Corrosion resistance of Nickel alloys to halogens (Hydrofluoric acid)
This article is prepared by Heanjia SuperMetals team to analyze the performance of various Nickel based alloys such
as Nickel, Monel 400, Inconel and Incoloy alloys in halogen acid conditions such as hydrofluoric acid. It has been
confirmed after conducting various tests at the lower, room and high temperatures.
Chemical composition of Nickel alloys that are used and corrosion tested
Element
Nickel Iron
Stainless
steel 304
Stainless
steel 304L
Stainless
steel 316
Stainless
steel 316L
Stainless
steel 317
Alloy 309
Cb
Stainless
steel 310
Stainless
steel 321
Steel 329
Steel 347
9.5
70
Chromium Molybdenum Copper Carbon Silicon Manganese Other
elements
18
.08
0.5
1.5
-
10
69
18
13
65
17
13
65
17
14
61
19
13
64
21
20
52
25
10
69
18
4.5
11
67
68
27
18
.03
0.5
1.3
.08
0.5
1.7
.03
0.5
1.8
.08
.4
1.6
0.25
.08
Ti 5XC min
.07
.08
.5
1
0.6
2
0.10
0.9
0.25
1
0.80
1
Antimonytantalum
10XC min.
N 0.10
Al 1
0.9
1.75
0.07
3.25
0.6
3.3
0.07
0.6
0.75
Cb + Ta
0.6
3.3
0.07
0.6
0.75
Cb + Ta
0.6
.07
1.80
.03
0.35
0.65
.03
0.35
1.3
0.05
0.35
1.3
Al 0.15, Ti
0.90
Tungsten
0.6
Cb Ta
2.12, Co
2.5 max
1.5
Steel 350
4.3
76
16.5
2.75
ARMCO
7
72
17
17-7 PH
ARMCO
7
72
15
2.5
PH 15-7
Mo
Iron base Nickel-chromium-copper-molybdenum alloys
Worthite
24
48
20
3
stainless
Carpenter 29
44
20
2.5
stainless
No. 20 Cb
Carpenter 34
39
20
2.5
stainless
steel No.
Cb-3
ACI type
29
44
20
2 min
CN-7M
Nickel base Iron-molybdenum alloys
Incoloy
41.8
30
21.5
3
825
Hastelloy
45
19.5 22.2
6.5
alloy 6
Hastelloy
47
17
22
6.5
F
Cb Ta
5XC min
Aluminum
1
Hastelloy
X
48
18.5 22
Nickel base chromium-molybdenum alloys
Illum B
52
1.15 28
8.5
alloy
Illum 98
55
1
28
8.5
alloy
Illum G
56
6.5 22.5
6.4
alloy
Illum R
68
1
21
5
alloy
Nickel base Molybdenum chromium alloys
Hastelloy
69
5
7
17
alloy N
Hastelloy
54
5
15.5
16
alloy C
Nickel base molybdenum alloy
Hastelloy
61
5
1
28
alloy B
Nickel base silicon alloy
Hastelloy
82
2
1
alloy D
Nickel alloyed cast irons
Ni- resist
15.5
69
2.5
kind 1
Ni resist
50
62
3
Kind 3
Nickel-Copper alloys
Monel
66
1.35 alloy 400
Monel
65
1
alloy K500
ACl M-35
64
3.5 Nickelcopper
alloy
Nickel64
2
Copper
alloy 505
Nickel64
1.5 Copper
alloy 506
Copper30
0.55 Nickel
alloy CA
715
Copper20
0.75 Nickel
alloy 710
Copper10
1
Nickel
alloy CA
706
Copper41
2
Nickel
0.10
Co 2.5
max, W
0.2 to 1
5.5
.05
3.5
1.25
B 0.05
5.5
.05
0.7
1.25
6.5
0.20
0.65
1.25
.05
0.7
1.25
.08
.8
.08
Co 2.5, W
4, V 0.4
.05
Co 2.5,
others 3
0.12
Co 1.5.
others 2
6.5
2.8
1.2
0.5
2.6
1.5
0.6
31.5
0.12
0.15
0.90
29.5
0.15
0.15
0.60
29
0.35
1.50
Al- 2.80, ti
0.50
-
29
.08
0.80
30
0.10
3.2
0.80
67
Lead .05,
zinc 1
74
Lead .05,
zinc 1
86.5
Lead .05,
zinc 1
55.7
1.25
alloy CA
720
Nickel Alloys
Nickel 200 99.5
Nickel 201 99.5
Duranickel 94
alloy 301
0.15 0.15 0.15 -
Nickel base chromium alloys
Corronel
55
5
36
alloy 230
.05
.05
0.15
.06
.01
.55
.05
.05
.25
.25
.20
.25
Aluminum
4.5,
titanium
0.50
.08
.06
Titanium
1,
aluminum
0.5
-
Inconel
600
Inconel
625
76
7.2
15.8
0.10
.04
.20
0.20
60
21.5
.10
.50
.50
Inconel
X750
73
6.75 15
.05
.04
.30
.70
0.30
.04
0.35
0.75
Iron-Nickel-Chromium alloy
Incoloy
32
46
20.5
alloy 800
Antimony
+ titanium
3.65
Titanium
2.50,
aluminum
0.80,
antimony
0.85
-
Abstract
The commercial use of hydrofluoric acid, hydrogen fluoride and fluorine is more recent as compared to various
heavy chemicals. Until the initial two decades of 20th century, only aqueous hydrofluoric acid and calcium fluorine
were have industrial importance. Through the development of procedures for major production of anhydrous
hydrogen fluoride in 1931 and, fluorine made from it, a latest edge in fluorine chemistry was possibly created.
The aim of this study is to show the corrosion resistance properties of nickel and nickel based alloys in hydrofluoric
acid (HF), hydrogen fluoride, fluorine and some fluorine based compounds.
If it is feasible to generalize, it may be stated that hydrofluoric acid, hydrogen fluoride and fluorine are less corrosive
to various metals and alloys as compare to other contrary halides. These rapidly combine with several metals to
produce fluoride layers that based on conditions, thin reliable and security to more reaction. It is normally a case
with alloys containing high nickel magnitude with the outcomes that several of these nickel based alloys are utilized
in dealing with fluorine compounds.
Hydrofluoric Acid
Hydrogen fluoride easily dissolves in water for large concentration limit, the water solutions are stated as HF.
Industrially, this acid is used in concentration of 30 to 70 %. An azeotropic mixture of 38.2 % produces that has a
boiling point of 234oF. Hence contents above 38.2 % are impossible to produce through evaporation and should be
produced through adsorption of anhydrous hydrogen fluoride in water.
Nickel-Copper alloys
The Nickel-Copper alloys referred as Monel alloy 400 and changes of this composition; attain outstanding corrosion
resistance to hydrofluoric acid for a broad range of acid concentrations ad temperature limits. The corrosion
resistance of Monel alloy is nominally influenced through acid content, temperature or speed as compare to
presence of oxygen in contact with the solution. The presence of air or oxygen in aqueous solutions of acid increases
corrosion rate as shown in the following table:
Alloy
Monel alloy 400
Nickel-Copper
alloy M35
Ni-Cu cast alloy
505
Ni-Cu cast alloy
506
Monel alloy 400
Nickel-Copper
alloy M35
Ni-Cu cast alloy
505
Ni-Cu cast alloy
506
Corrosion rate, mills per year
Saturated with air
86oF or 30oC
176oF or 80oC
25% HF acid
37
11
19
19
Cleaned with nitrogen N2
86oF or 30oC
176oF or 80oC
0.2
0.6
2.4
1.3
21
0.2
0.2
19
22
0.4
0.4
50% HF acid
8
6
39
37
<0.1
0.5
0.5
2
46
0.4
44
0.2
In the nitrogen condition tests, these alloys produced a protective fluoride layer of brown color rather than a loose,
non-consistent layer as that was produced in the aerated analyses.
The influence of oxygen has been evaluated for both liquid and vapor phase corrosion of Monel alloy 400 as shown
in the following table:
Cleansing gas,
nitrogen and
oxygen
Ppm O2
Less than 5
Less than 500
1500
2500
3500
4700
10,000
Ppm O2
Less than 5
Less than 500
1500
2500
3500
4700
10,000
Monel 400
Liquid
vapor
Cu-Ni alloy 70/30
Liquid
vapor
Boiling 38 % Hydrofluoric acid 234oF or 112oC
9.5
6.8
3.5
17
12
2.6
31
49
12
29
18
13
34
54
18
53
107
30
45
25
20
Boiling 48% Hydrofluoric acid 226oF or 108oC
11
3
3
22
4
7
28
24
7
27
9
13
34
29
19
43
83
22
48
75
29
Cu-Ni alloy 90/10
Liquid
vapor
3.2
2.9
43
48
54
144
80
2.4
2.9
11
13
17
53
18
2
3
53
42
61
170
83
1
12
30
42
60
91
132
2
7
11
17
29
36
1
40
54
65
118
156
These analyses show that a nominal boost in corrosion rate outcomes about 500 ppm oxygen in the cleansing gas
and a considerable improvement may take place with above 1500 ppm oxygen. Similar analyses were performed in
boiling 40% hydrofluoric acid as shown in following table, for successful application of Monel 400 with this acid
content, the oxygen in the layering gas should be kept at low levels, of the order of lower than 0.1 %.
