Method and device for measuring the power dissipated by a hydridation reaction in tubes and tubular claddings and the corresponding variation in electric resistance

Abstract

The invention relates to a method and device for measuring hydridation kinetics at different temperatures in tubular industrial components. The invention consists in measuring the power dissipated by a hydridation reaction over time as well as the variation in the electric resistance during said reaction. The inventive method and device can be used to optimise industrial components, such as tubes and fuel claddings for nuclear reactor cores. In this way, safety is increased, with the prevention of unplanned shutdowns of commercial reactors and a decrease in high-activity nuclear waste.

Description

RELATED APPLICATIONS

The present application is a Continuation of co-pending PCT Application No. PCT/ES2005/070011, filed Feb. 1, 2005 which in turn, claims priority from Spanish Application Serial No. P200400294, filed on Feb. 9, 2004. Applicants claim the benefits of 35 U.S.C. §120 as to the PCT application and priority under 35 U.S.C. §119 as to said Spanish application, and the entire disclosures of both applications are incorporated herein by reference in their entireties.

SECTOR OF THE ART

Measurement of hydridation reactions and kinetics of tubes and tubular claddings of metallic elements, metal alloys and any other material with and without protective coverings.

STATE OF THE ART

The massive hydridation of metallic industrial components is one of the causes of their becoming brittle and can lead to catastrophic fracture due to the formation of cracks. This process takes place in components in contact with water under pressure and/or boiling and at high temperature, and can become acute when the component is exposed to high concentrations of hydrogen as a consequence of other processes. A case that has been known for some years is the hydridation of tubular fuel claddings in the cores of nuclear reactors, which can take place massively from inside the cladding in the event of loss of airtightness as a result of a primary failure. Patent WO0223162 describes a method and device for measuring the resistance to hydridation in these tubular components in order to help in the selection of materials and design aimed at reducing these problems. Nevertheless, other measurements need to be determined in order to compare the hydridation kinetics, which permits the response to hydridation of the different elements and alloys of the tubular components to be compared and a choice to be made of those designs and compositions that will prevent or delay the appearance of these fractures in metallic industrial components.

So far, the determination of the hydridation kinetics of metals and alloys has been carried out by thermogravimetry and morphological studies of hydridation processes of pieces of material in an autoclave, which in some cases, as in the hydridation of fuel claddings, represents working conditions that are very different from those in which the hydridation of the component is produced.

DESCRIPTION OF THE INVENTION

BRIEF DESCRIPTION OF THE INVENTION

The present invention tackles the problem of providing new methods and tools for measuring the hydridation kinetics taking place in tubular components for industrial use.

The solution provided by this invention permits measurement of the hydridation kinetics in the actual tubular components, generally multi-layer, and under the same conditions of working temperature in which the hydridation of the component takes place, which is of particular economic relevance since it permits the design and choice of the appropriate composition of the different alloys used. An optimisation of these components will be able to help prevent unplanned shutdowns of commercial reactors. This possible improvement will also allow greater exploitation of the fuel by making it more robust, and a decrease in the mass of high-activity nuclear waste for the same amount of energy generated. By eliminating a possible source of leakage of components in the reactor water, the dosage of radiation received by maintenance personnel and personnel having to perform operations in the exchange zone will be reduced.

So, the first object of this invention consists of a new method for measuring hydridation kinetics at different temperatures, in industrial components, wherein it consists of measuring: a) the power dissipated by the hydridation reaction, hereinafter referred to as the dissipated hydridation power (DHP), as a function of time, along with its integral as a function of time hereinafter referred to as the dissipated hydridation energy (DHE), and b) the variation in electric resistance during that reaction, and in particular during the stage of dissolution of hydrogen in the component preceding the precipitation of hydrides in the material;

The second object of this invention consists of a device (FIG. 4) for carrying out the aforementioned measurement method consisting of:

• • a) a high or ultra-high vacuum chamber in which the component to be analysed is inserted,
  • b) a gas line for causing hydrogen or a mixture of hydrogen with other gas(es) to pass through the interior of the component,
  • c) heating systems by the Joule effect, thermocouples and systems for temperature control in the component, and
  • d) two electrodes in the form of a ring or other well-defined geometry, arranged on the component symmetrically and equidistant from the central thermocouple connected with the outside of the device where the measurements are going to be made.

Finally, the third object of this invention consists of the use of the said method and device for making measurements of hydridation kinetics in industrial components of metallic elements, metal alloys and any other material with and without protective coverings, preferably tubular components such as tubes and tubular claddings for fuel in the cores of nuclear reactors.

DETAILED DESCRIPTION OF THE INVENTION

The first object of this invention consists of a new method for measuring hydridation kinetics, herein after the inventive method, at different temperatures, in industrial components of metallic elements, metal alloys and any other material with and without protective coverings, wherein it consists of measuring:

• • a) the power dissipated by the hydridation reaction, hereinafter the dissipated hydridation power (DHP), as a function of time, along with its integral as a function of time hereinafter referred to as the dissipated hydridation energy (DHE),
  • b) the variation in electric resistance during that reaction, and in particular during the stage of dissolution of hydrogen in the component preceding the precipitation of hydrides in the material; and because the stages making up this method are:
  • i) insertion of the tubular component in a high or ultra-high vacuum chamber,
  • ii) circulation of hydrogen or a mixture of hydrogen with other gas(es) through the interior of the component, it being the permeation of the hydrogen via the wall of the component that causes the hydridation of the material,
  • iii) heating of the component by the Joule effect,
  • iv) determination of the dissipated hydridation power as a function of time, of the dissipated hydridation energy measured during the process, and of the electric resistance in the component by means of:
    • iv.1) the voltage drop along the component, and
    • iv.2) the variation in electric current applied for maintaining its temperature at the predetermined value for the hydridation reaction.

As used in the present invention, the term “industrial components” refers to tubular components, with a wall consisting of a single element or with multi-layer wall, as are tubes and tubular claddings for fuel in the cores of nuclear reactors.

The control of these industrial components by means of the inventive method will permit the design and choice of the suitable composition of the different alloys used for the manufacture of those components, thereby avoiding their fracture.

During the precipitation reaction and formation of hydrides, the heat of reaction causes a drop in the electric current being applied in order to keep the temperature constant, which leads to a decrease in the power necessary for maintaining that temperature. The variation or difference in the necessary power corresponds to the dissipated hydridation power (DHP) and is roughly proportional to the hydride precipitated per unit time. This variation or decrease is measured as a function of time and permits a comparison to be made of the hydridation kinetics in components of different structure and composition, which permits a criterion to be had for the choice of materials and design. During the process and by means of integration with respect to time, one obtains the energy dissipated in the hydridation reaction which is roughly proportional to the quantity of hydride precipitated.

The second object of this invention consists of a device (FIG. 4), hereinafter the inventive device, for carrying out the inventive measurement method and which consists of:

• • a) a high or ultra-high vacuum chamber in which the component to be analysed is inserted,
  • b) a gas line for causing hydrogen or a mixture of hydrogen with other gas(es) to pass through the interior of the component,
  • c) heating systems by the Joule effect, thermocouples and systems for temperature control in the component, and
  • d) two electrodes in the form of a ring or other well-defined geometry, arranged on the component symmetrically and equidistant from the central thermocouple connected with the outside of the device where the measurements are going to be made.

During the hydridation reaction, the temperature in the interior of the component has to remain constant, for which a thermocouple and a temperature control system is used which acts on the current applied for heating the component (c). Moreover, in order to measure the voltage drop, and consequently the variation in electric resistance and the power dissipated during the hydridation reaction along the component during said reaction, the two electrodes are used arranged on the component (d)

Finally, the third object of this invention consists of the use of the inventive method and device for making measurements of hydridation kinetics in industrial components of metallic elements, metal alloys and any other material with and without protective coverings, preferably tubular components such as tubes and tubular claddings for fuel in the cores of nuclear reactors.

DETAILED DESCRIPTION OF THE FIGURES

FIG. 1. Variation in electric resistance during the hydridation process. Following the variation in electric resistance owing to the increase in temperature, the first stage of growth, and once the temperature of the experiment has been reached, a sharp growth takes place, marked between the arrows, due to the dissolution of H in the metal, and the final maximum of this stage roughly coincides with the start of the precipitation of H in the form of hydrides.

FIG. 2. Variation in dissipated hydridation power. Once the temperature of the experiment has been reached, the DHP remains constant for a short interval, the incubation time, during which the H is dissolved without precipitating. Once that period has passed coinciding with the growth of electric resistance, the DHP grows rapidly, corresponding to the start of precipitation of H in the form of hydrides in the material.

FIG. 3. Variation in dissipated hydridation energy. This corresponds to the integral of FIG. 2.

FIG. 4. Diagram of the hydridation kinetics measurement device. This shows the position of the electrodes used for measuring the voltage drop in the tube.

EXAMPLES OF EMBODIMENT OF THE INVENTION

Example 1

Measurement of the Hydridation Kinetics in Tubes or Tubular Claddings

A method for measuring the dissipated power and the electric resistance and thereby obtain the hydridation kinetics in tubes or tubular claddings is embodied as stated below.

