TY - JOUR
A1 - Emmerling, Franziska
A1 - Martins, Ines
T1 - Carbamazepine Dihydroxybenzoic Acid Cocrystals: Exploring Packing Interactions and Reaction Kinetics
N2 - Herein, we present the mechanochemical formation of three new cocrystals containing the active pharmaceutical ingredient carbamazepine and dihydroxybenzoic acids as coformers (CBZ:2,4-DHBA 1:1, CBZ:2,5-DHBA 1:1, and CBZ:2,6-DHBA 1:1). Rietveld methods were used for three different purposes: (i) refining all structures solved using powder X-ray diffraction, (ii) performing a quantitative phase analysis of the diffraction data collected from ex situ mechanochemical reactions at different milling times, and (iii) determining the cocrystallization kinetic profiles. The rate of cocrystallization was found to be higher for the formation of CBZ:2,4-DHBA and CBZ:2,6-DHBA, reaching an equilibrium after 600 s of milling. In the case of CBZ:2,5-DHBA a short induction period of 20 s was detected prior to the start of the reaction and an equilibrium was reached after 1200 s. An empirical trend between the rate of cocrystallization and the structural complexity of the cocrystal product was found. The slowest cocrystallization rate observed for CBZ:2,5-DHBA corresponds to the crystal structure deviating substantially from the hydrogen-bonding motif found in the reactants.
KW - Mechanochemistry
KW - In situ real-time monitoring
KW - Kinetics
PY - 2021
DO - https://doi.org/10.1021/acs.cgd.1c00902
VL - 21
IS - 12
SP - 6961
EP - 6970
PB - ACS Publications
AN - OPUS4-54407
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Lakshmipathi, M.
A1 - Tothadi, S.
A1 - Emmerling, Franziska
A1 - Bhattacharya, Biswajit
A1 - Ghosh, S.
T1 - Different mechanical responses of dimorphic forms of Anthracene Schiffbase crystal
N2 - We obtained concomitant dimorphic forms of Anthracene Schiffbase (N-(anthracen-9-yl methylene)-2,5- dichloroaniline) from hexane solvent. Two polymorphs can be differentiated by their morphology and mechanical properties. One form is long acicular type and elastically bendable while another form is block shaped and brittle in nature. Mechanical property is attributed to underlying crystal packing. Hirsh- feld analysis and energy framework calculations were done to corroborate structure-property correlation of two forms.
KW - Elasticity
KW - Mechanical properties
KW - Anthracene schiff base
KW - Dimorphs
PY - 2021
DO - https://doi.org/10.1016/j.molstruc.2021.132182
VL - 1252
SP - 1
EP - 8
PB - Elsevier B.V.
AN - OPUS4-54356
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - de Oliveira Guilherme Buzanich, Ana
T1 - Time resolved in situ monitoring of mechanochemical transformations by X-ray spectroscopy (XAS)
N2 - Mechanochemical reactions promise a new direction for environmentally benign preparation of materials, and has been dubbed by IUPAC as one of the 10 chemical innovations that will change our world. Despite this significant promise, very little is known about the mechanisms that drive mechanochemical transformations, posing significant barriers to realizing their full potential. To this end, there is growing need to follow mechanochemical reactions in situ and in real time. We here describe advances in the development and application of XAS methods to monitor material synthesis in real time under mechanochemical conditions. We demonstrate the generality of our approaches by describing mechanochemical syntheses of materials by both vibratory ball milling and by Resonant Acoustic Mixing (RAM), where a time resolution of 1 second is for a whole XAS spectrum was achieved. Moreover, we describe how spectroscopic methods can be coupled to diffraction-based approaches, thereby providing new dimensions in understanding mechanochemical synthesis.
T2 - AfLS3
CY - Online meeting
DA - 14.11.2021
KW - Dipsersive XAS
KW - Mechanochemistry
KW - Time-resolved
KW - In situ
PY - 2021
AN - OPUS4-56256
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Rautenberg, Max
T1 - Ca-MOFs with varying fluorination degree
N2 - In current Li-ion batteries electrode materials consist typically of inorganic materials, such as LiCoO2, LiNixCoyMn1-zO2, LiFePO4, Li4Ti5O12. These materials struggle with toxicity or limited mineral resources, making them expensive. Therefore, eco-friendly, sustainable, and low-cost alternatives are researched for in recent years. A series of organic compounds were investigated as electrode materials for alkali-ion batteries. Among them organic carbonyl-based materials show reversible storage of lithium- or sodium-ions. Metal terephthalates stand out with their easy synthesis, moderate operational voltage and enhanced dissolution stability compared to other organic compounds. One degradation pathway consists of the dissolution of the electrode material by HF, formed in a side reaction by water and the fluorous electrolyte. Fluorinated metal terephthalates could offer higher dissolution stability against HF and less contamination by water due to their increased hydrophobicity.
The goal of this project is the synthesis and the investigation of the formation mechanism of a series of calcium-based MOFs with increasing fluorine content. For this purpose, we aimed for the construction of calcium-based MOFs with terephthalic acid (H2-pBDC), 2-fluoro-terephthalic acid (H2-2F-pBDC), 2,3,4,5-tetrafluoroterephthalic acid (H2-pBDC-F4), isophthalic acid (H2-mBDC) and 5-fluoro-isophthalic acid (H2-5F-mBDC).
T2 - SFB 1349 Wintersymposium 2022
CY - Berlin, Germany
DA - 15.03.2022
KW - Mechanochemistry
KW - Electrode materials
KW - Fluorinated MOFs
KW - In situ PXRD
PY - 2022
AN - OPUS4-54478
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Hieu, D.T.
A1 - Kosslick, H.
A1 - Riaz, M.
A1 - Schulz, A.
A1 - Springer, A.
A1 - Frank, M.
A1 - Jäger, Christian
A1 - Minh Thu, N.T.
A1 - Son, L.T.
T1 - Acidity and Stability of Bronsted Acid Sites in Green Clinoptilolite Catalysts and Catalytic Performance in the Etherification of Glycerol
N2 - Natural zeolite clinoptilolite CLIN with a framework ratio of Si/Al ≥ 4 containing mainly potassium and calcium ions in its internal channel system was used as a starting material. The acidic HCLIN catalysts were prepared under soft conditions avoiding the use of environmental less benign mineral acids. The starting material was ion exchanged using a 0.2 M aqueous ammonium nitrate solution at a temperature 80 ◦C for 2 h. The obtained NH4CLIN was converted into the acid HCLIN catalyst by calcination at 300–600 ◦C. The obtained samples were characterized by XRD, FTIR, SEM/TEM, AAS, and EDX element mapping. The state of aluminium and silicon was studied by 27Al- and 29SiMAS NMR spectroscopy. The textural properties of the catalysts were investigated by nitrogen adsorption and desorption measurements. The Brønsted acidity of the HCLIN catalysts was studied by temperature-programmed decomposition of the exchanged ammonium ions releasing ammonia as well as 1H MAS NMR, {1H–27Al} Trapdor, and {1H–27Al}
Redor experiments. The strongly agglomerated samples were crystalline and thermally stable up to >500 ◦C. Although a part of the clinoptilolite framework is maintained up to 600 ◦C, a loss of crystallinity is already observed starting from 450 ◦C. The specific surface areas of the starting CLIN and ammonium exchanged NH4CLIN are low with ca. 26 m2/g. The pores are nearly blocked by the exchangeable cations located in the zeolite pores. The thermal decomposition of the ammonium ions by calcination at 400 ◦C causes an opening of the pore entrances and a markable increase in the specific micropore area and micropore volume to ca. 163 m2/g and 0.07 cm3/g, respectively. It decreases with further rising calcination temperature indicating some structural loss. The catalysts show a broad distribution of Brønsted acid sites (BS) ranging from weak to strong sites as indicated the
thermal decomposition of exchanged ammonium ions (TPDA). The ammonium ion decomposition leaving BS, i.e., H+ located at Al–O–Si framework bridges, starts at ≥250 ◦C. A part of the Brønsted sites is lost after calcination specifically at 500 ◦C. It is related to the formation of penta-coordinated aluminium at the expense of tetrahedral framework aluminium. The Brønsted sites are partially recreated after repeated ammonium ion exchange. The catalytic performance of the acidic HCLIN
catalysts was tested in the etherification of glycerol as a green renewable resource with different C1 -C4 alcohols. The catalysts are highly active in the etherification of glycerol, especially with alcohols containing the branched, tertiary alkyl groups. Highest activity is observed with the soft activated catalyst HCLIN300 (300 ◦C, temperature holding time: 1 min). A total of 78% conversion of glycerol to mono and di ether were achieved with tert-butanol at 140 ◦C after 4 h of reaction.
The mono- and di-ether selectivity were 75% and 25%, respectively. The catalyst can be reused.
KW - Etherification
KW - Glycerol
KW - Zeolite
KW - Clinoptilolite
KW - Bronsted acidity
KW - Dehydroxylation
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-546982
DO - https://doi.org/10.3390/catal12030253
VL - 12
IS - 3
SP - 1
EP - 24
PB - MDPI
AN - OPUS4-54698
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Sechi, R.
A1 - Fackeldey, K.
A1 - Chewle, Surahit
A1 - Weber, M.
T1 - SepFree NMF: A toolbox for analyzing the kinetics of sequential spectroscopic data
N2 - This work addresses the problem of determining the number of components from sequential spectroscopic data analyzed by non-negative matrix factorization without separability assumption (SepFree NMF). These data are stored in a matrix M of dimension “measured times” versus “measured wavenumbers” and can be decomposed to obtain the spectral fingerprints of the states and their evolution over time. SepFree NMF assumes a memoryless (Markovian) process to underline the dynamics and decomposes M so that M = WH, with W representing the components’ fingerprints and H their kinetics. However, the rank of this decomposition (i.e., the number of physical states in the process) has to be guessed from pre-existing knowledge on the observed process. We propose a measure for determining the number of components with the computation of the minimal memory effect resulting from the decomposition; by quantifying how much the obtained factorization is deviating from the Markovian property, we are able to score factorizations of a different number of components. In this way, we estimate the number of different entities which contribute to the observed system, and we can extract kinetic information without knowing the characteristic spectra of the single components. This manuscript provides the mathematical background as well as an analysis of computer generated and experimental sequentially measured Raman spectra.
KW - Kinetics from experiments
KW - Separability assumption
KW - Sequential spectroscopic data
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-559046
DO - https://doi.org/10.3390/a15090297
SN - 1999-4893
VL - 15
IS - 9
SP - 1
EP - 16
PB - MDPI
CY - Basel
AN - OPUS4-55904
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Dalgic, Mete-Sungur
T1 - Discrimination effects in MALDI-MS of Ternary Polymer Mixtures
N2 - MALDI-TOF MS is a viable method to determine molecular weights of polymers. However, quantification using MALDI-TOF MS presents specific challenges due to intensity biases caused by instrumental and sample-specific parameters. In this presentation, the influence of molar masses on MALDI-TOF mass spectra is explored. The intensities of a ternary PMMA blend with different mixture ratios are depicted in contour plots.
T2 - SALSA Make and Measure 2022
CY - Berlin, Germany
DA - 15.09.2022
KW - MALDI-TOF MS
KW - Ternary polymer blends
KW - PMMA
PY - 2022
AN - OPUS4-62212
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Pollard, M.
T1 - Functionalized Poly(ethylene glycol)s (PEGs) as a Reference Material for Detection of Polymeric end Groups via SEC Hyphenated with FTIR and 1H-NMR (80 MHz)
N2 - With the online coupling (or hyphenation) of chemically-resolved spectroscopy detection with classical size-exclusion chromatography (SEC) it is possible to correlate polymer molecular size with chemical structure in a single in-situ or on-flow measurement. Medium-resolution 1H-NMR (60 MHz) spectroscopy (i.e., “desktop NMR”) and Fouriertransform Infrared Spectroscopy (FTIR) have both been developed as coupled methods (SEC-MR-NMR, SEC-FTIR) for the detection of polymer analytes by monitoring e.g. alkene or carbonyl functionality.1,2 Here, we have investigated the potential for the detection of polymer end groups, using a slightly higher field-strength spectrometer (80 MHz 1H Larmor frequency) and taking advantage of a columnless injection method that provides bulk spectra for reference. End-functionalized polymers were synthesized by reaction of PEG with toluene isocyanate, yielding ,-functionalized polymers with exactly 2 IR- and NMR-detectable functional groups per chain, as proven by MALD-TOF mass spectrometry. We have investigated the sensitivity (limit of detection) and spectral resolution for these functional groups in chloroform, THF, and water. Results have demonstrated a good feasibility for the simultaneous online detection of PEG backbone (M~4000 g/mol) and these end groups at the level of ca. 2 mol%.
T2 - 33rd International Symposium on Chromatography
CY - Budapest
DA - 18.09.2022
KW - Size exclusion chromatography
KW - Polyethyleneglycol
KW - MALDI-TOF MS
KW - NMR
PY - 2022
AN - OPUS4-56716
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Lilensten, L.
A1 - Provost, K.
A1 - Perrière, L.
A1 - Fonda, E.
A1 - Couzinié, J.
A1 - Amman, F.
A1 - Radtke, Martin
A1 - Dirras, G.
A1 - Guillot, I.
T1 - Experimental investigation of the local environment and lattice distortion in refractory medium entropy alloys
N2 - EXAFS analysis of pure elements, binary and ternary equiatomic refractory alloys within the Nb-Zr-Ti-Hf- Ta system is performed at the Nb and Zr K-edges to analyze the evolution of the chemical local environ- ment and the lattice distortion. A good mixing of the elements is found at the atomic scale. For some compounds, a distribution of distances between the central atom and its neighbors suggests a distortion of the structure. Finally, analysis of the Debye-Waller parameters shows some correlation with the lat- tice distortion parameter δ², and allows to quantify experimentally the static disorder in medium entropy alloys.
KW - BAMline
KW - Refractory alloys
KW - EXAFS
KW - Debye-Waller parameter
PY - 2022
DO - https://doi.org/10.1016/j.scriptamat.2022.114532
SN - 1359-6462
VL - 211
SP - 1
EP - 6
PB - Elsevier Ltd.
AN - OPUS4-55287
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Bruna, F. G.
A1 - Prokop, M.
A1 - Bystron, T.
A1 - Loukrakpam, R.
A1 - Melke, J.
A1 - Lobo, C. M. S.
A1 - Fink, M.
A1 - Zhu, M.
A1 - Voloshina, E.
A1 - Kutter, M.
A1 - Hoffmann, H.
A1 - Yusenko, Kirill
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Röder, B.
A1 - Bouzek, K.
A1 - Paulus, B.
A1 - Roth, C.
T1 - Following adsorbed intermediates on a platinum gas diffusion electrode in H3PO3‑containing electrolytes using in situ X‑ray absorption spectroscopy
N2 - One of the challenges of high-temperature polymer electrolyte membrane fuel cells is the poisoning of the Pt catalyst with H3PO4. H3PO4 is imbibed into the routinely used polybenzimidazole-based membranes, which facilitate proton conductivity in the temperature range of 120−200 °C. However, when leached out of the membrane by water produced during operation, H3PO4 adsorbs on the Pt catalyst surface, blocking the active sites and hindering the oxygen reduction reaction (ORR).
The reduction of H3PO4 to H3PO3, which occurs at the anode due to a combination of a low potential and the presence of gaseous H2, has been investigated as an additional important contributing factor to the observed poisoning effect. H3PO3 has an affinity toward adsorption on Pt surfaces even greater than that of H2PO4 −. In this work, we investigated the poisoning effect of both H3PO3 and H3PO4 using a half-cell setup with a gas diffusion electrode under ambient conditions. By means of in situ X-ray absorption spectroscopy, it was possible to follow the signature of different species adsorbed on the Pt nanoparticle catalyst (H, O, H2PO4 −, and H3PO3) at different potentials under ORR conditions in various electrolytes (HClO4, H3PO4, and H3PO3). It was found that H3PO3 adsorbs in a pyramidal configuration P(OH)3 through a Pt−P bond. The competition between H3PO4 and H3PO3 adsorption was studied, which should allow for a better understanding of the catalyst poisoning mechanism and thus assist in the development of strategies to mitigate this phenomenon in the future by minimizing H3PO3 generation by, for example, improved catalyst design or adapted operation conditions or changes in the electrolyte composition.
KW - H3PO4 life cycle
KW - XAS
KW - In situ coupling
KW - High-temperature fuel cells
KW - Δμ XANES
KW - H3PO3
PY - 2022
DO - https://doi.org/10.1021/acscatal.2c02630
SN - 2155-5435
VL - 12
IS - 18
SP - 11472
EP - 11484
PB - ACS
CY - Washington, DC
AN - OPUS4-55815
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Radtke, Martin
T1 - Getting more efficient – The use of Bayesian optimization and Gaussian processes at the BAMline
N2 - For more than 20 years, BAM is operating the BAMline at the synchrotron BESSY II in Berlin Adlershof. During this time, the complexity of the setup and the amount of data generated have multiplied. To increase the effectiveness and in preparation for BESSY III, algorithms from the field of machine learning are increasingly used.
After a short introduction to BO and GP, the first example is the automatic alignment of our double multilayer monochromator (DMM).
The second example is the optimization of measurement time in XRF scanning.
T2 - SNI2022 conference
CY - Berlin, Germany
DA - 05.09.2022
KW - Artificial Inelligence
KW - Machine Learning
KW - Bayesian Statistics
KW - Gaussian process
KW - X-ray fluorescence
KW - BAMline
PY - 2022
AN - OPUS4-56255
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - de Oliveira Guilherme Buzanich, Ana
T1 - Time resolved in situ monitoring of mechanochemical transformations by X-ray absorption spectroscopy (XAS)
N2 - Mechanochemical reactions promise a new direction for environmentally benign preparation of materials, and has been dubbed by IUPAC as one of the 10 chemical innovations that will change our world. Despite this significant promise, very little is known about the mechanisms that drive mechanochemical transformations, posing significant barriers to realizing their full potential. To this end, there is growing need to follow mechanochemical reactions in situ and in real time. We here describe advances in the development and application of XAS methods to monitor material synthesis in real time under mechanochemical conditions. We demonstrate the generality of our approaches by describing mechanochemical syntheses of materials by both vibratory ball milling and by Resonant Acoustic Mixing (RAM), where a time resolution of 1 second is for a whole XAS spectrum was achieved. Moreover, we describe how spectroscopic methods can be coupled to diffraction-based approaches, thereby providing new dimensions in understanding mechanochemical synthesis.
T2 - Advances X ray Analytics Seminar at TU Berlin
CY - Berlin, Germany
DA - 14.06.2022
KW - XAS
KW - Mechanochemistry
KW - Time resolved
KW - In situ
PY - 2022
AN - OPUS4-56259
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Radtke, Martin
T1 - Getting more efficient – The use of Bayesian optimization and Gaussian processes at the BAMline
N2 - For more than 20 years, BAM is operating the BAMline at the synchrotron BESSY II in Berlin Adlershof. During this time, the complexity of the setup and the amount of data generated have multiplied. To increase the effectiveness and in preparation for BESSY III, algorithms from the field of machine learning are increasingly used.
In this paper, several examples in the areas of beamline alignment and measurement time optimization based on Bayesian optimization (BO) with Gaussian processes (GP) are presented. BO is a method for finding the global optimum of a function using a probabilistic model represented by a GP. The advantage of this method is that it can handle high-dimensional problems, does not depend on the initial estimate, and also provides uncertainty estimates.
