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논문자료 9cr corrosion 부식 pitting
논문자료 9cr corrosion 부식 pitting
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Zhengfei Hu
Tongji University
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The corrosion behavior of martensitic steel in chloride and supercritical water environment View
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Journal of Engineering Materials and Technology JULY 2015, Vol. 137 / 031009-1
C 2015 by ASME
Copyright V
C Mn P S Si Cr W Mo V Nb N B Al Ni
ASTM A335-2003 0.07–0.13 0.3–0.6 0.02 0.01 0.5 8.5–9.5 1.5–2.0 0.3–0.6 0.15–0.25 0.04–0.09 0.03 0.07 0.001–0.006 0.04 0.4
Test 0.1 0.45 0.015 0.008 0.3 8.82 1.57 0.35 0.2 0.078 0.037 0.0027 0.006 0.11
Temperature/ C 0.2% proof strength/ (MPa) Tensile strength/ (MPa) Elongation at fracture/ (%) Reduction of area/ (%)
20 465 660 20 15
Fig. 4 The Nyquist plots of P92 steel during 296 hr immersion in water and various NaCl con-
centrations: (a) distilled water, (b) 1.0% NaCl, and (c) 3.5% NaCl
Journal of Engineering Materials and Technology JULY 2015, Vol. 137 / 031009-3
Table 4 Effect of immersion time on the impedance fitting parameters of P92 steels
Time/hr
1.0% NaCl Rs/X 20.230 19.170 19.140 17.200 15.610 16.490 10.940
R1/X 108 106 118 123 129 156 143
n1 0.80 0.80 0.80 0.86 0.81 0.75 0.81
R2/X 2859 2953 3768 7670 5315 4711 4397
n2 0.84 0.93 0.87 0.81 0.86 0.79 0.80
3.5% NaCl Rs/X 6.961 6.687 6.736. 5.567 3.590 3.287 3.206
R1/X 15 16 15 25 35 13 13
n1 0.80 0.81 0.82 0.80 0.85 0.84 0.86
R2/X 2613 2785 2830 1804 1637 1582 1446
n2 0.80 0.86 0.82 0.83 0.81 0.81 0.76
Fig. 7 (a) PD for P92 steel before exposure in water and chlo- the pits in Fig. 10(d) reveals that the corrosion products inside cor-
ride solution and (b) PD after 22 days exposure rosion pits are mostly iron oxide and chromium oxide. It has been
proved that the oxide scales formed on P92 steel after immersion
Table 5 Potentiodynamitic polarization parameters for differ- consist an outer layer Fe-rich magnetite and an inner layer Cr-rich
ent conditions Fe–Cr spinel [7], so it can be inferred that the corrosion products
in the pits contain residues originated from the breakdown of ox-
Conditions Solution Ecorr/V Ebd/V Erp/V ide film. In some pits, tungsten peaks are also present, which are
associated with the tungsten carbide precipitates or inclusions in
Original Distilled water 0.363 0.184 0.001 P92 steel. These inclusions may serve as preferential sites for pit
1.0% NaCl 0.345 0.228 0.597
initiation in these steels.
3.5% NaCl 0.344 0.292 0.620
After 22 days exposure Distilled water 0.305 0.251 0.402 The results of OM examination of specimens exposed to the
1.0% NaCl 0.724 0.682 0.614 chloride solutions after long-term exposure are shown in Fig. 11.
3.5% NaCl 0.763 0.710 0.618 The grains and grain boundaries can be distinguished clearly. It
can be seen in Fig. 11(a) that there are pits, like A, in the grains
and pits, like B, at the grain boundaries. Merged pits can also be
seen in the grain (Fig. 11(b)) in higher chloride concentration,
SEM was used to confirm the electrochemical results. Each which may due to the fast uniform corrosion and some pit growth
specimen was immersed for 22 days in the distilled water and re- coalescence. The inclusions in the grains and the carbide particles
spective chloride solution at RT, then rinsed gently with distilled at the grain boundaries are the sites most susceptible to pitting ini-
water, dried and stored in a desiccator before examination. Pit tiation. These sites exhibited a lower surface potential than the
analysis after tests, shown in Fig. 10, indicates the average pit size matrix, which adversely affected the pitting resistance [21]. Pas-
increases in higher chloride concentrations but the density of the sive film of boundaries between steel matrix and inclusions is
pits declines, which may probably because some corrosion pits weak and the early pitting corrosion may occur at these sites [22].
had coalesced to form bigger pits. No pitting was observed on the The size of inclusions in the grains, like MnS [23] silicate, alumi-
sample immersed in the distilled water (Fig. 10(a)). However, at num oxide, and sulphide type of inclusions [24], is about
Cl concentration higher than a threshold value, the morphology 25–35 lm, and it is easy to be peeled from the matrix during expo-
of the surface was quite different from the samples exposed to the sure. It can also be seen that merged pits (Fig. 11(c)) and scatter
lower concentration of chlorides and the rough surface (the pits (Fig. 11(d)) distribute along grain boundaries, which shows
amount of corrosion products and the number of pits) is virtually the grain boundary is also susceptible to pitting and becomes the
reduced (Fig. 10(c)). This conspicuous variation in the microstruc- weak site during exposure. The content of Cr at the grain bounda-
tures of the surface was mostly due to the fast uniform corrosion ries is not expected to decrease and the chromium depleted region
and some pit growth and coalescence [12,20]. Corrosion products generally does not appear for this type of steel [25]. Thus, the
are deposited inside the pits due to their low solubility in solutions scattered pits along the grain boundaries may be related to the car-
(Fig. 10(d)). Energy dispersive spectroscopy (EDS) analysis of bide particles along grain boundaries, which are produced during
Journal of Engineering Materials and Technology JULY 2015, Vol. 137 / 031009-5
the martensite transformation. The size of carbide particles at the can be explained by the bigger size of the inclusions in the grains.
grain/lath boundaries, like M23C6 [26], is about 0.1–0.2 lm, and it The scattered pits join together and become the merged pits, dis-
can also be the pitting initiation site during the exposure. More tributed along the grain boundaries (Fig. 11(d)), with the time of
pits are observed in the grains than that at grain boundaries, which the immersion in chloride solutions. The corroded grain
Fig. 11 Metallographic microstructure of P92 steel after 22 days immersion in chloride solu-
tions: (a) and (c) 1.0% NaCl solution and (b) and (d) 3.5% NaCl solution
Journal of Engineering Materials and Technology JULY 2015, Vol. 137 / 031009-7
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