Research on the Properties of Wasteforms after Direct Involvement of Uranium-Containing Silica Gel in Glass Network Formation.

Uranium-containing silica gel (UCSG) is a secondary waste generated during the advanced treatment of nuclear wastewater. In order to reduce the growing storage pressure for UCSG, from the perspective of building a borosilicate glass network, UCSG was used to replace SiO2 in the glass-cured formula to directly achieve the immobilization of UCSG. SEM-EDS results showed that uranium was uniformly distributed in the matrix, and the maximum solid solubility of UCSG (two components: silica gel and uranyl ions) in the formula was as high as 55 wt %. At the same time, TG-MS proved that silica gel lost OH groups (down about 4.61 wt %) and formed Si-O-Si bond by condensation. FT-IR and XPS proved a change in the number of Si-O-Si bond, and new Si-O-B and Si-O-Al bond appeared on the spectrum. This was evidence that silica gel could self-involved participate in the construction of glass networks. EPR analysis obtained the changes in the coordination environment of U atom, the U atom decreased spin electrons number in the glass than in uranyl crystals. The glass also has good physical properties (hardness: 6.51 ± 0.23 GPa; density: 2.3977 ± 0.0056 g/cm3) and chemical durability (normalized leaching rate: LRU = 2.34 × 10-4 ± 2.05 × 10-6 g·m2·days-1 after 42 days), this research provided tactics for simple treatment of uranium-containing silica gel in one step.

Homogenizing microwave pyrolysis of oily sludge using nano-Fe3O4: volatile gas product analysis.

To improve the homogeneity of heating, the magnetic absorbing material Fe3O4 is considered to use in microwave pyrolysis of oily sludge. Therefore, the effect of Fe3O4 on the microwave pyrolysis of oily sludge is investigated based on gas volatile products. Thermogravimetric mass spectrometry result certifies that Fe3O4 will increase the weight-loss ratio from 13.0% to 14.1%. Also, the characteristic peak intensity of CO in gas products decreases from 5.41 × 10-10 A/g to 1.95 × 10-10 A/g, while H2O increases from 3.57 × 10-10 A/g to 7.32 × 10-10 A/g and CO2 increases from 6.87 × 10-10 A/g to 8.92 × 10-10 A/g. This is caused by the esterification of alcohols and esters and the reduction of Fe3O4 by CO. Based on the decrease in activation energy and enthalpy values of Stage II and IV, it infers that Fe3O4 catalyzes the pyrolysis process of oily sludge to some extent. Similarly, gas chromatography-mass spectrometry results show that Fe3O4 can make the types of gas products increase. Especially, the number of molecular species increases from 5 to 46 under 200-300 °C. Finally, a simple molecular dynamics simulation model is conducted, and the results are in agreement with the experimental results. This study shows that Fe3O4 improves the pyrolysis homogeneity and the pyrolysis efficiency also improves.

Long-Wavelength Near-Infrared Divalent Nickel-Activated Double-Perovskite Ba2MgWO6 Phosphor as Imaging for Human Fingers.

Transmission near-infrared (NIR) imaging technology has great potential for biomedical imaging because of its lower water absorption coefficient and highly reduced photon scattering effect in biological tissues compared to visible light. The extent of biological tissue photon scattering is inversely proportional to wavelength; therefore, in principle, imaging with long-wavelength NIR helps improve the resolution of the optical image, but deep tissue high-resolution luminescence imaging is still very challenging technically. Here, we report the discovery of a Ba2MgWO6:Ni2+ double perovskite phosphor that emits broadband long-wavelength NIR (1200-2000 nm) under 365 nm near-ultraviolet (UV) excitation, with a full width at half-maximum of 255 nm. The luminescence quantum efficiency of the phosphor with optimized composition reached 16.67%. The analysis of the crystal structure of Ba2MgWO6:Ni2+ suggests that Ni2+ ions preferentially occupy the W6+ site in octahedrons with a weak crystal field, which leads to a large Stokes shift. An as-prepared long-wavelength NIR pc-LED device was built by packaging an optimized phosphor with a low-power near-UV-LED chip, which was tested to generate clear imaging of venous vessels in human fingers. These unique properties of the Ba2MgWO6:Ni2+ double perovskite phosphor makes it a promising application in the field of imaging sources for body tissue..

