铍的高温氧化行为及特性研究

在不同温度下对金属铍（Be）进行热氧化,采用热重、AES和SEM对Be的热氧化过程、氧化后表面状态、微区成分和氧化层厚度进行表征和分析,探讨了不同温度下Be的氧化行为和氧化特性。结果表明：室温～400 ℃范围内,Be样品的氧化增重主要服从抛物线规律;400～900 ℃范围内,主要呈线性变化。在较低温度下,Be表面形成的钝化层具有良好的保护作用,比较耐蚀。高温对Be样品的氧化影响较大,认为600 ℃以下Be的氧化主要受Be原子向表面的热扩散控制;800 ℃以上,氧通过晶界和孔洞扩散进入材料体内、氧化膜受热膨胀以及应力作用开裂等,导致Be发生严重的氧化腐蚀。     

Preliminary safety analysis of ex-vessel LOCA for the European HCPB TBM system

Ex-vessel loss of coolant accident caused by a double-ended pipe break of the helium coolant system inside port cell is considered as one of the most critical accident for the European Helium Cooled Pebble Beds Test Blanket Module (HCPB TBM) system. The resulting rapid helium blow-down causes an immediate block of the TBM cooling, which requires a prompt plasma shutdown. Even after the plasma shutdown the temperature can increase over the design limit and the accident sequence can lead up to a break of the TBM box protection after the failure of different protection systems. Thus air ingresses in the vacuum vessel from the damaged TBM system and steam from the surrounding ITER blanket and divertor structures. The evaluation of this sequence is very important for the definition of the correct protection strategy of the system. To consider all these different events a methodology has been developed in KIT combining different codes for a complete analysis of the accident. In particular, this paper shows an application of MELCOR code to model beryllium–steam reaction in a particular accidental sequence for the long term cooling.     

Real-time measurement of hydrogen generation level during beryllium dust oxidation by steam depending on the dust arrangement geometry

The paper concentrates on the safety issues in the International Thermonuclear Experimental Reactor (ITER) and describes the experiment on the measurement of hydrogen generation rate in case of Ingress of Coolant Event (ICE)—leak inside the vacuum vessel during interaction between water and beryllium (Be) dust. The ICE situation in ITER was simulated in a facility; the active spectroscopy was used to define the hydrogen content by the dynamics of oxidant concentration at a sampling frequency up to 10 Hz. Hydrogen release in time at temperatures of 500-900 °C is investigated, and different versions of dust arrangement are considered, i.e. on the surface and in a slot between armoring tiles at different initial density. The obtained results are compared with the known experiments.     

Steam oxidation of Zr-1.5Nb-0.4Sn-0.2Fe-0.1Cr and Zircaloy-4 at 900-1200 °C

The steam oxidation characteristics for the Zr-1.5Nb-0.4Sn-0.2Fe-0.1Cr (HANA-4) and Zircaloy-4 claddings were elucidated at LOCA temperatures of 900-1200 °C by using a modified thermo-gravimetric analyzer. After the oxidation tests, the oxidation behaviors, oxidation rates, surface appearances, and microstructures of the as-received, as-oxidized, and burn-up simulated claddings were evaluated in this study. The high-temperature oxidation resistance of the as-received HANA-4 cladding was superior to that of the Zircaloy-4. The superior oxidation resistance of the HANA-4 cladding could be attributed to the higher Nb and the lower Sn within its cladding. The pre-oxidized layer formed at the low temperatures below 500 °C could retard the oxidation rate at the high temperatures above 900 °C. And the soundness of the pre-oxidized layer formed at a lower temperature could influence the oxidation kinetics and the rate constants during a steam oxidation at LOCA temperatures from 900 to 1200 °C.     

