Technical Reference on Hydrogen Compatibility of Materials

Plain Carbon Ferritic Steels:

C-Mn Alloys (code 1100)

Prepared by:

B.P. Somerday, Sandia National Laboratories, Livermore CA

Editors
C. San Marchi
B.P. Somerday
Sandia National Laboratories

This report may be updated and revised periodically in response to the needs of the technical
community; up-to-date versions can be requested from the editors at the address given below or
downloaded at http://www.sandia.gov/matlsTechRef/. The content of this report will also be
incorporated into a Sandia National Laboratory report (SAND2008-1163); the most recent
version can be obtained from the link above. The success of this reference depends upon
feedback from the technical community; please forward your comments, suggestions, criticisms
and relevant public-domain data to:
Sandia National Laboratories
Matls Tech Ref
C. San Marchi (MS-9402)
7011 East Ave
Livermore CA 94550.

IMPORTANT NOTICE
WARNING: Before using the information in this report, you must evaluate it and determine if it
is suitable for your intended application. You assume all risks and liability associated with such
use. Sandia National Laboratories make NO WARRANTIES including, but not limited to, any
Implied Warranty or Warranty of Fitness for a Particular Purpose. Sandia National Laboratories
will not be liable for any loss or damage arising from use of this information, whether direct,
indirect, special, incidental or consequential.

Sandia National Laboratories is a multi-program laboratory operated by Sandia Corporation, a

wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy’s
National Nuclear Security Administration under contract DE-AC04-94AL85000.
 Technical Reference on Hydrogen Compatibility of Materials
Plain Carbon Ferritic Steels:

C-Mn Alloys (code 1100)

1. General
Carbon and alloy steels can be categorized by a variety of characteristics such as
composition, microstructure, strength level, material processing, and heat treatment [1]. The
carbon and alloy steel categories selected for the Technical Reference on Hydrogen
Compatibility of Materials are based on characteristics of the steels as well as available data. In
this chapter, the steels are distinguished by the primary alloying elements, i.e., carbon and
manganese. Data on the compatibility of carbon steels with hydrogen gas exist primarily for the
following alloys: A515 Gr. 70, A516 Gr. 70, A106 Gr. B, A106 Gr. C, SA 105, and the 10xx
steels. In addition, a substantial amount of data has been generated for the API 5L steels, grades
X42 to X80. Since a full range of properties in hydrogen gas is not available for each steel, data
for all carbon steels are presented in this chapter. Although plain carbon ferritic steels exhibit
some metallurgical differences, the basic trends in the data are expected to apply generally to this
class of steels.
Carbon steels are attractive structural materials in applications such as pipelines because the
steels can be formed and welded, and adequate mechanical properties can be achieved through
normalizing heat treatments or hot rolling. The API 5L steels may contain additional alloying
elements, such as small quantities of niobium and vanadium. These "microalloying" additions as
well as processing through controlled rolling impart a combination of elevated strength and
improved low-temperature fracture resistance.
Despite the attractive properties of carbon steels, these materials must be used judiciously in
structures exposed to hydrogen gas. Hydrogen gas degrades the tensile ductility of carbon steels,
particularly in the presence of stress concentrations. Additionally, hydrogen gas lowers fracture
toughness, and certain metallurgical conditions can render the steels susceptible to crack
extension under static loading. Hydrogen gas also accelerates fatigue crack growth, even at
relatively low hydrogen gas partial pressures, suggesting that small fractions of hydrogen in gas
blends must be considered in fatigue life assessments. The severity of these manifestations of
hydrogen embrittlement depends on mechanical, environmental, and material variables.
Variables that influence behavior in hydrogen gas include loading rate, load cycle frequency, gas
pressure, gas composition, and the presence of welds. Control over these variables may allow
carbon steels to be applied safely in hydrogen gas environments. For example, limiting the
magnitude and frequency of load cycling can improve the compatibility of carbon steels with
hydrogen gas.
This chapter presents a range of data for carbon steels in hydrogen gas, including tensile and
crack growth properties. The crack growth data emphasize fracture mechanics properties, since
pipeline design can benefit from defect-tolerant design principles, particularly for hydrogen
environments.

1100 - 1
Plain Carbon Ferritc Steels C-Mn Alloys

1.1 Composition and microstructure

Table 1.1.1 lists the allowable composition ranges for carbon steels covered in this chapter.
Table 1.1.2 summarizes the compositions and product forms of steels from hydrogen
compatibility studies reported in this chapter. Table 1.1.3 details the heat treatments applied to
steels in Table 1.1.2. Additionally, Table 1.1.3 includes the yield strength, ultimate tensile
strength, total elongation, and reduction of area that result from the heat treatments.

1.2 Common designations

A515 Gr. 70: UNS K03103, ASTM A515 (70)
A516 Gr. 70: UNS K02700, ASTM A516 (70)
A106 Gr. B: ASTM A106 (B)
A106 Gr. C: ASTM A106 (C)
SA 105 Gr. II: ASME SA-105, ASTM A105
1020: UNS G10200, AISI 1020, ASTM A830 (1020)
1042: UNS G10420, AISI 1042, ASTM A830 (1042)
1080: UNS G10800, AISI 1080, ASTM A830 (1080)
X42: API 5L X42
X52: API 5L X52
X60: API 5L X60
X65: API 5L X65
X70: API 5L X70
X80: API 5L X80

2. Permeability, Diffusivity and Solubility

The permeability and solubility of hydrogen in 10xx carbon steels are mildly affected by
carbon content and microstructure [2]. In a single study, permeation experiments were conducted
on six carbon steels over the temperature range 500 to 900 K and gas pressure range 0.01 to 0.7
MPa [2]. The hydrogen permeability vs temperature relationships are plotted in Figure 2.1 (also
listed in Table 2.1) for the normalized microstructures and show that permeability systematically
decreases as carbon content increases. The difference in the permeability for 1010 steel
compared to 1095 steel is about a factor of three over the entire temperature range examined.
The solubility of hydrogen in 10xx carbon steels was determined from the ratio of
permeability and diffusivity [2]. Solubility vs temperature relationships are given in Table 2.1
and plotted in Figure 2.2 and demonstrate a trend similar to permeability, where solubility
generally decreases as carbon content increases. The difference in the solubility for 1010 steel
compared to 1095 steel is about a factor of two over the entire temperature range examined.
Permeability and solubility vs temperature relationships were reported for three different
microstructures [2]: normalized, spheroidized, and quenched and tempered. The permeability
was nearly identical for the three microstructures over the temperature range examined. The
solubility was highest in the normalized microstructure and lowest in the quenched and tempered
microstructure, but the difference was less than a factor of two over the temperature range.
The solubility is the Sievert's constant in Sievert's law and thus can be used to calculate the
concentration of hydrogen in the metal lattice. At lower temperatures, hydrogen segregates to

1100 - 2
Plain Carbon Ferritc Steels C-Mn Alloys

defects in metals, and the total hydrogen concentration is the sum of hydrogen in the lattice and
hydrogen at defects. The solubility relationships in Table 2.1 can be used to calculate the lattice
hydrogen concentration in carbon steels but not the total hydrogen concentration. More
information on calculating total hydrogen concentrations in steels at lower temperatures can be
found in Ref. [3].

3. Mechanical Properties: Effects of Gaseous Hydrogen

3.1 Tensile properties

3.1.1 Smooth tensile properties

Measurement of smooth tensile properties of carbon steels in high-pressure hydrogen gas
demonstrates that hydrogen degrades reduction of area but not ultimate tensile strength. Tables
3.1.1.1 and 3.1.1.2 summarize properties measured in 6.9 and 69 MPa hydrogen gas for a wide
range of carbon steels [4-6]. The reduction of area measurements in hydrogen gas are remarkably
consistent, where most values range from 35 to 47% independent of hydrogen gas pressure.
Although these absolute values remain relatively high in hydrogen gas, the loss of reduction of
area relative to values measured in air or inert gas can be as high as 50%. The most notable
exception to the general reduction of area trend is the high-carbon steel 1080, which exhibits a
reduction of area as low as 6% in hydrogen gas. However, the reduction of area for 1080 in
nitrogen gas (14%) is also relatively low.

