Sulfuric Acid Baking and Fe(III)-Cl--H2SO4 Leaching Behavior of Ni- and Cu-Containing Sulfide and Silicate Rich Suhanko Concentrate.

Ni- and Cu-rich concentrate from a new site in Suhanko, Finland, was investigated. Mineral phases identified included talc, chalcopyrite, kaolinite, and pyrrhotite with 3.2% Cu and 1.5% Ni, and the latter is associated with pyrrhotite. In addition, the concentrate contained the precious elements Pd (14.9 g/t), Ag (17.1 g/t), Pt (2.1 g/t), and Au (1.1 g/t). This concentrate was baked and leached using a Fe(III)-Cl--H2SO4 system. The results showed that the leaching efficiencies of Ni, Cu, and Si from raw concentrate were 60%, 40%, and 5%; however, those from baked concentrate were 96%, 60%, and below 0.1%, indicating that the baking process enhanced Ni and Cu extraction while simultaneously inhibiting the dissolution of Si, which was due to the baking process liberating the associated Ni and Cu by the oxidation of chalcopyrite and pyrrhotite and converting the acid-soluble silicate into an insoluble form. Sulfuric acid leaching solution with Fe(III) as oxidant and Cl- as lixiviant was shown to be effective at leaching Ni (97%), Cu (62%), and Ag (89%), while simultaneously enriching the PMs Pd, Pt, and Au in the residue.

Investigating turbulence distribution in the lower atmosphere using time-lapse imagery from a camera bank.

The atmosphere's surface layer (first 50-100 m above the ground) is extremely dynamic and is influenced by surface radiative properties, roughness, and atmospheric stability. Understanding the distribution of turbulence in the surface layer is critical to many applications, such as directed energy and free space optical communications. Several measurement campaigns in the past have relied on weather balloons or sonic detection and ranging (SODAR) to measure turbulence up to the atmospheric boundary layer. However, these campaigns had limited measurements near the surface. We have developed a time-lapse imaging technique to profile atmospheric turbulence from turbulence-induced differential motion or tilts between features on a distant target, sensed between pairs of cameras in a camera bank. This is a low-cost and portable approach to remotely sense turbulence from a single site without the deployment of sensors at the target location. It is thus an excellent approach to study the distribution of turbulence in low altitudes with sufficiently high resolution. In the present work, the potential of this technique was demonstrated. We tested the method over a path with constant turbulence. We explored the turbulence distribution with height in the first 20 m above the ground by imaging a 30 m water tower over a flat terrain on three clear days in summer. In addition, we analyzed time-lapse data from a second water tower over a sloped terrain. In most of the turbulence profiles extracted from these images, the drop in turbulence with altitude in the first 15 m or so above the ground showed a h m dependence, where the exponent m varied from -0.3 to -1.0, quite contrary to the widely used value of -4/3.

Quantification of surface layer turbulence using sensible heat values from energy balance versus aerodynamic methods.

Surface layer optical turbulence values in the form of the refractive index structure function C n2 are often calculated from surface layer temperature, moisture, and wind characteristics and compared to measurements from sonic anemometers, differential temperature sensors, and imaging systems. A key derived component needed in the surface layer turbulence calculations is the sensible heat value. Typically, the sensible heat is calculated using the bulk aerodynamic method that assumes a certain surface roughness and a friction velocity that approximates the turbulence drag on temperature and moisture mixing from the change in the average surface layer vertical wind velocity. These assumptions/approximations generally only apply in free convection conditions. To obtain the sensible heat, a more robust method, which applies when free convection conditions are not occurring, is via an energy balance method such as the Bowen ratio method. The use of the Bowen ratio--the ratio of sensible heat flux to latent heat flux--allows a more direct assessment of the optical turbulence-driving surface layer sensible heat flux than do more traditional assessments of surface layer sensible heat flux. This study compares surface layer C n2 values using sensible heat values from the bulk aerodynamic and energy balance methods to quantifications from sonic anemometers posted at different heights on a sensor tower. The research shows that the sensible heat obtained via the Bowen ratio method provides a simpler, more reliable, and more accurate way to calculate surface layer C n2 values than what is required to make such calculations from bulk aerodynamic method-obtained sensible heat.

