Nitric Acid Concentration Research Articles

Silver cementation mechanism for leaching silicon solar cells in nitric acid

Silicon solar panels are often overlooked in e-waste recycling technology, even though they contain precious silver (Ag). In order to help meet future global Ag demands and prevent contamination of the environment, all the Ag from end-of-life modules must be recovered instead of landfilled. The most mature Ag recycling recipes use high concentration nitric acid (HNO3) solutions often in combination with heating and agitation. After the Ag is leached, chemical precipitation or electrochemistry is used to recover metallic Ag. However, the process of Ag leaching in the HNO3 system with competing elements from silicon solar cells is not well understood. In this paper, we investigate the thermodynamics governing Ag leaching in low-concentration HNO3 without agitation or heating to expand fundamental knowledge in support of Ag recovery efforts from end-of-life solar panels. ICP-OES is used to quantify the amount of Ag leached in the HNO3 solution over time. Scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) are used to study the changes on the silicon solar cell surface. Our results suggest when trace tin (Sn) is used in solar cell fingers, it causes Ag to cement in dendritic form.

Styrene divinyl benzene beads (SM-2) functionalized with triisobutylphosphine sulfide for selective uptake of palladium(II) from nitric acid medium

Resins impregnated with organic extractants regarded as effective adsorbent materials due to their ability for selective sorption. These resins consist of a polymeric material that is infused with accessible organic extractants. Furthermore, these resins merge the unique properties and the distinctive characteristics of both liquid-liquid extraction and solid-liquid sorption processes. In this work, the impregnation of Styrene divinyl benzene beads (SM-2 beads) with triisobutylphosphine sulfide (TIBPS = CYANEX 471X) was prepared. A SM-2 bead functionalized with CYANEX 471X (SM-2-TIBPS beads) was characterized using scanning electron microscope (SEM) and Fourier-transform infrared spectroscopy (FT-IR) techniques and investigated for recovery and separation of palladium ions from a 3 M nitric acid solution. Various parameters were studied, as shaking time effect, nitric acid concentration, SM-2-TIBPS beads weight, Pd(II) concentration and temperature. The Pd(II)/SM-2-TIBPS sorption system has an endothermic nature and was fitted with a Langmuir isotherm model with a 0.9860 regression factor. The kinetics modeling was fitted with PSO and IPD models with regression factors of 0.9889 and 0.9959, respectively. The maximum monolayer sorption capacity of SM-2-TIBPS was found to be 17.47 ± 0.9 mg/g. The sorption of Pd(II) from different media at 3 M takes the following sequence: HNO3 > HCl > H2SO4. Desorption of about 76.38 ± 2.4% was achieved with (1 M + 1 M) of thiourea + HCl after one desorption stage. Effect of other interfering ions, as Pt(II), Pb(II), Eu(III), Cu(II), Mo(VI), Co(III), Zr(IV), Fe(III), Cd(II), and Ce(III), indicates high separation factors between Pd(II) and other investigated metal ions, which ranged from 9.4 to 35.

Effect of nitric acid concentration on corrosion behavior of CrFeCoNi high entropy alloy

CrFeCoNi high entropy alloy (HEA) was prepared by the method of vacuum melting. Its corrosion behavior in HNO3 solution with different concentrations was studied. The electrochemical test results indicated that the corrosion resistance firstly increased with increasing HNO3 concentration from 0.1 M to 4 M, and then decreased with further increasing HNO3 concentration to 6 M. The CrFeCoNi HEA exhibited the best corrosion resistance in 4 M HNO3 solution. The discrepancy of corrosion property in different concentration of HNO3 solutions could be attributed to the different protection of passive film formed on HEA. XPS results indicated that the content of Cr2O3 in the passive film initially increased with increasing HNO3 concentration from 0.1 M to 4 M, and then decreased with further increasing HNO3 concentration to 6 M. Higher content of Cr2O3 in the passive film was responsible for better corrosion property.