Effects of irradiation behavior on physicochemical properties of glassy radioactive contaminated soil containing various contents of actinides nuclear waste.

The evaluation of radiation resistance of the treated radioactive contaminated soil is crucial. The irradiation behavior of simulated radioactive soil waste irradiated with 1.5 MeV Xe20+ ions at fluences of 1 × 1012-1 × 1015 ions/cm2 was studied. Before the irradiation experiment, all the samples were sintered by microwave. The results showed that microwave sintering may be used to treat radioactive contaminated soil. In addition, the irradiation experiment results show that when the Nd2O3 content was low (<20 wt.%), the irradiation has little effect on the sample. When the Nd2O3 content was higher, the Vickers hardness of the sample (25 wt.%) decreased by 7 % at a fluence of 1 × 1015 ions/cm2, which may be due to the high Nd2O3 content that destroyed the overall stability of the glass waste form. The low normalized leaching rate of the irradiated sample (LRNd, ∼10-6 g·m-2·d-1) also proved that it had good aqueous durability. Moreover, the radiation resistance of the sample was illustrated by studying the influence mechanism of 1.5 MeV Xe20+ irradiation on radioactive contaminated soil. This work can help to study the environmental pollution problems of radioactive contaminated soil containing various contents of actinide nuclear waste.

Rapid solidification of simulated radioactive contaminated soil by continuous microwave sintering: Effects of temperature and doping level.

In order to find a rapid, efficient, safe and reliable treatment technology for radioactive contaminated soil, the microwave sintering method was used to sinter the simulated radioactive contaminated soil with different CeO2 content at 1100 °C, 1200 °C and 1300 °C for 30 min to achieve vitrification. The phase, microstructure, morphology, mechanical properties, and chemical durability of the sintered samples were investigated. XRD and SEM-EDS results showed that Ce4+ did not participate in the formation of the glass network, but was fixed in the glass network structure. The amorphous fraction of the samples sintered at 1300 °C can reach up to 98%. EDS results showed that the element distribution was uniform. In addition, the density and hardness values of the sintered matrices were in the range of 1.875-2.543 g/cm3 and 6.667-7.112 GPa, respectively. Our results show that the density and hardness values are related to the sintering temperature and CeO2 content. The normalized leaching rate of Ce in samples reached 10-7 g/(m2·d) after 28 d.

Experimentally and Theoretically Revealing the Co-Doping Effects of Ce-Sr in Gd2Zr2O7.

To safely dispose radioactive waste (including, e.g., thorium and radiostrontium), Ce4+ and Sr2+ were chosen as simulated surrogates of α and ß waste and were introduced into the Gd3+ site in Gd2Zr2O7 to maintain the average cationic radius and to compensate for charge. A series of Gd2-xSrx/2Cex/2Zr2O7 (0.00 ≤ x ≤ 0.25) compounds were examined by experimental and theoretical calculations to investigate the co-doping effects of α and ß waste in a Gd2Zr2O7-based matrix. The effects of Ce4+ and Sr2+ content on the phase, unit cell parameters, active modes, mechanical property, and microstructure were studied systematically. Moreover, the limit of incorporation of Ce4+ and Sr2+ in Gd2Zr2O7 pyrochlore and the lattice parameters were also calculated through virtual crystal approximation theory, and the results were found to well agree with experimental results.

Bismuth Coordinates with Iodine Atoms to Form Chemical Bonds for Existing Stabilization in Boron Glass.

