Determining cement composition by Fourier transform infrared spectroscopy

A diffuse reflectance mid-infrared Fourier transform spectroscopy (DRIFTS) method is described for obtaining high quality Fourier transform infrared (FTIR) spectra of cements. DRIFT spectra of synthetic C₃S, C₂S, C₃A, and C₄AF and of pure gypsum, bassanite, anhydrite, syngenite, and calcite are shown. Typical spectra of American Petroleum Institute class G and class A cements display characteristic features which can be related qualitatively to variations in the constituent minerals. For quantitative analysis, the FTIR spectra of 156 cements of varied origin and known elemental composition have been used to construct multivariate calibration models. These relate the spectrum to composition (expressed in terms of nine mineral components and five minor oxides) and allow the composition of unknown cements to be determined rapidly from the FTIR spectrum alone. Error estimates are given.     

Fourier transform infrared detection in miniaturized total analysis systems for sucrose analysis

In this work, a flow system containing a micromachined lamella-type porous silicon reactor and a novel mid-IR fiber-optic flow cell were used for the enzymatic determination of sucrose in aqueous solution. The method relies on the enzymatic hydrolysis of sucrose to fructose and glucose catalyzed by β-fructosidase and on the acquisition of FT-IR spectra before and after complete reaction. β-Fructosidase was covalently bound to the porous silicon surface of the channels in the microreactor. The porous silicon was achieved by anodization of the silicon reactor in a HF/ethanol mixture. For the measurement of small amounts of aqueous solution, a miniaturized flow cell was developed which consisted of two AgCl(x)Br(1)(-)(x) fiber tips (diameter, 0.75 mm) coaxially mounted in a PTFE block at a distance of 23 μm. The flowing stream was directed through the gap of the two fiber tips which served to define the optical path length and to bring the focused mid-IR radiation to the place of measurement. Using this construction, a probed volume of ～10 nL was obtained. The calibration curve was linear between 10 and 100 mmol/L sucrose. Furthermore, the potential of this method was demonstrated by the analysis of binary sucrose/glucose mixtures showing no interference from glucose and by the successful determination of sucrose in real samples.     

Quantitative analysis of polyethylene blends by Fourier transform infrared spectroscopy

The quantitative analysis of binary polyethylene (PE) blends by Fourier transform infrared (FT-IR) spectroscopy has been achieved based on the ratio of two absorbance peaks in an FT-IR spectrum. The frequencies for the absorbance ratio are selected based on structural entities of the PE components in the blend. A linear relationship between the absorbance ratio and the blend composition was found to exist if one of the absorbance peaks is distinct to one of the components and the other peak is common to both components. It was also found that any peak resulting from short-chain branching in copolymers (such as linear low-density polyethylene (LLDPE) or metallocene-catalyzed LLDPE (mLLDPE)), is suitable for use as the peak that is designated as being distinct to that component. In order to optimize the linearity of the equation, however, the selection of the second common peak is the most important and depends on the blend system studied. Indeed, under certain circumstances peaks that are not spectrally distinct can be used successfully to apply the method. The method exhibits potential for the routine analysis of PE blends that have been calibrated prior to its application.     

Time-resolved Fourier transform infrared spectroscopic imaging

Fourier transform infrared (FT-IR) imaging allows simultaneous spectral characterization of large spatial areas due to its multichannel detection advantage. The acquisition of large amounts of data in the multichannel configuration results, however, in a poor temporal resolution of sequentially acquired data sets, which limits the examination of dynamic processes to processes that have characteristic time scales of the order of minutes. Here, we introduce the concept and instrumental details of a time-resolved infrared spectroscopic imaging modality that permits the examination of repetitive dynamic processes whose half-lives are of the order of milli-seconds. As an illustration of this implementation of step-scan FT-IR imaging, we examine the molecular responses to external electric-field perturbations of a microscopically heterogeneous polymer-liquid crystal composite. Analysis of the spectroscopic data using conventional univariate and generalized two-dimensional (2D) correlation methods emphasizes an additional capability for accessing of simultaneous spatial and temporal chemical measurements of molecular dynamic processes.     

