Heat capacity of hydrogenated Zircaloy-2 and high Fe Zircaloy

Heat capacities (C_p) of non-hydrogenated and hydrogenated Zircaloy-2 and high Fe Zircaloy were measured in the temperature range from 350 to 873 K, using a differential scanning calorimeter. The hydrogen concentrations in the two types of alloys ranged from 26 to 1004 ppm. The C_p values of the as-received alloys with 26-29 ppm hydrogen were in good agreement with literature data for low hydrogen Zircaloys. From this finding and observation of almost the same enthalpy changes for hydride dissolution for both alloys, it was concluded that there was no difference in C_p values between the two types of hydrogenated Zircaloys. The dissolution enthalpy of hydrides calculated from C_p data was 41.0 kJ/g-atom H. For Zircaloy-2 samples with higher hydrogen concentrations than 700 ppm, the phase transition from α+δ to α+β was observed at the eutectoid temperature of 824-827 K. Two types of models describing an additional heat capacity due to the hydride dissolution were presented based on the present C_p data and previously derived terminal solid solubility of hydrogen.     

The influence of hydride blisters on the fracture of Zircaloy-4

The fracture behavior under near plane-strain deformation conditions of Zircaloy-4 sheet containing solid hydride blisters of various depths has been examined at 25 and 300 °C. The study was based on material with either model ‘blisters’ having diameters of 2 and 3 mm or a continuous layer of hydride; in all cases, the substrate material contained discrete hydride precipitates. The fracture strains decrease rapidly with increasing hydride blister/layer depth to levels of about 100 μm deep, and then remain roughly constant. For a given blister depth, the material is significantly more ductile at 300 °C than at room temperature although measurable ductility is retained even at 25 °C and for large blister depths. The material is somewhat more ductile if the hydride is in the form of a blister than in the form of a continuous layer (rim). The hydride blisters/layers are brittle at all temperatures, and crack shortly after yielding of the ductile substrate. Consequently, both experimental evidence and analytical modeling indicate that fracture of the sheet is controlled by the crack growth resistance of the substrate at 25 °C. At elevated temperatures, the hydride particles within the substrate are quite ductile, inhibit crack growth, and failure eventually occurs due to a shear instability.     

Dissolution and precipitation behavior of hydrides in Zircaloy-2 and high Fe Zircaloy

In order to elucidate the terminal solid solubility during the dissolution of hydrides at heatup (TSSD) and during the precipitation of hydrides at cooldown (TSSP) for hydrogenated Zircaloy-2 and high Fe Zircaloy, differential scanning calorimetry (DSC) measurements have been carried out in the temperature range of 50-600 °C. The hydrogen concentrations in the two kinds of alloys ranged from 40 to 542 ppm. There was no difference in either TSSD or TSSP solvi between Zircaloy-2 and high Fe Zircaloy, and best-fit equations were derived for the two curves. In the present TSSP data, two different activation energies, separating into high and low temperature ranges at 260 °C, were obtained. Based on the widths of the DSC peak obtained during cooldown, the average precipitation (nucleation plus growth) rates of zirconium hydrides from super-saturated state were assessed. The activation energy of the precipitation rate was approximately equivalent to reported values of hydrogen diffusion coefficients of Zr and Zircaloys.     

Characterization of hydrogen concentration in Zircaloy-4 using ultrasonic techniques

The relationship between hydrogen concentration precipitated as hydride particles and ultrasonic parameters, such as velocity and attenuation, was examined in Zircaloy-4 samples for potential applications in the Non-Destructive Test Field. Different amounts of hydrogen (up to 517 ppm) were introduced in the samples by gaseous charging. Ultrasonic attenuation measurements were performed with compressive waves at frequencies of 10 and 30 MHz, and propagation velocity measurements were performed at 10 MHz. Ultrasonic velocity showed an approximately linear increase with hydrogen concentration and it could be used as an assessment parameter when the hydrogen level is high enough. Attenuation versus hydrogen concentration has been fitted by a logarithmic equation at 10 MHz. At 30 MHz a fluctuating behavior of the attenuation prevented measurement of the hydrogen concentration.     

