TY - JOUR
A1 - Wurzler, Nina
A1 - Schutter, Jan David
A1 - Wagner, R.
A1 - Dimper, Matthias
A1 - Lützenkirchen-Hecht, D.
A1 - Özcan Sandikcioglu, Özlem
T1 - Abundance of Fe(III) during cultivation affects the microbiologically influenced corrosion (MIC) behaviour of iron reducing bacteria Shewanella putrefaciens
N2 - The effect of the presence of Fe(III) during the cultivation on the electrochemical activity and corrosion behaviour of dissimilatory iron reducing bacteria Shewanella putrefaciens was studied by means of ex situ and in situ X-ray absorption near-edge spectroscopy (XANES). Stainless steel AISI 304 and thin iron films were studied as substrates. XANES analysis indicated an accelerated iron dissolution and growth of an oxide/hydroxide film for the culture grown with Fe(III) in comparison to the culture grown in absence of Fe(III). Electrochemical Analysis indicated that the biofilm resulted in acceleration of the general corrosion but provides protection against local corrosion.
KW - Stainless Steel
KW - XANES
KW - Iron
KW - Cyclic Voltammetry
KW - Microbiological Corrosion
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-513788
DO - https://doi.org/10.1016/j.corsci.2020.108855
VL - 174
SP - 108855
PB - Elsevier Ltd.
AN - OPUS4-51378
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wurzler, Nina
A1 - Schütter, J. D.
A1 - Wagner, R.
A1 - Dimper, M.
A1 - Lützenkirchen-Hecht, D.
A1 - Özcan Sandikcioglu, Özlem
T1 - Trained to corrode: Cultivation in the presence of Fe(III) increases the electrochemical activity of iron reducing bacteria – An in situ electrochemical XANES study
N2 - This paper reports results from in situ electrochemical X-ray absorption near-edge spectroscopy (XANES) studies of the corrosion processes on model thin iron films in the presence of iron reducing bacteria Shewanella putrefaciens. Here we investigate the electrochemical activity of two cultures grown in the presence and absence of Fe(III) citrate in the culture medium. The XANES spectra and the OCP data of the Fe sample incubated with the culture grown in absence of Fe(III) did not show any significant changes during twenty hours of monitoring. In the case of the culture grown in Fe(III) containing medium, an accelerated dissolution of the iron film was observed together with the formation of a mixed Fe(II)-Fe(III) hydroxide surface layer. The open circuit potential (OCP) steadily approached the free corrosion potential of iron in neutral chloride containing electrolytes, indicating a continuous dissolution process without passivation.
KW - Microbiologically influenced corrosion
KW - XANES
KW - Electrochemistry
KW - Iron reducing bacteria
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-505732
DO - https://doi.org/10.1016/j.elecom.2020.106673
VL - 112
SP - 106673
PB - Elsevier B.V.
AN - OPUS4-50573
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wurzler, Nina
A1 - Schütter, Jan David
A1 - Wagner, R.
A1 - Dimper, Matthias
A1 - Hodoroaba, Vasile-Dan
A1 - Lützenkirchen-Hecht, D.
A1 - Özcan Sandikcioglu, Özlem
T1 - Preconditioning of AISI 304 stainless steel surfaces in the presence of flavins—Part II: Effect on biofilm formation and microbially influenced corrosion processes
N2 - Biofilm formation and microbially influenced corrosion of the iron-reducing microorganism Shewanella putrefaciens were investigated on stainless steel surfaces preconditioned in the absence and presence of flavin molecules by means of XANES (X-ray absorption near-edge structure) analysis and electrochemical methods. The results indicate that biofilm formation was promoted on samples preconditioned in electrolytes containing minute amounts of flavins. On the basis of the XANES results, the corrosion processes are controlled by the iron-rich outer layer of the passive film. Biofilm formation resulted in a cathodic shift of the open circuit potential and a protective effect in terms of pitting corrosion. The samples preconditioned in the absence of flavins have shown delayed pitting and the samples preconditioned in the presence of flavins did not show any pitting in a window of −0.3- to +0.0-V overpotential in the bacterial medium. The results indicate that changes in the passive film chemistry induced by the presence of minute amounts of flavins during a mild anodic polarization can change the susceptibility of stainless steel surfaces to microbially influenced corrosion.
KW - Biofilms
KW - XANES
KW - Microbially influenced corrosion (MIC)
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-528130
DO - https://doi.org/10.1002/maco.202012192
VL - 72
IS - 6
SP - 983
EP - 994
PB - Wiley
AN - OPUS4-52813
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Wurzler, Nina
A1 - Sobol, Oded
A1 - Altmann, Korinna
A1 - Radnik, Jörg
A1 - Özcan Sandikcioglu, Özlem
T1 - Preconditioning of AISI 304 stainless steel surfaces in the presence of flavins—Part I: Effect on surface chemistry and corrosion behavior
N2 - Stainless steel AISI 304 surfaces were studied after a mild anodic polarization for oxide growth in the presence and absence of two derivatives of vitamin B2 (riboflavin and flavin mononucleotide) that can be secreted by metal‐reducing bacteria and act as a chelating agent for iron species. The alterations in oxide chemistry were studied by means of surface‐sensitive techniques such as X‐ray photoelectron spectroscopy and time‐of‐flight secondary ion mass spectrometry analysis. The complementary electrochemical characterization revealed a preferential growth of an oxide/hydroxide iron‐rich film that is responsible for an altered pit initiation and nucleation behavior. These findings suggest that as the corrosion behavior is determined by the interplay of the chemical and electronic properties, only a mild anodic polarization in the presence of redox‐active molecules is able to alter the chemical and electronic structure of the passive film formed on stainless steel AISI 304. This helps to achieve a profound understanding of the mechanisms of microbially influenced corrosion (MIC) and especially the possible effects of the redox‐active biomolecules, as they may play an important role in the corrosion susceptibility of stainless steel surfaces.
KW - Corrosion
KW - Stainless steel
KW - Surface analysis
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-528117
DO - https://doi.org/10.1002/maco.202012191
VL - 72
IS - 6
SP - 974
EP - 982
PB - Wiley
AN - OPUS4-52811
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Yesilcicek, Yasemin
A1 - Haas, S.
A1 - Suárez Ocano, Patricia
A1 - Zaiser, E.
A1 - Hesse, René
A1 - Többens, D. M.
A1 - Glatzel, U.
A1 - Manzoni, Anna Maria
T1 - Controlling Lattice Misfit and Creep Rate Through the γ' Cube Shapes in the Al10Co25Cr8Fe15Ni36Ti6 Compositionally Complex Alloy with Hf and W Additions
N2 - Trace elements play an important role in the fine-tuning of complex material properties. This study focuses on the correlation of microstructure, lattice misfit and creep properties. The compositionally complex alloy Al10Co25Cr8Fe15Ni36Ti6 (in at. %) was tuned with high melting trace elements Hf and W. The microstructure consists of a γ matrix, γ' precipitates and the Heusler phase and it is accompanied by good mechanical properties for high temperature applications. The addition of 0.5 at.% Hf to the Al10Co25Cr8Fe15Ni36Ti6 alloy resulted in more sharp-edged cubic γ′ precipitates and an increase in the Heusler phase amount. The addition of 1 at.% W led to more rounded γ′ precipitates and the dissolution of the Heusler phase. The shapes of the γ' precipitates of the alloys Al9.25Co25Cr8Fe15Ni36Ti6Hf0.25W0.5 and Al9.25Co25Cr8Fe15Ni36Ti6Hf0.5W0.25, that are the alloys of interest in this paper, create a transition from the well-rounded precipitates in the alloy with 1% W containing alloy to the sharp angular particles in the alloy with 0.5% Hf. While the lattice misfit has a direct correlation to the γ' precipitates shape, the creep rate is also related to the amount of the Heusler phase. The lattice misfit increases with decreasing corner radius of the γ' precipitates. So does the creep rate, but it also increases with the amount of Heusler phase. The microstructures were investigated by SEM and TEM, the lattice misfit was calculated from the lattice parameters obtained by synchrotron radiation measurements.
