Corrosion Resistance of Nickel and Nickel

CORROSION RESISTANCE OF
NICI<EL AND NICI<EL-CONTAINING ALLOYS

IN CAUSTIC SODA
AND OTHER ALI<ALIES
Publication NQ 281
NiDI
(CEB-2)
Distributed by the
Nickel Development Institute,
courtesy of Inco Limited
Table of Contents
Page
PART I. INTRODUCTION
PART II. CORROSION BY CAUSTIC SODA...........................
A. Nickel .................................... _. . . . . . . . . . . . . . . . .
1. Effect of Concentration, Temperature and Carbon Content ...... _ . . . . . .
2. Effect of Velocity ............... _ ... __ ..................... _
3. Effect of Aeration ..........................................
4. Effect of System Thermal Gradients ..............................
5. Effect of Impurities .,. _................. _ ............ _ . . . . . . .
6. Effect of Stress .............................................
7. Effect of Dissimilar Metal Contact .. _ ...... _ ...... _ ............. '.
8. Cathodic Protection. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
B. Nickel-Chromium Alloys (Alloy 600) .. _ . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
C. NickelCopper Alloys (Alloy 400, Alloy K-500) ....................... _.
D. Copper-Nickel Alloys .... _ ...... _............. ___ ............ _.,
Copper-Nickel Alloy CA 706 (90-10)
E. Iron-Nickel-Chromium Alloys (Alloy BOO) ......... _ .............. _ . ..
f. Austenitic Chromium-Nickel Stainless Steels (AISI 300 Series) . . . . . . . . . . ..
G. Iron-Base NickelChromium...copper-MoJybdenum AHoys and Nickel-Base Chromium...copper-Molybdenum Alloys .......... _ ....... __ ............. ,
{Alloy 825. CARPENTER 20Cb-3, HASTELlOY alloy G and cast ACt CN-7M alloys}
H. Nickel-Base Molybdenum or MolybdenumChromium-lron Alloys. . . . . . . . . . .
(HASTElLOY alloy C-276, Alloy 625. HASTEllOY alloy B)
I. Cast Irons and Ni-Resists .... _ . _ .... __ .. __ . __ . . . . . . . . . . . . . . . . . . . .
PART
m.
CORROSON BY OTHER ALKAliES.. ............... .... ....
A. Caustic Potash (KOH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..

B. Ammonia and Ammonium Hydroxide ...............................
C. Other Alkaline Solutions of Sodium and Potassium Salts ................
PART IV. INDUSTRIAL APPLICATIONS. ... .... . ............... ......

A.
B.
C.
D.
E.
Caustic Soda Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..

Caustic Potash Manufacture .....................................
Caustic Soda Storage and Transportation .......................... ".
Soap Manufacture ....................... _ ......... _ . . . . . . . . . ..
Pulp and Paper Industry ...... __ ............... _ .. _ . . . . . . . . . . . ...
1_ Digesters _............................................ ...
2. liquor Heaters .............................................
3. Black liquor Evaporators .................. _ . . . . . . . . . . . . . . .
4. Recausticizing .............................................
f. Aluminum Industry. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
G. Caustic fusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..
H. Petroleum Refining ............ _.............. _ . _ . . . . . . . . . . . . ..
I. Caustic DescaJing . _. _.................... _ . . . . . . . . . . . . . . . .
J_ Reclaiming Caustic for Economy and Pollution Control. . . . . . . . . . . . . .
PART V. WELDING ............. __ ..... _. . . . . . . . . . . . . . . . . . . . . .
4
4
4
6
6
7
7
8
8
9
9
10
11
13
13
15
16
17
19
19
20
22
24
24
28
28
30
32
32
33
34
34
35
35
36
37
37
38
A. fabrication of NickelClad Equipment .. _ ..................... "

38.
B. Repair of Equipment in Caustic Service ......... _ ...... _ . . . . . . . . . . .. 39
References .......... _ ......................................... ' 40
Trademarks ..................................... . . ... Inside back cover
Table I
Nominal Compositions of Nickel Alloys in Use or Corrosion Tested in Caustic Solutions
Composition. %
Hi
M;aterial
Fe
Cr
WROUGHT MATERIALS
Nickel
Hickel 200
99.5
0.15
Hickel20t
99.5
0.15
DURAH.CKEL alloy 30t
94.0
0.15
Nickel-Chromium Alloys
.HCOHEL alloy 600
16.0
7.2
H.MONtC alloy 75
71.4
0.5
Nickel-Copper Alloys
MONU alloy 400
66.0
1.35
MON!., al'lI1 K.SO!!:.
65.0
leO
Copper-NiCkel Alloys
Copper-Nkke:1 allo, CA 706
10.0
1.25
CopperNickel alloy CA 710
20.0
0.75
CoppefNlekel alloy cA 715
30.0
0.55
IronNickel-Chromium Alloys
'NCOLO"- alloy 800'
32.0
46.0
Stainless Steels
AISI Type :202
5.0
67.0
AISI Type 31)2
70.5
9.0
AI5ITy,. 304
70.0
9.5
AISI TYlle 304l
10.0
69.0
AISI tYPe 316
13.0
65.0
AISI tJllO 316l
13.0
65.0
AISI Type 309
13.5
60.5
AISI Type 310
20.0
52.0
AISI Type 330
41.0
35.0
AISI Type 347
11.0
68.0
AISI Type. 438
Bal
Iron Base NicketChromium-Copper-MoIybxlenum Alloys
c;"'Rn'n:~- Stainless No. 20 <1'
29.0
43.0
CARPEfC-rR' Sta,"t~$s No. 2OCb-3
34.0
39.0
Nickel Ba';'e l'bn-ChromiumMoIybdenum Anoys
'HCOl.OY- a!Joy 825
41.8
30.0
HASTLLO.. " alloy G
45.0
19.5
HASTt..~OY :alloy C ~2)
~.O
5.0
Si
0.05
0.05
0.15
0.06
0.01
0.55
0.05
0.05
0.25
0.25
0.20
0.25
0.10
0.04
0.10
0.20
0.20
Ii 0.l5; AI 0.15
--
ll.5
29.5
0.12
0.15
0.15
0.15
0.90
0.60
AI 2.8: Ti 0.5
88.0
78.0
61.0
Pb 0.05 max; In 1.0 rna.

Pb 0.05 rna.; Zn 1.0 max
Pb 0.05 max; In 1.0 max
Mo
Cu
--
15.8
20.5
---
18.0
18.0
18.0
18.0
17.0
17.0
23.0
25.0
1.5.1)
18.0
17.0
-2.0mi..
2.0 min
--
20.0
20.0
2.0 min
2.5
20.5
Mn
0.3
0.4
0.5
0.30
O.M
0.35
0.75
1.0 max
0.5
0.5
0.5
0.5
0.5
1.0 max
1.0 max
1.0 rna.
1.0 max
8.1
1.5
1.5
0.15ma.
0.15 max
0J)8 max
0.03 max
O.OS max
0.03 max
0.20 malt
0.25mn
0.25 rna.
0.08mu
0.12 max
3.0m;n
3.3
0.07 max
0.01 max
1.0
0.6
0.8
08
0.03
0.03
0.08 max
0.35
0.35
1.0 rna.
0.65
1.3
1.0 max
---
21.5
22.2
15.5
3.0
6.5
16.0
1.8
2.0
1.3
1.7
1.8
2.0m3X
2.0ma.
2.0 mal
2.0mu
Otber
AI 4.5; Ii 0.5
N 0.25 max
---Cb;- Ta IOxC min

Cb+Ta 0.6
AI 0.15: Ii 0.9
W 0.5; Cn ,. Ta 2.12
Co 2.5ma<;
W 4.0: V 0.4 max
Co 2.5 rna.;
W 4.0: V OA max
Cb- Ta 3.65
54.0
5.0
15.5
16.0
0.02 max
0.05max
1.0max
alloy 625
60.0
5.0ma.
21.5
9.0
0.10 max
0.5 max
0.5 max
Nickel Base Molybdenum Alioy

..ASULLO'\'- alloy B
61.0
5.0
28.0
0.05 max
1.0 max
2.. 0
1.5 max
15.5
0.3
3.0 max
1.5 max
O.OS
(1.35 mall
4.0
2:.0 mat
0.80
1.5 max
--
0.08mllll:
OJl8 max
0.ISm3l
0,20mu'
2.0m,n
1.5ma.
1.5mu
).0 rna.
1.5 mall
1.5 max
1.0ma.
O.S
1.75
3.0 min
0.1)7 max
0.01 milx
3.3
1.0
0.6
UiJlnax
---
-$.5
0.01ma1l
0.20
1.0
0.65
1.0
1.25
HASTELLO.. 'HC_I:L -
alloy C2l6
1.0 max
CAST MATERIALS
Nickel
America.. Casti"e Institute
95.0 min
1.5 max
ACI CZl00
NickelCh.romlumfron Alloy
ACI CY40
70.0
9.5
Nickel-Copper Alloys
HickelCopper alloy 50S
64.0
2.0
64.0
ACI "'-35
3.5 max
Stainless Steels
ACI Cr-8
19.5
66.0
ACI Cf8M
19.5
63.0
ACI CAtS
1.0 max 83.0
ACt HA
87.0
Iron Base Nickel-ChromiUm-CjPper Alloys
wo......tn: Stainless
24.0
48.0
ACI CN-7M
29.0
44.0
Nickel Base 'ron-ChromiumMolybdenum Alloys
CHLORIMT" 3
60.0
2.0
ILLIUM' alloy to
56.0
6.5
Nickel Base Molybdenum Alloy
cHt.o,nMII!T 2
63.0
3.0ma.
Nic,kel Base Sitleon Alloy
"AS.TEL~OY alloy D
82.0
2.0lllllx
Nickel Alloyed Cast Irons
NIRes)st Type 1
15.5
69.0
HIRu;st Type 2
20.0
70.0
HI-Resist Type 3
30.0
62.0
NiResist Type 4
30.5
55.0
NiResist Type D2
20.0
72.0
HIResist Type D3
30.0
61.0
"'0
(1) An improved version of this alloy.
CARPENTER'"
29.0
29.5
9.5
10.5
12.8
9.0
20.0
20.0
-2.5
Q.5max
1.1
3.0
2.0 mill
18.0
22.5
JUt
U
32.0
1.0 rna.
2.2
2.2
3.0
5.0
2.1
3.0
.'
--
---
--
0.15
IIIa~
1.0
1. 0
3.0
O.l?max
90
0.51.25
6.5
05ma.
O.Sma.
0.5 rna.
2.8
3.0 max
2.6ma.
2.6 mal
3.0 max
2.6 max
2.0
1.9
1.5
5.5
2 ..f
2.2
1.2
--
stainless',No. 20Cb3. has replaced
CARPENJR'" ~ta'nie~s
(2) An improved version of this alloy. HASTEllOY alloy C276. has replaced ..ASTUt:OY alloy C.
(3) Cast Alloy 20 alloys such as DUR,MUO alloy 20. ALOYCO" alloy 20. etc
See ins;de back cover for registered trademarks.
1.2
0.6
06
0.9
O.Sma.
No. 20
Co 2.5 rna.: V 0.20A;

P 0.025 rna.;
S 0.030 max
Co 1.5 max
_.-
---
Corrosion Resistance of Nickel and Nickel-Containing

Alloys in Caustic Soda and Other Alkalies
PART I. INTRODUCTION
purities in the caustic, the necessity for product
purity. corrosion rate, susceptibility to stresscorrosion cracking (caustic embrittlement) and
economics. Caustic soda can be handled in cast
iron or steel equipment at low temperatures. if
iron contamination is not detrimental to end use.
At elevated temperatures, however, iron and steel
are subject to caustic embrittlement and high corrosionrates. Plant and laboratory tests and operating experience over many years have demonstrated that nickel and nickel alloys are the
preferred materials for handling caustic solutions in many applications. Nickel can be used for
practically an concentrations and temperatures.
In addition to caustic soda. several other important alkalies are discussed in this bulletin. but
no attempt has been made to be all-inclusive.
Nominal compositions of alloys referred to in
the text are shown in Table L Materials other
than nickel-eontaining alloys included in a number of tests are reported for reference purposes.
An corrosion rates are reported as mils penetration per year (mpy). (1 mil 0.001 inch.)
Caustic soda (sodium hydroxide) is the most

widely used and avaBablealkaline material. In the
United States almost all of the caustic soda is produced as a co-product in the production of chlorine
by the electrolysis of sodium chloride. The electrolytic cells used can be divided into two general
types: mercury cells and diapllragm cells. With
mercury cells,high purity SOt;(. caustic is produced directly, whereas with diaphragm cells. the
caustic concentration produced is within the
range of 9 to 15 per cent, and has to be further
purified and concentrated before sale. A small
amount of caustic soda is produced by the limesoda proce$S which WaS formerly the prime source
for this chemical.
Caustic soda is generally marketed in concentrations of 50 percent, 73 per cent or anhydrous.
The chemical industry is the largest consumer of
caustie soda, followed by the rayon and film industries. the pulp and paper industry and the
aluminum industry.
A large number of alloys can be used for handling caustic soda, and selection is based upon
such factors as concentration. temperature, im-
Fig. 1 - These caustic soda evaporator units are a

combination of both solid Nickel 200 and steel clad
with Nickel 200. Diaphragm cell liquor feeds into the
double-effect evaporator: overflow from a settler tank
feeds the single'effect evaporator for conc.entration to
50% caustic soda. The system produces 700 tons of
salt and delivers 434 tons of NaOH (100%1 per day.
Ph%qraDh by courtesy ot
the Swenson Division Of Whiting Corporation.
PART II. CORROSION BY CAUSTIC SODA

A. Nickel
1. Effect of Concentration, Temperature
and Carbon Content
Corrosion test results for nickel in commercial
caustic soda solutions were obtained by a number
of investigators at different times and locations.
Typical test data are shown in Table II and these
have been incorporated in the isocorrosion chart,
Figure 2. Only at high caustic concentration near
the boiling point does the corrosion rate exceed
one mil per year. This isocorrosion chart is intended only as a guide; there are specific conditions under which higher or possibly lower corrosion rates can prevaiL These conditions are
discussed later.
700 r - - - . . , . - - - - - r - - - r - - - - . . , . - - - " r " > 371
..:;
600
316
500
]60
u... 4
Fig. 3 - View of caustic transfer piping from marine storage

tank area to terminal where rayon grade 50% caustic soeta
is loaded into a barge. Several hundred feet of lightweight.
welded Nickel 200 piping in 8-inch and 12-inch sizes are
used.
oo
In caustic concentrations above 75 per cent and

including molten caustic soda. nickel is second
only to silver in resistance to corrosion. When
nickel is to be used at temperatures above 316 C
(600 F). a low-carbon grade, Nickel 201 (0.02% C
max). should be employed to preclude the possibility of graphite precipitation in the grain boundaries and a resultant loss in ductility. Nickel 201
is often used for the construction of tubular evaporators for continuous vacuum concentration of
caustic soda from 50 and 73 per cent to anhydrous at temperatures up to 404 C (760 F). with
nickel pickup in the finished caustic of only one
to two ppm. 3
Molten caustic soda has been considered as a
heat transfer medium for nuclear energy application. In static tests at Harwell in England,
Gregory. et aL.~ concluded that Nickel 201 was a
satisfactory container material for molten caustic soda at temperatures up to 580 C (l076 F)_
Some of their data are shown in Table IV.
"0
Q;
Q
~ 100
f-
'13
200
"- 0.1 mpy
<OJ mpy
38
100
o '--_ _....l.-_.L---l._ _- - ' ' - -_ _...L-_ _
20
40
60
80
17.8
100
Fig. 2 -Isocorrosion chart for Nickel 200 and Nickel 201

in sodium hy~roxide.l
Some tests which have been carried out at

elevated temperature and pressure in autoclaves
indicate satisfactory performance for nickel in
caustic soda solutions even above the atmospheric
boiling point, as shown in Table IIU
4
Table II
Typical Corrosion Test Data for Nickel and High Nickel Alloys in Caustic Soda Solutions
Corrosion Rate, mils per year
HaOH
;oncen-
Temperature
tration,
Test
A.e1ation
Agitation
Period,
days
NickelCopper
Alloy
Chromium
(MONEL
ltNCONEl
Nickel-
Alloy
Comments
Hicke!
200
alloy
40ll)
alloy
6nO\
D-1
3{l
86
Nooe
Hone
27
Test coupons removed,

cleaned and dried each day
fOf lOdays
0.01
0.01
nW
30
86
Hone
None
1&2
Average of tests run at

8 separate laboratories
0.05
0.16
3{l
86
Air agitated
Air agitated
1&2
Average of tests run at

