculated to be 1.47 × 10⁻³¹ esu, comparable with stilbazolieum derivatives, a well-known class of optical materials for photonics and biophotonics applications. The chromophore shows its optical power limiting behavior in all the three polymer matrices. All these results suggest that this moiety has potential for the application of all-optical limiting and switching devices. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008