3.1.2 Notched tensile properties

High-pressure hydrogen severely degrades the reduction of area of carbon steels when
measurements are conducted using notched specimens. In addition, hydrogen mildly reduces
tensile strength in notched specimens. Table 3.1.2.1 summarizes data for a range of carbon steels
tested in 6.9 MPa hydrogen gas [4]. Similar to trends from smooth specimens, the reduction of
area values from notched specimens are in a consistent range (5 to 9%). However, the reduction
of area loss measured from notched specimens is much more pronounced than the reduction of
area loss measured from smooth specimens; e.g., the reduction of area loss from notched
specimens can be as high as 80% in hydrogen gas. The reduction of notched tensile strength is
generally less than 15% for specimens tested in hydrogen gas.
Measurements for notched specimens in 69 MPa hydrogen gas (Table 3.1.2.2) [7] show
trends similar to measurements in 6.9 MPa hydrogen gas, however absolute values cannot be
compared directly since the notch geometries are different. Nonetheless, Table 3.1.2.2 shows that
hydrogen induces reduction of area losses as high as 70%. Notched tensile strength losses are as
high as 25% in hydrogen gas.

3.2 Fracture mechanics

3.2.1 Fracture toughness

The fracture toughness and crack propagation resistance of carbon steels are lower in high-
pressure hydrogen gas compared to properties measured in air or inert gas. Table 3.2.1.1 lists
fracture toughness and crack propagation resistance results for a range of carbon steels tested in
hydrogen gas up to 35 MPa pressure [5, 6, 8-11]. At a constant pressure of 6.9 MPa, the fracture
toughness is degraded by as much as 50% in hydrogen gas. However, absolute fracture

1100 - 3
Plain Carbon Ferritc Steels C-Mn Alloys

toughness remains high, where most values are near 100 MPam1/2. Hydrogen has a more
pronounced effect on crack propagation resistance; dJ/da values measured in hydrogen gas can
be 90% lower than values measured in air or inert gas.
The fracture toughness measured in hydrogen gas is sensitive to both the loading rate and gas
pressure. Figure 3.2.1.1 shows that the fracture toughness for X42 steel in 4 MPa hydrogen gas is
constant at displacement rates from 3x10-5 to 3x10-4 mm/s but then increases by 30% as the
displacement rate increases to 3x10-3 mm/s [11]. Figure 3.2.1.2 displays the fracture toughness vs
hydrogen gas pressure data for X42 and A516 steel from Table 3.2.1.1 [8, 9, 11]. For both sets of
data, fracture toughness decreases as gas pressure increases but appears to be approaching a
lower limiting value. Fracture toughness values are higher for A516 compared to X42, but this
difference may be due in part to the higher loading rate for tests on A516.
Fracture toughness can depend sensitively on gas composition, as illustrated in Figure 3.2.1.3
[6]. In this figure, fracture toughness measurements are shown for X42 and X70 steels in
nitrogen, methane, and hydrogen, as well as mixtures of hydrogen, methane, carbon monoxide,
and carbon dioxide. The results for hydrogen and nitrogen are the same data from Table 3.2.1.1.
The data in Figure 3.2.1.3 show that methane does not adversely affect fracture toughness,
however a mixture of methane and hydrogen causes a reduction in fracture toughness.
Furthermore, fracture toughness is not degraded in gas mixtures containing hydrogen and carbon
monoxide. In these cases, carbon monoxide hinders hydrogen uptake into the steel and precludes
hydrogen-assisted fracture [6], at least on the time scale of the fracture toughness test.

3.2.2 Threshold stress-intensity factor

Subcritical crack extension can occur when materials are exposed to static loading and
hydrogen gas concurrently. Testing was conducted on A106 Gr. B and X70 steels to assess the
resistance of these materials to subcritical cracking in 6.9 and 4.1 MPa hydrogen gas partial
pressures, respectively [6, 9]. Subcritical crack extension was not detected for either steel.
Similarly, testing was conducted on A516 and A106 Gr. C steels to measure the threshold stress-
intensity factor for subcritical crack extension (i.e., KTH) at high hydrogen gas pressures [12]. As
summarized in Table 3.2.2.1., no crack extension was measured at the reported stress-intensity
factors.

3.3 Fatigue

3.3.1 Low-cycle and high-cycle fatigue

No known published data in hydrogen gas.

3.3.2 Fatigue crack propagation

Hydrogen gas enhances the fatigue crack growth rate of carbon steels. Figure 3.3.2.1 shows
crack growth rate (da/dN) vs stress-intensity factor range (K) relationships for a range of carbon
steels in approximately 7 MPa hydrogen gas [6, 10, 13-16]. Several general trends are apparent
from the data in Figure 3.3.2.1. The fatigue crack growth rates in hydrogen become increasingly
greater relative to crack growth rates in air or inert gas as K increases. In the higher range of
K, fatigue crack growth rates are at least ten-fold greater than crack growth rates in air or inert
gas. While the da/dN vs K relationships in air and inert gas are remarkably similar, the da/dN

1100 - 4
Plain Carbon Ferritc Steels C-Mn Alloys

vs K relationships in hydrogen are noticeably more varied. In the higher range of K, crack
growth rates in hydrogen can vary by more than a factor of 10.
The da/dN vs K relationships in hydrogen gas can be affected by numerous variables,
including gas pressure, load ratio, load cycle frequency, and gas composition. The effects of
these variables are described in the following paragraphs.

Effect of gas pressure

Fatigue crack growth rates generally increase as hydrogen gas pressure increases [13, 16].
Figure 3.3.2.2 shows da/dN vs K relationships for 1020 steel in hydrogen gas from 0.02 to
7 MPa and for SA 105 steel in hydrogen gas from 7 to 100 MPa [13, 16]. The effect of hydrogen
gas pressure on crack growth rates appears to depend on K. At higher K, the da/dN vs K
relationships measured in hydrogen merge, suggesting that crack growth rates are not as sensitive
to gas pressure at these K levels. At lower K, crack growth rates can increase by more than a
factor of 10 as gas pressure increases from 0.02 MPa to 100 MPa.
The da/dN vs K relationship for 1020 steel in 0.02 MPa hydrogen gas is particularly
striking. At this low gas pressure (less than 1 atmosphere), the crack growth rate can be a factor
of 10 greater than the crack growth rate in air. This result indicates that gases containing even
low partial pressures of hydrogen may accelerate fatigue crack growth in carbon steels.

Effect of load ratio

The cyclic load ratio (R, defined as the ratio of the minimum and maximum loads in the load
cycle) does not control fatigue crack growth rates in hydrogen gas [10]. Figure 3.3.2.3 shows
crack growth rates measured for X42 steel in hydrogen gas as a function of load ratio at a fixed
K. While the crack growth rate is independent of load ratio for values between 0.1 and 0.4, the
crack growth rate increases at higher load ratios. This increase in crack growth rates is controlled
not by the load ratio but by the maximum stress-intensity factor (Kmax) in the load cycle. Since
K  K max (1  R) , an increase in R at fixed K requires that Kmax increase as well. The crack
growth rate accelerates at higher load ratios because Kmax is approaching the fracture toughness
in hydrogen gas (e.g., the values in Table 3.2.1.1) [10].
Although Figure 3.3.2.3 shows that crack growth rates in hydrogen gas are not a function of
load ratio in the range from 0.1 to 0.4, crack growth rates in nitrogen are a strong function of
load ratio. Thus, as load ratio increases from 0.1 to 0.4, hydrogen has less effect on crack growth
rate relative to the crack growth rate in nitrogen. The varying effect of load ratio on crack growth
rates in hydrogen and nitrogen has been attributed to crack closure. It has been suggested that
plasticity-induced crack closure is less pronounced in hydrogen compared to environments such
as nitrogen [10].
Other measurements of fatigue crack growth rates in hydrogen gas indicate that da/dN vs K
relationships do not depend on load ratio. The da/dN vs K relationships for 1020 steel in 7 MPa
hydrogen gas are nearly identical at load ratios of 0.15 and 0.37 [13].

Effect of load cycle frequency

Fatigue crack growth rates in hydrogen gas generally increase as the load cycle frequency
decreases. This trend is illustrated in Figure 3.3.2.4, which displays da/dN vs K relationships

1100 - 5
Plain Carbon Ferritc Steels C-Mn Alloys

for SA 105 steel in 100 MPa hydrogen gas over a range of load cycle frequencies from 0.001 to 1
Hz [16]. As frequency decreases from 1 to 0.001 Hz, the crack growth rate increases by about a
factor of 5.
Additional data for SA 105 steel in 100 MPa hydrogen gas demonstrate that the load cycle
profile can be important as well. Figure 3.3.2.5 shows fatigue crack growth rates plotted against
the cycle duration (reciprocal of frequency) [16]. These data were generated using two different
load profiles, where the time to reach maximum load was either 0.5 or 100 seconds. While the
fatigue crack growth rate generally increases as the cycle duration increases, crack growth rates
for the 100 second ramp appear to increase more rapidly than crack growth rates for the 0.5
second ramp.
The effect of load cycle frequency on fatigue crack growth rates in hydrogen gas has been
demonstrated for other steels. Fatigue crack growth rates for 1020 steel in 0.14 MPa hydrogen
gas decreased as frequency increased from 1 to 10 Hz [13].