Preparing efficient self-healing polyimide coating for enhancing stability of electromagnetic interference shielding film

Electromagnetic interference (EMI) shielding films were widely utilized in various electronic devices, but they were prone to damage and performance degradation in harsh environments. Therefore, it was urgent to maintain stable performance of EMI shielding films. In this work, we adopt the reactions between aldehyde-modified diamine monomers and dianhydride monomers with dynamic imine bond to successfully prepare a self-healing PI (SHPI) film. Benefit from dynamic imine and imide bond, the SHPI film possessed excellent thermal stability (T5 %=527.7°C), tensile strength (72 MPa) and self-healing efficiency (94.4 %). As protecting coating layer, the SHPI film was able to maintain the commercial aluminized polyimide (PI/Al) film with good EMI shielding performance in acid environment. The electromagnetic shielding film with self-healing coating still had average EMI shielding effectiveness value of 44.5 dB after exposed to 10 % concentration nitric acid solution for 30 min. It is noteworthy that when damaged by external forces, the electromagnetic shielding film with self-healing coating could achieve rapid healing, while the tensile strength was up to 87 MPa and the self-healing efficiency reached 92.5 %. This work provided an effective self-healing protective layer for EMI shielding material against corrosion in acidic environments and damage from external pressures.

Pulse-constructed energy–saving PbO2 electrode for copper electrowinning

Energy-saving PbO2 exhibit significant application potential in the non-ferrous metal electrowinning industry. By optimizing the deposition time, heteropolar spacing, nitric acid concentration, pulse current density and pulse frequency, the optimum conditions for deposition of PbO2 electrode were obtained. Meanwhile, the effects of electrodeposition parameters on the electrochemical performance, phase structure and morphology of β-PbO2 were systematically evaluated. The mechanism of action of pulse and direct current deposition was proposed. The simulated copper electrowinning experiment shows that an improved current efficiency (91.6%) was achieved and the low energy consumption (1855.1 kW⋅h/t) for copper production per ton was significantly reduced. Compared with the electrode prepared by direct current deposition, the current efficiency of copper is increased by 4.3% and the energy consumption is reduced by 198.6 kWh/t. Additionally, the PbO2 electrode produced by the optimized pulse deposition process exhibits excellent stability, which service-time is increased by approximately 99.4%. This research offers insights for developing energy-efficient and long-lived electrode materials.

Selective separation and recovery of rare-earth elements (REEs) from acidic solutions and coal fly ash leachate by novel TODGA-Impregnated organosilica media

Rare-earth elements (REEs) are essential in a wide range of applications including magnets and satellite technology, with demand driven by geopolitical factors. While multiple techniques exist for REE recovery including solvent extraction and selective precipitation, solid–liquid extraction offers key advantages in selectivity, scalability, and recyclability. N, N, N′, N′-tetraoctyl diglycolamide (TODGA) is a tridentate ligand widely used in solvent extraction, but the incorporation in a solid support to separate individual lanthanides from acid solutions remains largely unexplored. A novel TODGA-organosilica sorbent material was developed and tested to evaluate recovery of 17 elements (REEs and thorium) in terms of selectivity, kinetics, and equilibrium isotherms in 0.01 to 15.9 M nitric acid. Characterization of the new sorbent was performed before and after sorption using FTIR, XPS, and SSA techniques to help elucidate sorption mechanisms and limiting variables. REE adsorption increased from 1.26 mg g−1 to 10 mg g−1 with nitric acid concentrations of 0.01 M and 15.9 M, respectively. TODGA-organosilica exhibits high selectivity towards heavy REEs (Dy to Lu), with minimal sorption of lighter REEs (Ce to Gd). Batch adsorption experiments confirm pseudo-second-order kinetics and a Langmuir adsorption isotherm with TODGA binding to REEs in a 3:1 complex. A packed bed column study confirmed the high selectivity of TODGA-impregnated organosilica towards heavy REEs and a proof-of concept experiment with coal fly ash leachate shows high selectivity for REEs over Al, Fe, and Ca present in several orders of magnitude higher concentrations. Fractionation was observed where loading cycle effluent contained 84 % light REEs while strip cycle effluent contained 80 % heavy REEs. More than 90 % of loaded REEs were successfully stripped with water as the stripping agent.