KW - High entropy alloy
KW - Lattice misfit
KW - Creep
KW - Transmission electron microscopy
KW - X-ray diffraction
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-565655
DO - https://doi.org/10.1007/s44210-022-00009-1
SP - 1
EP - 9
PB - Springer
AN - OPUS4-56565
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Yildirim, Arda
A1 - Sentker, K.
A1 - Smales, Glen Jacob
A1 - Pauw, Brian Richard
A1 - Huber, P.
A1 - Schönhals, Andreas
T1 - Collective orientational order and phase behavior of a discotic liquid crystal under nanoscale confinement
N2 - The phase behavior and molecular ordering of hexakishexyloxy triphenylene (HAT6) DLC under cylindrical nanoconfinement is studied utilizing differential scanning calorimetry (DSC) and dielectric spectroscopy (DS), where cylindrical nanoconfinement is established through embedding HAT6 into the nanopores of anodic aluminum oxide membranes (AAO), and a silica membrane with pore diameters ranging from 161 nm down to 12 nm. Both unmodified and modified pore walls were considered, and in the latter case the pore walls of AAO membranes were chemical treated with n octadecylphosphonic acid (ODPA) resulting in the formation of a 2.2 nm thick layer of grafted alkyl chains. Phase transition enthalpies decrease with decreasing pore size, indicating that a large proportion of the HAT6 molecules within the pores has a disordered structure, which increases with decreasing pore size for both pore walls. In the case of the ODPA modification the amount of ordered HAT6 is increased compared to the unmodified case. The pore size dependencies of the phase transition temperatures were approximated using the Gibbs Thomson equation, where the estimated surface tension is dependent on the molecular ordering of HAT6 molecules within the pores and upon their surface. DS was employed to investigate the molecular ordering of HAT6 within the nanopores. These investigations revealed that with a pore size of around 38 nm, for the samples with the unmodified pore walls, the molecular ordering changes from planar axial to homeotropic radial. However, the planar axial configuration, which is suitable for electronic applications, can be successfully preserved through ODPA modification for most of the pore sizes.
KW - Discotic Liquid Crystals
KW - Nanoconfinement
PY - 2019
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-475222
DO - https://doi.org/10.1039/c8na00308d
SN - 2516-0230
VL - 1
IS - 3
SP - 1104
EP - 1116
PB - RSC
AN - OPUS4-47522
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Yusenko, Kirill
A1 - Domonov, D.
A1 - Pechenyuk, S.
A1 - Belyevskii, A.
T1 - Formation of Nanostructured Carbon from [Ni(NH3)6]3[Fe(CN)6]2
N2 - The products of thermal decomposition in an argon atmosphere of [Ni(NH3)6]3[Fe(CN)6]2 as a precursor has been studied. Decomposition products were studied up to 800◦C. Above 600◦C, all coordination bonds in the residues are broken with a formation of Ni3Fe, Fe, and free carbon with a small admixture of nitrogen. Elementary carbon can be easily separated from metals by treatment with a water solution of hydrochloric acid. Only carbon is responsible for the specific surface of the composite products. The released carbon has a high degree of graphitization and begins to oxidize in air above 500°C and is completely oxidized above 700°C.
KW - Carbon materials
KW - Double complex compound
KW - Thermal decomposition
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-508188
DO - https://doi.org/10.3390/nano10020389
VL - 10
IS - 2
SP - 389
PB - MDPI
CY - Basel
AN - OPUS4-50818
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Yusenko, Kirill
A1 - Kabelitz, Anke
A1 - Schokel, Alexander
A1 - Wagner, Ralf
A1 - Prinz, Carsten
A1 - Kemnitz, E
A1 - Emmerling, Franziska
A1 - Krahl, Thoralf
A1 - de Oliveira Guilherme Buzanich, Ana
T1 - Local Structure of Europium-Doped Luminescent Strontium Fluoride Nanoparticles: Comparative X-ray Absorption Spectroscopy and Diffraction Study
N2 - Rare-earth based luminescent materials are key functional components for the rational design of light-conversion smart devices. Stable Eu3+-doped strontium fluoride (SrF2) nanoparticles were prepared at room temperature in ethylene glycol. Their luminescence depends on the Eu content and changes after heat treatment. The crystallinity of heat-treated material increases in comparison with as-synthesized samples. Particles were investigated in solution using X-ray diffraction, small-angle X-ray scattering, and X-ray spectroscopy. After heat treatment, the size of the disordered nanoparticles increases together with a change of their local structure. Interstitial fluoride ions can be localized near Eu3+ ions. Therefore, non-radiative relaxation from other mechanisms is decreased. Knowledge about the cation distribution is key information for understanding the luminescence properties of any material.