Effect of gas composition

Additives to hydrogen gas can reduce fatigue crack growth rates, however this phenomenon
has not been explored at low load cycle frequencies. Figure 3.3.2.6 shows da/dN vs K
relationships for X42 steel in 6.9 MPa hydrogen gas containing three different additives: oxygen,
sulfur dioxide, or carbon monoxide [6]. In each case, the gas additive lowers the fatigue crack
growth rate to the crack growth rate measured in nitrogen, at least for the relatively high
frequency (1 Hz) used in the study.
The effect of hydrogen gas mixtures on fatigue crack growth was also explored for 1020 steel
at a load cycle frequency of 1 Hz and low total gas pressure. Figure 3.3.2.7 shows da/dN vs K
relationships for three gas mixtures: hydrogen and carbon dioxide, hydrogen and natural gas, and
hydrogen and water [17]. The addition of carbon dioxide to hydrogen has no effect on fatigue
crack growth rates, as the da/dN vs K relationship for the gas mixture is similar to the
relationship for pure hydrogen. The crack growth rate in water plus hydrogen is lower than the
crack growth rate in pure hydrogen; however, hydrogen plus water vapor raises the crack growth
rate above the crack growth rate in pure water vapor. Finally, the crack growth rate in hydrogen
plus natural gas is similar to the crack growth rate in pure hydrogen. In addition, the crack
growth rate in pure natural gas is nearly the same as the crack growth rate in air.

3.4 Recent mechanical property measurements

3.4.1 Fracture toughness

The fracture toughness was measured for X60 and X80 steels in 5.5 and 21 MPa hydrogen
gas [18, 19]. Although fracture toughness values were notably higher for the X80 steel compared
to the X60 steel (Table 3.2.1.1), values for both steels were comparable to others listed in Table
3.2.1.1, i.e., near 100 MPam1/2. The varying hydrogen gas pressure did not significantly affect
fracture toughness for either the X60 steel or the X80 steel.

3.4.2 Fatigue crack propagation

Figure 3.4.2.1 and Figure 3.4.2.2 show crack growth rate (da/dN) vs stress-intensity factor
range (K) relationships for X60 and X80 steels in hydrogen gas [18, 19]. These relationships
were measured at two gas pressures (5.5 and 21 MPa) and two R ratios (0.1 and 0.5) for each

1100 - 6
Plain Carbon Ferritc Steels C-Mn Alloys

steel. The general trends of the fatigue crack growth rates in Figure 3.4.2.1 and Figure 3.4.2.2 are
similar to the trends in Figure 3.3.2.1, i.e., crack growth rates in hydrogen become increasingly
greater relative to crack growth rates in air as K increases. The magnitudes of the fatigue crack
growth rates are also similar, as demonstrated by including data for A516 steel from Figure
3.3.2.1 in the plots for X60 and X80 in Figure 3.4.2.1 and Figure 3.4.2.2.
The effects of R ratio and gas pressure on the da/dN vs K relationships for X60 and X80
steels are not readily established from the data in Figure 3.4.2.1 and Figure 3.4.2.2. In the higher
K range, increasing R ratio leads to modestly higher crack growth rates but varying gas
pressure has essentially no effect on crack growth rates. In the lower K range, the only clear
trend for the X80 steel is that crack growth rates are highest in 21 MPa hydrogen gas at R=0.5.
For the X60 steel at lower K, crack growth rates appear higher for R=0.5 but the effect of gas
pressure is not clear.

4. Fabrication

4.1 Heat treatment

Heat treating A516 steel to produce different microstructures does not significantly affect
fatigue crack growth rates in hydrogen gas [14, 15]. The da/dN vs K curves for A516 in three
different heat treatment conditions (see Table 1.1.3) are plotted in Figure 4.1.1. The heat
treatments produced the following three microstructures: ferrite plus pearlite with a 35 m prior
austenite grain size, ferrite plus pearlite with a 180 m prior austenite grain size, and bainite plus
continuous grain boundary ferrite with a 200 m prior austenite grain size. The yield strengths of
these microstructures are between 305 and 415 MPa (see Table 1.1.3). Despite the wide range in
microstructures, the da/dN vs K relationships are nearly identical at higher K. The primary
difference in the da/dN vs K relationships is a mild shift in the threshold stress-intensity range
(KTH) values, i.e., KTH varies from 8 to 11.5 MPam1/2 [14, 15].
An unexpected result was found when comparing the fatigue crack growth responses of X42
and 1080 steels in 6.9 MPa hydrogen gas [5]. The reduction of area (Table 3.1.1.1) and fracture
toughness (Table 3.2.1.1) in hydrogen gas are lower for the 1080 steel compared to the X42
steel, but fatigue crack growth rates in 1080 steel are less affected by hydrogen gas. This is
demonstrated from the da/dN vs K relationships in Figure 4.1.2. It was suggested that hydrogen
facilitates fatigue crack growth in the ferrite phase, so that fatigue crack growth rates are higher
in the X42 steel with a ferrite plus pearlite microstructure compared to the 1080 steel with a fully
pearlitic microstructure [5] .

4.2 Properties of welds

The tensile, fracture toughness, and fatigue crack growth properties of carbon steel welds
have been measured in hydrogen gas. These properties are considered in the following
paragraphs.

Tensile properties
A large amount of data has been generated for the tensile properties of carbon steel welds in
6.9 MPa hydrogen gas. Properties from both smooth and notched tensile specimens are
summarized in Tables 4.2.1 through 4.2.4.

1100 - 7
Plain Carbon Ferritc Steels C-Mn Alloys

The trends for smooth tensile specimen properties of welds in hydrogen gas are similar to
those for the base metals (section 3.1.1). Table 4.2.1 lists measurements from tensile specimens
that were oriented perpendicular to the weld [4, 20]. Most reduction of area values range from 30
to 40%, which represent reduction of area losses of approximately 50% from values measured in
air. These reduction of area properties were measured primarily for shielded metal arc and
submerged arc welds. The lowest reduction of area values (12 to 20%) were measured for an
electric resistance weld, a gas tungsten arc weld, and a gas metal arc weld. The weld with the
reduction of area of 12% fractured in the transition zone between the heat affected zone and the
base metal. Some of the highest reduction of area values measured (66 to 77%) were from
specimens that fractured in the fusion zone.
Other smooth tensile specimens were tested in an orientation parallel to the weld, where the
specimens were centered either in the fusion zone or heat affected zone. Table 4.2.2 shows that
reduction of area values in hydrogen gas are mostly in the range 38 to 47% [20]. These values
are generally greater than those measured from specimens oriented perpendicular to the weld.
Weld properties measured from notched tensile specimens in hydrogen gas are remarkably
consistent, independent of specimen orientation relative to the weld. Tables 4.2.3 and 4.2.4 show
that reduction of area values are in the range 9 to 17%, which represent reduction of area losses
of 50 to 70% from values measured in air [4, 20]. In addition, hydrogen lowers the tensile
strength by less than 15%. The reduction of area properties for welds are better than the
properties reported for base metals (section 3.1.2) when measured using notched tensile
specimens. The notched tensile strength properties for welds and base metals are similar.

Fracture toughness
The fracture toughness of welds in hydrogen gas depends on the type of weld and location of
crack propagation, as summarized in Table 4.2.5. The fracture toughness and crack propagation
resistance of submerged arc welds in X60 steel are high when crack propagation is in the fusion
zone [8]. The fracture toughness of the weld fusion zone (103 MPam1/2) is equal to the fracture
toughness of the base metal (Table 3.2.1.1). Furthermore, the crack propagation resistance of the
weld fusion zone (267 MPa) exceeds the crack propagation resistance of the base metal (43 MPa,
Table 3.2.1.1). In contrast, the fracture toughness of the heat affected zone was low and could
not be measured reliably, since cracks ultimately propagated in a rapid, subcritical manner. The
fracture toughness of the heat affected zone in electric resistance welded X42 was measured, and
this value (48 MPam1/2) was lower than the fracture toughness of the base metal (107 MPam1/2,
Table 3.2.1.1). No subcritical crack propagation was measured in the X42 weld heat affected
zone when tested under static load in 6.9 MPa hydrogen gas [6].

