Materials For Hydrofluoric Acid Service in The New Millennium (51300-01345-Sg)

Paper No.
01345
CORROSION 2001
MATERIALS FOR HYDROFLUORIC ACID SERVICE

IN THE NEW MILLENNIUM
Herbert S. Jennings
DuPont Fluoroproducts
Materials Engineering
Senior Engineering Associate
PO Box 347
LaPorte, TX77572-0347
ABSTRACT
In the new millennium there will be demands for fluoropolymer and flourochemical
processes to provide higher throughput and higher purity products. Meanwhile materials of
construction for anhydrous hydrogen fluoride (AHF) and hydrofluoric acid (HF) will be pushed
to higher temperatures, pressures and exposed to new and higher concentration impurities.
This is a review of corrosion data and degradation information for metal alloys and nonmetals
exposed to environments of AHF and HF with other acids, and impurities.
INTRODUCTION
Both AHF and HF are very useful industrial chemicals. Uses include cleaning metal,
stone and bricks; etching glass and silicon microchips; acid treating oil wells; dissolving ores,
refining of uranium, tantalum, beryllium and other specialty metals; recovering spent nuclear
fuel; producing sodium fluoride, fluoborates, fluosilicates, and fluorosulfuric acid; and aluminum
fluoride and synthetic cryolite for aluminum production. AHF is used as a catalyst for
alkylation, disproportionation, isomerization, transalkylation, condensation, polymerization, and
dehydration reactions. AHF is used in the manufacture or fluorine, perfluoro acids and their
derivatives. AHF is reacted with organic materials for the manufacture of fluorinated
hydrocarbons used as refrigerants, blowing agents, aerosol propellants, cleaning agents,
Copyright
2001 by NACE International. Requests for permission to publish this manuscript in any form, in part or in whole must be in writing to NACE
International, Publications Division, 1440 South Creek Drive, Houston, Texas 77084-4906. The material presented and the views expressed in this paper are
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solvents, lubricants, paints and fire extinguishing agents. Certain fluorochemicals are used to
produce fluoromonomers, which are used in the manufacture of fluorosurfactants,
fluoropolymers, perfluorinated copolymer membranes, fluoroelastomers and
perfluoroelastomers.
Anhydrous hydrogen fluoride (defined as <400-PPM water by Hydrogen Fluoride

Industry Practices Institute (HFIPI)) is a clear, colorless, corrosive liquid with a sharp,
penetrating odor, with an atmospheric boiling point of 19.5C (67.1F). Aqueous HF is
commercially available in bulk shipments at 49 and 70% concentrations, while smaller
quantities may be available in other concentrations. HF will give a constant boiling mixture
(azeotrope) at 37.7 weight % and 111.4C (232F).
Anhydrous hydrogen fluoride and HF are extremely hazardous as liquid or vapors.

They cause severe burns to skin and eyes, and damage to lungs that may not be immediately
painful or visible. Overexposure causes painful, deep-seated and slow healing burns and
ulcers. They may be absorbed through the skin in toxic amounts and if untreated may cause
death.
NACE publication 5A-171 "Materials for Receiving, Handling, and Storing Hydrofluoric
Acid" 1 presents good, practical, general information on materials that are commonly used for
AHF and HF up to 49C (120F). Corrosion information for a number of alloys used in HF is
presented in Figure 11. The Hydrogen Fluoride Industry Practices Institute (HFIPI) has
guidelines for materials of construction for handling AHF 2 and HE 3, as well as guidelines for
personal protective equipment, bulk storage, tank truck and car unloading, and
inspection/evaluation of storage and transportation vessels. Each user of these should consult
and follow their current government regulations and requirements.
Throughout the text when first mentioned the alloy common name is given followed by
the UNS Number. Thereafter only the UNS number will be used. For reference Table A1 is
attached listing referenced alloys' common name and UNS Number. Also throughout the text
AHF will be used to mean anhydrous hydrogen fluoride, while I-IF will mean aqueous
hydrofluoric acid.
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C oF
120 - 248
- 212
176
140
104
68
32
10 20 30 40 50 60 "tO 80 90 100
Wt. % Hydrofluoric Acid in Water
FIGURE 1: Metals and Alloys for Hydrofluoric Acid 1

Isocorrosion Regions Where Observed Corrosion Rates Are 0.5 mm/y (20 mpy) or less
A - - N02200, N06030, N06600, N06985, N08007, N08020, N08825
B - N06022, N06059, N06200, N06686, N10276, N10665, N10675, N26022, N26455, N30007, N30107
C - - Carbon steel* (* May suffer Hydrogen Assisted Stress Corrosion Cracking), (limit 70% HF velocity to 0.6
m/s (2 fps))
D - C70600, C71500, N04400, N24135, P00020, P04995, P07015, R03600
Refer to text on nickel-rich and nickel-based alloys for information on stress corrosion cracking (SCC). This
information is for guidance only. It represents low-flow, oxygen-free, uncontaminated conditions. Velocity or
impurities may make these selections unsuitable.
This figure has idealized corrosion data in that the data is from many different laboratory
immersion tests on annealed, wrought metals, with reagent grade HF, based on hours to days
of exposure at constant temperature, under static conditions. Therefore, use this data for
guidance on the types of suitable alloys for additional testing. It does not include all alloys or
materials that may have corrosion resistance in one group of conditions. It is impractical to
note all the issues that can influence corrosion due to the multitude of variables that influence
corrosion. These variables could include impurities like oxygen, localized corrosion at the
liquid vapor interface, vapor phase condensation, weld metal compositions, different welding
processes, transient conditions that may result from feed stock impurities or differences in day
to day operations in a commercial facility. It is known that some impurities in HF can increase
corrosion or cause cracking of alloys. Velocity and temperature can have a dramatic affect on
corrosion rates. There is much to be discovered and documented regarding corrosion or
degradation in AHF and HF.
When new processes are planned it is important to use the general information in
Figure 1 or corrosion data from materials manufacturers to select candidate materials for
laboratory tests. Then, based on these tests, construct pilot facilities in which the equipment
is fabricated from the candidate materials, weld metals and weld processes, and operated with
intended feed stocks at conditions and recycle streams planned for the commercial facilities.
Preferably the pilot facility would be operated for many months to allow time to discover
materials failures when business conditions are less urgent. After pilot operations at least the
critical equipment should be inspected, measured, and examined metallurgically. Longer tests
give a better indication of service performance. When new processes are designed, many
experts should be consulted to gather experiences, and equipment designs should include
conservative corrosion allowances and safety factors. Equipment exposed to HF and AHF
need periodic in-service inspections and corrosion monitoring to track corrosion, detect
problems and avoid unexpected failures.
The new millennium will see new materials of construction, new demanding processes,
increasing demand for higher purity products, including those to make faster, smaller and
denser microelectronics, and for biotechnology. There will be challenges and opportunities to
meet higher safety standards, minimize waste generation, recycle waste streams and comply
with environmental requirements. Competitive demands will require increasingly higher
reliability as well as longer intervals between maintenance. Materials of construction will be
required to resist AHF and HF at higher temperatures when mixed with other acids or
impurities. Supercritical processes will be more commonly used to treat fluoride waste
streams. Higher temperature thermal incinerators will be handling fluoride wastes. These
demands will require creative application and blend of multiple disciplinary materials
technology.
The seeds of future materials developments in this millennium are embedded in the
materials successes and failures of today. This article will give a review of established, as
well as recent corrosion data in pure AHF and HF, and their mixtures with other acids and
impurities.
METALLIC MATERIALS
Carbon and Alloy Steels
Carbon and low alloy steels are used extensively for processing, storage and
transportation of AHF. Carbon steels are used in only a limited range of HF concentrations.
However, experience has shown that carbon steels are susceptible to corrosion, blistering and
cracking in AHF and HF. Care must be taken to specify steels properly for their appropriate
applications. Several steel manufacturers produce steels per ASME/ASTM Standards with low
sulfur, low oxide content and treatments (such as A516 (UNS K02700)) which have better
resistant to hydrogen induced cracking (HIC) and blistering. These steels are typically
specified to lower strength or require post weld heat treatments to avoid weld heat affected
zone (HAZ) cracking. Common practice is to order normalized pressure vessel steels for HF
and AHF service to assure good fracture toughness.
Steel Corrosion
Carbon steels corrode rapidly when initially exposed to AHF and HF but the corrosion
rates diminish with time due to the formation of an adherent layer of corrosion products.
HF. Carbon steels are useful in HF services over 70% HF when limited to 32C (90F)
and 0.62 m/s (2 fps). Commercial 70% HF storage tanks, tank trucks and railcars are lined
with fluoropolymers or chlorobutyl rubber to minimize product iron contamination. Carbon steel
corrosion data in HF are presented in Figure 21.
.; "1OO i
,o
o 1o 2o ~ 4b so so 7o IIo 4o ~oo
Wt.% Hydrofluoric Acid in Water
FIGURE 2: HF Corrosion Data for Carbon Steel at 21 to 38C (70 to 100F) 1

This information is for guidance only. It represents corrosion rates on carbon steel at the indicated
Temperature range in hydrofluoric acid that is free of contamination and at low- or no-flow conditions.
Rates shown for 70 to 100% represent laboratory data and service experiences.
The data in Figure 2 are from laboratory and service experiences at temperatures from
21 to 38C (70 to 100F). Steel corrosion rates in HF are lower at lower temperatures.
Degnan 4 reported that HF total acidity was increased with fluorosilicic and sulfuric acids, which
may explain reported low corrosion rates for steels in less than 70% HF. High velocity,
temperature, aeration, or impurities increase steels' corrosion rates.
AI-IF. For liquid AHF carbon steels are commonly used from ambient temperature up to
about 66C (150F) with velocity limited to 1.8 m/s (6 fps). Velocity limits are based on service
experience. Figure 35 presents corrosion rates of carbon steel exposed to liquid and vapor AHF
at various temperatures. These data were generated in stagnant 100-hour (average) tests.
Carbon steel is normally used for AHF railcars, storage tanks and piping at ambient
temperatures. Carbon steels used for AHF product storage for over 38 years, at ambient
conditions of 0 to 40C (32 to 104F), have less than 0.013 mrn/y (0.5 mpy) corrosion rates.
Vapors of AHF are less corrosive and can be handled in carbon steel up to 200C (392F) with a
velocity limit of 10 m/s (33 fps).
Carbon steel is subject to erosion-corrosion in liquid AHF with velocity, turbulence, or

impingement due to the disruption or removal of the protective iron-fluoride film. Steel vessels
and piping can be passivated by exposure to AHF in stagnant vapor or liquid for about 24 hours
prior to velocity exposure.
CORROSION OF CARBON STEEL IN ANHYDROUS HYDROGEN
FLUORIDE
1000
uJ - 100
I-,,,
J
n,,,,
z
0
~ 10
60 100 150 t 88 200 300 400 500

TEMPERATURE, gC
Figure 3: Corrosion of carbon steel in AHF liquid and vapor over a range of
temperatures s.
Galvanic Effects. Blanchard 6 and Mack reported galvanically accelerated corrosion

rates on carbon steels welded to higher alloys, exposed to 70% HF, at 52C (125F) and no
flow. Compared to 70% HF, corrosion rates at 82% and 100% HF (same conditions)
decreased significantly.
Trace Elements. Alloy elements in carbon steels can produce a loose, porous, non-
protective corrosion product layer and cause increased corrosion in HF or AHF. Dilute HF
(1.7N) is more corrosive to steels with 1.35 to 17% chromium than to carbon steel. 7
Hashim 8 and Valerioti presented case studies from alkylation services in which selective
carbon steel piping or fittings had high corrosion. Pipe and fittings with copper, nickel and
chromium over 0.2% (alone or in total) had higher corrosion. Higher temperature and velocity
conditions seemed to accelerate corrosion on these components. They concluded that these
residual elements were detrimental to corrosion resistance of carbon steels in HF because
they disrupted or destabilized the iron fluoride corrosion film.
A fluorochemical plant had corrosion of about 25.4 mm/y (1000 mpy) on pipe, while
carbon steel fittings on either side had only 0.89 to 1.27 mm/y (35 to 50 mpy). The conditions
were about 10% AHF and 90% organic at 80C (176F). Investigation found the pipe a was low
temperature alloy steel per ASTM A333, grade 9 (UNS K22035) with copper (0.81%) and
nickel (1.86%). The fittings had no copper, nickel or chromium. Table 1 data is from in-plant
and lab AHF corrosion studies of steels with varied alloy compositions 5.
TABLE 1
Carbon and Alloy Steels Exposed to AHF Liquid, 40-90C
Corrosion Rates: MM/Y (MPY)
" TM 2 WK LAB 1.3 Y, PLANT 1.3 Y, PLANT 6 MO PLANT