A study on recovery strategies of graphite from mixed lithium-ion battery chemistries using froth flotation.

The growing electric vehicle industry has increased the demand for raw materials used in lithium-ion batteries (LIBs), raising concerns about material availability. Froth flotation has gained attention as a LIB recycling method, allowing the recovery of low value materials while preserving the chemical integrity of electrode materials. Furthermore, as new battery chemistries such as lithium titanate (LTO) are introduced into the market, strategies to treat mixed battery streams are needed. In this work, laboratory-scale flotation separation experiments were conducted on two model black mass samples: i) a mixture containing a single cathode (i.e., NMC811) and two anode species (i.e., LTO and graphite), simulating a mixed feedstock prior to hydrometallurgical treatment; and ii) a graphite-TiO2 mixture to reflect the expected products after leaching. The results indicate that graphite can be recovered with > 98 % grade from NMC811-LTO-graphite mixtures. Additionally, it was found that flotation kinetics are dependent on the electrode particle species present in the suspension. In contrast, the flotation of graphite from TiO2 resulted in a low grade product (<96 %) attributed to the significant entrainment of ultrafine TiO2 particles. These results suggest that flotation of graphite should be preferably carried out before hydrometallurgical treatment of black mass.

Analogical environmental cost assessment of silicon flows used in solar panels by the US and China.

Achieving carbon neutrality requires deployment of large-scale renewable energy technologies like solar photovoltaic (PV) panels. Nevertheless, methods to ascertain the overall environmental impacts PVs and further improve their sustainability are under-investigated. In an effort to provide more understanding of this crucial topic, this research focuses on silicon flows-a key element for manufacturing crystalline silicon PVs. Using system dynamics modeling, we conduct a comprehensive environmental cost assessment of the silicon flows used in PVs based on a comparative analysis between the United States and China as the leading global PV manufacturers. Despite the advancement in wafer quality, material usage reductions and overall price decreases achieved in recent decades, our results project a substantial increase in energy and water consumption in China related to Metallurgical Grade Si (MG-Si), Solar Grade Si (SoG-Si) and cell manufacturing by 2030. An approximate 6.5 times increase of energy and water consumption is observed for c-Si cell manufacturing in China between 2010 and 2020. In 2030, increases of 70% in energy consumption and 69% in water use are estimated for Chinese MG-Si and SoG-Si production. The most significant environmental impact is observed in silicon cell and module manufacturing in both countries, particularly concerning GHG, SOx and NOx emissions. This study provides valuable insights into the environmental impacts of these two major solar panel manufacturing countries by examining the silicon life cycle, from production to end-of-life.

Sweet Side Streams: Sugar Beet Pulp as Source for High-Performance Supercapacitor Electrodes.

Valorization of the lignocellulosic side and waste streams is key to making industrial processes more efficient from both an economic and ecological perspective. Currently, the production of sugars from beets results in pulps in large quantities. However, there is a lack of promising opportunities for upcycling these materials despite their promising properties. Here, we investigate beet pulps from two different stages of the sugar manufacturing process as raw materials for supercapacitor electrodes. We demonstrate that these materials can be efficiently converted to activated, highly porous carbons. The carbons exhibit pore dimensions approaching the size of the desolvated K+ and SO42- ions with surface areas up to 2600 m2 g-1. These carbons were subsequently manufactured into electrodes, assembled in supercapacitors, and tested with environmentally friendly aqueous electrolytes (6 M KOH and 1 M H2SO4). Further analysis demonstrated the presence of capacitance-enhancing functionalities, and up to 193 and 177 F g-1 in H2SO4 and KOH, respectively, were achieved, which outperformed supercapacitors prepared from commercial YP80 F. Overall, our study suggests that side streams from sugar manufacturing offer a hidden potential for use in high-performance energy storage devices.

A translationally active ligand based on a [2]rotaxane molecular shuttle with a 2,2'-bipyridyl core.

A rigid H-shaped, [2]rotaxane molecular shuttle comprised of an axle containing two benzimidazole recognition sites and a central 2,2'-bipyridyl (bipy) group interlocked with a 24-crown-8 (24C8) wheel was synthesized using a threading followed by stoppering protocol. The central bipy chelating unit was shown to act as a speed bump that raised the barrier to shuttling for the [2]rotaxane. Coordination of a PtCl2 moiety to the bipy unit in a square planar geometry created an insurmountable steric barrier to shuttling. Addition of one equivalent of NaB(3,5-(CF3)2C6H3)4 removed one of the chloride ligands allowing for translation of the crown ether along the axle into the coordination sphere of the Pt(ii) centre but full shuttling of the crown ether could not be activated. In contrast, addition of Zn(ii) ions in a coordinating solvent (DMF) allowed shuttling to occur using a ligand exchange mechanism. DFT calculations showed this likely occurs via coordination of the 24C8 macrocycle to the Zn(ii) centre bound to the bipy chelate. This interplay of the rotaxane axle and wheel components is an example of a translationally active ligand that utilises the large amplitude displacement of a macrocycle along an axle in a molecular shuttle to access ligand coordination modes not possible with conventional ligand designs.

Fishtail Deformity after Type 2 Supracondylar Humerus Fracture with Development of Symptomatic Loose Body: A Case Report.

Introduction: Supracondylar humerus fractures are one of the most common fractures in children and have been reported to represent up to 16% of all pediatric fractures. While most fractures heal uneventfully with appropriate treatment, there are several known complications that can occur including loss of motion, malunion, and neurovascular injury. One uncommon, yet significant, complication is termed the "Fishtail" deformity. This is represented radiographically with apparent proximal migration of the trochlea, which is thought to be secondary to avascular necrosis and resulting growth arrest. Case Report: This case describes a 11-year-old male who developed a fishtail deformity at age 5, 5 months after percutaneous pinning of a Type II supracondylar humerus fracture. Initially demonstrating a tolerable loss of elbow range of motion (ROM) and being lost to follow-up, he returned 7-years postoperatively, demonstrating diffuse elbow degenerative changes and worsening mechanical symptoms secondary to a loose body which necessitated arthroscopic debridement and loose body removal. Conclusion: This case illustrates the rare fishtail deformity in a Type II supracondylar humerus fracture with acute onset mechanical symptoms of the elbow secondary to a large loose body. Patients with history of supracondylar humerus fractures can develop acute or worsening changes in elbow ROM secondary to the development of osteochondral loose bodies even in the setting of previously known motion deficits secondary to fishtail deformities.

Acute Iliotibial Band ACL Reconstruction at Time of Tibial Plateau Fracture Fixation: A Case Report.

Introduction: Tibial plateau fractures are frequently associated with associated soft-tissue injuries. Typical treatment algorithms prioritize bony stabilization followed by delayed soft-tissue reconstruction. However, when the soft-tissue injury needs urgent intervention to optimize patient outcome, early soft-tissue reconstruction may be indicated. Case Report: This case report features a high-energy tibia plateau fracture-dislocation with associated anterior cruciate ligament (ACL) and bucket-handle lateral meniscus tear sustained after a fall. The treatment of both bony and soft-tissue injury took place during a single anesthetic event by utilizing a novel application of a previously described technique for ACL reconstruction with iliotibial band (ITB) autograft. Conclusion: The ITB ACL reconstruction technique can be used in adults with concomitant ACL rupture and tibial plateau fracture. This allows patients to undergo a single anesthetic event for treatment of both bony and soft-tissue injuries.

Esophageal Adenocarcinoma in an Active Duty Sailor: A Case Report.

Esophageal adenocarcinoma develops when normal squamous epithelia are replaced by dysplastic intestinal columnar cells in response to chronic gastroesophageal reflux disease (GERD). In addition to squamous cell carcinoma, the two malignancies account for over 95% of esophageal malignancies. This case describes a sailor deployed onboard an aircraft carrier who initially presented with typical GERD symptoms and later developed multifactorial weight loss confounded by the operational environment. Upon return to homeport, he was diagnosed with stage III gastroesophageal junction adenocarcinoma. This case emphasizes the difficulty in identifying and diagnosing a rare and dangerous pathology in the resource-limited, operational environment.

Idiopathic Granulomatous Lobular Mastitis: A Mimicker of Inflammatory Breast Cancer.

Background: Idiopathic granulomatous lobular mastitis (IGLM) is a rare, chronic inflammatory breast disease without a known etiology. Even though the current literature proposes several treatment strategies, there is no universal consensus for long-term management. Case Presentation: A 43-year-old White woman (gravida 5, para 4) presented with a 2-week history of right lower outer quadrant breast tenderness, heaviness, warmth, and redness. Mammography and ultrasound were concerning for inflammatory breast cancer. Biopsies returned as granulomatous mastitis without malignancy. After 8 months of unsuccessful therapy with prednisone and methotrexate, surgeons excised the breast tissue. Cultures and special stains were negative for other organisms. At the 7-month follow-up, no evidence of recurrence was seen. Conclusions: As there remains no consensus behind the etiology or management of IGLM, our case demonstrates a reasonable and successful stepwise treatment beginning with medical therapy before proceeding to surgical cure. Because of possible malignancy risk with chronic IGLM, patients should not delay surgical excision if their condition remains refractory to medical therapy alone.

A New Hydrometallurgical Process for Metal Extraction from Electric Arc Furnace Dust Using Ionic Liquids.

This research proposes a new hydrometallurgical method for Zn, In, and Ga extraction, along with Fe as a common impurity, from electric arc furnace dust (EAFD), using ionic liquids. EAFD is a metal-containing waste fraction generated in significant amounts during the process of steelmaking from scrap material in an electric arc furnace. With valuable metal recovery as the main goal, two ionic liquids, [Bmim+HSO4-] and [Bmim+Cl-], were studied in conjunction with three oxidants: Fe2(SO4)3, KMnO4, and H2O2. The results indicated that the best combination was [Bmim+HSO4-] with [Fe2(SO4)3]. An experimental series subsequently demonstrated that the combination of 30% v/v [Bmim+HSO4-], 1 g of [Fe2(SO4)3], S/L ratio = 1/20, a 240 min leaching time, and a temperature of 85 °C was optimal, resulting in maximum extractions of 92.7% Zn, 97.4% In, and 17.03% Ga. In addition, 80.2% of the impurity metal Fe was dissolved. The dissolution kinetics of these four elements over a temperature range of 55-85 °C was found to be diffusion controlled. The remaining phases present in the leached residue were low amounts of ZnO, Fe3O4, ZnFe2O4, and traces of Ca(OH)2 and MnO2, and additional sharp peaks indicative of PbSO4 and CaSO4 appeared within the XRD pattern. The intensity of the peaks related to ZnO and Fe3O4 were observed to have decreased considerably during leaching, whereas some of the refractory ZnFe2O4 phase remained. SEM-EDS analysis revealed that the initial EAFD morphology was composed of spherical-shaped fine-grained particle agglomerates, whereas the leached residue was dominated by calcium sulphate (Ca(SO4))-rich needle-shaped crystals. The results clearly demonstrate that [Bmim+HSO4-] is able to extract the target metals due to its acidic properties.

Disparities Associated With Patient Adherence to BI-RADS 3 Assessment Follow-up Recommendations for Mammography and Ultrasound.

OBJECTIVE: To assess the relationship between sociodemographic factors and adherence rates in patients with a BI-RADS 3 assessment. METHODS: This retrospective cohort study reviewed data from all patients with a BI-RADS 3 assessment on mammography and ultrasound examinations at a single, multisite academic institution, which serves a diverse urban-suburban population, from January 1, 2015, to December 13, 2017. Appropriate follow-up was defined as returning for the first follow-up examination 3 to 9 months after the index examination. Associations between BI-RADS 3 adherence rates and patient sociodemographic characteristics were evaluated using logistic regression. RESULTS: There were 4,038 patients in our study period; 2,437 patients (60%) had appropriate follow-up, 765 (19%) patients had delayed follow-up, and 836 patients (21%) were lost to follow-up. The overall malignancy rate was 1.4% (46 of 3,202). Older age, retired employment status, and Medicare insurance status were associated with increased adherence to BI-RADS 3 follow-up recommendations. Black race, single relationship status, Medicaid and self-pay insurance status, and living in a top 15% disadvantaged zip code were associated with decreased adherence. On multivariate analysis, older age remained associated with increased adherence and Medicaid insurance status with decreased adherence. Time between index examination and cancer diagnosis was shorter in patients who had timely follow-up (202 days [interquartile range 183-358] versus 392 days [interquartile range 365-563], P ≤ .001), although there was not a significant difference in stage at diagnosis (P = .46). DISCUSSION: Multiple sociodemographic factors are associated with low adherence to BI-RADS 3 follow-up recommendations suggesting that more frequent and targeted interventions are needed to close disparity gaps.

Pillar Modularity in fsc Topology Hybrid Ultramicroporous Materials Based upon Tetra(4-pyridyl)benzene.

Hybrid ultramicroporous materials (HUMs) are porous coordination networks composed of combinations of organic and inorganic linker ligands with a pore diameter of <7 Å. Despite their benchmark gas sorption selectivity for several industrially relevant gas separations and their inherent modularity, the structural and compositional diversity of HUMs remains underexplored. In this contribution, we report a family of six HUMs (SIFSIX-22-Zn, TIFSIX-6-Zn, SNFSIX-2-Zn, GEFSIX-4-Zn, ZRFSIX-3-Zn, and TAFSEVEN-1-Zn) based on Zn metal centers and the tetratopic N-donor organic ligand tetra(4-pyridyl)benzene (tepb). The incorporation of fluorinated inorganic pillars (SiF6 2-, TiF6 2-, SnF6 2-, GeF6 2-, ZrF6 2-, and TaF7 2-, respectively) resulted in (4,6)-connected fsc topology as verified using single-crystal X-ray diffraction. Pure-component gas sorption studies with N2, CO2, C2H2, C2H4, and C2H6 revealed that the large voids and narrow pore windows common to all six HUMs can be leveraged to afford high C2H2 uptakes while retaining high ideal adsorbed solution theory (IAST) selectivities for industrially relevant gas mixtures: >10 for 1:99 C2H2/C2H4 and >5 for 1:1 C2H2/CO2. The approach taken, systematic variation of pillars with retention of structure, enables differences in selectivity to be attributed directly to the choice of the inorganic pillar. This study introduces fsc topology HUMs as a modular platform that is amenable to fine-tuning of structure and properties.

Descriptive Epidemiology of a Surgical Patellofemoral Instability Population of 492 Patients.

Background: Patellofemoral instability (PFI) occurs most commonly in pediatric and adolescent patients, with evolving indications for surgery and changes in surgical techniques over the past decade. Purpose: To characterize the demographic, clinical, and radiologic characteristics of a large cohort of patients undergoing PFI surgery and investigate longitudinal trends in techniques utilized over a 10-year period at a tertiary-care academic center. Study Design: Case series; Level of evidence, 4. Methods: Electronic medical records of patients younger than 25 years of age who underwent primary surgery for lateral PFI from 2008 to 2017 at a single center by 1 of 5 different sports medicine surgeons were retrospectively reviewed. Demographic, clinical, and radiographic parameters of instability were analyzed. Routine surgical techniques included medial retinacular plication/reefing/repair (MRP), medial patellofemoral ligament reconstruction (MPFLR), tibial tubercle osteotomy (TTO), or a combination thereof, with or without lateral retinacular release (LR) or lateral retinacular lengthening (LRL). Exclusion criteria, selected for potentially altering routine surgical indications or techniques, included fixed/syndromic PFI, a formally diagnosed collagen disorder, cases in which a chondral/osteochondral shear fragment underwent fixation or was >1 cm in diameter, and body mass index >30 kg/m2. Results: Of the 492 study patients (556 knees; 71% female; median age, 15.2 years; 38% open physes), 88% were athletes, with the most common sports participated in being soccer, basketball, dance, football, gymnastics, and baseball/softball. While 91% of the cohort had recurrent dislocations, the 9% with primary dislocations were more likely to have small osteochondral fractures/loose bodies (P < .001). Female patients were younger (P = .002), with greater patellar tilt (P = .005) than male patients. Utilization of MPFLR and TTO increased significantly over the study period, while use of MRP+LR decreased. Conclusion: Most patients younger than 25 years of age who underwent PFI surgery were skeletally immature, female, and athletes and had recurrent dislocations. The <10% who had primary dislocations and underwent surgery were likely to have osteochondral fractures. Surgical techniques have changed significantly over time, with increasing use of TTO and MPFLR, while the use of MRP+LR/LRL has significantly decreased.