Fatigue crack propagation

Welds in X60 steel are not more susceptible to fatigue crack growth than the base metal in
6.9 MPa hydrogen gas [14]. Figure 4.2.1 shows that the da/dN vs K relationships for the fusion
zone and heat affected zone of a submerged arc weld are nearly identical to the da/dN vs K
relationship for the base metal.

1100 - 8
Plain Carbon Ferritc Steels C-Mn Alloys

5. References
1. "Classification and Designation of Carbon and Low-Alloy Steels," in Metals Handbook,
Properties and Selection: Irons, Steels, and High-Performance Alloys, 10th ed., vol. 1,
ASM International, Materials Park OH, 1990, pp. 140-194.
2. VL Gadgeel and DL Johnson, "Gas-Phase Hydrogen Permeation and Diffusion in Carbon
Steels as a Function of Carbon Content from 500 to 900 K," Journal of Materials for
Energy Systems, vol. 1, 1979, pp. 32-40.
3. JP Hirth, "Effects of Hydrogen on the Properties of Iron and Steel," Metallurgical
Transactions A, vol. 11A, 1980, pp. 861-890.
4. WR Hoover, JJ Iannucci, SL Robinson, JR Spingarn, and RE Stoltz, "Hydrogen
Compatibility of Structural Materials for Energy Storage and Transmission," SAND80-
8202, Sandia National Laboratories, Livermore, CA, 1980.
5. HJ Cialone and JH Holbrook, "Microstructural and Fractographic Features of Hydrogen-
Accelerated Fatigue-Crack Growth in Steels," in Microstructural Science: Welding,
Failure Analysis, and Metallography, vol. 14, MR Louthan, I LeMay, and GF
VanderVoort, Eds., American Society for Metals, Metals Park, OH, 1987, pp. 407-422.
6. HJ Cialone and JH Holbrook, "Sensitivity of Steels to Degradation in Gaseous
Hydrogen," in Hydrogen Embrittlement: Prevention and Control, ASTM STP 962, L
Raymond, Ed., American Society for Testing and Materials, Philadelphia, 1988, pp. 134-
152.
7. RJ Walter and WT Chandler, "Influence of Gaseous Hydrogen on Metals Final Report,"
NASA-CR-124410, NASA, Marshall Space Flight Center AL, 1973.
8. WR Hoover, SL Robinson, RE Stoltz, and JR Spingarn, "Hydrogen Compatibility of
Structural Materials for Energy Storage and Transmission Final Report," SAND81-8006,
Sandia National Laboratories, Livermore CA, 1981.
9. SL Robinson and RE Stoltz, "Toughness Losses and Fracture Behavior of Low Strength
Carbon-Manganese Steels in Hydrogen," in Hydrogen Effects in Metals, IM Bernstein
and AW Thompson, Eds., The Metallurgical Society of AIME, Warrendale, PA, 1981,
pp. 987-995.
10. HJ Cialone and JH Holbrook, "Effects of Gaseous Hydrogen on Fatigue Crack Growth in
Pipeline Steel," Metallurgical Transactions A, vol. 16A, 1985, pp. 115-122.
11. F Gutierrez-Solana and M Elices, "High-Pressure Hydrogen Behavior of a Pipeline
Steel," in Current Solutions to Hydrogen Problems in Steels, CG Interrante and GM
Pressouyre, Eds., American Society for Metals, Metals Park, OH, 1982, pp. 181-185.
12. AW Loginow and EH Phelps, "Steels for Seamless Hydrogen Pressure Vessels,"
Corrosion, vol. 31, 1975, pp. 404-412.
13. HG Nelson, "On the Mechanism of Hydrogen-Enhanced Crack Growth in Ferritic
Steels," in Proceedings of the Second International Conference on Mechanical Behavior
of Materials, ASM, Metals Park, OH, 1976, pp. 690-694.
14. HF Wachob, "The Influence of Microstructure on the Resistance of Low Strength Ferrous
Alloys to Gas Phase Hydrogen Degradation," NASA-CR-166334, Failure Analysis
Associates, Palo Alto, CA, 1981.
15. HF Wachob and HG Nelson, "Influence of Microstructure on the Fatigue Crack Growth
of A516 in Hydrogen," in Hydrogen Effects in Metals, IM Bernstein and AW Thompson,
Eds., The Metallurgical Society of AIME, Warrendale, PA, 1981, pp. 703-711.

1100 - 9
Plain Carbon Ferritc Steels C-Mn Alloys

16. RJ Walter and WT Chandler, "Cyclic-Load Crack Growth in ASME SA-105 Grade II
Steel in High-Pressure Hydrogen at Ambient Temperature," in Effect of Hydrogen on
Behavior of Materials, AW Thompson and IM Bernstein, Eds., The Metallurgical Society
of AIME, Warrendale, PA, 1976, pp. 273-286.
17. HG Nelson, "Hydrogen-Induced Slow Crack Growth of a Plain Carbon Pipeline Steel
Under Conditions of Cyclic Loading," in Effect of Hydrogen on Behavior of Materials,
AW Thompson and IM Bernstein, Eds., The Metallurgical Society of AIME, Warrendale,
PA, 1976, pp. 602-611.
18. C SanMarchi, BP Somerday, KA Nibur, DG Stalheim, T Boggess, and S Jansto,
"Fracture and Fatigue of Commercial Grade API Pipeline Steels in Gaseous Hydrogen,"
in Proceedings of the ASME 2010 Pressure Vessels & Piping Division / K-PVP
Conference PVP2010, Bellevue, Washington, 2010, PVP2010-25825.
19. D Stalheim, T Boggess, C SanMarchi, S Jansto, B Somerday, and G Muralidharan,
"Microstructure and Mechanical Property Performance of Commercial Grade API
Pipeline Steels in High Pressure Gaseous Hydrogen," in Proceedings of IPC 2010 8th
International Pipeline Conference, Calgary, Alberta, 2010, IPC2010-31301.
20. WR Hoover, "Hydrogen Compatibility of Structural Materials for Energy Storage and
Transmission," SAND79-8200, Sandia National Laboratories, Livermore, CA, 1979.
21. "Metals & Alloys in the Unified Numbering System," Standard SAE HS-1086/2004, 10th
ed., SAE International, Warrendale, PA, 2004.
22. "Standard Specification for Seamless Carbon Steel Pipe for High-Temperature Service,"
Standard A 106/A 106M-04b, ASTM International, West Conshohocken PA, 2004.
23. "Standard Specification for Carbon Steel Forgings for Piping Applications," Standard A
105/A 105M-05, ASTM International, West Conshohocken, PA, 2005.
24. "Specification for Line Pipe," API Specification 5L, American Petroleum Institute,
Washington DC, 1999.

1100 - 10
Plain Carbon Ferritc Steels C-Mn Alloys

Table 1.1.1. Allowable composition ranges (wt%) for carbon steels.

Steel Specification Fe C Mn P S Si Other Ref.
A515 UNS 0.31 0.90 0.035 0.040 0.13
Bal — [21]
Gr. 70 K03101 max max max max 0.33
A516 UNS 0.27 0.79 0.035 0.040 0.13
Bal — [21]
Gr. 70 K02700 max 1.30 max max 0.45
A106 ASTM 0.30 0.29 0.035 0.035 0.10
Bal — [22]
Gr. B A106 (B) max 1.06 max max min
A106 ASTM 0.35 0.29 0.035 0.035 0.10
Bal — [22]
Gr. C A106 (C) max 1.06 max max min
SA 105 ASTM 0.35 0.60 0.035 0.040 0.10
Bal — [23]
Gr. II A105 max 1.05 max max 0.35
UNS 0.18 0.30 0.030 0.050
1020 Bal — — [21]
G10200 0.23 0.60 max max
UNS 0.40 0.60 0.030 0.050
1042 Bal — — [21]
G10420 0.47 0.90 max max
UNS 0.75 0.60 0.030 0.050
1080 Bal — — [21]
G10800 0.88 0.90 max max
API 5L 0.22 1.30 0.025 0.015
X42† Bal — Nb+Ti+V<0.15 [24]
X42 max max max max
API 5L 0.22 1.40 0.025 0.015
X52† Bal — Nb+Ti+V<0.15 [24]
X52 max max max max
API 5L 0.22 1.40 0.025 0.015 ‡
X60† Bal — Nb+Ti+V<0.15 [24]
X60 max max max max
API 5L 0.22 1.45 0.025 0.015 ‡
X65† Bal — Nb+Ti+V<0.15 [24]
X65 max max max max
API 5L 0.22 1.65 0.025 0.015 ‡
X70† Bal — Nb+Ti+V<0.15 [24]
X70 max max max max
API 5L 0.22 1.85 0.025 0.015 ‡
X80† Bal — Nb+Ti+V<0.15 [24]
X80 max max max max
†
composition limits for welded product in Product Specification Level 2 (PSL 2)
‡
other compositions may be established by agreement between purchaser and
manufacturer, but limit of Nb+Ti+V<0.15 must be satisfied

1100 - 11
Plain Carbon Ferritc Steels C-Mn Alloys

Table 1.1.2. Compositions (wt%) of carbon steels in hydrogen compatibility studies.