The growth of oxide and oxygen-stabilized alpha layers in steam-oxidized zircaloy

Experimental investigations of the oxidation of Zircaloy in steam at high temperatures suggest temperature gradients exist across the oxide and oxygen-stabilized α layers even when specimens are exposed under nominally isothermal conditions. This paper presents a simple model that permits one to calculate the ratio of the thickness, of the oxide to oxygen-stabilized α layers in the presence of temperature gradients as well as under truly isothermal exposure conditions. The shape of the oxide to oxygen-stabilized α thickness ratio curve as a function of temperature was found to be in excellent agreement with oxidation kinetics data that were used to derive a scaling factor for the model. Variations in the temperature dependence of this ratio from independent measurements can be reproduced if it is assumed that temperature differences on the order of 10°C exist between the oxide layer and the oxygen-stabilized α layer. Metallographic evidence is presented that suggests the rate-controlling oxidation step occurs in the vicinity of the interface between the oxide and oxygen-stabilized a layers     

Molten corium oxidation model

In order to model oxidation of Zr–O and U–Zr–O melts, post-test appearance of refrozen oxidised melts in the CORA and QUENCH bundle tests performed at the Research Centre Karlsruhe (FZK) are analysed. Furthermore, data from new separate effect tests on ZrO₂ crucible dissolution by molten Zry, specially designed for investigation of long-term behaviour during the melt oxidation stage, are taken into consideration. On this base, a new model on oxidation of molten Zr–O and U–Zr–O mixtures in steam was developed, which allows interpretation of melt oxidation and hydrogen production observed in various bundle tests. The complete formulation of the analytical model, development of the numerical model and its validation against the crucible tests are presented.     

The oxidation of zircaloy-4 at 900 and 1100°c in high pressure steam

Oxidation experiments on zircaloy-4 PWR tube specimens were conducted at 905 and 1101°C in flowing steam at piessures up to 10.34 MPa (1500 psi). Maximum exposure times were about 45 min at 905°C and 10 min at 1101°C. The growth characteristics of the oxide and oxygen-stabilized alpha layers after these exposures were examined and compared to those observed earlier for oxidation in steam at atmospheric pressure. At 1101°C, no differences in the growth rates of the layers were evident. However, the trend of the data at the lower oxidation temperature indicated that an increase in the rate of oxide layer growth does occur with increasing pressure. The magnitude of the observed effect on the oxide layer growth at 905°C was small for the reaction times studied and for pressures up to 6.9 MPa (1000 psi). For example, the maximum increase in oxide thickness observed at 6.9 MPa was less than 50% for times up to 30 min, and the kinetics continued to show negative deviations from ideal parabolic growth behavior. However, the few experiments at the highest pressure yielded oxide layer thicknesses approximately twice as thick as those anticipated for oxidation at atmospheric pressure. While a detailed mechanism is not apparent, metallographic examination of these oxide layers revealed that part of each layer was different structurally compared to that found for oxidation at atmospheric pressure. It is suggested that this difference is responsible for the increased growth rate of the oxide layer.     

Dust tracking techniques applied to the STARDUST facility: First results

An important issue related to future nuclear fusion reactors fueled with deuterium and tritium is the creation of large amounts of dust due to several mechanisms (disruptions, ELMs and VDEs). The dust size expected in nuclear fusion experiments (such as ITER) is in the order of microns (between 0.1 and 1000 μm). Almost the total amount of this dust remains in the vacuum vessel (VV). This radiological dust can re-suspend in case of LOVA (loss of vacuum accident) and these phenomena can cause explosions and serious damages to the health of the operators and to the integrity of the device. The authors have developed a facility, STARDUST, in order to reproduce the thermo fluid-dynamic conditions comparable to those expected inside the VV of the next generation of experiments such as ITER in case of LOVA. The dust used inside the STARDUST facility presents particle sizes and physical characteristics comparable with those that created inside the VV of nuclear fusion experiments. In this facility an experimental campaign has been conducted with the purpose of tracking the dust re-suspended at low pressurization rates (comparable to those expected in case of LOVA in ITER and suggested by the General Safety and Security Report ITER-GSSR) using a fast camera with a frame rate from 1000 to 10,000 images per second. The velocity fields of the mobilized dust are derived from the imaging of a two-dimensional slice of the flow illuminated by optically adapted laser beam. The aim of this work is to demonstrate the possibility of dust tracking by means of image processing with the objective of determining the velocity field values of dust re-suspended during a LOVA.     