Modeling net ecosystem carbon balance and loss in coastal wetlands exposed to sea-level rise and saltwater intrusion.

Coastal wetlands are globally important stores of carbon (C). However, accelerated sea-level rise (SLR), increased saltwater intrusion, and modified freshwater discharge can contribute to the collapse of peat marshes, converting coastal peatlands into open water. Applying results from multiple experiments from sawgrass (Cladium jamaicense)-dominated freshwater and brackish water marshes in the Florida Coastal Everglades, we developed a system-level mechanistic peat elevation model (EvPEM). We applied the model to simulate net ecosystem C balance (NECB) and peat elevation in response to elevated salinity under inundation and drought exposure. Using a mass C balance approach, we estimated net gain in C and corresponding export of aquatic fluxes ( F AQ $$ {F}_{\mathrm{AQ}} $$ ) in the freshwater marsh under ambient conditions (NECB = 1119 ± 229 gC m-2  year-1 ; FAQ  = 317 ± 186 gC m-2  year-1 ). In contrast, the brackish water marsh exhibited substantial peat loss and aquatic C export with ambient (NECB = -366 ± 15 gC m-2  year-1 ; FAQ  = 311 ± 30 gC m-2  year-1 ) and elevated salinity (NECB = -594 ± 94 gC m-2  year-1 ; FAQ  = 729 ± 142 gC m-2  year-1 ) under extended exposed conditions. Further, mass balance suggests a considerable decline in soil C and corresponding elevation loss with elevated salinity and seasonal dry-down. Applying EvPEM, we developed critical marsh net primary productivity (NPP) thresholds as a function of salinity to simulate accumulating, steady-state, and collapsing peat elevations. The optimization showed that ~150-1070 gC m-2  year-1 NPP could support a stable peat elevation (elevation change ≈ SLR), with the corresponding salinity ranging from 1 to 20 ppt under increasing inundation levels. The C budgeting and modeling illustrate the impacts of saltwater intrusion, inundation, and seasonal dry-down and reduce uncertainties in understanding the fate of coastal peat wetlands with SLR and freshwater restoration. The modeling results provide management targets for hydrologic restoration based on the ecological conditions needed to reduce the vulnerability of the Everglades' peat marshes to collapse. The approach can be extended to other coastal peatlands to quantify C loss and improve understanding of the influence of the biological controls on wetland C storage changes for coastal management.

Self-Assembly Synthesis of a [2]Catenane CoII Single-Molecule Magnet.

We describe herein the self-assembly synthesis of an octanuclear CoII [2]catenane {[Co4 (H2 L)6 ]2 16+ } formed by the mechanical interlocking of two {[Co4 (H2 L)6 ]8+ } rectangles of unprecedented topology. Subtle manipulation of the synthetic conditions allows the isolation of a mixed-valence [Co2 III /Co2 II ]10+ non-catenated rectangle. The CoII centers in the [2]catenane exhibit slow relaxation of their magnetic moment, i. e. single-molecule magnet properties, dominated by quantum tunneling and Raman relaxation processes. This work shows that metallo-supramolecular chemistry can precisely control the organization of single-molecule magnets in topologically complex arrangements.

The First Sulfate-Pillared Hybrid Ultramicroporous Material, SOFOUR-1-Zn, and Its Acetylene Capture Properties.