Effects of hydrogen content and temperature on fracture toughness of Zircaloy-4

The influence of hydrogen content and temperature on the fracture toughness of a Zircaloy-4 commercial alloy was studied in this work. Toughness was measured on CT specimens obtained from a rolled material. The analysis was performed in terms of J-integral resistance curves. The specimens were fatigue pre-cracked and hydrogen charged before testing them at different temperatures in the range of 293–473 K. A negative influence of the H content on material toughness was important even at very small concentrations, being partially restored when the test temperature increased. Except for some specimens with high H concentration tested at room temperature, the macroscopic fracture behaviour was ductile. The role of Zr-hydrides and Zr(Fe,Cr)₂ precipitates in the crack growth and the dependence with hydrogen content were analysed by observation of the fracture surfaces and determination of the Zr(Fe,Cr)₂ precipitates density on them.     

Delayed hydride cracking in Zr-2.5Nb tube with the cooling rate and the notch tip shape

The objective of this study is to demonstrate the feasibility of the Kim’s delayed hydride cracking (DHC) model. To this end, this study has investigated the velocity and incubation time of delayed hydride cracking (DHC) for the water-quenched and furnace-cooled Zr-2.5Nb tubes with a different radius of notch tip. DHC tests were carried out at constant K_I of 20 MPa √m on cantilever beam (CB) specimens subjected to furnace cooling or water quenching after electrolytic charging with hydrogen. An acoustic emission sensor was used to detect the incubation time taken before the start of DHC. The shape of the notch tip changed from fatigue cracks to smooth cracks with its tip radius ranging from 0.1 to 0.15 mm. The DHC incubation time increased remarkably with the increased radius of the notch tip, which appeared more strikingly on the furnace-cooled CB specimens than on the water-quenched ones. However, both furnace-cooled and water-quenched CB specimens indicated little change in DHC velocity with the radius of the notch tip unless their notch tip exceeded 0.125 mm. These results demonstrate that the nucleation rate of hydrides at the notch tip determines the incubation time and the DHC velocity becomes constant after the concentration of hydrogen at the notch tip reaches terminal solid solubility for dissolution (TSSD), which agrees well with the Kim’s DHC model. A difference in the incubation time and the DHC velocity between the furnace-cooled and water-quenched specimens is attributed to the nucleation rate of reoriented hydrides at the notch tip and the resulting concentration gradient of hydrogen between the notch tip and the bulk region.     

In situ crack growth observation and fracture toughness measurement of hydrogen charged Zircaloy-4

The effect of hydrogen on the fracture behaviour of a Zircaloy-4 alloy was analysed performing simultaneous fracture mechanics tests of small SE(B) specimens and in situ observation of crack initiation and propagation inside the chamber of a scanning electron microscope. Load and displacement were continuously measured and J_IC, J-R curves and CTOD determinations were obtained. Detailed images of the zone close to the crack tip were taken and the resistance to crack growth was correlated with hydrogen content and hydride morphology. The size and orientation of hydride precipitates showed an important influence on the fracture process. A good agreement with results obtained using standard CT specimens was met.     

Application of hydrogen analysis by neutron imaging plate method to Zircaloy cladding tubes

Effectiveness of neutron imaging plate (NIP) method for hydrogen analysis is investigated by using standard samples with known hydrogen concentrations. A relationship between hydrogen concentration in Zircaloy tubes and numerical data in the NIP images was obtained by image analysis process. By using the relationship, local hydrogen concentrations in segregated tubes with heterogeneous hydrogen distribution were estimated in a small area; 0.1 × 0.1 mm². Contribution of an oxide film in the tubes to the images is also investigated by using oxidized samples with and without hydrides. In the NIP images of the oxidized samples, oxide film was not recognized in the images of the sample. Results of numerical analysis also show no effect of the oxide film. These results show that the effect of oxygen in the image can be neglected when hydrogen analysis is performed on the Zircaloy tube with oxide film and hydrides by NIP method.     

Effect of radial hydrides on the axial and hoop mechanical properties of Zircaloy-4 cladding

The effect of radial hydrides on the mechanical properties of stress-relief annealed Zircaloy-4 cladding was studied. Specimens were firstly hydrided to different target hydrogen levels between 100 and 600 wt ppm and then thermally cycled in an autoclave under a constant hoop stress to form radial hydrides by a hydride reorientation process. The effect of radial hydrides on the axial properties of the cladding was insignificant. On the other hand, the cladding ductility measurements decreased as its radial hydride content increased when the specimen was tested in plane strain tension. A reference hydrogen concentration for radial hydrides in the cladding was defined for assessing the fuel cladding integrity based on a criterion of the tensile strength 600 MPa. The reference hydrogen concentration increased with the specimen (bulk) hydrogen concentration to a maximum of ∼90 wt ppm at the bulk concentration ∼300 wt ppm H and then decreased towards higher concentrations.     

Hydrogen absorption by Pd-coated ZrNi prepared by using Barrel-Sputtering System

To improve the durability of hydrogen storage materials against surface poisoning by impurity gases, effectiveness of Pd-coating layer prepared by using a Barrel-Sputtering System was examined for ZrNi powder. The effectiveness of Pd-coating was evaluated by activation temperature, at which Pd/ZrNi poisoned by air could be activated to absorb hydrogen. Characterization of Pd-coated ZrNi (denoted as Pd/ZrNi) by scanning electron microscopy, electron probe microanalysis and X-ray diffraction showed that a uniform Pd-coating layer was formed with the barrel-sputtering system. It was found that the poisoned Pd/ZrNi sample could be activated even at 423 K to absorb hydrogen at room temperature. This exhibits remarkable contrast to bare ZrNi, which could be only activated appreciably above 1073 K. It is concluded that the Pd-coating by barrel sputtering is quite effective to avoid the effect of surface poisoning of powdery hydrogen storage materials. However, the activation at excessively high temperature resulted in the loss of high activity to absorb hydrogen. It was concluded that this phenomenon was associated with reactions between Pd and ZrNi to form PdZr and other byproducts.     

Radionuclide release from high burnup spent fuel during corrosion in salt brine in the presence of hydrogen overpressure

In the case of a contact between groundwater and Fe-based spent fuel disposal containers in a repository large amounts of hydrogen will be produced by the corrosion of iron, which may result in significant hydrogen pressures. To quantify to what extent the hydrogen overpressure may counteract radiolysis enhanced matrix dissolution, related experimental work has been performed. High burnup spent fuel was corroded in 5.6 mol (kg H₂O)⁻¹ NaCl solution applying H₂ overpressures (experimental set 1) <0.17 bar by radiolysis, (experimental set 2) 2.8 bar by Fe corrosion, (experimental set 3) 3.2 bar by external H₂ gas. In the absence of Fe (experimental set 3) the UO₂ matrix dissolution rate decreased by a factor of about 10. In this test the concentrations of U, Np, Tc in solution were found to be decreasing by at least two orders of magnitude, and ranging within the same level as in the presence of Fe powder (experimental set 2). However, Pu and Am concentrations (experimental set 3) were less affected, due to the high sorption capacity for these radioelements onto Fe corrosion products.     

Characterization of hydrogen concentration in Zircaloy claddings using a low-frequency acoustic microscope with a PVDF/LFB transducer

Hydrogen embrittlement is one of the major mechanisms responsible for the degradation of ductility of Zircaloy cladding materials. Currently the characterization of hydrogen concentration (HC) very often relies on destructive methods that are time-consuming and costly. In this research, an ultrasound-based nondestructive evaluation (NDE) technique is reported for the determination of HC in Zircaloy claddings. This ultrasound-based NDE technique employs a low frequency acoustic microscope (AM) with a PVDF/LFB transducer and a Fourier-based signal processing technique. With this AM technique, a relation between the ultrasound wavespeed and the HC of Zircaloy is established. A resolution of HC measurements with the current technique is demonstrated to be better than 200 ppm. This NDE technique has been developed with an aim to have a better resolution and also to be potentially applied to poolside inspection.     