Stabilizing radioactive iodine in boron glass for disposal was the ultimate goal of this study. In this study, bismuth was used near a monument. Thermogravimetric analysis showed that bismuth could remarkably stabilize iodine atoms in boron glass (only 3.74% of the mass was lost at 850 °C). Scanning electron microscopy-energy dispersive spectrometry images showed that most of the AgI was uniformly immobilized in the glass network. X-ray photoelectron spectrometry and NMR results confirmed the change in the coordination number of boron in the samples. The density functional theory calculation helped to understand the reason for the stable presence of iodine in boron glass. Iodine atoms were difficult to bond directly with boron atoms but tended to bond with bismuth atoms. From the spatial distribution of the structural molecular orbitals, it was observed that the bismuth atom releases electrons when stimulated, and the iodine atom needs to gain an electron to reach stability. At a low treatment temperature of 550 °C, the maximum density of the immobilized sample containing bismuth is 2.42 g·cm-3, and its iodine leaching rate at day 7 can be as low as 3.77 × 10-6 g·m-2·d-1. This study provides a way to improve the properties of boron glass microscopically in the future.

Application of poly(vinylphosphonic acid) modified poly(amidoxime) in uptake of uranium from seawater.

To enhance the anti-biofouling properties and adsorption capability of poly(amidoxime) (PAO), vinylphosphonic acid (VPA, CH2[double bond, length as m-dash]CH-PO3H2) was polymerized on poly(acrylonitrile) (PAN) surface by plasma technique, followed by amidoximation treatment to convert the cyano group (-C[triple bond, length as m-dash]N) into an amidoxime group (AO, -C(NH2)[double bond, length as m-dash]N-OH). The obtained poly(vinylphosphonic acid)/PAO (PVPA/PAO) was used as an adsorbent in the uptake of U(vi) from seawater. The effect of environmental conditions on the anti-biofouling property and adsorption capability of PVPA/PAO for U(vi) were studied. Results show that the modified PVPA enhances the anti-biofouling properties and adsorption capability of PAO for U(vi). The adsorption process is well described by the pseudo-second-order kinetic model and reached equilibrium in 24 h. Adsorption isotherms of U(vi) on PVPA/PAO can be well fitted by the Langmuir model, and the maximum adsorption capability was calculated to be 145 mg g-1 at pH 8.2 and 298 K. Experimental results highlight the application of PVPA/PAO in the extraction of U(vi) from seawater.

Polyguanidine-modified adsorbent to enhance marine applicability for uranium recovery from seawater.

The marine applicability of adsorbents intended for recovering uranium from seawater is crucial. For such applicability, the materials must exhibit anti-biofouling properties, seawater pH adaptability (pH~8), and salt tolerance. Extracting uranium from seawater is a long-term project; hence, biofouling, high salt concentrations, and weak alkaline environments negatively affect the adsorption of uranium and damage the recovered materials. Most studies on the extraction of uranium from seawater focus on increasing the adsorption capacity of the employed adsorbent, while its marine applicability is neglected. In the present study, three types of guanidine polymer (GP)-modified acrylic fibers were prepared to investigate the impact of the introduced structure on the marine applicability of the fibers. After screening, the introduction of polyhexamethylene biguanidine (PHMB) is observed to produce PAO-PHMB-A, characterized by excellent marine applicability. The enhanced properties include high antimicrobial activity (109 CFU/mL, 99.71%), good salt tolerance, and optimal adsorption at a pH of 8. Owing to the synergistic effect of its functional groups, the PAO-PHMB-A material exhibits excellent adsorption performance (525.89 mg/g), as well as high selectivity and durability. More importantly, long-term marine tests revealed that PAO-PHMB-A shows a remarkable uranium adsorption capacity (30 d, 3.19 mg/g) and excellent antibacterial activity. Considering its excellent marine applicability and good adsorption performance, the PAO-PHMB-A material developed in this work could serve as a potential adsorbent for engineering applications associated with uranium recovery from seawater.

Transformation details of poly(acrylonitrile) to poly(amidoxime) during the amidoximation process.

