Proceedings of the 2012 9th International Pipeline Conference IPC2012 September 24-28, 2012, Calgary, Alberta, Canada

IPC2012-90313

CONTINUED MICROSTRUCTURE AND MECHANICAL PROPERTY PERFORMANCE EVALUATION OF COMMERCIAL GRADE API PIPELINE STEELS IN HIGH PRESSURE GASEOUS HYDROGEN

Douglas Stalheim DGS Metallurgical Solutions, Inc. 15003 NE 10th Street Vancouver, WA 98684 USA Ph. (360) 713-2407, Fax (360) 882-1775 dgstalheim@comcast.net Darren Bromley Powertech Labs Inc. 12388 - 88th Avenue Surrey, British Columbia, Canada, V3W 7R7 Ph. (604) 590-6616, Fax (604) 590-6659 darren.bromley@powertechlabs.com

Todd Boggess Secat, Inc. 1505 Bull Lea Road Lexington, KY 40551 USA Ph. (859) 514-4989, Fax (859) 514-4988 ToddBoggess@secat.net Steve Jansto Reference Metals Company 1000 Old Pond Road Bridgeville, PA 15017 USA Ph. (412) 220-3041, Fax (412) 221-7355 jansto@referencemetals.com

Shridas Ningileri Secat, Inc. 1505 Bull Lea Road Lexington, KY 40551 USA Ph. (859) 514-4989, Fax (859) 514-4988 sningileri@secat.net

ABSTRACT In spite of current world economic climates, recognition that alternative energy sources to the traditional fossil fuels has to be explored and understood. One potential energy source being researched and developed is hydrogen gas. Currently the most economical method of transporting large quantities of hydrogen gas is through steel pipelines. It is well known that hydrogen embrittlement has the potential to degrade steels mechanical properties when hydrogen migrates into the steel matrix. Consequently, the current pipeline infrastructure used in hydrogen transport is typically operated in a conservative fashion. This operational practice is not conducive to economical movement of significant volumes of hydrogen gas as an alternative to fossil fuels. The degradation of the mechanical properties of steels in hydrogen service is known to depend on the microstructure of the steel. Understanding the levels of mechanical property degradation of a given microstructure when exposed to hydrogen gas under pressure can be used to evaluate the

suitability of the existing pipeline infrastructure for hydrogen service and guide alloy and microstructure design for new hydrogen pipeline infrastructure. To this end, the microstructures of relevant steels and their mechanical properties in relevant gaseous hydrogen environments must be fully characterized to establish suitability for transporting hydrogen. Previously data from a US Department of Energy/private sector funded project to evaluate four commercially available pipeline steels alloy/microstructure performance in the presences of gaseous hydrogen was presented in 2010. Interest in this previous work from industry and the ASME B31.12 Hydrogen Piping and Pipeline Systems codes and standards committee resulted in additional funding for continued evaluation of additional pipeline steel alloys/microstructures in the presences of gaseous hydrogen. Samples from API grades X52 (1960s and current vintage designs), X70 (1980s and current vintage) and X80 along with various samples from an X52 induction bend pipe and one pressure vessel steel

