In this study, we investigated the suppression of the corrosion of cast iron in a copper–cast iron double-layered canister under local corrosion of the copper layer. The cold spray coating technique was used to insert metals with lower galvanic activity than that of copper, such as silver, nickel, and titanium, between the copper and cast iron layers. Electrochemically accelerated corrosion tests were performed on the galvanic specimens in KURT groundwater at a voltage of 1.0 V for a week. The results revealed that copper corrosion was evident in all galvanic specimens of Cu–Ag, Cu–Ni, and Cu–Ti. By contrast, the copper was barely corroded in the Cu–Fe specimens. Therefore, it was concluded that if an inactive galvanic metal is applied to the areas where local corrosion is concerned, such as welding parts, the disposal canister can overcome local or non-uniform corrosion of the copper canister for long periods.

Copper, mainly used as a material for outer canister, generates various corrosion products under aerobic and anaerobic conditions in the operational and/or post-closure phases of the deep geological repository. These products could affect performance of engineering barrier system (EBS) through interaction with surrounding bentonite that makes up the buffer and backfill materials. Accordingly, in this study, we suggested research items to be conducted to minimize degradation of EBS due to copper corrosion products, based on the phenomenological review results for copper corrosion mechanisms and interaction between resultant product and bentonite in the deep geological disposal environment. During the post-closure phase, condition in the disposal facility changes form aerobic to anaerobic over time, and thereby, causes and products of copper corrosion vary. Under aerobic condition, copper corrosion is mainly induced by oxygen (O2) in the repository, chloride (Cl-) and carbonate (CO3 2-) ions from groundwater flowing into the facility, resulting in corrosion products such as cuprite (Cu2O), tenorite (CuO), atacamite (CuCl2·3Cu(OH)2) and malachite (Cu2CO3(OH)2). And, copper corrosion under anaerobic condition is primarily due to hydrogen sulfide (H2S) and sulfate (SO4 2-) in groundwater flowing into the facility, leading to formation of chalcocite (Cu2S) and covellite (CuS) as corrosion products. Depending on environment of the disposal facility, copper corrosion products are dissolved and ionized to Cu2+ in groundwater, and subsequently adsorbed on the nearby smectite. Then, it causes a cation exchange reaction with exchangeable cations in the interlayer of smectite. As a result of reviewing the previous experiments, it was confirmed that Cu2+-exchanged bentonite has a slightly reduced basal spacing and swelling capacity. From the results as above, there is a possibility that performance of EBS may be degraded due to copper corrosion products. To minimize its effect of degradation in the domestic facility, items to be further studied are as follows: (a) Method for reducing copper corrosion such as selection of appropriate material and structure for the canister, and (b) How to control dissolution of copper canister product into groundwater through predicting type and ionization process. The results of this study could be directly used to developing design concept of EBS for the domestic disposal facility and to establishing roadmap of future R&D programs.

Currently, Korea is considering a disposal system based on Sweden’s KBS-3 model to dispose of high-level waste. The disposal system uses a multi-barrier concept to protect high-level waste with canister, buffer, backfill, and natural rock. In Korea, copper and iron are being considered for external and internal canisters, and bentonite is being considered as a buffer material. This is a similar choice to many overseas disposal systems. However, unlike the rolling, extrusion, and forging manufacturing methods being considered overseas for manufacturing external canister, domestic research is currently underway on manufacturing external copper canister using cold spray coating. The canister manufacturing method may vary depending on unit cost and manufacturing convenience. However, the properties of metal vary slightly depending on the manufacturing method of the metal. In this case, the characteristics of the canister may vary slightly depending on the canister manufacturing method, and eventually the corrosion resistance may also vary slightly. In order to understand how the copper canister manufacturing method affects corrosion resistance, corrosion rates were calculated and compared through electrochemical corrosion experiments at domestic groundwater ion concentration.

Chemical environments of near-field (Engineered barrier and surrounded host rock) can influence performance of a deep geological repository. The chemical environments of near-field change as time evolves eventually reaching a steady state. During the construction of a deep geological repository, O2 will be introduced to the deep geological repository. The O2 can cause corrosion of Cu canisters, and it is important predicting remaining O2 concentration in the near-field. The remaining O2 concentration in the near field can be governed by the following two reactions: oxidation of Cu(I) from oxidation of Cu and oxidation of pyrite in bentonite and backfill materials. These oxidation reactions (Cu(I) and pyrite oxidation) can influence the performance of the deep geological repository in two ways; the first way is consuming oxidizing agents (O2) and the second way is the changing pH in the near-field and ultimately influencing on the mass transport rate of radionuclides from spent nuclear fuel (failure of canisters) to out of the engineered barrier. Hence, it is very important to know the evolution of chemical environments of near-field by the oxidation of pyrite and Cu. However, the oxidation kinetics of pyrite and Cu are different in the order of 1E7 which means the overall kinetics cannot be fully considered in the deep geological repository. Therefore, it is important to develop a simplified Cu and pyrite oxidation kinetics model based on deep geological repository conditions. Herein, eight oxidation reactions for the chemical species Cu(I) were considered to extract a simplified kinetic equation. Also, a simplified kinetics equation was used for pyrite oxidation. For future analysis, simplified chemical reactions should be combined with a Multiphysics Cu corrosion model to predict the overall lifetime of Cu canisters.

Since spent nuclear fuel (SNF) should be isolated from the human life zone for at least 106 years, deep geological disposal (DGD) is considered a strong candidate for SNF management in many countries. Therefore, a disposal canister should be nearly immune to corrosion in such a long-term storage environment. Even though copper has a low corrosion rate of a few millimeters per million years in geological environments, the corrosion resistance of the copper welds must be preferentially validated, which inevitably occurs during the sealing of the disposal canister after the SNF is loaded. This is because the weld zone is a discontinuous area of microstructure, which can accelerate uniform and localized corrosion. In this study, the microstructural characteristics of copper welds in different welding conditions such as friction stir welding, electron beam welding, cold spray, were analyzed, focusing on the formation of microstructure, which affects resistance to corrosion. In addition, the microstructure and corrosion properties of the copper weld zone manufactured by recent wire-based additive manufacturing (AM) technology were experimentally evaluated. From this preliminary test result, it was found that the corrosion characteristics of the welds produced by the AM process using wire are comparable to those of the conventional forged copper plate.

Corrosion cells that simulates engineering barrier system have been stored in an aerobic KURT environment for 10 years, which were recovered and dismantled in 2021. The test specimens were compressed copper (Com. Cu), Cold spray copper (CSC Cu), Ti Gr.2, STS 304, and Cast nodular iron. The specimens were buffered by compact Ca-type Gyeongju bentonite (KJ-I) and compact Na-type Wyoming bentonite. And the corrosion cells were exposed to KURT groundwater at 30°C for about 10 years (3,675 days). As a result of the long-term experiment in aerobic environment, it was confirmed that Na-bentonite is more advantageous for inhibiting corrosion than Ca-bentonite. The corrosion thickness of the most specimens in Ca bentonite was slightly lower than in Na bentonite until the initial 500 days, but after 10 years, the corrosion thickness of copper and cast iron specimens in Na bentonite was clearly lower. The corrosion thickness of the copper specimen in Na bentonite was very low about 0.5 um in both Com. Cu and CSC Cu. Moreover, the corrosion thickness in Ca bentonite was very high about 4 um for Com. Cu and 6 um for CSC Cu. In the case of cast iron, the corrosion thickness in Na bentonite was about 13 um, and 15 um in Ca bentonite. The common feature of copper and cast iron specimens in Ca bentonite, which showed a high corrosion thickness, is the forming of a white mineral deposition layer on the specimen surface, which was presumed to be some kind of feldspar. On the other hand, it was found that the STS304 and Ti specimens were hardly corroded even after 10 years. In conclusion, when a white mineral deposition layer was formed on the specimen surface, the corrosion thickness always increased sharply than before, and thus it was estimated that the generation of the mineral deposition layer cause the increase of bentonite permeability, and rather the weakening of existing passive corrosion film.

In this paper, an approach developed by the Finnish nuclear waste management organization, Posiva, for the construction license of a geological repository was reviewed. Furthermore, a computer program based on the approach was developed. By using the computer program, the lifetime of a copper disposal canister, which was a key engineered barrier of the geological repository, was predicted under the KAERI Underground Research Tunnel (KURT) geologic conditions. The computer program was developed considering the mass transport of corroding agents, such as oxygen and sulfide, through the buffer and backfill. Shortly after the closure of the repository, the corrosion depths of a copper canister due to oxygen in the pores of the buffer and backfill were calculated. Additionally, the long-term corrosion of a copper canister due to sulfide was analyzed in two cases: intact buffer and eroded buffer. Under various conditions of the engineered barrier, the corrosion lifetimes of the copper canister due to sulfide significantly exceeded one million years. Finally, this study shows that it is necessary to carefully characterize the transmissivity of rock and sulfide concentration during site characterization to accurately predict the canister lifetime.

스프링클러설비에서 누수 하자가 발생되면 설비의 작동을 멈추는 경향이 많고 이는 입주자의 안전에 많은 지장을 초래하게 되며, 누수피해로 재산상의 손실도 발생하게 되므로 스프링클러설비는 화재진압 성능뿐만 아니라 내구성도 높아야 할 것이다. 동관 부식은 스프링클러설비 배관에서 주로 나타나는 특이한 현상으로서 그 동안 제시된 여러 학설들과 법원의 판단 등을 종합하여 검토한 결과, 동관의 부식은 매우 복합적인 요인에 의해 발생되고 있고, 하자보수 방법의 결정요인의 핵심은 보완시공을 통한 부식억제의 가능성 여부를 판단하는 것인데 실증적용 사례 연구 등을 통한 결론을 도출 하였다. 또한 스프링클러설비의 설비의 내구성 강화에 대한 법규적 미비점에 대해서도 연구를 통한 개선방안을 제시하여 향후 하자발생을 줄이고자 하였다.

Using alkali treatment solution, neutrality treatment solution and acid treatment solution, the surface corrosion layer of copper plates and bronze plates that have been artificially corroded using HCl, H2SO4 and HNO3 solutions were removed. In the case of alkali treatment solution, only air oxidation in the form of black tenorite and white cuproous chloride remained without being removed. In the case of using a neutrality treatment solution, a anhydrous type layer of reddish brown cupric chloride remained without being removed, together with this black and white corrosion substance. In the case of using an acid treatment solution, this red corrosion substance also remained, but all of the oxide was removed on the surface of the specimen that was treated by alternatively using alkali treatment solution and acid treatment solution. In the case of this treatment solution with the order of alkali-acid, oxidation no longer proceeded only through the distilled water cleaning process after treatment, thereby showing that oxidation from the cleaning solution no longer proceeded.

한국원자력연구원 처분시스템개발과제에서는 처분용기 재료로 개발중인 저온분사코팅 구리에 대한 틈새부식(Crevice Corrosion) 시험을 실시하였다. 본 시험을 통하여 틈새에서의 부식의 발생여부와 발생되는 시점인 재부동태 전위(Repassivation Potential)를 측정하고자 하였다. 틈새부식 시험 방법으로 (1) ASTM G61-86 : Cyclic Potentiodynamic Polarization Measurements, (2) SWRI의 PotentiodynamicPolarization plus intermediate Potentiostatic Hold method, 그리고 (3) ASTM G192-08 (THE method) :Potentiodynamic- Galvanostatic -Potentiostatic Method 등의 3가지 방법을 소개하였다. 실제 저온분사코팅구리의 부식시험에서는 ASTM G61-86에 따라서 틈새부식장치를 설치하고, 저온분사 코팅구리가 KURT 지하수를 모사한 용액에서 어떻게 틈새부식이 일어나는지 살펴보았다. 전기적 부식조건으로는 Cyclic Polarization Test, Potentiostatic Polarization Test, 및 Electrochemical Impedance Spectroscopy등을 사용하였다. 그리고 부식이 된 시편에 대해 Profilometer Measurement를 통해 실제 부식표면의 높낮이를 조사하여 틈새부식 유무를 관찰하였다. 최종적인 결론에서는 저온분사코팅구리는 틈새부식을 나타나지 않는다는 것을 확인할 수 있었다. 그리고 시험에 사용된 세종류의 구리에 대한 상대적인 부식평가를 한 결과, 부식전위를 나타내는 개방회로(Open Cell)에서의 전위는 구리의 제조방식과 상관없이 구리의 순도가 높을수록 높은 값을 보이는 것을 확인할 수 있었다. 결론적으로 KURT 심층지하수 조건에서는 구리는 틈새부식이 발생되지 않는다고 결론지었다.

Benzotriazole (B.T.A) which has been mainly used for the stabilization processing method of excavated copper and bronze artifacts is vaporized within 2~3 years after the usage because it is unstable at the acid conditions and cannot protect the surface of artifacts. In this study, NaOH method which has been used for the steel artifacts was applied as a stabilization process for the method of copper and bronze artifacts to gush chlorine ion out. For the reproduction of excavated samples, copper and bronze plates were dipped in 0.1M HCl for 26 hrs to form CuCl, rusted at 70˚C with RH 75% for the formation of corrosion products, and desalted in 0.1 M NaOH solution. The concentration of chlorine ion was measured by using ionchromatography. During the desalting process, a large quantity of chlorine ions was gushed out in early period and corrosion products were not additionally generated through the re-corrosion experiment. This NaOH desalting process was found to be a method of stabilization process for copper and bronze artifacts from the formation of Tenorite (CuO) during desalting as a protection layer for corrosion.

연구의 목적은 동제련슬래그를 혼입한 콘크리트의 철근부식저항성에 관한 특성을 분석하는데 있다. 물결합재비 35%-55%의 범위에서 보통포틀랜드 시멘트에 다양한 치환율로 포졸란재를 혼입하여 압축강도, 염화물 확산계수, 철근부식면적율 그리고 중량감소율을 시험을 통해 확인하였다. 결과는 보여준다. 포졸란재를 혼입한 콘크리트는 포졸란재를 혼입하지 않은 콘크리트에 비해 염화물 이온에 대한 저항성이 우수함을 보여주었다. 고로슬래그를 20%치환한 경우가 염화물 침투 깊이 및 각종 부식 시험에 대해 가장 우수한 결과를 나타내었으며, 동제련슬래그 10%를 치환한 배합 역시 보통 콘크리트에 비해 염화물 침투 깊이 및 각종 부식시험에 대해 뛰어난 결과를 보였다.