Ionic Crystals Research Articles

An ionic liquid crystal functionalized nanocellulose lubricant additives

Cellulose, one of nature's most abundant, clean, and sustainable resources, has often shown unsatisfactory results when used as bio-lubricant additives. Herein, nanocellulose (NC) from amorphous waste natural poplar was extracted using deep eutectic solvent encapsulation treatment and chlorine bleaching process. Subsequently, 1-hexadecyl-3-methylimidazolium bromide was integrated onto NC using a one-step hydrothermal treatment (high-temperature and high-pressure environment) to obtain ionic liquid crystal (ILC) functionalized products (named as ILC-NC). After ball-milling process and solid phase separation step, ILC-NC exhibits excellent dispersion stability and lubrication properties in the liquid phase (including water and vegetable oil). Based on the polar and colloidal activity properties of ILC, it can form an ordered molecular layer on NC surface and form a lubricating film-like structure, making NC smoother and sliding well. Compared to ILC/NC aqueous dispersion, ILC-NC reduces the coefficient of friction and wear rate on steel disk surface by 68.75 % and 74.07 %, respectively. The minimum coefficient of friction was further reduced to 0.032 as dispersing ILC-NC in sunflower oil, showing a reduction of 0.134 (77.91 %) compared to pure sunflower oil. Finally, the lubrication theoretical model calculation reveals the lubrication state of ILC-NC on the steel disk surface and proposes the lubrication mechanism.

Ferroelastic ionic organic crystals that self-heal to 95%

The realm of self-healing materials integrates chemical and physical mechanisms that prevent wear and fracturing and extend the operational lifetime. Unlike the favorable rheology of amorphous soft materials that facilitates efficient contact between fragments, the efficiency of recovery of atomistically ordered materials is restricted by slower interfacial mass transport and the need for ideal physical alignment, which limits their real-world application. We report drastic enhancements in efficiency and recovery time in the self-healing of anilinium bromide, challenging these limitations. Crystals of this material recovered up to 49% within seconds and up to 95% after 100 min via ferroelastic detwinning. The spatial evolution of strain during cracking and healing was measured in real time using digital image correlation. Favorable alignment and strong ionic bonding across the interface of partially fractured crystals facilitate self-healing. This study elevates organic crystals close to the best-in-class self-healing polymers and sets an approach for durable crystal-based optoelectronics.

Additive single atom values for thermodynamics IV: Formula volume, enthalpy, absolute entropy and heat capacity for ionic solids - Hydrate and anhydrate data

Atom Sums are optimized additive values for the chemical elements which may be used to predict thermochemical values of inorganic solids. Since they are based on the elements of the Periodic Table they are a complete set of parameters, subject only to the availability of reference thermochemical data. In the present publication, optimized data is presented for ambient formula unit volumes, enthalpies, entropies and heat capacities for both inorganic hydrates and anhydrates. These data complement previously published Atom Sum parameters for formation reaction entropies and for formation reaction Gibbs energies as well as complementing earlier data for undifferentiated inorganic solids.

Biocompatibility and antimicrobial efficacy of silver-doped borosilicate bioactive glass for tissue engineering application

Borate bioactive glasses are an auspicious material for tissue engineering applications due to their enhanced dissolution rate, bioactivity, and capacity to integrate therapeutic ions. In this study, borate-based S49B4 bioactive glass doped with silver at mass fraction of 0.5, 1, and 3 wt% were studied for bioactivity, degradation, antibacterial, and cytocompatibility. Thermogravimetric analysis revealed that the bioactive glasses were thermally stable between 600 and 700 °C. Fourier transform infrared spectroscopy and X-ray diffraction confirmed the successful synthesis of an amorphous phase of the doped borosilicate bioactive glasses and the incorporation of silver ion crystals within the structure, as well as associated contributions from borate and silicate network formers in the borosilicate bioactive glass. Morphological evaluation revealed that the borosilicate bioactive glasses exhibit a uniform and spherical shape across all formulations, with the mean particle size varying from 65 to 76 nm. An in-vitro acellular bioactivity in simulated body fluid medium showed that increasing the silver content increased the degradation rate and pH. Besides, scanning electron microscopy and Energy dispersive X-ray spectroscopy analysis revealed an upsurge in apatite production on the BBGs' surfaces as well as incremental Calcium-Phosphate ratio values of 1.50, 1.65 and 1.70 as the silver content increases. The antibacterial effect was tested against Escherichia coli and Staphylococcus aureus, while cytocompatibility was tested against human gingival epithelial cells. Silver integration at 1 wt percent yielded the most promising outcomes, which were particularly bactericidal at 79.8 % for Escherichia coli and 93.41 % for Staphylococcus aureus. Similarly, its Lactate Dehydrogenase percentage is significantly similar to the negative control employed in the study, indicating its biocompatibility. In contrast, 3 wt% silver exhibited the maximum bactericidal activity while also exhibiting mild cytotoxicity. In summary, our research indicates that elevated silver concentration enhances the bioactivity and antimicrobial characteristics of borosilicate bioactive glasses; nevertheless, a higher silver weight percent in this study also increases the possibility of cytotoxicity. It is therefore essential to carefully regulate the amount of silver doping at lower concentrations in order to maximize antibacterial action and minimize toxicity to human cells. The results presented here contribute to our understanding of the prospective use of silver doped borosilicate bioactive glasses as a possible material for tissue engineering applications.