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A516 Gr 70 are being evaluated. Microstructural characterization, fracture toughness and fatigue testing in the presence of gaseous hydrogen at 800 psig and 3,000 psig are being conducted. This paper will describe the fracture toughness results achieved to date on various commercially available pipeline steels used in the existing North American pipeline infrastructure in the presence of gaseous hydrogen at pressures relevant for transport in pipelines. Microstructures and fracture toughness performances will be compared between these in this study along with those published previously. In addition, recommendations for future work related to gaining a better understanding of steel pipeline performance in hydrogen service will be discussed. NOMENCLATURE DOE - US Department of Energy DOT US Department of Transportation YS Yield Strength TS Tensile Strength H2 Hydrogen Gas psig pounds per square inch JQ - Measured Elastic-plastic Fracture Toughness KEE Fracture Toughness Equivalent Energy KJQ - Fracture Toughness Determined From JQ COD Crack Opening Displacement PE Load Value Energy INTRODUCTION Fuel cell technology for the transportation sector continues to move forward with various dates in the not so distant future for automobile companies to release limited production fuel cell vehicles1. This technology will require large volumes of pressurized hydrogen gas to support it. The most economical method to move large volumes of any gas is through a pipeline infrastructure. The majority of todays pipeline infrastructure is made of steel. Degradation of the mechanical properties of the steel is always a concern when exposed to hydrogen gas. Previously, the DOE had funded research into selected pipeline steels performance and in particular the microstructures of those steels performance in gaseous hydrogen under pressure.2,3,4,5 In that research microstructural characterization along with tensile, fracture and fatigue performance were evaluated of a limited number of pipeline steels. It is known from the literature and experiences that microstructure along with internal steel cleanliness of the alloy play a major role in the interaction of hydrogen in the matrix and subsequent mechanical property performance6,7. The previous research published continued to demonstrate that microstructure does play a role in the mechanical property performance in the presence of gaseous hydrogen under pressure. That research generated interest within industry and ASME B31.12 Codes and Standards Committee Hydrogen Piping and Pipelines to expand the scope of the testing to additional pipeline steels representing a cross section of current and vintage steel technology currently in use in the North American oil and gas transmission pipeline infrastructure.

The focus of this additional research was to generate fracture toughness data of several different pipeline steels/microstructures at two hydrogen pressures. The two pressures chosen were 800 psig (5.5 MPa) and 3,000 psig (20.7 MPa). These two pressures were chosen for the additional fracture toughness data for two reasons: The pressures represent a low and high end of potential operational hydrogen transmission pressures. The pressures will allow for comparisons to be made to the previous research effort.

The previous research work as well as this current work focused on the base metal only. However, in the current study a comparison of base metal performance in hydrogen of induction bend pipe was included. Weld performance in hydrogen under pressure is being evaluated under a separate DOT funded project. A general description along with the microstructure characterization of each alloy evaluated in the previous work along with those in this current work can be found in Table 1.
TABLE 1: PREVIOUS AND CURRENT PIPELINE STEELS IN HYDROGEN STUDY
Grade API X70 API X80 API X80 API X60 HIC Description Late 1990s Alloy Design Early 2000s Alloy Design Early 2000s Alloy Design Current HIC Alloy Design Current X80 Alloy Design for Spiral Pipe Current X80 Alloy Design for Long Seam Pipe 1980s Alloy Design 1960 Alloy Design Early 1990s Alloy Design Current Alloy Design Current Alloy Design with Microalloy Current Alloy Design Current Alloy Design Project Code A B C D C (wt. %) 0.08 0.05 0.04 0.03 Microstructure/ Comments 92% PF/8% UB, Current Study 90% PF/10% AF, Reported Previous 90% PF/10% AF +Misc Not Studied 100% PF, Reported Previous 100% AF, Current Study

API X80

0.05

API X80

0.05

30% PF/70% AF, Current Study 90% PF/10% P, Current Study 70% PF/30% P, Current Study 85% PF/15 %P/BND, Current Study 92% PF/5% AF/3% P, Current Study 40% PF/60% P/BND, Current Study 95% PF/5% AF, Current Study 90% PF/10% AF, Current Study

API X70 API X52 API X70 API X52 A516 Gr70 Pressure Vessel API X52 Induction Bend API X52 No Induction Bend

G H I J

0.08 0.26 0.08 0.06

0.14

P Ind

0.06

P Nind

0.06

Microstructure Code: PF-Polygonal Ferrite, P-Pearlite, UB-Upper Bainite, AF-Acicular Ferrite, BND-Banded. Note volume fractions are reasonable approximations.

