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29.791
2
-0.22
32.462
4
-0.20
32.131
6
11/27/2006
91
1.723/22
32.532
8
32.197
0
11/21/2006
(%) kg/l@
O
C
loss
(%)
weight
loss
(%)
weight
loss
(%)
weight
Visual
Diagnosis
H
3
PO
4
Theoretic
al conc.
Acid
Density
ALLOY 20 HAST C CW2M C
Date
dark green
acid
93 1.75/24 -0.88
29.385
0
-0.85
32.186
9
-0.64
31.927
3 12/17/2006
dark green
acid
95 1.808/23 -0.77 29.561 -0.73
32.294
7
-0.53
32.024
8
12/11/2006
dark green
acid
97
1.832/24
29.791
2
-0.22
32.462
4
-0.20
32.131
6
11/27/2006
91
1.723/22
32.532
8
32.197
0
11/21/2006
(%) kg/l@
O
C
loss
(%)
weight
loss
(%)
weight
loss
(%)
weight
Visual
Diagnosis
H
3
PO
4
Theoretic
al conc.
Acid
Density
ALLOY 20 HAST C CW2M C
Date
Fig. 6 shows the
corrosion rates of A20
(CN7M), Std. and
Improved Hastelloy
CW-2M.
9.90
12.97
19.40
0
2
4
6
8
10
12
14
16
18
20
C
O
R
R
O
S
I
O
N
R
A
T
E
CW2MC CW2M A20
MATERIAL
Fig. 6.
Imp. CW-2M Std. CW-2M
16
Improved Hastelloy CW-2M has 31% lower corrosion rate than Std. Hastelloy CW-2M
and 99% lower corrosion rate than A20 (CN7M).
`
Arrows A, D and B point to three different shapes of corroded pits seen in Photo
21, 22 and 23. Arrow C in Photo 23 shows a shallow pit initiation location on the
Improved Hastelloy CW-2M sample. Arrow E in Photo 22 identifies an intergranular
corroded line which most likely is positioned within the former complex carbide area
located along the austenite grains of Std. Hastelloy CW-2M.
The main corrosion damage of all three alloys is pitting which depends on the solution
corrosivity, the specimen area and exposure time.
Generally mass loss alone is not a good indication of pitting damage. It is commonly
recommended to evaluate the relative resistance of alloys to pitting through a
combination of mass loss and visual inspection like density, depth and size of the
pits. [2]
The following is the density of the corroded pits counted on a 0.75mm
2
surface:
72 pits for A20 (CN7M);
38 pits for Std. Hastelloy CW-2M;
2 pits for Improved Hastelloy CW-2M;
Photo 21, 22 and 23 are SEM surface views at X100 magnification of the corroded
A20 (CN7M), Std. and Improved Hastelloy CW-2M samples.
Photo 21: A20
(CN7M)
72 Corroded pits
Photo 22: Std.
Hastelloy CW-2M
38 Corroded pits
Photo 23: Improved
Hastelloy CW-2M
2 Corroded pits
A
B
C
D
E
17
Photo 24, 25 and 26 are SEM corroded surface views at X800 magnification of the
A20 (CN7M), Std. and Improved Hastelloy CW-2M samples.
Fig 7 is a bar graph
representation of the
corrosion pits counted on
a 0.75 mm
2
sample
surface of A20 (CN7M),
Std. and Improved
Hastelloy CW-2M.
2
38
72
0
10
20
30
40
50
60
70
80
N
U
M
B
E
R
O
F
P
I
T
S
Imp.
CW-2M
Std.
CW-2M
A20
MATERIAL
Fig. 7.
Photo 24: A20
(CN7M)
Photo 25:
Std. Hastelloy
CW-2M.
Photo 26:
Improved Hastelloy
CW-2M.
A
B
D
C C
C
E
E
E
18
Arrows A, B and D in Photo 24 and 25 show corroded pits on the A20 (CN7M)
and Std. Hastelloy CW-2M samples. The pit identified with Arrow B isnt fully
developed. The three E Arrows seen in Photo 24, 25 and 26 show local corrosion attack
on the three alloys in sites where corrosive pits arent developed yet.
The corrosion pits grow gravitationally however if during testing the coupon is tilted the
corrosive product from inside the pit rolls downwards and produces a damaging corrosive
path like shown with the three C Arrows in Photo 24 and 25.
Concluding remarks on the corrosion resistance of A20 (CN7M), Std. and Improved
Hastelloy CW-2M in a service application containing 91-97% phosphoric acid, 0.96%
hydrochloric acid and 0.19% hydrofluoric acid at 115
0
(257
0
F).
The field duration test was 600 hours for Std. and Improved Hastelloy CW-2M and
480 hours for A20 (CN7M).
The intensity of the corrosive pitting attack was established through mass loss and
pit density.
The corrosion rate of Improved Hastelloy CW-2M was 31% lower than the Std.
Hastelloy CW-2M and 96% lower than A20 (CN7M).
The following pit density was counted on a 0.75 mm
2
sample surface: Improved
Hastelloy CW-2M = 2 pits, Std. Hastelloy CW-2M = 38 pits and A20 (CN7M) =
72 pits.
Contrary to Std.
Hastelloy CW-2M, the Improved Hastelloy CW-2M is without
any corrosive attack along the austenite grain boundaries.
THE CORROSION RATE OF IMPROVED HASTELLOY CW-2M IN 6%
HYDROCHLORIC ACID AT 60
0
C (140
0
F) IS NIL.
Hydrochloric acid is extremely hazardous and generates a ver y reducing corrosive
environment. Fi g. 8 shows the NACE published compounded hydrochloric acid Iso-
corrosion chart which defines five temperature acid concentration areas. The metals
contained within these individual regions have a corrosion rate lower than 20 MPY.
\
Fig. 8 shows the NACE published
compounded Iso-corrosion chart in
hydrochloric acid. The five
temperature acid concentration
areas define the metals which have
corrosion rates lower than 20 MPY.
60
A
1 6
Fig. 8.
19
Hastelloy C is part of #1 area. At higher temperatures the corrosion resistance of such
materials decreases consequently the recommended hydrochloric acid concentration
decreases and vice versa.
According to the Iso-corrosion chart at 60
0
C (140
0
F) Hastelloy C withstands only 1%
concentrated hydrochloric acid. After 72 hours of testing in 6% hydrochloric acid at 60
0
C
(140
0
F) the corrosion rate of Improved Hastelloy CW-2M was nil. The pumps
manufactured with I mproved Hastelloy CW-2M for this application were shipped in
service and performed well.
The machined marks seen in Photo 27 through Photo 30 are sharp, unaltered and free of
corrosion attack. In 6% concentrated hydrochloric acid at 60
0
C (140
0
F) the corrosion
resistance of Improved Hastelloy CW-2M is multifold higher than the NACE published
data for Std. Hastelloy C.
Photo 27, 28, 29 and 30 are sample surface views at X100, X500, X1000 and X5000
magnification of the Improved Hastelloy CW-2M tested coupon in 6% hydrochloric
acid at 60
0
C (140
0
). The corrosion rate was nil.
Photo 27. Photo 28.
Photo 29.
Photo 30.
20
Concluding remarks on the excellent corrosion resistance provided by I mproved
Hastelloy CW-2M in 6% concentrated hydrochloric acid at 60
0
C (140
0
F).
Generally Hastelloy C materials have some corrosion resistance in reducing
corrosive environments. Nonetheless the corrosion rate of Improved Hastelloy CW-
2M in 6% concentrated hydrochloric acid at 60
0
C was nil.
Based on this excellent corrosion rate established during a laboratory test the
service pumps build with I mproved Hastelloy CW-2M were shipped to the
customer and they performed well.
Improved Hastelloy CW-2M has multifold higher corrosion resistance than the
NACE published data of the compounded hydrochloric acid Iso-corrosion chart.
IMPROVED HASTELLOY CW-2M HAS EXCELLENT CORROSION
RESISTANCE IN 6% SODIUM HYPOCHLORITE AT 200
0
F.
Even at low temperature not many metals have good corrosion resistance in sodium
hypochlorite. It is widely accepted that the only metal which has consistent good
performance in sodium hypochlorite is titanium.
The comparative corrosion rate of titanium, zirconium and Hastelloy C published by
NACE in 1.5-6% NaOCl, 12-15% NaCl and 1% NaOH at 150-200
0
F is shown in
Table 4. [3]
Table 4.
Material Corrosion rate
[MPY]
Titanium 0.1
Zirconium 4
Std. Hastelloy C 46
Improved Hastelloy CW-2M and titanium have similar corrosion rates when they were
tested together in 6% sodium hypochlorite at 200
0
F and 4% sodium hypochlorite at
200
0
F. During the 72 hours corrosion test the sodium hypochlorite solution was refreshed
after each 24 hours of testing. The results are shown in Table 5.
Table 5.
Material Corrosion rate in 6%
NaOCl at 200
0
F
[MPY]
Corrosion rate in 4%
NaOCl at 200
0
F
[MPY]
Titanium nil Nil
Improved Hastelloy
CW-2M
0.14 Nil
21
When Std. Hastelloy CW-2M pumps are used the sodium hypochlorite solution colors
slightly yellow. Such coloration is unwanted by customers. During the laboratory tests of
Improved Hastelloy CW-2M in sodium hypochlorite at the very beginning the solution
became slightly yellowish nevertheless it quickly changed and remained pure white.
Concluding remarks established on the excellent ranked corrosion performance of
Improved Hastelloy CW-2M in 6% sodium hypochlorite at 200
0
F.
The NACE published corrosion rate of Hastelloy C in 1.5 6% sodium
hypochlorite at 150 200
0
F is 46 MPY.
Improved Hastelloy CW-2M and titanium have 0.14 MPY and nil corrosion rates in
6% sodium hypochlorite at 200
0
F.
Under the circumstances Improved Hastelloy CW-2M can replace titanium in some
sodium hypochlorite pumping applications. Such a material change provides
important savings.
THE YIELD STRENGTH OF IMPROVED HC276 IS 22% HIGHER THAN THE
YIELD STRENGTH OF STD. HC276.
The chemical composition of HC276 used to comparatively test the mechanical
properties, the corrosion resistance in fluosilisic acid and microstructure of Std. and
Improved HC276 is shown in Table 6.
Table 6.
Fig. 9 is a cross-section view of a 4- inch diameter Std. HC276 dissected bar-stock see
Arrows A-A. One half was additionally processed while the other was kept as-
purchased.
Balance 3.38 15.40 16.23 0.76 5.28 0.42 0.07 <0.01 % weight
concentration
Ni W Mo Cr Co Fe Mn Si C Element
Balance 3.38 15.40 16.23 0.76 5.28 0.42 0.07 <0.01 % weight
concentration
Ni W Mo Cr Co Fe Mn Si C Element
Fig. 9.
A
A
D=4
Fig. 9 is a cross-section view of a
4-inch Std. HC276 diameter bar-
stock which was mechanically
dissected through diameter see
Arrows A-A.
One half was additionally
processed.
22
The mechanical properties of Std. and Improved HC276 were tested with specimens
extracted from the half radius distance of the 4- inch diameter dissected HC276 bar-
stock. The results are shown in Table 7.
Table 7.
Tensile strength, elongation, ROA and hardness of Std. and Improved HC276 have minor
differences however the yield strength of Improved HC276 is 22% higher than the yield
strength of Std. HC276.
THE AVERAGE AUSTENITE GRAIN SIZE OF IMPROVED HC276 IS ABOUT
50% SMALLER THAN THE AUSTENITE GRAIN DIMENSION OF STD.
HC276.
Photo 31 and 32 are SEM microstructure views of Std. and Improved HC276 at X500
magnification. The average grain length of Std. HC276 is 120 mm whereas the average
grain length of Improved HC276 is 80 mm. The grain length of Improved HC276 was
50% diminished with the additional process.
Photo 31 and 32 are SEM microstructure views at X500 magnification of Std. and
Improved HC276.
163 75 62 69,500 110.000 Improved
HC276
156 72 63 57,000 110,000 Std.
HC 276
Hardness
[HBN]
ROA
[%]
Elongation
[%]
Yield
[PSI]
Tensile
[PSI]
Mechanical properties
Material
163 75 62 69,500 110.000 Improved
HC276
156 72 63 57,000 110,000 Std.
HC 276
Hardness
[HBN]
ROA
[%]
Elongation
[%]
Yield
[PSI]
Tensile
[PSI]
Mechanical properties
Material
Photo 31. Photo 32. 1 2
4 3
120 mm 80 mm
23
Arrows 1 through 4 in Photo 31 and Arrows Spectrum #1 through Spectrum #4
in Photo 32 indicate the locations in which EDS Energy Dispersive Spectroscopy
were performed. The selected points are located in the middle of the austenite grain,
closed to the grain boundaries and at the grain boundaries. A total of eight chemical
compositions were collected. The chemical composition ranges of molybdenum,
chromium, nickel, iron and silicon of Std. and Improved HC276 are presented in Table 8.
Table 8.
The molybdenum, chromium, iron and silicon composition ranges of Std. and Improved
HC276 are nearly identical however the nickel content range of Improved HC276 is
significantly smaller.
The difference between the upper and lower nickel content spread of Std. HC276 is
5.696%. This difference was diminished to 1.502% in Improved HC276 which indicates
that Improved HC276 is a more homogenous alloy.
Concluding remarks found on the higher yield strength, smaller grain size and chemical
homogeneity conferred by Improved HC276.
The comparative investigation of mechanical properties, grain size and chemical
composition ranges between Std. and Improved HC276 were conducted on two half
samples taken from a 4- inch diameter dissected bar -stock. One half had the
additional process.
The yield strength of Improved HC276 was 22% higher than the yield strength of
Std. HC276. Tensile strength, elongation, ROA and hardness of the two materials
have close values.
The average austenite grain length of I mproved HC276 is 50% smaller than the
average grain length of Std. HC276.
Eight EDS analyses of Improved and Std. HC276 showed that the nickel content
variation range was reduced from 5.696% to 1.502%. Since nickel the major
element of every Hastelloy is homogenously distributed Improved HC276 is a
better material than Std. HC276.
0.439
0.697
4.975
5.040
76.121
77.623
9.777
10.664
7.077
8.524
Improved HC276
Dif.=
0.203
Dif.=
0.426
Dif.=
5.696
Dif.=
0.555
Dif.=
0.695
Dif.=
0.258
Dif.=
0.065
Dif.=
1.502
Dif.=
0.887
Dif.=
1.447
0.488
0.691
4.603
5.029
70.570
76.266
10.241
10.796
7.754
8.449
Std. HC276
Si Fe Ni Cr Mo
Element ranges of eight EDS readings
[% weight] MATERIAL
0.439
0.697
4.975
5.040
76.121
77.623
9.777
10.664
7.077
8.524
Improved HC276
Dif.=
0.203
Dif.=
0.426
Dif.=
5.696
Dif.=
0.555
Dif.=
0.695
Dif.=
0.258
Dif.=
0.065
Dif.=
1.502
Dif.=
0.887
Dif.=
1.447
0.488
0.691
4.603
5.029
70.570
76.266
10.241
10.796
7.754
8.449
Std. HC276
Si Fe Ni Cr Mo
Element ranges of eight EDS readings
[% weight] MATERIAL
24
THE CORROSION RESISTANCE OF IMPROVED HC276 IS MULTIFOLD
HIGHER UNDER LABORATORY AND SERVICE CONDITIONS THAN STD.
HC276 AND HG30.
Photo 33 shows a HG30 rotary seal housing which failed in service after 13 weeks. The
pumping application was 20% fluosilisic acid at 140
0
F.
According to the NACE published corrosion resistance t ables for this application the
corrosion rate of HG30 is between 2 20 MPY which is ranked very good. However
the service corrosion rate was much higher than 20 MPY.
Arrow A shows a transgranular corrosion attack while Arrow B indicates an
intergranular corroded line. Arrow C points to a corrosion roughened area produced
through general corrosion.
This must solve problem was approached by running a corrosion test of Improved and
Std. HC276 in 20% fluosilisic acid at 140
0
F. After 72 hours of testing the corrosion rate
of Improved HC276 was 6 MPY versus 45 MPY corrosion rate of Std. HC276. This
renders a 7.5 lower corrosion rate of Improved HC276 over Std. HC276. Based on these
results all the HG 30 parts were replaced with I mproved HC276. After 18 months of
service the Improved HC276 pump parts continue to run successfully.
Photo 33 shows a returned
HG30 rotary seal housing
which miserable failed after 13
weeks in service.
A
B
C
Photo 33.
25
Photos 33 through 38 are SEM surface views of Improved and Std. HC276 corrosion
tested samples at X200, X1500 and X7000 magnifications.
Arrow A in Photo 34 shows that Improved HC276 has parallel vertical corroded lines.
In Std. HC276 the width of the corrosion lines is larger and some of the corrosion lines
are inclined see Arrows C and B in Photo 35.
Improved HC276 has fewer and shallower corrosion pits see Arrow D in Photo 36
while Std. HC276 has deeper and more numerous corrosion pits see Arrows E and
F in Photo 37.
Photo 34 and 35 are SEM surface views of the Improved and Std. HC276 corrosion
tested samples at X200 magnification.
Photo 36 and 37 are SEM surface views of the Improved and Std. HC276 corrosion tested
samples at X500 magnification.
Photo 35. Photo 34.
C
A
B
Photo 37. Photo 36.
F
E
D
26
The pit seen with Arrow G in I mproved HC276 of Photo 38 is shallow and has
microscopic crevice lines. Arrow H points to a significantly larger pit in Std. HC276
which developed vertically. Nonetheless adjacent to the main pit a harmful penetration
channel is identified - see Arrow I in Photo 39. The entire surface of the Std. HC276
sample is cross hatched with damaging crevice corrosion lines.
Concluding remarks regarding the lower corrosion rate of Improved HC276 in 20%
fluosilisic acid at 140
0
F established under laboratory and service conditions.
Subsequent to 13 weeks of service in 20% fluosilisic acid at 140
0
F the rotary seal
housing and the other seal components in HG30 failed. They were successfully
replaced with Improved HC276.
After more than 18 months in service the Improved HC276 parts continue to run
successfully.
Under laboratory conditions in 20% fluosilisic acid at 140
0
F the corrosion rate of
Improved HC276 was 6 MPY versus 45 MPY the corrosion rate of Std. HC276.
The corrosion resistance of Improved HC276 is 7.5 fold higher than Std. HC276.
Photo 38 and 39 are SEM surface views of Improved and Std. HC276 corrosion tested
samples at X7000 magnification.
Photo 38.
H
I
G
Photo 39.
27
FINAL CONCLUSION:
1. An optimized dissolution reaction of the harmful complex carbides was developed
through a proprietary process. When using this method the mechanical properties of
Hastelloy CW-2M increased significantly. Tensile strength, yield strength and
elongation are 25%, 17% and 95% higher than the minimum requirement of ASTM
A494.
2. The corrosion resistance of Improved Hastelloy CW-2M in 95% sulfuric acid at 250
0
F is 83% better than Std. Hastelloy CW-2M. In 75-90% sulfuric acid at 150
0
F the
corrosion rate of Improved Hastelloy CW-2M is 0.95 MPY. This corrosion rate is
multifold lower than the published corrosion rate of wrought Hastelloy C4.
3. The carbide dissolution process is applicable for any shape of as-cast, wrought and
final machined parts.
4. In 91-99% phosphoric acid, 0.96% hydrochloric acid and 0.19% hydrofluoric acid at
257
0
F the corrosion rate of Improved Hastelloy CW-2M was 31% lower than the
corrosion rate of Std. Hastelloy CW-2M. The corroded pit numbers on 0.75 mm
2
surface of I mproved Hastelloy CW-2M was two while the corroded pit numbers of
Std. Hastelloy CW-2M is 38.
5. Generally Hastelloy C materials have some corrosion resistance in reducing
environments like hydrochloric acid nonetheless the corrosion rate of Improved
Hastelloy CW-2M in 6% hydrochloric acid at 140
0
F is nil.
6. The corrosion rate of Improved Hastelloy CW-2M in 6% sodium hypochlorite at
200
0
F is 0.14 MPY. This value is multifold lower than 46 MPY the NACE published
corrosion rate of Hastelloy C in 1.5-6% sodium hypochlorite at 150-200
0
F.
7. The yield strength of the Improved HC276 is 22% higher than the yield strength of
Std. HC276.
8. In 20% fluosilisic acid at 140
0
F the corrosion rate of Improved HC276 was 6 MPY
versus 45 MPY the corrosion rate of Std. HC276. This is a 7.5 fold change for the
better. The Improved HC276 pump parts used in this application are successfully
running for more then 18 months while the previous parts failed after 13 weeks.
Bibliography.
1) Perricone M. J., Du Pont J.N. and Chieslak M.J. Solidification of Hastelloy
alloys: an Alternative Interpretation published in Metallurgical and Materials
Transactions A Volume 34A, May 2003.
2) CORROSION ASM International, Volume 13, Ninth Edition, page 232.
3) Process Industries Corrosion published by NACE, Library of Congress
Catalog Card #86-62318, page 306.