Phase evolution and microstructure of new Sr0.5Zr2(PO4)3-NdPO4 composite ceramics prepared by one-step microwave sintering

Sodium Zirconium Phosphate (NaZr₂(PO₄)₃, hereinafter NZP) and monazite are both potential materials for immobilization of nuclear waste. In this work, novel (1-x)Sr_0.5Zr₂(PO₄)₃-xNdPO₄ composite ceramics (x = 0, 0.2, 0.4, 0.6, 0.8, and 1.0) for simultaneously immobilizing the simulated fission product (FP) Sr and trivalent minor actinide (MA) Nd were prepared by one-step microwave sintering technique, in which Sr and Nd were immobilized into NZP and monazite type structures, respectively. The phase evolution and microstructure of the samples were investigated by X-ray diffraction (XRD), Raman, and backscattering scanning electron microscopy (BSE). The results showed that the expected composite ceramics were successfully obtained by one-step microwave sintering at 1050 °C for 2 h. The as-prepared samples consisted of Sr_0.5Zr₂(PO₄)₃ and NdPO₄ phases, and the content of the two phases varied regularly as x changed, generally conforming to the designed nominal chemical composition. Importantly, the composite ceramics presented the homogenous and dense microstructure. The relative density of the composite ceramics was more than 95%, meanwhile, the Vickers-hardness of the samples was higher than 600 MPa. It was indicated that NZP-monazite type composite ceramics could be a potential matrix for the simultaneous immobilization of actinide and fission product.     

An enzyme-loaded reactor using metal-organic framework-templated polydopamine microcapsule

Ultrathin polydopamine microcapsules with hierarchical structure and porosity were prepared for the immobilization of multienzymes using metal-organic framework (MOF) as the template. The multienzyme/MOF composite was first prepared using a “one-pot” co-precipitation approach via the coordination and self-assembly of zinc ions and 2-methylimidazole in the presence of enzymes. The obtained nanoparticles were then coated with polydopamine thin layer through the self-polymerization of dopamine under alkaline condition. The polydopamine microcapsules with an ultrathin shell thickness of ~48 nm were finally generated by removing the MOF template at acidic condition. Three enzymes were encapsulated in PDA microcapsules including carbonic anhydrase (CA), formate dehydrogenase (FateDH), and glutamate dehydrogenase (GDH). FateDH that catalyzed the main reaction of CO₂ reduction to formic acid retained 94.7% activity of equivalent free FateDH. Compared with free multienzymes, the immobilized ones embedded in PDA microcapsules exhibited 4.5-times higher of formate production and high catalytic efficiency with a co-factor-based formate yield of 342%.     

Immobilization of uranium in cristobalite ceramic through adsorption on mesoporous SBA-15 and further sintering process

The development of an adsorbent which can be easily transformed into stable ceramic waste forms through a simple route is necessary for the treatment of the radioactive wastewater. Herein, we report on the immobilization of uranium in cristobalite ceramic through adsorption on mesoporous SBA-15 and further sintering process. The mesoporous SBA-15 with short pore length was synthesized and employed to remove uranium from aqueous solution. Subsequently, the SBA-15 with adsorbed U (U/SBA-15) was solidified by sintering. The effects of sintering temperature and U content on the structure, densification and aqueous durability of the obtained cristobalite ceramic waste forms were investigated. The results indicate that the U/SBA-15 can be transformed into stable cristobalite ceramic after sintering at 1100–1400 °C for 6 h. Furthermore, all the obtained cristobalite ceramic waste forms exhibit good aqueous durability (∼10⁻⁴ g m^-2 d^-1). This work demonstrates a potential route and adsorbent to dispose the radioactive wastewater.     

Biohydrogen production by immobilized Enterobacter aerogenes on functionalized multi-walled carbon nanotube

Hydrogen production by immobilized Enterobacter aerogenes on functionalized multi-walled carbon nanotube (MWCNT-COOH) in repeated batch mode was studied. Fourier transform infrared (FTIR) spectroscopy and field emission scanning electron microscopy (FESEM) were employed to confirm immobilization of E. aerogenes successfully. The effect of MWCNT-COOH concentrations (0.2, 0.6, and 1.2 mg/mL) on hydrogen production was investigated. The present study showed that immobilized E. aerogenes on 1.2 mg/mL MWCNT-COOH resulted in higher hydrogen yield (2.2 moL/mol glucose), hydrogen production rate (2.72 L/L.h), and glucose degradation efficiency (96.20%) and shorter the lag phase (1 h) compared to the free E. aerogenes. Modified Gompertz and Logistic models were employed to predict the cumulative hydrogen production successfully.     

