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International Symposium on Vacuum Science & Technology and its Application for Accelerators IOP Publishing
Journal of Physics: Conference Series 390 (2012) 012038 doi:10.1088/1742-6596/390/1/012038

General and crevice corrosion study of the in-wall shielding

materials for ITER vacuum vessel

K S Joshi1, H A Pathak1, R K Dayal2, V K Bafna3, Ioki Kimihiro4, V. Barabash4

1
ITER-India, IPR, A-29, GIDC, Sector-25, Gandhinagar:382025, India
2
IGCAR, Kalpakkam: 603102, India (retired),
3
TCR Eng. Pvt. Ltd., New Mumbai: 400705, India
4
ITER Organization, Route de Vinon sur Verdon, 13115, Saint Paul, Lez Durance
France

E-mail: [email protected]

Abstract. Vacuum vessel In-Wall Shield (IWS) will be inserted between the inner and outer
shells of the ITER vacuum vessel. The behaviour of IWS in the vacuum vessel especially
concerning the susceptibility to crevice of shielding block assemblies could cause rapid and
extensive corrosion attacks. Even galvanic corrosion may be due to different metals in same
electrolyte. IWS blocks are not accessible until life of the machine after closing of vacuum
vessel. Hence, it is necessary to study the susceptibility of IWS materials to general corrosion
and crevice corrosion under operations of ITER vacuum vessel. Corrosion properties of IWS
materials were studied by using (i) Immersion technique and (ii) Electro-chemical Polarization
techniques. All the sample materials were subjected to a series of examinations before and after
immersion test, like Loss/Gain weight measurement, SEM analysis, and Optical stereo
microscopy, measurement of surface profile and hardness of materials. After immersion test,
SS 304B4 and SS 304B7 showed slight weight gain which indicate oxide layer formation on
the surface of coupons. The SS 430 material showed negligible weight loss which indicates
mild general corrosion effect. On visual observation with SEM and Metallography, all material
showed pitting corrosion attack. All sample materials were subjected to series of measurements
like Open Circuit potential, Cyclic polarization, Pitting potential, protection potential, Critical
anodic current and SEM examination. All materials show pitting loop in OC2 operating
condition. However, its absence in OC1 operating condition clearly indicates the activity of
chloride ion to penetrate oxide layer on the sample surface, at higher temperature. The critical
pitting temperature of all samples remains between 100° and 200°C.

1. Introduction
One of the key issues of study the corrosion attack on IWS materials during operation phase of ITER
vacuum vessel. As IWS block assemblies will be placed between shells of vessel and will be immersed
in water which will be used for baking and cooling of vacuum vessel. The IWS block assemblies
comprises of number of plates stacked together with spacers in between the plates. Thus there will be
numbers of crevices will be form and it may be cause rapid and extensive crevice corrosion. Also there
will be high possibility of galvanic corrosion due to various IWS materials in same electrolyte [1]. In
addition local accumulation of the aggressive compounds like chloride and other anions might be
higher for ITER condition due to the different operational modes [2].

Published under licence by IOP Publishing Ltd 1

International Symposium on Vacuum Science & Technology and its Application for Accelerators IOP Publishing
Journal of Physics: Conference Series 390 (2012) 012038 doi:10.1088/1742-6596/390/1/012038

The schematic diagram of IWS assemblies between inner shell and outer shell of vacuum vessel are
shown in figure 1.

Figure 1 schematic of In-wall shielding block between double shell vacuum vessel

The materials of IWS that used for corrosion study:

(1) Austenitic steel 316L(N) – IG – ribs, brackets, washers, fixing plates;
(2) Borated steel 304B7 (~ 1.75-2.25 % wt. B) – plates for inboard region;
(3) Borated steel 304B4 (~ 1 – 1.24 % wt. B) – plates for outboard region;
(4) Ferritic steel 430 – plates for outboard region;
(5) Austenitic steel XM-19 (bolts designation B8R) – bolts
The corrosion properties of IWS materials were studied by (1) Immersion technique and (2) Electro-
chemical Polarization techniques

2. Corrosion study
2.1. Corrosion study by Immersion method
Three custom designed Autoclaves from SS 316L material were used to conduct this study. The eight
test coupons of each material were placed in autoclaves and heated to three different operating
conditions for a specific time period as per table-1. The Operating cycle were repeated for 5 times in a
sequential manner [4].
Table 1 Operating cycle for immersion method
1 OC1 Water at a temperature of 100 °C and the pressure of 1.1MPa 5 Days
2 OC2 Water at temperature of 200 °C and the pressure of 2.4MPa 5 Days
Draining out water from the autoclave and then Using hot Nitrogen gas at
3 OC3 5 Days
150 to 200 °C
 OC1 = Water temperature 100° C, pressure 1.1 MPa
 OC2 = Water temperature of 200° C, pressure 2.4 MPa.
 OC3 = Hot Nitrogen gas 150-200 degree C after draining out the solution from the autoclave

