Recent progress and perspective on batteries made from nuclear waste

Sustainable energy sources are an immediate need to cope with the imminent issue of climate change the world is facing today.In particular,the long-lasting miniatured power sources that can supply energy continually to power handheld gadgets,sensors,electronic devices,unmanned airborne vehicles in space and extreme mining are some of the examples where this is an acute need.It is known from basic physics that radioactive materials decay over few years and some nuclear materials have their half-life until thousands of years.The past five decades of research have been spent harnessing the decay energy of the radioactive materials to develop batteries that can last until the radioactive reaction continues.Thus,an emergent opportunity of industrial symbiosis to make use of nuclear waste by using radioactive waste as raw material to develop bat-teries with long shelf life presents a great opportunity for sustainable energy resource development.However,the current canon of research on this topic is scarce.This perspective draws fresh discussions on the topic while highlighting future directions in this wealthy arena of research.Graphical abstract A long-lasting miniaturised nuclear battery utilising 14C radioactive isotope as fuel.

Earthquake-induced fracture displacements and transmissivity changes in a 3D fracture network of crystalline rock for spent nuclear fuel disposal

During the long service period of a nuclear waste repository in crystalline rock,large earthquake(s)may occur nearby the repository site and coseismically alter the local stress field around pre-existing fractures within the geological formation.The resulting fracture normal/shear displacements may lead to fracture opening and further promote the transport of leaked radionuclides into the groundwater system.Thus,it is of central importance to analyze the consequences of potential future earthquake(s)on the hydrogeological properties of a repository site for spent nuclear fuel disposal.Based on the detailed site characterization data of the repository site at Forsmark,Sweden,we conduct a three-dimensional(3D)seismo-hydro-mechanical simulation using the 3Dimensional Distinct Element Code(3DEC).We explicitly represent a primary seismogenic fault zone and its surrounding secondary fracture network associated with a power-law size scaling and a Fisher orientation distribution.An earthquake with a magnitude of M_(w)=5.6 caused by the reactivation of the primary fault zone is modeled by simulating its transient rupture propagating radially outwards from a predefined hypocenter at a specified rupture speed,with the faulting dynamics controlled by a strength weakening law.We model the coseismic response of the off-fault fracture network subject to both static and dynamic triggering effects.We further diagnose the distribution of fracture hydro-mechanical properties(e.g.mechanical/hydraulic aperture,hydraulic transmissivity)before and after the earthquake in order to quantify earthquakeinduced hydraulic changes in the fracture network.It is found that earthquake-induced fracture transmissivity changes tend to follow a power-law decay with the distance to the earthquake fault.Our simulation results and insights obtained have important implications for the long-term performance assessment of nuclear waste repositories in fractured crystalline rocks.

Volumetric lattice Boltzmann method for pore-scale mass diffusionadvection process in geopolymer porous structures

Porous materials present significant advantages for absorbing radioactive isotopes in nuclear waste streams.To improve absorption efficiency in nuclear waste treatment,a thorough understanding of the diffusion-advection process within porous structures is essential for material design.In this study,we present advancements in the volumetric lattice Boltzmann method(VLBM)for modeling and simulating pore-scale diffusion-advection of radioactive isotopes within geopolymer porous structures.These structures are created using the phase field method(PFM)to precisely control pore architectures.In our VLBM approach,we introduce a concentration field of an isotope seamlessly coupled with the velocity field and solve it by the time evolution of its particle population function.To address the computational intensity inherent in the coupled lattice Boltzmann equations for velocity and concentration fields,we implement graphics processing unit(GPU)parallelization.Validation of the developed model involves examining the flow and diffusion fields in porous structures.Remarkably,good agreement is observed for both the velocity field from VLBM and multiphysics object-oriented simulation environment(MOOSE),and the concentration field from VLBM and the finite difference method(FDM).Furthermore,we investigate the effects of background flow,species diffusivity,and porosity on the diffusion-advection behavior by varying the background flow velocity,diffusion coefficient,and pore volume fraction,respectively.Notably,all three parameters exert an influence on the diffusion-advection process.Increased background flow and diffusivity markedly accelerate the process due to increased advection intensity and enhanced diffusion capability,respectively.Conversely,increasing the porosity has a less significant effect,causing a slight slowdown of the diffusion-advection process due to the expanded pore volume.This comprehensive parametric study provides valuable insights into the kinetics of isotope uptake in porous structures,facilitating the development of porous materials for nuclear waste treatment applications.

Self-propagating High-temperature Synthesis of Sm and Zr Co-doped Gd2Ti2O7 Pyrochlore Ceramics as Nuclear Waste Forms

We reported a rapid synthesis of Sm^(3+)/Zr^(4+)co-doped Gd2Ti2O7 pyrochlore simulated nuclear wastes solidification by self-propagation plus quick pressing technique.With increment excess contents of Sm2O3 and ZrO2 from 0 to 10wt%,the phase composition of the products is a mixed phase of pyrochlore structure and defective fluorite structure by X-ray diffraction(XRD)analysis and Raman spectrum.In addition,the SEM results demonstrate the fracture surface and microstructure of Gd2Ti2O7-based pyrochlore.The densified pyrochlore waste form exhibits high bulk density of 5.56 g·cm^(-3) and vickers hardness of 11.20±0.2 GPa.The leaching tests show that the elemental leaching rates of Gd,Sm,and Cu after 42 days are 1.92×10^(-4),1.51×10^(-4),and 3.90×10^(-3) g·m^(-2)·d^(-1),respectively.

Bayesian partial pooling to reduce uncertainty in overcoring rock stress estimation

The state of in situ stress is a crucial parameter in subsurface engineering,especially for critical projects like nuclear waste repository.As one of the two ISRM suggested methods,the overcoring(OC)method is widely used to estimate the full stress tensors in rocks by independent regression analysis of the data from each OC test.However,such customary independent analysis of individual OC tests,known as no pooling,is liable to yield unreliable test-specific stress estimates due to various uncertainty sources involved in the OC method.To address this problem,a practical and no-cost solution is considered by incorporating into OC data analysis additional information implied within adjacent OC tests,which are usually available in OC measurement campaigns.Hence,this paper presents a Bayesian partial pooling(hierarchical)model for combined analysis of adjacent OC tests.We performed five case studies using OC test data made at a nuclear waste repository research site of Sweden.The results demonstrate that partial pooling of adjacent OC tests indeed allows borrowing of information across adjacent tests,and yields improved stress tensor estimates with reduced uncertainties simultaneously for all individual tests than they are independently analysed as no pooling,particularly for those unreliable no pooling stress estimates.A further model comparison shows that the partial pooling model also gives better predictive performance,and thus confirms that the information borrowed across adjacent OC tests is relevant and effective.

The Price of Engineering Ethics, a Personal Story

There are costs for doing the right thing,but regret is not one of those costs.I learned this lesson the hard way throughout a 42-year engineering career.As a young engineer,raising a family,I was more adaptable to management mandates,i.e.,I was more willing to be unethical to keep my job to make money and have health insurance for my family.As I grew in age,experience,and stamina,I was less adaptable,i.e.,I was more ethical.This article tells this story through events at various times in my engineering career1.Ethics define how we do the right thing.

Effect of temperature on copper corrosion in high-level nuclear waste environment

The effect of temperature on the corrosion behavior of copper in simulated high-level nuclear waste environment wassystematically studied.Electrochemical methods,including electrochemical impendence spectra,Mott–Schottky technology,cyclicpolarization,and potentiostatic polarization,were employed to characterize the corrosion behavior of copper at different temperatures.Stereoscopic microscopy and scanning electron microscopy were used to examine the surface morphology,and X-ray photoelectronspectroscopy analysis was used to identify the composition of the passive film.The experimental results show that corrosionresistance of the passive film does not blindly decrease with the increase of temperature but increases at60°C owing to a compactouter layer;there is a potential for pitting corrosion,which decreases as the temperature increases.The main product of copper in ananaerobic aqueous sulfide solution is Cu2S but the content of CuS increases at higher temperatures.The whole passivation rangeshows p-type semiconductor characteristics and the magnitude of the acceptor density is1023cm-3,which increases with increasingtemperature.