Analysis of the plasma-particle interaction during the plasma spraying of beryllium

Beryllium plasma-spray technology is being investigated as a method for coating plasma facing surfaces inside the international thermonuclear experimental reactor (ITER). This study investigated the plasma and plasma-particle interactions that occur during the plasma-spraying of beryllium. To evaluate the effect of the chamber pressure on the temperature, velocity, and trajectory profiles of the injected beryllium particles, the particles were numerically analyzed at three operating pressures (i.e., 101.3, 66.6 and 46.6 kPa) under a fixed operating condition. The thermal plasma was numerically modeled to predict the gas dynamics of the plasma column and plume. This information was then used as boundary conditions to solve the plasma—particle interaction problem at the various operating pressures. Calculations were performed for beryllium particles that ranged in diameter between 4 and 38 μm. Results of the numerical simulations describing the particle temperatures, velocities, and trajectories are discussed.     

Consequences of material effects on in-vessel retention

In-vessel retention (IVR) consists in cooling the corium contained in the reactor vessel by natural convection and reactor cavity flooding. This strategy of severe accident management enables the corium to be kept inside the second confinement barrier: the reactor vessel. The general approach which is used to study IVR problems is a “bounding” approach which consists in assuming a specified corium stratification in the vessel and then demonstrating that the vessel can cope with the resulting thermal and mechanical loads. Thermal loading on the vessel is controlled by the convective heat transfer inside the molten corium in the lower head. If there is no water in the vessel and if the corium pool is overlaid by a liquid steel layer, then the heat flux might focus on the vessel in front of the steel layer (“focusing effect”) and exceed the dry-out heat flux (CHF or DHF). One of the critical points of these studies is linked to the determination of the height of the molten steel layer that can stratify above the oxidic pool. The MASCA experiments have highlighted that part of molten steel may stratify under the oxidic corium which reduces the thickness of the steel layer on top of the pool. This behavior can be explained by chemical interaction between the oxide and metallic phases of the pool which confirms that these materials cannot be treated as inert species. Following these conclusions, a methodology which couples physicochemical effects and thermalhydraulics has been developed to address the IVR issue. The main purpose of this paper is to present this methodology and its application for given corium mass inventories. Attention focuses on the influence of parameters such as the ratio U/Zr and oxidation ratio of zirconia. For a 1000 MW PWR, approximately 10 t of steel stratify at the bottom of the vessel for 40% Zr oxidation, and 25 t for 30% Zr oxidation. This leads to a 25–50% increase of the mass of molten steel that is required for avoiding vessel melt-through.     

Study on the tritium behaviors in the VHTR system. Part 1. Development of tritium analysis code for VHTR and verification

A tritium permeation analyses code (TPAC) has been developed at Idaho National Laboratory (INL) by using MATLAB SIMULINK package for analysis of tritium behaviors in the VHTR integrated with hydrogen production and process heat application systems. The modeling is based on the mass balance of tritium-containing species and hydrogen (i.e., HT, H₂, HTO, HTSO₄, and TI) coupled with a variety of tritium source, sink, and permeation models. The code includes: (1) tritium sources from ternary fission and neutron reactions with ⁶Li, ⁷Li ¹⁰B, and ³He; (2) tritium purification system; (3) leakage of tritium with coolant; (4) permeation through pipes, vessels, and heat exchangers; (5) electrolyzer for high temperature steam electrolysis (HTSE); and (6) isotope exchange for SI process. Verification of the code has been performed by comparisons with the analytical solutions, the experimental data, and the benchmark code results based on the Peach Bottom reactor design. The results showed that all the governing equations are well implemented into the code and correctly solved. This paper summarizes all the background, the theory, the code structures, and some verification results related to the TPAC code development at INL.     