Uricase-immobilization on radiation grafted polymer support for detection of uric acid using Ag-nanoparticle based optical biosensor

A functional polymer support was designed for covalent immobilization of enzyme uricase, which was further utilized in a single enzyme based silver nanoparticles (Ag-NPs)-optical biosensor system for estimation of uric acid. A carboxylic acid functionalized polymer support was fabricated via gamma radiation induced mutual-irradiation grafting of polyacrylic acid (PAA) on to non-woven polypropylene (PP) matrix. Grafting parameters, such as dose, monomer concentration, homopolymer inhibitor and inorganic acid concentration were studied to optimize the grafting process. PAA-g-PP samples were characterized by grafting yield measurement, water uptake, FTIR, TGA and SEM techniques. Uricase enzyme was immobilized on to the PAA-g-PP support via covalent amide linkage using coupling agents, namely N-hydroxysuccinimide (NHS) and N-ethyl-N′-(3-(dimethylamino)propyl)carbodiimide (EDC). The catalytic activity of uricase was investigated spectrophotometrically using uric acid as a substrate. Study of kinetic parameters (K_m, V_max) revealed the value of K_m for covalently immobilized uricase to be ∼1.2-fold higher than that of free enzyme. The uricase-immobilized-PAA-g-PP samples could be repeatedly used for ∼20 cycles over a period of 30 days when stored in phosphate buffer (pH∼7.4) at 4°C without significant decrease in the enzyme activity. The uricase immobilized samples were successfully used in conjunction with the radiolytically synthesized Ag-NPs as a LSPR-optical biosensor for estimation of uric acid.     

Response of structure and mechanical properties of high entropy pyrochlore to heavy ion irradiation

Material with superior damage tolerance, chemical durability, and structure stability is of increasing interest in high-level radioactive waste management and structural components for advanced nuclear systems. In this paper, high-entropy (La_0.2Ce_0.2Nd_0.2Sm_0.2Gd_0.2)₂Zr₂O₇ with pyrochlore-type structure was synthesized through conventional solid-state method. The as-synthesized high-entropy oxide maintained crystalline after being irradiated by using Au³⁺ with 9.0 MeV energy at the fluence of 4.5 × 10¹⁵ ions·cm^-2, indicating its high tolerance to heavy-ion irradiation. The irradiation-induced order-disorder transition from pyrochlore structure to defective fluorite structure occurred in high-entropy (La_0.2Ce_0.2Nd_0.2Sm_0.2Gd_0.2)₂Zr₂O₇. After irradiation, no irradiation-induced segregation was observed at grain boundary. Moreover, the mechanical properties of high-entropy pyrochlore were improved. The heavy-ion irradiation resistance mechanisms of high-entropy pyrochlore were discussed in detail. Our work identified high-entropy (La_0.2Ce_0.2Nd_0.2Sm_0.2Gd_0.2)₂Zr₂O₇ can be a promising candidate for immobilization of high-level radioactive waste as well as advanced nuclear reactor system from the perspective of irradiation resistance.     

Effect of sintering temperature on lightweight aggregates manufacturing from copper contaminated soil

Manufacturing lightweight aggregate (LWA) at high temperature is an effective way to immobilize heavy metals in solid waste. This work investigated the performance and solidification mechanism of LWA prepared from copper contaminated soil. The volume expansion of LWA could reach a maximum of 28%, and its lowest density accounted of 1.5 g/cm³, which met the standard requirements. Optical microscope and micro-CT test illustrated that the addition of Cu leaded to obvious phase separation in LWA. The Cu leaching result of LWA first increased and then dropped with the temperature. The XRD test found that the main formation phase of Cu in LWA were t-CuFe₂O₄ and amorphous phase that they had different acid resistance ability. XPS revealed that the main cause of the agglomeration of liquid phase in LWA was the chain broken reaction between Cu and Si–O tetrahedron. SEM-EDS results showed that the distribution of Cu and Si had a strong correlation, which meant that Cu mostly formed amorphous phase. This work showed the uniqueness of Cu in the high temperature immobilization and pointed out the best immobilization target phase.     

