Green Deep Eutectic Solvents (DESs) for Sustainable Metal Recovery from Thermally Treated PCBs: A Greener Alternative to Conventional Methods.

Waste PCBs the core of e-waste is rich in copper, tin, zinc, iron, and nickel. Leaching base metals from PCB used to be done in toxic, corrosive acidic/alkali mediums. In this work, an environmentally friendly method for leaching metals from thermally treated PCBs (TPCBs) of mobile phones was proposed using choline chloride based deep eutectic solvents (DES). DES selectivity and solubility of metals from metal oxides were the main screening criteria. FA-ChCl had the maximum solubility of Cu, Fe, and Ni, while Urea-ChCl had high Zn selectivity and solubility. Oxalic acid has high selectivity for Sn. FA-ChCl extracted Cu and Fe best at 16 h, 100 °C, and 1/30 g/mL. Urea-ChCl extracted Zn (90.4±2.9 %) from TPCBs at 100 °C, 21 h, 1/20 g/mL, and 400 rpm. Oxalic acid (1 M) removed 92.3±2.1 % Sn from TPCBs in 1 h at 80 °C and 1/20 g/mL. The shrinking core model-based kinetic investigation of FA-ChCl for Cu extraction showed a diffusion-controlled process. The proposed method is greener than mineral acids utilized for metal extraction.

Nanofluids of Amphiphilic Kaolinite-Based Janus Nanosheets for Enhanced Oil Recovery: The Importance of Stable Emulsion.

To meet the increasing global demand for energy, better recovery of crude oil from reservoirs must be achieved using methods that are economical and environmentally benign. Here, we have developed a nanofluid of amphiphilic clay-based Janus nanosheets via a facile and scalable method that provides potential to enhance oil recovery. With the aid of dimethyl sulfoxide (DMSO) intercalation and ultrasonication, kaolinite was exfoliated into nanosheets (KaolNS) before being grafted with 3-methacryloxypropyl-triemethoxysilane (KH570) on the Alumina Octahedral Sheet at 40 and 70 °C to form amphiphilic Janus nanosheets (i.e., KaolKH@40 and KaolKH@70). The amphiphilicity and Janus nature of the KaolKH nanosheets have been well demonstrated, with distinct wettability obtained on two sides of the nanosheets, and the KaolKH@70 was more amphiphilic than the KaolKH@40. Upon preparing Pickering emulsion in a hydrophilic glass tube, the KaolKH@40 preferentially stabilized emulsions, while the KaolNS and KaolKH@70 tended to form an observable and high-strength elastic planar interfacial film at the oil-water interface as well as films climbing along the tube's surface, which were supposed to be the result of emulsion instability and the strong adherence of Janus nanosheets towards tube's surface. Subsequently, the KaolKH was grafted with poly(N-Isopropylacrylamide) (PNIPAAm), and the prepared thermo-responsive Janus nanosheets demonstrated a reversible transformation between stable emulsion and the observable interfacial films. Finally, when the samples were subjected to core flooding tests, the nanofluid containing 0.01 wt% KaolKH@40 that formed stable emulsions showed an enhanced oil recovery (EOR) rate of 22.37%, outperforming the other nanofluids that formed observable films (an EOR rate ~13%), showcasing the superiority of Pickering emulsions from interfacial films. This work demonstrates that KH-570-modified amphiphilic clay-based Janus nanosheets have the potential to be used to improve oil recovery, especially when it is able to form stable Pickering emulsions.

Exploiting breath figure reversibility for in situ pattern modulation and hierarchical design.

The breath figure (BF) method employs condensation droplets as dynamic templates for patterning polymer films. In the classical approach, dropwise condensation and film solidification are simultaneously induced through solvent evaporation, leading to empirically derived patterns with limited predictability of the final design. Here we use the temporally arrested BF methodology, controlling condensation and polymerisation independently to create diverse BF patterns with varied pore size, arrangement and distribution. External temperature control enables us to further investigate and exploit the inherent reversibility of the phase change process that governs the pattern formation. We modulate the level of subcooling and superheating to achieve subsequent regimes of condensation and evaporation, permitting in situ regulation of the droplet growth and shrinkage kinetics. The full reversibility of the phase change processes joined with active photopolymerisation in the current approach thus allows arresting of predictable BF kinetics at intermediate stages, thereby accessing patterns with varied pore size and spacing for unchanged material properties and environmental conditions. This simultaneous active control over both the kinetics of phase change and polymer solidification offers affordable routes for the fabrication of diverse predictable porous surfaces; manufacture of monolithic hierarchical BF patterns are ultimately facilitated through the advanced control of the BF assembly using the method presented here.

Competitive Adsorption of Interfacially Active Nanoparticles and Anionic Surfactant at the Crude Oil-Water Interface.

The interfacial activity of poly(N-isopropylacrylamide) (pNIPAM) nanoparticles in the absence and presence of an anionic surfactant (sodium dodecyl sulfate, SDS) was studied at a crude oil-water interface. Both species are interfacially active and can lower the interfacial tension, but when mixed together, the interfacial composition was found to depend on the aging time and total component concentration. With the total component concentration less than 0.005 wt %, the reduced interfacial tension by pNIPAM was greater than SDS; thus, pNIPAM has a greater affinity to partition at the crude oil-water interface. However, the lower molecular weight (smaller molecule) of SDS compared to pNIPAM meant that it rapidly partitioned at the oil-water interface. When mixed, the interfacial composition was more SDS-like for low total component concentrations (≤ 0.001 wt %), while above, the interfacial composition was more pNIPAM-like, similar to the single component response. Applying a weighted arithmetic mean approach, the surface-active contribution (%) could be approximated for each component, pNIPAM and SDS. Even though SDS rapidly partitioned at the oil-water interface, it was shown to be displaced by the pNIPAM nanoparticles, and for the highest total component concentration, pNIPAM nanoparticles were predominantly contributing to the reduced oil-water interfacial tension. These findings have implications for the design and performance of fluids that are used to enhance crude oil production from reservoirs, particularly highlighting the aging time and component concentration effects to modify interfacial tensions.

Behaviour of polymer-coated composite nanoparticles at bubble-stabilizing interfaces during bubble coarsening and accelerated coalescence: A Cryo-SEM study.

HYPOTHESIS: Dynamics of polymer-coated silica composite nanoparticles (CPs) during bubble coarsening is highly dominated by the behaviour of the polymer layer, while in-situ particle aggregation would lead to accelerated bubble coalescence. EXPERIMENTS: CPs-stabilized foams were prepared in 0.1 M and 0.55 M Na2SO4 solution, referring to the 0.1 M and 0.55 M foam/bubble respectively. The 0.1 M to 0.55 M transition foam was also prepared. High resolution Cryo-SEM was originally used to investigate the CPs behaviour at the bubble-stabilizing interface during bubble coarsening and accelerated coalescence. FINDINGS: The 0.1 M bubble-stabilizing interface buckles in uniaxial compression due to coarsening, with the CPs being observed to desorb from the interface. While the CPs were visualized to rearrange into crumpled particle multi-layers surrounding the shrinking 0.55 M bubbles, due to the adhesion between interpenetrating polymer chains and the unique lubrication effect of the PVP layers. The 0.1 M to 0.55 M transition foaming behaviour was also studied. Cracks and voids were observed at interfaces surrounding the transition bubbles driven by in-situ particle aggregation, resulting in accelerated bubble coalescence during the transition process.

Discontinuous dewetting dynamics of highly viscous droplets on chemically heterogeneous substrates.

HYPOTHESIS: Droplet spreading on heterogeneous (chemical/structural) surfaces has revealed local disturbances that affect the advancing contact line. With droplet dewetting being less studied, we hypothesize that a receding droplet can be perturbed by localized heterogeneity which leads to irregular and discontinuous dewetting of the substrate. EXPERIMENTS: The sessile drop method was used to study droplet dewetting at a wettability boundary. One-half of a hydrophilic surface was hydrophobically modified with either i) methyloctyldichlorosilane or ii) clustered macromolecules. A Lattice Boltzmann method (LBM) simulation was also developed to determine the effect of contact angle hysteresis and boundary conditions on the droplet dynamics. FINDINGS: The two surface treatments were optimized to produce comparable water wetting characteristics. With a negative Gibbs free energy on the hydrophilic-half, the oil droplet receded to the hydrophobic-half. On the silanized surface, the droplet was pinned and the resultant droplet shape was a distorted spherical cap, having receded uniformly on the unmodified surface. Modifying the surface with clustered macromolecules, the droplet receded slightly to form a spherical cap. However, droplet recession was non-uniform and daughter droplets formed near the wettability boundary. The LBM simulation revealed that daughter droplets formed when θR > 164°, with the final droplet shape accurately described by imposing a diffuse wettability boundary condition.

Polymer-Induced Drag Reduction in Dilute Newtonian and Semi-Dilute Non-Newtonian Fluids: An Assessment of the Double-Gap Concentric Cylinder Method.

Polymer-induced drag reduction (DR) in fluids was studied using a rotational rheometer with double-gap concentric cylinder geometry. Although both polymers (polyacrylamide (PAM) and 2-acrylamido-2-methylpropane sulfonic acid (SPAM)) had molecular weights of several MDa, the contrasting polymer charge, nonionic and anionic, led to different polymer overlap concentrations (c*), PAM ≫ SPAM, and fluid rheology, with PAM fluids mostly Newtonian and SPAM fluids non-Newtonian (shear-thinning). Based on these differences, it was important to account for the infinite shear viscosity and normalize the polymer concentration by the intrinsic concentration (c int) so that the DR performance of the two polymer fluids could be accurately compared. Both polymers induced DR, and the maximum DR by SPAM (DR% = 28) was slightly higher than that by PAM (DR% = 22) when Re p ∼ 1700. For PAM, the loss of DR with time diminished at higher polymer concentrations (≥100 ppm, at Re p = 3149) but was found to be sensitive to high Re p, with polymer chain scission the likely cause of the reduced performance. For the semi-dilute SPAM fluids, the shear stability contrasted that of PAM, showing negligible dependence on the polymer concentration and Re p. The apparent rapid loss of DR was predominantly attributed to a time-dependent effect and not polymer degradation. In pipe flow, the maximum DR for SPAM was higher than that measured by rheometry and was attributed to differences in the flow conditions. However, changes in the normalized DR/c with polymer concentration were found to be consistent between the two flow geometries. Furthermore, the high fluid stresses in pipe flow (at high Re p) led to drag reduction losses consistent with PAM, as the time-dependent effect was not seen.

Temporally Arrested Breath Figure.

Since its original conception as a tool for manufacturing porous materials, the breath figure method (BF) and its variations have been frequently used for the fabrication of numerous micro- and nanopatterned functional surfaces. In classical BF, reliable design of the final pattern has been hindered by the dual role of solvent evaporation to initiate/control the dropwise condensation and induce polymerization, alongside the complex effects of local humidity and temperature influence. Herein, we provide a deterministic method for reliable control of BF pore diameters over a wide range of length scales and environmental conditions. To this end, we employ an adapted methodology that decouples cooling from polymerization by using a combination of initiative cooling and quasi-instantaneous UV curing to deliberately arrest the desired BF patterns in time. Through in situ real-time optical microscopy analysis of the condensation kinetics, we demonstrate that an analytically predictable self-similar regime is the predominant arrangement from early to late times O(10-100 s), when high-density condensation nucleation is initially achieved on the polymer films. In this regime, the temporal growth of condensation droplets follows a unified power law of D ∝ t. Identification and quantitative characterization of the scale-invariant self-similar BF regime allow fabrication of programmed pore size, ranging from hundreds of nanometers to tens of micrometers, at high surface coverage of around 40%. Finally, we show that temporal arresting of BF patterns can be further extended for selective surface patterning and/or pore size modulation by spatially masking the UV curing illumination source. Our findings bridge the gap between fundamental knowledge of dropwise condensation and applied breath figure patterning techniques, thus enabling mechanistic design and fabrication of porous materials and interfaces.

Interfacial behavior of core-shell composite nanoparticles under compression and shear: Influence of polymer shell thickness.

HYPOTHESIS: The mobility of core-shell nanoparticles partitioned at an air-water interface is strongly governed by the compliance of the polymer shell. EXPERIMENTS: The compressional, relaxation and shear responses of two polymer-coated silica nanoparticles (CPs) were studied using a Langmuir trough and needle interfacial shear rheometer, and the corresponding structures of the particle-laden interfaces were visualized using Brewster angle and scanning electron microscopy. FINDINGS: The mobility of CPs partitioned at an air-water interface correlates to the polymer MW. In compression, the CPs40-laden interface (silica nanoparticles coated with 40 kDa PVP) showed distinct gas-liquid-solid phase transitions and when the surface pressure was reduced, the compressed particle-laden interface relaxed to its original state. The compressed-state of the CPs8-laden interface did not relax, and wrinkles in the particle-laden film that had formed in compression remained due to greater adhesion between the compressed particles. The increased mobility of the CPs40-laden interface translated to lower surface shear moduli, with the viscoelastic moduli an order of magnitude or more lower in the CPs40-laden interface than the CPs8-laden interface. Ultimately this contributed to changing the stability of particle-stabilized foams, with less mobile interfaces providing improved foam stability.

Dewetting dynamics of heavy crude oil droplet in low-salinity fluids at elevated pressures and temperatures.

HYPOTHESIS: Improved oil recovery by low-salinity injection correlates to the optimal brine concentration to achieve maximum dewetting of oil droplets on rock surfaces. While interfacial tension and electrical double layer forces are often cited as being determinant properties, we hypothesize that other structural/interfacial forces are more prominent in governing the system behavior. EXPERIMENTS: The sessile droplet technique was used to study the receding dynamics of oil droplets from flat hydrophilic substrates in brines of different salt type (NaCl and CaCl2) and concentration, and were studied at both low and elevated temperatures (60 and 140 °C) and pressures (1, 10, 100 and 200 bar). FINDINGS: At 1 bar and 60 °C, the minimum oil droplet-substrate adhesion force (FA) was determined at 34 mM NaCl and 225 mM CaCl2. For NaCl this strongly correlated to strengthening hydration forces, which for CaCl2 were diminished by long-range hydrophobic forces. These results highlight the importance of other non-DLVO forces governing the dewetting dynamics of heavy crude oil droplets. At 140 °C and 200 bar, the optimal brine concentrations were found to be much higher (1027 mM NaCl and 541 mM CaCl2), with higher concentrations likely attributed to weakening hydration forces at elevated temperatures.

Flotation using sodium dodecyl sulphate and sodium lauroyl isethionate for rapid dewatering of Mg(OH)2 radwaste suspensions.

Mg(OH)2 suspensions were floated utilising sodium dodecyl sulphate (SDS) and sodium lauroyl isethionate (SLI) collectors, for rapid dewatering of radwaste suspensions. Freundlich adsorption isotherms were first used to compare the adsorption densities of SDS and SLI on Mg(OH)2 surfaces, to determine the maximum monolayer coverage capacity, and were found to be 0.11 µmol m-2 at a dosed concentration of 172 µM for SDS and 0.05 µmol m-2 at a dosed concentration of 188 µM for SLI. The natural and salt induced coagulation kinetics of Mg(OH)2 were examined using static light scattering, where the influence of collector adsorption on particle size distributions was also investigated, to probe potential hydrodynamic limitations of flotation. Particle stabilised foam formation was then characterised using a Bikerman column test, where the dynamic foamability indices (DFIs) of SDS and SLI were determined to be 49 × 103 s L mol-1 and 321 × 103 s L mol-1 respectively. Flotation performance was measured, and a collection efficiency factor used to compare the solid-liquid separation ability of mixed 2.5 vol% suspensions with SDS or SLI, as well as MIBC frother. Optimal performance aligned with collector concentrations relating to predicted maximum monolayer coverage, and whilst both surfactants were effective, SDS systems performed better than SLI in all metrics. Recoveries of >80% of the Mg(OH)2 wastes were achieved, whilst only transferring 35% of the water mass at the optimum SDS dosed concentration of 82 µM, likely due to its denser surface adsorption and minimised lamella water entrainment.

The effect of cationic surfactants on improving natural clinoptilolite for the flotation of cesium.

Flotation using cationic surfactants has been investigated as a rapid separation technique to dewater clinoptilolite ion exchange resins, for the decontamination of radioactive cesium ions (Cs+) from nuclear waste effluent. Initial kinetic and equilibrium adsorption studies of cesium, suggested the large surface area to volume ratio of the fine zeolite contributed to fast adsorption kinetics and high capacities (qc = 158.3 mg/g). Adsorption of ethylhexadecyldimethylammonium bromide (EHDa-Br) and cetylpyridinium chloride (CPC) surfactant collectors onto both clean and 5 ppm Cs+ contaminated clinoptilolite was then measured, where distribution coefficients (Kd) as high as 10,000 mL/g were evident with moderate concentrations CPC. Measurements of particle sizes confirmed that adsorption of surfactant monolayers did not lead to significant aggregation of the clinoptilolite, while < 8% of the 5 ppm contaminated cesium was remobilised. Importantly for flotation, both the recovery efficiency and dewatering ratios were measured across various surfactant concentrations. Optimum conditions were found with 0.5 mM of CPC and addition of 30 µL of MIBC frother, giving a recovery of ∼90% and a water reduction ratio > 4, highlighting the great viability of flotation to separate and concentrate the contaminated powder in the froth phase.

Investigating Adsorbing Viscoelastic Fluids Using the Quartz Crystal Microbalance.

There is little research on using the quartz crystal microbalance (QCM) with adsorbing viscoelastic fluids. These fluids are widely encountered but often difficult to study as many are opaque and highly viscous. Since the QCM does not involve any scattering or reflection of input radiation, it has the potential to study these complex fluids to determine the relative viscoelasticity of the bulk fluid and surface adsorption of active species onto different substrates. In the current study, both Newtonian (sucrose) and viscoelastic (sodium polystyrene sulfonate (NaPSS)) fluids were introduced into the QCM, and the sensor responses were compared. QCM responses of Newtonian sucrose solutions matched the Kanazawa and Gordon model (KG model), as expected. The QCM responses with viscoelastic NaPSS solutions were well below those described by the KG model. A viscoelastic model was used to determine the fluid viscosity and shear modulus at a very high frequency. It was found that the viscosity of NaPSS did not change much compared with low-frequency rheometer measurements, but a significant increase in the shear modulus of several orders of magnitude was found at the QCM frequencies. Modifying the KG model frequency shifts by multiplying by the QCM shear wave decay length ratio, X = δV/δN, we were able to match the measured QCM values in viscoelastic NaPSS solutions. The QCM dissipation values for NaPSS were matched in a similar way by multiplying the KG model by X 1/3. By changing the QCM sensor from silica (no NaPSS adsorption) to alumina (NaPSS adsorption), it was shown that the adsorption isotherm of NaPSS on alumina could be recovered and fitted with a Langmuir isotherm despite the frequency response being only a small fraction of the total measured QCM signal.

Substrate Wettability Influences Internal Jet Formation and Mixing during Droplet Coalescence.

The internal dynamics during the axisymmetric coalescence of an initially static free droplet and a sessile droplet of the same fluid are studied using both laboratory experiments and numerical simulations. A high-speed camera captured internal flows from the side, visualized by adding a dye to the free droplet. The numerical simulations employ the volume of fluid method, with the Kistler dynamic contact angle model to capture substrate wettability, quantitatively validated against the image-processed experiments. It is shown that an internal jet can be formed when capillary waves reflected from the contact line create a small tip with high curvature on top of the coalesced droplet that propels fluid toward the substrate. Jet formation is found to depend on the substrate wettability, which influences capillary wave reflection; the importance of the advancing contact angle subordinated to that of the receding contact angle. It is systematically shown via regime maps that jet formation is enhanced by increasing the receding contact angle and by decreasing the droplet viscosity. Jets are seen at volume ratios very different from those accepted for free droplets, showing that a substrate with appropriate wettability can improve the efficiency of fluid mixing.

Bio-Inspired Preparation of Clay-Hexacyanoferrate Composite Hydrogels as Super Adsorbents for Cs.

A facile and low-cost fabrication route, inspired by the adhesive proteins secreted by mussels, has been developed to prepare a clay-based composite hydrogel (DHG(Cu)) containing hexacyanoferrate (HCF) nanoparticles for the selective removal of Cs+ from contaminated water. Initially, montmorillonite was exfoliated prior to coating with a thin layer of polydopamine (PDOPA) via the self-polymerization of dopamine. Mixing the composite (D-clay) with the HCF precursor, followed by the addition of copper ions, led to the self-assembly of the polymer-coated exfoliated clay nanosheets into a three-dimensional network and in situ growth of KCuHCF nanoparticles embedded within the gel structure. Analytical characterization verified the fabrication route and KCuHCF immobilization by a copper-ligand complexation. Rheology testing revealed the composite hydrogel to be elastic under low strain and exhibited reversible, self-healing behavior following high strain deformation, providing a good retention of KCuHCF nanoparticles in the membrane. The adsorbent DHG(Cu) showed a superior Cs+ adsorption capacity (∼173 mg/g), with the performance maintained over a wide pH range, and an excellent selectivity for Cs+ when dispersed in seawater at low concentrations of 0.2 ppm. On the basis of its excellent mechanico-chemical properties, the fabricated hydrogel was tested as a membrane in column filtration, showing excellent removal of Cs+ from Milli-Q water and seawater, with the performance only limited by the fluid residence time. For comparison, the study also considered other composite hydrogels, which were fabricated as intermediates of DHG(Cu) or fabricated with Fe3+ as the cross-linker and reactant for HCF nanoparticle synthesis.

Effective removal of cesium from wastewater via adsorptive filtration with potassium copper hexacyanoferrate-immobilized and polyethyleneimine-grafted graphene oxide.

As an attractive alternative to radioactive cesium removal, we introduced an adsorptive filtration method using a composite membrane consisting of potassium copper hexacyanoferrate (KCuHCF) and graphene-based support. Polyethyleneimine-grafted reduced graphene oxide (PEI-rGO), used as an immobilizing matrix, was effective not only in distributing KCuHCF inside the composite with the aid of abundant amino-functionality, but also in achieving high water flux by increasing the interlayer spacing of the laminar membrane structure. Due to the rapid and selective cesium adsorption properties of KCuHCF, the fabricated membrane was found to be effective in achieving complete removal of cesium ions under a high flux (over 500 L m-2 h-1), which is difficult in a conventional membrane utilizing the molecular sieving effect. This approach offers strong potential in the field of elimination of radionuclides that require rapid and complete decontamination.

Sediment Microstructure and the Establishment of Gas Migration Pathways during Bubble Growth.

Soft sediments exhibit complex and varied deformation behavior during in situ bubble growth; however, the sediment microstructure is often neglected when predicting bubble networking or fracture propagation dynamics. This study considers three chemically similar Mg(OH)2-rich sediments, which differ slightly in their particle size distributions and morphologies but exhibit significant differences in their porosity, stiffness, and pore throat dimensions at equivalent yield strengths. At low yield strengths, microstructure greatly influenced the size distribution and connectivity of spherical bubble populations, with narrow sedimentary pore throats promoting coarser bubbles with diminished connectivity. Increased connectivity of the bubble population appeared highly significant in limiting bed expansion, either by establishing pathways for gas release or by dissipating excess internal bubble pressure, thereby diminishing further growth. During in situ gas generation, each sediment demonstrated a critical fracture strength, which demarcated the populations with high void fractions (0.27 < ν < 0.4) of near-spherical bubbles from a fracturing regime supporting reduced void fractions (ν ≈ 0.15) of high aspect ratio cracks. However, critical fracture strengths varied significantly (in the 60-1000 Pa range) between sediments, with coarser-grained and higher porosity sediments promoting fracture at lower strengths. Fracture propagation greatly enhanced the connectivity and diminished the tortuosity of the void networks, thereby augmenting the continuous gas release flux.

Stimuli-Responsive Hybrid Polymer for Enhanced Solid-Liquid Separation of Industrial Effluents.

In the current study, a novel stimuli-responsive hybrid polymer with aluminum hydroxide colloids incorporated into a cationic copolymer of N-isopropylacrylamide and N-[3-(dimethylamino)propyl]methacrylamide was synthesized to enhance the settling and filtration performance of fine clay suspensions. The conformation of the synthesized hybrid copolymer was shown to respond to changes in both temperature and pH. Compared with a cationic copolymer of similar structure without aluminum hydroxide colloids, settling and filtration rates were significantly enhanced using the hybrid copolymer, which is attributed to the synergy between the inorganic aluminum hydroxide cores and organic copolymer. While the ideal treatment protocol for the hybrid polymer involved the addition of the polymer at room temperature, followed by heating to 45 °C for enhanced settling and dewatering, the synergistic effect between colloidal cores and polymer also allowed the hybrid polymer to perform well when added at temperatures above the LCST, demonstrating the robustness of the hybrid polymer to the process environment. The ideal treatment protocol resulted in an optimal adsorption of polymer on clays before inducing a coil-globule transition to form large and dense flocs, resulting in a more porous filter cake.

Amino-functionalized magnetic chitosan beads to enhance immobilization of potassium copper hexacyanoferrate for selective Cs+ removal and facile recovery.

Potassium copper hexacyanoferrate (KCuHCF)-incorporated magnetic chitosan beads (HMC) were synthesized for both selective Cs+ removal in aqueous solutions and facile recovery of the spent adsorbent. To disperse and immobilize large amounts of the KCuHCF, methyl acrylate and diethylenetriamine were sequentially grafted onto the one-step synthesized magnetic chitosan beads. The additional introduction of amino functionality led to the enriched Cu2+ ions on the bead surface to incorporate KCuHCF into the grafting matrix. Consequently, the HMC exhibited a high Cs+ capacity calculated to be 136.47 mg g-1 from the Langmuir model, and the equilibrium was established within 4 h. Moreover, the HMC exhibited excellent stability in a wide pH range from 4 to 11 and an outstanding Cs+ selectivity (>97%) in seawater (1.11 mg L-1 Cs+). From a practical point of view, the HMC was stable during five successive adsorption cycles and easily recovered by magnets, enabling continuous operation to decontaminate a large volume of wastewater.

Synthesis and Physical Property Characterisation of Spheroidal and Cuboidal Nuclear Waste Simulant Dispersions.

This study investigated dispersions analogous to highly active nuclear waste, formed from the reprocessing of Spent Nuclear Fuel (SNF). Non-radioactive simulants of spheroidal caesium phosphomolybdate (CPM) and cuboidal zirconium molybdate (ZM-a) were successfully synthesised; confirmed via Scanning Electron Microscopy (SEM), powder X-ray diffraction (PXRD) and Fourier transform infrared (FTIR) spectroscopy. In addition, a supplied ZM (ZM-b) with a rod-like/wheatsheaf morphology was also analysed along with titanium dioxide (TiO2). The simulants underwent thermal gravimetric analysis (TGA) and size analysis, where CPM was found to have a D50 value of 300 nm and a chemical formula of Cs3PMo12O40·13H2O, ZM-a a D50 value of 10 µm and a chemical formula of ZrMo2O7(OH)2·3H2O and ZM-b to have a D50 value of 14 µm and a chemical formula of ZrMo2O7(OH)2·4H2O. The synthesis of CPM was tracked via Ultraviolet-visible (UV-Vis) spectroscopy at both 25 °C and 50 °C, where the reaction was found to be first order with the rate constant highly temperature dependent. The morphology change from spheroidal CPM to cuboidal ZM-a was tracked via SEM, reporting to take 10 days. For the onward processing and immobilisation of these waste dispersions, centrifugal analysis was utilised to understand their settling behaviours, in both aqueous and 2 M nitric acid environments (mimicking current storage conditions). Spheroidal CPM was present in both conditions as agglomerated clusters, with relatively high settling rates. Conversely, the ZM were found to be stable in water, where their settling rate exponents were related to the morphology. In acid, the high effective electrolyte resulted in agglomeration and faster sedimentation.