After a short introduction to BO and GP, the first example is the automatic alignment of our double multilayer monochromator (DMM). To achieve optimal performance, up to three linear and two angular motor positions have to be optimized. To achieve this with a grid scan, at least 100^5 measurement points would be required. Assuming that all positions can be aligned independently, 100*5 points are still necessary. We show that with BO and GP less than 100 points are sufficient to achieve equal or better results.
The second example is the optimization of measurement time in XRF scanning. Here we will show the advantage of the BO GP approach over point-by-point scanning. As can be seen in Fig. 1, the number of points required and thus the measurement time can be reduced by a factor of 50, while the loss in image quality is acceptable. The advantages and limitations of this approach will be discussed.
T2 - European Conference on X-ray Spectrometry 2022
CY - Bruges, Belgium
DA - 26.06.2022
KW - Artificial Inelligence
KW - Machine Learning
KW - Bayesian Statistics
KW - Gaussian process
KW - Neural network
KW - BAMline
KW - Synchrotron
PY - 2022
AN - OPUS4-56251
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - de Oliveira Guilherme Buzanich, Ana
T1 - Time resolved in situ monitoring of mechanochemical transformations by X-ray absorption spectroscopy (XAS)
N2 - Mechanochemical reactions promise a new direction for environmentally benign preparation of materials, and has been dubbed by IUPAC as one of the 10 chemical innovations that will change our world. Despite this significant promise, very little is known about the mechanisms that drive mechanochemical transformations, posing significant barriers to realizing their full potential. To this end, there is growing need to follow mechanochemical reactions in situ and in real time. We here describe advances in the development and application of XAS methods to monitor material synthesis in real time under mechanochemical conditions. We demonstrate the generality of our approaches by describing mechanochemical syntheses of materials by both vibratory ball milling and by Resonant Acoustic Mixing (RAM), where a time resolution of 1 second is for a whole XAS spectrum was achieved. Moreover, we describe how spectroscopic methods can be coupled to diffraction-based approaches, thereby providing new dimensions in understanding mechanochemical synthesis.
T2 - European Conference on X-ray Spectrometry 2022
CY - Bruges, Belgium
DA - 27.06.2022
KW - XAS
KW - Mechanochemictry
KW - Time resolved
KW - In situ
PY - 2022
AN - OPUS4-56258
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Radtke, Martin
T1 - BAMline@BESSY2 - Advanced Techniques and Applications
N2 - Synchrotron radiation sources offer a wide range of possibilities in materials research due to their unique properties in terms of intensity, polarization and adjustability. A basic introduction about the creation and special properties of synchrotron radiation will be given. Examples of current work at BAMline, the high-energy measuring facility of the Federal Institute for Materials Research and Testing at the synchrotron BESSY, are used to illustrate the possibilities and limitations of existing measuring methods.”
T2 - GDCH Kolloquium
CY - Clausthal-Zellerfeld, Germany
DA - 17.11.2022
KW - Synchrotron
KW - BAMline
KW - XRF
KW - XANES
PY - 2022
AN - OPUS4-61706
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Radtke, Martin
T1 - From Egypt to Hiddensee – Analysis of Gold with Synchrotron Radiation IV
N2 - Gold is one of the seven metals already known in antiquity and was used from time immemorial as a medium of exchange and for the production of jewelry because of its luster and rarity. In addition, it is easy to work and largely resistant to chemical influences. Investigations of gold using synchrotron radiation excited X-ray fluorescence analysis are non-destructive and provide information about the chemical elements present in the sample under investigation. The investigations presented here at BAMline focus on questions such as the origin, manufacturing process, and association of gold findings. The different questions are explained by a number of examples ranging from the Viking treasure from Hiddensee to the Nebra Sky Disk and finds from Egypt. The find from Bernstorf is discussed in detail. A Bayesian treatment of the authenticity is shown.
T2 - Ringvorlesung Einführung in die Archäometrie
CY - Berlin, Germany
DA - 04.11.2022
KW - Synchrotron
KW - BAMline
KW - Bayesian Statistics
KW - Gold
KW - Röntgenfluoreszenz
PY - 2022
AN - OPUS4-56252
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Radtke, Martin
T1 - News from the BAMline
N2 - A presentation of recent measurements at the BAMline with focus on AI and ML applications
T2 - Seminar: Strahlenphysikalische Anwendungen in Technik und Medizin
CY - Vienna, Austria
DA - 18.05.2022
KW - Synchrotron
KW - BAMline
KW - Bayesian Statistics
KW - Gold
KW - X-ray fluorescence
PY - 2022
AN - OPUS4-56253
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Radtke, Martin
T1 - Big to Small - Getting Smarter@BAMline
N2 - In this talk an overview about artificial intelligence/machine learning applications @BAMline is given. In the first part, the use of neural networks for the quantification of XRF measurements and the decoding of coded-aperture measurements are shown. Then it is shown how Gaussian processes and Bayesian statistics can be used to achieve an optimal alignment of the set-up and in general for optimization of measurements.
T2 - Forschungsseminar Institut für Optik und Atomare Physik TU Berlin
CY - Berlin, Germany
DA - 25.10.2022
KW - Artificial Inelligence
KW - Machine Learning
KW - Bayesian Statistics
KW - Gaussian process
KW - Neural network
KW - BAMline
KW - Synchrotron
PY - 2022
AN - OPUS4-56249
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - de O. Primo, J.
A1 - Horsth, D.F.
A1 - de S. Correa, J.
A1 - Das, A.
A1 - Bittencourt, C.
A1 - Umek, P.
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Radtke, Martin
A1 - Yusenko, Kirill
A1 - Zanetta, C.
A1 - Anaissi, F.J.
T1 - Synthesis and Characterization of Ag/ZnO Nanoparticles for Bacteria Disinfection in Water
N2 - n this study, two green synthesis routes were used for the synthesis of Ag/ZnO nanoparticles, using cassava starch as a simple and low-cost effective fuel and Aloe vera as a reducing and stabilizing agent. The Ag/ZnO nanoparticles were characterized and used for bacterial dis-
infection of lake water contaminated with Escherichia coli (E. coli). Characterization indicated the formation of a face-centered cubic structure of metallic silver nanoparticles with no insertion of Ag into the ZnO hexagonal wurtzite structure. Physicochemical and bacteriological analyses described in “Standard Methods for the Examination of Water and Wastewater” were used to evaluate the efficiency of the treatment. In comparison to pure ZnO, the synthesized Ag/ZnO nanoparticles showed high efficiencies against Escherichia coli (E. coli) and general coliforms present in the lake
water. These pathogens were absent after treatment using Ag/ZnO nanoparticles. The results indicate that Ag/ZnO nanoparticles synthesized via green chemistry are a promising candidate for the treatment of wastewaters contaminated by bacteria, due to their facile preparation, low-cost synthesis,and disinfection efficiency.
KW - Synchrotron
KW - BAMline
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-562440
DO - https://doi.org/10.3390/nano12101764
SN - 2079-4991
VL - 12
IS - 10
SP - 1
EP - 18
PB - MDPI
CY - Basel
AN - OPUS4-56244
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Margreiter, R.
A1 - Baumann, J.
A1 - Mantouvalou, I.
A1 - Radtke, Martin
A1 - Reinholz, Uwe
A1 - Strub, E.
T1 - Investigations on fire-gilding
N2 - Fire-gilding is a historic technique for the application of golden layers on a number of different base materials utilizing a gold amalgam. This technique leaves a significant amount of Hg in the golden layer, giving archeometrists a reliable indicator to identify firegildings.
Recent findings on presumably fire-gilded objects have shown in several cases significantly lower Hg content than previously studied objects. This prompted a synchrotron-based X-ray fluorescence investigation into the Hg distribution along the material–gilding interface, as well as a series of measurements regarding the Hg content development in fire-gilded samples during artificial aging. This work presents findings on laboratory-prepared fire-gildings, indicating an Hg enrichment at the interface of firegilded silver samples. Notably, such an enrichment is missing in fire-gilded copper samples. Further, it is confirmed that fire-gilded layers typically do not undercut an Hg bulk content of 5%. In this light, it seems improbable that ancient samples that contain <5% Hg are fire-gilded. The results presented in this study might lead to a non-destructive method to identify the Hg enrichment at the interface. This might be obtained by a combination of different non-destructive measurements and might also work unambiguously in samples in which the gold top layer is altered.
KW - BAMline
KW - X-Ray Fluorescence
KW - Gilding
KW - Depth profile
KW - Archaeometry
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-552885
DO - https://doi.org/10.1111/arcm.12797
SN - 0003-813X
SP - 1
EP - 14
PB - Wiley online library
AN - OPUS4-55288
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Iro, M.
A1 - Ingerle, D.
A1 - Radtke, Martin
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Kregsamer, P.
A1 - Streli, C.
T1 - Investigation of polycapillary half lenses for quantitative confocal micro-X-ray fluorescence analysis
N2 - The use of polycapillary optics in confocal micro-X-ray fluorescence analysis (CMXRF) enables the destruction-free 3D investigation of the elemental composition of samples. The energy-dependent transmission properties, concerning intensity and spatial beam propagation of three polycapillary half lenses, which are vital for the quantitative interpretation of such CMXRF measurements, are investigated in a monochromatic confocal laboratory setup at the Atominstitut of TU Wien, and a synchrotron setup on the BAMline beamline at the BESSY II Synchrotron, Helmholtz-Zentrum-Berlin. The empirically established results, concerning the intensity of the transmitted beam, are compared with theoretical values calculated with the polycap software package and a newly presented analytical model for the transmission function.
The resulting form of the newly modelled energy-dependent transmission function is shown to be in good agreement with Monte Carlo simulated results for the complete energy regime, as well as the empirically established results for the energy regime between 6 keV and 20 keV. An analysis of possible fabrication errors was conducted via pinhole scans showing only minor fabrication errors in two of the investigated polycapillary optics. The energy-dependent focal spot size of the primary polycapillary was investigated in the laboratory via the channel-wise evaluation of knife-edge scans. Experimental results are compared with data given by the manufacturer as well as geometric estimations for the minimal focal spot size. Again, the resulting measurement points show a trend in agreement with geometrically estimated results and manufacturer data.
KW - BAMline
KW - Synchrotron
KW - Capillary
KW - confocal
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-562430
DO - https://doi.org/10.1107/S1600577522009699
SN - 1600-5775
VL - 29
SP - 1376
EP - 1384
PB - International Union of Crystallography
CY - Chester
AN - OPUS4-56243
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Smekhova, A.
A1 - Kuzmin, A.
A1 - Siemensmeyer, K.
A1 - Luo, C.
A1 - Taylor, J.
A1 - Thakur, S.
A1 - Radu, F.
A1 - Weschke, E.
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Xiao, B.
A1 - Savan, A.
A1 - Yusenko, Kirill
A1 - Ludwig, A.
T1 - Local structure and magnetic properties of a nanocrystalline Mn-rich Cantor alloy thin film down to the atomic scale
N2 - The huge atomic heterogeneity of high-entropy materials along with a possibility to unravel the behavior of individual components at the atomic scale suggests a great promise in designing new compositionally complex systems with the desired multi-functionality. Herein, we apply multi-edge X-ray absorption spectroscopy (extended X-ray absorption fine structure (EXAFS), X-ray absorption near edge structure (XANES), and X-ray magnetic circular dichroism (XMCD)) to probe the structural, electronic, and magnetic properties of all individual constituents in the single-phase face-centered cubic (fcc)-structured nanocrystalline thin film of Cr20Mn26Fe18Co19Ni17 (at.%) high-entropy alloy on the local scale. The local crystallographic ordering and component-dependent lattice displacements were explored within the reverse Monte Carlo approach applied to EXAFS spectra collected at the K absorption edges of several constituents at room temperature. A homogeneous short-range fcc atomic environment around the absorbers of each type with very similar statistically averaged interatomic distances (2.54–2.55 Å) to their nearest-neighbors and enlarged structural relaxations of Cr atoms were revealed. XANES and XMCD spectra collected at the L2,3 absorption edges of all principal components at low temperature from the oxidized and in situ cleaned surfaces were used to probe the oxidation states, the changes in the electronic structure, and magnetic behavior of all constituents at the surface and in the sub-surface volume of the film. The spin and orbital magnetic moments of Fe, Co, and Ni components were quantitatively evaluated. The presence of magnetic phase transitions and the co-existence of different magnetic phases were uncovered by conventional magnetometry in a broad temperature range.
KW - Magnetism
KW - High-entropy alloys
KW - Reverse Monte Carlo (RMC)
KW - Element-specific spectroscopy
KW - Extended X-ray absorption fine structure (EXAFS),
KW - X-ray magnetic circular dichroism (XMCD),
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-578254
DO - https://doi.org/10.1007/s12274-022-5135-3
SN - 1998-0124
SP - 5626
PB - Springer
AN - OPUS4-57825
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Getenet, M.
A1 - Garcia-Ruiz, J. M.
A1 - Otálora, F.
A1 - Emmerling, Franziska
A1 - Al-Sabbagh, Dominik
A1 - Verdugo-Escamilla, E.
T1 - A comprehensive methodology for monitoring evaporitic mineral precipitation and hydrochemical evolution of saline lakes: The case of Lake Magadi soda brine (East African Rift Valley, Kenya)
N2 - Lake Magadi, East African Rift Valley, is a hyperalkaline and saline soda lake highly enriched in Na+, K+, CO32–, Cl–, HCO3–, and SiO2 and depleted in Ca2+ and Mg2+, where thick evaporite deposits and siliceous sediments have been forming for 100 000 years. The hydrogeochemistry and the evaporite deposits of soda lakes are subjects of growing interest in paleoclimatology, astrobiology, and planetary sciences. In Lake Magadi, different hydrates of sodium carbonate/bicarbonate and other saline minerals precipitate. The precipitation sequence of these minerals is a key for understanding the hydrochemical evolution, the paleoenvironmental conditions of ancient evaporite deposits, and industrial crystallization. However, accurate determination of the precipitation sequence of these minerals was challenging due to the dependency of the different hydrates on temperature, water activity, pH and pCO2, which could induce phase transformation and secondary mineral precipitation during sample handling. Here, we report a comprehensive methodology applied for monitoring the evaporitic mineral precipitation and hydrochemical evolution of Lake Magadi. Evaporation and mineral precipitations were monitored by using in situ video microscopy and synchrotron X-ray diffraction of acoustically levitated droplets. The mineral patterns were characterized by ex situ Raman spectroscopy, X-ray diffraction, and scanning electron microscopy. Experiments were coupled with thermodynamic models to understand the evaporation and precipitation-driven hydrochemical evolution of brines. Our results closely reproduced the mineral assemblages, patterns, and textural relations observed in the natural setting. Alkaline earth carbonates and fluorite were predicted to precipitate first followed by siliceous sediments. Among the salts, dendritic and acicular trona precipitate first via fractional crystallization─reminiscent of grasslike trona layers of Lake Magadi. Halite/villiaumite, thermonatrite, and sylvite precipitate sequentially after trona from residual brines depleted in HCO3–. The precipitation of these minerals between trona crystals resembles the precipitation process observed in the interstitial brines of the trona layers. Thermonatrite precipitation began after trona equilibrated with the residual brines due to the absence of excess CO2 input. We have shown that evaporation and mineral precipitation are the major drivers for the formation of hyperalkaline, saline, and SiO2-rich brines. The discrepancy between predicted and actual sulfate and phosphate ion concentrations implies the biological cycling of these ions. The combination of different in situ and ex situ methods and modeling is key to understanding the mineral phases, precipitation sequences, and textural relations of modern and ancient evaporite deposits. The synergy of these methods could be applicable in industrial crystallization and natural brines to reconstruct the hydrogeochemical and hydroclimatic conditions of soda lakes, evaporite settings, and potentially soda oceans of early Earth and extraterrestrial planets.
KW - Crystallization
KW - Precipitation
KW - Crystals
KW - Evaporation
KW - Minerals
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-546712
DO - https://doi.org/10.1021/acs.cgd.1c01391
SN - 1528-7483
VL - 22
IS - 4
SP - 2307
EP - 2317
PB - ACS Publications
CY - Washington, DC
AN - OPUS4-54671
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Rautenberg, Max
A1 - Gernhard, M.
A1 - Radnik, Jörg
A1 - Witt, Julia
A1 - Roth, C.
A1 - Emmerling, Franziska
T1 - Mechanochemical synthesis of fluorine-containing Co-doped zeolitic imidazolate frameworks for producing electrocatalysts
N2 - Catalysts derived from pyrolysis of metal organic frameworks (MOFs) are promising candidates to replace expensive and scarce platinum-based electrocatalysts commonly used in polymer electrolyte membrane fuel cells. MOFs contain ordered connections between metal centers and organic ligands. They can be pyrolyzed into metal- and nitrogen-doped carbons, which show electrocatalytic activity toward the oxygen reduction reaction (ORR). Furthermore, metal-free heteroatom-doped carbons, such as N-F-Cs, are known for being active as well. Thus, a carbon material with Co-N-F doping could possibly be even more promising as ORR electrocatalyst. Herein, we report the mechanochemical synthesis of two polymorphs of a zeolitic imidazole framework, Co-doped zinc 2-trifluoromethyl-1H-imidazolate (Zn0.9Co0.1(CF3-Im)2). Time-resolved in situ X-ray diffraction studies of the mechanochemical formation revealed a direct conversion of starting materials to the products. Both polymorphs of Zn0.9Co0.1(CF3-Im)2 were pyrolyzed, yielding Co-N-F containing carbons, which are active toward electrochemical ORR.
KW - Mechanochemistry
KW - Metal-organic-frameworks
KW - Nobel-metal free electrocatalysis
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-546833
DO - https://doi.org/10.3389/fchem.2022.840758
SN - 2296-2646
VL - 10
IS - 840758
SP - 1
EP - 13
PB - Frontiers Media
CY - Lausanne
AN - OPUS4-54683
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Martins, Ines
A1 - Al-Sabbagh, Dominik
A1 - Bentrup, U.
A1 - Marquardt, Julien
A1 - Schmid, Thomas
A1 - Scoppola, E.
A1 - Kraus, Werner
A1 - Stawski, Tomasz
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Yusenko, Kirill
A1 - Weidner, Steffen
A1 - Emmerling, Franziska
T1 - Formation Mechanism of a Nano-Ring of Bismuth Cations and Mono-Lacunary Keggin-Type Phosphomolybdate
N2 - A new hetero-bimetallic polyoxometalate (POM) nano-ring was synthesized in a one-pot procedure. The structure consists of tetrameric units containing four bismuth-substituted monolacunary Keggin anions including distorted [BiO8] cubes. The nano-ring is formed via self-assembly from metal precursors in aqueous acidic medium. The compound (NH4)16[(BiPMo11O39)4] ⋅ 22 H2O; (P4Bi4Mo44) was characterized by single-crystal X-ray diffraction, extended X-ray absorption fine structure spectroscopy (EXAFS), Raman spectroscopy, matrix-assisted laser desorption/ionisation-time of flight mass spectrometry (MALDI-TOF), and thermogravimetry/differential scanning calorimetry mass spectrometry (TG-DSC-MS). The formation of the nano-ring in solution was studied by time-resolved in situ small- and wide-angle X-ray scattering (SAXS/WAXS) and in situ EXAFS measurements at the Mo−K and the Bi−L3 edge indicating a two-step process consisting of condensation of Mo-anions and formation of Bi−Mo-units followed by a rapid self-assembly to yield the final tetrameric ring structure.