Scaling of entangling-gate errors in large ion crystals

Scaling of entangling-gate errors in large ion crystals

Influence of the counterion on the structure and stability of the smectic C phase in ionic liquid crystals

ABSTRACT Ionic liquid crystals (ILCs) are built of ion pairs. These consist often of a small anion and a large mesogenic cation. The properties of the ILCs like e.g. the phase behaviour or structure parameters, depend not only on the large mesogenic cations but also on the small counteranions. Here the influence of the small anion on the formation and stability of the in ILCs rare smectic C (SmC) phase is investigated in a series of methylimidazolium azobenzene ILCs with the same cation but different anions. All ILCs synthesised show the rare SmC phase. The phase behaviour and the tilt angles of the compounds were studied using polarising optical microscopy and differential scanning calorimetry. Furthermore, layer spacing and layer shrinkage of the SmC phase were examined using X-ray scattering. We show that the structural parameters of the phase-like layer spacing and tilt angle are only weakly influenced by the anions, whereas the mesophase ranges are strongly influenced by the choice of the anions. The results are also compared to the Hofmeister series for anions and it is found that the anions stabilise the SmC phase more the more kosmotropic they are.

Composite organic ionic plastic crystal membranes: The effect of ether-functionalized cations on light-gas separation performance

In light of increasing concerns about climate change, there is a growing need for innovative solutions to address CO2 emissions. Addressing this urgency, this work presents a unique approach to CO2 separation utilizing composite membranes of organic ionic plastic crystals (OIPCs) with ether-functionalized cations and poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP). Here we report the gas separation performance of OIPC-based membranes of 3,3-dimethyloxazolidinium [C1moxa]+, 4-ethyl-4-methylmorpholinium [C2mmor]+ and 4-isopropyl-4-methylmorpholinium [Ci3mmor]+ cations paired with the bis(fluorosulfonyl)imide [FSI]- anion. These composites demonstrated very good gas separation properties, especially [C1moxa][FSI] which produced a permeability of 63 barrer for CO2 and an overall selectivity (CO2/N2) of 205, which is the highest amongst all the OIPCs reported so far. Additionally, a large change in separation performance was observed for the [Ci3mmor][FSI] membrane upon heating above the solid-solid phase transition (II - I) at 48 °C; the CO2 permeability increased from 7 to 163 barrer and an approximately 3-fold increase in selectivity was observed. These findings advance the design of composite membranes based on OIPCs towards increased selectivity and sustained effectiveness in the separation of light gases.

Coarse-Grained Simulations of Columnar Ionic Liquid Crystals: Comparison with Experiments.

We simulate a homologous series of guanidinium-based columnar ionic liquid crystals (ILCs) using coarse-grained molecular dynamics (MD) simulations with the Martini force field. We systematically vary the length of alkyl side chains, ILC-n (n = 8, 12, 16), and compare our results with previous experimental findings. Experimentally, ILC-8 exhibits a narrow mesophase window and weak columnar order, while ILC-12 and ILC-16 display a broad mesophase window and high columnar order. The MD simulations show that ILC-8 forms a percolated structure, whereas the longer chain analogues self-assemble into columns, with columnar assembly becoming more prominent as the side chain length increases, in qualitative agreement with the experiments. Furthermore, the intercolumnar distance increases monotonically with increasing side chain length and decreases with increasing temperature. Finally, we find that the diffusion coefficient and ionic conductivity decrease substantially with increasing chain length, consistent with experimental observations. We attribute this decrease in mobility to the formation of hexagonally ordered columns, which restrict transport more than percolated networks.

