Boril Chernev

Non-Destructive Determination of Ethylene Vinyl Acetate Cross-Linking in Photovoltaic (PV) Modules by Raman Spectroscopy:

Vibrational spectroscopy was found to be a suitable method for the determination of the degree of cross-linking of ethylene vinyl acetate (EVA) polymers. Spectral changes in the Raman spectra of EVA with increasing lamination time (which equals increasing degree of cross-linking) were mainly detected in the CH vibrational regions, namely, in the relative intensities of the characteristic CH3 and CH2 bands. These spectral regions were chosen for a chemometric evaluation where a calibration was performed with the Raman spectra of reference EVA samples and the results obtained from corresponding thermal analysis (differential scanning calorimetry) and Soxhlet extraction data. These datasets were subsequently used to non-destructively determine the progress of cross-linking in EVA foils, embedded in various mini-modules by Raman microscopy. Thus, we could show that Raman spectroscopy is a highly interesting method for quality control in the production of photovoltaic (PV) modules. However, this approach is valid only for a given grade of EVA, meaning a demand for a new calibration when changing the supplier or the type of EVA used. In addition, the applicability of infrared spectroscopy for the determination of the degree of cross-linking was tested. A good correlation of the decrease in intensity of the characteristic cross-linker infrared bands with increasing progress of the cross-linking was found, as determined by reference methods. However, this analytical method requires taking samples of the EVA foils and is, thus, unsuitable for the non-destructive determination of the degree of cross-linking of the EVA encapsulated within a PV module.

Formation of liquid and solid products from liquid phase pyrolysis

The aim of the present work was to improve the C:O ratio in biomass by preserving the lignin macrostructure of lignocellulosic feed. The intention of liquid phase pyrolysis is to liquefy biomass and prepare biomass for further upgrading steps like hydrogenation and deoxygenation. Pyrolysis was carried out in a non-aqueous liquid phase heat carrier. The process was carried out in a semi-batch reaction vessel under isothermal conditions at T=350°C, supported by a quench to stop reactions instantaneously in order to observe formation of solid intermediates. This pyrolysis system enables the observation of liquid and solid product formation. Transformation of biomass into biochar was analyzed by infrared spectroscopy and elemental analysis. Stable lignin structure throughout the whole transformation was confirmed. It was shown that the lignin frame in wood remains without substantial loss, while the major amount of carbohydrates is pyrolyzed during liquid phase pyrolysis at T=350°C.

Biofuels from liquid phase pyrolysis oil: a two-step hydrodeoxygenation (HDO) process

New biomass utilization technologies and concepts are needed to suffice future increasing energy demand. This paper contributes to the understanding of liquid phase pyrolysis (LPP) oil upgrading, which significantly differs from fast pyrolysis (FP) oil upgrading processes. A two-step hydrodeoxygenation (HDO) process was established to convert the LPP oil into a biofuel with diesel fuel-like properties. In the first HDO step (250 °C, 85 bar), the bulk of the water and most of the highly-oxygenated water-soluble carbonaceous constituents were removed, to lower hydrogen consumption in the second HDO step. In addition, the highly reactive compounds were stabilized in the first step. In the second HDO step (400 °C, 150/170 bar), the product specification was improved. This paper shows a proof-of-principle for a two-step HDO process for converting LPP oil to a diesel-like biofuel.

Spectroscopic Investigations on Thin Adhesive Layers in Multi-Material Laminates

Three different spectroscopic approaches, Raman linescans, Raman imaging, and attenuated total reflection Fourier transform infrared spectroscopy (ATR FT-IR) imaging were evaluated for the visualization of the thin adhesive layers (3–6 μm) present in polymeric photovoltaic backsheets. The cross-sections of the multilayer laminates in the original, weathered, and artificially aged samples were investigated spectroscopically in order to describe the impact of the environmental factors on the evenness and thickness of the adhesive layers. All three methods were found to be suitable tools to detect and visualize these thin layers within the original and aged polymeric laminates. However, as the adhesive layer is not very uniform in thickness and partly disintegrates upon weathering and/or artificial aging, Raman linescans yield only qualitative information and do not allow for an estimation of the layer thickness. Upon increasing the measuring area by moving from one-dimensional linescans to two-dimensional Raman images, a much better result could be achieved. Even though a longer measuring time has to be taken into account, the information on the uniformity and evenness of the adhesive layer obtainable using the imaging technique is much more comprehensive. Although Raman spectroscopy is known to have the superior lateral resolution as compared with ATR FT-IR spectroscopy, the adhesive layers of the samples used within this study (layer thickness 3–6 μm) could also be detected and visualized by applying the ATR FT-IR spectroscopic imaging method. However, the analysis of the images was quite a demanding task, as the thickness of the adhesive layer was in the region of the resolution limit of this method. The information obtained for the impact of artificial aging and weathering on the adhesive layer obtained using Raman imaging and ATR FT-IR imaging was in good accordance.