During the amidoximation process, transformation details of poly(acrylonitrile) (PAN) to poly(amidoxime) (PAO) is critical for optimizing amidoximation conditions, which determine the physicochemical properties and adsorption capabilities of PAO-based materials. Although the optimization of amidoximation conditions can be reported in the literature, a detailed research on the transformation is still missing. Herein, the effect of the amidoximation conditions (i.e. temperature, time, and NH2OH concentration) on the physicochemical properties and adsorption capabilities of PAO was studied in detail. The results showed that the extent of amidoximation reaction increased with increasing temperature, time, and NH2OH concentration. However, a considerably high temperature (>60 °C) and a considerably long time (>3 h) could result in the degradation and decomposition of PAO's surface topologies and functional groups, and then decrease its adsorption capability for U(vi). The optimal amidoximation condition was 3 h, 60 °C and 50 g L-1 NH2OH. At this condition, the PAO obtained presented the highest adsorption capability for U(vi) under experimental conditions. These results provide pivotal information on the transformation of PAO-based materials during the amidoximation process.

Rapid solidification of Sr-contaminated soil by consecutive microwave sintering: mechanism and stability evaluation.

Consecutive microwave sintering is a method proposed in this study to dispose soil contaminated by Sr during a nuclear accident by rapidly solidifying the contaminated soil. The results show that soil contaminated with 20 wt% SrSO4 and 30 wt% SrSO4 can be completely solidified by microwave sintering at 1100-1200 and 1300 â„ƒ, respectively, for 30 min. Sr was found to be cured into slawsonite (SrAl2Si2O8) and glass structures. Moreover, soil sintered at 1300 â„ƒ has large cured solubility (30 wt.%), good uniformity, and excellent hardness (6.9-7.2 GPa) and chemical durability (below 1.46 × 10-5 g m-2 d-1 at 28 d). Thus, consecutive microwave sintering technology may provide a new method for treating Sr-contaminated soil in case of a nuclear accident emergency.

Low-sintering-temperature borosilicate glass to immobilize silver-coated silica-gel with different iodine loadings.

To better deal with the radioactive iodine generated during the development of nuclear energy, B2O3, Bi2O3, ZnO, and SiO2 were used to sinter borosilicate glass for the immobilization of iodine. The effect of B2O3 on glass formation was discussed by changing the molar ratio of B2O3 in the matrix. When B2O3 content is 50 mol% and sintering temperature is 600 ℃, the amorphous degree of quaternary glass is the highest. The sintered body with the highest degree of amorphous was selected to study radioactive iodine. Then, the effects of different iodine loading concentrations for sintering borosilicate glass in terms of microstructure and phase change were discussed. With the increase in iodine content on silica-gel, the degree of amorphous of the specimens presented a decreasing trend, and there are obvious SiO2 peaks. When the content was 20 wt.%-30 wt.%, a large number of new phases were generated. When the iodine content is 20 wt.%, in addition to the enrichment of Si and O elements, the elemental distribution for B, Bi, Zn, I, and Ag was even. TEM results also showed that there was a crystalline phase in the sinter.

Heavy-ion irradiation effects on uranium-contaminated soil for nuclear waste.

In the field of radioactive waste immobilization, the investigation of irradiation stability is of considerable importance. In this study, uranium-contaminated soil samples were irradiated by 1.5 MeV Xe20+ ions with fluences ranging from 1 × 1012 to 1 × 1015 ions/cm2. Xe20+ heavy-ion radiation was used to simulate the self-irradiation of actinide nuclides. The uranium-contaminated soil samples were sintered via microwaves. Grazing incidence X-ray diffraction results showed that irradiation can cause crystallization of the sample. After irradiation, the Vickers hardness of the samples decreased slightly. Comparative analysis showed that the sample had good radiation resistance, and the leaching rate (28 d) of the sample increased slightly after irradiation, but the overall performance was stable. Our investigation reveals the corresponding mechanism of uranium-contaminated soil irradiation of 1.5 MeV Xe20+ ions.

Bifunctional Phosphorylcholine-Modified Adsorbent with Enhanced Selectivity and Antibacterial Property for Recovering Uranium from Seawater.