Group hexavalent actinide separation from lanthanides using sodium bismuthate chromatography

Advanced used nuclear fuel (UNF) reprocessing strategies are limited by the complex radiochemical separations and engineering required to achieve the separation of actinides (An) from neutron scavenging lanthanides (Ln). The accessibility of the hexavalent oxidation state for the actinides (U – Am) provides a pathway to achieving a group hexavalent actinide separation from the trivalent lanthanides and Cm. The solid oxidant and ion exchanger, sodium bismuthate (NaBiO3), has been demonstrated to quantitatively oxidize and separate Am from trivalent Cm in a column chromatographic system. This work expands on the use of NaBiO3 chromatography to characterize the adsorption, kinetic, and elution behavior of U, Pu, and Eu. Separation factors over 200 with rapid kinetics were observed at dilute nitric acid concentrations with a complete An/Ln separation achieved in under an hour. The adsorption and chromatographic behavior of key fission products present in various reprocessing raffinates was characterized which demonstrated potential application of a NaBiO3-based separation following a TRUEX process.

Comparison of dynamic tests of the modified purex process flowsheet using 30 and 45% TBF in isoparafin

Results of centrifugal contactor rig trials of the flowsheet of the first solvent extraction cycle in protective glove boxes using simulated solutions of spent nuclear fuel and 30 and 45% TBP in isoparaffin as a solvent are compared. It was shown that an increase in the TBP concentration to 45% resulted in deterioration of the quality of the products obtained by the same flowsheets with 30% TBP in Isopar L as a solvent. Comparison of experimental and computer simulated profiles of component distribution across the stages of extraction units demonstrated satisfactory agreement in nitric acid and uranium concentrations. At the same time, it was found that simulation model of zirconium, technetium, and neptunium extraction requires improvement considering interaction of these elements with complexing agents.

Effects of hydrogen peroxide and sodium nitrate on microwave-assisted polyethylene oxidative degradation in the presence of nitric acid

Polyethylene (PE) upcycling has been challenging due to the chemical robustness of non-activated C-C and C-H bonds. One promising strategy is oxidative degradation, in which a strong oxidizing agent, usually nitric acid, oxidizes PE to produce a mixture of organic acids (C4 to C7 diacids and acetic acid). However, current research focuses on how to utilize the obtained organic acids as feedstock (e.g. for plasticizer and gaseous hydrocarbon synthesis) rather than improving the process itself. In this study, we evaluated the effects of adding hydrogen peroxide and sodium nitrate at 200 °C, considering possible PE oxidation mechanisms in the presence of nitric acid. Hydrogen peroxide can partially replace nitric acid, thereby reducing the required amount of nitric acid in the process. This is because, at sufficient nitric acid concentrations, hydrogen peroxide accelerates PE oxidation, while nitric acid simultaneously prevents the overoxidation of the resulting organic acids by hydrogen peroxide. When a nitric acid/hydrogen peroxide solution (1:1 mol/L) was employed for 3 h, the carbon efficiency and total organic acid concentration were 35.6 % and 14.0 g/L, respectively. Furthermore, the addition of sodium nitrate improved overall reaction efficiency through the Baeyer-Villiger type oxidation, which involves a nucleophilic attack on the protonated carbonyls by the nitrate ions. When a nitric acid/sodium nitrate solution (1.5:0.5 mol/L) was employed for 1.5 h, the carbon efficiency and the organic acid yield increased to 39.0 % and 15.3 g/L, respectively. Finally, the potential for upcycling waste PE was also demonstrated using both HNO3/H2O2 and HNO3/NaNO3 conditions, producing organic acids from waste linear low-density polyethylene (LLDPE) and high-density polyethylene (HDPE). This study comfirms the potential to reduce the amount of nitric acid used in the microwave-assisted upcycling of waste PE, an aspect that had been previously overlooked. This reduction can contribute to a more environmentally friendly transformation of the proposed process, facilitating the conversion of waste PE into valuable chemicals.