Hybrid ultramicroporous materials, HUMs, are comprised of metal cations linked by combinations of inorganic and organic ligands. Their modular nature makes them amenable to crystal engineering studies, which have thus far afforded four HUM platforms (as classified by the inorganic linkers). HUMs are of practical interest because of their benchmark gas separation performance for several industrial gas mixtures. We report herein design and gram-scale synthesis of the prototypal sulfate-linked HUM, the fsc topology coordination network ([Zn(tepb)(SO4 )]n ), SOFOUR-1-Zn, tepb=(tetra(4-pyridyl)benzene). Alignment of the sulfate anions enables strong binding to C2 H2 via O⋅⋅⋅HC interactions but weak CO2 binding, affording a new benchmark for the difference between C2 H2 and CO2 heats of sorption at low loading (ΔQst =24 kJ mol-1 ). Dynamic column breakthrough studies afforded fuel-grade C2 H2 from trace (1 : 99) or 1 : 1 C2 H2 /CO2 mixtures, outperforming its SiF6 2- analogue, SIFSIX-22-Zn.

Study on valuable metal incorporation in the Fe-Al precipitate during neutralization of LIB leach solution.

The role of aluminum concentration and pH in the purification of waste Li-ion battery leach solution was investigated using NaOH and LiOH as neutralization agents ([H2SO4] = 0.313 M, t = 6 h). Solution was prepared from synthetic chemicals to mimic real battery leach solution. Results demonstrate that pH (3.5-5.5) has a significant effect on the precipitation of metals (Fe, Al, Ni, Cu, Co, Mn, and Li), whereas higher temperature (T = 30 and 60 °C) decreases the precipitation pH of metals. Iron and aluminum were both found to precipitate at ca. pH 4 and the presence of aluminum in PLS clearly decreased the separation efficiency of Fe vs. active material metals (Ni, Co, Li). In the absence of dissolved aluminum, Fe precipitated already at pH 3.5 and did not result in the co-precipitation of other metals. Additionally, the Al-free slurry had a superior filtration performance. However, aluminum concentrations of 2 and 4 g/L were found to cause loss of Ni (2-10%), Co (1-2%) and Li (2-10%) to the Fe-Al hydroxide cake at pH 4. The use of LiOH (vs. NaOH) resulted in 50% lower co-precipitation of Ni, Co and Li. Overall, these results demonstrate that hydroxide precipitation can be an effective method to remove iron from battery waste leach solutions at aluminum concentrations of < 2 g/L only. Although the highest level of lithium loss in the cake was found at pH 4, the loss was shown to decrease with increasing pH.

Biopolymeric Anticorrosion Coatings from Cellulose Nanofibrils and Colloidal Lignin Particles.

This study presents a process for preparation of cellulose-lignin barrier coatings for hot-dip galvanized (HDG) steel by aqueous electrophoretic deposition. Initially, a solution of softwood kraft lignin and diethylene glycol monobutyl ether was used to prepare an aqueous dispersion of colloidal lignin particles (CLPs) via solvent exchange. Analysis of the dispersion showed that it comprised submicron particles (D = 146 nm) with spherical morphologies and colloidal stability (ζ-potential = -40 mV). Following successful formation, the CLP dispersion was mixed with a suspension of TEMPO-oxidized cellulose nanofibers (TOCN, 1 and 2 g·L-1) at a fixed volumetric ratio (1:1, TOCN-CLPs), and biopolymers were deposited onto HDG steel surfaces at different potentials (0.5 and 3 V). The effects of these variables on coating formation, dry adhesion, and electrochemical properties (3.5% NaCl) were investigated. The scanning electron microscopy results showed that coalescence of CLPs occurs during the drying of composite coatings, resulting in formation of a barrier layer on HDG steel. The scanning vibrating electrode technique results demonstrated that the TOCN-CLP layers reduced the penetration of the electrolyte (3.5% NaCl) to the metal-coating interface for at least 48 h of immersion, with a more prolonged barrier performance for 3 V-deposited coatings. Additional electrochemical impedance spectroscopy studies showed that all four coatings provided increased levels of charge transfer resistance (Rct)-compared to bare HDG steel-although coatings deposited at a higher potential (3 V) and a higher TOCN concentration provided the maximum charge transfer resistance after 15 days of immersion (13.7 cf. 0.2 kΩ·cm2 for HDG steel). Overall, these results highlight the potential of TOCN-CLP biopolymeric composites as a basis for sustainable corrosion protection coatings.