8 separate laboratories
0.05
0.21
5-10
21-32
70-90
Extensive
due to
filling tank
124
Storage lank
0.15
O.ll
0.05
14
88
190
None
None
90
First effect of multipleeffect evaporator
0_02
0.05
0.03
22
50-60
12{)-140
None
due to
filling tank
133
Storage tank coupons

immersed 95% of time
nil
0_01
0_01
34
65
150
Extensive
Mild
37
Storage tank in which air was

bubbled through from bottom
0.03
0.03
30"50
81
178
None
None
16
Single-effect evaporator_
Rates are average of 3 tests
0.09
0.19
49-51
55-75
31165
131-167
av 149
None
due to
lining tank
30

fully immersed
0.02
0.03
0.02
50
55-61
31158
131-142
a1l 136
None
due to
filling tank
135
Storage tank
0.02
0.02
0.02
50
60-70
av65
14~158
al/ 149
Moderate
by lOOgpm
393
Transler piping. at pump

discharge
0.07
0.10
0.03
50
150
302
None
None
14
laboratory test on tubing;

average of 4 coupons
0.25
72-73
116
273
None
due to
filling tank
183
Storage tank
0.3
0.7
0.4
72
121
282
Moderate
due to
filling tank
119
Storage tank
OJ
0.3
0_1
73
95-100
203-212
None
by rocking
of tank
111
rest tank_ simulating action

of tank car
0.13
0.16
0.14
73
100-120 212-248
avll0 a1l230
None
due to
filling tank
52

immersed 95% of time
0.05
0.04
0.06
13
104-116 244-251
av 110 av248
None
due to
filling tank
126

lully immersed
0.02
0.10
0.0\
14
130
Not specified
by movement
of tank car
II trips
of 7-9
days
Coupons in railroad
tank car
0.3
0.4
Not specified
due 10
filling tank
35
Storage tank between

evaporator and finishing pots.
Ammonia Soda Process
1.6
1.7
1.3
None
None
Concentration in caustic
evaporator
3.9
13.4
15
135
266
271
60 to
15~260 302-500
nearly
anbydrnus
flow from
pump
Less than 0.005 mils per year.
Table llt
laboratory Corrosion Tests in Caustic Solutions at Elevated Temperatures
NaOH
Concentration,

Temperature
20
40
60
80
110
110
llO
110
262
262
20
40
60
80
115
262
Test
Period,
hr
15
15
15
262
15
ll5
US
272
272
272
272
19
19
19
162
162
162
162
355
355
355
355
19
19
20
40
60
149
149
332
332
332
20
40
GO
80
132
132
132
132
20
40
60
80
111
111
l7l
17l
270
270
270
270
340
340
340
340
19
19
19
]9
19
19
20
40
GO
86
156
156
15G
156
345
345
345
345
20
40
GO
80
20
46
GO
127
127
127
127
150
150
152
183
183
183
293
293
293
293
20
40
60
80
20
GO
80
115
149
334
334
336
394
394
394
Nickel
206
19
19
19
MONEL
alloy
400
sIs
(solution
quenched)
WORTHITE
Hi-
Resist
Type 2
Cast ACI
CN7M
nil
nil
nil
nil
nil
nil
nil
nil
nil
nil
nil
nil
nil
3
1
9
1
19
nil
19(2 tests}
19 (2 tests)
1912 testsl
19 (2 tests)
25,69
36.28
2,38
20
14
nil. nil
20
17
20
20
15
15
15
33
1
94
6
17
IS
28
18
18
19
15
15
15
10
1
12
nil
151
2
2. Effect of Velocity
3. Effect of Aeration
Velocity has little effect on the corrosion rate of

nickel in caustic at temperatures below 500 C
(932 F) but at 540 C (1004 F) and above, increasing velocity may cause a several-fold increase in
the rate of attack. Figure 4 shows the results of
two-week laboratory experiments by Gregory,
et al., in high temperature molten caustic soda
under dynamic conditions.
Aeration has not been observed to accelerate

corrosion in lower concentration caustic soda
solutions. However, at high concentrations and
temperatures, such as occur when concentrating
to anhydrous, precautions should be taken to
minimize aeration.
720 C (1328 Fl
M"lten Coust;c Sodo
480
taining atmosphere in the vicinity where corrosion is occurring. Forestieri and Lad found that,
as a result of the presence of chromite ion
(CrO:I- 1 ) , mass transfer and cOITosion were
essentially eliminated for 50 hours by one per
cent addition of 325-mesh chromium powder in
a test loop operating at a fluid velocity of 15 fps
and 816 C (i500 F) with a temperature difference
of either 11 C (20 F) or 22 C (40 F) .>1.9 However,
a small mass transfer deposit was obtained after
250 hours, indicating that a single chromium addition would not protect a nickel system indefinitely.
400
>-
680 C (1256 Fl
.----------
320
~
0
oc
c
_Q
240
(;
400 C ( 752
500 C
540 C (l004 F)
200
300
400
Fl
600 C {I I 12 Fl
580 C {1076 Fl
100
P 175
635 C
500
FI
I 952 F)
5. Effect of Impurities
600
Rotot;on $peed_ rpm
Fig. 4 speed.'
Chlorates in caustic can increase corrosion rates

as indicated in the later section on caustic soda
manufacture (page 27). Small amounts of sodium chlorate are produced in electrolytic diaphragm cells. The effect of the chlorate on corrosion rate is not critical unless the chlorate is decomposed. and thermal decomposition does not
occur below a temperature of 260 to 290 C (500 to
554 F). If it is intended to operate nickel equipment at or above this temperature range. four
alternatives are available:
Corrosion rate of nickel as a function of rotational
Table IV
Static Corrosion Rates of Nickel and Nickel Alloys
in Molten Caustic Soda
Temperature
Alloy
Hickel20t
a!toy e
HASTELt.OY aUoy D
MONEl. alloy 400
INCONEL aUoy 600
OURANICKEI. alloy 30t
NIMONIC all01 75
460e
(750 f)
0.9
HASTELLOY
0.7
1.8
U
1.7
1.1
500e
(932 f)
58fl e
(1076 f)
1.3
2.5
100.5
2.2
5.1
2.4
3.2
14.3
17.6
5.1
680e
(1256 f)
37.8
a. Use "rayon grade" caustic which has a specification of 5 ppm maximum chlorate content.
b. Use caustic produced by electrolytic mercury
cells or by the lime-soda process, or,
c. Use anhydrous caustic; there are no chlorates
in the anhydrous grade.
d. Add reducing agents as discussed in the section on caustic soda manufacture (page 27) .
9.9
10.4
20.8
(pitted)
66.4
40.7
47.6
Gained weight. Swollen outside surface largely oxide-heavily cor

roded.
4. Effect of System Thermal Gradients
The presence of oxidizable sulfur compounds

in caustic soda tends to increase the corrosion
rate of nickel at elevated temperatures. This is
noted particularly with hydrogen sulfide, mercaptans, or sodium sulfide, and to a much lesser
extent with partially oxidized compounds such as
thiosulfates and sulfites.
The effect of the addition of oxidizable sulfur
compounds to caustic soda on the corrosion rate
of nickel has been studied in the laboratory with
the results shown in Table V. Test 1 was made
during the evaporation of a commercial caustic
soda solution under 28 inches of vacuum. Sulfur
content of the original caustic. calculated as per
In molten caustic soda at temperatures above

about 550 C (1022 F), nickel is subject to thermal
gradient mass transfer.:; 4;. 7 In this type of attack, nickel is dissolved in caustic at a high temperature surface and is precipitated at a low
temperature surface in a circulating system.
Gregory, et at, concluded that the corrosion rate
of nickel in molten caustic soda could be ten times
as great under dynamic conditions as it was
under static conditions because of the solubilitytemperature relationship.:;
The mass transfer effect can be inhibited but
not prevented by maintaining a hydrogen-con7
(Nickel 201) will circumvent this problem.

Applied or residual stresses apparently do not
significantly affect the genera! corrosion rate of
nickeL 11
Table V
Effect of Oxidizable Sulfur Compounds on Corrosion
of Nickel 200 in Caustic Soda
Temperature: 130 C
c:::
5 C (266 F
c:::
9 Fl.
7. Effect of Dissimilar Metal Contact
Corrosion
Test
Rate,
No.
Corrosive
Commercial Sodium Hydroxide being concentrated
from 50 to 75% NaOH (Sulfur content at start.
calculated as H,S. 0.009%}
1.7
75% C.P. Sodium Hydroxide
0.6
75% C.P. Sodium Hydroxide plus 0.75% Sodium

Sulfide
22.8

Th~wlf~e
~9

Sulfite
5.2

Su!!ate
0.6
Galvanic corrosion can occur in caustic soda solutions if different materials of construction are
electrically connected. Whether this effect is academic or critical depends upon the specific conditions that exist in a partiCUlar installation. For
instance, the data in Table VII illustrate that gray
cast iron corrodes from about one and one-half
mils per year
Table VI
laboratory Tests in fused Caustic Soda with and
without Addition of 5% Sodium Peroxide
Temperature
Chemically pure.
cent H;!S in dry caustic, was 0.009 per cent. Test 2

was made in chemically pure caustic soda. Tests 3
through 6 were made in chemically pure caustic
to which the various sulfur compounds had been
added.
It has been found that the detrimental effect
of oxidizable sulfur compounds in caustic can be
counteracted by the addition of sufficient sodium
peroxide to form sulfates. An excess of peroxide
does not seem to be detrimental. as shown in
Table VI which compares the resistance of nickel,
iron, and copper to fused caustic soda with and
without an addition of 5c;. sodium peroxide. lo
In each test, 5 grams of the substance were fused
for four hours in a laboratory crucible of the
given metal and analyzed for metal pickup.
Caustic Soda
350
360
450
500
550
600
662
680
752
842
932
1022
1112
350
400
450
662
752
842
400
Caustic Soda
with 5% Sodium
Peroxide
Metal Pickup. grams
Imn
Nickel
COHosive
Copper
.4
.01.02
Irace.02
.01.02
.005.015
.426
.2.3
.2.3
.4.43
.i3.3
.024
.025
.0024
.0135
.OBI
.Il
trace
.013
.03
SI rangly attacked
Table VII
Galvanic Corrosion of Gray Cast Iron
Conditions: Corrodent: 5% sodium hydroxide.
Temperature: 43 C (ll 0 F).
Flow: 16 feet per minute.
Aeration: Saturated WIth air.
Cathode to anode area ratio 2: 1.
6. Effect of Stress
Experience has indicated that Nickel 200 is not
subject to stress-corrosion cracking in pure
caustic solutions. However, it is subject to
stress-corrosion cracking by mercury, and there
have been a few cases of cracking of nickel when
"upsets" occur in producing plants that utilize
mercury cells.
In addition, cracking along precipitated grain
boundary jTraphite in Nickel 200 has occurred
after caustic soda exposure above 316 C (600 F).
As indicated previously. a low-carbon grade
Corrosion Rate of
Gray Cast Iron.
mils per year
Cathodic
Material
Nickel 200
Nickel 200
MONEL alloy 400
MONEL alloy 400
Insulated
l.l
0.6
0)
0.6
0.75
Average
Slight welgh1 gain
In
Galvanic
Couple
1.5
]6
2.1
17
1.72
Average
Corros ion Rate of

Cathodic Material,
mils per year
Insulated
0
<01
0
In
Galvanic
Couple
<0.1
<0.1
0
to three times its normal rate when connected to

Nickel 200 or MONEL alloy 400, under the given
set of conditions. However, the normal rate for
cast it-on in 5~-;' caustic is so low that these higher
corrosion rates are usually tolerable.
At higher caustic concentrations, temperatures, and with large cathode to anode r;:ttios.
galvanic corrosion becomes more pronounced.
The galvanic current curves shown in Figure 5
are from tests made above and close to the upper
tube sheets of operating caustic evaporators. The
general conclusions to be drawn from these tests
are that in concentrated caustic soda solutions.
significant galvanic corrosion may occur on cast
iron or steel when in contact with nickel or copper. In the construction of caustic evaporators.
it is desirable, if not actuaHy necessary, to use
nickel or nickel-clad steel tube sheets in conjunction with nickel tubes.
8. Cathodic Protection
In the continuous production of anhydrous caustic, experience has shown that cathodic protection
can be applied successfully to nickel evaporating
equipment. In one such case, a cathode current
density of about 1 ampere per square foot of exposed nickel surface provided satisfactory protection. In other less corrosive applications, as in
storage of 75~( caustic, current densities as low
as 0.01 ampere per square foot have been reported
effective. Nickel 200 anodes are used in these applications_ Laboratory tests in 75% caustic soda
at 120 C (250 F) and also in fused anhydrous
caustic soda at 480 C (900 F) have shown that
\",ith equal areas of nickel for anode and c.athode,
and with an applied anode current density of
10 amps per square foot, the corrosion rate of
the nickel anode does not exceed that of uncoupled
nickel. A pure technical grade of sodium hydroxide was u~ed in these tests, which contained less
than 0.04 per cent of heavy metal impurities. The
result.c; are shown in Table VIn.
70r---~----'----r----.----r----'----r---.
u.
GoJvonrc Current Flow Between

C05-t 1on end Copper
b.O
~ 5.0
A"'?oe: c.,;~ !"on Ar~"

C,~d~ode:
Si
Ccpoe r
A~e'1
. C 3QS -;:: ;:.
0.*9"4 ;-::
=.
Table Viti
4.0
laboratory Tests of Nickel 200 Anodes and Cathodes

in 75 Per Cent and Fused Caustic Soda
{; 3.0
"
Temperature: 120C (250F) for 75% caustic.

480 C (900 F) for fused caustic.
" 1.0
~
Duration of Tests: 1821 hr.
.(
Volume of Solution Used: 1 liter.

Anode Current Density: 10 amp per sq ft.
JS
Area of Specimens: 0.066-0.087 sq ft.
7.0,-----,..-----,----,..-----.--__-,-____,--__-,-__--,
Average Corrosion Rate.

mils lIer year
Golvonic Cv ...enf flow Between

Cad Iron ond Niclel
A"\Cd:~: C~S~ h,)~ Af"-e:2 =-.C c.J~a ~ J c.
N;d:e~ Are~ ...:. il.24; 5.;)::.
C,+ode:
Nickel 200 Anode

Nickel 200 Cathode
NickeI200-Uncollpletl
75% Caustic
fused Caustic
0.8
0.2
1.0
11.3
0.9
11.2
.~
3.0
?"
2.0
U
"D
"
1.0
Note that the cathodic nickel surface benefited

from cathodic protection, while the corrosion rate
of the nickel anode was not increased.
.("
B. Nickel-Chromium Alloys
Fig. 5 -- Current measurements between cast <ron, copper

and nickel specimens set up above and near the upper tube
sheet of an evaporator concentrating caustic soda from 47
to 60 per cent. NaOH under 26 in. vacuum using steam at
a pressure of 75 Ib per sq in.
Nickel-chromium alloys, such as INCONEL alloy

600, are approximately equi\'alent to nickel in
9
corrosion resistance in caustic soda, as shown in

Tables II, IV and XL.
Alloy 600 is commonly used in equipment for
the production of anhydrous caustic when sulfurbearing fuels are used for heating because it is
more resistant to sulfidation than nickel.
There have been a few instances of stresscorrosion cracking of Alloy 600 in some strongly
alkaline environments. A review of these serviee
failures has indicated that they usually occurred
in concentrated caustic solutions at high temperatures, 190 to 450 C (374 to 842 F). In seven-day
laboratory tests, caustic concentration, temperature, and the presence of air were shown to be
important variables, as shown in Tables IX and
XIV. No stress-corrosion cracki ng occurred if the
Alloy 600 U-bend specimens were stress-relieved
at 900 C (1650 F) for one hour or 769 C (1400 F)
for four hours after bending.
Fig. 6 - This barge has eight tanks with a capacity of

34,000 barrels.. The tan~s are used to carry fuel oil or as
ph~lt. and a specli;ll 54.00barret tank fabricated of INCONEl
alloy 600-clad steel is used to carry 73 010 caustic soda, am
moniabasefertilizers, or jet fuels.
higher than nickel at temperatures above the

atmospheric boiling point, as shown in Table III.
However, it should be noted that even in those
cases where AHoy 400 is inferior to nickel, the
corrosion rates are still quite low.
There have been a few reports of stress-corrosion cracking of cold-worked and stressed Alloy
400 in caustic soda. However, the eXact conditions
under which most of these failures occurred are
not known. It is known that some of the reported
failures associated with mercury cell caustic were
caused by intergranular attaek by mercury and
subsequent loss of ductility.
Laboratory tests have shown that Alloys 400
and K-500 can be susceptible to stress-corrosion
cracking unde.r extreme exposure conditions. that
is, high stresses in combination with high temperatures and concentrated caustic soda can cause
cracking. Table X shows the results observed
with tensile loaded specimens tested at 300 C
(570 F) in condensing steam after being coated
with either potassium or sodium hydroxide.
Under these exposure conditions, Alloy 400,
which had been cold-worked or cold-worked and
stress-relieved prior to testing, was susceptible
to stress-corrosion cracking~ cold-worked material that had been annealed at 850 C (1560 F) or
950 C (1740 F) prior to testing was resistant. As
with Alloy 400. Alloy K-500 cracked when cold-
Table IX
StressCorrosion Cracking of INCONEl Alloy 600
U-Bend Specimens in Caustic SolutionsSeven-Day Tests
Temperature
Overpressure.
150 psi Caustic
200
250
300
200
250
300
200
390
480
570
Air
Air
Air
390
480
570
250
300
Caustic CORcentratiolt, weight %
10
50
NaOH
NaOH
NaO"
OK
OK
Argon
Argon
Argon
NaO"
NaOH
NaOH
OK
OK
OK
OK
390
Air
KOH
OK slight inter
granular
penetration
480
570
Air
Air
KOH
KOH
90
stress-cracked
OK stresscracked stresscracked
OK
OK
OK
OK
stresscracked
stress-cracked
Note: Testing performed in autoclaves under static conditions without

replenishment of air or argon.
C. Nickel-Copper Alloys
Nickel-copper anoys, such as MONEL alloy 400,
are practically as resistant to caustic soda as
nickel, as shown in Table II.
The corrosion rate of Alloy 400 is higher than
nickel at caustic soda concentrations above 75 per
cent when concentrating to anhydrous. It is also
10
Table X
Stress-Corrosion Tests on
Alloy
MONEL
MONEL
Alloy 400 and

Yield
Applie II
Strength,
Stress,
None-as cold-drawn
850 C (1562 fltIti hr/W.O.

