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Tee 145 / OCTOBER ;1969
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.

BULLETIN

Interpretive Report on Effect of Hydrogen in

Pressure-Vessel Steels
Section 1-Basic and Research Aspects
c. G. Interrante
Section II-Action of Hydrogen' on Steel at High
Temperature and High Pressures
G. A. Nelson
Section III-Practical Aspects of Hydrogen Damage
at Atmospheric Temperature
c. M. Hudgins, Jr.

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Interpretive Report on Effect of Hydrogen
in Pressure-Vessel Steels

Section I-Basic and Research Aspects

c. G. Interrante

Section II-Action of Hydrogen on Steel

at High Temperature and
High Pressures
G. A. Nelson

Section III-Practical Aspects of Hydrogen

Damage at Atmospheric Tempera-
ture
c. M. Hudgins
 CONTENTS
SECTION I-BASIC AND RESEARCH ASPECTS Part F-Research Areas for Future Work ....... 29
Abstract.................................... .. 1 References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 30
Introduction. . . . . . .......................... .. 1
SECTION II-ACTION OF HYDROGEN ON
Part A-Solubility, Diffusivity, Permeation, STEEL AT HIGH TEMPERATURE
and Removal of Hydrogen. . . . . . . . . . . . . . . . . . . . . 2 AND HIGH PRESSURES
True Solubility. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
Saturation Hydrogen Concentration. ... . ................ 2 Summary ..................................... 33
Residual Hydrogen...................................... 4 Surface Decarburization................................. 33
Diffusivity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4 Internal Decarburization. . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . 33
Permeation of Hydrogen................................ 6 Incubation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 35
Removal of Hydrogen....... ............................ 6 Effect of Cold Work. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 37
Part B-Sources of Hydrogen in SteeL...... .. 7 Effect of Hardness ....................................... 38
Steelmaking Practice. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7 Effect of Hydrogen on Stress-Rupture Strength at High
Processing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 Temperatures......................................... 38
Fabricating. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8 Effect of Hydrogen on Stress-Rupture Ductility at High
Service.................................................. 8 Temperatures. . . ...................................... 40
Detection of Hydrogen Damage.......................... 40
Part C-Properties and Behaviors of Steel Preventing High Temperature Hydrogen Damage........ 41
Containing Hydrogen ................ 10 Suggested Areas for Research. . . . . . . . . . . . . . . . . . . . . . . . . . . 42
Effects of Hydrogen on Ductility. . . . . ................... 10
Delayed-Failure Behavior. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 12 References .................................... 42
Incubation Period for Crack Initiation. . . . . . . . . . . . . . . . . .. 13
Crack Propagation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14 SECTION III-PRACTICAL ASPECTS OF HY-
Lower Critical Stress.. . . ................................ 14 DRoGEN DAMAGE AT ATMO-
Factors Affecting Delayed Failure....................... 14
Hyd rogen Concentration. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 14 SPH ERIC TEMPERATU RE
Strength Level. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 15 Summary ..................................... 43
Notch Acuity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 16
Temperature............................................ 16 Introduction .................................. 43
Critical Hyd rogen Concentration. . . . . . . . . . . . . . . . . . . . . . .. 16 Failures... ... ..........................................• 43
Effects of Hydrogen in Weldments...................... 16
Flaking.................................................. 18 Bliste rs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
Part D-Behavior of Steels Exposed to Hydro- Preventive Measures .......................... 44
gen Environments. . . . . . . . . . . . . . . . . .. 18 Material. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
Delayed Failure in Aqueous Media...................... 19 Microstructure.......................................... 46
Effective Hydrogen Pressure. . .......................... 19 Cold Work. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 47
Strength Level. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20 Welding ................................................. 47
Surface and Internal Microfissuring. ................... 20 Quality Control. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Hydrogen Sulfide Environments......................... 21 Heat Treatment.......................................... 47
Material Factors Affecting Behavior. . . . . . . . . . . . . . . . . . . .. 22 Service Problems........................................ 48
External Factors Affecting Behavior. . . . . . . . . . . . . . . . . . . .. 23 Field Repairs. . . . . . ...................................... 48
Gaseous Hydrogen. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 23 Blistering. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
Charging Rate in High-Pressure Hydrogen. ............. 23
Tensile Behavior. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 Separation of Environment and Structural
Fracture Behavior. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25 Material ....................................... 49
Accelerated Crack-Growth Rates. . . . . . . . . . . . . . . . . . . . . . . . 25 Multi-Layer Vessels...................................... 49
Predominance of Surface Effects........................ 25 Metallic Overlays. . . . . . . . . . .. . . .. . . . . . . . . . . . . . . . . . . . . . . . . 50
Factors Affecting Behavior. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26 Non-Metallic Coatings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50
Part E-Mechanisms of Hydrogen Damage .... 26
Effect of Hydrogen on Microcrack Propagation.......... 27 Alteration of Environment .... ; ................ 50
Effect of Hydrogen on Void Growth, Coalescence, and
Crack Growth. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 52
Significance of the Mechanism of Hydrogen Damage to
Pressure-Vessel Behaviors. . . . . . . . . . . . . . . . . . . . . . . . . . .. 28 References .................................... 52

FOREWORD
Many designers, fabricators and users of pres- ments can be classified quantitatively, such as
sure vessels have had only occasional and casual hydrogen at elevated temperature, the hydro-
contact with the problems of hydrogen. Welders genizing potential of corrosive environments can
were the only large group who had first-hand and usually be rated only qualitatively. Further,
frequent contact with the detrimental effects of the design methods commonly used for pressure
hydrogen and knew some of the means of combat- vessels generally ignore many properties of steels
ing them. Currently the increasing use of higher degraded by the effects of hydrogen. The quanti-
strength steels, as well as the more widespread use tative effects of hydrogen on load-carrying ability
of processes and operations capable of charging of the range of steels and geometries are not yet
steel with hydrogen, make detailed information adequately defined. This will be a broad field for
more necessary. This bulletin is published to future research. Nevertheless, the data in this
make available up-to-date summaries on the most bulletin should find ready application to many
important aspects of hydrogen damage, as well as problems in the design and use of pressure vessels
keys to the literature. and piping.
The information compiled is complete enough
to evaluate the need for special attention and is F. PRANGE, Chairman
sufficiently detailed so that many potential prob- PVRC Subcommittee on
lems can be avoided. While some of the environ- Hydrogen Eml)rittlement
 Section I-Basic and Research Aspects
by C. G. Interrante
ABSTRACT. The detrimental effects of a few parts per mil-
lion of hydrogen in steel at temperatures below about 400 F
have long been recognized. Common experience of such
effects include reduction of ductility and reduction of frac-
ture strength. More recently there has been added some
realization of accelerated subcritical crack propagation when
steel is exposed to hydrogen environments. All these ef-
fects are important to the application of pressure vessels for
high-pressure hydrogen, and for vessels exposed to corrosive
media capable of charging steels with hydrogen. From the
materials properties standpoint, damage is much more
apt to occur as the hardness or the strength level incre3ses.
Thus, the problem of damage by hydrogen is particularly
important in the application of higher strength steels, which
have the most favorable strength-to-weight ratio for pres-
sure vessels.
Although the detrimental effects of hydrogen are gener-
ally. recognized, the significance of many of the variables
has not been quantitatively established in terms that allow
direct application to pressure vessel design or use. Only
in a general way are the effect of notches or other stress
raisers known. The primary objectives of research pro-
grams should be to furnish quantitative information on
limiting values for mechanical properties and enviromental
factors so as to insure against low stress failures in environ-
ments capable of supplying hydrogen to the vessel steel.
The interpretation of the literature and experiences ex-
, amined in the report suggests that the predominant mode of
failure in the higher strength steels is a relatively brittle,
quasi-cleavage fracture which results from propagation
of microcracks, and that this mode may extend into the
realm of the lower strength steels also. Research should be
aimed toward establishing limiting conditions with respect
to strength levels, hydrogen content or effective hydrogen
pressure, and temperature for the change over from this
quasi-cleavage fracture behavior to one of ductile rupture.
C. G. Interrante is Sr. Research Metallurgist, Applied Research Labora-
tory, United States Steel Corporation, Monroeville, Pa.
This report was prepared for the Subcommittee on Hydrogen Em-
brittlement of the Pressure Vessel Research Committee.
Basic and Research Aspects
I ntrod uction
Service failures, with their potential serious con-
sequences, have led to extensive research studies
; n the effects of hydrogen in steel. The work of
the last two decades has led to an understanding
of the effects of temperature, of pressure, of crystal
structure, and of compositional and steel pro-
cessing variables on the solubility, on diffusivity
and on permeability of hydrogen in iron and steel.
However, although it is known that the harmful
effects of hydrogen in steel are governed by these
basic behaviors, many gaps still remain and much
more research work will be required to permit the
establishment of quantitative limitations of com-
position, strength level, microstructure, hydrogen
content, and environmental features necessary to
prevent service failures. The high-strength steels
used for the aerospace applications have been
studied most extensively. Particularly needed is
the applicable information for the lower strength
pressure-vessel steels.
In the first and second parts of this section of the
interpretive report on hydrogen in pressure-vessel
steels, background information is presented on
solubility, diffusivity, permeation, removal, and
sources of hydrogen. In the third and fourth
parts, the effects of hydrogen on mechanical
properties are discussed, both for steels containing
hydrogen and for steels exposed to hydrogen en-
vironments. The fifth part reviews the mech-
anisms that are proposed to explain the experimen-
tal observations. Finally, the further research
that is most needed to furnish pertinent data for
pressure-vessel applications is outlined.
1
Part A-Solubility, Diffusivity, Permeation, RELATIVE VOLUMES OF HYDROGEN TO IRON
and Removal of Hydrogen 0
I
0.4
I
O.S
I
1.2
I
1.6
I
2.0
I
2.4
I
ATOMIC PERCENTAGE HYDROGEN
True Solubility 0004 O.OOS 0.012 0.016
I otm~
Only the atomic (or perhaps a screened ionic) L+G
2Soo
form of hydrogen is soluble in iron and its alloys, ...."
£_--------?~
~
8+G

being contained in the interstices of the metallat- 1300 ,," 2400

tice. The solubility is thus the interstitial hydro- ,," r +G

/'
,,"" "-
gen content at equilibrium with a given environ- .... 2000
ui
;,,,/'/ 0:
ment. It varies primarily with temperature, pres- 910·
r------ J ...:::>
sure, and crystal structure. Equilibrium solubil- t--IO atm 1600
""
0:

ity values for hydrogen in iron, as a function of
the temperature and the partial pressure of hydro-
gen in the environment, are shown in the iron-
hydrogen equilibrium diagram depicted in Fig. 1. 33
This diagram is based on measurements of the
absorption boundary for iron in equilibrium with
a partial pressure of hydrogen of 1 atm. at tempera-
tures above 750 0 F; the isobars for the other pres-
sures of from 0.01 to 100 atm. represent calculated
values, based on the assumption that the solubil-
ity is proportional to the square root of the par-
tial pressure of hydrogen in accordance with Sie-
vert's law:
S = K (PH')!;' (1)
Deviations from this behavior have been obser-
ved, * particularly at the lower temperatures, so
that these isobars are not very accurate, but the
significant influence of the pressure of the hydro-
gen environment on the solubility of hydrogen in
iron is evident from this diagram.
This diagram shows that the solubility of hydro-
gen in liquid iron is much higher than in any of the
solid phases, being above 25 parts per million by
weight (1 ppm = 0.0001 %) at a pressure of 1 atm.
It is likewise apparent that the solid solubility in
face-centered gamma iron is much higher than in
body-centered alpha iron, being above 4 ppm at
1 atm. pressure in gamma iron and below 3 ppm at
1 atm. pressure in aJpha iron. The solubility in
alpha iron, furthermore, decreases very rapidly
with decreasing temperature. At temperatures
near room temperature, at which the deleterious
effects of hydrogen in steel are generally most pro-
nounced, the interstitial solubility is very low,
being about 0.002 ppm at 1 atm. pressure. The
difference between the interstitial solubility of
hydrogen in gamma and that of alpha iron presum-
ably reflects primarily the difference in the size of
the interstices of the two crystal structures.
Saturation Hydrogen Concentration
At temperatures below about 750 0 F, and par-
ticularly at temperatures below 400 0 F, measure-
ments of the solubility of hydrogen in iron and
steel indicate solubility values at a given pressure
*In thermodynamic terms the solubility is proportional to the square root
of the fugacity, p;" but the more familiar term, pressure, is used throughout
this report, and the error involved is not large except at very high pressures.'
I
/
"'::Ea.
I
I
/ 1200
"'
l-
/ a + G
/
I
/ SOO
/
I
I
400
I
0.0012 0.003
WEIGHT PERCENTAGE HYDROGEN
I I I I I I I
0 5 10 15 20 25 30
CUBIC CENTIMETERS OF HYDROGEN PER 100 GRAMS OF IRON
Fig. I-Equilibrium diagram, iron·hydrogen system, by C. A.
Zapffe (Ref. 33)
which are generally much higher than those which
would be predicted from an extrapolation of the
results of solubility measurements at tempera-
tures above 750 0 F. This behavior is illustrated
in Fig. 2, based on measurements by Hill and John-
son54 of the solubility of hydrogen at a partial
pressure of hydrogen of 100 atm. in pure iron
specimens. The departure from the extrapolated
values at temperatures below about 750 0 F is
immediately evident. Furthermore, the discrep-
ancy between the extrapolated value, which pre-
sumably represents the interstitial solubility, and
the measured value, increases with decreasing
temperature. This anomalous behavior has gen-
eraJly been explained on the basis that, at the lower
temperatures, the excess hydrogen, beyond that
which is dissolved interstitially, is retained in sites
in the steel which are commonly referred to as
"traps." The solubility value, or saturation con-
centration, as measured, includes both the inter-
stitially dissolved hydrogen and the "trapped"
hydrogen. *
The nature of the traps in which hydrogen is
retained has not, however, been fully established.
Observations of the densities of dislocations and
vacancies in steels have generally indicated that
they are several orders of magnitude smaller than
the number of trapped hydrogen atoms,135 and it
appears that such lattice imperfections could not
accommodate the amount of the "excess" hydrogen
which is trapped. Hydrogen can also be trapped
in voids, microcracks, microfissures, and larger
defects, where it may be present as chemisorbed
* The concept of hydrogen trapping was introduced by Darken and
Smith."

2 Basic and Research Aspects

 TEMPERATURE
00
00
~£:!
888 0
QcnGO ,...
0
0
0
0
.,0 § 8 8 0
0 >- (I cc NTP per gram = 89.9 ppm H I
) II i 1 1 1 1 '"1 1 '"1 '" '"I 1 .1 I
.,,...
00
0 0 g ., 0
0 § 8 0
0
0
0 .,
0 .,
o C
IA-, I I I
'" N

I 1 1
N

1 1 20 o
1.3 _ \ - - - GELLER AND SUN 731 0.3
(EXTRAPOLATED FROM I ATM I
- - HILL AND JOHNSON 54)
1.2 \ EXPERIMENTAL DATA FOR

1.0- \l
\ 100 ATM WITH 95 % CONFIDENCE
liMITS INDICATED ~ 100

-i~~'Oi
0.9
z

\
0.8- ~ 0.2
o
0.7f- '"
c
>-
::t:

.~
O.Gr-

0.5-

~ OA-
0.1

g
..J
0.3r-
\' "'J 2.0 ~
0.2r-

O.Ir- '~, l"'.( l~i~~~bT~AY~:~~EN ~

0.0- \\, "" - 1.0 g
• , 0.9 (TIME OF IMMERSION)1/2, sec l/2
-0.1-
\ \ " 0.8
• , " 0.7 Fig. 3~Effect of cold reduction on rate of hydrogen absorption
-0.2

-0.3
\ ,
. "0.6
'\.
0.5
and on saturation hydrogen concentration of wire stock ('/2 in.
\
\,--EXTRAPOLATED VALUES" diameter green rod) immersed in N H 2S04 at 35 C
• \ FOR INTERSTITIAL "
-0.4r-
\ ' SOLUBILITY " " - OA
-0.5f-

.'\'
\\ '\. 0.3
-0.6f-

-0·71- , \ - 0.2

-0.8"__ ;7;-rr-+r*-,l,;--+-,....."l,~\~'*-+-~:---;l"'""""'i..,---,~
1.0 1.2 1,4 1.6 1.8 2.0 2.2 2A 2.6 2.8 3.0 3.2 3A 3.6 3.8 by extraction at 155 0 C (311 0 F), ranged from 2
TEMPERATURE. lOOO/T"K
cc/l00 g (1.8 ppm) to 30 cc/l00 g (27 ppm). The
Fig. 2-Solubility of hydrogen in alpha iron at 100 atmospheres measured values were 30 cc/l00 g for enameling
of hydrogen gas
steels, 20 cc/l00 g for rimmed steels, 15 cc/l00 g
for silicon steel, 8 cc/l00 g for bessemer steel, 5
cc/l00 g for aluminum-killed steels, and 2 cc/l00
g for AISI Type 430 stainless steel. These wide
variations presumably reflect predominantly dif-
hydrogen, or may recombine to form a molecular ferences in the number of available trapping sites.
compound. Hydrogen may also be absorbed in Cold working usually affects both the saturation
certain nonmetallic phases that are present in steel, concentration of hydrogen and the time required to
such as MnS, TiC, TiN, and ~ carbide. saturate steel with hydrogen. The effect on the
As indicated in Fig. 2, in pure iron at room tem- saturation concentration, as shown in Fig. 3, can
perature, most of the hydrogen is present as trapped be very large, with the saturation concentration
hydrogen. Factors such as cold working or increasing from less than 2 ppm in the absence of
the presence of nonmetallic inclusions, which tend cold work to more than 35 ppm after a cold reduc-
to increase the number of trapping sites, can thus tion of about 76%. Cold-worked steel has a
markedly increase the apparent solubility or the decreased density which results from the formation
saturation concentration of hydrogen. Although of voids at inclusion-steel interfaces during plastic
the effects of environmental factors, such as tem- flow. These voids are presumed to be the princi-
perature and pressure, on the saturation concen- pal source of the trapping sites for hydrogen in
tration will be similar to their effect on the inter- cold-worked steel, and they affect both the satu-
stitial solubility, the combined effects of these ration concentration and the time required for
factors and the factors which change the trapping saturation in a given environment because they
behavior can be very large, and can lead to very must be filled when the steel is saturated with
wide variations in the saturation concentration of hydrogen. Annealing of a cold-worked steel, how-
hydrogen in steels exposed to hydrogenizing envi- ever, reduces the saturation concentration of
roments. The magnitude of such variations can hydrogen without significantly changing the den-
be illustrated by the results of measurements by sity, although the saturation concentration is still
Hudson, et al.,71 of the saturation concentration of higher than that before cold working. Much of
hydrogen in various steels which had been charged the increased trapping associated with cold work-
by immersion in a 2N H 2S04 solution at 38 0 C ing thus cannot be completely explained as result-
(100 0 F). The hydrogen contents, as measured ing from void formation, since annealing only par-

Basic and Research Aspects 3

 OA.---.-----r------,---_ _ _---,
° '_ _ _ O_ _ _E~
0.3
~
II
Z
8 0.2
0:
I
'"
~" I,
I:
V attack," may lead to decarburization, grain-boun-
(I cc NTP per grom = 89.9 ppm H)
9 ~_~ ___ ~_
-v-~
d=o:o=o===or'====::=::J
300 500 1000
(TIME OF IMMERSION )112, sec 112
Fig. 4-Amount of hydrogen absorbed by similar specimens
immersed in a solution of pH (a) 7.92; (b) 7.09; (c) 5.43; (d)
3.14; (e) 1.38, plotted against square root of time of immersion
(Ref. 77)
tially heals the traps. However, nothing short of
melting will restore the original low apparent solu-
bility of hydrogen of the cold-worked steel. The
significance of the voids as trapping sites is further
confirmed by the observation 136 that neither the
density nor the saturation concentration of very
pure iron is affected by cold working.
The effect of variations in the effective pressure
of the hydrogen environment on the rate of absorp-
tion and saturation concentration of hydrogen in a
steel, in which the number of trapping sites is pre-
sumably constant, is illustrated in Fig. 4. The
variations in effective hydrogen pressure result
from changes in the pH of the charging medium,
with a decreasing pH leading to an increasing
effective hydrogen pressure. This environmental
effect can obviously be very large, with the satura-
tion concentration of hydrogen increasing from
about 1 ppm to about 30 ppm when the pH of the
charging medium decreases from 8 to 1.4.
Residual Hydrogen
In addition to the hydrogen in interstitial solu-
tion or contained in traps, hydrogen may also be
present in steel in a comparatively immobile form,
commonly referred to as residual hydrogen. This
form of hydrogen cannot be readily extracted at
temperatures below about 1470° F, presumably
because it is present as a compound which is stable
below 1470° F. Johnson and Hill52 have suggested
that the compound may be methane. The rate of
chemical fixing of residual hydrogen in steel has
been found to be maximum at about 1110° F and
4 Basic and Research Aspects
to be very slow at temperatures below about 930°
F. Thus, if steel is rapidly cooled through the
temperature range 1470 to 930° F, very little
D
residual hydrogen would form. However, if steel
is slowly cooled through this temperature range, or
held for extended times within this range, extensive
conversion of diffusible to residual hydrogen can
c occur. Residual hydrogen contents of more than
20 ppm have been present in steels exposed to a
temperature of 1100° F for extended periods, and
methane formation has been observed 53 at tem-
peratures as low as 380° F (200° C). The forma-
tion of large amounts of methane at elevated tem-
peratures, commonly referred to as "hydrogen
dary weakening, and internal fissuring. Thus,
o_~_
hydrogen attack may lead to a significant perma-
nent deterioration in properties at both atmo-
1500
spheric and elevated temperatures. However, in
steels that are used for service at atmospheric tem-
peratures, the amount of residual hydrogen is much
smaller than the amount required to impair the
mechanical properties.
Diffusivity
The movement of hydrogen in steel occurs by the
migration of atoms through the lattice, and thus,
only the atomic form of hydrogen can diffuse.
Furthermore, the rates of diffusion of hydrogen in
single crystals and in poly crystalline iron are
nearly identical, indicating that diffusion occurs
primarily through the lattice, without a preferen-
tial diffusion along grain boundaries. The driving
force for the diffusion of hydrogen is an activity
gradient which generally results from a gradient in
the lattice hydrogen concentration, but can also
arise from a gradient in the hydrostatic component
of an elastic stress field. 94 Under such gradients,
hydrogen will diffuse from a region of high activ-
ity to a region of low activity until the chemical
potential of hydrogen is uniform throughout the
steel. For example, when a concentration gra-
dient exists in an unstressed body of uniform tem-
perature, hydrogen atoms will diffuse from a region
of higher interstitial concentration. This diffu-
sion rate is thus related to the hydrogen concentra-
tions in the lattice, and the lattice diffusivity, D.
(D is defined as the amount of hydrogen per square
centimeter which diffuses per second for a unit
concentration gradient. The units of Dare cm 3 /
cm -second or cm 2 / second.) This diffusion will,
in general, continue until the concentration gra-
dient has been eliminated, with the limiting con-
dition being one in which the lattice hydrogen con-
centration is equal to the equilibrium lattice solu-
bility throughout. The lattice diffusivity, D, will
vary with temperature in the same general manner
as the lattice solubility and can be expressed by the
normal Arrhenius equation:
D = Do e-
A plot of log D versus l/Tabs for pure iron,
based on measurements by Hill,60 is shown in Fig.
5. The values of the measured diffusivity, D, are
in accord with eq (2). However, the activation
energies for diffusion, represented by the slopes of
the two straight lines, are about 3000 cal/mol at
temperatures above about 400 0 F, and about 8000
cal/mol at temperatures below 400 0 F, with the
diffusivities ranging from about 3 X 10- 3 to
3 X 10- 4 cm2/sec at the higher temperatures, and
from about 10-5 to 10-7 cm2/sec at the lower tem-
peratures. The straight-line relationships indi-
cate that the behavior in both temperature ranges
is one of thermally activated interstitial diffusion.
The low apparent diffusivity, D, values, measured
at the low temperatures, and the much higher acti-
vation energy for diffusion at temperatures below
about 400 0 F, are explained on the basis that the
interstitial diffusion is hindered at these lower
temperatures by the presence of traps which cap-
ture and delay migrating hydrogen atoms.
Diffusivity values ranging from 10 -5 to 10- 9
cm2/sec have been reported for iron at room tem-
perature. The lower values are believed to have
presumably been influenced by surface trapping or
trapping behaviors. The value of 10-5 cm 2/sec,
which is in agreement with the value which would
be predicted by an extrapolation from higher tem-
peratures, is now generally accepted 94 as the most
probable value for the true diffusivity, D, in iron at
room temperature.
Similar Arrhenius plots depicting the results of
diffusivity measurements on alpha iron, gamma
iron and stainless steel by various investigators
Q
/
RT
(2) are ~hown in Fig. 6. The lattice diffusivity of
hydrogen in gamma iron is much lo~~r th~n in
alpha iron, and is still lower in austemtIc staml~ss
steel, presumably reflecting the relatively hIgh
alloy content of the latter material. .
Concentration gradients which normally prOVIde
the driving force for diffusion may be developed ~t
the surface of the steel exposed to hydrogen enVI-
ronments or internally at local sites, as, for exam-
ple, when hydrogen is released locally whe~. re-
tained austenite transforms to ferrite. In addItIOn,
stress gradients such as those produced by
notches, by oth~r sharp defects, or by bending
moments can also provide a driving force for
localized' diffusion of hydrogen. This driving
force results from the increased solubility of the
hydrogen in the stretched lattice of the triaxially
stressed region which develops when such stress-
concentrating factors are present, with a resultant
flow of hydrogen atoms into this region of ~igher
solubility. The amount of hydrogen that diffuses
into these regions of higher solubility will be pro-
portional to the gradient in the triaxial.c~mponent
of the stress in these regions. The dnvmg forces
provided by gradients in concentration or stress,
however, act independently, and the concen~ra­
tion of hydrogen at local triaxially stressed reg~o~
is a very important factor in the cha~a~tenstlC
delayed-failure behaviors of steels contammg hy-
drogen.
TEMPERATURE
00 0 010 CD
888888
to CDV ... .... '"
00 0
0 OJ CD
0'"
0
2
"'-- - I
F

0000 000 0 0 C
0000
~=(7)f"-. "' ....... '"0
000 2

TEMPERATURE, F
3
1400
---, 800
i
~oo 300
i
200
i
IOu
i
50
i ~~ a IRON (GELLER AND SUN)73)

10-' 600
1
400
1
TEMPERATURE,
200
I
C
100
1
25 4
" \
"'~
" .... ,~ "-

\ '\
u I~ % Ni -C,-Mo STEEL
,,
\ ,2
" I x 10-5
"'.:?:. 5 , 0 (HOBSON)
E
u
a IRON (JOHNSON AND
10 10 HILL) 52)
,: I X 10-6
!:::
>
iii
"'6
:: ,\ \ \
\ 0
:> \ \ \
l::: I X 10-7 7 \ \ \
Ci \ \ \
\' "'-, ' .....
I X 10-8 8 \,
\
\
\
\
' .....
'0
\ \
AUS SS(l8%C,- \ \ /yIRON (GELLER AND
8.9%Ni)(GELLER \ \ SUN)73)
9 AND SUN)73) \ \

10-7
~ \
1 ~ ~ 1 ~ \ \
0.8 1.2 1.6 2.0 2.4 2.8 32 3.6 10 I , \
10' o I 3 4 5 6
TloKI RECIPROCAL TEMPERATUF1E, 1000/oK

Fig. 5-Diffusivity of hydrogen in iron (Ref. 60) Fig. 6-Diffusivity of hydrogen in iron and steel