Instant Synthesis of 2,5‐Diformylfuran from Concentrated 5‐Hydroxymethylfurfural without Catalyst and Organic Solvent

Abstract5‐Hydroxymethylfurfural (HMF) was transformed into 2,5‐diformylfuran (DFF) with nitric acid as the oxidant. The initial HMF content was as high as 12.5 wt %, and water was the sole solvent. This is an intensely exothermic reaction along with the emission of NO2 gas. A high DFF yield of 83.2 % was achieved if the oxidation ability of nitric acid matched with the requirement of target oxidation reaction while mismatched those of side reactions by regulating the initial concentration of nitric acid (59.5 wt %) and reaction temperature (50–60 °C). The oxidation reaction of HMF, overoxidation of HMF, and skeleton‐cracking reaction of FDCA preferred concentrated HNO3, hot HNO3, and concentrated or hot HNO3, respectively. After liquid‐liquid extraction, filtration, and column chromatography, light‐yellow DFF powders with purity of 92.1 wt % and isolated yield of 40.2 % were obtained and confirmed by NMR, FTIR, UV‐Vis, and elemental analysis. HMF was the dominant impurity due to its affinity to DFF. In addition, chromogenic substances were obtained as a byproduct, and they were potential pH indicators. These chromogenic substances had highly conjugated molecular structures, and they were generated via successive β‐protonation‐based ring‐opening reaction of HMF, aldol reaction, and dehydration reaction.

Tetradentate Ligand's Chameleon-Like Behavior Offers Recognition of Specific Lanthanides.

The surging demand for high-purity individual lanthanides necessitates the development of novel and exceptionally selective separation strategies. At the heart of these separation systems is an organic compound that, based on its structural features, selectively recognizes the lighter or heavier lanthanides in the trivalent lanthanide (Ln) series. This work emphasizes the significant implications resulting from modifying the donor group configuration within an N,O-based tetradentate ligand and the changes in the solvation environment of Ln ions in the process of separating Lns, with the unique ability to achieve peak selectivity in the light, medium, and heavy Ln regions. The structural rigidity of the bis-lactam-1,10-phenanthroline ligand enforces size-based selectivity, displaying an exceptional affinity for Lns having larger ionic radii such as La. Modifying the ligand by eliminating one preorganization element (phenanthroline → bipyridine) results in the fast formation of complexes with light Lns, but, in the span of hours, the peak selectivity shifts toward middle Ln (Sm), resulting in time-resolved separation. As expected, at low nitric acid concentrations, the neutral tetradentate ligand complexes with Ln3+ ions. However, the change in extraction mechanism is observed at high nitric acid concentrations, leading to the formation and preferential extraction of anionic heavy Ln species, [Ln(NO3)x+3]x-, that self-assemble with two ligands that have undergone protonation, forming intricate supramolecular architectures. The tetradentate ligand that is structurally balanced with restrictive and unrestrictive motifs demonstrates unique, controllable selectivity for light, middle, and heavy Lns, underscoring the pivotal role of solvation and ion interactions within the first and second coordination spheres.

Orthogonal signal correction assisted multivariate regression approach for the estimation of uranium and acidity in PUREX process streams

A direct UV–Visible absorbance spectrophotometric method was developed for the simultaneous determination of uranium and nitric acid concentration in the PUREX process samples. The simulated system consisted of uranium and nitric acid in concentration range corresponding to reprocessing of spent nuclear fuel discharged from nuclear reactor was prepared. The absorbance of these samples was measured in the range of 400–470 nm at a scan speed of 100 nm/s and resultant spectra were recorded. The changes in wavelength maxima of U(VI) absorption spectrum at different nitric acid concentration was utilized to determine the concentration of uranium and nitric acid in the sample by orthogonal signal correction assisted principal component regression. After the principle component regression the RMSEP for test data (Uranium: 3–21 g/L and acidity: 2–12 M) were 0.7 g/L and 0.4 M respectively. This method is superior to conventional method being followed for routine analysis of plant control samples in view of minimizing the generation of radioactive analytical waste consisting other corrosive reagents and reducing radiation exposure to operators during analysis. This method is amenable for online monitoring also.

