Profiling hot isostatically pressed canister–wasteform interaction for Pu-bearing zirconolite-rich wasteforms

Zirconolite-rich full ceramic wasteforms designed to immobilize Pu-bearing wastes were produced via hot isostatic pressing (HIP) using stainless steel (SS) and nickel (Ni) HIP canisters. A detailed profiling of the elemental compositions of the major and minor phases over the canister–wasteform interaction zone was performed using scanning electron microscopy combined with energy-dispersive X-ray spectroscopy (SEM-EDS) characterization. Bulk sample analyses from regions near the center of the HIP canister were also conducted for both samples using X-ray diffraction and SEM-EDS. The sample with the Ni HIP canister showed almost no interaction zone with only minor diffusion of Ni from the inner wall of the canister into the near-surface region of the wasteform. The sample with the SS HIP canister showed ∼100–120 μm of interaction zone dominated by high-temperature Cr diffusion from canister materials to the wasteform with the Cr predominantly incorporated into the durable zirconolite phase. We also examined, for the first time, changes to the HIP canister wall thickness caused by HIPing and demonstrated that no canister wall thinning occurred. Instead, in the areas examined, the canister wall thickness was observed to increase (up to ∼20%) due to the compression occurring during the HIP cycle. Further, only sparse formation of (Cr, Mn)-rich oxide particles were noted within the HIP canister inner wall area immediately adjacent to the ceramic material, with no evidence for reverse diffusion of ceramic materials. Though the HIP canister–wasteform interaction extends to ∼120 μm when using an SS HIP canister for the system investigated, this translates to <<1 vol.% for an industrial scale HIPed wasteform. Importantly, the HIP canister–wasteform interactions did not produce any obviously less durable phases in the wasteform or had any detrimental impact on the HIP canister properties.     

A novel foam glass obtained from solid waste: A sustainable strategy for application in the degradation of an environmental pollutant

Foams glass were obtained from solid waste of flat glass and exhausted alkaline batteries. The physical, chemical, crystalline and morphological properties of the samples were obtained using the Archimedes principle, X-ray diffractometry (XRD), scanning electron microscopy (SEM). The results revealed glass foams with apparent porosities in the range of 55–64% and apparent densities in the range of 0.40–0.79 g cm^?3. The manganese oxide and graphite contained within the cathode of alkaline batteries acted as both oxidizing agents and as foaming agents. The zinc contained in the anode acted as a pore stabilizing agent and the zinc oxide as a semiconductor material. The foam glass that was composed of flat glass with an anode of Zn and ZnO, and a cathode of Mn₂O₃ and Mn₃O₄ (named An8), showed the greatest potential for heterogeneous photocatalysis, with a maximum efficiency of 95.9% after 3 h of treatment of solution containing dye. These results suggest the feasibility of producing foam glass from waste, as well as its potential application in photocatalytic systems, such as in the low-cost treatment of water.     

Improvement of gaseous bioenergy production from spent coffee grounds Co-digestion with pulp wastewater by physical/chemical pretreatments

Two steps of hydrolysis and anaerobic biogas production processes was investigated in this study. In the first step, subcritical water (SBW) hydrolysis and chemical (acid/alkali) pretreatments were carried out to enhance hydrolysis efficiency by obtaining and analyzing the total volatile fatty acids (TVFA), chemical oxygen demand (COD), and total sugar productions from spent coffee grounds (SCG) hydrolysate. The subcritical water (SBW) hydrolysis under the condition of temperature 150 °C for 30 min can greatly improve the organic matter breakdown and reached the COD concentration of 1010 g/L which was 30% higher than the untreated raw SCG. For chemical pretreatments, it was found that the alkaline hydrolysis of SCG resulted in the greatest total sugar concentration of 181 g/L whereas the operation conditions were 2.0 M NaOH at 60 °C for 1 h. The peak of TVFA concentration 3725 mg/L was found at the acid hydrolysis of SCG with 1.0 M H₂SO₄ acid, 60 °C for 1 h. The optimal biomethane yield of 115 mL/g COD was obtained when 1.0 M H₂SO₄ acid hydrolysate co-digestion with pulp wastewater which increase methane yield production 8 times of raw pulp wastewater. The pretreatment process was confirmed in this study can significant improve the converting of the biowastes to bioenergy efficiency.     

饱和块状混合回填土地基的一维固结分析

用块状渣土置换软弱地基和回填低洼谷地等是处置工程渣土的有效途径。为了分析饱和块状混合回填土地基的固结性状，运用混合物理论建立了其一维固结模型。首先，假定块状土固相和充填土固相之间满足等应变条件，获得了饱和块状混合回填土中各相应变与块状土孔隙变形和充填土孔隙变形的关系式。其次，在小应变条件下，根据自由能势函数方程建立了饱和块状混合回填土的一维线弹性本构方程，再结合达西定律和应力平衡方程获得了一维固结控制方程。再次，利用分离变量法得到一维固结解析解，通过退化本文模型与已有模型进行对比，验证了本文模型的正确性。最后，基于所得解析解，分析了充填土孔隙渗透系数、块状土孔隙渗透系数以及流体交换参数等因素对饱和块状混合回填土地基固结性状的影响。分析结果表明：充填土孔隙渗透系数对饱和块状混合回填土地基整体固结性状起主导作用；在固结初期，块状土超孔压会有一定程度的上升，且3个参数具有相似的作用机理。     

Numerical study of strain development in high-density polyethylene geomembrane liner system in landfills using a new constitutive model for municipal solid waste

Tensile strain development in high-density polyethylene (HDPE) geomembrane (GMB) liner systems in landfills was numerically investigated. A new constitutive model for municipal solid waste (MSW) that incorporates both mechanical creep and biodegradation was employed in the analyses. The MSW constitutive model is a Cam-Clay type of plasticity model and was implemented in the finite difference computer program FLAC?. The influence of the friction angle of the liner system interfaces, the biodegradation of MSW, and the MSW filling rate on tensile strains were investigated. Several design alternatives to reduce the maximum tensile strain under both short- and long-term waste settlement were evaluated. Results of the analyses indicate that landfill geometry, interface friction angles, and short- and long-term waste settlement are key factors in the development of tensile strains. The results show that long-term waste settlement can induce additional tensile strains after waste placement is complete. Using a HDPE GMB with a friction angle on its upper interface that is lower than the friction angle on the underlying interface, increasing the number of benches, and reducing the slope inclination are shown to mitigate the maximum tensile strain caused by waste placement and waste settlement.     