Figure 2 Schematic of test autoclave

2.1.1. Testing procedure for Immersion test in W1000 HP water chemistry

2
International Symposium on Vacuum Science & Technology and its Application for Accelerators IOP Publishing
Journal of Physics: Conference Series 390 (2012) 012038 doi:10.1088/1742-6596/390/1/012038

These tests were carried out with the Chloride concentration level of 1000ppb and Hydrogen Peroxide
of 2ppm (referred as W1000HP water) in each of the autoclaves. The test coupons of IWS sample
materials were subjected to a series of examinations before and after the Immersion Test as follows:

 Loss or gain of weight of sample

 Micro structural analysis using optical microscope and SEM
 Analysis of elements on area to be covered by crevice former before the test
 Analysis of elements over corrosion affected area.
 Measurement of surface profile and hole diameter of test coupons near the crevice location
before and after the test
 Material hardness of each sample for (i) as received and (ii) after preparing and (iii) after
completion of test
 Oxygen concentration in water was measured before and after each cycle of OC1 and OC2.

The test specimens clamped by XM-19 crevice former and M10 nuts at the torque of 80 N-m. All the
crevice assembly was kept on their respective stand and placed the stand into their respective
autoclaves. Water chemistry of W1000HP was checked before starting the experiment, prior to filling
the water into the autoclaves. To minimize the oxygen concentration and chloride concentration in
water, Argon gas was purged for 48 hours at 150cm3/min before start of testing (temperature rising of
autoclave). The water chemistry achieved as described in table 2.

Table 2 W1000HP water chemistry

Required Operational
Test Result of initial water Test results after Argon purging
Parameters
Conductivity (at 20o C) µS/cm At 27.8oC, 199.800 µS/cm At 27.8oC , 199.800 µS/cm
Oxygen, µg/kg 6500 µg/kg 1080 µg/kg
Chloride µg/kg 5800 µg/kg 1000 µg/kg
Sulphate, µg/kg 200 µg/kg 200 µg/kg
Copper, µg/kg Not Detectable Not Detectable
Iron, µg/kg 15000 µg/kg 15000 µg/kg
Hardness (Ca, Mg etc.) µg/kg 20900 µg/kg 20900 µg/kg
Oil products, organic, µg/kg Nil Nil
pH at RT 6.6 6.6

All the autoclaves were then cycled through following Operating conditions described in table 3.

Table 3 Operation cycle

Autoclave Immersion Test Sample No. of Samples Operating Conditions
1 ITS 1: SS 304B4 + CF1 +CF1 8 OC 1 OC 2 OC 3
2 ITS 2: SS 304B7 + CF1 +CF1 8 OC 1 OC 2 OC 3
3 ITS 3: SS 430 + CF1 +CF1 8 OC 1 OC 2 OC 3

2.1.2. Observations
(a) Material hardness of test samples
Material hardness was measured at the surface of the specimen with 2.5 mm diameter tungsten ball at
187.5 kg load. Two samples were taken before the Immersion test to generate the base line data and
compared with the hardness after test.

3
International Symposium on Vacuum Science & Technology and its Application for Accelerators IOP Publishing
Journal of Physics: Conference Series 390 (2012) 012038 doi:10.1088/1742-6596/390/1/012038

Table 4 Material hardness of samples

Average Hardness After
Average Hardness Before Immersion Test
Material Immersion Test
(HB 2.5/187.5)
(HB 2.5/187.5)
SS 304B4 176 190
SS 304B7 195.5 221
SS 430 145 167

(b) Weight loss/gain measurement

Each sample was weighed before and after the test to find out % weight loss due to corrosion. The
marginal weight loss observed in SS 430 coupon material and hence the corrosion rate calculated by
following formula.
Rate of corrosion (mm/year) = (87480 x W) / ( A x t x D)
Here W = Weight loss, A = Area under crevice, t = time of exposure and D = Density
The corrosion rate calculation is shown in table 5.
Table 5 Weight measurement of samples
Cross Sectional Average
Weight loss Corrosion Rate in
Specimen No. Area of entire Corrosion Rate
(gm) mm/Yr
Specimen (cm2) in mm/Yr
0 37.441 0.0156 0.00261
5 37.572 0.0155 0.00259
6 37.609 0.0153 0.00255
7 37.696 0.0153 0.00254
0.00267
8 37.572 0.0152 0.00254
9 37.528 0.0175 0.00293
10 37.572 0.0177 0.00296
11 37.528 0.0159 0.00266

(c) Optical Microscopy

The samples removed from the experiment were followed by diamond polishing and optical
observation at both side. The crevice corrosion has found on both sides of samples. Following table 6
shows the images of crevice at 100X and 200X magnification showing presence of crevice corrosion.
Table 6 Microscopic images of samples
SS 304 B4 SS 304 B7 SS 430
100x

200x

(d) Scanning Electron Microscopy (SEM)

The SEM analysis was carried out on samples of each IWS materials before immersion which
considered as base line data. After test, two samples of each material were polished by 600 grit
polishing paper and followed by SEM analysis. Following table 7 shows images of SEM analysis.

4
International Symposium on Vacuum Science & Technology and its Application for Accelerators IOP Publishing
Journal of Physics: Conference Series 390 (2012) 012038 doi:10.1088/1742-6596/390/1/012038

Table 7 SEM images of samples

SS 304 B4 SS 304 B7 SS 430
Before test

After Test

(e)Microstructure Examination
Microstructure examination was carried out at sample surface for all the materials to collect the
evidences of the corrosion under optical metallography. The testing was carried out on two samples of
each material to collect the baseline data of each material type. Two samples from each material were
considered for microstructure after the test from top and bottom position in the autoclave as per the
testing procedure.
Table 8 Microstructure of samples
SS 304 B4 SS 304 B7 SS 430
Before test

After Test

(f) Conclusion of Immersion testing:

 On visual observation, along with SEM and metallography of the crevice former area and nut
tightening area of the specimen of all material type showed pitting corrosion attack for
W1000HP water condition. Therefore, immersion test and observation was repeated for
operating condition with W100HP water and found that all material specimens showed pitting
attack.
 The materials SS304 B4 and SS 304 B7 showed marginal weight gain after crevice corrosion
experiment. The marginal weight gain is due to a thin layer of oxidation on the surface after
exposure.
 SS 430 material after crevice corrosion experiments showed weight loss of very negligible
quantity indicating that the material in a given environment showed mild effect of general
corrosion. The corrosion rate is calculated as 0.00267 mm/year.

2.2. Corrosion study by Electro-Chemical Polarization method

The susceptibility of various materials for galvanic/general corrosion was studied as part of the
Electro-Chemical Polarization test method. Test specimen materials considered for the Electro-
Chemical Polarization test study included SS 304 B4, SS 304 B7, Ferritic SS 430, XM-19, SS
316LN(IG) and three samples (SS 304 B4, SS304 B7 and SS 430), which were exposed for immersion
testing. One custom designed autoclave from SS 316L material was used to conduct this study as
shown in figure 3.

5
International Symposium on Vacuum Science & Technology and its Application for Accelerators IOP Publishing
Journal of Physics: Conference Series 390 (2012) 012038 doi:10.1088/1742-6596/390/1/012038

WI V Temperature
Potentiostat Controller
PG
WOV T
PS
PC

ELOCTRODE HOLDERS
Electrical
Connection

ELECTRODES HC
A
Figure 3 Schematic of test autoclave
These testing were carried out with the water having a chloride concentration level of level of 1000ppb
and hydrogen peroxide of 2ppm (referred as W1000HP water) and chloride concentration level of
level of 100ppb and hydrogen peroxide of 2ppm (referred as W100HP water) in the autoclave.
Following table-9 shows the test matrix of test sample, water chemistry and operating condition.
Table 9 Test matrix of electro-chemical polarization test
Sr. No. Test Material Water chemistry Operating condition
1 ET3 SS 304 B4 W1000H OC1
2 ET4 SS 304 B4 W1000H OC2
3 ET7 SS 304 B7 W1000H OC1
4 ET8 SS 304 B7 W1000H OC2

The following observations were made for each test listed as per the above table:
 Cyclic Potential measurement before start of polarization.
 Polarization curve (Tafel slope and corrosion rate will be calculated).
 Reverse curve for Pitting potential and behavior.
 Difference between pitting potential and protection potential.
 Critical anodic current density for passivation and passivation potential.
 Corrosion potential.
 Micro structural analysis using optical microscope and SEM before and after the test.
 Oxygen concentration in water will be measured before and after each test.

2.2.1. Test Procedure

The entire specimen polished with 120 grit emery sheet and ensures that it does not contaminate the
test solution. Specimens of all eight materials observed using Optical Microscope at the magnification
of 100X, 800X and SEM. The sample were inserted from flange of the autoclave and fixed the test
specimen and platinum electrodes in their respective position. Autoclave filled with the test solution
W1000HP or W100HP and temperature increased to 100 ± 10 or 200 ± 10 degree C. Test was
executed by the control and measured software in computer and measured Open Circuit Potential
(OCP) till steady graph is observed.

By Filling-in experimental parameters in software, the temperature and pressure values were measured
till the experiment is complete.

2.2.2. Observations
(a) Micro Structure examination of samples
Microstructure examination was carried out on all materials surface to collect base line information. It
was carried out on one sample of each material for the baseline data. All samples were considered for
microstructure at cross section after the electrochemical test as per the procedure.

6
International Symposium on Vacuum Science & Technology and its Application for Accelerators IOP Publishing
Journal of Physics: Conference Series 390 (2012) 012038 doi:10.1088/1742-6596/390/1/012038

Table 10 Microstructure images of samples

SS 304 B4 SS 304 B7 SS 430 SS 316L(N) IG XM-19
After
OC1

After
OC2

(b) Scanning electron Microscopy (SEM)

Scanning Electron Microscopy was carried out at sample surface for all the materials to collect the
detailed evidences of the corrosion initiation sites and its nature. SEM was carried out on one sample
of each material before test to generate the baseline data. Also, SEM analysis was carried out on
samples which showed pitting behaviour in electrochemical tests. SEM examination before test was
carried out on surface of the sample prepared with 600 grit polishing paper. Following are the images
of Sample surface at 1000X, as there was no evidence of pitting in Electro-Chemical test in OC1
condition whereas OC2 Condition indicated pitting hence SEM was carried out after OC2 cycle and
compared with baseline data.
Table 11 SEM images of samples
SS 304 B4 SS 304 B7 SS 430 SS 316 L(N) XM-19
IG
Before
Test

After
OC2
Cycle

(c) Electro-Chemical test data

Electro-Chemical tests were conducted on all materials including coupons from immersion test for

OC1 and OC2 operation condition with W1000HP water chemistry. The following parameters were
measured by software.

 Open Circuit Voltage: to study steady state polarization.

 Tafel Plot: To measure the general corrosion rate of the material in a particular test condition.
 Cyclic Polarization Curve: To characterize the susceptibility of material to pitting for a given
test condition.

7
International Symposium on Vacuum Science & Technology and its Application for Accelerators IOP Publishing
Journal of Physics: Conference Series 390 (2012) 012038 doi:10.1088/1742-6596/390/1/012038

Table 12 Tafel plots of samples

SS 304 B4 SS 304 B7 SS 430 SS 316L(N) IG XM-19
OC1

OC2

(d) Result summary

 OC1 Condition:
Pitting loop was not observed in OC1 operating condition at 100 C in all the samples. ICC value of
XM-19 sample was lowest (1.85 E-03) and that of SS 430 sample was the highest (0.00149 E-03).
Lower ICC value denotes easy passivation. Metallography and SEM did not show any corrosion
damage on the surface when compared to before and after exposure to the OC1 condition.
 OC2 Condition:
Pitting loop was observed in all experiments as per OC2 operating conditions. In OC2 operating
condition, the ICC value of SS 304 B7 was the highest (6.7038E-03). Under OC2 conditions, Eb – Ep
value was the lowest in SS 430 sample. Where this value is high, pitting can take place more easily.
SEM, EDS and metallography results showed pitting at all samples tested at OC2 condition.
(e) Conclusion of Electro-chemical potential test
 General corrosion Rate of the samples:
The General corrosion rate under OC1 conditions is lowest with SS 304 B7 and highest for SS430
material in as supplied conditions. Under OC2 conditions SS 304 B7 showed highest corrosion rate
and XM19 showed lowest in as supplied conditions. Overall the materials evaluated in the OC2
conditions showed higher corrosion rates then the OC1 conditions. This can be explained by the fact
that Increase in temperature would increase the corrosion rate.

 Pitting corrosion behaviour:

Absence of pitting loop in OC1 operating condition, and its presence in OC2 operating condition,
clearly indicates the activity of chloride ion to penetrate oxide layer on the sample surface, at higher
temperature. The results show that critical pitting temperature of all samples remains between 100°
and 200° C. At higher temperature, reaction rate (corrosion rate) of alloy with water increases, and
kinetic energy of aggressive ions like chloride increases. In the absence of dissolved oxygen, this
severely affects the passive layer break-down frequency, and at OC2 operating conditions, it becomes
evident that the rate of oxide film breakdown becomes more than the rate of film build-up.

3. References
[1] Ioki K “Detailed Design Document 1.5 Vacuum vessel”, ITER IDM ref. IDMUID 22FPWQ
[2] Fontana Mars G, Greene Norbert D “Corrosion Engineering (Materials Science and
Engineering)” (ISBN: 0071003606 / 0-07-100360-6 )
[3] Kaushal Joshi, H.A.Pathak and V.K.Bafna “Final report of corrosion testing of ITER In wall
Shielding material”, ITER IDM Ref. II-2PPDOWL-v1_0.
[4] Kaushal Joshi, H.A.Pathak and V.K.Bafna, “Final completion report of crevice corrosion study-
Immersion test of ITER In wall shield materials.” ITER IDM Ref. II-CRY8X0L_v1.0.