Performance of Nickel alloys in hot gaseous fluorine

Nickel alloy 200 and Monel 400 have achieved wide attention for applications that include operation in hot fluorine
gas due to the production of intense nickel fluorides on their surfaces. The vapor pressure of this fluoride as an
action of temperature shows that the fluoride layer might provide significant security up to high temperature limits.
It is found that ignition temperature of nickel available in fluorine is about 2075oF or 1135oC. The experiments were
conducted with nickel in fluorine at temperature limits of 570oF to 1110oF or 300oC to 600oC shown that at 570oF
an 750oF a logarithmic reaction rate low was followed, however at the elevated temperatures, parabolic reaction
rate occurs. The corrosion rates depending on short term exposures for a unit time may be quite larger than the
rates of long time tests, particularly at temperatures above 750oF or 400oC.
The mechanism of nickel-fluorine interaction at temperatures about 1110oF to 1300oF was observed , at which
temperature the parabolic rate occurs. Following radioactive marker tests, it was found that fluorine instead nickel,
shifts through the fluoride scale while reaction period. Fluorine moves to the nickel surface through wide motion by
pores or cracks in the fluoride scale or through some transit procedure through the most of the scale. It was due to a
method included fluorine transit through the scale is more feasible in this temperature limit.
Obtaining quantitative corrosion information in warm fluorine gas has, unluckily, often limited to the small test times
that are likely to result in abruptly high rates for conditions where a parabolic reaction rate occurs. The data made
from three analyses are shown in the following tables:
Corrosion of Nickel based alloys in fluorine conditions (test time 4 to 15 hours)
Temperatur
e
Alloys

Nickel 200
Monel 400

oF

392

482

572

662

752

842

93
2
50
0

111
2
600

120
2
650

129
2
700

o 200
250
C
Corrosion rate, mpy
-

300

350

400

450

8
6

23
18

60
24

350
720

190
960

200
0
-

156
0
-

410
180
0
600
0
-

Inconel 600

455

1150

Stainless steel
347
Stainless steel
309Cb
Stainless steel
310
Sheet steel

Nomina
l
Nomina
l
Nomina
l
Nomina
l
24

1740

255
0
900

6200

9500

74
0
-

5500

8000

370

4250

6750

--

48

2.4

144

3600

180

6500

6500

18,00
0

Nomina
l
Nomina
l
192

SAE 1030 sheet

96
108 Nomin
steek
al
SAE 1020 sheet
455
5750
800 1770
steel
0
Corrosion of Nickel alloys in 99.5% Pure fluorine
Temperature oF
oC
Alloy
Nickel 200

