Platinum tip ECP sensor and fabrication thereof

Details Platinum tip ECP sensor and fabrication thereof Platinum tip ECP sensor and fabrication thereof

1998-12-30

2001-04-24

Patel, Vip (Department: 2879)

Electric lamp and discharge devices

Electrode and shield structures

C313S631000

Reexamination Certificate

active

06222307

ABSTRACT:

FIELD OF THE INVENTION
The present invention relates to electrodes, especially platinum tip ECP sensors having improved sensor life, and methods for their fabrication.
BACKGROUND OF THE INVENTION
Nuclear reactors are used in central-station electric power generation, research and propulsion. A reactor pressure vessel contains the reactor coolant, i.e. water, which removes heat from the nuclear core. Respective piping circuits carry the heated water or steam to the steam generators or turbines and carry circulated water or feedwater back to the vessel. Operating pressures and temperatures for the reactor pressure vessel are about 7 MPa and 288° C. for a boiling water reactor (BWR), and about 15 MPa and 320° C. for a pressurized water reactor (PWR). The materials used in both BWRs and PWRs must withstand various loading, environmental and radiation conditions.
Some of the materials exposed to high-temperature water include carbon steel, alloy steel, stainless steel, nickel-based, cobalt-based and zirconium-based alloys. Despite careful selection and treatment of these materials for use in water reactors, corrosion occurs in the materials exposed to the high-temperature water. Such corrosion contributes to a variety of problems, e.g., stress corrosion cracking, crevice corrosion erosion corrosion, sticking of pressure relief valves and buildup of the gamma radiation-emitting Co-60 isotope.
Stress corrosion cracking (SCC) is a known phenomenon occurring in reactor components, such as structural members, piping, fasteners and welds exposed to high-temperature water. As used herein, SCC refers to cracking propagated by static or dynamic tensile stressing in combination with corrosion at the crack tip. The reactor components are subject to a variety of stresses associated with, e.g., differences in thermal expansion, the operating pressure needed for the containment of the reactor cooling water, and other sources such as residual stress from welding, cold working and other asymmetric metal treatments. In addition, water chemistry, welding, heat treatment, and radiation can increase the susceptibility of metal in a component to SCC.
It is well known that SCC occurs at higher rates when oxygen is present in the reactor water in concentrations of about 5 ppb (parts per billion) or greater. SCC is further increased in a high radiation flux where oxidizing species, such as oxygen, hydrogen peroxide, and short-lived radicals, are produced from radiolytic decomposition of the reactor water. Such oxidizing species increase the electrochemical corrosion potential (ECP) of metals. Electrochemical corrosion is caused by a flow of electrons from anodic to cathodic areas on metallic surfaces. The ECP is a measure of the thermodynamic tendency for corrosion phenomena to occur, and is a fundamental parameter in determining rates of, e.g., SCC, corrosion fatigue, corrosion film thickening, and general corrosion.
In a BWR, the radiolysis of the primary water coolant in the reactor core causes the net decomposition of a small fraction of the water to the chemical products H
2
, H
2
O
2
, O
2
and oxidizing and reducing radicals. For steady-state operating conditions, equilibrium concentrations of O
2
, H
2
O
2
, and H
2
are established in both the water which is recirculated and the steam going to the turbine. This concentration Of O
2
, H
2
O
2
, and H
2
is oxidizing and results in conditions that can promote intergranular stress corrosion cracking (IGSCC) of susceptible materials of construction. One method employed to mitigate IGSCC of susceptible material is the application of hydrogen water chemistry (HWC), whereby the oxidizing nature of the BWR environment is modified to a more reducing condition. This effect is achieved by adding hydrogen gas to the reactor feedwater. When the hydrogen reaches the reactor vessel, it reacts with the radiolytically formed oxidizing species to reform water, thereby lowering the concentration of dissolved oxidizing species in the water in the vicinity of metal surfaces. The rate of these recombination reactions is dependent on local radiation fields, water flow rates and other variables.
The injected hydrogen reduces the level of oxidizing species in the water, such as dissolved oxygen, and as a result lowers the ECP of metals in the water. However, factors such as variations in water flow rates and the time or intensity of exposure to neutron or gamma radiation result in the production of oxidizing species at different levels in different reactors. Thus, varying amounts of hydrogen have been required to reduce the level of oxidizing species sufficiently to maintain the ECP below a critical potential required for protection from IGSCC in high-temperature water. As used herein, the term “critical potential” means a corrosion potential at or below a range of values of about −0.230 to −0.300 V based on the standard hydrogen electrode (SHE) scale. IGSCC proceeds at an accelerated rate in systems in which the ECP is above the critical potential, and at a substantially lower or zero rate in systems in which the ECP is below the critical potential. Water containing oxidizing species such as oxygen increases the ECP of metals exposed to the water above the critical potential, whereas water with little or no oxidizing species present results in an ECP below the critical potential.
It has been shown that IGSCC of Type 304 stainless steel (composition in weight % 18.0-20.0 Cr, 8.0-10.0 Ni, 2.00 Mn, 1.0 Si, 0.08 C, 0.08 S, 0.045 P) used in BWRs can be mitigated by reducing the ECP of the stainless steel to values below −0.230 V(SHE). An effective method of achieving this objective is to use HWC. However, high hydrogen additions, e.g., of about 200 ppb or greater, that may be required to reduce the ECP below the critical potential, can result in a higher radiation level in the steam-driven turbine section from incorporation of the short-lived N-16 species in the steam. For most BWRs, the amount of hydrogen addition required to provide mitigation of IGSCC of pressure vessel internal components results in an increase in the main steam line radiation monitor by a factor of five. This increase in main steam line radiation can cause high, even unacceptable, environmental dose rates that can require expensive investments in shielding and radiation exposure control. Thus, recent investigations have focused on using minimum levels of hydrogen to achieve the benefits of HWC with minimum increase in the main steam radiation dose rates.
In order to evaluate or predict a material's performance at operating conditions of a reactor, it is important to know the ECP values of the various structured components. Electrochemical potential monitoring is typically carried out employing paired electrochemical half-cell probes or electrodes which are mounted within the recirculation piping and accessed to the external environment through gland-type mountings or the like. Where the electrode system of interest involves a metal-metal ion couple, the reference electrode may conveniently be a metal-metal insoluble salt-anion electrode. A suitable reference electrode may be based, for example, on the half-cell reaction between silver and silver chloride. Calibration of the cell defining electrode pair is carried out by appropriate Nernst-based electrochemical calculations, as well as thermodynamic evaluation in combination with laboratory testing within a simulated environment against a standard electrode.
A reference electrode which is currently employed is a platinum tip reference electrode for monitoring the ECP. According to conventional design, a platinum cap is brazed to a metallized sapphire insulator post using pure silver braze. However, the metallizing process is not consistently reproducible and, in many cases, results in early failure. The silver braze forms an alloy with the platinum cap at high brazing temperature which, in turn, causes delamination of the metallized layer from the sapphire, which is a further reason for early life failure. In addition, it has been

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