Fourier transform spectroscopy of LaS in the infrared

We recorded the emission spectrum of diatomic lanthanum sulfide on the Los Alamos Fourier transform spectrometer. In the region 7500-16,000 cm(-1), we identified over 120 bands and assigned them to the A(2)∏(r)-X(2)Σ(+) and B(2)Σ(+)-X(2)Σ(+) transitions. Each of these bands is four headed.     

Optimum condition of Fourier transform infrared multiple-angle incidence resolution spectrometry for surface analysis

A novel measurement technique of pure out-of-plane vibrational modes of thin films on a nonmetallic substrate has recently been proposed, which is named multiple-angle incidence resolution spectrometry (MAIRS). Since this technique could not be replaced by other conventional techniques, MAIRS was expected to be a promising tool for analysis of thin soft materials and surface adsorbates. Nevertheless, some experimental conditions have been found to be inappropriate for MAIRS, which yields incorrect results. In the present study, therefore, the problems in the technique have been investigated in terms of optics to improve the accomplishments of MAIRS. The problems have been found to have a strong relationship with optics in FT-IR, which is influenced by refractive index of the sample material and angle of incidence. In particular, optimization of the size matching of the detector surface and the infrared spot at the detector was a key to having MAIRS perform properly. It has been concluded that reliable MAIRS measurements require overfilling of the detector and a substrate with a high-refractive index.     

Attenuated total reflection Fourier transform infrared spectroscopy analysis of human hair fiber structure

The structure of human hair was studied by attenuated total reflection Fourier transform infrared (ATR-FT-IR) spectroscopy. The use of Ge, ZnSe, and Si internal reflection elements, various incident light angles, and difference spectra allowed detailed analysis of the cuticle, cortex, and cuticle-cortex intercellular regions without physically or mechanically removing the cuticle of the hair fiber. The ATR-FT-IR data showed the cuticle to be composed of protein having predominantly beta-sheet and disorder and beta-turn configurations. In contrast, the cortex spectra showed alpha-helical structures due to the presence of intermediate filaments of alpha keratin plus beta-sheet, beta-turn and disorder structures. In the cuticle-cortex interface region the protein structures were primarily disorder and beta-turn with small amounts of beta-sheet configurations. The spectral analyses are consistent with the general information on hair fiber structure proposed in the literature.     

Application of Fourier transform infrared spectroscopy in cement Alkali quantification

Alkali in cement is responsible for the Alkali–silica-reaction phenomenon that manifests itself in the form of premature cracking in concrete structures such as bridge decks and concrete pavements. X-ray fluorescence spectroscopy (XRF) is commonly used for cement Alkali quantification but a simpler and faster analytical procedure based on Fourier transform infrared spectroscopy (FTIR) has been expanded for this purpose. An analytical absorption band at 750 cm^?1 in the FTIR spectra of cement samples belonging to Alkali solid solution of tricalcium aluminate [C₃A(ss)] is used for Alkali quantification. Regression analysis of a plot correlating FTIR absorption band area ratio (750/923 cm^?1) to equivalent Alkali Na₂O _e (Na₂O _e  = % Na₂O + 0.658 × % K₂O) measured by XRF shows a linear correlation coefficient, R ², of 0.97. High Alkali cement samples show a higher microstructural disorder coefficient, C _d, which is a reactivity criterion introduced by Bachiorrini and co-authors (Proceedings of the seventh international conference on concrete alkali-aggregate reactions? 1986) for ASR-susceptible aggregates. Results of this research indicate applicability of FTIR technique to quantitatively predict cement vulnerability to ASR through the \( A_{{750\,{\text{cm}}^{ - 1} }} \) to \( A_{{923\,{\text{cm}}^{ - 1} }} \) band area ratio and the magnitude of the disorder coefficient (C _d).     

