Marcobre Corrosion Testing: Phase 2.

Prepared for;

Tim Doddridge
Manager Engineering – Technical Solutions
Ausenco
144 Montague Road
South Brisbane QLD
4101, Australia
Tim.Doddridge@ausenco.com

Prepared By:
S. Clarke

SJC Materials Engineering Ltd.

Report Date: Jan 29th, 2018

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Introduction

SJC Materials Engineering was asked to perform corrosion testing of candidate

alloys for process equipment for the Marcobre operation in Peru. This report
describes corrosion testing that was carried out primarily for pumps and piping in
the PLS, oxide leach and electrowinning areas. Candidate alloys were selected
and exposed to synthetic solutions that were intended to be as close as possible
to those in the process. For the PLS area a base case corrosion test was done
with the expected “normal” chloride concentration at the anticipated operating
temperature and an additional test was performed at an increased chloride
concentration. Testing was done by exposure of candidate alloys in the process
for a fixed time and then measuring the weight loss to determine the average
general corrosion rate. The samples were then examined for evidence of localized
corrosion (pitting and crevice corrosion). A890 3A, A890 5A, Zeron 100 and 2507
are all 25% Cr “superduplex” stainless steels, which are attractive for corrosive
service because of their very good corrosion resistance and high strength at
acceptable cost. One of the key purposes of including these alloys in the tests was
to determine if these lower-cost alloys are acceptable for the intended services.
NiCrMo alloys and titanium were included in the tests to confirm that those alloys
could be used in the event that the superduplex stainless steels proved unsuitable.

Procedure

The test alloys are shown in Table 1 below. All wrought coupons were
autogenously welded across the centre of the coupon but the cast coupons were
not. Each sample supported a PTFE castellated crevice washer with 12 individual
crevice pads. Two sets of coupons were used. In all tests, coupons were fully
immersed in the solution and in the test in the electro-winning solution, there was
also a set of coupons that were semi-immersed so that there was a tidal line in the
coupon. The oxide pumps test solution was agitated with a glass impeller. The
solutions were aerated and were enclosed in borosilicate glass kettles to prevent
evaporative loses. Temperatures were maintained in isothermal baths at the
relevant temperatures. The exposure period in the solutions was 734 hours (30 ½
days). The composition of the solution was provided by Ausenco and made from
reagent grade chemicals and distilled water. The compositions of the test solutions
are given in Table 2.

All coupons were ground to 240 grit on silicon carbide paper and then washed in
distilled water and then dried in methanol followed by flowing air. The coupons
were measured to ± 0.01mm and weighed to ± 0.0001 g.

After the exposure the coupons were washed and scrubbed with a nylon brush

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then cleaned in an ultrasonic bath for a minimum of 60 minutes. The samples were
rinsed in ethanol and dried in flowing air then weighed to an accuracy of ± 0.0001g.
The corrosion rates were calculated from the surface areas of each coupon, mass
loss, density of the alloy and exposure time of the test. The calculated corrosion
rates are shown in Table 2.

Exposure Alloy UNS

A890 5A* J93404
Oxide Pumps solution at 654-SMO S32654
31˚C CW6M*… -
Gr. 2 Titanium R50400
2507 S32750
PLS Solution “normal Zeron 100 S32760
chloride” 32˚C C276 N10276
Gr.7 Ti R53400
2507 S32750
PLS Solution “high Zeron 100 S32760
chloride” 32˚C C276 N10276
Gr.7 Ti R53400
A890 3A* J93371
Electrowinning 316L S31603
2205 S32205
…Cast version of C276. No UNS number.

Table 1: Alloys used in the corrosion tests. The cast samples are denoted * and
were supplied by Sulzer in Finland. The rest of the alloys were wrought.

PLS
PLS High Oxide Electro-
Compound ß Normal
Cl- Pumps winning
Cl-
H2SO4 96.5% 2.0725 2.0725 10.36 186.53
CuSO4.5H2O 27.00 27.00 0.67 137.53
FeSO4.7H2O 18.00 18.00 17.92 2.99
Fe2(SO4)2 *5H2O 10.50 10.50 10.53 1.75
Al2(SO4)3 .18 H2O 40.75 40.75 43.22 0.62
CaSO4 *2H2O 2.25 2.25 2.15 0.04
MgSO4 7.25 7.25 22.28 0.35
MgCl2.6H2O 25.50 25.50 0 0.003
MnSO4 *H2O 0.25 0.25 0.18 4.77
NaCl 25.41 53.36 53.36 0.018
Temperature (˚C) Þ 32 32 31 50

Table 2. Compositions of the four test solutions and test temperatures.

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After the corrosion rates had been calculated, the coupons were examined under
a low power optical microscope to determine the extent (if any) of localized
corrosion. The intent was that if there had been any evidence of pitting or cracking,
the coupons would be sectioned through those areas to determine the extent and
morphology of damage, thereby determining the mechanism of attack.

Results

The corrosion rates of the cleaned coupons were calculated from the mass loss
over the exposure time. The results are shown in Table 3. The results show that
if only corrosion rates based on weight loss are considered, all the alloys tested
appear to be acceptable. All corrosion rates are below the generally accepted cut-
off for “low” corrosion rates at 3 mpy (0.076 mm/y). In most cases this holds true -
most of the alloys in most of the test conditions have low or very low corrosion
rates based on mass loss and show no evidence of localized corrosion. However,
in three cases, there was localized corrosion, which casts the corrosion resistance
of the alloy into doubt. The A890 Gr. 5A underwent localized corrosion in the oxide
pumps test and the maximum measure depth of attack was over 0.5 mm. The
Zeron 100 underwent localized corrosion in the high chloride PLS environment
with a maximum depth of attack of 0.15mm. Zeron 100 also underwent some minor
crevice attack on the shoulder washer in the low chloride PLS test.

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 Weight Corrosion Rates Localized
Alloy Location
Loss (g) mm/y mpy Crevices Depth
Oxide Pumps solution at 31˚C
A890 5A 0.0126 0.0060 0.24 1 of 12 560
654-SMO 0.00003 0.0001 0.00 0
Immersed
CW6M 0.002 0.0008 0.03 0
B367 C-3 Ti 0.0003 0.0004 0.01 0
PLS Solution “normal chloride” 32˚C
2507 0.0004 0.0003 0.01 0
3 indications under
Zeron100 0.0002 0.0001 0.01 shoulder washer on the
Immersed back of the coupon.
C276 0.0003 0.0002 0.01 0
Gr.7 Ti 0 0.0000 0.00 0
PLS Solution “high chloride” 32˚C
2507 0.0004 0.0003 0.01 0
Zeron 100 0.0012 0.0008 0.03 2 of 12 154
Immersed
C276 0.0004 0.0003 0.01 0
Gr.7 Ti 0.0002 0.0002 0.01 0
Electrowinning 35˚C
A890 3A 0.0002 0.0001 0.00 0
316L Immersed 0.0007 0.0005 0.02 0
2205 0.0007 0.0005 0.02 0
316L 0.0005 0.0002 0.01 0
Tide-line
2205 0.0008 0.0002 0.01 0

Table 3. Corrosion rates for the candidate alloys in the four test conditions.

Discussion

The corrosion test data shows that all of the alloys performed well in the
electrowinning solution. This is the common experience where the vast majority
of electrowinning equipment in operating plants is made from 316L and performs
very well.

In the PLS solutions the results indicated that Zeron 100 underwent localized
corrosion. This was notable in the high chloride solution where there were visible
pits under the crevice washers and the maximum penetration was 0.15 mm. The
same alloy also underwent some minor crevice attack on the shoulder washer in
the low chloride PLS test. Zeron 100 contains copper and tungsten, which improve

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corrosion resistance in acidic environments so it was expected that this alloy would
outperform 2507 which has similar chromium content but no tungsten or copper.
This result is surprising but indicated that the superduplex stainless steels are at
risk of localized corrosion in the high chloride PLS solution.

The results from the oxide pumps test also indicated that the superduplex stainless
steels were susceptible to localized corrosion in the test solution. A severe pit was
observed under one of the crevice pads on the A890 Gr. 5A coupon.

The corrosion that was observed in these superduplex stainless steels occurred
over a 30 day exposure, which proved to be a sufficient incubation period for the
crevice corrosion under the PTFE crevice washer and shoulder washer to become
established. A longer test may have resulted in further crevice attack on these
alloys and could possibly have resulted in attack on the 654 SMO.

The other alloys that were tested performed very well in all test environments.
However, it must be noted that the corrosion resistance of all of the alloys will be
very sensitive to their microstructures, which will be determined by their heat
treatment. Solution annealing of high alloy stainless steels such as 654 SMO and
NiCrMo alloys such as C276 is notoriously difficult and must be monitored very
closely. Verification of solution annealing procedures should be an integral part of
the purchasers inspection and test plan, which in turn must be included in the
purchase package.

Conclusions

• Superduplex stainless steels are not suitable for use in the PLS or Oxide
Pumps environments.
• NiCrMo alloy C276 (and the cast equivalent C6MW) are acceptable for use
in the environments tested.
• The titanium alloys tested are acceptable for use in the environments
tested.
• 654SMO is attractive for the Oxide Pumps environment. Given the cost of
the alloy and the criticality of the service, a confirmatory test for a longer (90
day) period should be considered.

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Figure 1. A890 5A in the Oxide Pumps corrosion test. There has been localized
corrosion under the crevice washer.

Figure 2. Close up of the localized corrosion shown in Figure 1.

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Figure 3. Zeron 100 in the high chloride PLS solution at 32˚C. There are two attack
sites under the crevice washer pads. The greatest depth of attack was 0.154 mm.

Figure 4. Close up view of the crevice attack shown in Figure 3. Two areas of
crevice attack are indicated.

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