KW - Bismuth
KW - In situ EXAFS
KW - In situ SAXS/WAXS
KW - Lacunary Keggin ion
KW - Polyoxometalates
KW - Self-assembly
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-546823
DO - https://doi.org/10.1002/chem.202200079
SN - 0947-6539
VL - 28
IS - 27
SP - 1
EP - 7
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-54682
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Zänker, Steffen
A1 - Scholz, G.
A1 - Marquardt, Julien
A1 - Emmerling, Franziska
T1 - Structural changes in Ba-compounds of different hardness induced by high-energy ball milling – evidenced by 137Ba NMR and X-ray powder diffraction
N2 - Changes in the global bulk and local structures, of three different barium compounds (BaZrO3, BaF2, and BaFCl),were induced by mechanical milling and followed using X-ray powder diffraction (PXRD), subsequent microstructure analysis, and 137Ba solid state NMR spectroscopy. Harder materials like BaZrO3 experience significantly higher structural changes upon milling than softer materials like BaF2. Moreover, soft materials with layered structures, like BaFCl, show a pronounced structural change during the milling process. By combining PXRD and solid state NMR, detailed information on the changes to the global and local structures were obtained, which are of interest for mechanochemical synthesis, mechanically treated catalysts or ionic conductors.
KW - Mechanochemistry
KW - X-ray diffraction
KW - Solid state NMR
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-547397
DO - https://doi.org/10.1002/zaac.202200026
SN - 0044-2313
VL - 648
IS - 10
SP - 1
EP - 8
PB - Wiley-VCH
CY - Weinheim
AN - OPUS4-54739
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Accorsi, M.
A1 - Tiemann, M.
A1 - Wehrhan, L.
A1 - Finn, Lauren M.
A1 - Cruz, R.
A1 - Rautenberg, Max
A1 - Emmerling, Franziska
A1 - Heberle, J.
A1 - Keller, B. G.
A1 - Rademann, J.
T1 - Pentafluorophosphato-Phenylalanines: Amphiphilic Phosphotyrosine Mimetics Displaying Fluorine-Specific Protein Interactions
N2 - Phosphotyrosine residues are essential functional switches in health and disease. Thus, phosphotyrosine biomimetics are crucial for the development of chemical tools and drug molecules. We report here the discovery and investigation of pentafluorophosphato amino acids as novel phosphotyrosine biomimetics. A mild acidic pentafluorination protocol was developed and two PF5-amino acids were prepared and employed in peptide synthesis. Their structures, reactivities, and fluorine-specific interactions were studied by NMR and IR spectroscopy, X-ray diffraction, and in bioactivity assays. The mono-anionic PF5 motif displayed an amphiphilic character binding to hydrophobic surfaces, to water molecules, and to protein-binding sites, exploiting charge and H−F-bonding interactions. The novel motifs bind 25- to 30-fold stronger to the phosphotyrosine binding site of the protein tyrosine phosphatase PTP1B than the best current biomimetics, as rationalized by computational methods, including molecular dynamics simulations.
KW - Chemical Biology
KW - Drug Development
KW - Pentafluorophosphates
KW - Phosphotyrosine Biomimetics
KW - Protein Tyrosine Phosphatases
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-549984
DO - https://doi.org/10.1002/anie.202203579
SN - 1433-7851
VL - 134
IS - 25
SP - 1
EP - 6
PB - Wiley-VCH GmbH
AN - OPUS4-54998
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Belenguer, A.
A1 - Lampronti, G.
A1 - Michalchuk, Adam
A1 - Emmerling, Franziska
A1 - Sanders, J.
T1 - Quantitative reversible one pot interconversion of three crystalline polymorphs by ball mill grinding
N2 - We demonstrate here using a disulfide system the first example of reversible, selective, and quantitative transformation between three crystalline polymorphs by ball mill grinding. This includes the discovery of a previously unknown polymorph. Each polymorph is reproducibly obtained under well-defined neat or liquid-assisted grinding conditions, revealing subtle control over the apparent thermodynamic stability. We discovered that the presence of a contaminant as low as 1.5% mol mol−1 acting as a template is required to enable all these three polymorph transformations. The relative stabilities of the polymorphs are determined by the sizes of the nanocrystals produced under different conditions and by surface interactions with small amounts of added solvent. For the first time, we show evidence that each of the three polymorphs is obtained with a unique and reproducible crystalline size. This mechanochemical approach gives access to bulk quantities of metastable polymorphs that are inaccessible through recrystallisation.
KW - Mechanochemistry
KW - Polymorph
KW - XRD
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-549934
DO - https://doi.org/10.1039/D2CE00393G
SP - 1
EP - 7
PB - Royal Society of Chemistry
AN - OPUS4-54993
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Cakir, Cafer Tufan
A1 - Radtke, Martin
A1 - Haider, M. Bilal
A1 - Emmerling, Franziska
A1 - F. M. Oliveira, P.
A1 - Michalchuk, Adam
T1 - Dispersive x-ray absorption spectroscopy for time-resolved in situ monitoring of mechanochemical reactions
N2 - X-ray absorption spectroscopy (XAS) provides a unique, atom-specific tool to probe the electronic structure of solids. By surmounting long-held limitations of powder-based XAS using a dynamically averaged powder in a Resonant Acoustic Mixer (RAM), we demonstrate how time-resolved in situ (TRIS) XAS provides unprecedented detail of mechanochemical synthesis. The use of a custom-designed dispersive XAS (DXAS) setup allows us to increase the time resolution over existing fluorescence measurements from ∼15 min to 2 s for a complete absorption spectrum. Hence, we here establish TRIS-XAS as a viable method for studying mechanochemical reactions and sampling reaction kinetics. The generality of our approach is demonstrated through RAM-induced (i) bottom-up Au nanoparticle mechanosynthesis and (ii) the synthesis of a prototypical metal organic framework, ZIF-8. Moreover, we demonstrate that our approach also works with the addition of a stainless steel milling ball, opening the door to using TRIS-DXAS for following conventional ball milling reactions. We expect that our TRIS-DXAS approach will become an essential part of the mechanochemical tool box.
KW - In situ studies
KW - Dipsersive XAS
KW - Mechanochemistry
KW - Time-resolved
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-567659
DO - https://doi.org/10.1063/5.0130673
SN - 1089-7690
VL - 157
IS - 21
SP - 1
EP - 12
PB - American Institute of Physics
CY - Melville, NY
AN - OPUS4-56765
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Linberg, Kevin
A1 - Röder, Bettina
A1 - Al-Sabbagh, Dominik
A1 - Emmerling, Franziska
A1 - Michalchuk, Adam
T1 - Controlling polymorphism in molecular cocrystals by variable temperature ball milling
N2 - Mechanochemistry offers a unique opportunity to modify and manipulate crystal forms, often providing new products as compared with conventional solution methods. While promising, there is little known about how to control the solid form through mechanochemical means, demanding dedicated investigations. Using a model organic cocrystal system (isonicotinamide:glutaric acid), we here demonstrate that with mechanochemistry, polymorphism can be induced in molecular solids under conditions seemingly different to their conventional thermodynamic (thermal) transition point. Whereas Form II converts to Form I upon heating to 363 K, the same transition can be initiated under ball milling conditions at markedly lower temperatures (348 K). Our results indicate that mechanochemical techniques can help to reduce the energy barriers to solid form transitions, offering new insights into controlling polymorphic forms. Moreover, our results suggest that the nature of mechanochemical transformations could make it difficult to interpret mechanochemical solid form landscapes using conventional equilibrium-based tools.
KW - Mechanochemistry
KW - Polymorphism
KW - TRIS
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-564728
DO - https://doi.org/10.1039/d2fd00115b
SP - 1
EP - 16
PB - Royal Society of Chemistry
AN - OPUS4-56472
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Linberg, Kevin
A1 - Emmerling, Franziska
A1 - Michalchuk, Adam
T1 - Unintended Rate Enhancement in Mechanochemical Kinetics by Using Poly(methyl methacrylate) Jars
N2 - Time-resolved in situ (TRIS) X-ray diffraction has changed how mechanochemical transformations are studied but requires the use of X-ray transparent jars often made from poly(methyl methacrylate) (PMMA). However, using PMMA jars can alter the apparent kinetics of mechanochemical polymorphism by an order of magnitude, questioning the interpretability of established TRIS methods. Our results suggest that rate enhancement in PMMA jars may not be dominated by chemical effects of the polymer, but rather a result of different equilibrium temperatures within the jar. These features must be better understood before control over mechanochemical reactions can be achieved.
KW - Mechanochemistry
KW - Organic compounds
KW - Polymers
KW - Materials
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-565276
DO - https://doi.org/10.1021/acs.cgd.2c01227
SN - 1528-7483
SP - 1
EP - 5
PB - ACS Publications
AN - OPUS4-56527
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Falkenhagen, Jana
T1 - Coupling of chromatographic and spectrometric techniques for polymer characterization
N2 - Coupling of chromatographic and spectrometric techniques for polymer characterization; focus topics: LCxMALDI-TOF-MS and UPLC x ESI-TOF-MS
T2 - 16. Tagung des Arbeitskreises Polymeranalytik
CY - Online meeting
DA - 22.03.2022
KW - Liquid chromatography
KW - Mass spectrometry
KW - Polymers
KW - Two-dimensional chromatography (2D-LC)
PY - 2022
AN - OPUS4-54567
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Heilmann, Maria
A1 - Prinz, Carsten
A1 - Bienert, Ralf
A1 - Wendt, R.
A1 - Kunkel, B.
A1 - Radnik, Jörg
A1 - Hoell, A.
A1 - Wohlrab, S.
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Emmerling, Franziska
T1 - Size-Tunable Ni–Cu Core–Shell Nanoparticles—Structure, Composition, and Catalytic Activity for the Reverse Water–Gas Shift Reaction
N2 - A facile and efficient methodology is described for the solvothermal synthesis of size-tunable, stable, and uniform NiCu core–shell nanoparticles (NPs) for application in catalysis. The diameter of the NPs is tuned in a range from 6 nm to 30 nm and to adjust the Ni:Cu ratio from 30:1 to 1:1. Furthermore, the influence of different reaction parameters on the final NPs is studied. The NPs are structurally characterized by a method combination of transmission electron microscopy, anomalous small-angle X-ray scattering, X-ray absorption fine structure, and X-ray photoelectron spectroscopy. Using these analytical methods, it is possible to elucidate a core–shell–shell structure of all particles and their chemical composition. In all cases, a depletion from the core to the shell is observed, with the core consisting of NiCu alloy, surrounded by an inner Ni-rich shell and an outer NiO shell. The SiO2-supported NiCu core–shell NPs show pronounced selectivity of >99% for CO in the catalytic reduction of CO2 to CO using hydrogen as reactant (reverse water–gas shift reaction) independent of size and Ni:Cu ratio.
KW - Nanoparticles
KW - Core-shell
KW - Catalysis
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-543606
DO - https://doi.org/10.1002/adem.202101308
SN - 1438-1656
SP - 1
EP - 13
PB - Wiley VCH
AN - OPUS4-54360
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Mazzeo, P. P.
A1 - Prencipe, M.
A1 - Feiler, Torvid
A1 - Emmerling, Franziska
A1 - Bacchi, A.
T1 - On the mechanism of cocrystal mechanochemical reaction via low melting eutectic: A time-resolved in situ monitoring investigation
N2 - Mechanochemistry has become a sustainable and attractive cost-effective synthetic technique, largely used within the frame of crystal engineering. Cocrystals, namely, crystalline compounds made of different chemical entities within the same crystal structure, are typically synthesized in bulk via mechanochemistry; however, whereas the macroscopic aspects of grinding are becoming clear, the fundamental principles that underlie mechanochemical cocrystallization at the microscopic level remain poorly understood. Time-resolved in situ (TRIS) monitoring approaches have opened the door to exceptional detail regarding mechanochemical reactions. We here report a clear example of cocrystallization between two solid coformers that proceeds through the formation of a metastable low melting binary eutectic phase. The overall cocrystallization process has been monitored by time-resolved in situ (TRIS) synchrotron X-ray powder diffraction with a customized ball milling setup, currently available at μ Spot beamline at BESSY-II, Helmholtz-Zentrum Berlin. The binary system and the low melting eutectic phase were further characterized via DSC, HSM, and VT-XRPD.
KW - Mechanochemistry
KW - In situ
KW - Cocrystal
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-552977
DO - https://doi.org/10.1021/acs.cgd.2c00262
SN - 1528-7505
VL - 22
IS - 7
SP - 4260
EP - 4267
PB - ACS Publ.
CY - Washington, DC
AN - OPUS4-55297
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Rautenberg, Max
A1 - Bhattacharya, Biswajit
A1 - Witt, Julia
A1 - Jain, Mohit
A1 - Emmerling, Franziska
T1 - In situ time-resolved monitoring of mixed-ligand metal–organic framework mechanosynthesis
N2 - The mechanism of mixed-ligand metal–organic framework (MOF) formation, and the possible role of intermediate single-ligand metal complexes during mechanosynthesis, have not been explored yet. For the first time, we report here in situ real-time monitoring of the mechanochemical formation mechanism of mixed-ligand MOFs. Our results show that binary phases can act as intermediates or competing products in one-pot and stepwise synthesis.
KW - Mechanochemistry
KW - Metal-organic-frameworks
KW - In situ X-ray diffraction
KW - Mixed-ligand MOFs
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-558167
DO - https://doi.org/10.1039/D2CE00803C
SP - 1
EP - 4
PB - Royal Society of Chemistry
AN - OPUS4-55816
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Cakir, Cafer Tufan
T1 - Bayesian optimization for depth resolved analysis of complex alloys with grazing exit XANES
N2 - Compositionally complex alloys (CCAs) are a new class of alloys containing at least 5 elements with concentrations between 5 and 35 atomic percent. Due to their adjustable composition, which enables modifications of mechanical properties (such as hardness, strength and ductility etc) and their stability at high temperatures, CCAs have been the focus of various studies [1,2]. Especially the corrosion behavior of CCAs has been a wide research interest.
However, there are only few studies that deals with the degradation process on such materials, which is highly relevant for the safety aspect for future component design. To thoroughly investigate the corrosion processes and to determine oxidation states of metal components within the reaction products, we need special analytical tools. Since the grazing exit X-ray fluorescence (GEXRF) offers a non-destructive way to collect notable information regarding the high temperature oxidation, we consider it as a useful method to investigate how CCAs behave in corrosive environments.
The main idea of grazing geometry is to enhance the fluorescence signal of the surface. This enables highly sensitive surface analyses of thin protective film on surface in sub-micrometer scale [3]. When compared to a conventional CCD-based camera, the advantage and most important feature of the detector system (Color X-Ray Camera (CXC)) is that each pixel is an energy sensitive detector. The position and area sensitive detector, with 264x264 pixel detector area, provides information regarding the signal emitted from the sample as a function of the emission angle and thus allows depth-sensitive analysis. Furthermore, the data collected from samples of an incidence energy which can be controlled with a resolution of 0.5 eV provides XANES data to determine oxidation states.
In this contribution, we address the feasibility of our setup and new optimization procedure (Bayesian Optimization and Gaussian Regression). The results of a conceptual study regarding layer properties of the reference sample (Cr-Oxide layer (300nm) on Cr layer (500nm) on Si wafer) and CrCoNi (Cr-Oxide (>1µm) layer on CrCoNi substrate) medium entropy alloy.
T2 - European Conference on X-ray Spectrometry. EXRS 2022
CY - Bruges, Belgium
DA - 26.06.2022
KW - GEXRF
KW - High entropy alloys
KW - XANES
KW - Grazing exit
KW - High entropy materials
KW - XAS
KW - Optimization
PY - 2022
AN - OPUS4-56272
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Emmerling, Franziska
T1 - In situ investigations of mechanochemical processes
N2 - Overview of the present BAM activities in the field of in situ analytics of mechanochemical processes. Recent results for the synthesis of metal organic frameworks and cocrystals are presented.
T2 - HZB Seminar
CY - Online meeting
DA - 21.01.2022
KW - Mechanochemistry
KW - In situ real-time monitoring
PY - 2022
AN - OPUS4-54296
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kulow, Anicó
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Reinholz, Uwe
A1 - Emmerling, Franziska
A1 - Hampel, S.
A1 - Fittschen, UEA
A1 - Streli, C.
A1 - Radtke, Martin
T1 - Reconstruction for coded aperture full-field x-ray fluorescence imaging
N2 - X-ray fluorescence imaging is a well-established tool in materials characterization. In this work, we present the adaption of coded aperture imaging to full-field X-ray fluorescence imaging at the synchrotron. Coded aperture imaging has its origins in astrophysics, and has several advantages: Coded apertures are relatively easy to fabricate, achromatic, allow a high photon throughput, and high angular acceptance. Coded aperture imaging is a two-step-process, consisting of the measurement process and a reconstruction step. Different programs have been written, for the raytracing/forward projection and the reconstruction. Experiments with coded aperture in combination with a Color X-ray Camera and an energy-dispersive area detector, have been conducted at the BAMline. Measured samples were successfully reconstructed, and gave a 9.1-fold increase in count rate compared to a polycapillary optic.
KW - Synchrotron
KW - BAMline
KW - Coded Aperture
PY - 2022
SN - 1097-0002
VL - 65
SP - 57
EP - 70
PB - Cambridge University Press
CY - Cambridge
AN - OPUS4-56350
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Casali, C.
A1 - Feiler, Torvid
A1 - Heilmann, Maria
A1 - Braga, D.
A1 - Emmerling, Franziska
A1 - Grepioni, F.
T1 - Too much water? Not enough? In situ monitoring of the mechanochemical reaction of copper salts with dicyandiamide
N2 - n situ monitoring of mechanochemical reactions between dicyandiamide (DCD) and CuX2 salts (X = Cl−, NO3−), for the preparation of compounds of agrochemical interest, showed the appearance of a number of phases. It is demonstrated that milling conditions, such as the amount of water added in wet grinding and/or the milling frequency, may affect the course of the mechanochemical reactions, and drive the reaction towards the formation of different products. It has been possible to discover by in situ monitored experiments two novel crystalline forms, namely the neutral complexes [Cu(DCD)2(OH2)2(NO3)2] (2) and [Cu(DCD)2(OH2)Cl2]·H2O (4), in addition to the previously known molecular salt [Cu(DCD)2(OH2)2][NO3]2·2H2O (1, DIVWAG) and neutral complex [Cu(DCD)2(OH2)Cl2] (3, AQCYCU), for which no synthesis conditions were available. Compounds 2 and 4 were fully characterized via a combination of solid-state techniques, including X-ray diffraction, Raman spectroscopy and TGA.
KW - Mechanochemistry
KW - In situ
PY - 2022
DO - https://doi.org/10.1039/d1ce01670a
VL - 24
IS - 6
SP - 1292
EP - 1298
PB - RSC
AN - OPUS4-54344
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Cakir, Cafer Tufan
T1 - Scanning-Free Grazing Exit XANES Analysis of Stratified Samples and the Optimization of the Data Collection Process
N2 - The components that are used in structural and in high temperature applications generally face significant challenges with respect to oxidation behaviours and metalworking processes. In most of the cases, harsh environmental conditions lead materials to degrade due to corrosion. To thoroughly investigate the corrosion processes and to determine oxidation states of metal components within the reaction products, we need special analytical tools. Grazing exit X-ray fluorescence (GEXRF) offers a non-destructive way to collect this information in sub-micrometre depth range.