6-(6-Methyl-1,2,4,5-Tetrazine-3-yl)-2,2'-Bipyridine: A N-Donor Ligand for the Separation of Lanthanides(III) and Actinides(III).

Here, we report the synthesis of the 6-(6-methyl-1,2,4,5-tetrazine-3-yl)-2,2'-bipyridine (MTB) ligand that has been developed for lanthanide/actinide separation. A multimethod study of the complexation of MTB with trivalent actinide and lanthanide ions is presented. Single-crystal X-ray diffraction measurements reveal the formation of [Ce(MTB)2(NO3)3], [Pr(MTB)(NO3)3H2O], and [Ln(MTB)(NO3)3MeCN] (Ln = Nd, Sm, Eu, Gd). In addition, the complexation of Cm(III) with MTB in solution was studied by time-resolved laser fluorescence spectroscopy. The results show the formation of [Cm(MTB)1-3]3+ complexes, which occur in two different isomers. Quantum chemical calculations reveal an energy difference between these isomers of 12 kJ mol-1, clarifying the initial observations made by time-resolved laser fluorescence spectroscopy (TRLFS). Furthermore, quantum theory of atoms in molecules (QTAIM) analysis of the Cm(III) and Ln(III) complexes was performed, indicating a stronger covalent contribution in the Cm-N interaction compared to the respective Ln-N interaction. These findings align well with extraction data showing a preferred extraction of Am and Cm over lanthanides (e.g., max. SFAm/Eu = 8.3) at nitric acid concentrations <0.1 mol L-1 HNO3.

Printing resolution effect on mechanical properties of porous boehmite direct ink 3D printed structures

Direct ink writing (DIW) is one of the facile and versatile manufacturing techniques for additive manufacturing of ceramics. 3D printed porous boehmite structures fabricated via DIW can offer significant benefits in terms of their high specific surface area and robust mechanical properties, rendering them suitable for applications like catalysis, adsorption, etc. The characteristics of the boehmite structures produced through 3D printing are significantly influenced by several parameters associated with the DIW process, including but not limited to solids concentration in the ink, resolution, and drying time. In this work, for the first time, we try to optimize the DIW parameters for 3D printing of porous boehmite structures to achieve better shape stability, resolution, and mechanical properties. A shear-thinning boehmite ink was prepared by peptization of boehmite powder in nitric acid and the rheological properties were optimized by varying concentrations of boehmite and nitric acid. Boehmite ink with a solid loading of 37 % and a pH of 4 was found to have the optimal rheological properties and printability. A Menger sponge porous structure was printed by DIW using the optimized ink with different sample sizes and resolutions. The resolution and size were optimized for better shape accuracy of printing and structural integrity. Crack-free boehmite structures were obtained by optimizing the drying time. Boehmite structures printed with higher resolution resulted in enhanced compressive strength and energy absorption, i.e., compressive strength and energy absorption of 0.5 mm resolution boehmite structure is enhanced by 208 % and 144 %, respectively, compared to the 1 mm resolution structure.

Removal of calcium from phosphoric acid produced by the nitric acid process using solvent extraction with TCHDGA and stripping with water

The phosphoric acid produced by the nitric acid method cannot be used as an industrial-grade product as a result of the high calcium nitrate content. It can only be used for fertilizer production due to difficulty of complete removal of calcium nitrate. Herein, an efficient approach for the removal of calcium nitrate from the phosphoric acid produced by the nitric acid process was studied. The proposed process is based on solvent extraction with N, N, N′, N′-tetracyclohexyl-3-oxyglutaramide (TCHDGA). The effects of time, diluent, temperature, impurity ions, and the concentrations of extractant and nitric acid on the extraction of Ca2+ were considered. A series of characterization tests involving FT-IR spectroscopy, XPS analysis, slope analysis and X-ray single crystal diffracted analysis revealed that the stoichiometry of the complex is (Ca(NO3)2)(TCHDGA)3. The concentration of Ca2+ in phosphoric acid drops below 5 mg/L a three-stage cross-current extraction process. The stripping efficiency of calcium nitrate in the organic phase by water is above 99.9%. The extraction efficiency of Ca2+ by TCHDGA remained above 96.8% after ten extraction-stripping cycles, realizing the efficient removal of calcium nitrate in the phosphoric acid produced by nitric acid process without changing the traditional production conditions.

Method and mechanism for efficient radium isolation from bulk thorium based on anion exchange

In recent years, targeted-α-nuclide therapy (TAT) has been widely concerned in the world. As one of the few representative TAT nuclides, 212Pb showed good efficacy in cancer treatment; however, the amount remains scarce. Separating 228Ra and 224Ra from 232Th is expected to fundamentally solve this issue, since they both are the parent nuclides of 212Pb and can be used in generators. In this work, an efficient method for trace radium isolation from bulk thorium was proposed and verified through a systematic investigation of the adsorption behaviors of an anion exchanger denoted IRA900 toward thorium and barium/radium. Batch experiments suggested that IRA900 had unique selectivity for thorium in nitric acid solution, with almost no barium adsorbed. The thorium adsorption performance kept improving with increasing concentration of nitric acid and decreasing temperature. The adsorption kinetics and adsorption isotherm could be well fitted by the pseudo-second-order kinetic model and the Langmuir model, respectively. Column experiments suggested that thorium could be effectively immobilized by a column packed with IRA900, while barium was directly penetrated. For desorbing the fixed thorium, 0.1 M HNO3 was optimal. A final hot test demonstrated the successful radium isolation from bulk thorium, with high chemical yield and purity. The selective separation mechanism was attributed to the formation of an anionic [Th(NO3)5]− complex, while barium or radium existed in the cationic form in any nitric acid concentration. This work provides a promising method for separating trace radium from thorium, which will be significant for promoting the large-scale utilization of 212Pb.

Adsorption of terbium (III) on DGA and LN resins: Thermodynamics, isotherms, and kinetics

Two commercially available extraction chromatography (EXC) resins containing N,N,N’,N’-tetra-n-octyldiglycolamide (DGA Resin, Normal, 50 – 100 μm) and Bis(2-ethylhexyl) phosphate (LN Resin, 100 – 150 μm) were used as adsorbents to study fundamental adsorption properties such as thermodynamic values, equilibrium isotherms, and kinetic uptake models for terbium(III) adsorption. Weight distribution ratios (Dw) for terbium on DGA and LN resins were measured using a [160Tb]Tb3+radiometric tracer in nitric acid as a function of acidity, temperature, initial analyte concentration, and equilibrium time. The Dw values showed increasing binding affinity for DGA resin at high nitric acid concentrations and decreasing binding affinity for LN resins. Thermodynamic studies for DGA and LN resins revealed that the Gibbs free energy (ΔG) increased consistently with temperature. To model equilibrium data, increasingly higher parameter equilibrium isotherm models (Henry (1) < Langmuir, Freundlich (2) < Redlich-Peterson (3) < Fritz-Schluender (4)) were compared on their root mean squared errors (RMSE) and adjusted determination coefficients to determine the most applicable model. In all cases, the empirical four-parameter Fritz-Schluender isotherm demonstrated a superior fit. Similar comparisons for reaction-based kinetic models (Pseudo-first-order < Pseudo-second-order < Pseudo-n-order) revealed that the higher-order PNO model yielded a superior fit of kinetic data for both resins. However, in some cases, adsorption isotherms and kinetic models could also be modeled by a lower-order model with minimal change in error parameters. Weber-Morris plots revealed that two linear sections are observed for each resin, where the first linear segment is attributed to fast (film diffusion) adsorption of terbium, followed by slower intraparticle diffusion of terbium through the pores as the rate-limiting step. Based on the Weber-Morris plot, both film and intraparticle diffusion are involved in controlling the kinetic rate of adsorption for DGA and LN resins.

