Designing Accurate Moment Tensor Potentials for Phonon-Related Properties of Crystalline Polymers

The phonon-related properties of crystalline polymers are highly relevant for various applications. Their simulation is, however, particularly challenging, as the systems that need to be modeled are often too extended to be treated by ab initio methods, while classical force fields are too inaccurate. Machine-learned potentials parametrized against material-specific ab initio data hold the promise of being extremely accurate and also highly efficient. Still, for their successful application, protocols for their parametrization need to be established to ensure an optimal performance, and the resulting potentials need to be thoroughly benchmarked. These tasks are tackled in the current manuscript, where we devise a protocol for parametrizing moment tensor potentials (MTPs) to describe the structural properties, phonon band structures, elastic constants, and forces in molecular dynamics simulations for three prototypical crystalline polymers: polyethylene (PE), polythiophene (PT), and poly-3-hexylthiophene (P3HT). For PE, the thermal conductivity and thermal expansion are also simulated and compared to experiments. A central element of the approach is to choose training data in view of the considered use case of the MTPs. This not only yields a massive speedup for complex calculations while essentially maintaining DFT accuracy, but also enables the reliable simulation of properties that, so far, have been entirely out of reach

Designing Accurate Moment Tensor Potentials for Phonon-Related Properties of Crystalline Polymers

The phonon-related properties of crystalline polymers are highly relevant for various applications. Their simulation is, however, particularly challenging, as the systems that need to be modeled are often too extended to be treated by ab initio methods, while classical force fields are too inaccurate. Machine-learned potentials parametrized against material-specific ab initio data hold the promise of being extremely accurate and also highly efficient. Still, for their successful application, protocols for their parametrization need to be established to ensure an optimal performance, and the resulting potentials need to be thoroughly benchmarked. These tasks are tackled in the current manuscript, where we devise a protocol for parametrizing moment tensor potentials (MTPs) to describe the structural properties, phonon band structures, elastic constants, and forces in molecular dynamics simulations for three prototypical crystalline polymers: polyethylene (PE), polythiophene (PT), and poly-3-hexylthiophene (P3HT). For PE, the thermal conductivity and thermal expansion are also simulated and compared to experiments. A central element of the approach is to choose training data in view of the considered use case of the MTPs. This not only yields a massive speedup for complex calculations while essentially maintaining DFT accuracy, but also enables the reliable simulation of properties that, so far, have been entirely out of reach

Anisotropic Phonon Bands in H‑Bonded Molecular Crystals: The Instructive Case of α‑Quinacridone

Phonons play a crucial role in the thermodynamic and transport properties of solid materials. Nevertheless, rather little is known about phonons in organic semiconductors. Thus, we employ highly reliable quantum mechanical calculations for studying the phonons in the α-polymorph of quinacridone. This material is particularly interesting, as it has highly anisotropic properties with distinctly different bonding types (H-bonding, π-stacking, and dispersion interactions) in different spatial directions. By calculating the overlaps of modes in molecular quinacridone and the α-polymorph, we associate Γ-point phonons with molecular vibrations to get a first impression of the impact of the crystalline environment. The situation becomes considerably more complex when analyzing phonons in the entire 1st Brillouin zone, where, due to the low symmetry of α-quinacridone, a multitude of avoided band crossings occur. At these, the character of the phonon modes typically switches, as can be inferred from mode participation ratios and mode longitudinalities. Notably, avoided crossings are observed not only as a function of the length but also as a function of the direction of the phonon wave vector. Analyzing these avoided crossings reveals how it is possible that the highest frequency acoustic band is always the one with the largest longitudinality, although longitudinal phonons in different crystalline directions are characterized by fundamentally different molecular displacements. The multiple avoided crossings also give rise to a particularly complex angular dependence of the group velocities, but combining the insights from the various studied quantities still allows drawing general conclusions, e.g., on the relative energetics of longitudinal vs transverse deformations (i.e., compressions and expansions vs slips of neighboring molecules). They also reveal how phonon transport in α-quinacridone is impacted by the reinforcing H-bonds and by π-stacking interactions (resulting from a complex superposition of van der Waals, charge penetration, and exchange repulsion)

Anisotropic Phonon Bands in H‑Bonded Molecular Crystals: The Instructive Case of α‑Quinacridone

Phonons play a crucial role in the thermodynamic and transport properties of solid materials. Nevertheless, rather little is known about phonons in organic semiconductors. Thus, we employ highly reliable quantum mechanical calculations for studying the phonons in the α-polymorph of quinacridone. This material is particularly interesting, as it has highly anisotropic properties with distinctly different bonding types (H-bonding, π-stacking, and dispersion interactions) in different spatial directions. By calculating the overlaps of modes in molecular quinacridone and the α-polymorph, we associate Γ-point phonons with molecular vibrations to get a first impression of the impact of the crystalline environment. The situation becomes considerably more complex when analyzing phonons in the entire 1st Brillouin zone, where, due to the low symmetry of α-quinacridone, a multitude of avoided band crossings occur. At these, the character of the phonon modes typically switches, as can be inferred from mode participation ratios and mode longitudinalities. Notably, avoided crossings are observed not only as a function of the length but also as a function of the direction of the phonon wave vector. Analyzing these avoided crossings reveals how it is possible that the highest frequency acoustic band is always the one with the largest longitudinality, although longitudinal phonons in different crystalline directions are characterized by fundamentally different molecular displacements. The multiple avoided crossings also give rise to a particularly complex angular dependence of the group velocities, but combining the insights from the various studied quantities still allows drawing general conclusions, e.g., on the relative energetics of longitudinal vs transverse deformations (i.e., compressions and expansions vs slips of neighboring molecules). They also reveal how phonon transport in α-quinacridone is impacted by the reinforcing H-bonds and by π-stacking interactions (resulting from a complex superposition of van der Waals, charge penetration, and exchange repulsion)