In order to obtain structural information, such as regarding oxidation states or atomic/molecular geometric arrangement, the GEXRF approach can also be combined with the X-ray absorption spectroscopy (XAS) method. The position and energy sensitive detector, with 264x264 pixel detector area, provides information regarding the signal emitted from the sample as a function of the emission angle and thus allows depth-sensitive analysis. Furthermore, the data collected from samples of an incidence energy which can be controlled with a resolution of 0.5 eV provides XANES data to determine oxidation states.
We address the feasibility of our setup and provide a new optimization procedure (Bayesian Optimization and Gaussian Regression) to decrease measuring time. The results settle on a conceptual study on a reference sample (Cr-Oxide layer (300nm) on Cr layer (500nm) on Si wafer).
T2 - Denver X-Ray Conference DXC 2022
CY - Washington D.C., USA
DA - 07.08.2022
KW - GEXRF
KW - High entropy alloys
KW - High entropy materials
KW - Optimization
KW - XANES
KW - Grazing exit
KW - XAS
PY - 2022
AN - OPUS4-56271
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Cakir, Cafer Tufan
T1 - High Speed for High Entropy Materials
N2 - Time is the most valuable parameter in synchrotron experiments. This is costly and some of the experiments suffer from low efficiency due to low counting statistics. With today's high processing power long experiments are run in a shorter time and increase efficiency. With optimization algorithms time in "counting-hungry" experiments reduced by factor of 10. Our project is to develop a new method to analyze the chemical properties of complex materials non-destructively and efficiently, such as high entropy materials subjected to corrosion processes. A better understanding of the corrosion process will help to develop corrosion-resistant materials and reduce the cost of corrosion damage, which averages around 2.5 trillion USD annually.
T2 - Berlin Science Week
CY - Berlin, Germany
DA - 01.11.2022
KW - GEXRF
KW - High entropy alloys
KW - XANES
KW - High entropy materials
KW - Grazing exit
KW - XAS
KW - Optimization
PY - 2022
AN - OPUS4-56269
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Cakir, Cafer Tufan
T1 - Optimization of Depth Resolved X-Ray Absorption Spectroscopy in Grazing Emission Mode for Characterizing Compositionally Complex Alloys
N2 - The components that are used in structural and in high temperature applications generally face significant challenges with respect to oxidation behaviours and metalworking processes. In most of the cases, harsh environmental conditions lead materials to degrade due to corrosion. To thoroughly investigate the corrosion processes and to determine oxidation states of metal components within the reaction products, we need special analytical tools. Grazing exit X-ray fluorescence (GEXRF) offers a non-destructive way to collect this information in sub-micrometre depth range.
In order to obtain structural information, such as regarding oxidation states or atomic/molecular geometric arrangement, the GEXRF approach can also be combined with the X-ray absorption spectroscopy (XAS) method. The position and energy sensitive detector, with 264x264 pixel detector area, provides information regarding the signal emitted from the sample as a function of the emission angle and thus allows depth-sensitive analysis. Furthermore, the data collected from samples of an incidence energy which can be controlled with a resolution of 0.5 eV provides XANES data to determine oxidation states.
We address the feasibility of our setup and provide a new optimization procedure (Bayesian Optimization and Gaussian Regression) to decrease measuring time. The results settle on a conceptual study on a reference sample (Cr-Oxide layer (300nm) on Cr layer (500nm) on Si wafer).
T2 - XAFS 2022, The 19th International XAFS Conference
CY - Sydney, Australia
DA - 10.07.2022
KW - GEXRF
KW - High entropy alloys
KW - XANES
KW - Grazing exit
KW - High entropy materials
KW - Optimization
KW - XAS
PY - 2022
AN - OPUS4-56270
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Radtke, Martin
T1 - Energy Resolved Imaging with Coded Apertures
N2 - Our aim is to develop a simple and inexpensive method for full field X-ray fluorescence imaging.We combine an energydispersive array detector with a coded aperture to obtain high resolut ion images. To obtain the information from the recorded image a reconstruction step is necessary. The reconstruction methods we have developed, were tested on simulated data and then applied to experimental data. The first tests were carried out at the BAMline @BESSY II. This method enables the simultaneous detection of multiple elements,which is important e.g. in the field of catalysis.
T2 - SRI 2021
CY - Online meeting
DA - 28.3.2022
KW - Synchrotron
KW - BAMline
KW - Machine Learning
KW - Coded Aperture
PY - 2022
AN - OPUS4-56298
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Heilmann, Maria
T1 - Size-Tunable Ni-Cu Core-Shell Nanoparticles: Structure, Composition, and Catalytic Activity
N2 - Nanoparticles (NPs) have become important materials for a variety of chemical technologies, including catalysis. One of the main challenges is the reduction of green house gases, such as CO2. One opportunity besides the capturing is the conversion to synthesis gas via the reverse water-gas shift reaction.
A facile and efficient method is described for the solvothermal synthesis of size-tunable, stable, and uniform NiCu core-shell NPs. The diameter of the NPs can be tuned in a range from 6 nm to 30 nm and the Ni:Cu ratio from 30:1 to 1:1. The NPs are structurally characterized with combination of transmission electron microscopy, anomalous small-angle X-ray scattering, X-ray photoelectron spectroscopy, and X-ray absorption fine structure. Using these analytical methods, a core-shell-shell structure their chemical composition is elucidated. A depletion from the core to the shell is observed, with the core consisting of NiCu alloy, surrounded by an inner Ni-rich shell and an outer NiO shell. The SiO2-supported NiCu core-shell NPs show pronounced selectivity of >99% for CO in the catalytic reduction of CO2 to CO using hydrogen as reactant (reverse water–gas shift reaction).
T2 - Nanoalloys: recent developments and future perspectives Faraday Discussion
CY - London, UK
DA - 21.09.2022
KW - Nanoparticles
KW - Core-shell
KW - Catalysis
PY - 2022
AN - OPUS4-56831
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Linberg, Kevin
T1 - Polymorphism in molecular cocrystals controlled by variable temperature ball milling
N2 - Mechanochemistry offers a unique opportunity to modify or synthesize new crystal forms. Although the method is very promising, little is known about the mechanochemical means to control the synthesis of a solid form. Using an polymorphic organic cocrystal system, we show here that mechanochemistry can be used to obtain a polymorph transformation under the apparently conventional (thermal) transition point.
T2 - Bessy User Meeting 2022
CY - Online meeting
DA - 08.12.2022
KW - Mechanochemistry
KW - Polymorphism
KW - TRIS
PY - 2022
AN - OPUS4-56473
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Dalgic, Mete-Sungur
T1 - Einfluss der Konformation auf das Ionisationsverhalten in MALDI-TOF MS
N2 - MALDI-TOF Massenspektrometrie ist eine wichtige Methode zur Bestimmung von Molekulargewichten von Polymeren. Jedoch wird die quantitative Analyse von Polymeren durch verschiedene Faktoren erschwert. In dieser Präsentation wird unter anderem der Einfluss der molaren Massen auf die Massenspektren näher betrachtet. Dabei werden Konturplots von ternären PMMA- und PS-Mischungen gezeigt.
T2 - 27. Kolloquium - Massenspetrometrische von Polymeren
CY - Berlin, Germany
DA - 09.05.2023
KW - MALDI-TOF MS
KW - Ternäre Polymermischungen
KW - PMMA und PS
PY - 2023
AN - OPUS4-62214
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - GEN
A1 - Pauw, Brian Richard
A1 - Röder, Bettina
A1 - Smales, Glen Jacob
T1 - High temperature in-vacuum flow-through sample holder (sandwich design version 1.1)
N2 - Technical drawings and documents for building a compact, heated, vacuum compatible flow-through sample holder. This holder is in use at the BAM MOUSE instrument as well as at the I22 beamline at the Diamond Light Source (see references for instrument details).
This holder has several features:
- The holder can be used in vacuum environments as well as in atmosphere
- It has two G 1/4" UNF fittings to attach HPLC tubing for (optionally) flowing a medium through the sample cell
- There are two additional (unflowed) sample positions for backgrounds and calibrants, held at the same temperature
- The low-mass design coupled with a 250W heating element can achieve heating rates of 1 degree C per second, when coupled (for example) with an Omron E5CC PID controller.
- The sample holder insert can be made from various materials depending on the application. Sealing the sample from the vacuum can be achieved using kapton, teflon or Magic tape, depending on the temperature requirements. The inlet and outlet holes will need to be punctured with a needle to enable flow.
- Large exit cones ensure a clear exit angle of at least 45 degrees two theta.
- It has been tested with temperatures up to 400 degrees C.
- Compression area has been raised and polished to ensure a good vacuum seal.
KW - SAXS
KW - X-ray scattering
KW - Sample cell
KW - Sample holder
KW - Heated
KW - Flow-through
KW - Vacuum compatible
KW - XRD
KW - WAXS
PY - 2023
DO - https://doi.org/10.5281/zenodo.7501030
PB - Zenodo
CY - Geneva
AN - OPUS4-56777
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Becker, Roland
A1 - Scholz, Philipp
A1 - Jung, Christian
A1 - Weidner, Steffen
T1 - Thermo-Desorption Gas Chromatography-Mass Spectrometry for investigating the thermal degradation of polyurethanes
N2 - Thermo-Desorption Gas Chromatography-Mass Spectrometry (TD-GC-MS) was used to investigate the thermal degradation of two different polyurethanes (PU). PU samples were heated at different heating rates and the desorbed products were collected in a cold injection system and thereafter submitted to GC-MS. Prospects and limitations of the detection and quantification of semi-volatile degradation products were investigated. A temperature dependent PU depolymerization was
found at temperatures above 200 °C proved by an increasing release of 1,4-butanediol and methylene diphenyl diisocyanate (MDI) representing the main building blocks of both polymers. Their release was monitored quantitatively based on external calibration with authentic compounds. Size Exclusion Chromatography (SEC) of the residues obtained after thermodesorption confirmed the initial competitive degradation mechanism indicating an equilibrium of crosslinking and depolymerization as previously suggested. Matrix-Assisted Laser Desorption Ionization (MALDI) mass spectrometry of SEC fractions of thermally degraded PUs provided additional hints on degradation mechanism.
KW - Thermo-desorption
KW - Mass spectrometry
KW - Polyurethanes
KW - Thermal degradation
PY - 2023
DO - https://doi.org/10.1039/D3AY00173C
SN - 1759-9660
SP - 1
EP - 6
PB - Royal Society for Chemistry
AN - OPUS4-57307
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Pollack, M.
T1 - Functionalized poly(ethylene glycol)s (PEGs) as a reference material for detection of polymeric end groups via SEC hyphenated with FTIR and 1H-NMR (80 MHz)
N2 - Benchtop 1H-NMR and FTIR have both been successfully developed for size-exclusion chromatography (SEC) applications. The latest implementations of these methods by Wilhelm and collaborators[1-3] have taken advantage of commerically available low-cost equipment, and a provide a means to obtain slice-by-slice spectra for the monitoring of functional groups in polymer separations. Demonstrated applications include the detection of highly diluted chains in a polymer blend (e.g., PS/PMMA), copolymer content determination (e.g., styrene-methyl methacrylate), and butadiene isomer detection. To synthesize and characterize an end-labelled low molecular wt. poly(ethylene glycol) as a model polymer to aid in the development and validation of spectroscopic detection (FTIR and 1H-NMR) for SEC applications. A particular focus is to improve quantitation and/or detection of highly diluted funtional groups (e.g., polymer chain ends or sparsely functionalized chains) In the first approach, an isocyanate with IR- and NMR-active functional groups was reacted with PEG (4000 and 10000 g/mol) to form end-functionalized chains by means of an addition reaction. The functionalization of the 10000 g/mol PEG was found to be non-homogeneous (not discussed further). The 4000 g/mol PEG was successfully functionalized to 100%, found to be homogeneous across the molecular weight distribution and could therefore serve as a model polymer for analysis by the coupled methods.
T2 - 10th International Symposium on the Separation and Charcterization of Natural and Synthetic Macromolecules
CY - Amsterdam, Netherlands
DA - 01.02.2023
KW - PEG
KW - Reference materials
KW - NMR
KW - MALDI-TOF MS
PY - 2023
AN - OPUS4-57071
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Nguyen, H. G.
A1 - Toman, B.
A1 - van Zee, R.
A1 - Prinz, Carsten
A1 - Thommes, M.
A1 - Ahmad, R.
A1 - Kiska, D.
A1 - Salinger, J.
A1 - Walton, I.
A1 - Walton, K.
A1 - Broom, D.
A1 - Benham, M.
A1 - Ansari, H.
A1 - Pini, R.
A1 - Petit, C.
A1 - Adolphs, J.
A1 - Schreiber, A.
A1 - Shigeoka, T.
A1 - Konishi, Y.
A1 - Nakai, K.
A1 - Henninger, M.
A1 - Petrzik, T.
A1 - Kececi, C.
A1 - Martis, V.
A1 - Paschke, T.
A1 - Mangano, E.
A1 - Brandani, S.
T1 - Reference isotherms for water vapor sorption on nanoporous carbon: results of an interlaboratory study
N2 - This paper reports the results of an international interlaboratory study sponsored by the Versailles Project on Advanced Materials and Standards (VAMAS) and led by the National Institute of Standards and Technology (NIST) on the measurement of water vapor sorption isotherms at 25 °C on a pelletized nanoporous carbon (BAM-P109, a certified reference material). Thirteen laboratories participated in the study and contributed nine pure water vapor isotherms and four relative humidity isotherms, using nitrogen as the carrier gas. From these data, reference isotherms, along with the 95% uncertainty interval (Uk=2), were determined and are reported in a tabular format.
KW - BAM-P109
KW - Interlaboratory study
KW - Nanoporous carbon
KW - Reference isotherm
KW - VAMAS
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-576560
DO - https://doi.org/10.1007/s10450-023-00383-1
SN - 0929-5607
SP - 1
EP - 12
PB - Springer
CY - Heidelberg
AN - OPUS4-57656
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Kossatz, Philipp
T1 - Upconversion Nanoparticles for Luminescent Barcodes and as Reporters for Optical Sensors
N2 - Counterfeiting of goods has serious economic implications worldwide and can be a threat to human health and safety. Upconversion nanoparticles (UCNPs)are ideal candidates for optical encoding of various materials. Particles with tailor-made emission patterns can be used as anti-counterfeiting markers and luminophores in security inks and to track material flows. Microenvironment-specific changes in the emission properties of the UCNP tags can be used to study, signal, and sense changes of physico-chemical parameters in different environments, e.g., building
materials.
T2 - ANAKON 2023
CY - Vienna, Austria
DA - 11.04.2023
KW - Nanomaterials
KW - Anti-Counterfeiting
KW - Fluorescence Spectroscopy
PY - 2023
AN - OPUS4-59035
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Kossatz, Philipp
T1 - Lanthanide Nanocrystals as Authentication and Security Tags and Reporters for Optical Sensors
N2 - Counterfeiting of goods has serious economic implications worldwide and can present a considerable threat to human health and national security, rendering product authentication more and more important. This led to an increasing interest in simple tags for anticounterfeiting and authentication applications for the integration into different materials and matrices that are robust enough to survive the respective production processes and can be read out in-situ with simple instrumentation.
Here we present a platform of chemically inert, multi-color luminescent lanthanide nanocrystals (LnNC) consisting of a NaYF4 matrix doped with Yb, Er, Tm, or Ho as promising candidates for such applications.
LnNC with characteristic multi-color emission patterns, composed of narrow bands of varying intensity in the ultraviolet, visible, near-infrared, and short-wave were synthesized via a thermal decomposition approach under inert conditions[1]. The tailor-made design of different emission pattern was achieved by tuning particle size, material composition, and particle surface chemistry in upscaleable syntheses.[2] Particle size and morphology were determined by dynamic light scattering and transmission electron microscopy and the optical properties were characterized by absorption and fluorescence spectroscopy as well as fluorescence lifetime measurements.
The particles were then incorporated into security inks and consumer products. In addition, microenvironment-specific changes in the emission properties of the LnNC tag were utilized to study and sense changes of physico-chemical parameters in different matrices.
T2 - JCF Frühjahrssymposium 2023
CY - Gießen, Germany
DA - 21.03.2023
KW - Lanthanide Nanocrystals
KW - Anti-Counterfeiting
KW - Fluorescence Spectroscopy
PY - 2023
AN - OPUS4-59037
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Chabbah, T.
A1 - Chatti, S.
A1 - Jaffrezic-Renault, N.
A1 - Weidner, Steffen
A1 - Marestin, C.
A1 - Mercier, R.
T1 - Impedimetric sensors based on diethylphosphonate-containingpoly(arylene ether nitrile)s films for the detection of lead ions
N2 - This article describes the elaboration and characterization of diethylphosphonate-containing polymers coated electrodes as sensors for the detection of heavy metalstraces, by electrochemical impedance spectroscopy. Diethylphosphonate groupswere chosen as heavy metals binding sites. Two different series of polymers bearingthese anchoring groups were synthesized. Whereas the diethylphosphonate groupsare directly incorporated in the aromatic macromolecular chain in some polymers, analiphatic spacer is removing the chelating site from the polymer backbone in others.The influence of the macromolecular structure on the sensing response was studied,especially for the detection of Pb2+,Ni2+,Cd2+and Hg2+. Polymer P6, including thehigher amount of diethylphosphonate groups removed from the polymer chain by ashort alkyl spacer gave the higher sensitivity of detection of lead ions, with a detec-tion limit of 50 pM
KW - Heavy metals
KW - Phosphonate esters
KW - Lead ions
KW - MALDI TOF MS
PY - 2023
DO - https://doi.org/10.1002/pat.6065
SN - 1042-7147
SP - 1
EP - 11
PB - John Wiley & Sons, Ltd
AN - OPUS4-57356
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Lisec, Jan
A1 - Recknagel, Sebastian
A1 - Prinz, Carsten
A1 - Vogel, Kristin
A1 - Koch, Matthias
A1 - Becker, Roland
T1 - eCerto—versatile software for interlaboratory data evaluation and documentation during reference material production
N2 - The statistical tool eCerto was developed for the evaluation of measurement data to assign property values and associated uncertainties of reference materials. The analysis is based on collaborative studies of expert laboratories and was implemented using the R software environment. Emphasis was put on comparability of eCerto with SoftCRM, a statistical tool based on the certification strategy of the former Community Bureau of Reference. Additionally, special attention was directed towards easy usability from data collection through processing, archiving, and reporting. While the effects of outlier removal can be flexibly explored, eCerto always retains the original data set and any manipulation such as outlier removal is (graphically and tabularly) documented adequately in the report. As a major reference materials producer, the Bundesanstalt für Materialforschung und -prüfung (BAM) developed and will maintain a tool to meet the needs of modern data processing, documentation requirements, and emerging fields of RM activity. The main features of eCerto are discussed using previously certified reference materials.
