Engineering Compounds for the Recovery of Critical Elements from Slags: Melt Characteristics of Li5AlO4, LiAlO2, and LiAl5O8.

Engineered artificial minerals (EnAMs) are the core of a new concept of designing scavenger compounds for the recovery of critical elements from slags. It requires a fundamental understanding of solidification from complex oxide melts. Ion diffusivity and viscosity play vital roles in this process. In the melt, phase separations and ion transport give rise to gradients/increments in composition and, with it, to ion diffusivity, temperature, and viscosity. Due to this complexity, solidification phenomena are yet not well understood. If the melt is understood as increments of simple composition on a microscopic level, then the properties of these are more easily accessible from models and experiments. Here, we obtain these data for three stoichiometric lithium aluminum oxides. LiAlO2 is a promising EnAM for the recovery of lithium from lithium-ion battery pyrometallurgical processing. It is obtained through the addition of aluminum to the recycling slag melt. The high temperature properties spanning from below to above the liquidus temperature of three stoichiometric Li-Al-Oxides: Li5AlO4, LiAlO2, and LiAl5O8 are determined using molecular dynamic simulations. The compounds are also synthesized via the sol-gel route. The Li+ ion exhibits the largest diffusivity. They are quite mobile already below the liquidus temperature, i.e., for LiAlO2 at T = 1700 K, the diffusion coefficient of the lithium ion equals D = 3.0 × 10-9 m2 s-1. The other ions Al3+ and O2- do not move considerably at that temperature. The diffusivity of Li+ is largest in the lithium-rich compound Li5AlO4 with D = 32 × 10-9 m2 s-1 at 2500 K. The lower the viscosity, the higher the lithium content. The Li5AlO4 exhibits a viscosity of η = 2.2 mPa s at 1328 K which matches well with the experimentally determined 2.5 mPa s at this temperature. The viscosity of LiAlO2 at 1800 K is more than two times higher. These data sets can help to describe the melts on a microscopic level and understand how the melt properties will change due to gradients in the Li/Al concentration.

Control of Interface Migration in Nonequilibrium Crystallization of Li2SiO3 from Li2O-SiO2 Melt by Spatiotemporal Temperature and Concentration Fields.

During liquid-solid transformation, bulk mass and thermal diffusion, along with the evolved interfacial latent heat, work in tandem to generate interfacial thermodynamic and kinetic forces, the interplay of which decides the solidification velocity and consequently the solidified phase attributes. Hence, access to interface dynamics information in dependence of bulk transfer processes is pivotal to tailor the desired quantity of solid phases of unique compositions. It finds particular application for engineering concentrated Lithium (Li) phases out of Li-ion battery slags, thus generating a high value-added product from a conventional waste process stream. However, considerable challenge exists to predict the impact of the diverse external cooling rates on the evolving internal transfer processes and thus tuning solidification routes for achieving phases of interest. Hence, in this work, a thermodynamically consistent nonequilibrium model, by considering spatiotemporal temperature and concentration fields, is developed and applied to study solidification of Li2SiO3 from a Li2O-SiO2 melt that constitutes an important subsystem of the Li containing battery-recycling slags. The approach treats the sharp solid/liquid interface as a moving heat source. In the presence of different heat extraction profiles, it evaluates the spatial temperature heterogeneity and its implicit correlation to internal material fluxes resulting from maximization of dissipation and consequently the interrelation to interface velocities. Model calculations revealed that irrespective of the external cooling rate, for an initial short time duration, the magnitude of which increased with decreasing cooling rates, the interface velocities show a reducing trajectory directly relatable to the reducing thermodynamic forces due to localized interfacial temperature rise from the generated latent heat of fusion from the initial solidification. This is followed by a thermodynamically controlled regime, whereby for each cooling rate, the interface velocities increase until a maxima, the magnitude of which decreases with decreasing cooling rates. Finally, the interface propagation speeds decrease as controlled by the kinetic regime.

Macromolecular Architecture-Dependent Polymorphous Crystallization Behavior of PVDF in the PVDF/γ-BL System via Thermally Induced Phase Separation.

This study investigates the effect of the macromolecular architecture of poly(vinylidene fluoride) (PVDF) on its thermally induced phase separation (TIPS) behavior and polymorphic crystallization in the PVDF/γ-butyrolactone (PVDF/γ-BL) system. Preparative PVDF fractions with specific macromolecular architecture and phase constitution are generated. The results show that PVDF's macromolecular architecture, particularly the degree of branching and regio-defects, plays a significant role in its temperature-dependent crystallization and resulting polymorphic phases. While regio-defects dominate crystallization in the temperature range between 30 and 25 °C, the degree of branching becomes decisive in the 25-20 °C interval. The developed fractions of PVDF are further analyzed in terms of their molecular weight distribution, revealing that the PVDF fractions crystallized out of solution have similar molecular weight distributions with lower dispersity compared with the feed polymer. These findings are crucial for macromolecular separation and adjustment of PVDF polymorphic properties and hence for the development of tailor-made PVDF matrix materials for composites and membranes. The findings suggest the possibility of polymorphous phase tailoring of PVDF based on macromolecular architecture due to temperature-controlled crystallization out of solution and strongly motivate further research to reveal deeper knowledge of regio-defect and branching influence of PVDF solution crystallization.