Heterogeneous dynamics of diffusive motion in organic ionic plastic crystal studied using spin–spin relaxation time: N,N-diethylpyrrolidinium bis(fluorosulfonyl)amide

Abstract The temperature dependences of the spin–spin relaxation times (T2) of 1H and 19F nuclei were measured for N,N-diethylpyrrolidinium bis(fluorosulfonyl)amide with a plastic crystal phase. In the plastic crystal phase, 2 types of T2 were observed in both 1H and 19F experiments, which were considered to be the appearance of heterogeneous dynamics of diffusive motion. By examining temperature dependences of the T2 values and the existence ratios, the following conclusions were reached. (i) The prepared plastic crystal sample was in a polycrystalline state, and each crystallite comprised 2 phases: the core phase (plastic crystal phase) and the surface phase formed to relieve surface stress. (ii) The 1H-T2 (19F-T2) values of the 2 phases differed, and ions in the surface phase were more mobile. The 1H-T2 (19F-T2) values for the 2 phases increased with temperature rise. In particular, the 1H-T2 (19F-T2) values of the surface phase were smoothly connected to the liquid T2 values. (iii) The cations and anions exhibited a cooperative diffusive motion. (iv) When the temperature was considerably lower than the melting point, the ratio of the surface phase did not significantly differ from when it first formed. However, it rapidly increased near the melting point and became liquid.

Lyotropic Aqueous 2-Picolinium Ionic Liquid Crystals and Their Shear-Induced Foams.

1-Dodecyl-2-methylpyridinium bromide ([C12-2-Pic][Br]) and 1-hexadecyl-2-methylpyridinium bromide ([C16-2-Pic][Br]) are two ionic liquid crystals presenting thermotropic smectic phases above 80 °C. Aiming to take advantage of the liquid crystalline properties at lower temperatures, lyotropic aqueous systems were prepared from these two organic salts. Both systems were characterized by polarized optical microscopy (POM), X-ray powder diffraction (XRD), and fast field cycling nuclear magnetic resonance (FFC-NMR) relaxometry to assess their texture, phase structure, and molecular dynamics, respectively. The mesomorphic behavior was induced at room temperature. Moreover, the lyotropic [C12-2-Pic][Br]aq revealed a smectic phase with higher separation between layers, different from the lamellar phases found in the thermotropic system (S1 and SA), which is thermally stable up to 50 °C. Furthermore, the surfactant nature of the ionic liquids diluted solutions investigated in this work allowed the formation of foams. It was found that the precursor solutions of the lyotropic dilutions with the longest alkyl chain ([C16-2-Pic][Br]aq) originated liquid foams with more stable structures than those of [C12-2-Pic][Br]aq.

Many-Body MYP2 Force-Field: Toward the Crystal Growth Modeling of Hybrid Perovskites.

Hybrid perovskites are well-known for their optoelectronic and photovoltaic properties. Molecular dynamics simulations allow the study of these soft and ionic crystals by including dynamical effects (e.g., molecular rotations, octahedra tilting, ionic diffusion and hysteresis), yet the high computational cost restricts the use of accurate ab initio forces for bulk or small atomic systems. Hence, great interest exists in the development of classical force-fields for hybrid perovskites of low and linear scaling computational cost, via both empirical methods and machine-learning. This work aims at extending the transferability of our MYP0 model, which has been successfully tailored to methylammonium lead iodide (MAPI) and applied to the study of molecular rotations, vibrations, diffusion of defects, and many other properties. The extended model, named MYP2, improves the description of inorganic or hybrid fragments and the processes of crystal formation while preserving a good description of bulk properties. More importantly, it allows for the direct simulation of the crystal growth of cubic MAPI from deposition of PbI and MAI precursors on the surfaces. Our findings pave the way toward classical force-fields able to model the microstructure evolution of hybrid perovskites and the crystalline synthesis from deposition in vacuo.