Visualisation and characterisation of ageing induced changes of polymeric surfaces by spectroscopic imaging methods

A polymeric resin material was chosen as the model system to visualise the ageing-induced chemical surface changes with molecular spectroscopic imaging techniques and correlate these results to physical properties such as colour changes. The influence of light radiation, temperature and humidity on the polymeric surfaces was analysed by means of attenuated total reflection infrared imaging, Raman imaging spectroscopy and scanning electron microscopy. Samples were analysed before, during and after the weathering/ageing tests. From these combined data, the mechanisms for the damaging of the resin surface under the various environmental conditions (as applied in the accelerated ageing tests) were deduced. Photo-oxidative decay of the resin leading to a degradation of the uppermost surface layers as well as hydrolysis of the aged surface was identified. The combination of the spectral and spatial data as obtained from spectroscopic imaging with the morphological and elemental information of scanning electron microscopic mapping experiments turned out to be highly advantageous for the elucidation of ageing processes. A correlation between the molecular spectroscopic data and the results from the macroscopic colour difference measurements was found.

New possibilities for soft matter applications: eliminating technically induced thermal stress during FIB processing

Heating effects on focused ion beam processing have been identified as a strong convolution of intrinsic and technically induced contributions via experiments and simulations. The systematic parameter variation reveals that classic serpentine- or raster-like patterning strategies can imply an additional heating of more than one order of magnitude above the intrinsic temperature increase during single ion beam pulses. This rise in temperature can lead to severe chemical damage of materials with a low melting point, such as polymers or biological samples. Based on these findings, an alternative patterning sequence is introduced which is able to eliminate this technically induced heating whereas process times are not affected. It is shown that chemical damage of the (polypropylene) test polymers is strongly reduced and can be compared to the results after classic FIB processing with low ion beam currents (500 pA → 50 pA, 30 kV primary energy) or at cryogenic sample temperatures (−150 °C). The successful reduction of local thermal stress towards the intrinsic and unavoidable limit – related to single pulse effects – might open new possibilities for focused ion beam processing of soft matter.

Spectroscopic Characterization of the Oligomeric Surface Structures on Polyamide Materials Formed During Accelerated Aging

Crystalline surface species were observed at the surface of polyamide 12 materials upon accelerated aging. After detection of the depositions with scanning electron microscopy (SEM), the crystalline surface precipitations were analyzed with Fourier transform infrared (FT-IR) and Raman imaging microscopy. These surface species were supposed to be cyclic oligomers (dimer and trimer) of the PA12 monomer laurolactam, which are usually present in polyamide materials and tend to migrate to the surface when the material is subjected to accelerated aging. The evidence for the chemical identity of the crystalline surface structures to be mainly the cyclic dimer and trimer of laurolactam was given by melting-point identification and mass spectroscopic analysis of the methanol eluate of the surface. The Raman and FT-IR spectra of the mixture were extracted from the recorded images.

Tunable Semicrystalline Thin Film Cellulose Substrate for High-Resolution, In-Situ AFM Characterization of Enzymatic Cellulose Degradation

In the field of enzymatic cellulose degradation, fundamental interactions between different enzymes and polymorphic cellulose materials are of essential importance but still not understood in full detail. One technology with the potential of direct visualization of such bioprocesses is atomic force microscopy (AFM) due to its capability of real-time in situ investigations with spatial resolutions down to the molecular scale. To exploit the full capabilities of this technology and unravel fundamental enzyme-cellulose bioprocesses, appropriate cellulose substrates are decisive. In this study, we introduce a semicrystalline-thin-film-cellulose (SCFTC) substrate which fulfills the strong demands on such ideal cellulose substrates by means of (1) tunable polymorphism via variable contents of homogeneously sized cellulose nanocrystals embedded in an amorphous cellulose matrix; (2) nanoflat surface topology for high-resolution and high-speed AFM; and (3) fast, simple, and reproducible fabrication. The study starts with a detailed description of SCTFC preparation protocols including an in-depth material characterization. In the second part, we demonstrate the suitability of SCTFC substrates for enzymatic degradation studies by combined, individual, and sequential exposure to TrCel6A/TrCel7A cellulases (Trichoderma reesei) to visualize synergistic effects down to the nanoscale.