Steel Product form Fe C Mn P S Si Other Ref.

A515 Gr. 70 0.95 cm plate Bal 0.27 0.71 0.011 0.018 0.19 — [7]
[14,
A516 Gr. 70 1.25 cm plate Bal 0.22 1.10 0.009 0.023 0.21 —
15]
<0.04 Al, Cr, Mo,
A516 Gr. 70 nr Bal 0.24 1.12 0.013 0.022 0.21 [12]
Ni
A516 Gr. 70 [4, 8,
2.5 cm plate Bal 0.21 1.04 0.012 0.020 0.21 —
(U.S. grade) 9, 20]
A516
plate Bal 0.26 0.79 0.013 0.033 0.17 — [4]
(Japan grade)
[4,
A106 Gr. B pipeline nr
20]
A106 Gr. C nr Bal 0.26 1.06 0.011 0.023 0.23 — [12]
59 cm OD,
SA 105 Gr. II 37 cm ID Bal 0.23 0.62 0.010 0.015 0.15 — [16]
hemisphere
[13,
1020 3.8 cm plate nr
17]
1020 0.95 cm rod Bal 0.17 0.47 0.011 0.037 — — [7]

1042 0.95 cm rod Bal 0.44 0.76 0.008 0.020 0.20 — [7]

1080 rail web section Bal 0.85 0.79 0.007 0.042 0.173 — [5]
30.5 cm OD, <0.04 Cr, Cu, Mo,
[5, 6,
X42 28.6 cm ID Bal 0.26 0.82 0.020 0.026 0.014 Ni ;
10]
pipeline <0.005 Al, Sn
X42 nr Bal 0.10 0.70 0.033 0.022 0.26 0.17 Co, 0.15 Cr [11]
[4,
X52 pipeline Bal 0.14 0.98 0.015 0.012 0.29 <0.012 Al, Nb
20]
[4,
X60 pipeline Bal 0.26 1.39 0.006 0.022 0.03 0.050 V
20]
<0.03 Cr, Cu, Mo, [8,
X60 1.25 cm plate Bal 0.12 1.29 0.014 0.016 0.25
Nb, Ni, V 14]
[4,
X65 pipeline Bal 0.22 1.23 — — 0.11 0.020 Nb
20]
<0.42 Al, Cr, Cu,
101.6 cm OD,
X70 Bal 0.09 1.50 0.008 0.006 0.31 Mo; [6]
98.6 ID pipeline
<0.084 Nb, Ni, Sn
<0.30 Cu, Ni; [4,
X70 pipeline Bal 0.11 1.44 0.013 0.002 0.27
<0.09 Al, Nb, V 20]
X70 [4,
pipeline Bal 0.06 1.70 0.010 0.009 0.20 0.30 Mo, 0.062 Nb
(Arctic grade) 20]
0.16 Cr, 0.14 Ni,
[18,
X60 plate Bal 0.03 1.14 0.008 0.001 0.18 0.084 Nb, 0.034
19]
Al, 0.014 Ti
0.25 Cr, 0.14 Ni,
[18,
X80 plate Bal 0.05 1.52 0.007 0.003 0.12 0.092 Nb, 0.036
19]
Al, 0.012 Ti
nr = not reported; ID = inner diameter; OD = outer diameter

1100 - 12
Plain Carbon Ferritc Steels C-Mn Alloys

Table 1.1.3. Heat treatments and mechanical properties of carbon steels in hydrogen
compatibility studies.
Sy Su RA
Steel Heat treatment Ref.
(MPa) (MPa) (%)
A515 Gr. 70 HR 338 504 66 [7]
A516 Gr. 70
N 1173 K/45 min + FC 330 565 —
(F+P, GS = 35 m)
A516 Gr. 70
N 1473 K/45 min + FC 305 — — [14, 15]
(F+P, GS = 180 m)
A516 Gr. 70 A 1473 K/45 min + ISQ + T 723
415 — —
(B, GS = 200 m) K/90 min
A516 Gr. 70 HR 290 572 62 [12]
A516 Gr. 70 [4, 8, 9,
HR 375 535 69
(U.S. grade) 20]
A516
nr 364 566 72 [4]
(Japan grade)
A106 Gr. B nr 462 559 58 [4, 20]
A106 Gr. C N 1130 K/75 min + AC 345 558 68 [12]
SR 894 K/240 min + 0.9 K/min
SA 105 Gr. II 269 462 63 [16]
cool
1020 HR 207 379 — [13, 17]
1020 HR 373 490 65 [7]
† † †
1042 N 1172 K/60 min + AC 400 621 59 [7]
† † †
1080 N 1123 K/60 min + FC 414 814 16 [5]
X42 HR 366 511 56 [5, 6, 10]
X42 nr 280 415 58 [11]
X52 nr 414 609 60 [4, 20]
X60 nr 427 594 49 [4, 20]
X60 nr 473 675 62 [8, 14]
X65 nr 504 605 57 [4, 20]
X70 CR 584 669 57 [6]
X70 nr 626 693 77 [4, 20]
X70
nr 697 733 77 [4, 20]
(Arctic grade)
†
X60 nr 434 486 88 [18, 19]
†
X80 nr 565 600 81 [18, 19]
nr = not reported; A = austenitize; AC = air cool; B = bainite; CR = controlled rolled; F =
ferrite; FC = furnace cool; GS = grain size; ISQ = isothermal quench; HR = hot rolled; N =
normalized; P = pearlite; SR = stress relief
†
properties measured in high-pressure nitrogen or helium gas

1100 - 13
Plain Carbon Ferritc Steels C-Mn Alloys

Table 2.1. Hydrogen permeability () and solubility (S) vs temperature relationships for carbon
steels and iron.*
   o exp( E  / RT ) S  S o exp( E S / RT )
Temp. Pressure o E So ES
Material range range Ref.
 mol H 2   kJ   mol H 2   kJ 
(K) (MPa)      3   
m s  MPa1/2  mol  m  MPa1/2  mol 
Iron 2.513 x 10-5 31.69 180.1 23.66
1010 3.442 x 10-5 34.18 202.4 24.70
-5
1020 3.77 x 10 35.07 159.0 23.54
1035 500 - 900 0.01 - 0.7 3.603 x 10-5 36.16 188.6 24.63 [2]
-5
1050 2.097 x 10 34.13 82.89 21.10
-5
1065 1.602 x 10 34.73 65.63 21.54
1095 1.039 x 10-5 33.43 41.98 19.28
* Diffusivity (D) can be obtained from the ratio of permeability and solubility, i.e.,
D  /S

