Heinz W. Siesler

Near-Infrared Spectroscopic Monitoring of the Diffusion Process of Deuterium-Labeled Molecules in Wood. Part II: Hardwood

The diffusion process of several molecules (D2O, n-butanol (OD) and t-butanol (OD)) in softwood (Sitka spruce) was investigated by means of a deuterium exchange method and Fourier transform near-infrared (FT-NIR) polarization spectroscopy. The location of OH groups in different states of order of cellulose in wood was clarified by analyzing the FT-NIR transmission spectra ranging from 7200 to 6000 cm−1. Four absorption bands were assigned to 2 × v(OH) absorptions of the amorphous regions, OH groups in semi-crystalline regions, and two types of intramolecular hydrogen-bonded OH groups in the crystalline regions, respectively. The saturation level of accessibility was very different for these absorption bands (i.e., 70–80, 60, and 40–50% for the amorphous, semi-crystalline, and crystalline regions, respectively). However, the saturation accessibilities for each absorption band varied little with molecular structure and geometry of the diffusants. The diffusion rate of D2O was much faster than that of n-butanol (OD) and t-butanol (OD) for all states of orders. The size effect of the butanols led to slight differences in the diffusive transport in the crystalline regions.

New Developments and Applications of Handheld Raman, Mid-Infrared, and Near-Infrared Spectrometers

Abstract: Recently, miniaturization of Raman, mid-infrared (IR), and near-infrared (NIR) spectrometers has made substantial progress. Though mid-infrared systems are based exclusively on attenuated total reflection (ATR) measurements, near-infrared spectrometers operate in the diffuse reflection or transmission mode. The reduction in size, however, must not be accompanied by deterioration in measurement performance, and portable instrumentation will only have a real impact on quality and process control if Raman, IR, and NIR spectra of comparable quality to laboratory spectrometers can be obtained. In the present communication, a short overview on the building principles of novel handheld systems will be provided and the results of qualitative and quantitative analyses of selected liquid and solid sample systems obtained with these Raman, Fourier transform infrared (FTIR), and NIR spectrometers will be evaluated in terms of their comparability with laboratory instruments and their suitability for on-site and field measurements.

Difference of the Crystal Structure of Cellulose in Wood after Hydrothermal and Aging Degradation: A NIR Spectroscopy and XRD Study

The change of crystalline structure in hydrothermally treated hinoki wood was investigated by means of Fourier-transform near-infrared spectroscopy in combination with a deuterium exchange method and X-ray diffraction. The results were compared with analogous data of dry-exposed archeological wood taken from an old wooden temple. Although the decomposition of the amorphous regions in cellulose and hemicelluloses, which corresponds to an increase of the degree of crystallinity, was observed for both, archeologically and hydrothermally treated wood, the increase of crystallite thickness was confirmed only for hydrothermally treated wood. The increase of the average size of crystallites corresponds well to the measured decrease of the deuteration accessibility of the crystalline regions. As the accessibility of the crystalline regions decreased for both, D(2)O and t-butanol, it is assumed that due to the expansion of the crystalline domains by hydrothermal treatment several elementary fibrils are arranged at distances below 0.3 nm.

FT-IR imaging spectroscopy of phase separation in blends of poly(3-hydroxybutyrate) with poly(L-lactic acid) and poly(epsilon-caprolactone).

The detection of phase separation and identification of miscibility in biopolymer blends is an important aspect for the improvement of their physical properties. In this article, the phase separation in blends of poly(3-hydroxybutyrate) (PHB) with poly(L-lactic acid) (PLA) and poly(epsilon-caprolactone) (PCL), respectively, has been studied as a function of the blend composition by FT-IR imaging spectroscopy. For both polymer blend systems, a miscibility gap has been found around the 50:50% (w/w) composition of the two components. Furthermore, the separating phases have been identified as blends of the two polymer components and their compositions could be determined from calibrations based on the spectra of the blends in the compositional range of miscibility. The data derived from FT-IR spectroscopic imaging were corroborated by additional DSC analyses and mechanical stress-strain measurements of polymer blend films, which exhibited a characteristic fracture behavior as a function of PHB composition.

Near-infrared spectroscopic observation of the ageing process in archaeological wood using a deuterium exchange method

The ageing degradation of the fine wood structure of dry-exposed archaeological wood was investigated by Fourier transform near-infrared spectroscopy with the aid of a deuterium exchange method. The archaeological wood sample was taken from an old wooden temple in Japan (late 7th century), which has been designated as a UNESCO world heritage site. Comparing the analytical results with those of a modern wood sample of the same species, the ageing process of archaeological wood was clarified as a change in the state of order on a macromolecular structural level. It can be concluded from NIR spectra that the amorphous region, and partially semi-crystalline region, in cellulose, hemicellulose, and lignin decreased by the ageing degradation, whereas the crystalline region in cellulose was not affected by the ageing. The accessibility of the diffusant to effect H/D-exchange was monitored by an OH-related absorption band obtained from FT-NIR transmission spectroscopy and characteristically varied with the ageing process of the wood samples, the absorption bands characteristic of a specific state of order and the diffusion agent. Finally, we proposed a morphological model to describe the variation of the fine structure of the microfibrils in the cell wall with ageing degradation. The state of microfibrils changed loosely by ageing, so that elementary fibrils were arranged loosely under 5 A, whereas several elementary fibrils in the modern wood were arranged in very close proximity under 3 A to each other.