KW - Reference material
KW - Statistics
KW - Software
KW - Collaborative trial
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-591851
DO - https://doi.org/10.1007/s00216-023-05099-3
SP - 1
EP - 9
PB - Springer Science and Business Media LLC
AN - OPUS4-59185
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Kossatz, Philipp
T1 - Upconversion Nanoparticles as Luminescent Probes for Cement
N2 - Safety is a key parameter for the design and construction of buildings. The most widely used construction material to date is concrete that consists of about 15-20 wt.-% cement, which is responsible for the main concrete properties, i.e., strength and durability. Despite many standards regulating the quality of cement, at present, there exists no viable method to track the cement life cycle “from cradle to grave”. This led to an increasing interest in simple and robust methods for studying the processes and changes occurring during the life cycle of cement. In this context, we explored the applicability of fluorescence measurements which can be performed with relatively inexpensive and miniaturized instrumentation yet require robust optical probes which survive the harsh cement environment. Therefore, we developed a platform of lanthanide-based upconversion nanoparticles (UCNPs), consisting of a NaYF4 matrix doped with Yb3+ and Er3+ with sizes between 20 nm and 55 nm, which show characteristic multi-color emission patterns, composed of narrow bands of varying intensity in the ultraviolet, visible, near-infrared, and short-wave spectral region and examined their potential for cement probing and the non-invasive monitoring of the hydration processes occurring during cement formation.
UCNPs of different size and chemical composition were synthesized via a thermal decomposition approach under inert conditions. The tailor-made design of different emission patterns was achieved by tuning particle size and morphology, material composition, and particle surface chemistry in upscaleable syntheses. For cement probing, different types of UCNPs were added to cement and the evolution of the UCNP emission pattern was used to probe in-situ changes of physico-chemical parameters in the cementitious environment during hydration, utilizing a simple and portable custom-designed optical setup. The observed changes in the UCNP emission patterns are characteristic for a given particle size, surface chemistry, and cement composition. In addition to fluorescence measurements, conventional isothermal heat flow calorimetry was used to study the influence of UCNP addition on cement hydration kinetics. Subsequently, both sets of measurements were correlated. Our results underline the potential of our optical approach ad UCNPs for the non-invasive probing of cementitious systems and cement hydration. This can be also exploited for cutting-edge applications of construction materials such as 3D concrete printing.
T2 - Summer School Exciting Nanostructures
CY - Bad Honnef, Germany
DA - 31.07.2023
KW - Cement Hydration
KW - Upconversion
KW - Fluorescence Spectroscopy
PY - 2023
AN - OPUS4-58203
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - GEN
A1 - Radnik, Jörg
A1 - Chemello, Giovanni
A1 - Knigge, Xenia
A1 - Al-Sabbgh, Dominik
A1 - Hodoroaba, Vasile-Dan
T1 - XPS, HAXPES, XRD and SEM datasets of functionalized graphene nanoplateletes
N2 - The datasets from (Hard Energy) X-ray photoelectron spectroscopy, X-ray diffraction and Scanning Electron Microsopy are related to the publication
G. Chemello, X. Knigge, D. Ciornii, B.P. Reed, A.J. Pollard, C.A. Clifford, T. Howe, N. Vyas, V.-D. Hodoroaba, J. Radnik
"Influence of the morphology on the functionalization of graphene nanoplatelets analyzed by comparative photoelectron spectroscopy with soft and hard X-rays"
Advanced Materials Interfaces (2023), DOI: 10.1002/admi.202300116.
KW - Graphene related 2D materials
KW - X-ray photoelectron spectroscopy
KW - Hard-energy X-ray photoelectron spectroscopy
KW - Scanning electron microscopy
KW - Powder X-ray diffraction
PY - 2023
DO - https://doi.org/10.5281/zenodo.7956497
PB - Zenodo
CY - Geneva
AN - OPUS4-57898
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Guerra, M.F.
A1 - Neri, E.
A1 - Radtke, Martin
T1 - Gold leaf tesserae: tracing the origins of gold using synchrotron-based techniques
N2 - To gain insight into the possible origin of the gold used in the production of tesserae containing gold leaf less than 0.5 μm thick placed between two layers of glass, we propose a non-destructive synchrotron radiation (SR) XRF protocol based on sequential analysis under optimised analytical conditions. Using this protocol, trace element analysis is achieved with detection limits of 1–6 mg/kg. As Pt and Au have adjacent fluorescence energies, we tested the most challenging situation, when Pt is present in very low concentrations in gold. Data obtained by double-dispersive XRF (D2XRF) and μXRF for fourth–ninth-century mosaics decorating nine Eastern and Western religious buildings show that the Eastern and Western tesserae are made from different alloys.
However, these alloys are identical to those used to make gold leaf for gilding, because plastic deformation requires the use of gold alloys with high ductility and malleability. Although trace element composition of gold used in the concerned period is only available for coins, by comparing the amounts of Pt contained in the tesserae and in the coins we show that Roman tesserae are made from Roman gold, as described in the documentary sources. We observe for the Byzantine period the use of a Byzantine gold and of gold supposedly from different stages of recycling, and we suggest the use of Umayyad and Abbasid gold for the production of Islamic tesserae.
KW - Gold
KW - XRF
KW - Synchrotron
KW - BAMline
KW - D2XRF
KW - Tesserae
PY - 2023
DO - https://doi.org/10.1140/epjp/s13360-022-03638-y
SN - 2190-5444
VL - 138
IS - 2
SP - 1
EP - 15
AN - OPUS4-57208
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Radtke, Martin
T1 - Enhancing efficiency at bamline: employing data science and machine learning for x-ray research
N2 - This talk discusses how data science and machine learning techniques are being applied at the BAM Federal Institute for Materials Research and Testing to enhance efficiency and automation at the BAMLine synchrotron facility. The methods presented include Gaussian processes and Bayesian optimization for beamline adjustment and optimization of X-ray measurements. These statistical techniques allow automated alignment of beamline components and active learning scanning to reduce measurement time.
Additional machine learning methods covered are neural networks for quantification of X-ray fluorescence (XRF) data and decoding coded apertures.
T2 - 17th International Work-Conference on Artificial Neural Networks (IWANN2023)
CY - Ponta Delgada, Portugal
DA - 19.06.2023
KW - Bayesian Optimization
KW - Gaussian Process
KW - BAMline
PY - 2023
AN - OPUS4-58605
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Pauw, Brian Richard
A1 - Smales, Glen Jacob
A1 - Anker, A. S.
A1 - Annadurai, V.
A1 - Balazs, D. M.
A1 - Bienert, Ralf
A1 - Bouwman, W. G.
A1 - Breßler, Ingo
A1 - Breternitz, J.
A1 - Brok, E. S.
A1 - Bryant, G.
A1 - Clulow, A. J.
A1 - Crater, E. R.
A1 - De Geuser, F.
A1 - Del Giudice, A.
A1 - Deumer, J.
A1 - Disch, S.
A1 - Dutt, S.
A1 - Frank, K.
A1 - Fratini, E.
A1 - Garcia, P. R. A. F.
A1 - Gilbert, E. P.
A1 - Hahn, Marc Benjamin
A1 - Hallett, J.
A1 - Hohenschutz, M.
A1 - Hollamby, M.
A1 - Huband, S.
A1 - Ilavsky, J.
A1 - Jochum, J. K.
A1 - Juelsholt, M.
A1 - Mansel, B. W.
A1 - Penttilä, P.
A1 - Pittkowski, R. K.
A1 - Portale, G.
A1 - Pozzo, L. D.
A1 - Rochels, L.
A1 - Rosalie, Julian
A1 - Saloga, Patrick E. J.
A1 - Seibt, S.
A1 - Smith, A. J.
A1 - Smith, G. N.
A1 - Spiering, G. A.
A1 - Stawski, Tomasz M.
A1 - Taché, O.
A1 - Thünemann, Andreas
A1 - Toth, K.
A1 - Whitten, A. E.
A1 - Wuttke, J.
T1 - The human factor - Results of a small-angle scattering data analysis round robin
N2 - A round-robin study has been carried out to estimate the impact of the human element in small-angle scattering data analysis. Four corrected datasets were provided to participants ready for analysis. All datasets were measured on samples containing spherical scatterers, with two datasets in dilute dispersions and two from powders. Most of the 46 participants correctly identified the number of populations in the dilute dispersions, with half of the population mean entries within 1.5% and half of the population width entries within 40%. Due to the added complexity of the structure factor, far fewer people submitted answers on the powder datasets. For those that did, half of the entries for the means and widths were within 44 and 86%, respectively. This round-robin experiment highlights several causes for the discrepancies, for which solutions are proposed.
KW - Round Robin
KW - Data analysis
KW - Small-angle scattering
KW - Nanomaterials
KW - Interlaboratory comparability
KW - Nanostructure quantification
KW - Methodology
KW - MOUSE
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-587091
DO - https://doi.org/10.1107/S1600576723008324
SN - 1600-5767
VL - 56
IS - 6
SP - 1618
EP - 1629
PB - Wiley-Blackwell
CY - Oxford
AN - OPUS4-58709
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - INPR
A1 - Pauw, Brian Richard
A1 - Smales, Glen Jacob
A1 - Anker, A. S.
A1 - Balazs, D. M.
A1 - Beyer, F. L.
A1 - Bienert, Ralf
A1 - Bouwman, W. G.
A1 - Breßler, Ingo
A1 - Breternitz, J.
A1 - Brok, E. S.
A1 - Bryant, G.
A1 - Clulow, A. J.
A1 - Crater, E. R.
A1 - De Geuser, F.
A1 - Giudice, A. D.
A1 - Deumer, J.
A1 - Disch, S.
A1 - Dutt, S.
A1 - Frank, K.
A1 - Fratini, E.
A1 - Gilbert, E. P.
A1 - Hahn, Marc Benjamin
A1 - Hallett, J.
A1 - Hohenschutz, Max
A1 - Hollamby, M. J.
A1 - Huband, S.
A1 - Ilavsky, J.
A1 - Jochum, J. K.
A1 - Juelsholt, M.
A1 - Mansel, B. W.
A1 - Penttilä, P.
A1 - Pittkowski, R. K.
A1 - Portale, G.
A1 - Pozzo, L. D.
A1 - Ricardo de Abreu Furtado Garcia, P.
A1 - Rochels, L.
A1 - Rosalie, Julian
A1 - Saloga, P. E. J.
A1 - Seibt, S.
A1 - Smith, A. J.
A1 - Smith, G. N.
A1 - Annadurai, V.
A1 - Spiering, G. A.
A1 - Stawski, Tomasz
A1 - Taché, O.
A1 - Thünemann, Andreas
A1 - Toth, K.
A1 - Whitten, A. E.
A1 - Wuttke, J.
T1 - The human factor - Results of a small-angle scattering data analysis round robin
N2 - A Round Robin study has been carried out to estimate the impact of the human element in small-angle scattering data analysis. Four corrected datasets were provided to participants ready for analysis. All datasets were measured on samples containing spherical scatterers, with two datasets in dilute dispersions, and two from powders.
Most of the 46 participants correctly identified the number of populations in the dilute dispersions, with half of the population mean entries within 1.5 % and half of the population width entries within 40 %, respectively. Due to the added complexity of the structure factor, much fewer people submitted answers on the powder datasets.
For those that did, half of the entries for the means and widths were within 44 % and 86 % respectively. This Round Robin experiment highlights several causes for the discrepancies, for which solutions are proposed.
KW - Round robin
KW - Sall-angle scattering
KW - Nanostructure quantification
KW - Nanostructure
KW - SAXS
KW - MOUSE
KW - X-ray scattering
KW - Size distribution
KW - Nanoparticles
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-571342
DO - https://doi.org/10.48550/arXiv.2303.03772
SP - 1
EP - 23
PB - Cornell University
CY - Ithaca, NY
AN - OPUS4-57134
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Förste, F.
A1 - Bauer, L.
A1 - Streeck, C.
A1 - Radtke, Martin
A1 - Reinholz, Uwe
A1 - Kadow, D.
A1 - Keil, C.
A1 - Mantouvalou, I.
T1 - Quantitative Analysis and 2D/3D Elemental Imaging of Cocoa Beans Using X‑ray Fluorescence Techniques
N2 - As an important raw material for the confectionery industry, the cocoa bean (Theobroma cacao L.) has to meet certain legal requirements in terms of food safety and maximum contaminant levels in order to enter the cocoa market. Understanding the enrichment and distribution of essential minerals but also toxic metals is of utmost importance for improving the nutritional quality of this economically important raw food material. We present three X-ray fluorescence (XRF) techniques for elemental bio-imaging of intact cocoa beans and one additional XRF technique for quantitative analysis of cocoa pellets. The interrelation of all the methods presented gives a detailed picture of the content and 3D-resolved distribution of elements in complete cocoa beans for the first time.
KW - BAMline
KW - Synchrotron
KW - XRF
KW - CXC
KW - Cocoa
PY - 2023
DO - https://doi.org/10.1021/acs.analchem.2c05370
VL - 95
SP - 5627
EP - 5635
PB - ACS Publications
AN - OPUS4-57832
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CHAP
A1 - Radtke, Martin
A1 - Reinholz, Uwe
A1 - Guerra, M.F.
A1 - Martinón-Torres, M.
A1 - Lemasson, Q.
A1 - Moignard, B.
A1 - Pacheco, C.
A1 - Pichon, L.
A1 - Macdonald, L.
A1 - Hess, M.
A1 - Tissot, I.
ED - Guerra, M. F.
ED - Martinón-Torres, M.
ED - Quirke, S.
T1 - Analytical approaches to Egyptian goldwork
N2 - The structure and composition of ancient gold objects retain information about their long history of manufacture, from the exploitation of the ore to the finishing touches, as well as evidence of their use, deposition, and degradation. By developing an efficient analytical strategy, it is possible to retrieve that information. This chapter sets the necessary foundation 131to explore fully the analytical results presented in the following chapters of this volume. The techniques employed in the analyses of the Egyptian jewellery are described and the analytical parameters provided. For more established techniques, only brief introductions are presented, while more recent developments are presented in greater detail.
KW - Gold
KW - Synchrotron
KW - D2XRF
KW - Egypt
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-586039
DO - https://doi.org/10.17863/CAM.99681
SP - 131
EP - 191
AN - OPUS4-58603
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Tannenberg, Robert
A1 - Paul, Martin
A1 - Röder, Bettina
A1 - Gande, S. L.
A1 - Sreeramulu, S.
A1 - Saxena, K.
A1 - Richter, C.
A1 - Schwalbe, H.
A1 - Swart, C.
A1 - Weller, Michael G.
T1 - Chemiluminescence biosensor for the determination of cardiac troponin I (cTnI)
N2 - Cardiac troponin I (cTnI) is a crucial biomarker for diagnosing cardiac vascular diseases, including acute myocardial infarction (AMI). This study presents a proof-of-concept chemiluminescence-based immunosensor for rapid and accurate measurement of cTnI, with the potential for online monitoring. The immunosensor incorporates a flow cell design and a sensitive complementary metal-oxide-semiconductor (CMOS) camera for optical readout. A microfluidic setup was established to enable selective and quasi-online determination of cTnI within ten minutes. The sensor was tested with recombinant cTnI in phosphate buffer, demonstrating measurements in the concentration range of 2–25 µg/L, with a limit of detection (LoD) of 0.6 µg/L (23 pmol/L) achieved using the optimized system. The immunosensor exhibited high selectivity, as no cross-reactivity was observed with other recombinant proteins such as cTnT and cTnC at a concentration of 16 µg/L. Measurements with diluted blood plasma and serum yielded an LoD of 60 µg/L (2.4 nmol/L) and 70 µg/L (2.9 nmol/L), respectively. This biosensor offers a promising approach for the rapid and sensitive detection of cTnI, contributing to the diagnosis and management of acute myocardial infarction and other cardiac vascular diseases.
N2 - Das kardiale Troponin I (cTnI) ist ein wichtiger Biomarker für die Diagnose von Herz-Kreislauf-Erkrankungen, einschließlich des akuten Myokardinfarkts (AMI). In dieser Studie wird ein auf Chemilumineszenz basierender Immunsensor für die schnelle und genaue Messung von cTnI vorgestellt, der das Potenzial für eine Online-Überwachung hat. Der Immunsensor besteht aus einer Durchflusszelle und einer empfindlichen CMOS-Kamera (Complementary Metal-Oxide-Semiconductor) zur optischen Detektion. Es wurde ein mikrofluidischer Aufbau entwickelt, der eine selektive und quasi Online-Bestimmung von cTnI innerhalb von zehn Minuten ermöglicht. Der Sensor wurde mit rekombinantem cTnI in Phosphatpuffer getestet und zeigte einen Messbereich von 2-25 µg/L, wobei mit dem optimierten System eine Nachweisgrenze (LoD) von 0,6 µg/L (23 pmol/L) erreicht wurde. Der Immunsensor zeigte eine hohe Selektivität, da keine Kreuzreaktivität mit anderen rekombinanten Proteinen wie cTnT und cTnC bei einer Konzentration von 16 µg/L beobachtet wurde. Messungen mit verdünntem Blutplasma und Serum ergaben einen LoD von 60 µg/L (2,4 nmol/L) bzw. 70 µg/L (2,9 nmol/L). Dieser Biosensor bietet einen vielversprechenden Ansatz für den schnellen und empfindlichen Nachweis von cTnI, der zur Diagnose und Behandlung des akuten Myokardinfarkts und anderer kardialer Gefäßerkrankungen beitragen kann.
KW - Acute myocardial infarction
KW - Heart attack
KW - Emergency
KW - Diagnosis
KW - Cardiac troponin
KW - Biomarker
KW - Immunosensor
KW - Biosensor
KW - Chemiluminescence
KW - Luminol
KW - Peroxidase
KW - Monoclonal antibodies
KW - Flow injection immunoassay
KW - Immunometric assay
KW - Immunometric biosensor
KW - Microfluidic system
KW - Monolithic column
KW - Online biosensor
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-575471
DO - https://doi.org/10.3390/bios13040455
SN - 2079-6374
VL - 13
IS - 4
SP - 1
EP - 20
PB - MDPI
CY - Basel
AN - OPUS4-57547
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Peters, Stefan
A1 - Kunkel, Benny
A1 - Cakir, Cafer Tufan
A1 - Kabelitz, Anke
A1 - Witte, Steffen
A1 - Bernstein, Thomas
A1 - Bartling, Stephan
A1 - Radtke, Martin
A1 - Emmerling, Franziska
A1 - Abdel-Mageed, Ali Mohamed
A1 - Wohlrab, Sebastian
A1 - de Oliveira Guilherme Buzanich, Ana
T1 - Time-, space- and energy-resolved in situ characterization of catalysts by X-ray absorption spectroscopy
N2 - A novel setup for dispersive X-ray absorption spectroscopy (XAS) with simultaneous resolution of space, time and energy for in situ characterization of solid materials is demonstrated.
