Analysis of Cu segregation to oxide–metal interface of Ni‐based alloy in a metal‐dusting environment

Doi, Takashi; Kitamura, Kazuyuki; Nishiyama, Yoshitaka; Ōtsuka, N.; Kudo, Takeo; Sato, Masugu; Ikenaga, Eiji; Ueda, Shigenori; Kobayashi, Keisuke

doi:10.1002/sia.2910

Cited by 14 publications

(6 citation statements)

References 20 publications

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“…photoelectron spectroscopy by means of synchrotron source[30]. The thickness of Cusegregation layer formed below the Cr 2 O 3 scale was about 0.25nm and Cu content was about 50%.Although the alloy and oxidation condition in the present study is different, Cu segregation at the scale/alloy interface in the initial oxidation stage in the present study is expected, because Cu cannot be oxidized once a NiO scale is formed as shown in Fig.…”

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confidence: 53%

Effect of Cu on oxidation behaviour of FCC Fe-Ni-Cr-Al and Ni-Cr-Al based alloys

et al. 2020

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confidence: 53%

Effect of Cu on oxidation behaviour of FCC Fe-Ni-Cr-Al and Ni-Cr-Al based alloys

et al. 2020

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“…One of evidences has been demonstrated by using hard X-ray photoelectron spectroscopy (HX-PES). 29 At high temperatures, Cu was segregated at a few atomic layers between oxide /metal interface of Ni-Cr-Cu alloys. For the Ni-17.2 at.% Cu alloy, Cu has greatly segregated at 65at.% on the alloy surface after heating at 923 K for 10min.…”

Section: Resultsmentioning

confidence: 99%

Non-Dissociative Adsorption of Carbonaceous Gases on Ni Containing Group-13, 14, and 15 Elements

Nishiyama

Moriguchi

Ōtsuka

2011

J. Electrochem. Soc.

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We present a joint experimental and theoretical study on metal dusting phenomena in Ni binary alloys containing group-13, 14, and 15 elements in the periodic series. Laboratory metal dusting test of several Ni binary alloys was conducted in a simulated syngas atmosphere consisting of CO, H 2 , CO 2 , and H 2 O at 923 K for 100 h. The Ni alloys containing the group-14 and 15 elements exhibited excellent metal dusting resistance, while those containing the group-13 did not. This behavior is reasonably interpreted from the Blyholder mechanism and the electron filling concept in the p-d hybridization states for the associated alloys.Metal dusting, a type of corrosion which is resulted from catastrophic carburization or graphitization of steels and alloys in carbonaceous atmosphere, is a prominent cause of corrosion damage for high temperature materials used in plants for ammonia, methanol, dimethyl ether and gas-to-liquids production. 1-4 Once the metal dusting occurs on the metal surface, a pit like wastage continues to grow during exposure to the carbon-bearing gases at intermediate temperatures. Recent literatures demonstrated that Ni alloys containing Cu of 20 at.% and more were resistant against metal dusting attack. 5, 6 Alloy of Ni30%Cr-2%Cu-1.5%Si that formed oxide scales of Cr 2 O 3 also showed the excellent resistance to metal dusting. 7 The basic experiments revealed that the Cu reduced the atomistic interaction of CO with the metal and restrains the carbon penetration. The most basic principle for the CO adsorption on metal surfaces is on the difference between the dissociative and non-dissociative properties. The accepted model so far is the donation and back-donation mechanism proposed by Blyholder. 8 Based on the mechanism, the electronic structure calculations have proven that the element where d-band is fully occupied by the electron is effective against the dissociative adsorption of CO on their surface. 5 For multicomponent alloys e.g. Ni-Cu, the Fermi level (E F ) in d-band states shifts upper side owing to electron donor elements compared to that for pristine Ni metal, resulting in suppression of dissociative adsorption of CO. A new Ni-Cr-Si-Cu alloy adopting the hybrid technique "surfactant-mediated suppression" and "protective oxides barrier" was developed and has successfully experienced that no pits have occurred for more than 2 years in a laboratory test. 9,10 Considering the proposed approach, representative (typical) elements in the right side of periodic table should exhibit the surfactantmediated suppression effect. The objective of this study is to clarify the effect of the representative elements on the dissociative adsorption of carbonaceous gases. ExperimentalBinary alloys of Ni-X (X = Ga, In, Tl, Ge, Sn, Pb, P, Sb, and Bi) were prepared in an ark-melting furnace under an inert argon atmosphere. Elements of Ga, In, and Tl belong to group-13 in the periodic table. Those of Ge, Sn, and Pb belong to group-14 and the rests are in group-15. Purity of metals ratio are 99.97%Ni, 99.99%Ga, 9...

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“…It is considered that the corrosion resistance against the metal dusting was improved because of Cu segregation on the Ni‐based alloy in the metal dusting environments. In a previous work, we showed that Cu segregates in the oxide–metal interface of Ni–Cr–Cu alloys exposed to the metal dusting environment by hard X‐ray photoelectron spectroscopy . However, the segregation behavior of Cu under the oxidation environment has not become clear.…”

Section: Introductionmentioning

confidence: 99%

Investigation of segregation during oxidation of Ni–Cu alloy by in situ photoelectron spectroscopy

Doi

Nishiyama

Yoshigoe

et al. 2016

Surface & Interface Analysis

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Ni‐based alloys has been widely used for plant application because of their high strength and excellent oxidation resistance. In particularl, the addition of Cu in Ni‐based alloys significantly improves the metal dusting resistance. It is indicated that Cu is segregated on the alloy surface in the metal dusting environment; however, the details have not been clarified yet. The behavior of Ni–2Cu alloy under a high temperature oxidation environment was investigated using in situ X‐ray photoelectron spectroscopy. It was confirmed that Cu have been segregated at the surface of Ni–2Cu alloy during oxidation. These results propose that the Cu segregation improves the metal dusting resistance. Copyright © 2016 John Wiley & Sons, Ltd.

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Analysis of Cu segregation to oxide–metal interface of Ni‐based alloy in a metal‐dusting environment

Cited by 14 publications

References 20 publications

Effect of Cu on oxidation behaviour of FCC Fe-Ni-Cr-Al and Ni-Cr-Al based alloys

Effect of Cu on oxidation behaviour of FCC Fe-Ni-Cr-Al and Ni-Cr-Al based alloys

Non-Dissociative Adsorption of Carbonaceous Gases on Ni Containing Group-13, 14, and 15 Elements

Investigation of segregation during oxidation of Ni–Cu alloy by in situ photoelectron spectroscopy

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