DESIGNATION TEST: TEST: 100% TEST: 100% TEST: 10%AHF,
CU;NI;CR [SUM], AHF, 90C AHF,75-80C AHF, 40-45C 1.4%CL2
WT. % ORGANIC, 90C
A516 GRADE 55 1.19 0.55 0.12 0.84
0.03; 0 . 0 2 ; ~ (33.O)
A516 GRADE 55 1.88 0.89
0.09; 0 . 0 7 ; ~
A106 GRADE B 2.79 0.77 0.11 1.22
0.28; 0.11; 0.1010.49] (48.0)
A588 GRADE A >0.94 " 0.14 1.63
0.35; 0.61; 0.20 [1.16] (64.0)
A203 GRADE E 4.09 >1.14" 0.17 1.40
--; 3.47; --- [3.47]
A710 GRADE A 5.54 >1.27 * 0.19 1.02
1.05; 0 . 7 7 ~
* Coupon missing, this corrosion rate is estimated.
This study indicates that steels with copper, nickel, and chromium are susceptible to
higher corrosion in AHF and that rates increase with increasing temperature. There is also
increased corrosion with increased proportion of AHF versus organics in the process. From in-
plant observations areas of turbulence had higher corrosion rates.
There are reports that HF alkylation piping around depropanizers may have weld
corrosion in the form of '~Normholes" in the root pass due to variations in weld composition or
quality9. Two types of localized corrosion experiences have been reported from HF alkylation
units: those with high or very low residual elements. High residual element steels have high
corrosion rates in hot vaporizing HF such as the depropanizer feedline and overhead, hot
zones of the isostripper and regenerator overhead. Low residual element steels have high
corrosion when galvanically coupled to high residual element components in condensing or
free acid settlement areas such as the isostripper overhead, HF stripper and alumina/KOH
treaters 1. There are various reports 11' 12 and investigations of erratic corrosion performance of
carbon steels in HF alkylation services where HF ranges from 60 to 100% from 25C (77F) to
90C (194F). Dramatic galvanic corrosion effects have been shown between steels with high
and low residual elements 11. An additional influence may be the level of carbon, the carbide
form and the carbide distribution in the steel 12.
Steel Blistering
Carbon steels with higher oxide and sulfide content will develop hydrogen blisters when in
AHF and HF service. Blistering is a combined effect of dirty steel and hydrogen generated by
corrosion. Atomic hydrogen liberated by corrosion often combines with another hydrogen atom
to produce molecular hydrogen. Eventually hydrogen pressure may build in closed AHF
equipment or cylinders. Sulfides or arsenic, which are common AHF impurities, act as "poisons"
to inhibit the combination of atomic hydrogen and thus atomic hydrogen diffuses in to the steel 4.
Atomic hydrogen may diffuse completely through the steel, combine with elements in the steel,
accumulate and recombine to molecular hydrogen at voids or laminations, and collect at oxide
and sulfide inclusions. Over time molecular hydrogen accumulates at laminations or inclusions
in the steel and builds internal pressure to the point that deformation occurs. Semi-killed steels
are susceptible to hydrogen blistering in both HF13 and AHF TM. Previously silicon fully killed
steels were more resistant to blistering than aluminum killed steels. But now aluminum fully
killed steels, with low sulfur and oxide levels have very good resistance to blistering, and when
produced by fine grain practice have superior low temperature toughness. Warren 15 advised
that steels for blistering environments be hot-rolled or annealed rather than cold rolled, and to
avoid rimmed, semi-killed and free-machining steels. High corrosion conditions produce more
hydrogen and will tend to quickly blister susceptible steels.
Steels produced with only low sulfur are more resistant but not completely immune to
hydrogen blistering. Seastrom 16 explained that both oxygen and sulfur are determinants for the
distribution of oxide and sulfide inclusions. Merrick 17 reviewed H2S and AHF experiences that
caused hydrogen blistering, hydrogen-induced step-wise cracking and stress-oriented hydrogen-
induced cracking. He proposed application of NACE Standard TM0284-96 to test steels for
resistance to hydrogen blistering and step-wise cracking. Cleaner steels are produced with low
sulfur (typically <0.003%) and are processed with vacuum degassing to minimize oxides. They
also include calcium for inclusion shape-control to reduce the number and cross section area of
detrimental inclusions. NACE document 5A-171 has a discussion of the specifications and
testing that may be applied to these types of steels.
Steel Cracking
Hydrogen CrackinG. Another effect of atomic hydrogen generated by HF and AHF

corrosion is cracking of carbon and alloy steels with hardness over HRc 22, or approximate
tensile strength of 793 MPa (115,000 psi) or higher. This hardness or tensile strength may be a
result of either cold-work (plastic deformation) or thermal quenching. Susceptibility for cracking
is increased by residual or applied stresses.
Carbon and low-alloy steel fasteners with hardness above 22 HRc and exposed to HF or
AHF have failed by hydrogen-assisted stress corrosion cracking. In at least one instance
several fasteners meeting ASTM A193 Grade B7 (G41400) requirements, with hardness of 30 to
35 HRC, failed upon exposure to AHF resulting in a spill and fatalities. Therefore, to avoid
cracking from HF exposure, lower strength A193 Grade B7M (G41400) with a maximum
hardness of HRc 22 are commonly specified. ASTM A307 Grade B fasteners are also used in
AHF flanged joints. However, even these lower-strength steels, if over-torqued and cold worked
from repeated yielding, may crack due to hydrogen embrittlement. Fasteners exposed to
HF/AHF from gasket leakage are subject to corrosion. Good practice is to immediately stop any
leaks and replace all exposed fasteners. Above 120C (248F) the potential for hydrogen
embrittlement is reducedlS; higher-strength steel fasteners have been successfully used above
this temperature in AHF services.
In AHF, cold worked carbon steels are susceptible to cracking as well as stress oriented
corrosion. These effects have been observed in severely cold bent pipe and rolled (van stone)
flanges 5.
Note that some steel plate specifications for pressure vessels in HF and AHF service
have tensile strength limited to 545 MPa (79,000 psi). Thick steel plates may act as a heat sink
to quench the weld or weld heat-affected-zone (HAZ) which could result in hard welds or HAZ.
Higher strength steels tend to have harder weld HAZ than the base metal or weld, and hard weld
HAZ is typically where cracking is found after exposure to HF and AHF.
Carbon and alloy steel pressure vessels in HF and AHF service have cracked at weld heat
affected zones (HAZ) and hard welds, with some cracks penetrating the vessel wall. Therefore,
steels for these services are hardness controlled by limits on alloy composition, and are often
post-weld heat-treated (PWHT) to further reduce hardness and residual tensile stresses. Certain
elements in steels tend to act like carbon when the steel is quenched, and equation 1 is
commonly accepted to calculate the carbon equivalency (CE) for steel 1.
CE = % C +
I %Mn (%Cu + %Ni) 4 (%Cr+ O/~Mo+ %V)] (1)
15
Some steels less than one inch thick (<2.54 cm) and a CE<0.42 may have acceptably
soft weld HAZ without PWHT. Typical PWHT temperature for steel in AHF or HF service is
1150F (621C). Steels with a CE>0.5 may require a PWHT temperature of 1250F (677C) 16to
obtain hardness of HRc <22. Micro-alloying elements (V, Ti, Nb and B) must be limited to
ensure softening of the HAZ during PWHT.
Some lower strength carbon steels such as ASTM A516 grade 55 or 60 (K01800 or
K02100) with a specified maximum tensile strength of 545 MPa (79,000 psi) have produced
acceptably soft weld HAZ with only welding preheat and high heat input during welding. A more
detailed discussion on steps to minimize carbon steel's susceptibility to cracking can be found in
NACE Standard RP0472.
The width of weld HAZ may be only 0.5 to 1 mm (20 to 40 mils). Microhardness testing is
the only method with the capability to measure hardness in such a narrow zone. Preparation in
place for field microhardness measurements requires local removal of the weld crown. Then
surface preparation by abrasive disk sander (successively applying paper of 100, 120 and 180
grit) to insure a flat, smooth surface that is free of scratches. The HAZ is revealed then by
etching with 10% nital (10% nitric acid and 90% methanol). Hardness surveys are made by
traversing from weld into base metal in 0.25-mm (10 mil) increments; readings are also made on
a calibration block before and after each survey. Two or more contiguous readings over 250 Hv
should be evaluated for corrective action. New vessel and field repair quality assurance plans
have required portable field microhardness readings. However, some fabrication specifications
require laboratory microhardness readings of samples for ASME Weld Procedure Qualification
Records using the thickest steel plate for the fabrication.
AHF and AsFs. Arsenic pentafluoride in AHF has been found to cause intergranular
corrosion and crackin(j of carbon steels 5. AHF service pipe, ASTM A106 Grade B (K03006), at
-15 C (-26F) cracked through wall next to a weld. Investigation found a normalized, ferrite
pearlite microstructure with intergranular corrosion and cracking near a weld, Figures 4 and 5.
The ferrite was preferentially attacked which suggested an anodic process. The steel base
metal hardness was HRb 60 and the weld HAZ HRb 76. It was concluded that this was not
hydrogen cracking due to cathodic charging. Samples of the recycled AHF near the time of
cracking had up to 0.5 Wt.% arsenic compounds (as AsF3 and AsFs) which raised suspicions
that there was a correlation between the arsenic and the intergranular corrosion and cracking of
carbon steel. There were also suspicions that water may have entered the system due to a heat
exchanger failure. Tests were made on carbon steel exposed in AHF with additions of arsenic,
chlorine and water. The test results are presented in Table 2.
Figure 4. Intergranular corrosion of carbon Figure 5. Intergranular stress corrosion

steel pipe exposed to AHF with AsF5, cracking of carbon steel pipe exposed to AHF
hardness HRb 60 (original magnification and AsFs. hardness HRb 76 (original
400x). magnification 400x).
All cracking emanated from die stamped markings or grind marks. There were no special
stress corrosion cracking coupons used in this study. Cracking only occurred when AsF5 was
present at 0.8 to 3.5%. When 19.6% AsFs was present in AHF the corrosion rates were very
high and thus cracking could not occur, however there was intergranular corrosion. Water
reduced the rate of steel corrosion, however cracking still occurred. The micrographs of cracked
test samples looked like those from the pipe. It was concluded that AsFs was the compound
responsible for the intergranular corrosior, and cracking of carbon steel. Subsequent
investigation found that small amounts of arsenic were in fluorospar (CaF2) and in the fresh AHF
(mainly as AsF3). No water sources were found in the system. When AHF and AsF3 were
processed with chlorine the AsF3 was oxidized to AsFs. Since the arsenic was not consumed in
the process, it accumulated in the recycled AHF. The AHF/AsF5 system is known to be super
acidic; that is, it contains an increased amount of H2F , relative to AHF, which is very corrosive TM.
TABLE 2
Autoclave Corrosion Tests of Carbon Steel in Anhydrous Hydrogen Fluoride with
Arsenic, 23C (73F), Compositions in Weight %, Exposure times 42 to 140 hrs 5,
COMPOSITION AVERAGE CORROSION RATE OBSERVATIONS

TESTED MM/Y (MPY) [No. of coupons]
AHF 0.125 (5) [2]
AHF, 2.3% CI2 0.229 (9) [2]
AHF, 5.1% AsF3 0.076 (3) [2]
AHF, 3.3% AsF3 0.127 (5) [6]
AHF, 19.6% AsFs 14.27 (562) [3] Slight Intergranular Corrosion
AHF, 2.8% AsFs, 1.47 (58) [2] Cracking and Intergranular
2.3% 012 Corrosion
AHF, 3.5% AsF5, 1.35 (53) [2] Intergranular Corrosion (No
3.6 % OI2, cracking)
AHF, 3.5% AsFs, 0.79 (31) [2] Cracking from Stamped Numbers,
3.6% OI2, 0.4 % H20 hardness HRb 97
AHF, 0.8% AsFs, 0.25 (10) [2] Fine cracks perpendicular to surface
4.8% CI2, 0.5 % H20 grind marks, hardness HRb 97
AUSTENITIC STAINLESS STEELS
Austenitic Stainless Steel Corrosion
HF. Aqueous HF produces very high corrosion rates on austenitic stainless steels CF-3
(J92500), CF-8 (J92600), 304 SS ($30400), and 304L SS ($30403) that are an order of
magnitude higher than rates for carbon steels at similar concentrations and temperatures. Only
austenitic stainless steels CF3-M (J92800), CF-8M (J92900), 316 SS ($31600), and 316L SS
($31603) exhibit useful resistance in <10% HF at temperatures below 23C (73F)19; however,
these alloys may pit under these conditions. Pawel recorded very high corrosion rates at 24C
(75F) for $31600 in 5% and 10%HF2.
AHF. In pure liquid AHF at ambient temperatures austenitic stainless steels $30400,
$30403, $31600, $31603, J92800, and J92900 have been used for pumps, valves, piping,
storage tanks and transportation equipment. $30400 and $31600 fasteners, produced per
ASTM A193 B8 Class 2 and B8M Class 2, have been used for external bolting for pipe and
equipment in AHF, where there were no chloridesS. Tests with liquid AHF at 100C (212F)
produced <0.127 mm/y (<5 MPY) corrosion on austenitic stainless steels $30400, $30403,
$31600, and $316035. In liquid AHF above 100C (212F) the performance of these stainless
steels are erratic in tests as well as service. However, in AHF vapors at 200C (392F) $30400
had 0.3mm/y (12 MPY) corrosion rates in stagnant 100 hr tests 5.
Austenitic Stainless Steel Cracking
Hydroqen. Alloys 301 SS ($30100), 302 SS ($30200), 303 SS ($30300) and $30400,
when cold worked, may develop alpha martensite. Cold worked stainless steels have cracked in
12% (impure) HF at 70C, as well as hot 40 to 50% HF. Degnan 19 explained the cracking
mechanism as hydrogen embrittlement of the alpha martensite which may form in the austenitic
stainless steels with less than 10% nickel. Fasteners for flanged joints in AHF services are
sometimes specified as ASTM A193 B8 Class 2 (strain hardened UNS $30300 or $30400).
Degnan 19 reported a HF plant failure of a cold worked, magnetic, $30300 fastener. Since the
magnetic permeability increases with alpha martensite, each of these fasteners may be tested
by Severin Gauge (12.5 maximum) to avoid hydrogen embrittlement from HF exposure.
HF. There are reports of HF cracking of $30400 and $31600 in severely corrosive
conditions. $30400 cracked in hot 40 to 50% HF 19. Also, cold worked $31600 fasteners had
transgranular cracking in 12% (impure) HF at 70C ~9.
AHF. $31600 tubing with severe cold work cracked in AHF at 40C (104F) s. Cracking
mixed mode, with primary cracking transgranular and secondary cracking intergranular. Since
alloy $31600 has 10 to 14% nickel it should be metallurgically stable and not develop alpha
martensite. In this case there seemed to be fluoride induced environmental cracking.
Fluoride and Chloride. Chloride stress corrosion cracking (SCC) is greatly aggravated
by the simultaneous presence of acid fluorides21. Takemoto, et al., investigated SCC from
welding electrode coating (with CaF and 3NaF=AIF3) and chlorides for sensitized $30400. In
sodium fluoride (NaF) solution sensitivity for SCC ranged from 50 to 80C (122 to176F) with 40
to 400 ppm Fluoride. The simultaneous presence of chloride and fluoride reduced the SCC
threshold to 10 to 100 PPM Fluorides. Annealed 304 SS was immune to SCC.
NaF. Cragnolino and MacDonald 22 developed a potential-pH equilibrium diagram for

sensitized $30400 in NaF solutions, Figure 6. This figure shows decreasing electrochemical
potentials for SCC with increasing fluoride concentration. With increasing pH (0 to 8) there are
decreases in the electrochemical potential for SCC (-0.25V (SCE) to about -0.75V (SCE)) and
no cracking is observed below these conditions.
> o 1.0 I
-'o O.5 ! ~ ~ -B---- _~_o~,~~ - i -
-0.5
-1.0
0 2 4 6 8
0 : S C C potential
pH
O : corrosion potential
A : maximum corrosion potential In Open circuit
I Figure 6: Influence of potential and pH on intergranular stress corrosion

cracking for sensitized $30400 in NaF solution at 66C (150F)~.
Zucchi 23, et al., conducted slow strain rate (SSR) tests on sensitized S30400 in NaF at
25 , 50 , and 80C. Figure 7 is a plot of the ratio of percent elongation in aggressive media to
that in an inert environment versus NaF concentration. At 80C a NaF level of 2 PPM was as
aggressive as 500 PPM at 25C. Thus, the level of NaF and temperature had a strong effect on
intergranular SCC susceptibility.
1.o! ,, 25C
EA ~,~ o 5OOC
Et ~ C
0.5
0.5 5 50 500
NaFConcentro~ion,ppm
Figure 7: Ratio of percent elongation from slow strain rate tests in NaF (EA)
and inert environment (E~) at 25 , 50 and 80C for sensitized $3040023.
Table 3 presents data from Z u c c h i 23 o n SSR test time to SCC failure in NaF at 25 , 50 ,
and 80C for sensitized $30400. This SSR test data indicates that time to SCC failure in NaF
decreases with increasing NaF concentration and temperature. With oxide damage from strain
the fluoride ion can readily attack sensitized grain boundaries. Under dynamic SSR test
conditions, when there is a break or disruption in the oxide layer, fluoride can be very aggressive
at chromium depleted grain boundaries.
TABLE 3 23
Slow Strain Rate Failure Time, h, Applied Load 10 kg/mm2
NaF Concentration, 25C (77F) 50C(122F) 80C(176F)

PPM
420 22 12 5.5
42 91.5 33.5 9.2
4.2 >240 . . . .
0.42 >240* >240* 198
* No Attack
From these studies on sensitized $30400 in the presence NaF, damage to the oxide layer
either by corrosive conditions or strain may result in intergranular cracking. Increased fluoride
levels and temperature increase the susceptibility for intergranular cracking.
NICKEL RICH A U S T E N I T I C STAINLESS STEELS
Nickel Rich Austenitic Stainless Steel Corrosion
HF. In HF service, nickel rich (nickel >30%) austenitic stainless steels with chromium,
molybdenum and copper, such as Alloy G-30 (N06030), G-3 (N06985), CN-7M (N08007), 20
(N08020), and 825 (N08825) have limited useful corrosion resistance. Their useful HF
concentration and temperature ranges are indicated in Figure 1. Isocorrosion diagrams, from
Crum 24, for N08825 and N06030 are shown in Figures 8 and 9, respectively. These figures are
a compilation of corrosion data presented in isocorrosion format with a line representing 0.5
mm/y (20-mpy) corrosion rates. Because of their resistance to HF in flowing conditions, these
types of alloys are used for limited applications as pumps, valves and heat exchanger tubing.
120 ~ . . . . . . . . . . . . . . . . . . . . ................ 248

i ~ ; , ...... =-~.~ . . . . . . . .~..- Atm0spheric
i boi,,,g0o,n,
I '~- - 40 ................ ~....... ! ............. ~ ............. ~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104 I"~
==
0 ~ ...................E...................' ..........................................................
r........................................................~..................T...................i 32
0 10 20 30 40 50 50 70 80 90 100
Wt% Hydrofluoric Acid
Figure 8: Isocorrosion curve for N08825 in HF 24. Corrosion rates in mm/y,

dashed line and below indicates rates are <0.51 mm/y (20 mpy).
120 : : ~ ~ - ~ i. . . . ~ AtmDspheric : 248

- / ! / i ~i ~"~.,~k~ boiling= p o i n t , : ~i
. . . . . . . :..... i curve .......... : . :~.~
P 80 , ............. !..... 176
I--
o --i ................... T. . . . . . . . . . . . . . . . . . . ~. . . . . . . . . . . . . . . . . . . i................ T ................... i ....................................... ~. . . . . . . . . . . . . . . . . . . ~. . . . . . . . . . . . . . . . . . . . r ................... i 32
0 10 20 30 40 50 60 70 80 90 100
VVt% Hydrofluoric Acid
I Figure 9: Isocorrosion curve for N06030 in HF 24. Corrosion rates in

mm/y, dashed line and below indicates rates are <0.51 mm/y (20 mpy)
Pawel 2 reported N08825 had high corrosion in HF vapor exposure and at the liquid-vapor
interface in 10% HF at 24 , 50 and 76C. Also, N08020 had high corrosion in 10% HF vapors.
AHF. In liquid AHF service high nickel austenitic stainless steels with chromium,
molybdenum and copper N06030, N06985, N08007, N08020, and N08825 have excellent
corrosion resistance up to at least 125C (257F). Their resistance to AHF in flowing conditions
makes these alloys useful for applications such as pumps, valves and heat exchanger tubing.
Welds. Welds in alloys N08020, N08825, Alloy G (N06007) and N06030 are susceptible
to corrosion when exposed to AHF and HF. Autogenous welds in N08020 tubing had 10 mpy
(2.54 mm/y) rates versus 1 mpy (0.254 mm/y) rates on the base metal when exposed to 10%
AHF, 1 % 012, and chlorofluorocarbons at 95C 5.
Weld attack of N08825 and N06007 has been reported in HF-HNO3 mixtures 25. Also,
preferential weld attack of N06030 welded with ER NiCrMo-11 (N06030) has been reported in
HNO3 with HF 26. Weld attack of these alloys may be the influence of weld alloy segregation as
well as the detrimental affect of reactive metals such as tantalum, niobium and titanium. These
reactive metals may be alloyed in the base metal as well as in some welding consumables.
HF With Air. N08020, N08825, N06985 and N06030 have higher HF corrosion rates in
presence of air 27. Figures 10 and 11 are corrosion data for a number of alloys in aerated HF
and nitrogen deaerated HF. There is a remarkable reduction in corrosion in nitrogen purged 20
and 40% HF for N06030 and N06985. Schmitt and Losackerw observed that in aerated HF
solutions the corrosion resistance of these alloys benefits primarily from chromium and
molybdenum content with nickel adding some limited positive effects. In deaerated HF solutions
positive benefits in corrosion resistance result for alloys with nickel, molybdenum and copper
(beneficial at 100 mVH). The combination of nickel and copper are attributed to low corrosion
rates of N06985 and N06030 in deaerated 40% HF.
1 /--'~- 125 oc ........................................

2' -o.=.o=~o~~''-
........................................................................................ ~ ~ 11251HF'cI
N2 7
DIN 1.4539N
,,,.,=,
DIN 1.4539N
= o.i ...................... U N S NO698S
~ 0 . 1 '" ="~' ..........................................
o
~
I!o,._.
I! o'"'-"'`'
.
. ~
UNS N06030
UNS N ~ 2 0
0 -,-- , / o-o I............

O. 01 ~,.= .o6o3o ..............................................
"" "'"-'"""--'"'"""J" "
5 10 20 40
HF-Concentration [Mass.-%]
5 20
H F-Concentration [Mass.-%]
40 10
Figure 10: Corrosion of various alloys in HF Figure 11 : Corrosion of various alloys in
with air at 250 27. HF in nitrogen at 250 27.
HF With HCl. Air has a greater influence than 2% HCI in 10% HF for corrosion of
N06030 and Alloy AI6XN (N08367). Corrosion rates for N06030 and N08367 in 10% HF, 2%
HCI and 10%HF with 2% HCI at 66C (151F) without and with solution purging are presented in
Table 4 s.
TABLE 4
CORROSION RATES IN MM/Y (MPY) ON UNS N06030 AND N08367 WHEN
EXPOSED TO 10% HF AND 2% HCL AT 66C - WITH AND WITHOUT PURGING s.
Alloy 2%HCI, 10%HF, 10% HF + 2% HCI,

No Purge No Purge Air Purge No Purge N2 Purge
N06030 0.008 (0.3) 1.7 (67) 2.8 (110) 1.2-1.9 (46-75) 0.3 (12)
Ave. 1.64 (Ave. 64.7)
N08367 0.01 (0.4) 2.9 (115) 4.6 (180) 2.4-9.0 (95-356) 2.0 (78)
Ave. 4.64 (Ave. 183)
There is negligible effect from the 2% HCI on corrosion of these alloys. Both alloys have
lower corrosion rates in nitrogen purged HF-HCI solutions. The corrosion rates are erratic if no
purge is applied. With air purged through the solution the corrosion rates are significantly higher
compared to rates from nitrogen purged solutions.
Sulfuric With HF. Shridhar examined corrosion of various alloys exposed to sulfuric acid
with HF additions, with and without velocity 28. He observed lower corrosion rates for nickel-
based alloys compared to iron based alloys in HF. In dilute sulfuric acid the addition of HF
accelerated corrosion rates. In concentrated sulfuric acid, HF switched to acting as an inhibitor
and the corrosion rates were reduced. For nickel-based alloys with chromium the sulfuric acid
concentration at which switching occurred ranged from 60 to 80%, dependent on the copper
content of the alloy. Figure 12 is corrosion data over a range of sulfuric acid concentrations with
1% HF for some nickel based alloys with and without copper. For alloys with no copper (Alloys
C-22 (N06022), C-276 (N10276), 625 (N06625) and H-9M (N06920)) the switching
concentration was about 80%, whereas for alloys with copper ($255 ($32550), N06985 and
N06030) it was about 60%. A model was proposed based on a semi-protective chromium oxide
film that is formed in concentrated sulfuric acid and dipolar HF adsorbs to higher potential defect
sites. Cupric ions beneficially increase the potential at 60% sulfuric acid and promote the
beneficial adsorption of HF. There was no observed velocity effect in concentrated sulfuric,
however, in dilute sulfuric there was an increase in corrosion with velocity.
q. t 8 I , I ~-~ OOOOO $32550 (2 Cu)
\ .06030 cu/
10 '~ " " \ AAAAA N 0 6 0 2 2
~. ~ \ -A--A-*-k-k N10276
1 , ~ ~ AA4AA N06985 (2Cu)
..... N06625
o I0 '
\ i__1o000
rvrv
o=-
~ 10-'
20 4~0 6 0; w
80 1 ~)0
I SULFURIC
Figure 12: Effect of alloy content on switching from corrosion to

inhibition in H2SO4with 1% HF at 79C 2s.
AHFIAsFdCl2. Liquid AHF, with AsF5 and chlorine, at 60C (140F), caused very high
corrosion rates on N08020 internal packing, trays and rupture discs used in a distillation
column s. The column packing and trays dissolved in less than two months. Process samples
from the system found AsF3 and AsFs impurities in the AHF. Analysis of fresh incoming AHF
found only AsF3. AsF5 may form in a process reactor by the reactions in equations 2 and 3:
2HF + CI2 + AsF3 ~ AsFs + 2HCI (2)
2CI2 + AsF3 ~ [AsCI4]+[AsF6] (3)
Corrosion studies used a linear polarization resistance (LPR) corrosion probe to measure
the instantaneous corrosion rate of N08020 in 148 g AHF, 4 g AsFs and CI2 at 21C (70F). With
AHF and AsFs in the autoclave test, less than 0.05 mm/y (2 mpy) corrosion rates were observed
over a 24-hour period. However, after the addition of CI2 to the AHF and AsFs the corrosion rate
rapidly increased to 4.57 mm/y (180 mpy) then decreased over the next 48 hours to less than
0.05 mm/y (2 mpy). Weight loss corrosion rates for the three LPR elements correlated well with
the integration of plotted corrosion data.
The AHF/AsF5 system is known to be super acidic; that is, it contains an increased
amount of H2F relative to AHF (see equation 4) 18. This system is more corrosive than a normal
AHF system. The rapid corrosion after chlorine addition may indicate an interaction between
chlorine and AsFs, a strong Lewis acid, which would polarize the CI-CI bond enhancing the
oxidizing power of chlorine.
2HF + AsFs ~ H2F+AsF6" (4)
Nickel Rich Austenitic Stainless Steel Cracking
HF. Pawel 2 reported cracking of N08020 and N08825 exposed to 10% HF vapors at
76C. Pawel noted that these cracked samples had either a thin layer of copper deposits or
significant staining. N08020 also had intergranular attack while the N08825 had surface etching.
These effects suggest vapor phase condensation corrosion, with accumulation and
concentration of CuF on the sample surface. The CuF is oxidized to CuF2 in the presence of
oxygen. This may not occur when the metal is submerged in HF due to dilution of corrosion
products so there is only minimal accumulation on the metal surface.
AHF. Alloys N08020, N08825 and N06030 have given satisfactory service in AHF
environments that have SO2, air or oxygen which have caused stress corrosion cracking of
Nickel-copper alloy 400 (N04400). However, there have been cases of in-service stress
corrosion cracking of these nickel-rich austenitic stainless steel alloys when exposed to AHF and
cupric fluoride. These were located downstream of copper bearing alloys ~.
NICKEL AND NICKEL ALLOYS
Nickel and Nickel Alloy Corrosion
Nickel and nickel alloys have a range of corrosion resistance and usefulness in AHF
and HF.
HF. Figure 1 shows that nickel alloys from groups B and D are useful across the range
of HF concentrations up to the indicated temperatures. Oxygen in HF increases corrosion of
these alloys. The presence of oxidizing salts in HF may be beneficial to nickel-chromium
alloys, and detrimental to nickel-copper and nickel-molybdenum alloys.
Pawel 2 studied corrosion on a number of nickel alloys in HF solutions. Table 5 and 6 are
data from this study. Both sets of data emphasize the effect of air in HF vapors to cause high
corrosion rates. In Table 5 each nickel alloy has acceptable corrosion rates under immersion
conditions. However, in HF vapors and air alloys 200 (N02200), N04400 and 600 (N06600)
experienced high corrosion rates. Also, N02200, N04400 and N06600 exhibited liquid-vapor
interface attack, and adherent products that may influence the corrosion rate.
TABLE 5
Nickel Alloy Corrosion Rates (mm/y) From Weight Loss During Immersion Tests ~A~,20.
Alloy HF 24C 50C 76C

Concentration Immersed Vapor Immersed Vapor Immersed Vapor
N02200 1.0% 0.06 1.11' 0.20 1.851" 0.18 3.53 I"
10.0% 0.07 1.87 / 0.27 4.47 j"
N04400 1.0% 0.04 0.91 0.18 3.38 0.21 2.27
10.0% 0.05 2.24 J 0.15 5.87 / 0.30 4.39
N06600 1.0% 0.05 1.06 0.33 3.36 0.22 2.59
10.0% 0.07 8.361 0.36 10.7 0.33 5.00
N06022 1.0% 0.01 0.005 0.05 0.04 0.19 0.59
10.0% 0.03 0.09 0.19 1.25 0.39 2.33
N 10276 1.0% 0.02 0.04 0.12 0.32 0.21 1.25 w
10.0% O.06 0.35 0.21 2.35 0.34 2.57

Rates are calculated assuminguniformweight loss.
Indicates extremeattack at vapor-solution interface.
Adherentcorrosion products on sampleleading to underestimation of corrosion rate.
Pawel selected wrought alloys 22 (N06022) and N04400, and welded samples of these
alloys for exposure at 24% and 48% HF concentrations. Table 6 contains the results of this
study. All immersion samples had lower corrosion rates than respective vapor samples. Alloy
N06022 had acceptable rates (0.51 mm/y (20 mpy) or less) up to 50C but high rates when
immersed in 24% HF at 76C. The welded panel of N06022 had high rates when immersed in
both 24% and 48% HF at 50C and 76C. Alloy N06022 and the welded sample exposed in HF
vapors in air had acceptable rates at 24C in both concentrations, but unacceptable rates at
higher temperatures. Each alloy N06022, and welded N06022, sample exposed to HF vapors in
air had lower rates than alloy N04400 for similar conditions. However, Alloy N04400 in
immersion conditions had lower rates than N06022. Even though welded N04400 had generally
higher rates than wrought N04400 panels these rates were generally lower than rates of welded
N06022 in similar immersion conditions.
III I
TABLE 6
Corrosion Rates (mm/y) of UNS N06022 and N04400 From Weight Loss in 24% and 48%
HF During Immersion Tests 2.
Alloy HF 24C 50C 76C

Concentration Immersed Vapor Immersed Vapor Immersed Vapor
N06022 24% 0.06 0.48 0.29 1.51 1.42 3.81
48% 0.06 0.50 0.19 0.95 0.43 3.81
N06022 w 24% 0.38 0.43 0.68 1.90 1.63 3.30
48% 0.34 0.60 1.65 1.14 3.00 2.34
N04400 24% 0.08 1.67 0.28 5.26 0.36 5.21
48% 0.06 1.94 0.34 6.17 0.44 5.61
N04400 w 24% 0.08 1.55 0.34 5.72 0.36 5.21
48% 0.44 2.02 0.33 5.41 0.69 5.28
,v indicates a welded test panel
Figure 132', by Crum, is a summary HF iso-corrosion chart for various alloys in which a
line is drawn indicting the HF concentration and temperature conditions that produce 0.51
mm/y (20 mpy) or less corrosion rates. From this figure alloy N04400 has acceptable rates up
to the boiling point at all concentrations. Notable among the Ni-Cr-Mo alloys is the lower
useful conditions for alloy 625 (N06625). N06625 has 3.5% Nb which is attributed to this
alloy's reduced HF corrosion resistance. These data represent corrosion rates in HF free of
air. By contrast, in the same Crum 24study, tests were performed under condensing conditions
at 50C with 5% HF, 15% H20 and 8% 02. The corrosion rates on alloy N04400 and alloy 25-
6Mo (N08926) were unacceptably high, while rates for N06022, N06600, alloy 686 (N06686),
N08825, and alloy C-276 (N10276) were very good to moderate.
Figure 14 29 is an isocorrosion chart for UNS N04400 indicating corrosion rates in HF

when aerated and air-free. Immersed N04400 in aerated 30% to 75% HF has significantly
higher corrosion rates compared to air-free exposure. Vapor phase HF and air may cause
even higher corrosion. Also, aerated HF, or HF vapors in air, produced SCC on alloy N04400.
Furthermore, denickelification of N04400 has been reported 13in concentrated HF with air. In
severe cases this was identified by a characteristic scaly copper layer, and in mild cases by
only a thin adherent surface film.
120 - ................ ; ......... ~. ........ ~. ........
i
T .............
i ! :~ ~npspnenc
.~.................. ~....... -~:"-~ ...... :":"- .......... "r- .....
i
.248
!
....... i!
o~,,, 8 0 ~ : ~ ~ " ~ ' - ~ ~ - - ~ ' ~ f NI=0665 l'i----~-'i .... ~ ....... ~ ........ i 176 ~
E 40i-""1
~" 4 ~ " k ~' ". ...... - ........i104"~=i
~"" ~
0 , ~ ~ ~ . . . . t. . . . . . . . ~ 32
0 10 29 30 40 50 60 70 a0 90 100
Wt% Hydrofluoric Acid

Figure 13: Summary hydrofluoric acid isocorrosion chart showing 0.51 mm/y (20 mpy)
curves for various alloys 24.
250
Atmospheric " I
212 boiling point curve 1 O0
200 -i " " I " Alr-fr'ee \" I " " "
| / <20 m p y ~ '
l ~(<O.51 mrn/a)i"~.
, w -- 80
/ , ~ : Aemtecl' ~
I ~I~ > 2 0 m R ~
,~ , , --,.= (>O.51 mn'IJa) ,~ ,
~_~
,oo \ , \ , -- 60
~g~ Air-free Aerated i

E ~ <10 mpy ; <25 mpy ! ~ -- 40 E
I~- 1 O 0 ~ : (<0.25 mrn/a) -(<0.63 mrn/a) -k I~-
i 'l '!
20
Air-free Aerated--
<1 mpy J <10 mpy
50 (<0.025 mm/a) (<0.25 mrn/a)
-- O
O 10 20 --30
I t
4'0 50
,
60 ~0 so 90 100
Acid concentration, % by vvt.
Figure 14: Isocorrosion chart for UNS N04400 in hydrofluoric acid air-free and with
aeration 29.
Rebak reported on HF corrosion for a number of alloys. Figure 15 are data on N10276
and alloy C-2000 (N06020) 3. Alloy N06200 had the lowest corrosion rates in this comparison
as well among all alloys tested.
,oooo
.......tZ3 .... I N10276, 52C l .............. r.......... -1................ T ....... ~
(-;', ....... N10276, 79C :
...... I I N06200, 52C
9D-- N06200, 79C t "....... '~:'-"~"~'" '~::[
100.0 -]
~ (: j-" <~ - t
1
10.0
1.0 U ....::!
- - t
~ q
-!n
0.1
: ..................~ ...... i ,--i- r ,--- i
o 1o 20 30 40 50
H F C o n c e n t r a t i o n (%)
Figure 15: Corrosion rates of UNS N10276 and N06200 in HF at

52C and 79C 3.
He noted that alloys with higher iron contents had correspondingly higher corrosion
rates in HF. Rebak observed that in the tested range of HF, those alloys with higher nickel and
molybdenum had lower corrosion rates. However, all alloys had increased corrosion with
increased temperature and HF concentration.
AHF. Nickel alloy N02200 is used in AHF vapor up to 600C, and for rupture disks in
AHF storage tanks and railcars at ambient temperatures. Nickel-chromium alloy N06600 is
used in valves, piping, and tubing for AHF up to at least 149C (300F) and up to 590 C in
metal oxide hydrofluorination application 19. N04400 is used up to at least 149C (300F) in
AHF alkylation applications such as distillation columns, heaters, recovery towers, pumps, and
valves where process conditions have water under air-free vapor and immersion conditions.
The Ni-Cr-Mo alloys N06022, N06200, N06625, N10276 and Ni-Mo alloys B-2 (N10665) and
B-3 (N010675) are resistant to AHF vapors and liquid to at least 149C (300F).
Niobium in Nickel and Nickel Alloy Welds and Castings
HF. Spence reported on cast nickel-copper alloys M-35-1 (N024135) and M-30C
(N024130) 31. Table 7 are HF corrosion data for these cast alloys and weld materials with
various amounts of niobium. The cast alloy N024135 with less than 0.5% Nb had lower
corrosion than N024130 (1.3% Nb) in 49%HF. Weld deposits with 2.08% Nb had higher
corrosion in aerated and nitrogen purged 40% HF than those without Nb 29.
TABLE 7
Effect of Niobium in Nickel-Copper on Corrosion Rates in HF, Rates mm/y (mpy)29,31
Metal (Nb) 49 % HF, 40% HF, N2 40% HF, 40% HF, N2 40% HF,
49C (120F), Purge, 70C Aerated, 70C Purge, 70C Aerated, 70C
120h (158F), 16.5 d (158F), 16.5 d (158F), 12 d {158F), 12 d
M35-1 0.35 (14)
(0.5%)
M30C 0.62 (24.5)a
(1.3%)
Weld Filler 0.09 (3.6) 1.7 (67) 0.05 (2) 1.07 (42)
(No Nb)
Weld Filler 0.71 (28) 2.64 (104) 0.05 (2) 1.32 (52)a
(2.08%)
(a) - Localizedattack
Welds in N04400 made with gas tungsten arc (GTAW) with ERNiCu7 (N04060) and
shielded metal arc weld (SMAW) ENiCu7 (W84190) processes were selectively corroded in 5-
15% HF with sulfuric acid. Weld repairs and restoration were made with C71500 welding
consumables ECuNi (W60715) and ERCuNi (C71580) which show no attacks.
AHF. Weld deposits of alloy 62 filler metal (N06062, with 1.5-3% Nb), alloy 82 filler
metal (N06082, with 2-3% Nb), alloy 132 electrode (W86132, with 1.5-4% Nb) and alloy 182
electrode (W86182, with1-2.5% Nb) were exposed to AHF at 350 to 400C for two weeks.
These weld deposits had corrosion rates of 0.25 to 0.58 mm/y (10 to 23 mpy) while the base
metal N06600 had only 0.05 mm/y (2 mpy) s. In-service weld attack of these alloys in pipe and
pressure vessels was noted in AHF starting at 150C. The weld attack increased with
temperature. At 350C N06062 had corrosion rates of 0.4 mm/y (16mpy) and N06082 of 0.61
mrn/y (24 mpy) versus rates on the base metal, N06600, of 0.025 mm/y (1 mpy). A signature
of this weld attack was black corrosion deposits on welds. These corrosion deposits were
higher in niobium, tantalum and titanium than the weld metal. These elements are detrimental
to weld corrosion resistance in AHF over 150C.
Nickel and Nickel Alloys in High Temperature HF and AHF
Nickel and nickel alloys are commonly used for high temperature (over 300C) HF and
AHF. Corrosion resistance of these metals in high temperature conditions is dependent on
the formation of thin, adherent, protective, metal fluoride films. Nickel fluoride films are
relatively stable compared to other nickel halides and provide protection to the extent that they
have higher melting points than the service temperature and vapor pressure of less than or
equal to 104 atm 32.
Most published corrosion data for metals in high temperature AHF or HF is from
exposure tests of a few hours to a few days, which is appropriate for ranking relative corrosion
resistance and observation of short term physical changes in the metal. Above 400C (752F)
metallurgical changes like aging or long range ordering may occur that reduce fracture
toughness, creep ductility or corrosion resistance. Therefore, consider this corrosion data as
guidance for longer-term investigations at high temperature conditions.
Myers and Delong 33 reported on corrosion in AHF at 500 to 600C (Table 8). Also,
they exposed metals in 50% HF and 50% steam, from 550 to 750C (Table 9). From Table 8
the lowest corrosion rates were on N02200, followed by copper, N04400 and N06600. All iron-
based alloys had high corrosion rates. Those iron based alloys with higher chromium and
niobium (S30900, S31000 and S34700) had the highest corrosion rates at the 600C. The
high rates and variability are due to short duration tests.
TABLE 8
Corrosion of Selected Metals in AHF at 500 and 600 C, Tests were 4 to 15 hours in
duration, Corrosion rates in mm/y (mpy)33.
Metal 500C (932F) 600C (1112F

N02200 0.91 (36) 0.91 (36)
N04400 1.22 (48) 1.83 (72)
N06600 1.52 (60) 1.52 (60)
COPPER 1.52 (60) 1.22 (48)
G10200 15.54 (612) 7.62 (300)
$30400 13.41 (528)
$34700 183 (7200) 177 (6960)
$30940 5.79 (228) 168 (6600)
$31000 12.2 (480) 305 (12,000)
$43000 1.52 (60) 11.6 (456)
Table 9 data indicates increasing corrosion of both nickel alloys with temperature. At
700 and 750C alloy N04400 had higher corrosion rates than N02200. In comparison to
Table 8 data, steam in HF may increase corrosion of N02200 but decrease corrosion on
N04400 at 600C.
TABLE 9
Corrosion of N02200 and N04400 in 50% HF and 50% Steam, Tests Were 4 to 15
Hours in duration, Corrosion rates mm/y (mpy)33.
Metal 550C 600C 650C 700C 750C

(1022F) (1112F) (1202F) (1292F) (1382F)
N02200 0.79 (31) 1.83 (72) 2.74 (108) 3.66 (144) 3.05 (120)
N04400 0.61 (24) 1.52 (60) 3.96 (156) 5.18 (204)
Table 1029are 36 hour test data on nickel and nickel alloys in AHF at 500 to 600C.
Notably, these longer tests gave lower corrosion rates than those from shorter duration tests.
Each corrosion rate is low enough for further consideration of the alloy. However, the lowest
corrosion rates were from alloys B (N10001), C (N10002) and N06600. In these tests, alloys
with molybdenum and nickel had lower corrosion rates.
TABLE 10
Corrosion Tests in AHF at 500 to 600C for Nickel and Nickel Alloys, Tests were 36-
hour duration, Corrosion rates mm/y (mpy)29
Metal Corrosion Rate Comments

N10002 0.01 (0.3) Iridescent tarnish film
N06600 0.02 (0.7) Iridescent tarnish film
N10001 0.05 (2) Black film
N02200 0.23 (9) Black film
N02201 0.36 (14) Black film
N04400 0.33 (13) Adherent dark film
N05500 0.41 (16) Adherent dark film
Tyreman and Elliott34 studied pure metals after 10-hour AHF exposures at 850C.
N02200, cobalt, copper and molybdenum (R03600) had lower corrosion rates. High rates
were observed on iron and chromium (R20994) while niobium (R04210) and tantalum
(R05400) were consumed in ten hours. Also, various alloys were examined after 50-hour
exposures, to 90% HF and 10% steam at 850C. Alloys $30400, 310 SS ($31000), and alloy
800 (N08800) had thick, brittle, corrosion products and porous metal matrix. Their corrosion
rates were 102 to127 mm/y (4000 to 5000 mpy). Alloy N06600 had external nodular (iron
oxides) scaling and internal precipitation (chromium fluorides) and section loss from fluoride
penetration equated to 23 mm/y (900 mpy). Alloy N06625 had an external scale rich in
niobium and oxygen and internal corrosion and intergranular precipitation (chromium fluorides)
to a depth of 6.5 mm/y (256 mpy). The authors noted permeation of fluoride in pure nickel is
five times that of oxygen and twice that of chlorine at 750C. Permeability is a product of
fluoride diffusivity and solubility in nickel. The formation of NiF2 is protective for nickel due to
its low vapor pressure. Chromium, niobium and tantalum are reactive with fluoride at the
surface as well as internally and increase corrosion loss as well as internal alloy loss.
Marsh and Elliott35 studied Ni-Cr alloys after exposure to AHF and HF with steam at
650C. Alloys with more chromium had higher corrosion rates in AHF. Internal chromium
fluorides were found after AHF exposure and alloys with more chromium had a higher reaction
rate. Exposure to HF with steam produced a chromium oxide rich surface scale with fluorides
in the underlying alloy; also there was an internal corrosion product network with Cr203 and
chromium fluorides (CrF2 and CrF3).
II I
Table 11 is 100 hour and 155 hour corrosion data for various alloys in 5% HF, 8% 02,
15% H20 (balance as CO2 and N2) at 450C 24. These corrosion rates are all very low which
may be due to water vapor and oxygen promoting a protective metal oxide on these alloys.
TABLE 11
Corrosion Rates for Various Metal Alloy Coupons and U-Bends in 5% HF,
02, 15% H20 and balance as CO2 and N2 at 450 C (842F) 24.
Corrosion Rate mm/y (mpy) SCC - yes/no

UNS Number 100 hours 155 hours 100 hours 155 hours
N06600 o.ol (0.4) 0 Yes Yes
N04400 0 0.002 (0.1) No No
N08825 0.01 (0.4) 0 No No
N10276 0 0 No No
N06686 0 0 No No
N06622 0 0 No No
N08926 0 0 No No
Same specimens were evaluated at 100 hours and after an additional 55 hours exposure.
With a mixture of 40% oxygen and 60% AHF at 377 to 627C corrosion rates of more
than 1 mm/h (40 mils per hour) were observed on stainless steel fuel cladding 36. Fluoride
attack of iron is accelerated in the presence of oxygen in AHF.
Barnes investigated metals and alloys after exposure in Ar-5% AHF for 15 hours at
1000C 37 (Table 12). High purity nickel alloy 227 (N02270) had the lowest corrosion rates
among the tested nickel and nickel based alloys. Examination of nickel coupons after 50-hour
exposure found no measurable internal fluoridation. A nickel sample holder, exposed for about
1600 hours in this environment, had nickel fluoride particles at 20 ~m from the surface. Barnes
attributed low fluorine penetration in nickel samples to the low vapor pressure and high melting
point of NiF2 that was present on the surface acting to reduce ingress of fluoride into the nickel.
Chromium is detrimental to fluorination resistance and increases corrosion susceptibility of
nickel-based alloys by formation of chromium fluorides that have high vapor pressures as well
as low melting corrosion products in comparison to NiF2.
TABLE 12
Corrosion Rates and Observations on Pure Metals Exposed in Ar-5% AHF at 1000C
For 15 hours 37.
Material Weight Corrosion Rate Appearance Comments

Change mm/y (mpy)
(m1/cm2)
Or * -35.25 Green Extensive internal fluorides to a depth
of: 0.21 mm (8.3 mils)/side; assuming
linear rates 36.7 mm/y (1445 ml3y)
N02200 -0.1 0.036 (1.4) Unchanged No evidence of internal fluorides
N02201 -0.1 0.036 (1.4) Unchanged No evidence of internal fluorides
N02270 0 0 Unchanged No evidence of internal fluorides
*Chromium exposed for 50 hours at 1000C in Ar-5% AHF
Alloys based on nickel and cobalt had higher corrosion rates than pure nickel, and
exhibited internal fluoride formation. Table 13 presents the metallographic measurements and
observations for the alloys. The nickel-molybdenum alloys had the lowest corrosion rates
among alloys tested. Alloys 242, N10675, 188 (R30188) and Nickel Aluminide (IC-221 M) had
thin surface scales and less internal fluoride formation than other alloys. Extensive internal
fluorides were found with N06600, alloy 617 (N06617) and 602CA (N06025).
TABLE 13
Metallographic Measurements and Observations on Alloys Exposed in Ar-
5% AHF, at 1000C, for 15 hours 37.
Alloy Maximum depth of Appearance Comments

affected metal,
mm/side (mils/side)
242 0.015 (0.6) Surface Scale Also resistant in Ar-35% AHF
N 10675 0.020 (0.8) Surface Scale

IC-221M 0.025 (1.0) Surface Scale Extensive Corrosion in Ar- 35% AHF
R30188 0.051 (2.0) Surface Scale
N06617 0.13 (5.3) Nodules on Surface Extensive internal fluorides
N06600 0.15 (5.9) Nodules on Surface Extensive internal fluorides
N06025 0.18 (7.1) Surface Scale: Molten Extensive internal fluorides
corrosion product
Nickel and Nickel Alloys in HF Mixed with Other Acids
Sulfuric With HF. Shridar's 28 workon mixed H 2 S O 4 - H F acids included nickel alloys
N06022, N06625 and N10276. Figure 12 includes information on these alloys in sulfuric acid
with 1% HF. These alloys do not have copper; and therefore, they switch from corrosion to
inhibition at about 80% sulfuric acid and higher concentration. As noted in the section on
Nickel Rich Austenitic Stainless Steels, for alloys with copper the switching concentration was
about 60%. Shridar's model for inhibition by HF is based on a semi-protective chromium oxide
film formed in concentrated sulfuric acid where dipolar HF adsorbs to higher potential defect
sites. The nickel-based alloys with chromium but no copper apparently require higher
concentration sulfuric acid to promote the beneficial adsorption of HF.
HF with HCl. Table 14 presents corrosion data on several nickel alloys immersed in
mixtures of HF with HCI at 66C (151F) for 48 hours 5. All air-purged mixtures had higher
corrosion rates. Alloy N04400 had the highest corrosion rates in 10% HF with 2% HCI, air-
purged conditions. Alloy N10665 had lower rates than N10276 corrosion rates in air purged
conditions at 53% HF with 8.3% HCI. Notably, under no purge conditions alloy N10665 had
lower corrosion rates in 53% HF with 8.3% HCI than in 10% HF with 2% HCI. Lower corrosion
of UNS N10665 in the more concentrated acids may suggest a protective nickel-molybdenum
corrosion product with limited solubility.
TABLE 14
Corrosion rates of nickel alloys immersed in mixtures of HF and HCl, for 48 hours
At 66C (151F), with and without purges through the solution,
corrosion rates mm/y (mpy)5.
Alloy 10% HF with 2% HCI 53% HF with 8.3% HCI

Air Purged No Purge N2 Purged Air Purged No Purge
N10665 0.69 (27) 0.43 (17) 0.08 (3) 0.16 (6.3) 0.05 (2)
N 10276 0.79 (31) 0.58 (23) 0.36 (14) 0.55 (21.5) 0.09 (3.5)
N04400 2.54 (100) 0.58 (23) 0.10 (4)
Nickel and Nickel Alloys in AHF with Impurities
AHF/AsF_s/CIz. AHF, chlorine and AsF5 at ambient temperatures (20 - 35C) caused
over 50.8 mrn/y (2000 mpy) corrosion rates on cast nickel-copper Alloy M-35-1 (UNS N24135)
used for pump impellers in submerged pumps 5. The pump impeller tip speed was 37.2 m/s
(122 fps). The AHF was a mixture of fresh and recycled material. The recycled material
normally contained 800 to 2500 PPM chlorine. Samples of the recycled AHF at the time of
high corrosion contained up to 0.5% arsenic, while the pump was exposed to 900 to 1500 PPM
arsenic. The arsenic was present as AsF3 and AsF5. Static and agitated autoclave, weight
loss corrosion coupon tests, were run for 100 hours, with HF, CI2, AsF3 and AsF5. These tests
produced corrosion rates of only 0.76 to 1.3 mm/y (30 to 50 mpy) for N04400. An LPR
corrosion probe was applied for several autoclave corrosion studies. The following is a
description of one of the tests with alloy N04400 at 21C (70F). AHF (58 g) was introduced
and no significant corrosion was observed. When 0.8 g AsF5 was added the corrosion rate
increased to 17mm/y (670 mpy). Then CI2 was added and the corrosion rate increased to 54.1
mm/y (2130 mpy). Over the next four hours the corrosion rate diminished to 3.7 mm/y (146
mpy) and 12 hours later to about 0.13 mm/y (5 mpy). Then an additional 0.7g of AsFswas
introduced. In 15 minutes the corrosion increased to 63.5 mm/y (2500 mpy); five hours later
the rate declined to 2 mm/y (80 mpy), and 12 hours after that rate was 0.42 mm/y (17mpy).
The corrosion rates given above were adjusted to the rates from weight loss corrosion rates
after testing. The indicated real time LPR rates were 4.2 times lower than the actual corrosion
loss.
The LPR probe data indicate that N04400 was corroded by the AsF5/AHF superacid
system. As in the case of N08020, in the section on Nickel Rich Austenitic Stainless Steels, a
large increase in corrosion occurred when chlorine was added to the system. The
AHF/AsF5/CI2 system is very corrosive. Chlorine may oxidize the AsF3 to AsF5, by equilibrium
equations 2 and 3, thus increasing the acidity of the system. The decay in corrosion rate with
time may reflect reduction of the As (V) to As (111)during the corrosion process. AsF3 does not
form a superacid with AHF. Reintroduction of AsFs, an oxidizing agent and acid, restores the
corrosivity until reduction to As (111)again takes place.
In this case, impeller corrosion resulted from superacid formation (H2F+AsF6") and the
oxidizing power of chlorine in this media. For superacid formation see reaction equation 4 in
the section on Nickel Rich Austenitic Stainless Steels.
NaF*HF. Sodium acid fluoride (NaF*HF) may be formed by reaction of sodium

hydroxide, soda ash or NaF with HF or AHF. Sodium acid fluoride is very soluble in HF and
AHF and when a mixture is heated or hot it may be very corrosive to many alloys. Table 15 29
present's corrosion data on selected nickel alloys in HF with sodium acid fluoride.
TABLE 15
Saturated solution containing 85 g/I of sodium acid fluoride and 30 g/I of HF, plus
Crystalline sodium acid fluoride, some air and liquid flow, 30-day test, 80C (175F) 29.
Material Corrosion Rate

mmly (mpy)
N04400 1.75 (69)
N02200 1.02 (40)

N06600 3.0 (118)
N10001 2.16 (85)
N10002 0.64 (25)
An AHF superheater with N06600 tubes had a series of internal corrosion failures
corresponding to an area where the heat transfer media impinged on the outside of the tubes 5.
Typically failures were from pitting and general corrosion along the bottom half of the tube with
the heaviest corrosion at the bottom. Other areas only inches away showed little or no
corrosion loss. Samples of deposits from the corroded area were rich in nickel, chromium and
iron fluorides, typical of alloy N06600 in AHF. Often sodium fluoride or sodium acid fluorides
were also identified in these deposits. Sodium fluoride was also found in deposits on the AHF
vaporizer up-stream of the superheater. Sometimes the vaporizer "U"-tubes had pits or
general loss on the bottom side of the bottom tubes. Since NaF is very soluble in AHF it could
be carried in vapor droplets to the superheater. Autoclave tests were made with AHF and NaF
at 170C; the results are presented in Table 16s.
TABLE 16
Corrosion of N06600 exposed at 170C in AHF with NaF, corrosion rates in mm/y (mpy) s.
AHF with no AHF with 10.8 AHF with 20 AHF with 22

NaF weight % NaF weight % NaF weight % NaF
0.025 (1.0) 3.8 (150) 3.7 (144) 5.1 (200)
From this data it was concluded that sodium acid fluoride in AHF was corrosive to
N06600. It appears there is a threshold amount of sodium acid fluoride that damages the
oxide layer and interferes with restoration of the layer in AHF.
Nickel and Nickel Alloy Cracking
Stress corrosion cracking of alloys N04400 and alloy 500 (N05500) occurs in wet HF
vapors with oxygen. Cracking of N04400 also occurs in AHF when oxygen enters systems
that are opened to air for maintenance or inspections.
N04400 and N05500. Schussler 38 studied welded N04400 after exposure to 5% and
48% HF. SCC was observed in vapor exposed samples. He noted that oxygen saturation in
the vapor space and the level of stress played a roll in the severity of SCC. No SCC was
found on submerged samples. Cracking was found in the base metal and weld metal of as
welded samples. Cracking was also found in welded and stress relieved samples that were
welded with shielded metal arc (SMAW) process. No cracking was observed on wrought,
solution annealed samples. No cracking was observed on welded and stress relieved samples
that were welded with gas tungsten arc (GTAW) process. He recommended a full anneal, but,
at a minimum, stress relief of N04400 after welding to avoid SCC.
Copson and Cheng 39 investigated SCC of a number of nickel alloys in HF (Table 17).
They observed intergranular and transgranular cracking of N04400 and alloy N05500 in vapors
of 48%HF at 60C (140F). The high-strength alloy N05500, in the hot-rolled, or the aged
condition, was susceptible to SCC. U-bends of annealed or cold rolled N04400 cracked. The
welded samples of NO4400 cracked in the base metal and weld metal. N04400 with addition
of 1-% silicon had SCC. Also a special alloy with 85% nickel cracked profusely. From
immersion tests in 48% HF with no aeration, after 30 days there were no cracked samples.
From immersion tests in 48% HF with aeration, there was cracking of alloy UNS N05500 after
15 days.
Their recommendations to avoid SCC of N04400 included eliminating tensile stresses

by design, and also reducing internal residual stress by a full anneal or by thermal stress relief
at 593 to 649C (1100 to 1200F). Additionally, keeping the metal immersed and avoiding
aeration by continuous nitrogen purges may prevent SCC.
TABLE 17
Results from Nickel Alloy U-bends Exposed in 48% HF Vapors at 600 (140F) 39.
Alloy UNS Condition Hardness First Observed

Number VHN HRc Cracking, Days
30pd
N05500 Hot Rolled 148-210 2-6
N05500 Aged 32 5
N04400 Annealed 109-136 4-15
N04400 Cold Rolled 250 6-15
N04400 Welded 4-14
N04400 + 1% Si Cold Rolled 293 15
85 Ni, 15 Cu Annealed 147 5
N02200 Cold Rolled 232 14
N06600 Cold Rolled 295 14-15
Graf and Wittich 4 investigated SCC of nickel-copper alloys in HF with CuF2 at 23C
(73F), (Figure 16). This graph indicates that when stressed to 80% of ultimate tensile
strength, the minimum time to crack resulted from alloys with 65 to 80% nickel, and the most
SCC susceptible composition was an alloy with about 69% nickel (N04400 ranges from 63 to
70% Nickel). Alloys with 70% copper are not susceptible for SCC in HF with CuF2. From this
work, increasing concentration of CuF2in HF reduces time for SCC, and increasing tensile
stresses reduced time for SCC.
SCC Of Ni--Cu Alloys in HF 4- CuF

Solutions Stressed To 80~ UTS; 23C
it
._~ 10 4
E
Z2~
O
Ix_
o 1 0 5~'
O (0.64 wt~ Cu g2+

E
o__ 0.76 wt~. HF) Solution
n (4.26 wt: Cu Fg+
1 w t ~ HF') S o l u ~ o n
10 2 O (7.61 wt~ Cu F2+
36 wt~ HF)Solution
I I I I I I I I I I
O 20 40 60 80 1OO
100 wt~ NI - ~ wt~--Cu
Figure 16. Plot of time for stress corrosion cracking of various

Nickel-Copper alloys, exposed to HF with C u F 2 at 23C (73F)
while stressed at 80% of ultimate tensile strength 4.
General practice in HF alkylation service is to stress relieve cold worked or welded
N04400 at 593 to 621C (1,100 to 1,150F). In similar systems, where HF exposed metal is
rarely exposed to oxygen this is a prudent practice.
However, for N04400 equipment and piping that will be routinely exposed to HF or AHF
and oxygen, even if only during inspections, stress-relief at 700C (1,300F) may only delay
SCC and will not prevent intergranular corrosion s. In such cases other alloys should be
considered.
N02200. From Table 17 it is notable that cold rolled N02200 had SCC in vapors of 48%
HF at 60C (140F). Copson and Cheng 39reported deep intergranular attack on the tension side
of the U-bend. These cracks opened up with additional bending. There has been no
explanation of the N02200 cracking mechanism, under the high corrosion rate conditions in this
study.
There are reports that welded N02200 in AHF service had SCC due to exposure to CuE2
that was transferred from copper bearing alloys up-stream ] .
N06600. Table 17 also reports SCC of cold rolled N06600 in vapors of 48% HF at 60C
(140F). Copson and Cheng 39 reported transgranular cracking on the tension side of N06600.
They noted considerable corrosion and pitting. Again there has been no explanation of the
NO6600 cracking mechanism from this study.
Users of N06600 have reported SCC in HF or AHF when CuF2is present ].
Table 11 includes a report of SCC of N06600 in 5% HF, 8% 02, 15% H20 (balance as
CO2 and N2) at 450C 24. This was a very low corrosion rate environment and cracking
occurred within 100 hours on U-bend samples that were not initially cold worked but subject to
strain when bent.
In-service cracking of N06600 has occurred in AHF at 135C (275F), and AHF with 5%
CI2 at 100C (212F). In both cases, the environments caused only very low corrosion rates
and transgranular cracking occurred within days of initial service. The cracks were found only
in cold-formed dished heads 5. No investigation was made into the cracking mechanism. Weld
repairs were made without difficulty. In similar environments, annealed N06600 had no
cracking. It was concluded that to prevent cracking in AHF, alloy N06600 should be solution
annealed after cold forming.
N10276 and N10665. Alloys N10276 and N10665 may be susceptible to SCC in HF and
AHF environments when CuF2 is present. There are reports by users of SCC in HF and AHF
when these alloys were down-stream from copper bearing alloys.
OTHER METALS AND ALLOYS
Copper Alloys
Corrosion in HF. Schussler~ studied 70-30 Cu-Ni (C71500) and welds exposed
to 5% and 48% HF (Table 18). Higher corrosion rates occurred for samples exposed in air over
48% HF. Heat treatment had only a slight effect on corrosion rates. Although intergranular
corrosion was noted, there was no SCC of C71500. Heavy corrosion was noted at the liquid-
vapor interface and in HF vapor-air exposed portions of the samples.
TABLE 18
Corrosion rates on UNS Alloy C71500, from exposure to 5% and 48% HF
At 66C (150F), rates in mm/y (mpy) 38.
Condition 5%HF 48% HF

Partially Immersed Partially Immersed
Immersed Immersed
As-received 0.74 (29) 0.08 (3) 1.93 (76) 0.13 (5)
As-welded 0.86 (34) 0.10 (4) 2.16 (85) 0.18 (7)
Weld, Stress-relieved 0.84 (33) 0.15 (6) 2.31 (91) 0.18 (7)
@ 482C (900F)
Weld, Annealed 0.69 (27) 0.10 (4) 2.03 (80) 0.15 (6)
@816C (1500F)
Weld, Annealed 0.81 (32) 0.10 (4) 2.74(108) 0.18 (7)
@ 927C (1700F)
Base Metal, Annealed 0.51 (20) 0.05 (2) 1.68 (66) 0.10 (4)
@816C (1500F)
Copper tubing has been used for short-term services in 70% HF, free of oxygen at
ambient temperature. Copper sheets have been applied inside distillation columns in areas that
are subject to HF concentration s.
Corrosion in AHF. Copper-nickel alloys 90-10 Cu-Ni (C70600) and C71500 have been
used for heat exchanger tubes in liquid AHF cooling services due to low corrosion rates in
flowing conditions. Fasteners made of alloy C71500 have been used in AHF, in lieu of UNS
N04400, because of SCC resistance. Copper tubing has been used at ambient temperature for
AHF liquid and vapors at low velocities. Also see the section on Unsuitable Materials.
Denickelification in HF. Holmberg and Prange 13 reported denickelification of copper

nickel alloys in HF services pressurized with air. However, the denickelification of copper-nickel
alloys was less severe than alloy N04400. Less nickel in the Ni-Cu/Cu-Ni alloy system reduces
the susceptibility for denickelification in HF service.
Saldanha 41 reported denickelification of C70600 and C71500 base metals and welds
(including welds with filler metals ERNiCu-7 (N04060), and C71500 {ERCuNi and ECuNi} in a
HF and H2SO4mixture, with 5-15% acid and the balance water, at 150 to170C. Severe
denickelification was observed on equipment made from C71500 while C70600 had only minor
effects. Areas under washers had notable denickelification for both C70600 and C71500.
Welded C71500 was exposed in a plant environment. General corrosion of the base metal
was high but there was preferential denickelification of weldments (Table 19).
TABLE 19
General and dealloying corrosion of welded 70/30 Cu-Ni; samples exposed in
process unit to 5-15% mixed acids of HF and H2SO4 in water at 150 to 170C,
corrosion rates in mm/y (mpy) 41.
Weld Process- General Corrosion Rate Base Metal

Filler mm/y/mpy) Denickelification
GTAW- ERCuNi 1.07 (42) 2.87 (1 3)
SMAW- ECuNi 1.30 (51) 9.53 (375)
G T A W - ERNiCu-7 2.84 (112) 5.23 (206)
The weld metal denickelification was two to eight times higher than the base metal.
Denickelification strongly varied with the heat of material, which suggested differences in
themomechanical processing. Therefore, corrosion tests were also made on un-welded,
wrought samples with various amounts of cold work and thermal treatments; Table 20 contains
this data.
T A B L E 20
Effect of Thermomechanical Processing Conditions on Susceptibility to
Denickelification, wrought samples exposed in process equipment to 5-15% mixed
acids of HF and H2SO4 in water at 150 to 170C, corrosion rates in mm/y (mpy) 41.
Cold Work, Heat Treatment Corrosion Rate of

% Base Metal
mm/y (mpy)
0 None 0.58 (23)
725C, Air Cool 0.56 (22)
725C, Water Quench 0.61 (24)
25 None 0.36 (14)
725C, Air Cool 0.36 (14)
50 None 0.30 (12)
725C, Air Cool 0.38 (15)
725C, Water Quench 0.41 (16)
The samples with cold work had lower general corrosion rates, denickelification was
continuing but at a lower rate than in previous tests. In comparison to Table 19 the process
conditions during the Table 20 exposures were less corrosive, thus the denickelification was
localized and not uniform. From observations on control samples exposed during both periods
there was no significant change in the rate of denickelification with various thermomechanical
processing. No preventive measures were defined for this problem.
Precious and Other Metals
Silver (P07015), gold (P00020), platinum (P04995), tungsten (R07005) and molybdenum
(R03600) resist HF and AHF.
HF. P07015 has low corrosion rates in boiling HF, and HF at higher temperatures.
P07015 has been used in HF services such as stills, heating coils, condensers, rupture disks
and pressure diaphragms. However, P07015 in HF service has high corrosion rates when also
exposed to oxygen, hydrogen sulfide or sulfur contamination. 19 Sulfur or sulfur compounds may
be present in commercial HF.
Also, iridium, osmium, ruthenium, rhodium (P05981), and palladium (P03995) resist 40%
HF at room temperature 42. P03995 may have higher corrosion rates in aerated HF or in HF with
concentrated sulfuric acid.
AHF. P07015 has been used in AHF services such as stills, heating coils, condensers,
rupture disks and pressure diaphragms. However, P07015 in AHF service has high corrosion
rates when also exposed to oxygen, hydrogen sulfide or sulfur contamination. 19 Sulfur or sulfur
compounds may be present in commercial AHF.
Barnes3~ exposed P00020, P03995 and P04995 to Ar 5%-AHF at 1000C for 15 hours.
P00020 was unchanged and had no corrosion. P04995 turned matte grey and had a corrosion
rate of 0.03 mm/y (1.1 mpy). P03995 had a weight gain but the appearance was unchanged.
NON-METALLIC MATERIALS
Organic Materials
Plastics and Elastomers. Some plastics and elastomers have useful chemical
resistance to HF and AHF, and their inertness and lower cost compared to metal alloys make
them attractive materials. However, plastics and elastomers may change physical properties
with exposure to HF and AHF. Also, there will be AHF permeation through the plastic or
elastomer with time. Therefore materials selection must include design consideration for
pressure containment and for safely handling the AHF that permeates the plastic or elastomer.
Some plastics and elastomers with acceptable performance in HF or AHF have lost strength,
swelled, cracked, or embrittled in service because of contamination or transient temperature
conditions. Most are sensitive to heat excursions, very cold temperatures, mechanical abuse,
and ultraviolet light from the sun. Therefore, in hazardous chemical services, like HF and AHF,
plastics and elastomers are used only as liners inside a metal or reinforced thermosetting plastic
(RTP) vessel or pipe.
Thermoplastics. Fluorinated plastics are resistant to HF and AHF up to and above the
boiling point and have been used as linings (1.5 mm [60 mils] or thicker). Fully fluorinated
plastics, such as polytetrafluoroethylene (PTFE), do not lose strength, swell, crack, embrittle and
are not chemically attacked by HF and AHF. However, AHF will permeate through fully
fluorinated plastics and the rate of permeation increases with increasing temperature,
concentration, vapor pressure, and with decreasing liner thickness. The information in Figure
171 reflects service experience with commercial fluoropolymer-lined pipe and equipment. The
temperature limits in Figure 17 are based on the permeation of fluoropolymer lined pipe with
nominal 3mm (0.120") thick liners. To avoid liner collapse due to external AHF pressure there
must be provision to safely vent AHF. Bonding systems with adhesives and glass fabric backing
have been attacked by AHF that permeated the liner. Thicker fluoropolymer coated lining
systems with mechanical bonding systems have given satisfactory performance even at higher
temperature AHF exposures than indicated in Figure 17. Regardless of the bonding or lining
system, insulation on the outer surfaces helps to minimize thermal gradients and thus reduce the
rate of AHF permeation. There are now chemically modified PTFE fluoropolymers that are
weldable, which have increased permeation resistance, and improved deformation resistance
under load and creep conditions.
When selecting a fluoropolymer lining system, it is important to perform Atlas cell tests
per ASTM C-868. These are lined blind flange service-exposure tests, conducted with the
highest HF concentration expected, for at least 90 days to include transient temperature
conditions. Then the samples or equipment should be analyzed for chemical attack, permeation,
and loss of bond strength or disbonding. The bonding system is normally the weak link in
fluoropolymer lined or coated equipment.
Fluoropolymer gaskets with fillers of carbon, calcium fluoride, or reinforcement by metal

alloys, have been used in HF and AHF. Barium sulfate filler has been attacked in AHF service.
Fillers improve resistance to deformation under load, "cold flow," and thermal set behavior in
fluoropolymers. Since AHF permeation of fluoropolymer gaskets causes corrosion of exposed
flanges and fasteners some users specify spiral wound gaskets.
,,| ,1 1~ 1 1 3O2
140~- 284
150 2 - - 2 2 2 - 266
120 3 ' 3 248
110
/ ~ ~,--.-Atmospheric
100 ~ ~ boiling point ~ Z12
CURVE
gO
80 116 OF
0c
70 - \ ,-
60
5 - -
4G
2@--
1 - ~'] SO
I r I I I I I I ! 52 ~ Vapor only
10 20 30 40 SO 60 TO I10 gO 100
Wt.% Hydrofluoric Acid in Water Means Limit
FIGURE 17: Plastics and Elastomers in Hydrofluoric Acid ]

This information is for guidance only. Regions below the numbered line and from left to the line represent
areas of satisfactory service in uncontaminated HF. Permeation and blistering can occur with time.
. PTFE, perfluoroalkoxy (PFA)
2. Fluorinated ethylene propylene (FEP)
3. Ethylene tetrafluoroethylene (ETFE)
4. Polyvinylidene fluoride (PVDF), Ethylene chlorotrifluoroethylene (ECTFE)
5. Polypropylene
6. Chlorobutyl, bromobutyl
7. Cross-linked, high-density, low-density, or copolymer polyethylene
8. Chlorosulfonated polyethylene
9. Soft natural rubber, polychloroprene
10. Butyl rubber, ethylene propylene diene monomer
11. Polyvinyl chloride (PVC) (unplasticized)
Within the temperature limits shown in Figure 17, these fluorocarbon plastics have given
good service in HF and AHF]:
PTFE Polytetrafluoroethylene &

FEP Fluorinated ethylene propylene Higher Temperature
PFA Perfluoroalkoxy Fully Fluorinated
ECTFE Ethylene chlorotrifluoroethylene Lower Temperature

ETFE Ethylene tetrafluoroethylene
PVDF Polyvinylidene fluoride
CTFE Polymonochlorotrifluoroethylene
Other thermoplastic materials such as polyethylene, polypropylene, CPVC and PVC are
less costly but are limited to lower temperatures and concentrations as indicated in Figure 17.
They have been used at ambient temperature for lining pipe and vessels in HF concentrations
below 70%. However, the chemical resistance and mechanical properties of thermoplastics may
be degraded by organic and inorganic impurities (e.g., solvents, wetting agents, oils, soaps,
detergents, chlorine, and oxygen) in HF environments.
Special shipping containers and laboratory bottles for HF are made of high-density
polyethylene (HDPE). Tanks fabricated from HDPE ribbon as helical weld seams have provided
over 15 years of satisfactory service in concentrations of 5 to 70% HF at ambient temperatures
and atmospheric pressure, with no measurable deterioration of properties43. However, a
rotational-molded HDPE tank has cracked through wall at the bottom knuckle by environmental
stress cracking (ESC) after two years of service 1 Small mid-wall blisters, containing HF, have
formed in low-density polyethylene (LDPE) and HDPE after a year's exposure to concentrations
over 60% HF at 30C (86F), but with no deterioration of mechanical properties. Cross-linked
polyethylene has been reported to give good service in HF at ambient temperatures.
Polypropylene and some types of polyethylene have given several years of satisfactory service
in vapors of AHF at ambient temperature. Unplasticized PVC and chlorinated polyvinyl chloride
(CPVC) have resistance to HF solutions and AHF vapors; however, PVC and CPVC plasticized
with vinyl acetate or vinyl chloride are not resistant.
Thermosetting Plastics, Reinforced thermosetting plastic (RTP) resins commonly

recommended for HF services are epoxy vinyl esters. Epoxy vinyl esters have been used in
10% HF concentrations below 65C (150F) for water scrubbers. The cure system typically used
for HF services is based on methylethylketoneperoxide with cobalt napthenate. The corrosion-
resistant barrier should have a double layer (0.25 mm (10 mils) each) of apertured synthetic
polyester, apertured ECTFE, or carbon-reinforcing veil materials followed by at least two layers
of 1.5 oz/sq, yd. chopped strand mat. Some users have specified corrosion-resistant barriers
with more than two veils for enhanced performance. Normally an elevated temperature cure
improves the chemical resistance of these resins in HF exposure. Additional resin information
may be obtained from resin manufacturers. Note that eventually glass fiber and glass flake filled
resins are attacked in HF service.
A dual laminate scrubber with 3-mm (120-mil)-thick FEP fluoropolymer with fiberglass
backing and RTP structural lay-up have provided over ten years of satisfactory service at
temperatures up to 93C (200F) and concentrations up to 49% HF.
Elastomers. Carbon-filled and peroxide-cured fluoroelastomers (1) and

perfluoroelastomers (2) have been used as "O"-rings in HF at ambient temperatures and above ],
These elastomers have better HF resistance compared to others. Generally, the higher fluorine
content of the elastomer the better the chemical resistance in HF and AHF. Manufacturers may
be consulted for guidance on the best compounds, fillers, and cures for specific HF
concentrations and temperatures. Carbon-filled fluoroelastomers and perfluoroelastomers are
(1)Designated FKM by ASTM D 1418 (latest revision), "Standard Practice for Rubber and Rubber Lattices--Nomenclature"
(Philadelphia, PA: ASTM).
(2) Designated FFKM by ASTM D 1418.
subject to AHF permeation in thinner sections. Coatings and bonded linings may have different
properties from the parent material.
Process equipment for HF services may be economically lined with sheet elastomers. As
noted in Figure 17 synthetic soft rubbers (e.g., chlorobutyl, butyl, polychloroprene, and ethylene
propylene elastomer [EPDM]) are useful in HF concentrations below 60% at temperatures below
70C (160F). Consultation with the rubber supplier is essential to assure that available rubbers
will have low silica or magnesia compounding (below 0.3 Wt.%) for HF service. Specific
formulations of chlorobutyl rubber are used more frequently than other rubbers for lining
containers (tank cars, tank trucks, or storage tanks) for 70% acid. In 70% HF service, typically
chlorobutyl rubber has more vapor phase attack than in the liquid phase. This is explained by
the enrichment by AHF in the vapor and because these unwetted surfaces are heated by
sunlight to exceed 32C (90F). Therefore to reduce the vapor space temperature, tanks are
typically shielded from the sun and the exteriors are painted white. In 70% HF the useful life of
chlorobutyl in warm climates is about three years while in cool climates it is 4 to 6 years. Longer
chlorobutyl service life is experienced with lower HF concentrations. The presence of organic
contaminants in HF can result in swelling and failure of rubber linings.
Bromobutyl rubbers have been used in HF service in Europe. Table 21 presents 50% HF
elastomeric exposure data at 22C (72F) that would support its application in other regions'~.
TABLE 21
Results of Polymer Exposures in 50%HF at 22C (72F) for 30 days 44.
Polymer % Weight % Volume

Change change
Chlorobutyl 5.24 6.02
Chlorobutyl/natural blend 2.57 2.57
Bromobutyl 2.03 2.02
Chlorinated Polyethylene 40.86 38.19
Carbonaceous Materials
Carbon and graphite resist HF and AHF. Silicon and furan-based cements, sealants, and
impregnants have been attacked in some services. Impervious graphite impregnated with PTFE
fluoropolymer has provided satisfactory service to at least 80% HF at 150C (302F).
Impervious graphite impregnated with phenolics has provided satisfactory service to 110C
(230F) for 48% HF and to 85C (185F) for 60% HF. Impervious graphite impregnated with
furan has cracked in HF services 4.
Phenolic cements have been used successfully at higher temperatures than sulfur
cements for carbon brick. Carbon brick linings (ash content below 1%) with phenolic mortar and
fluorinated plastic membranes have been applied in carbon steel vessels for high-temperature
AHF-water scrubbers.
Flexible graphite has been used for gaskets and packing materials in HF and AHF
services. Carbon-carbon composites have excellent resistance to HF and AHF, however their
use is limited to internal components since they are permeable.
Barnes37exposed two grades of graphite (with <5 PPM and 700-PPM total ash) to Ar-5%
AHF, for 15 hours at 1000C. Both samples showed no weight change and appeared
unchanged.
Inorganic Materials
HF. Alumina (>99.7% purity), sapphire, and silicon carbide (alpha grade with no free
silicon) are used in HF.
Mikeska and Bennison 4s exposed commercially available polycrystalline alumina and

sapphire (single crystal alumina) to 38% (20M) HF at 90C for two weeks. All of the
polycrystalline alumina had high corrosion rates and most samples were consumed during the
exposure. Sapphire had a 7 l~m/y (0.27 mpy) corrosion rate. Polycrystalline alumina examined
after exposure had attack of silicate-based, glassy grain boundary films. Residues examined
after tests were found to be alumina grains. Sapphire had a low dissolution rate because as a
single crystal it has no corrosion-susceptible grain boundaries. Special samples made with high
purity alumina and doped with 500 PPM MgO, exposed in the same environment, had corrosion
rates of less than 25 ~m/y (1 mpy) compared to samples without MgO that had 0.25 to 7.6 mm/y
(10 to 300 mpy) corrosion rates.
Mikeska46, et al., exposed various commercially available ceramic oxides, carbides,

nitrides and borides to 38% (20M) HF at 90C for two weeks. The polycrystalline oxide ceramics
like AI203, mio2, ZrO2 were severely attacked. But, polycrystalline MgO corroded at only 10 I~m/y
(0.4 mpy). The ceramics with the best resistance were sapphire and pure polycrystalline
carbides like SiC, B,C, WC, and TiC. Notably the pure SiC and alpha silicon carbides with no
free silica or silicon ranged from no attack, up to 5 ~m/y (0.2 mpy). However, commercial
reaction-bonded and sintered SiC had corrosion rates of 0.18 to 3.8 mm/y (7 to 150 mpy).
Zirconium and aluminum fluoride glasses had relatively high rates of attack but less than that of
many polycrystalline ceramic oxides. The least resistant of tested materials were SIN4, AIN, BN,
and TiB which all disintegrated during testing. Virtually all commercially available polycrystalline
oxide ceramics and non-oxide ceramics were severely attacked. Sapphire and pure
polycrystalline carbides had the lowest corrosion rates.
AHF. Alumina (>99.7% purity), sapphire (single crystal alumina), ruby, and silicon
carbide (alpha grade with no free silicon) have resistance to and are used in AHF.
Barnes 37exposed sapphire, polycrystalline alumina, sintered SiC, SiC and Si3N4at
1000C in AR-5% AHF; Table 22 contains his data. All of these materials had poor resistance
under these conditions.
TABLE 22
Changes and Observations from Ceramic Materials Exposed for 15 Hours at
1000C in Ar-5% AHF37.
Material Type Weight Corrosion Rate Comments

Change mm/y (mpy)
(mg/cm 2)
AI203 Polycrystalline -2.4 3.6 (141) General Wastage
AI203 Sapphire -0.9 1.3 (52) Frosted Appearance
SiC Sintered Silicon -5.7 10.4 (411) General Wastage
Carbide
SSiC Bulk CVD -6.4 11.6 (458) General Wastage
Silicon Carbide
Si3N4 Silicon nitride -2.2 3.9 (155) General Wastage
Unsuitable Materials
Copper Alloys
HF. Copper-zinc and copper-tin alloys are not resistant to HF with velocity, aeration or
oxidizing contaminants. Copper, yellow brass, admiralty brass, silicon bronze have high
corrosion rates in HF with velocity 13. Although red brass and admiralty brass have low to
moderate corrosion in HF they have failed in wet-dry conditions, and are subject to high
corrosion in velocity conditions.
AHF. Copper-zinc and copper-tin alloys are not used for AHF services since they are
subject to embrittlement or are sensitive to velocity.
Cast Irons
Gray cast irons are brittle and should not be used in HF or AHF service because of the
hazardous nature of these services. These cast irons may have sand inclusions, porosity, and
silicon rich areas that have high general corrosion as well as local attack in HF or AHF. Rapid
cracking may occur along graphite flakes. Nodular cast irons have enhanced ductility compared
to gray cast irons, but they have higher general corrosion than carbon steel.
Carbon Steels
In HF and AHF pressure vessel steels with an ultimate tensile strength over 545 MPa
(79,000 psi) may develop high hardness weld heat affected zones that are susceptible to
hydrogen assisted stress cracking. Heat-treated alloy steels with hardness HRc > 22 or
ultimate tensile strength over 793 MPa (115,000 psi) are susceptible to hydrogen assisted
stress corrosion cracking.
Welds in steel plates made with higher tensile strength steel E80XX electrodes; alloy
electrodes with 3% nickel ENi2 (K21010) and ENi3 (K31310); 309 filler E309/ER309 ($30980);
or E320/ER320LR (AWS ENiCrMo-3) filler without proper post weld heat treatment have
cracked in AHF service. Welds made from these and similar weld consumables produce high
hardness weld HAZ and mixed alloy regions that promote hydrogen charging, which leads to
cracking. Welding dissimilar metals may create a galvanic couple in HF that accelerates
corrosion of the carbon steel.
Steels made with fine grain practice, with sulfur over 0.01% (without inclusion-shape
control and vacuum degassing) are prone to hydrogen blistering. High phosphorus and free-
machining steels are notch sensitive in HF and AHF.
Stainless Steels
HF. Austenitic, martensitic and ferritic grades are not used for HF service because they
exhibit high corrosion rates and can crack. Extensive cracking has been reported of $41000
elbows that were mistakenly installed in HF alkylation service 47.
AHF. Martensitic and ferritic stainless steels are not used in AHF due to the potential for
hydrogen cracking.
Reactive Metals
R04210, R05400, titanium (R50250), and zirconium (R60001) have high corrosion rates
and may experience hydrogen embrittlement in HF or AHF. Hydriding in HF and AHF services
has occurred even at part-per-million levels. Niobium carbides and titanium carbides have been
attacked in HF at ambient temperatures and AHF at higher temperatures. HF and AHF have
preferentially attacked various alloy castings and weld deposits containing these elements.
Inorganic Materials
HF and AHF attack asbestos, glass, porcelain, stoneware, most refractories, quartz,
silicon, and silica-based materials. Polycrystalline oxide ceramics like AI203, TiO2, ZrO2 and
nitrides like SIN4, AIN, BN, and TiB disintegrate in 38% HF at 90C.
ACKNOWLEDGMENTS
The author thanks and acknowledges the assistance and contributions of J. M.

Chandler, T.W. Cowley, R.L. Freed, J.P. Frenck, M.M. James, J.M. Jarosz, C.E. Mighton, K.R.
Mikeska, B.J. Saldanha, F. Schramm, L.D. Schwarz, C.C. Seastrom, A.C. Sievert and S.P.
Springer.
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Handling, and Storing Hydrofluoric Acid. (Houston, TX: NACE International).
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Edition) Hydrogen Fluoride Industry Practices Institute (HFIPI), 3050 K Street, NW,
Washington, DC 20007.
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HFIPI, 3050 K Street, NW, Washington, DC 20007.
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Industries Corrosion, (NACE, 1975) p229.
5. DuPont, Private Communication.
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Range of Hydrofluoric Acid Concentrations at 125F, '' CORROSION/92, paper no. 452
(Houston, TX: NACE International, 1992).
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of Low-Alloyed Chromium Steels in Hydrofluoric Acid Solutions," Materials Performance
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Alkylation Service," Materials Performance 32, 11 (1993): pp. 50.
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Corrosion/98, San Diego, CA, 1998.
10. A. Gysbers, "HF Alkylation Unit Experiences with Localized Corrosion", Presentation to
NACE Committee T5A-36, CORROSION/98, San Diego, CA, 1998.
11. O. Forsen, J.Aromaa, M.Somervuori. "Materials Performance in HF-Alkylation Units",

Corrosion/95, Paper 342 (Houston, TX: NACE International, 1995).
12. G.Chirinos, S.Turgoose and R.C.Newman, "Effects Of Residual Elements On The

Corrosion Resistance Of Steels In HF", Corrosion/97, Paper 513 (Houston, TX: NACE
International, 1997).
13. M.E.Holmberg, F.A.Prange. Industrial and Engineering Chemistry, Vol.37, No.11. November
1945, pp. 1030-1033.
14. R.L. Schuyler, "Hydrogen Blistering of Steel in Anhydrous Hydrofluoric Acid," Materials
Performance 18, 8 (1979): p. 9.
15. D.Warren, "Hydrogen Effects on Steel", Materials Performance, Vo1.26, No. 1,(1987)
pp. 38-48.
16. C.C. Seastrom, "Minimizing Hydrogen Damage in Carbon Steel Vessels Exposed to
Anhydrous Hydrogen fluoride." 1990 Mechanical Working and Steel Processing
Proceedings, P507-514, Iron and Steel Society
17. R.D. Merrick, "An Overview of Hydrogen Damage to Steels at Low Temperatures",
Materials Performance, Vol.2, February (1989), pp. 53-54.
18. G. A. Olah, G.K.S. Prakash, J. Sommer, "Superacids", Chapter 1, John Wiley & Sons:
New York, 1985.
19. T.F. Degnan, "Materials of Construction for Hydrofluoric Acid and Hydrogen Fluoride", p
285, Process Industry Corrosion, The Theory and Practice, (Houston, TX: NACE 1986).
20. S.J.Pawel, "Corrosion of High-Alloy Materials In Aqueous Hydrofluoric Acid

Environments, Corrosion, Vol. 50, No.12, December 1994, p.963-971.
21. M.Takemoto, T.Shonohara, M.Shirai and T.Shinogays, "Case Study of External Stress
Corrosion Cracking (ESCC) of Austenitic Stainless Steels, and A Simulation Test,"
22. I.G.Cragnolino, D.D.MacDonald, Corrosion, 38(1982) p.406.
23. T.Zucchi, G.Trabanelli, G.Demetzis, "The Intergranular Stress Corrosion Cracking of a

Sensitized AISI 304 in NaF and NaCI Solutions," Corrosion Science 28,1 (1988) p.69.
24. J.R. Crum, G.D. Smith, M.J.McNallan and S.Hirnyl "Characterization of Corrosion
Resistant Materials in Low and High Temperature HF Environments," Corrosion/99,
Paper 382 (Houston, TX: NACE International, 1999).
25. B.E.Paige, "Evaluation of Welds and Stresses in High Nickel Alloys in Fluoride
Solutions", Corrosion/77, Paper 80, (Houston,TX:NACE, 1977)
26. B.C. Norby, "Improved Corrosion Resistance on UNS NO6030 in Nitric/Hydrofluoric

Acid solutions by Welding with a Dissimilar Weld Wire", Corrosion/92, Paper 107
(Houston, TX: NACE, 1992).
27. G. Schmitt, S. Losaker, "Performance of CRA In Hydrofluoric Acid", EUROCORR'97

Proceedings Volume 1, European Federation of Corrosion, Trondheim, Norway, pp.
677-682.
28. N. Shridhar,"The Effect of Velocity on Corrosion In H2SO4 + HF Mixtures",
29. Corrosion Resistance of Nickel-Containing Alloys in Hydrofluoric Acid, Hydrogen

Fluoride and Fluorine, INCO Publication CEB-5, 1968., 34 pages.
30. R. B. Rebak, "Corrosion Behavior of Nickel and Iron Base Alloys in HF", presentation to
NACE International Committee T5A-36 in Corrosion/98, March 26, 1998.
31. T. C. Spence, "Cast Ni-Cu Alloys in HF", presentation to NACE International Committee
T5A-36 in Corrosion/97, March 11,1997.
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#4, April (1989) pp. 57-66.
33. W.R. Myers and W.B. Delong, "Fluorine Corrosion", Chemical Engineering Progress,
1948 (Vol.44, No.5), pp.359-362.
34. C.J. Tyreman and P. Elliott, "High Temperature Metallic Corrosion in HF-Containing
Gases", Corrosion/88, Paper 135 (Houston, TX: NACE International, 1988).
35. G. Marsh, and P. Elliott, High Temperature Corrosion in Energy Systems, M.F.Rothman
(editor), The Metallurgical Society of AIME, Warrendale, PA (1985), pp. 467-481.
36. George Y. Lai, High-Temperature Corrosion of Engineering Alloys, ASM International,

1990, pp.111-112.
37. J.J. Barnes, "Materials Behavior In High-Temperature HF-Containing Environments",

38. M. Schussler, "Metal Materials for Handling Aqueous Hydrofluoric Acid", Ind.
Eng.Chem., 47,135 (1955).
39. H.R.Copson and C.F.Cheng, "Stress Corrosion Cracking of Monel in Hydrofluoric Acid",
Corrosion, Vol. 12, No.12, December 1956, p.647-653.
40. L. Graf and W. Wittich, Werkstoffe Und Korrosion, Vo1.17, p.385, 1966.
41. B. Saldanha, "Denickelification of Cu-Ni Alloys", presentation to NACE International

Committee T5A-36 in Corrosion/2000, March 27, 2000.
42 Gaylord Smith and Edward Zysk "Corrosion of the Noble Metals," in ASM Handbook,
Volume 13: Corrosion, 9th ed. (Materials Park, OH: ASM International, 1989) p. 793-807.
43 J.C. Stonehill, presentation to NACE International Committee T5A-36 in Corrosion/95,
March 28, 1995.
44 L. DeLashmit, "Rubber Linings for Hydrofluoric Acid" presentation to NACE International

Committee T5A-36 in Corrosion/2000, March 27, 2000.
45 K.R. Mikeska and S.J. Bennison, "Corrosion of Alumina in Aqueous Hydrofluoric Acid,
Journal of the American Ceramic Society, 82(12) pp. 3561-3566, (1999).
46 K.R. Mikeska, S.J. Bennison, and S.L. Grise, "Corrosion of Ceramics in Aqueous
Hydrofluoric Acid", Journal of the American Ceramic Society, 83(5) pp. 1160-1164,
(2OO0).
47 B.E.Hopkinson and F.Hernandez O., "Corrosion Problems In HF Alkylation Units",

"Corrosion/89, Paper 260 (Houston, TX: NACE International, 1989).
APPENDIX A: METALS AND ALLOYS MENTIONED IN TEXT
Table A1 lists the metals and alloys mentioned the text with their UNS designations.
TABLE A1:
UNS Numbers of Metals and Alloys Mentioned in the Text (A)
Name/ACI (B) Number UNS Name/ACI Number UNS

Number Number
90-10 copper nickel C70600 Alloy 400 N04400
70-30 copper nickel C71500 Alloy 500 N05500
ERCuNi C71580 Alloy G N06007
AISI 1020 Steel G10200 Alloy 22, Alloy 622 N06022
ASTM A193 B7 and B7M G41400 Alloy 602CA N06025
CF-3, Cast 304L SS, ASTM A 744 J92500 Alloy G-30, ERNiCrMo11 N06030
CF-8, Cast 304 SS, ASTM A 744 J92600 Alloy 59 N06059
CF-3M, Cast 316L SS, ASTM A J92800 Alloy 62 Filler N06062
744
CF-8M, Cast 316 SS, ASTM A J92900 Alloy 82 Filler N06082
744
Steel ASTM A516 Grade 55 K01800 Alloy 2000 N06200
Steel ASTM A516 Grade 70 K02700 Alloy 625, ERNiCrMo3 N06625
Steel ASTM A285 Grade C K02801 Alloy 686 N06686
Steel pipe - ASTM A106 Grade B K03006 Alloy 690 N06690
ASTM A588 Grade A K12040 Alloy H-9M N06920
ASTM A710 Grade A K20747 Alloy G-3 N06985
ENi2 K21010 CN-7M, Cast Alloy 20, ASTM N08007
A 744
ASTM A333 Grade 9 K22035 Alloy 20 N08020
ASTM A203 Grade E K32018 ER320LR N08022
ENi3 K31310 AL 6XN N08367
Alloy 200 N02200 Alloy 800 N08800
Alloy 201 N02201 Alloy 825 N08825
Alloy 227 N02270 Alloy 25-6M0 N08926
ERNiCu7 N04060 Alloy B N10001
Alloy C N 10002
Alloy C-276 N10276 Type 301SS $30100
Alloy B-2 N10665 Type 302 SS $30200
Alloy B-3 N10675 Type 303 SS $30300
M-30C, Cast Alloy 400, ASTM N24130 Type 304 SS $30400
A494
M-35-1, Cast Alloy 400,ASTM N24135 Type 304L SS $30403
A494
CX-2MW, Cast Alloy 22, N26022 Type 309 SS $30900
ASTM A494
CW-2M, Cast Alloy C4, ASTM N26455 Type 309Cb SS $30940
A494
N7M, Cast Ni-Mo alloy, ASTM A N30007 ER309 $30980
494
CW6M, Cast Ni-Mo-Cr alloy, N30107 Type 310 SS $31000
ASTM 494
Gold P00020 Type 316 SS $31600
Palladium P03995 Type 316L SS $31603
Platinum P04995 Alloy 255 $32550
Rhodium P05981 Alloy 654 SMO $32654
Iridium P06100 Type 347 SS $34700
Silver P07015 Type 410 SS $41000
Molybdenum R03600 Type 430 SS $43000
Niobium R04210 ECuNi W60715
Tantalum R05400 ENiCu W84190
Tungsten R07005 Alloy 132 Electrode W86132
Chromium R20994 Alloy 182 Electrode W86182
Alloy 188 R30188 E320LR W88022
Titanium R50250
Zirconium R60001
(A) Casting designations are per the Alloy Casting Institute (ACI); cast alloy specifications are
~BerASTM A494 and ASTM A744.
The Alloy Casting Institute (ACI) is no longer in existence, however, ASTM (see
Appendices in ASTM A 703 and A 781 has adapted the ACI casting designation system).

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MATERIALS FOR HYDROFLUORIC ACID SERVICE

Anhydrous hydrogen fluoride (defined as <400-PPM water by Hydrogen Fluoride

Anhydrous hydrogen fluoride and HF are extremely hazardous as liquid or vapors.

FIGURE 1: Metals and Alloys for Hydrofluoric Acid 1

Carbon and Alloy Steels

Wt.% Hydrofluoric Acid in Water

FIGURE 2: HF Corrosion Data for Carbon Steel at 21 to 38C (70 to 100F) 1

Carbon steel is subject to erosion-corrosion in liquid AHF with velocity, turbulence, or

60 100 150 t 88 200 300 400 500

Galvanic Effects. Blanchard 6 and Mack reported galvanically accelerated corrosion

" TM 2 WK LAB 1.3 Y, PLANT 1.3 Y, PLANT 6 MO PLANT

Hydrogen CrackinG. Another effect of atomic hydrogen generated by HF and AHF

Figure 4. Intergranular corrosion of carbon Figure 5. Intergranular stress corrosion

COMPOSITION AVERAGE CORROSION RATE OBSERVATIONS

AUSTENITIC STAINLESS STEELS

Austenitic Stainless Steel Corrosion

NaF. Cragnolino and MacDonald 22 developed a potential-pH equilibrium diagram for

I Figure 6: Influence of potential and pH on intergranular stress corrosion

NaF Concentration, 25C (77F) 50C(122F) 80C(176F)

Nickel Rich Austenitic Stainless Steel Corrosion

120 ~ . . . . . . . . . . . . . . . . . . . . ................ 248

I '~- - 40 ................ ~....... ! ............. ~ ............. ~ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104 I"~

Wt% Hydrofluoric Acid

Figure 8: Isocorrosion curve for N08825 in HF 24. Corrosion rates in mm/y,

120 : : ~ ~ - ~ i. . . . ~ AtmDspheric : 248

P 80 , ............. !..... 176

o --i ................... T. . . . . . . . . . . . . . . . . . . ~. . . . . . . . . . . . . . . . . . . i................ T ................... i ....................................... ~. . . . . . . . . . . . . . . . . . . ~. . . . . . . . . . . . . . . . . . . . r ................... i 32

I Figure 9: Isocorrosion curve for N06030 in HF 24. Corrosion rates in

1 /--'~- 125 oc ........................................

0 -,-- , / o-o I............

Alloy 2%HCI, 10%HF, 10% HF + 2% HCI,

Figure 12: Effect of alloy content on switching from corrosion to

2HF + CI2 + AsF3 ~ AsFs + 2HCI (2)

2CI2 + AsF3 ~ [AsCI4]+[AsF6] (3)

2HF + AsFs ~ H2F+AsF6" (4)

NICKEL AND NICKEL ALLOYS

Nickel and Nickel Alloy Corrosion

Alloy HF 24C 50C 76C

10.0% O.06 0.35 0.21 2.35 0.34 2.57

Alloy HF 24C 50C 76C

Figure 14 29 is an isocorrosion chart for UNS N04400 indicating corrosion rates in HF

Wt% Hydrofluoric Acid

~g~ Air-free Aerated i

Figure 15: Corrosion rates of UNS N10276 and N06200 in HF at

Niobium in Nickel and Nickel Alloy Welds and Castings

Nickel and Nickel Alloys in High Temperature HF and AHF

Metal 500C (932F) 600C (1112F

Metal 550C 600C 650C 700C 750C

N04400 0.61 (24) 1.52 (60) 3.96 (156) 5.18 (204)

Metal Corrosion Rate Comments

Corrosion Rate mm/y (mpy) SCC - yes/no

Material Weight Corrosion Rate Appearance Comments

Alloy Maximum depth of Appearance Comments

N 10675 0.020 (0.8) Surface Scale

Nickel and Nickel Alloys in HF Mixed with Other Acids

Alloy 10% HF with 2% HCI 53% HF with 8.3% HCI

Nickel and Nickel Alloys in AHF with Impurities

NaF*HF. Sodium acid fluoride (NaF*HF) may be formed by reaction of sodium

Material Corrosion Rate

N02200 1.02 (40)

AHF with no AHF with 10.8 AHF with 20 AHF with 22

Nickel and Nickel Alloy Cracking

NaFHF. Sodium acid fluoride (NaFHF) may be formed by reaction of sodium