KW - Dispersive XAS
KW - Catalysis
KW - In situ
KW - Structure analysis
PY - 2023
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-584924
DO - https://doi.org/10.1039/d3cc03277a
SN - 1359-7345
SP - 1
EP - 4
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-58492
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Radtke, Martin
A1 - Yusenko, Kirill
A1 - Stawski, Tomasz
A1 - Kulow, Anicó
A1 - Cakir, Cafer Tufan
A1 - Röder, Bettina
A1 - Naese, Christoph
A1 - Britzke, Ralf
A1 - Sintschuk, Michael
A1 - Emmerling, Franziska
T1 - BAMline - A real-life sample materials research beamline
N2 - With increasing demand and environmental concerns, researchers are exploring new materials that can perform as well or better than traditional materials while reducing environmental impact. The BAMline, a real-life sample materials research beamline, provides unique insights into materials’ electronic and chemical structure at different time and length scales. The beamline specializes in x-ray absorption spectroscopy, x-ray fluorescence spectroscopy, and tomography experiments. This enables real-time optimization of material properties and performance for various applications, such as energy transfer, energy storage, catalysis, and corrosion resistance. This paper gives an overview of the analytical methods and sample environments of the BAMline, which cover non-destructive testing experiments in materials science, chemistry, biology, medicine, and cultural heritage. We also present our own synthesis methods, processes, and equipment developed specifically for the BAMline, and we give examples of synthesized materials and their potential applications. Finally, this article discusses the future perspectives of the BAMline and its potential for further advances in sustainable materials research.
KW - Extended X-ray absorption fine structure
KW - Energy storage
KW - Environmental impacts
KW - Nondestructive testing techniques
KW - X-ray fluorescence spectroscopy
KW - Corrosion
KW - Near edge X-ray absorption fine structure spectroscopy
KW - X-ray absorption spectroscopy
PY - 2023
DO - https://doi.org/10.1063/5.0157194
VL - 158
IS - 24
SP - 1
EP - 22
PB - AIP Publishing
AN - OPUS4-57824
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Karafiludis, Stephanos
A1 - Kochovski, Z.
A1 - Scoppola, E.
A1 - Retzmann, Anika
A1 - Hodoroaba, Vasile-Dan
A1 - ten Elshof, J. E.
A1 - Emmerling, Franziska
A1 - Stawski, Tomasz Maciej
T1 - Nonclassical Crystallization Pathway of Transition Metal Phosphate Compounds
N2 - Here, we elucidate nonclassical multistep crystallization pathways of transition metal phosphates from aqueous solutions. We followed precipitation processes of M-struvites, NH4MPO4·6H2O, and M-phosphate octahydrates, M3(PO4)2·8H2O, where M = Ni, Co, or NixCo1–x, by using in situ scattering and spectroscopy-based techniques, supported by elemental mass spectrometry analyses and advanced electron microscopy. Ni and Co phosphates crystallize via intermediate colloidal amorphous nanophases, which change their complex structures while agglomerating, condensing, and densifying throughout the extended reaction times. We reconstructed the three-dimensional morphology of these precursors by employing cryo-electron tomography (cryo-ET). We found that the complex interplay between metastable amorphous colloids and protocrystalline units determines the reaction pathways. Ultimately, the same crystalline structure, such as struvite, is formed. However, the multistep process stages vary in complexity and can last from a few minutes to several hours depending on the selected transition metal(s), their concentration, and the Ni/Co ratio.
KW - Non-classical crystallization theory
KW - Transition metals
KW - Phosphates
KW - Amorphous phases
KW - Intermediate phases
PY - 2023
DO - https://doi.org/10.1021/acs.chemmater.3c02346
SN - 1520-5002
VL - 35
IS - 24
SP - 10645
EP - 10657
PB - American Chemical Society (ACS)
CY - Washington D.C.
AN - OPUS4-59135
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Cakir, Cafer Tufan
A1 - Piotrowiak, T.
A1 - Reinholz, Uwe
A1 - Ludwig, A.
A1 - Emmerling, Franziska
A1 - Streli, C.
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Radtke, Martin
T1 - Exploring the Depths of Corrosion: A Novel GE-XANES Technique for Investigating Compositionally Complex Alloys
N2 - In this study, we propose the use of nondestructive, depth-resolved, element-specific characterization using grazing exit X-ray absorption near-edge structure spectroscopy (GE-XANES) to investigate the corrosion process in compositionally complex alloys (CCAs). By combining grazing exit X-ray fluorescence spectroscopy (GE-XRF) geometry and a pnCCD detector, we provide a scanning-free, nondestructive, depth-resolved analysis in a sub-micrometer depth range, which is especially relevant for layered materials, such as corroded CCAs. Our setup allows for spatial and energy-resolved measurements and directly extracts the desired fluorescence line, free from scattering events and other overlapping lines. We demonstrate the potential of our approach on a compositionally complex CrCoNi alloy and a layered reference sample with known composition and specific layer thickness. Our findings indicate that this new GE-XANES approach has exciting opportunities for studying surface catalysis and corrosion processes in real-world materials.
KW - Degradation mechanisms
KW - Grazin exit XANES
KW - Depth resolved XANES
KW - Compositional complex alloys
KW - Corrosion
PY - 2023
DO - https://doi.org/10.1021/acs.analchem.3c00404
VL - 95
SP - 4810
EP - 4818
PB - ACS Publications
AN - OPUS4-57823
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - GEN
A1 - Prinz, Carsten
A1 - Zimathies, Annett
A1 - Emmerling, Franziska
T1 - Experimantal raw data sets associated with certified reference material BAM-P116 (titanium dioxide) for comparison of nitrogen and argon sorption, available in the universal adsorption information format (AIF)
N2 - These data sets serve as models for calculating the specific surface area (BET method) using gas sorption in accordance with ISO 9277.
The present measurements were carried out with nitrogen at 77 Kelvin and argon at 87 Kelvin.
It is recommended to use the following requirements for the molecular cross-sectional area:
Nitrogen: 0.1620 nm²
Argon: 0.1420 nm²
Titanium dioxides certified with nitrogen sorption and additionally measured with argon for research purposes were used as sample material.
The resulting data sets are intended to serve as comparative data for own measurements and show the differences in sorption behaviour and evaluations between nitrogen and argon.
These data are stored in the universal AIF format (adsorption information file), which allows flexible use of the data.
KW - Physisorption
KW - Surface area
KW - AIF
KW - Argon
KW - Nitrogen
PY - 2023
DO - https://doi.org/10.5281/zenodo.10199628
PB - Zenodo
CY - Geneva
AN - OPUS4-59102
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Somasundaram, S. K.
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Emmerling, Franziska
A1 - Krishnan, S.
A1 - Senthilkumar, K.
A1 - Joseyphus, R.J.
T1 - New insights into pertinent Fe-complexes for the synthesis of iron via the instant polyol process
N2 - Chemically synthesized iron is in demand for biomedical applications due to its large saturation magnetization compared to iron oxides. The polyol process, suitable for obtaining Co and Ni particles and their alloys, is laborious in synthesizing Fe. The reaction yields iron oxides, and the reaction pathway remains unexplored. This study shows that a vicinal polyol, such as 1,2-propanediol, is suitable for obtaining Fe rather than 1,3-propanediol owing to the formation of a reducible Fe intermediate complex. X-ray absorption spectroscopy analysis reveals the ferric octahedral geometry and tetrahedral geometry in the ferrous state of the reaction intermediates in 1,2-propanediol and 1,3-propanediol, respectively. The final product obtained using a vicinal polyol is Fe with a γ-Fe2O3 shell, while the terminal polyol is favourable for Fe3O4. The distinct Fe–Fe and Fe–O bond lengths suggest the presence of a carboxylate group and a terminal alkoxide ligand in the intermediate of 1,2-propanediol. A large Fe–Fe bond distance suggests diiron complexes with bidentate carboxylate bridges. Prominent high-spin and low-spin states indicate the possibility of transition, which favors the reduction of iron ions in the reaction using 1,2-propanediol.
KW - XAS
KW - Nanoparticle
PY - 2023
DO - https://doi.org/10.1039/D3CP01969A
SN - 1463-9076
VL - 25
IS - 33
SP - 21970
EP - 21980
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-58073
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Gugin, Nikita
A1 - Villajos Collado, José Antonio
A1 - Dautain, O.
A1 - Maiwald, Michael
A1 - Emmerling, Franziska
T1 - Optimizing the Green Synthesis of ZIF-8 by Reactive Extrusion Using In Situ Raman Spectroscopy
N2 - We report the scale-up of a batch solid synthesis of zeolitic imidazolate framework-8 (ZIF-8) for reactive extrusion. The crystalline product forms in the extruder directly under the mixture of solid 2-methylimidazole and basic zinc carbonate in the presence of a catalytic amount of liquid. The process parameters such as temperature, liquid type, feeding rate, and linker excess were optimized using the setup specifically designed for in situ Raman spectroscopy. Highly crystalline ZIF-8 with a Brunauer–Emmett–Teller (BET) surface area of 1816 m2 g–1 was quantitatively prepared at mild temperature using a catalytic amount of ethanol and a small excess of the linker. Finally, we developed a simple and comprehensive approach to evaluating the environmental friendliness and scalability of metal–organic framework (MOF) syntheses in view of their large-scale production.
KW - Mechanochemistry
KW - In situ Raman
KW - Large-scale processing
KW - Metal−organic frameworks
KW - Twin-screw extrusion (TSE)
PY - 2023
DO - https://doi.org/10.1021/acssuschemeng.2c07509
SN - 2168-0485
VL - 11
IS - 13
SP - 5175
EP - 5183
PB - ACS Publications
AN - OPUS4-57366
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Radtke, Martin
T1 - Insights into materials with hard x-rays: capabilities of the bamline
N2 - This contribution provides an overview of the BAMline synchrotron radiation beamline, which specializes in hard X-ray spectroscopy techniques for materials research. The BAMline offers X-ray absorption spectroscopy (XAS), x-ray fluorescence spectroscopy (XRF), and tomography to study materials' electronic structure, chemical composition, and structure. Key capabilities include standard and dispersive XAS for electronic structure, micro-XRF for elemental mapping, coded aperture imaging, and depth-resolved grazing exit XAS. The BAMline enables in situ characterization during materials synthesis and functions for energy, catalysis, corrosion, biology, and cultural heritage applications.
Ongoing developments like the implementation of machine learning techniques for experiment optimization and data analysis will be discussed. For instance, Bayesian optimization is being used to improve beamline alignment and scanning. An outlook to the future, where the BAMline will continue pioneering dynamic and multi-scale characterization, aided by advanced data science methods, to provide unique insights into materials research, will be given.
T2 - μ-XRF at Elettra 2.0: challenges and opportunities
CY - Trieste, Italy
DA - 11.09.2023
KW - Synchrotron
KW - XRF
KW - XANES
KW - Bayes
PY - 2023
AN - OPUS4-58607
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Dalgic, Mete-Sungur
T1 - Lösemittelfreie Probenpräparation zur Untersuchung von Polymerblends mittels MALDI-TOF MS
N2 - Die Probenpräparation ist ein wichtiger Schritt für die Qualität der Massenspektren in MALDI-TOF MS. Es werden Polymerproben, die lösungsmittelbasiert und lösungsmittelfrei präpariert worden sind, verglichen. Dabei werden die Intensitätsverhältnisse von ternären Mischungen von PEG-, PS- und PMMA-Polymeren beachtet.
T2 - 28. Kolloquium - Massenspektrometrische Techniken zur Untersuchung synthetischer Polymere
CY - Berlin, Germany
DA - 14.05.2024
KW - Polymere
KW - Massenspektrometrie
KW - Probenpräparation
PY - 2024
AN - OPUS4-60032
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Cakir, Cafer Tufan
T1 - Enhancing the Efficiency and Accessibility of Grazing Exit X-ray Absorption Spectroscopy for Corrosion and Layered Materials Analysis
N2 - In the field of materials science, there is a critical need for efficient and effective characterization techniques, especially in the investigation of corrosion processes of compositionally complex alloys (CCAs) or the analysis of layered structures. This talk presents an advanced approach that combines grazing-exit X-ray absorption near-edge structure spectroscopy (GE-XANES) with Bayesian optimization (BO) to significantly improve the efficiency of data acquisition while retaining the depth-resolved, element-specific analysis capabilities that are critical for studying these materials under ambient conditions. Using a non-destructive, scan-free GE-XANES setup coupled with a pnCCD detector and grazing exit X-ray fluorescence spectroscopy (GE-XRF) geometry, our method enables precise analysis at sub-micrometer depths without the need for high vacuum environments or extensive sample preparation. The integration of BO reduces experimental time by a factor of 50, overcoming the practical limitations of conventional GE-XANES and increasing its applicability in the study of surface catalysis and corrosion processes. We validate this optimized approach through comparative studies on a CrCoNi alloy and a reference layered sample, demonstrating its potential to revolutionize materials analysis by increasing both efficiency and accessibility.
T2 - Gesellschaft Deutscher Chemiker (GDCh)
CY - Clausthal-Zellerfeld, Germany
DA - 20.06.2024
KW - GEXRF
KW - GEXANE
KW - ML
PY - 2024
AN - OPUS4-61788
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Weidner, Steffen
A1 - Meyer, A.
A1 - Kricheldorf, H.
T1 - Transformation of poly(L-lactide) crystals composed of linear chains into crystals composed of cycles
N2 - A poly(L-lactide) with a trifluoroethyl ester end group and an average degree of polymerization (DP) of 50 was synthesized by ROP of L-lactide initiated with trifluoroethanol. Small-angle X-ray scattering (SAXS) in combination with differential scanning calorimetry (DSC) measurements revealed an average crystal thickness of 13 nm, corresponding to 45 repeat units. This suggests that most crystallites were formed by extended PLA chains, and both flat surfaces were covered by CF3 groups. The crystalline PLAs were annealed at 140 or 160 °C in the presence of two catalysts: tin(II) 2-ethylhexanoate, (SnOct2) or dibutyltin bis(pentafluorophenoxide) (BuSnPhF). The chemical reactions, such as polycondensation and cyclization, proceeded in the solid state and were monitored by matrix-assisted laser desorption/ionization time-offlight (MALDI TOF) mass spectrometry and gel permeation chromatography (GPC) measurements. Under optimal conditions a large fraction of linear chains was transformed into crystallites composed of extended cycles. Additionally, MALDI TOF MS analysis of GPC fractions from samples annealed for 28 or 42 days detected chain elongation of the linear species up to a factor of 20.
KW - Polylactide
KW - MALDI-TOF MS
KW - Crystalinity
KW - Transesterification
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597250
DO - https://doi.org/10.1039/D3PY01370G
SN - 1759-9954
VL - 15
IS - 12
SP - 1173
EP - 1181
PB - Royal Society for Chemistry
AN - OPUS4-59725
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kricheldorf, H.
A1 - Weidner, Steffen
A1 - Meyer, A.
T1 - About alcohol-initiated polymerization of glycolide and separate crystallization of cyclic and linear polyglycolides
N2 - Alcohol-initiated polymerizations of glycolide (GL) catalyzed by tin(II) 2-ethylhexanoate (SnOct2) were carried out in bulk with variation of GA/In ratio, temperature and time. Due to a rather strong competition of cyclization polyglycolide (PGA) free of cycles were never obtained. When the cyclic catalysts 2,2-dibutal-2-stanna − 1,3-dithiolane (DSTL) or 2-stanna 1,3-dioxo-4,5,6,7 bibenzepane (SnBiph) were used in combination with 1,4-butanediol the influence of cyclization was even stronger. Furthermore, the degrees of polymerization were higher than the GA/alcohol ratio due to rapid polycondensation in the solid state. At 160 °C or below, the matrixassisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectra indicated separate crystallization of low molar mass cyclic and linear PGAs from the same reaction mixture (also observed for poly(L-lactide)s).
KW - MALDI TOF MS
KW - Polyglycolide
KW - Ring opening polymerization
KW - Cyclization
KW - Crystallization
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-607282
DO - https://doi.org/10.1016/j.polymer.2024.127440
SN - 0032-3861
VL - 309
SP - 1
EP - 9
PB - Elsevier Ltd.
AN - OPUS4-60728
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Weidner, Steffen
A1 - Scheliga, Felix
A1 - Kricheldorf, Hans R.
T1 - Polycondensation, Cyclization and Disproportionation of Solid Poly(L-lactide) Trifluoroethyl Esters and the Simultaneous Formation of Extended Chain Crystals and Extended Ring Crystals
N2 - Two poly(L-lactide)s (PLAs) with a degree of polymerization (DP) of 20 or 100 were prepared by trifluoroethanol-initiated ring-opening polymerization (ROP) catalyzed by tin(II) 2-ethyl hexanoate (SnOct2). These PLAs were annealed at 140 ◦C or at 160 ◦C in the presence of SnOct2, and the changes in topology and molecular weight distribution (MWD) were monitored by matrix-assisted laser desorption/ionization time-of flight (MALDI TOF) mass spectrometry and gel permeation chromatography (GPC). For the PLA with a DP 20, the main reaction was polycondensation combined with higher dispersities. In the case of the DP 100, PLA polycondensation was combined with disproportionation and the formation of a new MWD maximum around m/z 3500. In addition, extensive cyclization occurred, and the resulting cyclic PLAs crystallized separately from the linear chains in the form of extended ring crystals. These results also suggest that both extended chain and extended ring crystals posses the same crystal thickness as a result of thermodynamically controlled transesterification in the solid state.
KW - Polycondensation
KW - MALDI
KW - Polylactide
KW - Cyclization
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-616441
DO - https://doi.org/10.1016/j.polymer.2024.127800
VL - 315
SP - 1
EP - 9
PB - Elsevier Ltd.
AN - OPUS4-61644
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kricheldorf, Hans R.
A1 - Weidner, Steffen
A1 - Meyer, A.
T1 - About Polycondensation, Disproportionation, and Cyclization of Acetylated Poly(L-Lactide) Esters
N2 - L-lactide (LA) is polymerized with ethyl L-lactate or trifluoroethanol as initiators (LA/In = 30/1), and the resulting poly(L-lactide) esters are acetylated with acetic anhydride. The acetylated PLA esters are mixed with SnOct2, dibutyltin bis(4-chlorophenoxide), or dibutyltin bis(pentafluorophenoxide) in solution and crystallized at 120 °C. The doped crystals are annealed at 140 °C or at 160 °C for 7, 14, and 28 days, and the chemical modifications that occurred in the solid state are monitored by matrix-assisted laser desorption/ionization time-of-flight (MALDI TOF) mass spectrometry, gel permeation chromatography (GPC), and differential scanning calorimetry (DSC) measurements. All catalysts promoted polycondensation, while no significant formation of cycles is observed. However, in the presence of SnOct2, disproportionation of chains occurred upon annealing at 120 or 140 °C, and crystallites consisting of extended chains with Mn values ≈3500 – 3600 and low dispersities (Ð < 1.5) are formed.
KW - MALDI-TOF MS
KW - Polycondensation
KW - Polylactides
KW - Transesterifcation
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-630349
DO - https://doi.org/10.1002/macp.202400175
SN - 1521-3935
VL - 225
IS - 19
PB - Wiley VHC-Verlag
AN - OPUS4-63034
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Trimpin, Sarah
A1 - Yenchick, Frank S.
A1 - Lee, Chuping
A1 - Hoang, Khoa
A1 - Pophristic, Milan
A1 - Karki, Santosh
A1 - Marshall, Darrell D.
A1 - Lu, I-Chung
A1 - Lutomski, Corinne A.
A1 - El-Baba, Tarick J.
A1 - Wang, Beixi
A1 - Pagnotti, Vincent S.
A1 - Meher, Anil K.
A1 - Chakrabarty, Shubhashis
A1 - Imperial, Lorelei F.
A1 - Madarshahian, Sara
A1 - Richards, Alicia L.
A1 - Lietz, Christopher B.
A1 - Moreno-Pedraza, Abigail
A1 - Leach, Samantha M.
A1 - Gibson, Stephen C.