One‐Pot Lipase Entrapment Within Silica Particles to Prepare a Stable and Reusable Biocatalyst for Transesterification

In order to enhance the reusability, Rhizomucor miehei lipase was entrapped in a single step within silica particles having an oleic acid core (RML@SiO₂). Characterization of RML@SiO₂ by scanning and transmission electron microscopy and Fourier transform infrared studies supported the lipase immobilization within silica particles. The immobilized enzyme was employed for transesterification of cottonseed oil with methanol and ethanol. Under the optimum reaction conditions of a methanol‐to‐oil molar ratio of 12:1 or ethanol‐to‐oil molar ratio of 15:1, stirring speed of 250 revolutions/min (flask radius = 3 cm), reaction temperature of 40 °C, and biocatalyst concentration of 5 wt% (with respect to oil), more than 98 % alkyl ester yield was achieved in 16 and 24 h of reaction duration in case of methanolysis and ethanolysis, respectively. The immobilized enzyme did not require any buffer solution or organic solvent for optimum activity; hence, the produced biodiesel and glycerol were free from metal ion or organic molecule contamination. The activation energies for the immobilized enzyme‐catalyzed ethanolysis and methanolysis were found to be 34.9 ± 1.6 and 19.7 ± 1.8 kJ mol^?1, respectively. The immobilized enzyme was recovered from the reaction mixture and reused in 12 successive runs without significant loss of activity. Additionally, RML@SiO₂ demonstrated better reusability as well as stability in comparison to the native enzyme as the former did not lose the activity even upon storage at room temperature (25–30 °C) over an 8‐month period.     

A geometric approach to automated fixture layout design

Fixtures are used in many manufacturing processes to hold objects. Fixture layout design is to arrange fixturing elements (fixels) on the object surface such that the object can be held in form-closure and totally immobilized. It is well known that 4/7 fixels are sufficient for immobilizing a 2D/3D object without rotational symmetry and their locations satisfy form-closure if and only if the convex hull of their primitive wrenches forms a 3D/6D simplex in the wrench space containing the origin as an interior point. This paper presents a method for finding form-closure locations of 4/7 fixels with enhanced immobilization capability. First, the Gilbert-Johnson-Keerthi distance algorithm and the Gram-Schmidt process are used to yield the fixel locations such that the simplex with vertices at their primitive wrenches is 3D/6D and contains the origin. Then, an interchange algorithm is developed for altering the fixel locations to meet form-closure and increase an immobilization capability index of fixture layouts. The meanings of this index in fixture localization accuracy and force balance capability are elucidated as well. Its value is proved to be equal to the minimum distance from the wrench origin to the facets of the wrench simplex in terms of a unit-invariant norm for wrench vectors. Without using any general optimization techniques, this method determines an optimal fixture layout very efficiently, so that it can be tried with various initial conditions to attain a result approaching the global optimum or with other good performance qualities.     

Prolonged hydrogen production by Nostoc in photobioreactor and multi-stage use of the biological waste for column biosorption of some dyes and metals

Hydrogen production by Nostoc linckia was studied using both free and alginate immobilized biomass of the cyanobacterium in separate lab-scale photobioreactors (PBRs). Hydrogen production rates improved significantly when immobilized cyanobacterial biomass was used in PBR and the production continued up to 25 days by maintaining required anoxic conditions and carbohydrate supplement. Average hydrogen production rate over 25 days was 132 μmolH₂/h/mg Chl a. The biological waste from the PBRs was utilized for sequestration of two toxic heavy metals (chromium and cobalt) and carcinogenic dyes (Reactive Red 198 and Crystal Violet) from aqueous solutions in packed-bed column. From the PBR containing free N. linckia cells, the spent biomass was collected after 7 d, dried and immobilized in alginate matrix, and used as a biosorbent for optimizing bed height and flow rate of the column. Breakthrough capacity of the packed-bed column was determined and breakthrough curves were analyzed using BDST model. Three PBRs containing immobilized cyanobacterial biomass were run for 5, 15 and 25 days, and the biological waste collected at the end of the operation was used for biosorption studies under optimized conditions (bed height, 25 cm; flow rate, 3 mL/min). Biosorption efficiency of the waste biomass was found to be influenced by the operation time of the hydrogen photobioreactor.