Authors:S. Shoval, K. Michaelian, M. Boudeulle, G. Panczer, I. Lapides, and S. Yariv
The products of dickite heated in air at 1000 to 1300°C were studied using curve-fitting of transmission and photoacoustic infrared and micro-Raman spectra. The spectra were compared with those of mullite, Al-spinel, corundum, cristobalite, amorphous silica and meta-dickite. Bands that characterize crystalline phases appeared at 1100°C and became stronger with increasing temperature. Mullite, Al-spinel, corundum and amorphous silica were identified by their characteristic bands. The characteristic IR bands of cristobalite overlap those of mullite and amorphous silica, and its presence was therefore established from intensity ratios of the appropriate bands. The research clearly demonstrated the advantage of using curve-fitting for the identification of high temperature phases in the study of the thermal treatment of kaolin-like minerals by infrared and Raman spectroscopy. This technique seems to be a useful method for materials analysis in the ceramic industry.
Oxo-centered trinuclear mixed-valence iron fumarate [Fe3O(O2CCH=CHCO2)3(H2O)3]·nH2O and iron malonate [Fe3O(O2CCH2CO2)3(H2O)3] have been prepared and studied by variable temperature Mössbauer spectroscopy. Iron fumarate complex showed a temperature dependent valence delocalization process. At 6 K two quadrupole split doublets corresponding to high-spin Fe(III) and high-spin Fe(II) state with an area ratio of 2:1 were observed and at 298 K there was only an averaged singlet peak. On the other hand malonate complex showed a localized valence state of high-spin Fe(III) and Fe(II) from low temperature to room temperature only with a slight variation in area ratio and spectral line broadening for Fe(II).
Ion association has been studied by positron lifetime spectroscopy in aqueous solutions containing the Ni2+ and SO
ions at 294 K with the double aim of assessing the reliability of the method for quantitative determination of complex formation constants and of probing the validity of various expressions to calculate single-ion activity coefficients at high ionic strength. The existence of two complexes, identified as NiSO4 and Ni2SO
, is shown by the data analysis. Considering the formation constant of the former, KI=(196±10)M–1, determined in previous works leads to discarding several of the expressions commonly used for activity corrections. Two possible values are retained for KI, (193±20)M–1 and (179±20)M–1, while KII related to Ni2SO
is better defined, as (2.57±0.14)M–1.
Authors:Madan Lal, R. Choudhury, D. Joseph, H. Bajpai, and C. Tyer
Analysis by Energy Dispersive X-ray Fluorescence spectroscopy of monazite ores from Kerala /Chavara and Manavalakurichi/, Orissa /Chattrapur/ and Tamil Nadu /Tirunelveli/ has been carried out for the determination of their elemental composition using109Cd /annular/ and241Am /disc/ radioisotope sources. The elements Y, Zr, Mo, Pb, Th and U were analyzed using a109Cd source, and the elements La, Ce, Pr, Nd, Sm, Gd and Dy were analyzed using the241Am source in side source geometry. Quntitative results on these 13 elements present in these ores were obtained by the EDXRF technique. It was seen that despite the diverse geological settings, there is remarkable similarity in the elemental composition of these ores, although some trace elements do show certain variations from sample to sample. These results are presented and discussed in this paper.
An activity predictor software was previously developed to foresee activities, exposure rates and gamma spectra of activated
samples for Radiation Science and Engineering Center (RSEC), Penn State Breazeale Reactor (PSBR), Neutron Activation Analysis
(NAA) measurements. With Activity Predictor it has been demonstrated that the predicted spectra were less than satisfactory.
In order to obtain better predicted spectra, a new detailed model for the RSEC NAA spectroscopy system with High Purity Germanium
(HPGe) detector is developed using Geant-4. The model was validated with a National Bureau of Standards certified 60Co source and tree activated high purity samples at PSBR. The predicted spectra agreed well with measured spectra. Error in
net photo peak area values were 8.6–33.6%. Along with the previously developed activity predictor software, this new model
in Geant-4 provided realistic spectra prediction for NAA experiments at RSEC PSBR.
Authors:M. Oshtrakh, V. Semionkin, V. Grokhovsky, O. Milder, and E. Novikov
An improvement in velocity resolution of Mössbauer spectroscopy permitted us to carry out a more detailed study of iron chemical
state in various iron-containing compounds in a wide range of research. New possibilities of Mössbauer spectroscopy with high
velocity resolution were shown in the studies of meteorites, nanocomposites, pharmaceuticals and biological subjects.
