Microstructural evolution of zirconium alloy under dynamic compression at strain rate of 1000s^(-1)

Microstructural evolution of the zirconium alloy deformed at a strain rate of about 1000 s-1 was investigated. Four different strain levels of the zirconium alloy subjected to dynamic compression were designed by several-times impacting at almost the same strain rate. The results show that abundant low angle boundaries at different strain levels were observed in the deformed microstructures, and the quantity and density of low angle boundary increase dramatically with the strain increasing. Besides low angle boundaries and high angle boundaries observed in grain boundary maps, the twin boundaries including the tensile twins {10 2}, {11 1} and compressive twins {11 2} were distinguished at different strain levels, and most twin boundaries were indexed as {10 2} twins. With the stain increasing, the twin boundary density in the deformed microstructures increases indistinctively. Based on the characterization of the deformed microstructures at the different strain levels, the deformation and evolution processes of the zirconium alloy subjected to dynamic loading were proposed. Microhardness measurements show that the microhardness in the impacted specimens increases gradually with the strain increasing, which should be associated with the strain hardening caused by the tangled dislocation.

EFFECT OF MELT OVER-HEATING AND ZIRCONIUM ALLOYING ON THE MORPHOLOGY OF Al_9FeNi PHASE AND MECHANICAL PROPERTIES OF 2618 ALLOY

The effect of melt over-heating on the morphology of Al_9FeNi phase in 2618aluminum alloy with high contents of Fe and Ni and 0.22 wt. percent zirconium has been investigatedby optical microscopy. SEM and TEM. The mechanical properties of 2618 aluminum alloy after hotextrusion and quenching/aging have been tested. The results show: melt over-heating treatment of2618 alloy with high contents of Fe and Ni at 960 deg C led to finer and better-distributedneedle-like Al_9FeNi phase in cast microstructure and fine Al_9FeNi particles after hot extrusion;the grain size of the alloy after hot extrusion could also be refined evidently by alloying ofzirconium; the ambient and high temperature tensile strength and elongation of 2618 alloy have beenapparently enhanced due to fine Al_9FeNi particles and dispersed Al_3Zr as well as fine grain size.

Effects of annealing treatments on forming performance of zirconium alloys

The effects of annealing treatments(ATs)on the microstructure of Zr-Sn-Nb alloy strips were studied.Based on the characteristics of strips for nuclear fuel assemblies,punching experiments were carried out and the formability of zirconium alloy strips was quantitatively evaluated.The results indicate that the proportions of small-angle grain boundaries of the zirconium alloy under conditions of annealing treatment at 580°C(ATⅠ)and annealing treatment at 620°C(ATⅡ)are 14.3%and 23.2%,respectively,while that of the as-received material is 12.4%.And the forming limit margin fields of the zirconium alloy under ATⅠcan reach 0.43%,while the values of the as-received material and the ATⅡare-0.35%and-2.8%,respectively.The annealing process affects the evolution process of the strip recrystallization texture and the grain size.Moreover,the total texture and pole density are closely related to the degree of anisotropy of the strip.Besides,the small-angle grain boundary affects the strain path and crack expansion of the necking unit during the strip punching process,while the grain size affects the hardening exponent of the material.

Interfacial reaction between zirconium alloy and graphite mold/yttrium oxide ceramic mold

Zirconium alloys are active in the molten state and tend to react with the mold during casting. The casting technology of zirconium is not yet well established; especially in selecting the mold materials, which are difficult to determine. In the present work, the interfacial reactions between zirconium casting and casting mold were studied. The zirconium alloy was melted in a vacuum arc skull furnace and then cast into the graphite mold and ceramic mold, respectively. The zirconium casting samples were characterized using SEM, EDS and XRD with an emphasis on the chemical diffusion of elements. A reaction layer was observed at the casting surface. Chemical analysis shows that chemical elements C, O and Y from the mold are diffused into the molten zirconium, and new phases, such as ZrC, Zr30, YO1.335 and Y6ZrO11, are formed at the surface. In addition, an end product of zirconium valve cast in a yttria mold has a compact structure and good surface quality.

Relations of Microstructural Attributes and Strength-Ductility of Zirconium Alloys with Hydrides

As the first safety barrier of nuclear reactors,zirconium alloy cladding tubes have attracted extensive attention because of its good mechanical properties.The strength and ductility of zirconium alloy are of great significance to the service process of cladding tubes,while brittle hydrides precipitate and thus deteriorate the overall performance.Based on the cohesive finite element method,the effects of cohesive strength,interfacial characteristics,and hydrides geometric characteristics on the strength and ductility of two-phase material(zirconium alloy with hydrides)are numerically simulated.The results show that the fracture behavior is significantly affected by the cohesive strength and that the overall strength and ductility are sensitive to the cohesive strength of the zirconium alloy.Furthermore,the interface is revealed to have prominent effects on the overall fracture behavior.When the cohesive strength and fracture energy of the interface are higher than those of the hydride phase,fracture initiates in the hydrides,which is consistent with the experimental phenomena.In addition,it is found that the number density and arrangement of hydrides play important roles in the overall strength and ductility.Our simulation provides theoretical support for the performance analysis of hydrogenated zirconium alloys during nuclear reactor operation.

OUT-OF-PILE CORROSION RESISTANCE OF NEW ZIRCONIUM ALLOYS IN 500 ℃/10 3MPa STEAM

he out of pile corrosion resistance of new Zirconium alloys in 500℃/10 3MPa steam has been investigated and the effect of alloying elements, Sn,Nb,Fe,Cr on the property has been analyzed. The results show that the new alloys have better corrosion resistance than Zircaloy 4. That no nodular corrosion is found during test cycles shows the nodular corrosion resistance can be dramatically improved by addition of alloying elements Nb. The Fe/Cr ratio should be properly controlled if there is Cr addition in the alloys when developing new alloys.

Creep-induced redistribution of alloying elements in CZ1 zirconium alloys

Introducing minor alloying elements is an effective strategy to improve the corrosion and mechanical properties of zirconium alloys for nuclear applications.During in-reactor service,external environment and stress can affect the distribution of alloying elements,substantially changing the degradation process of zirconium alloys.To date,there is a lack of in-depth understanding of the interaction between creep and microchemistry changes.Here,we conducted systematic transmission electron microscopy(TEM)and atom probe tomography(APT)investigations to address creep-induced redistribution of alloying elements in CZ1(Zr-Sn-Nb-Fe-Cr-Cu)zirconium alloy with different initial microstructures.Nb,Fe,Sn,and Cu are found to co-segregate at grain boundaries.The higher the intermediate annealing temperature,the larger the Gibbsian interfacial excesses of solute elements are.We further demonstrate that creep can reduce the excess value of Fe at grain boundaries due to the coarsening of Zr-Fe-Cr second phase particles via grain boundary and dislocation pipe diffusion.At the same time,the excess value of Sn is increased by diffusing from the matrix to grain boundaries.Moreover,Cu as a minor element in the concentration range of 0.05-0.3 wt.%is found to segregate at dislocations to form the Cottrell atmosphere and develop Cu-rich nanoclusters for suppressing dislocation motion.The new understanding of the segregation and clustering of minor alloying elements provides guidance for developing zirconium alloys with enhanced creep resistance.

Optimization of N18 Zirconium Alloy for Fuel Cladding of Water Reactors

In order to optimize the microstructure and composition of N18 zirconium alloy （Zr-1Sn-0.35Nb-0.35Fe-0.1Cr, in mass fraction, %）, which was developed in China in 1990s, the effect of microstructure and composition variation on the corrosion resistance of the N18 alloy has been investigated. The autoclave corrosion tests were carried out in super heated steam at 400 ~C/10.3 MPa, in deionized water or lithiated water with 0.01 mol/L LiOH at 360 ~C/18.6 MPa. The exposure time lasted for 300-550 days according to the test temperature. The results show that the microstructure with a fine and uniform distribution of second phase particles （SPPs）, and the decrease of Sn content from 1% （in mass fraction, the same as follows） to 0.8% are of benefit to improving the corrosion resistance; It is detrimental to the corrosion resistance if no Cr addition. The addition of Nb content with upper limit （0.35%） is beneficial to improving the corrosion resistance. The addition of Cu less than 0.1% shows no remarkable influence upon the corrosion resistance for N18 alloy. Comparing the corrosion resistance of the optimized N18 with other commercial zirconium alloys, such as Zircaloy-4, ZIRLO, E635 and Ell0, the former shows superior corrosion resistance in all autoclave testing conditions mentioned above. Although the data of the corrosion resistance as fuel cladding for high burn-up has not been obtained yet, it is believed that the optimized N18 alloy is promising for the candidate of fuel cladding materials as high burn-up fuel assemblies. Based on the theory that the microstructural evolution of oxide layer during corrosion process will affect the corrosion resistance of zirconium alloys, the improvement of corrosion resistance of the N18 alloy by obtaining the microstructure with nano-size and uniform distribution of SPPs, and by decreasing the content of Sn and maintaining the content of Cr is discussed.

Improvement of multi-functional properties by fabricating micro-pillar arrays structures on zirconium alloy surface

Although using the microstructure of a surface to enhance specific functions has immense applicability in numerous fields,few studies have been conducted on the multi-functional properties of nuclear fuel elements in harsh environments.In this study,surfaces with zirconium alloy micro-pillar arrays were prepared using micro-milling and ultraviolet nanosecond laser technology,and their functional properties such as the wettability,structural stability,and corrosion resistance were investigated.It was found that the geometric dimension of the micro-pillar arrays prepared using these two methods could meet the design requirements,but the micro-milling process had the best dimensional accuracy.Micro-nano multi-scale structures were obtained by laser ablation.However,these multi-scale structures exhibited weak structural stability,and the nanostructures were easily corroded.By contrast,the micro-pillar arrays manufactured using micro-milling were confirmed to have better structural stability and corrosion resistance.On one hand,the area mass loss of the micro-milled structure was lower than that of a flat surface after experiencing high-pressure fluid scouring at 8 and 38 m/s.On the other hand,the oxidation weight gain of the surface with the micro-milled structure was lower than that of a flat surface,and the oxide film was 22.5% thinner after 100 days of deionized water corrosion at 360℃ and 18.7 MPa.

The Influence of Different Contents of Bi Addition on the Corrosion Behavior of Various Zirconium-Based Alloys

Zr-4(Zr-1.5Sn-0.2Fe-0.1Cr,wt%), S5(Zr-0.8Sn-0.34Nb-0.39Fe-0.1Cr), T5(Zr-0.7Sn-1.07Nb-0.32Fe-0.08Cr) and Zr-1Nb were adopted to prepare Bi-containing zirconium alloys for systematically investigating the effect of Bi addition on the corrosion resistance of zirconium alloys. The specimens were corroded in superheated steam at 400℃/10.3 MPa, and in lithiated water with 0.01 M LiOH or in deionized water at 360℃/18.6 MPa by autoclave testing. Results show that the corrosion resistance increases with the increasing of Bi content dissolved in α-Zr. But the presence of Bi-con- taining second phase particles (SPPs) is unfavorable for the enhancement of corrosion resistance. This indicates that the Bi dissolved in α-Zr matrix plays an important role in improving the corrosion resistance, while the precipitation of the Bi-containing SPPs does harm to the corrosion resistance.

Oxide formation mechanism of a corrosion-resistant CZ1 zirconium alloy

Tailoring microstructure and microchemistry by altering elemental compositions and thermomechanical treatment parameters enables superior corrosion performance in zirconium alloys for nuclear applications.However,our understanding of the relationship between various defects and the corrosion process remains limited in the newly developed zirconium alloys.Here we report the oxide formation mechanism of a CZ1 zirconium alloy with corrosion resistance surpassing many other zirconium alloy systems,such as Zircaloy-4 and Zr-1Nb-1Sn alloys.Autoclave experiments of CZ1 alloy and Zr1Nb-1Sn model alloy were performed in 360°C water for up to 820 d.We quantitively determined oxide phases by transmission Kikuchi diffraction(TKD)and examined lateral cracks,nano-porosity,and second-phase particles in oxide scales by transmission electron microscopy(TEM).Compared to the Zr-1Nb-1Sn model alloy,CZ1 alloy with lower Nb and Sn concentrations has shown smaller and lower-density lateral cracks but slightly larger oxide grains,reducing the diffusion route for oxidating species.Using analytical scanning and transmission electron microscopy,we demonstrate that due to the lower content of Sn(∼0.9 wt.%),there is less tetragonal ZrO_(2) phase formed in the oxide,and the level of tetragonal to the monoclinic phase transition is reduced.Although the Nb content(0.1 wt.%–0.3 wt.%)is lower than the solid solution limit of Nb in Zr,by introducing minor elements such as Fe,Cr,and Cu,there are still a reasonable number of second-phase particles to relieve the high stress associated with the metal-to-oxide transformation.These mechanisms have substantially changed the density and distribution of lateral cracks in the oxide,thus reducing the corrosion rate of zirconium alloys.

Effect of Normal Force on Fretting Wear Behavior of Zirconium Alloy Tube in Simulated Primary Water of PWR

The effect of normal force on fretting wear behavior of zirconium alloy tube mated with grid dimple in simulated primary water of pressurized water reactor nuclear power plant was investigated.Results showed that the maximum wear depth,wear volume and wear coefficient of Zr alloy tube in simulated primary water at 315℃ gradually increased with increasing normal force,while the friction coefficient gradually decreased.Fretting process could be divided into four stages according to the variation of friction coefficient during test.When normal force exceeds 30 N,the fretting regime would transition from gross slip regime to partial slip regime after 3×10^(7 )cycles.Delamination was aggravated with increasing normal force,while abrasive wear became slighter.A thicker third-body layer with monoclinic ZrO_(2) was formed by the tribo-sintering mechanism under higher normal force.In addition,the schematic evolution processes of delamination and third-body layer formation were displayed according to morphology observation.

Microstructure of Bi-containing zirconium alloys

The effect of Bi addition(0.05 wt%-0.50 wt%)on the microstructure of zirconium alloys,including T5(Zr-0.7 S n-1.0 Nb-0.3 Fe-0.1 Cr),S5(Zr-0.8 Sn-0.35 Nb-0.4 Fe-0.1 Cr),Zr-4(Zr-1.5 Sn-0.2 Fe-0.1 Cr) and Zr-1 Nb,was investigated by transmission electron microscopy(TEM),energy-dispersive spectroscopy(EDS) and selected area electron diffraction(SAED).Results show that with the increase in Bi content,h-Zr(Fe,Cr,Nb)2,o-Zr(Fe,Sn,Bi)_(2) and Zr-Fe-Cr-Nb-Sn-Bi second-phase particles(SPPs) precipitate successively in the T5+xBi and S5+xBi alloys;in the Zr-4+xBi alloys,h-Zr(Fe,Cr)2,o-Zr(Fe,Sn,Bi)2,Zr-Fe-Cr-Sn-Bi and Zr-Fe-Cr-Bi SPPs are detected successively.While as for Zr-1 Nb+xBi alloys,Bi-free SPPs appear.The addition of Bi promotes the precipitation of SPPs with Sn in the alloys.The concentration of Bi dissolved in α-Zr matrix increases with the decrease in Sn content in the alloys.Adding reasonable Bi has little influence on the solid solution content of Nb in α-Zr matrix.

Effect of Different Laser Energy Nitriding on the Fretting Wear Performance of Zr Alloy

The zirconium(Zr)alloy fuel cladding is one of the key structural components of a nuclear reactor and the first and most important line of defense for accommodating fission products.During the operation of nuclear reactors,Zr alloy fuel cladding is subjected to extreme harsh environments,such as high temperature,high pressure and high flow rate for a long period of time.The wear and corrosion resistance of Zr alloys is important for the safe operation of nuclear reactors.Surface modification can effectively improve the corrosion and wear resistance of fuel cladding.Compared with coating technology,nitriding technology does not have problems for bonding between the coating and the substrate.Current research on surface nitriding of Zr alloys mainly focuses on plasma nitriding and ion implantation techniques.Research on laser nitriding of Zr alloy surfaces and their fretting wear characteristics is scarce.In this study,the surface of Zr alloy was treated with laser nitriding at different laser energies.The microstructure of Zr alloy treated with different laser energies and its fretting wear performance were studied.The results showed that after nitriding with different laser energies,the surface of the Zr alloy showed a typical molten state after melting,vaporizing and cooling under the thermal effect of the laser,and this state was more obvious with the increase of the laser energy.At the same time,doping of N atoms and formation of the ZrN phase led to different cooling rates in the molten zone that produced large tensile stresses after cooling.This led to cracks on the surface of Zr alloys after laser nitriding at different energies,and the crack density increased with increasing laser energy.This also led to an increase in the surface roughness of the Zr alloy with increasing laser energy after laser nitriding treatment.Due to the presence of water in the industrial nitrogen,nitrides were generated on the surface of the sample along with some oxides.When the laser energy was 100 mJ,there was no ZrN generation,and N existed mainly as a diffusion layer within the Zr alloy substrate.ZrN generated when the laser energy reached 200 mJ and above,which increased with the increase of laser energy.Due to the generation of ZrN phase and the presence of some oxides,the surface Vickers hardness of Zr alloys after laser nitriding treatment at different energies increased by 37.5%compared to Zr alloys.After laser nitriding treatment,the wear mechanism of Zr alloys changed.For the untreated Zr alloys,the wear mechanism was dominated by delamination and spalling wear,accompanied by oxidative and abrasive wear.The phenomenon of delamination and peeling decreased with the increase of laser energy.Wear mechanisms changed to predominantly abrasive wear with oxidative wear and delamination spalling.The wear volume of sample nitriding with laser energy 400 mJ was reduced by 46.5%compared with that of untreated Zr alloy.

Plasma electrolytic oxidation of zircaloy-4 alloy with DC regime and properties of coatings

The plasma electrolytic oxidation（PEO） coatings on zircaloy？4 alloy were prepared in silicate,phosphate and pyrophosphate electrolyte systems or their combination by DC current regime.The proper processing parameters were determined and the coatings were evaluated by electrochemistry technique,micro-hardness,SEM and XRD.The results show that the coating prepared in pure silicate system is uneven and after the addition of phosphate solution,the homogeneity of the coating is still poor.The coating prepared in pure pyrophosphate electrolyte system is homogeneous,but its hardness value is low.After the addition of silicate into the pyrophosphate electrolytic system,both the uniformity and hardness of the coating are improved.The XRD results show that the phase compositions are m-ZrO2 and t-ZrO2,the addition of silicate is beneficial to the formation of t-ZrO2.The results of polarization curves show that the coatings prepared in pyrophosphate and the mixture of pyrophosphate and silicate have better corrosion resistance.

Microstructure evolution and recrystallization behavior of cold-rolled Zr-1Sn-0.3Nb-0.3Fe-0.1Cr alloy during annealing

The effects of cold-rolling reduction,annealing temperature,and time on recrystallization behavior and kinetics of cold-rolled Zr-1Sn-0.3Nb-0.3Fe-0.1Cr alloy were investigated using the Vickers hardness test,scanning electronic microscopy(SEM),transmission electron microscopy(TEM)and electron backscatter diffractometry(EBSD).The results show that the rate of the recrystallization increased with increasing annealing temperature and rolling reduction.Recrystallized grains nucleated preferentially at sites with high density dislocation and deformation stored energy and then grew into integral grains.Recrystallization texture changed from-1010-//RD to-1120-//RD.The grain orientation changed from random orientation to the orientation with the maximum misorientation around 30°.Recrystallization kinetics and maps were constructed based on the Johnson-Mehl-Avrami-Kolmogorov(JMAK)equation to derive parameters sensitive to the microstructure.The activation energies for recrystallization of 30%,50%and 70%cold-rolling reductions were determined to be 240,249 and 180 kJ/mol,respectively.

Effect of dissolved oxygen on corrosion behavior of Zr-0.85Sn-0.16Nb-0.37Fe-0.18Cr alloy in 500℃ and 10.3 MPa super-heated steam

To better understand the role of dissolved oxygen(DO) in affecting corrosion behavior of zirconium alloys,the Zr-0.85 Sn-0.16 Nb-0.37 Fe-0.18 Cr(wt.%) alloy was corroded in super-heated steam at 500℃ and 10.3 MPa under 1×10-6 DO and deaeration conditions.The microstructure of the alloy and oxide films was investigated by SEM,TEM,EDS and EBSD.Results show that the corrosion is aggravated under 1×10-6 DO.Compared with the deaeration condition,the oxide film is looser,and has more micro-cracks and more uneven inner surface under DO condition.For the oxide film forming under deaeration condition,the selected area diffraction(SAED) spots of planes(002)m,■ and(101)t are strong,while those of the(001)m and■ are weak.However,for the oxide film forming under DO condition,the SAED spots of planes(111)m,(200)m and(101)t are strong,while those of the(100)m and(110)m are weak.The higher DO content in super-heated steam accelerates the growth of oxide films,thus decreasing the corrosion resistance of zirconium alloys.

Corrosion behavior of Zr–Nb–Cr cladding alloys

Zr-Nb-Cr alloys were used to evaluate the effects of alloying elements Nb and Cr on corrosion behavior of zirconium alloys. The microstructures of both Zr substrates and oxide films formed on zirconium alloys were characterized. Corrosion tests reveal that the corro- sion resistance of ZrxNb0.1Cr （x = 0.2, 0.5, 0.8, 1.1; wt%） alloys is first improved and then decreased with the increase of the Nb content. The best corrosion resistance can be obtained when the Nb concentration in the Zr matrix is nearly at the equilibrium solution, which is closely responsible for the formation of columnar oxide grains with protective characteristics. The Cr addition degrades the corrosion resistance of the Zrl.lNb alloy, which is ascribed to Zr（Cr,Fe,Nb）2 precipitates with a much larger size than β-Nb.

Eutectic reaction and cored dendritic morphology in yttrium doped Zr-based amorphous alloys

The microalloying effect of yttrium on the crystallization behaviors of （Zr0.525Al0.10Ti0.05Cu0.179Ni0.146）100-xYx, and （Zr0.55Al0.15- Ni0.10Cu0.20）100-xYx （x=0, 0.4, and 1, thus the two alloy systems were denoted as Zr52.5, Zr52.5Y0.4, Zr52.5Y1, and Zr55, Zr55Y0.4, Zr55Y1, respectively） was studied. Transmission electron microscopy （TEM） results suggested that the crystalline phases were different in the two Zr-based alloys and with different yttrium contents. ZrNi-phase and Al3Zr5 phase precipitations can be well explained by the mechanisms of nucleation and growth. Al3Zr5 phase is mainly formed by a peritectic-like reaction, while ZrNi-phase by a eutectic reaction. The contents of elements Y, A1, and Ti may dominate the reaction types. The orientation relationship between Y203 particles and A13Zr5 phase is also discussed.

CREEP BEHAVIOR OF Zr-1.5Nb-0.4Sn-0.1Fe-0.1Cu ALLOY

Creep behavior of the Zr-1.5Nb-0.4Sn-0.1Fe-0.1Cu alloy sheet is investigated from 300℃ to 400℃ in the stress range from 50 MPa to 180 MPa along the rolling direction. The measured strain rates range from 8.8 × 10^-10 s^-1 to 4.7 × 10^-7 s^-1. The activation energies are estimated to assess the creep deformation mechanisms in this alloy. The strain rate is slightly different at low stress, while it shows a distinct difference at high stresses. Stress exponents of this alloy increase with increasing applied stress at all testing temperatures. It is concluded that the creep deformation of the Zr-1.5Nb-0.4Sn-0.1Fe-0. 1 Cu alloy is controlled by the diffusion creep at low stress region and by the climbing of dislocations at high stress region.