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At least 271 records · Page 15

Ceramic reinforced zirconium alloy nuclear fuel cladding with intermediate oxidation resistant layer

The invention relates to compositions and methods for coating a zirconium alloy (e.g., ceramic-containing) cladding tube for use with fuel rods in a nuclear water reactor. The coating includes an intermediate oxidation resistant layer and a SiC containing layer at least partially deposited on the intermediate oxidation resistant layer. The SiC containing layer can include a plurality of fibers. The SiC containing layer may also be on the outer surface of end plugs. The invention provides improved capability for the zirconium alloy cladding to withstand normal and accident conditions in the nuclear water reactor.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Process for preparing doped lithium lanthanum zirconium oxide

A process for preparing doped-lithium lanthanum zirconium oxide (doped-LLZO) is described herein. The method involves dry doping of a co-precipitated lanthanum zirconium oxide (LZO) precursor. Dry doping is a process in which a dry powdered dopant is ground and mixed with a pre-prepared co-precipitated LZO precursor and a lithium salt to provide a LLZO precursor composition, which is subsequently calcined to form a doped-LLZO. The process described herein comprises calcining a dry, powdered (e.g., micron, sub-micron or nano-powdered) mixture of a co-precipitated LZO precursor, a dopant salt or oxide, and a lithium salt under an oxygen-containing atmosphere at a temperature in the range of about 500 to about 1100° C., and recovering the doped-LLZO after calcining.

Durham, Jessica L.↗

A hydride reorientation model for irradiated zirconium alloy cladding

This paper presents a hydride reorientation model for irradiated, but de-fueled, zirconium-based alloy cladding tubes for water cooled reactors subjected to temperature and stress conditions of interest to storage of commercial spent nuclear fuel under dry, inert conditions. The present development builds upon and updates an existing hydride precipitation model developed in 2003, and was motivated by recent findings that the old model underestimated the amount of radial hydrides for applied hoop stresses below 100 MPa. The data used to support the development of the new model were obtained from an NFIR-sponsored experimental program on de-fueled cladding tubes irradiated in light-water reactors. The irradiated material consisted of three types of zirconium-based alloys sampled from high burnup fuel rods: cold-worked stress-relieved (CWSR) Zircaloy-4 (Zr-4), CWSR Zirlo{sup TM}, and recrystallized annealed (RXA) Zircaloy-2 (Zr-2). The majority of the hydride re-orientation tests for the irradiated cladding specimens were conducted under constant pressure with a mean cooling rate of about 1 Celsius degree/mn. The remaining tests were conducted at slower cooling rates with the pressure being kept proportional to the temperature change during the cooling process to simulate dry storage conditions. The parameters of the hydride re-orientation model were fitted to the test data. Fitting parameters were determined for (CWSR) Zircaloy-4 (Zr-4) and CWSR Zirlo{sup TM} respectively. The cooling rate effect was empirically accounted for in the model. General good agreement between model prediction and measured radial hydride content is achieved, with a standard error less than 12 ppm. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Characterization of zirconium carbide microspheres synthesized via internal gelation

Microspheres of zirconium carbide with grain size 40-320 nm were synthesized using internal gelation techniques and characterized by scanning electron microscopy, synchrotron X-ray diffraction, and neutron total scattering. Compared with a polycrystalline benchmark ZrC sample prepared by plasma vapor phase deposition, the microspheres display lower variance in grain size and considerably lower microstrain representative of a more homogenous internal microstructure. However, excess carbon was present in the microspheres, evident in both the X-ray and neutron diffraction data as well as a corresponding hypostoichiometric ZrC phase. Furthermore, the excess carbon phase is assumed to be pockets of carbon that remained unreacted through the combined internal gelation and subsequent carbothermic reduction synthesis process. Atomic-scale structural characterization with neutron PDF analysis confirmed the presence of localized nano-sized domains of graphite-like carbon material.

36 MATERIALS SCIENCE↗

Influence of hydride precipitation on the corrosion kinetics of Zircaloy-4: effect of the nano-structure and grain boundary properties of the zirconium oxide layer on oxygen diffusion flux - 2016-0073

Hydride precipitation at the oxide-metal interface is frequently proposed as causing the corrosion acceleration of Zircaloy-4 at high burnup in pressurized water reactors (PWRs). In order to identify the local mechanisms possibly involved, we studied the nano-structure of oxides formed on massive zirconium hydrides and reference Zircaloy-4 with an innovative grain mapping technique with the use of transmission electron microscopy (TEM). In autoclave PWR-conditions, the presence of a precipitated hydride phase, previously formed by a cathodic charging technique at the surface of Zircaloy-4, clearly increased the corrosion rate, and a higher oxygen diffusion flux along oxide grain boundaries is observed compared with the reference Zircaloy-4. The texture, grain size, and adjacent grain misorientation in the oxide layer were studied in detail along the direction of the oxide growth using an automated crystal orientation mapping technique associated with TEM for both pre-hydrided and reference Zircaloy-4 samples. The texture in the growth direction is similar on pre-hydrided and reference samples, but the grain-to-grain mis-orientations showed differences. Indeed, on the pre-hydrided sample, the misorientation of 90 deg. C with respect to the [001] monoclinic axis is less probable than in the reference oxide, and more mis-orientations of 50-70 deg. C and 120-150 deg. C, corresponding to larger mismatches between neighboring grain boundaries, are observed. A smaller average diameter of the columnar monoclinic grains is also clearly revealed for the oxide grown on the pre-hydrided sample that leads to a larger number of diffusion paths for oxidizing species. These results are discussed and used for simulating oxygen diffusion flux through the polycrystalline microstructure of the oxide layer as a function of the grain size. (authors)

36 MATERIALS SCIENCE↗

Physical and mechanical metallurgy of zirconium alloys for nuclear applications: a multi-scale computational study

In the post-Fukushima world, the stability of materials under extreme conditions is an important issue for the safety of nuclear reactors. Because the nuclear industry is going to continue using advanced zirconium cladding materials in the foreseeable future, it become critical to gain fundamental understanding of the several interconnected problems. First, what are the thermodynamic and kinetic factors affecting the oxidation and hydrogen pick-up by these materials at normal, off-normal conditions, and in long-term storage? Secondly, what protective coatings (if any) could be used in order to gain extremely valuable time at off-normal conditions, e.g., when temperature exceeds the critical value of 2200°F? Thirdly, the kinetics of oxidation of such protective coating or braiding needs to be quantified. Lastly, even if some degree of success is achieved along this path, it is absolutely critical to have automated inspection algorithms allowing identifying defects of cladding as soon as possible. This work strives to explore these interconnected factors from the most advanced computational perspective, utilizing such modern techniques as first-principles atomistic simulations, computational thermodynamics of materials, diffusion modeling, and the morphological algorithms of image processing for defect identification. Consequently, it consists of the four parts dealing with these four problem areas preceded by the introduction and formulation of the studied problems. In the 1st part an effort was made to employ computational thermodynamics and ab initio calculations to shed light upon the different stages of oxidation of ziraloys (2 and 4), the role of microstructure optimization in increasing their thermal stability, and the process of hydrogen pick-up, both in normal working conditions and in long-term storage. The 2nd part deals with the need to understand the influence and respective roles of the two different plasticity mechanisms in Zr nuclear alloys: twinning (at low T) and crystallographic slip (higher T’s). For that goal, a description of the advanced plasticity model is outlined featuring the non-associated flow rule in hcp materials including Zr. The 3rd part describes the kinetic theory of oxidation of the several materials considered to be perspective coating materials for Zr alloys: SiC and ZrSiO 4 . In the 4th part novel and advanced projectional algorithms for defect identification in zircaloy coatings are described. In so doing, the author capitalized on some 12 years of his applied industrial research in this area. Our conclusions and recommendations are presented in the 5th part of this work, along with the list of used literature and the scripts for atomistic, thermodynamic, kinetic, and morphological computations.

36 MATERIALS SCIENCE↗

Synthesis and structures of zirconium complexes [Et{sub 2}H{sub 2}N]{sup +}{sub 2}[ZrCl{sub 6}]{sup 2–}, [Me{sub 3}NCH{sub 2}Ph]{sup +}{sub 2}[ZrCl{sub 6}]{sup 2–}•MeCN, [Ph{sub 3}PC{sub 6}H{sub 4}(CHPh{sub 2}-4)]{sup +}{sub 2}[ZrCl{sub 6}]{sup 2–}•2 MeCN, and [Ph{sub 4}Sb]{sup +}{sub 2}[ZrCl{sub 6}]{sup 2–}