Qualitative and quantitative pharmaceutical analysis with a novel hand-held miniature near infrared spectrometer

Although miniaturisation of vibrational spectrometers began approximately a decade ago, only within the last couple of years have real hand-held Raman, infrared and near infrared (NIR) scanning spectrometers became commercially available. On the customer end the development of portable instrumentation was driven by the request for more flexibility of on-site measurements and on the manufacturer side it was supported by the potential and advantages of micro-electromechanical systems (MEMS) production and the implementation of new technologies. With reference to NIR spectroscopy the expectations for a real hand-held system (<100 g) have been recently realised by a pocket-sized spectrometer with a linear variable filter technology (LVF) as monochromator principle and the additional benefit of significantly reduced costs compared to other portable systems. For a real breakthrough and impact of this instrument, however, it had to be demonstrated that competitive analytical results can be achieved. In this respect, the present communication has put to test the performance of this micro-NIR system with reference to selected qualitative and quantitative pharmaceutical applications.

Rheo-Optical Fourier Transform Infrared and Raman Spectroscopy of Polymers

This article is intended to review recent results of simultaneous mechanical and Fourier transform infrared spectroscopic—so-called rheo-optical—measurements for polymer deformation studies. The technique will also be discussed in terms of the application of Fourier transform near-infrared light-fiber and Raman spectroscopy. Specifically, data on the bidirectional drawing of poly(ethylene terephthalate) and the strain-induced conformational changes of poly(vinylidene fluoride) will be presented.

Miniature Near-Infrared (NIR) Spectrometer Engine For Handheld Applications

While substantial progress has been made recently towards the miniaturization of Raman, mid-infrared (IR), and near-infrared (NIR) spectrometers, there remains continued interest from end-users and product developers in pushing the technology envelope toward even smaller and lower cost analyzers. The potential of these instruments to revolutionize on-site and on-line applications can only be realized if the reduction in size does not compromise performance of the spectrometer beyond the practical need of a given application. In this paper, the working principle of a novel, extremely miniaturized NIR spectrometer will be presented. The ultra-compact spectrometer relies on thin-film linear variable filter (LVF) technology for the light dispersing element. We will also report on an environmental study whereby the contamination of soil by oil is determined quantitatively in the range of 0-12% by weight of oil contamination. The achieved analytical results will be discussed in terms of the instruments competitiveness and suitability for on-site and in-the-field measurements.

Characterization of the electric-field-induced orientation and relaxation dynamics of liquid crystals by time-resolved step-scan Fourier transform infrared spectroscopy

Abstract In the present communication the improvement in time resolution of a Fourier transform infrared spectrometer by the implementation of the step-scan technique is demonstrated with reference to the study of the electric-field-induced orientation and relaxation phenomena of a liquid crystal. The analysis of spectra taken with 0.5 ms time resolution shows no difference in response rates upon application of the electric field for the rigid and flexible part of the liquid crystalline molecule. The results are discussed with reference to examples where such differences have been detected.

Monitoring the melt-extrusion transesterification of ethylene-vinylacetate copolymer by self-modeling curve resolution analysis of on-line near-infrared spectra.

The transesterification of molten ethylene-vinylacetate (EVA) copolymers by octanol with sodium methoxide as catalyst in an extruder has been monitored by on-line near infrared (NIR) spectroscopy. A total of 60 NIR spectra were acquired for 37 min with the last spectrum recorded 31 min after the addition of octanol and catalyst was stopped. The experimental spectra show strong baseline fluctuations which are corrected for by multiplicative scatter correction (MSC). The chemometric methods of the orthogonal projection approach (OPA) and multivariate curve resolution (MCR) were used to resolve the spectra and to derive concentration profiles of the species. The detailed analysis reveals the absence of completely pure variables which leads to small errors in the calculation of pure spectra. The initial estimation of a concentration that is necessary as an input parameter for MCR also presents a non-trivial task. We obtained results that were not ideal but applicable for practical concentration control. They enable a fast monitoring of the process in real-time and resolve the spectra of the EVA copolymer and the ethylene-vinyl alcohol (EVAL) copolymer to be very close to the reference spectra. The chemometric methods used and the decomposed spectra are discussed in detail.