0 evaluări0% au considerat acest document util (0 voturi)
17 vizualizări1 pagină
1) Micro- and macroelectrochemical studies showed that the interface between MnS inclusions and the steel matrix is the weakest zone, where pitting initiates.
2) Preferential dissolution of Mn leads to S-rich MnS remnants being pushed out and forming worm-like structures in Na2SO4 solution.
3) Dissolution of Mn species above 700 mV forms a Mn-rich deposit film on the steel surface.
1) Micro- and macroelectrochemical studies showed that the interface between MnS inclusions and the steel matrix is the weakest zone, where pitting initiates.
2) Preferential dissolution of Mn leads to S-rich MnS remnants being pushed out and forming worm-like structures in Na2SO4 solution.
3) Dissolution of Mn species above 700 mV forms a Mn-rich deposit film on the steel surface.
1) Micro- and macroelectrochemical studies showed that the interface between MnS inclusions and the steel matrix is the weakest zone, where pitting initiates.
2) Preferential dissolution of Mn leads to S-rich MnS remnants being pushed out and forming worm-like structures in Na2SO4 solution.
3) Dissolution of Mn species above 700 mV forms a Mn-rich deposit film on the steel surface.
Micro- and Macroelectrochemical Studies of amounts of sulfur.
Several micro and macro electro-
Pit Initiation at MnS Inclusions in Stainless chemical measurements indicated that preferential Steels dissolution of Mn (peak A in Fig. 2a) led to sulfur rich T. Suter and H. Bhni MnS remnants. Since dissolved Mn species are more voluminous, the S rich remnant were pushed out, Swiss Federal Institute of Technology Zrich forming the worm like structures. The manganese rich ETH Hnggerberg, CH 8093 Zrich, Switzerland deposit film was formed at potential above 700 mV (peak B in Fig. 2a). Introduction Conclusions The corrosion resistance of stainless steels is often limited by chemical or structural heterogeneities. The interface inclusion/matrix is the weakest zone of Inclusions, mainly manganese sulfide inclusions, play a an MnS inclusion. key role as initiation sites of pitting and crevice corrosion Preferential dissolution of Mn leads to sulfur rich [1, 2]. In this work pit initiation studies were performed MnS remnants in 1 M Na2SO4. at MnS inclusions on 304 and 303 stainless steels. The References goal was to evaluate the critical factors for stable pitting [1] Z. Szlarska-Smialowska, Pitting Corrosion of at MnS inclusions. The steels were investigated in Metals, NACE, Houston, TX (1986). different electrolytes and in different scales. The results of [2] G. S. Eklund, J. Electrochem. Soc., 121, 467 large and small scale measurements provided information (1974). about the dissolution chemistry of the MnS inclusions [3] T. Suter, Ph. D. Thesis No 11962, ETH Zrich, and allowed determining the weakest zone of MnS (1997). inclusion. Figures Experimental 3 The large scale measurements were performed in a 10 SEM before a b Current density [A/cm ] MnS 2
standard electrochemical cell. The microelectrochemical
cell consisted of a glass microelectrode (tip dia. = 1 m - 2 10 interface a 1000 m) filled with the electrolyte and sealed with a b layer of silicone rubber to prevent leaking. The current 1 c 10 detection limit of 10 fA enabled to detect processes bulk occurring in the m and nm range [3]. Additional surface 0 analytical investigations performed before and after the 10 microelectrochemical experiments allowed correlating -1 localized corrosion at single inclusions with the measured 10 currents. d area = 2.5 m -2 Results 10 Pit initiation experiments on 304 stainless steels were -500 0 500 1000 12 m performed in 1 M NaCl. A 100 m microcapillary was Potential [mV] (SCE) used to study pit intiation at single MnS inclusions of different composition, structure, and size. Electrochemical c AFM after measurements using capillary with a tip diameter in the 1 m range of 1 to 3 m allowed investigation of different zones of a single inclusion. Hence, the corrosion Pit behavior of the weakest zone of an inclusion could be c b determined. Figure 1a shows polarization curves measured 10 m with a 2.5 m capillary. The investigated zones of the 10 m MnS inclusion are indicated with white circles on the Fig. 1: Corrosion behavior of different zones of single SEM picture taken before the corrosion experiments (Fig. MnS inclusion on a SS 304 plate in 1 M 1 b). Figure 1 c shows the AFM picture taken after the NaCl, a) polarization curves, b) investigated corrosion experiments. Several measurement proofed that spots, c) AFM picture of the spot c and b. the interface inclusion / bulk is the weakest zone. The AFM picture on the interface (spot b) indicates that a pit 10 3
or microcrevice was formed on the adjacent bulk matrix, a b SEM after
Current density [A/cm ] 2
but not on the MnS inclusion. On the contrary, "nm 2
A B 10 hills" were formed at the border of the inclusion. On spot c (center of inclusion) only "nm hills" are visible, but no 1 pits. EDX and Auger measurements indicated a high 10 sulfur, but a low manganese content for the "hills". 0 To clarify the formation of the "nm hills", we performed 10 experiments in sodium sulfate, a solution in which MnS -1 inclusions are active but SS does not pit [1]. To obtain 10 statistical information large scale polarization curve were d area = 1 cm measured on a 303 stainless steel rod with a high number -2 10 of MnS inclusions (Figure 2a). After the corrosion experiment the surface was covered with "worm like" -500 0 500 1000 MnS remnants (Figure 2a). EDX and Auger measure- Potential [mV] (SCE) 3 m ments showed, that the "worms" contained 70% to 80% sulfur, 10% to 20% chromium and smaller amounts of Fig. 2: Corrosion behavior of a SS 303 rod in 1 M manganese. The deposited film ("crust") around the N a 2 S O 4 , a) polarization curves, b) SEM "worms" contained mainly manganese, but only smaller picture taken after the corrosion experiment.