Microwave-assisted acid treatment for the mineral transformation of chrysotile as an alternative for asbestos waste management

In this work, the effect of microwave-assisted acid treatments on the morphological and crystallochemical characteristics of chrysotile fibers is investigated. A low concentration of nitric acid (0.2 N) is used to remove Mg2+-species located in the octahedral sheet of its structure, thereby causing a crystallo-chemical change forming a skeleton of non-crystalline amorphous silica. This skeleton maintains an elongated morphology but characterized by rounded -not sharp-edges and porous surfaces whose physical resistance under stress is reduced when compared with the initial fibers of chrysotile, favoring a lower pathogenicity of the fibers. Thus, microwave-assisted acid treatment rise as a low-cost, fast and effective option in avoiding the dangerousness associated with asbestos waste management.

Extractive Mass Transfer of Zr(IV) into a Hydrophobic Ionic Liquid Medium Containing Diglycolamide Extractant: Solvent Extraction and Spectroscopic Analysis.

Solvent extraction of Zr(IV) in ionic liquid (IL) medium is less known and Zr(IV) - IL chemistry indeed needs exploration to realize the coordination approach of Zr(IV) in IL phase. In view of this, in the present work, a strongly hydrophobic imidazolium based IL: 1-methyl-3-octylimidazolium bis(trifluoromethylsulfonyl)imide ([C8mim][NTf2]) as the medium containing a diglycolamide (DGA) extractant: N,N,N',N'-tetra-n-octyldiglycolamide (TODGA) was opted to understand the extraction behavior of Zr(IV) from nitric acid medium. Different experimental parameters such as the concentration of initial nitric acid, initial feed metal concentration, equilibration time and ligand concentration were tuned to unravel the extraction efficiency of the proposed IL phase towards Zr(IV). The extraction scenario was completely dependent on the hydrophobicity of IL diluent and increasing extraction trend with an increase in feed acidity along with the coordination of two TODGA molecules ensured Zr(IV) - complex formation in a neutral solvation mechanistic pathway. The extraction trend of Zr(IV) was compared with molecular diluent (n-dodecane (n-DD)) containing TODGA and a phase modifier: N,N-dihexyloctanamide (DHOA). The coordination aspect of Zr(IV) with ligand in IL phase was ascertained spectroscopically to validate Zr(IV) loading in IL phase. Thermodynamics of Zr(IV) extraction revealed the nature of the extraction process and the complex formation.

A thermogravimetric analysis of residual char formation by gilsonite-filled, polyfurfuryl alcohol composites: acid treatment of gilsonite

Gilsonite (GLS), a natural bitumen containing a considerable amount of asphaltenes, is expected to leave heavy char after pyrolysis; however, its high potential as an efficient filler to enhance the thermal properties of composite materials is surprisingly neglected throughout the literature. On the other hand, polyfurfuryl alcohol (PFA) has attracted much attention as a thermosetting resin due to its excellent char-leaving characteristics, the renewable nature of the monomer(s), and high accessibility at an affordable cost. This study aimed to investigate the thermal stability and char-forming performance of composites made of a PFA resin matrix filled with chemically modified GLS. To modify the ash and sulfur contents of GLS, the nitric acid leaching process was performed according to a D-optimal experimental design approach. The nitric acid concentration (10, 20, and 30 wt.%), treatment time (30, 75, and 120 min), and reaction temperature (30 °C, 50 °C, and 70 °C) were set as the input variables. The morphology (SEM), chemical structure (FTIR), thermal stability (TGA), sulfur content, and ash content of the GLS particles were characterized before and after acid treatment. Thermogravimetric analysis revealed the lowest ash content for GLS after treatment with 10 wt.% acid conc. at 75 °C for 75 min. The nitric acid concentration, reaction temperature, and time were the most influential parameters for improving the ash content of GLS according to their order of appearance. In addition, the inorganic form of sulfur, pyrite, was separated through the acid leaching process. Then, the PFA resin matrix was filled with modified GLS particles at different weight percentages (5, 10, 15, and 20 wt.%) and cured in the presence of an acid catalyst. The thermal stability of the PFA resin was negatively affected by the presence of GLS, probably due to oxidation reactions and disruption of the integrity of the resin structure.