1100 - 14
Plain Carbon Ferritc Steels C-Mn Alloys

Table 3.1.1.1. Smooth tensile properties of carbon steels in 6.9 MPa hydrogen gas at room
temperature. Properties in either air or nitrogen gas are included for comparison. The tensile
specimen orientation is longitudinal (L) unless otherwise specified.
Strain
Test Sy Su Elt RA
Steel rate Ref.
environment (MPa) (MPa) (%) (%)
(s-1)
A516 Air 375 535 17 69
~ 3x10-4* [4]
(U.S. grade) 6.9 MPa H2 364 551 19 43
A516 Air 364 566 22 72
~ 3x10-4* [4]
(Japan grade) 6.9 MPa H2 359 571 18 37
Air 462 559 14 58
A106 Gr. B ~ 3x10-4* [4]
6.9 MPa H2 503 576 11 50
6.9 MPa N2 414 814 12 16
1080
6.9 MPa H2 421 794 7.5 7.2
1x10-4 [5]
6.9 MPa N2 414 814 10 14
1080 (T)
6.9 MPa H2 407 787 7.4 6.5
Air 366 511 21 56
X42 [5,
6.9 MPa H2 331 483 20 44
1x10-4 6,
Air 311 490 21 52
X42 (T) 10]
6.9 MPa H2 338 476 19 41
Air 414 609 19 60
X52 ~ 3x10-4* [4]
6.9 MPa H2 429 597 15 37
Air 427 594 13 49
X60 ~ 3x10-4* [4]
6.9 MPa H2 422 590 10 27
Air 504 605 15 57
X65 ~ 3x10-4* [4]
6.9 MPa H2 506 611 15 36
Air 584 669 20 57
X70
6.9 MPa H2 548 659 20 47
1x10-4 [6]
Air 613 702 19 53
X70 (T)
6.9 MPa H2 593 686 15 38
Air 626 693 16 77
X70 ~ 3x10-4* [4]
6.9 MPa H2 566 653 14 37
X70 Air 697 733 14 77
~ 3x10-4* [4]
(Arctic grade) 6.9 MPa H2 695 733 12 37
T = transverse oriented specimen
* calculated based on displacement rate and specimen gauge length

1100 - 15
Plain Carbon Ferritc Steels C-Mn Alloys

Table 3.1.1.2. Smooth tensile properties of carbon steels in 69 MPa hydrogen gas at room
temperature. Properties in air and/or helium gas are included for comparison.
Strain
Test Sy Su Elt RA
Steel rate* Ref.
environment (MPa) (MPa) (%) (%)
(s-1)
69 MPa He 400† 621 29 59
1042 3.3x10-5 [7]
69 MPa H2 - 614 22 27
Air 373† 490 — 65
‡ -5 †
1020 69 MPa He 3.3x10 283 435 40 68 [7]
69 MPa H2 276† 428 32 45
†
Air 338 504 — 66
A515 69 MPa He 3.3x10-5 276† 448 42 67 [7]
†
69 MPa H2 297 442 29 35
* strain rate in elastic range
†
defined at deviation from linearity on load vs time plot
‡
prestrained under tension in air immediately prior to testing

Table 3.1.2.1. Notched tensile properties of carbon steels in 6.9 MPa hydrogen gas at room
temperature. Properties in air are included for comparison.
Displ.
Test Sy*  s RA Ref
Steel Specimen rate
environment (MPa) (MPa) (%) .
(mm/s)
A516 Air 375 759 30
(a) 8.5x10-3 [4]
(U.S. grade) 6.9 MPa H2 364 629 5.4
Air 462 618 26
A106 Gr. B (a) 8.5x10-3 [4]
6.9 MPa H2 503 619 8.0
Air -3 414 818 15
X52 (a) 8.5x10 [4]
6.9 MPa H2 429 707 7.0
Air -3 427 847 23
X60 (a) 8.5x10 [4]
6.9 MPa H2 422 782 8.4
Air -3 504 806 21
X65 (a) 8.5x10 [4]
6.9 MPa H2 506 758 6.1
Air -3 626 946 45
X70 (a) 8.5x10 [4]
6.9 MPa H2 566 845 8.7
X70 Air 697 1027 42
(a) 8.5x10-3 [4]
(Arctic grade) 6.9 MPa H2 695 949 8.6
* yield strength of smooth tensile specimen
(a) V-notched specimen: 90o included angle; minimum diameter = 2.44 mm; maximum
diameter = 2.87 mm; notch root radius = 0.025 to 0.051 mm.

1100 - 16
Plain Carbon Ferritc Steels C-Mn Alloys

Table 3.1.2.2. Notched tensile properties of carbon steels in 69 MPa hydrogen gas at room
temperature. Properties in air and/or helium gas are included for comparison.
Displ.
Test Sy*  s RA
Steel Specimen rate Ref.
environment (MPa) (MPa) (%)
(mm/s)
69 MPa He 400 1056 8.5
1042 (a) ~ 4x10-4 [7]
69 MPa H2 — 793 2.8
Air 373 787 12
§ -4
1020 (a) 69 MPa He ~ 4x10 283 724 14 [7]
69 MPa H2 276 621 8.3
69 MPa He 276 731 8.1
A515 (a) ~ 4x10-4 [7]
69 MPa H2 297 559 2.3
* yield strength of smooth tensile specimen
(a) V-notched specimen: 60o included angle; minimum diameter = 3.81 mm; maximum
diameter = 7.77 mm; notch root radius = 0.024 mm. Nominal stress concentration factor
(Kt) = 8.4.

1100 - 17
Plain Carbon Ferritc Steels C-Mn Alloys

Table 3.2.1.1. Fracture toughness for carbon steels in hydrogen gas at room temperature. The
fracture toughness in air, nitrogen, or helium is included for comparison. The crack propagation
direction is parallel to the longitudinal orientation of the material product form.
Displ.
Sy† RA† Test KIc KIH‡ dJ/da
Steel rate 1/2 1/2 Ref.
(MPa) (%) environment (MPam ) (MPam ) (MPa)
(mm/s)
Air 166* 516
3.5 MPa H2 131 47
A516 375 69 6.9 MPa H2 8.5x10-3 113 55 [8, 9]
20.7 MPa H2 98 54
34.5 MPa H2 90 57
6.9 MPa N2 2.5x10-4 - 111 42
1080 414 16 [5]
6.9 MPa H2 2.5x10-3 81 13

6.9 MPa N2 2.5x10-4 - 178* 70 [5, 6,

X42 366 56
6.9 MPa H2 2.5x10-3 107 63 10]
Air 147* 111
2.0 MPa H2 101-128 —
4.0 MPa H2 85 36
6.5 MPa H2 69 31
X42 280 58 7.0 MPa H2  3.3x10-4 73 — [11]
8.0 MPa H2 59 —
10.0 MPa H2 53 —
12.2 MPa H2 57 —
16.0 MPa H2 46 —
6.9 MPa He 142 123
X60 473 62 8.5x10-3 [8]
6.9 MPa H2 104 43

6.9 MPa N2 2.5x10-4 - 197 251

X70 584 57 [6]
6.9 MPa H2 2.5x10-3 95 23

5.5 MPa H2 8.3x10-5 - 85

X60 434 88 — — [18]
21 MPa H2 8.3x10-4 82

5.5 MPa H2 8.3x10-5 - 105

X80 565 81 — — [18]
21 MPa H2 8.3x10-4 102
†
yield strength and reduction of area of smooth tensile specimen in air
‡
calculated from relationship K  JE 1   2
* reported fracture toughness may not be valid plane strain measurement

measured from burst tests on pipes with machined flaws

1100 - 18
Plain Carbon Ferritc Steels C-Mn Alloys

Table 3.2.2.1. Threshold stress-intensity factor for carbon steels in high-pressure hydrogen gas at
286 K. The crack propagation direction is parallel to the longitudinal orientation of the material
product form.
Sy† RA† KIc† Test KTH
Steel Ref.
(MPa) (%) (MPam1/2) environment (MPam1/2)
A516 290 62 * 69 MPa H2 NCP 82 [12]
A106 Gr. C 345 68 * 97 MPa H2 NCP 55 [12]
NCP = no crack propagation
†
properties measured in air
* specimen dimensions precluded valid measurement

Table 4.2.1. Smooth tensile properties of carbon steel welds in 6.9 MPa hydrogen gas at room
temperature. Properties in air are included for comparison. The tensile specimen orientation is
perpendicular to the weld.
Strain
Test Sy Su Elt RA Fracture
Steel / Weld rate Ref.
environment (MPa) (MPa) (%) (%) location
(s-1)
A106 Gr. B / Air 393 615 21 77
~ 3x10-4* nr [4]
SMA 6.9 MPa H2 385 553 14 40
Air 513 633 10 40
X52 / ERW ~ 3x10-4* nr [4]
6.9 MPa H2 499 621 6.1 20
Air 516 633 13 56
X65 / SA ~ 3x10-4* nr [4]
6.9MPa H2 505 624 10 30
X70 / SA Air 649 686 12 69
~ 3x10-4* nr [4]
(Arctic grade) 6.9 MPa H2 643 678 9.5 37
Air 338 531 23 72 BM
Air 386 545 13 69 FZ
6.9 MPa H2 366 524 17 31 BM
A516 / SMA nr [20]
6.9 MPa H2 373 545 18 48 FZ
6.9 MPa H2 462 531 14 77 FZ
6.9 MPa H2 435 552 12 66 FZ
Air 435 593 16 71 BM
A516 / GTA 6.9 MPa H2 nr 435 593 15 38 BM [20]
6.9 MPa H2 462 580 6 20 FZ
Air 373 573 23 73 FZ
A516 / GMA nr [20]
6.9 MPa H2 386 517 3 12 TZ
nr = not reported; BM = base metal; ERW = electric resistance weld; FZ = fusion zone;
GMA = gas metal arc; GTA = gas tungsten arc; SA = submerged arc; SMA = shielded metal
arc; TZ = transition zone
* calculated based on displacement rate and specimen gauge length

