TY - JOUR A1 - Mendive Tapia, Eduardo A1 - Patrick, Christopher E A1 - Hickel, Tilmann A1 - Neugebauer, Jörg A1 - Staunton, Julie B T1 - Quantification of electronic and magnetoelastic mechanisms of first-order magnetic phase transitions from first principles: application to caloric effects in La(FexSi1-x)(13) N2 - La(FexSi1−x)13 and derived quaternary compounds are well-known for their giant, tunable, magneto- and barocaloric responses around a first-order paramagnetic-ferromagnetic transition near room temperature with low hysteresis. Remarkably, such a transition shows a large spontaneous volume change together with itinerant electron metamagnetic features. While magnetovolume effects are well-established mechanisms driving first-order transitions, purely electronic sources have a long, subtle history and remain poorly understood. Here we apply a disordered local moment picture to quantify electronic and magnetoelastic effects at finite temperature in La(FexSi1−x)13 from first-principles. We obtain results in very good agreement with experiment and demonstrate that the magnetoelastic coupling, rather than purely electronic mechanisms, drives the first-order character and causes at the same time a huge electronic entropy contribution to the caloric response. KW - Caloric effects KW - Ab initio thermodynamics KW - Magnetoeleastic couplin PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-587882 DO - https://doi.org/10.1088/2515-7655/acd027 SN - 2515-7655 VL - 5 IS - 3 SP - 1 EP - 16 PB - IOP Publishing AN - OPUS4-58788 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Tehranchi, Ali A1 - Chakraborty, Poulami A1 - López Freixes, Martí A1 - McEniry, Eunan J. A1 - Gault, Baptiste A1 - Hickel, Tilmann A1 - Neugebauer, Jörg T1 - Tailoring negative pressure by crystal defects: Microcrack induced hydride formation in Al alloys N2 - Climate change motivates the search for non-carbon-emitting energy generation and storage solutions. Metal hydrides show promising characteristics for this purpose. They can be further stabilized by tailoring the negative pressure of microstructural and structural defects. Using systematic ab initio and atomistic simulations, we demonstrate that an enhancement in the formation of hydrides at the negatively pressurized tip region of the microcrack is feasible by increasing the mechanical tensile load on the specimen. The theoretical predictions have been used to reassess and interpret atom probe tomography experiments for a high-strength 7XXX-aluminium alloy that show a substantial enhancement of hydrogen concentration at structural defects near a stress-corrosion crack tip. These results contain important implications for enhancing the capability of metals as H-storage materials. KW - Physics and Astronomy (miscellaneous) KW - Hydrogen storage KW - Ab initio Simulation KW - Microcracks PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-587878 DO - https://doi.org/10.1103/PhysRevMaterials.7.105401 SN - 2475-9953 VL - 7 IS - 10 SP - 105401-1 EP - 105401-12 PB - American Physical Society (APS) AN - OPUS4-58787 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Karafiludis, Stephanos A1 - Bhattacharya, Biswajit A1 - de Oliveira Guilherme Buzanich, Ana A1 - Fink, Friedrich A1 - Feldmann, Ines A1 - ten Elshof, J. E. A1 - Emmerling, Franziska A1 - Stawski, Tomasz T1 - Thermally processed Ni-and Co-struvites as functional materials for proton conductivity N2 - We present how mesoporosity can be engineered in transition metal phosphate (TMPs) materials in a template-free manner. The method involves the transformation of a precursor metal phosphate phase, called M-struvite (NH4MPO4·6H2O, M = Mg2+, Ni2+, Co2+, NixCo1−x2+). It relies on the thermal decomposition of crystalline M-struvite precursors to an amorphous and simultaneously mesoporous phase, which forms during degassing of NH3 and H2O. The temporal evolution of mesoporous frameworks and the response of the metal coordination environment were followed by in situ and ex situ scattering and diffraction, as well as X-ray spectroscopy. Despite sharing the same precursor struvite structure, different amorphous and mesoporous structures were obtained depending on the involved transition metal. We highlight the