KW - SrF2
KW - EXAFS
KW - Eu
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-540094
DO - https://doi.org/10.1002/cnma.202100281
VL - 7
IS - 11
SP - 1221
EP - 1229
PB - Wiley Online Library
AN - OPUS4-54009
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Yusenko, Kirill
A1 - Khandarkhaeva, S.
A1 - Bykov, M.
A1 - Fedotenko, T.
A1 - Hanfland, M.
A1 - Sukhikh, A.
A1 - Gromilov, S.
A1 - Dubrovinsky, L.
T1 - Face-centered cubic refractory alloys prepared from single-source precursors
N2 - Three binary fcc-structured alloys (fcc–Ir0.50Pt0.50, fcc Rh0.66Pt0.33 and fcc–Rh0.50Pd0.50) were 14 prepared from [Ir(NH3)5Cl][PtCl6], [Ir(NH3)5Cl][PtBr6], [Rh(NH3)5Cl]2[PtCl6]Cl2 and 15 [Rh(NH3)5Cl][PdCl4]·H2O, respectively, as single-source precursors. All alloys were prepared by 16 thermal decomposition in gaseous hydrogen flow below 800 °C. Fcc–Ir0.50Pt0.50 and fcc–Rh0.50Pd0.50 17 correspond to miscibility gaps on binary metallic phase diagrams and can be considered as 18 metastable alloys. Detailed comparison of [Ir(NH3)5Cl][PtCl6] and [Ir(NH3)5Cl][PtBr6] crystal 19 structures suggests that two isoformular salts are not isostructural. In [Ir(NH3)5Cl][PtBr6], specific 20 Br…Br interactions are responsible for crystal structure arrangement. Room temperature 21 compressibility of fcc–Ir0.50Pt0.50, fcc–Rh0.66Pt0.33 and fcc–Rh0.50Pd0.50 has been investigated up to 50 GPa 22 in diamond anvil cells. All investigated fcc-structured binary alloys are stable under compression. 23 Atomic volumes and bulk moduli show good agreement with ideal solutions model. For fcc–24 Ir0.50Pt0.50, V0/Z = 14.597(6) Å3·atom-1, B0 = 321(6) GPa, B0' = 6(1); for fcc–Rh0.66Pt0.33, V0/Z = 14.211(3) 25 Å3·atom-1, B0 =259(1) GPa, B0' = 6.66(9); for fcc–Rh0.50Pd0.50, V0/Z = 14.18(2) Å3·atom-1, B0 =223(4) GPa, 26 B0' = 5.0(3).
KW - High-pressure
KW - Refractory alloys
KW - Platinum group metals
KW - Single-source precursors
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-508176
DO - https://doi.org/10.3390/ma13061418
VL - 13
IS - 6
SP - 1418
PB - MDPI
CY - Basel
AN - OPUS4-50817
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Yusenko, Kirill
A1 - Sukhikh, A.
A1 - Kraus, Werner
A1 - Gromilov, S.
T1 - Synthesis and Crystal Chemistry of Octahedral Rhodium(III) Chloroamines
N2 - Rhodium(III) octahedral complexes with amine and chloride ligands are the most common starting compounds for preparing catalytically active rhodium(I) and rhodium(III) species. Despite intensive study during the last 100 years, synthesis and crystal structures of rhodium(III) complexes were described only briefly. Some [RhClx(NH3)6-x] compounds are still unknown. In this study, available information about synthetic protocols and the crystal structures of possible [RhClx(NH3)6−x] octahedral species are summarized and critically analyzed. Unknown crystal structuresof(NH4)2[Rh(NH3)Cl5],trans–[Rh(NH3)4Cl2]Cl·H2O,andcis–[Rh(NH3)4Cl2]Clarereported based on high quality single crystal X-ray diffraction data. The crystal structure of [Rh(NH3)5Cl]Cl2 was redetermined. All available crystal structures with octahedral complexes [RhClx(NH3)6-x] were analyzed in terms of their packings and pseudo-translational sublattices. Pseudo-translation lattices suggest face-centered cubic and hexagonal closed-packed sub-cells, where Rh atoms occupy nearly ideal lattices.
KW - Pseudo-translationalsublattices
KW - Rhodiumcomplexes
KW - Ligandsubstitution
KW - Crystalstructure
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-508194
DO - https://doi.org/10.3390/molecules25040768
VL - 25
IS - 4
SP - 768
PB - MDPI
CY - Basel
AN - OPUS4-50819
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Zhang, Kun
A1 - Carrod, Andrew J.
A1 - Del Giorgio, Elena
A1 - Hughes, Joseph
A1 - Rurack, Knut
A1 - Bennet, Francesca
A1 - Hodoroaba, Vasile-Dan
A1 - Harrad, Stuart
A1 - Pikramenou, Zoe
T1 - Luminescence Lifetime-Based Sensing Platform Based on Cyclometalated Iridium(III) Complexes for the Detection of Perfluorooctanoic Acid in Aqueous Samples
N2 - Luminescence lifetimes are an attractive analytical method for detection due to its high sensitivity and stability. Iridium probes exhibit luminescence with long excited-state lifetimes, which are sensitive to the local environment. Perfluorooctanoic acid (PFOA) is listed as a chemical of high concern regarding its toxicity and is classified as a “forever chemical”. In addition to strict limits on the presence of PFOA in drinking water, environmental contamination from industrial effluent or chemical spills requires rapid, simple, accurate, and cost-effective analysis in order to aid containment. Herein, we report the fabrication and function of a novel and facile luminescence sensor for PFOA based on iridium modified on gold surfaces. These surfaces were modified with lipophilic iridium complexes bearing alkyl chains, namely, IrC6 and IrC12, and Zonyl-FSA surfactant. Upon addition of PFOA, the modified surfaces IrC6-FSA@Au and IrC12-FSA @Au show the largest change in the red luminescence signal with changes in the luminescence lifetime that allow monitoring of PFOA concentrations in aqueous solutions. The platform was tested for the measurement of PFOA in aqueous samples spiked with known concentrations of PFOA and demonstrated the capacity to determine PFOA at concentrations >100 μg/L (240 nM).
KW - Perfluorooctanoic Acid (PFOA)
KW - Cyclometalated iridium (III) complexes
KW - Luminescent lifetime
KW - Optically active surfaces
KW - ToF-SIMS
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594535
UR - https://pubs.acs.org/doi/10.1021/acs.analchem.3c04289
DO - https://doi.org/10.1021/acs.analchem.3c04289
VL - 96
IS - 4
SP - 1565
EP - 1575
PB - American Chemical Society (ACS)
AN - OPUS4-59453
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Zhao, H.
A1 - Chakraborty, Poulami
A1 - Ponge, D.
A1 - Hickel, Tilmann
A1 - Sun, B.
A1 - Wu, C.-H.
A1 - Gault, B.
A1 - Raabe, D.
T1 - Hydrogen trapping and embrittlement in high-strength Al alloys
N2 - Ever more stringent regulations on greenhouse gas emissions from transportation motivate efforts to revisit materials used for vehicles. High-strength aluminium alloys often used in aircrafts could help reduce the weight of automobiles, but are susceptible to environmental degradation. Hydrogen ‘embrittlement’ is often indicated as the main culprit; however, the exact mechanisms underpinning failure are not precisely known: atomic-scale analysis of H inside an alloy remains a challenge, and this prevents deploying alloy design strategies to enhance the durability of the materials. Here we performed near-atomic-scale analysis of H trapped in second-phase particles and at grain boundaries in a high-strength 7xxx Al alloy. We used these observations to guide atomistic ab initio calculations, which show that the co-segregation of alloying elements and H favours grain boundary decohesion, and the strong partitioning of H into the second-phase particles removes solute H from the matrix, hence preventing H embrittlement. Our insights further advance the mechanistic understanding of H-assisted embrittlement in Al alloys, emphasizing the role of H traps in minimizing cracking and guiding new alloy design.