A1 - Elia, Efstathios A.
A1 - Thawoos, Shameemah M.
A1 - Woodall, Daniel W.
A1 - Jarois, Dean R.
A1 - Davis, Eric T.J.
A1 - Liao, Guochao
A1 - Muthunayake, Nisansala S.
A1 - Redding, McKenna J.
A1 - Reynolds, Christian A.
A1 - Anthony, Thilani M.
A1 - Vithanarachchi, Sashiprabha M.
A1 - DeMent, Paul
A1 - Adewale, Adeleye O.
A1 - Yan, Lu
A1 - Wager-Miller, James
A1 - Ahn, Young-Hoon
A1 - Sanderson, Thomas H.
A1 - Przyklenk, Karin
A1 - Greenberg, Miriam L.
A1 - Suits, Arthur G.
A1 - Allen, Matthew J.
A1 - Narayan, Srinivas B.
A1 - Caruso, Joseph A.
A1 - Stemmer, Paul M.
A1 - Nguyen, Hien M.
A1 - Weidner, Steffen
A1 - Rackers, Kevin J.
A1 - Djuric, Ana
A1 - Shulaev, Vladimir
A1 - Hendrickson, Tamara L.
A1 - Chow, Christine S.
A1 - Pflum, Mary Kay H.
A1 - Grayson, Scott M.
A1 - Lobodin, Vladislav V.
A1 - Guo, Zhongwu
A1 - Ni, Chi-Kung
A1 - Walker, J. Michael
A1 - Mackie, Ken
A1 - Inutan, Ellen D.
A1 - McEwen, Charles N.
T1 - New Processes for Ionizing Nonvolatile Compounds in Mass Spectrometry: The Road of Discovery to Current State-of-the-Art
N2 - This Perspective covers discovery and mechanistic aspects aswell as initial applications of novel ionization processes for use in massspectrometry that guided us in a series of subsequent discoveries, instrumentdevelopments, and commercialization. Vacuum matrix-assisted ionization onan intermediate pressure matrix-assisted laser desorption/ionization sourcewithout the use of a laser, high voltages, or any other added energy wassimply unbelievable, at first. Individually and as a whole, the variousdiscoveries and inventions started to paint, inter alia, an exciting new pictureand outlook in mass spectrometry from which key developments grew thatwere at the time unimaginable, and continue to surprise us in its simplisticpreeminence. We, and others, have demonstrated exceptional analyticalutility. Our current research is focused on how best to understand, improve, and use these novel ionization processes throughdedicated platforms and source developments. These ionization processes convert volatile and nonvolatile compounds from solid orliquid matrixes into gas-phase ions for analysis by mass spectrometry using, e.g., mass-selected fragmentation and ion mobilityspectrometry to provide accurate, and sometimes improved, mass and drift time resolution. The combination of research anddiscoveries demonstrated multiple advantages of the new ionization processes and established the basis of the successes that lead tothe Biemann Medal and this Perspective. How the new ionization processes relate to traditional ionization is also presented, as wellas how these technologies can be utilized in tandem through instrument modification and implementation to increase coverage ofcomplex materials through complementary strengths.
KW - Mass spectrometry
PY - 2024
DO - https://doi.org/10.1021/jasms.3c00122
SN - 1879-1123
VL - 35
IS - 12
SP - 2753
EP - 2784
PB - American Chemical Society (ACS)
AN - OPUS4-61417
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Dalgic, Mete-Sungur
A1 - Weidner, Steffen
T1 - Solvent-free sample preparation for matrix-assisted laserdesorption/ionization time-of-flight mass spectrometry ofpolymer blends
N2 - Solvent-free sample preparation offers some advantages over solvent-based techniques, such as improved accuracy, reproducibility and sensitivity, for matrix-assisted laser desorption/ionization (MALDI) analysis. However, little or no information is available on the application of solvent-free techniques for the MALDI analysis of polymer blends. Solvent-free sample preparation by ball milling was applied with varying sample-to-matrix ratios for MALDI time-of-flight mass spectrometry analysis of various polymers, including polystyrenes, poly(methyl methacrylate)s and poly(ethylene glycol)s. The peak intensity ratios were compared with those obtained after using the conventional dried droplet sample preparation method. In addition, solvent-assisted milling was also applied to improve sample homogeneities.
Depending on the sample preparation method used, different peak intensity ratios were found, showing varying degrees of suppression of the signal intensities of higher mass polymers. Ball milling for up to 30 min was required to achieve constant intensity ratios indicating homogeneous mixtures. The use of wet-assisted grinding to improve the homogeneity of the blends was found to be disadvantageous as it caused partial degradation and mass-dependent segregation of the polymers in the vials.The results clearly show that solvent-free sample preparation must be carefully considered when applied to synthetic polymer blends, as it may cause additional problems with regard to homogeneity and stability of the blends.
KW - MALDI TOF MS
KW - Sample preparation
KW - Polymer blends
KW - Solvent-free
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-598570
DO - https://doi.org/10.1002/rcm.9756
SN - 0951-4198
VL - 38
IS - 12
SP - 1
EP - 9
PB - Wiley online library
AN - OPUS4-59857
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Grimmer, Christoph
A1 - Richter, Matthias
A1 - Neuhaus, T.
A1 - Prinz, Carsten
A1 - Strzelczyk, Rebecca Skadi
A1 - Colakoglu, Irem
A1 - Horn, Wolfgang
T1 - Towards a multi-VOC emission reference material with temporally constant emission profile for QA/QC of materials emission testing procedures
N2 - Emission reference materials (ERMs) are sought after to further control and improve indoor air quality. The impregnation of porous materials with volatile organic compounds (VOCs) is a promising approach to produce ERMs. Different VOCs were used to impregnate various porous materials (mainly zeolites, activated carbons and a metal organic framework). The influence of different methodological parameters and material properties were studied to optimize the impregnation procedure and to find the best material/VOC combination. The impregnation procedure remains quite irreproducible, nevertheless, very good ERM candidates were identified. Two materials (zeolite 4 and AC 1 impregnated with n-hexadecane) showed a very stable emission over 14 days (<10 % change). Another material (AC 1 impregnated with toluene) showed a declining emission profile but with a very good in-batch reproducibility and a storage stability of up to 12 months.
KW - Emission reference material
KW - Porous materials
KW - Indoor air quality
KW - Emission test chamber
KW - CO2 assisted impregnation
KW - EN 16516
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-612238
DO - https://doi.org/10.1016/j.chemosphere.2024.143437
SN - 1879-1298
VL - 366
SP - 1
EP - 8
PB - Elsevier
AN - OPUS4-61223
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Valentim Gelamo, Rogério
A1 - Bueno Leite, Natália
A1 - de Sousa Amadeu, Nader
A1 - Reis Pedreira Muniz Tavares, Michel
A1 - Oberschmidt, Dirk
A1 - Klemm, Sophie
A1 - Fleck, Claudia
A1 - Cakir, Cafer-Tufan
A1 - Radtke, Martin
A1 - Aparecido Moreto, Jéferson
T1 - Exploring the Nb2O5 coating deposited on the Ti-6Al-4V alloy by a novel GE-XANES technique and nanoindentation load-depth
N2 - This research group has been demonstrating the significant advantages of using Nb2O5 coatings for functionalizing titanium, aluminium, and stainless steels. Regarding the biomedical sector and considering Ti-6Al-4V alloy, the reactive sputtering technique improved the cell viability, the osteogenic performance of cells involved in the osseointegration process as well as the ability to delay bacterial proliferation. The characteristics of the Nb2O5 coatings were assessed before by using standard methods, which provide information only a few tens of nanometers depth. Given that the Nb2O5 coating fabricated in this work exhibits a thickness of approximately 300 nm, the GE-XANES technique emerges as the most suitable method for this analysis. Additional information was provided with the aid of nanoindentation load-depth (P-h) curves. GE-XANES results indicated the formation of a homogeneous layer of Nb2O5 coating on the Ti-6Al-4V surfaces. The deposition process improved the surface hardness of the Ti-6Al-4V alloy (4.38 GPa versus 5.62 GPa) considering the 2 mN load.
KW - BAMline
KW - GE-XANES
KW - Synchrotron
PY - 2024
DO - https://doi.org/10.1016/j.matlet.2023.135584
SN - 0167-577X
VL - 355
SP - 1
EP - 4
PB - Elsevier B.V.
AN - OPUS4-60835
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Radtke, Martin
T1 - ChatGPT and EPICS: LLM-Enhanced Control Systems for Synchrotron Beamlines
N2 - The document highlights ChatGPT-EPICS integration for synchrotron beamline automation, employing tools like motor records, PV naming systems, and LLM inference. It evaluates efficiency and challenges in implementing automated motor optimization and handling EPICS controls.
T2 - BESSY science seminar
CY - Online meeting
DA - 22.11.2024
KW - Chatgpt
KW - EPICS
KW - BAMline
PY - 2024
AN - OPUS4-61896
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Radtke, Martin
T1 - From Egypt to Hiddensee – Analysis of Gold with Synchrotron Radiation V
N2 - Gold is one of the seven metals already known in antiquity and was used from time immemorial as a medium of exchange and for the production of jewelry because of its luster and rarity. In addition, it is easy to work and largely resistant to chemical influences. Investigations of gold using synchrotron radiation excited X-ray fluorescence analysis are non-destructive and provide information about the chemical elements present in the sample under investigation. The investigations presented here at BAMline focus on questions such as the origin, manufacturing process, and association of gold findings. The different questions are explained by a number of examples ranging from the Viking treasure from Hiddensee to the Nebra Sky Disk and finds from Egypt. The find from Bernstorf is discussed in detail. A Bayesian treatment of the authenticity is shown.
T2 - Ringvorlesung Einführung in die Archäometrie
CY - Berlin, Germany
DA - 01.11.2024
KW - Gold
KW - Synchrotron
KW - XRF
KW - BAMline
KW - Bayes
PY - 2024
AN - OPUS4-61699
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Radtke, Martin
T1 - Decoding the Elemental Fingerprints of Ancient Gold: A Synchrotron-based Approach
N2 - This contribution focuses on the application of synchrotron radiation X-ray fluorescence (SR XRF) for the analysis of ancient gold objects at the BAMline, showcasing several noteworthy examples. One prominent artifact is the Sky Disc of Nebra, which presented a relatively straightforward question to be addressed: Do the gold inlays belong together, and can we glean insights about their origin? In contrast, the analysis of the Bernstorf gold, an alleged Bronze Age treasure composed of exceptionally pure gold, posed a more intricate challenge. The debate surrounding its authenticity prompted an in-depth investigation utilizing SR XRF with different experimental conditions. This approach, involving the analysis of trace elements, played a pivotal role in elucidating the nature and age of the gold, offering valuable insights into its production Platinum emerges as a crucial trace element for gold analysis, given its typically low concentration in gold artifacts, often in the range of a few parts per million (ppm). Accurately measuring Platinum in the presence of overlapping emission lines from gold is arduous. To overcome this challenge, BAMline developed a wavelength dispersive set-up known as D2XRF, employing a pixelated energy-dispersive X-ray detector (pnCCD). This innovative approach enables the resolution of overlapping emission lines, leading to a remarkable detection limit of 1 ppm for Platinum in gold samples. Furthermore, the application of the pnCCD for imaging element distributions on a Phoenician ivory artifact will be showcased. This technique allows for the visualization and mapping of various elements, which opens the possibility to reconstruct the original appearance. The comprehensive analysis of ancient gold artifacts at BAMline has provided valuable insights into the craftsmanship, trade, and technological advancements of ancient civilizations. By unraveling the complex stories these artifacts carry, our studies contributed significantly to the fields of archaeology, history, and materials science. It underscores the importance of interdisciplinary approaches in piecing together the puzzle of human history, revealing the interconnectedness of cultures through the lens of non-destructive analysis.
T2 - Denver X-ray Conference 2024
CY - Denver, CO, USA
DA - 04.08.2024
KW - Gold
KW - Synchrotron
KW - XRF
KW - BAMline
PY - 2024
AN - OPUS4-61701
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Leidigkeit, Carolin
A1 - Shokr, Mohammad
A1 - Tosson, Amir
A1 - Cakir, Cafer Tufan
A1 - Radtke, Martin
A1 - Pietsch, Ullrich
A1 - Christ, Hans-Jürgen
T1 - Using Energy-Dispersive Laue Diffraction to Study Dislocation Arrangements in Materials Showing Wavy and Planar Slip Behavior
N2 - The present work shows an approach to monitor the evolution of the dislocation arrangement of a metallic material caused by cyclic plastic strain using white X-ray radiation in combination with an energy-dispersive detector. The method is demonstrated by single-shot experiments performed on polycrystalline nickel and α-brass, representing the pure wavy and the pure planar dislocation slip behavior. To correlate the resulting diffraction patterns with various dislocation arrangements of both metals, fatigue tests were carried out up to certain numbers of cycles and at predetermined plastic strain amplitudes. The differences in dislocation microstructure and internal stress distributions give rise to an appreciable change in the peak shape of Laue reflections, leading to unique characteristics in the respective diffraction patterns. Nickel reflections are elongated due to the high amount of cell structures leading to bending and misorientation of the lattice, whereas the present stacking faults in α-brass result in powder-like diffraction.
KW - Slip behavior
KW - Energy-Dispersive
KW - Laue Diffraction
KW - Dislocation
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-637964
DO - https://doi.org/10.1111/ffe.14535
SN - 1460-2695
VL - 48
IS - 3
SP - 1341
EP - 1351
PB - Wiley
AN - OPUS4-63796
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Radtke, Martin
T1 - ChatGPT and EPICS: LLM-Enhanced Control Systems for Synchrotron Beamlines
N2 - The BAMline at BESSY II represents a hard X-ray spectroscopy facility enabling non-destructive analysis across diverse research areas like materials science, chemistry, biology, and cultural heritage studies. As a multipurpose beamline serving users from various disciplines, it underscores the necessity of adaptable and efficient control systems to maximize beamline utilization and scientific output.
In this contribution, we detail the innovative integration of ChatGPT , OpenAI’s state-of-the-art Large Language Model (LLM), with the Experimental Physics and Industrial Control System (EPICS) which underpins the operational framework of the BAMline. This integration leverages the advanced natural language processing (NLP) capabilities of ChatGPT, presenting a revolutionary approach to beamline control that markedly simplifies user interaction. Through this, we facilitate a user-friendly pathway to executing complex experimental setups, eliminating the barrier imposed by conventional scripting languages and the often-challenging graphical user interfaces. This innovation promises to significantly streamline experimental workflows, thereby enhancing the efficiency of scientific research conducted at the beamline.
Further enhancing this user-centric approach, we introduce an advanced graphical user interface (GUI) application. This novel application seamlessly melds the LLM’s NLP capabilities with EPICS, thereby enabling researchers to articulate experimental requirements through simple textual or voice commands. This interface interprets these commands to manipulate various beamline components, including but not limited to the Double Crystal Monochromator (DCM), Double Multilayer Monochromator (DMM), as well as various filters and slits. By parsing user input, extracting pertinent parameters, and generating a structured JSON object that reflects the desired device positions and experimental settings, the GUI application bridges the gap between complex control commands and intuitive user interactions. This advancement not only lowers the entry threshold for new users but also streamlines the operational workflow for experienced researchers.
Looking ahead, we aim to extend the system to cover the entire experimental cycle, from setup to data analysis. Using LLMs, one could translate plain-language experiment descriptions into precise operational commands, revolutionizing the research process and making advanced scientific exploration more accessible to a wider community.
T2 - European X-ray Spectrometry Conference
CY - Athens, Greece
DA - 24.06.2024
KW - EPICS
KW - ChatGPT
KW - BAMline
KW - Synchrotron
PY - 2024
AN - OPUS4-61702
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Radtke, Martin
T1 - Vergangenheit verifiziert: Datierung und Authentizität mittels Bayes’scher Methoden
N2 - In der Archäologie ist die präzise Datierung von Funden und die Verifikation ihrer Authentizität von entscheidender Bedeutung, um Erkenntnisse über vergangene Zivilisationen zu gewinnen. Während traditionelle Methoden wie die Radiokarbon-Datierung bereits seit Jahrzehnten etabliert sind, hat die Anwendung der Bayes’schen Statistik in den letzten Jahren an Bedeutung gewonnen. Dieser Ansatz erlaubt es, vorhandene Unsicherheiten in archäologischen Daten systematisch zu berücksichtigen und bietet somit eine leistungsfähige Ergänzung zu herkömmlichen Methoden.
Die Bayes’sche Theorie basiert auf der Aktualisierung von Wahrscheinlichkeiten anhand neuer Daten. Dies ist besonders nützlich in der Archäologie, wo neue Funde oft bestehende Theorien und Annahmen in Frage stellen. Durch die Kombination von Prior-Wissen mit neuen Daten ermöglicht die Bayes'sche Methode eine adaptive und flexible Datierung und Verifizierung.
Ein Beispiel für die Anwendung dieser Methode ist die Radiokarbon-Datierung. Während die traditionelle Radiokarbon-Datierung einen geschätzten Zeitraum bietet, kann die Bayes'sche Analyse dazu verwendet werden, die Unsicherheit dieses Zeitraums zu quantifizieren und zu verfeinern. Dies ist besonders wertvoll bei der Datierung von Artefakten aus Zeiträumen, in denen mehrere historische Ereignisse stattfanden.
Zudem ist die Bayes'sche Methode auch bei der Überprüfung der Authentizität von Funden nützlich. Durch die Kombination verschiedener Datenquellen, wie z.B. Inschriften, Materialanalysen und Kontextinformationen, können Archäologen die Wahrscheinlichkeit der Echtheit eines Artefakts bestimmen.
Trotz ihrer Stärken ist die Anwendung der Bayes’schen Statistik in der Archäologie nicht ohne Herausforderungen. Die Wahl der Prior-Wahrscheinlichkeit kann subjektiv sein und die Methode erfordert eine sorgfältige Überlegung und Expertise.
Die Bayes’sche Methode in der Archäologie ein leistungsfähiges Werkzeug, um Datierungen zu verfeinern und die Authentizität von Funden zu überprüfen. Während traditionelle Methoden weiterhin eine zentrale Rolle spielen, ermöglicht der Bayes’sche Ansatz eine nuanciertere und adaptivere Analyse, die das Potential hat, unser Verständnis der Vergangenheit zu vertiefen.
T2 - NAHM workshop
CY - Bonn, Germany
DA - 18.10.2023
KW - Bayes
KW - Bernstorf
KW - Gold
KW - Datierung
KW - Herkunft
KW - Suchtheorie
PY - 2024
AN - OPUS4-61705
LA - deu
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Radtke, Martin
T1 - ChatGPT and EPICS: LLM-Enhanced Control Systems for Synchrotron Beamlines
N2 - The BAMlineat BESSY II represents a hard X-ray spectroscopy facility enabling non-destructive analysis across diverse research areas like materials science, chemistry, biology, and cultural heritage studies. As a multipurpose beamline serving users from various disciplines, it underscores the necessity of adaptable and efficient control systems to maximize beamline utilization and scientific output.