systematic differences in absolute surface area, pore shape, pore size, and phase transitions depending on the metal cation present in the analogous M-struvites. The amorphous structures of thermally decomposed Mg-, Ni- and NixCo1−x-struvites exhibit high surface areas and pore volumes (240 m2 g−1 and 0.32 cm−3 g−1 for Mg and 90 m2 g−1 and 0.13 cm−3 g−1 for Ni). We propose that the low-cost, environmentally friendly M-struvites could be obtained as recycling products from industrial and agricultural wastewaters. These waste products could be then upcycled into mesoporous TMPs through a simple thermal treatment for further application, for instance in (electro)catalysis. KW - Struvite KW - Phosphates KW - Transition metals KW - Proton conductivity PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-575862 DO - https://doi.org/10.1039/D3DT00839H SN - 1477-9226 SP - 1 EP - 13 PB - Royal Society of Chemisty (RSC) CY - London/Cambridge AN - OPUS4-57586 LA - deu AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. A1 - Scheliga, F. A1 - Weidner, Steffen T1 - Syntheses of Cyclic Poly(l-lactide)s by Means of Zinc-Based Ring-Opening Polymerization with Simultaneous Polycondensation (ROPPOC) Catalysts N2 - Ring-opening polymerizations of l-lactide are studied in bulk at 140 or 160 °C with zinc n-hexanoate, zinc 4-chlorothiophenolate, and zinc pentafluoro thiophenolate (ZnSPF) as catalysts. The reactivity increases in the given order. With all three catalysts a high fraction of cycles is obtained only at polymerization (annealing) times around 7 d. With ZnSPF weight average molecular weights (Mw) up to 178 000, a Tm around 199 °C and a 𝚫Hm around 99 J g−1 were achieved. The samples annealed for 4 or 7 d also display a saw tooth pattern of the mass peak distribution in the matrix-assisted laser desorption/ionization time of flight spectra indicating transesterification reactions across the surface of extended ring crystals. This process optimizes the thermodynamical properties of the crystalline cyclic polylactides and is responsible for the high Tm and 𝚫Hm values. KW - Polylactide KW - MALDI-TOF MS KW - Ring opening polymerization KW - Polymerization PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-578264 DO - https://doi.org/10.1002/macp.202300070 SN - 1022-1352 SP - 202300070 PB - Wiley VHC-Verlag AN - OPUS4-57826 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. A1 - Weidner, Steffen T1 - Cyclic and linear poly(L-lactide)s by ring-expansion polymerization with Bu2SnO, Oct2SnO, and Bu2SnS N2 - To elucidate the usefulness of commercial Bu2SnO as catalyst for syntheses of linear and/or cyclic polylactides L-Lactide was polymerized in bulk with variation of the LA/Cat ratio, temperature and time. Based on a ring-expansion polymerization (REP) mechanism cyclic polylactides (PLAs) with weight average molecular weights in the range of 200,000–300,000 are obtained at the highest temperature (180 °C). Polymerizations at 150 °C yielded crystalline, mainly cyclic polylactides which, after annealing, showed high melting temperatures (up to 197.5 °C) and high crystallinities (>80%). Polymerization at 120 °C confirmed the trend towards more linear chains with lower temperatures but yielded extended-ring crystals showing a “saw-tooth pattern” in the mass spectra. Oct2SnO gave similar results as Bu2SnO. Bu2SnS proved a sluggish polymerization catalyst, but a good transesterification catalyst in solid PLA. KW - MALDI TOF MS KW - Biobased polymers KW - Polylactide KW - Ring-expansion polymerization PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-584121 DO - https://doi.org/10.1002/pol.20230515 SN - 2642-4169 SP - 1 EP - 10 PB - Wiley CY - Hoboken, NJ AN - OPUS4-58412 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kricheldorf, H. R. A1 - Weidner, Steffen A1 - Meyer, A. T1 - About the Influence of (Non-)Solvents on the Ring Expansion Polymerization of l-Lactide and the Formation of Extended Ring Crystals N2 - Ring-expansion polymerizations (REPs) catalyzed by two cyclic tin catalysts (2-stanna-1.3-dioxa-4,5,6,7-dibenzazepine [SnBiph] and 2,2-dibutyl-2-stanna-1,3-dithiolane [DSTL]) are performed at 140 °C in bulk. Small amounts (4 vol%) of chlorobenzene or other solvents are added to facilitate