Basic and Research Aspects 5

Permeation of Hydrogen
The permeation of hydrogen through steel in-
volves, in addition to its diffusion through the bulk
metal, its entrance at one surface, and its exit at
the other surface. The permeation rate, P, at
which hydrogen passes through a slab of thickness,
I, and unit area will be established by the diffu-
sivity and the difference between the hydrogen con-
centration at the entrance and exit surface. Thus,
(3)
When the entrance and exit surfaces are at equi-
librium with their respective environments, the
values of C1 and C2 are the respective equilibrium
interstitial solubilities at these surfaces. If the
exit surface is exposed to an environment that
reduces the value of C2 to zero, the permeation
rate is governed by the value of the diffusivity,
D, and the true solubility of hydrogen at the
entrance surface. At temperatures above 750 0 F,
at which diffusion is not inhibited by trapping and
at which all the hydrogen is dissolved intersti-
tially, the permeating rate under these conditions
can be described by a simplified form of eq (3):
P = DS (4)
I
This relationship can be used to establish true diffu-
sivity, D, values, or the effective pressure of hydro-
gen environments at temperatures above 750 F, 0
from permeating experiments in which permeation
rates and the hydrogen content at the entrance
surface, Cl, during steady-state permeating are
measured, since the solubility will vary with the
square root of the effective pressure in accordance
with Sievert's law.
At lower temperatures eq (3) still applies; how-
ever, trapping will occur and measured values of
C1 and C2 will not represent the interstitial con-
centration which governs the diffusion rate. When
unfilled, the traps will also hinder the diffusion. 75 ,78
Therefore, at these temperatures, permeation rates
are anomalously low initially, increasing with
time as the traps become filled, until the traps are
completely filled and steady-state permeation
occurs at a rate controlled by the interstitial con-
centration gradient. Thus, the results of measure-
ments of such steady-state permeabilities will be
indicative of the interstitial diffusion rate, but
non-steady-state permeation behaviors will also be
influenced by the trapping behavior. Such perme-
ation measurements thus permit separate evalua-
tions of the effects of environmental factors on solu-
bility' and of the effects of such factors as composi-
tion, microstructure, or processing variables on
trapping behaviors. Much of the information on
the solubility and diffusivity of hydrogen in steel,
as presented in the preceding section, has been ob-
tained from experiments of this type.
() Basic and Research Aspects
However, because the diffusion rate is governed
by the difference in interstitial hydrogen concentra-
tions C1 and C2 at entrance and exit surfaces, the
effective pressure at these boundary locations can
markedly affect the permeation rate. The envi-
ronment surfaces which govern the effective pres-
sures at these locations are therefore very impor-
tant. Thus, for example, either prior etching in
nitric acid or anodic polarization, which activates
the entrance surface, can increase permeation
rates on cathodic charging by increasing the value
of the concentration of hydrogen at the cathodi-
cally charged surface, C1• Similarly, the more
rapid removal of hydrogen when an exit surface is
exposed to an aqueous environment than when
exposed to a vacuum can be explained on the basis
that C 2 at the exit boundary location is higher, and
the concentration gradient correspondingly lower,
for the vacuum environment, because of the very
slow recombination reaction at the steel-vacuum
boundary. Furthermore, if the entrance surface
reaction is slow, relative to the permeation rate,
such as for a relatively thin membrane, a steady-
state permeation may occur before the surface con-
centration is in equilibrium with the partial pres-
sure of hydrogen in the environment. The mea-
sured steady-state permeation rate would then be
anomalously low, since it would be governed by
the rate at which hydrogen atoms are absorbed at
the entrance surface, rather than by the rate
of diffusion through the membrane. With an
increase in the thickness of the membrane, the
value of C1 would increase until the membrane
thickness is greater than some citical value, above
which the value of C1 is constant, and equal to the
equilibrium value. For any thickness greater
than this critical thickness, the permeation rate is
therefore not limited by the surface behavior;
rather, it is governed by the diffusion rate through
the membrane.
Removal of Hydrogen
The removal of hydrogen from steels containing
hydrogen is of particular interest to the steel sup-
plier or user. The time required to reduce the
hydrogen content to a desired amount by outgass-
ing has commonly been expressed in terms of a
residual fraction, U, which is the ratio of the hy-
drogen content after time, t, to the original hydrogen
concentration of homogeneously charged samples.
The time, t, increases exponentially with increas-
ing volume and decreases with increasing surface
area. For infinitely long cylinders, the time-U
relationship 92 can be approximated for values of
U below about 0.5 by the following equation:
-r2
t = 2.5D (log U + 0.25) (5)
where D is the diffusivity and r is the radius of the
Table ~-Effect of Temperature on the Rate of Hydrogen Evolu-
tion From 21/,% Ni - Cr - Mo Steel in Air (Ref. #72.)
Ratio of Time
at Room Tem-
perature to
Time at Indi-
Temperature Time to Reach cated Tem-
°C of U = 0.5hr perature
-78 -108 ~1250 0.018
(RT)a (RT)a 23 1 15
50 122 5.5 4.2
100 212 0.55 41.9
200 392 0.11 209
a Room temperature.
cylinder. Obviously, the removal from very large
masses with a large value of r is slow. D, however,
increases markedly with increasing temperature,
and aging at elevated temperatures can signifi-
cantly reduce the times required for hydrogen
removal. This effect of temperature is illustrated
in Table 1, based on the results of Hobson,72 who
studied the effect of temperature over the range of
-78 0 C (-108° F) to 200 0 C (392° F) on the rate
of evolution of hydrogen from precharged 11 mm
diameter cylinders of a 21/2% Ni-Cr-Mo steel
during exposure to air. The time required to
remove 50% of the hydrogen was about 40 times
shorter at boiling-water temperature and about 50
times longer at -108 0 F than the time at room
temperature. Thus, the rate of hydrogen removal
can be markedly accelerated by even moderate
increases in temperature. However, because of
the much lower diffusivity and much higher solu-
bility of hydrogen in austenite, aging at tempera-
tures above the transformation temperature for
the alpha-gamma iron transformation is relatively
ineffective, and the removal rate will be highest at
aging temperatures near but below the transfor-
mation temperature.
Nevertheless, even at this most advantageous
temperature, the times for removal of hydrogen
from heavy sections such as forgings may be ex-
tremely long. Hewitt57 has calcuJated the soak-
ing time at 650° C (about 1200° F) required to
reduce the level of hydrogen to a presumably safe
level of 1.8 ppm at the center of forgings of various
sizes and initial hydrogen contents. These data
are presented in Table 2. For example, for 5 in.
diameter forgings with an original hydrogen con-
tent of 2.7 ppm, a soaking time of 20 hrs at 650 0 C
(1200° F) is required to reduce the hydrogen con-
tent to 1.8 ppm; for an original hydrogen content
of 9 ppm, a soaking time of 64 hrs is required to
reduce the hydrogen content to 1.8 ppm. For
larger forgings, the required times increase expon-
entially with increasing diameter. In addition, as
shown in eq (5), the rate of hydrogen removal
decreases as the hydrogen content decreases.
The rate of hydrogen removal may also be sig-
Basic and Research Aspects
Table 2-Soaking Time Required to Reduce Various Initial
Hydrogen Levels to a Maximum of 2 ml/100 g at Center of
Forging (Ref. 57)
Forging Soaking Time at 650 0 C, hr, at indicated
Diameter, Initial Hydrogen Level, ml/100 g
tn. 3.0 4.0 5.0 6.0 7.0 B.O 9.0 10.0
5 20 28 35 41 46 50 57 64
7.5 37 53 66 76 84 92 100 108
10 58 82 102 115 128 140 150 160
108 150 185 210 230 255 270 290
20 175 245 295 335 370 395 420 450
25 255 350 425 490 535 565 600 640
30 350 485 585 670 730 770 820 880
nificantly affected by surface or environmental fac-
tors. For example, increasing surface roughness
may accelerate hydrogen removal by increasing
the area of metal exposed to the environment.
The increased rate of removal of hydrogen in an
aqueous environment as compared with that in a
vacuum, as observed by Hudson and co-workers,74
is an outstanding example of the influence of the
suriace-environment reaction on hydrogen-removal
rates. The rate of hydrogen removal may by de-
minished by oxide films, which form in visible
amounts during heat treatment. Likewise, very
slow outgassing occurs when the surface is covered
with a nonporous plating of a metal with a low
hydrogen diffusivity, such as cadmium or chro-
mium. Then the removal rate is controlled by the
rate at which hydrogen diffuses through the plat-
ing, illustrative of an extreme case of surface-con-
trolled permeation.
Part B. Sources of Hydrogen in Steel
The most common, but not the most significant,
source of hydrogen in steel is the atomic hydrogen
liberated by the iron-water reaction, xFe + yH 2 0
+=t FexO y + 2yH +, which can occur whenever steel
surfaces come in contact with aqueous environ-
ments. Of greater significance to the steel fabri-
cator and user is the hydrogen charging that ac-
companies electrolytic and corrosion processes in
which hydrogen atoms are liberated on cathodic
surfaces. In some instances, particularly at higher
temperatures, the dissociation of molecular hy-
drogen itself, in accordance with the reaction H2
-- 2H +, may also be a significant source of hydro-
gen. Hydrogen atoms liberated in any of these
processes will dissolve and diffuse in the steel in ac-
cordance with the behaviors described in the sec-
tions on solubility and diffusion of hydrogen.
Steelmaking Practice
Some hydrogen is introduced into steel during
the original steel melting and casting operations,
with the principal sources of hydrogen being water
vapor in the combustion gases and ill the atmo-
7
sphere, or moisture in the charge materials. Fac-
tors which can influence the hydrogen content of
the steel when it is tapped from the melting fur-
nace include the charge materials, the furnace
atmosphere, the slag composition, the oxygen con-
tent of the liquid metal, the intensity of the carbon
boil, and the moisture and hydrogen contents of
the additions, With suitable control of the opera-
tion, in either the electric furnace or the open-
hearth furnace, the hydrogen content at tap may
be as low as 2 ppm, but under unusually unfavor-
able conditions it may be as high as 10 ppm. The
hydrogen content of steels produced by the basic-
oxygen process is generally relatively low, and a
level of 2 to 3 ppm is not uncommon. After deoxi-
dation of the bath, water vapor readily adds hydro-
gen to liquid steel. Therefore, care must be taken
to minimize the exposure of the molten steel to
humid atmospheres or to other sources of mositure
such as moisture laden refractories in rummers,
ladles, or molds.
Hydrogen is most effectively removed from liq-
uid steel by vacuum-degassing processes, in which
the liquid steel is cast at pressures below 1 mm of
mercury. At this pressure the solubility of hydro-
gen, even at the liquid-steel temperature, is very
low. The hydrogen content of commercially
degassed steels is generally less than 2 ppm, and in
many steels is less than 1 ppm. However, these
very low hydrogen contents, obtainable by vacuum
degassing, are not required for steels for most pres-
sure-vessel applications. Vacuum melting will
also reduce the hydrogen content of steel to very
low levels, but because of its cost, it is usually used
only when other advantages of vacuum melting,
as improved cleanliness, are required.
Processing
Processing operations, such as hot-working and
heat-treating processes, generally result in a
decrease in the hydrogen content of the product, as
a result of outgassing occurring during cooling from
hot working or during heat treatment at tempera-
tures at which the steel is ferritic and the solu-
bility of hydrogen is relatively low. This outgas-
sing is, however, slow for heavy sections. Conse-
quently, practices such as controlled, very slow
cooling from hot-working operations, or prolonged
heat treatments at sub critical temperatures, are
commonly used to assure a suitably low hydrogen
content in such products.
Fabricating
Fabrication by arc welding can, however, lead to
marked increases in the hydrogen content in the
weld area. The intense heat of the welding arc
can decompose any hydrogen-containing sub-
stances that are found in welding materials. The
atomic hydrogen which is thus liberated is readily
8 Basic and Research Aspects
absorbed by the molten steel. Under unfavorable
conditions, the solubility of hydrogen in the molten
steel may be exceeded and porosity or cracking
may result in the solidified weld metal.
The usual sources of hydrogen in arc welding are
moisture, cellulose minerals, and hydrocarbons
which may be present in the welding materials.
Typical contaminants include moisture and hydro-
carbons on the plates to be joined, moisture in the
shielding gas, in the flux or in the electrode coat-
ings, and drawing compounds that are trapped in
the electrode. The hydrogen content of the elec-
trode wire itself may also be an important source,
particularly since the electrode is cold-worked
during processing, and thus is capable of occluding
large amounts of hydrogen during pickling.
Service
At atmospheric temperatures the atomic hydro-
gen resulting from cathodic reaction which occurs
when steel is exposed to aqueous media, is by far,
the most significant source of hydrogen in steel.
This reaction can occur in service when steel sur-
faces are exposed to aqueous environments or to
gaseous environments from which aqueous conden-
sate may form, or in processing operations such as
pickling, cleaning, or electroplating.
This cathodic reaction involves the reduction of
hydrogen ions to nascent hydrogen by electrons at
cathodic surfaces. The hydrogen atoms are
adsorbed on the steel surface, and are absorbed into
the steel at active, high-energy sites. Most of the
nascent hydrogen, however, recombines to form
molecular hydrogen, which normally is evolved as
bubbles. Simplified equations describing these
behaviors are as follows:
H +(Aq. soln.) + e- - H(adsor~ed)
cathodic reaction (6)
H(adsorbed) - H(absorbed)
dissolution reaction (7)
2H(adsorbed) - H2 t
recombination reaction (8)
Fe - Fe++ + 2e- anodic reaction (9)
The rate of adsorption by the cathodic reaction,
Eq (6), will increase with increasing hydrogen
ion concentration (decreasing pH) or with an
increased electron flow, whether caused by an
increased rate of the anodic reaction, Eq (9) or by
an impressed current. An increase in the rate of
adsorption will usually lead to increases in both the
dissolution and recombination reactions [Eqs (7)
and (8)], so that more hydrogen is absorbed by the
steel and also more molecular hydrogen is evolved.
Thus, the hydrogen content of the steel tends to
increase with decreasing pH values and increasing
cathodic current. This increase, however, levels,
off at high cathodic-current levels at which the
surface is assumed to be "completely" covered
with adsorbed hydrogen. The recombination
reaction [Eq (8)] may then predominate, and the
fraction of hydrogen absorbed by the steel may
therefore decrease, and in some systems the total
amount absorbed may also decrease. 97
The marked effect of pH on hydrogen absorp-
tion, as illustrated by the results of the experiments
of Darken and Smith,77 in which the hydrogen con-
tents of similar specimens immersed in solutions of
sulfuric acid of varying pH values were measured,
is shown in Fig. 4. Hydrogen absorption in low-
pH solutions occurs rapidly when the corrosion
rate in these solutions is high; on the other hand,
hydrogen absorption occurs at a very slow rate in
neutral solutions (pH 7) containing oxygen, both
because of the low hydrogen ion concentration, and
because the corrosion current is dependent upon
the diffusion of oxygen in such solutions.
The rate of the cathodic reaction [eq (6)], and
therefore the rate of hydrogen absorption, can also
be increased by impressing a cathodic current from
an external d-c source or from a sacrificial anode.
The use of such impressed currents furnishes a con-
venient means of obtaining controlled variations
in hydrogen absorption in laboratory studies.
Cathodic reactions also lead to hydrogen absorp-
tion during electroplating in acid baths. Hydro-
gen ions can be reduced at the steel (cathode)
surfaces when the plating potential is greater than
the hydrogen over-voltage, such as during the
plating of Cd, Cr, Zn, Sn, and Ni.
The rate of cathodic absorption of hydrogen at
steel surfaces can also be markedly altered by the
presence of surface adsorbants, which strongly
affect the rates of the dissolution and recombina-
tion reactions [eqs (7) and (8)]. The presence of
elements (or certain of their compounds), such as
S, P, As, Se, Sb, and Te, and the CN- ion, leads to
a blocking action on the recombination reaction
[eq (8)], and they are therefore referred to as "poi-
sons" or promoters. As a result of this blocking
action, the amount of hydrogen absorbed in the
metal by the dissolution reaction [eq (7)] is
increased. Other adsorb ants, on the other hand,
which are usually polar organic compounds, exert
a blocking action on either the dissolution or the
anodic reactions [eqs (7) and (9)] by forming
strong chemisorptive bonds on the steel surface at
active sites, and thus retard the absorption of
hydrogen. These compounds are therefore re-
ferred to as inhibitors.
Small traces of poisons, especially S, P, and As,
are found in many commercial solutions as impuri-
ties, and in some instances, extremely small con-
centrations (as low as 0.1 ppm) of the poison have
been found to promote absorption of hydrogen.
When poisons are present, a damaging amount of
hydrogen may be absorbed from neutral or rela-
Basic and Research Aspects
tively high-pH solutions, from which a significant
amount of hydrogen would not ordinarily be
absorbed in the absence of the poison. The pres-
ence of such poisons in industrial or natural envi-
ronments has led to innumerable problems, such as
the cracking, blistering, or corrosion fatigue that
occurs when oil-field equipment, storage vessels,
and pipe lines are exposed to "sour" oils contain-
ing H 2S. Poisons are, however, sometimes inten-
tionally added to laboratory solutions as a con-
venient means of accelerating hydrogen absorption.
Inhibitor compounds are used predominantly to
minimize hydrogen absorption during commercial
acid pickling operations. Inhibitor effectiveness
generally increases with the molecular weight and
with the dipole moment of the inhibitor. Inhibi-
tor concentrations of 5 to 100 ppm have been used
in corrosive environments to reduce the deleter-
ious effects of H 2S in oil-water systems, but the
mechanism by which H 2S tends to catalyze hydro-
gen absorption is not fully understood, and no sin-
gle inhibitor has been found which is suited to all
corrosive environments.
The marked effects of poisons and inhibitors
emphasize the importance of surface behaviors as
factors influencing hydrogen absorption. Our
knowledge of the mechanisms involved in these
behaviors is very limited, and an extension of this
knowledge is badly needed. This should include
a better understanding of the nature of the steel
surface itself, as well as of the mechanisms involved
in the surface-adsorb ant effects.
The high saturation hydrogen contents or the
high steady-state permeation rates which can be
attained by cathodic charging either with solutions
of low pH or with impressed cathodic currents in
high pH solutions indicate a hydrogen solubility
value which would be in equilibrium with a very-
high-pressure hydrogen environment. The aque-
ous environment can thus be considered as exert-
ing an effective pressure of hydrogen that is very
high. In one investigation,7° a current density of
0.015 amp/cm 2 was found to produce the same
permeation as hydrogen gas at a pressure of 250
atm. From this observation, the following ap-
proximate expression was developed relating the
effective hydrogen pressure (atmospheres) to the
impressed current density (amp/cm2) for iron in a
2% NaOH solution:
PH, = 17,000 (i) (10)
In acid solutions, and particularly in those contain-
ing poisons, the proportionality factor in eq (10)
would, however, be much higher than 17,000. 66
Although the effective pressures of such solutions
can obviously be very high, very little quantita-
tive data of the type of which Equation 10 is based
are available. Such data are badly needed, not
only as a basis for an improved understanding of
9
 Hydrogen
the mechanisms of hydrogen embrittlement, but 100
H2 ABSE~
• Concen·
also to establish quantitative relationships which .~ 90 tration
21
would permit the application of laboratory studies g- 12 DAYS ....• DAYS Aging mil
of cathodically charged steels to investigations of
"-
c
~
80 2 DAYS, .tt; DAYS Period 100g ppm
!? ~I DAY
H2 absent 0.1 0.1
the behaviors of steels for pressure vessels to be 21 days 1.4 1.3
~
70 I HOUR
used for the storage of high-pressure hydrogen. ~ 12 days 2.8 2.5
7 days 3.7 3.3
(j)
(j) 2 days 4.6 4.1
w
a: 1 day 4.4 4.0
Part C. Properties and Behaviors of Steel I-
50 5.3 4.8
(j)
1 hour
Containing Hydrogen w
::J
a: 40 -
The predominant effect of hydrogen on the I-

30L-~ __~__L--l__~~
properties of steel is a decrease in ductility and true o 0.1 0.2 0.3 0.4 0.5 0.6
stress at fracture. This effect is manifested in ten- TRUE STRAIN
sion tests with smooth specimens as a decrease in LOGIO (Ao / A) = 2.303

reduction of area and elongation, in tension tests
with notched specimens as a decrease in notch
tensile strength, and in bend tests as a decrease in
bend ductility. This effect of hydrogen, com-
monly referred to as hydrogen embrittlement, is
also generally associated with an increased propen-
sity for a cleavage or quasi-cleavage mode of frac-
ture.
The magnitude of these effects increases with
increasing hydrogen contents in the steel. How-
ever, it is also dependent on both material char-
acteristics and external factors, with the principal
material characteristics being crystal structure and
strength level, and the principal external factors
being strain rate and temperature. Hydrogen has
little or no effect on the properties or behavior of
austenitic steels except at very high hydrogen con-
tents, but all ferritic steels are affected in varying
degrees. The magnitude of the effects in ferritic
steels increases markedly with increasing strength
level. The effects of hydrogen may be observed
within the broad range of temperatures from
-300 to 400 0 F, but are usually most pronounced
at temperatures near room temperature and at
very slow strain rates. At very low temperatures,
or at very fast strain rates, the properties and
behaviors of steels containing hydrogen do not dif-
fer significantly from those of hydrogen-free steels.
Under either of these extreme conditions the
mechanism of hydrogen damage is inhibited
because hydrogen movement is greatly limited.
Because of the strain-rate effect, impact proper-
ties are usually unaffected by the presence of hy-
drogen in steel. On other hand, the magnitude of
the effects of hydrogen generally increases mark-
edly with decreasing strain rate. In service, fail-
ures of steels containing hydrogen are characteristi-
cally delayed failures, which occur at relatively
low stress levels after the steel has been in service
for relatively long periods of time.
Such delayed failures are aggravated by the
presence of stress concentrators, such as defects and
notches, which cause hydrogen to segregate at
local regions in members that are subject to ten-
sile of bending stresses. Delayed failures can
occur either in steels which contain hydrogen,
Fig. 7-True·stress-true-strain curves for a hydrogen-impreg-
nated 3Cr- Mo steel after standing in air for varying periods
(Ref. 80)
when they are put into service, or III services
which add hydrogen.
The effects of high-temperature high-pressure
hydrogen on the properties and behaviors of steel
will be described in a forthcoming section of this
report, where the damaging effects of hydrogen
under these conditions of exposure, resulting prin-
cipally from the methane reaction which leads to
decarburization and intergranular cracking, are
discussed in detail.
Effects of Hydrogen on Ductility
Steels containing hydrogen characteristically
fracture after the onset of necking but at lower
normal strain values, as illustrated in Fig. 7 given
by Hobson and Sykes80 for smooth tensile bars of
an 0.26C - 3Cr - 0.4 Mo steel tempered to a strength
level of 51.8 tsi (116 ksi) and containing hydrogen
contents varying from 0.1 to 4.8 ppm. In this
work the hydrogen content was decreased by aging
as indicated in Fig. 7. This plot shows that the
true stress at fracture decreases as the hydrogen
concentration in the steel increases, but fracture
occurs only after the apparent maximum stress
has been reached, and necking is in progress.
Thus, the presence of hydrogen does not signifi-
cantly affect the flow behavior, but fracture occurs
at decreasing levels of strain and true stress as the
hydrogen content increases.
In addition to the effect of the hydrogen content
itself, the measured tensile properties are affected
by the temperature and strain rate of the test, by
the stress concentration of the specimen, and by
the strength level of the steel and the amount of
prior cold work which it has received. The effect
of strength level is most significant. In higher
strength steels comparatively small amounts of
hydrogen lead to large changes in properties, but
in steels with lower strength the influence of hydro-

10 Basic and Research Aspects

 80r----.----,-----r----.----_
..
c:
..
"
Q.
20
<1
W
0::
<1
~ 80~---,----.---_.----~--~
z
o DUCTILITY (IN aolat)
I-
g 60
a
w
0::
40
20
O~ __~____~____L __ _~_ _ _ _~
I 2 4 6
HYDROGEN CONTENT, ml / 100 9
(0) 94 TONS/SQ IN. TO 51-112 TONS/ SQ IN.
(b) 51-112 TONS/SQ IN. TO 41 TONS/SQ IN.
Fig. 8-Relationship between hydrogen content and reduction
of area for 3% Cr - Mo steel tempered to various strength levels.
(Figures against curves show ultimate tensile strength in tons/
sq in., Ref. 80)
gen decreases_ This effect is illustrated in Fig. 8a
by tests conducted on the previously mentioned
0.26C - 3Cr - OAMo steeL 80 At the highest
strength level, the reduction-of-area values for
this steel are markedly decreased by small hydro-
gen concentrations, but the effect of hydrogen de-
creases as the ultimate tensile strength is decreased
by progressive tempering to lower strength levels,
down to a strength level of 51.5 tsi (115 ksi).
However, if tempering is prolonged to produce
spheroidized structures with still lower strength,
this steel becomes more sensitive to hydrogen dam-
age, as indicated in Figure 8b, suggesting a micro-
structural effect_ Thus, over the broad range of
strength levels at which this steel might commonly
be used, the susceptibility to hydrogen damage de-
creases with decreasing strength, although an opti-
mum strength level for this steel, at which the sus-
ceptibility to hydrogen damage is a minimum, is
indicated as a value of 115 ksi. These effects of
hydrogen content, and the marked influence of
strength level, are typical of the effects of hydrogen
in steel, as observed by many investigators. These
points are pertinent to the behavior of pressure-
vessel steels, since these steels are typically rela-
tively low in strength. They would therefore be
expected to have only a moderately decreased duc-
tility in the presence of hydrogen unless their hy-
drogen contents are very high.
(0)
DUCTILITY tiN a,lat)
STRAIN RATE, in. / in.lmin
TEMPERATURE. F
-1.2
STRAIN RATE, in./in.lmin
TEMPERATURE, F
Fig. 9-Ductility of an SAE 1020 steel as a function of strain rate
and temperature (Ref. 55). (a) As-annealed at 1250 F for 168
hours. (b) As-charged cathodically at 1 amp/cm, for 1 hr in a
8 10 4% sulfuric acid solution containing phosphorus and sulfide
poisons. Curve i, in Figure b, bounds the range of strain rates
and temperatures where a decrement in ductility is observed.
Curve ii defines the temperature of minimum ductility for a
given strain rate
The general effects of temperature and strain
rate on the ductility of steels containing hydrogen
can be deduced by comparing Fig. 9a and 9b given
by Toh and Baldwin55 and Baldwin and Brown. 82
The ductility of an annealed SAE 1020 steel, in
terms of the true strain at fracture, is shown as a
function of temperature and strain rate, for the
precharged steel (Fig. 9b) and for the uncharged
steel (Fig. 9a). Because the charging was done in
an H 2S0 4 solution with a relatively low pH, with
added poison, and with an impressed cathodic cur-
rent, the hydrogen contents of the charged speci-
mens were presumably relatively high, although
hydrogen analyses were not reported. The re-
sults for the charged specimens, plotted in Fig.
9b, show that the magnitude of the decrease in
ductility increases with decreasing strain rate, and
that hydrogen influences ductility over the range of
temperatures from about -250° to 130 0 F, which
is the highest testing temperature. The minimum
ductility occurs at a temperature of -30 0 F at the
slowest strain rate, and the temperature of mini-
mum ductility increases with increasing strain rate
to a temperature of about 110 0 F at the highest
strain rate. This sensitivity to strain rate and
temperature suggests that hydrogen movement is
involved in the mechanism leading to the ductility
changes.
The decreased tensile ductility and true frac-
ture stress of steels containing hydrogen are par-
ticularly significant with respect to behaviors at
Basic and Research Aspects 11
notches or regions of stress concentration, at which
the plastic strain, which precedes the fracture at a
reduced stress in the presence of hydrogen, will be
localized. Thus, when notched specimens are
tested, the reduced ductility, resulti ng from the
presence of hydrogen, is reflected in an actual
decrease in notch strength. However, since the
notch strength, as measured by notched tension-
test specimens, is dependent upon the tensile
ductility, the effects of factors , such as tempera-
ture, strain rate, hydrogen content, or strength
level, on the notch strengths of steels con taining
hydrogen will be qualitatively similar to their
effects on tensile ductility. Furthermore, as t he
notch acuity or the elastic stress concentration
factor is increased, the red uction in notch strength
at a given level of the other factors will be greater
because of the increased strain localization.
The effect of hydrogen content on notch strength
is illustrated in Fig. 10, based on tests recently
conducted by the British Welding Research Asso-
ciation (BWRA)'·l on thermally charged notched
tensile specimens of 0.30C - Ni - Cr - Mo marten-
sitic steel, which had been aged for various times to
provide a range of hydrogen concentratio ns up to
about 3.7 ml/ 100 g (3.3 ppm) . A function ( uo-
uu ) / Uu of the notch tensile strength (where Uo
and UH are room-temperature notch strengths for
the hydrogen-free and the hydrogen-ch arged speci-
mens, respectively) is plotted against the hydrogen
content. The value of this function, which in-
creases with decreasing values of UH, increases
linearly with increasing hydrogen content. T he
behavior is similar to and reflects the straight-
line decrease in tensile ductility which is observed
12~--~--T---'------'
• •
'0 • smooth fracture , the dark region shown in Fig. 11.
,
•
l>l'b
S' I z 6
:oj O
0~_1----L_-'--_
o 2:3 4 BAKING TIME
TOTAL HYDROGEN CONCENTRATION (HI, mI/IOO;
Fig. lO-Plot of (UII - UH)/UH against total hydrogen content fa
steel samples tested at room temperature (Ref. 93)
12 Bll~ ic
IIItension tests of smooth specimens, illustrated
in Fig. 7. The plots of Figs. 10 and 7 also il-
lustrate that the effects of hydrogen are reversible,
since the tensile properties of both the smooth-bar
and the notched-bar specimens are shown to be
essentially unimpaired after the hydrogen con-
centration of the charged samples is decreased to
zero by aging treatments. The effects of strain
rate and temperature on the notch tensile strength
of charged specimens of a plain-carbon steel were
also investigated in this BWRA study, and the
behaviors were likewise found to be generally
analogo us to the effects of these variables on the
reduction of area of charged smooth tension speci-
mens, which were illustrated in Fig. 9.
Delayed-Failure Behavi or
When subject to a sustained load, a steel con-
taining hydrogen may fail at a stress level which is
much below its tensile strength as measured in a
sh ort-time test. This behavior is variously termed
delayed failure, hydrogen-stress failure , and de-
layed, low-stress brittle failure, and is the most
common type of failure encontered in service appli-
cations of steels containing hydrogen or exposed to
hydrogen environments. It represents essen-
tially a manifestation of the decreased fradure
stress or strain at fracture in the presence of hy-
drogen, as exemplified by the results of the notch
tension tests just described, with the fracture ini-
tiating in regions of highly localized stress in which
hydrogen is concentrated as a result of the aug-
mented diffusion of hydrogen into triaxially
stressed sites.
T he term "brittle," which is SOlnetunes used in
connection with this effect of hydrogen, is indica-
tive of the increase in the cleavage or quasi-cleav-
age mode of failure that is generally observed on
the fracture surfaces of such failures. For exam-
ple, the fracture surfaces of notched-bar, charged
tensile samples generally have an outer ri.ng of
JJO 000 PS I 32 4 000 PS I
fRACTURE STIIESS
] HOURS 12 HOURS
175 , 000P51 200 . 000 P 51
APPliED STIlESS
Fig. ll-Fracture surfaces of precharged, sharply notched ten·
sile samples (Ref. 19)
alld l?l:st arc/r A . . Iuds
 /NOTCHED TENSILE lower critical stress (LCS), which represent the
STRENGTH
UPPER CRITICAL STRESS highest and lowest applied-stress levels leading to
~----------~-- delayed failure. At stresses above the UCS,
FAILURE
failure occurs without a time delay, and at stresses
ff)
REGION below the LCS, hydrogen is not damaging. At
/~
ff)
w
ex: e/- /'VCf.
intermediate stress levels, failure is inevitable and
occurs as a series of events involving crack initia-
l-
ff)

a
0;/~1l90
~ ~
tion and crack propagation.
w
...J
a.
CRACK INITIATION
CURVE DEFINING
V0'O't-'V
(/, Q

/
Q
'V
FAILURE CURVE

~~-t-.:..J'''::-
a.
<l
I NCUBATION PER I 00
REGION OF NO DAMAGE
LOG TIME - - - -
Fig. 12-Schematic drawing of characteristic failure behavior of
notched tension specimens containing hydrogen
Both transgranular and inter granular fractures
have been reported for failures occurring by the
hydrogen-stress mechanism. Hydrogen-stress
fractures are not readily distinguishable, with the
unaided eye, from other low-stress failures, such
as those from stress-corrosion cracking, since the
fracture surfaces may appear quite similar. How-
ever, cracking caused by a hydrogen-stress mecha-
nism generally does not exhibit the branching of
the type that is often characteristic of stress-corro-
sion cracking. In stress-corrosion cracking, sev-
Incubation Period for Crack Initiation
_ _ _ _ _ _--'----i
At the intermediate stress leveis an incubation
period, which in Fig. 12 is bounded by the crack-
initiation curve, is presumably required to initiate
a crack because the average hydrogen concentra-
tion in the steel is lower than the hydrogen concen-
tration required for crack initiation at potential
cracking sites. During the incubation period the
distribution of hydrogen in the steel is changing.
Hydrogen is diffusing ahead of the notch to local
highly stressed regions at which cracks initiate
after a critical hydrogen concentration has accu-
mulated. The kinetics of the crack-initiation pro-
cess are therefore dependent on the temperature
and the stress gradient as they relate to the diffu-
sion and concentration of hydrogen in the steel.
The applied-stress level exerts only a minor influ-
ence on the incubation period, as is indicated in
Fig. 12. However, the effect of temperature on
the incubation period is much greater, as shown in
an Arrhenius plot (Fig. 13) for similar notched,
precharged tension specimens that were tested at
an applied stress level of 150,000 psi at tempera-
tures between room temperature and -50 F. 0

eral secondary cracks are usually produced in addi- The activation energy for crack initiation, as cal-
tion to the major crack, and small branching cracks culated from these data, is 7610 cal/mole, which is
are seen emanating from these larger cracks.
Fractographic techniques have, furthermore, been
reported 134, 139 for distinguishing stress-corrosion
from hydrogen-stress fractures.
Because of its importance, this delayed-failure 5,0',---,----,---.--TT--,---------,
behavior of precharged steels has been extensively
investigated in laboratory studies by many investi-
gators including Troiano and his associates. 22 In 2,0
the Troiano experiments, quenched and tempered
4340 steel specimens of various notch geometries
were cathodically charged, cadmium-plated, and
then baked at 300 F to give "homogeneously"
0

distributed, and reproducible, levels of hydrogen 0.5

throughout the test samples. These precharged
samples were used to determine the effect of
Q2
selected variables on the constant-load-to-rupture
behavior of the steel. The Troiano experiments
show that delayed failure in notched, precharged 0,1

steel samples occurs as a series of events: incuba-

tion, crack initiation, and crack propagation. 0.05

This behavior is represented by two stress-time

curves, one for crack initiation and one for frac- 3,0 5.4

ture, as depicted in the schematic drawing of Fig.

12. Both of these curves are bounded by two Fig. 13-Arrhenius plot of incubation time for an applied stress
stress levels, an upper critical stress (UCS) and a of 150,000 psi (Ref. 16)

Basic and Research Aspects 13

consistent with that for the diffusion of hydrogen,
as calculated from evolution experiments, and
indicates that crack initiation in notched, pre-
charged steel samples is controlled by the trapped
hydrogen in the steel sample.
Notches and defects in steel may influence the
crack-initiation process by increasing the local
stress level and thereby providing potential crack-
initiation sites. They also provide a stress gra-
dient with a relatively high triaxial component,
and this component induces hydrogen to diffuse
to and concentrate at and near these potential
cracking sites. The triaxial component of stress
gives rise to hydrogen diffusion because it increases
the solubility of hydrogen 94 in the steel at these
triaxially stressed local sites, as descirbed above in
the section on diffusivities. Thus, under sustained
loading, hydrogen tends to concentrate at triaxi-
ally stressed regions, such as the region just beyond
the root of a notch in notched tension samples or
the region just beyond the tip of a sharp defect.
Hydrogen apparently 94 has no increased tendency
for precipitation, adsorption, or chemical reaction
in these local regions of increased solubility until
the stress field changes, as for example when a
microcrack (or crack) initiates. After such stress-
field changes do occur, however, the region may
be supersaturated in hydrogen with a greatly in-
creased tendency for precipitation, adsorption,
and chemical reaction locally.
Crack Propagation
After the first crack initiates, a period of
slow crack growth usually follows. During this
slow-crack-growth period, which may be moni-
tored by stress-wave emission 141 or electrical-resis-
tance 17 ,18 measurements, crack propagation occurs
discontinuously as a series of crack initiations,
which may begin very shortly after loading to
stress levels above the lower critical stress, and
which eventually lead to failure when the fracture
grows to a critical size either for brittle failure or
for a ductile tensile failure of the uncracked mate-
rial. Each new crack initiation occurs in the bulk
of the steel at the highly stressed region located
just ahead of the tip of an existing crack. This
slow crack-growth process is generally analogous
to the crack initiation process described above, and
both the initiation and propagation of cracks are
dependent upon hydrogen diffusion in precharged
steel. Temperature and the hydrogen content of
the steel may therefore affect the time interval
between crack initiations by influencing the dif-
fusion process and the time required to accumu-
late a critical hydrogen concentration. Thus, an
increase in either the temperature or the hydrogen
content may decrease the time required for each
new crack initiation, and thereby accelerate the
crack growth rate. The extent to which crack
14 Basic and Research Aspects
growth by this process continues before failure
occurs will, however, be established by the stress
level and the fracture toughness of the steel, if
failure occurs by unstable fracture; or by the
stress level, the tensile strength of the steel, and
the geometry of the specimen, if the final failure
is ductile tensile failure.
The delay time for failure generally appears to
be relatively insensitive to stress level. However,
the maximum time to failure at the upper critical
stress differs from the minimum time to failure at
the lower critical stress by about one order of mag-
nitude in low-alloy high-strength steels, and by as
much as two orders of magnitude in some alloy
steels. This reflects differences in incubation and
propagation characteristics of these materials, and
a significant sensitivity to stress level that has not
as yet been fully characterized.
Lower Critical Stress
The lower critical stress (LeS) represents the
lowest sustained, applied-stress level that may
result in delayed failure; and it is, therefore, of
great practical importance. The LeS is a thresh-
old stress above which failure is inevitable if the
load is sustained. Below this level, the steel is not
damaged by hydrogen. The principal factors
affecting the LeS are hydrogen concentration,
stress concentration, strength level, and tempera-
ture. The applied-stress level required for delayed
failure of steel can vary widely from near zero to
levels approaching the fracture stress of the un-
hydrogenated steel.
Factors Affecting Delayed Failure
The delayed-failure behavior of precharged
steels may be affected by various material and
external factors. The principal material, or inter-
nal, factors are the hydrogen concentration and
the strength level, but compositional and process-
ing factors may also affect the behavior. The
principal external factors are the notch acuity and
the temperature, both of which strongly influence
the observed behavior.
Hydrogen Concentration
An increase in the hydrogen concentration nor-
mally leads to a decrease in both the upper and
lower critical stresses and to shorter delay times
for failure. This effect is shown in Fig. 14 for
similarly notched, precharged, and baked samples
of 4340 steel tempered to a strength level of 230
ksi. The hydrogen concentration is greater for
shorter baking times, although the maximum
hydrogen concentration in the steel in these tests
was very low, probably about 0.2 ppm. Thus,
with increasing hydrogen concentrations up to
(as little as) 0.2 ppm, the propensity for the
delayed-failure behavior increases and the load-
carrying ability of a sharply notched, high-strength
steel containing hydrogen may be only a fraction
of its yield strength.
Strength Level
The effect of strength level is very marked,
although this effect, like the effect of hydrogen
concentration, is also strongly influenced by the
presence of notches. In general, with increasing
strength levels, the failure curve shifts in the
direction that would be anticipated for increasing
hydrogen contents. In pre charged steels this
shift is normally observed to occur only in notched
samples, although unnotched samples may be
affected but generally to a much lesser degree.
This behavior is illustrated in Fig. 15 for 4340 steel
tempered to various strength levels from 165 to
275 ksi, corresponding to tempering temperature
of 1000 and 400 0 F, respectively. The behavior
of sharply notched samples (K = 10) given in Fig.
15a is significantly different from that of unnotched
samples (K = 1) given in Fig. 15b. In the former,
the stress that is sustained by these steels is in all
cases significantly lower than their respective
"unembrittled" notch tensile strengths. The LeS
is very low for the higher strength steels that were
tempered at lower tempering temperatures. In
contrast with this behavior, the applied stress that
is sustained by smooth tension specimens with the
same hydrogen concentrations that were used in
the notched samples (average of about 2.5 ppm*)
was the same as, or only slightly lower than, that
of samples which were not precharged with hydro-
gen. Thus, the delayed-failure behavior is greatly
inhibited in the smooth-bar specimens at all
strength levels shown. However, in the notched
specimens, low-stress delayed failures are observed
and the applied-stress level required for failure
generally decreases as the strength level increases.
The delayed-failure behavior was shown above
to be strongly influenced by the presence of a notch
in a tension bar. Such notches are stress raisers
that cause local plastic deformation, stress gradi-
ents, and consequent hydrogen segregation in the
steel sample. Delayed failure occurs in higher
strength materials at lower applied-stress levels
than the levels required to fail steels of lower
strength because larger gradients in stress arise at
the notch in the stronger materials and the yield
strength of the steel limits the maximum value of
stress that can be sustained by the steel before
plastic deformation relieves the stresses. In addi-
tion, the fracture toughness of steel, and the ten-
dency toward high-energy shear fracture, generally
decrease as the strength is increased, and the
higher strength steels are therefore inherently more
susceptible to low-stress failure.
TEMPERING TENSILE STRENGTH, psi
TEMPERATURE, F (UNPLATED)
o 400 275,000
t:.. 500 270,000
o 700 235,000
215,000
"7 800
• 1000 165,000

* I~ these tests hydrogen was codepos;ted during the electroplating of

cadmIUm on the test samples, and the indicated average concentration in-
~~gg ~ }"UNEMBRITTLED"
300,000 =,=-=='-:-/700 and 800 F NOTCH STRENGTH
cludes the hydrogen present in the cadmium plating.
~IOOOF
•'-::::~~::~======~-"7 • / 1000F
* I""
~

~,~.--
Q.
200,000
(J)
(J)
\" 800F....-
D~"7_
ILl
cr
I-
(J)
100,000 o "7500 F
t:r-

O~~ __~____~~~~~~~~____~
0.01 1000
TIME TO RUPTURE, hours

FIG. ~ BEHAVIOR OF SHARPLY NOTCHED TENSION SAMPLES

300pOOr------.------,------,,------r------,

.;;;
Q.

u;
(J) ~~~~-------.,-----------.--
ILl
cr
l-
(/) 100,000

BAKE 0.5 HR O~----~----~~--~~----~----~

0.1 1000

50~____~~____~____~~____~~____~ TI ME TO RUPTURE, hours

0.01 1000
FRACTURE TIME, hours FIG.!.§Jl BEHAVIOR OF SMOOTH TENSION SAMPLES

Fig. 14-Static fatigue curves for various hydrogen concentra· Fig. 15-Stress vs time-to-rupture for cadmium-plated 4340
tions corresponding to different baking times at 300 F. Sharply steel austenitized at 1525 F, oil-quenched, and tempered as
notched specimens of 4340 steel at 230,000 psi strength level indicated. Stress concentration; Fig. a, K = 10, Fig. b, K =
(Ref. 9) 1 (Ref. 86)

Basic al1d Research Aspects 15

Notch Acuity
The effect of increasing notch acuity has been
shown by Johnson and others 9 to be generally
similar to the effect of increasing the hydrogen con-
centration in the steel. The failure time, the upper
critical stress (UeS), and the lower critical stress
(LeS) are all similarly affected by these two fac-
tors. The range of stresses for delayed failure in
high-stress 4340 steel samples that were precharged
and tested with various notch configurations is
shown as the shaded area in Fig. 16. The notch
tensile strength of the uncharged steel is also given
for the various notch configurations. In the mildly
notched samples, with an air value of 0.1, both the
ues and the LeS of the pre charged steel are only
slightly lower than the notch strength of the
uncharged steel, however, as the notch acuity
increases, the stress required for delayed failure
decreases to values much lower than the notch
strength. In sharply notched samples of this
steel, such as those with an air value of 100, the
ues and LeS are much lower than the notch
strength, and delayed failure occurs at stress levels
well below the yield strength of the steel.
Temperature
The effect of temperature on the delayed-failure
behavior is interpreted as resulting from the com-
bined effects of temperature on the diffusivity and
availability of hydrogen and on the fracture tough-
ness of the steel. At temperatures above about
0
400 F, the mechanisms leading to delayed failure
are not operative. (However, a hydrogen-attack
mechanism may be operative.) With decreasing
temperatures below this temperature the diffu-
sivity of hydrogen decreases, leading to longer incu-
bation times for crack initiation, until a low tem-
perature is reached at which the hydrogen is essen-
tially immobile and crack initiation does not occur.
However, as the temperature of the steel decreases,
its fracture toughness also decreases and the steel
is more susceptible to delayed failure, so that,
although longer times may be required for the first
crack initiation, crack propagation occurs more
readily and cracks may initiate at lower levels of
applied stress, so that the slow-crack-growth pe-
riod, the DeS, and the LeS are decreased. This
behavior was observed in the Troiano experiments
9,16,19,25,142 in tests conducted on 4340 steel at tem-
peratures from 180 to -50 0 F. However, these
investigators also observed that the susceptibility
to delayed failure decreases at a still lower tem-
perature, probably because of a dislocation-hydro-
gen interaction which decreases the availability of
hydrogen.
Critical Hydrogen Concentration
The combined effects of hydrogen concentration
and stress concentration indicate that, in pre-
16 Basic and Research Aspects
350'.---------;-------r-----,----,---~
300
-~ 250
o
o
~
" 200
'"'"
W
II:
l-
V} 150
100
5~:';;.O'1----;to.'1--7----:i ':::-o--;';;IOAO-~IOOO
NOTCH SHARPNESS, ai,
Fig. 16-Lower critical stress, charged and uncharged notch
strength for various notch sharpnesses (Ref. 9)
charged steel, a critical combination of stress state
and hydrogen concentration is required for the
crack-initiation process. If a large stress gradient
is sustained by the steel, the critical hydrogen con-
tent for cracking may be attainable with a very low
average hydrogen content, whereas much higher
hydrogen contents are required to fail the same
material in the absence of a large stress gradient.
These observations are also pertinent to pressure-
vessel behaviors, as they indicate that, at the rela-
tively low strength levels of currently used pres-
sure-vessel steels, the probability of the occurrence
of low-stress delayed failure should generally be
low.
The role of stress has been said to be subordi-
nate 16 to the role of hydrogen in this cracking pro-
cess because the experimental observations indi-
cate strongly that a crack initiates only when a
critical concentration of hydrogen accumulates at
the crack initiation site, with the stress providing
a driving force for the diffusion of hydrogen to
this site, and thereby lowering either the time or
the average hydrogen content required for crack
initiation. This viewpoint is supported by the
observation that cracking may occur in highly
charged steel without the application of external
loads, even in instances in which the level of
residual stress is known to be low. Nevertheless,
except in such highly charged steels, an applied
stress (or a relatively high residual stress) is gen-
erally a prerequisite for the occurrence of cracking
in steels containing hydrogen.
Effects of Hydrogen in Weldments
The effects of hydrogen in weldments are gen-
erally similar to and consistent with the previously
described effects of hydrogen in precharged steel.
Hydrogen in weldments can lead to cold cracking,
a delayed-failure phenomenon which occurs under
static loading conditions. However, in we'dments
the stresses leading to the cracking are the residual

,
I
r,,,
\
~ 8
\
\ that will result in cracking in the Lehigh restraint
..
--' ;;
'"
\
~o
::> f-
~ ~ 7
'"'"
z .E
--'
u
..
u;
!oJ '"
U
U'"
'!;
_ _ 0 _____ _
PERCENT HYDROGEN IN WELDING
Fig. 17-Effect of hydrogen concentration in the welding atmo.
sphere on the cracking sensitivity of HY·80 steel (low chemistry)
welded with an alloy electrode (Ref. 85)
stresses of welding. The fracture surfaces of weld-
metal tension samples and of cold cracks will, in
general, tend to exhibit a cleavage or quasi-cleav-
age mode of fracture, and they sometimes contain
small bright areas, commonly referred to as "fish-
eyes," which are regions of cleavage fracture sur-
rounding inclusions. Their presence indicates
that excessive hydrogen was contained in the steel
weld metal. As might be expected, impact speci-
mens do not normally contain fisheyes because the
hydrogen-stress mechanism is not operable at the
fast strain rates that are associated with impact
testing.
Cracking caused by hydrogen in weldments
usually occurs at or near room temperature and
generally after a delay of 24 hrs of less. 85 This
cracking phenomenon is therefore called delayed
cracking or hydrogen-induced cold cracking.
This behavior is consistent with the overall
experience with delayed cracking in steels contain-
ing hydrogen. Hydrogen may lead to cold crack-
ing in either the weld metal or the heat-affected
zone (HAZ). It can occur in various orientations
and locations, such as longitudinal and trans-verse
cracking, and root and underbead cracking. Its
occurrence in weldments is governed by hydrogen
concentration, stress level, strength, composition,
cooling rate, transformation temperature, and
bead size.
The susceptibility to cold cracking increases,
with a decrease in the threshold stress for cracking,
as the hydrogen concentration of the weld deposit
increases. This effect is shown in Fig. 17 taken
from work by Interrante and Stout85 for welded
HY -80 steel samples of similar notch acuity, chem-
ical composition, and cooling rate. The stress
level is semiquantitatively related to inches of re-
straint in the Lehigh restraint test, and the hydro-
gen concentration is expressed as the percentage of
hydrogen in the shielding gas of the welding arc.
The critical restraint is the lowest residual stress
test under fixed welding conditions. The critical
restraint is shown to decrease markedly as the
hydrogen in the welding arc increases from zero to
6%. This corresponds to room-temperature dif-
fusible-hydrogen concentrations in the cold weld
deposit ranging from near zero to about 0.2 ppm
(0.22 cc hydrogen per 100 g of weld deposit).
Thus, even relatively low levels of hydrogen may
cause delayed cracking in susceptible steels such as
those with high HAZ hardness. The residual
ATMOSPHERE
stresses in weldments are accentuated by internal
microdefects in the steel and by external notches,
such as discontinuities in the contour of welded
joints. Thus, local residual stresses, being at the
level of the yield strength in local sites, can be very
high in high-strength steels. However, much
higher hydrogen concentrations, as high as 10 ppm
or even higher, may be tolerable in some lower
strength weldments, since ferrous materials vary
widely in their susceptibilities to cold cracking.
The cold-cracking susceptibility of steel is
strongly affected by composition, since composi-
tion affects both strength level and transformation
temperature. Because weldments generally cool
very rapidly, the hardness levels of both the weld
metal and the heat-affected zone will approach the
maximum attainable hardness level for a given
composition. The microstructures of such rapidly
cooled areas are often those of self-tempered or
untempered martensite and bainite, and these
microstructures are most susceptible to hydrogen-
induced, delayed, brittle failure. However, the
influence of composition on transformation tem-
perature is also important, since hydrogen out-
gassing from the weldment will decrease as the
temperature of transformation decreases.
The susceptibility to cold cracking can be empiri-
cally related to the composition of steel. This
relationship is often expressed in terms of a "carbon
equivalent" of the various alloying elements
because carbon is particularly effective in promot-
ing cold cracking in weldments. However, there
is no general agreement on the most appropriate
factors for each of the alloying elements. One of
the commonly used carbon-equivalent formulas
is given below: 85
Carbon 01 C + % Mn + % Cr +
equivalent /0 4 10
% Ni % Cu %Mo %V
(11)
20 +-.w-
----
50 10
Basic and Research Aspects 17
This equation was derived on the basis of cold-
cracking tests on normalized low-alloy steels and
may not be generally applicable to steels outside
the range of compositions and processing variables
on which it is based. The factor for manganese
has the subject of much controversy, and a factor
of % Mn/6 has been frequently used for plain-car-
bon steels. Carbon-equivalent formulas are used
in establishing the precautions that are required to
avoid cold cracking in welding selected grades of
steel, and in developing new grades of steel when
optimum weldability is required.
Cold cracking can normally be eliminated by
preheating and, under certain conditions, by post-
heating practices. These are beneficial because
they retard the cooling rate, and thereby decrease
residual stresses and provide a less susceptible
microstructure, but a significant benefit results
from holding the weldment at elevated tempera-
tures at which the susceptibility to delayed crack-
ing is low and the outgassing of hydrogen is very
rapid. These treatments are especially important
in weldments of heavy-gage materials, in which
residual stresses are high, because the rate at
which hydrogen escapes from weldments decreases
roughly as the square of the section thickness.
The probability for exceeding the incubation time
for delayed cracking therefore increases markedly
with an increase in the size of the weld deposit.
Flaking
rates.
The flaking behavior is analogous to the delayed
cracking caused by hydrogen in steel weldments.
Delayed flaking has been reported, and a limiting
temperature above which flaking does not occur is
also observed. Those factors which promote cold
cracking, such as high hydrogen concentration,
low transformation temperature, high residual
stress, and temperatures near room temperature,
should similarly promote the formation of flaking
in steel.
Part D. Behavior of Steels Exposed to
Hydrogen Environments
In service, steels are frequently placed under
load for extended periods in various hydrogen-
charging environments, including industrial con-
tainers for low-pH solutions, corrosive aqueous
media, with and without cathodic protection,
boilers containing warm caustics in the high-pH
range, and gaseous media containing hydrogen at
high pressures. Such environments sometimes lead
to deleterious hydrogen levels in steel, and in such
instances behaviors generally analogous to those
described in the previous section for precharged
steels will occur. However, other effects, such as
blistering and decarburizing, may also occur.
Environments containing hydrogen sulfide or acid
are outstanding examples, and subject the steel to
an effective hydrogen pressure which is very high.

The presence of hydrogen in steel in heavy sec-

tions may lead to internal defects that are variously
known as (snow) flakes, hairline cracks, white
400.----,-----r----.-~--r_--_.----_r--_,
spots, and shatter cracks. These defects, which
occur when steel cools below the temperature of
about 400 0 F (at which the mechanism of hydrogen
damage becomes operable), may result in the mill
rejection of an appreciable tonnage of steel; and
f- 300
makers must control hydrogen in steelmaking to '"
....
f-
assure products free of these defects. :J: - AI R-COOLED
<.> HOOD-COOLED
The susceptibility of steel to "flaking" has been f-
.... --- SLAG-COOLED
related to the hydrogen content of steel in a general '"
....
Q.
way by many investigators. Hodge and others2
reported that for a given steel composition a '"
.... 200
"<t
...J
"threshold" level of hydrogen exists above which U.

u.
the susceptibility to flaking greatly increases, and 0
1
below which very little flaking occurs. This '"
.... I
I

behavior is shown in Fig. 18, which gives the num- '"

::;;
::::l I
I

Z I
100 I
ber of flakes found by macroetching and visually Ni-Mo-V I
I

rating the surfaces of 12 in. squares (transverse STEEL I

I

l!.
sections taken from 12 by 12 by 24 in. test speci- I

./ P
I 6 - 1 0 8 0 STEEL
mens) from each of two steels that were cast at I
I

various reduced pressures to produce a range of / /' ,r'

0 ~/ I 15.
hydrogen contents. Typical threshold hydrogen 0 2 3 4 5 6 7
concentrations for carbon and low-alloy steel are HYDROGEN CONTENT, ppm
in the range 1.5 to 3.5 ppm. Above the threshold
Fig. 18-Effect of hydrogen content on flaking of Ni - Mo - V
value the number of flakes increases with increasing and 1080 steels cooled at various rates from the finish rolling
hydrogen concentrations and with faster cooling temperature (Ref. 2)

18 Basic and Research Aspects

In these instances, not only will the hydrogen con-
tent of the steel tend to be high, but a high con-
centration will be established at the surface, and
surface factors therefore become very important.
In the following section, the effects of exposure
to aqueous environments will be described. The
behavior in the presence of hydrogen sulfide, which
represents a severe environment that is frequently
encountered in service, will be discussed in detail.
Behaviors in the presence of gaseous hydrogen at
high pressures, encountered in storage of high-
pressure hydrogen, will also be described and dis-
cussed.
Delayed Failure in Aqueous Media
Failures in steels exposed to aqueous environ-
ments are most commonly of the delayed-failure
type, and the behaviors are in most respects analo-
gous to the previously described delayed failures
of precharged steels. Incubation is required for
crack initiation, and slow crack growth is usually
involved in the crack propagation that precedes
failure. The behavior is also similarly affected by
the same internal or material factors, particularly
by the strength level.
The principal external factors affecting the be-
havior are the stress level and the effective hy-
drogen pressure of the environment, which governs
the hydrogen content of the exposed steel. Those
factors which increase the effective hydrogen pres-
sure-such as low pH, high cathodic current den-
sities, and particularly the presence of poisons in
the solution-affect the behavior by decreasing the
time to failure at the intermediate stress level be-
tween the upper and lower critical stresses because
these factors increase the rate of hydrogen absorp-
tion. These same factors may also decrease both
the threshold stress for cracking and the ductility
of steel because they increase the hydrogen con-
centration in the steel at saturation. Thus, in
general, the behavior of steel exposed to charging
ronments at these effective pressures, the pressure of
hydrogen inside the defect or micro defect in the
steel increases to a high value at which it leads to
an expansion of the defect. This process, referred
to as fissuring or microfissuring, may occur, of
course, even in steel that is not externally loaded.
Such fissures, whether contained within the steel or
exposed to the surface of the steel, can act as sharp
local notches which may accentuate the effects of
hydrogen in steel and lead to brittle failure at less
than the yield-strength stress level. The con-
tinued expansion of such defects by hydrogen may
form gross cavities, which are commonly referred
to as blisters.
Effective Hydrogen Pressure
The extent to which the properties of steel are
affected by aqueous environments are thus seen to
be primarily dependent upon the effective hydrogen
pressure of the environment. It is known that the
effective hydrogen pressure increases as the sever-
ity of a given charging environment increases, but
the actual effective-pressure values have not been
quantitatively established. In one study con-
ducted at Battelle Memorial Institute and re-
ported 129 by Slaughter and others, the delayed-fail-
ure characteristics were determined for unnotched
tension samples of an SAE 4340 steel with an ulti-
mate tensile strength of 230,000 psi. Sustained-
load tests were conducted in unpoisoned aqueous
solutions containing 1/2 % sodium hydroxide at two
current densities, 125 mA/in. 2 and 500 mA/in. 2 ,
respectively referred to as Battelle Charging Con-
ditions C and D. The results of this study are
illustrated in Fig. 19. At higher current densities,
200
\
160
0,,- °
0
c-
° 0",- ,, DO

environments is consistent with the behavior of 0

2
steels containing hydrogen. yj
120
i~ -500 ma/i;;:-2(Dl
°~
° 0 '0..., 0-

However, laboratory studies have shown that,

(f)
w
0:
~
~
125 malin. (Cl
TEST IN PROGRESS
° 0", "
0 ........
....0
f- . -... 0,
(f) 80
in certain aqueous hydrogen-charging environ-
~--
0
w <::ONDITION A INCLUDED
ments, both smooth and notched tension samples ::i
a.
• FOR COMPARISON o 0-- - - - __
a. 40
may fail at stress levels that are significantly lower " ----------------
than the tensile strength, whereas in smooth speci-
mens of precharged steels delayed failure does not
normally occur at low applied-stress levels. This
delayed failure of smooth tension specimens ex- TIME TO RUPTURE. days

posed to hydrogen-charging environments may re-
sult at low stress levels whenever the environment is
so severe that it leads to surface and internal fissur-
ing of the steel. The effective pressure of certain
aqueous environments can be very high, sometimes
reaching 10 4 to 106 atm., and these pressures may
be beyond the bursting strength of the steel. I t is
believed that when steel is exposed to such envi-
Fig. 19-Delayed-fai/ure behavior during cathodic charging of an
SAE 4340 steel with an ultimate strength of 230,000 psi (Ref. 129).
Battelle Charging Condition C: Electrolyte: 1/2% sodium hy-
droxide in water; current density: 125 mA/in.2; poisons: none.
Battelle Charging Condition D: Electrolyte: 1/2% sodium hy-
droxide in water; current density: 500 mA/in.2; poisons: none.
Battelle Charging Condition A: Electrolyte: 4% (by weight)
aqueous solution of sulfuric acid; current density: SmA/in.2;
poisons 5 drops per liter of poison containing 2 grams of phos-
phorus in 40 ml of CS 2

Basic and Research Aspects 19

 failure occurred in shorter times and at lower stress
levels, presumably because the effective hydrogen
pressure is greater at the higher current density.
In general, the effective pressure of acid solu-
tions, particularly those containing poisons, should
be much higher than thatofa dilutesodiumhydrox-
ide solution. This assumption was substantiated
by the results of tests conducted in a poisoned, 4 %
sulfuric acid solution at only 8 mAjin. 2 , Battelle
Charging Condition A, which are shown in Fig. 19
for comparison with the results of the tests in the
sodium hydroxide electrolyte. Failures occurred
after shorter delay times and at lower applied-
stress levels. In addition, data from permeability
experiments129 indicated that the hydrogen con-
tent of specimens charged under Condition A was
greater than that under Condition D. It was
, found 13G that the permeation rates through an
0.010 in. thick cathodic steel foil ranged from
0.3 X 10- 3 to 5.0 X 10- 3 in. 3/in. 2 /min in the poi-
soned sulfuric acid electrolyte at current densities
ranging from 10 to 300 mA/in. 2 , and from 0.002 X
10- 3 to 0.05 X 10- 3 in. 3/in. 2 /min in the unpoi-
soned sodium hydroxide electrolyte at current den-
sities ranging from 40 to 600 rnA/in 2 • The permea-
tion rate for either electrolyte increased as the cur-
rent density increased, but the permeation rate
produced by the poisoned acid solution was much
greater at all current densities than in the sodium
hydroxide solution. Thus, those conditions which
increase the effective hydrogen pressure of the
environment, as measured by the rate of permea-
tion through steel foils, tend to decrease both the
time to failure and the threshold stress for failure,
and in this regard the sulfide poison is most effec-
tive.
The time to failure will also be affected by the
applied-stress level, as shown in Fig. 20 for an SAE
4340 steel with an ultimate tensile strength of
190,000 psi tested under static loads in a poisoned
acid electrolyte at a range of current densities.
These severe testing conditions give effective hy-
drogen pressures which are qualitatively expressed
in this figure as an equivalent permeation rate
through an 0.010 in. thick specimen. These data
indicate that the time to failure is related (for a
given steel) in a systematic way to the effective
hydrogen pressure and the applied-stress level.
Strength Level
In contrast with the results of unnotched tensile
tests of precharged steels, low-stress delayed fail-
ures occur when smooth bars are tested in severe
charging environments. Compare the precharged
specimens in Fig. 15b with those of Fig. 21. These
results indicate that strength level is also a pre-
dominant factor influencing behavior in charging
environments. Both time to failure and the lower
critical stress decrease with increasing strength
level. In this respect, the behavior of unnotched
specimens under severe hydrogenizing conditions
approaches that of the sharply notched precharged
specimens of Fig. 15a. Furthermore, these un-
notched tension samples failed at applied-stress
levels significantly lower than the threshold stress
that one might predict from results of tests of
precharged steels with sharp notches. I t is be-
lieved that failure occurs at such low stress levels
with the Battelle Charging Condition A because
this poisoned acid charging medium is ver'!
severe, and the effective hydrogen pressure 18
so high that internal and surface fissuring of the
steel occurs.
Surface and Internal Microfissuring
In the Battelle study previously cited,129 it was
demonstrated that surface microfissuring is not a

200~-'------'-------'------'-------'---

CONTINUOUSLY CHARGED
" 150,OOO-PSI
x 125.000- PSI
APPLIED
APPLIED
STRESS
STRESS
•\230.000 ps; USING BATTELLE
CONDITION A (GIVEN IN
_ 100.000- PSI APPLIED STRESS FIGURE 19)
o 75,000 - PSI APPLIED STRESS .~ 150
"
\'='"
+ 50.000 - PSI APPLIED STRESS
o
o
o
(f)
W (f)
a: UJ

"~..
:::> a: 100
il: 10 f-
(f) \\:2,000 pSI 0
:::>
a: o

\~~SI
UJ
o ::i
..
f-
Cl.

PSI
LU Cl.
::;
i= 50
~
.-.~­
~.
,,-------- --
-,150,000 0

!.".-.L----:\::----*.------;rfM.---I01~--5500"OOO
EQUIVALENT PERMEATION RATE FOR VARIOUS CHARGING
TIME TO RUPTURE, m;nutes
CONDITIONS, 10-3 ;n,3/in,2/m;n

Fig.20-Rupture time for SAE 4340 steel at the 190,000 psi Fig. 21-Delayed·failure behavior during cathodic charging of
strength level as' a function of cathodic charging condition unnotched tension samples of SAE 4340 steel heat-treated to
(Ref. 130) • • • •...
, t various strength levels (Ref. 36)

20 Basic and Research Aspects

 ----------- ----------
li-o
..- - - - - - 8"------.1
1
~
-
ELECTROLYTE
LUCITE CELL\, / (LEAD ANODE
~RO~' ~
I HYCAR RUBBER
-S~ ~
=-IN=
r
~ ;8
~ ~g~CI~6
GASKET
BENDING
THICKNESS
Fig. 22-Schematic arrangement of the electrolytic cell and
specimen used in the bend tests of Figure 23 (Ref. 129). Charg-
ing Condition: Electrolyte: 4% sulfuric acid; current density:
33 mA/in.2; poison: presumably the same as that used for
Battelle Charging Condition A given in Figure 19
necessary condition for low -stress failure of steel
in severe environments. In this study the envi-
ronment was permitted to contact only the com-
pressively loaded side of a notched bending speci-
men, as shown in Fig. 22, while the tension side was
exposed to air. This technique inhibits the forma-
tion of surface micro-fissures, because the surface
exposed to the charging medium is loaded in com-
pression. Permeation of hydrogen is not signifi-
cantly affected, and it is believed that the effective
hydrogen pressures that develop inside the speci-
men are very high at steady state. The test speci-
mens were an SAE 4340 steel heat-treated to an
ultimate tensile strength of 230,000 psi. Failures
at stress levels considerably lower than the tensile
strength of the steel were observed, as indicated in
Fig. 23, and none of these failures originated at the
compressively loaded cathodically charged surface.
It can be argued that in this instance, the action of
the electrolyte at the specimen surface does not
influence the behavior by producing surface micro-
fissures which may then propagate at low applied-
stress levels, leading eventually to failure of the
sample. However, if it is assumed that under
these conditions the effective hydrogen pressure at
this cathodic surface is very high (it seems reason-
able to assume that the effective pressure of this
solution is very high, perhaps in the range 10 4 to
105 atm.), then it follows that at steady state very
high internal pressures develop in the tensile region
beyond the neutral axis of this specimen, even
though the pressure approaches zero at the surface
of maximum tensile stress where the sample is
exposed to the atmosphere. These authors right-
fully concluded that low-stress failure in this in-
stance resulted from the combined effects of a low
uniaxial tensile stress (neglecting any effect from
the notch) and a high hydrogen content generated
by the severe charging conditions. By comparing
this charging condition with those previously dis-
Basic and Research Aspects
200
:
i
g
Q
ui
<n
~ 80
in
160
12
\ x
x O.075-IN. ROOT THICKNESS
"
" "
o
~~--·~------~____~x_~
6 6 X 6-~X-
" 0.125 -IN. ROOT THICKNESS
~ g~E~9MkNN ~~<rN~~I~~~ESS
40
WITHOUT FAILURE
I
TIME TO RUPTURE, minutes
I I I I
0.01 0.1 0.5124
TIME TO RUPTURE, days
Fig. 23-Stress-rupture characteristics of notched specimens of
SAE 4340 steel heat-treated to an ultimate tensile strength of
230,000 psi and loaded in bending while being charged cathod-
ically with hydrogen in a poisoned sulfuric acid electrolyte (Ref.
129)
cussed86 for electroplated unnotched samples of
steel containing 2.5 ppm hydrogen (Fig. 15b), one
may conclude that the hydrogen concentrations in
the Battelle samples are much higher at the loca-
tion where failures are presumed to have initiated,
because failures occur at much lower stress levels.
However, the charging conditions found in most
service environments are normally not as severe as
those of Charging Condition A. It follows that
the hydrogen content of steel in most service envi-
ronments is also generally much lower.
Hydrogen Sulfide Environments
Exposure to hydrogen sulfide environments,
commonly encountered in oil-field and refinery
service, has frequently led to low-stress failures.
Extensive laboratory studies have shown that these
failures are delayed failures which will occur on
exposure to most aqueous solutions containing
hydrogen sulfide, because the effective hydrogen
pressure is markedly increased when hydrogen
sulfide is present in most aqueous solutions. This
includes aqueous solutions at any pH level from
zero to 9, as indicated by the data given in Fig. 24,
after Hudgins and others. 40 In this illustration
the severity of solutions with and without sulfides
and at various pH levels is compared in tests with
notches "C" ring specimens of steel at a hardness
level of 33 Rockwell C. The samples were tested
under a sustained load at 115 % of the yield defor-
mation. The sulfide solutions are much more
severe, as the failure times in the sulfide solutions
are much shorter at aU pH levels. This is in agree-
ment with the findings of others, including those of
the Battelle investigators discussed earlier, who
found the poisoned Charging Condition A to be
severe compared with sulfide-free environments.
Accordingly, the acceptable strength level for
steels for service in sulfide environments will gener-
21
 II
10
9 35
7
6
;. 5
4 J:
3
1700-1900_ TOTAL SULFIDE IN 5'" HaC
pH WAS ADJUSTED WITH NoOH AND HCI
X HCI SOLUTIONS
~ ~~r:T~O~d: I~ '; ~:~~CI
NOTCHED'C' RINGS, RC 33 ±I, STRESSED AT 115"'YD
I 100
TIME TO FAILURE, hours
Fig. 24-Failure times as a function of pH, with and without H.S
(Ref. 40)
ally be much lower than that for steels for appli-
cation in sulfide-free environments.
Material Factors Affecting Behavior
Both laboratory tests and service performance
have indicated that, as with precharged steels, the
principal material factor affecting the behavior of
steel exposed to environments containing hydrogen
sulfide is the strength level. However, at the high
hydrogen contents resulting from the high effective
pressure of these environments, even relatively low-
strength steels may be significantly affected. For
steels for petrochemical service, strength level is
commonly expressed in terms of hardness, which is
more convenient to measure. Approximate rela-
tionships between hardness and failure in hydrogen
sulfide environments have been given by Hudgins
and others. 40 Harder steels fail in shorter time, as
indicated in Fig. 25 for samples at various hardness
levels, tested in 5% NaCI solutions containing var-
ious concentrations of hydrogen sulfide. The hard-
ness level also governs the maximum stress level
that can be sustained by the steel in a sulfide envi-
ronment. This is illustrated in Fig. 26 for carbon
steels tested in a 5 % N aCI solution containing
3000 ppm H 2S. Steels at lower hardness levels
sustain a yield-point stress level without failing,
whereas steels at higher hardness levels sustain
only subyield stress levels.
These data indicate that the stress level that
may be sustained by steel in a given environment
is related in a systematic manner to the hardness of
the steel. This interdependence of stress level and
hardness has been expressed quantitatively by
Naumann and Carius 126 , 143 for steels tested in an
aqueous solution saturated (at 1 atm.) with pure
hydrogen sulfide. These authors give the ex-
pression
0'·HV10 constant ~ 21,000 kgjmm2
22
Hf
a: 30
u
en
...enz 25
c
a:
~
20
15 STRESS LEVEL-130% YO
TIME TO FAILURE, hours
1000
Fig. 25-Approximate correlation of failure time with hardness of
steels in 5% NaCI containing various concentrations of H.S
(Ref. 40)
where 0' is the applied tensile stress in kgjmm2
(1 kgjmm2 = 1.422 ksi) and HV10 is the Vickers
hardness number as measured with a 10-kg load.
If this product of stress and hardness number is
less than 21,000 kgjmm2 (29,900 ksi) , infinite life is
predicted. These authors report that this equation
was found to apply to all steels tested (carbon and
stainless chromium steels), regardless of whether
the hardness level was affected by quenching,
tempering, isothermal transformation, or cold roll-
ing. However, it should be noted that the behav-
ior of steel in H 2S environments has been shown by
others to be sensitive to composition, micro-
structure, and processing history, and that very
small amounts of cold working may be deleterious.
At a given strength level, tempered structures are
generally better than untempered structures, and
structures of tempered maitensites and bainites
generally appear to exhibit better performance
than ferritic or pearlitic structures. However, the
effects of heat treatment and microstructure are
not entirely clear because the data are sparse and
often confused by other variables, particularly by
strength level.
It has been generally recognized that steels with
a hardness level of 22 to 25 Rockwell C or above
may be susceptible to hydrogen-stress failure in
sulfide environments. Therefore, it is essential
that, for welded structures used in sulfide service,
the hardness in the heat-affected zone (HAZ) be
considered, in addition to that of the unwelded
steel. Because of the rapid cooling rate in the
heat-affected zone of weldments, the maximum
hardness in the as-welded heat-affected zone will
generally be much higher than the hardness of the
unaffected steel. Therefore, when the heat-affected
zone hardness of the steels used in welded struc-
tures intended for hydrogen sulfide service is
unacceptably high, a stress-relief heat treatment
(12) must be used to reduce the hardness to acceptable
Basic and Research Aspects

35
c.> 3 However, the mechanism leading to failure in sul-
a:
(/)
(/)
ILl
is 25
a:
<I
J:
20
3000 ppm H2S IN
5 PERCENT NoCI
15
DAY WEEK
TIME TO FAILURE. hours
Fig. 26-Approximate correlation of failure time with hardness
and applied stress for carbon steel (Ref. 40)
levels at these local regions. When the design of
the vessels does not permit a stess-relief heat treat-
ment, su~h as in very large storage tanks, only
steels whICh develop an acceptable Jevel of heat-
affected zone hardness in the as-welded condition
should be used for such service.
External Factors Affecting Behavior
CONCENTRATION. The effect of concentration
of H 2S is illustrated in Fig. 25 as approximate cor-
relations with failure time for steels of various
levels of hardness that are stressed well into the
plastic range. Failures occur in shorter times in
the more concentrated solutions. Sulfide concen-
trations of only 1 ppm H 2S, corresponding to a
partial pressure of 0.0005 psi H 2S in the gas phase,
may be sufficient to cause cracking in harder steels,
but the failure time is greatly extended in solutions
with such low sulfide concentration. At the other
end of the concentration spectrum, it is seen that
steels of lower hardness fail in solutions contain-
ing 60,000 ppm H 2S, and the failure times in this
concentrated solution are much shorter at any
hardness leveL
pH LEVEL. Hydrogen sulfide may also extend
the range of pH values at which cracking may
occur, as shown in Fig. 24. In this work, cracking
of notched "C" ring samples loaded at 130% of the
yield deformation occurred only at low pH levels
in a sulfide-free chloride system, whereas cracking
occurred at pH levels well into the alkaline range
in the high-sulfide solutions.
IMPRESSED CURRENTS. The use of impressed
currents can affect the behavior of steel in sulfide
environments. In general, when failures are
caused by a hydrogen-stress mechanism, the appli-
cation of a cathodic current shortens the failure
time and the application of an anodic current
Basic and Research Aspects
lengthens the failure time. Anodic currents can
therefore be helpful in reducing of eliminating
cracking in sulfide environments when these envi-
ronments promote hydrogen-stress cracking (HSC).
fide environments is not always an HSC mecha-
nism. In some instances it may be a stress-cor-
rosion cracking (SCC) mechanism or a combina-
tion of SCC and HSC acting simultaneously. The
SCC mechanism operates by anodic dissolution
along an active path, 41 whereas the HSC mechanism
operates by cathodic absorption of hydrogen.
MONTH The SCC process is therefore accelerated by
impressed anodic currents, and anodic currents
may therefore be used to minimize cracking only
under selected conditions in which the mechanism
is known and the current densities are closely
controlled. However, the increased possibility
for SCC and the increase in the general corrosion
rate under anodic currents may often prohibit
the use of anodic currents.
Gaseous Hyd rogen
Pressure-vessel steels have been used as con-
tainer materials for the room-temperature storage
of hydrogen at elevated pressures for many
years without failure of detectable evidence of
damage. 144 Other typical examples of the suit-
ability of steels for high-pressure hydrogen service
are found in processes for ammonia synthesis and
the hydrogenation of fats. However, the effects
of exposure to gaseous hydrogen on the behavior
of steel are not fully understood so research is
active in this field.
Charging Rate in High-Pressure Hydrogen
Pressures of 100 to 1000 atm., at which hydrogen
is commonly stored, are much lower than the
effective hydrogen pressures of severe aqueous
environments of 1000 to 1,000,000 atm. This
should be reflected in the rate and quantity of
charging from high-pressure hydrogen. However,
only limited data are available and these are not
readily interpreted. In one study 28 only cold-
worked materials were examined, and time of expo-
sure was not systematically varied. Other inves-
tigators 27 , 89 relied on bend ductility of steels to
indicate the degree of charging.
The data of Figs. 27 and 28 for bend-test samples
tested in air show the degree of impairment as a
function of time of exposure to hydrogen at pres-
sures in the range 7000 to 60,000 psi. Time for
saturation for 1/16 in. thick specimens exceeded 10
days. Even at 60,000 psi gaseous hydrogen pres-
sure, charging is slow compared to charging in
acid, as shown in Figs. 3 and 4 for 1/2 in. rounds.
Tensile Behavior
Tension tests in hydrogen at up to 10,000 psi
23
 25r----,----,----,-I---,-I---,----'I----,----,
25.---'1---.1----.-1--.-1--'1----.---.-1--'1---.

jg 2d~ • • \ (jJ e.-,,__O~,,---'®'_----® I/)

o
-

.\'0,
- ~20~
z
UJ
III
"-
o
~
\'
", "" , III
l5 ~. 0 ___ ----_@_
®

ffi ~ A. -
0:
UJ
III
~
151-
'-''0,
- g)
:::>
15-
.-.--yo
'-... ----0
--0-
:::> z
z
~ lO- -
~ leI- - t: KEY:
KEY:
t: SS 430
..J SS 420
..J
;:: III 7,000 PSI ~:::> ® 7,500 PSI 046,000 PSI

~
5- o 15,000 PSI d'52,ooo PSI -
• ~ 15,000 PSI
"
5 5'- " • 36,000 PS I -
o 36,000
40,000
PSI
PSI
.60,000 PSI

" , '-c! g.. ;~:ggg ~~:

• 60,000 PSI o
I I
4
I
9 16
I
25
I
36 49
I I I
64
0~0-~--~1---~1---~'1---~±-1--~~1--~--~
4 9 16 25 36 49 64
EXPOSURE TIME IN DAYS - SQUARE ROOT SCALE

EXPOSURE TIME IN DAYS - SQUARE ROOT SCALE Fig. 28-Ductility of AISI Type 420 martensitic stianless steel
tested in air after exposure to hydrogen gas at room tempera-
Fig. 27-Ductility of AISI Type 430 ferritic stainless steel tested
ture (Ref. 28)
in air after exposure to hydrogen gas at room temperature
(Ref. 28)

pressure showed that the unnotched strength is not
significantly affected, but the notched-bar ductility
and strength may be greatly impaired. 29 - 32 , 132
Figs. 29 and 30 show results for Armco iron and
two carbon steels loaded immediately after hy-
drogen at 2200 psi was introduced into the testing
chamber. As shown in Fig. 29, the reduction-of-
area values are significantly reduced to about
half of the values obtained for specimens tested
in air. Figure 30 compares the strengths of these
steels in tests conducted with notched and
unnotched specimens in hydrogen. The strength,
as measured by the smooth-bar specimens, is gen-
erally unaffected by exposure to hydrogen at 2200
psi, but the strength of the notched-bar specimens
is lower in hydrogen than in air. However, higher
strength steels are more markedly impaired by
exposure to high-pressure hydrogen. For ex-
ample, tests of two steels of about 230,000-psi
tensile strength 30 -32 showed that the strength of
notched specimens tested in hydrogen is below the
strength of unnotched specimens tested in air.
Notched specimens tested under high-pressure
hydrogen normally fail at low stress levels with-
out a significant time delay, and the incubation
period, characteristic of the behavior of precharged
specimens, is normally either absent or very short.
One example of a delayed failure in high-pressure
hydrogen has, however, been reported by Hof-
mann and Rauls. 32 In this instance, notched
specimens of a concrete-reinforcing steel at a
strength level of 233,000 psi tested under 100
atm. of hydrogen failed at a stress level of 215,000
psi; when smooth-bar specimens were tested under
similar conditions they failed at 200,000 psi. The
probability of delayed failures in steels exposed to
high-pressure hydrogen thus appears to be quite
remote.

1...J·:o[
w
;~1
~------~----~--~-----~I-----~I~-~
OJ
~ 80~--- r--- 11141JOO PSIL
80,--------------------------------------, , _ , IIOO,OOo!,~
0-

~ =-1---- 60 - - - - - - - _17" ~!hQ()()~SIL

~QPS!L
; 6 - ________ ~ -.---- -[7---
( 57000 PSI)
?i -r__ ~ 40 ['1--- -
(43000 PSI)
IL 40 '8 :n ,--- -17-
o ~ 20- - 1- - A---------1
z o I/)
o
i= --~o~--------------~g--- ~
r
r--
_ _ _ _--'
g 20 TESTS IN
OL-~~~LL~~~~~LLLL~~LL~

ARMCO-IRON STEEL CK 22 STEEL C45

o • ,AIR, AT I ATM NORMALIZED NORMALIZED
W
_0:: o HYDROGEN, AT 150 ATM
TESTS ON 0 UNNOTCHED SPECIMEN IN 0 AIR, AT I ATM

CARBON CONTENT IN %
B NOTCHED SPECIMEN
f/I
ILl
HYDROGEN, AT 150 ATM
RECALCULATED TO I ATM
Fig. 29-Ductility of Armco iron, CK 22 N (0.22% C - normalized)
steel, and C 45 N (0.45% C - normalized) steel tested in air at Fig. 30-Tension tests on notched and unnotched specimens of
1 atmosphere and under high·purity hydrogen at 150 atmo- Armco iron, CK 22 N (0.22% C - normalized) steel, and C 45 N
spheres. Deformation rate, 3% per minute (Ref. 32) (0.45% C - normalized) steel in air and iri hydrogen (Ref. 32)

24 Basic and Research Aspects

Fracture Behavior
In smooth tension specimens that are fractured
under hydrogen at elevated pressure, many surface
cracks form at locations at which considerable
plastic flow has occurred. The largest cracks, com-
prising the fracture front, lead to premature fail-
ure after the onset of necking. This premature
failure results in a decrease in the reduction of area
at fracture, which presumably occurs when a criti-
cal level of normal stress is reached at the surface.
In notched specimens the observed behavior is
analogous to that in the smooth specimens, with
cracking apparently initiating as a cleavage frac-
ture when a critical level of normal stress is reached
in the region of stress concentration below the
notch. The nominal stress level required to
achieve this level of normal stress is generally some-
what higher for notched specimens than that for
smooth specimens because the triaxial stress state
below the notch area increases the nominal stress
for fracture and because stress relaxation occurs
by plastic flow at the root of the notch. However,
in high-strength steels in which hydrogen is rela-
tively more effective, such stress relaxation is much
more limited and the resultant nominal stress at
failure may be lower for notched samples than for
smooth samples, reflecting a decrease in the engi-
neering stress for failure of notched high-strength
steels.
Fractographic examination reveals that the
reduction of mechanical properties resulting from
the presence of high-pressure hydrogen during
loading to failure is always accompanied by a shift
of failure mode from dimpled rupture to a less duc-
tile, more rapid fracture mode. In the low-
strength steels the fracture mode in air is predom-
inantly dimpled rupture, and fracture in the pres-
ence of high-pressure hydrogen occurs by discon-
tinuous quasi-cleavage mixed with dimpled shear.
In high-strength steels, discontinuous quasi-
cleavage is observed in sharply notched samples
even when tested in air, but when tested in high-
pressure hydrogen such samples fail rapidly by
catastrophic cleavage.
Accelerated Crack-Growth Rates
In tension or fatigue tests of precracked flat spec-
imens of high-strength steels, the rate of growth
of the crack, at stress levels at which crack growth
occurs very slowly when the testing is done in air,
is markedly accelerated when the testing is done in
an environment of pure hydrogen at atmospheric
pressure. Recent work by Hancock and John-
son 133 has demonstrated that such sub critical
crack growth may occur at low stress levels and
with high growth rates when high-strength steel is
exposed to pure hydrogen gas at atmospheric pres-
sure. The acceleration of the crack-growth rate
occurs essentially immediately upon exposure to
Basic and Research Aspects
hydrogen, so that the time required for the growth
of the crack to a critical size for rapid, unstable
fracture is markedly decreased by the presence of
pure hydrogen. This behavior can, however, be
inhibited or completely eliminated by the addition
of small amounts of oxygen to the hydrogen gas.
The inhibiting capacity of oxygen is believed to be
related to the ability (of oxygen) to contaminate
the surface of steel, and prevent or greatly limit
the adsorption of hydrogen at the exposed surfaces.
I t thus appears that hydrogen is effective only
when it can contact the surfaces of the steel at
clean, freshly exposed sites, such as the virgin
metal that is created in Johnson's precracked sam-
ples by the crystal slip resulting from tensile load-
mg.
Unfortunately, very little is known about the
surface behaviors associated with the adsorption
and absorption from gaseous hydrogen; however,
the magnitude of the heat of adsorption is such
that almost full monolayer coverage 94 of atomic
hydrogen is possible at gas pressures as low as 0.1
torr (1.3 X 10- 4 atm.). However, most steel sur-
faces are dirty, and the fractional coverage on
dirty surfaces may be considerably smaller because
hydrogen in the environment does not contact
virgin metal; rather, it contacts other surface
adsorbates or compounds on the exposed surfaces.
Thus, even at very low pressures, hydrogen may
interact with clean steel surfaces, but interaction
with hydrogen may be greatly limited by surface
contaminants and adsorbates such as oxygen.
Predominance of Surface Effects
The observed behaviors under hydrogen gas
strongly indicate that surface behaviors govern
the properties of steel in gaseous hydrogen environ-
ments. The charging rate in gaseous hydrogen
is very slow, and extensive charging requires an
extended exposure to gaseous hydrogen at elevated
pressures. However, the tensile properties are
affected immediately after exposure to high-pres-
sure hydrogen, and a hold time before testing does
not appear to significantly affect this behavior,
indicating that tensile properties are principally
affected by surface effects. A predominant sur-
face behavior is further illustrated by surface
cracking observed on tensile specimens at locations
at which considerable plastic flow has occurred
under gaseous hydrogen at elevated pressures.
Furthermore, atmospheric-pressure hydrogen
causes no significant charging of the bulk steel, but
full monolayer coverage of hydrogen on clean
metal surfaces under hydrogen at atmospheric
pressure leads to sub critical crack growth at accel-
erated rates under low stresses in high-strength
steels.
25
 h:[ I,:::-:::::f]
'" ~
zo
C!> ..
"-CK 22 N

!c::[ ~OQO~~o

]
Z
9
~O
20
o
z ~
o 0
000 '"
Q ; o ~ 15'~====~~~~==~========~==~======~
70r

~60~
t; <>. 20

§~ 0 I I I I I I
~ 50~ ~ ~ .:::--~
II II
100%~10~~1~~1~0-+1~-10~-2~~104-3~-1~~~4~-10~-~5~
..
AIR OXYGEN CONTENT IN HYDROGEN IN VOL. %
~ 40'___ """""------Ii 0-8_ ARMCO-IRON
o : _ _, ~~
Fig. 31-Effect of trace impurities in 100 atm (partial pressure) i= 30 -,___ _ ::-..,.... CK 22 N
.~.
hydrogen on the elongation and reduction of area of CK 22 N 15u • • ...-C45 N
(0.22% C - normalized) steel (Ref. 32) '" 20·~__~~~~~~~~~~wu~~~~~~~
~ I 5 10 20 50 100 200 500
HYDROGEN PRESSURE IN ATM

Fig. 32-Ductility of Armco iron, CK 22 N (0.22% C - normalized)

steel, and C 45 N (0.45% C - normalized) steel tested under
high-purity hydrogen gas at pressures below 200 atmospheres.
Deformation rate, 3% per minute (Ref. 32)
Factors Affecting Behavior

The effect of exposure to gaseous hydrogen on

the tensile properties of steel may be strongly
influenced by the composition of the gas, but is
only moderately influenced by the pressure. The
effect of composition is illustrated in Fig. 31,
given for smooth-bar tension specimens of a nor-
malized 0.22 % carbon steel tested under a pres-
sure of 100 atm. In pure hydrogen gas, the duc-
tility, as measured by the reduction of area and
elongation, is lower than the ductility in air, but
the addition of as little as 10 -3 volume percent
oxygen to the gas partially restores the ductility
to a level near the ductility in air, and the ductil-
ity is completely restored by the addition of 2 %
oxygen.
Under pure hydrogen gas, the tensile properties
are affected somewhat more at higher pressures
than at lower pressures, but an increase in pres-
sure over the practical operating range of pres-
sures used for hydrogen storage leads to only a
moderate decrease in the tensile properties of those
steels used for hydrogen storage. The effect of
pressure is illustrated in Fig. 32 for tests under
high-purity hydrogen gas at pressures from 1 to 150
atmospheres. The ductility of Armco iron and two
carbon steels is shown to generally decrease with
increasing gas pressures, but an increase in pres-
sure beyond some critical value results in little or
no increase in the effect of hydrogen, as indicated
for the C 45 N steel of Fig. 32. For this steel, any
pressure from 50 atm. (740 psi) to 150 atm. (2200
psi) is equally effective. Additionally, recent
work at Rocketdyne I32 on pressure-vessel steels
indicates that an increase in pressure from about
3000 to 10,000 psi leads to only a moderate de-
crease in the tensile properties.
High-pressure hydrogen apparently affects the
steels only after yielding has occurred, and in
smooth-bar tension tests its effect is to decrease
the ductility without significantly affecting the
ultimate tensile strength. This behavior is not
markedly affected by the strength level over the
range of strength levels used for pressure-vessel
steels. For notched specimens, in which localized
plastic flow at the notch occurs at relatively low
nominal stress levels, so that the effects of high-
pressure hydrogen are much more pronounced, its
effect is to markedly decrease the notch strength;
this effect will become more pronounced as either
the strength level of the steel, or the notch acuity
at a given strength level, increases.
The tensile behaviors in high-pressure hydrogen
are relatively insensitive to strain rate over the
range of strain rates normally expected in service,
although a strain-rate effect has been reported. 32
The effect of hydrogen may be markedly reduced
at faster deformation rates of the order of 100 to
300% per minute.
Part E. Mechanisms of Hydrogen Damage
Although many uncertainties and inconsisten-
cies still remain, it is generally agreed that the
harmful effects of hydrogen in steel result primar-
ily from its precipitation at local internal sites,
with the resulting pressure exerting a local stress
which augments the applied stress and acceler-
ates crack propagation, either by increasing void
nucleation and growth or by promoting the propa-
gation of microcracks by cleavage fracture, so that
the strain at fracture is significantly decreased.
In addition, the marked decrease in surface
energy resulting from the presence of an adsorbed
layer of hydrogen on the internal surfaces may also
significantly lower the stress level at which unsta-
ble propagation of microcracks by cleavage can
occur. Both the pressure-augmented stress and

26 Basic and Research Aspects

the decreased surface energy lead to the commonly
observed characteristic of an increased susceptibil-
ity to cleavage fracture at low applied-stress levels.
Effect of Hydrogen on Microcrack Propagation
The gross movement of dislocations that occurs
during plastic deformation in high-strength steels
gives rise to the formation of micro-cracks which
form by the coalescence of dislocations which may
pile up at a grain boundary or at some other
barrier to the movement of dislocations through
the lattice. Such a microcrack is wedge-shaped
and a potent stress raiser, which generally persists
only while the shear stress that acts to form the
pileup is maintained. If the stress on the pileup
is relaxed, either by releasing the applied load or
by plastic relaxation at the tip of the microcrack,
the stored energy of the pileup is dissipated, and
and the potency of the micro crack is diminished.
Such a pileup of dislocations may grow to form
a cleavage crack when the stress on the microcrack
reaches the critical level required for its growth.
The stress required for growth of a pileup of n dis-
locations of Burgers' vector b is given by
21'
(TG = nb (13)
where l' is the work done in the micro crack propa-
gation. This work includes the work done in
creating new surface and the plastic work that may
occur at the crack tip. The effect of hydrogen on
this process is to reduce the applied stress required
for unstable growth of the microcrack. It may
do this either by decreasing the value of l' by
decreasing the amount of work required to create
new surface, or by augmenting the applied stress
with gas pressure 3 from within the microcrack.
The surface-energy-Iowering effect of hydrogen
may be a predominant factor in the propagation
of microcracks in high-strength steels of relatively
low ductility. I t is well known that the surface
energy of iron is lowered by the adsorption of hy-
drogen' and such adsorption occurs on clean sur-
faces, even at very low pressures of hydrogen, so
that the value of surface energy of the iron with
adsorbed hydrogen, 1's(H), represents only a
fraction of the energy of the clean surface, 1'8'
However the energy involved in the stability of a
microcrack, 1', includes this surface energy, 1'., and
an energy of relaxation of plastic work, p, done at
the crack tip. Until recently, it has been believed
that the energy of plastic work must dominate the
energy for creating new surfaces in iron, being
about 20 times as large as the true surface energy.
However, it is very doubtful that this is true in all
cases. For example, it is generally known that
fracture of steels at higher strength and at lower
temperatures may result with very little plastic
work. Additionally, a significant lowering of this
Basic and Research Aspects
plastic-work term has been given in a recent analy-
sis by Hahn and Rosenfeld,138 indicating that the
total energy may, in general, be lower than had
previously been believed. Thus it appears that
the effect of hydrogen in lowering the surface en-
ergy, as originally proposed by Petch 24 for the
case of pre-existing cracks, may well be a signifi-
cant factor in decreasing the stress required for
microcrack propagation. However, this effect is
only important in steels that are of relatively low
ductility, and in which the plastic-work term is
smalL Such steels include high-strength steels and
steels at relatively low temperatures. However,
in steels that are more ductile at atmospheric tem-
peratures, and even in high-strength steels at much
above atmospheric temperatures, the plastic-relax-
ation term is very much larger and becomes rela-
tively much more significant, so that the surface-
energy effect of adsorbed hydrogen becomes rel-
atively insignificant.
In all steels, the applied stress required for growth
of a micro crack may be decreased by the pressure
of hydrogen gas in the void space of a<mi~rocrack.
This pressure augments the applied stre~& and can
lead to unstable crack growth, even up~eFcondi­
tions requiring a significant contribution of plastic
relaxation to the energy of microcra~k growth.
The buildup of pressure in a microcrack may result
from the normal diffusion of hydrogen that occurs
to relieve gradients in the activity of hydrogen in
steels. By this process, the pressure inside the
void spaces tends to equilibrate with the effective
pressure (fugacity) of hydrogen in solution in the
lattice; this pressure, will of course, be high when
the fugacity of hydrogen within the steel is high.
Moreover, a nonequilibrium overpressure of hydro-
gen may result from the movement of dislocations
through the lattice. Bastien's137 conclusion that
moving dislocations transport hydrogen to the
region where the motion of the dislocations is ter-
minated suggest this behavior.
Thus, microcracks propagate under some critical
combination of the effects of the decreased surface
energy resulting from hydrogen adsorption, the
pressure of hydrogen gas in the microcrack, and
the applied stress, resulting in the nucleation and
growth of cleavage cracks, which under unfavor-
able conditions may rapidly propagate to cata-
strophic failure. When plastic relaxation of the
microcrack results before this critical combination
is attained, additional stressing may be required
until, through work hardening, the stress exerted
on the microcrack is sufficient for microdeavage
cracking. Therefore, greater strains are normally
required for the growth of microdeavage cracks in
lower-strength, higher-ductility steels; in addition,
under a fixed level of strain, the hydrogen content
or the internal hydrogen pressure required for mi-
crodeavage cracking is much greater for such
steels.
27
Effect of Hydrogen on Void Growth, Coalescence, and
Crack Growth
In the more ductile steels, the principal effect of
hydrogen is to augment the normal rupture process
in which fracture occurs as the result of the nuclea-
tion, slow growth, and coalescence of voids. The
range of strength levels and temperatures at which
this latter behavior predominates is generally much
more typical of the steels and operating conditions
of pressure vessels than the higher strength levels
and moderately lower temperatures at which the
cleavage mechanism of micro-crack propagation
predominates.
In the early stages of plastic flow, the normal
rupture process begins with the interaction of dis-
locations with other dislocations and other lattice
imperfections, with a resultant void formation at
microsites. Such void formation is most pro-
nounced around second-phase particles, which act
as void nuclei about which the matrix, with lower
flow stress than that of the particle, is deformed.
With further straining, additional voids are formed,
and nearby voids coalesce and form larger voids or
cracks. Because the stress concentration at the
tips of cracks is much higher than that around
other voids, the void-formation process is acceler-
ated in the region ahead of the initial cracks, and
the cracks tend to grow by repetitions of this
process. This slow crack growth continues to the
point of instability, at which fracture either (1)
occurs as a ductile tensile failure if the fracture
strength of the remaining uncracked area is
exceeded, or (2) occurs by unstable crack propaga-
tion if the crack reaches the critical size given by
the Griffiths-Irwin relationship, which is
7fC = (KcI a-)2 (14)
where C = 1/2 critical crack length, in inches;
Ke =critical stress intensity for unstable fracture,
in psiVin.; (]" = applied stress, in psi.
Fracture by the nucleation and growth of voids
occurs at relatively lower levels of strain when
hydrogen is present, since both the nucleation and
the growth phases of this normal rupture process
may be accelerated by the pressure of hydrogen
inside voids and cracks. This local augmentation
of the applied stress by hydrogen pressure will lead
both to additional void nucleation at sites of lower
stress concentration at which voids would not be
nucleated by the applied stress alone and to the
achievement of the local stress levels required for
the plastic expansion of voids at lower applied-
stress levels. Thus, the pressure-augmented stress
leads to instability at lower levels of strain, and
fracture occurs at lower applied-stress levels.
This effect of hydrogen pressure on the normal
rupture process will be time-dependent. Although
the voids in the unstrained steel contain hydrogen
at the equilibrium pressure, the pressure in the
28 Basic and Research Aspects
voids decreases as the void volume increases.
Therefore, the pressure-augmented applied stress,
which expands the voids and leads to void coales-
cence and crack growth, is diminished in the
larger volume in which hydrogen is contained
at some pressure below the equilibrium level.
With time, the pressure in the expanded voids
builds up to the equilibrium level at which its
effect is again more pronounced. This effect of a
pressure decrease in the expanded void volume
will tend to make the effects of hydrogen pressure
intermittent so that crack growth may stop and
restart, with the crack growth rate being governed
by the rate of hydrogen diffusion into the voids and
cracks.
Significance of the Mechanism of Hydrogen Damage
to Pressure-Vessel Behaviors
Because the avoidance of low-stress, rapidly prop-
agating fracture is of principal concern in pressure-
vessel applications, the mechanism of damage by
hydrogen is primarily important in relation to its
role in promoting such rapid, unstable fracture.
As described in the preceding section, hydrogen may
accelerate the slow crack growth that precedes the
unstable crack growth to fracture. Therefore, the
hydrogen-augmented slow crack growth processes
are important in considering whether a crack will
penetrate the pressure-vessel wall before the critical
crack size for rapid propagation is realized. When
such penetration of the wall by a slow crack growth
process occurs before the crack is of a critical size,
the resulting failure by leaking is generally more
desirable and much less dangerous than rapid,
unstable fracture from a part-through, critical-size
crack. Thus, when failure is. by rapid, unstable
fracture, the role of hydrogen in the mechanism for
the failure becomes a very significant consideration.
In this context, the fracture toughness, in terms
of the critical stress intensity value, K e, which
establishes the limiting conditions of stress level and
crack size for unstable fracture, presents a very
important consideration with respect to both pres-
sure-vessel performance and the significance of the
effect of hydrogen on pressure-vessel safety. If the
fracture toughness is high enough to assure that
general yielding will occur through the thickness of
a pressure vessel when a through-thickness crack
develops, the effect of hydrogen on the slow crack
growth leading to the development of the penetra-
tion will be significant only because it has somewhat
reduced the stress level at which the penetration and
the resultant leaking are developed. The minimum
fracture-toughness level which will assure this leak-
ing behavior, when a through-thickness crack of a
length equal to twice the plate thickness is present,
has been shown by considerations based on the
Grffiths-Irwin equation to be represented by the
following equation:

(15)
where Kc = critical stress intensity, in psiVin.;
YS = 0.2% offset yield strength, in psi; B =
plate or wall thickness, in inches.
Since fracture toughness or K c values, in general,
increase with a decreasing yield strength, this equa-
tion shows that a decrease in strength level would
generally very markedly favor the general yielding
behavior, and would increase the plate or wall-
thickness range over which a desirable "leak before
break" behavior would be assured.
If, however, the fracture toughness is too low,
relative to the yield strength, to permit a general-
yielding behavior to occur at the wall thickness of
the application, the augmentation of the slow crack
growth process by hydrogen becomes of very serious
concern, not only as a source of low-stress failure,
but also, and more importantly, because this failure,
when it occurs, will be rapid and may be cata-
strophic.
Part F. Research Areas for Future Work
It is apparent from this report that the research
work in the field of hydrogen in steel has been very
extensive and that the literature on the subject is
very voluminous. However, although these exten-
sive researches have resulted in the establishment of
a considerable background of quantitative informa-
tion about the behavior of hydrogen in steel and
about its effect on the properties of steels containing
hydrogen or exposed to environments which contain
hydrogen, the applicability of much of this informa-
tion to pressure-vessel steels, and particularly to the
service performance of pressure vessels fabricated
from such steels, is distinctly questionable. These
extensive research programs have, furthermore, led
to a reasonable degree of understanding of the
mechanisms involved in the observed behaviors and
effects, but again, many uncertainties remain.
These are most evident in the areas of the behavior
and effects of hydrogen in steels of the relatively
low strength and relatively high ductility which
typify the pressure-vessel steels.
The postulated mechanism for hydrogen damage,
which involves the propagation of microcracks as a
result of the reduced surface energy and the pres-
sure which develops when hydrogen diffuses into
the microcracks, appears to be entirely consistent
with the observed behaviors and with the predomi-
nance of cleavage or quasi-cleavage fracture behav-
iors observed in the fractures of high-strength
steels in the presence of the hydrogen. In lower
strength steels, however, in which the prevalence of
microcracking is far lower than in the high-strength
steels, and in which the predominant fracture mode,
at least in the absence of hydrogen, is by void coales-
cence rather than by cleavage, the applicability of
Basic and Research Aspects
this mechanism is obviously questionable, and many
uncertainties remain about the mechanisms of hydro-
gen damage in such steels. An important objective
of further research in this field would, therefore, be
to establish the extent to which the increased sus-
ceptibility to failure by the microcrack-propagation
mechanism, which is the predominant source of the
harmful effects of hydrogen in the higher strength
steels, remains as a predominant factor in the be-
havior of the lower strength steels in the presence
of hydrogen.
This could be investigated by delayed-failure
tests of sharply notched or, preferably, precracked
specimens exposed to hydrogen environments.
Such tests should be conducted with hydrogen pres-
sure (or fugacity), temperature, and strength level
as variables, and the propensity to micro-cleavage
failure, as a function of these variables, should be
investigated by electron-fracto graphic studies of
failed specimens. The planning of further research
programs would then be largely dependent upon the
results of this program. If these results indicate
that failure in the microcleavage mode still predom-
inates at conditions of temperature, strength
level, and hydrogen contents or effective pressures
which are within the ranges applicable to pressure-
vessel operations, the emphasis on further research
should be on the establishment of limiting condi-
tions for these variables with respect to this behav-
Ior.
If these limiting conditions are found to be such
that operation outside of these limits would be
impractical for specific pressure-vessel applications
of concern, the significance of the hydrogen effects
with respect to the danger of low-stress failures
should be quantitatively evaluated by delayed
failure tests of precracked specimens, such as
notch-bend, cantilever-beam, or wedge-opening-
loaded specimens, under conditions of temperature,
strength level, and hydrogen content or effective
pressure representative of the application. The
specimens for these tests should preferably be thick
enough to assure an essentially plane-strain behav-
ior; the test results would then be in terms of a
threshold stress-intensity value, K IH , below which
failure would not occur even after long exposure
times. In addition, it would be desirable to monitor
the crack growth during tests at KI values above
the threshold value, so that the effect of hydrogen
on crack growth rates would also be quantitatively
established as a function of stress intensity. If the
wall thickness of the application of concern is such
that plane-strain behavior would not be probable,
this testing should be done with full wall thickness
specimens, and the emphasis would be on the estab-
lishment of crack growth rates as a function of
stress intensity, as a basis for the establishment of
limiting times for the growth of through-thickness
cracks.
If, however, the initial program should indicate
29
that operation of pressure vessels would be feasible
under conditions in which ductile rupture rather than
microcleavage behaviors would predominate, the
emphasis in further programs should be on the
effect of hydrogen on the plastic behaviors which
govern the void nucleation and coalescence leading
to failure in the ductile-rupture fracture mode.
The significance of hydrogen effects on ductile-
rupture behaviors could be qualitatively evaluated
by delayed-failure tests of precracked notched
specimens under conditions in which general yield-
ing occurs before the specimen fails. However,
tension tests of wide plate specimens with part-
through surface cracks, which would simulate more
closely the service failure conditions, would be more
appropriate for quantitative evaluations of hydrogen
effects when failure is by ductile rupture.
These evaluation programs should be supple-
mented by hydrogen permeation and solubility
measurements. Such measurements will furnish
a basis for the quantitative establishment of test
conditions with respect to the hydrogen contents
or the effective pressure of environments which
is essential for meaningful and broadly appli-
cable evaluations. In addition, such measurements
will furnish information on trapping behaviors and
on the relative significance of "trapped" and lattice-
dissolved hydrogen with respect to the effects ob-
served in the evaluation programs. This informa-
tion would also serve as a basis for investigations of
the significance of factors such as inclusions, carbide
particles, or voids, which would represent probable
trapping sites, with respect to observed behaviors
in either the micro cleavage or ductile-rupture frac-
ture regimes.
The above-suggested research programs represent
a long-range approach which it is believed would
furnish the pertinent answers required to establish
realistically the significance of hydrogen as a factor
affecting pressure-vessel performance. However,
because of the difficulties and very considerable
time and expense involved in some of the phases of
the overall program, it is important that careful
consideration be given to the planning of individual
programs so that the most pertinent and immedi-
ately urgent answers are obtained first. The basic
importance of the initial programs, aimed at estab-
lishing the limiting conditions for failure by micro-
cleavage-fracture propagation, has been emphasized
in this discussion, and the desirability of initial
programs with this objective is apparent.
In addition, the initial efforts should be aimed at
obtaining answers which are applicable to problem
areas of most immediate concern. Because pres-
sure vessels for the containment of high-pressure
hydrogen and pressure vessels exposed to environ-
ments containing hydrogen sulfide represent two
such problem areas of immediate concern, an in-
itial program is suggested which would involve
sustained load tests of notched and fatigue-
30 Basic and Research Aspects
cracked specimens of pressure-vessel steels with
yield strengths ranging from about 40 to 125
ksi in environments of dry gaseous hydrogen at pres-
sures ranging from 1 to 100 atm. (representative of
the range of effective pressures encountered in high-
pressure hydrogen), and in aqueous environments
at pH levels of about 4 and 7 and with and without
H 2S additions (representative of environments of
relatively high effective pressures of hydrogen).
Threshold stresses for failure in 100 hr. would be
measured and the microfracture behavior would
be evaluated by electron microfractography. Al-
though tests as a function of temperature would
be desirable, this would involve experimental diffi-
culties; the initial testing would therefore be con-
ducted at room temperature. These tension tests
should be supplemented by permeation and solubil-
ity measurements to provide quantitative evalua-
tion of effective hydrogen pressures. The results of
such a program should, however, furnish pertinent
information both on the significance of microcleav-
age-fracture behaviors, in relation to low-stress
failures, and on the significance of strength level and
effective hydrogen pressure as factors affecting
the microfracturing behaviors. This information
would then form a sound basis for the planning of
further research programs which should furnish
more definite and quantitative answers within these
problem areas.
Acknowledg ments
The author wishes to thank the management of
the Applied Research Laboratory of U. S. Steel
Corporation for permission to write this report.
The author appreciates the efforts of colleagues,
among whom are W. D. Doty, J. H. Gross, C. D.
Kim, R. D. Manning, W. J. Murphy, M. A. Ore-
hoski, R. A. Oriani, and E. H. Phelps, who reviewed
the report, and J. M. Hodge whose willing ear and
general counsel were of great value to the author in
the writing of the report. Finally, the author
acknowledges the members of the Materials Divi-
sion of the PVRC for reviewing the report and in
particular F. Prange, for his encouragement and
constant interest which he offered as Chairman of
the Subcommittee on Hydrogen Embrittlement.
References
1. Kerlie, W. L., and Richards. J. H., "Origin and Elimination of Hy-
drogen in Basic Open Hearth Steels," Jnl. Metals, 9,1541-1548 (Dec. 1957).
2. Hodge, J. M., Orehoski, M. A., and Steiner, J. E., "Effect of Hydro-
gen Content on Susceptibility to Flaking," Trans. AIME, 230, 1182-1192
(Aug. 1964).
3. Garafalo, F., Chou, Y., and Amhegaokav, V., "Effect of Hydrogen on
Stability of Microcracks in Iron and Steel," Acta Met., 8(8), 504-512
(1960).
4. Gulyaev, B. B., and Solntsev, Yu. P., "Hydrogen in Liquid Steel,"
Gases in Cast Metals, Consultants Bureau, 1965, pp. 5-11.
5. Orehoski, M. A., and Hornak, J. N., "Effect of Vacuum Stream De-
gassing on Properties of Forging Steels," Elec. Furnace Cont., Proc, , 16,
68-84 (1958).
6. Sievert, A., "Solubility of Hydrogen in Copper, Iron, and Nickel,"
Z. Phys. Chem., 77, 591 (1911).
7. Darken, L. S., and Gurry, R. W., Physical Chemistry of Metals,
McGraw-Hill, N ew York, 1953, p. 210.
8. Barnartt, S., "General Concepts of Stress-Corrosion Cracking,"
Corrosion, 18 (9), 322t (Sept. 1962).
 9. Johnson, H. H., Morlet, J. G., and Troiano, A. R., "Hydrogen, Crack
Initiation, and Delayed Failure in Steel," WADC-TR-57-262, May 1957.
10. Foster, G. L., Dakes, B. D., and Duuera, C. H., "Acetylenic Cor-
rosion Inhibitors," Ind. Eng. Chem., 51, 825-828 (1959).
11. Edwards, K. N., Nowacki, L. J., and Mueller, E. R., "Acetylenic
Alcohol-Inhibited Pickling Bath as a Pretreatment Prior to Lining Steel Pipe,"
Corrosion, 15, 275t-278t (1959).
12. Heyn, E., and Bauer, 0., "Influence of the Treatment on the Solu-
bility of Steel in Sulfuric Acid" Jnl. Iron Steellnst., 79, 109-241 (1909).
13. Phalen, D. 1., Adelson, E., Austin, A. E., and Vaughan, D. A., "Struc-
tural Changes in High-Strength Steel Associated with Stress Corrosion and
Its Relationship to Delayed Failure," Contract No. NOw-66-0201-C, Project
No. WR007-01-01, Code RRMA-25.
14. Riggs, O. L., Jr., and Radd, F. J., "Physical and Chemical Study of an
Organic Inhibitor for Hydrogen Sulfide Attack," Corrosion, 19(1), It-8t
(January 1963).
15. Jackson, A., Oxygen Steelmaking for Steelmakers, George Newnes,
Ltd., Towerhouse, Southampton St., London, W. C., 2, 1964.
16. Steigerwald, E. A., Schaller, F. W., and Troiano, A. R., "Effect of
Temperature on the Static Fatigue Characteriatics of Hydrogen Embrittled
4340 Steel," W ADC TR 58-178, April 1958, 20 pages.
17. Steigerwald, E. A., "Delayed Failure of High-Strength Steel in
Liquid Environments," Am. Soc. Testing Mater. Proc., 60, 750-760, (1960).
18. Johnson, H. H., and Willner, A. M., "Moisture and Stable Crack
Growth in High Strength Steel," Appl. Mater. Res., 4(1) 34-40 (January
1965).
19. Johnson, H. H., Morlet, J. G., and Troiano, A. R., "Hydrogen.
Crack Initiation, and Delayed Failure in Steel," Trans. AIME, 212, 528-
532 (August 1958).
20. Hancock, G. G., and Johnson, G. G., "Hydrogen, Oxygen, and Sub-
critical Crack Growth in High-Strength Steel," Trans. AIME, 236, 513
(April 1966).
21. Dahlberg, E. P., "Fatigue Crack Propagation in High Strength 4340
Steel and Humid Air," Trans. ASM, 58, 46-53 (1965).
22. Troiano, A. R., "The Role of Hydrogen and Other Interstitials in the
Mechanical Behavior of Metals," Trans. ASM, 52, 54-80 (1960).
23. Li, J. C. M., Oriani, R. A., and Darken, L. S., "The Thermodynamics
of Stressed Solids," Z. Physik. Chern. Neue Folge, 49(3/5), 271-290 (1966).
24. Petch, N. J., "Lowering of the Fracture Stress Due to Surface Ad-
sorption," Phil. Mag., I, 331-335 (1956).
25. Steigerwald, E. A., Schaller, F. W., and Troiano, A. R., "The Lower
Critical Stress for Delayed Failure," W ADC TR 59-445, August 1959, 30
pages.
26. Mihelich, J. L., and Troiano, A. R., "Delayed Failure in a Hydro-
genated Face Center Cubic Alloy of Nickel," Nature, 197, 996-997 (March
1963).
27. Van Ness, H. C., and Dodge, B. F., "Effect of Hydrogen at High
Pressures on the Mechanical Properties of Metals," Chern. Engrg. Prog.,
51(6),266-271 (June 1955).
28. Perlmutter, D. D., and Dodge, B. F., "Effects of Hydrogen on Prop-
erties of Metals," Ind. Eng. Chern., 48(5), 885-893 (May 1956).
29. Hofmann, W., Rauls, W., and Vogt, J., "Versprodung von Stadl
durch eine aussere Wasser Stoffatmosphlire bei Raumtemperatur," Acta
Met., 10, 688-690 (July 1962).
30. Cavett, R. H., and Van Ness, H. C., "Embrittlement of Steel by High
Pressure Hydrogen Gas," WELDING JOURNAL, 42(7), 3168-319s (July 1963).
31. Steinman, J. B., Van Ness, H. C., and Ansell, G. S., "The Effects of
High-Pressure Hydrogen Upon the Notch Tensile Strength and Fracture
Mode of 4140 Steel," WELDING JOURNAL, 44(5), 221s-224s (May 1965).
32. Hofmann, W., and Rauls, W., "Ductility of Steel Under the In-
fluence of External High Pressure Hydrogen," WELDING JOURNAL, 44(5),
225s-320s (May 1965).
33. Metals Handbook, ASM (1948), p. 1208.
34. Smith, P. P., Hydrogen in Metals, The University of Chicago Press,
Chicago, Ill., 1948.
35. Scheutz, A. E., and Robertson, W. D., "Hydrogen Absorption, Em-
brittlement, and Fracture of Steel," Corrosion, 13(7), 437t-458t (July 1957).
36. McEowen, L. J., and Elsea, A. R., "Behavior of High Strength Steels
Under Cathodic Protection," Corrosion, 21(1),28-37 (January 1965).
37. Spitzig, W. A., and Wei, R. P., "A Fractographic Investigation of the
Effect of Environment on Fatigue-Crack Propagation in an Ultrahigh-
Strength Steel," ASM Trans. Quart., to be published.
38. Besnard, S., "Influence De La Haute Purete Du Fer Sur Son Apti-
tude Au Chargement en Protons (Hydrogene Cathodique) Et Sur Sa Frag-
ilite a Basse Temperature," Ph.D. Thesis, University of Paris, 1961.
39. Elsea, A. R., "Studies on Hydrogen Stress Cracking," Pipeline Re-
search Committee of AGA, Symposium on Line Pipe Research, Nov. 1965,
pp. 197-214.
40. Hudgins, C. M., McGlasson, R. L., and Rosborough, W. M., "Hy-
drogen Sulfide Cracking of Carbon and Alloy Steels," Corrosion, 22(8),
238-251 (August 1966).
41. Fletcher, E. E., Berry, W. E., and Elsea, A. R., HStress-Corrosion
Cracking and Hydrogen-Stress Cracking of High-Strength Steels," DMIC
Report 232, July 1966, 20 pages.
42. Sardisco, J. B., and Pitts, R. E., "Mechanism of Sulfide Film For-
mation and Kinetics of Corrosion Reaction," Corrosion, 21(8), 245-255
(August 1965).
43. Herzog, E., "Development of Steels Resistant to Hydrogen Sulfide,"
Ind. Eng. Chem., 53(9), 64A-68A (September 1961).
44. Sardisco, J. B., and Pitts, R. E., "Protectiveness of the Sulfide Film
as a Function of pH," Corrosion, 21 (11), 350-354 (November 1965).
45. Mazanec, K., and Vejnoha, R., "Delayed Fractures in Martensite,"
Trans. AIME, 233,1602-1607 (August 1965).
46. Fletcher, E. E., and Elsea, A. R., "Hydrogen Movement in Steel-
Entry, Diffusion, and Eliminstion," DMIC Report 219, June 1965, 80 pages,
196 references.
47. Elsea, A. R., and Fletcher, E. E., "Hydrogen-Induced, Delayed, Brit-
tle Failures of High-Strength Steels," DMIC Report 196, January 1964,
154 pages, 11 7 references.
48. Holshouser, W. L., and Bennett, J. A., "Gas Evolution From Metal
Surfaces Duriog Fatigue Stressing," ASTM Proc., 62, 683-694 (1962).
Basic and Research Aspects
49. Spitzig, W. A., Talda, P. M., and Wei, R. P., "Fatigue Crack Prop-
agation and Fractographic Anslyais of 18Ni (250) Maraging Steel Tested in
Argon and Hydrogen Environments," Eng. Fracture Meeh., 1(1), 155-166
(June 1968).
50. Wei, R. P., Talda, P. M., and Li, Che-Yu, "Fatigue-Crack Propagation
in Some Ultra-High-Strength Steels," Symposium on Fatigue Crack Propaga-
tion, Sixty-Ninth Annual Meeting of the ASTM, Preprint 41, June 1966.
51. Farrel, K., and Quarrel, A. G., "Hydrogen Embrittlement of an Ultra-
High-Tensile Steel," Jnl. Iron Steel Inst., 202(12), 1002-1011 (December
1964).
52. Johnson, E. W., and Hill, M. L., "The Diffusivity of Hydrogen in
Alpha Iron," Trans. Met. Soc., AIME, 218, 1104-1112 (December 1960).
53. Podgurski, H. H., "Trapping of Hydrogen in Cold Worked Steel,"
Trans. Met. Soc., AIME, 221(4), 389-394 (April 1961).
54. Hill, M. L., and Johnson, E. W., "The Solubility of Hydrogen in Alpha
Iron," Trans. Met. Soc., AIME, 221(12), 622-629 (December 1961).
55. Toh, T., and Baldwin, W. M., "Ductility of Steel with Varying Con-
centrations of Hydrogen," Stress Corrosion Cracking and Embrittlement,
Robertson, W. D., ed., John Wiley and Sons, Inc., New York, 1956, pp.
176-186.
56. Hill, M. L., and Johnson, E. W., "Hydrogen in Cold Worked Iron
Carbon Alloys and the Mechanism of Hydrogen Embrittlement," Trans.
AIME, 215(8),717-725 (August 1959).
57. Hewitt, J., "Recent Work on Hydrogen in Liquid Steel," Hydrogen. in
Steel, Harrogate Conference, British Iron and Steel Resesrch Association,
The Iron and Steel Institute, Oct. 1961, pp. 15-23.
58. Taylor, D. M., "Calcareous Coatings: Corrosion Engineer's Off-
shore Ally," Pipe Line Ind., 10, 36-39 (March 1959).
59. Uhlig, H. H., Corrosion and Corrosion Control, Wiley & Sons, New
York, N. Y., 1963, p. 188.
60. Hill, M. L., "The Behavior of Hydrogen in Iron and Steel," Hydro-
gen Embrittlement in Metal Finishing, Read, H. J., ed., Reinhold Publishing
Corp., New York, 1961, pp.46-60.
61. Cae, F. R., and Moreton, J., "Diffusion of Hydrogen in Low-Alloy
Steel," Jnl. Iron Steel Inst., 205(4), 366-370 (April 1966).
62. Hudson, R. M., "Hydrogen Adsorption by and Dissolution Rate of
Low-Carbon Steel in Sulfuric, Hydrochloric, Phosphoric and Nitric Acids,"
Corrosion, 20 (8), 245t-25lt (August 1964).
63. Dalezin, S. A., and Nikol'skii, I. V., "Hydrogen Absorption as a
Function of Carbon Content During Nitric Acid Pickling of Steel," Uch.
Zap. Mos. Gos. Ped. Inst., 99; Kafedra Obshch. Anal. Khim., 6, 23-26 (1957).
64. Balezin, S. A., and Nikol'skii, I. V. "Hydrogen Brittleness of Low-
Carbon Steel Developed in the Process of Pickling in Nitric Acid," Nauchn.
Dokl. Vysshei Shkoly, Met., 2,224-226 (1959).
65. Sachs, K., and Odgers, M., "Hydrogen Absorption and Ductility of
Mild Steel Mter Pickling or Cathodic Treatment," Metallurgia, 69,105-113
(March 1964).
66. Smialowski, M., Hydrogen in Steel, Addison-Wesley Publishing Co.,
Inc., 1962.
67. Bockris, J. O. M., and Devanathan, M. A. V., Hydrogen Evolution:
The Effect of Surface Concentration, Final Report to Office of Naval Research,
Contract Nonr 551 (22) NR 036-028, Office of Technical Services, AD608001.,
Nov. 1964.
68. Konar, J., and Banerjee, G., "Dissolution of Steel and Absorption of
Hydrogen by Steel During Acid Pickling in the Presence of Inhibitors,"
NML Tech Jnl., 7(4), 4-6 (Nov. 1965).
69. Bolton, K., and Shreir, L. L., "Factors Affecting Hydrogen Absorp-
tion of High Strength Steel During Cathodic Polarization," Corrosion Sci.,
3(1), 17-33 (1963).
70. Borelius, G., and Liodblom, S., "Solubility and Diffusion of Hydrogen
io Metals," Ann. Physik, 82(4), 201-226 (1927).
71. Hudson, R. M., Magor, J. K., and Stragand, G. L., "Relationship
Between Hydrogen Solubility and Reboiling Tendency in Enameling Steels,"
Jnl. Am. Ceram. Soc., 41, 23-27 (1958).
72. Hobson, J. D., "The Diffusion of Hydrogen in Steel at Temperatures
of -78 0 C to 200 0 C," Jnl. Iron Steellnst., 189, 315-321 (1958).
73. Geller, W., and Sun, T., "Influence of Alloy Additions on Hydrogen
Diffusion in Iron and Contributions to the System Iron-Hydrogen," Arch.
Eisenhuettenw., 21, 423-430 (1950).
74. Hudson, R. M., Norris, W. G., and Stragand, G. L., "Effect of En-
vironment on the Rate of Hydrogen Removal From Steel," Ind. Eng. Chem.,
51(3),319-324 (1959).
75. Foster, P. K., McNabb, A., and Payne, C. M., "On the Rate of Loss
of Hydrogen From Cylinders of Iron and Steel," Trans. Met. Soc. AIME,
233,1022-1031 (1965).
76. Hudson, R. M., Riedy, K. J., and Stragand, G. L., "Influence of Cold
Reduction and Heat Treatment Combinations on Hydrogen Solubility and
Permeability in Steel," Corrosion, 17(7), 334t-336t (July 1961).
77. Darken, L. S., and Smith, R. P., "Behavior of Hydrogen in Steel
During and After Immersion in Acid," Corrosion, 5, 1-16 (1949).
78. McNabb, A., and Foster, P. K., "A New Analysis of the Diffusion of
Hydrogen in Iron and Ferritic Steels," Trans. Met. Soc. AIME, 227, 618-
627 (June 1963).
79. Seabrook, J. B., Grant, N. J., and Carney, D. J., "Hydrogen Em-
brittlement of SAE 1020 Steel," Trans. AIME, 188, Jnl. Metals, 2, 1317-
1321 (Nov. 1950).
80. Hobson, J. D., and Sykes, C., "Effect of Hydrogen on the Properties
of Low-Alloy Steels," Jnl. Iron Steel Inst., 169, 209-220 (Oct. 1951).
81. "Discussion on Effects of Hydrogen on Harder Steels," Jnl. Iron
Steel Inst., 203, 1031-1036 (Oct. 1965).
82. Brown, J. T., and Baldwin, W. M., Jr., "Hydrogen Embrittlement of
Steels," Jnl. Metals, 6, 298-303 (Feb. 1954).
83. Plusquelleo, J., Azou, P., and Bastein, P., "Influence des durees de
chargement et du maintien a l'ambiante sur la fragilite due a l'hydrogene
dans les aciers," Compt. Rend., 246(5), 3454-3457 (1958).
84. Vaughan, H. G., and DeMorton, M. E., "Hydrogen Embrittlement of
Steel and Its Relationship to Weld Metal Cracking," Brit. Welding Jnl.,
4,40 (1957).
85. Interrante, C. G., and Stout, R. D., "Delayed Cracking in Steel
Weldments," WELDING JOURNAL, 43(4), 146s-160s (April 1964).
86. Klier, E. P., Muvdi, B. B., and Sachs, G., "The Response of High-
31
Strength Steels in the Range of 180,000 to 300,000 psi to Hydrogen Embrittle-
ment From Cadmium-Electroplating," ASTM Proc. 58, 597-622 (1958).
87. Srawley, J. E., "Hydrogen-Embrittlement Susceptibility of Some
Steels and Nonferrous Alloys," NRL Report 5392, PB151937, Oct. 19, 1959.
88. Grant, N. J., and Lunsford, J. L., "How Important Is Hydrogen
Embrittlement," Iron Age, 175(22), 92-95 (June 1955).
89. Mills, R. L., and Edeskuty, F. J., "Hydrogen Embrittlement of Cold-
Worked Metals," Chern. Engl. Prog., 52(11), 477-480 (Nov. 1956).
00. Hudson, R. M., and Riedy, K. J., "Influence of Cold Reduction on
Hydrogen Behavior in High Purity Iron, Jnl. Am. Ceram. Soc., 44(10),
467-471 (Oct. 1961).
91. Boniszewski, T., and Moreton, J., "Effect of Micro- Voids and Man-
ganese Sulfide Inclusions in Steel on Hydrogen Evolution and Embrittle-
ment," Brit. Welding Jnl., 14(6), 321-333 (June 1967).
92. Coe, R., and Moreton, J., UEstimation of Diffusivity Coefficients for
Hydrogen in Ferrous Materials," Brit. Welding Jnl., 14(6), 313-320 (June
1967).
93. Graville, B. A., Baker, R. G., and Watkinson, F., "Effect of Tempera-
ture and Strain Rate On Hydrogen Embrittlement of Steel," Brit. Welding
Jnl., 14(6), pp. 337-342 (June 1967).
94. Oriani, R. A., "Hydrogen in Metals," to be published in Proc. Symp.
Stress Corrosion, Columbus, Ohio, Sept. 1967.
95. Naeser, G., and Dantzenberg, N., "Der Einfluss des Kaltwaizgrades
auf die Wasserstaffaufnahme "on wuchem Eisen zwischen 200 und 1000° C
und ihre Veranderung durch geringe Kohienstoffgehaltee," Arch. Eisen-
huettenv., 36(3), 175-181 (March 1965).
96. Harhai, J. G., Viswanathan. T. S., and Davis, H. M., "Mechanism of
Storage of Occluded Hydrogen by Cold Worked Iron·Carbon Alloys,"
ASM Trans. Quart., 58(2), 210-220 (June 1965).
97. LeBougher, B., "Etude du degagement Cathodeque de I'hydrogene
Bur Ie fur en presence d'hydrogine sulfure," Rev. I nst. Franc. Petrole. 116
(6),1-66 (April 1963).
98. Lillys, P., and Wehrenberg, A. E., "Effect of Tempering Temperatures
on Stress Corrosion Cracking," Trans. ASM, 48, 327-346 (1956).
99. Frazer, J. P., and Treseder, R. S., "Cracking of High Strength Steels
in H,s Solutions," Corrosion, 8, 1952, pp. 342-350.
100. Vollmer, L. W., "Hydrogen Sulfide Corrosion Cracking of Steels,"
Corrosion, S(lO), Oct. 1952, pp. 326-332.
101. Warren, D., and Beckman, G. W., "Sulfide Cracking of Strength
Batting Material," Corrosion, 13(10), 1957, pp. 63lt·646t.
102. Prange, P. A., "Hydrogen Embrittlement Tests on Various Steels,"
Corrosion, 8(10), pp. 355-357 (Oct. 1952).
103. Baldy, M. F., and Bowden, R. C., Jr., "The Effect of Martensite on
Sulfide Stress Corrosion Cracking," Corrosion, 11(10), 417t (Oct. 1955).
104. Cauchois, L., Didier, J., and Herzog, E., "A Special N-80 Steel Tub-
ing Developed in France to Resist Sulfide Stress Corrosion in Sour Gas
Wells," Corrosion, 13(4), 263t (April 1957).
105. Fraser, J. P., Eldredge, G. G., and Treseder, R. S., "Laboratory and
Field Methods for Quantitative Study of Sulfide Corrosion Cracking," Cor-
rosion, 14(11), 517t (Nov. 1958).
106. Truman, J. E., "Tensile Failure of Carbon and Stainless Steel Wires
in the Presence of Water and Hydrogen Sulfide," Metallurgia, 43, 8-10
(1951).
107. Bastian, P., and Amiot, P., "Mechanism of the Action of Ionized
Solutions of Hydrogen Sulfide on Iron and Steel," Compt. Rend., 235(18),
1031-1033 (1952).
108. Treseder, P. S., Report of Technical Unit Committee 2-G, "Sulfide
Corrosion Cracking of Production Equipment," NACE, Publication 54-5,
Corrosion, 10(11), 413 (Nov. 1954).
109. Brickell, W. F., Greco, E. C., and Sardisco, J. B., "Corrosion of Iron
in an H,S-CO,-H,O System: Influence of (Single Iron) Crystal Orientation
on Hydrogen Penetration Rate," Corrosion, 20(7), (1964) pp. 235t-236t.
110. Doty, W. D., "Development of High-Strength Constructional Steels
for Oil Storage," World Petrol. Congr. Proc., 7th, 6(3), 25 (April 1967).
111. Bastien, P., Vevon, H., and Roques, C., "Special Steels Resistant to
Corrosion by Hydrogen Sulfide," Rev. Met., 55, 301-312; disc 313-317
(1958).
112. Bohner, P. W., "Polarization of Iron in H2S-NaHS Buffers," Cor-
rosion, 21(3), 69-75 (March 1965).
113. Hackerman, N., "Recent Advances in Understanding Inhibitors,"
Corrosion, 18(9), 332t-37t (Sept. 1962).
114. Iofa, Z. A., and Tomoshova, G. N., "Joint Action of Hydrogen Sul-
fide and Organic Compounds on Corrosion and Embrittlement," Corrosion,
19(1), 12t·16t (Jan. 1963).
115. Matsushima, I., Deegan, D., and Uhlig, H. H., "Stress Corrosion and
Hydrogen Cracking of 17-7 Stainless Steel," Corrosion, 22(1), 23-27 (Jan.
1966).
116. Phelps, E. H., "Stress-Corrosion Behavior of High-Yield-Strength
32 Basic and Research Aspects
Steels," World Petrol. Congr., Proc., 7th, 6(3), P.D. 27 (April 1967).
117. Bhatt, H. J., and Phelpa, E. H., "Effect of Solution pH on the Mech-
anism of Stress Corrosion Cracking of a Martensitic Stainless Steel/' Cor-
rosion, 17(9), 430t·434t (Sept. 1961).
118. Baldy, M. F., "Sulfide Stress Cracking of Steels for API Grade
N-80 Tubular Products," Corrosion, 17(11), 50!Jt.513t (Nov. 1961).
119. Fraser, J. P., and Eldridge, G. G., "Influence of Metallurgical Vari-
ables on Resistance of Steels to Sulfide Corrosion Cracking," Corrosion, 14
(11), 524t-530t (Nov. 1958).
120. Prange, F., "Hydrogen Embrittlement Tests on Various Steels,"
Corrosion, 8(8), 326-360 (1952).
121. Bowers, C. N., McGuire, W. J., and Wiehe, A. E., "Stress Corrosion
Cracking of Steel Under Sulfide Conditions," Corrosion, 8(8), 333-341
(Oct. 1962).
122. Treseder, R. S., Report of Technical Practices Committee l·G,
"Field Experience With Cracking of High·Strength Steels in Sour Gas and
Oil Wells," Corrosion, 8(8), 351-354 (Oct. 1962).
123. Vollmer, L. W., "The Behavior of Steels in Hydrogen Sulfide,"
Corrosion, 14(7), 324t-328t (July 1958).
124. Riggs, O. L., Jr., and Radd, F. J., "Physical and Chemical Study of
an Organic Inhibitor for Hydrogen Sulfide Attack," Corrosion, 19(1),
It·8t (Jan 1963).
125. Reinoehl, J. E., Beck, F. H., and Fontana, M. G., "Corrosion, Im-
munityand Passivation From an Engineering Viewpoint," Corrosion, 21(12),
379-381 (Dec. 1965).
126. Naumann, F. K., and Carius, W., uThe Significance of the Corrosion
Process in Aqueous Hydrogen Sulfide Solutions for the Formation of Cracks
in Steels," Archiv Eisenhuettenw., 30(5), 283-292 (May 1959).
127. Lorenz, K. and Medawar, G., "Behavior of Steel and Iron Alloys
Under the Effect of Hydrogen Sulfide," Erdoel Kohle, 17(12), 1015-1020
(Dec. 1964).
128. Snape, E., "Sulfide-Stress Corrosion of Some Medium and Low Alloy
Steels," Corrosion, to be published.
129. Slaughter, E. R., Fletcher, E. E., Elsea, A. R., and Manning, G. K.,
"An Investigation of the Effects of Hydrogen on the Brittle Failure of High-
Strength Steels," W ADC TR 56-83, April 1956.
130. Simcoe, C. R., Elsea, A. R., and Manning, G. K., "An Investigation
of Absorbed Hydrogen in Ultra-High·Strength Steel," W ADC TR 56-598,
November 15, 1956.
131. NACE Committee T-1B Report, Mater. Protection, 2(3), 89-93
(1963).
132. Walter, R. J., and Chandler, W. T., "Effects of High-Pressure Hy-
drogen on Storage Vessel Materials," ASM Tech. Paper No. W8·2.4, ASM,
Metals Park, Ohio, 1968.
133. Hancock, G. G., and Johnson, H. H., "Hydrogen, Oxygen, and Sub-
critical Crack Growth in a High-Strength Steel," Trans. Met. Soc. AIME,
236,513-516 (April 1966).
134. Phillips, A., Kerlins, V., Rawe, R. A., and Whiteson, B. V., "Elec-
tron Fractography Handbook, Supplement 1, Specific Applications of Elec-
tron Fractography," AFML-TR-64-416, December 1966.
135. Ono, K., and Rosales, L. A., "On the Anomalous Behavior of Hydro-
gen in Iron at Lower Temperatures," Trans. AIME, 242, 244 (1968).
136. Keeler, J. H., and Davis, H. M., "Density and Hydrogen Occlusion
of Some Ferrous Metals," Trans. AIME, 197, 44-48 (January 1953).
137. Bastien, P. G., "The Phenomena of Cracking and Fracture of Steel
in the Presence of Hydrogen," Physical Metallurgy of Stress Corrosinn. 1i'rac-
lure, Vol. 4, Interscience Publishers, New York, 1959, pp. 311-340.
138. Hahn, G. T., and Rosenfeld, A. R., "A Modified Double Pile-Up
Treatment of the Influence of Grain Size and Dispersed Particles on Brittle
Fracture," Acta Met., 14,1815-1825 (December 1966).
139. Whiteson, B. V., Phillips, A., Kerlins, V., and Rawe, R. A., "Special
Fractographic Techniques for Failure Analyais," Electron Fractography,
ASTM STP 436, American Society for Testing and Materials, 1968, pp.
151-178. .
140. Tetelman, A. S., and McErily, A. J., Jr., Fracture of Structural Ma-
terials, John Wiley and Sons, New York, 1967.
141. Hartbower, C. E., Gerberick, W. W., and Crimmins, P. P., "Moni-
toring Subcritical Crack Growth by Detection of Elastic Stress Waves,"
WELDING JOURNAL, 47(1), 1s-18s (January 1968).
142. Steigerwald, E. A., Schaller, F. W., and Troiano, A. R., "Discon-
tinuous Crack Growth in Hydrogenated Steel," Trans. AIME, 215(12),
1048-1052 (December 1959).
143. Naumann, F. K., and Carius, W., "Crack Formation in Steels Under
the Influence of Aqueous Hydrogen Sulfide Solutions," Archiv Eisenhuet-
tenw., 30(4), 233-238 (April 1959).
144. McPherson, W. B., and Cataldo, C. E., "Recent Experience in High
Pressure Gaseous Hydrogen Equipment Operated at Room Temperature,"
ASM TR-D8-14.1, October 1968, 12 pages.
Section II-Action of Hydrogen on Steel at High Temperature
and High Pressures
by G. A. Nelson
SUMMARY. The first section of this report discussed the
general effects of hydrogen in various forms, but largely
excluded the effects at elevated temperature. The addi-
tion of temperature aggravates the effects of high pressure
hydrogen. This section of the report will discuss the effects
of hydrogen combined with temperature. The most sensi-
tive parameters are the partial pressure of hydrogen, the
temperature, and the material chemistry. While some of
the other effects that were of great significance at low tem-
perature, such as the stress and cold work, are still signifi-
cant, the effects of high temperature are less sensitive to these
or cannot be summarized so neatly.
The areas to which this section applies are those in which
hydrogen or hydrogen containing fluids are handled at high
temperatures (above 430 0 F) and high hydrogen pressures
(up to 13,000 psia). Under these conditions carbon steel
will be unsatisfactory as a constructional material because
of both chemical and physical changes that occur.
Mechanisms for producing the chemical changes are dis-
cussed together with alloying lequirements to prevent the
damage. Additional sections are devoted to incubation
periods before chemical changes occur and to effects of hard-
ness, cold work and stress at high temperature. Methods
of preventing high temperature damage to pressure vessels
by specialized design or suitable alloying are also discussed.
Surface Decarburization
When carbon steel is exposed to hydrogen at
high temperature (above 1050° F and at pressures
below 200 psia) surface decarburization occurs
with a resultant loss in strength and an increase
in ductility; in this respect being similar to steels
decarburized by exposure to other gases, such as
air, oxygen or carbon dioxide. A number of
theories have been proposed to explain this
phenomenon 1 ,2 but the presently accepted view
is based on a continuous migration of carbon to
the surface, at which place it is removed as gaseous
compounds of carbon~CH4 or CO (when carbon
dioxide is present). Moisture obviously hastens
the reaction. Carbon in solution must diffuse to
the surface, and the rate control ing mechanism
is apparently diffusion of carbon. The addition
of carbide stabilizing elements to the steel can
The late G. A. Nelson was a metallurgical consultant in Berkeley, Calif.
and formerly with Shell Development Company, Emeryville, Calif.
This report was prepared for the Subcommittee on Hydrogen Em-
brittIement of the Pressure Vessel Research COInmittee.
High Temperature and Pressures
decrease the rate of surface decarburization,
since the carbon in solution is supplied continually
from the carbides and the more stable carbides
give lower dissolved carbon content.
Actual values of pressure-temperature com-
binations at which surface decarburization be-
comes pronounced have not been extensively
studied, but the limits defined by Naumann 3
probably give the most accurate appraisal. Fig-
ure 1, a graphical presentation of operating
limits for steel in hydrogen service, includes data
points determined by Naumann. The mode of
damage is indicated by the shading. In addition
to his references, based on 100 hr tests, several
additional long time references from industrial
service are included. These show a slightly lower
level of susceptibility to decarburization than the
100 hr tests. Limits for surface decarburization
of Cr-Mo steels, as shown on Fig. 1, have been
extended only to 6000 psia. At pressures above
this figure, the Cr-Mo steels must be further
fortified with other carbide stabilizers such as
vanadium or tungsten to make them resistant to
surface decarburization.
Internal Decarburization (Hydrogen Attack)
When carbon steel is exposed to hydrogen at
temperatures above ca. 430° F and at pressures
above 200 psia, it becomes internally damaged;
it loses tensile strength and ductility, and some-
times cracks and blisters. The deterioration of
mechanical properties is caused by atomic hydro-
gen permeating the steel and reacting with other
elements to form other gases. 4 For example,
it may react with carbon in solution to form
methane. The methane thus formed cannot
diffuse out of the steel and accumulates princi-
pally at grain boundaries. High local stresses
eventually develop and become of such magnitude
that the metal cracks or blisters. The formation
of methane gas by exposure of steel to hot hydrogen
33
....
C;;;

HYOROGEN PARTIAL PRESSURE, Kg/em' obs.

50 100 150 200 400 600 800
LEGENO REfERENCES FOOTNOTES
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IfI'OROGEN PARTIAL PRESSURE, L b/in' obs.

OPERATING LIMITS FOR STEELS IN HYDROGEN SERVICE

G A N JAN 66

Fig. I-Operating limits for steels in hydrogen service


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~[ .. IILnC
.AfA"' ..... DOWN ",TO
S_(AOln"L ,. ...... "
Fig. 2-Core from carbon steel fitting attacked by hydrogen
showing decarburization of pearlite
at high pressures has been co nfirmed by many
investigators; however, they found that during
the initial period of exposure, this reaction is
preceded by a period where hydrogen in the steel
does not create permanent damage. This phe-
nomenon will be discussed later under " Incuba-
tion ."
Cracks in hydrogen-damaged steel are initially
microscop ic in size; however, in advanced stages
of attack, they are so numerous that they produce
a substantial deterioration of such mechanjcal
properties as tensile strength, hardness, and duc-
tility . For example, steel with an initial tensile
strength of 60,000 psi may have its strength
reduced to 25,000 psi when th is steel is completely
decarburized and extensively cracked by the
action of hydrogen; the elongation is similarly
reduced to zero from the initial va lue of 30 <;; .
Figure 2 shows the appearance of a piece of
carbon steel which has suffered from internal
decarburization and cracking. It is seen that the
original lamellae of the pearlite are breaking down
into spheroidal shape, a process involving solution
and migration of carbon. At the same time,
carbon dissolving into the ferrite is migrating to
grain boundary voids where it combines with
hydrogen to form methane.
For prevention of hydrogen attack , additions
of carbide stabilizer elements to the steel are
necessary. Those elements commonly used are
nlolybdenum, chron1iunl, tungsten , vanadium ,
and niobium. Their primary function is to
combine with carbon in such a stable carbide that
little of the carbon is available for the formation
of methane. Another proposed alternative mecha-
nism is deta iled in reference 4.
The pressure-temperature conditions under
S_CAO'O'Zeo
0'10-
which carbon steel is subject to internal decar-
burization (h ydrogen attack) is shown by the
solid curve on Fig. 1. Below and to the left of
the curve, hydrogen attack has not been noted,
while above and to the right of it, many failures
have been reported. Additional curves on Fig. 1
reflect t he added resistance to internal attack
when relatively small amounts of molybdenum 01'
chromium are added. Resistance to attack pro-
vided by trace amounts of carbide stabilizers are
shown on the insert at the t.op of the chart. Ele-
ments. such as silicon or nickel, which are not
strong carbide formers , have shown little or no
( U, ... CLU,[)
effect in preventing hydrogen damage.
Whether or not a steel deteriorates in hydrogen
by surface decarburization or internal attack is
dependent on several variables temperature,
pressure, alloy content, heat t.reatnlent, stress
level, etc. A,though a steel may never exhibit
internal hydrogen attack at a given temperature
and pressure, it may eventually decarburize or
show surface cracks. If surface decarburizat ion
proceeds faster t han intern a l attack , a steel may
become completely decarburized before internal
attack can ocrur. On the other h and, as pressures
are increased the hydrogen partial pressure in-
creases but temperatures are lowered, carbon
mobility is decreased , and internal attack may
occur in the a bsence of a significant amount of
surface decarburization. It follows that when
both pressures a nd temperatures are sufficiently
high, both phenomena can occur simultaneously.
Incubation
Damage to steels by high pressme-high temper-
ature hydrogen is preceded by a period of time
where no noticeable change in properties can be
detected . Subsequently , cracking proceeds at a
rate depending on temperature, pressure and
alloy content. The length of time before attack
begins has been termed the " incubation period,"
and varies with the type of steel and severity of
exposure. This may be only a few hours at
extreme conditions and progressively longer at
lower temperatures and pressures, and under some
conditions no damage can be detected by com-
mercial testing methods even after many years
of exposure. Many investigators have proposed
theories to explain reasons for the incubation
period. The most recent and plausible proposition
has been prepared by Vitovec.· In essence, he
maintains that in the initial stage met.hane pres-
sure huilds up in submicroscopic voids. At
first, this pressure is resisted and ba lanced by
surface tension so t h at a void can only grow
slowly . The action at this stage is reversible with
:~.;
 HYDROGEN PARTIAL PRESSURE. Kg/cm 2 abs.
o 50 100 150
1000'-IrT-"~~~'-~Ir~--~--~----------~--'-------------'---+---------'
3000) 30E) 100)
A) AMERICAN OIL COMPANY (PRIVATE CONNUNICATlON), 1960
< 100.)
• B) CIUFFREDA AND ROWLAND PROC. API MID-YEAR IlEETING, NAY 1957
C) C. A. ZAPFFE, 'SOlLER ENBRITTLENENT: TRANS. ASME, FEBRUARY 1944 500
280E) 65 El 25El 0) R. E. ALLEN, ET AL, API, PREPRINT, MAY 1961
900 1--++--+--+-......::......----1~-----++ E) L. C. WEI NER, 'CORROSION', VOL 17, PP. 109-115, 1961
F) HUR, DEICHLER, AND WORRELL, OIL AND GAS JOURNAL, OCTOBER 29, 1960
G) F. K. NAUNANN, TECH. NITT. KRUPP. VOL I, NO. 12, 1938
a.> 10001
H) HASAGAYlA, TETSU TO HAGANE, VOL 46, 1960
J) T. C. EVANS, MECH. ENG., IIAY 1948
800 1--++-+-+-......-+--~-----1~+ K) AIR PRODUCTS, INC., (PRIVATE CONMUNICATlON), 1960

...... L) API REFINERY SURVEY, 1957

M) I CLASS STAHL~UND EISEN VOL 80 AUGUST 1960 400 ~
< 1000) ....
IX
4'31 E) (800' Fl ....
::>
e
=
....
....
.,
.......
6001~~~~~~~~~~~~~~~~::~~~~~r-~----
r ~ 400 HOURS ____ ~~~;:~~;;::~>IDOGl(4200PSIA) 300
>280Ml( 7000PSIA)

500
__~~~~__-=1f::::~:=~:;~1r~~::~~~:;~~I'~OO~0:~HO~U~RS~::::~~~<5~5~0~OG~I~(I~25~0~OP~S~IA~)~
t NO ATTACK
10,000 HOURS

500 1000 1500 2000 2500

HYDROGEN PARTIAL PRESSURE, Lb/in2 a bs.

Fig. 3-Time for incipient attack of carbon steel in hydrogen service (Note-The American Petroleum Institute, as one of its
continuing projects, will bring these curves up to date. It may be desirable to refer to current literature for best data)

HYDROGEN PARTiAl PRESSURE, Kg/em abs.

50 100 150 200
1000 .---~~L---~.-~.-+---~~.-----------+-,--------------r--+----------r--------+----,
LEGEND
"l NO ATTACK
""III HYDROGEN ATTACK (TIME 1M HOURS)
AI SHELL DEVELOPMENT DRGS • VT6688 l VT 661-4 500
B) PC ROSENTHAL ET AL, API PREPRINT 05-63, MAY 13,1963
900 C) F.K. NAUMANN, TECH MITT KRUPP VOl. I, 1938

< 100Cl4200PSIA'
~

::;
-
-<

--- - - --
= 800
~

-
'"
~ ,.. 200 HOURS

-- ,-400 HOURS 400

Al
"'l

600 L--L~ __ ~~ __ L--L~L-~~ __~-L__L--L~L-~~__L--L__L--L~__~~__L--L__L--L~__~~

o 500 1000 1500 2000 2500 3000
2
HYDROGEN PARTIAL PRESSURE, Lb/in abs.

Fig. 4-Time for incipient attack of 0.50 Mo steel in hydrogen service

36 High Temperature and Pressures

hydrogen pressure and no change occurs in mechan-
ical propert.ies. When a void reaches a critical
size, it grows more rapidly by a process of lattice
vacancy condensation. As the void becomes •
still larger, the growth rat.e increases furth er with
the controlling mechanism becoming creep. Ex-
pansion of cavities to microscopically visible
fissw'es result in a significant reduction of Inechan-
ica I properties.
The length of the incubat.ion period is of cOn-
siderable practical importance as it is only during
this period that equipment can be considered to
have its initial strength retained. After this
period has elapsed, degradation proceeds at vary-
ing rates, depending on temperature, pressure
and type of stee\. For many years a need h as
existed for a table or chart to serve as a guide for
det.ermining approximate safe operating times for
steels operating above thei.r prescribed levels. Fig. 5-Characteristic shape of fissures in annealed SAE 1020
steel after 245 hours of exposure to 900 psi hydrogen pressure
The desired data have been summarized" and at 1000' F (600x)
incubation curves for carbon steel (Fig. 31 and
0.50 Mo steel (Fig. 4 1have been prepared.
and the fact that the fissures develop immediately
Effect of Cold Wo rk
over the entire interfacial area of the reaction
During the initial stage of crack formation in site. In the steel cold worked 39"; (Fig. 71 the
annealed steel, Allen, et Cl/.,'· noted that the char- almost parallel fissures are s taggered with respect
acterist ic shape was a series of spheroidal open- to each other, and as the fissures expand the
ings. The majority of cracks, developed under material in between them is sheared apart.
the test conditions of 900 psi and 1000 F. were 0
The microstructw-es described above are asso-
selectively formed at t.he interface between ferrite ciated wit.h marked differences of behavior as
grains a nd pearlite co lonies (see Fig. 51 . indicated by specific gravity measurement.s made
In cold worked steels the shape of fissures is during a testing program sponsored by t.he Amer-
changed. For example, in contrast to the sphe- ican Petroleum lnstitute. The work was sum-
roidal shape of annealed samples, cold worked marized by Nelson.' In the sununary paper,
materials I Figs. 6 and 7 ) form fissures which have references in seven papers presented during prog-
a more prismatic shape. The apparently pris- ress of the work were given. Figure 8, taken
matic shape results from the alignment of nu- from the review paper, compares the specific
cleation sites for the fissures by the cold rolling gravities of SAE 1020 steel with varyi.ng degrees of

, .'
•

.,
~-
,. ..
.",....
, ~~
, / ~/-
:--"--""'\.; .
• , .... ,-r:a -
••
}
" . •
•
~
~
£ .,. - --
Fig. 6-Characteristic shape of fissures in 5% cold worked SAE Fig. 7-Characteristic sha pe of fissure s in 39% cold worked SAE
1020 steel after 245 hours of exposure to 900 psi hydrogen pres- 1020 steel after 245 hours of exposure to 900 psi hydrogen pres·
sure at 10000 F (800x) sure at 1000' F (800x)

H iV}1 'j'IIII/IUOfuI'C al/d ]) rclSsllr(JIj 37

 mass of cracks in the annealed material. I t is
possible that the longitudinal fissures permitted
gas to escape at the ends, whereas in the annealed
100 _ _ _ _ _ _ _ _ _ __
sample gas was trapped in the interior.
~
-
.
.
.
,
98 Steel with 39 % strain showed no incubation
96
period at any temperature, indicating that cracking
0% STRAIN had started immediately upon exposure to the
94
hydrogen. After attack had reached a maximum,
92 no further loss in specific gravity could be noted.
These tests are considered significant for ex-
100t-~ _ __ plaining the cause for cracks sometimes found in
98
an otherwise resistant steel and also emphasizes
SPECIFIC
700F
the need for stress relief in hydrogen containing
GRAVITY 96
RETAINED,
equipment. Sharp notches should also be avoided
5% STRAIN
PER CENT as they provide points of high stress concentration.

100
98
96
- - - - - - - - -_ _ 700 F
94
-
------80OF
_ _ _ 1000F
92
200 400
TIME, HOURS
Fig. 8-Effect of temperatures and cold work on specific gravity
of SAE 1020 steel exposed to hydrogen at 900 psi
cold work after exposure to 900 psi hydrogen
pressure at 700, 900, and 1000 F. For the an-
nealed set of samples (0 % strain) the curves show
incubation periods, followed by a decrease in
specific gravity and a final diminishing rate of
loss. The decrease in specific gravity indicates
the presence of internal fissures.
Steel with 5 % strain showed different character-
istics than the annealed samples. The specific
gravity of the 700 0 F specimen began to decrease
at a shorter time and to a greater degree than the
annealed sample. The same was true for the
800 0 F sample. The 1000 0 F sample, however,
showed no incubation period and specific gravity
decreased less than the annealed sample. This
apparent reversal of the extent of attack in the
5% sample was attributed to the development of
parallel longitudinal fissures in the cold rolled
samples in contrast to the heterogeneous oriented
Effect of Hardness
Steels shown on Fig. 1 are considered to be in
the stress relieved condition. Heat treatments to
stabilize carbides increase the strength and en-
hance hydrogen resistance. Usual treatments are
39% STRAIN
normalizing followed by tempering, although
quenching followed by tempering has also been
performed. Caution should be exercised with
600 800 1000 1200 heat treatments to avoid excessiveJy high hard-
ness. Long time service has been attained with
low alloy steels, heat treated to a maximum hard-
ness of Rockwell C-23. However, experiences
have shown that brittle fractures can occur when
harder steels (above Rockwell C-30) are subjected
to high stresses, either residual or applied, while in
0
contact with high-temperature, high-pressure
hydrogen. Instances of brittle failures of equip-
ment while operating at high-temperatures and
pressures are shown on Table 1. Cases 1, 2,
and 4 are border line for alloy content. However,
even though equipment had shown a slight surface
effect of 0.02 in., when the hardness was below
Rockwell C-23 no failures were reported. Harder
materials of same analysis exposed in the same
unit failed in a brittle manner at 1400 psi hydrogen
0
pressure and a temperature of 800 to 850 F.
After some redesign and use of softer materials no
further problems occurred.
Effect of Hydrogen on Stress-Rupture
Strength at High Temperatures
When steels are under strain at high tempera-
tures, even where hydrogen attack may not

Table 1-Equipment Failures by H2 Embrittlement at High Temperature

Metal H2 Pressure psia Temp, 0 F Time to Failure
Case 1 SAE 4140 bolts and nuts 1400 800-850 Unknown
(heat treated)
Case 2 1.3 Cr - 0.5 Mo weld 1400 800-850 Several days
Case 3 5 Cr - 0.5 Mo bolts 3500 900 Several days
(annealed)
Case 4 1.3 Cr - 0.5 Mo flange 1400 800-850 24,000 hI'
(R,36)

HiUh TemlJeratUl'e and Pressures

 100
ORIGINAL
STRESS
RUPTURE
STRENGTH
RETAINED,
PER CENT
50
50 100 150 200
TIME, HOURS
Fig. 9-Effect of pressure on stress·rupture strength of SAE 1020
steel exposed to hydrogen at 800 0 F. Based on samples in
argon as 100%
occur, stress-rupture strengths are lower in hydro-
gen than in other atmospheres. This was demon-
strated by Vitovec and associates 8 - 1o • Figures
9-12 were prepared from these works to illustrate
decreases in stress-rupture strengths of various
steels when tested at elevated temperatures in
hydrogen. The curves demonstrate that the
presence of strains created by applied stress de-
creases the stress-rupture strength of carbon and
low alloy steels. In fact, ]oss in stress-rupture
strength of carbon steel is experienced at pressures
as low as 50 psia, whereas in the unstressed
condition no attack by hydrogen can be detected.
Improvement in stress-rupture strength occurs
when elements such as molybdenum or chromium
are added.
Figure 9 compares stress-rupture strengths of
SAE 1020 steel tested in hydrogen at various
pressures at 800° F in relation to its strength when
tested in argon. It is noted that all samples
immediately declined in relative strength upon
application of load and further decreased in
strength at the same high rate for approximately
50 hr. This time of rapid decline in stress-rupture
strength corresponds approximately to that of
the incubation time for unstrained samples where
no attack is occurring (see Fig. 8). Following
the steady rate decline, stress-rupture strength
decreased in direct relation to the applied pres-
sure.
Figure 10 compares relative stress-rupture
strength of SAE 1020 stee] when tested in hydrogen
at various pressures and in argon at 1000° F.
Trends are the same as in the 800 ° F samples,
but initially the reduction in stress-rupture
strength of the samples exposed to hydrogen is
High Temperature and Pressures
100
90
80
STRESS
RUPTURE
70
STRENGTH
RETAINED,
PER CENT
60
150 50
40
900 PSI
50 100 150 200 250
TIME, HOURS
Fig. lO-Effect of pressure on stress·rupture strength of SAE
1020 steel exposed to hydrogen at 10000 F. Based on samples in
argon as 100%
at a much steeper s]ope. I t is also to be noted
that in a short test at 50 psi and 1000° F the loss
in relative stress-rupture strength is the same as
when the pressure was 400 psi, indicating the
extreme sensivitity of strained metal to hydrogen
at any pressure. As previously mentioned, this
sample would be unaffected when in the unstrained
condition.
Improvement in stress-rupture strength is ac-
complished by addition of strengthening elements
such as molybdenum or chromium. Figure 11
compares relative stress-rupture strength of SAE
1020 steel with low-alloy steels when tested in
hydrogen at 900 psi and 1000° F. An immediate
improvement from alloying is noted but full
stress-rupture strength is not retained in these
short-time tests until the alloy steel grade reaches
2 1/ 4 Cr-l Mo.
Figure 12 compares the relative stress-rupture
strength of high purity iron at two levels of carbon
content when tested in hydrogen at 900 psi and
1000° F with that in argon at 1000° F. The
higher carbon material was in the initial condition
of a vacuum annealed 3/8 in. thickness strip
which had been vacuum normalized at 1650° F
for 1 hr. The lower carbon material had been
further treated by heating in hydrogen at 1800° F
for 500 hr. During this exposure the carbon
content was reduced from 90 to 15 ppm. It is
:m
 100
2!, CR-I MO

90
100 - - DECARBU RIZED
HIGH PURITY IRON

STRESS
RUPTURE
80
STRENGTH 90
RETAINED,
STRESS
RUPTURE
PER CENT
70
STRENGTH
RETAINED, 80
PER CENT
HIGH PURITY IRON
60

150
50
TIME, HOURS

Fig. 12-Effect of decarburization on stress· rupture strength of

0
high purity iron exposed to hydrogen at 900 psi and 1000 F.
Based on samples in argon as 100%
100 200 3;0 400 500
TIME, HOURS

Fig. ll-Effect of exposure time on stress·rupture strength of

steels exposed to hydrogen at 900 psi and 10000 F. Based on overheated while at operating pressure. In
samples in argon as 100% straight oil service such tubes fail in a ductile
fashion. Rapid temperature changes cannot be
tolerated by furnace tubing in hydrogen service.
When steels are cooled from high temperatures,
noted that the original iron decreased in relative the absorbed hydrogen diffuses out very slowly;
stress-rupture strength immediately upon exposure hence a situation can exist where the steel is
to hydrogen. However, the decarburized sample supersaturated by hydrogen, and thus is brittle at
showed better strength than the sample exposed to low temperature. Table 2 shows that both 5
argon. This favorable behavior is attributed to Cr - 0.5 Mo and 18 Cr - 8 Ni suffer from this
insufficient carbon in the sample to allow for- effect. In both instances, the high temperature
mation of methane. conditions were not severe enough to create
decarburization. Hence, it is recommended that
Effect of Hydrogen on Stress-Rupture Ductility large and rapid temperature changes be avoided;
at High Temperatures expansion and contraction stresses in hydrogen-
The reduction of area at fracture in stress- charged steels should be kept to a minimum.
rupture tests is generally lower in hydrogen than Where thick wall pressure vessels are involved,
in argon. This degradation Of ductility due to a cooling rate of 75° F max per hour should be
hydrogen: 1. generally increases in severity with prescribed.
increasing hydrogen pressure up to 1400 psi, 2.
Detection of Hydrogen Damage
occurs even during the incubation time for hydro-
gen attack, and 3. becomes progressively more There is actually no dimensional loss of the
severe at longer time to fracture (until complete steel when it is affected by high-temperature
decarburization is attained). This effect was
demonstrated for 1020 carbon steel 9 and for a
commercial steel containing 0.5% molybde-
num. IO However, for a steel containing 1 % Table 2-Results of Ductility Tests from Test Bars Inserted in
chromium and half per cent molybdenum lo the 0
Reactor Furnaces Exposed at Temperatures up to 1000 F and
stress rupture ductility when tested in hydrogen Pressure of 3500 psi
was equal to or better than the ductility in argon, Elongation in 2 in. %
Duration of at Room Temperature
even though the stress-rupture strength in hydro- Type of Steel Test, hr Before After
gen was less than that in argon. 3% Cr 4,000 25 14
Plant experience indicates some caution is 5% Cr 4,000 31 26
necessary in operation of furnace tubing when in 5% Cr 14,000 31 10
18 Cr - 8 Ni 4,000 65 44
hydrogen service. In one instance 5 Cr - 0.5 Mo 18 Cr- 8 Ni 14,000 65 39
steel tubes failed in a brittle manner when rapidly

40 High Temperature and Pressures

hydrogen damage; in fact, a slight growth occurs.
Since no appreciable dimensional changes of an
affected piece of steel occur, inspection methods
other than visual or direct lneasurement are
required. Several tests have proved useful for
revealing the presence of affected areas, but the
most reliable are of a destructive type.
The simplest test is a bend or flattening test at
room temperature. The normal ductility of low-
carbon steels is such that a ' I in. thick sample can
be flattened through an angle of 180 deg without
showing evidences of cracking. When a piece of
hydrogen cracked steel is subjected to this test,
it breaks at a much lower angle of bending ;
in fact, it may break without any elongation.
Flattening tests of pipe sections are also usefu l for
indicating reduction of duct.iJity resulting from
hydrogen attack. Figure 13 shows the appearance
of hydrogen damaged pipes after a flattening test.
Macroetching by immersing a sample in a 1: 1
solu tion of hydrochloric acid at a tempera ture of
about 180 F for 20 min will reveal the presence of
0
cracked areas. Steel which has suffered hydrogen
damage by cracks or decarburization will have a
lower Rockwell or Brinell hardness, indicating the
degree of sponginess.
In addition to the above tests, tensile tests or
micro examination will reveal the presence of
weakened areas in the steel.
In the inspection of operating equipment in
hydrogen service, it may not be possible to obtain
a large sample for any of the above tests. In
these cases, it is sometimes possible to remove a
small chip and have it analyzed for its carbon
content to show how much this element has been
depleted from its original level.
Ultrasonic inspection is also useful for revealing
the presence of microscopic intergranular cracks.
When a beam of supersonic vibration is projected
through a piece of perfect steel a distinct sharp
reflection is returned from the opposite wall.
If, however, the wall contains intergranular
c"acks, a fuzzy or scattered signal is returned.
Pulse echo instruments such as the Sonoray or
Reflertoscope are used to perform such tests.
Preve nting High Temperatu re Hydrogen Damage
Process equipment exposed to hydrogen at
elevated temperatmes may require the use of
alloy steels or the use of specialized design and
fabrication techniques. As shown in Fig. 1,
plain carbon steels are entirely satisfactory for
hydrogen processes which are carried out at
fairly low temperatmes and high pressme, or at
low pressures and high temperature. At high
temperatures and high pressmes increasing
amounts of alloying elements are required to resist
the decarburizing action of hydrogen. This inter-
ll igh 'I'f' JlI}J (!)' allll'c and
Fig . 13- Crush tests of carbon steel pipes after exposure to high
pressure-high temperature hydrogen
dependence of pressure and temperature upon the
alloy content of the steel influences the design of
pressme vessels and piping.
In some high pressure-high temperature hydro-
gen processes it is the practice to use heavy wall
vessels of solid alloy steel. If the alloy content of
the steel is sufficient to resist the decarburizing
action of the hydrogen, these ves~els have proved
entirely successful. The cost of solid alloy vessels,
especially in large sizes, is appreciable. Further-
more there is a limit to the wall thickness of
vessels fabricated of solid alloy steel. To overcome
these difficulties several unique construction
techniques have been used.
Vessels lined with alloy steels have been designed
to withstand the most severe hydrogen environ-
ments. Liner materials with sufficient alloy con-
tent will be resistant to hydrogen attack, but
hydrogen will still diffuse through the liner and
accumulate between the liner and the plain carbon-
steel strength shell. The diffusion of hydrogen
through the liner material varies with the alloy
content and is dependent on temperature and
pressure. Work by Naumann shows that at a
pressure 330 kg per sq cm (4300 psi) and a tem-
perature of 300 0 C (572 0 F l that hydrogen will
diffuse through a 5 mm thick plate of 1 ";. Cr
steel at the rate of 0.5 cc , cm ' hr. Under the
same conditions 17 Cr steel permitted only 0.03
cc/ cm ' ; hr to diffuse through. It is evident from
data provided by such tests that hydrogen will
diffuse through chromium steels at rates which
decrease regularly as the chromium content in-
creases ; however, if the alloy content is sufficient to
resist decarburization and internal cracking, one
need only to provide for protection of the carbon
steel strength shell from the hydrogen which could
accumulate between the liner and the shell. '1'0
avoid the pressure conditions favoring attack of
the carbon steel, this hydrogen pressure can be
relieved by venting through weep holes in the
P r(!ss ll t'c~
shell. The small weep holes do not appreciably
affect the strength of the outer shell. Multiwall
or layer-built vessels are easily adapted to this
technique; the inner sheet being alloy with
subsequent layers constructed of carbon steel.
Many of today's processes for refining crude
oils operate under high pressures and temperatures
of hydrogen. Reactor sizes are becoming so
large (15 ft diameter x 6 in. thick x 60 ft long)
that few manufacturers are equipped to handle
them. Thickness of vessels can be reduced by
the use of interior insulation to lower temperatures
of the wall. McDowell et al., 11 have described cold
wall pressure vessels for refining processes above
725° F, which are internally insulated with casta-
ble refractories, so that the design temperature of
the shell is lowered below the creep-rupture range.
Another method is to use a solidly bonded inner
liner of steel with an alloy content sufficient to
resist the hydrogen. This is applied to a carbon-
steel or low-alloy backing. In this case, the
liner is applied only when it is required for the
purpose of resisting corrosives such as hydrogen
sulfide. It is apparent in this construction that
the hydrogen diffusing through the liner will
affect the backing material, and it is therefore
necessary that the backing material be of such
alloy content as to resist the effect of hydrogen
which diffuses through the liner material. Vent-
ing of the strength shell is also required.
Since the damaging effects of hydrogen are
dependent upon the temperature of the steel
as well as the pressure of hydrogen in the process,
some vessels have been constructed of carbon
or low alloy steel using the vessel wall as a heat
transfer surface and thereby lowering the metal
temperature to within safe limits. In exother-
mic hydrogen processes this type of construction
not only reduces the need for alloy steel but also
provides a means of temperature control and
possible heat recovery.
42 High Temperature and Pressures
Suggested Areas for Research
1. As little is known concerning safe hardness
levels for steels in high-temperature, high-pressure
service, it is suggested that work be done to
determine workable parameters.
2. Further work is needed between the low
temperature range of delayed fracture and the
high temperature range where methane formation
is the cause of failure. The range is estimated
at 300-600° F.
3. Creep and creep-rupture tests in hydrogen
are needed which extend over long periods of
time, i.e., 10,000 and 100,000 hr. Data pub-
lished so far are for short periods of time at stresses
approaching the yield point.
References
1. Pennington, N. A., Trans. ASM, 37 (1946).
2. Fletcher, E. H., and Elsen, A. F., DMIG Report 202, Battelle Me-
morial Institute (1964).
3. Naumann, F. K., "Influence of Alloy Additions to Steel upon Resist-
ance to Hydrogen under High Pressure," Tech. Mitt. Krupp., 1 (12) 223-
234 (1938).
4. Vitovec, F. H., "The Growth Rate of Fiasures during Hydrogen At-
tack of Steel," Proe.API,Hl (1964).
5. Nelson, G. A., "Operating Limits and Incubation Times for Steels in
Hydrogen Service," Preprint API Meeting, May 1965.
6. Allen, R. E., Jansen, R. J., Rosenthan, B. C., and Vitovec, F. H.,
"The Rate of Irreversible Hydrogen Attack of Steel at Elevated Tempera-
tures" Proc. API 41, Section 111, Refining (1964).
7: Nelson, G. A., "Steel Deterioration in Hydrogen," Preprint No. 33-67,
American Petroleum Institute, May 18, 1967.
8. Thoma, P. A., Vitovec, F. H., and Mullendore, J. A., "Effect of Hy-
drogen on the Creep Rupture Properties of Iron," Proe. API, Ref. 46, 345-
351 (1966).
9. Allen, R. E., Rosenthal, P. C., and Vitovec, F. H., "Stress Rupture
Behaviour of Mild Steel under conditions of Hydrogen Attack," Preprint
API Meeting, San Francisco, May 16, 1962.
10. Sutherland, W. C., Vacca, P. J., Rosenthal, P. C., and Vitovec, F. H.,
"Effect of Stress Concentration and Gas Preasure on the Creep Strength of
Steel in Hydrogen Environment," Preprint API Meeting, Montreal, May
10,1965.
11. McDowell, D. W., Jr., Milligan, J. D., and Kevin, A. D., "Cold vs.
Hot Wall Pressure Vessels," Hydrocarbon Proceas Petrol. Refiner, Mar.
(1966).
Section III-Practical Aspects of Hydrogen
Damage at Atmospheric Temperature
Charles M. Hudgins, Jr.

SU~fMAH.Y. The fi rst section of this interpretive report laid hydrogen that enters the steel often comes from
the theoretical foundation for the study of effects of hydro-
gen. The second discussed the effects of h ydrogen at corrosion reactions but can come from hydrogen
elevated temperatw·es. The purpose of t his section is to gas as well.
discuss the particai aspects of the lo wer temperature damage
by hydrogen. The selection of materials, then' use, pitfalls Failures
to be avoided, and some possible problems wi ll be reviewed.
Some examples of this type of failure will be
given. Figure 1 shows a moderately high strength
Introduction
tubing joint which completely parted shortly after
A brief summru:y of the types of damage along being lowered into a well producing sulfide fluids.
with some examples will serve to introduce the ExposUTe time of the failed joint was only a few
reader to the natme of problems which have been hours. The hardness was about RC 29, corre-
encountered. The examples have been largely sponding to approximately 110- 120,000 psi yield
drawn from the petroleum industry because of the strength . Numerous failures of valve trim parts
author's background. Another author with a (stems, seats, springs, etc. ) occurred when very
different background could cite different examples sour (up to 50 % H ,S) high preSSUTe gas wells were
of the same type of problems. Throughout the first being produced in Canada, East Texas and
paper one theme will keep appearing- bulk prop- France. The stresses were usually very low, but
erties and average nominal stresses do not ade- the hardnesses were quite high . A typical ex-
quately account for observed problems. Localized ample is shown in Fig. 2. Bourdon tubes made of
property differences at welds or coldworked areas high strength carbon steel or 400 series staiuless
may make them susceptible to hydrogen damage steels have failed when exposed to high pressure
while the bulk material remains nonsusceptible.
Stress concentrations at welds, threads, defects,
nozzles, etc., may render those areas susceptible to
damage. What subsequently propagates from
these locations is influenced by bulk properties.
Delayed fracture at low stress is perhaps the
most serious of t he types of problems because it can
result in complete and <I instantaneous" parting of
a material without warning after a period of time
has passed. The stresses can be well below the
yield strength, even as low as 10 % of the y ield.
Failure can occur within lninutes or 1110nths after
the stress is applied and the environment contacts
the material. This complete type of failure is
usually restricted to higher strength materials.
Transgranular cracking usually p redominates over
intergranular, with relatively little branching
being present in the majority of cases. The
Fi g. I -Cracking of N·80 grade oil well tubing. 2 ~/B in. 00 . The
C. 1\1. Hudgins is with the Conlinenlal Oil Cnmpony, POIICII City, cracking occu rred at a tong mark within a few minutes after
OklahomK.
The preparation of this report was sponsored by the SubcommIttee on contactin g well fl uids con tami nated wi th hydrogen sulfide.
Hydrogen Embrittlemeot of the Pressure Vesse l Researc h Committee. Hardness of the steel was Rockwell C·29

.411lbient TeI1l1)eJ'ature 43

Fig. 2-Carbon steel relief valve spring after exposure to hy·
drogen sulfide environment (Reprinted with permission of the
American Chemical Society from Ind . & Engrg. Chem ., 44 (10)
1952, p. 2500)
pure hydrogen gas. I Cracking has occurred in the
shells of transport trucks fabricated from high
strength A-517 steel within hoUl's after sour natural
gasoline was loaded. High strength tUl'bine com-
pressor blades failed after three month service re-
cycling H ,S contaminated hydrogen gas in a re-
finery .' Cracking failures have occUl'red in hard
welds in softer, " non-susceptible" storage tank
materials for crude oil. ' FailUl'es of A-517F hydro-
gen storage tanks (5000 psi) were associated with
welds.! Some of the tanks were found to have had
cracks before service so that this example might
better be considered an example of interaction of
high hardness, defects, and hydrogen gas.
Blistering
Hydrogen blistering results from hydrogen gas
collecting in defects. Hydrogen can enter and
move rather freely t hrough many materials as long
as the hydrogen exists as an atom. If the hydro-
gen atoms combine to molecular hydrogen in a void
or defect in the material, hydrogen is rather ir-
reversibly trapped. Continued accumulation of
molecular hydrogen gas in the defect can lead to
very high preSSUl'es and the formation of blisters in
softer steels. The large blisters observed in
storage tanks containing soul' crude oil is perhaps
the most common example of this problem (Fig. 3).
However, blistering of heavy walled refinery
reactor vessels was a lTIore serious problelll because
of the pressure involved. The use of alloy linings
and multiwalled carbon steel vessels has minimized
this problem, but the inner liner must be vented to
prevent hydrogen accumulation which could
collapse the linear. Piping is generally less sus-
A I1Ibieni 'Temperature
ceptible to blistering but certainly is not immune.
Figure 4 shows blisters in fully killed, seamless
Grade B line pipe ('" x 13 in. ) caused by lamina-
tion defects due to inadequate cropping of the
ingot. Inclusions in electric-resistance-welded
pipe made from semi-killed steel led to the !issw'es
and blisters shown in Fig. 5.
Dissolved hydrogen greatly reduces the ability
of steel to deform. This is important even in
materials too soft to be susceptible to the delayed
failures discussed above. The force required to
unseat or unstick an oilfield downhole pump is
frequently large enough to exceed the yield
strength of the sucker rods. Each 25-ft rod will
normally stretch a foot or more past yield without
breaking, offering considerable "safety factor" to
the operator. In sour wells, however, the rods will
part with very little permanent elongation. Bend-
ing or flattening of embrittled pipe will usually
result in fractUl'e at much less strain than normal.
The wall of the blister shown in Fig. 4 has parted
with little evidence of yielding, whereas the new
pipe could be almost flattened without any separa-
tion.
Preventive Measu res
There are numerous ways to combat hydrogen
problems, the actual choice usually being con-
t.rolled by economic as well as technical limitations.
Fortunately, hydrogen damage at atmospheric tem-
peratUl'es can often be largely circumvented by
careful attention to material selection and fabrica-
tion practices. Moreover, the additional cost is
often relatively minor. Restriction of the maxi-
mum strength level is the single most important
material consideration. This includes weldments,
cold-rolled threads, etc., as well as bulk material.
Elimination of cold work, stress raisers, and hard
weld areas are critical in fabrication, especially for
stronger steels. A combination of these measw'es
has virtually eliminated value failw-es in the pro-
duction and handling of sulfide-containing oil, gas
and salt water.' Often it is more desirable to
Fig. 3-Cross section of a hydrogen blister in ~/u in. thick plate
from a sour crude oil storage tank
 -
Fig. 4- Bli stering of Grad e B line pipe- 12 in. 00 x '/4 in. wa ll.
Thi s had been exposed in the laboratory to 5% sodium chloride
solution sat urated with hydrogen sulf ide
separate the structural material from the environ-
ment. This approach is used in many refinery
applications where a thin alloy liner is used to
prevent damage to the thick carbon steel pressure
shell.' A third approach involves ch anging the
envirOlunent to reduce its aggressiveness. Con-
trol of pH in drilling muds' and refinery wash
streams7 are instances which have met with con-
siderable success.
Let us now exalnine these approaches in con-
siderably more detail. It should be pointed out
that most of the supporting data and considerable
additional information is included in Section I of
this bulletin . The engineer faced with a specific
problem would be well a dvised to stud y pertinent
areas there also.
Materials
The best technical solution to delayed fracture
problems u sually is to select a material that is not
susceptible to this mode of failure and fabricate
and use it in such a lnanner so as not to induce
susceptibility. A number of the factors involved
in this approach will now be discussed. Es-
sentially all investigators who have studied hydro-
gen damage from any h ydrogenizing source have
found that strength level of material is the most
significant single variable.'
CARBON AND LOW-ALLOY STEELS. For the rel-
atively severe sulfide h ydrogenizing environment
it has been found that most steels with yield
A mbient 'Tenl/Jeratu re
Fig. 5-Magnetic particle ind ications of fissures associated with
hydrogen blister formation in electric·resistance-welded line
pipe in sour service. The blisters occurred at inclusions in steel
strength less than approximately 90,000 psi
will be resistant to cracking failures. ' This
corresponds roughly to Rockwell C22 hardness.
This latter is mentioned because it has been used
as a criteria in NACE , API and other specifica-
tions," and is particularly useful for nondestructive
testing in the laboratory or in the field, even on
complex shapes. It should be emphasized that
the 90,000 psi yield presently represents a maxi-
mum in the available useable strength for carbon
a nd low alloy steels in sulfide service. This in-
formation has led to the introduction of a special
grade, C-75, for oilfield tubing and casing for
hydrogen sulfide service. A major factor in this
specification is the restriction of the yield strength
to a range of 75,000- 90,000 psi. At higher
strengths, the threshold stress to failure actually
decreases by approximately 10,000 psi for each
10,000 psi increase in yield strength. This has
been confirmed by a number of investigators. '"
For example, low alloy steels with a yield strength
of 150,000 p si can be expected to fail with only
20,000- 30,000 psi applied stress in a corrosive
sulfide environment. Likewise, it is important to
point out that welding or excessive cold work on
l1ol1susceptible lnaterials can increase theil' sus-
ceptibility. Figure 6 shows two failed B-7 bolts
(RC 31- 34) removed from the floating head of a
heat exchanger exposed to a sour gas. The failure
can be prevented by using softer (RC 22 max.)
materials, if compatible with strength require-
-15

Fig. 6-Typical fa ilures of 8-7 bol ts (Rockwell C 31-34) in sour
petroleum refinery fluids_ T hese bolt s were removed from a
debutanizer overhead condenser
m ents, or by changing to K-Monel.
The composition of cal'bon and low alloy steels
h as been shown by a number of investigators to be
relatively unimportant." Other data indicates
some constituents may be important, but t he data
is frequently conflicting." The number of vari-
ables involved makes it very difficult to prove the
usefulness or h armfulness of any single constituent
beyond a shadow of a doubt. At any rate, the
differences are relatively minor when compared to
the effect of strength level. However, the com-
position can h ave a significant effect on t he hard-
ness and transformation temperatw-e of the weld
zones in products that are fabricated by welding.
Special preheat and postheat treatments can be
and frequently are used to minimize such un-
desirable effects. The composition can also h ave a
significant effect in low alloy steels if the critical
temperatw-e of the steel is lowered sufficiently to
prevent adequate softening by tempering without
exceeding t he critical temperatw-e.
MAR'l'ENSITIC STAINLESS STEELS. The high cor-
rosion resistance of martensitic stainless steels will
often result in less corrosion-generated hydrogen.
The addition of chromium (at least up to 18 %1 also
red uces the permeation drast ically ." These fac-
tors should lead to better performance; h owever,
experience with 12 chl'ome steels in sulfide sel'vice
has shown that they can be even more susceptible
to cracking than carbon steels. Heat treatment
and chemistry can be very important, probably
re lat ing to heterogeneous structures. " This can
be particularly true in the case of vessels requiring
welding. Exu'eme caution must be exercised with
these higher alloys in order to prevent quench cool-
ing and the resulting high hardness and high
residual sU'esses in t he weld area.
AUSTENITIC STAINLESS STEELS. Experience with
austenitic stainless steels has shown t hat th ey are
essentially immune to hydrogen damage. Con-
sequently, they have found many applications in
refinery vessels, preSSUl"e gages, valves, pumps,
JG
wire lines, etc. Major factors reslricting their
wider use have been cost and strength limitations.
Some recent work "· " has shown that under
severe conditions of cold work and stress, even
these materials can be adversely affected by
hydrogen ; when the austenite is u'ansformed to
martensite by cold-work, the steel may be suscep-
tible. Such a condition is indicated by a high
degree of magnetism.
K-MONEL. Mention should be made of the ou t-
standillg u tility of K-Monel in severe environ-
ments such as hydrogen sullide saturated salt
water. This alloy is one of the few high strength
materials which is almost immune to sullide crack-
ing problems. It has found wide acceptance as
springs, valve stems, valve seats, plunger and other
miscellaneous applications where high strength
hard materials are a necessity. K-Monel is often
used in internal bolting in process vessels handling
sour gas or gasoline. In critical situations such as
the high pressure wellhead of a sour gas well,
K-Monel bolts will even be used for flanges which
are not normally exposed to the embrittling en-
vironment but which might become exposed if the
flange should leak. Age-hardened Inconels have
also found use for compressor valve parts for
sulfide service. A word of caution is in order,
since wldel' some conditions when oxygen is pres-
ent, the Monel is subject to stress-corrosion
cracking.
MARAGING STEEL. The maraging steels cover a
variety of different types, some of which have
promise for increased strength level with reduced
susceptibility to hydrogen embrittlement and
sulfide cracking. Most of these steels are rela-
tively new and initial development work has been
directed towill'ds inert or moderately reactive
envirolUllents. The increase alloy content is
expected to reduce the hydrogen permeability of
t he alloy and may prevent hydrogen generation by
C01TOSlon. Both effects should result in somewhat
more resistant alloys. Little actual operating
data has been accumulated to date on these steels
in more severe environments. The 17-4 PH
group of steels has met with some success as an
alternative for K-Monel in the valve trim parts
discussed above, although the useful strength level
is usually lower than for K-Monel when such steels
are in the softer tempers. Much of the tinle the
Rockwell C221imitation applies to t he 17-4 PH.
Microstructure
Workers in the sulfide cracking area have gen-
erally fo und tempered martensite to be the most
resistant microstructure for carbon and low alloy
steels." T his structure is usually obtained by a
quench and temper treatment. Un tempered mar-
tensite has been found to be unusually sensitive
Jbllbien( T CIIIIJeralu7"l'
to hydrogen cracking. 16 The fine carbide disper-
sion usually associated with tempered martensite is
considered advantageous while the coarser precipi-
tates of carbides, such as pearlite, are less desir-
able. 17 To some extent this superior performance
is due to crack propagation resistance. The
maximum effect of the differences in microstructure
appears to be approximately 15,000 psi increase in
useable strength as long as the untempered mar-
tensite is excluded. Useful strengths to 107,000
psi were recently attained by a double tempering
process whereby newly formed martensite was
tempered in the second treatment. IS
Cold Work
The adverse effect of cold work has been ob-
served by almost every investigator who has
studied hydrogen embrittlement. 19 There is little
doubt that more than about 5 % cold work will
result in a marked increase in the susceptibility to
hydrogen damage and cracking failures. Below
5%, however, it appears that the significance of the
damage will depend on the original properties of
material. For example, materials that are barely
safe in the non-cold worked condition might be-
come dangerously susceptible with a small incre-
ment of cold work, while soft materials would not
be significantly affected by the same amount of
cold work. One source of damage that should
generally be restricted is cold straightening of
tubular goods during processing without subse-
quent stress relieving. Another example where
problems can result is the cold bending of tubular
goods during installation, for example the installa-
tion of pipelines in hilly terrain. Cold formed
pressure vessel heads have been found to be un-
usually susceptible to hydrogen damage. Like-
wise, cold formed tray support rings welded to the
inside of a vessel have been observed to crack when
exposed to sour environments, that is, refinery
1luids containing H 2S and cyanides.
Welding
I t is no coincidence that delayed cracking failures
of pressure vessels are frequently initiated in and
often propagate along the weld area (including both
the weld metal and the heat affected zone). These
failures generally re1lect higher hardness in the
weld metal or in the heat affected zone. For
example, Bates 3 reported on a study of moderate
to high strength steels exposed to sour crude oil
environments. One of his most important con-
clusions was that welding of the higher strength
steels greatly increased the probability of cracking
failure. Metallographic examination revealed
that cracks in the welded specimens usually oc-
curred in the weld zones. Of the 72 welded
specimens that failed, only one specimen cracked
in a spot remote from the weld. Hardnesses in
the heat affected zone were generally 10 to 20
Ambient Temperature
Rockwell C units higher than in the adjoining base
metal. It should be emphasized that only one
material did not fail in this series of tests-and
that one was the A-285-C steel (which has a
specified minimum tensile strength of 55,000 psi).
In other more severe environments outside of
above tests, A-285 steel, cold-worked by bending
to less than 5 % strain and under yield-strength
loading, did fail in operating equipment. Mc-
Pherson and Cataldo I reported on a number of
failures of A-517-F steels in high pressure hydrogen
gas service. Essentially all of the failures were
associated with welds, either in nozzle area or in
longitudinal and circumferential internal welds.
While many of the failures were associated with
poor quality welds the authors concluded that
under present fabrication techniques high strength
steel is not satisfactory for gaseous hydrogen ser-
vice.
Quality Control
The importance of quality control throughout
the welding process cannot be overemphasized.
Defective welds provide stress concentrations, laps,
porosity, etc., which can greatly aggravate hydro-
gen damage. Likewise, high hardnesses result in
greater susceptibility to hydrogen-induced delayed
failure. An important step in minimizing high
weld area hardness is to specify base metal and
welding electrodes that do not have unnecessarily
high carbon and alloy contents. This usually
means restricting the carbon, manganese, nickel,
and chrome contents to the minimum value con-
sistent with the properties of the base metal. A
suitable preheat practice may be required to mini-
mize quench cooling in the heat affected zones as
well as insure a dry material so that minimum
amounts of hydrogen will be introduced during the
welding process. Note that specifications for
welding electrodes do not always control the high
side of mechanical properties.
Good design and welding techniques should be
used at all times. Rounded corners, a minimum
number and limitation on severity of stress raisers,
full penetration of welds, minimum porosity,
smooth changes in cross section, etc., are quite
important. Random arc strikes on a vessel wall
nearly always leave hard spots and should be
rigorously avoided. Inspection of critical welds
should include X-ray for determination of porosity
and also magnetic-particle or dye-penetrant ex-
amination to find cracks.
Heat Treatment
Heat treatments after fabrication are commonly
used to reduce residual stresses and hardnesses to
acceptable levels and minimize the effect of cold
work. The importance of these operations in the
fabrication of pressure vessels, containers, pipe
47
values, etc., has been proven time and time again.
Specific practices are included in many specifica-
tions and codes. These operations are especially
important in a low temperature hydrogenizing
environment. For example, the introduction of
the NACE specification (1-F-1-66) for valves for
sour service' virtually eliminated cracking failures
cracks originating at such areas will not propagate
into failure of the vessel, pipe or unit. Sufficient
notch ductility in the base metal to accept such
small cracks is vital when equipment is to be used
in hydrogenizing service.
Field Repairs

in this severe hydrogenizing environment. A
major factor in the success has been the required
heat treatment at 1150 0 F after all welding repair,
overlay, cold work, etc., has been completed.
At temperatures in this range residual stresses are
reduced to relatively low values because most
steels have lost much of the strength. Perhaps
more important, however, is t he tempering that
will occur. Tempering at 1150 0 F will soften
nearly all carbon or low alloy steels to below RC
30 and most to RC 20- 25, thereby greatly reducing
the probability of a cracking failure. Selection of
specmc treatments must necessarily take wall
thickness into account as well as type of steel.
The effect of Lhe treatment of other properties
(e.g. , impact strength and corrosion resistance)
must also be considered. Nevertheless, hard weld
areas constitute an inunediate threat to the integ-
rity of the vessel whenever hydrogenizing condi-
tions are present. Hardnesses in these areas
should be kept as low as feasible, even at some
sacrifice of other properties. Hydrogen introduced
during the weld operation can be removed during
a post-fabrication heat treatment.
Service Pro blems
Repair of equipment in the field poses even more
severe problems than the original construdion.
There is nearly always an urgency to get the sys-
tem back on stream. It often is almost completely
impractical to heat treat a pressure vessel in the
field after welding repairs. Very careful control
must be exercised in localized heat treatments to
avoid creating still more problems. Selection of
welding electrodes is very important, especially if a
different base metal is to be used for a modification.
Pads or patches added to a vessel can introduce
residual stresses as well as heat affected zones
which enhance susceptibility to delayed cracking
failure. The low-hydrogen rods ease weld crack-
ing, but do little for the hardness of the heat-
affected zone . A very common source of high
hardness weld metal is high manganese welding
electrodes or flux.
Blistering
Another problem which may seriously affect
pressure vessels exposed to hydrogen charging
media is that of blistering, which occurs most com-
monly in hydrogen sulfide or hydrofluoric acid

Even if a system is fabricated in the proper

manner from suitable materials, problems may
arise in service. Most structmes have points at
which the stresses are at yield strength level.
This stress level may make the st.ructure sensitive
to a combination of hydrogen damage and fatigue.
Oil production gives an example of this. When
casing is run into a crooked hole and the " dog-leg"
is too severe, high stresses and possibly a little
plastic strain will occm at the last engaged thread
of the pin end. In sour oil the added deleterious
action of hydrogen sulfide results in occasional
failure of the threaded joint. Valve stem breakage
also increases in hydl'ogenizing environments;
excessive torque must be avoided. In oil wells the
presence of hydrogen sulfide reduces the useable
stress in fatigue and also introduces some new
phenomena. Sucker rod couplings which have
been hammered and then subjected to hydrogen
sulfide fluids will contain notches, cold work and
residual stresses leading to the cracking shown in
Fig. 7. Small sensitive spots, such as arc strikes
and small cold worked areas, cannot be completely
prevented . Hammer marks, skid scars, forced
fits, small dents and contact impressions are pres- Fig. 7-Cracking of hardened sucker rod coupling exposed to
sour well fluids. Note that cracks more nearly reflect residual
ent on all vessels as they go into service. The st ress and cold work of the hammer damage than the tensile
base material should be so selected that small stress of the load

.4 mbie1l1 '1'(111 perature

service. This problem may be the one most
familiar to plant personnel since it is readily ap-
parent to the naked eye. Hydrogen accumulates
at defects in the steel, building pressure until it
finally causes a large cavity to form and finally to
rupture. This blistering problem is usually mani-
fested in low strength steels only.
Approaches to preventing this blistering problem
involve the selection of materials which are sound
and free of large defects which can collect molec-
ular hydrogen. A fully killed steel, rather than a
rimmed or semi-killed steel should be specified in
order to obtain a steel free of blow holes, lamina-
tions, porosity, etc. The nonmetallic content
should also be as low as feasible and the cropping
practice should be adequate to assure a sound
product. Laminations in the heavy wall (3/ 4 in.)
pipeline steel mentioned earlier (Fig. 4) were de-
tected by welders during double-jointing. Ul-
trasonic inspection located a number of these
defects-always within one to two feet of the end
of the joint. This particular problem was traced
to incomplete cropping of the ingot. In some
instances it may be possible to achieve economies
by allowing blistering to occur on noncritical parts.
For example, blistering has occurred on rimmed
steel used for internal baffles in hydrofluoric acid
alkylation units in refineries, but because of the
function of a baffle no problems result. Fully
killed steel used for the vessel shells show no blister-
ing even though exposed to the same fluid.
The suitability of materials for this type of
service can be evaluated by nondestructive testing
procedures, especially ultrasonics. The pulse-
echo technique is especially useful in detecting
lamination type defects in plate and large diameter
tubes. I t is preferable to set a limit on number
and maximum size of these defects. However,
selection of these limits is somewhat arbitrary,
depending upon the economics involved, as well as
the specific application. In the sour-gas pipeline
example above, the maximum acceptable size was
0.25 sq in. In some cases it may be desirable to
vent relatively small, isolated voids to the exterior
surface. This venting can be done with a pressure
gage and a valve so that one can monitor the rate
of the hydrogen build-up in the void as well as
determine if a failure of the internal surface of the
defect occurs. Large numbers of small defects or
very large defects which might affect the integrity
of the vessel should be rejected. Sometimes it is
difficult to tell whether laminations or layers of
microporosity are present with ultrasonic instru-
ments. Since both types of defects can ultimately
lead to blister formation, it is not too important to
know which is which.
Blisters that have formed can be vented by
drilling with a 1/16 in. drill. It should be remem-
bered that the hydrogen gas is under high pressure.
A collar can be used around the drill bit to divert
Ambient Temperature
the flow of gas. To minimize the chance of ignit-
ing the hydrogen stream, an air-powered drill can
be used. Whether or not the blisters should be
vented to the inside or to the outside depends on
how close the void is to the surface as well as the
nature of the process fluid. For instance, if the
blister were near the inside surface and the fluid
were highly toxic, it would not be wise to drill from
the outside. Blistering at stress and strain con-
centration points should be viewed with more con-
cern than in a straight cylinderical portion of a
vessel. Obviously the through-thickness direction
properties have been impaired when appreciable
blistering has occurred.
Separation of Environment and
Structural Materials
Multi-Layer Vessels
One of the more successful approaches to hand-
ling hydrogenation reactions has been the separa-
tion of environment from the structural materials.
This can be accomplished by using multi-layered
shells on a large vessel. The inner liner which is ex-
posed to the high pressure gas can be made from a
low strength carbon steel if corrosion is not a prob-
lem. The outer layers can be made from higher
strength steel to minimize the total weight of the
vessel and the amount of steel required.
The annulus between the inner liner and the
outer structural members should be vented to the
exterior. This serves two purposes: the rate at
which the hydrogen is coming through the inner
steel can be monitored to give some indication of
the aggressiveness of the environment. Even
more important, the vent lines provide the means
for removing the hydrogen which permeates
through the inner liner and collects in the annulus
between this liner and the structural layers. Since
hydrogen can accumulate up to very high pres-
sures, removal is necessary to prevent the collapse
of the internal liner. Continuous removal of this
hydrogen is particularly important if pressure
cycling occurs in the process stream. I t should be
taken into consideration in the design of any vessels,
however, because sooner or later the process stream
will either intentionally or unexpectedly be de-
pressured. Reinforcing pads are one form of
layering that is frequently not recognized as a
potential problem. Unless the pocket under the
pad is vented, hydrogen can accumulate and warp
both the base shell and pad materials.
In many cases the internal layer of the multi-
layer vessel will be fabricated from an alloy selected
to resist corrosion and degradation of the metal in
the environment. When corrosion resistance is
the primary function of the lining, it is extremely
critical that any loss of integrity of the lining will
be rapidly detected so that appropriate shut down
and repair procedures can be instigated. This is
49
particularly important when the external layers
are high strength steel and the primary concern is
cracking rather than blistering. Considerable
care must be exercised in the fabrication procedures,
especially where various internal support members
are connected to the main structural body. Par-
ticular care must also be exercised so that vibration
and thermal fluctuations will not result in fatigue
cracking of the protective lining. Since the higher
alloy content usually results in less corrosion
generated hydrogen and lower permeation, the
rate of accumulation of hydrogen in the annulus
will be reduced, resulting in a corresponding re-
duction in the probability of a collapse failure of
the inner liner.
Fabrication of multi-layered vessels is more com-
plicated than single layered vessels. Details are
beyond the scope of this paper, but several im-
portant items should be pointed out. First of all,
there should be a minimum number of welds which
connect an inner layer of carbon steel to the outer
layer. Whenever there is a continuous metallic
bond between the two layers, hydrogen can diffuse
through the bonds without having to go through
the gaseous phase. This, in effect, reduces the
effectiveness of the multi-layer construction.
Secondly, even more rigid precautions and specifi-
cations must be used in welding the seams on the
inner liner. If this liner should crack, a high
strength external layer could be immediately
exposed to the full impact of the hydrogen environ-
ment with an increased possibility of a catastrophic
failure. Provision must be made so that a rapid
pressure buildup in the annulus will trigger shut-
down procedures and slow depressurization of the
vessel. Precautions must be taken in welding
alloy liners to the outer layers to minimize hard
spot formation and residual stresses that can result
from the welding of dissimilar metals of this type.
Metallic Overlays
Recent developments in metallic coatings show
considerable promise for improving the economics
and the effectiveness of control of corrosion and
permeation of hydrogen. The integral liners can
be weld overlays or the more recently introduced
explosive clad type. Actual operating experience
with the latter type of materials is still rather
limited. Some significant successes, however,
have been observed in the petroleum industry with
aluminized steels for various refinery applications.
While the primary purpose of the coating is usually
to resist moderately high temperature sulfide
corrosion, it may also minimize the permeation of
hydrogen into the underlying steel. It would be
very desirable, however, for any linings such as
this to be 100% complete. Pin holes can lead to
hydrogen entry into the structural material and
also to undercutting of the surrounding coating
50 Ambient Temperature
because of metal loss. Sprayed aluminum coatings
have been used very successfully to protect relief
value springs.
Nonmetallic Coatings
Nonmetallic coatings also have a definite role
in preventing hydrogen damage, especially where
corrosion is the source of the hydrogen. When
the right coating is properly applied, a very high
degree of protection can be obtained. Properties
of these materials have been improving over the
last few years. Temperature limits have been
raised and materials are now available for above
400 0 F in fairly severe chemical environments.
Reasonably good information should be available
on the use characteristics of the coating before it is
relied on the protect high strength steel. In
addition, it is highly desirable to have some sort of
monitoring system available to detect the first
stages of deterioration of the coating. This would
prevent a premature coating failure from resulting
in a catastrophic failure of the pressure containing
wall. The bonding characteristics of the material
are also quite important. It may be that minor
defects can be tolerated for steels that are only
moderately sensitive to embrittlement if the re-
mainder of the coating will remain bonded. This
is so because the hydrogen which contacts the steel
at a point defect will be able to diffuse away from
the defect in hemispherical permeation geometry,
resulting in relatively low concentrations in es-
sentially all of the metal. Rapid depressurization
can be a serious problem to coatings. Gases ab-
sorbed into the plastic should have time to diffuse
from the plastic without disintegrating it or dis-
bonding it from the base metal. Plastic coatings
have the distinct advantage of being able to be
applied after the rest of the vessel is completely
fabricated.
There are a number of process vessels which are
glass lined for corrosion protection from very
severe corrosive environments. Many of the
same criteria discussed for the plastic coatings, also
apply here. The complete vessel wall must be
covered. To date most of these lining techniques
involve thermal treatments of the entire vessel
which must be performed in the fabricators shop.
Care must be taken in subsequent transportation
and installation to prevent damage to the coating.
Alternation of Environment
As mentioned in a number of cases through the
report, the amount of hydrogen actually entering
the steel is greatly influenced by the presence of
certain contaminants such as hydrogen sulfide,
hydrogen cyanide, arsenic compounds, phosphorus
compounds, etc. One approach to minimizing and
perhaps eliminating the problem in some circum-
stances is to remove or inactivate the so-called
poisons. Perhaps the most well known example of
this is the practice of removing H 2S from natural
gas down to very low levels of a few ppm. While
this serves many purposes, the most important is
to minimize subsequent corrosion problems in the
gas pipeline network.
Another example is the practice of adding small
amounts of oxygen or ammonium polysulfide to
the refinery process streams which are contami-
nated by H 2S or cyanide. 7 The practice appar-
ently converts the H 2S to polysulfide and the
cyanide to thiocyanate ions, neither of which cata-
lyze hydrogen entry. Close pH control is required
in this practice to avoid severe weight loss corro-
sion. Hydrogen sulfide can also be oxidized to
sulfur or sulfate ion. Chlorine has been used in a
number of oil field applications to provide a com-
bination of hydrogen sulfide oxidation and bacte-
rial control in brines. Control of pH itself can
sometimes result in significantly less hydrogen
entry. Drilling muds can be maintained at as
high a pH value as practical (pH 10-12) in order to
minimize sulfide cracking. 6 However, particular
care should be exercised in the pH control when-
ever there is a possibility that the solution will be
evaporated towards dryness and where the carbon-
ate or sulfide content of the solution is high.
Under these circumstances one can get into a
caustic embrittlement problem which, in part, is a
result of hydrogen embrittlement. 20
Corrosion is one of the most serious sources of
hydrogen in plant service, since any aqueous
corrosion process is a potential source. Whether
hydrogen damage actually occurs depends on
whether or not hydrogen is liberated and whether
that hydrogen goes into the steel. To minimize
the hydrogen damage one can thus interfere with
either one or both of these processes. In many
situations the problem can be drastically reduced,
if not completely eliminated, by maintaining the
aqueous dew point of a process stream at a low
temperature. In most systems corrosion will not
proceed (or will proceed at an extremely slow rate)
unless a conductive liquid phase, which is required
for the electrochemical corrosion mechanism, is
present. In the majority of cases this phase would
be water, with or without contaminating electro-
lytes. However, we should hasten to point out
that there are many nonaqueous solvents with
adequate conductivity to allow corrosion to pro-
ceed electrochemically. If these solvents will also
furnish hydrogen for the cathode reaction exposure
to them may lead to hydrogen embrittlement prob-
lems. The anhydrous hydrogen fluoride used in
petroleum alkylation processes is perhaps the most
important commercial example. The increasing
attention being given nonaqueous solvents in both
academic and industrial research laboratories may
be a prelude to more widespread commercial ap-
Ambient Temperature
plication. If so, some material compatibility
tests will certainly be in order, as the present state
of knowledge does not allow us to anticipate these
problems.
Considerable success has been encountered in
many fields using corrosion inhibitors such as
filming amines to control weight loss corrosion.
There is little doubt that such inhibitors have a
place in reducing hydrogen embrittlement from
corrosion generated hydrogen. A number of
factors should be considered, however, before
relying on this approach to protect susceptible
high strength steels. First of all, only a small
amount of hydrogen will crack highly susceptible
materials. This means that levels of inhibition
must be very high, approaching 100%. Secondly,
the time required for the cracking to occur may be
only a matter of minutes for a highly susceptible
steel in a severe environment. This means that a
fail-safe continuous inhibition system must be
used. Both of these requirements strongly suggest
that high concentrations of highly persistent
inhibitor will be required. This approach may be
suitable for closed systems where the aggressive
fluid is at a fixed volume; however, for a "once-
through" stream the economics and disposal
considerations may make this approach of ques-
tionable value. The intermediate condition where
a safe or perhaps a moderately susceptible steel
is exposed to corrosive environment probably
represents the best possibility for using this ap-
proach. This is also essentially the conclusion
that Bates" reached from his test data mentioned
earlier. Failures of the less susceptible nonwelded
specimens were almost eliminated by adding
inhibitor. Failure fraction of the welded speci-
mens was reduced to 13% from 39%, but this is
hardly satisfactory for engineering use. If the
application involves one side attack (hydrogen
diffuses through the material and out the back
side) then a reduction of 80 to 90 % in the hydrogen
generation rate may keep the concentration of
hydrogen in the steel down to a tolerable level.
Conversely, if the exposure is for a short time only,
inhibition may prevent failure for the required
time.
A widespread successful practice is the use of
inhibitors on wirelines used in downhole operations
in oil wells. The lines are very susceptible (232,-
000 psi tensile strength) but inhibitors allow
successful use in mild environments for a few
hours. In moderately high H 2S environments,
stainless steel (170,000 psi tensile strength) plus
inhibitors is required. In severe environments it is
usually necessary to fill the tubing with an in-
hibited hydrocarbon fluid to prevent failure of the
wire line. Unfortunately, there is no adequate
quantitative data to determine the hydrogen per-
meation rate or concentration required to produce
cracking in specific steels. The use of corrosion
51
inhibitors ordinarily should be considered as a good
insurance technique rather than a primary control
procedure to prevent hydrogen embrittlement
from hydrogen generated by corrosion.
There are also some subtle sources of hydrogen.
A common means of cleaning process equipment is
to clean it with acids. If iron sulfide is present,
copious quantities of hydrogen sulfide can be
released. This hydrogen sulfide dissolved in
water and forming condensed droplets or dissolved
in the acidic solution is a potent cracking agent.
Some metal loss inhibitors may aggravate the
entry of hydrogen into the steel. Electroplating,
electrogalvanizing and cathodic cleaning are also
sources of hydrogen leading to cracking and some-
times to formation of small blisters. On the very
high strength steels even rusting can introduce
enough hydrogen to crack the steel if high stresses
are present from imposed loads or from residual
stress. If welds are present, the heat-affected
zones give both the high hardness and the residual
stresses.
Conclusions
The examples used in this report demonstrate
the complexities of designing for hydrogenizing
environments. Pitfalls are many, the most serious
being those associated with welding of the more
hardenable steels. Such steels need not always be
exotic, since damage to A-515 steels is frequent
enough. There is no steel in common use which is
not sensitive to the most severe of exposures.
Fortunately the most common environments are
indeed compatible with the ordinary carbon steels.
Oil refinery and sour streams, oil well fluids, hydro-
fluoric acid, hydrogen sulfide, cyanides, high pres-
sure hydrogen, and cathodic currents at high cur-
rent density all require specialized attention.
52. Ambient Temperature
Applications of new materials for these must be
made with great caution. In conclusion, it is
truly amazing that one of the elements of water
can exert so much influence on the choice of pres-
sure vessel materials and design.
References
1. McPherson, W. B., and Cataldo, C. E., "Recent Experience in High
Pressure Gaseous Hydrogen Equipment Operated at Room Temperature,"
presented at the 1968 Materials Engineering Exposition and Congress,
Oct. 14-17. ASM Technical Report No. D·8-14.1.
2. Kohut, G. B., and McGuire, W. J., "Materials for Centrifugal Com-
pressors Operating in Refinery Environments Containing Hydrogen Sulfide,"
Materials Protection, 7,17 (June 1968).
3. Bates, J. F., "Sulfide Stress Cracking of High Yield Strength Steels
in Sour Crude Oils, "Materials Protection, 8, 33 (January 1969).
4. Preliminary report of NACE Committee T-1B presented at Western
Canadian Regional Conference, February 7-9, 1962, at Calgary, Alberta.
Reported in Materials Protection, 2, 89 (March 1963). Also NACE pub-
lication 1F1-66 published in Materials Protection, Ii, 81, (September 1966). .._
5. McCabe, J. S., and Hickey, K. J., "Field Assembly of High Pressure
Reactors Comes of Age," Oil Gas Jnl., 113 (May 19, 1969).
6. Hudgina, C. M., McGlasson, R. L., Mehdizadeh P., and Rosborough,
W. M., "Hydrogen Cracking of Carbon and Alloy Steels," Corrosion, 22, 238
(August 1966).
7. Wilson, J. G., Bonner, W. A., Burham, H. D., and Skei, T., "Occlusion
of Hydrogen in Steel," Proc. 4th World Petrol. Congr., Section VIlIC Paper 3,
1955.
8. Groeneveld, E. Fletcher, E., and Elsea, A. R., "Special Report on
Review of Literature on Hydrogen Embrittlement," NASA Report CR-
74034, STARF Accession No. N 66-23505, January 1966.
9. Treseder, R. S. and Swanson, T. M., "Factors in Sulfide Corrosion
Cracking of High Strength Steels," Corrosion, 24,31 (February 1968).
10. Warren, D., Beckman, G. W., "Sulfide Corrosion Cracking of High
Strength Bolting Material," Corrosion, 13, (10), 63lt (October 1957).
11. Fletcher, E. E. Berry, W. E., and Elsea, A. R., "Stress Corrosion
Cracking and Hydrogen-Stress Cracking of High-Strength Steel," DMIC
Report 232,Defense Metals Information Center, Battelle Memorial Institute,
Columbus, Ohio, July 29, 1966.
12. Smialowski, M., "Hydrogen in Steel," Addison-Wesley Publishing
Co., Inc., Reading, Mass., 1962, p. 102.
13. Truman, J. E., Perry, R., and Chapman, G. N., "Stress-Corrosion
Cracking of Martensitic Stainless Steels, Jnl. Iron Steel Inst., 745 (September
1964).
14. Whiteman M. B. and Troiano, A. R. "Hydrogen Embrittlement of
Austenitic Stainless Steel," Corrosion, 21, 53 (1965).
15. Vennett R. M. and Ansell, G. S. "The Effect of High Pressure Hydro-
gen Upon the Tensile Properties and Fracture Behavior of 304L Stainless
Steel," Trans. ASM, 60, 242 (1967).
16. Baldy, M. F., and Bowden, R. C., Jr., "The Effect of Martensite on
Sulfide Stress Corrosion Cracking," Corrosion, 11 (10), 417t (October 1955).
17. Snape, E., "Roles of Composition and Microstructure in Sulfide
Cracking of Steel," Corrosion, 24, (9) 261 (September 1968).
18. Snape, E., Schaller, F. W., and Forbes Jones, R. M., "A Method for
Improving Sulfide Cracking Resistance of Low Alloy Steels," presented at
the 25th Annual Conference of the National Association of Corrosion Engi-
neers, Houston, Texas, March 10, 1969.
19. Bowers, C. N., McGuire, W. J., and Wiehe, A. E., "Stress Corrosion
Cracking of Steel Under Sulfide Conditions," Corrosion, 8, 333 (1952).
20. Smialowski, M. op. cit., p. 416.