Mechanical Consequences of Dynamically Loaded NiTi Wires under Typical Actuator Conditions in Rehabilitation and Neuroscience.

In the field of rehabilitation and neuroscience, shape memory alloys play a crucial role as lightweight actuators. Devices are exploiting the shape memory effect by transforming heat into mechanical work. In rehabilitation applications, dynamic loading of the respective device occurs, which in turn influences the mechanical consequences of the phase transforming alloy. Hence in this work, dynamic thermomechanical material behavior of temperature-triggered phase transforming NiTi shape memory alloy (SMA) wires with different chemical compositions and geometries was experimentally investigated. Storage modulus and mechanical loss factor of NiTi alloys at different temperatures and loading frequencies were analyzed under force-controlled conditions. Counterintuitive storage modulus- and loss factor-dependent trends regarding the loading frequency dependency of the mechanical properties on the materials' composition and geometry were, hence, obtained. It was revealed that loss factors showed a pronounced loading frequency dependency, whereas the storage modulus was not affected. It was shown that force-controlled conditions led to a lower storage modulus than expected. Furthermore, it turned out that a simple empirical relation could capture the characteristic temperature dependency of the storage modulus, which is an important input relation for modeling the rehabilitation device behavior under different dynamic and temperature loading conditions, taking directly into account the material behavior of the shape memory alloy.

Embedded NiTi Wires for Improved Dynamic Thermomechanical Performance of Silicone Elastomers.

The extraordinary properties of shape memory NiTi alloy are combined with the inherent viscoelastic behavior of a silicon elastomer. NiTi wires are incorporated in a silicon elastomer matrix. Benefits include features as electrical/thermal conductivity, reinforcement along with enhanced damping performance and flexibility. To gain more insight of this composite, a comprehensive dynamic thermomechanical analysis is performed and the temperature- as well as frequency-dependent storage modulus and the mechanical loss factor are obtained. The analyses are realized for the composite and single components. Moreover, the models to express the examined properties and their temperature along with the frequency dependencies are also presented.

Adherence Kinetics of a PDMS Gripper with Inherent Surface Tackiness.

Damage and fiber misalignment of woven fabrics during discontinuous polymer processing remain challenging. To overcome these obstacles, a promising switchable elastomeric adherence gripper is introduced here. The inherent surface tackiness is utilized for picking and placing large sheets. Due to the elastomer's viscoelastic material behavior, the surface properties depend on loading speed and temperature. Different peeling speeds result in different adherence strength of an interface between the gripper and the substrate. This feature was studied in a carefully designed experimental test set-up including dynamic thermomechanical, as well as dynamic mechanical compression analyses, and adherence tests. Special emphases were given to the analyses of the applicability as well as the limitation of the viscoelastic gripper and the empirically modeling of the gripper's pulling speed-dependent adherence characteristic. Two formulations of poly(dimethylsiloxane) (PDMS) with different hardnesses were prepared and analyzed in terms of their applicability as gripper. The main insights of the analyses are that the frequency dependency of the loss factor tanδ is of particular importance for the application along with the inherent surface tackiness and the low sensitivity of the storage modulus to pulling speed variations. The PDMS-soft material formulation exhibits the ideal material behavior for an adhesive gripper. Its tanδ varies within the application relevant loading speeds between 0.1 and 0.55; while the PDMS-hard formulation reveals a narrower tanδ range between 0.09 and 0.19. Furthermore, an empirical model of the pulling speed-dependent strain energy release rate G(v) was derived based on the experimental data of the viscoelastic characterizations and the probe tack tests. The proposed model can be utilized to predict the maximum mass (weight-force) of an object that can be lifted by the gripper.

Thermodynamic Principles for the Design of Polymers for Drug Formulations.

Polymers play an essential role in drug formulation and production of medical devices, implants, and diagnostics. Following drug discovery, an appropriate formulation is selected to enable drug delivery. This task can be exceedingly challenging owing to the large number of potential delivery methods and formulation and process variables that can interact in complex ways. This evolving solubility challenge has inspired an increasing emphasis on the developability of drug candidates in early discovery as well as various advanced drug solubilization strategies. Among the latter, formulation approaches that lead to prolonged drug supersaturation to maximize the driving force for sustained intestinal absorption of an oral product, or to allow sufficient time for injection after reconstitution of a parenteral lyophile formulation, have attracted increasing interest. Although several kinetic and thermodynamic components are involved in stabilizing amorphous dispersions, it is generally assumed that maximum physical stability, defined in terms of inhibition of drug crystallization, requires that the drug and excipient remain intimately mixed. Phase separation of the drug from its excipient may be the first step that ultimately leads to crystallization. We discuss the role of advanced thermodynamics using two examples: ASD and vitamin E-stabilized ultrahigh-molecular weight polyethylene implants.