transesterification reactions (ring–ring equilibration) in the solid poly(l-lactide)s. In the mass range up to m/z 13 000 crystalline PLAs displaying a so-called saw-tooth pattern in the MALDI-TOF mass spectra are obtained indicating the formation of extended-ring crystals. The characteristics of extended-ring crystallites and folded-ring crystallites are discussed. Furthermore, extremely high melting temperatures (Tm’s up to 201.2 °C) and melting enthalpies (𝚫Hm’s up to 106 J g−1)) are found confirming that 𝚫Hm max, the 𝚫Hm of a perfect crystal, is around or above 115 J g−1 in contrast to literature data. KW - Polylactide KW - MALDI-TOF MS KW - Ring-expansion polymerization KW - Biobased PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-573063 DO - https://doi.org/10.1002/macp.202200385 VL - 224 IS - 5 SP - 1 EP - 8 PB - Wiley VHC-Verlag AN - OPUS4-57306 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Sänger, Johanna Christiane A1 - Schwentenwein, Martin A1 - Bermejo, Raúl A1 - Günster, Jens T1 - Hybridizing Lithography-Based Ceramic Additive Manufacturing with Two-Photon-Polymerization N2 - Stereolithography processes such as lithography-based ceramic manufacturing (LCM) are technologies that can produce centimeter-sized structures in a reasonable time frame. However, for some parts specifications, they lack resolution. Two-photon-polymerization (2PP) ensures the highest geometric accuracy in additive manufacturing so far. Nevertheless, building up parts in sizes as large as a few millimeters or even centimeters is a time-consuming process, which makes the production of 2PP printed parts very costly. Regarding feedstock specification, the requirements for 2PP are different to those for LCM, and generally, feedstocks are designed to meet requirements for only one of these manufacturing technologies. In an attempt to fabricate highly precise ceramic components of a rather large size, it is necessary to develop a feedstock that suits both light-based technologies, taking advantage of LCM’s higher productivity and 2PP’s accuracy. Hybridization should bring the desired precision to the region of interest on reasonably large parts without escalating printing time and costs. In this study, specimens gained from a transparent feedstock with yttria stabilized zirconia (YSZ) particles of 5 nm at 70 wt% were presented. The resin was originally designed to suit 2PP, while being also printable with LCM. This work demonstrates how hybrid parts can be sintered into full YSZ ceramics. KW - Additive Manufacturing KW - Transparent ceramic KW - Nano-powder PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-584541 DO - https://doi.org/10.3390/app13063974 SN - 2076-3417 VL - 13 IS - 6 SP - 1 EP - 9 PB - MDPI CY - Basel AN - OPUS4-58454 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Müllner, S. A1 - Held, T. A1 - Tichter, Tim A1 - Rank, P. A1 - Leykam, D. A1 - Jiang, W. A1 - Lunkenbein, T. A1 - Gerdes, T. A1 - Roth, C. T1 - Impact of Functional Groups in Reduced Graphene Oxide Matrices for High Energy Anodes in Lithium-Ion Batteries N2 - Most high capacity anode materials for lithium-ion batteries (LiB) require a carbonaceous matrix. In this context one promising material is reduced graphene oxide (rGO). Herein, we present the influence of different reduction degrees of rGO on its physico-chemical properties, such as crystallinity, specific surface area, electrical conductivity and electrochemical lithiation/delithiation behavior. It is found that a heat treatment under inert and reducing atmospheres increases the long-range order of rGO up to a temperature of 700 °C. At temperatures around 1000 °C, the crystallinity decreases. With decreasing oxygen content, a linear decrease in irreversible capacity during cycle 1 can be observed, along with a significant increase in electrical conductivity. This decrease in irreversible capacity can be observed despite an increase in specific surface area indicating the more significant influence of the oxygen content on the capacity loss. Consequently, the reversible capacity increases continuously up to a carbon content of 84.4 at% due to the thermal reduction. Contrary to expectations, the capacity decreases with further reduction. This can be