A nuclear fuel cladding of Zircaloy 2 is inserted in a high or ultra-high vacuum chamber; hydrogen or mixtures of hydrogen with other gas(es) is made to circulate via the interior of the tube at a pressure of 1 atmosphere and a renewal stream of 200 cm³ per minute. The partial pressure in the vacuum zone is 10⁻⁹ Torr owing to the permeation of hydrogen through the walls of the cladding. The cladding is heated by the Joule effect and the temperature in the centre of the cladding is monitored and kept constant at 360° C. (or other pre-established value) with a thermocouple and a temperature control system which acts on the current being applied in order to heat the cladding, the amount of current needed in order to maintain a constant temperature of 360° C. in the absence of reaction being 30 A. The electrodes, located on both sides of the thermocouple, provide a measurement of the voltage drop in the cladding during the hydridation reaction. Together with the measurement of the current applied, this permits us to obtain the value of the power necessary for keeping the temperature constant, and to measure the electric resistance of the cladding. When the dilution of the hydrogen in the cladding starts, the electric resistance can grow up to 3% (FIG. 1), though this variation can be less if the cladding previously contains a quantity of hydrogen, and no major changes are observed in the power necessary for keeping the temperature constant. When the precipitation and the formation of hydride starts, the heat of reaction means that the power necessary for keeping the temperature constant decreases, the difference in which gives us the value of DHP and, by integration, the dissipated hydridation energy or DHE. The DHP is roughly proportional to the hydride precipitated per unit time and the DHE to the total quantity of precipitated hydride. By stopping the process at different value of DHE, samples can be obtained with different thicknesses of the hydrides ring. These samples are very useful for mechanical studies and studies of the geometry of the precipitated hydrides. The comparison of the DHP curves permits a criterion to be had for selection of materials and design. FIG. 1 shows the variation curve of electric resistance, in which the first maximum corresponds to the end of the dissolution process of hydrogen and the final maximum corresponds to the end of the hydridation process. FIG. 2 shows the DHP curve, in which the maximum indicates that the precipitation reaction is very rapid at the start of the process. FIG. 3 corresponds to the DHE curve.

Claims

1. Method for measuring hydridation kinetics, at different temperatures, in industrial components such as tubes and tubular claddings of metallic elements, metal alloys and any other material with and without protective coverings, wherein it consists of the measurement of:

a) the power dissipated by the hydridation reaction, hereinafter dissipated hydridation power, as a function of time, and of the dissipated hydridation energy, measured during the process, and

b) the variation in electric resistance during that reaction, and in particular during the stage of dissolution of hydrogen in the component preceding the precipitation of hydrides in the material.

the stages making up this method being:

i) insertion of the tubular component in a high or ultra-high vacuum chamber,

ii) circulation of hydrogen or a mixture of hydrogen with other gas(es) through the interior of the component, it being the permeation of the hydrogen via the wall of the component that causes the hydridation of the material,

iii) heating of the component by the Joule effect,

iv) determination of the power dissipated by the hydridation reaction as a function of time, of the dissipated hydridation energy measured during the process, and of the electric resistance in the component by means of: iv.1) the voltage drop along the component, and iv.2) the variation in electric current applied for maintaining its temperature at the predetermined value for the hydridation reaction.

2. Device for carrying out the measurement method of hydridation kinetics at different temperatures, in industrial components such as tubes and tubular claddings of metallic elements, metal alloys and any other material with and without protective coverings, wherein it comprises the following elements:

a) a high or ultra-high vacuum chamber in which the component to be analysed is inserted,

b) a gas line for causing hydrogen or a mixture of hydrogen with other gas(es) to pass through the interior of the component,

c) heating systems by the Joule effect, thermocouples and systems for temperature control in the component, and

d) two electrodes in the form of a ring or other well-defined geometry, arranged symmetrically and equidistant from the central thermocouple.

3. The method according to claim 1, wherein the measurements of hydridation kinetics are made in industrial components of metallic elements, metal alloys and any other material with and without protective coverings.

4. The method according to claim 3, wherein the industrial components are tubular, among others, the tubes and tubular claddings for fuel in the cores of nuclear reactors.

5. The device according to claim 2, wherein the measurements of hydridation kinetics are made in industrial components of metallic elements, metal alloys and any other material with and without protective coverings.

6. The device according to claim 5, wherein the industrial components are tubular, among others, the tubes and tubular claddings for fuel in the cores of nuclear reactors