Disintegration characteristics and mechanism of red clay improved by steel slag powder

Red clay is prone to softening and disintegration when exposed to water, often triggering severe geological disasters. To enhance its resistance to disintegration, this paper employs a homemade wet-dry cycling disintegration apparatus, combined with XRD, SEM, MIP, and fractal theory, to analyze the effects of different activators on the disintegration characteristics and microscopic mechanisms of SSP-improved soil. Under wet-dry cycling, the disintegration process of SSP-improved soil can be divided into five stages: rapid water absorption, saturation wetting, rapid disintegration, softening and dissolution, and stable non-disintegration. As the activator and SSP content increase, the resistance to disintegration of SSP-improved soil gradually enhances. After the addition of activators, the porosity, pore area, pore length and width, and probability entropy of SSP-improved soil decrease (i.e., 7 % NS < 7 % CSW < 7 % NH < undisturbed soil), while the average shape factor, regional probability distribution index, and fractal dimension increase. This is because activators promote ion exchange, cementation, crystallization, and carbonation reactions in SSP-improved soil, generating a substantial amount of hydration products such as C-S(A)-H, Ca(OH)2 and CaCO3, which fill and encapsulate inter-particle pores, thereby reducing water flow channels within the pores. In contrast, the pore structure between particles in undisturbed soil is simple and well-connected, providing favorable conditions for the migration and dissolution of fine particles and the loss of cementing materials, which accelerates the destruction and disintegration of the soil structure.

Water-mediated super-correlated proton-assisted transport mode for solid-state K−O2 batteries

A comprehensive understanding of the behavior nature of fast ions at the atomic level is essential for the development of advanced solid-state ionic conductors. The inadequate inter-ion correlation effects of current ion transport models lead to a conductivity bottleneck in designing conductors. Herein, based on water-mediated proton-assisted ion transport, a novel transport mode with simultaneous anion-cation and inter-cation coupling is designed, enabling the K-ions of the modeled solid-state ionic conductor K2Fe4O7 crystals to achieve an ultra-high conductivity of 7.6 × 10–2 S cm–1, an enhancement of two orders of magnitude. The principle of the accelerated K-ion diffusion through the rotation and vibration of water molecules around the framework oxygen atom is elaborated, and the coupling correlation between proton and K-ion transport is confirmed using in-situ impedance spectroscopy under labeled isotopes. The application of this mechanism enabled the fabricated K−O2 solid-state battery exhibit an ultra-low overpotential (0.1 V) and excellent rate performance. Further, the mechanism is also applicable for Li and Na-ion conductors, providing significant theoretical guidance for breaking existing universal design rules and for the development for faster ionic conductors.

Tuning Proton Conduction by Staggered Arrays of Polar Preyssler-Type Oxoclusters.

Polyoxometalates (POMs), anionic nanosized oxoclusters that can be considered as fragments of metal oxides, have been extensively studied for their diverse composition and structure, showing promise in various fields such as catalysis and electronics. Proton conduction, relevant to catalysis and electronics, has attracted interest in materials chemistry, and POM anions are advantageous in terms of their proton carrier density and mobility. Recently, polar POMs have attracted attention for their unique ferroelectric behaviors, yet they have been little studied with regard to proton conduction, as their polarity has generally been believed to have a negative impact. Here, we propose that polar POMs can be used to align polar proton carriers, such as H2O and polymers, to construct efficient proton-conducting pathways. In this study, we present ionic crystals composed of polar Preyssler-type POMs ([Xn+(H2O)P5W30O110](15-n)-, Xn+ = Ca2+, Eu3+) and K+ exhibiting ultrahigh proton conductivity surpassing 10-2 S cm-1, which is required for practical applications. In contrast, ionic crystals with nonpolar Preyssler-type POMs show an order of magnitude lower proton conductivity. Structural and spectroscopic studies combined with theoretical calculations reveal that proton carriers align with the aid of staggered arrays of polar POMs, forming a hydrogen-bonding network favorable for proton conduction. This study integrates molecular chemistry by the design of POMs and solid-state chemistry by exploring long-range proton conduction mechanisms, offering novel insights for future materials design.

Organic Ionic Plastic Crystal/Polymer Composite Electrolyte Prepared By Solution Casting Method for Solid-State Lithium Batteries