1020
550

1200
650

1380
750

4.4

Monel 400

59
314
41

3
816
2900
3500

Inconel 600

3200
4800

7100
6000

24,000
25,600
33,500

Corrosion of Nickel based alloys in gaseous fluorine

Alloy
Monel 400

Nickel 200

Stainless
steel
304/304L
Stainless
steel 347
Illium R
Inconel 600

Temperature oF
Time, hours oC
5
24
24
120
5
24
24
120
5
4
120
5

80
27
2.4
0.5
0.2
1
0.9
0
1.7
0.6
0
2.7

400
204
0.5
0.5
0.7
0.1
3.3
0.5
0.3
0.1
6.1
7.5
25.4
4

700
370
1.9
1.7
2.4
1.2
1.7
1.2
0.5
0.4
1565
6018
4248

1000
538
29.8
11.3
21.3
7.2
24.5
16.1
44.5
13.8
-

5
5

1.5
1.1

6
0.6

12.7
78

4038
3451

Fluorine used in these analyses comprised of nominal magnitude of oxygen and it is feasible that the received
outcomes are more than would show for fluorine without oxygen. The corrosion rates were depending on
calculation on weight gain and film thickness. The alloys describing large corrosion rates in the elevated
temperatures had lost their weights, showing that the corrosion layers were not secure.
Nickel 200 and Monel alloy 400 produce dense, symmetrical fluoride layers, and have considerable resistance to
minimum temperature 1000oF or 540oC. The reaction rates were observed at the both at low and elevated
temperatures. High pressure of fluorine gas increased the corrosion rate of Nickel 200 and Monel 400 at 1000oF or
540oC however not at 700oF or 370oC or smaller temperatures.
While the outcomes of these three analyses do not essentially offer same corrosion rates , they do not show the
acceptable corrosion rate of Nickel 200 and Monel 400 at temperatures about 950oF to 1000oF or 510oC to 540oC.
The Inconel alloy 600, Illum R and nickel stainless steels seem to be limited to lower temperatures.
In connection with the fluorination of uranium tetrafluoride to the hexafluoride, alloy 400 has become a significant
alloy for operations at temperatures about 800oF to 1000oF or 430oC to 540oC.
Corrosion of Nickel alloys in hot gaseous hydrogen fluoride
The use of fluorine was extended in some analyses for the effects of anhydrous hydrogen fluoride and a hydrogen
fluoride steam mixture at the high temperatures. The outcomes for nickel based alloys are described in the following
tables:
Temperature
oF
Alloy
oC
Nickel 200
Monel 400
Inconel 600
Stainless steel 304

932
500
36
48
60
-

1022
550
48
-

1112
600
36
72
60
530

Stainless steel 347

Stainless steel 309 Cb
Stainless steel 310
SAE 1020 steel

7200
230
480
610

18,000
1680
4000
580

7000
6600
12000
300

Corrosion of Nickel alloys in Hydrogen fluoride- steam mixture at high temperatures

Temperature oF
Alloys
oC
Nickel 200
Monel 400

1022
550
31
-

1112
600
72
24

1202
650
108
60

1292
700
144
156

1382
750
120
204

Nickel 200, Monel 400 and Inconel 600 offer significant corrosion resistance in the hot hydrogen fluoride at
temperatures of 1110oF or 600oC however nickel stainless steels do not offer acceptable operations at temperature
of 930oF or 500oC, the minimum temperature for which tests were performed. The combination of hydrogen
fluoride and steam did not badly affect the corrosion nature of Nickel 200 and Monel 400.
Similar to hot fluorine, the tests for short intervals are performed in gaseous hydrogen fluoride to receive corrosion
rates due to the parabolic reaction rates. The following table shows significantly smaller corrosion rates for Nickel
based alloys and excellent conduct of Hastelloy alloy C and Inconel 600.
Corrosion analyses in HF gas
At temperature 930 to 1110oF or 500oC to 600oC for 36 hours, 7lb HF per hour at 4 psi was moved through a lab
furnace for hydrofluorination of metal oxides.
Alloy
Hastelloy C
Inconel 600
Hastelloy B
Nickel 200
Nickel 201
Monel 400
Monel K500
Copper-Nickel alloy 70/30

Corrosion rate, mpy

0.3
0.7
2
9
14
13
16
16

Remarks
Iridescent tarnish layer
Iridescent tarnish layer
Black layer
Black layer
Black layer
Reliable dark layer
Reliable dark layer
Reliable dark layer

Inconel alloy 600 is used widely in hydrofluorination of uranium dioxide with hydrogen fluoride at temperatures
above 600oF or 316oC. Inconel alloy 600 prevents the damaging effects of sulfur compounds at temperatures from
1000oF to 1200oF and it is the recommended alloy in the presence of such conditions.
Hydrofluoric acid Production
HF acid is traditionally made through the reaction of concentrated sulfuric acid with fluorspar, comprising 98%
calcium fluoride. The generator may be a rotary kiln or U shaped covered trough equipped with a screw conveyor.
The HF gas with unwanted but preventable pollutants like silicon tetrafluoride and sulfur compounds are condensed
for refining and purification. The granular calcium sulfate comes out from the exit side of kiln.
Carbon steel is a useful material for rotary kiln production, using replaceable steel linings for the intense corrosive
regions. Hastelloy alloy C has been widely used as a welded in place strip lining for the feed end of rotary kiln
generators and carpenter stainless steel 20 Cb I used for lining of exit from where calcium sulfate is discarded
through screw conveyor. The steel rails may be used inside the generator, tumbling as the kiln moves to retain the

reacting mass from agglomerating. This mechanical action while advantageous to the procedure, can result in
mechanical deterioration of the alloy lining.
A procedure for producing anhydrous hydrofluoric acid uses a specific premixer that creates complete combination
of reactants and speeds up their reaction in the furnace. The wet components of premixer have been made from
35% nickel, 15% chromium and 4.5% molybdenum.
The warm gases exiting the furnace, comprising of HF gas , combined with sulfuric acid and silicon tetrafluoride are
extremely corrosive. In past years, cast piping of Illium 98 has given economical solution in many plants. While
cleaning the furnace gases to eradicate the entrained solids and sulfuric acid, mixtures of sulfuric acid, hydrofluoric
acid and water occurred. In a plant that included sulfuric acid as the prime element and temperatures about 200oF
or 93oC, Carpenter stainless steel 20Cb has given suitable performance regardless without considerable metal loss.
Following the cleaning process, gases are condensed in order to crude dry HF acid in carbon steel condensers. The
remaining hydrogen fluoride in gases leaving the condensers is absorbed in concentrated sulfuric acid. At ambient
operation temperatures, carbon steel attains medium corrosion rate and carpenter stainless steel 20Cb3 and
stainless steel 316 offer good resistance and recommended for manufacturing absorber.
The crude dry hydrofluoric acid from first condensation is double distilled to provide very pure product. In initial
distillation the low boiling impurities, sulfur dioxide and silicon tetrafluoride, move overhead and are retracked to
the earlier steams for revival. Carbon steel is used to make this column and reboiler.
In the subsequent distillation unit, HF moves overhead with bottoms comprising of a ternary mixture of hydrogen
fluoride as the main element, sulfuric acid and water. The carbon steel acts good for the above portion of this unit,
Monel 400 is valuable for the lower part and reboiler. The pure dry hydrogen fluoride is condensed and stored in
carbon steel apparatus.
In a plant, 70% diluted hydrofluoric acid is made by combining controlled magnitudes of dry acid and water in
mother liquor containing 70% acid content. As the reaction is exothermic, quenching is essential and Monel 400 heat
exchangers are used for this portion of the process apparatus.
Production and Dealing Fluorine
From several years, fluorine has been manufactured on the small level as per the requirement and utilized quickly
due to the difficulty of its storage in pure form. In the mid of 19th century, the need for storage and transportation of
gas in huge magnitudes emerged, it was discovered that gas fluorine can be securely handled in cylinders of welded
Nickel 200 or Monel 400 at high pressures about 400 psi. It is feasible a fluorine reacts actively only with these
metals, quickly producing a thin and reliable layer of fluoride that secures the base metal from the further corrosion.
This layer also produces on iron, aluminum, brass, magnesium and copper, therefore these metals are chosen for
suitable dealing fluorine at room temperature.
A prime fluorine producer recommends the following process as a surface pretreatment for fluorine operation:
The corrosion resistance of all metals and alloys of operation utilized with fluorine based on the production of a
security fluoride layer. Hence prior to any apparatus lines or fittings are used in operation these should be
completely cleaned of all unwanted materials, flushed through a non-aqueous degreasing and preliminary drying
solvent like acetone, trichloroethylene or carbon tetrachloride, completely cleaned with dry nitrogen steam and
corroded. The corrosion process includes slight substitution of dry nitrogen in the system through fluorine bleeding .
The substitution process is continued a long as a filter paper piece or cotton swatch kept close to the exit through a
long metal forceps starts to burn. The apparatus is then valved off and the fluorine operation pressure is applied.
Within five to ten minutes, passivation completes. Fluorine is then vented and the system is locked.

It is also possible to achieve passivation through using chlorine trifluoride in a way specified above by using fluorine,
with extra step of purging and displacing the chlorine trifluoride with arid nitrogen before locking the system.
Electrolytic cells and electrodes
Gaseous fluorine is widely made by electrolysis of anhydrous hydrogen fluoride from molten bath of KF> 2HF. Broad
data on materials of construction of fluorine cells have been stated. Tests have shown that affordable and lasting
electrolytic cells for fluorine production at moderate temperatures of 212 to 300oF or 100 to 150oC may be made
with carbon anodes and a Monel 400 container possessing a steel water jacket. The benefits of Nickel 200 an alloy
400 containers become widely pronounced in high temperatures cells at 480oF to 570oF or 250oC to 300oC.
Anode, as the place where the fluorine is accumulated, is possibly the most fertile cell difficulty. Nickel 200 anodes in
cells performed at intermediate temperatures have benefit of discarding polarization complexities to which carbon
anodes are occasionally sensitive. These can function adequately in broader temperature rages and hydrogen
fluoride contents as compare to carbon anodes and being more jagged, are suitable to prevent the rare nominal
blats that may occur in the fluorine production cell. Second essential factor is that Nickel 200 anodes are not badly
affected by the availability of water in electrolyte.
Nickel alloy 200 exhibit smaller current efficiency as compare to carbon, specifically at lower temperatures and after
attack creates a sludge that may cause electrolyte fouling. Copper, iron, silver, magnesium and Monel 400 anodes
have been assessed but these were found to provide less suitable performance as compare to Nickel 200 at
temperatures lower than 300oF.
Carbon anodes are commonly utilized, these also have drawbacks in that these need dry electrolyte and are found to
be contaminated due to carbon fluorides that may result into swelling due to the production of an interstitial
compound of carbon monofluoride. The cracking rate can be large in the rugged condition of fluorine cell, however
this problem can be solved by some limit through copper impregnation. High potential, power efficiency and
electrolyte economy are the factors on which decision of using carbon anode depends in the several fluorine
manufacturing units.
As Nickel 200 anodes perform good in wet electrolytes it is usual to combine some of them in cells to prevent water
through basic electrolysis. The cathodes are usually made of steel where hydrogen is released, in few cases the cell
wall is utilized as an alternative. In few countries, silver cathodes and magnesium cell walls are utilized. Monel 400
screen diaphragms, gas welded at the joints and silver soldered into place, have provided excellent performance in
separating the anode and cathode cell portions like screens and skirts have been broadly followed. The electrolyte
container and other cell hardware has been made of Monel 400 with excellent result. In a significantly secured and
efficient 600-ampere cell functioned at 530oF or 275oC, serious problems due to sludge deposits in the electrolyte
were removed by using Monel alloy 400 for all metal parts subjected to the hot melt.
Pumps, Cylinders and Tubing
Fluorine gas is quickly liquefied through diaphragm pumps directly linked to the cells. A test pump made of Monel
400 diaphragms and heads was observed to be in outstanding condition after functioning for 500 hours. Following
the potential of these positive outcomes, another two pumps six times larger than earlier size were configured. Rare
replacement or maintenance of diaphragms was required in period of 18 months of service.
The liquid fluorine can be stored in clean dry copper or steel cylinders. For the highest protection it is preferred by
some manufacturers that cylinders should be produced of Monel 400 or Nickel 200 since it is tough to ignite these
metals in the normal environments. One test states that Nickel 200 cylinders comprising of fluorine at pressures
about 20 atmospheres were not attacked after 365 days of service.
Valves

The repair of tight valves shows the major difficulties in correspondence of dealing fluorine. When valve is used
there is an clear capacity towards the eradication of security layers through abrasion with resultant leakage
throughout the seat and the surrounding stuffing box. Nickel 200 and Monel 400 are recommended for valve stems
and seats due to production of fluoride layer on them is thin, secure and reliable. Teflon is commonly used for
packing in low pressure service and as a seat similar to Monel 400 or Nickel 200 parts.
At the high pressures, diaphragms and below-sealed valves and needle valves of Monel 400 packed with Teflon or its
similar to be utilized. Non-metallic seats or discs are not used for high pressure operation.
As a security precaution when application with pure fluorine at the high pressures the valves should be made with
extension handles moving through concrete shields.
Fluorine Removal
The excellent property of fluorine services often leaves significant magnitudes of gas not fully utilized in the process
as well as unhealthy removal problem for the large magnitude of gas. For these common reasons, this gas cannot be
disposed to the atmosphere. Huge fluorine magnitude should be removed completely through a chemical reaction.
The popular reaction with water recommends itself quickly as the simplest option to change fluorine into
comparatively nontoxic compounds and the reaction has been examined by many specialists as a removal method.
Fluorine combines with water in two manners, under conditions that are similar. It burns under water releasing a
purple flame. In other case, it combines with water softly and slightly without releasing any flame. Then it moves to
the flame reaction, creating a strong blast. Therefore the water reaction is not followed. The reaction of fluorine
with normal low temperature steam has also been found to be unmanageable and it causes strong blasts.
The fluorine removal problem can be suitably resolved through allowing preheated fluorine to combine with superheated steam. In this way, it is transformed to hydrogen fluoride without causing any blasts. This reaction at high
temperature creates a large amount of heat, in the region of fluorine and steam combination nozzle.