The recovery of uranium from seawater is of great concern because of the growing demand for nuclear energy. Though amidoxime-functionalized adsorbents as the most promising adsorbents have been widely used for this purpose, their low selectivity and vulnerability to biofouling have limited their application in real marine environments. Herein, a new bifunctional phosphorylcholine-modified adsorbent (PVC-PC) is disclosed. The PVC-PC fiber is found to be suitable for use in the pH range of seawater and metals that commonly coexist with uranium, such as alkali and alkaline earth metals, transition metals, and lanthanide metals, have no obvious effect on its uranium adsorption capacity. PVC-PC shows better selectivity and adsorption capacity than the commonly used amidoxime-functionalized adsorbent. Furthermore, PVC-PC fiber exhibits excellent antibacterial properties which could reduce the effects of biofouling caused by marine microorganisms. Because of its good selectivity and antibacterial property, phosphorylcholine-based material shows great potential as a new generation adsorbent for uranium recovery from seawater.

Porous NiFe-oxide nanocubes derived from prussian blue analogue as efficient adsorbents for the removal of toxic metal ions and organic dyes.

A novel porous NiFe-oxide nanocubes (NiFe NCs) binary material was successfully fabricated via a facile and scalable tactic, which involved a morphology-inherited heat treating of Ni3[Fe(CN)6]2·xH2O prussian blue analogue nanocubes as self-sacrificial templates. Consequently, it was demonstrated that the NiFe NCs consisted of primary nanostructure units and interconnected pores, with an average size of ˜80 nm. When employed as adsorbents, the as-prepared NiFe NCs displayed remarkable adsorption capacities for heavy metal ions (232.3 mg g-1 for As(V) and 350.71 mg g-1 for Cr(VI)) and organic dyes (284.99 mg g-1 for XO and 31.97 mg g-1 for CR at 298 K). The resulting NiFe NCs further revealed efficient regeneration and reusability even after five consecutive adsorption/desorption cycles. The microscopic spectrum analysis demonstrated that the interaction between As(V) and NiFe NCs was mainly ascribed to the metal-oxide bonds (MO) and hydroxyl groups (OH), while Cr(VI) adsorption was in conjunction with the reduction reaction of Cr(VI) to Cr(III). Furthermore, the adsorption of organic dyes on NiFe NCs depended on the pore structure and molecule sizes of the organic dye molecules. These findings make cost-efficient NiFe NCs materials a powerful candidate for remediating water contaminated with inorganic and organic contaminants.

Heavy-ion irradiation effects on U3O8 incorporated Gd2Zr2O7 waste forms.

In this research, the heavy-ion irradiation effects of U-bearing Gd2Zr2O7 ceramics were explored for nuclear waste immobilization. U3O8 was designed to be incorporated into Gd2Zr2O7 from two different routes in the form of (Gd1-4xU2x)2(Zr1-xUx)2O7 (x = 0.1, 0.14). The self-irradiation of actinide nuclides was simulated by Xe20+ heavy-ion radiation under different fluences. Grazing incidence X-ray diffraction (GIXRD) analysis reveals the relationship between radiation dose, damage and depth. The radiation tolerance is promoted with the increment of U3O8 content in the discussed range. Raman spectroscopy testifies the enhancement of radiation tolerance and microscopically existed phase evolution from the chemical bond vibrations. In addition, the microstructure and elemental distribution of the irradiated samples were analyzed as well. The amorphization degree of the sample surface declines as the U content was elevated from x = 0.1 to x = 0.14.

Rapid immobilization of simulated radioactive soil waste by microwave sintering.

A rapid and efficient method is particularly necessary in the timely disposal of seriously radioactive contaminated soil. In this paper, a series of simulated radioactive soil waste containing different contents of neodymium oxide (3-25wt.%) has been successfully vitrified by microwave sintering at 1300°C for 30min. The microstructures, morphology, element distribution, density and chemical durability of as obtained vitrified forms have been analyzed. The results show that the amorphous structure, homogeneous element distribution, and regular density improvement are well kept, except slight cracks emerge on the magnified surface for the 25wt.% Nd2O3-containing sample. Moreover, all the vitrified forms exhibit excellent chemical durability, and the leaching rates of Nd are kept as ∼10-4-10-6g/(m2day) within 42days. This demonstrates a potential application of microwave sintering in radioactive contaminated soil disposal.