MONEL alloy
40(1
Alloy K-500
ton/ S1l in. tonI sq in.
Heat Treatment
alloy 4(1(1
MONEl
Cracking
NaO\(
KO\(
43.8
12.8
33.1
16.3
IIG
5
41'11
5
24.0
20.1
OIG
OIG
Stress relieved
540 C 11004 fl/ z hr
Type and Degree of
MONEL alloy 40(1
Works anneal
950 C U742 fll Y2 hr
11.4
8.3
MONEL alloy
None-as COld-drawn
870 C U598 f)f5 min/W.O.
580 C(1076 fl/S hf/fC
810 C US98 A/S min/W.O.
580 C{1016 fl/16 hr/FC
52.5
21.2
65.5
33.1
10.3
37.2
3IG+TG
5
4TG
5
5
5
44.9
37.2
OrG
OIG
None-as colddrawn
870 C(1598 fl/5 min/W.O.
580 C n076 AIS hrl FC
870 C (1598 fl/5 min/W.Q.
+ saocno76 flfl6 hr/fe
53.2
NO
NO
33.1
10.3
37.2
4NI
5
OIG
NO
37.2
DIG
MONEL
KS(I(I
alloy K500
Fumace-coaled at about 10 C (18 Fl/nr to 480 C
(896 Fl then "if.-coa!ed to room lef'lperature.

NO = Not Determined
= Shallow cracks visible under microscope
= No cracks
= Transgranular cracks
IG == Intergranula. cracks
I'll = Type of cracking nQt jdentified-cracks very
TG
o == Specimen fractured
1 == Coarse 'cracks visible to naked eye
2 == Fine cracks visible to naked eye
3 == Deep cracks visible under microscope
short.
worked and was resistant in the annealed condition. However. the thermal-hardening treatment
at 580 C (1076 F) rendered the alloy very susceptible to cracking.
The practical interpretation of these data is
difficult because threshold values of stress, caustic
soda concentration, and temperature at which
stress-corrosion cracking will occur have not been
established. With these limitations in mind, it
would appear prudent to stress-relieve AHoy 400
in the range of 538 to 566 C (1000 to 1050 F) or
anneal it ill the range of 760 to 816 C (1400 to
1500 F) for one to three hours when it is to be
used in higher strength caustic at elevated temperatures.
>-
0-
o'" 12
a::
5 8
.;;;
l?
20
40
60
100
Per Cent Nidel in Copper.Nickel Alloys
Fig. 7 - Results of corrosion tests of copper-nickel alloys

in 50% caustic soda evaporator.
Copper-nickel alloy CA 715 (70% Cu-30% Ni)

possesses excellent resistance to dilute concentrations of caustic soda at low temperatures and
appears to have useful resistance to caustic soda
solutions of up to 73 per cent at the boiling point.
However, this resistance does not extend to fused
caustic. Alloy CA 715 has been used successfully
as evaporator tubes for concentrating to 50 per
cent where copper pickup by the caustic could be
tolerated.
Copper-nickel alloys CA 706 (90(~ Cu-lO('~ Ni)
D. Copper-Nickel Alloys
The corrosion resistance of copper-nickel alloys
in can.stic soda solutions is dependent upon the
nickel content of the alloy, as illustrated in Figure 7. There are a limited amount of additional
data which are shown in Table XI.
11
Table XI
Corrosion of Copper-Nickel Alloys by Caustic Soda Solutions
HaOM
Concentration,
%
Nominal
Alloy
Composition
CopperHickel Wt% Wt%

Alloy
Hi
Cu
Temperature
F
Test Corrosion
Dura- Rate,
tion, mils per
year
days
Comments
40
40
15-20
59-68
Hot-Exact temperature
unknown
21
25
Nil
0.5
laboratory test in glass bottle.

Diaphragm cell liquor
coupons in distributor box to settlers.
70
70
30
21
25
Nil
4.3
70
70
70
70
70
30
30
30
30
30
1520 .1. 59-68

Hot-Exact temperature
unknown
203
95
65
149
105
221
150-175
302347
150260
302500
67
30
118
2
0.8
Nil
1.2
4.4
21

Diaphragm cell liquor
coupons in distributor box to settlers.
Velocity 1.8 ftl sec. Salt saturated.
In storage tank.
100
70
30
400410
752770
70
5
6075
80
80
20
20
1520
150-175
5968
302347
21
liz
60100
80
20
150260
302500
28
100
80
20
400410
752770
90
90
10
95
203
67
1.8
90
10
105
221
118
2.0
60
11
60
5
11
50
50
73
60-75
60-1Im
CA 715
30
l/Z
Nil
8.1
CA 710
50
CA 706
73
In evaporator concentrating from 60-75%.

In evaporator concentrating
from 60% to anhydrous.
In anhydrous melt.
from 6075%.
from 60% to anhydrous.
In anhydrous melt.
Velocity 1.8 ft/sec. Salt
saturated.
,. Less than 0.1 mit per year.
and CA 710 (80% Cu-20% Ni) have useful resistance to caustic soda solutions but their application is limited to lower concentrations and temperatures than AHoy CA 715. Because of the
limited data available it is difficult to define limits
for these two alloys.
While corrosion of the copper-nickel alloys by
caustic solutions may be aggravated by the presence of sulfur compounds, Alloy CA 715 is able
to resist attack under some conditions, as shown
in Table XII. No data appear to be available on
the susceptibility of these alloys to stress-corrosion cracking in caustic soda solutions.
Table XII
Corrosion Rate of Copper-Nickel Alloy CA 715
in Alkaline Solutions Containing Sulfur Compounds
Conditions of Exposure
1. In open tank used to boil 1822 per cent
NaGH to release mercaptans at 80 C (175 fl
2. In reboiler of caustic stripper, 12 per cent
NaDH.3 per cent Na,S. 10 per cent sodium
phenolate + 0.7 mg per liter as sodium
mercaptides at 124 C (255 Fl
3. In 10 per cent sodium sulfide in storage
tank at atmospheric temperature
4. In 60 per cent sodium sulfide in flaker
feed tank at 171 C (340 f)
5. In regenerator reboiler for steam stripping
of mercaptans from solutizer solution
25.2 per cent potassium hydroxide
37.8 per cent potassium isobutyrate
5.5 per cent potassium sulfide
1.9 per cent potassium mercaptides
2.1 per cent potassium carbonate
at 141 C (286 f)
6. In vapors from solution in item 5
~
12
Pitting up to 3 mils depth.
Corrosion
Rate,
Duration,
mils per year
days
30
131
25
81
28
14
140
140
15
12
E. IronNickelChromium Alloys
Table XIV
Based upon data obtained in several test exposures and shown in Tables Xln and XL, it appears
that INCOLOY alloy 800 approaches INCONEL alloy
600 in resistance to caustic soda. However, Alloy
800 is more susceptible to stress-corrosion cracking than Alloy 600, as shown in Table XIV.
There has not been sufficient experimental
work on the stre.ss-corrosion cracking of Alloy
800 to determine if stress-relieving in a temperature range which will cause sensitization (precipitation of chromium carbides in a continuous
network) renders the alloy more susceptible to
this form of attack. Therefore, it would appear
prudent to anneal the alloy in the range of 1120 to
1150 C (2050 to 2100 F) or stress-relieve and stabilize at 870 C (1600 F) for one to two hours when
it is to be used in higher strength caustic soda
at elevated temperatures.
Laboratory Tests-Results of U-Bend

Specimens in 90% Caustic Soda at 300 C (572 F)
Maximum Depth of Cracks, mils
Material
INeOLOY
INCONEL
Argon
15 psig
atm.
1 week
air
50 psig
air
8 weeks
150 psig
air
10
0
7
0
120lal
75
1151bl
115
100
110
alloy 800
alloy 600
Type 304
Stainless Steel
1 week
11
1 week
10
(a) Removed at four weeks.

(b) Twoweek test.
Note: Testing performed in autoclaves under static conditions without

replenishment of air or argon.
Table XIII
(.
Plant Tests-Corrosion Rates in Caustic Production Equipment Using Electrolytic Diaphragm Cell Caustic
Exposure times vary from 24 to 29 days
Conditions
'"
'"
=
.,.'"'"
NaOH
"'",.
Temperature
tration,
NaGI
Concen
tration,
12
88
93
116
93
121
190
200
240
200
250
91
104
127
104
124
195
220
82
82
102
71
119
180
180
215
160
245
Concen-
10
23
35-40
50
72
J.8
67
1015
?
Av
0
~
0
Min
Max
2~0
220
255
"~
'"
'"
=
~
"
'""z '"
~
'"
'"
N
0;
~
~
"~
<0.1 <0.1 <0.1 <0.1

0.3
0.1
0.2
0.1
0.5
0.6
0.4
1
0.2 <0.1
<0.1 <0.1
OJ <0.1
0.1 <0.1
:s~
~
~
~
:'a;
~
~
~
:Sa:;
M
~
!9~
<n<n
~~
<n<n
.e.e
<n<n
M
'"
'"
'"
.;;;
~
~
~
~
'"
"
0.2
0.4
0.9
0.4
0.3
0.2
1
3
0.4
5
5
9
46
5
4
.,.
~
~
.,.
M
~
~
0.2 <0.1
0.4
2
1
2
0.2
0.2
4
3
.,.
M
~
~
.~
]
t;
"'
1':
~
~
4
2
49
6
16
concentrated solutions and at higher temperatures. An isocorrosion chart (Figure 8) summarizes the corrosion behavior of austenitic
stainless steels in caustic soda.
Typical corrosion rates for several stainless
steels are shown in Tables XV and XL. Type 316
stainless steel does not appear to offer any appreciable improvement in corrosion resistance
over Type 304 stainless steel in caustic soda solutions.
F. Austenitic Chromium-Nickel
Stainless Steels
Austenitic chromium-nickel stainless steels offer
good corrosion resistance to boiling caustic soda
solutions up to about 10 per cent concentration,
but from 10 to 50 per cent, the temperature for
satisfactory service probably would not exceed
93 to 100 C (200 to 212 F). Generally more severe
but inconsistent corrosion rates occur in more
13
700 .-----r-------,-----r----r------.-. 3 It
600
lib
500
2&0
'-'-. 400
"
E
Q.
~lOO
I
\.
..o..pF=".Jre~
Therefore. post-weld heat treatment of regular

(0.08 max) carbon grades or the selection of a
low-carbon or stabilized grade of stainless steel
does not appeal' to be required for these exposure
conditions. However, intergranular corrosion of
sensitized Type 304 stainless steel was observed
by Agrawal and Staehle in boiling solutions of
20 to 80('; NaOH.I:t
Chromium-nickel stainless steels are subject
to stress-corrosion cracking in caustic soda solutions at elevated temperatures. Nathorst H reported several cases of stress-corrosion cracking
of austenitic stainless i3teels caused by alkalies.
A comparison of the cracking behavior of Type
304 and Alloys 600 and 800 is given in Table XIV.
A stress-corrosion cracking zone based upon these
and other known failures reported in the literature is shown in Figure 8. A dashed line was used
to indicate the temperature-concentration boundary because this zone is probably not completely
defined. Agrawal and Staehle have shown that
sensitized Type 304 stainless steel is more prone
than annealed material to stress-corrosion cracking in boiling caustic sodaP A portion of their
data is shown in Figure 9. The cracking obtained
was predominantly intergranular in the sensitized material and predominantly transgranular
in the annealed material.
Commercial standard grade 50r;. caustic soda
from diaphragm cells can have up to 11.000 ppm
chlorides. and commercial 50 c ; caustic soda from
mercury cells and reagent grade anhydrous caustic can have up to 50 ppm chlorides. It has been
5tre~~\CO(fOs~O':"I
C'OC';"1 Bou"cio,y
.1\
:""";)-~oher;.:
Bo;';n9
0'
P;i", C~rve
30moy
to
' .......
50 m py
f
200
Q)
.-: 1 ::npv
AU Grades
100
19
OL-____~--L-~----~L-----~----J
20
&0
,,-'
17 S
100
fig. 8 - Isocorrosion chart for austenitic chromium nickel

'stainless steels in sodium hydroxide,
J. M. Stone observed that Type 304 stainless

steel sensitized for one hour at 677 C (1250 F)
was not susceptible to intergranular corrosion
during 40-week exposures in: 1:!0
1. 10% NaOH at room temperature
2. 10% NaOH boiling at about 102 C (216 F)
3. 50% NaOH at room temperature. and
4. 50% NaOH at 60 C (140 F).
Table XV
Corrosion of Stainless Steels by Caustic Soda Solutions
AISI
Type
HaOH
Concel!tration.
%
302
309
310
304
309
310
309
3to
202
304
20
20
20
22
34
34
50
50
50
50
5060
50-60
50-60
50..60
65
65
21
21
5065
50..65
122140
122140
122140
122140
149
149
70
70
122149
122149
days
Corrosion
Rate.
mils per year
Comments
134
134
134
133
37
37
134
134
167
167
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<001
<0.1
0.5
<01
storage tank
storage tank
storage tank
storage tank
storage tank
;Iorage tank
storage tank
storage tank
storage tank
storage tank
Test
Duration.
Temperature
14
10'
L
'".}
j
10
So;\;"9
lcood
So:"<,~;
JOO e "_
~J
Y e':i >'tres,"
,O','="O----::l:?O=----=li:-O--..-'=0---SOL----/,L.O---L70---180
Fig. 9 - Stresscorrosion cracking of annealed and sensi

tized Type 304 stainless steel in caustic soda solutions. l3
suggested that unreported chloride impurities

are responsible for some of the stress-corrosion
cracking. I;; Whether the reported cracking was
caused by caustic solutions or the chlorides these
solutions contain is an academic point. In any
case. consideration should be given to the temperature and stress limitations of austenitic
stainless steel in caustic soda solutions.
Autoclave tests have been run on some of the
cast stainless steels at temperatures both above
and below the boiling point. II; Data for ACI alloy
CF-8 from these tests are shown in Table XVI.
Fig. 10 - Piping and certain internal parts of these two

KAMYR digesters used in the pulp and paper industry are
Type 316L stainless steel to resist caustic soda and sodium
sulfide. Insulation sheathing is Type 304 stainless steel to
resist alkaline spills.
See inside back cove<for registered trademarks_
The authors reported that the results for ACI

CF-8M were similar. Alloys CF-8 (cast equivalent
of wrought Type 304) and CF-8M (cast equivalent of wrought Type 316) both exhibited increasing corrosion rates with increasing temperature.
G. Iron-Base Nickel-ChromiumCopper-Molybdenum Alloys

and
Nickel-Base Chromium-CopperMolybdenum Alloys
Table XVI
Corrosion of Cast ACI AUoy CF8
in Caustic Soda at High Temperature
HaOH
Concentration,
Temperature
20
119
138
185
40
119
245
280
365
245
280
365
425
245
280
365
425
245
280
365
138
185
219
60
80
119
138
185
219
119
138
185
Corrosion Rate Range,

mils per year
The limited corrosion test data for wrought alloys

such as CARPENTER 20Cb-3. INCOLOY alloy 825.
HASTELLOY alloy G, and cast ACI CN-7M compositions in caustic soda solutions. shown in Tables
III, XVII and XL, indicate appreciable corrosion
resistance. These alloys fall between the austenitic
chromium-nickel stainless steels su!:h as Type 304
or cast ACI CF-8 and the nickel-chromium alloys
such as Alloy 600 in resistance to caustic soda
solutions. They are markedly superior to Type
304 stainless steel and ACf CF-8 in concentrated
solutions above 95 C (205 F)_
At least one plant has used WORTHITE stainless
steel pumps for handling 73('; caustic soda at
05
2050
20-50
05
20-50
50-200
>200
5-20
50-200
50-200
>200
0-5
5-20
2050
15
Table XVIII
140 C (284 F).I' However, the same reference

also cites high corrosion rates for alloys of less
than 70'; nickel, which would include WORTHITE
stainless steel, in a storage tank handling 73'";
caustic soda at temperatures ranging from 120 to
171 C (248 to 340 F). Thus, the 140 C (284 F) application may be at the upper limit of usefulness
for this aHoy.
if these alloys are to be used in conjunction
with nickel and high nickel alloy equipment in
strong caustic soda solutions at elevated temperatures, consideration should be given to electrical
insulation between the dissimilar alloys so as to
prevent harmful galvanic effects.
Corrosion of HASTEllOY Alloys Band C

in Caustic Soda Solutions 18
NaOH
Concentration.
HASTEllOY
HASTELlOY
alloy B
aUoyC
5
5
5
Room
66
102
Room
103
121
107
Room
66
166
Room
Room
150
215
Room
217
250
225
Room
150
240
Room
261
Room
150
291
750
328
375
Nil
Nil
Nil
Nil
Nil
Nil
Nil
Nil
<2
220
<2
220
Nil
Nil
Nil
Nil
<2
220
to
10
20
25
25
30
40
40
50
50
50
50
60
70
Materials such as HASTELLOY alloys Band C-276.

INCONEL alloy 625 and cast CHLORIMET alloys 2
and 3 have not been used to any great extent in
caustic soda solutions. Ag a result. corrosion data
for them are rather mea~er. Tables IV and XVIII
show the results of some iabonltory corrOfiion
tests. From these data. it is evident that HASTELLOY alloy B can be u:~ed in concentrations up to 50
per cent at the boiling point and that the temperature limit for HASTELLOY alloy C-276 would be
somewhat less than with Alloy B. Temperature
limitations in caustic soda concentrations ~reater
Corrosion Rate. mils per year
10
H. Nickel-Base Molybdenum or
Molybdenum-Chromium-Iron Alloys
Temperature
128
Room
66
144
400
165
191
Nil
Nil
<2
2-20
Nil
Nil
Nil
Nil
<2
220
152
220
2-20
220
220
Note: I) N.t means no measurable corrosion was observed in five

24hour test periods.
2) 2-20 means corrosion (ate was within this range.
than 50 per cent C.lllnot be determined with the

exi::;ting data. HASTELLOY alloy C and INCONEL
alloy 625 were both found to be subject to stre::;scorrosion cracking in seven-day tests in aerated
90'; NaOH at 300 C (572 F). but did not crack if
ar~on was Sub5tituted for the air in tests at the
Paul D. Merica Rese~lrch Laboratory of The International Xickel Company. Inc.
Table XVII
Iron Base Nickel-Chromium-Copper-Molybdenum Alloys
and
Nickel Base ChromiumCopper-Molybdenum Alloys
in Caustic Soda Solutions
HaOH
toncel}tration.
%
10
10
13
74
Temperature
C
24
75
66
130
Test
Period.
days
150
95100 203212
265
220
Comments
Corrosion
Rate.
mils per year
laboratory test.
INCOLOY alloy 825
<0.1
laboratory test.
INCOlOY alloy 825
<0.1
Test tank simulating

action of lank car.
WORTHITE stainless steet
111
II trips
of 79 days
16
rest iOl tank car.

alloy 20
CARP[NHR
0.2
0.30.9
I. Cast Irons and Ni-Resists

The beneficial etred of nickel additions 011 the
corro:,ioll t'esistance of cast irons in moderately
concentrated caustic alkali is shown by data in
Tables XIX, XX Hnd XX I. It is evident that nickel
contents of 20 to 30 per cent pro\'ide vet'y marked
improvement in resistance to corrosion as compared 'with unalloyed cast iron. It is also apparent
that as lo'w as 3 to 5 c ; nickel may improve the
corrosion resistance of cast iron in some concentration ranges,
Table XIX
Effect of Nickel Additions on Corrosion Rates
of Cast Irons in 50 to 65% Caustic Soda
Temperature: Boiling under 26 in. (mercury) vacuum.
Fig. 11 - Moiten sodium hydroxide at an initial tempera

ture of 370 C (700 F) is converted to flake caustic by this
flaker and breaker. All surfaces exposed to caustic are nickel
except for l'li'Resist Type 3 cooling drum.
Duration: 81 days.
Corrosion Rate,
mils per year
Nickel, %
Table XXI
73
o
o
91
86
3.5
5
15
20
20 (plus 2% Chromiuml
30
47
49
30
3.3
Plant Corrosion Test in 74%

Caustic Soda in Storage Tank
Specimens exposed for total of 32 days (20 days in liquid
and 12 days in vapor).
Corrosion rates based on 20 days exposure to liquid.
Temperature:. 125 C (260
S.O
0.4
n.
Material
In practice. the nickel cast irons most widely

used with caustic solutions, where minimum contamination of the caustic is desired. are the NiResist alloys and their spheroidHl graphite counterparts. the ductile Ni-Resist alloys, The corrosion rates of these alloys fora number of different
exposures are shown in Table XXII.
alloy 400
H.i-Resist Type 3
HiResist Ductile rron Type 02
Hi-Resist TYlIe 2
Type 304 Stainless Steel
Mild Steel
Cast Iron
MONEl.
Corrosion of Nickel Cast Irons in the

Evaporation of Caustic Soda from 37 to 50 Per Cent
Average Temperature: 120 C (248 F).
Duration: 51 days.
Chromium,
%
28.60
28.37
14.26
19.40
19.02
20.53
1.71
2.39
2.90
Copper,
%
6.08
Silicon.
%
1.30
1.50
1.62
1.42
1.22
1.25
Corrosion
Carbon.
Rate.
mils per year
%
2.87
2.72
3.15
3.15
3.18
2.91
0.9
2.5
5
6
15
75
76
Copper-free Ni-Resist Type 2 may be used in

preference to Xi-Resist Type 1 (6.50:-; copper)
where it is desired to keep copper content of the
solution at a minimum, The 30 r ;. nickel cast iron
(Ni-Resist Type 3), in addition to having somewhat g-rcater resistance to corrosion by hot caustic solutions than Ni-Resist TypeS 1 and 2, has a
low coefticient of expansion, an advantage for
expOSUI"C conditions invo!\'ing sudden changes in
temperature.
Of the fi\'e basic types of ~i-nesist. Type 3 appear:' to be the best suited to meet the requirements for caustic sen"ice. !'\i-l1e::;ist Type 3 or
Type D3 can be con::;idered as alternate materials
Table XX
Nickel,
%
Corrosion Rate,
mils per year
17
18
22
24
28
31
17
to nickel and the high nickel alloys for caustic

soda concentrations up to 73 per cent, but nickel
is preferred for higher concentrations.
There have been occasional stress-corrosion
cracking failures with the Ni-Resists in high-
chloride aqueous environments. Although these

environments did not include caustic soda, it
\\"ollld appear a reasonable precaution to stressreliew these alloys at 677 C (1250 F) for one
hour before use in hot caustic soda solutions.
Table XXII
Corrosion Rates of the Ni-Resists in Caustic Soda
Corrosion Rate.
NaOH
Concentration,
%
8.5-9
82
180
None
due to
filling tank
32
plus 1515.5%
NaCI in storage
tank
10
88
190
Moderate
due to
filling tank
279
plus 12');' NaCl

in storage tank
14
88
190
None
due loevap.
90
lirst eHect of
multiple effect
evaporator
Temperature
Aeration
Agitation
'"
"'~
Test
Period,
days
"'",
'70..
200
Moderate
Medium
48
plus 7-8% NaCI

in salt settler
30
85
185
Moderate
Moderate
82
plus heavy concentratlOn of

suspended NaG!
in sail settler
35-45
116
240
Moderate
Small
24
plus 6-7% NaGI

in salt settler.
Intermittent exposure to vapor
49-51
55
149
None
due to
filling tank
30
storage tank
50
55
131
Moderate
1.8 Ips
160-220
Moderate
1 Ips
50
95
203
Moderate
1.8 Ips
50
21-127
70-260
None
None
Boiling
50-70
121
72
'70..
. - >.
X..-
~.~~
'"
"'", .~o::
'70..
. - >.
XI-
201-
=:Ii ..!. >..
c2O>-
0.8
1.5
0.2
c
C>
'"'"
c..>
15
173
!
!
I 1.2
0.8
0.4
plus heavy concent ration of

suspended NaGl
in transfer line
10 days
laboratory test
0.5
0.2
1.0
81
due to evap.
10
I I
121
250
Moderate
very small
74
127
260
Above &
Below
liquid
level
Slight
20
specImens
exposed in storage
lank for 32 days
(20 days in liquid
and 12 days in vaporl.
Corrosion
rales based on 20 days
exposure in liquid
100
510
950
None
Moderate
14
concentratIOn in
open pot
30
3.3
0.4
11
5.0
OA
86
90
star age lank
290
4.7
!60
70
1.2
0.6
in evaporator
0.2
<0.1
4.7
None
49
I,
OA
250
18
0.5
II
II
due to evap.
1]9
0.1
plus 1015% NaG!

in cooling tank
67
21
3.3
plus heavy concen,ration of

suspended NaC!
in transfer line
llS
None
'" v
"Vi
'"
2.5
@250F
& 4 days
@70r
50-65
"'",
per year
93
71-104
'~("')
"'",
'70..
. - >.
-x>>-
23
50
'"
";:;fN
mils
15
2.5
87
5.5
534
60
141
PART III. CORROSION BY OTHER ALKALIES

caustic soda of similar concentration and temperature can be used to approximate corrosion
resistance in caustic potash. Iff
Under extreme conditions, some nickel alloys
are subject to stress-corrosion cracking in caustic
potash solutions. However, the information presented in Tables IX and X suggests that stress
corrosion cracking of Alloy 600, Alloy 400 and
Alloy K-500 is not quite as severe with caustic
potash as with caustic soda.
The beneficial effect of nickel in cast iron exposed to caustic potash is shown in Table XXIV.
The reductions in corrosion rates are similar to
those obtained in caustic soda solutions.
Table XXV shows the results of laboratory corrosion tests of several Ni-Resist alloys in hot. concentrated caustic potash. Lower corrosion rates
would be expected with a decrease in either temperature or caustic potash concentration. NiResist Type 3 appears to have equivalent, and
sometimes superior. corrosion resistance in comparigon to Types 1 and 2.
A. Caustic Potash (KOH)

Caustic potash is produced by the electrolysis
of muriate (potassium chloride) brine. Several
types and concentrations of KOH are available,
but 45 and 50 per cent liquid and 85 and 90 per
cent solid are most commonly marketed. Above
about 50 per cent concentration, caustic potash
has a higher boiling point than caustic soda of
the same concentration. This differential is especially pronounced at high concentrations. For
this reason. the commercial product is usually not
concentrated above 90 per cent because of the
high temperatures involved.
In general. those materials which are useful in
caustic soda are also suitable for caustic potash.
Nickel 200 and INCONEL aHoy 600 are both suitable for service in hot caustic potash. as indicated
by the data presented in Table XXIII. Negligible
data exist for other nickel alloys in caustic potash.
Gegner has suggested that because caustic potash
is so similar to caustic soda. the corrosion data in
Table XXIII
Corrosion Tests in Caustic Potash Solutions
KO"
COllcentration.
Temperature
Aeration
Agitation
13
30
85
None
due to
filling tank
30
113
236
None
47
139
281
50
28
82
50
150
Test
Period.
days
Comments
INCONEl.
MONEl.
Nickel
200
alloy
600
aUoy
400
nil
207
storage tank impuritiesKJeo J 3 gpl. KCf 170 gpl.

KClO .. 0.1%
nil'
nil
Boiling
26
laboratory test-saturated
with KCf. 0.05% KClO,
l. 0.2
V.0.3
l. 0.1
V.O.1
None
Boiling
26
laboratory test-saturated
with KG\. 0.18% KClO,
l. 0.1
V.O.3
l. 0.4
V.O.1
None
due to
lilting lank
storage tank impurilies-
nil
nil
laboratory test-UBend
specimen showed
no cracking
nil
0.5
35
laboratory test
nil
0.5
laboratory test
0.4
0.7
35
laboratory test
1.6
5.7
300
None
2\.61pm
207
K,CO. 0.3%. KGI 0.75%.

KGto, 0.10%
7
50
150
300
None
3481pm'
10
150
300
None
21.6fpm
10
150
300
None
3481pm"
nil-less than 0.05 mils pel'" year.
l-liQuid
V-Vapor
." Specimens m~ved at th!s veloc11y fof'" 8 hr each working day and at zero ft per mtn overn1ght and duong
weekends. Th,s was equlvatent to ten 24 hour days at the high velocity rate.
19
nil
Considerable amounts of Types 316 and 316L

stainless steels are used in the ammonia-soda
process for the production of soda ash (Na 2C0 3 ) .
The main reaction involves the carbonation of an
ammoniated brine to form sodium bicarbonate
and ammonium chloride. The ammonia is recov-
Table XX'V
Effect of Nickel in Cast Iron
on Corrosion by Caustic Potash
Concentration: 950 g KOH per liter.
Temperature: 400 C (750 F).
Nickel Content of Alloy Iron,

%
Corrosion Rate,
mils per year
Table XXVI
21-30
3.0
3
6.5
12.4
Plant Corrosion Test in Ammonia

Surge Vessel of Urea Manufacturing Plant
2.0
0.4
Solution: 22% NH, 71 %

NH.NO, .
H,O, 7% CO, and trace of
Temperature: 66C (150 F).

Test Period: 300 days.
Table XXV
Aeration: None.
Corrosion of Ni-Resists in Caustic Potash

Hi-Resist
Type
Exposure
68-hour test in 81 % KOlt at 225 C (437
f)
30
68-hour test in 81% KOH at 225 C (437
f)
20
68-hour test in 81 % KOH at 225 C (437
f)
10
36-hour test in 92% KOlt at 268 C 1516
f)
10
3S-hour test in 92% KOlt at 268 C (516
f)
10
Agitation: Moderate.
Location: Uquid phase at bottom of aqua ammonia surge
vessel.
ClIrrosjon Rate,
mils per year
Corrosion Rate,
mUs per year
Material
INCOlOY alloy 825
Type 304 Stainless Steet
Type 316 Stainless Steel <Sensitized)
CARPENTER alloy 20
INCONEL alloy 600
Type 304 Stainless SteellSensitized)
B. Ammonia and
Ammonium Hydroxide
Mild Steel
Most of the nickel-base alloys, with the exception

of the nickel-copper alloys and nickel itself, resist
all concentrations of ammonium hydroxide up to
the boiling point.
Among the nickel-containing alloys, the austenitic stainless steels are most frequently employed in ammonia and ammonium hydroxide
solutions. Austenitic stainless steels exhibit good
resistance to all concentrations of ammonia and
ammonium hydroxide up to the boiling point.
Tables XXVI through XXIX show the results of
plant corrosion tests in ammonia- and ammonium
hydroxide-containing process streams.
Stone .determined that Type 304 stainless steel,
which had been sensitized at 677 C (1250 F) for
one hour, was not subject to intergranular corrosion during a 40-week exposure in 28% NH 4 0H
at room temperature. 12 However, this resistance
does not extend to elevated temperatures in commercial solutions, as shown in Table XXVI.
<0.1
<0.1
<0.1
0.3
0.3
0.4
3.4
7.6
Missing-presumed
corroded away
Missing-presumed
corroded away
Table XXVII
Plant Corrosion Test in Mixed Ammonia-Carbon
Dioxide Gas Stream in a Chemical Plant
Gas: Mixture of NHJ and CO2 with probably some moisture
present.
Temperature: 20 to SOC (68 to 176 F).
Aeration: None.
Agitation: Gas flow.
Location: Suspended in gas stream.
Corrosion Rate,
mils per year
Material
MONEL alloy 400
tNCONEL alloy 600
Mild Steel
Nickel 200
Silicon Bronze
Nil
20
== Less than 0.01
mill><" year.
Nil
Nil
2.2
3.0
5.1
5.3
72
Table XXX
Table XXVIII
Plant Corrosion Test in Ammonia-Carbon
Dioxide Gas Stream in a Metal Refining Plant
Plant Corrosion Test in Ammonia Recovery Still,

Ammonia-Soda Process for Production
of Sodium Carbonate
Gas: 26% NH J 14% CO,. balance water vapor.
ro 93 C (150 to 200 F); Average 82 C

(l80 F).
Middle Section
Temperatur-e: 66
Temperature: 60 to 71 C (140 to 160 F).
Liquor Composition:
NH1CO~
NH l ,
9% NH.CI,
Agitation; 25 to 40 fps gas flow.

Location:
2%
14% NaCl, 2% CO2
Aeration: Moderate.
stripping still overhead line.
Top Section
Corrosion Rate.
mils per year
Material
INCOlOY alloy 825
INCOLOY alloy 800
INCONEl alloy 600
Mild Steet
Liquor Composition: 5% NH l
9% NH.CI,
14% NaCl, 3.4% CO2
<0.1
<0.1
<0.1
<0.1
1.5
4.1
0.1
Material
Zirconium
Titanium
HASTEllOY alloy C
Nickel 200
Mild Steet
20
22
Table XXIX
Middle
Section
lop
Section
OJ
0.1
0.1
0.1
0.1
>33"
>73"
0.1
0.2
14'
>32"
>71"
Specimen pitted in crevice beneath insulating wasber.
Plant Corrosion Test in Contaminated

Ammonia Vapors in a Coke By-Products Plant
Specimens cQrroded away..
Nickel is not attacked by anhydrous ammonia,

but is resistant to ammonium hydroxide solutions
in concentrations only up to about one per cent.
Aeration may induce passivity in concentrations
under 10 per cent, but even in the presence of air,
more concentrated solutions are highly corrosive
to nickel. The corrosion data shown in Table XXXI
were obtained in room-temperature laboratory
tests ()f 48-hour duration in one normal ammonium hydroxide, following a previous 48-hour ex-
Gas: Ammonia vapors plus H,S. CO,. HCN. phenols and

steam.
Temperature: 100 to 110 C (212 to 230 F); Average 105 C
(221 F).
Aeration: None.
Agitation: High velocity gas flow.
location: Ammonia liquor still vapor outlet.
Material
I NCONEl alloy 600
Mild Steel
MONEL alloy 400
Nickel 200
Corrosion Rate,
mils per year
KiINil'
0.1
S.O
>40
(corroded away)
Table XXXI
Corrosionof Nickel 200 in One Normal
Ammonium Hydroxide (1.7% NHa)
>40
(corroded away)
Nil "" 1.ess tban 0.04 mils per year.
Test Condition
ered in this process for reuse. Table XXX shows

corrosion rates for metals and alloys in an ammonia recovery still in a soda ash plant. The possibility of pitting must be taken into account in
the design of equipment where there are such
high chloride levels, so as to avoid crevices where
chlorides can concentrate to even higher levels
and promote crevice corrosion.
Corrosion Rate,
milspllryear
Total Immersion
Quiet
Air"'Agitated
0.8
<0.1
Alternate Immersion
Conti!luous
lntermittent
2.7
0.4
Spray {4 to 30 Daysl
<0.1
Specimens exposed at room temperature tor 2 days after a previous

2-day exposure except for spray expo'Sure.
21
posure. The re~ults of 20-hour tests in highly

agitated ammonium hydroxide solutions at room
tempelature are shown in Table XXXII. Typical
corrosion rates for Nickel 200 in several industrial exposures are also given in Table3 XXVII,
XXIX and XXX.
Table XXXU
Corrosion of Nickel 200 in
Ammonium Hydroxide Solutions
CCIfI"lISion Rate,
mils per year
NH.OH Cancentration,
%
1.1
12.9
20.2
560
Fig. 12 - Sodium carbonate filters use Type 304 stainless

steel or MONEL alloy 400 for the perforated backing sheet or
winding wire. The same materials are also used for back
ing wire cloth and facing cloth .
370
180
27.1
Tests run to agitated solution at room temperature for 20 hours.
salt solutions can be handled in the same materials

suitable for caustic soda. As with caustic soda,
dilute solutions at low temperature are not very
corrosive to carbon steel and may even act as corrosion inhibitors, but concentrated solutions at
high temperatures often require nickel or high
nickel alloys.
The results of tests within an evaporator handling sodium metasilicate are shown in Table
XXXIV.
Another plant test in a kettle during the dissolving of silicates in strong caustic soda gave the
corrosion rates shown in Table XXXV.
The superiority of Alloy 400 and austenitic
stainless steels for a phosphate hydration was
demonstrated in a short-duration test shown in
Table XXXVI.
Nickel and high nickel alloys offer good resistance to corrosion by sodium sulfide solutions. In
Nickel-copper alloys. such as Alloy 400, are resistant to anhydrous ammonia and are slightly
more resistant than commercially pure nickel in
ammonium hydroxide solutions. as shown in Table
XXXIII. However, their usefulness is restricted
to dilute solutions up to about 3<1 ammonium
hydroxide. In solutions of higher concentration.
corrosion rates are increased considerably by
aeration and agitation.
TableXXXm
MONEL
laboratory Corrosion Tests of

alloy 400 in Ammonium Hydroxide
Temperature: Room. Test Period: 20 hours.

Agitation: 371 feet per minute.
HH3 Cancentration,
%
2.7
Carrosian Rate,
mils per year
3.6
70
5.5
8.2
11.1
18.3
25.8
317
327
231
298
Table XXXIV
Corrosion Tests in Sodium Metasilicate
Composition: 50% sodium silicate. 50% sodium hydroxide.
36
Ave~age Temperature: HOC (230 F). Test Period: 6 weeks.
Material
C. Other Alkaline Solutions of

Sodium and Potassium Salts
Nickel 200
alloy 400
INCONEL alloy 600
MONEL
Salts su~h as sodium sulfide. sodium carbonate,

sodium silicates, trisodium phosphate and others
form alkaline water solutions. These alkaline
Hi-Resist Type 1
Mild Steel
Cast Iron
22
Corrosion Rate.
mils per year
<0.1
<0.1
<0.1
0.4
13
18
Table XXXV
Corrosion Te.sts During Dissolving of
Silicates in Caustic Soda
Location: Test specimens suspended near bottom of kettle.
Temperature: 77 C (170 f). Test Period; 32 days.
COffoswn Rate,
mils per year
Material
Nickel 200
Ni:Resist Type 3
Ni:Resist Type 2
Nickel Cast Iron (3% Ni)
Cast Iron
Mild Steel
0.1
0.2
0.5
8
33
41
centrate sodium sulfide from 25 to 60 per cent

are given in Tables XXXVIU and XXXIX. Operating experience over a number of years with
evaporator tubes in sodium sulfide evaporation
has shown that Nickel 200 and Alloy 400 are
satisfactory for this application.
Experience has also demonstrated that Alloy
600 is useful .for direct-tired pans in which sodium
sulfide is eoncentrated from 25 per eent to 60 per
cent. Operating temperatures on the order of 150
to 177 C (300 to 350 F) prevaiL Under sueh conditions. Alloy 600 has given a service life of up to
eight years.
Table XXXVI
Conosion Tests in Phosphate Hydrator
Composition: 50% solution of sodit.t1l1 tripolyphosphate and
Table XXXVIlI
Plant Corrosion Test in DirectFired Open Pot Used
for Concentrating Sodium Sulfide to 60 Per Cent
sodit.tm tetrapotyphosphate.
Average Temperature: 74 C (165 F}. Test Period: 60 hours.
Temperature: 100 to 180C (212 to 356 f).
Aeration: Extensive. Agitation: Considerable.
Corroswn Rate,
mils pet year
Material
MONEt. alloy 400
Mild Steel
altoy 400
alloy 600
Nickel 200
Copper-Nickel alloy CA 715
HASTELLOY alloy B
ILLiUM G
KASrELLOY alloy C
DURIMEr alloy 20
MONEL
0.1
0:4
fMCOJltEl..
0.7
133
10:t sodium sulfide. the corrosion rates are quite

Jow. as shown in Table XXXVII. The most severe
service conditions are encountered in hot. concentrated solutions. The results of two plant corrosion tests in direct-fired evaporators which con-
8
10
16
20
22
48
>72*
>73*
>85*
110
Specimens corroded away.
Table XXXIX
Table XXXVII
Plant Corrosion Test in Gas-fired

Open Tray Used for Concentrating
Sodium Sulfide from 25 to 60 Per Cent
Plant Corrosion Test in a

Sodium Sulfide Storage Tank
Solution: 10% Na 2 S.
Corrosion Rate.
mils per year
Material
Aeration: Open tank.
Temperature: 125to 175C (257 to 347 f).
Temperature: Atmospheric. Agitation: Only due to filling tank.
Matl!rial
Material
Corrosiolt Rate.
mils per year
alloy 400
Nickel 200
INcoNELa1loy 600
Type 3D2 Stainless Steel
Mild Steel
MONEL
. Nickel lO!l
MQNEL alloy 400
tNCONEL alloy 600
KASrELLOY all.oy B
HAsrULOY atloy C
ILLlUM G
DURIMEr 20
Copper-Nickel alloy CA 715
<OJ
<OJ
<OJ
<0.1
<OJ
<0.1
<0.1
<fU
<0.1
1.3
Spedmens corroded away.
23
Corroswn Rate.
mils per year
3
7
8
11
22
84
230
>290*
>300'
>600*
PART IV. INDUSTRIAL APPLICATIONS

equipment such as evaporators, heat exchanger
tubing, pumps, crystallizers, valves, fittings, etc.,
used in the concentration and handling of caustic
soda. Corrosion test data cited earlier in this bulletin were obtained largely in caustic soda manufacturing processes.
A comparison of the corrosiveness of caustic
soda produced from mercury cells with that produced by diaphragm cells was made by Committee
T5A-3D of the National Association of Corrosion
Engineers. Data obtained in this survey are
shown in Table XL. It appears that there is not a
A. Caustic Soda Manufacture

Service records, often dating back for 20 to 30
years, have demonstrated the satisfactory service
of nickel and nickel alloys in caustic soda manufacture. In one plant, nickel centrifugal pumps
handling 50% caustic soda from mercury cells are
27 years old and are still in operation. In another
plant, nickel evaporators continue to give good
service after 30 years' use. Nickel 200, low-carbon Nickel 201, Alloy 600, Alloy 400 and their
cast counterparts are "standard" materials of
construction, either solid or as a cladding for
Fig. 13 - Triple-effect evaporators for the concentration of diaphragm cell liquor to 50% caustic soda_ All threeevaporators are constructed entirely of Nickel 200 and Nickel 200-clad steel.
Photograph courtesy of Blaw-Knox Company_
24
Table Xl
"Round Robin" Test Program by Four Caustic Soda Producers-Comparison of
Corrosiveness of Diaphragm Cell vs. Mercury Cell CausticConducted by NACE Committee TSA-3D
Average Temperature
Corrosion Rate.
mils per year
Company
1
Material
Nickel 200
Hickel 200
Hickel 200
Nickel 200
Nickel 20:0
Nickel 20:0
Nickel 200
Nickel 200
INCONEL alloy tioo:
INCONEL alloy 601}
INCONEL alloy 600
INCONEL alloy 600
INCONEl alley 600
INCONEL alley 600
INCONEl alloy 6{}0
INCONEL alley 600:
MONEL alloy 400:
MONR alloy 400
MONEL aliDY 41111
MONEL aUoy 400
MONEL alloy 400
MONEL alloy 400
MONEL alley 400
MONEL aUoy 400
INCOLOY alloy 800
INCOLOY alloy 800
INCOLOY alloy 800
INCOLOY alloy 800
INCOLOY alloy 800
IHCOLOY alloy 800
IHCOLOY alloy 800
INCOLOY alloy 800
CARPENfER alloy 20 Cb3
CARPEtffER alloy 20 Cb-3
CARPENfER alloy 20 Cb3
CAftPEtffER alloy 20 Cb~
CARPENTER alloy 20 Ch3
CARPENTER allDY 20 (:b3
CARPENTER alley 20 tb3
CARPENTER alllly20 (:b3
ACI tN-7M
ACt CN7M
ACI CtOM
ACl eN7M ACt CN-1M
ACI CN-1M
ACI CN-7M
ACI CN"7M
NiRe.sist Type 3
Ni-Resist Type 3
Hi-Resist Type 3
Corredent
50% NaOH-Oiaphragm Cell
50% NaaHt>iaphragm Cell
50% NaOHMercury Ceil
50% NaOHMercury Cell
73% NaOMHapluagm Cell
73~4 NaOHMercury Cell
50% NaOK-Diaphragm Cell
50% HaOMDiaphragm Cel!
50~{' NaOHMercury Cell
50~{' NaOH-Mercury Cell
73% NaOH-Diaphragm Cell
73% NaOHDiaphragm Cell
50% NaOHOiaphraglll Cen
50% N~OH'Diaphragm Cell
50% NaOH;Mercury Cell
50% NaOH-Mercury Cell
73kNaoHOlaphraglll Cell
73% NaOH-Diaphraglll Cell
13% HIlOaMercury Cell
50% NIlOHOiaphragm Cell
50%: HIlOHtliaphragm Cell
50% NaOHMercury Celt
5{)%NaOH.Mercury Cell
50~i. NaOH.Mercury Cell
73% NaOIH)iaphragm Cell
73% NaOH-Diaphragm Cell
73% NaoNMercury Cell
50'!';' NaOHDiaphragm Cell
50'!" NaOHOiaphragm Cell
50% NaOK-Mercury Cell
50% NaOH,Mercury Cell
50% NaON-Mercury Cell
73% NaOHOiapllragm Cell
73% NaOHOiilplnagm Cell
50% NaOHOiaphragm Cell
50?{. NaOHMer(;ury Cell
504 NaOHMen:ury Cell
50% NaOHMeJ.eury Cell
73'l~NaOH-Dlaplmlgm Cell
73'}~ NlIOH,OillPhraCm Cell
13% NaOH.MetClifY Cell
50% NaOHDiapbragm Cell
35
40
38
37
95
104
100
98
119 246
125 257
114236
35 95
40 104
38 100
37 98
- 119
125
114
35
40
38
37
29 85
88 190
- - - 29 85
- 105 221
45 113
Ambient
246
257
236
- - - -
95
29 85
- -
104
100
98
- -
119246
125.257.
114236
35 95
40 104
38100
37 98
- -
119246
125251
U4.236
35 95
40 104
38100
37 98.
- -
U9246
125 257
H4236
35 95
40 104
38 100
37 98
- -
119
125
114
35
40
38
246
257
236
95
104
100
- 105 221
45 113
Ambient
105 221
45 113
Ambient
82 180
- -
- 99 210
- - 88 190
- 82 180
- - -
99210
- -
C.Dmpany
54 130
Ambient
60 140
Ambient
Ambient
- -
- 54 130
Ambient
60 140
Ambient
Ambient
--
- -
54 130
Ambient
82180 60140
Ambient
Ambient
99 210
88190
- - -,...,...
,.... - - - - - - 29 85 88 190. 54130
- - Ambient
-
105 221
45 113
Ambient
- -
82180
99.210
- -
-29 -85
105 221
45.113
Ambient
--
88 190
- - - 82 1811
~
60 140
Ambient
Ambienl
- - 54 130
Ambient
60 140
Ambient
Ambient
210 - - - - - -- - - - -
29" 85
- -
105 221
45 il3
Ambient
- 29 85
- 105 221
8'8 190
- 82 180
-
99210
54130
Ambient
60 140
Ambient
Ambient
-'
- -
88 190
- 82 180
54 130
Ambient
60 140
<0_1
<0.1
<0'\
<0.1
2
<0.1
<0.1
<0'\
<0.1
<0J
1.0
<0.1
-0.2
0.3
<0.1 (l) <0.1
<0.1
<0.1
<0J
<O.!
<0.\
<0.1
<0.1
0.3
0.2
<0.1
<OJ
<OJ
<O.}
4
<OJ
<0.1
<0.1
<0.1
<0.1
0.2
<0.1
<0.1
<0.1
<0.1
<OJ
<0.1
<0.1
0.2
<0.1
<0.1
0.1
0.2
<0J
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
0.8
<0.1
0.4
0.5
<OJ
<IU
<0.1
<0.1
<0.1
<0.1
l.l
<OJ
<0.1
<0.1
OJ
0.5
O.3IU
<0.1
<0.1
<0.1
<(j.l
<OJ
<0.1
<OJ
<OJ
0.4
0.5
0.4
<0.1
<0.1
<0.\
<0.1
<0.1
<OJ
<0.1
<0.1
lU
1.2 (J)
G.4
0.2
<0.1
0.6
<0.1
<0.1
<0.1
<0.1
<OJ
<0.1
<OJ
4..l (2)
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
1.5(3)
<0.1
<0.1
<0.1
<OJ
<0.1
<0.1
<0.1
9.3
0.4 (4)
<0.1
<0.1
0.2
<01
Table XL (Cont'd.)
"Round Robin" Test Program by Four Caustic Soda Producers-Comparison of
Corrosiveness of Diaphragm Cell vs. Mercury Cell CausticConducted by NACE Committee T5A-3D
Average Tempe,ature
Corrosion Rate.
mils per year
Company
2
Corrodent
Material
HiResist Type 3
Ni:Resist Type 3
Ni:Resist Type 3
Hi:Resist Type 3
Hi:Resist Type 3
Type 3.16 Stainless Steel
Type 3Ui Stainless Steel
Type 316 Stainless .Steet
Type 3l6.stainless Steet
Type :116 Stainless Steel
Type 304Stainle$$.Sieei
Type ~04 Stainle$~ Steel
50% NaOM.Mercury Cell

50% NaOJ1,Mercury Cell
73% NaOM-Diaphragm Cell
50% NaOH~iapllragm Cell
50% NaOH~iaphragm Cell
50% NaOHMercuI}' Celt

1ype304 StaiRtessSteel
Type 304 Stainles$.steel
Ductile Cast Iren
Ductile Cast Iron
Ductile Cast Iron
Dllctil~cast Iron
Ductile Cast IllIn
D1Ictile Cast Iren
Ductile Cast illln
Ductile cast Iron
Gray Cast Iron
Gray Cast Iroll
Gray Cast Iron
Gray Cast Iron
Gray Cast Iron
Gray Cast Iron
Gray Cast Iron
Gray Cast Iron
MildSteeJ
Mild Steel
Mild Steel

50% NaGH.Mercury Cell
5~%
NaOHMercury Cell
73% NaOH~.iapllragm Cell
13% NaOH-Oiapbragm Cell
13% NaOH'Mercury Cell
50% NaOHDiapllragm Cell
50% NaOlH)iallhragm Cell
50% NaOn-Mercury Cell
73~
37 98
- -
119 241>
125 257
114 236
35
40
38
31
95
104
100
98
119 246
-
125 257
114236
35 95
40 104
38 100
37 98
NaOH-Oiapbragm Cell

50% NaOllDiaphragm Celt
50% NaOli-Diaphragm Cell
50% NaOliMercury Ce:t
50% NaOJt..Men:l.lry tet!
73% NaOH~iapllfagm Cell
73% NaOH~iaph[agm Celt
13% NaOH.MercuI)' Celt
50% Na(lli-Diaphragm Cell
50% NaQli-Mercury Cell
50% NaOli-Mercury Cell
73% NaOli-Dia.phragm CeU
73% NaOn-Diaphragm Cell
73% NaOK-MereuI}' Cell
50% HaOH-Oiapbragm Cell
50% NaOH~iallhragmCeIi
3
f
45 113
Ambient
29 85
105 221
45 113
Ambient
35
40
38
31
95
104
100
98
H9246
125 257
114 236
35 95
4D 104
38 100
45 113
29 85
0.3
2.3
1.2
88 190
- 82 180
54 130
Ambient
60 140
Ambient
Ambient
- -
- -99 210
- -
88 190
Ambient
- - - 54130
82 180
60 140
Ambient
- - -
Ambient
Ambient
105 221
45113
- -
<0.1
0.2
<0.1
<0.1
<0.1
<0.1
<0.1
<0.1
Ambient
0.1
0.2
8.4
<0.1
3.3
<0.1
0.1
<0.1
0.2
<0.1
1.1
0.1 n. 61
11.0
<0.1
<OJ
0.3
15 (4)
19.4 t5}
15 (4)
1.4
l.5!S)
0.4
1.8
13
3.1
0.3
2 (81
3.7
- -
29 85
88 190
54 130
Ambi'lnt
2.1
1.9
1.9
- -99 2It}
-
60140
0.4
2 t9)
Ambient
Ambient
2.1
3
4.5
105 221
45 113
Ambient
- -- -- -- - --
29 85
82 100
105 221
Mild Steel
73% NaOMMercury Cell
114 236
45 113
Ambient
88 190
0.6
2.6
52
1.0
6.2(2
2.6
18
103
13
2.6
2.9
7.9
1.7
5.1
3.5
21
54
44
82
54130
UJ5}
82 180
60 140
1.5 (5)
O.SISI
Ambient
1.4
showed stress-acce1erated local attack.
26
73
Iynbient
(5) Pitted to a ma.ximlJm depth Qt 3 mils.

(6) Mercury droplets in tao". 2 rates shown
are for the duplicate speCimens
(not averaged): specimen with high rate
0.4
<0.1
106
- - Ambient
99210 - - - - - - - -
<0.1
<0.1
<0.1
12
- -
<0.1
<0.1
<0.1
0.3
<0.1
8.7
- - - -
0.1
<0.1
- - -
99 210
6 (4)
13.1(5)
10 {4}
Ambient
Pitted to a maximum dept" Qt 1 mHo

Pitted to a maximum depth of 4 mils.
Pitted t<> a maximum depth of 5 mils.
Stress-corrosion crack through
one of the identifying punch marks.
- - - -
- -
- -
(1)
(2)
(3)
(4)
0.2
82 180 .60 140
119 246
125 251
Ambient
Ambient
105 221

50% NaOM-Mercury Cell
13% NaOHl)iapilragm Cell
73% NaOfl..Diapbragm Cell
37 98
54 130
Mild Steel
Mild Steel Mild Steel
Mild Steel
-99 2W
Ambient
- - -
- -
88190
119246
125 257
114 236
119246
125 251
114236
C f
Ambient
95
104
100
98
- -
29 85
- -
35
40
38
37
- - 99 210 - - - - - -. -
Company
1.4 nO}
3 {6.1ID
21
2
5.1
20
1.8m
2.1
3.2
1.2
2.9(5
1.9
5.7
59
dissolved
>38
71
(1)
(8)
(9)
(10)
Pitted
Pitted
Pitted
Pitted
to a
to a
to a
to "
maximum depth of 8 mils.

maximum depth of 2 milS.
great deal of difference in the corrosiveness of the

caustic produced by these two types of cells, al,'ld
that other variables such as temperature and concentration are more important in influencing corrosion rates.
Prior to about 1946, the concentration of 50%
or 73 % caustic soda to anhydrous was carried out
entirely in direct-tired caustic pots in a batch
operation. These pots Were usually constructed of
gray cast iron. Nicl<:el could not be used because
of the practice of "sulfur shading" (sulfur addition for the removal of iron and other contaminants to achieve higher purity and better product
color), which caused severe sulfur embritllement
of the nickel at the high temperatures involved.
Subsequent to 1946, these pots have been
repla<:ed to a very great extent by nicl<:el and
nickel anoy equipment for continuous vacuum
evaporation, which has proven to yield a higher
quality product more economically.3.20 The production of anhydrous caustic soda in corrosionresistant Nickel 201 and AHoy 600 equipment has
eliminated the necessity of sulfur shading.
rates. Some corrosion test data showing the effects of chlor;;ltes upon the corrosion of Nickel 200
and INCONEL alloy 600 in high temperature caustic soda are shown in Tables XLI and XLII. There
are several means by which chlorates can be reTable XU
Plant Corrosion Test During Concentration of
Diaphragm Cell Caustic Soda from
50 Per Cent to Anhydrous
Feed liquor c.ontained 0.24% scdium chl.orate and 1.0%
scdium chloride .on S.olid caustic basis. Rapid circulation
of liqu.or.
Temperature: 400 C (750 fl.
Test Period: 243 hcurs .operaticn.

Material
liquid
Vapor
Hickel 2DD
tHCONEt. anoy 6IJD
51.0
87.0
0.5
5.0
TableXUl
laboratory Corrosion Test in Evaporation
of Caustic Soda from 73 tQ 96 Per Cent
with and without Chlorate
Temperature: 180 C (360 F) t.o 450 C (840 F).
lest Pericd: 24 h.ours.

Corrosion Rate, mils pef year
Material
Nickel 2IltJ
IHCOHEt. alloy
6flO
Without
Chlorate
Witll fl.3% Clllorate

(Solid C;tIIStic Basis)
1.5
2.2
260
380
moved; the addition of sucrose (U. S. Patent

2,610,105) or dextrin (British Patent 778.226)
appear to be the most common. While these additions minimize corrosion and attendant metal
contamination of the product,- they do increase
the carbonate concentration. Bradbury and
Cooper have shown that the addition of sorbitol
and subsequent heating will also remove chlorates but with the formation of less carbonate.21
Liquid-liquid extraction with ammonia is also
widely used to remove chlorates and chlorides.22
In the continuous vacuum concentration and
production of anhydrous caustic soda, low-carbon
Nickel 201 and Nickel 201-clad steel equipment
have given excellent service as evaporator tubes.
tube sheets and shells, and as receiving tanks and
piping.
fig. 14 --Evaporator bodies and vapor piping at a large

chlorine-caustic soda plant for concentraticn t.o 730/0 NaOH.
All evaporatcrs are constructed entirely .of Nickel 200 and
Nickel 200clad steel.
Chlorates are removed from diaphragm cell

caustic soda when concentrating to anhydrous in
nickel or high nickel alloys to minimize corrosion
27
Alloy 600 has also been used extensively for

producing anhydrous caustic soda and is the
preferred material of construction where the
heating is accomplished with any media in which
there is a po:.;sibility of sulfur compounds being
present. Alloy 600 for this service should be
stress-relieved or annealed as indicated in the discussion of nickel-chromium alloys in Part II of
this bulletin.
caustic potash at concentratiolls of 90 per cent

and above.
C. Caustic Soda Storage and

Transportation
After extreme care has been taken to assure
high purity in the production of caustic. it is
important that storage and transportation facilities provide for continuing product purity. NickeIclad steel tank cars have been used for transporting iron-free caustic since 1930. Nickel and nickelclad steel barrels are also in use for the transportation of smaller quantities. More recently. nickelplated steel tank cars and piping have been
employed.
The first tank-trailer constructed of INCOLOY
alloy 825 was put in service in 1963 to haul 50%
caustic soda. This alloy was selected because of its
versatility in its ability to transport other corrosive materials induding sulfuric. nitric and phosphoric acids. INCONEL aHoy 600 was selected for
barge tanks to carry 73 (-; caustic one way and
return with ammonia-base fertilizers or jet fueL
Fig. 15 - Tubes fabricated from Nickel 200 afe used in the

inclined heat exchanger in front of the Nickel 200-dad
evaporator which prodl.l<.:es 50% caustic soda.
separator atop the system. which separates
sodium chloride and other salts from the caustic solution.
is also Nickel 200.
B.Caustic Potash Manufacture

The production of caustic potash is carried out
in nickel and nickel alloy equipment in a similar
manner t9 the production of caustic soda. One
important difference. however, is the higher
boiling point encountered in caustic potash above
50 per cent concentration. Because of the higher
temperahx ~~; involved. cathodic protection is
often used for low-carbon Nickel 201 or high
nickel alloy equipment u:=;ed for the production of
Fig. 16 - Marine terminal where caustic soda is unloaded

from barge. Nickel 200 lined caustic transfer pipe is at right
foreground.
28
Tt'an;;fer of materia! to and from storage tanks

usually requires pumps. Table XLIII shovv's the
results of a plant test in which Xickel 200, MONEL
alloy 400 and INCONEL alloy 600 corrosion coupons
wet'e subject to turbulent flow just downstream of
a pump handling 50('~ caustic soda. Similar corrosion resistance would be expected fl'O!1l the cast
counterparts of these wrought materials (ACI
CZ-IOO, M-35 and CY-40). Pumps cast from ACI
CZ-IOOhave given over 25 years service as previollsly noted.
Table XLIII
field Test in 50% Caustic Soda
Just Downstream of a Pump
Temperature: 60 to 70 C (140 to 158 f);
AI/erage 65 C (149 f).
Aeration: Moderate.
fig. 17 ~ This barge carries 50%. caustic soda from a

mercury cell plant to storage facilities'along the Tennessee.
Ohio and Mi
Rivers. Four cylindrical tanks have a
total capacit
liquid tons. To insure a long sef\lice
life for the
ge and to protect product purity. all cargo
piping is either solid Nickel 200 or Nickel 2oo-clad steel with
Nickel 200 fittings: The cargo fromal! four tanks empties
into a Ni,ckeI2oo-clad steel well from which ,it ispl.lmped to
on-shore facilities_'
.'
. '
flow; 100 gpm in 3inch pipe.
Corrosion Rate.
mils per year
Material
Nidle1200
alloy 600
MONEL aUoy 400
a.OJ
0.03
lNCON~L
0.10
The use of nickel;..cla<i steel .tanks offers particularj\dvantage.<; in the storage and shipment
of 13~ caustic soda. To a\'Qid solidification;caustic of. this st~ngth must be loaded hot and main-
..
fig. J,8 -:- INCOLOY aUoy 8,25 ,is used for the inner tank and all internal parts that come into contact with corrosil/e cargoes
in these two trailers-inner shell and heads. manhole ring and cover. dip tubes. spill dam and discharge pipe. Although
presently used for hauling 50% caustic soda. the corrosion resistance of this material will allow the hauling of a variety of
corrosives.
tained above the freezing point. Tables XLIV and

XLV give the results of tests in transportation
and storage facilities.
It is common practice to load and unload cars
of 73% caustic through Nickel 200 heat exhangers, pumps and piping.
D. Soap Manufacture
Soaps are made by the reaction, called "saponification,"between alkali and fatty oils (gly_
cerides) and fatty acids of animal or vegetable
origin, or a mixture of both. The largest production, and the most familiar, is "hard" soap made
with caustic soda as the saponifier. Caustic potash
produces a "soft" or liquid soap.
In certain high grade soaps, it is necessary to
avoid contamination by such metals as iron and
copper in order to obtain a high quality product.
Therefore, pure caustic must be used in combination with corrosion-resistant equipment. The
matter of iron contamination is particularly significant in soap-boiling kettles because the soap
spends so much time there. particularly in the fuHboiled process. This is especially significant in the
upper parts of the kettles where corrosion rates
are highest. Table XLVI shows the results of one
plant corrosion test in a soap-boiling kettle. Some
of the earliest applications of ~orrosion-resistant
materials were in the construction of soap kettles.
Table XLIV
Field Test in Tank Car Transporting
74% Caustic Soda
Test Period: 11 trips of 79 days.
Aeration: None. Agitation: By movement of tank cars.
Material
Nit;lle1200
INCOlOY alloy 825
MONEL alloy 400
CARPENTER alloy 20
Corrosion Rate,
mils per year
0.3
0.3
0.4
0.9
8.4
Table XLVI
Plant Corrosion Test in SoapBoiling Kettle
Specimens immersed near the top of the settling cone duro
ing saponification and graining.
Material
Hit;ke1200
MONEL alloy 400
.NCOffEl. alley 600
HiResist Type 1
Mild Steel
Cast Iron
Fig. 19 - 1300 feet of transfer pipe with a rolled and

welded internal lining of Nicke1 200 carries 50% caustic
soda from a marine terminal to a Nickel 2ooc1ad storage
tank. Nickel 200-clad tank cars are in the background.
Table XLV
Field Test in Storage Tank for 73% Caustic Soda
Aeration: None. Agitation: None except for filling of tank.
Nickel 200
I NCONEl alloy 600
MONEL alloy 400
Zirconium
Titanium
Mild Steel
<0.1
<0.1
<0.1
0.1
3.2
11.0
The first step. in most cases, was to line the upper

portions of existing steel kettles with Nickel 200.
AHoy 400 or either Type 304 or Type 316 stainless steel. Because of occasional difficulties win
these lined vessels (usually weld cracks in thE
liner because of differential thermal expansior
between the steel kettle and the liner) , new vessel:
were sometimes constructed completely from cla(
plate. The same materials are also used for heat
ing coils. swing pipe, kettle covers and othe
accessory equipment.
-Material
Corrosion Rate.
mils per year
Corrosion Rate,
mils per year
0.3
0.4
0.7
L4
4.7
Destroyed during test
30
Much of the corrosion test work in soap plants

has been concerned with the treatment of spent
soap lye and recovery of glycerine. since these
processes represent particularly corrosive conditions. The pH of the solution during acid treatment is usually 4 to 4.5 and sometimes as low as
3, due to the presence of hydrochloric or sulfuric
acids. Agitation of the mixture with air, a common practice, tends to increase the corrosion rate
of steel. The results of six tests during acid treat-
ment in four different soap plants are shown in

Table XLVII.
Alloy 400 and Nickel 200 or steel clad with
these materials are used for both acid-treating
and caustic-treating tanks because of their resistance in both environments. Austenitic chromiumnickel stainless steel and Alloy 600 are also used
but pitting is possible with these alloys under
certain conditions as shown in Table XLVII. NiResist Type 3 is used instead of Types 1 or 2 for
Table XLVII
Plant Corrosion Tests in Acid Treatment of Spent Soap lye

Test 1: Immersed in acid treating tank in mixture of 13% NaCI and 4.5% glycerine to which
is added 150 Ib of 28% HCI and 75 Ib of 17% aluminum sulfate per 30,000 Ib soap
lye. Temperature: 1 to 82 C (30 to 180 F). Test Period: 167 days. Plant L
Test 2: Immersed halfway down in acid treating tank in mixture of 18% NaCI plus glyce.rine
to which is added 0.5% solution of aluminum chloride. Aerated. Average tempera
ture: 74 C (160 F). Test Period: 65 days. Plant 2.
Test 3: Immersed in trough of filter in acid treated filtrate from Test 2. Aerated. Average
temperature: 71 C (160 F}. Test Period: 65 days. Plant 2.
Test 4: Immersed halfway down in acidtreating tank in mixture of 8 to 10% NaCI and 4.5%
glycerine made acid to pH 4.5 with HCI and ferric chloride. Air agitation. Temperature:
21 to 71 C (70 to 160 F). Test period: 28 days. Plant 3.
Test 5: In acid treating tank in spent soap lye made acid to pH 4.5 with HCI and ferric chlo
ride, and aluminum sulfate. Agitated wiUl1iIir. Temperature: 54 to 79 C (130 to 114 F).
Test Period: 45 days. Plant 3.
a. Immersed in bottom of tank near air inlet.
b. In vapor in top of tank.
.
Test 6: Immersed halfway down in solution containing 13 to .16% NaCI plus Na2S0. and
10 to 12% glycerine made acid to pH 4.5 with sulfuric acid and ferric chloride.
Aerated. Temperature: 32 to 100 C (90 to 212 fl. Average 85 C (180 Fl. Test Period:
105 days. P\ant4.
C.onosion llate.lIllJs per year

Material
alloy 400
Hickel 200
MOHEL
IHCOHEL aUoy SOO

Type 302 stainless steel
Test 1 Test 2
Plant 1 Plant 2
.9
1.1
.6

0.3
0.9
Test 3
Plant!
4.8
3.7
2.9
L8
<.1
<.1
.7
.7 (a)
<.1
A (b)
Test Sa
Plal1t3
Test Sh
Plant 3
TestS
fitaltt4
4.4
5.6
5.1
4.7
16.0
10.0
.7
0.8
O.5!d
LOlh)
LO(i)
.5!d

Aluminum. Type 1100
27.0
4.4 (d)
HiResist Type 3
Hi Resist Type 2
2.7
1.0
4.0
HiResist Type 1
Mild Steel
2.5
5.3
0.9
3.0
3.4
17.0
11.0
6.0
16.0
Wrought Iron
Cast Iron
. TesH
Plant 3
3.0
(a)
(bl
(e)
(d)
Perlorated by pitting. original thickness 31 mils.

Pitted to maximum depth of 11 mils.
Pitted to maximum depth of 5 mils.
Pitted to maximum depth of 3 milS.
(e) Pitted to maximum depth of 20 mils.
16.0
29.0 (e)
34.0(gl
18.0
24.0 (f)
44.01gl
Pitted to maximum
(gl Pitted to maximum
(h) Pitted to maximum
(i) Pitted to maximum
(f)
31
depth of 9 milS.
depth of 8 mils.
depth of 6 mils.
depth of 14 mils.
5.0
14.0
14.0
14.0
the construction of soap lye filters and filter plates

to withstand possible therma' shock when the hot
solutions enter a cold filter process. Pumps of
iron-base nickel-chromium-copper-molybdenum
alloys such as WORTHITE or DURIMET 20 have given
good performance handling both acid- and
alkali-treated soap lye. Austenitic chromiumnickel stainless steels, usually Type 304, have been
used to advantage for "finishing and packaging"
equipment.
Although a considerable amount of the world's
soap is still produced batch-wise, efforts to reduce
the 4 to 11 days required with the fun-boiled kettle
method have resulted in a number of continuous
processes for soap manufacture. In one such
process, blended fats with zinc oxide catalyst are
reacted countercurrently with water in a 65-foothigh. Type 316 stainless steel hydrolyzing tower
maintained at 282 to 260 C (450 to 5(,)0 F) and
600-700 psi. Fatty acids are continuously drawn
off the top and crude glycerol off the bottom of the
column. The fatty acids arevacuum-distiUed and
then neutraiized in a high-speed mixer with a
caustic soda solution containing salt. thus producing soap in about four hours.24
In other continuous processes which usually
utilize centrifuges. the corrosives encountered
are much the same and considerable quantities of
austenitic chromium-nickel stainless steel. Alloy
400 and Nickel 200 are utilized. Tables XLVIII
and XLIX indicate the corrosion rates eneoun-
tered in a lye tank and a centrifuge in one of these

processes.
Table XLIX
Plant Corrosion Test in Third-Stage Centrifuge
Specimens located at soap discharge. Mixture contained
15% NaOH and 11 % NaC!. Low aeration, flow 350 gallons
per hour through 4inch pipe.
.
Material
Nickel ZOO
MONEL alloy 400
I/'ICONE.L alloy 600
Hi-Resist Type 1
Mild Steel
Cast Iron
MaOH and
Nickel
zno
alloy 400
INcolfEl aUoy 600
HiResist Type 1
Mild Steel
Cast Iron
MONEL
Corrosion Rate,
mils per year
Maximum Depth
of Pitting, mils
Nil o
Nil
Nit
Nil
Nil
0.1
0.1
1.0
3.0
None
None
None
None
None
None
None
7
None
None
None
None
None
None
None
Perforated
55
10
12
E. Pulp and Paper Industry
Material
Nil o
Nil
Nil
0.1
0.1
0.1
0.4
Over a million tons of caustic soda are used

annually in the pulp and paper industry, principally for the extraction of alkali-soluble impurities in multistage bleaching and for pH control.
Small amounts are used for preimpregnation of
wood chips and for the production of soda pulp.
More than two-thirds of aU paper is pX'Qduced
by the Kraft process. Digestion of certain soluble
portions of wood chips is accomplished by a hot
alkaline liquor consisting of a mixture of dilute
caustic soda and sodium sulfide with a total alkalinity of about 3 per cent. The following are principal areas where carbon steel may corrode at
an excessive rate and nickel-containing alloys
(usually austenitic chromium-nickel stainless
steels) can be used to advantage.
Plant Corrosion TestinfourthStage lye Tank

2%
Maximum Depth
of Pitting, mils
Less than 0.05 mils per year.
Table XLVIII
Immersed in tank containing soap lye with
11% MaC!..
Temperature: 88 to 96C (190 to 205 F).
Corrusion Rate,
mils pef year
1. Digesters
Batch-type Kraft digesters are commonly built
of carbon steel with a corrosion allowance in
excess of one inch. Until recent years this resulted
in a service life of about 15 years, but with the
increasingly severe conditions imposed. by modern
pulping methods, service life was reduced to about
7 to 9 years. Weld overlays employing AWS E310,
22
Less than 0.05 mils pel' year.
32
or A WS E310-Mo. have been employed to extend

the service life of corroded steel batch digesters.
Table L indicates the excellent corrosion resistance of stainless steel and several other nickel
alloys in one Kraft digester.
Table l
Table LI
Plant Corrosion Test in a Digester Utilizing
a Duplex Sulfate Process
Temperature: 100 to 171 C (212 to 340 f).
Cycle: Chips steamed for one hour, temperature rises from
100 C to 118 C (212 to 244 f). Acid liquor removed.
Alkaline liquor containing 82 gpl NaOH and 25 gpl
Na,S added. Charge brought to 171 C (340 f). cooked
for total of 5 hours.
location: In vapor. Test Period: 731 days.
Plant Corrosion Test in a Sulfate Process,

Alkaline, Wood Pulp Digester
Type. 316 Stainless Steel

CARPENTER alloy 20
Aeration: None.
Agitation:
Corrosion Rate,
mils per year
Material
Temperature: 177 C (350 f).
Violent boiling during cook.

Top--Vapors in the top of the digester. Occa
sional splashing of chips, pulp and cooking
liquors.
Bottom-Liquid and slurry on bottom screen of
digester.
INCj)NELalloy
Spo
MONEL alloy 400
Titanium
Mild Steel
0.1
0.1
0.1
OJ
23
55
107
Specime(ls: Combination of stress and general COrrosion.

Strips were stressed beyond the yield point by
bolting down over a fulcrum. Some specimens
were welded or contained weld overlays as
noted. No stress corrosion cracking occurred.
Corrosion Rate,
mils per year
Material
alloy 600
alloy 20
INCoNEL alloy 600
INCOlOY alloy 825
INCOlOY alloy 825
Type 316t. StainJess steel
Type 31Sl Stainless Steef
AViS Eltflllveriay on Steel
INCONEL
CARPENTR
Condition
Top
Bottom
Plate. asreceived
Welded
Welded
Plat.e. asreceived
Welded
Plate, asreceived
Plate. asreceived
Welded
Welded
Weld Overlay
0.02
0.03
0.03
0.03
0.03
0.04
0.05
0.06
0.06
0.05
0.21
0.09
0.23
0.09
0.15
0.17
0.15
0.17
Note: A dash indicates no coupon was exposed.
There are a few Kraft digesters that utilize a

duplex process in which the charge is initially acid
(pH 4) and later alkaline. Table LI shows corrosion rates in this process.
There are several hundred continuous digesters
operating on wood chips in the United States.
These are constructed primarily from carbon
steel with high corrosion rate areas lined or clad
with Type 316L stainless steeL These high corrosion rate areas include the upper section. where
fresh, hot alkaline liquor is injected, and the
bottom section in the area of the blow valve.
Internal accessories such as scrapers and chip
screens are usually fabricated from Type 316L
stainless steeL Construction of digesters with clad
Type 316L stainless steel would allow for con-
Fig. 20 ~ This top separator on a KAMYR continuous di

gester separates the chips from the flushing liquor. With the
exception of the drive mechanism. this separator is can
structed of Type 304 stainless steel.
siderably reduced wall thickness and much lower

maintenance costs.
2. liquor Heaters
Shell and tube heat exchangers are used to heat
the digester liquor prior to its introduction into
33
Table lit
Corrosion Test in Kraft Pulping
Exposed 68 Days in Head of liquor Heater
both batch and continuous digesters., Results of a

corrosion test in such a heater are shown in Table
LII. These data may indicate a lower than actual
corrosion rate for carbon steel, since the heat
exchanger tube walls are at a temperature higher
than the liquor in which the test specimens were
exposed. The liquor contains a large proportion of
fresh caustic and sulfide in addition to some black
liquor recovered from a previous digester cook.
Experience over many years has proven the adequacy of annealed Type 304 stainless steel for this
service. The use of "as-welded" tubes has sometimes resulted in failure by intergranular corrosion immediately adjacent to the weld. This type
of corrosion has not been observed when tubes
are used that have been made in compliance with
ASTM A 249. This specification caUs for welded,
drawn, quench-annealed tubing. Tubes of this
type have been known to last in excess of.10 years,
but service life is dependent on specific operating
conditions. In a few instances, the Type 304 stainless steel tubes have been subject to failure by
chloride stress-corrosion crackng. Alloy 600 and
Alloy 20 have been successfully employed to resist
this type of attack.
Flow rate of 2400 gpm at temperature of 173 C (344 F).
Material
INCONEL alloy 600
MONEL alloy 400
Nickel 200
Mild Steel
Cast Iron
Corrosion Rate,
mils per year
0.5
0.8
0.9
38
57
95
342
Vapor domes in the hottest effects are often clad

with Type 804Lor Type 316L stainless steel, since
carbon steel in this area may corrode at a rate
exceeding 100 mils per year. There are also installations where sta.inless-elad steel has been used for
the entire evaporator body. Advantages of such
construction.inelude less carry..over of corrosion
products and less fouling of the evaporator tubes
by these products.
Defiectorpla.tes and auxiliary piping are usuany made of solid Type 804L stainless steeL For
valves and pumps, Ni-Resist Type 2, CF-8 and
CF-8M castings are used.
3. Black liquor Evaporators
4. Recausticizing
To permit recovery of chemical values in the

digester liquor when chip cooking is complete, it
is necessary to concentrate the liquor, together
with the chip wash water. This is required to raise
the solids content to more than 50 per cent. which
will permit burning in the recovery furnace.
Kraft liquor vacuum evaporators are multiple
units usually consisting of one or more sets of six
long tube vertical effects connected in series.
Corrosive conditions on the tubes are somewhat
less severe than in digester liquor heaters since
the vacuum operation results in lower boiling
temperatures. The first effect operates at the
highest temperature of about 135 C (275 F). Temperatures decrease in each succeeding effect. It
has been customary to use Type 304 stainless
steel for tubes in the first effect and often in the
second effect. A number of installations have used
Type 304 stainless steel tubes in all effects, resulting in less frequent downtime fer cleaning,
long service Hfe, and maintenance of high heat
transfer rates.
As part of the operation to regenerate chemicals reclaimed from the recovery furnace, sodium
carbonate is treated
calcium hydroxide
(milk of lime) to produce sodium hydroxide.
Table lin
Corrosion Test in Kraft Pulping
Exposed 68 days in green Uquor. 175 to ~5 gpl as Na 2 CO,
in flow bQx.from recovery furnace to claSSIfiers.
Temperature: 66 to 99 C.(150to 210 F).
Some aeration and agitation.
Material
tN(:ONEL alloy 600
Type 302 Stain1ess Steel
Nickel 200
MONEL alloy 400
Mild Steel
Cast Iron
34
Corrosion Rate,
mils per year
<0.1
0.1
0.1
0.1
0.2
0.3
0.5
115
176
Carbon steel, with a corrosion allowance. has

been used for most of the equipment. As shown
in Table LIII, fairly high rates can occur on carbon steeL Light gauge Type 304 stainless steel
is an economic selection for troublesome areas.
Indu~try
Despite extensive use of caustic soda by the
aluminum illdustry for the extractioRofhydrated
alumina from bauxite in the Bayer process, rela-
F. Aluminum
tively smallam{llwts of nickel and nickel altoys

have been utiJized in these plants.
Alloy 400 tubes have been successfully employed for digester preheaters. and Alloy 400
insert ferrules have been used to overcome the
inlet end corrosion in other steel preheater tubes.
Relatively thick (30 mils minimum) electroplated
nickel {lll steel has been used to advantage for
piping and digester preheater channels. Nickel
weld-overlays haVe proven \Iseful on pump casings, and cast nickel (ACI CZ-IOO) has given good
service as pump impellers. valve bodies and for
other instrumentation.
However. the present practice with bauxite
digesters is to use thick-walled carbon steel at
low stress levels. Some cases of stress-corrosion
cracking (If steel have occurred in plants handling
caustic soda solutions in the Bayer extraction
process. z::>
The recent trend awaYI;r;om ores high in gibbsite C{lntent toward the use of Ores relatively high
in boehmite c()ntent has necessitated digester
operation at higher pressures and temperatures.
This increases the pos!;;ibHity of caustic embrittlement of steeL Thus. nickel or nickel-clad steel
should be given consideration for the processing
of these higher boehmite bauxites.
G. Caustic FuSions
Nickel 200 and Nickel 201 are useful as materials of construction for vessels for the caustic
fusi{ln of organic comp{lunds. Where temperatures exceed 316 C (600 F). the low.-carb{ln
Nickel 201 is preferred to preclude grain boundary precipitation of carbon which greatly reduces
duetility. For those reactions where sulfur compounds are present at temperatures over 250 to
300 C (482 to 572 F). either in the process or the
heating medium, nickel may be attacked intergranularly and Alloy 600 is preferred.
One process for the production of resorcinol
has involved the caustic fusion of benzene meta
disulfonic acid at 325 C (617 F). Equipment for
this production has been made of wrought Alloy
600 and ACI CY -40 castings. Both alloys should
be stress-relieved as indicated in the section on
nickel-chromium alloys (Part II B).
Fig. 21 - This llfoot long. 16inch diameter pipe has been

electmplated with nickel to yield a 30-mil thick deposit on
the inner diameter and about 2 mils on the outer diameter.
Sections like this are welded toget:he( to form piping used
in bauxite refining in the aluminum industry. Lengths of
greater than 11 feet can also be plated.
Photo by courtesy of Plating Engineering Company. Milwaukee. Wise.
35
H. Petroleum Refining
Cau~tic soda or, occasionally, caustic potash or
sodium carbonate is used in petroleum refining
for acid neutralization and the removal of undesirables such as mercaptans and hydrogen sulfide.
Aqueous solutions may range from 2 to 50
per cent.
For many of the applications where temperature and concentration are low, the corrosive
conditions are mild enough that steel can be used.
Where the corrosive conditions are more aggressive, Nickel 200, AHoy 400 or Alloy 600 are used.
Very often Alloy 400 is used because it appears to
have a greater tolerance for the impurities
present in the process.
In the t'egeneration of caustic solutions, it is

common practice to use Alloy 400 in critical portions of the system where steel is unsuitable.
These locations include the regenerator reboiler,
preheaters and piping for handling hot caustic
solutions and sometimes for the bottom sections
of the regenerator towers. These components may
be either solid or clad. ACI CZ-IOO, ACI M-35
ductile Ni-Resists and WORTHITE stainless steei
have been used for valves and pumps. The results
of plant corrosion tests in the reboilers of caustic
regenerator units are shown in Table LIV.
Table ltV
Plant Corrosion Tests in
Caustic Regeneration Units
Test A-In open tank used to boil 18 to 22% caustic soda
plus merca pta ns and cresolates for regeneration of
caustic solution. Test specimens were immersed in
solution above heating coils.
Temperature 38 to 104 C (100 to 220 F).
Average 80 C (175 F).
Test a-Just ab~ve reboiler inlet below bottom tray of reo
generating tower. Solution 18% caustic soda for
tified with naphthenic acid. cresols and phenols to
22 to 28 Be. Solution also contained 0.040/0 mer
captan sulfur.
Temperature: 21 to 116 C (70 to 240 f).
Average 107 C (225 F).
Test C-At bottom of stripping tower 18 inches above reo
boiler tubes. Solution 7 % caustic soda with trace
of mercaptans.
Average 135 C (275 Fl.
Test o-In vapor sectj~n of caustic soda regeneration unit.
Solution entenng contained' 13.2% caustic soda.
0.37% sulfide sulfur and 0.80% mercaptide sulfur.

Material
INCONEl alloy 600
Type 304 Stainless Steel"
Nickel 200
MONEL alloy 400
Type 316 Stainless Steel"
HiResist Type 1
Cast Iron
Carbon Steel
Fig. 22 - Nickelcopper alloy 400 was used for the walls of

the caustic stripper towers. reboiler tube bundles and hot
caustic lines in this refinery. After 10 years of service. the
Alloy 400 components continue to withstand the corrosive
mineral acids. sulfur compounds and hot caustic soda in
the fluid hydroformer and caustic regenerating equipment.
TestA
TestS
Test C Test D
<0.1
0.1
0.1
0.3
0.4
1.1
<0.1
0.1
0.2
0.1
0.2
<0.1
0.1
0.3
1.1
2.0
2.0
3.8
13.0
4.0
10.0
29
.., Subject to pitting.

"') May be 'Subject to stress-corrosion cracking_
36
0.9
12.0
4.5
13.0
33.0
In view of its good resistance to caustic alkalies

containing hydrogen sulfide and mercaptans, Alloy 600 is also a useful material for evaporator
tubes or other parts of regenerator systems. Alloy
600, rather than Nickel 200 or AHoy 400, should be
used in this service where metal temperatures in
excess of about 250 to 300 C (482 to 572 F) are
encountered, since Nickel 200 and Alloy 400 are
subject to sulfidation at higher temperatures.
A caustic stripper, at a major Louisiana refinery, constructed of MONEL alloy 400, exhibited no
detectable metal loss after more than 4 l'2 years'
service handling up to 45<; caustic soda at temperatures up to 143 to 149 C (290 to 300 F). It is
still giving repair-free service after 15 years.
In one Texas refinery, mercaptains are removed
by the Dualayer Process * which utilizes two
layers of immiscible solvents. The first solvent
layer, a water solution of caustic potash and
potassium cresylate, removes the mercaptans.
The second and lower layer is a water solution
of caustic potash that maintains the composition
of the upper layer. Water and potassium hydroxide migrate between lower and upper levels, sustaining the equilibrium. MONEL alloy 400 was used
for the stripper preheater, reboiler. and stripping
tower trays and. in a cast form (ACI M-35), for
the bottom pump. The tower itself was lined with
MONEL aHoy 400 and stress-relieved. This equipment continues in operation after 20 years.
Nickel-copper alloy 505 has excellent nongalling properties and can be combined with cast
nickel-copper alloy ACI M-35 in pump assemblies
to avoid seizing. particularly in mixtures containing gasoline or similar solvent materials where
lubrication is practically impossible.
I n one process, the parts to be descaled are immersed in a 370 C (700 F) bath of molten caustic soda
containing 1.5-2% sodium hydride. Other processes operate with molten caustic at 480 C (900
F) or higher.
Carbon steels are often used for the equipment
handling these fused caustic baths up to about
480 C (900 F). In cases where carbon steel has
not proven satisfactory. Nickel 201 and Alloy
600 have been demonstrated to give good performance. Nickel 201 is used for sodium hydride
generators in one process. Both Nickel 201 and
Alloy 600 are used for sheathing on electric heating elements in caustic baths. AHoy 600 is used
for gas-fired heater tubes in some cases. In cases
where the caustic baths are operated at higher
temperatures than usual, such as 566 to 621 C
(1050 to 1150 F), Nickel 201 is used instead of
carbon steel for pickling tanks and associated
equipment. A plant corrosion test in a commercial
molten caustic pickling bath operating at 482 C
(900 F) showed a corrosion rate of one mil per
year for nickel in a 60-day test.
J. Reclaiming Caustic for Economy

and Pollution Control
In the diverse industries which make use of
caustic solutions, numerous companies have
found that it is economically attractive to reclaim
and concentrate the caustic values of their effiuents. Even
the return on investment for
caustic recovery units is not high enough for justification on this basis alone. pollution control is
desirable and may become mandatory as local
anti-pollution laws become more stringent.
Recovery and concentration plants are commercially available for some industries. Of the total
caustic soda purchased yeariy by a textile mill
for mercerizing cotton. often as much as 65 per
cent can be recovered from the mercerizingframes
and up to 95 per cent at the mercerizer. The concentration of caustic soda is from about 5 per cent
in contaminated liquor to the de~;jred concentration for the particular mercerizing operation.
These plants utilize nickel or high nickel alloys for
evaporators and associated equipment .
L Caustic Oescaling
Several processes involving molten caustic soda
are in commercial use for the descaling of various
metals and-alloys, particularly the stainless steels.
Some of these processes involve addition to the
caustic of reducing agents to reduce the metallic
oxides to metal or lower metal oxides, most of
which flake off in the subsequent water quench.
Patented Process. Mohil Oil Corp.
37
PART V. WELDING
Table LV
A. Fabrication of
Nickel-Clad Equipment
Corrosion of IronContaminated Nickel Welds

in 73% Caustic Soda at 121 C (250 F) 27
In the welding of nickel-clad equipment, a certain amount of iron dilution of the nickel weld
deposit occurs. Special precautions are usually
taken in order to minimize this dilution. With
special precautions, the nick~l welds in a nickelclad tank for a chemical tanker were limited to
an iron content of 0.35-3.29%.26 Gegner has suggested that considerably more iron than this can
be tolerated. 27
Although iron-contaminated nickel weld metal
and nickel-iron alloys are not severely attacked in
73% caustic soda at 121 C (250 F). as shown by
data in Tables LV and LVI, nickel-iron alloys can
be the anode in an electrolytic cell with nickel,
as shown in Table LVII. Note that the 20% iron
alloy corroded at three to five times the rate it did
when it was not coupled to nickel. Even greater .
increases in rate would be expected in large pieces
of equipment where the relative ratio of cathodic
area (cladding) to anodic areas (weld) is greater
than the 10:1 ratio of the test.
First
Exposure,
30 days
Second
Exposure,
60 days
Total
Exposure,
90 days
0.51
5.56
11.43
13.15
17.62
22.85
8
8
7
7
7
6
5
5
6
6
5
4
5
5
5
5
5
Iron
in Weld,
Table lVI
Corrosion of Nickel and NickellronAlloys
in 73% Caustic Soda at 121 C {250 f)27
Corrosion Rate,
mils per year
Iron. %
7
7
8
0
0
5
5
8
6
8
8
10
to
20
20
Table LVII
Galvanic Corrosion Tests in Caustic Soda
of Nickel to Nickel-Iron Alloy Couples
Area: Nickel
Nickellron Alloy
Aeration: None.
0.5 sq dm
O.05sq dm
Motion: None.

Couple
No.
Couple
Materials
23% NaOH at 105 C (221 Fl

Coupled
Uncoupled
50% HaOH at
15C (161 Fl 15% NaOH at 126 C (259 Fl
Coupled
Coupled
Uncoupled
5% FeNi
Nickel
1.6
0.6
1.4
0.4
2.4
0.8
1.0
1.6
1.0
1.5
10% feNi
Nickel
2.6
0.4
L2
0.4
2.0
0.6
1.5
LO
1.4
1.5
20% FeNi
Nickel
3.6
0.6
0]
0.4
1.6
0.4
1.8
1.1
0.6
1.5
Notes:
1. The ironnicket alloys were in the form of castings.

2. No tests were made, uncoupled. in the 500/0 NaOH solution.
38
B. Repair of Equipment in
Caustic Service
Before doing any repair or maintenance welding of nickel or nickel-containing alloys or dadsteel plate that has been in caustic service, it is
necessary to remove products of corrosion, and
any other foreign material, from the vicinity of
the area to be welded. (The caustic soda and other
impurities present can cause loss of ductility and
cracking if present during welding.) Therefore,
great care should be taken to obtain a clean, bright
metal surface over an area extending 2 to 3 inches
from the site of welding on both sides of the piece.
Cleaning mechanicalIy, by grinding with either a
fine wheel or a disc grinder, or chemically, by

pickling, is recommended. After cleaning, the
welding procedures outlined for new metal should
be followed in every detaiL
Flash pickling solutions are effective for cleaning nickel and high nickel alloy surfaces. These
may be applied with long-handled swabs or
brushes where equipment is large, or may be held
in glass or ceramic crocks for pieces that are
easily handled. such as the ends of nickel caustic
evaporator tubes that have been removed from
evaporator service and are to be used for pipelines. The tubes can be dipped vertically and
cleaned for a minimum distance of 3 inches from
the end.
AVAILABLE LITERATURE
The following Corrosion Engineering Bulletins are available for your use:
"Resistance of Nickel and High Nickel Alloys to Corrosion by Sulfuric

Acid"
"Corrosion Resistance of Nickel and Nickel-Containing Alloys in Caustic
Soda and Other Alkalies"
"Resistance of Nickel and High Nickel Alloys to Corrosion by Hydrochloric Acid, Hydrogen Chloride and Chlorine"
"Corrosion Resistance of Nickel-Containing Alloys
In
Phosphoric Acid"
"Corrosion Resistance of Nickel-Containing Alloys in Hydrofluoric Acid,

Hydrogen Fluoride and Fluorine"
39
REFERENCES
1. Swandby, R. K., "Corrosion Charts: Guides to Materials Selection", Chen!. Eng., Vol. 69, No. 11, Nov.
12, 1962, p. 197.
2. Fontana, M. G., "Corrosion at Elevated Temperatures
and Pressures", The Ohio State University Research
Foundation, Report No. 10, Project 350, May 1, 1951,
p.F2.
3. Badger, W. L. and Standiford, F. C., "Anhydrous
NaOH: Today's Technology", Chern. Eng., 61, Feb.
1954, pp. 183-187.
4. Gregory, J. N., Hodge, N. and Iredale, J. V. G., "The
Static Corrosion of Nickel and Other Materials in
Molten Caustic Soda", AERE CIM 272, March, 1958.
5. Gregory, J. N., Hodge, Nand Iredale, J. V. G., "The
Corrosion and Erosion of Nickel by Molten Caustic
Soda and Sodium Uranate Suspensions Under Dynamic Conditions", AERE CIM 273, March, 1956.
6. Lad, R. A. and Simon, S. L., "A Study of Corrosion
and Mass Transfer of Nickel by Molten Sodium
Hydroxide", Corrosion, 10, December. 1954, pp. 435439.
7. Smith; G. P., Sieidlitz, M' E. and Hoffman, E. E.,
"Corrosion and Metal Transport in Fused Sodium
Hydroxide", Co)Tosion. 13, September, October, 1957.
pp. 561t-564tand 627t-630t.
8. Forestieri, A. F. and Lad, R. A., "The Use of Metallic
Inhibitors for Eliminating Mass Transfer and Corrosion in Nickel and Nickel Alloys by Molten Sodium
Hydroxide", Lewis Flight Propulsion Laboratory,
Cleveland, Ohio, February, 1955, NACA RM E54L13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
9. May, C. E_, "Correlation Between Hydro~en Pressure

and Protective Action of Additives in the Molten
Sodium Hydroxide-Nickel System", Lewis Flight
Propulsion Laboratory, Cleveland, Ohio, February,
1966. NACA RM E55LOl.
10. Wallace, T. and Fleck, A., "Some Properties of Fused
Sodium Hydroxide", Jourl/al Chelll. Suc., 119, 1921,
p. 1839.
11. Uhlig, H. H., Ed., Corrosion Handbook. N. Y., John
Wiley, and Sons, Inc., 1948, pp. 576-577.
12. Stone, J. M., "Solutions Causin~ Intergranular Corrosion of Stainless Steels", Information from Internal
Document by courtesy of E. L du Pont de Nemours and
Co., October, 1955.
13. Agrawal, A. K. and Staehle, R. W., "Stress-Corrosion Cracking of Fe-Cr-Ni Alloys in Caustic Environ-
23.
24.
2;).
26.
27.
40
ments", Report No. COO-2018-21 (Q6) for period

April 15, 1970-July 14, 1970, Ohio State University,
Columbus, Ohio.
Nathorst, H., "Stress Corrosion Cracking of Stainless
Steels-Part I Practical Experiences", Welding Research Council Bulletin, No.6, October, 1950, pp. 6-7
and 10.
ASM Committee on Stainless Steel in Chemical Corrosion Service,lHetals Handbook, Am. Soc. Metals, 1961,
p.566.
Beck, F. H. and Fontana, M. G., "Corrosion by
Aqueous Solutions at Elevated Temperatures and
Pressures", Corrosiun, Vol. 9, No.8, August, 1953. pp.
287-293.
Pratt. W. E., "Corrosion Resistance of Worthite in
Caustic Soda", Chemical EnginC(!ring, Vol. 56, No. 12,
1949, pp. 213-214 and VoL 57, No.1, 1950, pp. 213-214.
"Hastelloy Corrosion-Resistant Alloys", Union Carbide Corporation, 10th Edition, May, 1957 and private
communication from Haynes Stellite Co.
Ge~ner, P. J., "Corrosion in Alkaline Environments",
ProcecdiJlgs of Shmt Course 0)/ Pl"(lCeSS Industry
Corrosio)t, National Association of Corrosion Engil!eers, September 12-16. 1960, p. 1 L
McCallion, J., et at, "Switch to Continuous Evaporation Boosts Capacity But Not Manpower", Chemical
P"ocessing, August, 1968. pp. 20-21.
U. S. Patent 3,380,806, April 30, 1968.
Twiehaus, H. C. and Ehlers, N. J., "Caustic Purification by Liquid-Liquid Extraction", Chemical Industries, August, 1948, pp. 230-233.
Friend, '.V. Z. and Mason, J. F., "Corrosion Tests in
the Processing of Soap and Fatty Acids", Corrosion,
Vol. 5, No. 11, 1949, p. 358.
Kirk-Othmer, Ellcyclopl'tiia <If Chcmical Technology,
Second Edition, 1969, Vol. 18, p. -123.
Champion, F. A., "Some Aspects of the Stress-Corrosion of Steel in Caustic Soda Solutions", Chemistr1l
{fllel Il/dustl'1f, July 13, 1957, pp. 967-975.
Phelps, H. C .. "NickelLined Ship for Liquid Chemicals", The Weldil/g Engil/eer, Vol. 39, No.4, 1954,
pp. 41-44.
Gegner, P. J., "Corrosion in Caustic of Nickel-Iron
Welds Obtained in Fabrication of Nickel-Clad Vessels", CUI'rosiol/, Vol. 12, No.6, 1!:5C, pp. 26lt-262t.
TRADEMARKS
Following is a list of the registered trademarks referred to in this publication

together with the names of the trademark owners.
ALOYCO
Registered trademark of Aloyco Inc.
CARPENTER
Registered trademark of Carpenter Technology Corporation.
CHLORIMET
Registered trademark of The Duriron Company. Inc.
DURANICKEL
DURIMET
HASTELLOY
Registered trademark of The International Nickel Company. Inc.

Registered trademark of The Duriron Company. Inc.
Registered trademark of Cabot Corporation.
ILLIUM
Registered trademark of Stainless Foundry & Engineering, Inc.
I NCOLOY
INCONEL
KAMYR
Registered trademark of Kamyr Inc.
MONEL
NIMONIC
WORTHITE
Registered trademark of Worthington Corp.

Corrosion Resistance of Nickel and Nickel

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Corrosion Resistance of Nickel and Nickel

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CORROSION RESISTANCE OF

NICI<EL AND NICI<EL-CONTAINING ALLOYS

CORROSON BY OTHER ALKAliES.. ............... .... ....

A. Caustic Potash (KOH) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..

PART IV. INDUSTRIAL APPLICATIONS. ... .... . ............... ......

Caustic Soda Manufacture . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ..

PART V. WELDING ............. __ ..... _. . . . . . . . . . . . . . . . . . . . . .

A. fabrication of NickelClad Equipment .. _ ..................... "

Pb 0.05 max; In 1.0 rna.

---Cb;- Ta IOxC min

Nickel Base Molybdenum Alioy

(1) An improved version of this alloy.

stainless',No. 20Cb3. has replaced

Co 2.5 rna.: V 0.20A;

Corrosion Resistance of Nickel and Nickel-Containing

Caustic soda (sodium hydroxide) is the most

Fig. 1 - These caustic soda evaporator units are a

PART II. CORROSION BY CAUSTIC SODA

Fig. 3 - View of caustic transfer piping from marine storage

In caustic concentrations above 75 per cent and

o '--_ _....l.-_.L---l._ _- - ' ' - -_ _...L-_ _

Fig. 2 -Isocorrosion chart for Nickel 200 and Nickel 201

Some tests which have been carried out at

Test coupons removed,

Average of tests run at

Average of tests run at

First effect of multipleeffect evaporator

Storage tank coupons

Storage tank in which air was

Storage tank coupons

Transler piping. at pump

laboratory test on tubing;

rest tank_ simulating action

Storage tank coupons

Storage tank coupons

Storage tank between

Less than 0.005 mils per year.

Corrosion Rate, mils per year

Velocity has little effect on the corrosion rate of

Aeration has not been observed to accelerate

M"lten Coust;c Sodo

Rotot;on $peed_ rpm

Chlorates in caustic can increase corrosion rates

Corrosion rate of nickel as a function of rotational

Gained weight. Swollen outside surface largely oxide-heavily cor

4. Effect of System Thermal Gradients

The presence of oxidizable sulfur compounds

In molten caustic soda at temperatures above

(Nickel 201) will circumvent this problem.

7. Effect of Dissimilar Metal Contact

75% C.P. Sodium Hydroxide

75% C.P. Sodium Hydroxide plus 0.75% Sodium

75% C.P. Sodium Hydroxide plus 0.75% Sodium

75% C.P. Sodium Hydroxide plus 0.75% Sodium

75% C.P. Sodium Hydroxide plus 0.75% Sodium

mils per year

cent H;!S in dry caustic, was 0.009 per cent. Test 2

Metal Pickup. grams

Slight welgh1 gain

Corros ion Rate of

to three times its normal rate when connected to

GoJvonrc Current Flow Between

A"'?oe: c.,;~ !"on Ar~"

. C 3QS -;:: ;:.