Filtern
Dokumenttyp
- Vortrag (139)
- Zeitschriftenartikel (108)
- Posterpräsentation (63)
- Beitrag zu einem Tagungsband (9)
- Buchkapitel (4)
- Sonstiges (4)
- Dissertation (3)
- Forschungsdatensatz (3)
- Forschungsbericht (2)
- Monografie (1)
Sprache
- Englisch (245)
- Deutsch (90)
- Mehrsprachig (4)
Schlagworte
- Process Analytical Technology (38)
- Prozessanalytik (33)
- Prozessindustrie (29)
- Online NMR Spectroscopy (23)
- CONSENS (22)
- Soil (18)
- Digitalisierung (16)
- NMR spectroscopy (16)
- Process analytical technology (16)
- Benchtop-NMR (15)
Organisationseinheit der BAM
- 1.4 Prozessanalytik (339) (entfernen)
Paper des Monats
- ja (3)
Eingeladener Vortrag
- nein (139)
Biofuels including ethanol and biodiesel (FAME) represent a renewable fuel alternative to petroleum-derived transport fuels. The aim of this work was to study the interaction between high density polyethylene (HDPE) with permeation barriers in form of polyamide (PA) and fluorination, and biofuels such as E85 (fuel with 85 % ethanol), biodiesel and B10 (heating oil with 10 % biodiesel). 10 l jerrycans made of polyethylene with permeation barrier of PA were filled with E85 and biodiesel and exposed to temperatures of 20 °C and 40 °C for 5 years. Half of the 20 l jerrycans of HDPE for filling with B10 were fluorinated at the inner layer to prevent permeation before the exposure. Tensile properties were determined once a year, and FTIR-spectroscopy was used to evaluate possible changes.
The tensile properties tensile strength and breaking elongation of HDPE jerrycan cuttings with permeation barrier decreased, but not significantly, after immersion in E85, biodiesel and B10. The elasticity modulus of the polyethylene grades was especially reduced during exposure to E85.
The FTIR spectra of HDPE jerrycan cuttings with permeation barrier showed that immersion tests for five years with the test fuels at 20 °C and 40 °C did not lead to a decomposition of the permeation barriers.
Biofuels including ethanol and biodiesel (FAME) represent a renewable fuel alternative to petroleum-derived transport fuels. The aim of this work was to study the interaction between high density polyethylene (HDPE) with permeation barriers in form of polyamide (PA) and fluorination, and biofuels such as E85 (fuel with 85 % ethanol), biodiesel and B10 (heating oil with 10 % biodiesel). 10 l jerrycans made of polyethylene with permeation barrier of PA were filled with E85 and biodiesel and exposed to temperatures of 20 °C and 40 °C for 5 years. Half of the 20 l jerrycans of HDPE for filling with B10 were fluorinated at the inner layer to prevent permeation before the exposure. Tensile properties were determined once a year, and FTIR-spectroscopy was used to evaluate possible changes.
The tensile properties tensile strength and breaking elongation of HDPE jerrycan cuttings with permeation barrier decreased, but not significantly, after immersion in E85, biodiesel and B10. The elasticity modulus of the polyethylene grades was especially reduced during exposure to E85.
The FTIR spectra of HDPE jerrycan cuttings with permeation barrier showed that immersion tests for five years with the test fuels at 20 °C and 40 °C did not lead to a decomposition of the permeation barriers.
The increasing pollution of terrestrial and aquatic ecosystems with plastic debris leads to the accumulation of microscopic plastic particles of still unknown amount. To monitor the degree of contamination analytical methods are urgently needed, which help to quantify microplastics (MP). Currently, time-costly purified materials enriched on filters are investigated both by micro-infrared spectroscopy and/or micro-Raman. Although yielding precise results, these techniques are time consuming, and are restricted to the analysis of a small part of the sample in the order of few micrograms. To overcome these problems, here we tested a macroscopic dimensioned NIR process-spectroscopic method in combination with chemometrics. For calibration, artificial MP/soil mixtures containing defined ratios of polyethylene, polyethylene terephthalate, polypropylene, and polystyrene with diameters < 125 µm were prepared and measured by a process FT-NIR spectrometer equipped with a fiber optic reflection probe. The resulting spectra were processed by chemometric models including support vector machine regression (SVR), and partial least squares discriminant analysis (PLS-DA). Validation of models by MP mixtures, MP-free soils and real-world samples, e.g. and fermenter residue, suggest a reliable detection and a possible classification of MP at levels above 0.5 to 1.0 mass% depending on the polymer. The benefit of the combined NIRS chemometric approach lies in the rapid assessment whether soil contains MP, without any chemical pre-treatment. The method can be used with larger sample volumes and even allows for an online prediction and thus meets the demand of a high-throughput method.