Integrated LaB6/g-C3N4 solar absorber for solving dye accumulation during solar steam generation

Solar steam generation has attracted considerable interest due to its easy accessibility and sustainability. However, dye molecules were gradually concentrated on bulk water or the surface of solar absorbers during the disposal of dye wastewater. Herein, LaB₆/g-C₃N₄ composites were immobilized on porous cotton cloth, served as a solar absorber resistant to dye clogging. The optimal solar absorber possessed solar harvesting of 92.3% and showed great application potential in the field of the treatment of dye wastewater. This study presented a new approach for the treatment of dye wastewater.     

The kinetics of copper corrosion in nitric acid

The strategy for the permanent disposal of high-level nuclear waste in Canada involves sealing it in a copper-coated steel container and burying it in a deep geologic repository. During the early emplacement period, the container could be exposed to warm humid air, which could result in the condensation of nitric acid, produced by the radiolysis of the humid air, on the copper surface. Previous studies have suggested that both nitrate and oxygen reduction will drive copper corrosion, with the nitrate reduction kinetics being dependent on the concentration of soluble copper(I) produced by the anodic dissolution of copper in the reaction with oxygen. This study focused on determining the kinetics of nitrate and oxygen reduction and elucidating the synergistic relationship between the two processes. This was investigated using corrosion potential and polarization measurements in conjunction with scanning electron microscopy and X-ray photoelectron spectroscopy. Oxygen reduction was shown to be the dominant cathodic reaction with the oxidation of copper(I) to copper(II) by nitrate, promoting the catalytic cycle involving the reaction of copper(II) with copper to reproduce copper(I).     

Thermal transport and chemical conversion in single reacting sorbent particles

The effects of particle size and carbon dioxide concentration on chemical conversion in engineered spherical particles undergoing calcium oxide looping are investigated. Particles are thermochemically cycled in a furnace under different carbon dioxide concentrations. Changes in composition due to chemical reactions are measured using thermogravimetric analysis. Gas composition at the furnace exit is evaluated with mass spectroscopy. A numerical model of thermal transport phenomena developed previously is adapted to match the physical system investigated in the present study. The model is used to elucidate effects of reacting medium characteristics on particle temperature and reaction extent. Experimental and numerical results show that (1) an increase in particle size results in a decrease in carbonation extent, and (2) the carbonation step consists of fast and slow reaction regimes. The reaction rates in the fast and slow carbonation regimes increase with increasing carbon dioxide concentration. The effect of carbon dioxide concentration and the distinction between the fast and slow regimes become more pronounced with increasing particle size.     

Irradiation-induced large bubble formation and grain growth in super nano-grained ceramic

In this work, 0.5TRPO•0.5Gd₂Zr₂O₇ ceramic with an average grain size of only ∼15 nm was prepared by a high pressure (5 GPa/520 °C) sintering method. Phase evolutions and microstructure changes of the as-fabricated super nano and micron-grained ceramics under a high-dose displacement damage induced by 300 keV Kr²⁺ ions were investigated. The results show that the super nano-grained ceramic has low degree of amorphization, obvious grain growth (2–3 times in grain size) and big Kr bubbles (10–68 nm) formation after irradiation. The micron-grained ceramic was severely amorphized after irradiation and many microcracks were formed parallel to its surface. The formation mechanism of Kr bubbles in the super nano-grained ceramic is on account of grain boundary diffusion and migration induced by the accumulation of the injecting Kr ions and irradiation defects. Nevertheless, microcracks formed in the micron-grained sample are caused by the accumulation of Kr atoms.     

Configurational Isomers Induced Significant Difference in All-Polymer Solar Cells

The design of polymer acceptors plays an essential role in the performance of all-polymer solar cells. Recently, the strategy of polymerized small molecules has achieved great success, but most polymers are synthesized from the mixed monomers, which seriously affects batch-to-batch reproducibility. Here, a method to separate γ-Br-IC or δ-Br-IC in gram scale and apply the strategy of monomer configurational control in which two isomeric polymeric acceptors (PBTIC-γ-2F2T and PBTIC-δ-2F2T) are produced is reported. As a comparison, PBTIC-m-2F2T from the mixed monomers is also synthesized. The γ-position based polymer (PBTIC-γ-2F2T) shows good solubility and achieves the best power conversion efficiency of 14.34% with a high open-circuit voltage of 0.95 V when blended with PM6, which is among the highest values recorded to date, while the δ-position based isomer (PBTIC-δ-2F2T) is insoluble and cannot be processed after parallel polymerization. The mixed-isomers based polymer, PBTIC-m-2F2T, shows better processing capability but has a low efficiency of 3.26%. Further investigation shows that precise control of configuration helps to improve the regularity of the polymer chain and reduce the π–π stacking distance. These results demonstrate that the configurational control affords a promising strategy to achieve high-performance polymer acceptors.