Search

The electrochemical and charge storage performance of a fluorine-free structurally flexible hybrid pyrrolidinium-based ionic liquid electrolyte (HILE) in a symmetric graphite-based supercapacitor is thoroughly investigated. The HILE revealed thermal decomposition at above 230°C, a glass transition (Tg) temperature of below −70°C, and ionic conductivity of 0.16 mS cm−1 at 30°C. The chemical and electrochemical properties are investigated using a systematic variable temperature 1H and 31P NMR spectroscopy and diffusometry, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge (GCD). The supercapacitor demonstrated a notable specific capacitance of 186 F g−1 at a scan rate of 1 mV s−1 and a specific capacitance of 122 F g−1 at a current density of 0.5 A g−1. The maximum energy density of 48.8 Wh kg−1, a power density of 450 W kg−1 at a current density of 0.5 A g−1, and a potential window of 4 V were obtained. Altogether, this study demonstrates that the new HILE can be used in symmetric graphite-based supercapacitors over a wide potential window of 4 V and a temperature range from −20°C to 90°C., Validerad;2024;Nivå 1;2024-04-04 (signyg)License full text: CC BY-NC-ND 4.0

Due to their intriguing electronic properties and structural composition, transition metal oxides (TMOs) such as AOx, AxOx, and AxB3-xOx; A, B = Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Mo, W, etc., and their designed composites have tremendous potential in energy storage devices such as supercapacitors (SCs) and metal ion batteries (MIBs). Some outstanding properties of TMOs and their composites for applications as electrode materials in energy storage devices include their high conductivity, charge storage characteristics, doping potential, and composite forming propensity. The significant interactions of TMOs with heteroatoms, conductive polymers, and carbon nanomaterials (CNMs) drastically change the reactive parameters and electrical characteristics. This review covers the most recent advances in TMO research and development, ranging from mechanism design to device performance, with a main focus on essentials such as design, synthesis, manufacturing, and energy-storing properties. The electrochemical pyrolysis, in-situ preparation, solvothermal/hydrothermal approach, and other critical approaches and their implications are also discussed. The synergetic improvement of designed TMO/graphene, TMO/rGO, TMO/heteroatoms, TMO/polymers, TMO/halide/hydride, TMO/Chalcogens through ionic interactions, and investigation of the electrode–electrolyte interfaces have been discussed in detail. In addition, the effect of electrolytes, surface behavior, and performance evaluation parameters on the SC device performance have been included. Furthermore, parameters and models, reliability design and profile lifetime, common mistakes in performance evaluation of SC, and other obstacles and mitigation have been described in depth. Altogether, a well-grasped overview and potential strategies extended from the overall analysis of electrode materials and electrolytes are offered to lift advancement in developing futuristic materials for energy storage applications., Validerad;2023;Nivå 2;2023-10-02 (joosat);Funder: European Union;Full text license: CC BY

Ionic liquids (ILs) have emerged as viable solutions for developing new-age lubricants, both as neat lubricants and lubricant additives. Enabled by the presence of discrete ions, ILs have the possibility to render electrically conductive lubricants, which is a feasible strategy for developing lubricant systems compatible with modern e-drive conditions. However, this requires the characterization of the electrical properties of lubricants, which is a bottleneck for developing electrically conductive greases, given their complex architecture. This work introduces an electrochemical impedance spectroscopy measurement methodology to evaluate grease samples’ electrical properties. Compared to the commonly used conductivity meters, this method, through its multi-frequency alternating current (AC) impedance approach, can effectively distinguish the individual contributions of the bulk and the sample-electrode interface to the measured electrical response. Impedance spectra of grease samples are obtained using an electrochemical cell with parallel plate electrodes, mounted on a temperature-controlled cell stand and coupled with a potentiostat. The grease's bulk conductivity is extracted by fitting the impedance data to relevant equivalent electrical circuits. The bulk conductivity of lithium complex grease doped with ILs is evaluated and compared to greases with conventional conductivity additives (copper powder and conductive carbon black). The analysis of temperature-dependent conductivity reveals the rather different conductivity mechanisms for different additives. For greases doped with ILs, a comparison against the electrical conductivity of neat ILs reveals that, in addition to the ion dissociation, the interaction of the ions with the different grease components (base oil, thickener) is crucial in defining the grease conductivity., QC 20240115

Ionic liquids (ILs) have emerged as viable solutions for developing new-age lubricants, both as neat lubricants and lubricant additives. Enabled by the presence of discrete ions, ILs have the possibility to render electrically conductive lubricants, which is a feasible strategy for developing lubricant systems compatible with modern e-drive conditions. However, this requires the characterization of the electrical properties of lubricants, which is a bottleneck for developing electrically conductive greases, given their complex architecture. This work introduces an electrochemical impedance spectroscopy measurement methodology to evaluate grease samples' electrical properties. Compared to the commonly used conductivity meters, this method, through its multi-frequency alternating current (AC) impedance approach, can effectively distinguish the individual contributions of the bulk and the sample-electrode interface to the measured electrical response. Impedance spectra of grease samples are obtained using an electrochemical cell with parallel plate electrodes, mounted on a temperature-controlled cell stand and coupled with a potentiostat. The grease's bulk conductivity is extracted by fitting the impedance data to relevant equivalent electrical circuits. The bulk conductivity of lithium complex grease doped with ILs is evaluated and compared to greases with conventional conductivity additives (copper powder and conductive carbon black). The analysis of temperature-dependent conductivity reveals the rather different conductivity mechanisms for different additives. For greases doped with ILs, a comparison against the electrical conductivity of neat ILs reveals that, in addition to the ion dissociation, the interaction of the ions with the different grease components (base oil, thickener) is crucial in defining the grease conductivity., Validerad;2024;Nivå 2;2024-03-28 (hanlid);Full text: CC BY License

Ionic liquids (ILs) are a class of salts existing in the liquid state below 100 degrees C, possessing low volatility, high thermal stability as well as many highly attractive solvent and electrochemical capabilities, etc., making them highly tunable for a great variety of applications, such as lubricants, electrolytes, and soft functional materials. In many applications, ILs are first either physi- or chemisorbed on a solid surface to successively create more functional materials. The functions of ILs at solid surfaces can differ considerably from those of bulk ILs, mainly due to distinct interfacial layers with tunable structures resulting in new ionic liquid interface layer properties and enhanced performance. Due to an almost infinite number of possible combinations among the cations and anions to form ILs, the diversity of various solid surfaces, as well as different external conditions and stimuli, a detailed molecular-level understanding of their structure-property relationship is of utmost significance for a judicious design of IL-solid interfaces with appropriate properties for task-specific applications. Many experimental techniques, such as atomic force microscopy, surface force apparatus, and so on, have been used for studying the ion structuring of the IL interface layer. Molecular Dynamics simulations have been widely used to investigate the microscopic behavior of the IL interface layer. To interpret and clarify the IL structure and dynamics as well as to predict their properties, it is always beneficial to combine both experiments and simulations as close as possible. In another theoretical model development to bridge the structure and properties of the IL interface layer with performance, thermodynamic prediction & property modeling has been demonstrated as an effective tool to add the properties and function of the studied nanomaterials. Herein, we present recent findings from applying the multiscale triangle experiment-simulation-thermodynamic

The electrochemical and charge storage performance of a fluorine-free structurally flexible hybrid pyrrolidinium-based ionic liquid electrolyte (HILE) in a symmetric graphite-based supercapacitor is thoroughly investigated. The HILE revealed thermal decomposition at above 230°C, a glass transition (Tg) temperature of below −70°C, and ionic conductivity of 0.16 mS cm−1 at 30°C. The chemical and electrochemical properties are investigated using a systematic variable temperature 1H and 31P NMR spectroscopy and diffusometry, cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and galvanostatic charge-discharge (GCD). The supercapacitor demonstrated a notable specific capacitance of 186 F g−1 at a scan rate of 1 mV s−1 and a specific capacitance of 122 F g−1 at a current density of 0.5 A g−1. The maximum energy density of 48.8 Wh kg−1, a power density of 450 W kg−1 at a current density of 0.5 A g−1, and a potential window of 4 V were obtained. Altogether, this study demonstrates that the new HILE can be used in symmetric graphite-based supercapacitors over a wide potential window of 4 V and a temperature range from −20°C to 90°C., Validerad;2024;Nivå 1;2024-04-04 (signyg)License full text: CC BY-NC-ND 4.0

Ionic liquids (ILs) have emerged as viable solutions for developing new-age lubricants, both as neat lubricants and lubricant additives. Enabled by the presence of discrete ions, ILs have the possibility to render electrically conductive lubricants, which is a feasible strategy for developing lubricant systems compatible with modern e-drive conditions. However, this requires the characterization of the electrical properties of lubricants, which is a bottleneck for developing electrically conductive greases, given their complex architecture. This work introduces an electrochemical impedance spectroscopy measurement methodology to evaluate grease samples' electrical properties. Compared to the commonly used conductivity meters, this method, through its multi-frequency alternating current (AC) impedance approach, can effectively distinguish the individual contributions of the bulk and the sample-electrode interface to the measured electrical response. Impedance spectra of grease samples are obtained using an electrochemical cell with parallel plate electrodes, mounted on a temperature-controlled cell stand and coupled with a potentiostat. The grease's bulk conductivity is extracted by fitting the impedance data to relevant equivalent electrical circuits. The bulk conductivity of lithium complex grease doped with ILs is evaluated and compared to greases with conventional conductivity additives (copper powder and conductive carbon black). The analysis of temperature-dependent conductivity reveals the rather different conductivity mechanisms for different additives. For greases doped with ILs, a comparison against the electrical conductivity of neat ILs reveals that, in addition to the ion dissociation, the interaction of the ions with the different grease components (base oil, thickener) is crucial in defining the grease conductivity., Validerad;2024;Nivå 2;2024-03-28 (hanlid);Full text: CC BY License

The utilization of metal–organic frameworks (MOFs) in energy storage applications is constrained by their limited electrical conductivity and insufficient chemical robustness, posing various challenges and limitations. Nevertheless, research has demonstrated that MOF structures with exceptional porosity and adaptable architectures yield a wide range of composites, presenting promising prospects for improving their electrochemical performance in energy storage devices. When combined with other advanced materials, MOFs form composite structures overcoming these constraints by exhibiting superior electrical conductivity, electrochemical activity, and stability in comparison to pure MOFs. This article comprehensively overviews the designed chemistry of MOF-composites for metal-ion batteries (MIBs) and metal-ion capacitors (MICs). The synthesis and properties of various composites involving MOFs, including MOF-MXene, MOF-carbon nanomaterials (CNM)/graphene/carbon, MOF-transition metal oxide (TMO), MOF/polymers, MOF-derived layered double hydroxide (LDH), as well as the challenges and mitigation strategies have been discussed. A brief overview of MOF-composites as electrode materials for MIBs, including lithium-ion batteries (LIBs), sodium-ion batteries (SIBs), and potassium-ion batteries (KIBs) is presented. The recent developments in MICs, such as lithium-ion capacitors (LICs), magnesium-ion capacitors (MGICs), zinc-ion capacitors (ZICs), sodium-ion capacitors (SICs), and potassium-ion capacitors (KICs) have also been included. Furthermore, the electrochemical performance of the MOF composites has been assessed using a range of metrics, including output voltage, capacity, cycle stability, energy density (ED), and power density (PD). A comprehensive analysis has also been conducted to identify potential obstacles and possible mitigations to explore future possibilities. Overall, a comprehension of MOF-based materials and potential approaches for enhancing the futuristic, Validerad;2024;Nivå 2;2024-07-05 (joosat);Full text license: CC BY

The solvation structure, dynamics, and transport properties, as well as thermal and electrochemical stabilities of “solvent-in-salt” (SIS) electrolytes, also known as highly concentrated electrolytes, are far from fully understood. Furthermore, these special types of electrolytes are almost without exception based on fluorinated salts. In contrast, here we report on fluorine-free SIS electrolytes comprising ambient temperature liquid sodium bis(2-(2-ethoxyethoxy)ethyl)phosphate (NaDEEP) salt and tris(2-(2-ethoxyethoxy)ethyl)phosphate (TEOP) solvent, for which the ionic conductivities and ion diffusivities are altered profoundly as the salt concentration is increased. A careful molecular level analysis reveals a microstructure with a “solvent-rich” phase with almost an order of magnitude faster ion diffusion than in a “salt-rich” phase. Aggregated ionic structures in these SIS electrolytes lead to higher ionic conductivities alongside lower glass transition temperatures, <−80 °C, but also agreeable thermal stabilities, up to 270 °C, and improved anodic stabilities, possibly up to 7.8 V vs. Na/Na+ and at least >5 V vs. Na/Na+. Altogether, this provides a foundation for both better understanding and further development of fluorine-free SIS electrolytes for sodium batteries., Validerad;2024;Nivå 1;2024-04-09 (sofila);Full text license: CC BY 3.0

A new class of fluorine-free ionic liquids (ILs) and electrolytes based on aliphatic flexible oligoether anions, 2-(2-methoxyethoxy)acetate (MEA) and 2-[2-(2-methoxyethoxy)ethoxy]acetate (MEEA), coupled with pyrrolidinium and imidazolium cations is introduced. For the ILs with MEEA anions, Li+ conducting electrolytes are created by doping the ILs with 30 mol % of LiMEEA. The structural flexibility of the oligoether functionality in the anion results in glass transition temperatures (Tg) as low as −60 °C for the neat ILs and the electrolytes. The imidazolium-based ILs and electrolytes reveal better thermal stabilities but higher Tg and lower electrochemical stabilities than the corresponding pyrrolidinium-based analogues. All neat ILs show comparable transport properties for the cations and these decrease by the addition of lithium salt – the pyrrolidinium-based electrolyte being affected the most., Validerad;2024;Nivå 2;2024-05-22 (joosat);Full text: CC BY license

The solvation structure, dynamics, and transport properties, as well as thermal and electrochemical stabilities of “solvent-in-salt” (SIS) electrolytes, also known as highly concentrated electrolytes, are far from fully understood. Furthermore, these special types of electrolytes are almost without exception based on fluorinated salts. In contrast, here we report on fluorine-free SIS electrolytes comprising ambient temperature liquid sodium bis(2-(2-ethoxyethoxy)ethyl)phosphate (NaDEEP) salt and tris(2-(2-ethoxyethoxy)ethyl)phosphate (TEOP) solvent, for which the ionic conductivities and ion diffusivities are altered profoundly as the salt concentration is increased. A careful molecular level analysis reveals a microstructure with a “solvent-rich” phase with almost an order of magnitude faster ion diffusion than in a “salt-rich” phase. Aggregated ionic structures in these SIS electrolytes lead to higher ionic conductivities alongside lower glass transition temperatures, <−80 °C, but also agreeable thermal stabilities, up to 270 °C, and improved anodic stabilities, possibly up to 7.8 V vs. Na/Na+ and at least >5 V vs. Na/Na+. Altogether, this provides a foundation for both better understanding and further development of fluorine-free SIS electrolytes for sodium batteries., Validerad;2024;Nivå 1;2024-04-09 (sofila);Full text license: CC BY 3.0

A new class of fluorine-free ionic liquids (ILs) and electrolytes based on aliphatic flexible oligoether anions, 2-(2-methoxyethoxy)acetate (MEA) and 2-[2-(2-methoxyethoxy)ethoxy]acetate (MEEA), coupled with pyrrolidinium and imidazolium cations is introduced. For the ILs with MEEA anions, Li+ conducting electrolytes are created by doping the ILs with 30 mol % of LiMEEA. The structural flexibility of the oligoether functionality in the anion results in glass transition temperatures (Tg) as low as −60 °C for the neat ILs and the electrolytes. The imidazolium-based ILs and electrolytes reveal better thermal stabilities but higher Tg and lower electrochemical stabilities than the corresponding pyrrolidinium-based analogues. All neat ILs show comparable transport properties for the cations and these decrease by the addition of lithium salt – the pyrrolidinium-based electrolyte being affected the most., Validerad;2024;Nivå 2;2024-05-22 (joosat);Full text: CC BY license

Due to their intriguing electronic properties and structural composition, transition metal oxides (TMOs) such as AOx, AxOx, and AxB3-xOx; A, B = Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Mo, W, etc., and their designed composites have tremendous potential in energy storage devices such as supercapacitors (SCs) and metal ion batteries (MIBs). Some outstanding properties of TMOs and their composites for applications as electrode materials in energy storage devices include their high conductivity, charge storage characteristics, doping potential, and composite forming propensity. The significant interactions of TMOs with heteroatoms, conductive polymers, and carbon nanomaterials (CNMs) drastically change the reactive parameters and electrical characteristics. This review covers the most recent advances in TMO research and development, ranging from mechanism design to device performance, with a main focus on essentials such as design, synthesis, manufacturing, and energy-storing properties. The electrochemical pyrolysis, in-situ preparation, solvothermal/hydrothermal approach, and other critical approaches and their implications are also discussed. The synergetic improvement of designed TMO/graphene, TMO/rGO, TMO/heteroatoms, TMO/polymers, TMO/halide/hydride, TMO/Chalcogens through ionic interactions, and investigation of the electrode–electrolyte interfaces have been discussed in detail. In addition, the effect of electrolytes, surface behavior, and performance evaluation parameters on the SC device performance have been included. Furthermore, parameters and models, reliability design and profile lifetime, common mistakes in performance evaluation of SC, and other obstacles and mitigation have been described in depth. Altogether, a well-grasped overview and potential strategies extended from the overall analysis of electrode materials and electrolytes are offered to lift advancement in developing futuristic materials for energy storage applications., Validerad;2023;Nivå 2;2023-10-02 (joosat);Funder: European Union;Full text license: CC BY

The utilization of metal–organic frameworks (MOFs) in energy storage applications is constrained by their limited electrical conductivity and insufficient chemical robustness, posing various challenges and limitations. Nevertheless, research has demonstrated that MOF structures with exceptional porosity and adaptable architectures yield a wide range of composites, presenting promising prospects for improving their electrochemical performance in energy storage devices. When combined with other advanced materials, MOFs form composite structures overcoming these constraints by exhibiting superior electrical conductivity, electrochemical activity, and stability in comparison to pure MOFs. This article comprehensively overviews the designed chemistry of MOF-composites for metal-ion batteries (MIBs) and metal-ion capacitors (MICs). The synthesis and properties of various composites involving MOFs, including MOF-MXene, MOF-carbon nanomaterials (CNM)/graphene/carbon, MOF-transition metal oxide (TMO), MOF/polymers, MOF-derived layered double hydroxide (LDH), as well as the challenges and mitigation strategies have been discussed. A brief overview of MOF-composites as electrode materials for MIBs, including lithium-ion batteries (LIBs), sodium-ion batteries (SIBs), and potassium-ion batteries (KIBs) is presented. The recent developments in MICs, such as lithium-ion capacitors (LICs), magnesium-ion capacitors (MGICs), zinc-ion capacitors (ZICs), sodium-ion capacitors (SICs), and potassium-ion capacitors (KICs) have also been included. Furthermore, the electrochemical performance of the MOF composites has been assessed using a range of metrics, including output voltage, capacity, cycle stability, energy density (ED), and power density (PD). A comprehensive analysis has also been conducted to identify potential obstacles and possible mitigations to explore future possibilities. Overall, a comprehension of MOF-based materials and potential approaches for enhancing the futuristic, Validerad;2024;Nivå 2;2024-07-05 (joosat);Full text license: CC BY

Five new ionic materials comprising fluorine-free aromatic heterocyclic anions based on pyridine and pyrazine combined with a common n-tetrabutylphosphonium cation, (P4444)+, result in two room temperature ionic liquids (RTILs), one semi-solid, and two organic ionic plastic crystals (OIPCs) with melting points >20 °C. The OIPCs showed a plastic crystalline phase, multiple solid–solid transitions, and plastic crystalline and melt phases. For both the neat RTILs and the Li+ conducting electrolytes, the nature and strength of the ion–ion interactions mainly depend on the position of the nitrogen atom with respect to the carboxylate group in the anions. Furthermore, for the RTILs the ionic conductivity is effected by the electronic structure and flexibility of the ions and the anions diffuse faster than the (P4444)+ cation, but are slowed down in the electrolytes due to the strong electrostatic interactions between the carboxylate group of the anions and the Li+, as shown both experimentally and computationally. Overall, this study describes the effect of structural tuning of aromatic anions on the ion–ion interactions and introduces new ionic materials with promising properties to be used as solid and liquid electrolytes in energy storage devices., Validerad;2023;Nivå 2;2023-02-10 (joosat);Licens fulltext: CC BY License

Five new ionic materials comprising fluorine-free aromatic heterocyclic anions based on pyridine and pyrazine combined with a common n-tetrabutylphosphonium cation, (P4444)+, result in two room temperature ionic liquids (RTILs), one semi-solid, and two organic ionic plastic crystals (OIPCs) with melting points >20 °C. The OIPCs showed a plastic crystalline phase, multiple solid–solid transitions, and plastic crystalline and melt phases. For both the neat RTILs and the Li+ conducting electrolytes, the nature and strength of the ion–ion interactions mainly depend on the position of the nitrogen atom with respect to the carboxylate group in the anions. Furthermore, for the RTILs the ionic conductivity is effected by the electronic structure and flexibility of the ions and the anions diffuse faster than the (P4444)+ cation, but are slowed down in the electrolytes due to the strong electrostatic interactions between the carboxylate group of the anions and the Li+, as shown both experimentally and computationally. Overall, this study describes the effect of structural tuning of aromatic anions on the ion–ion interactions and introduces new ionic materials with promising properties to be used as solid and liquid electrolytes in energy storage devices., Validerad;2023;Nivå 2;2023-02-10 (joosat);Licens fulltext: CC BY License

Five new n-tetrabutylphosphonium (P4444)+ cation based ionic liquids (ILs) with oligoether substituted aromatic carboxylate anions have been synthesized. The nature and position of the oligoether chain affect thermal stability (up to 330 ºC), phase behaviour (Tg < -55 ºC) and ion transport. Furthermore, with the aim of application in lithium batteries, electrolytes were created for two of the ILs by 10 mol% doping using the corresponding Li-salts. This affects the ion diffusion negatively, from being higher and equal for cations and anions to lower for all ions and unequal. This is due to the stronger ionic interactions and formation of aggregates, primarily between the Li+ ions and the carboxylate group of the anions. Electrochemically, the electrolytes have electrochemical stability windows up to 3.5 V, giving some promise for battery application., Validerad;2023;Nivå 2;2023-08-15 (marisr);License fulltext: CC-BY-NC. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.

Alkali metal salts usually have high melting points due to strong electrostatic interactions and solvents are needed to create ambient temperature liquid electrolytes. Here, we report on six phosphate-anion-based alkali metal salts, Li/Na/K, all of which are liquids at room temperature, with glass transition temperatures ranging from −61 to −29 °C, and are thermally stable up to at least 225 °C. While the focus herein is on various physico-chemical properties, these salts also exhibit high anodic stabilities, up to 6 V vs. M/M+ (M = Li/Na/K), and deliver some battery performance – at elevated temperatures as there are severe viscosity limitations at room-temperature. While the battery performance arguably is sub-par, solvent-free electrolytes based on alkali metal salts such as these should pave the way for conceptually different Li/Na/K-batteries, either by refined anion design or by using several salts to create eutectic mixtures., Validerad;2023;Nivå 2;2023-03-09 (joosat);Licens fulltext: CC BY License

Ion transport measures and details as well as physico-chemical and electrochemical properties are presented for a small set of structurally flexible pyrrolidinium (Pyrr) and morpholinium (Morph) cation-based ionic liquids (ILs), all with oligoether phosphate-based anions. All have high thermal stabilities, low glass transition temperatures, and wide electrochemical stability windows, but rather moderate ionic conductivities, whereas both the anions and the cations of the Pyrr-based ILs diffuse faster than those of the Morph-based ILs. Overall the former ILs have significantly more promise as high-temperature supercapacitor electrolytes, rendering a specific capacitance of 164 F g−1 at 1 mV s−1, a power density of 241 W kg−1 and a specific energy density of 30 Wh kg−1 at 90 °C in a symmetric graphite supercapacitor., Validerad;2023;Nivå 2;2023-08-17 (joosat);Licens fulltext: CC BY 3.0

Alkali metal salts usually have high melting points due to strong electrostatic interactions and solvents are needed to create ambient temperature liquid electrolytes. Here, we report on six phosphate-anion-based alkali metal salts, Li/Na/K, all of which are liquids at room temperature, with glass transition temperatures ranging from −61 to −29 °C, and are thermally stable up to at least 225 °C. While the focus herein is on various physico-chemical properties, these salts also exhibit high anodic stabilities, up to 6 V vs. M/M+ (M = Li/Na/K), and deliver some battery performance – at elevated temperatures as there are severe viscosity limitations at room-temperature. While the battery performance arguably is sub-par, solvent-free electrolytes based on alkali metal salts such as these should pave the way for conceptually different Li/Na/K-batteries, either by refined anion design or by using several salts to create eutectic mixtures., Validerad;2023;Nivå 2;2023-03-09 (joosat);Licens fulltext: CC BY License

Five new n-tetrabutylphosphonium (P4444)+ cation based ionic liquids (ILs) with oligoether substituted aromatic carboxylate anions have been synthesized. The nature and position of the oligoether chain affect thermal stability (up to 330 ºC), phase behaviour (Tg < -55 ºC) and ion transport. Furthermore, with the aim of application in lithium batteries, electrolytes were created for two of the ILs by 10 mol% doping using the corresponding Li-salts. This affects the ion diffusion negatively, from being higher and equal for cations and anions to lower for all ions and unequal. This is due to the stronger ionic interactions and formation of aggregates, primarily between the Li+ ions and the carboxylate group of the anions. Electrochemically, the electrolytes have electrochemical stability windows up to 3.5 V, giving some promise for battery application., Validerad;2023;Nivå 2;2023-08-15 (marisr);License fulltext: CC-BY-NC. This is an open access article under the terms of the Creative Commons Attribution-NonCommercial License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited and is not used for commercial purposes.

Ion transport measures and details as well as physico-chemical and electrochemical properties are presented for a small set of structurally flexible pyrrolidinium (Pyrr) and morpholinium (Morph) cation-based ionic liquids (ILs), all with oligoether phosphate-based anions. All have high thermal stabilities, low glass transition temperatures, and wide electrochemical stability windows, but rather moderate ionic conductivities, whereas both the anions and the cations of the Pyrr-based ILs diffuse faster than those of the Morph-based ILs. Overall the former ILs have significantly more promise as high-temperature supercapacitor electrolytes, rendering a specific capacitance of 164 F g−1 at 1 mV s−1, a power density of 241 W kg−1 and a specific energy density of 30 Wh kg−1 at 90 °C in a symmetric graphite supercapacitor., Validerad;2023;Nivå 2;2023-08-17 (joosat);Licens fulltext: CC BY 3.0

Ionic liquids (ILs) are room temperature molten salts that possess preeminent physicochemical properties and have shown great potential in many applications. However, the use of ILs in surface-dependent processes, e.g. energy storage, is hindered by the lack of a systematic understanding of the IL interfacial microstructure. ILs on the solid surface display rich ordering, arising from coulombic, van der Waals, solvophobic interactions, etc., all giving near-surface ILs distinct microstructures. Therefore, it is highly important to clarify the interactions of ILs with solid surfaces at the nanoscale to understand the microstructure and mechanism, providing quantitative structure-property relationships. Atomic force microscopy (AFM) opens a surface-sensitive way to probe the interaction force of ILs with solid surfaces in the layers from sub-nanometers to micrometers. Herein, this review showcases the recent progress of AFM in probing interactions and microstructures of ILs at solid interfaces, and the influence of IL characteristics, surface properties and external stimuli is thereafter discussed. Finally, a summary and perspectives are established, in which, the necessities of the quantification of IL-solid interactions at the molecular level, the development of in situ techniques closely coupled with AFM for probing IL-solid interfaces, and the combination of experiments and simulations are argued.

Surface-enhanced Raman scattering (SERS) is an attractive technique for studying trace detection. It is of utmost importance to further improve the performance and understand the underlying mechanisms. An ionic liquid (IL), the anion of which is derived from biomass, [P6,6,6,14][FuA] was synthesized and used as a trace additive to improve the SERS performance of cytochrome c (Cyt c) on TiO2 nanotube arrays (TNAs). An increased and better enhancement factor (EF) by four to five times as compared to the system without an IL was obtained, which is better than that from using the choline-based amino acid IL previously reported by us. Dissociation of the ILs improved the ionic conductivity of the system, and the long hydrophobic tails of the [P6,6,6,14]+ cation contributed to a strong electrostatic interaction between Cyt c and the TNA surface, thereby enhancing the SERS performance. Atomic force microscopy did verify strong electrostatic interactions between the Cyt c molecules and TNAs after the addition of the IL. This work demonstrates the importance of introducing the phosphonium-based IL to enhance the SERS performance, which will stimulate further development of more effective ILs on SERS detection and other relevant applications in biology.

Ionic liquids (ILs) interact strongly with many different types of solid surfaces in a wide range of applications, e.g. lubrication, energy storage and conversion, etc. However, due to the nearly immeasurable large number of potential ILs available, identifying the appropriate ILs for specific solid interfaces with desirable properties is a challenge. Theoretical studies are highly useful for effective development of design and applications of these complex molecular systems. However, obtaining reliable force field models and interaction parameters is highly demanding. In this work, we apply a new methodology by deriving the interaction parameters directly from the experimental data, determined by colloid probe atomic force microscopy (CP-AFM). The reliability of the derived interaction parameters is tested by performing molecular dynamics simulations to calculate translational self-diffusion coefficients and comparing them with those obtained from NMR diffusometry.

There is a growing interest in sustainable and high performance supercapacitors (SCs) operating at elevated temperatures as they are highly demanded in heat-durable electronics. Here, we present a biomass-derived nonfluorinated ionic liquid (IL) [P4444][HFuA] and its structural analogue [P4444][TpA] as electrolytes for supercapacitors comprising multiwall carbon nanotubes and activated charcoal (MWCNTs/AC) mixed carbon composite electrodes. A detailed investigation of the effect of scan rate, temperature, potential window and orientation of ions on the electrodes surfaces is performed. The supercapacitors exhibited relatively lower specific capacitance for both [P4444][HFuA] and [P4444][TpA] ILs at room temperature. However, the specific capacitance has significantly increased with an increase in temperature and potential window. The equivalent serie resistances of the SCs is deceased with increasing temperatures, which is a result of improved ionic conductivities of the IL electrolytes. In CV cycling at 60 °C, the capacitor with [P4444][HFuA] IL-based electrolyte retained about 90% of its initial capacitance, while the capacitor with [P4444][TpA] IL-based electrolyte retained about 83% of its initial capacitance. Atomistic computations revealed that the aromatic [FuA]− and [TpA]− anions displayed perpendicular distribution that can effectively neutralize charges on the carbon surfaces. However, the [HFuA]− anion exhibited somewhat tilted configurations on the carbon electrode surfaces, contributing to their outstanding capacitive performance in electrochemical devices.

It is crucial to understand the behaviour and interfacial interactions as well as properties of ionic liquids (ILs) at electrode surfaces on the molecular level for developing IL-based electrochemical energy storage devices including supercapacitors and batteries. In this work, a colloid probe atomic force microscopy (CP-AFM) -based experimental approach is presented to determine the molecular interaction forces between ILs and differently charged SiO2 microspheres. The effects of structural variations in ILs and the nature surface charges of SiO2 on the molecular interaction force are systematically studied. The surface charges of SiO2 were achieved by grafting quaternary ammonium and –COOH, –NH2 groups. The determined molecular interaction force is found to be strongly dependent on the surface charge, in which, the force enhances at a more negatively charged surface. Furthermore, the ILs with longer alkyl chains on cations exhibit stronger molecular interaction forces with the charged SiO2. These reported experimental results on the molecular level provide new insights for model development and molecular simulations of ILs interacting with charged surfaces and guide the design of ILs-based supercapacitor and battery systems.

Phosphonium ionic liquids with orthoborate anions have been studied in terms of their interfacial film formation, both physisorbed and sacrificial from chemical breakdown, in sheared contacts of varying harshness. The halogen-free anion architecture was varied through (i) the heteronuclear ring size, (ii) the hybridisation of the constituent atoms, and (iii) the addition of aryl functionalities. Time of Flight-Secondary Ion Mass Spectrometry analysis revealed the extent of sacrificial tribofilm formation allowing the relative stability of the ionic liquids under tribological conditions to be determined and their breakdown mechanisms to be compared to simple thermal decomposition. Overall, ionic liquids outperformed reference oils as lubricants; in some cases, sacrificial films were formed (with anion breakdown a necessary precursor to phosphonium cation decomposition) while in other cases, a protective, self-assembly lubricant layer or hybrid film was formed. The salicylate-based anion was the most chemically stable and decomposed only slightly even under the harshest conditions. It was further found that surface topography influenced the degree of breakdown through enhanced material transport and replenishment. This work thus unveils the relationship between ionic liquid composition and structure, and the ensuing inter- and intra-molecular interactions and chemical stability, and demonstrates the intrinsic tuneability of an ionic liquid lubrication technology., QC 20211230

It was found that Li[BOB]center dot nH(2)O salts were not readily suitable for the synthesis of high-purity orthoborate-based tetraalkylphosphonium ionic liquids, as exemplified here for trihexyl(tetradecyl)phosphonium bis(oxalato)borate, [P-6,P-6,P-6,P-14][BOB]; along with [BOB](-), a metastable transition anionic complex (TAC) of dihydroxy(oxalato)borate with oxalic acid, [B(C2O4)(OH)(2)center dot(HOOC-COOH)](-), was also formed and passed into the ionic liquid in the course of the metathesis reaction with trihexyl(tetradecyl)phosphonium chloride. On the contrary, Na[BOB] was found to be a more suitable reagent for the synthesis of this IL, because [BOB](-) anions safely passed into the final IL without hydrolysis, when metathesis reactions were performed using aqueous-free media. Since ultra-pure Na[BOB] is not commercially available, in this work, a preparation protocol for ultra-pure (>99%) Na[BOB] was developed: (i) molar ratios of boric and oxalic acids were optimised to minimise boron-containing impurities, (ii) the Na[BOB] product was thoroughly purified by sequential washing of a fine powder product in hot acetonitrile and ethanol and (iii) characterised using powder X-ray diffraction and solid-state B-11 MAS NMR spectroscopy. The physico-chemical properties of the prepared boron-impurity-free IL, i.e., its density, viscosity, electric conductivity, glass-transition temperature and thermal stability, were found to be significantly different from those of the previously reported [P-6,P-6,P-6,P-14][BOB], containing ca. 45 mol% of TAC, [B(C2O4)(OH)(2)center dot(HOOC-COOH)](-). It was found that a high-purity [P-6,P-6,P-6,P-14][BOB] prepared in this work has a considerably lower viscosity, a higher viscosity index and a wider electro-chemical window (ECW) compared to those of the sample of [P-6,P-6,P-6,P-14][BOB] with ca. 45 mol% of TAC. Interestingly, [B(C2O4)(OH)(2)center dot(HOOC-COOH)](-) in the latter sample almost completely transformed into [BOB](-), QC 20210422

Non-halogenated boron-based ionic liquids (ILs) composed of phosphonium cations and chelated orthoborate anions have high hydrolytic stability, low melting point and exceptional properties for various applications. This study is focused on ILs with the same type of cation, trihexyltetradecylphosphonium ([P-6,P-6,P-6,P-14](+)), and two orthoborate anions, such as bis(salicylato)borate ([BScB](-)) and bis(oxalato)borate ([BOB](-)). We compare the results of this study with our previous studies on ILs with bis(mandelato)borate ([BMB](-)) and a variety of different cations (tetraalkylphosphonium, dialkylpyrrolidinium and dialkylimidazolium). The ion dynamics and phase behavior of these ILs is studied using H-1 and B-11 pulsed-field-gradient (PFG) NMR. PFG NMR is demonstrated to be a useful tool to elucidate the dynamics of ions in this class of phosphonium orthoborate ILs. In particular, the applicability of B-11 PFG NMR for studying anions without H-1, such as [BOB](-), and the limitations of this technique to measure self-diffusion of ions in ILs are demonstrated and discussed in detail for the first time., QC 20200625

Here we focus on the thermal and variable temperature electrochemical stabilities of two ionic liquids (ILs) having a common tributyloctyl phosphonium cation [P4,4,4,8]+ and two different orthoborate anions: bis(mandelato)borate [BMB]− and bis(salicylato)borate [BScB]−. The thermo-gravimetric analysis data suggest that [P4,4,4,8][BScB] is thermally more stable than [P4,4,4,8][BMB] in both nitrogen atmosphere and air, while the impedance spectroscopy reveals that [P4,4,4,8][BScB] has higher ionic conductivity than [P4,4,4,8][BMB] over the whole studied temperature range. In contrast, the electrochemical studies confirm that [P4,4,4,8][BMB] is more stable and exhibits a wider electrochemical stability window (ESW) on a glassy carbon electrode surface as compared to [P4,4,4,8][BScB]. A continuous decrease in the ESWs of both ILs is observed as a function of operation temperature., Validerad;2020;Nivå 2;2020-06-10 (alebob)

The formation of crosslinked bonds between wood constituents is believed to be an effective way to stabilize wood against wet conditions. The possibility to use maleic anhydride (MA) combined with sodium hypophosphite (SHP) as crosslinking agents was studied, using Scots pine sapwood and a model compound. The modified wood showed weight gain and bulking effect after treatment and subsequent Soxhlet extractions, which indicated penetration into the wood cell wall and reaction of the chemicals with the wood constituents. The FTIR spectra confirmed the formation of an ester bond between the wood and MA. Furthermore, a decrease of intensity of band at 1635 cm-1 indicated a reduction of the double bond between carbons in MA after further treatment with SHP, especially at 170 ̊C. Such reactions were studied using monomethyl maleate (MMM) and SHP. The 13C NMR spectra of the reaction product confirmed a reduction of the double bond between carbons. This paper outlines studies undertaken to date, along with outlining aims of ongoing and future work.

Here we focus on the thermal and variable temperature electrochemical stabilities of two ionic liquids (ILs) having a common tributyloctyl phosphonium cation [P4,4,4,8]+ and two different orthoborate anions: bis(mandelato)borate [BMB]− and bis(salicylato)borate [BScB]−. The thermo-gravimetric analysis data suggest that [P4,4,4,8][BScB] is thermally more stable than [P4,4,4,8][BMB] in both nitrogen atmosphere and air, while the impedance spectroscopy reveals that [P4,4,4,8][BScB] has higher ionic conductivity than [P4,4,4,8][BMB] over the whole studied temperature range. In contrast, the electrochemical studies confirm that [P4,4,4,8][BMB] is more stable and exhibits a wider electrochemical stability window (ESW) on a glassy carbon electrode surface as compared to [P4,4,4,8][BScB]. A continuous decrease in the ESWs of both ILs is observed as a function of operation temperature., Validerad;2020;Nivå 2;2020-06-10 (alebob)

The corrosion inhibitive capabilities of some ferrocene-based Schiff bases on aluminium alloy AA2219-T6 in acidic medium were investigated using Tafel polarization, electrochemical impedance spectroscopy (EIS), weight loss measurement, FT-IR spectroscopy and scanning electron microscopic (SEM) techniques. The influence of molecular configuration on the corrosion inhibition behavior has been explored by quantum chemical calculation. Ferrocenyl Schiff bases 4,4′-((((ethane-1,2-diylbis(oxy))bis(4,1-phenylene))bis(methaneylylidene))bis(azaneylylidene))bisferrocene (Fcua), 4,4′-((((ethane-1,2-diylbis(oxy))bis(2-methoxy-1,4-phenylene))bis(methaneylylidene))bis(azaneylylidene))bisferrocene (Fcub) and 4,4′-((((ethane-1,2-diylbis(oxy))bis(2-ethoxy-1,4-phenylene))bis(methaneylylidene))bis(azaneylylidene))bisferrocene (Fcuc) have been synthesized and characterized by FT-IR, 1H and 13C NMR spectroscopic studies. These compounds showed a substantial corrosion inhibition against aluminium alloy in 0.1 M of HCl at 298 K. Fcub and Fcuc showed better anticorrosion efficiency as compared with Fcua due to the electron donating methoxy and ethoxy group substitutions, respectively. Polarization curves also indicated that the studied biferrocenyl Schiff bases were mixed type anticorrosive materials. The inhibition of the aluminium alloy surface by biferrocenyl Schiff bases was evidenced through scanning electron microscopy (SEM) studies. Semi-empirical quantum mechanical studies revealed a correlation between corrosion inhibition efficiency and structural functionalities., Validerad;2020;Nivå 2;2020-02-24 (johcin)

The corrosion inhibitive capabilities of some ferrocene-based Schiff bases on aluminium alloy AA2219-T6 in acidic medium were investigated using Tafel polarization, electrochemical impedance spectroscopy (EIS), weight loss measurement, FT-IR spectroscopy and scanning electron microscopic (SEM) techniques. The influence of molecular configuration on the corrosion inhibition behavior has been explored by quantum chemical calculation. Ferrocenyl Schiff bases 4,4′-((((ethane-1,2-diylbis(oxy))bis(4,1-phenylene))bis(methaneylylidene))bis(azaneylylidene))bisferrocene (Fcua), 4,4′-((((ethane-1,2-diylbis(oxy))bis(2-methoxy-1,4-phenylene))bis(methaneylylidene))bis(azaneylylidene))bisferrocene (Fcub) and 4,4′-((((ethane-1,2-diylbis(oxy))bis(2-ethoxy-1,4-phenylene))bis(methaneylylidene))bis(azaneylylidene))bisferrocene (Fcuc) have been synthesized and characterized by FT-IR, 1H and 13C NMR spectroscopic studies. These compounds showed a substantial corrosion inhibition against aluminium alloy in 0.1 M of HCl at 298 K. Fcub and Fcuc showed better anticorrosion efficiency as compared with Fcua due to the electron donating methoxy and ethoxy group substitutions, respectively. Polarization curves also indicated that the studied biferrocenyl Schiff bases were mixed type anticorrosive materials. The inhibition of the aluminium alloy surface by biferrocenyl Schiff bases was evidenced through scanning electron microscopy (SEM) studies. Semi-empirical quantum mechanical studies revealed a correlation between corrosion inhibition efficiency and structural functionalities., Validerad;2020;Nivå 2;2020-02-24 (johcin)

Ionic liquids (ILs) composed of tetra(n-butyl)phosphonium [P-4444](+) and tetra(n-butyl)ammonium [N-4444](+) cations paired with 2-furoate [FuA]-, tetrahydo-2-furoate [HFuA](-), and thiophene-2-carboxylate [TpA]- anions are prepared to investigate the effects of electron delocalization in anion and the mutual interactions between cations and anions on their physical and electrochemical properties. The [P-4444](+) cations-based ILs are found to be liquids, while the [N-4444](+) cations-based ILs are semi-solids at room temperature. Thermogravimetric analysis revealed higher decomposition temperatures and differential scanning calorimetry analysis showed lower glass transition temperatures for phosphonium-based ILs than the ammonium-based counterparts. The ILs are arranged in the decreasing order of their ionic conductivities as [P-4444][HFuA] (0.069 mS cm(-1)) > [P-4444][FuA] (0.032 mS cm(-1)) > [P-4444][TpA] (0.028 mS cm(-1)) at 20 degrees C. The oxidative limit of the ILs followed the sequence of [FuA](-)> [TpA](-)> [HFuA](-), as measured by linear sweep voltammetry. This order can be attributed to the electrons' delocalization in [FuA](-) and in [TpA](-) aromatic anions, which has enhanced the oxidative limit potentials and the overall electrochemical stabilities.

The formation of crosslinked bonds between wood constituents is believed to be an effective way to stabilize wood against wet conditions. The possibility to use maleic anhydride (MA) combined with sodium hypophosphite (SHP) as crosslinking agents was studied, using Scots pine sapwood and a model compound. The modified wood showed weight gain and bulking effect after treatment and subsequent Soxhlet extractions, which indicated penetration into the wood cell wall and reaction of the chemicals with the wood constituents. The FTIR spectra confirmed the formation of an ester bond between the wood and MA. Furthermore, a decrease of intensity of band at 1635 cm-1 indicated a reduction of the double bond between carbons in MA after further treatment with SHP, especially at 170 ̊C. Such reactions were studied using monomethyl maleate (MMM) and SHP. The 13C NMR spectra of the reaction product confirmed a reduction of the double bond between carbons. This paper outlines studies undertaken to date, along with outlining aims of ongoing and future work.

Bis-aldehyde monomers 4-(4′-formyl-phenoxy)benzaldehyde (3a), 3-methoxy-4-(4′-formyl-phenoxy)benzaldehyde (3b), and 3-ethoxy-4-(4′-formyl-phenoxy)benzaldehyde (3c) were synthesized by etherification of 4-fluorobenzaldehyde (1) with 4-hydroxybenzaldehyde (2a), 3-methoxy-4-hydroxybenzaldehyde (2b), and 3-ethoxy-4-hydroxybenzaldehyde (2c), respectively. Each monomer was polymerized with p-phenylenediamine and 4,4′-diaminodiphenyl ether to yield six poly(azomethine)s. Single crystal X-ray diffraction structures of 3b and 3c were determined. The structural characterization of the monomers and poly(azomethine)s was performed by FT-IR and NMR spectroscopic techniques and elemental analysis. Physicochemical properties of polymers were investigated by powder X-ray diffraction, thermogravimetric analysis (TGA), viscometry, UV–vis, spectroscopy and photoluminescence. These polymers were subjected to electrical conductivity measurements by the four-probe method, and their conductivities were found to be in the range 4.0 × 10−5 to 6.4 × 10−5 Scm−1, which was significantly higher than the values reported so far., Validerad;2019;Nivå 2;2019-09-18 (johcin)

PEGylated tetra(aniline) ABA triblock structure PEG-TANI-PEG (2) consisting of tetra(aniline) (TANI) and polyethylene glycol (PEG) was synthesized by coupling the tosylated-PEG to boc-protected NH2/NH2 TANI (1) through a simple nucleophilic substitution reaction. Deprotection of 2 resulted in a leucoemeraldine base state of TANI (2-LEB), which was oxidized to stable emeraldine base (2-EB) state. 2-EB was doped with 1 M HCl to emeraldine salt (2-ES) state. FTIR, 1H and 13C NMR and UV-Vis-NIR spectroscopy, and MS (ESI) was used for structural characterization. The synthesized triblock structure exhibited good electroactivity as confirmed by CV and UV-Vis-NIR spectroscopy. Self-assembling of the triblock structure in aqueous medium was assessed by DLS, TEM, and SEM. Spherical aggregates were observed with variable sizes depicting the effect of concentration and oxidation of 2-LEB. Further, the aggregates showed acid/base sensitivity as evaluated by doping and dedoping of 2-EB with 1 M HCl and 1 M NH4OH, respectively. Future applications in drug delivery and sensors are envisaged for such tunable self-assembled nanostructures in aqueous media., Validerad;2019;Nivå 2;2019-08-06 (johcin)

Bis-aldehyde monomers 4-(4′-formyl-phenoxy)benzaldehyde (3a), 3-methoxy-4-(4′-formyl-phenoxy)benzaldehyde (3b), and 3-ethoxy-4-(4′-formyl-phenoxy)benzaldehyde (3c) were synthesized by etherification of 4-fluorobenzaldehyde (1) with 4-hydroxybenzaldehyde (2a), 3-methoxy-4-hydroxybenzaldehyde (2b), and 3-ethoxy-4-hydroxybenzaldehyde (2c), respectively. Each monomer was polymerized with p-phenylenediamine and 4,4′-diaminodiphenyl ether to yield six poly(azomethine)s. Single crystal X-ray diffraction structures of 3b and 3c were determined. The structural characterization of the monomers and poly(azomethine)s was performed by FT-IR and NMR spectroscopic techniques and elemental analysis. Physicochemical properties of polymers were investigated by powder X-ray diffraction, thermogravimetric analysis (TGA), viscometry, UV–vis, spectroscopy and photoluminescence. These polymers were subjected to electrical conductivity measurements by the four-probe method, and their conductivities were found to be in the range 4.0 × 10−5 to 6.4 × 10−5 Scm−1, which was significantly higher than the values reported so far., Validerad;2019;Nivå 2;2019-09-18 (johcin)

PEGylated tetra(aniline) ABA triblock structure PEG-TANI-PEG (2) consisting of tetra(aniline) (TANI) and polyethylene glycol (PEG) was synthesized by coupling the tosylated-PEG to boc-protected NH2/NH2 TANI (1) through a simple nucleophilic substitution reaction. Deprotection of 2 resulted in a leucoemeraldine base state of TANI (2-LEB), which was oxidized to stable emeraldine base (2-EB) state. 2-EB was doped with 1 M HCl to emeraldine salt (2-ES) state. FTIR, 1H and 13C NMR and UV-Vis-NIR spectroscopy, and MS (ESI) was used for structural characterization. The synthesized triblock structure exhibited good electroactivity as confirmed by CV and UV-Vis-NIR spectroscopy. Self-assembling of the triblock structure in aqueous medium was assessed by DLS, TEM, and SEM. Spherical aggregates were observed with variable sizes depicting the effect of concentration and oxidation of 2-LEB. Further, the aggregates showed acid/base sensitivity as evaluated by doping and dedoping of 2-EB with 1 M HCl and 1 M NH4OH, respectively. Future applications in drug delivery and sensors are envisaged for such tunable self-assembled nanostructures in aqueous media., Validerad;2019;Nivå 2;2019-08-06 (johcin)

PEGylated tetra(aniline) ABA triblock structure PEG-TANI-PEG (2) consisting of tetra(aniline) (TANI) and polyethylene glycol (PEG) was synthesized by coupling the tosylated-PEG to boc-protected NH2/NH2 TANI (1) through a simple nucleophilic substitution reaction. Deprotection of 2 resulted in a leucoemeraldine base state of TANI (2-LEB), which was oxidized to stable emeraldine base (2-EB) state. 2-EB was doped with 1 M HCl to emeraldine salt (2-ES) state. FTIR, 1H and 13C NMR and UV-Vis-NIR spectroscopy, and MS (ESI) was used for structural characterization. The synthesized triblock structure exhibited good electroactivity as confirmed by CV and UV-Vis-NIR spectroscopy. Self-assembling of the triblock structure in aqueous medium was assessed by DLS, TEM, and SEM. Spherical aggregates were observed with variable sizes depicting the effect of concentration and oxidation of 2-LEB. Further, the aggregates showed acid/base sensitivity as evaluated by doping and dedoping of 2-EB with 1 M HCl and 1 M NH4OH, respectively. Future applications in drug delivery and sensors are envisaged for such tunable self-assembled nanostructures in aqueous media., Validerad;2019;Nivå 2;2019-08-06 (johcin)

Bis-aldehyde monomers 4-(4-formyl-phenoxy)benzaldehyde (3a), 3-methoxy-4-(4formyl-phenoxy)benzaldehyde (3b), and 3-ethoxy-4-(4-formyl-phenoxy)benzaldehyde (3c) were synthesized by etherification of 4-fluorobenzaldehyde (1) with 4-hydroxybenzaldehyde (2a), 3-methoxy-4-hydroxybenzaldehyde (2b), and 3-ethoxy-4-hydroxybenzaldehyde (2c), respectively. Each monomer was polymerized with p-phenylenediamine and 4,4-diaminodiphenyl ether to yield six poly(azomethine)s. Single crystal X-ray diffraction structures of 3b and 3c were determined. The structural characterization of the monomers and poly(azomethine)s was performed by FT-IR and NMR spectroscopic techniques and elemental analysis. Physicochemical properties of polymers were investigated by powder X-ray diffraction, thermogravimetric analysis (TGA), viscometry, UV–vis, spectroscopy and photoluminescence. These polymers were subjected to electrical conductivity measurements by the four-probe method, and their conductivities were found to be in the range 4.0 × 10−5 to 6.4 × 10−5 Scm−1, which was significantly higher than the values reported so far.

Bis-aldehyde monomers 4-(4-formyl-phenoxy)benzaldehyde (3a), 3-methoxy-4-(4formyl-phenoxy)benzaldehyde (3b), and 3-ethoxy-4-(4-formyl-phenoxy)benzaldehyde (3c) were synthesized by etherification of 4-fluorobenzaldehyde (1) with 4-hydroxybenzaldehyde (2a), 3-methoxy-4-hydroxybenzaldehyde (2b), and 3-ethoxy-4-hydroxybenzaldehyde (2c), respectively. Each monomer was polymerized with p-phenylenediamine and 4,4-diaminodiphenyl ether to yield six poly(azomethine)s. Single crystal X-ray diffraction structures of 3b and 3c were determined. The structural characterization of the monomers and poly(azomethine)s was performed by FT-IR and NMR spectroscopic techniques and elemental analysis. Physicochemical properties of polymers were investigated by powder X-ray diffraction, thermogravimetric analysis (TGA), viscometry, UV–vis, spectroscopy and photoluminescence. These polymers were subjected to electrical conductivity measurements by the four-probe method, and their conductivities were found to be in the range 4.0 × 10−5 to 6.4 × 10−5 Scm−1, which was significantly higher than the values reported so far.

Bis-aldehyde monomers 4-(4-formyl-phenoxy)benzaldehyde (3a), 3-methoxy-4-(4formyl-phenoxy)benzaldehyde (3b), and 3-ethoxy-4-(4-formyl-phenoxy)benzaldehyde (3c) were synthesized by etherification of 4-fluorobenzaldehyde (1) with 4-hydroxybenzaldehyde (2a), 3-methoxy-4-hydroxybenzaldehyde (2b), and 3-ethoxy-4-hydroxybenzaldehyde (2c), respectively. Each monomer was polymerized with p-phenylenediamine and 4,4-diaminodiphenyl ether to yield six poly(azomethine)s. Single crystal X-ray diffraction structures of 3b and 3c were determined. The structural characterization of the monomers and poly(azomethine)s was performed by FT-IR and NMR spectroscopic techniques and elemental analysis. Physicochemical properties of polymers were investigated by powder X-ray diffraction, thermogravimetric analysis (TGA), viscometry, UV–vis, spectroscopy and photoluminescence. These polymers were subjected to electrical conductivity measurements by the four-probe method, and their conductivities were found to be in the range 4.0 × 10−5 to 6.4 × 10−5 Scm−1, which was significantly higher than the values reported so far.

Nowadays, hydropower plants are forced to have more frequent power control and the self-lubricated bearings used in the applications are one of the most critical components affected by the continuously changing operating conditions. In this study, microstructure and composition of two commercially available bearing materials (Orkot TXM Marine and Thordon ThorPlas) used in hydropower turbines were studied. In addition, the influence of sliding speed and applied pressure on the friction and wear behavior of the materials was investigated systematically for dry sliding conditions. The bearing materials were characterized using X-ray microtomography, Nuclear Magnetic Resonance (NMR) spectroscopy and Inductively Coupled Plasma–Sector Field Mass Spectrometry (ICP-SFMS) techniques. Friction and wear tests were carried out with a polymer pin sliding against a stainless steel (SS2333) plate with a linear reciprocating motion. Test conditions were: room temperature, 9–28 MPa pressure and 10–40 mm/s sliding speed ranges. Surface analysis of the polymer pins and the wear tracks were performed by optical profilometry, Scanning Electron Microscope (SEM) and Energy Dispersive Spectroscopy (EDS) techniques. Test results show that, for both materials, the coefficient of friction (COF) is decreasing at higher pressures. Surface analysis reveals higher concentrations of solid lubricants in the transfer layers formed at higher pressures, explaining the decrease in COF. Furthermore, the specific wear rate coefficients are increasing at higher sliding speeds, especially at lower pressures. Results of this study demonstrate that, under dry sliding conditions, changes in sliding speed and pressure have a significant influence on the tribological behavior of these bearing materials., Validerad;2018;Nivå 2;2018-05-02 (andbra)

Nowadays, hydropower plants are forced to have more frequent power control and the self-lubricated bearings used in the applications are one of the most critical components affected by the continuously changing operating conditions. In this study, microstructure and composition of two commercially available bearing materials (Orkot TXM Marine and Thordon ThorPlas) used in hydropower turbines were studied. In addition, the influence of sliding speed and applied pressure on the friction and wear behavior of the materials was investigated systematically for dry sliding conditions. The bearing materials were characterized using X-ray microtomography, Nuclear Magnetic Resonance (NMR) spectroscopy and Inductively Coupled Plasma–Sector Field Mass Spectrometry (ICP-SFMS) techniques. Friction and wear tests were carried out with a polymer pin sliding against a stainless steel (SS2333) plate with a linear reciprocating motion. Test conditions were: room temperature, 9–28 MPa pressure and 10–40 mm/s sliding speed ranges. Surface analysis of the polymer pins and the wear tracks were performed by optical profilometry, Scanning Electron Microscope (SEM) and Energy Dispersive Spectroscopy (EDS) techniques. Test results show that, for both materials, the coefficient of friction (COF) is decreasing at higher pressures. Surface analysis reveals higher concentrations of solid lubricants in the transfer layers formed at higher pressures, explaining the decrease in COF. Furthermore, the specific wear rate coefficients are increasing at higher sliding speeds, especially at lower pressures. Results of this study demonstrate that, under dry sliding conditions, changes in sliding speed and pressure have a significant influence on the tribological behavior of these bearing materials., Validerad;2018;Nivå 2;2018-05-02 (andbra)

QC 20171115