Characterisation of the Mechanical Properties of Natural Fibre Polypropylene Composites Manufactured with Automated Tape Placement

The integration of natural fibre thermoplastic composites, particularly those combining flax fibres with polypropylene, offers a promising alternative to traditional synthetic composites, emphasising sustainability in composite materials. This study investigates the mechanical properties of flax/polypropylene composites manufactured using flashlamp automated tape placement and press consolidation, individually and in combination. Tensile, compression, three-point bending, and double cantilever beam tests are utilised for comparing these manufacturing processes and the mechanical performance of the resulting composites. The microstructure of the tapes is investigated using cross-sectional microscopy, and the thermophysical behaviour is analysed utilising thermogravimetric analysis and differential scanning calorimetry. The temperature during placement is monitored using an infrared camera, and the pressure is mapped with pressure-sensitive films. The natural fibre tapes show a good aptitude for being manufactured with automated tape placement. The tensile performance of tapes manufactured with automated tape placement is close to that of press consolidated samples. Compression, flexural properties, and the mode I fracture toughness critical energy release rate all benefit from a second consolidation step

Measurements for refractory protection in pyrometallurgical recycling of lithium-ion batteries

Recycling lithium-ion batteries (LIB) has become a key priority within the European Union's resource strategy, inducing a regulatory framework with ambitious recycling targets. Currently, no recycling technology meets these targets while remaining economically viable. The InduRed reactor, with its innovative pyrometallurgical approach via carbothermic reduction, presents a potential solution. A critical challenge, however, is the crucible's performance in the highly corrosive environment of aggressive melts and reducing gases. To address this, two protective measurements for a magnesium-oxide (MgO) crucible were investigated: one involved applying a thin graphite coating to minimize lithium diffusion, while the other utilized varying sizes of graphite cubes to create a protective temperature gradient. In addition, this study included the simulation of temperature distribution within the crucible using the OpenFOAM multi-region framework as a reason for the high impact of temperature on several different chemical and physical phenomena within the recycling process. Experimental findings show minimal lithium diffusion and corrosion in the graphite-coated crucible, with transfer coefficients above 90 % for all elements and up to 99 % for lithium. As revealed by Micro XRF cross-sectional analysis, the crucible with varying susceptor material sizes showed no contact between the input material and the refractory. This configuration can effectively act as a thermal and physical shield, providing an optimal barrier that prevents corrosion and diffusion effects at the crucible wall. This study demonstrates the potential of combining coatings and varied susceptor sizes for crucible protection, offering promising prospects for the InduRed reactor in future industrial applications

<i>GIDInd</i>: an automated indexing software for grazing-incidence X-ray diffraction data

Grazing-incidence X-ray diffraction (GIXD) is a widely used technique for the crystallographic characterization of thin films. The identification of a specific phase or the discovery of an unknown polymorph always requires indexing of the associated diffraction pattern. However, despite the importance of this procedure, only a few approaches have been developed so far. Recently, an advanced mathematical framework for indexing of these specific diffraction patterns has been developed. Here, the successful implementation of this framework in the form of an automated indexing software, named GIDInd, is introduced. GIDInd is based on the assumption of a triclinic unit cell with six lattice constants and a distinct contact plane parallel to the substrate surface. Two approaches are chosen: (i) using only diffraction peaks of the GIXD pattern and (ii) combining the GIXD pattern with a specular diffraction peak. In the first approach the six unknown lattice parameters have to be determined by a single fitting procedure, while in the second approach two successive fitting procedures are used with three unknown parameters each. The output unit cells are reduced cells according to approved crystallographic conventions. Unit-cell solutions are additionally numerically optimized. The computational toolkit is compiled in the form of a MATLAB executable and presented within a user-friendly graphical user interface. The program is demonstrated by application on two independent examples of thin organic films.</jats:p

Identifying the Internal Network Structure of a New Copper Isonicotinate Thin‐Film Polymorph Obtained via Chemical Vapor Deposition

Abstract The preparation of thin films is often associated with the appearance of unknown polymorphs, as both the substrate and deposition method can heavily influence crystallization processes. Here, chemical vapor deposition is used to obtain thin films of a copper‐isonicotinate (Cu‐INA) metal–organic framework (MOF). Starting from copper‐based precursor layers (copper oxide and hydroxide), a solid‐vapor conversion with vaporized isonicotinic acid in either a dry or humidified atmosphere, yields a new Cu‐INA MOF polymorph. It is found that the crystalline order of the precursor layer has a strong impact on the texture of Cu‐INA thin films. Furthermore, a novel methodology is introduced to determine the structure of a previously unknown thin‐film phase of Cu‐INA. Although only a few diffraction peaks are found via synchrotron grazing incidence X‐ray diffraction (GIXRD), a triclinic unit cell can be determined, and Patterson functions can be calculated. The latter reveals the position of the copper atoms within the unit cell and the alignment of the INA linkers defining the coordination network structure. This work introduces how the combination of GIXRD data with Patterson functions can be used to identify the structure of an unknown thin‐film MOF polymorph