In this contribution, we detail the innovative integration of ChatGPT, OpenAI’s state-of-the-art Large Language Model (LLM), with the Experimental Physics and Industrial Control System (EPICS) which underpins the operational framework of the BAMline. This integration leverages the advanced natural language processing (NLP) capabilities of ChatGPT, presenting a revolutionary approach to beamline control that markedly simplifies user interaction. Through this, we facilitate a user-friendly pathway to executing complex experimental setups, eliminating the barrier imposed by conventional scripting languages and the often-challenging graphical user interfaces. This innovation promises to significantly streamline experimental workflows, thereby enhancing the efficiency of scientific research conducted at the beamline.
Further enhancing this user-centric approach, we introduce an advanced graphical user interface (GUI) application. This novel application seamlessly melds the LLM’s NLP capabilities with EPICS, thereby enabling researchers to articulate experimental requirements through simple textual or voice commands. This interface interprets these commands to manipulate various beamline components, including but not limited to the Double Crystal Monochromator (DCM), Double Multilayer Monochromator (DMM), as well as various filters and slits. By parsing user input, extracting pertinent parameters, and generating a structured JSON object that reflects the desired device positions and experimental settings, the GUI application bridges the gap between complex control commands and intuitive user interactions. This advancement not only lowers the entry threshold for new users but also streamlines the operational workflow for experienced researchers.
Looking ahead, we aim to extend the system to cover the entire experimental cycle, from setup to data analysis. Using LLMs, one could translate plain-language experiment descriptions into precise operational commands, revolutionizing the research process and making advanced scientific exploration more accessible to a wider community.
T2 - International Conference on Synchrotron Radiation Instrumentation (SRI)
CY - Hamburg, Germany
DA - 26.08.2024
KW - Chatgpt
KW - EPICS
KW - BAMline
KW - Synchrotron
PY - 2024
AN - OPUS4-61700
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Radtke, Martin
T1 - Getting more efficient – The use of Bayesian optimization and Gaussian processes at the BAMline
N2 - The BAMline, a beamline for material science research at BESSY II, has been operated by the Bundesanstalt für Materialforschung und -prüfung for over two decades. In the last few years, Bayesian optimization (BO) with Gaussian processes (GP) has been introduced as a transformative method in this setting. This contribution highlights the integration and impact of BO and GP in refining BAMline operations.
We will explore the impact of integrating Bayesian methods, especially when combined with Gaussian processes, on the operational efficiency of the BAMline. Our discussion commences with an overview of the fundamental concepts of active learning and optimization. This is followed by an in-depth analysis of specific case studies, drawing on our direct experience with these innovative methods.
For this our focus is on three key applications:
Alignment of Optical Elements (DCM and DMM): The implementation of
Bayesian optimization using Gaussian processes has revolutionized the
alignment process for the Double Crystal Monochromator (DCM) and the
Double Multilayer Monochromator (DMM). This approach greatly reduced
manual effort and enhanced the efficiency and effectiveness of the
alignment procedure.
Optimal Spot Selection for Spatial Mapping in XRF Studies: In X-ray
fluorescence (XRF) experiments, determining the most informative
sampling spots is crucial. The introduction of BO, informed by GP,
has significantly improved the selection process, especially in large
or heterogeneous samples. This methodology ensures maximum
information gain, optimizing the balance between comprehensive
mapping and resource management.
Selection of Optimal Energies for XANES Measurements in GEXANES
Geometry: In the specific context of X-ray Absorption Near Edge
Structure (XANES) studies using Grazing Exit (GEXANES) geometry, the
Bayesian approach with Gaussian processes is now utilized to identify
the most effective energy settings. This results in detailed spectral
data acquired in a much shorter time.
We also address challenges and limitations encountered during implementation. Additionally, the versatility of this approach in addressing a range of different research questions will be demonstrated.
T2 - Machine Learning Conference for X-Ray and Neutron-Based Experiments
CY - Garching bei München, Germany
DA - 08.04.2024
KW - BAMline
KW - Synchrotron
KW - XRF
KW - Bayes
PY - 2024
AN - OPUS4-61703
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - CONF
A1 - Radtke, Martin
T1 - Machine learning - Examples from BAM Line
N2 - This talk explores applications of artificial intelligence in the field of spectroscopy, with a special focus on research conducted at BAMline. We begin with an overview of synchrotron radiation and its unique capabilities in material analysis. The first part of the talk will cover the integration of AI algorithms in quantifying X-ray fluorescence measurements, providing enhanced precision and efficiency in data analysis. Following this, we will examine the role of language models in spectroscopic research, showcasing how these tools can facilitate the control of complex experimental set-ups
T2 - Analytical Academy
CY - Berlin, Germany
DA - 12.11.2024
KW - ChatGPT
KW - Neural networks
KW - XRF
KW - Synchrotron
KW - BAMline
PY - 2024
AN - OPUS4-61698
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Dobosy, Péter
A1 - Nguyen, Hoang Thi Phuong
A1 - Záray, Gyula
A1 - Streli, Christina
A1 - Ingerle, Dieter
A1 - Ziegler, Philipp
A1 - Radtke, Martin
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Endrédi, Anett
A1 - Fodor, Ferenc
T1 - Effect of iodine species on biofortification of iodine in cabbage plants cultivated in hydroponic cultures
N2 - Iodine is an essential trace element in the human diet because it is involved in the synthesis of thyroid hormones. Iodine deficiency affects over 2.2 billion people worldwide, making it a significant challenge to find plant-based sources of iodine that meet the recommended daily intake of this trace element. In this study, cabbage plants were cultivated in a hydroponic system containing iodine at concentrations ranging from 0.01 to 1.0 mg/L in the form of potassium iodide or potassium iodate. During the experiments, plant physiological parameters, biomass production, and concentration changes of iodine and selected microelements in different plant parts were investigated. In addition, the oxidation state of the accumulated iodine in root samples was determined. Results showed that iodine addition had no effect on photosynthetic efficiency and chlorophyll content. Iodide treatment did not considerably stimulate biomass production but iodate treatment increased it at concentrations less than 0.5 mg/L. Increasing iodine concentrations in the nutrient solutions increased iodine content in all plant parts; however, the iodide treatment was 2–7 times more efficient than the iodate treatment. It was concluded, that iodide addition was more favourable on the target element accumulation, however, it should be highlighted that application of this chemical form in nutrient solution decreased the concetrations of selected micoelement concentration comparing with the control plants. It was established that iodate was reduced to iodide during its uptake in cabbage roots, which means that independently from the oxidation number of iodine (+ 5, − 1) applied in the nutrient solutions, the reduced form of target element was transported to the aerial and edible tissues.
KW - BAMline
KW - XANES
KW - Synchrotron
KW - Lodine
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-608330
DO - https://doi.org/10.1038/s41598-024-66575-z
VL - 14
IS - 1
SP - 1
EP - 12
PB - Springer Science and Business Media LLC
AN - OPUS4-60833
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Huang, Junhao
A1 - Klahn, Marcus
A1 - Tian, Xinxin
A1 - Bartling, Stephan
A1 - Zimina, Anna
A1 - Radtke, Martin
A1 - Rockstroh, Nils
A1 - Naliwajko, Pawel
A1 - Steinfeldt, Norbert
A1 - Peppel, Tim
A1 - Grunwaldt, Jan‐Dierk
A1 - Logsdail, Andrew J.
A1 - Jiao, Haijun
A1 - Strunk, Jennifer
T1 - Fundamental Structural and Electronic Understanding of Palladium Catalysts on Nitride and Oxide Supports
N2 - The nature of the support can fundamentally affect the function of a heterogeneous catalyst. For the novel type of isolated metal atom catalysts, sometimes referred to as single‐atom catalysts, systematic correlations are still rare. Here, we report a general finding that Pd on nitride supports (non‐metal and metal nitride) features a higher oxidation state compared to that on oxide supports (non‐metal and metal oxide). Through thorough oxidation state investigations by X‐ray absorption spectroscopy (XAS), X‐ray photoelectron spectroscopy (XPS), CO‐DRIFTS, and density functional theory (DFT) coupled with Bader charge analysis, it is found that Pd atoms prefer to interact with surface hydroxyl group to form a Pd(OH)x species on oxide supports, while on nitride supports, Pd atoms incorporate into the surface structure in the form of Pd−N bonds. Moreover, a correlation was built between the formal oxidation state and computational Bader charge, based on the periodic trend in electronegativity.
KW - BAmline
KW - XANES
KW - Catalyst
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-608341
DO - https://doi.org/10.1002/anie.202400174
SN - 1433-7851
VL - 63
IS - 20
SP - 1
EP - 9
PB - Wiley
AN - OPUS4-60834
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Peters, Stefan
A1 - Bartling, Stephan
A1 - Parlinska-Wojtan, Magdalena
A1 - Wotzka, Alexander
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Wohlrab, Sebastian
A1 - Abdel-Mageed, Ali M.
T1 - Stabilization of intermediate Mo oxidation states by Nb doping enhancing methane aromatization on Mo/HZSM-5 catalysts
N2 - The dehydroaromatization of methane is a promising process to produce aromatics and ultra-pure hydrogen. Increased yields and stability of Mo/HZSM-5 against irreversible deactivation were achieved via a redox interaction by doping with otherwise inert Nb.
KW - General Materials Science
KW - Sustainability and the Environment
KW - General Chemistry
KW - Renewable Energy
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-597670
DO - https://doi.org/10.1039/D3TA07532J
SN - 2050-7488
SP - 1
EP - 16
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-59767
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Senges, Gene
A1 - de Oliveira Guilherme Buzanich, Ana
A1 - Lindič, Tilen
A1 - Gully, Tyler A.
A1 - Winter, Marlon
A1 - Radtke, Martin
A1 - Röder, Bettina
A1 - Steinhauer, Simon
A1 - Paulus, Beate
A1 - Emmerling, Franziska
A1 - Riedel, Sebastian
T1 - Unravelling highly oxidized nickel centers in the anodic black film formed during the Simons process by in situ X-ray absorption near edge structure spectroscopy
N2 - The electrofluorination after Simons has been used for the last century to produce everyday life materials. An in situ XANES investigation of the controversially debated black film apparent in the Simons process revealed high-valent nickel centers.
KW - Synchrotron
KW - BAMline
KW - XANES
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-608366
DO - https://doi.org/10.1039/d3sc06081k
SN - 2041-6520
VL - 15
IS - 12
SP - 4504
EP - 4509
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-60836
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Meyer, Andreas
A1 - Weidner, Steffen
A1 - Kricheldorf, Hans R.
T1 - Star-shaped poly(l-lactide)s based on pentaerythritol: About crystallization and polycondensation plus disproportionation and ring formation in the solid state
N2 - Star-shaped poly( L-lactide)s (s-PLAs), were prepared by ring-opening polymerization of with pentaerythritol and catalyzed by tin(II) 2-ethylhyexanoate (SnOct out in bulk at either 120 ◦ C or 160 ◦ L-lactide (LA) initiated 2 ). Two small series of ROPs were carried C with variation of the LA/initiator ratio. Matrix-assisted laser desorption/ ionization time-of-flight (MALDI-TOF) mass spectra revealed traces of cycles in 120 ◦ C samples only at low initiator/catalyst ratios. In contrast, higher fractions of cycles were detected in samples prepared at 160 C, suggesting a "back-biting" origin. The influence of arm length and thermal history on crystallinity was investigated by differential scanning calorimetry (DSC) and wide-angle x-ray scattering (WAXS). It was shown that annealing increased the melting temperature (T ◦ ◦ m ) and crystallinity. However, annealing at 140 ◦ C for 14 d also caused significant solid-state transesterification. In addition, crystallites composed of s-PLAs with extended arms and, simultaneously, crystallites composed exclusively of extended rings were formed, identified by their typical "sawtooth" pattern in the MALDI mass spectra. Small angle x-ray scattering (SAXS) indicated that the crystal thickness was lower than that of linear PLAs annealed under identical conditions, but increased upon annealing at 140 C.
KW - MALDI-TOF MS
KW - Polylactide
KW - Crystallisation
KW - AStar-shaped polymers
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-636832
DO - https://doi.org/10.1016/j.polymer.2025.128709
SN - 0032-3861
VL - 334
SP - 1
EP - 11
PB - Elsevier Ltd.
AN - OPUS4-63683
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kricheldorf, Hans R.
A1 - Weidner, Steffen
T1 - H2O-Initiated Polymerization of L-Lactide
N2 - Water-initiated ring-opening polymerizations (ROPs) of L-lactide (LA) were performed in bulk at 140 °C, whereupon 11 different salts or complexes of low-toxic metal ions such as tin (II), Zn(II), Zr(IV), and Bi(III) were used as catalysts. Only four catalysts gave satisfactory results despite a long reaction time (24 h). The influence of the temperature was studied with tin (II) 2-ethylhexanoate (SnOct2), dibutyltin oxide (Bu2SnO), and zinc bis-acetylacetonate (Zn(acac)2) and zirconium acetylacetonate (Zr(acac)4). With SnOct2, Bu2SnO and Zr(acac)4 the time was varied at 140 °C to compare their reactivity. Furthermore, two series of ROPs were carried out with variation of the LA/H2O ratio to verify the control of the molecular weight by the monomer-initiator ratio. Bi- or tri-modal molecular weight distributions (MWD) were found for most of the ROPs and bimodal melting endotherms in the differential scanning calorimetry (DSC) heating traces. The thickness and dependence of the 3D packing of the crystallites were monitored by small-angle X-ray scattering (SAXS) measurements.
KW - MALDI-TOF MS
KW - Polylactide
KW - Ring-opening polymerization
KW - Crystallization
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-628761
DO - https://doi.org/10.1007/s10924-025-03565-w
SN - 1572-8919
VL - 33
IS - 6
SP - 2843
EP - 2857
PB - Springer Science and Business Media LLC
CY - New York, NY
AN - OPUS4-62876
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kricheldorf, Hans R.
A1 - Weidner, Steffen
A1 - Scheliga, Felix
T1 - Polycondensation of L-lactic acid: a deeper look into solid state polycondensation
N2 - L-Lactic acid (LA) was condensed in the presence of SnCl2 or 4-toluenesulfonic acid (TSA) at 140 °C, and chain growth without cyclization was observed. In addition, poly(L-lactic acid)s (PLAs) with a degree of polymerization (DP) of 25, 50 or 100 were prepared by water-initiated ring-opening polymerization (ROP). These PLAs were annealed in the solid state at 140 °C and 160 °C in the presence of tin(II) 2-ethylhexanoate (SnOct2, SnCl2 or TSA). The changes in the molar mass distribution and in the topology were characterized by means of matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) mass spectrometry and size exclusion chromatography (SEC). With increasing time, fewer side reactions caused higher molar masses and increasing fractions of cyclic polylactides (cPLA) were obtained. Their “saw tooth” pattern in the MALDI-TOF mass spectra indicated the formation of extended ring crystallites in the solid state. TSA was the most active catalyst and caused fewer side reactions than SnCl2, which was the least reactive catalyst. Acetylation of the CH-OH end groups hindered polycondensation and prevented the formation of cPLAs. Reaction mechanisms will be discussed.
KW - MALDI-TOF MS
KW - Polycondensation
KW - Polylaktide
KW - Solid state
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-625271
DO - https://doi.org/10.1039/d4py01191k
SN - 1759-9962
SP - 1
EP - 9
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-62527
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Rösler, Alexander
A1 - Weidner, Steffen
A1 - Klamroth, Tillmann
A1 - Müller, Axel HE
A1 - Schlaad, Helmut
T1 - Kinetics of anionic polymerization of β‐myrcene in hydrocarbon solvents
N2 - AbstractThe kinetics of anionic polymerization of β‐myrcene initiated by sec‐butyllithium were examined in saturated and unsaturated hydrocarbon solvents, i.e. cyclohexane, cyclohexene, 4‐vinylcyclohexene and dl‐limonene. Polymerizations usually proceeded in a living manner, i.e. in the absence of termination and chain transfer reactions, in all solvents, to produce well‐defined polymyrcenes with high content (85%) of cis‐1,4 units. However, polymyrcenyllithium chains exhibited limited long‐term stability in 4‐vinylcyclohexene solution, most probably due to chain transfer to solvent. Reaction orders with respect to the concentration of active chains were found to be one‐quarter in cyclohexane increasing to one‐half in unsaturated solvents, indicating that the polymyrcenyllithium chains are present as tetrameric or dimeric associates, respectively. Apparent activation energies were found to be 81 kJ mol−1 in cyclohexane and 77 kJ mol−1 in dl‐limonene solution, which are close to the values obtained by quantum chemical calculations. © 2025 The Author(s). Polymer International published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.
KW - Myrcene
KW - Anionic polymerization
KW - Reaction order
KW - Activation energy
KW - Microstructure
KW - Quantum chemical calculation
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-636840
DO - https://doi.org/10.1002/pi.6772
SN - 0959-8103
SP - 1
EP - 8
PB - Wiley
AN - OPUS4-63684
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Kricheldorf, H. R.
A1 - Weidner, Steffen
T1 - Syntheses of cyclic polylactides and the problem of catenane formation
N2 - Cyclic poly(L-lactide)s (PLAs) were prepared in bulk either by ring-expansion polymerization (REP) or by ring-opening polymerization (ROP) with simultaneous polycondensation (ROPPOC). In contrast to REP the latter method involves formation of linear chains and thus, may involve formation of polydisperse catenanes that affect crystallization. The reprecipitated PLAs were annealed at 120 °C and compared with regard to melting temperature (Tm) and melting enthalpy (ΔHm). For similar molar masses the PLAs prepared by REP and ROPPOC had almost identical Tm's and crystallinities. Furthermore, the influence of REP and ROPPOC catalysts on the morphology of the virgin reaction products was compared.
KW - MALDI-TOF MS
KW - Catenane
KW - Polylactide
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-625061
DO - https://doi.org/10.1039/d4ra08683j
VL - 15
IS - 5
SP - 3686
EP - 3692
PB - RSC
AN - OPUS4-62506
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Rösler, Alexander
A1 - Weidner, Steffen
A1 - Klamroth, Tillmann
A1 - Müller, Axel H. E.
A1 - Schlaad, Helmut
T1 - Kinetics of anionic polymerization of β‐myrcene in hydrocarbon solvents
N2 - The kinetics of anionic polymerization of β‐myrcene initiated by sec‐butyllithium were examined in saturated and unsaturated hydrocarbon solvents, i.e. cyclohexane, cyclohexene, 4‐vinylcyclohexene and dl‐limonene. Polymerizations usually proceeded in a living manner, i.e. in the absence of termination and chain transfer reactions, in all solvents, to produce well‐defined polymyrcenes with high content (85%) of cis‐1,4 units. However, polymyrcenyllithium chains exhibited limited long‐term stability in 4‐vinylcyclohexene solution, most probably due to chain transfer to solvent. Reaction orders with respect to the concentration of active chains were found to be one‐quarter in cyclohexane increasing to one‐half in unsaturated solvents, indicating that the polymyrcenyllithium chains are present as tetrameric or dimeric associates, respectively. Apparent activation energies were found to be 81 kJ mol−1 in cyclohexane and 77 kJ mol−1 in dl‐limonene solution, which are close to the values obtained by quantum chemical calculations.
KW - MALDI-TOF MS
KW - Anionic polymerization
KW - β‐myrcene
KW - Kinetics
KW - Reaction order
KW - Activation energy
KW - Microstructure
KW - Quantum chemical calculations
PY - 2025
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-630900
DO - https://doi.org/10.1002/pi.6772
SN - 1097-0126
SP - 1
EP - 8
PB - Wiley
CY - New York, NY
AN - OPUS4-63090
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -