Crystal Phase Ionic Liquids for Energy Applications: Heat Capacity Prediction via a Hybrid Group Contribution Approach.

In the selection and design of ionic liquids (ILs) for various applications, including heat transfer fluids, thermal energy storage materials, fuel cells, and solvents for chemical processes, heat capacity is a key thermodynamic property. While several attempts have been made to develop predictive models for the estimation of the heat capacity of ILs in their liquid phase, none so far have been reported for the ILs' solid crystal phase. This is particularly important for applications where ILs will be used for thermal energy storage in the solid phase. For the first time, a model has been developed and used for the prediction of crystal phase heat capacity based on extending and modifying a previously developed hybrid group contribution model (GCM) for liquid phase heat capacity. A comprehensive database of over 5000 data points with 71 unique crystal phase ILs, comprising 42 different cations and 23 different anions, was used for parameterization and testing. This hybrid model takes into account the effect of the anion core, cation core, and subgroups within cations and anions, in addition to the derived indirect parameters that reflect the effects of branching and distribution around the core of the IL. According to the results, the developed GCM can reliably predict the crystal phase heat capacity with a mean absolute percentage error of 6.78%. This study aims to fill this current gap in the literature and to enable the design of ILs for thermal energy storage and other solid phase applications.

Preparation and Characterization of Date Palm Bio-Oil Modified Phenolic Foam.

In this work, the potential of biomass-derived date palm bio-oil as a partial substitute for phenol in the phenolic resin was evaluated. Date palm bio-oils derived from date palm were used for the partial substitution of phenol in the preparation of phenolic foam (PF) insulation materials. Date palm waste material was processed using pyrolysis at 525 °C to produce bio-oil rich in phenolic compounds. The bio-oil was used to partially replace phenol in the synthesis of phenolic resin, which was subsequently used to prepare foams. The resulting changes in the physical, mechanical, and thermal properties of the foams were studied. The substituted foams exhibited 93%, 181%, and 40% improvement in compressive strength with 10%, 15%, and 20% bio-oil substitution, respectively. Due to the incorporation of biomass waste material, the partial reduction in phenol uses, and the favorable properties, the date palm bio-oil substituted phenolic foams are considered more environmentally benign alternatives to traditional phenolic foams.

Comparison of Toughening Effects of Various Additives on Phenolic Foam.

Phenolic foams (PFs) are considered excellent insulation materials owing to their flame retardancy and low thermal conductivity. However, their mechanical properties often lag behind those of other polymeric insulation materials. To fully exploit their properties and broaden end-use applications, the mechanical properties of PFs must be enhanced. In this study, various modifications were introduced into the PF matrix with the aim of enhancing its properties. The toughening effects of four additives: urea (U), nano clay (NC), sodium silicate (SS), and lignin (Li) were studied and compared. Changes that occurred in the density, cell morphology, thermal conductivity, compressive strength, and thermal stability after the addition of these fillers were analyzed. Both compressive strength and thermal stability increased with the inclusion of all additives, and the SS-toughened foam shows the biggest improvement. Li and NC addition resulted in a 34% improvement in compressive strength, while SS and U addition displayed increases of 52 and 11%, respectively. SS-toughened PF shows greater improvements in all of the important properties compared with those of the other toughened foams. Several PFs were prepared by changing the SS concentration to optimize the formulation, which yielded improvements in properties. The effects of SS concentration on density, thermal conductivity, and compressive strength were studied. The formulation with 0.37% sodium silicate concentration (PF-SS1) shows a 15% improvement in mechanical properties.

Desulfurization of Diesel Using Ionic Liquids: Process Design and Optimization Using COSMO-Based Models and Aspen Plus.

Sulfur dioxide emissions from fossil fuel combustion have been known to cause detrimental health and environmental effects. The currently used hydrodesulfurization (HDS) method employed by refineries has several drawbacks, such as excessive hydrogen consumption, high energy demand, and inability to remove complex organosulfur compounds, which have limited its ability to produce ultralow sulfur diesel (ULSD) at reasonable operating and capital costs. Ionic liquids (ILs) have been widely studied for their potential to replace conventional HDS. However, while their success has been demonstrated at the laboratory level, studies on industrial-scale feasibility and their integration into process simulators such as Aspen Plus are limited. In this work, 26 commercially available ILs have been screened using COSMO-based models and Aspen Plus for the desulfurization of diesel fuel and several possible process configurations have been examined. In particular, the challenge of ionic liquid regeneration, which has largely been ignored in the literature, has also been addressed and several potential regeneration methods have been proposed including extractive regeneration (E-RE) and stripping regeneration using nitrogen and air as stripping media (S-RE). The results indicate that, among the 26 ILs studied, 1-butyl-3-methylimidazolium thiocyanate is the most promising as a solvent for extractive desulfurization (EDS), E-RE, and S-RE. E-RE was found to be more effective for the removal of dibenzothiophene (DBT), while S-RE is more suited to the removal of thiophene and benzothiophene (BT). As a result, an optimized diesel desulfurization process using 1-butyl-3-methylimidazolium thiocyanate has been proposed that achieves ULSD with <10 ppm total sulfur in simulation studies, with complete recycling of the IL and minimal loss of the model diesel.

Clay-Alginate Beads Loaded with Ionic Liquids: Potential Adsorbents for the Efficient Extraction of Oil from Produced Water.

Produced water (PW) generated from the petroleum industry, during the extraction of oil and gas, has harmful impacts on human health and aquatic life, due to its complex nature. Therefore, it is necessary to treat it before discharging it into the environment in order to avoid serious environmental concerns. In this research, oil adsorption from PW was investigated using clay-alginate beads loaded with ionic liquids (ILs), as the adsorbent material. The effects of several process parameters, such as the initial concentration of oil, contact time, pH, and temperature on the removal efficiency of the beads, were analyzed and optimized. Different characterization methods, such as the Fourier transform infrared spectrophotometer (FTIR), scanning electron microscopy (SEM), energy dispersive X-ray (EDX), and thermal gravimetric analysis (TGA), were used to investigate the surface morphology, the chemical bond structure and functional group, and the thermal stability of the ILs-based beads. The results revealed that the clay-alginate-ILs beads indicated a removal efficiency of 71.8% at the optimum conditions (600 ppm initial oil concentration, 70 min contact time, 10 pH, and at room temperature) with an adsorption capacity of 431 mg/g. The FTIR analysis confirmed the successful chemical bond interaction of the oil with the beads. The SEM analysis verified that the beads have a porous and rough surface, which is appropriate for the adsorption of oil onto the bead's surface. The TGA analysis provides the thermal degradation profile for the clay-alginate-ILs. The beads used in the adsorption process were regenerated and used for up to four cycles.

Ionic Liquid Agar-Alginate Beads as a Sustainable Phenol Adsorbent.

Cleaning wastewater containing low concentrations of phenolic compounds is a challenging task. In this work, agar-alginate beads impregnated with trihexyltetradecylphosphonium bromide ([P66614][Br]) ionic liquid adsorbent were synthesized as a potential adsorbent for such applications. FTIR, TGA, SEM, EDX and PZC studies were performed to characterize and understand the physicochemical properties of the adsorbent. The Fourier transformation infrared spectroscopy (FTIR) study showed that [P66614][Br] ionic liquid was effectively incorporated into the agar-alginate structure. TGA and SEM confirmed comparative enhanced thermal stability and porous surface, respectively. Chemical reaction rate-altering parameters, i.e., pH, contact time, initial phenol concentration and temperature, are optimized at highest phenol removal. It was found that the maximum phenol adsorption capacity and highest removal efficiency by the adsorbent occurred at pH 2, initial phenol concentration of 150 mg/L, beads dosage of 6 mg/mL and contact time of 2 h with values of 16.28 mg/g and 65.12%, respectively. The pseudo-second order model fitted the adsorption kinetics well, and the Freundlich isotherm model gave the experimental data the best fit. Analysis of thermodynamic data demonstrated that the adsorption process is fundamentally exothermic in nature, and low temperature favors spontaneity of the chemical reaction. Regeneration studies indicated that the adsorbent can at least be used for four cycles in such applications without any considerable loss in adsorption efficiency.

Group Contribution Estimation of Ionic Liquid Melting Points: Critical Evaluation and Refinement of Existing Models.

While several group contribution method (GCM) models have been developed in recent years for the prediction of ionic liquid (IL) properties, some challenges exist in their effective application. Firstly, the models have been developed and tested based on different datasets; therefore, direct comparison based on reported statistical measures is not reliable. Secondly, many of the existing models are limited in the range of ILs for which they can be used due to the lack of functional group parameters. In this paper, we examine two of the most diverse GCMs for the estimation of IL melting point; a key property in the selection and design of ILs for materials and energy applications. A comprehensive database consisting of over 1300 data points for 933 unique ILs, has been compiled and used to critically evaluate the two GCMs. One of the GCMs has been refined by introducing new functional groups and reparametrized to give improved performance for melting point estimation over a wider range of ILs. This work will aid in the targeted design of ILs for materials and energy applications.

Sustainable management of cut flowers waste by activation and its application in wastewater treatment technology.

Cut flowers and floral waste (CFW) is a major concern in the present era. This study emphasizes the reuse of cut flowers as a neat bioadsorbent and activated carbon (AC). The biomass from the cut flowers was utilized as a neat bioadsorbent for the removal of the antibiotic levofloxacin and lead ions from water. The results revealed that the neat bioadsorbent was able to remove 60% levofloxacin and 45% of lead ions. Upon chemical activation of the CFW (using KOH), almost all levofloxacin and more than 99% of lead ions were removed. Physical activation (using CO2) gave a material that removed 90% of levofloxacin and 85% of lead ions. The adsorption of levofloxacin and lead ions on all the adsorbents followed Langmuir isotherms and pseudo-second-order kinetic model. The results have been further explained via the prediction of interaction energies between the adsorbates and adsorbents using COSMO-RS simulation.

Ionic liquids and deep eutectic solvents for the recovery of phenolic compounds: effect of ionic liquids structure and process parameters.

Water pollution is a severe and challenging issue threatening the sustainable development of human civilization. Besides other pollutants, waste fluid streams contain phenolic compounds. These have an adverse effect on the human health and marine ecosystem due to their toxic, mutagenic, and carcinogenic nature. Therefore, it is necessary to remove such phenolic pollutants from waste stream fluids prior to discharging to the environment. Different methods have been proposed to remove phenolic compounds from wastewater, including extraction using ionic liquids (ILs) and deep eutectic solvent (DES), a class of organic salts having melting point below 100 °C and tunable physicochemical properties. The purpose of this review is to present the progress in utilizing ILs and DES for phenolic compound extraction from waste fluid streams. The effects of IL structural characteristics, such as anion type, cation type, alkyl chain length, and functional groups will be discussed. In addition, the impact of key process parameters such as pH, phenol concentration, phase ratio, and temperature will be also described. More importantly, several ideas for addressing the limitations of the treatment process and improving its efficiency and industrial viability will be presented. These ideas may form the basis for future studies on developing more effective IL-based processes for treating wastewaters contaminated with phenolic pollutants, to address a growing worldwide environmental problem.

Bio-Based Alternatives to Phenol and Formaldehyde for the Production of Resins.

Phenol-formaldehyde (PF) resin continues to dominate the resin industry more than 100 years after its first synthesis. Its versatile properties such as thermal stability, chemical resistance, fire resistance, and dimensional stability make it a suitable material for a wide range of applications. PF resins have been used in the wood industry as adhesives, in paints and coatings, and in the aerospace, construction, and building industries as composites and foams. Currently, petroleum is the key source of raw materials used in manufacturing PF resin. However, increasing environmental pollution and fossil fuel depletion have driven industries to seek sustainable alternatives to petroleum based raw materials. Over the past decade, researchers have replaced phenol and formaldehyde with sustainable materials such as lignin, tannin, cardanol, hydroxymethylfurfural, and glyoxal to produce bio-based PF resin. Several synthesis modifications are currently under investigation towards improving the properties of bio-based phenolic resin. This review discusses recent developments in the synthesis of PF resins, particularly those created from sustainable raw material substitutes, and modifications applied to the synthetic route in order to improve the mechanical properties.

Thermal Conductivities of Choline Chloride-Based Deep Eutectic Solvents and Their Mixtures with Water: Measurement and Estimation.

The thermal conductivities of selected deep eutectic solvents (DESs) were determined using the modified transient plane source (MTPS) method over the temperature range from 295 K to 363 K at atmospheric pressure. The results were found to range from 0.198 W·m-1·K-1 to 0.250 W·m-1·K-1. Various empirical and thermodynamic correlations present in literature, including the group contribution method and mixing correlations, were used to model the thermal conductivities of these DES at different temperatures. The predictions of these correlations were compared and consolidated with the reported experimental values. In addition, the thermal conductivities of DES mixtures with water over a wide range of compositions at 298 K and atmospheric pressure were measured. The standard uncertainty in thermal conductivity was estimated to be less than ± 0.001 W·m-1·K-1 and ± 0.05 K in temperature. The results indicated that DES have significant potential for use as heat transfer fluids.

Fabrication of cerium oxide nanoparticles: characterization and optical properties.

Ceria (CeO(2)) is a technologically important rare earth material because of its unique properties and various engineering and biological applications. A facile and rapid method has been developed to prepare ceria nanoparticles using microwave with the average size 7 nm in the presence of a set of ionic liquids based on the bis (trifluoromethylsulfonyl) imide anion and different cations of 1-alkyl-3-methyl-imidazolium. The structural features and optical properties of the nanoparticles were determined in depth with X-ray powder diffraction, transmission electron microscope, N(2) adsorption-desorption technique, dynamic light scattering (DLS) analysis, FTIR spectroscopy, Raman spectroscopy, UV-vis absorption spectroscopy, and Diffuse reflectance spectroscopy. The energy band gap measurements of nanoparticles of ceria have been carried out by UV-visible absorption spectroscopy and diffuse reflectance spectroscopy. The surface charge properties of colloidal ceria dispersions in ethylene glycol have been also studied. To the best of our knowledge, this is the first report on using this type of ionic liquids in ceria nanoparticle synthesis.

Theoretical and experimental correlations of gas dissolution, diffusion, and thermodynamic properties in determination of gas permeability and selectivity in supported ionic liquid membranes.

Supported ionic liquid membranes (SILMs) has the potential to be a new technological platform for gas/organic vapour separation because of the unique non-volatile nature and discriminating gas dissolution properties of room temperature ionic liquids (ILs). This work starts with an examination of gas dissolution and transport properties in bulk imidazulium cation based ionic liquids [C(n)mim][NTf2] (n=2.4, 6, 8.10) from simple gas H(2), N(2), to polar CO(2), and C(2)H(6), leading to a further analysis of how gas dissolution and diffusion are influenced by molecular specific gas-SILMs interactions, reflected by differences in gas dissolution enthalpy and entropy. These effects were elucidated again during gas permeation studies by examining how changes in these properties and molecular specific interactions work together to cause deviations from conventional solution-diffusion theory and their impact on some remarkably contrasting gas perm-selectivity performance. The experimental perm-selectivity for all tested gases showed varied and contrasting deviation from the solution-diffusion, depending on specific gas-IL combinations. It transpires permeation for simpler non-polar gases (H(2), N(2)) is diffusion controlled, but strong molecular specific gas-ILs interactions led to a different permeation and selectivity performance for C(2)H(6) and CO(2). With exothermic dissolution enthalpy and large order disruptive entropy, C(2)H(6) displayed the fastest permeation rate at increased gas phase pressure in spite of its smallest diffusivity among the tested gases. The C(2)H(6) gas molecules "peg" on the side alkyl chain on the imidazulium cation at low concentration, and are well dispersed in the ionic liquids phase at high concentration. On the other hand strong CO(2)-ILs affinity resulted in a more prolonged "residence time" for the gas molecule, typified by reversed CO(2)/N(2) selectivity and slowest CO(2) transport despite CO(2) possess the highest solubility and comparable diffusivity in the ionic liquids. The unique transport and dissolution behaviour of CO(2) are further exploited by examining the residing state of CO(2) molecules in the ionic liquid phase, which leads to a hypothesis of a condensing and holding capacity of ILs towards CO(2), which provide an explanation to slower CO(2) transport through the SILMs. The pressure related exponential increase in permeations rate is also analysed which suggests a typical concentration dependent diffusion rate at high gas concentration under increased gas feed pressure. Finally the strong influence of discriminating and molecular specific gas-ILs interactions on gas perm-selectivity performance points to future specific design of ionic liquids for targeted gas separations.

Bilateral renal masses in a 10-year-old girl with renal failure and urinary tract infection: the importance of functional imaging.

Renal sonography is a routine step in the evaluation of new onset renal failure. When renal masses are discovered in this setting, functional imaging may be critical. We report a case of bilateral renal masses in a girl with urinary tract infection and renal insufficiency found to have vesicoureteral reflux. Renal scintigraphy revealed these masses to be the only remaining functional renal tissue, preventing potentially harmful resection.

Ultrasound-assisted green synthesis of nanocrystalline ZnO in the ionic liquid [hmim][NTf2].

For the first time, zinc oxide nanoparticles have been synthesized by the sonochemical method in an ionic liquid, 1-hexyl-3-methylimidazolium bis (trifluoromethylsulfonyl) imide, liquid [hmim][NTf(2)] as a solvent. The morphology and structure of ZnO nanoparticles have been characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). A possible mechanism is proposed to explain the formation of ZnO nanostructures.

Physical therapy alone compared with core decompression and physical therapy for femoral head osteonecrosis in sickle cell disease. Results of a multicenter study at a mean of three years after treatment.

BACKGROUND: Osteonecrosis of the femoral head is a common complication in patients with sickle cell disease, and collapse of the femoral head occurs in 90% of patients within five years after the diagnosis of the osteonecrosis. However, the efficacy of hip core decompression to prevent the progression of osteonecrosis in these patients is still controversial. METHODS: In a prospective multicenter study, we evaluated the safety of hip core decompression and compared the results of decompression and physical therapy with those of physical therapy alone for the treatment of osteonecrosis of the femoral head in patients with sickle cell disease. Forty-six patients (forty-six hips) with sickle cell disease and Steinberg Stage-I, II, or III osteonecrosis of the femoral head were randomized to one of two treatment arms: (1) hip core decompression followed by a physical therapy program or (2) a physical therapy program alone. Eight patients withdrew from the study, leaving thirty-eight who participated. RESULTS: Seventeen patients (seventeen hips) underwent decompression combined with physical therapy, and no intraoperative or immediate postoperative complications occurred. Twenty-one patients (twenty-one hips) were treated with physical therapy alone. After a mean of three years, the hip survival rate was 82% in the group treated with decompression and physical therapy and 86% in the group treated with physical therapy alone. According to a modification of the Harris hip score, the mean clinical improvement was 18.1 points for the patients treated with hip core decompression and physical therapy compared with 15.7 points for those treated with physical therapy alone. With the numbers studied, the differences were not significant. CONCLUSIONS: In this randomized prospective study, physical therapy alone appeared to be as effective as hip core decompression followed by physical therapy in improving hip function and postponing the need for additional surgical intervention at a mean of three years after treatment.