1100 - 19
Plain Carbon Ferritc Steels C-Mn Alloys

Table 4.2.2. Smooth tensile properties of A516 steel welds in 6.9 MPa hydrogen gas at room
temperature. Properties in air are included for comparison. The tensile specimen orientation is
parallel to the weld.
Strain
Test Sy Su Elt RA Specimen
Steel / Weld rate Ref.
environment (MPa) (MPa) (%) (%) location
(s-1)
Air 424 505 25 82 FZ
A516 / Air 483 593 13 66 HAZ
nr [20]
SMA 6.9 MPa H2 444 528 15 46 FZ
6.9 MPa H2 386 559 15 38 HAZ
Air 600 690 13 67 FZ
Air 421 566 26 64 HAZ
A516 / GTA nr [20]
6.9 MPa H2 517 600 8.7 44 FZ
6.9 MPa H2 497 600 15 58 HAZ
Air 600 690 17 67 FZ
A516 / Air 331 559 27 70 HAZ
nr [20]
GMA 6.9 MPa H2 580 676 11 42 FZ
6.9 MPa H2 407 566 18 47 HAZ
nr = not reported; FZ = fusion zone; GMA = gas metal arc; GTA = gas tungsten arc;
HAZ = heat affected zone; SMA = shielded metal arc

Table 4.2.3. Notched tensile properties of carbon steel welds in 6.9 MPa hydrogen gas at room
temperature. Properties in air are included for comparison. The notched tensile specimen
orientation is perpendicular to the weld.
Displ.
Test Sy* s RA
Steel / Weld Specimen rate Ref.
environment (MPa) (MPa) (%)
(mm/s)
A106 Gr. B / Air 393 719 49
(a) 8.5x10-3 [4]
SMA 6.9 MPa H2 385 603 14
X70 / SA Air 649 1002 35
(a) 8.5x10-3 [4]
(Arctic grade) 6.9 MPa H2 643 973 10
X70 / SMA Air 551 1025 20
(a) 8.5x10-3 [4]
(Arctic grade) 6.9 MPa H2 595 901 9.0
SA = submerged arc; SMA = shielded metal arc
* yield strength of smooth tensile specimen
(a) V-notched specimen: 90o included angle; minimum diameter = 2.44 mm; maximum
diameter = 2.87 mm; notch root radius = 0.025 to 0.051 mm.

1100 - 20
Plain Carbon Ferritc Steels C-Mn Alloys

Table 4.2.4. Notched tensile properties of A516 steel welds in 6.9 MPa hydrogen gas at room
temperature. Properties in air are included for comparison. The notched tensile specimen
orientation is parallel to the weld.
Displ.
Steel / Test Sy* s RA Specimen
Specimen rate Ref.
Weld environment (MPa) (MPa) (%) location
(mm/s)
Air 424 738 62 FZ
A516 / Air 483 828 32 HAZ
(a) nr [20]
SMA 6.9 MPa H2 444 642 10 FZ
6.9 MPa H2 386 842 17 HAZ
Air 600 945 36 FZ
A516 / Air 421 821 32 HAZ
(a) nr [20]
GTA 6.9 MPa H2 517 800 17 FZ
6.9 MPa H2 497 697 9 HAZ
Air 600 945 25 FZ
A516 / Air 331 780 34 HAZ
(a) nr [20]
GMA 6.9 MPa H2 580 835 12 FZ
6.9 MPa H2 407 655 10 HAZ
nr = not reported; FZ = fusion zone; GMA = gas metal arc; GTA = gas tungsten arc;
HAZ = heat affected zone; SMA = shielded metal arc
* yield strength of smooth tensile specimen
(a) V-notched specimen: 90o included angle; minimum diameter = 2.27 mm; maximum
diameter = 2.87 mm; notch root radius = 0.051 mm.

1100 - 21
Plain Carbon Ferritc Steels C-Mn Alloys

Table 4.2.5. Fracture toughness for carbon steel welds in hydrogen gas at room temperature. The
fracture toughness in nitrogen or helium is included for comparison.

Sy† Test Displ. rate KIc‡ KIH‡ dJ/da Specimen

Steel / Weld Ref.
(MPa) environment (mm/s) (MPam1/2) (MPam1/2) (MPa) location

6.9 MPa N2 2.5x10-4 - 67 97 HAZ

X42 / ERW 366 [6]
6.9 MPa H2 2.5x10-3 48 69 HAZ

6.9 MPa He 188* 452 FZ

X60 / SA 6.9 MPa He 205* 171 HAZ
(1 pass) 6.9 MPa H2 103 267 FZ
6.9 MPa H2 -3 109# §
HAZ
473 8.5x10 [8]
6.9 MPa He 188* 452 FZ
X60 / SA 6.9 MPa He 77 253 HAZ
(2 pass) 6.9 MPa H2 103 267 FZ
§ §
6.9 MPa H2 HAZ
ERW = electric resistance weld; FZ = fusion zone; HAZ = heat affected zone;
SA = submerged arc
†
yield strength of base metal from smooth tensile specimen in air
‡
calculated from relationship K  JE 1   2
* reported fracture toughness may not be valid plane strain measurement
#
calculated from J-integral value at onset of rapid, subcritical crack extension
§
not measured due to rapid, subcritical crack extension

1100 - 22
Plain Carbon Ferritc Steels C-Mn Alloys

10-5

Permeability,  (molm-1s-1MPa-1/2)
Carbon Steels iron
1010 steel
1020 steel
10-6 1035 steel
1050 steel
1065 steel
1095 steel
10-7

10-8

10-9
1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0
-1
1000/T (K )
Figure 2.1. Permeability vs temperature relationships for carbon steels and iron [2].

103
Carbon Steels iron
Solubility, S (molm-3MPa-1/2)

1010 steel
1020 steel
102 1035 steel
1050 steel
1065 steel
1095 steel
101

100

10-1
1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 1.9 2.0
-1
1000/T (K )
Figure 2.2. Solubility vs temperature relationships determined from permeability and
diffusivity vs temperature relationships for carbon steels and iron [2].

1100 - 23
Plain Carbon Ferritc Steels C-Mn Alloys

140
X42 steel
Fracture toughness (MPam )
1/2
H2 gas pressure = 4 MPa

120

100

80

60
1e-5 1e-4 1e-3 1e-2
Displacement rate (mm/s)
Figure 3.2.1.1. Effect of displacement rate on fracture toughness in hydrogen gas for X42
steel [11].

200
-4
Carbon Steels X42 (3.3x10 mm/s)
Fracture toughness (MPam )

-3
A516 (8.5x10 mm/s)
1/2

160

120

80

40

0
0 8 16 24 32 40
H2 gas pressure (MPa)
Figure 3.2.1.2. Effect of hydrogen gas pressure on fracture toughness for carbon steels [8, 9,
11]. The displacement rate used in the fracture toughness tests is indicated for each steel.

1100 - 24
Plain Carbon Ferritc Steels C-Mn Alloys

320
Carbon Steels X42

Fracture toughness (MPam )

total gas pressure = 6.9 MPa
1/2
280 X70
-4 -3
displacement rate = 2.5x10 -2.5x10 mm/s
240

200

160

120

80

40

0
N2 CH4 H2 60% H2+ 60% H2+ 60% H2+
40% CH4 24% CO+ 24% CO+
16% CH4 10% CO2+
6% CH4

Figure 3.2.1.3. Effect of gas composition on fracture toughness for carbon steels [6].

10-1
Carbon Steels
frequency = 0.1 to 1 Hz
Fatigue crack growth rate, da/dN (mm/cycle)

load ratio = 0.1 to 0.15

10-2

X70 (6.9 MPa H2)

10-3
X42 (6.9 MPa H2)
X60 (6.9 MPa H2)
A516 (6.9 MPa H2)
10-4 1020 (7.0 MPa H2)
SA 105 (6.9 MPa H2)
X70 (6.9 MPa N2)
10-5 X42 (6.9 MPa N2)
X60 (air)
A516 (air)
1020 (air)
10-6 SA 105 (34.5 MPa He)

10-7
1 10 100
Stress intensity factor range, K (MPam )
1/2

Figure 3.3.2.1. Fatigue crack growth rate vs stress-intensity factor range relationships for
carbon steels in hydrogen gas [6, 10, 13-16]. Fatigue crack growth rate data in air, nitrogen,
or helium are included for comparison.

1100 - 25
Plain Carbon Ferritc Steels C-Mn Alloys

10-1
Carbon Steels
frequency = 0.1 to 1 Hz

Fatigue crack growth rate, da/dN (mm/cycle)

load ratio = 0.1 to 0.15
SA 105 Steel
10-2 100 MPa H2
70 MPa H2
7 MPa H2
34.5 MPa He

10-3 1020 Steel

7 MPa H2
2.2 MPa H2
0.14 MPa H2
0.02 MPa H2
10-4
air

10-5
10 100
Stress intensity factor range, K (MPam1/2)

Figure 3.3.2.2. Effect of hydrogen gas pressure on fatigue crack growth rate vs stress-
intensity factor range relationships for carbon steels [13, 16]. Fatigue crack growth rate data
in air or helium gas are included for comparison.

100
Crack growth rate, da/dN (mm/cycle)

X42 Steel 7 MPa H2 gas

K = 10 MPam
1/2
7 MPa N2 gas
10-1
frequency = 1 Hz

10-2

10-3

10-4

10-5

10-6
0.0 0.2 0.4 0.6 0.8 1.0
Load Ratio
Figure 3.3.2.3. Effect of load ratio on fatigue crack growth rate for X42 steel in hydrogen gas
at fixed stress-intensity factor range [10]. Fatigue crack growth rate data in nitrogen gas are
included for comparison.

1100 - 26
Plain Carbon Ferritc Steels C-Mn Alloys

10-1
SA 105 Steel
H2 gas pressure = 100 MPa

Fatigue crack growth rate, da/dN (mm/cycle)

load ratio = 0.1

10-2 1 Hz
0.1 Hz
0.01 Hz
0.001 Hz
1 Hz (34.5 MPa He)

10-3

10-4
0 20 40 60
Stress intensity factor range, K (MPam1/2)

Figure 3.3.2.4. Effect of load cycle frequency on fatigue crack growth rate vs stress-intensity
factor range relationships for SA 105 steel in hydrogen gas [16]. Fatigue crack growth rate
data in helium gas are included for comparison.

0.04
Crack growth rate, da/dN (mm/cycle)

SA 105 Steel
H2 gas pressure = 100 MPa
K = 44 MPam
0.03
load ratio = 0.1

0.02

0.01

0.5 sec ramp

100 sec ramp
0.00
0 200 400 600 800 1000 1200 1400
Seconds Per Cycle
Figure 3.3.2.5. Effect of load cycle duration on fatigue crack growth rate for SA 105 steel in
hydrogen gas at fixed stress-intensity factor range [16]. Data for two different loading ramp
rates are displayed.

1100 - 27
Plain Carbon Ferritc Steels C-Mn Alloys

10-1
X42 Steel
frequency = 1 Hz

Fatigue crack growth rate, da/dN (mm/cycle)

load ratio = 0.1
6.9 MPa H2
10-2
6.9 MPa H2+100 ppm O2
6.9 MPa H2+2% SO2
6.9 MPa H2+2% CO
6.9 MPa N2
10-3

10-4

10-5

10-6
1 10 100
Stress intensity factor range, K (MPam1/2)

Figure 3.3.2.6. Effect of hydrogen gas composition on fatigue crack growth rate vs stress-
intensity factor range relationships for X42 steel [6]. Fatigue crack growth rate data in
nitrogen gas are included for comparison.

10-2
1020 Steel
frequency = 1 Hz
Fatigue crack growth rate, da/dN (mm/cycle)

load ratio = 0.05

10-3

10-4 0.088 MPa H2

0.081 MPa H2+0.007 MPa CO2
0.075 MPa H2+0.013 MPa nat. gas
0.088 MPa nat. gas
0.081 MPa H2+0.003 MPa H2O
0.003 MPa H2O
0.101 MPa air
10-5
10 100
Stress intensity factor range, K (MPam )
1/2

Figure 3.3.2.7. Effect of gas composition on fatigue crack growth rate vs stress-intensity
factor range relationships for 1020 steel in low-pressure hydrogen gas [17]. Fatigue crack
growth rate data in natural gas, water, and air are included for comparison.

1100 - 28
Plain Carbon Ferritc Steels C-Mn Alloys

10-2

Crack growth rate, da/dN (mm/cycle)

X60 Steel
f=1Hz
10-3 298 K
A516
6.9 MPa H2, R=0.15

10-4

10-5
21 MPa H2, R=0.5
5.5 MPa H2, R=0.5
10-6 21 MPa H2, R=0.1
5.5 MPa H2, R=0.1
air, R=0.5
10-7
5 10 20 50
Stress intensity factor range, K (MPa m1/2)

Figure 3.4.2.1. Fatigue crack growth rate vs stress-intensity factor range relationships for X60
steel in hydrogen gas [18]. These relationships were measured at two gas pressures and two
R ratios. Two additional sets of data are included for comparison: data for X60 in air and data
for A516 steel in hydrogen gas from Figure 3.3.2.1.

10-2
Crack growth rate, da/dN (mm/cycle)

X80 Steel
f=1Hz
10-3 298 K
A516
6.9 MPa H2, R=0.15

10-4

10-5
21 MPa H2, R=0.5
5.5 MPa H2, R=0.5
10-6 21 MPa H2, R=0.1
5.5 MPa H2, R=0.1
air, R=0.5
10-7
5 10 20 50
Stress intensity factor range, K (MPa m1/2)

Figure 3.4.2.2. Fatigue crack growth rate vs stress-intensity factor range relationships for X80
steel in hydrogen gas [18]. These relationships were measured at two gas pressures and two
R ratios. Two additional sets of data are included for comparison: data for X80 in air and data
for A516 steel in hydrogen gas from Figure 3.3.2.1.

1100 - 29
Plain Carbon Ferritc Steels C-Mn Alloys

10-2
A516 Steel
frequency = 1 Hz

Fatigue crack growth rate, da/dN (mm/cycle)

load ratio = 0.15

10-3

F+P, GS = 35 m (6.9 MPa H2)

F+P, GS = 180 m (6.9 MPa H2)
B, GS = 200 m (6.9 MPa H2)
10-4
F+P, GS = 35 m (air)
F+P, GS = 180 m (air)
B, GS = 200 m (air)

10-5

10-6
1 10 100
Stress intensity factor range, K (MPam1/2)

Figure 4.1.1. Effect of microstructure on fatigue crack growth rate vs stress-intensity factor
range relationships for A516 steel in hydrogen gas [15]. Data are shown for both ferrite plus
pearlite and bainitic microstructures at different grain sizes. Fatigue crack growth rate data in
air are included for comparison. B = bainite; F = ferrite; GS = grain size; P = pearlite.

10-1
Carbon Steels
frequency = 1 Hz
Fatigue crack growth rate, da/dN (mm/cycle)

load ratio = 0.1

10-2

10-3 X42 (6.9 MPa H2)

1080 (6.9 MPa H2)
X42 (6.9 MPa N2)
1080 (6.9 MPa N2)
-4
10

10-5

10-6

10-7
1 10 100
Stress intensity factor range, K (MPam )
1/2

Figure 4.1.2. Effect of microstructure on fatigue crack growth rate vs stress-intensity factor
range relationships for carbon steels in hydrogen gas [5]. Fatigue crack growth rate data in
nitrogen gas are included for comparison.

1100 - 30
Plain Carbon Ferritc Steels C-Mn Alloys

10-2
X60 Steel
frequency = 1 Hz

Fatigue crack growth rate, da/dN (mm/cycle)

load ratio = 0.15

10-3 base metal (6.9 MPa H2)

fusion zone (6.9 MPa H2)
HAZ (6.9 MPa H2)
base metal (air)
fusion zone (air)
HAZ (air)

10-4

10-5
1 10 100
Stress intensity factor range, K (MPam1/2)

Figure 4.2.1. Fatigue crack growth rate vs stress-intensity factor range relationships for
welded X60 steel in hydrogen gas [14]. Data are shown for both the fusion zone and heat-
affected zone of the weld as well as the base metal. Fatigue crack growth rate data in air are
included for comparison.

1100 - 31