Solid-state electrolytes have been considered as a promising candidate to address the safety issues for next-generation lithium batteries. Organic ionic plastic crystals (OIPCs) are attracting increasing interests as solid electrolyte materials due to their unique advantages, such as plasticity, nonflammability, good thermal and electrochemical stability. In this study, an OIPC-based composite electrolyte consisting of the OIPC 1-ethyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (Pyr12TFSI), lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) and the polymer polyvinylidene fluoride (PVDF) has been developed by a facile solution casting strategy. A free-standing and flexible OIPC/polymer composite membrane was fabricated by the solution casting method, which not only provides flexibility and better electrode/electrolyte contact, but also is more compatible with current battery processing methods. The composite membrane used in Li/Li symmetric cell was cycled stably over 900 h at a current density of 0.1 mA cm−2 at 50 °C, demonstrating that the OIPC/polymer composite electrolyte enabled the reversible and stable lithium plating and stripping behaviors. Further tests of the OIPC/polymer composite as solid electrolyte in LiFePO4/Li cell presented a high specific capacity of 149 mAh g−1 at 0.1 C and a long cycle life of over 440 cycles with capacity retention of 89% at 0.5 C at 50 °C, which showed improved rate capability and cycling stability in comparison with the composites with similar compositions but obtained by powder pressing method. This study demonstrated the potential of the OIPC/polymer composite solid electrolyte prepared by solution casting method and will promote the development of high-performance OIPC-based composite electrolytes for solid-state batteries.

Additive single atom values for thermodynamics III: Formation entropies and Gibbs energies for ionic solids – Hydrate and anhydrate data, and a correction

In the initial two publications in this series we established predictive additive Atom Sum thermochemical quantities for inorganic solids for each of the chemical elements. With the chemical elements being a finite set, these data cover the whole of the domain of inorganic solids so far as reference data is currently available.We here introduce a dataset augmented in hydrates, and divide our analysis between the hydrates and anhydrates. The Atom Sum terms are better directed independently to these disparate inorganic groups thus providing improved estimates of the corresponding predicted thermochemical quantities. In this paper we provide both updated formation reaction entropies and previously unpublished Gibbs energies.

Influence of inter-ion Coulomb interaction on the dynamics of ionic crystal vibrations under pulse loading

Abstract The low frequency (acoustic) oscillations of an ionic crystal under pulse loading are considered. Considering the large contribution of the Coulomb energy to the binding energy for ionic crystals, the dynamic equations of the oscillations are written using the Maxwell stress tensor determined by the second moment 〈EiEk 〉 of the electromagnetic stress field. The analysis of Maxwell’s and Euler’s equations allows us to establish the dependence of the elastic moduli on the RMS value of the electromagnetic stress field in ionic crystals. At the initial moment of stress, this value is equal to zero and we obtain the value of the volume modulus of the liquid, which is confirmed by experiment.

Realization of a chip-based hybrid trapping setup for 87Rb atoms and Yb+ ion crystals.

Hybrid quantum systems integrate laser-cooled trapped ions and ultracold quantum gases within a single experimental configuration, offering vast potential for applications in quantum chemistry, polaron physics, quantum information processing, and quantum simulations. In this study, we introduce the development and experimental validation of an ion trap chip that incorporates a flat atomic chip trap directly beneath it. This innovative design addresses specific challenges associated with hybrid atom-ion traps by providing precisely aligned and stable components, facilitating independent adjustments of the depth of the atomic trapping potential, and positioning trapped ions. Our findings include the simultaneous loading of the ion trap with linear Yb+ ion crystals and the loading of neutral 87Rb atoms into a mirror magneto-optical trap.

Individually Addressed Quantum Gate Interactions Using Dynamical Decoupling

A leading approach to implementing small-scale quantum computers has been to use laser beams, focused to micron spot sizes, to address and entangle trapped ions in a linear crystal. Here we propose a method to implement individually addressed entangling gate interactions, but driven by microwave fields, with a spatial resolution of a few microns, corresponding to 10−5 microwave wavelengths. We experimentally demonstrate the ability to suppress the effect of the state-dependent force using a single ion, and find the required interaction introduces 3.7(4)×10−4 error per emulated gate in a single-qubit benchmarking sequence. We model the scheme for a 17-qubit ion crystal, and find that any pair of ions should be addressable with an average crosstalk error of approximately 10−5. Published by the American Physical Society 2024

Bose–Einstein distribution temperature features of quasiparticles around magnetopolaron in Gaussian quantum wells of alkali halogen ions

Abstract We have applied strong coupling unitary transformation method combined with Bose–Einstein statistical law to investigate magnetopolaron energy level temperature effects in halogen ion crystal quantum wells. The obtained results showed that under magnetic field effect, magnetopolaron quasiparticle was formed through the interaction of electrons and surrounding phonons. At the same time, magnetopolaron was influenced by phonon temperature statistical law and important energy level shifts down and binding energy increases. This revealed that lattice temperature and magnetic field could easily affect magnetopolaron and the above results could play key roles in exploring thermoelectric conversion and conductivity of crystal materials.