Fourier transform infrared spectral analysis of degenerative cartilage: an infrared fiber optic probe and imaging study

A preliminary investigation into the diagnostic potential of an infrared fiber optic probe (IFOP) for evaluating degenerative human articular cartilage is described. Twelve arthritic human tibial plateaus obtained during arthroplasty were analyzed using the IFOP. Infrared spectra were obtained from IFOP contact with articular surface sites visually graded normal or degraded (Collins Scale grade 1 and grade 3, respectively). Comparisons of infrared spectral parameters (peak heights and areas) were made to elucidate spectral indicators of surface degeneration. IFOP spectral analysis revealed subtle but consistent changes between grades 1 and 3 sites. Infrared absorbance bands arising from type II collagen were observed to change with degradation. More degraded tissues exhibited increased amide II (1590-1480 cm(-1))/1338 cm(-1) area ratio (p=0.034) and decreased 1238/1227 cm(-1) peak ratio (p = 0.017); similar changes were seen with Fourier transform infrared imaging spectroscopy (FT-IRIS) analysis. Grades 1 and 3 cartilage showed consistent spectral differences in the amide II, III, and 1338 cm(-1) regions that are likely related to type II collagen degradation that accompanies cartilage degeneration. These results suggest that it may be possible to monitor subtle changes related to early cartilage degeneration, allowing for IFOP use during arthroscopy for in situ determination of cartilage integrity.     

Characterization of magnetic paper using Fourier transform infrared spectroscopy

Magnetic papers were prepared by using the co-precipitation method. The spectral data of the magnetic fibres were obtained by using the photoacoustic Fourier transform infrared spectroscopy (FTIR-PAS) and attenuated total reflection (ATR). It was found that the elevated loading degree increased the IR absorption and reduced the tensile strength of the paper. The partial-least-squares analyses showed that the FTIR-ATR data were strongly correlated with the degree of loading and the correlation obtained was better than that of the FTIR-PAS spectral data.     

Fourier transform infrared attenuated total reflection and transmission spectra studied by dispersion analysis

Fourier transform infrared transmission (FT-IR) and attenuated total reflection (ATR) spectra of water-ethanol mixtures are recorded and reconstructed thanks to a causal dispersion analysis technique. As expected, the Beer's law technique is an empirical approximate method that cannot account for complex spectral features. On the other hand, a rigorous analysis performed by using the theoretical optical paths for both experimental techniques and Gaussian dispersion analysis (GDA) allows the dielectric functions of the pure liquids to be calculated. Simulations of the whole mid-infrared spectra in the range 500-4000 cm(-1) match the experimental data very well, whatever the water-ethanol mixtures. This method is a powerful tool to quantify such model mixtures and more generally could be the first step toward software for assistance to the FT-IR spectrum analysis.     

Calibration transfer algorithm for automated qualitative analysis by passive Fourier transform infrared spectrometry

The automated qualitative analysis of passive Fourier transform infrared (FT-IR) remote sensing data is made difficult by the presence in the data of background and instrument-specific variation. For data collected with a single instrument, variation in the data arises from changes in the infrared background radiance, changes in the atmospheric composition within the field-of-view of the spectrometer, and changes in the instrument response function arising from temperature variation in the spectrometer. When more than one spectrometer is used, the variation in detector responses and phase signatures between instruments serves to complicate further the task of implementing an automated processing algorithm for detecting the signature of a target compound. In this work, a combination of signal processing and pattern recognition methodology is applied directly to the interferogram data collected by the FT-IR spectrometer to implement an automated compound detection procedure that is independent of background and instrument-specific variation. The key to this algorithm is the use of highly attenuating digital filters to isolate in the interferogram the frequencies associated with an analyte absorption or emission band while suppressing information at other frequencies. For the test compounds, acetone and sulfur hexafluoride, it is demonstrated that when this digital filtering procedure is coupled with either piecewise linear discriminant analysis or a back-propagation neural network, an automated detection algorithm can be developed with data from a primary instrument and then subsequently used to predict the presence of analyte signatures in data collected with a secondary spectrometer. Correct classification rates in excess of 92% are obtained for both compounds when the algorithm is applied to data collected with the secondary instrument.