KW - Atomistic models
KW - Hydrogen
KW - Metals and alloys
KW - Mechanical properties
PY - 2022
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-543631
DO - https://doi.org/10.1038/s41586-021-04343-z
SN - 1476-4687
VL - 602
IS - 7897
SP - 437
EP - 441
PB - Nature Publ. Group
CY - London
AN - OPUS4-54363
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Zorn, R.
A1 - Szymoniak, Paulina
A1 - Kolmangadi, Mohamed Aejaz
A1 - Malpass-Evans, R.
A1 - McKeown, N.
A1 - Jalarvo, N.
A1 - Tyagi, M.
A1 - Böhning, Martin
A1 - Schönhals, Andreas
T1 - Microscopic molecular mobility of high-performance polymers of intrinsic microporosity revealed by neutron scattering – bend fluctuations and signature of methyl group rotation
N2 - Polymers of intrinsic microporosity exhibit a combination of high gas permeability and reasonable permselectivity, which makes them attractive candidates for gas separation membrane materials. The diffusional selective gas transport properties are connected to the molecular mobility of these polymers in the condensed state. Incoherent quasielastic neutron scattering was carried out on two polymers of intrinsic microporosity, PIM-EA-TB(CH3) and its demethylated counterpart PIM-EA-TB(H2), which have high Brunauer–Emmett–Teller surface area values of 1030 m2 g-1 and 836 m2 g-1, respectively. As these two polymers only differ in the presence of two methyl groups at the ethanoanthracene unit, the effect of methyl group rotation can be investigated solely. To cover a broad dynamic range, neutron time-of-flight was combined with neutron backscattering. The demethylated PIM-EA-TB(H2) exhibits a relaxation process with a weak intensity at short times. As the backbone is rigid and stiff this process was assigned to bendand-flex fluctuations. This process was also observed for the PIM-EA-TB(CH3). A further relaxation process is found for PIM-EA-TB(CH3), which is the methyl group rotation. It was analyzed by a jump-diffusion in a three-fold potential considering also the fact that only a fraction of the present hydrogens in PIM-EATB(CH3) participate in the methyl group rotation. This analysis can quantitatively describe the q dependence of the elastic incoherent structure factor. Furthermore, a relaxation time for the methyl group rotation can be extracted. A high activation energy of 35 kJ mol-1 was deduced. This high activation energy evidences a strong hindrance of the methyl group rotation in the bridged PIM-EA-TB(CH3) structure.
KW - Polymers of Intrinsic Microporosity
KW - Neutron Scattering
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-604114
DO - https://doi.org/10.1039/d4sm00520a
SP - 1
EP - 11
PB - RSC
AN - OPUS4-60411
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Zorn, R.
A1 - Szymoniak, Paulina
A1 - Kolmangadi, Mohamed Aejaz
A1 - Malpass-Evans, R.
A1 - McKeown, N.
A1 - Tyagi, M.
A1 - Böhning, Martin
A1 - Schönhals, Andreas
T1 - Low frequency vibrations and diffusion in disordered polymers bearing an intrinsic microporosity as revealed by neutron scattering
N2 - The microscopic diffusion and the low frequency density of states (VDOS) of PIM-EATB(CH3) are investigated by inelastic and quasi-elastic neutron scattering where also the demethylated counterpart of PIM-EA-TB(H2) is considered. These intrinsic microporous polymers are characterized by large BET surface area values of several hundred m2/g and pore sizes between 0.5 and 2 nm. Detailed comparison is made to the archetype of polymers of intrinsic microporosity, PIM-1, and polynorbornenes also bearing a microporosity. Due to the wavelength of neutrons, the diffusion and vibrations can be addressed on microscopic length and time scales. From the inelastic neutron scattering experiments the low frequency density of states (VDOS) is estimated which shows excess contributions to the Debye-type VDOS known as Boson peak. It was found that the maximum frequency of the Boson peak decreases with increasing microporosity characterized by the BET surface area. However, besides the BET surface area, additional factors such as the backbone stiffness govern the maximum frequency of the Boson peak. Further the mean squared displacement related to microscopic motions was estimated from elastic fixed window scans. At temperatures above 175 K, the mean squared displacement PIM-EA-TB(CH3) is higher than that for the demethylated counterpart PIM-EA-TB(H2). The additional contribution found for PIM-EATB(CH3) is ascribed to the rotation of the methyl group in this polymer because the only difference between the two structures is that PIM-EA-TB(CH3) has methyl groups where PIM-EA-TB(H2) has none. A detailed comparison of the molecular dynamics is also made to that of PIM-1 and the microporous polynorbornene PTCNSi1. The manuscript focuses on the importance of vibrations and the localized molecular mobility characterized by the microscopic diffusion on the gas Transport in polymeric separation membranes. In the frame of the random gate model localized fluctuations can open or close bottlenecks between pores to enable the diffusion of gas molecules.
KW - Polymer of intrisic microporosity
KW - Neutron scattering
KW - Boson peak
KW - Methyl group rotation
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-538490
DO - https://doi.org/10.3390/cryst11121482
VL - 11
IS - 12
SP - 1
EP - 16
PB - MDPI
CY - Basel
AN - OPUS4-53849
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Zosef, M.
A1 - Fahmy, Alaa
A1 - El Hotaby, W.
A1 - Hassan, A.
A1 - Khalil, A.
A1 - Anis, B.
T1 - High performance graphene-based PVF foam for lead removal from water
N2 - The synthesis and optimization of superior and eco-friendly sorbents for Pb(II) pose a great challenge in the field of water treatment. The sorbent was developed by introducing graphene oxide (GO) into the matrix of polyvinyl formaldehyde (PVF) foam. The immobilization of GO in PVF results in significant increase in the maximum adsorption capacity (Qt) of GO powder for Pb(II), from ≈800 to ≈1730 mg g−1 in the case of GO/PVF foam. As compared with GO powder in Pb(II) aqueous solutions, PVF matrix keeps GO sheets stable without any agglomeration. The large surface area of GO sheet allows the abundant oxygenated functional groups on its surface to participate effectively in the Pb(II) adsorption process, leading to the huge increase of the Qt. Adsorption isotherms and kinetic studies indicated that the sorption process of Pb(II) on GO/PVF was done on heterogenous surface by ion-exchange reaction. The GO/PVF foam showed an excellent reusability for more than 10 cycles with almost the same efficiency and without any significant change in its physical properties.
KW - Water treatment
KW - Graphene oxide
KW - Lead ions
KW - Polyvinyl formaldehyde foam
KW - Superior sorbent
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-523013
DO - https://doi.org/10.1016/j.jmrt.2020.08.011
VL - 9
IS - 5
SP - 11861
EP - 11875
PB - Elsevier B.V.
AN - OPUS4-52301
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Zou, T.
A1 - Nonappa, N.
A1 - Khavani, M.
A1 - Vuorte, M.
A1 - Penttilä, P.
A1 - Zitting, A.
A1 - Valle-Delgado, J. J.
A1 - Elert, Anna Maria
A1 - Silbernagl, Dorothee
A1 - Balakshin, M.
A1 - Sammalkorpi, M.
A1 - Österberg, M.
T1 - Experimental and Simulation Study of the Solvent Effects on the Intrinsic Properties of Spherical Lignin Nanoparticles
N2 - Spherical lignin nanoparticles (LNPs) fabricated via nanoprecipitation of dissolved lignin are among the most attractive biomass-derived nanomaterials. Despite various studies exploring the methods to improve the uniformity of LNPs or seeking more application opportunities for LNPs, little attention has been given to the fundamental aspects of the solvent effects on the intrinsic properties of LNPs. In this study, we employed a variety of experimental techniques and molecular dynamics (MD) simulations to investigate the solvent effects on the intrinsic properties of LNPs. The LNPs were prepared from softwood Kraft lignin (SKL) using the binary solvents of aqueous acetone or aqueous tetrahydrofuran (THF) via nanoprecipitation. The internal morphology, porosity, and mechanical properties of the LNPs were analyzed with electron tomography (ET), small-angle X-ray scattering (SAXS), atomic force microscopy (AFM), and intermodulation AFM (ImAFM). We found that aqueous acetone resulted in smaller LNPs with higher uniformity compared to aqueous THF, mainly ascribing to stronger solvent−lignin interactions as suggested by MD simulation results and confirmed with aqueous 1,4-dioxane (DXN) and aqueous dimethyl sulfoxide (DMSO).