Application of a Zircaloy/Steam Oxidation Model to a CFD Code and its Validation against a CANDU Fuel Channel Experiment: CS28-2

Oxidation of a Zircaloy cladding exposed to high-temperature steam is an important phenomenon in the safety analysis of CANDU reactors during a postulated loss-of-coolant accident (LOCA), since a Zircaloy/steam reaction is highly exothermic and results in hydrogen production. As part of a computational fluid dynamics (CFD) simulation of the CS28-2 high-temperature experiment for this accident analysis, two Zircaloy/steam reaction models based on a parabolic rate law are implemented in a commercial CFD code (CFX-10) through a user FORTRAN. It is confirmed that the present oxidation models for the CFX-10 reproduce the results of each empirical correlation in the verification tests well. Then the CFX-10 predictions of a temperature rise and hydrogen production due to Zircaloy/steam oxidation are compared with the results of the CS28-2 experiment. From these validation processes, it is shown that the Urbanic-Heidrick model, which is widely used in CANDU fuel channel codes, is also applicable to a CFX-10 simulation of Zircaloy/steam oxidation in a CANDU fuel channel.     

Fusion Safety Studies in Russia in 1996

The paper seeks to provide a summary report of observations and results of some Russian fusion safety studies performed in 1996. Release of tritium and helium from neutron irradiated beryllium at relatively high neutron fluences has a burst nature. With the growth of the beryllium temperature-increase rate to 90 K/s, the temperature of tritium burst release decreases from 800 to 450–500°C and for helium decreases from 1200 to 500°C. Characterization of carbon and tungsten dust produced in experiments simulating plasma disruptions revealed that dust particle distribution of sizes for graphites and carbon fiber composites has a bimodal nature with maxima in the range of 0.01–0.03 and 2–4 m for composite UAM and in the range of 0.14–0.18 and 2–4 m for graphite MPG-8. Chemical reactivity of beryllium with air was studied as well. A mathematical model for beryllium weight gain under its chemical interaction with air at temperatures of 700–800°C as a function of beryllium porosity, temperature, and interaction duration was developed.     

Modeling of heat and mass transfer in accelerator targets during postulated accidents

The modeling of thermal-chemical behavior of targets used in accelerator applications is an important part of safety analysis. Tungsten is considered as a target material to produce tritium in a linear proton accelerator. The prediction of the chemical reactivity of tungsten in a steam flow at high temperatures is the most important part of a safety analysis of target design. The oxidation and volatilization of tungsten in steam at high temperatures is a complex phenomenon that involves various mechanisms (depending on the temperature), steam pressure, and steam velocity. A simple diffusion model that considers chemical equilibrium at the reaction interface and effective diffusion thickness, including the boundary and oxide layers, is proposed for predicting the volatilization rate. The proposed simple model predicts the available data reasonably well. The proposed model is implemented into a computer program that is developed to predict the radiological releases during postulated loss-of-coolant accidents (LOCAs). The computer program models heat production, heat transfer, and oxidation reactions in the multiple radiation enclosures representing the accelerator target elements. It treats each element of the radiation enclosures as a lumped control volume, or heat structure. Each heat structure may generate or lose heat by conduction, convection, or radiation and is subject to mass loss as a result of oxidation, melting, and volatilization. Postulated beyond-design-basis LOCAs are simulated with this computer program for the accelerator-production-of-tritium target. Sample calculations demonstrate oxidation/volatilization model capabilities and sensitivity to the assumptions selected.     

The effect of oxidation-and-quenching process during a LOCA on the behavior of the oxidation and embrittlement of Zircaloy-4 cladding under reheating transients

Two-sided oxidation tests, ring compression tests and semi-integral quench tests on Zircaloy-4 cladding specimens were conducted under temperature transient conditions simulating a post-quench reheat transient in order to evaluate the effect of high-temperature oxidation and quenching during a loss-of-coolant accident (LOCA) on the behavior of the oxidation and embrittlement of the cladding under a loss of long-term core-cooling condition. Test specimens prepared from non-irradiated Zircaloy-4 cladding tube were oxidized at a temperature between 1173 and 1473 K in steam flow and quenched by soaking the specimen in room temperature water. Re-heating tests were performed on the specimens in steam flow at a temperature between 1173 and 1473 K. The suppression of oxide layer growth and weight gain was observed under certain reheating-after-quenching conditions. Nevertheless, it seemed that the temperature transients including quenching-and-reheating process did not significantly affect the embrittlement of cladding. It was found that the embrittlement behavior of cladding during the temperature transients including quenching-and-reheating process could be dealt with on the basis of the Equivalent Cladding Reacted (ECR) based on the Baker–Just correlation.     