A process spectroscopic approach for the monitoring of microplastics in environmental samples
(2018)
The potential of Raman and NIR process-spectroscopic as a rapid approach for the estimation of microplastics (MP) in soil matrix were tested. For this purpose, artificial MP/soil mixture samples consisting of standard soils or sand with defined ratios of MP (0,5 – 10 mass% polymer) from polyethylene (PE), polypropylene (PP), polystyrene (PS) and polyethylene terephthalate (PET) were prepared. MP particles with diameters < 2 mm and < 125 µm were obtained from industrial polymer pellets after cryo-milling. Spectra of these mixtures were collected by (i) a process FT-NIR spectrometer equipped with a reflection probe, (ii) by a cw-process Raman spectrometer and (iii) by a time-gated Raman spectrometer using fiber-optic probes. The evaluation of process-spectra was performed by chemometric methods. Whereas MP could be detected by Raman spectroscopy in coastal sand at 0.5 mass%, in standard soil detection of MP was limited to 10 – 5 mass% with the large fraction, but samples containing particles of the 125µm mass-fraction yielded no positive result at all. One reason for the lacking sensitivity could be fluorescence by soil organic matter and thus, in a next test time-gated Raman spectroscopy was applied. However, although being indeed more sensitive to the small particles this method failed at MP < 5 mass% indicating that fluorescence was not the major problem. Finally, FT-NIR was tested. Depending on the polymer, MP contents of 0,5 or 1 mass%, respectively, could be detected in standard soils and polymers identified. Furthermore, this approach could be used for the investigation of mixtures of up to four polymers and in real-world samples from bio-waste fermenter residues.
The impact of nanoparticles, NPs, at the single cell level has become a major field of toxicological research and different analytical methodologies are being investigated to obtain biological and toxicological information to better understand the mechanisms of cell–NP interactions. Here, inductively coupled plasma mass spectrometry in the single cell measurement mode (SC-ICP-MS) is proposed to study the uptake of silver NPs, AgNPs, with a diameter of 50 nm by human THP-1 monocytes in a proof-ofprinciple experiment. The main operating parameters of SC-ICP-MS have been optimized and applied for subsequent quantitative analysis of AgNPs to determine the number of particles in individual cells using AgNP suspensions for calibration. THP-1 cells were incubated with AgNP suspensions with concentrations of 0.1 and 1 µg/mL for 4 and 24 hours. The results reveal that the AgNP uptake by THP-1 monocytes is minimal at the lower dose of 0.1 µg/mL (roughly 1 AgNP per cell was determined), whereas a large cell-to-cell variance dependent on the exposure time is observed for a 10 times higher concentration (roughly 7 AgNPs per cell). The method was further applied to monitor the AgNP uptake by THP-1 cells differentiated macrophages incubated at the same AgNP concentration levels and exposure times demonstrating a much higher AgNP uptake (roughly from 9 to 45 AgNPs per cell) that was dependent on exposure concentration and remained constant over time. The results have been compared and validated by sample digestion followed by ICP-MS analysis as well as with other alternative promising techniques providing single cell analysis.
Most of the experimental density data of the methane−hydrogen binary system available at the time of the development of the equation of state for natural gases and related mixtures, GERG-2008, at temperatures above 270 K were limited to hydrogen contents higher than 0.20 (amount-of-substance fraction). On the contrary, for mixtures with hydrogen contents lower than 0.20, experimental data were limited to temperatures below 270 K. This work intends to close the gap and provides accurate experimental (p, ρ, and T) data for three binary mixtures of methane and hydrogen, (0.95 CH4 + 0.05 H2), (0.90 CH4 + 0.10 H2), and (0.50 CH4 + 0.50 H2), at temperatures of 240, 250, 260, 275, 300, 325, and 350 K, thus extending the range of available experimental data to higher temperatures for mixtures with hydrogen contents lower than 0.20 and, accordingly, to lower temperatures for mixtures with hydrogen contents higher than 0.20. The density measurements were performed by using a single-sinker densimeter with magnetic suspension coupling at pressures up to 20 MPa. Experimental data were compared to the corresponding densities calculated from the GERG-2008 and the AGA8-DC92 equations of state, respectively. The experimental data are within the uncertainty of both equations of state, except at the lower temperatures of 240 and 250 K and pressures over 14 MPa for the mixtures with a hydrogen content of 0.05 and 0.10, respectively. The virial coefficients B(T, x) and C(T, x), as well as the second interaction virial coefficient B12(T) for the methane−hydrogen binary system, were also calculated from the experimental data set at temperatures from 240 to 350 K using the virial equation of state.
Solubility data of carbon dioxide (CO2) in the two ionic liquids 1-butyl-3-methylimidazolium tetrafluoroborate [BMIM][BF4] and 1-butyl-3-methylimidazolium tetrachloroferrate [BMIM][FeCl4] at T = (273.15-413.15) K and pressures up to p = 4.5 MPa are presented. In Addition to the experiments, a literature review was done to compare the new results with published solubility data. The measurements were carried out using an isochoric method which operates in decrements of deltaT = 20 K within the investigated temperature range and at selected four different pressure steps ranging from a pressure p of around 4.5 MPa to around 0.5 MPa. The solubility of CO2 decreases in both ionic liquids with increasing temperatures. Within the p,T-range investigated, CO2 displayed a solubility in [BMIM][BF4] from a mole fraction x = 0.0117 and a corresponding molality m = 0.0526 mol/kg at T = 413.15 K and p = 0.417 MPa up to x = 0.4876 and m = 4.2094 mol/kg at T = 293.15 K and p = 4.349 MPa. The corresponding values for the solubility in [BMIM][FeCl4] start at a mole fraction x = 0.0268 and a corresponding molality m = 0.0818 mol/kg at T = 413.15 K and p = 0.443 MPa and end at x = 0.5126 and m = 3.1216 mol/kg at T = 293.15 K and p = 4.478 MPa. At a constant temperature, CO2 is better soluble in [BMIM][FeCl4] than in [BMIM][BF4] and the mean value of the solubility difference related to mole fraction x over the pressure range investigated amounts to about 4 % at T = 273.15 K and monotonously increases to about 92 % at T = 413.15 K. Henry's law constant as well as derived thermodynamic properties, such as the Gibbs energy of solvation, the enthalpy of solvation, the entropy of solvation, and the heat capacity of solvation, were calculated and discussed regarding the solute-solvent molecular interactions.
Aim of the Federal Institute for Materials Research and Testing (BAM) in the frame of I4S - “Intelligence for Soil” is the characterization of an X-ray fluorescence (XRF) based sensor for robust online-application of arable land.Fast soil mapping for agricultural purpose allows the site-specific optimized introduction of plant essential nutrients like S, K, Ca, and Fe. This is important given that the distribution of minor and trace elements varies widely. The non-destructive and contactless XRF is suitable for rapid in-situ analysis on the field due to minimal sample preparation and simultaneous multi-element analysis.
Soils are already considered as a complex matrix due to their wide range of elements in different contents, especially light elements with low atomic numbers (Z<19). Problems by measuring soil samples also arise from heterogeneity of the sample and matrix effects. Large grain size distribution causes strong inhomogeneity and matrix effects occur through physical properties related to high concentration of main components. Matrix-specific calibration strategies for determination of total major and minor plant essential nutrients are particularly important regarding these difficulties. For accurate calibration, data treatment and evaluation must also be considered. Empirical univariate and multivariate data analysis were compared regarding their analytical figures of merit. Using principal component analysis (PCA) it was possible to classify German soils in different groups as sand, clay and silt. A calibration curve was obtained by partial least squares regression (PLSR) and the elemental content of German soils was predicted. Elemental distribution maps for different German arable lands were created and the results compared to reference measurements. The correlation between predicted values and reference values were in good agreement for most major and minor nutrients.
In respect of an efficient cultivation of agricultural cropland, a site-specific fertility management is necessary. Therefore, affordable and extensive mapping methods are needed. The research projects I4S (intelligence for soil) has the goal to develop a system for this purpose. I4S is one of ten interdisciplinary research project associations of the innovation programme called BonaRes, which is funded by the German Federal Ministry of Education and Research (BMBF).
The system includes a sensor platform, which contains different sensors, like XRF, VIS-NIR, Gamma and LIBS. The main task of LIBS measurements in this project is the real-time determination of the elemental contents of major and minor nutrients in soils, like calcium, magnesium, potassium. LIBS (laser-induced breakdown spectroscopy) is known as a fast and simultaneous multi-element analysis with little or no sample preparation. The main task of LIBS measurements in this project is the real-time determination of the elemental contents of nutrients in soils, like calcium, magnesium, potassium. For this purpose, a special setup has been designed. The sample uptake operates with the help of a rotatable sample plate which circulates with different velocities to simulate the application on the field. To provide a higher intensity and a better reproducibility of the obtained signal, a double-pulse Nd:YAG laser (1064 nm)was used. In order to minimize dust formation from the soil during the operation of the laser, a dust removal by suction has been integrated. When using relative methods such as LIBS, a suitable calibration curve is needed for absolute quantification. The complex matrix of soils, as well as the influence of moisture and grain size in soils makes the absolute quantification by LIBS challenging. To overcome these influences, chemometric methods were used. With the principal component analysis (PCA) a classification of soils into different soil types was performed and a calibration curve based on partial least squares regression (PLSR) was generated. With this calibration model’s elemental distribution maps for different German agricultural fields were created.
The quantification of the elemental content in soils with laser-induced breakdown spectroscopy (LIBS) is challenging because of matrix effects strongly influencing the plasma formation and LIBS signal. Furthermore, soil heterogeneity at the micrometre scale can affect the accuracy of analytical results. In this paper, the impact of univariate and multivariate data evaluation approaches on the quantification of nutrients in soil is discussed. Exemplarily, results for calcium are shown, which reflect trends also observed for other elements like magnesium, silicon and iron. For the calibration models, 16 certified reference soils were used. With univariate and multivariate approaches, the calcium mass fractions in 60 soils from different testing grounds in Germany were calculated. The latter approach consisted of a principal component analysis (PCA) of adequately pre-treated data for classification and identification of outliers, followed by partial least squares regression (PLSR) for quantification. For validation, the soils were also characterised with inductively coupled plasma optical emission spectroscopy (ICP OES) and X-ray fluorescence (XRF) analysis. Deviations between the LIBS quantification results and the reference analytical results are discussed.