More importantly, we report that both LNPs were compact particles with relatively homogeneous density distribution and very low porosity in the internal structure. The stiffness of the particles was independent of the size, and the Young’s modulus was in the range of 0.3−4 GPa. Overall, the fundamental understandings of LNPs gained in this study are essential for the design of LNPs with optimal performance in applications.
KW - Lignin
KW - Electron tomography
KW - Intermodulation AFM
KW - Modulus
KW - SAXS
PY - 2021
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-546948
DO - https://doi.org/10.1021/acs.jpcb.1c05319
SN - 1520-5207
VL - 125
IS - 44
SP - 12315
EP - 12328
PB - ACS
AN - OPUS4-54694
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -
TY - JOUR
A1 - Zuffa, Caterina
A1 - Cappuccino, Chiara
A1 - Casali, Lucia
A1 - Emmerling, Franziska
A1 - Maini, Lucia
T1 - Liquid reagents are not enough for liquid assisted grinding in the synthesis of (AgBr)(n-pica) n
N2 - This study investigates the mechanochemical reactions between AgBr 3-picolylamine and 4-picolylamine. The use of different stoichiometry ratios of the reagents allows [(AgBr)(n-pica)]n and [(AgBr)2(n-pica)]n to be obtained, and we report the new structures of [(AgBr)2(3-pica)]n and [(AgBr)2(4-pica)]n which are characterized by the presence of the following: (a) infinite inorganic chains, (b) silver atom coordinated only by bromide atoms and (c) argentophilic interactions. Furthermore, we studied the interconversion of [(AgBr)(n-pica)]n/[(AgBr)2(n-pica)]n by mechanochemical and thermal properties. The in situ experiments suggest that [(AgBr)(3-pica)]n is kinetically favoured while [(AgBr)2(3-pica)]n is converted into [(AgBr)(3-pica)]n only with a high excess of the ligand. Finally, the liquid nature of the ligands is not sufficient to assist the grinding process, and the complete reaction is observed with the addition of a small quantity of acetonitrile.
KW - Mechanochemistry
KW - Complex
PY - 2024
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-594755
DO - https://doi.org/10.1039/d3cp04791a
SN - 1463-9076
SP - 1
EP - 10
PB - Royal Society of Chemistry (RSC)
AN - OPUS4-59475
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 - Zänker, Steffen
A1 - Scholz, G.
A1 - Xu, W.
A1 - Kemnitz, E.
A1 - Emmerling, Franziska
T1 - Structure and properties of fluorinated and non-fluorinated Ba-coordination polymers - the position of fluorine makes the difference
N2 - As the most electronegative element, fluorine has a strong influence on material properties such as absorption behaviour or chemical and thermal stability. Fluorine can be easily integrated into coordination polymers (CPs) via a fluorinated acetate, here trifluoroacetate in Ba(CF3COO)2, or directly via a metal fluorine bond (BaF(CH3COO)). In the present study both possibilities of fluorine integration were tested and their effect on structure and properties of barium coordination polymers was investigated in comparison with the non-fluorinated barium acetate (Ba(CH3COO)2). In addition to the study of their thermal behaviour and their decomposition temperature, the CPs structures were tested for their application as possible anode materials in lithium ion batteries and for their sorption of water and ammonia. The properties of the CPs can be traced back to the individual structural motifs and could thus trigger new design ideas for CPs in LIBs and/or catalysis.
KW - Alkaline earth metal coordination polymers
KW - Lithium-ion battery
KW - Water stability
KW - Fluorine coordination
PY - 2020
UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-524041
DO - https://doi.org/10.1002/zaac.202000360
SN - 0044-2313
VL - 647
IS - 9
SP - 1014
EP - 1024
PB - Wiley-VCH GmbH
AN - OPUS4-52404
LA - eng
AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany
ER -