Embrittlement of Zircaloy-4 due to Oxidation in Environment of Stagnant Steam

With a view to examining the embrittlement behavior of Zircaloy due to inner surface oxidation occurring in an LWR loss-of-coolant accident, ring-like Zircaloy-4 cladding specimens were heated at the isothermal oxidation temperature ranging 890~1,194°C in an environment of stagnant steam, which simulated the atmospheric condition inside the ruptured cladding.

The embrittlement of the specimen due to oxidation in an environment of stagnant steam is influenced primarily by the amount of hydrogen absorbed by the Zircaloy-4. Ring compression tests conducted at 100°C on oxidized ring-like cladding specimen showed that Zircaloy containing more than about 500wt.ppm of hydrogen had become brittle.

The results of the present experiment support the idea supposed in the previous paper that the hydrogen absorption on the inner surface of the ruptured cladding, causing severe embrittlement, is strongly related with the atmospheric condition inside the ruptured cladding.     

The effect of droplet sprinkling on the oxidation kinetics of zirconium cladding in steam

The influence of oxide layer cracking on the acceleration of Zr cladding oxidation in steam was investigated. Cracking occurs due to temperature gradients, which arise during cooling of the cladding surface by droplet jets. Experimental results on characteristics of heat removal and the temperature gradients induced are presented for different regimes of sprinkling. A model for the calculation of mechanical stresses under the experimental conditions was developed in frame of the theory of envelopes. It was shown that the stresses are sufficiently high to induce cracking of the outer oxide layer. Experimental investigations of oxidation kinetics of Zr-1%Nb cladding were carried out under the conditions of surface cooling by droplet jets. The results of these experiments confirmed that the reaction of oxidation can be strongly accelerated by sprinkling.     

Implanted Deuterium Retention and Release in Carbon-Coated Beryllium

Deuterium implantation experiments have been conducted on samples of clean and carbon-coated beryllium. These studies entailed preparation and characterization of beryllium samples coated with carbon thicknesses of 100, 500, and 1000 Å. Heat treatment of a beryllium sample coated with carbon to a thickness of approximately 100 Å revealed that exposure to a temperature of 400°C under high vacuum conditions was sufficient to cause substantial diffusion of beryllium through the carbon layer, resulting in more beryllium than carbon at the surface. Comparable concentrations of carbon and beryllium were observed in the bulk of the coating layer. Higher than expected oxygen levels were observed throughout the coating layer as well. Samples were exposed to deuterium implantation followed by thermal desorption without exposure to air. Differences were observed in deuterium retention and postimplantation release behavior in the carbon-coated samples as compared with bare samples. For comparable implantation conditions (sample temperature of 400°C and an incident deuterium flux of approximately 6 × 10¹⁹ D/m²-s), the quantity of deuterium retained in the bare sample was less than that retained in the carbon-coated samples. Further, the release of the deuterium took place at lower temperatures for the bare beryllium surfaces than for carbon-coated beryllium samples.     

高温气冷堆蒸汽发生器中石墨粉尘重悬浮规律研究

高温气冷堆中石墨粉尘的运动规律对反应堆安全具有重要意义。本文采用数值模拟方法计算得到蒸汽发生器中的流场分布,在此基础上分析了蒸汽发生器中石墨粉尘重悬浮的规律。结果表明,对于粒径为0.1 μm的石墨粉尘,粉尘的重悬浮率几乎为0,对于粒径为1 μm以上的石墨粉尘,随着氦气流速的增大,蒸汽发生器中石墨粉尘的重悬浮率增大;在相同氦气流速下,随着石墨粉尘粒径的增大,石墨粉尘重悬浮率增大。