Evaluating the water chemistry in the primary circuit and the effect of chemical decontamination of the heat exchanger tubes performed by the AP-CITROX procedure at Paks NPP (Hungary), a project dealing with the comprehensive investigation of the general corrosion state of the steam generators (SGs) has been initiated. Owing to the fact that there is no investigation method available for the in-situ monitoring of the inner surfaces of heat exchanger tubes, a research program based on sampling as well as on ex-situ electrochemical and surface analytical measurements were developed and elaborated. In the time period of 2000-2008 - within the frame of the above project - 45 stainless steel specimens, cut out from various locations of the steam generators of the Paks NPP were investigated. Besides to the corrosion characteristics (corrosion rate, thickness and chemical composition of the protective oxide-layer) surface properties (morphology, chemical and phase compositions) of the passive layer formed on the inner surface of above heat exchanger tubes were studied, too. The passivity of the inside surface of the stainless steel specimens was measured by voltammetry, the morphology, chemical and phase compositions of the oxide layer formed on the surface were analyzed by SEM-EDX, XRD and CEMS methods. The great number of experimental results allowed us to develop an electronic database which involves the results of the above corrosion experiments, and also some special characteristics of the tubes (e.g. location in the SGs, surface pretreatment by decontamination, if any, etc). Evaluating the main relations among these parameters may contribute to the identification of important processes affecting the corrosion state of steam generators, and highly decisive concerning a life time prolongation project of VVER-type nuclear reactors. In the present work we provide a brief overview on these experiments, some characteristic results, the database developed, as well as some novel findings.

At some VVER-type pressurized water nuclear reactors (Russian-type PWR) different versions of the so-called AP-CITROX method have been widely used for the chemical decontamination of the heat exchanger tubes of steam generators. In the period of 2000-2007, within the frame of a joint-project dealing with the comprehensive investigation of the corrosion state of the steam generators of the Paks Nuclear Power Plant, Hungary, effects of the AP-CITROX chemical decontamination procedure on the corrosion and surface characteristics of the heat exchanger tubes have been studied. These studies provide evidences that some adverse features (formation of a "hybrid" layer with accelerated corrosion rate and great mobility) can be detected after 1-3 years of applying the AP-CITROX procedure. The present work is a continuation of the above program and focused on the long-term trends in the corrosion state and structure of protective oxide-layer grown on the decontaminated surfaces. The results of electrochemical (voltammetric), surface analytical (SEM-EDX, CEMS) and mobility (ICP-OES) studies have revealed that (1) some beneficial changes in the corrosion characteristics, mobility and chemical composition of the inner surfaces of decontaminated heat exchanger tubes can be observed in the long run, and (2) the passivity of the oxide-layers formed on decontaminated surfaces of steel tubes exhibits favorable tendency after 4-7 years under normal operation conditions. © 2009 Elsevier Ltd. All rights reserved.

Our previous studies have revealed that a "hybrid" structure of the amorphous and crystalline phases is formed in the outermost surface region of the austenitic stainless steel tubes of steam generators (SGs) as an undesired consequence of the industrial application of the AP-CITROX decontamination technology. The formation of this mobile oxide-layer increased the amount of the corrosion products in the primary circuit significantly (∼80 kg/block), resulting in magnetite deposition on fuel assemblies. As deposits blocked the cooling channels, the flow rate of water coolant through the reactor core decreased. Consequently, the power capacity of three nuclear reactor units had to be reduced, and full core fuel replacement became necessary. In the light of the above events, the present work gives a brief overview on the general corrosion state of the heat exchanger tubes of SGs, concerning the long-term effects of the AP-CITROX procedure on the chemical composition and structure of the protective oxide-layer. Owing to the fact that there is no investigation method available for the in-situ monitoring of the inner surfaces of heat exchanger tubes, a research project based on sampling as well as on ex-situ electrochemical and surface analytical measurements was elaborated. Within the frame of this project, comprehensive investigation of the general corrosion state and metallographic features of 36 stainless steel specimens, cut out from various locations of the four steam generators of the Paks NPP has been performed. Electrochemical (voltammetric) and surface analytical (SEM-EDX, CEMS, and XRD) results reveal that some beneficial changes in the corrosion properties, morphology and chemical composition of the inner surfaces of heat exchanger tubes can be observed in the time period of 2000-2006.