explained by the loss of functional groups that will be lithiated reversibly, and a simultaneous reduction of long-range order, as concluded from dq/dU analysis in combination with XRD analysis. KW - Batteries KW - Functional Materials KW - Graphene Oxide PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-606852 DO - https://doi.org/10.1149/1945-7111/ace70a SN - 0013-4651 VL - 170 IS - 7 SP - 1 EP - 12 PB - The Electrochemical Society AN - OPUS4-60685 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Solberg, S. B. B. A1 - Zimmermann, P. A1 - Wilhelmsen, Ø. A1 - Bock, Robert A1 - Burheim, O. S. T1 - Analytical treatment of ion-exchange permselectivity and transport number measurements for high accuracy N2 - We analyse electromotive force measurements of concentration cells using non-equilibrium thermodynamics, and determine the transference coefficients of ion-exchange membranes in aqueous KCl solutions. By taking advantage of the analytical expression for the permselectivity, we extract transport coefficients with high accuracy. The transport number of K+ and the transference coefficient of water in the Selemion CMVN cationexchange membrane are found to be 100𝑡K+ = 99.59 ± 0.56 and 𝑡𝑤 = 3.69 ± 0.40 respectively, while for the Selemion AMVN anion-exchange membrane they are 100𝑡Cl− = 100.21 ± 0.37 and 𝑡𝑤 = −3.75 ± 0.27. These results suggest that the membranes are perfectly selective to the target ion, and that each ion carries 3-4 water molecules through the membrane, which reduces the membrane permselectivity. In these concentration cells, the electrical potential contribution of the membrane alone was more easily isolated with bare Ag/AgCl electrodes without reference solutions and liquid junction plugs. Additionally, we find a large contribution to the measured concentration cell voltage from concentration gradients across the porous plug of the reference electrode, which cannot be explained by Henderson’s equation alone. For most of the concentration range, the transport number of the porous plug is determined to be 100𝑡K+ = 49.43 ± 0.78 with negligible water transport, similar to literature values for bulk electrolyte. In dilute electrolyte solutions with concentrations below 0.1 mol kg−1, the plug shows anomalous behaviour consistent with an increase in K+ selectivity and water co-transport. KW - Ion-exchange membranes KW - Electrodialysis KW - Non-equilibrium thermodynamics KW - Electroosmosis KW - Transport number PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-580654 DO - https://doi.org/10.1016/j.memsci.2023.121904 SN - 1873-3123 VL - 2023 IS - 685 PB - Elsevier CY - New York, NY [u.a.] AN - OPUS4-58065 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Baensch, Franziska A1 - Baer, Wolfram A1 - Wossidlo, Peter A1 - Habib, Abdel Karim T1 - Damage evolution detection in a pipeline segment under bending by means of acoustic emission N2 - A steel pipeline segment of 2.5 m length was subjected to quasi-static four-point bending load in three steps for studying the initial cracking and damage accumulation based on the Acoustic Emission (AE) technique and by the direct current potential drop (DCPD) technique. For the latter, a new post-test analysis method was established. AE is found more sensitive to crack initiation than DCPD. Formation of mesoscopic and macroscopic cracks as well as their closure and the resulting friction generate weighted peak frequencies below 400 kHz, whereas microscopic cracking produces AE with broad band spectra identifiable by weighted peak frequencies above 400 kHz. Critical states alike the maximum load level and the leak opening were accompanied by peak amplitudes above 85 dBAE. This rather fundamental study provides a data base for possibly developing advanced strategies of detection and alarm systems based on acoustic monitoring of pipelines, or at least, steel structures. KW - Crack KW - Accoustic emission KW - Frequency domain KW - Potential drop technique KW - Fracture PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-565171 DO - https://doi.org/10.1016/j.ijpvp.2022.104863 SN - 0308-0161 VL - 201 IS - 104863 SP - 1 EP - 9 PB - Elsevier Science CY - Amsterdam AN - OPUS4-56517 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -