Several mechanism-related aspects of the corrosion of zirconium alloys have been investigated using different examination techniques. The microstructure of different types of oxide layers was analyzed by transmission electron microscopy (TEM). Uniform oxide mainly consists of m-ZrO2 and a smaller fraction of t-ZrO2 with columnar grains and some amount of equiaxed crystallites. Nodular oxides show a high open porosity and the grain shape tends to the equiaxed type. A fine network of pores along grain boundaries was found in oxides grown in water containing lithium. An enrichment of lithium within such oxides could be found by glow discharge optical spectroscopy (GD-OES) depth profiling. In all oxides, a compact, void-free oxide layer was observed at the metal/oxide interface. Compressive stresses within the oxide layer measured by an X-ray diffraction technique were significantly higher compared to previously published values. Electrical potential measurements on oxide scales showed the influence of the intermetallic precipitates on the potential drop across the oxide. In long-time corrosion tests of Zircaloy with varying temperatures, memory effects caused by the cyclic formation of barrier layers could be observed. It was concluded that the corrosion mechanism of zirconium-based alloys is a barrier-layer controlled process. The protective properties of this barrier layer determine the overall corrosion resistance of zirconium alloys.
In order to get a better understanding of the mechanisms governing corrosion of Zr-based alloys, several examinations have been performed on a variety of samples with uniform and nodular corrosion and different oxide layer thicknesses. The results point to a barrier layer concept. The oxide layer becomes porous at a critical thickness. Open porosity increases from 0.01% at 10 μm to 3% at 100 μm. Between the outer porous oxide and the metal, a dense interlayer exists. This is only ≤30 nm in nodular oxide but has been found to be several hundred nm in uniform post-transition oxide. The barrier layer is obviously influenced by the crystallization of the oxide at the interface. This crystallization leads either to a columnar monoclinic, an equiaxed tetragonal, or to a fine equiaxed monoclinic oxide. The latter, which probably forms only under the mineralizing effect of hydrogen, was found in nodular oxide. It easily cracks at the grain boundaries. Well developed columnar oxide is seen in uniform oxide, when corrosion resistance is high. Recrystallization seems to be responsible for the pore or microcrack formation at the transition. The intermetallic precipitates influence the corrosion behavior significantly. They probably oxidize slowly. This oxidation starts with the zirconium and is accompanied by iron diffusion into the surrounding oxide.
During corrosion of Zr alloys in pressurized water at high temperatures a fraction of the corrosion-hydrogen is picked up by the metal. Long-term out-of-pile corrosion experiments have shown that chemical composition of Zr alloys and the size of second-phase particles (SPP) in Zircaloy-4 (Zry-4) affect the corrosion and the corrosion-hydrogen pickup fraction. The mechanism of hydrogen pickup is not well understood, although several influencing parameters were evaluated or discussed in the literature. One of the parameters that might influence hydrogen pickup is the electrical potential gradient that develops over the oxide during corrosion. Long-term electrochemical measurements of Zry-4 samples with different SPP sizes and Fe content and of Zr-2.5Nb in pressurized water at 350°C with and without polarization were used to check this influence. The potential difference between the reaction interface and the oxide surface is due to the oxidation reaction of the Zr metal resulting in electrons that have to move through the highly resistive oxide to the surface. Tests without polarization showed the potential difference proportional to the corrosion rate and depending on metallurgical aspects as the alloy composition and the SPP size. The lowest potential difference has been found for Zry-type material with large SPP and for Zr-2.5Nb. A negative polarization voltage of the samples against a Pt-reference electrode increases the H pick up and even leads to an accelerated corrosion at large potential differences. Analysis of H pickup clearly shows that, besides corrosion-H, H from the electrochemical surface reaction is also picked up. Samples with oxide layers exhibiting high electrical resistance pick up relatively more H than samples exhibiting oxide layers with low resistance. Zr-2.5Nb forming a very low-resistant oxide layer picks up only very little H. The effect of the SPP sizes can, at least partially, be explained by their influence on the electrical resistance of the oxide layer. The results of this study identify the potential gradient formed over the oxide layer as an important parameter for the relative amount of H pickup.
Zircaloy in boiling water reactor (BWR) systems often exhibits, besides slight uniform corrosion, a nodular type of corrosion. Highest nodular corrosion was found with materials never β-quenched during their fabrication, whereas β-quenched materials generally showed an improved behavior. Results of nodule thickness measurements after increasing burnup were normalized by using a correlation w ∼ (BU)0.7 (w = average nodule oxide thickness, BU = burnup). The scatterband of the normalized data was different for different reactors. The statistical distribution was generally Gaussian with a tail at high values. To find reasons for the material-inherent scatter of the in-pile corrosion behavior, archive samples were examined by electron microscopy and high-pressure steam tests. The latter led to a comparable ranking if the specimens were fully recrystallized before testing. The microstructural examinations indicate a correlation of the in-pile corrosion with the size distribution of the intermetallic precipitates and the spacing between the precipitates. High-pressure steam tests have been used to identify the fabrication steps which influence nodular corrosion. According to these tests it is mainly the β-quenching treatment and all annealing or working steps in the upper α-phase range that have an influence. Low nodular corrosion was achieved using quenching rates >5 K/s if the subsequent annealing stays in the low α-range. In the cold-worked condition, nodular corrosion in general was less pronounced. However, with respect to the in-reactor performance, no marked difference was found between stress-relieved and fully recrystallized cladding tubes. For actual practice it is concluded that an appropriate β-treatment is needed and that temperature treatments of the material after its last β-quenching should stay within a range in which the distribution of the alloying elements is not affected unduly. Several in-pile programs are under way in cooperation with utilities to confirm the progress achieved.
Laboratory corrosion tests have always been an important tool for Zr alloy development and optimization. However, it must be known whether a test is representative for the application in-reactor. To shed more light on this question, coupons of several Zr alloys were exposed under isothermal conditions in all or most of the following environments: In-Reactor: (1) PWR core at 300 to 340°C up to six years. (2) BWR core with a low sensitivity to nodular corrosion up to four years. (3) BWR core with a high sensitivity to nodular corrosion up to two years. Ex-Reactor (in Autoclave): (1) 350°C/pressurized water up to three years. (2) 400°C/100-bar steam up to two years. (3) 350°C/0.01 M LiOH water up to two years. (4) 500 to 515°C/high-pressure steam 16 to 24 h. In addition, the material condition of several of the examined Zr alloys was varied over a wide range. For evaluation of the in-PWR tests and for comparison of out-of-pile and in-pile tests, the different temperatures and times were normalized to a temperature-independent “normalized time” by assuming an activation temperature (Q/R) of 14 200 K. Comparison of in-PWR and out-of-pile corrosion behavior of Zircaloy shows that corrosion deviates to higher values in PWR if a weight gain of about 50 mg/dm2 is exceeded. In the case of the Zr2.5Nb alloy, a slight deviation of corrosion as compared to laboratory results starts in PWR only above a weight gain of 100 mg/dm2. In BWR, corrosion of Zircaloy is enhanced early in time if compared with out-of-pile. Zr2.5Nb exhibits higher corrosion results in BWR than Zircaloy-4. Alloying chemistry and material condition affect corrosion of Zr alloys. However, several of the material parameters have shown a different ranking in the different environments. Nevertheless, several material parameters influencing in-reactor corrosion like the second phase particle (SPP) size or in-PWR behavior as the Sn and Fe content can be optimized by out-of-pile corrosion tests.
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