The complexes [Et{sub 2}H{sub 2}N]{sup +}{sub 2}[ZrCl{sub 6}]{sup 2–} (1), [Me{sub 3}NCH{sub 2}Ph]{sup +}{sub 2}[ZrCl{sub 6}]{sup 2–}•MeCN (2), [Ph{sub 3}PC{sub 6}H{sub 4}(CHPh{sub 2}-4)]{sup +}{sub 2}[ZrCl{sub 6}]{sup 2–}•2 MeCN (3), and [Ph{sub 4}Sb]{sup +}{sub 2}[ZrCl{sub 6}]{sup 2–} (4) were synthesized by the reaction of zirconium tetrachloride with tetraorganylammonium, -phosphonium, and -stibonium chlorides in acetonitrile and structurally characterized. The nitrogen, phosphorus, and antimony atoms in the cations have a distorted tetrahedral geometry. The Zr–Cl distances in the centrosymmetric octahedral [ZrCl{sub 6}]{sup 2−} anions of complexes 1–4 have similar values, the longest bonds being observed in the anion of complex 4. Acetonitrile molecules are involved in the structural organization of the crystals of complex 3via weak hydrogen bonding with phenyl hydrogen atoms of the organylphosphonium cations. In the crystal of 2, no hydrogen bonds between the cations and solvent molecules are observed; acetonitrile molecules fill the cavities formed by cations and anions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and Tribological Performance of Different Particle-Sized Nickel-Ion-Exchanged α-Zirconium Phosphates

Nickel-ion-exchanged α-zirconium phosphate (Ni-α-ZrP) was synthesized by a mild hydrothermal synthesis method. Different raw material ratios (NaF/H{sub 3}PO{sub 4}/Ni(CH{sub 3}COO){sub 2}·4H{sub 2}O) influence the particle size of the Ni-α-ZrP samples. The grain size could be controlled and distributed from 20 to 600 nm. Ni-α-ZrP was evaluated as an additive in lithium grease in a four-ball test. A 3.0 wt.% addition of Ni-α-ZrP to lithium grease yielded maximum non-seizure load values of 1235 N, and the wear scar diameter on the lower balls is 0.42 mm at 294 N. Compared with smaller particles, the addition of Ni-α-ZrP with a larger particle size to grease yields a better load-carrying capacity.

36 MATERIALS SCIENCE↗

Synthesis and hydration behavior of calcium zirconium aluminate (Ca{sub 7}ZrAl{sub 6}O{sub 18}) cement

Calcium zirconium aluminate (Ca{sub 7}ZrAl{sub 6}O{sub 18}) cements were prepared by solid state reaction and polymeric precursor methods, and their phase evolution, morphology, and hydration behavior were investigated. In polymeric precursor method, a nearly single phase Ca{sub 7}ZrAl{sub 6}O{sub 18} was obtained at relatively lower temperature (1200 °C) whereas in solid state reaction, a small amount of CaZrO{sub 3} coexisted with Ca{sub 7}ZrAl{sub 6}O{sub 18} even at higher temperature (1400 °C). Unexpectedly, Ca{sub 7}ZrAl{sub 6}O{sub 18} synthesized by polymeric precursor process was the large-sized and rough-shaped powder. The planetary ball milling was employed to control the particle size and shape. The hydration behavior of Ca{sub 7}ZrAl{sub 6}O{sub 18} was similar to that of Ca{sub 3}Al{sub 2}O{sub 6} (C3A), but the hydration products were Ca{sub 3}Al{sub 2}O{sub 6}·6H{sub 2}O (C3AH6) and several intermediate products. Thus, Zr (or ZrO{sub 2}) stabilized the intermediate hydration products of C3A.

36 MATERIALS SCIENCE↗

Deposition and characterization of zirconium nitride (ZrN) thin films by reactive magnetron sputtering with linear gas ion source and bias voltage

Zirconium nitride thin films have been prepared on stainless steel substrate (304L grade) by reactive cylindrical magnetron sputtering method with Gas Ion Source (GIS) and bias voltage using optimized coating parameters. The structure and surface morphologies of the ZrN films were characterized using X-ray diffraction, atomic microscopy and scanning electron microscopy. The adhesion property of ZrN thin film has been increased due to the GIS. The coating exhibits better adhesion strength up to 10 N whereas the ZrN thin film with bias voltage exhibits adhesion up to 500 mN.

36 MATERIALS SCIENCE↗

FP-LAPW investigation of electronic, magnetic, elastic and thermal properties of Fe-doped zirconium nitride

Full Potential- Linear Augmented Plane Wave (FP-LAPW) method has been employed to study the electronic, magnetic, elastic and thermal properties of Fe-doped Zirconium nitride. In this work, Fe-atoms were doped into the super cell of ZrN in doping concentrations of 12.5%, 25% and 37.5% to replace Zr atoms. Electronic properties such as band structure and DOS were plotted and compared for the doped compounds. Charge density contours were plotted for all the doped compounds. The non-magnetic ZrN doped in different Fe concentrations were found to be ferromagnetic. Magnetic moments have been calculated and compared. Elastic properties have been studied and compared with electronic properties. Appearance of magnetic ordering and its influence with the elastic properties have been reported. Impact of 3d states of Fe in DOS plot on the elastic nature of the compounds has been highlighted. Thermal properties such as Debye temperature and molar heat capacities at low temperature have been determined. Debye temperature is found to decrease with higher doping concentrations. Molar heat capacities are found to increase with higher concentrations of Fe atoms.

36 MATERIALS SCIENCE↗

The temperature-dependent diffusion coefficient of helium in zirconium carbide studied with first-principles calculations

The temperature-dependent diffusion coefficient of interstitial helium in zirconium carbide (ZrC) matrix is calculated based on the transition state theory. The microscopic parameters in the activation energy and prefactor are obtained from first-principles total energy and phonon frequency calculations including the all atoms. The obtained activation energy is 0.78 eV, consistent with experimental value. Besides, we evaluated the influence of C and Zr vacancies as the perturbation on helium diffusion, and found the C vacancy seems to confine the mobility of helium and the Zr vacancy promotes helium diffusion in some extent. These results provide a good reference to understand the behavior of helium in ZrC matrix.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Silicidation of Tantalum Carbide and Zirconium Carbide Powders in a Gaseous SiO Environment

Tantalum carbide and zirconium carbide powders have been silicided in a gaseous SiO atmosphere at 1400°C. X-ray diffraction and energy dispersive X-ray microanalysis results demonstrate that the silicidation products are Ta{sub 5}Si{sub 3} and TaSi{sub 2} in the case of TaC and ZrSi in the case of ZrC. The silicidation rate has been shown to influence the percentages of these silicides in the reaction products. The degree of silicidation reached in this study is about 20% in the case of TaC and about 16% in the case of ZrC.

36 MATERIALS SCIENCE↗

Study of the synthesis of nanocrystalline mixed tantalum–zirconium carbide

The synthesis conditions of refractory tantalum–zirconium carbide Ta{sub 0.8}Zr{sub 0.2}C on the basis of Ta{sub 2}O{sub 5}–ZrO{sub 2}–C ultrafine initial blend prepared via the sol–gel method are explored. The initial blend is prepared via hydrolysis in the presence of Ta(OC{sub 5}H{sub 11}){sub 5} and [Zr(O{sub 2}C{sub 5}H{sub 7}){sub 4–x}(OC{sub 5}H{sub 11}){sub x}] carbon source polymer solutions, gel drying, and carbonization at a temperature of 450°C. A series of the carbothermal synthesis experiments is implemented at various temperatures and exposure times. The synthesis conditions are shown to affect not only the phase composition of products but also their oxidation resistance related to the particle size.

36 MATERIALS SCIENCE↗

Numerical comparison of hydrogen desorption behaviors of metal hydride beds based on uranium and on zirconium-cobalt

In this paper, the hydrogen delivery capabilities of uranium (U) and zirconium-cobalt (ZrCo) are compared quantitatively in order to find the optimum getter materials for tritium storage. A three-dimensional hydrogen desorption model is applied to two identically designed cylindrical beds with the different materials, and hydrogen desorption simulations are then conducted. The simulation results show superior hydrogen delivery performance and easier thermal management capability for the U bed. This detailed analysis of the hydrogen desorption behaviors of beds with U and ZrCo will help to identify the optimal bed material, bed design, and operating conditions for the storage and delivery system in ITER. (authors)

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Transmission electron microscopy examinations of metal-oxide interface of zirconium-based alloys irradiated in Halden reactor-IFA-638 - 2016-0039

This paper provides the results of investigations by transmission electron microscopy (TEM) on the selected materials from in-reactor oxidation tests in the Halden test reactor (Reference No. IFA-638) from 1998 to 2006. The objective of the IFA-638 test was to study the corrosion behavior of modern zirconium-based claddings to high burnup in pressurized water reactor water chemistry and thermal hydraulic conditions. The aim of this paper is to report on the microstructure of selected materials (ZIRLO{sup R}, E635, and Alloy A) after the irradiation to different burnup levels to determine the modifications induced by irradiation and to correlate results to their oxidation behavior. The TEM examinations revealed the nature of secondary phase particles (SPPs) and their modification under irradiation. Four types of SPPs were observed, namely β-niobium precipitates, Zr{sub 0.5}Nb{sub 0.3}Fe{sub 0.2} (mainly in the ZIRLO alloy), Zr(Fe,Nb){sub 2} (in E635), and (Cr,Fe){sub 2}Zr,Nb with varying niobium content (present in Alloy A: Zr-0.58Sn-0.31Nb-0.36Fe-0.26Cr). TEM observations showed that all three materials contained still several precipitates after irradiation and in the case of the ZIRLO alloy even after high burnups. Furthermore, the analysis of the metal side of the interface and its comparison with the oxide side led to the conclusion that all types of precipitates dissolved to some extent under irradiation and that their alloying element content decreased. The dissolution was intensified in the oxide. However, a more detailed examination showed that the β-niobium precipitates dissolved at a slower rate, or knowing that their composition was much richer in niobium, the time needed for the precipitates to become fully depleted from niobium was longer. Regarding the amorphization under irradiation, the b-niobium- and chromium-containing precipitates did not amorphize in the metal part of the interface. This was not the case for the other types of precipitates. Furthermore, these two types of SPP both showed delayed oxidation and due to this behavior the typical crack above the SPP in the oxide was also observed. These results are discussed to gain an improved understanding of the oxidation behavior of materials studied as a function of irradiation and residence time. (authors)

36 MATERIALS SCIENCE↗

Understanding corrosion and hydrogen pickup of zirconium fuel cladding alloys: The role of oxide microstructure, porosity, sub-oxides, and second-phase particles - 2016-0071

We used a range of advanced microscopy techniques to study the microstructure, nanoscale chemistry, and porosity in zirconium alloys at different stages of oxidation. Samples from both autoclave and in-reactor conditions were available, including ZIRLO{sup TM}, Zr-1.0Nb, and Zr-2.5Nb samples with different heat treatments. Scanning transmission electron microscopy (STEM), transmission Kikuchi diffraction (TKD), and automated crystal orientation mapping with TEM were used to study the grain structure and phase distribution. Significant differences in grain morphology were observed between samples oxidized in the autoclave and in-reactor, with shorter, less well-aligned monoclinic grains and more tetragonal grains in the neutron-irradiated samples. A combination of energy-dispersive X-ray mapping in STEM and atom probe tomography analysis of second-phase particles (SPPs) can reveal the main and minor element distributions respectively. Neutron irradiation seems to have little effect on promoting fast oxidation or dissolution of β-niobium precipitates but encourages the dissolution of iron from Laves-phase precipitates. An electron energy-loss spectroscopy (EELS) analysis of the oxidation state of niobium in β-niobium SPPs in the oxide revealed the fully oxidized Nb{sup 5+} state in SPPs deep into the oxide but Nb{sup 2+} in crystalline SPPs near the metal-oxide interface. EELS analysis and automated crystal orientation mapping with TEM revealed Widmanstatten-type suboxide layers in some samples with the hexagonal ZrO structure predicted by ab initio modeling. The combined thickness of the ZrO suboxide and oxygen-saturated layers at the metal-oxide interface correlated well to the instantaneous oxidation rate, suggesting that this oxygen-rich zone is part of the protective oxide that is rate limiting in the transport processes involved in oxidation. Porosity in the oxide had a major influence on the overall rate of oxidation, and there was more porosity in the rapidly oxidizing annealed Zr-1.0Nb alloy than in either the recrystallized alloy or the similar alloy exposed to neutron irradiation. (authors)

36 MATERIALS SCIENCE↗

Mechanistic understanding of zirconium alloy fuel cladding Performance - 2016-0095

A review is presented of work performed in our group over the years in the areas of radiation damage, corrosion, hydrogen pickup, hydriding, and the mechanical behavior of zirconium alloy nuclear fuel cladding with the goal of developing a greater mechanistic understanding of cladding performance in service. (authors)

36 MATERIALS SCIENCE↗