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Hydrogen Cracking in Specialty Steels: Knolls Atomic Power Laboratory Schenectady, New York
Hydrogen Cracking in Specialty Steels: Knolls Atomic Power Laboratory Schenectady, New York
Hydrogen Cracking in Specialty Steels: Knolls Atomic Power Laboratory Schenectady, New York
Stephen F. Floreen
Knolls Atomic Power Laboratory
Schenectady, New York
INTRODUCTION
Specialty steels could also be called ultra-high-strength
steels. For present purposes we define these materials as
steels that can be heat treated to yield strengths greater than
1000 MPa. The emphasis on heat treating is a practical one,
since for most service applications only heat treating is used
to produce high-strength parts or structures. While specifying
strengths over 1000 MPa is arbitrary, it helps focus on certain
types of steel and strength levels where hydrogen embrittlement
is always a problem.
Table I gives the nominal compositions of some of the
commercial steels of interest. Three different varieties of
steel are presented and it helps future discussion to briefly
describe their hardening behavior. The medium-carbon low-alloy
steels are generally older alloys characterized by carbon
contents of about 0.3-0.5 percent and by relatively low alloy
contents. Because these steels have limited hardenability they
commonly are solution treated at temperatures of about 800-
900°C, and then quenched to form a hard, brittle martensite.
The martensitic structure then is tempered for several hours at
temperatures ranging from 200 to 600°C, depending upon the
desired strength level. Tempering relieves transformation
stresses, eliminates retained austenite and produces a disper-
sion of epsilon carbide particles that are the major source of
strengthening. With higher tempering temperatures, the carbides
coarsen and eventually are replaced by cementite. Alloying
elements alter the tempering behavior, such as in 30OM, where a
Si addition to the chemistry of a 4340 steel is used to retard
cementite formation and to allow higher tempering temperatures.
The medium-carbon low-alloy steels are fairly inexpensive,
but for more critical applications they are often deficient in
fabricability, ductility, toughness and weldability. To miti-
gate these shortcomings, various grades of air-hardening steels
were developed. These alloys have lower carbon contents and
higher concentrations of alloying elements. The higher alloy
content improves the hardenability so that quenching is not
required. The higher Cr and Mo levels also promote the forma-
tion of alloy carbides during tempering and provide secondary
TABLE I
NOMINAL COMPOSITIONS OF SPECIALTY STEELS
Alloy
Designation C Mn Si Cr NJ. Mo Other
Medium Carbon Low Alloy Steels
4130 0.30 0.5 0.15 1.0 - 0.2
4340 0.40 0.7 0.25 0.8 1.8 0.25
30OM 0.45 0.8 1.60 0.8 1.8 0.35 .07V
D-6a 0.45 0.7 0.25 1.0 0.5 1.0 .07V
Air Hardening Steels
H-Il 0.40 0.3 0.9 5.0 - 1.3 0.5V
HP 9-4-20 0.20 0.3 0.1 0.75 9.0 1.0 O.IV,4.5Co
HP 9-4-30 0.30 0.3 0.1 1.0 7.5 1.0 O.IV,4.5Co
AF-1410 0.14 0.8 - 2.0 10.0 1.0 14.0Co
Maraging Steels
18 Ni (200) .03 max - - - 18,0 3.3 8.5Co,0.2Ti
18 Ni (250) .03 max - - - 18.0 5.0 8.5Co,O.4Ti
18 Ni (300) .03 max - - - 18.0 5.0 9.OCo,O.7Ti
confidence intervals
Stage Il Crack Growth Rate (m/s)
Crack Growth Rate (m/s)
Figure 30-IA: (Left) Crack growth rate data for 4340 steel in
dry H2 at 133 kPa (Ref. 21).
Figure 30-1B: (Right) Stage-II data from Figure IA plotted
versus reciprocal temperature (Ref. 21).
Earlier studies demonstrated that crack growth could take
place in hydrogen gas at atmospheric or sub-atmospheric pressures
(11,12). These results were of considerable interest because
they evidently refuted the pressure theory of hydrogen embrittle-
ment, since high pressure-deposits of molecular hydrogen gas
inside the steel should not exist in thermodynamic equilibrium
with low-pressure external hydrogen. Numerous subsequent experi-
ments confirmed that crack growth in high-strength steels can
occur at quite low hydrogen gas pressures, particularly if care
is taken to remove impurities from the gas system that interfere
with hydrogen absorption. Most of the current interpretations
of hydrogen cracking in ultra-high-strength steels usually are
based on Troiano-type mechanisms of localized weakening of
atomic bonds by hydrogen. Cracking due to internal hydrogen gas
sometimes can be seen in blisters, fish-eyes, etc., where
extremely high local concentrations of hydrogen can be achieved,
but this mechanism does not appear to be a common means of
hydrogen embrittlement in these steels.
Gas composition markedly affects the cracking behavior.
Nelson, et al. (13) showed that atomic hydrogen produced crack
growth rates several orders of magnitude faster than molecular
hydrogen. Various gaseous hydrogen compounds such as CH4, HCl,
HBr, H2S, HF and H 2 O also can cause crack growth, but not NH3
(14-19). Of these various compounds the most potent is H2S,
which can produce crack growth rates in excess of one mm/s (20).
Minor additions of a second gaseous species can markedly
accelerate or inhibit crack growth in hydrogen. Small amounts
of oxygen, in particular, halt crack growth in hydrogen (11), as
can SO2, CO, and NH3 (17). Conversely, additions of H2S
considerably reduce the threshold stress intensity and increased
the crack growth rate by 1000 fold (15). These potent effects
have been attributed to the additives either inhibiting or pro-
moting the supply of hydrogen atoms at the metal surface.
Oxygen can react rapidly and preferentially with steel to form
an oxide layer that inhibits the uptake of hydrogen (17-21).
The accelerating effect of H 2 S appears to be related to the
formation of a surface compound of sulfur that catalyzes the
absorption of hydrogen (17,20).
Attempts have been made to relate crack growth rates in
hydrogen-containing gases to the thermodynamic activities of the
hydrogen. However these predictions do not work well in gas
mixtures where strong inhibiting or catalytic effects are
present, such as from oxygen or sulfur, because of the difficul-
ties in estimating hydrogen activities in these circumstances.
In water vapor environments the crack growth rates in H-Il
steel increased with relative humidity values up to about 40
percent, but at higher pressures the results were identical to
those in liquid water (22). The saturation behavior at higher
humidity was attributed to capillary condensation of water vapor
at the tip of the crack.
Wei and co-workers have conducted a series of experiments
to identify the chemical reactions controlling the crack growth
rates in gaseous environments (20,21,23-26). Figure 30-1B shows
Stage-II (rate independent of K) data from Figure 30-1A plotted
versus reciprocal temperature. At lower temperatures the data
follow an Arrhenius- type relationship with an apparent activa-
tion energy of 14.7 kJ/mole. Similar activation energies have
been found with other steels in dry hydrogen. In water vapor
or in water the values are about 33-38 kJ/mole. For H2S
however, the activation energy was only 4.6 kJ/mole. Surface
chemistry measurements were also made to study the kinetics of
the surface reactions between the steels and the gases. The
results of these studies suggested that the surface reaction
between the hydrogen gas and the steel is the rate-limiting step
in the crack growth kinetics in pure hydrogen. In water vapor
the surface reaction associated with oxidation of the steel and
the associated liberation of hydrogen is rate controlling, with
the resulting surface oxide inhibiting the reaction. In H2S, on
the other hand, the surface reaction is extremely rapid and the
rate-limiting step is the transport of H2S gas to the crack tip.
K. ksi >/Jnch
Figure 30-2: Threshold stress intensities for crack growth of
4340 steel versus gas pressure in hydrogen and deuterium (Ref.
27).
*Heat A
Critical Stress Intensity (MNm'2 \/m)
*Heat B
=Heat C
=Heat D
^K000(Cu)
OK
W«CHAJ«)
HYDROGEN LEVEL IS ABOUT I PPM
APPROXIMATE STRENGTH WHERE
K
Regime A Regime B C
final
NON-CONTINUUM CONTINUUM MECHANISM failure
MECHANISMS (striation growth)
large influence of: little influence of.
i microstructure i microstructure
ii mean stress ii mean stress
iii dilute environment
iv thickness
da/dN , mm/cycle
Regime C
'STATIC MODE* MECHANISMS
(cleavage, inttrgranular and
fibrous)
targt influence of:
i microstructure
ii mean stress
iii thickness
little influence of:
iv environment
threshold AK 0
log AK
METALLURGICAL EFFECTS
A great many studies have been made of the effects of
composition and microstructure on the HE behavior of steels. In
all steels the dominant factor is the yield strength. At lower
yield strengths around 1000 MPa, composition and microstructure
can be fairly important, and better cracking resistance has been
achieved through control of these variables. At higher
strengths however, the crack growth resistance falls off
sharply, and at yield strengths on the order of 1500 MPa all
steels possess comparably poor resistance to hydrogen cracking.
HEAT F
°f = 0O - Aa imp - Aa H (2)
Microstructure can also pay a role, but the effects are not
always clear cut. It is agreed that twinned martensite is much
more susceptible to cracking than lath martensite (4,67).
Tempered martensite or bainite usually are considered the best
microstructures, and untempered martensite the worst (67).
Judging from the rather comparable KJSQQ values of the carbide-
hardened steels and the maraging steels, it would seem that
there is little effect of carbides versus intermetallic com-
pounds as precipitate particles. Grain size is difficult to
categorize, since different studies have found that finer grain
size is beneficial, deleterious, or has no effect. Gerberich
and Wright (68) have reviewed much of the earlier work and con-
cluded that the effects of grain size depend upon the alloy
purity. In high-purity heats increasing the grain size leads to
greater impurity segregation in the grain boundaries and thus is
deleterious. In "dirty" heats the grain boundaries are saturat-
ed with impurities at all grain sizes. Coarser grain sizes then
are beneficial because the micro-fracture zone size is larger
and suitably oriented grains will be able to retard crack growth.
Other microstructural processing effects are even less
certain. Ausforming has been examined several times with
mixed results. Various attempts also have been made to improve
the hydrogen resistance by introducing either untransformed
or reverted austenite into the microstructure. Austenite could
be beneficial for several reasons, e.g., slowing hydrogen diffu-
sion, absorbing harmful impurities, relaxing local stresses,
etc., and some studies have indicated that austenite improves
the stress corrosion resistance. However, the results have been
difficult to reproduce. In maraging steels, for example, heat
treatments intended to produce reverted austenite gave widely
different results in different heats of the same alloy because
minor variations in processing history, segregation, etc.,
drastically altered the austenite morphology (65).
More generally, it should be remarked that the stress
corrosion data for ultra-high-strength steels often show
considerable scatter. Part of this scatter is no doubt due to
variations in composition and process history. Scatter of this
kind may depend upon when the steel was made, since newer pro-
cessing and inspection techniques and better understanding of
the metallurgical effects should at least tend toward eliminat-
ing the production of bad heats. There is also some sense of
progress at lower-strength levels in that new steels, such as
AF 1410, may provide higher KJ^QQ values. At yield strengths of
about 1500 MPa however, no visible improvement in KJCJQQ has been
evident in many years.
Is it possible, assuming optimum control of composition,
processing steps, etc., to achieve significant improvements in
KJSQQ at these very high strength levels? One new way to
examine this question is through the use of trap theory (69-71).
Traps in steels were first noticed when permeability experiments
showed that significant amounts of hydrogen are retained at
certain sites within the lattice. Since that time various
experiments have shown that hydrogen can be preferentially
absorbed at traps such as grain boundaries, particle boundaries,
dislocations and solute atoms. In particular, the use of
tritium autoradiography has directly demonstrated hydrogen trap-
ping often occurs associated with C or C-containing particles
(72).
A fairly detailed methodology (69,71) been developed to
predict the redistribution of hydrogen atoms during straining.
Some sites, depending upon temperature and strain rate, are
shallow, reversible traps that will surrender hydrogen atoms to
dislocations. Other sites are irreversible traps that retain
hydrogen. Dislocations provide transport of hydrogen atoms
between the traps. Fracture begins when the combination of
local stress and hydrogen content at irreversible traps is
sufficient to nucleate cracking. Several interesting conclu-
sions arise from this analysis. One is the distinction between
exterior and interior sources of hydrogen. When hydrogen is
being supplied from an exterior source during loading it is
desirable to have a very high density of both reversible and
irreversible traps, because more hydrogen will then be drawn
away from crack nucleation sites into innocuous trap sites.
However, when hydrogen is initially within the steel, such as in
precharged material, reversible traps will be bad because more
hydrogen will be made available for cracking. Thus the differ-
ent forms of hydrogen supply require different alloy design.
The best overall microstructure is to have no reversible
traps and a high, uniform density of small, incoherent particles
that will act as irreversible traps (69,71). By providing a
large number of irreversible traps the hydrogen build-up at any
individual trap would thus be minimized.
Such a microstructure also should be effective in homo-
genizing slip, and thus reducing local stress concentrations at
the particles. Indeed, if one were to design a high-strength
steel with an optimum combination of strength and toughness the
desired particle morphology would be essentially the same. Thus
a steel optimized for hydrogen cracking resistance should have
excellent toughness. The reverse is not necessarily true. For
example, a steel could have good fracture toughness but a low
KISCC because of segregation of an impurity to the grain
boundaries. Many investigators have commented that there is
little overall correlation between Kj^ and Kjgg^ data. And yet
the maximum values of Kjgpp often seem to be limited by Kj^.
For steels in the 1500-2000 MPa strength range the data for
tests under freely corroding conditions in aqueous environments
generally show that the maximum Kjs££ values are about half of
Kj£. A relationship of this kind suggest that crack initiation
occurs at the same sites in both types of tests, which may be
plausible for materials with optimum resistance to HE. Regard-
less of the interpretation, the relationship indicates that to
double KJSCC would require doubling the KJQ. This is an
extremely difficult problem that would probably require an
entirely new type of steel. Seen in this light, the magnitude
of the problem of achieving a significantly higher Kjg^ is
apparent.
To date there have apparently not been any practical
attempts to produce a very high-strength steel using the teach-
ings of trap theory. Practical examples of this theory do
exist, however. Hydrogen flakes in plate steels, for example,
are much more numerous in heats with lower sulfur levels, pre-
sumably because the fewer sites for hydrogen occlusion lead to
higher local hydrogen contents in the low sulfur steels (73).
a = oy + 2 a K (3)
a = ay (4)
Aa H = 3 CH (7)
1. Trip Steels
Weldments
Much of what has been said about HE also applies to welds,
but the nature of the welding process causes further problems.
Hydrogen can be easily picked up from various sources during
welding, and precautions must be taken to decrease this absorp-
tion. The thermal history during welding can promote cracking
in the heat-affected zone (HAZ) of the base plate steel and/or
in the weld metal. The weld metal itself is, of course, a cast
structure, with the penalties such microstructures can impose.
Specialized tests such as implant tests (81) or augmented strain
tests (82) have been developed to study hydrogen cracking in
welds, and detailed analyses to predict the simultaneous distri-
butions of stress and hydrogen in weldments are being attempted
(83).
Gooch (84) has summarized the results of extensive stress
corrosion tests of a variety of ultra-high-strength steel welds
in 3% NaCl solutions. Tests of HAZ regions showed steels with
high C contents to be especially susceptible to cracking because
of the high hardnesses in these regions. Post-weld heat treat-
ments that softened the HAZ, particularly when the hardness was
lowered to that of the base plate, considerably improved the
properties. Preheating and post-weld heating also are exten-
sively used to promote hydrogen diffusion out of the weld region.
Cracking in weld metal was influenced somewhat by segrega-
tion during solidification (84) . More important was the micro-
structure. Twinned martensite in particular was found to be
very susceptible to cracking. Once again post-weld heat treat-
ments were helpful because of the tempering of the martensitic
structures. In maraging steels Kenyon, et al. (85) found that
solution annealing and aging after welding gave much better
stress corrosion resistance than just aging.
With suitable post-weld heat treatment it appears possible
to achieve hydrogen cracking resistance in weldments comparable
to base plate properties. With large structures however, such
post-weld heat treatments are not possible. In these cases,
weld properties usually are somewhat inferior to base plate.
Figure 30-8 shows the Kjgcc data for HY-130 weld metal and base
plate versus the cathodic potential. The weld metal values were
consistently about 20 MPa/m lower than the base plate. Maraging
steels at various yield strengths shows a comparable separation
between welds and base plate (85). Both sets of data were for
gas tungsten arc welds, and other welding processes can further
degrade weld properties. Welding processes that produce small
beads give better properties because of the finer-grained struc-
tures produced and because of the greater reheating of previous
deposits by the next weld bead (86). Weld metal chemistry as
such is less important as long as a fine-grained, tempered
martensite structure can be achieved.
DESIGN CONSIDERATIONS
Clearly, successful use of ultra-high-strength steels
require recognition of the potential problems of HE. It also
should be recognized that despite these limitations these steels
have been used successfully in a variety of applications.
Perhaps the best example of use in a critical application is the
employment in landing gears of 30OM steel tempered to tensile
strengths of about 1800 MPa. Such usage clearly requires care-
ful alloy selection, specification, and inspection both before
and during service. Attention must also be paid to the design
to reduce stress concentrations, and to machining and heat-
treating procedures to avoid introducing harmful residual
stresses.
Coatings of all sorts have been used on these steels. Most
coatings act as diffusion barriers to prevent or delay hydrogen
entry into the steel. More recently it has been shown that even
partial coatings may be extremely effective if they retard the
dissociation of hydrogen molecules to form adsorbed hydrogen
atoms at the steel surface (87,88). Thermal treatments that
alter the surface oxide can also have a considerable effect on
hydrogen permeability (89).
BASE METAL
WELD METAL
E VS A^AgCI (VOLTS)
CONCLUDING REMARKS
Hydrogen embrittlement of ultra high-strength steels con-
tinues to be an active area of research, and much has been
accomplished in recent years in achieving a clearer.understand-
ing of this problem. We now have a better picture of hydrogen
entry and transport within the steel, and the roles of trapping
and impurity segregation are becoming clear. The details
surrounding crack nucleation are less certain. Hopefully,
future work will better define the interactions of alloy chemis-
try, micr9Structure and stress state on the initiation of hydro-
gen cracking.
In the practical sense, less has been accomplished. At
lower strengths, of about 1000 MPa, composition and microstruc-
ture are important and some general ground rules have been
established that have helped to produce better properties. At
higher yield strengths it appears that strength itself is the
overwhelming factor that dominates the metallurgical variables.
There has been no improvement in properties to speak of in many
years, and it is difficult even to suggest how one might try to
achieve any significant advance. Composite-type steels seem to
offer this best possibility for combining high strength and
resistance to hydrogen, but these materials clearly would have
limited usage.
While hydrogen cracking is an ever present danger, these
steels have found widespread usage. The key to their success no
doubt resides in the fact that the dangers are well known, and
that procedures have been developed in the production and employ-
ment of these materials that reduce the hazards to acceptable
levels.
REFHRENCEiS