Influence of oxygen on Monel 400 corrosion rate
Lab test for 1000 hours in 40% HF boiling 266oF or 130oC
Volume % oxygen in H2
cleansing gas
0
0.1
1
Air cover ( absence of H2 gas)
Corrosion rate, mpy
Liquid
11
21
75
22
Vapor
1
2
12
1000
Employing a cleansing gas comprising of 1% oxygen in nitrogen examined the influence of acid content on the
corrosion nature of Monel 400 at temperature about 140oF or 60oC in liquid, interface and vapor phase exposures.
These analyses show that for liquid exposure the acid content had nominal influence on the corrosion rate and that
boundary and vapor phase exposures were more prone to corrosion with a highest corrosion rate for 40% acid
content.
A 30 day test was conducted on alloy 400 in 5 and 48% HF acid solutions at 150oF or 66oC, completely and partially
submerged. The small corrosion rates with uniform corrosion overcome for samples that were completely plunged.
Although, in the submerged part, the surfaces were subjected to the aerated vapors attacked at significantly larger
rates and in a non-uniform way.
The outcomes of the various lab analyses of Monel 400 in hydrofluoric acid solutions are described in the following
table:
Hydrofluoric Temp,
acid %
oF
Aeration
0.5
150
Nominal
Agitaiton Test
time,
days
14
150
Nominal
14
8.7
10
136
60
None
None
None
None
0.67
30
10
25
30
30
35
35
35
40 to 60
45
48
48
48
50
60
70
176
70
70
230
248
248
70
275
70
150
240
70
70
Nominal
Saturated
Nominal
None
Nominal
None
Saturated
Nominal
Some
None
-
None
None
None
None
None
None
None
None
None
None
-
2
4
2
6
2
33
13
8
4
2
Re test
environment
Nickel 200
Monel 400
Some air upon
liquid
Some air upon
liquid
-
30
13
26
20
Lower than
0.1
Open to air
Open to air
18
Air upon liquid
110
Nitrogen cleaning Air cleaning
In storage tank
Exposed to air
9
Air upon liquid
74
In closed bomb
9
-
8
Lower than 0.1
9
33
8
4
47
1
294
3
3
Lower than 0.1
17
1
5
15
70
70
70
90
90
90
93
98
98
98
98
99.5
100
100
100
100
100
100
70
122
240
40
70
70
70
70
130
240
93 to
110
50
50
70
70
122
100
300
None
None
None
None
None
None
None
None
None
None
Nominal
None
None
None
None
Nominal
None
None
None
None
None
None
8
4
8
0.2
1
1
8
8
8
8
3.6
In closed bomb
In closed bomb
In closed bomb
In closed bomb
In closed bomb
In closed bomb
In closed bomb
In closed bomb
Air in vapor
1
44
6
1
3
2.3
Lower than 0.1
4.2
18
1.3
0.8
1.5
3
2
1
2
2.5
None
None
None
slight
None
None
None
None
None
None
None
None
None
None
35
35
1
1
4
8
8
Exposed to air
In closed bomb
In closed bomb
In closed bomb
0
0
0
4.8
0.5
1
1
In these analyses that had large corrosion rate, the presence of air or oxygen was noticed.
In anhydrous acid, the influence of aeration is significantly less intense than n aqueous solution and due to
unavailability of oxygen. Monel 400 attains outstanding corrosion resistant up to temperature of 300oF or 149oC,
the maximum temperature at which it was analyzed.
Influence of weld metal composition for welding Ni-Cu alloy 400
Earlier nominal focus was on the influences that weld metals composition might cause on the corrosion nature of
welded Monel 400 structures in hydrofluoric acid conditions. The acid solutions containing small amounts of oxygen
are not specifically corrosive. In these conditions, nominal alloys composition differences would not be supposed to
show considerable variations in corrosion resistance nature and for these conditions, option of welding electrode
has not been crucial.
When oxygen cannot be fully discarded, the selection of welding materials can be essential to the corrosion nature
of the welded joints. It was noticed while the initialization of a model plant for recovery of hydrofluoric acid that
could not discard air completely.
Influence of Stress
Monel alloy 400 and enhancements of this alloy have been observed to be prone to stress corrosion cracking in the
moist aerated vapors of hydrogen fluoride and to a much smaller magnitude in aerated conditions of acid. The
transgranular and intergranular cracking are noticed. Identical cracking prone was noticed for nickel 200, Inconel
600, age hardened Duranickel alloy 301 and age hardens Inconel X750. Although in an un-aged condition, Duranickel
301 and Inconel X750 attained high resistance to stress corrosion cracking and have been used in the operations that
included impossible stress relieving of Monel 400.
Actually, stress corrosion cracking may be decreased or prevented through changing the condition of hydrofluoric
acid by preventing oxygen or through heat processing of the device to decrease stress. While internal stress can be
prevented through complete annealing, stress relief processing for 60 minutes at 1000oF to 1200oF then slight
quenching for practical processing for the produced structures of Monel alloy 400.
Brazing of Nickel-Copper Monel 400
In few cases, it may be further required to forge components of Monel 400 through brazing instead welding. The
received brazing possess smaller surface area of brazed alloy as compare to the area of the adjacent base material.
Therefore, it is essential to choose a brazing alloy that has sufficient corrosion resistance as well as it acts as cathode
to the base metal. In the corrosion analyses, a brazing alloy made of 60% silver, 25% copper, 15% zinc and alloy
made of 50% silver, 15% copper, 15.5% zinc and 18% cadmium, both attained significant corrosion resistance. when
combined to a same area of Monel 400, the alloy containing high silver content acted as cathode while the low silver
alloy acted as anode. The outstanding corrosion resistance for 72% silver-28 % copper brazing alloy in conditions of
boiling 38% and 48% hydrofluoric acid was noticed. This brazing alloy act as cathode to alloy 400 in galvanic couple
analysis.
The outcomes state that for Monel 400 apparatus to be utilized in the aqueous HF acid solutions a brazing alloy of
60% silver should be utilized to prevent the increased corrosion rate of the connected point.
Large magnitudes of hydrofluoric acid at temperatures of 235oF to 300oF may result into embrittlement of brazing
alloys. The brazed joints for these conditions raise a query and should be evaluated for the specific application
environments prior to choose a way of production.
Copper-Nickel alloys
The copper-nickel alloy grades Cu-Ni alloy 90/10 and Cu-Ni alloy 70/30 have similar corrosion resistance properties
as that of Monel 400 in unaerated HF acid. Although the corrosive effects of aeration in the vapor phase are even
more vigorous in alloys containing high magnitude of copper. It was found that interface and vapor releases were
highly attacking as compare to in immersed exposure for acid solutions containing 50% acid content. The negative
effects of oxygen on both copper alloys were apparent. For partial plunging conditions in presence of air, corrosion
can be very intense at the liquid scale. It is assumed that oxygen changes the cuprous fluoride corrosion layer to the
cupric state that changes the corrosive conditions in contact with the metal, creating a more vigorous corrosive
condition.
Copper-nickel alloys were assumed to attain high corrosion resistance in unaerated diluted HF acid solutions of all
contents up to the boiling points, but controlled resistance to aerated conditions.
Nickel 200 or Nickel alloy 200
Nickel 200 has lower resistance properties than Monel 400 to hydrofluoric acid in both aerated and unaerated
conditions. It is less attractive in corrosion analyses as compare to other alloys. The availability of oxygen or air in
diluted HF solutions causes to increase corrosion rate of Nickel 200 to a larger level than that of Monel 400 and the
significance of alloy 200is limited in oxygen deficient conditions at temperatures lower than 170oF to 180oF. In
analyses in anhydrous hydrogen fluoride, Nickel alloy 200 is resistant at temperature limits 300oF or 150oC. It offers
the highest resistance in hot gaseous HF conditions.
Nickel-Chromium Alloys
The Nickel-Chromium alloys specifically Inconel 600 is offers good resistance to aqueous solutions at ambient points
or to necessarily anhydrous hydrogen fluoride. However it is attacked at a considerable rate in warm dilute acid
conditions. An availability of ferric salts in acid improves the functionality of Inconel 600. Ni-Cr alloys are widely
resistant to gaseous hydrogen fluoride.
Chromium-Nickel and Chromium-Nickel-Molybdenum-Iron alloys
Cr-Ni-Fe alloys show controlled resistance to hydrofluoric acid conditions. These are actually resistant to dry acid and
dilute solutions at room temperature but attain corrosion at the elevated temperatures. The stainless steel offer low
resistance in warm conditions. Molybdenum based alloys offer better resistance than alloys without molybdenum
only in specific conditions. The stainless steels are prone to stress corrosion cracking in hot HF solutions. The samples
of steel 302 and stainless steel 316 got intense transgranular stress corrosion racking at machined edges. In such
conditions, the corrosion of these alloys is intense.
