The removal of trace plutonium(Pu)from uranium products and organic wastes during spent nuclear fuel reprocessing remains a critical challenge,resulting in excessive plutonium content in uranium products and waste org...The removal of trace plutonium(Pu)from uranium products and organic wastes during spent nuclear fuel reprocessing remains a critical challenge,resulting in excessive plutonium content in uranium products and waste organic liquid.Currently,most organic ligands with selective separation functions are lipophilic,while research on water-soluble,highly selective ligands is relatively scarce,and there are also few reports on the single crystal of these ligands coordinating with plutonium.Herein,a hydrophilic multiamide ligand,N,N,N′,N″,N″-hexaethyl-nitrilotriacetamide(NTAamideC2),was synthesized and evaluated for its Pu(Ⅳ)back-extraction efficiency under harsh conditions.Systematic experiments revealed that NTAamideC2 achieved>99%Pu(Ⅳ)back-extraction rate within 15 min across a wide nitric acid concentration range(0-5 M),even with elevated dibutyl phosphate(DBP≤20000 ppm).Remarkably,the separation factor(SFPu/U)reached 767 at 1.5 M HNO_(3),demonstrating exceptional selectivity over uranium(Ⅵ).Spectrophotometric titration and DFT calculations confirmed the formation of 1:1 and 1:2 Pu(Ⅳ)-NTAamideC2 complexes,with log β values of 7.42±0.01 and 13.23±0.02,respectively.Single-crystal X-ray diffraction analysis of{[Pu_(2)(H_(2)O)_(2)(NTAamideC2)_(4)](H_(2)O)_(2)(NO_(3))(ClO_(4))_(7)}revealed a nine-coordinated PuO_(7)N_(2)geometry,where two NTAamideC2 molecules bind via six O and two N atoms.Compared to conventional agents(AHA/HSC),NTAamideC2 exhibited superior acid tolerance and selectivity,aligning with the CHON principle for sustainable nuclear waste management.This work provides a robust strategy for Pu(Ⅳ)removal in uranium purification cycles and advances fundamental insights into Pu coordination chemistry,offering significant potential for industrial nuclear fuel reprocessing.展开更多
The electronic structures and properties of PuO2 and Pu2O3 have been studied according to the first principles by using the all-electron projector-augmented-wave （PAW） method. The local density approximation （LDA）...The electronic structures and properties of PuO2 and Pu2O3 have been studied according to the first principles by using the all-electron projector-augmented-wave （PAW） method. The local density approximation （LDA）＋U and the generalized gradient approximation （GGA）＋U formalisms have been used to account for the strong on-site Coulomb repulsion among the localized Pu 5f electrons. We discuss how the properties of PuO2 and Pu2O3 are affected by choosing the values of U and exchange-correlation potential. Also, the oxidation reaction of Pu2O3, leading to the formation of PuO2, and its dependence on U and exchange-correlation potential have been studied. Our results show that by choosing an appropriate U it is possible to consistently describe structural, electronic, and thermodynamic properties of PuO2 and Pu2O3, which enable the modelling of the redox process involving Pu-based materials.展开更多
This study evaluated the nuclear data libraries for a small 100 Mega Watt electric(MWe)Molten Salt Reactor with plutonium fuel.The reactor has a power output of 100 MWe,which meets the demand for electricity generatio...This study evaluated the nuclear data libraries for a small 100 Mega Watt electric(MWe)Molten Salt Reactor with plutonium fuel.The reactor has a power output of 100 MWe,which meets the demand for electricity generation in several regions or provinces outside Java Island.Several nuclear data libraries,such as JEFF 3.1,ENDF/B-VII.0,JENDL 3.3,and JENDL 4.0,were used for a more comprehensive evaluation.LiF–BeF_(2)–ThF_(4)–PuF_(4) was used as the initial fuel composition.The thorium and plutonium concentrations in the fuel salt were varied to obtain the optimum fuel composition,leading to critical conditions.The results showed some neutronic parameters,such as the conversion ratio,neutron spectra,and effective multiplication factors,from three different nuclear data libraries.By changing the plutonium concentration in the initial fuel salt composition,the minimum plutonium loaded for the reactor criticality during 2000 days of operation time was determined to be 0.995,0.91,0.87,and 0.90 mol%for JEFF 3.1,ENDF/B-VII.0,JENDL 3.3,and JENDL 4.0,respectively.The differences in the values of each parameter were due to several factors,such as the cross-section values and number of nuclides in the nuclear data libraries.Several safety parameters were also investigated to ensure the possibility of utilizing PuF_(4) in the reactor.展开更多
Pu can be loaded with H forming complicated continuous solid solutions and compounds,and causing remarkable electronic and structural changes.Full potential linearized augmented plane wave methods combined with Hubbar...Pu can be loaded with H forming complicated continuous solid solutions and compounds,and causing remarkable electronic and structural changes.Full potential linearized augmented plane wave methods combined with Hubbard parameter U and the spin-orbit effects are employed to investigate the electronic and structural properties of stoichiometric and non-stoichiometric face-centered cubic Pu hydrides（PuHx,x=2,2.25,2.5,2.75,3）.The decreasing trend with increasing x of the calculated lattice parameters is in reasonable agreement with the experimental findings.A comparative analysis of the electronic-structure results for a series of PuH x compositions reveals that the lattice contraction results from the associated effects of the enhanced chemical bonding and the size effects involving the interstitial atoms.We find that the size effects are the driving force for the abnormal lattice contraction.展开更多
In a thorium-based molten salt reactor(TMSR),it is difficult to achieve the pure 232Th–^(233)U fuel cycle without sufficient^(233)U fuel supply.Therefore,the original molten salt reactor was designed to use enriched ...In a thorium-based molten salt reactor(TMSR),it is difficult to achieve the pure 232Th–^(233)U fuel cycle without sufficient^(233)U fuel supply.Therefore,the original molten salt reactor was designed to use enriched uranium or plutonium as the starting fuel.By exploiting plutonium as the starting fuel and thorium as the fertile fuel,the high-purity^(233)U produced can be separated from the spent fuel by fluorination volatilization.Therefore,the molten salt reactor started with plutonium can be designed as a^(233)U breeder with the burning plutonium extracted from a pressurized water reactor(PWR).Combining these advantages,the study of the physical properties of plutonium-activated salt reactors is attractive.This study mainly focused on the burnup performance and temperature reactivity coefficient of a small modular molten-salt reactor started with plutonium(SM-MSR-Pu).The neutron spectra,^(233)U production,plutonium incineration,minor actinide(MA)residues,and temperature reactivity coefficients for different fuel salt volume fractions(VF)and hexagon pitch(P)sizes were calculated to analyze the burnup behavior in the SM-SMR-Pu.Based on the comparative analysis results of the burn-up calculation,a lower VF and larger P size are more beneficial for improving the burnup performance.However,from a passive safety perspective,a higher fuel volume fraction and smaller hexagon pitch size are necessary to achieve a deep negative feedback coefficient.Therefore,an excellent burnup performance and a deep negative temperature feedback coefficient are incompatible,and the optimal design range is relatively narrow in the optimized design of an SM-MSR-Pu.In a comprehensive consideration,P=20 cm and VF=20%are considered to be relatively balanced design parameters.Based on the fuel off-line batching scheme,a 250 MWth SM-MSR-Pu can produce approximately 29.83 kg of ^(233)U,incinerate 98.29 kg of plutonium,and accumulate 14.70 kg of MAs per year,and the temperature reactivity coefficient can always be lower than−4.0pcm/K.展开更多
A modified analytic embedded atom method （MAEAM） potential is constructed for fcc 5-Pu. Molecular dynamics （MD） simulations with the potential are performed to investigate the interactions between two symmetrical ...A modified analytic embedded atom method （MAEAM） potential is constructed for fcc 5-Pu. Molecular dynamics （MD） simulations with the potential are performed to investigate the interactions between two symmetrical tilt grain boundaries （GBs） and point defects such as He atom, vacancy and self-interstitial atom （SIA） in Pu. The calculated results show that point defect formation energies are on average lower than those in the lattice but variations from site to site along the GBs are very remarkable. Both substitutional and interstitial He atoms are trapped at GBs. Interstitial He atom is more strongly bound at the GB core than the substitutional He atom. The binding energy of SIA at GB core is higher than those of He atom and vacancy. GB core can bind many He atoms and SIAs due mainly to the fact that it contains many vacancies. Compared with He atom and SIA, the vacancy far from GB core is difficult to diffuse into the core. The GBs can act as sinks and sources of He atoms and SIAs, which may be a reason for the swelling of Pu after a period of self-irradiation because of the higher concentration of vacancy in the bulk.展开更多
Investigations of ^(239+240)Pu and ^(238)Pu in the surface layer(0–5 cm) of bottom sediment in the Crimean 10 salt lakes from 4 geographical groups were carried out for the first time. The ^(239+240)Pu varied widely ...Investigations of ^(239+240)Pu and ^(238)Pu in the surface layer(0–5 cm) of bottom sediment in the Crimean 10 salt lakes from 4 geographical groups were carried out for the first time. The ^(239+240)Pu varied widely between regional geographical groups of lakes as well as within groups too and ranged from 11±4 to 451±43 mBq^(239+240)Pu/kg. The highest levels of ^(239+240)Pu—419±27, 443±24 and 451±43 mBq/kg were observed in the Yevpatoriya(Lake Kyzyl-Yar), the Tarkhankut(Dzharylhach) and the Kerch group(Tobechik), respectively. The lowest values of ^(239+240)Pu were identified in three lakes of the Perekop group and were 20±12, 24±6 and 48±6 mBq/kg. In all lakes ^(238)Pu was an order of magnitude lower than 239+240 Pu and varied from 4.8±2.6 to 30.7±5.5 mBq/kg. The ^(238)Pu activity was decay-corrected to 1986. The characteristic ratio of the ^(238)Pu/239+240 Pu activities in the sediment and percentage of the Chernobyl-derived Pu was calculated. The largest percentages of the Chernobyl-derived Pu were observed in the Evpatoriya group(Lake SasykSivash)—16.2%±8.26%, the Tarkhankut group(Dzharylhach)—8.4%±2.10% and the Kerch group(Aktash)—10.5%±5.56%. The study of the depth distribution of plutonium in the Lake Kyzyl-Yar bottom sediment core(0–25 cm) was fulfilled. It was shown that 239+240 Pu was high enough in all studied layers of bottom sediment, but the highest activity ratio ^(238)Pu/239+240 Pu(0.062±0.020) was found in the deepest layer of 15–20.5 cm and the percentage of Chernobyl-derived Pu was estimated at 6.8%±2.85% in this layer.展开更多
Plutonium(Pu)is an anthropogenic radionuclide which mainly derived from atmospheric nuclear tests in the environment.In this study,the Pu isotopes(^(239)Pu and^(240)Pu)in aerosol samples collected during the sandstorm...Plutonium(Pu)is an anthropogenic radionuclide which mainly derived from atmospheric nuclear tests in the environment.In this study,the Pu isotopes(^(239)Pu and^(240)Pu)in aerosol samples collected during the sandstorm and non-sandstorm period were measured by accelerator mass spectrometry(AMS)and the behavior of Pu was studied.The activity concentrations of ^(239)Pu and ^(240)Pu in the aerosol samples of Beijing were ranged from 0.62 nB q/m^(3)to 99.6 n Bq/m^(3)for ^(239)Pu and 3.51 nBq/m^(3)to 60.23 n Bq/m^(3)for ^(240)Pu,respectively.^(239)Pu and ^(240)Pu concentrations exhibited a remarkable seasonal variation trend,with the higher results showed in spring,and the relatively lower concentrations in winter.The observed higher concentration of^(239)Pu and^(240)Pu detected in sandstorm samples further indicated Pu was closely related to the occurrence of sandstorms.The global fallout characteristics of^(240)Pu/^(239)Pu atom ratios(average0.20,ranging from 0.16 to 0.27)in aerosol samples indicating that global fallout was the major source of Pu in the atmosphere.Using aluminum(Al)as an indicator of soil resuspension,significant positive correlation between^(239)Pu and Al(r^(2)=0.934),240Pu and Al(^(r)2=0.525)revealed that soil resuspension was a primary source of atmospheric Pu in Beijing.These results implied that the combination of^(239)Pu,^(240)Pu and Al could be used as the potential tracer of sandstorm.展开更多
Hybrid density functional theory is employed to systematically investigate the structural,magnetic,vibrational,thermodynamic properties of plutonium monocarbide（Pu C and Pu C0.75）.For comparison,the results obtained...Hybrid density functional theory is employed to systematically investigate the structural,magnetic,vibrational,thermodynamic properties of plutonium monocarbide（Pu C and Pu C0.75）.For comparison,the results obtained by DFT,DFT ＋ U are also given.For Pu C and Pu C0.75,Fock-0.25 hybrid functional gives the best lattice constants and predicts the correct ground states of antiferromagnetic（AFM） structure.The calculated phonon spectra suggest that Pu C and Pu C0.75 are dynamically stable.Values of the Helmholtz free energy ？F,internal energy ？E,entropy S,and constant-volume specific heat Cv of Pu C and Pu C0.75 are given.The results are in good agreement with available experimental or theoretical data.As for the chemical bonding nature,the difference charge densities,the partial densities of states and the Bader charge analysis suggest that the Pu–C bonds of Pu C and Pu C0.75 have a mixture of covalent character and ionic character.The effect of carbon vacancy on the chemical bonding is also discussed in detail.We expect that our study can provide some useful reference for further experimental research on the phonon density of states,thermodynamic properties of the plutonium monocarbide.展开更多
The spatial distributions of ^(239+240)Pu and ^(137)Cs in soils from Longji Rice Terraces were investigated to evaluate soil erosion.The activity concentrations of ^(239+240)Pu and ^(137)Cs in the surface soils of the...The spatial distributions of ^(239+240)Pu and ^(137)Cs in soils from Longji Rice Terraces were investigated to evaluate soil erosion.The activity concentrations of ^(239+240)Pu and ^(137)Cs in the surface soils of the paddy fields were in the range of 0.089–0.734 and1.80–7.88 mBq/g,respectively.The activities of ^(239+240)Pu and ^(137)Cs showed very similar distribution trends,first increasing and then decreasing with increasing elevation.The 240Pu/239Pu atom ratios in the surface soils ranged from 0.162 to 0.232.The activities of ^(239+240)Pu and ^(137)Cs in the soil cores tended to be uniformly distributed within the plowed layer and declined exponentially below this depth.The mean soil erosion rates of Longji Rice Terraces estimated by ^(239+240)Pu and ^(137)Cs tracer methods were 5.44 t/(ha·a)and 5.16 t/(ha·a),respectively,which demonstrated that plutonium can replace ^(137)Cs as an ideal tracer for soil erosion research in the future.Landform features are the main factors affecting the distribution of plutonium and ^(137)Cs as well as soil erosion in the Longji Rice Terraces.展开更多
A molten salt reactor(MSR)has outstanding features considering the application of thorium fuel,inherent safety,sustainability,and resistance to proliferation.However,fissile material^(233)U is significantly rare at th...A molten salt reactor(MSR)has outstanding features considering the application of thorium fuel,inherent safety,sustainability,and resistance to proliferation.However,fissile material^(233)U is significantly rare at the current stage,thus it is difficult for MSR to achieve a pure thorium-uranium fuel cycle.Therefore,using plutonium or enriched uranium as the initial fuel for MSR is more practical.In this study,we aim to verify the feasibility of a small modular MSR that utilizes plutonium as the starting fuel(SM-MSR-Pu),and highlight its advantages and disadvantages.First,the structural design and fuel management scheme of the SM-MSR-Pu were presented.Second,the neutronic characteristics,such as the graphite-irradiation lifetime,burn-up performance,and coefficient of temperature reactivity were calculated to analyze the physical characteristics of the SM-MSR-Pu.The results indicate that plutonium is a feasible and advantageous starting fuel for a SM-MSR;however,there are certain shortcomings that need to be solved.In a 250 MWth SM-MSR-Pu,approximately 288.64 kg^(233)U of plutonium with a purity of greater than 90% is produced while 978.00 kg is burned every ten years.The temperature reactivity coefficient decreases from -4.0 to -6.5 pcm K^(-1) over the 50-year operating time,which ensures a long-term safe operation.However,the amount of plutonium and accumulation of minor actinides(MAs)would increase as the burn-up time increases,and the annual production and purity of^(233)U will decrease.To achieve an optimal burn-up performance,setting the entire operation time to 30 years is advisable.Regardless,more than 3600 kg of plutonium eventually accumulate in the core.Further research is required to effectively utilize this accumulated plutonium.展开更多
Supercritical fluid extraction (SFE) of plutonium in its nitrate form from actual waste, i.e. plutonium bearing cellulose matrix was demonstrated using 0.1 litre capacity extraction vessel. Complete recovery of pluton...Supercritical fluid extraction (SFE) of plutonium in its nitrate form from actual waste, i.e. plutonium bearing cellulose matrix was demonstrated using 0.1 litre capacity extraction vessel. Complete recovery of plutonium was demonstrated using modified supercritical carbon dioxide (Sc-CO2), i.e. Sc-CO2 containing octylphenyl-N, N-diisobutyl-carbamoyl- methylphosphine oxide (φCMPO). Near complete recovery of uranium was demonstrated from simulated waste matri- ces, i.e. uranium bearing teflon, glass and cellulose matrices using preparative scale SFE, i.e. from 1 litre capacity ex- traction vessel. The recovery of uranium was established using Sc-CO2 modified with acetyl acetone.展开更多
In these studies the isotopic inventories and corresponding activities of important nuclides for different fuel cycles of a CANDU reactor have been compared. The calculations have been performed using the computer cod...In these studies the isotopic inventories and corresponding activities of important nuclides for different fuel cycles of a CANDU reactor have been compared. The calculations have been performed using the computer code WIMSD4. The isotopic inventories and activities have been calculated versus the fuel burn-up for the natural UO2 fuel, 1.2% enriched UO2 fuel and for the 0.45% PuO2-UO2 fuel. It is found that 1.2% enriched uranium fuel has the lowest activity as compared to other two fuel cycles and vice versa for the 0.45% PuO2-UO2 fuel.展开更多
It is shown that the capture and fission cross-sections of 238U and 239Pu increase with temperature within 1000 K - 3000 K range, in contrast to those of 235U, that under certain conditions may lead to the so-called b...It is shown that the capture and fission cross-sections of 238U and 239Pu increase with temperature within 1000 K - 3000 K range, in contrast to those of 235U, that under certain conditions may lead to the so-called blow-up modes, stimulating the anomalous neutron flux and nuclear fuel temperature growth. Some features of the blow-up regimes in neutronmultiplying media are discussed.展开更多
Nucleco is the Sogin Group’s Italian leading company in the sector of radiological services,radioactive waste management,decontamination and reclamation of industrial sites and nuclear power plants.Nucleco is 60%owne...Nucleco is the Sogin Group’s Italian leading company in the sector of radiological services,radioactive waste management,decontamination and reclamation of industrial sites and nuclear power plants.Nucleco is 60%owned by Sogin and 40%by ENEA-National Agency for New Technologies.The waste characterization carried out by Nucleco SpA includes a large variety of radionuclides belonging to the gamma,beta and alpha emitter families.The determination of Uranium and Plutonium isotopes plays a key role in the waste characterization.Nucleco SpA has distinguished itself in characterizations of radioactive waste in complex and nuclear plant matrices.These matrices have large amounts of alpha emitters,in particular isotopes of Uranium,Thorium and Plutonium.A significant presence of U238 results in such a large amount of Th234(and daughters)that interferes with the determination of Pu241.Hence,there is the need of finding a pre-treatment,extraction and subsequent purification technique that would allow Th234 to be detached and thus Pu241 to be determined in complex high-activity matrices.The above elements are extracted using chromatography columns.An isotope of the element to be analyzed,with known activity,is added at the beginning of the process to determine the extraction yield.Before being eluted into the column,the sample undergoes a series of treatments in order to be purified of any interferents.The method developed by Nucleco involves the oxidation of Pu at valence+6 and the subsequent precipitation,in fluorides form,of the elements with valence+4 and+3(i.e.Th234).Pu241 is then measured by LSC(Liquid Scintillation Counting),while the other isotopes are measured by alpha spectrometry after electrodeposition on a metal plate.展开更多
The molten salt reactor(MSR), as one of the Generation Ⅳ advanced nuclear systems, has attracted a worldwide interest due to its excellent performances in safety, economics, sustainability, and proliferation resistan...The molten salt reactor(MSR), as one of the Generation Ⅳ advanced nuclear systems, has attracted a worldwide interest due to its excellent performances in safety, economics, sustainability, and proliferation resistance. The aim of this work is to provide and evaluate possible solutions to fissile 233 U production and further the fuel transition to thorium fuel cycle in a thermal MSR by using plutonium partitioned from light water reactors spent fuel. By using an in-house developed tool, a breeding and burning(B&B) scenario is first introduced and analyzed from the aspects of the evolution of main nuclides, net 233 U production, spectrum shift, and temperature feedback coefficient. It can be concluded that such a Th/Pu to Th/^(233)U transition can be accomplished by employing a relatively fast fuel reprocessing with a cycle time less than 60 days. At the equilibrium state, the reactor can achieve a conversion ratio of about 0.996 for the 60-day reprocessing period(RP) case and about 1.047 for the 10-day RP case.The results also show that it is difficult to accomplish such a fuel transition with limited reprocessing(RP is 180 days),and the reactor operates as a converter and burns the plutonium with the help of thorium. Meanwhile, a prebreeding and burning(PB&B) scenario is also analyzed briefly with respect to the net 233 U production and evolution of main nuclides. One can find that it is more efficient to produce 233 U under this scenario, resulting in a double time varying from about 1.96 years for the 10-day RP case to about 6.15 years for the 180-day RP case.展开更多
There are six independent constituents with 4 chemical elements, i.e. PuH 2.7 (s), PuN(s), Pu 2O 3(s), N 2, O 2 and H 2, therefore , the system described involves of 2 independent reactions ,both ΔG°0. The cal...There are six independent constituents with 4 chemical elements, i.e. PuH 2.7 (s), PuN(s), Pu 2O 3(s), N 2, O 2 and H 2, therefore , the system described involves of 2 independent reactions ,both ΔG°0. The calculated equilibrium compositions are in agreement with those of the experimental, which indicates that the chemical equilibrium is nearly completely approached. Therefore, it is believed that the reaction rate of plutonium hydride with air is extremely rapid. The present paper has briefly discussed the simultaneous reactions and its thermodynamic coupling effect.展开更多
The demand for ^(238)Pu(nuclear battery heat source)drives the separation of its precursor,^(237)Np,from spent nuclear fuel(SNF).However,the co-existence of multi-valence states(IV/V/VI)of Np and similar redox behavio...The demand for ^(238)Pu(nuclear battery heat source)drives the separation of its precursor,^(237)Np,from spent nuclear fuel(SNF).However,the co-existence of multi-valence states(IV/V/VI)of Np and similar redox behavior with Pu(IV)hinder the effective separation of Np.N-Butyraldehyde(n-C_(3)H_(7)CHO)selectively reduces Np(VI)to Np(V)without reducing Pu(IV).Herein,we examined the reduction mechanisms of Np(VI)and Pu(IV)by n-C_(3)H_(7)CHO using relativistic density functional theory.Based on the results of the potential energy profiles,the reductions of both Np(VI)and Pu(IV)by n-C_(3)H_(7)CHO are thermodynamically feasible,whereas only the former is kinetically achievable.It uncovers that n-C_(3)H_(7)CHO can only reduce Np(VI)to Np(V)owing to kinetically controlled selective reduction.The analyses of spin density and bond distance indicate that the reduction nature for the first Np(VI)/Pu(IV)belongs to hydrogen atom transfer,whereas that for the second one involves outer-sphere electron transfer.Localized molecular orbitals(LMOs)analysis discloses the bonding evolution during the reduction process of Np(VI)/Pu(IV).This study elucidates the reason behind the kinetically controlled selective reduction of Np(VI)/Pu(IV)by n-C_(3)H_(7)CHO at the molecular level and offers in-depth perspectives on the isolation of specific metal ions from the view of kinetic control.展开更多
Crystalline coordination complexes of actinides,especially in atypical oxidation states,are not only fundamentally important for expanding the notably limited knowledge on the bonding nature of actinides but could als...Crystalline coordination complexes of actinides,especially in atypical oxidation states,are not only fundamentally important for expanding the notably limited knowledge on the bonding nature of actinides but could also provide critical information toward the development of nuclear fuel cycle,waste management,and national security.Plutonium(Pu)is the only element in the periodic table that could exist in four oxidation states in aqueous solutions simultaneously.展开更多
基金supported by the China Institute of Atomic Energy。
文摘The removal of trace plutonium(Pu)from uranium products and organic wastes during spent nuclear fuel reprocessing remains a critical challenge,resulting in excessive plutonium content in uranium products and waste organic liquid.Currently,most organic ligands with selective separation functions are lipophilic,while research on water-soluble,highly selective ligands is relatively scarce,and there are also few reports on the single crystal of these ligands coordinating with plutonium.Herein,a hydrophilic multiamide ligand,N,N,N′,N″,N″-hexaethyl-nitrilotriacetamide(NTAamideC2),was synthesized and evaluated for its Pu(Ⅳ)back-extraction efficiency under harsh conditions.Systematic experiments revealed that NTAamideC2 achieved>99%Pu(Ⅳ)back-extraction rate within 15 min across a wide nitric acid concentration range(0-5 M),even with elevated dibutyl phosphate(DBP≤20000 ppm).Remarkably,the separation factor(SFPu/U)reached 767 at 1.5 M HNO_(3),demonstrating exceptional selectivity over uranium(Ⅵ).Spectrophotometric titration and DFT calculations confirmed the formation of 1:1 and 1:2 Pu(Ⅳ)-NTAamideC2 complexes,with log β values of 7.42±0.01 and 13.23±0.02,respectively.Single-crystal X-ray diffraction analysis of{[Pu_(2)(H_(2)O)_(2)(NTAamideC2)_(4)](H_(2)O)_(2)(NO_(3))(ClO_(4))_(7)}revealed a nine-coordinated PuO_(7)N_(2)geometry,where two NTAamideC2 molecules bind via six O and two N atoms.Compared to conventional agents(AHA/HSC),NTAamideC2 exhibited superior acid tolerance and selectivity,aligning with the CHON principle for sustainable nuclear waste management.This work provides a robust strategy for Pu(Ⅳ)removal in uranium purification cycles and advances fundamental insights into Pu coordination chemistry,offering significant potential for industrial nuclear fuel reprocessing.
基金Project supported by the National Natural Science Foundation of China (Grant No 10604010)
文摘The electronic structures and properties of PuO2 and Pu2O3 have been studied according to the first principles by using the all-electron projector-augmented-wave （PAW） method. The local density approximation （LDA）＋U and the generalized gradient approximation （GGA）＋U formalisms have been used to account for the strong on-site Coulomb repulsion among the localized Pu 5f electrons. We discuss how the properties of PuO2 and Pu2O3 are affected by choosing the values of U and exchange-correlation potential. Also, the oxidation reaction of Pu2O3, leading to the formation of PuO2, and its dependence on U and exchange-correlation potential have been studied. Our results show that by choosing an appropriate U it is possible to consistently describe structural, electronic, and thermodynamic properties of PuO2 and Pu2O3, which enable the modelling of the redox process involving Pu-based materials.
文摘This study evaluated the nuclear data libraries for a small 100 Mega Watt electric(MWe)Molten Salt Reactor with plutonium fuel.The reactor has a power output of 100 MWe,which meets the demand for electricity generation in several regions or provinces outside Java Island.Several nuclear data libraries,such as JEFF 3.1,ENDF/B-VII.0,JENDL 3.3,and JENDL 4.0,were used for a more comprehensive evaluation.LiF–BeF_(2)–ThF_(4)–PuF_(4) was used as the initial fuel composition.The thorium and plutonium concentrations in the fuel salt were varied to obtain the optimum fuel composition,leading to critical conditions.The results showed some neutronic parameters,such as the conversion ratio,neutron spectra,and effective multiplication factors,from three different nuclear data libraries.By changing the plutonium concentration in the initial fuel salt composition,the minimum plutonium loaded for the reactor criticality during 2000 days of operation time was determined to be 0.995,0.91,0.87,and 0.90 mol%for JEFF 3.1,ENDF/B-VII.0,JENDL 3.3,and JENDL 4.0,respectively.The differences in the values of each parameter were due to several factors,such as the cross-section values and number of nuclides in the nuclear data libraries.Several safety parameters were also investigated to ensure the possibility of utilizing PuF_(4) in the reactor.
基金Project supported by the National Natural Science Foundation of China (Grant No. 20971114)
文摘Pu can be loaded with H forming complicated continuous solid solutions and compounds,and causing remarkable electronic and structural changes.Full potential linearized augmented plane wave methods combined with Hubbard parameter U and the spin-orbit effects are employed to investigate the electronic and structural properties of stoichiometric and non-stoichiometric face-centered cubic Pu hydrides（PuHx,x=2,2.25,2.5,2.75,3）.The decreasing trend with increasing x of the calculated lattice parameters is in reasonable agreement with the experimental findings.A comparative analysis of the electronic-structure results for a series of PuH x compositions reveals that the lattice contraction results from the associated effects of the enhanced chemical bonding and the size effects involving the interstitial atoms.We find that the size effects are the driving force for the abnormal lattice contraction.
基金supported by the Chinese TMSR Strategic Pioneer Science and Technology Project(No.XDA02010000)Shanghai Pilot Program for Basic Research-Chinese Academy of Science,Shanghai Branch(No.JCYJ-SHFY-2021-003)the Chinese Academy of Sciences Special Research Assistant Funding Project.
文摘In a thorium-based molten salt reactor(TMSR),it is difficult to achieve the pure 232Th–^(233)U fuel cycle without sufficient^(233)U fuel supply.Therefore,the original molten salt reactor was designed to use enriched uranium or plutonium as the starting fuel.By exploiting plutonium as the starting fuel and thorium as the fertile fuel,the high-purity^(233)U produced can be separated from the spent fuel by fluorination volatilization.Therefore,the molten salt reactor started with plutonium can be designed as a^(233)U breeder with the burning plutonium extracted from a pressurized water reactor(PWR).Combining these advantages,the study of the physical properties of plutonium-activated salt reactors is attractive.This study mainly focused on the burnup performance and temperature reactivity coefficient of a small modular molten-salt reactor started with plutonium(SM-MSR-Pu).The neutron spectra,^(233)U production,plutonium incineration,minor actinide(MA)residues,and temperature reactivity coefficients for different fuel salt volume fractions(VF)and hexagon pitch(P)sizes were calculated to analyze the burnup behavior in the SM-SMR-Pu.Based on the comparative analysis results of the burn-up calculation,a lower VF and larger P size are more beneficial for improving the burnup performance.However,from a passive safety perspective,a higher fuel volume fraction and smaller hexagon pitch size are necessary to achieve a deep negative feedback coefficient.Therefore,an excellent burnup performance and a deep negative temperature feedback coefficient are incompatible,and the optimal design range is relatively narrow in the optimized design of an SM-MSR-Pu.In a comprehensive consideration,P=20 cm and VF=20%are considered to be relatively balanced design parameters.Based on the fuel off-line batching scheme,a 250 MWth SM-MSR-Pu can produce approximately 29.83 kg of ^(233)U,incinerate 98.29 kg of plutonium,and accumulate 14.70 kg of MAs per year,and the temperature reactivity coefficient can always be lower than−4.0pcm/K.
基金supported by the National Natural Science Foundation of China (Grant No.20801007)the Science and Technology Foundation of China Academy of Engineering Physics (Grant No.2009A0301019)
文摘A modified analytic embedded atom method （MAEAM） potential is constructed for fcc 5-Pu. Molecular dynamics （MD） simulations with the potential are performed to investigate the interactions between two symmetrical tilt grain boundaries （GBs） and point defects such as He atom, vacancy and self-interstitial atom （SIA） in Pu. The calculated results show that point defect formation energies are on average lower than those in the lattice but variations from site to site along the GBs are very remarkable. Both substitutional and interstitial He atoms are trapped at GBs. Interstitial He atom is more strongly bound at the GB core than the substitutional He atom. The binding energy of SIA at GB core is higher than those of He atom and vacancy. GB core can bind many He atoms and SIAs due mainly to the fact that it contains many vacancies. Compared with He atom and SIA, the vacancy far from GB core is difficult to diffuse into the core. The GBs can act as sinks and sources of He atoms and SIAs, which may be a reason for the swelling of Pu after a period of self-irradiation because of the higher concentration of vacancy in the bulk.
基金supported by the Russian Foundation for Basic Research Grant No.16-05-00134
文摘Investigations of ^(239+240)Pu and ^(238)Pu in the surface layer(0–5 cm) of bottom sediment in the Crimean 10 salt lakes from 4 geographical groups were carried out for the first time. The ^(239+240)Pu varied widely between regional geographical groups of lakes as well as within groups too and ranged from 11±4 to 451±43 mBq^(239+240)Pu/kg. The highest levels of ^(239+240)Pu—419±27, 443±24 and 451±43 mBq/kg were observed in the Yevpatoriya(Lake Kyzyl-Yar), the Tarkhankut(Dzharylhach) and the Kerch group(Tobechik), respectively. The lowest values of ^(239+240)Pu were identified in three lakes of the Perekop group and were 20±12, 24±6 and 48±6 mBq/kg. In all lakes ^(238)Pu was an order of magnitude lower than 239+240 Pu and varied from 4.8±2.6 to 30.7±5.5 mBq/kg. The ^(238)Pu activity was decay-corrected to 1986. The characteristic ratio of the ^(238)Pu/239+240 Pu activities in the sediment and percentage of the Chernobyl-derived Pu was calculated. The largest percentages of the Chernobyl-derived Pu were observed in the Evpatoriya group(Lake SasykSivash)—16.2%±8.26%, the Tarkhankut group(Dzharylhach)—8.4%±2.10% and the Kerch group(Aktash)—10.5%±5.56%. The study of the depth distribution of plutonium in the Lake Kyzyl-Yar bottom sediment core(0–25 cm) was fulfilled. It was shown that 239+240 Pu was high enough in all studied layers of bottom sediment, but the highest activity ratio ^(238)Pu/239+240 Pu(0.062±0.020) was found in the deepest layer of 15–20.5 cm and the percentage of Chernobyl-derived Pu was estimated at 6.8%±2.85% in this layer.
基金supported by the financial supports from the National Natural Science Foundation of China(Nos.U1932103,U1832212,11875266)Key Deployment Projects of Chinese Academy of Sciences(No.ZDRW-CN-2018–1)Beijing Natural Science Foundation(No.7191008)。
文摘Plutonium(Pu)is an anthropogenic radionuclide which mainly derived from atmospheric nuclear tests in the environment.In this study,the Pu isotopes(^(239)Pu and^(240)Pu)in aerosol samples collected during the sandstorm and non-sandstorm period were measured by accelerator mass spectrometry(AMS)and the behavior of Pu was studied.The activity concentrations of ^(239)Pu and ^(240)Pu in the aerosol samples of Beijing were ranged from 0.62 nB q/m^(3)to 99.6 n Bq/m^(3)for ^(239)Pu and 3.51 nBq/m^(3)to 60.23 n Bq/m^(3)for ^(240)Pu,respectively.^(239)Pu and ^(240)Pu concentrations exhibited a remarkable seasonal variation trend,with the higher results showed in spring,and the relatively lower concentrations in winter.The observed higher concentration of^(239)Pu and^(240)Pu detected in sandstorm samples further indicated Pu was closely related to the occurrence of sandstorms.The global fallout characteristics of^(240)Pu/^(239)Pu atom ratios(average0.20,ranging from 0.16 to 0.27)in aerosol samples indicating that global fallout was the major source of Pu in the atmosphere.Using aluminum(Al)as an indicator of soil resuspension,significant positive correlation between^(239)Pu and Al(r^(2)=0.934),240Pu and Al(^(r)2=0.525)revealed that soil resuspension was a primary source of atmospheric Pu in Beijing.These results implied that the combination of^(239)Pu,^(240)Pu and Al could be used as the potential tracer of sandstorm.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.21371160 and 21401173)
文摘Hybrid density functional theory is employed to systematically investigate the structural,magnetic,vibrational,thermodynamic properties of plutonium monocarbide（Pu C and Pu C0.75）.For comparison,the results obtained by DFT,DFT ＋ U are also given.For Pu C and Pu C0.75,Fock-0.25 hybrid functional gives the best lattice constants and predicts the correct ground states of antiferromagnetic（AFM） structure.The calculated phonon spectra suggest that Pu C and Pu C0.75 are dynamically stable.Values of the Helmholtz free energy ？F,internal energy ？E,entropy S,and constant-volume specific heat Cv of Pu C and Pu C0.75 are given.The results are in good agreement with available experimental or theoretical data.As for the chemical bonding nature,the difference charge densities,the partial densities of states and the Bader charge analysis suggest that the Pu–C bonds of Pu C and Pu C0.75 have a mixture of covalent character and ionic character.The effect of carbon vacancy on the chemical bonding is also discussed in detail.We expect that our study can provide some useful reference for further experimental research on the phonon density of states,thermodynamic properties of the plutonium monocarbide.
基金supported by the National Natural Science Foundation of China(No.12175046)the Guangxi Natural Science Foundation(No.2021GXNSFBA196001)the One-HundredTalents Program of Guangxi Colleges。
文摘The spatial distributions of ^(239+240)Pu and ^(137)Cs in soils from Longji Rice Terraces were investigated to evaluate soil erosion.The activity concentrations of ^(239+240)Pu and ^(137)Cs in the surface soils of the paddy fields were in the range of 0.089–0.734 and1.80–7.88 mBq/g,respectively.The activities of ^(239+240)Pu and ^(137)Cs showed very similar distribution trends,first increasing and then decreasing with increasing elevation.The 240Pu/239Pu atom ratios in the surface soils ranged from 0.162 to 0.232.The activities of ^(239+240)Pu and ^(137)Cs in the soil cores tended to be uniformly distributed within the plowed layer and declined exponentially below this depth.The mean soil erosion rates of Longji Rice Terraces estimated by ^(239+240)Pu and ^(137)Cs tracer methods were 5.44 t/(ha·a)and 5.16 t/(ha·a),respectively,which demonstrated that plutonium can replace ^(137)Cs as an ideal tracer for soil erosion research in the future.Landform features are the main factors affecting the distribution of plutonium and ^(137)Cs as well as soil erosion in the Longji Rice Terraces.
基金supported by the Chinese TMSR Strategic Pioneer Science and Technology Project(No.XDA02010000)Chinese Academy of Sciences Talent Introduction Youth Program(No.SINAP-YCJH-202303)Chinese Academy of Sciences Special Research Assistant Funding Project and Shanghai Pilot Program for Basic Research-Chinese Academy of Science,Shanghai Branch(JCYJ-SHFY-2021-003)。
文摘A molten salt reactor(MSR)has outstanding features considering the application of thorium fuel,inherent safety,sustainability,and resistance to proliferation.However,fissile material^(233)U is significantly rare at the current stage,thus it is difficult for MSR to achieve a pure thorium-uranium fuel cycle.Therefore,using plutonium or enriched uranium as the initial fuel for MSR is more practical.In this study,we aim to verify the feasibility of a small modular MSR that utilizes plutonium as the starting fuel(SM-MSR-Pu),and highlight its advantages and disadvantages.First,the structural design and fuel management scheme of the SM-MSR-Pu were presented.Second,the neutronic characteristics,such as the graphite-irradiation lifetime,burn-up performance,and coefficient of temperature reactivity were calculated to analyze the physical characteristics of the SM-MSR-Pu.The results indicate that plutonium is a feasible and advantageous starting fuel for a SM-MSR;however,there are certain shortcomings that need to be solved.In a 250 MWth SM-MSR-Pu,approximately 288.64 kg^(233)U of plutonium with a purity of greater than 90% is produced while 978.00 kg is burned every ten years.The temperature reactivity coefficient decreases from -4.0 to -6.5 pcm K^(-1) over the 50-year operating time,which ensures a long-term safe operation.However,the amount of plutonium and accumulation of minor actinides(MAs)would increase as the burn-up time increases,and the annual production and purity of^(233)U will decrease.To achieve an optimal burn-up performance,setting the entire operation time to 30 years is advisable.Regardless,more than 3600 kg of plutonium eventually accumulate in the core.Further research is required to effectively utilize this accumulated plutonium.
文摘Supercritical fluid extraction (SFE) of plutonium in its nitrate form from actual waste, i.e. plutonium bearing cellulose matrix was demonstrated using 0.1 litre capacity extraction vessel. Complete recovery of plutonium was demonstrated using modified supercritical carbon dioxide (Sc-CO2), i.e. Sc-CO2 containing octylphenyl-N, N-diisobutyl-carbamoyl- methylphosphine oxide (φCMPO). Near complete recovery of uranium was demonstrated from simulated waste matri- ces, i.e. uranium bearing teflon, glass and cellulose matrices using preparative scale SFE, i.e. from 1 litre capacity ex- traction vessel. The recovery of uranium was established using Sc-CO2 modified with acetyl acetone.
文摘In these studies the isotopic inventories and corresponding activities of important nuclides for different fuel cycles of a CANDU reactor have been compared. The calculations have been performed using the computer code WIMSD4. The isotopic inventories and activities have been calculated versus the fuel burn-up for the natural UO2 fuel, 1.2% enriched UO2 fuel and for the 0.45% PuO2-UO2 fuel. It is found that 1.2% enriched uranium fuel has the lowest activity as compared to other two fuel cycles and vice versa for the 0.45% PuO2-UO2 fuel.
文摘It is shown that the capture and fission cross-sections of 238U and 239Pu increase with temperature within 1000 K - 3000 K range, in contrast to those of 235U, that under certain conditions may lead to the so-called blow-up modes, stimulating the anomalous neutron flux and nuclear fuel temperature growth. Some features of the blow-up regimes in neutronmultiplying media are discussed.
文摘Nucleco is the Sogin Group’s Italian leading company in the sector of radiological services,radioactive waste management,decontamination and reclamation of industrial sites and nuclear power plants.Nucleco is 60%owned by Sogin and 40%by ENEA-National Agency for New Technologies.The waste characterization carried out by Nucleco SpA includes a large variety of radionuclides belonging to the gamma,beta and alpha emitter families.The determination of Uranium and Plutonium isotopes plays a key role in the waste characterization.Nucleco SpA has distinguished itself in characterizations of radioactive waste in complex and nuclear plant matrices.These matrices have large amounts of alpha emitters,in particular isotopes of Uranium,Thorium and Plutonium.A significant presence of U238 results in such a large amount of Th234(and daughters)that interferes with the determination of Pu241.Hence,there is the need of finding a pre-treatment,extraction and subsequent purification technique that would allow Th234 to be detached and thus Pu241 to be determined in complex high-activity matrices.The above elements are extracted using chromatography columns.An isotope of the element to be analyzed,with known activity,is added at the beginning of the process to determine the extraction yield.Before being eluted into the column,the sample undergoes a series of treatments in order to be purified of any interferents.The method developed by Nucleco involves the oxidation of Pu at valence+6 and the subsequent precipitation,in fluorides form,of the elements with valence+4 and+3(i.e.Th234).Pu241 is then measured by LSC(Liquid Scintillation Counting),while the other isotopes are measured by alpha spectrometry after electrodeposition on a metal plate.
基金supported by the Chinese TMSR Strategic Pioneer Science and Technology Project(No.XDA02010000)the National Natural Science Foundation of China(No.91326201)the Frontier Science Key Program of the Chinese Academy of Sciences(No.QYZDY-SSW-JSC016)
文摘The molten salt reactor(MSR), as one of the Generation Ⅳ advanced nuclear systems, has attracted a worldwide interest due to its excellent performances in safety, economics, sustainability, and proliferation resistance. The aim of this work is to provide and evaluate possible solutions to fissile 233 U production and further the fuel transition to thorium fuel cycle in a thermal MSR by using plutonium partitioned from light water reactors spent fuel. By using an in-house developed tool, a breeding and burning(B&B) scenario is first introduced and analyzed from the aspects of the evolution of main nuclides, net 233 U production, spectrum shift, and temperature feedback coefficient. It can be concluded that such a Th/Pu to Th/^(233)U transition can be accomplished by employing a relatively fast fuel reprocessing with a cycle time less than 60 days. At the equilibrium state, the reactor can achieve a conversion ratio of about 0.996 for the 60-day reprocessing period(RP) case and about 1.047 for the 10-day RP case.The results also show that it is difficult to accomplish such a fuel transition with limited reprocessing(RP is 180 days),and the reactor operates as a converter and burns the plutonium with the help of thorium. Meanwhile, a prebreeding and burning(PB&B) scenario is also analyzed briefly with respect to the net 233 U production and evolution of main nuclides. One can find that it is more efficient to produce 233 U under this scenario, resulting in a double time varying from about 1.96 years for the 10-day RP case to about 6.15 years for the 180-day RP case.
文摘There are six independent constituents with 4 chemical elements, i.e. PuH 2.7 (s), PuN(s), Pu 2O 3(s), N 2, O 2 and H 2, therefore , the system described involves of 2 independent reactions ,both ΔG°0. The calculated equilibrium compositions are in agreement with those of the experimental, which indicates that the chemical equilibrium is nearly completely approached. Therefore, it is believed that the reaction rate of plutonium hydride with air is extremely rapid. The present paper has briefly discussed the simultaneous reactions and its thermodynamic coupling effect.
基金supported by the National Natural Science Foundation of China(Nos.22376197,U2441225,22076188).
文摘The demand for ^(238)Pu(nuclear battery heat source)drives the separation of its precursor,^(237)Np,from spent nuclear fuel(SNF).However,the co-existence of multi-valence states(IV/V/VI)of Np and similar redox behavior with Pu(IV)hinder the effective separation of Np.N-Butyraldehyde(n-C_(3)H_(7)CHO)selectively reduces Np(VI)to Np(V)without reducing Pu(IV).Herein,we examined the reduction mechanisms of Np(VI)and Pu(IV)by n-C_(3)H_(7)CHO using relativistic density functional theory.Based on the results of the potential energy profiles,the reductions of both Np(VI)and Pu(IV)by n-C_(3)H_(7)CHO are thermodynamically feasible,whereas only the former is kinetically achievable.It uncovers that n-C_(3)H_(7)CHO can only reduce Np(VI)to Np(V)owing to kinetically controlled selective reduction.The analyses of spin density and bond distance indicate that the reduction nature for the first Np(VI)/Pu(IV)belongs to hydrogen atom transfer,whereas that for the second one involves outer-sphere electron transfer.Localized molecular orbitals(LMOs)analysis discloses the bonding evolution during the reduction process of Np(VI)/Pu(IV).This study elucidates the reason behind the kinetically controlled selective reduction of Np(VI)/Pu(IV)by n-C_(3)H_(7)CHO at the molecular level and offers in-depth perspectives on the isolation of specific metal ions from the view of kinetic control.
基金funding support from the Science Challenge Project(TZ2016004)the National Natural Science Foundation of China(21825601,21790374,21806118,and 21727801)+1 种基金The computational work was financially supported by the Foundation of President of China Academy of Engineering Physics(no.YZJJSQ2017072)by the National Natural Science Foundation of China(21590792,21433005,and 21701006).
文摘Crystalline coordination complexes of actinides,especially in atypical oxidation states,are not only fundamentally important for expanding the notably limited knowledge on the bonding nature of actinides but could also provide critical information toward the development of nuclear fuel cycle,waste management,and national security.Plutonium(Pu)is the only element in the periodic table that could exist in four oxidation states in aqueous solutions simultaneously.