Adsorption studies of organophosphonic acids on differently activated gold surfaces

In this study, the formation of self-assembled monolayers consisting of three organophosphonic acids (vinyl-, octyl-, and tetradecylphosphonic acid) from isopropanol solutions onto differently activated gold surfaces is studied in situ and in real time using multiparameter surface plasmon resonance (MP-SPR). Data retrieved from MP-SPR measurements revealed similar adsorption kinetics for all investigated organophosphonic acids (PA). The layer thickness of the immobilized PA is in the range of 0.6-1.8 nm corresponding to monolayer-like coverage and correlates with the length of the hydrocarbon chain of the PA molecules. After sintering the surfaces, the PA are irreversibly attached onto the surfaces as proven by X-ray photoelectron spectroscopy and attenuated total reflection infrared and grazing incidence infrared spectroscopy. Potential adsorption modes and interaction mechanisms are proposed.

WEAR AND FRICTION BEHAVIOR OF THE AEROSPACE BEARING STEEL M50 AND A NITROGEN-ALLOYED STAINLESS STEEL UNDER LUBRICATED SLIDING CONDITIONS.

The material requirements on aircraft engine mainshaft bearings increase due to an elevated speed index (bearing bore diameter multiplied by rotational shaft speed) and slip ratios [1]. The formation of reaction layers on surfaces in mechanical contact is strongly affected by the tribological loading conditions, the materials used, the lubricant, and the service temperature. An appropriate reactivity between material and lubricant in tribological systems decreases wear and friction and increases the durability [2,3]. Goal of the paper is to compare wear and friction properties of standard aerospace bearing steel AMS 6491 (M50) with that of the high strength stainless steel grade AMS 5898. The nominal chemical compositions are 0.82C-4.1Cr-1V-4.2Mo (wt%) and 0.3C-0.4N-15.2Cr-1Mo (wt%), respectively. In order to characterize the material behavior under pure sliding conditions, ball on disc (BOD) experiments were performed with a contact pressure of 1GPa and a sliding speed of 10 cm/s at room temperature and at 150°C. As lubricant the jet engine oil Mobil Jet II was used. It is assumed that the reaction layer formation depends on the material composition and is also effected by the counterpart and the lubricant additives. Thus, the experiments were performed with two different ball materials. The first ball material was the same standard aerospace bearing steel (M50) as mentioned above and the second was a ceramic (Si3 N4 ). The homogeneity and the distribution of the reaction layers as well as the wear rate were determined in the contact zone by means of optical profilometry, scanning electron microscopy (SEM) and Fourier transformation infrared spectroscopy (FTIR). The study showed that wear is significantly higher on the stainless steel grade compared to M50 (Fig. 1a and Fig. 1b). The dark areas in Fig. 2 are phosphorus rich regions on the wear track of M50. This reaction layer is mainly built up of phosphates, which result from the TCP lubricant additive. In the FT-IR spectra (Fig. 3) absorption bands at 1130 cm−1 (room temperature-BOD test) and at 1160 cm−1 (150°C-BOD test) are visible, which result from the P=O stretching [4]. The shift of the absorption band to lower wave numbers with decreasing test temperature is probably due to hydrogen bonding [5]. Contrary to AMS 6491 no measurable reaction layer was found on AMS 5898 after testing at room temperature (Fig. 1b). The friction coefficients of the two steels against Si3 N4 balls determined in the BOD tests are compared in Fig. 4. AMS 5898 shows an abrupt increase of the friction coefficient after a sliding distance of 3.5 m. The reason for that is a material transfer of disc material to the ceramic ball as can be seen in Fig. 5. This transfer material causes a plowing of the disc and thus, an increased wear can be observed. The different Cr-contents and consequently oxide layers of AMS 5898 and AMS 6491, which react differently with TCP, might explain this behavior. AMS 5898 does not sufficiently react with TCP at room temperature to form a protective layer. Consequently, material transfer and increased wear occurs. In case of AMS 6491 an increase of the operating temperature cause a change of the reaction layer (see Fig. 3) and to an increase in the wear rate.© 2005 ASME