Active source seismic imaging on near-surface granite body:case study of siting a geological disposal repository for high-level radioactive nuclear waste

In order to research whether it is suitable to set a geological disposal repository for high-level radioactive nuclear waste into one target granite body,two active source seismic profles were arranged near a small town named Tamusu,Western China.The study area is with complex surface conditions,thus the seismic exploration encountered a variettraveltimey of technical difculties such as crossing obstacles,de-noising harmful scattered waves,and building complex near-surface velocity models.In order to address those problems,techniques including cross-obstacle seismic geometry design,angle-domain harmful scattered noise removal,and an acoustic wave equation-based inversion method jointly utilizing both the and waveform of frst arrival waves were adopted.The fnal seismic images clearly exhibit the target rock’s unconformable contact boundary and its top interface beneath the sedimentary and weathered layers.On this basis,it could be confrmed that the target rock is not thin or has been transported by geological process from somewhere else,but a native and massive rock.There are a few small size fractures whose space distribution could be revealed by seismic images within the rock.The fractures should be kept away.Based on current research,it could be considered that active source seismic exploration is demanded during the sitting process of the geological disposal repository for nuclear waste.The seismic acquisition and processing techniques proposed in the present paper would ofer a good reference value for similar researches in the future.

Atomistic Simulation Study of Defect Structure of Zircon as a High-Level Nuclear Waste Host Form

A set of potential parameters for modeling zircon was obtained by atomistic simulation techniques and a reasonable structural model of zircon was established by fitting some important properties of zircon.Based on the equilibrium configuration of zircon, authors calculated the formation energies of basic point defects and intrinsic disorders. The heats of solution of substituting Pu for Zr showed that there was an immiscible gap at the composition of (Pu75%-Zr25%, in mole fraction), which suggests that the amount of Pu substituting for Zr in zircon be≤50%.

Sol-Gel Processing of Silica Nuclear Waste Glasses

A complex Sol-Gel process has been used for synthesis of silica glasses designed to contain high-level nuclear wastes. Cs, Sr, Co, and Nd (generically denoted Me) were used, the last as surrogate for actinides. Gels in the form of powders and sintered compacts were prepared by hydrolysis and polycondensation of tetraethoxide/Me nitrate solutions, which contained ascorbic acid as a catalyst. Thermal treatment studies were conducted on the resulting gels. Transformation to final products was studied by thermogravimetric analysis, infrared spectroscopy, and X-ray diffraction. Preliminary testing of Me leaching was also completed in quiescent water. Only a single dense form was resistant to

Proposed Flexibility to USA Nuclear Waste Management Strategy

USA nuclear waste management program has stalled due to its continued insistence upon using Yucca Mountain for its disposal of DOE （Department of Energy） and commercial power plants NSF （nuclear spent fuel）. Increased flexibility and significant changes in DOE program are proposed. They include a private waste company to manage it; the construction and operation of ICS （interim centralized storage） facilities for NSF; the search for an AGR （alternate geological repository）; the use of a different methodology involving key local and state participants; a new ＂as safe as practical＂ strategy with defined benefits to the involved locations and states. Assured removal of NSF from ICS and providing limited Price Anderson indemnity for the program will enhance its acceptance. Minimum politics, regular information meetings, compromises, good cost projections and meeting schedules will be necessary to increase the chances of the proposed nuclear waste management program.

A MIXED FINITE ELEMENT APPROXIMATIONFOR COMPRESSIBLE FLOW OF CONTAMINATION FROM NUCLEAR WASTE IN POROUS MEDIA

A compressible nuclear waste disposal contamination in porous media. is modeled by a coupled system of partial differential equations. The approximation of this system using a finite element method for the brine, radionuclides, and heat combined with a mixed finite element method for the pressure and velocity are analyzed. Optimal order error estimates in H-1 and L-2 are derived. This paper improves upon previously derived estimates in two aspects. Firstly, the error analysis is given with no restriction on the diffusion tensors. That is, it has included the effects of molecular diffusion and dispersion. Secondly, the 'complete compressibility' case is considered.

Chemical Durability, Properties and Structural Approach of the Glass Series xFe2O3-(45-x) PbO-55P2O5 (with 0 ≤ x ≤ 20;mol%)

The synthesis for glasses series xFe2O3-(45-x)PbO-55P2O5, (with 0 ≤ x ≤ 20;mol%) carried out in a temperature (1050 ± 10)°C, leads to obtaining transparent glasses, brown in color and with a non-hygroscopic appearance. The study of glasses dissolution rate, immersed in distilled water at 90°C for 24 days, indicates a considerable chemical durability. The increase in the Fe2O3 content in the vitreous network to the detriment of PbO is a favorable factor for the chemical durability improvement. Different techniques have been used such as X-ray diffraction, infrared spectroscopy, DSC, SEM and density for the study of these glasses. These techniques have led to establish correlations between chemical and structural properties. Thus the results obtained confirmed the creation of P-O-M bonds (M = Pb, Fe) with a strongly covalent nature to the detriment of the hydrated P-O-P bonds and led to the formation, mainly, of pyrophosphate groups. The low melting point of Pb-O makes it possible to play an important role, at the same time, on the viscosity, on the equilibrium between the vitreous bath and the crystallites formed. The dissolution rate obtained is 100 times smaller than that of silicate glasses used as an alternative form for the vitrification of radioactive waste.

Effect of temperature on soil-water characteristics and hysteresis of compacted Gaomiaozi bentonite

Laboratory tests under different constraint conditions were carried out to obtain the soil-water retention curves(SWRCs) of highly-compacted confined/unconfined Gaomiaozi(GMZ) bentonite at 20,40 and 80 ℃,respectively. The effect of temperature on the soil-water characteristics of the highly-compacted GMZ bentonite was analyzed. The results show that the water retention capacity of the highly-compacted GMZ bentonite decreases as the temperature increases under unconfined and confined conditions. At a certain temperature,the constraint conditions have little influence on the water retention capacity of the compacted bentonite at high suction,but the water retention capacity of the confined specimen is lower than that of the unconfined specimen at low suction. Under unconfined conditions,the hysteretic behaviour of the compacted bentonite decreases with increasing temperature. At high suction(>4 MPa) ,the hysteretic behaviour of the unconfined bentonite tends to increase with the decrease of the suction. In summary,the hysteretic behaviour of the compacted bentonite is not significant.

TIMODAZ:A successful international cooperation project to investigate the thermal impact on the EDZ around a radioactive waste disposal in clay host rocks

Disposal of spent nuclear fuel and long lived radioactive waste in deep clay geological formations is one of the promising options worldwide. In this concept of the geological disposal system, the host clay formation is considered as a principal barrier on which the fulfillment of key safety functions rests. Between 2006 and 2010, the European Commission project TIMODAZ, which gathered 15 partners from 8 countries, has investigated the coupled thermo-hydro-mechanical （THM） effects on clay formations for geological disposal of radioactive waste, and specific attention was paid to investigating the thermal effect on the evolution of the damaged zone （DZ）. Three types of potential host clay formations were investigated： the Boom Clay （Belgium）, the Opalinus Clay （Switzerland） and the Callovo-Oxfordian argillite （France）. Intensive experimental （laboratory and in situ in underground research laboratories） and numerical studies have been performed. Multi-scale approach was used in the course of the project. High degree of similarities between the failure modes, sealing process, stress paths, deformation, etc., observed in laboratories and in situ has been obtained, which increased the confidence in the applicability of laboratory test results and up-scaling perspective. The results of the laboratory and in situ tests obtained allowed the parameters for numerical models at various scales to be derived and provided the basis for the simplified performance assessment models that are used to assess the long-term safety of a repository. The good cooperation between the numerical modeler and experimenters has allowed an in-depth analysis of the experimental results and thus better understanding the underlying processes, and consequently increased the capabilities to model the THM effects in claystones. This paper presents the main achievements obtained by TIMODAZ project and shows how a European scientific community investigates a problem of concern in a collaborative way and how the obtained main results are applied to the performance assessment of a geological repository.

Selection and Basic Properties of the Buffer Material for High-Level Radioactive Waste Repository in China

Radioactive wastes arising from a wide range of human activities are in many different physical and chemical forms, contaminated with varying radioactivity. Their common features are the potential hazard associated with their radioactivity and the need to manage them in such a way as to protect the human environment. The geological disposal is regarded as the most reasonable and effective way to safely disposing high-level radioactive wastes in the world. The conceptual model of geological disposal in China is based on a multi-barrier system that combines an isolating geological environment with an engineered barrier system. The buffer is one of the main engineered barriers for HLW repository. It is expected to maintain its low water permeability, self-sealing property, radio nuclides adsorption and retardation properties, thermal conductivity, chemical buffering property, canister supporting property, and stress buffering property over a long period of time. Bentonite is selected as the main content of buffer material that can satisfy the above requirements. The Gaomiaozi deposit is selected as the candidate supplier for China＇s buffer material of high level radioactive waste repository. This paper presents the geological features of the GMZ deposit and basic properties of the GMZ Na-bentonite. It is a super-large deposit with a high content of montmorillonite （about 75 %）, and GMZ-1, which is Na-bentonite produced from GMZ deposit is selected as the reference material for China＇s buffer material study.

Sealing of fractures in claystone

The sealing behavior of fractures in clay rocks for deep disposal of radioactive waste has been comprehensively investigated at the GRS laboratory. Various sealing experiments were performed on strongly cracked samples of different sizes from the Callovo-Oxfordian argillite and the Opalinus clay under rel- evant repository conditions. The fractured samples were compacted and flowed through with gas or synthetic pore-water under confining stresses up to 18 MPa and elevated temperatures from 20 ℃ to 90℃. Sealing of fractures was quantified by measurements of their closure and permeability. Under the applied thermo-hydro-mechanical （THM） conditions, significant fracture closure and permeability decrease to very low levels of 10^-19 to 10^-21 m^2 were observed within time periods of months to years. The properties of the resealed claystones are comparable with those of the intact rock mass. All test results suggest high sealing potentials of the studied claystones.

Swelling ability and behaviour of bentonite-based materials for deep repository engineered barrier systems:Influence of physical,chemical and thermal factors

Compacted bentonite-sand(B/S)mixtures have been used as a barrier material in engineered barrier systems(EBSs)of deep geological repositories(DGR)to store nuclear wastes.This study investigates the individual and combined effects of different chemical compositions of deep groundwaters(chemical factor)at potential repository sites in Canada(the Trenton and Guelph regions in Ontario),heat generated in DGRs(thermal factor),dry densities and mass ratios of bentonite and sand mixtures(physical factors)on the swelling behavior and ability of bentonite-based materials.In this study,swelling tests are conducted on B/S mixtures with different B/S mix ratios(20/80 to 70/30),compacted at different dry densities(ρd=1.6-2 g/cm^(3)),saturated with different types of water(distilled water and simulated deep groundwater of Trenton and Guelph)and exposed to different temperatures(20℃-80℃).Moreover,scanning electron microscopy(SEM)analyses,mercury intrusion porosimetry(MIP)tests and X-ray diffractometry(XRD)analyses are carried out to evaluate the morphological,microstructural and mineralogical characteristics of the B/S mixtures.The test results indicate that the swelling potential of the B/S mixtures is significantly affected by these physical and chemical factors as well as the combined effects of the chemical and thermal factors.A significant decrease in the swelling capacity is observed when the B/S materials are exposed to the aforementioned groundwaters.A large decrease in the swelling capacity is observed for higher bentonite content in the mixtures.Moreover,higher temperatures intensify the chemically-induced reduction of the swelling capacity of the B/S barrier materials.This decrease in the swelling capacity is caused by the chemical and/or microstructural changes of the materials.The results from this research will help engineers to design and build EBSs for DGRs with similar groundwater and thermal conditions.

Microstructure and anisotropic swelling behaviour of compacted bentonite/sand mixture

Pre-compacted elements （disks, tutus） of bentonite/sand mixture are candidate materials for sealing plugs of radioactive waste disposal. Choice of this material is mainly based on its swelling capacity allowing all gaps in the system to be sealed, and on its low permeability. When emplaced in the gallery, these elements will start to absorb water from the host rock and swell. Thereby, a swelling pressure will develop in the radial direction against the host rock and in the axial direction against the support structure. In this work, the swelling pressure of a small scale compacted disk of bentonite and sand was experimentally studied in both radial and axial directions. Different swelling kinetics were identified for different dry densities and along different directions. As a rule, the swelling pressure starts increasing quickly, reaches a peak value, decreases a little and finally stabilises. For some dry densities, higher peaks were observed in the radial direction than in the axial direction. The presence of peaks is related to the microstructure change and to the collapse of macro- pores. In parallel to the mechanical tests, microstructure investigation at the sample scale was conducted using microfocus X-ray computed tomography （BCT）. Image observation showed a denser structure in the centre and a looser one in the border, which was also confirmed by image analysis. This structure heterogeneity in the radial direction and the occurrence of macro-pores close to the radial boundary of the sample can explain the large peaks observed in the radial swelling pressure evolution. Another interesting result is the higher anisotropy found at lower bentonite dry densities, which was also analysed by means ofμCT observation of a sample at low bentonite dry density after the end of test. It was found that the macro-pores, especially those between sand grains, were not filled by swelled bentonite, which preserved the anisotropic microstructure caused by uniaxial compression due to the absence of microstructure collapse.

Pellet mixtures in isolation barriers

Granular mixtures made of high-density pellets of bentonite are being evaluated as an alternative buffer material for waste isolation. Ease of handling is an often-mentioned advantage. The paper describes the experimental program performed to characterize the hydro-mechanical （HM） behaviour of compacted pellet mixtures. Grain size distribution was adjusted to a maximum pellet size compatible with the specimen＇s dimensions. Dry densities of statically compacted specimens varied in most of the cases in the range from 1.3 to 1.5 Mg/m^3. Pellets had a very high dry density, close to 2 Mg/m^3. The outstanding characteristic of these mixtures is their discontinuous porosity. Pore sizes of the compacted pellets varied around 10 nm. However, the inter-pellet size of the pores was four to five orders of magnitude higher. This double porosity and the highly expansive nature of the pellets controlled all the hydraulic and mechanical properties of the mixture. Performed tests include infiltration tests using different water injection rates and mechanisms of water transfer （in liquid and vapour phases）, suction-controlled oedometer tests and swelling pressure tests. The interpretation of some performed tests required back analysis procedures using a hydro-mechanical （HM） computer code. Material response was studied within the framework of the elastoplastic constitutive model proposed by Alonso et al. （1990） （Barcelona basic model, BBM）. Parameters for the model were identified and also a set of hydraulic laws are necessary to perform coupled HM analysis. A large scale in-situ test （the ＂EB＂ test in Mont Terri, Switzerland） was described and analyzed. Rock barrier parameters were adjusted on the basis of available tests. The test excavation, barrier emplacement and forced hydration were simulated by means of the CODEBRIGHT program. The comparison between measurements and computed results include data on relative humidity in the rock and the buffer, swelling pressures and displacements.