Mechanisms of stress relief cracking in titanium stabilised austenitic stainless steel

The heat affected zone (HAZ) of AISI 321 welds may exhibit a serious form of cracking during service at high temperature. This form of damage, called ‘stress relief cracking’, is known to be due to work hardening but also to aging due to Ti(C,N) precipitation on dislocations which modifies the mechanical behaviour of the HAZ. The present study aims to analyse the latter embrittlement mechanism in one specific heat of 321 stainless steel. To this end, different HAZs are simulated using an annealing heat-treatment, followed by various cold rolling and aging conditions. Then, we study the effects of work hardening and aging on Ti(C,N) precipitation, on the mechanical (hardness, tensile and creep) behaviour of the simulated HAZs and on their sensitivity to intergranular crack propagation through stress relaxation tests performed on pre-cracked CT type specimens tested at 600 °C. It is shown that work hardening is the main parameter of the involved mechanism but that aging does not promote crack initiation although it leads to titanium carbide precipitation. Therefore, the role of Ti(C,N) precipitation on stress relief cracking mechanisms is discussed. An attempt is made to show that solute drag effects are mainly responsible for this form of intergranular damage, rather than Ti(C,N) precipitation.     

The effect of alloying modifications on hydrogen uptake of zirconium-alloy welding specimens during corrosion tests

The hydrogen uptake behavior during corrosion tests for electron beam welding specimens made out of Zircaloy-4 and zirconium alloys with different compositions was investigated. Results showed that the hydrogen uptake in the specimens after corrosion tests increased with increasing Cr content in the molten zone. This indicated that Cr element significantly affected the hydrogen uptake behavior. Fe and Cr have a low solubility in α-Zr and exist mainly in the form of Zr(Fe,Cr)₂ precipitates, which is extremely reactive with hydrogen in its metallic state. It is concluded that the presence of Zr(Fe,Cr)₂ second phase particles (SPPs) is responsible for the increase in the amount of hydrogen uptake in the molten zone of the welding samples after corrosion, as Zr(Fe,Cr)₂ SPPs embedded in α-Zr matrix and exposed at the metal/oxide interface could act as a preferred path for hydrogen uptake.     

Trapping of radiolytic hydrogen by amorphous cobalt oxysulfide

Hydrogen production from the radiolysis of liquid and gaseous hydrocarbons was studied in the presence of several transition metal sulfides. Cobalt oxysulfide obtained by aqueous precipitation was the most efficient admixture to decrease radiolytic production of hydrogen by pure hydrocarbons or mixtures of saturated and unsaturated hydrocarbons. Cobalt oxysulfide was characterized by XRD, scanning and transmission microscopy, and IR spectroscopy. It seems to be amorphous compound with the impurities of lamellar Co(OH)₂ phase. The organic phases were analysed before and after irradiation by γ-rays or protons in order to elucidate the origin of the effect. It has been shown that the solid does not change the composition neither the amount of the organic radiolysis products, neither in liquid nor in gas phase experiments. Therefore the presence of solid does not influence any radiolysis processes in the organics. Amorphous cobalt oxysulfide acts essentially as a trap of hydrogen, being able to absorb considerable amounts of H₂ (up to 0.5 mol H₂/at. Co). The study of the solid-gas interaction showed that slow reaction of cobalt oxysulfide with hydrogen occurs at ambient conditions independently of the irradiation of the system.     

Failure behavior of Zircaloy-4 cladding after oxidation and water quench

Simulated LOCA (loss of coolant accident) tests and subsequent mechanical tests on Zircaloy-4 cladding were carried out to evaluate the failure behavior of the cladding. Zircaloy-4 claddings were oxidized in a steam environment from 900 to 1250 °C for a given time period followed by a flooding of cool water to simulate LOCA tests. After the simulated LOCA test, the ductility of the oxidized cladding was evaluated by mechanical tests such as ring compression test and 3-point bend test. Evaluation of the absorbed contents such as hydrogen and oxygen were also carried out. The results showed that Zircaloy-4 cladding failed during thermal shock when the ECR (equivalent cladding reacted) value exceeded 20%. Lower boundary of brittle failure at thermal shock corresponds to 20% of ECR line calculated by the Baker-Just equation regardless of test temperature. On the other hand, boundary of ductile failure by the mechanical test did not followed after the ECR line. It rapidly decreased above 1000 °C to show that all Zircaloy-4 claddings behaved brittle fracture above 1150 °C when it oxidized at 300 s. Microstructural analysis revealed that boundary of ductile failure by the mechanical test fitted well when the absorbed oxygen content inside the prior-β layer was below 0.5 wt%.     

Micro-engineered first wall tungsten armor for high average power laser fusion energy systems

The high average power laser program is developing an inertial fusion energy demonstration power reactor with a solid first wall chamber. The first wall (FW) will be subject to high energy density radiation and high doses of high energy helium implantation. Tungsten has been identified as the candidate material for a FW armor. The fundamental concern is long term thermo-mechanical survivability of the armor against the effects of high temperature pulsed operation and exfoliation due to the retention of implanted helium. Even if a solid tungsten armor coating would survive the high temperature cyclic operation with minimal failure, the high helium implantation and retention would result in unacceptable material loss rates. Micro-engineered materials, such as castellated structures, plasma sprayed nano-porous coatings and refractory foams are suggested as a first wall armor material to address these fundamental concerns. A micro-engineered FW armor would have to be designed with specific geometric features that tolerate high cyclic heating loads and recycle most of the implanted helium without any significant failure. Micro-engineered materials are briefly reviewed. In particular, plasma-sprayed nano-porous tungsten and tungsten foams are assessed for their potential to accommodate inertial fusion specific loads. Tests show that nano-porous plasma spray coatings can be manufactured with high permeability to helium gas, while retaining relatively high thermal conductivities. Tungsten foams where shown to be able to overcome thermo-mechanical loads by cell rotation and deformation. Helium implantation tests have shown, that pulsed implantation and heating releases significant levels of implanted helium. Helium implantation and release from tungsten was modeled using an expanded kinetic rate theory, to include the effects of pulsed implantations and thermal cycles. Although, significant challenges remain micro-engineered materials are shown to constitute potential candidate FW armor materials.     

Characterization and modeling of creep mechanisms in Zircaloy-4

The deformation microstructure and creep mechanisms of Zircaloy-4 have been investigated. Four Zircaloy-4 specimens were tested at different temperatures and stress levels and the deformation microstructures of these specimens were analyzed using transmission electron microscopy. On the basis of microstructural observation of a-type screw dislocations in prismatic slip systems, the modified jogged-screw model has been applied as a rate controlling mechanism for creep of Zircaloy-4. In addition, the stress dependency of dislocation density, jog spacing, and jog height has been evaluated via modeling and experimental observations. The purpose of this study is to provide a detailed understanding of the creep deformation of Zircaloy-4 and prediction of creep rates in this alloy based on the microstructural information obtained from TEM analysis.     

Comparative study and imaging by PhotoElectroChemical techniques of oxide films thermally grown on zirconium and Zircaloy-4

The oxidation of iron and chromium that are present as impurities in zirconium metal or as alloying elements in Zircaloy-4 was investigated with PhotoElectroChemical techniques (PEC), highlighting the chemical nature, the size and the lateral distribution of Fe and Cr-containing phases in thin zirconia scales formed during the oxidation of pure zirconium and Zircaloy-4 at 470 °C in oxygen. In the case of zirconium, iron and chromium impurities led to the formation of oxides distributed in a homogeneous way in the zirconia scale, while in the case of Zircaloy-4 these elements, present in the form of intermetallic particles in the substrate, led to the formation of localised haematite Fe₂O₃, rhomboedric solid solution (Fe_xCr_1−x)₂O₃ and chromia Cr₂O₃ phases. These phases were accurately studied via the measurement of their respective band-gap (Fe₂O₃: 2.2 eV, (Fe_xCr_1−x)₂O₃: 2.6 eV and Cr₂O₃: 3.0 eV). It is concluded that PEC techniques represent a sensitive and powerful way to locally analyse the various semiconductor phases in the oxide scale at a micron scale.