A combination alpha and conversion electron spectrometer was developed to quantify 239Pu/240Pu and 238Pu/241Am isotopic ratios of plated sources. The spectrometer was constructed with a commercially available low noise passivated ion-implanted planar silicon (PIPS) detector that was cooled to 77 K with liquid nitrogen. The combination spectrometer was used to quantify alpha-particles, conversion electrons, gamma-rays and X-rays associated with the decay of various plutonium isotopes and 241Am. Two amplifiers operated in parallel with different gains allowed for simultaneous acquisition of the lower energy region (21-60 keV) for internal conversion electrons, gamma-rays and X-rays, and the higher energy region (5050 keV-5550 keV) for alpha-particles. Energy resolutions of 2.2 keV FWHM (full-width at half maximum) for the 38.7 keV M conversion electrons and 11.2 keV for the 5499.2 keV alpha-particles from 238Pu were measured. The energy resolution combined with a spectral deconvolution method was sufficient to be able to quantify the radioactivity using the alpha-spectra as well as the electron spectra; however, quantification of the radioactivity using the internal conversion electron spectra was more problematic because of the presence of X-rays, gamma-rays, Compton scatter electrons and the number of electron peaks present. Deconvolution of the alpha-spectra yielded 239Pu and 240Pu activities (as % of total Pu activity), which differed from expected values by -3.0% to 5.4%. Deconvolution of an internal conversion electron spectrum of a high 239Pu and low 241Am activity sample yielded 239Pu and 240Pu activities, which differed by -17.1 and -35.5% relative to the alpha-measurements, respectively. Determination of the Pu activity using the electron spectra was more problematic in samples where the 241Am activity dominated. Determination of 238Pu and 241Am activity by the electron spectroscopy data was also obtained and compared with the alpha-spectroscopy results. Theoretical investigation of the removal of 241Am or use of a 400 eV electron spectrometer indicated that the internal conversion electron spectra could be used to determine the 238Pu, 239Pu, 240Pu/241Am (when present) activity with and without spectral deconvolution, respectively.
Authors:Christine Fräulin, Günter Rinke, and Roland Dittmeyer
Cyclohexane oxidation is an economically important process. To maintain high selectivities of 70 to 90%, the reaction is performed at low conversion up to 6%. To improve this process, investigations on the reaction mechanism are of high interest, which requires measurement techniques able to detect chemical species precisely even at very low concentrations. For this purpose, an in-situ measurement technique based on laser Raman spectroscopy with superior detection sensitivity and an optically transparent microchannel to monitor the process of cyclohexane oxidation has been developed.
The challenge is now to adapt this system to required conditions. In this article, we show that the influence of pressure is negligible. However, increasing temperatures influence the intensity of the Raman spectra significantly. As the temperature influence on the intensity of the Raman light is specific for each species, a temperature dependent calibration must be done to determine the concentrations of the chemical species precisely. In order to reach low detection limits also at high temperatures, the charge-coupled device (CCD) integration time had to be increased. For temperatures below 486 K, the limits of detection are less than 0.05 m/m %.
Thermal decomposition of poly(lactic acid) (PLA) has been studied using thermogravimetry coupled to Fourier transform infrared
spectroscopy (TGA-FTIR). FTIR analysis of the evolved decomposition products shows the release of lactide molecule, acetaldehyde,
carbon monoxide and carbon dioxide. Acetaldehyde and carbon dioxide exist until the end of the experiments, whereas carbon
monoxide gradually decreases above the peak temperature in that the higher temperature benefits from chain homolysis and the
production of carbon dioxide. A kinetic study of thermal degradation of PLA in nitrogen has been studied by means of thermogravimetry.
It is found that the thermal degradation kinetics of PLA can be interpreted in terms of multi-step degradation mechanisms.
The activation energies obtained by Ozawa–Flynn–Wall method and Friedman’s method are in good agreement with that obtained
by Kissinger’s method. The activation energies of PLA calculated by the three methods are 177.5 kJ mol−1, 183.6 kJ mol−1 and 181.1 kJ mol−1, respectively.
A portable prompt gamma neutron activation (PGNA) spectroscopy system has been developed to analyze the elemental composition (Ca, Si, Al, etc.) of reinforced concrete and to measure chloride contamination. The portable PGNA system consists of a high purity germanium (HPGe) gamma detector with a 70% relative efficiency, a 252Cf neutron source and moderator subsystem, and a portable multichannel analyzer system integrated with a laptop computer. Two types of activation experiments were performed to evaluate the device: first, a detector calibration using a Cl gamma standard provided by a PGNA facility; second, an evaluation of the actual performance of the complete system with the 252Cf source using full scale test slabs containing known amounts of chloride. Both methods indicate that it is feasible to use this device to measure the chloride content of reinforced concrete in the field. The chloride level for the corrosion threshold can be measured with a precision of 10% for a counting time of roughly 6 minutes. This makes the PGNA method competitive with the conventional destructive method.