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As seen in Table 1 an induction bend pipe was included in this phase of the study. The purpose was to evaluate if the induction bending process had any positive, negative or neutral effects on fracture toughness when exposed to hydrogen under pressure. The as-received pipe consisted of a straight non-heated section and then the heated section. This means that samples from P Ind and P Nind came from the same original mother pipe. In addition a sub-category was created for the induction bend pipe as testing was done on both inner and outer radius of the pipe to further examine if any differences could be noted by bending stresses when exposed to hydrogen under pressure. As can be seen by the list of steels tested in Table 1 a relatively good cross section of transmission pipeline microstructures currently in the North American transmission pipeline infrastructure was evaluated. It should be noted that the list was discussed and agreed to with members of ASME B31.12 Codes and Standards Committee Hydrogen Piping and Pipelines. TESTING PROCEDURE8 Powertech Labs in Surrey, BC Canada was chosen to do the fracture toughness testing for this study. Powertech Labs is one of the laboratories in North America with equipment and capabilities to do fracture toughness testing in a high pressure hydrogen environment. As there are many different ways to test the fracture toughness of a material, a testing procedure was adapted with guidance from the following ASTM standards: E399 08 Standard Test Method for Linear-Elastic Plane-Strain Fracture Toughness KIC of Metallic Materials E992 84 (1989) Standard Practice for Determination of Fracture Toughness of Steels Using Equivalent Energy Methodology E1820 08 Standard Test Method for Measurement of Fracture Toughness

FIGURE 2: COMPACT TENSION SPECIMEN DIMENSIONS

In order to eliminate error caused by variations in notch geometry, a fatigue precrack was initiated in ambient conditions at the tip of the machined notch in each specimen. Approximate material properties were used to estimate of the maximum stress intensity factor, (Kmax) to be applied during precracking such that crack-tip blunting can be avoided. According to equation A2.1 of ASTM E1820, Kmax will occur at the load Pm, which is calculated from the following equation: =
2 0.4

In Equation 1, B is the thickness of the sample, bo is the initial un-cracked ligament, W is the distance from the load line to the end of the sample, and ao is the distance from the load line to the machined notch tip. The effective yield strength, Y, is merely the average of ys and uts. Equation A2.2 from ASTM E1820 is used to find Kmax as follows: =

2+

[1]

Specimens were oriented with the notch transverse to the rolling direction (LT) orientation as shown in Figure 1 and machined according to the dimensions shown in Figure 2.

For test specimens of the compact tension type, the function f(a/W) is calculated as per Equation 3 (ASTM E1820 equation A2.3), letting a/W be x: () =
(2+)0.886+4.6413.32 2 +14.72 35.60 4
3 (1) 2

[2]

[3]

FIGURE 1: CT SPECIMEN ORIENTATIONS

To precrack the samples, a cyclic load was implemented at 10 Hz in a sine waveform. For precracking, the loading ratio R was set to 0.1, which defines Kmin as 0.1 Kmax (i.e. K = 0.9 Kmax). A compliance crack growth measurement method was used with a decreasing K control mode. The precracking continued until the crack propagated approximately 2 mm past the end of the machined notch (approximately 12.7 mm from the load line). Side grooves have been shown to help maintain the near plane strain conditions necessary for fracture toughness testing of thick specimens. As suggested by ASTM standard E1820, side-grooving was performed following fatigue precracking on all materials except for the thin specimens (alloys G and H). The side grooves were cut with a 45o cutting tool having a tip 0.5 mm in diameter.

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Fracture toughness tests were conducted in accordance with ASTM standard E992, Standard Practice for Determination of Fracture Toughness of Steels Using Equivalent Energy Methodology. Tests were conducted inside a gaseous hydrogen environment using an Instron servo-hydraulic test frame coupled with a pressure vessel designed and built by Powertech Labs, as shown in Error! Reference source not found.. An external load cell was used in line with the loading axis to set safety limit triggers, and as a secondary confirmation of applied load. Actual load applied to the specimen was measured within the pressure vessel in order to avoid errors induced by friction in the pull rod seals.

PE

Pmax

[4]

LOAD

DISPLACEMENT

FIGURE 4: GRAPHIC REPRESENTATION OF EQUIVALENT ENERGY METHODOLOGY

FIGURE 3: HIGH PRESSURE HYDROGEN TESTING EQUIPMENT AT POWERTECH LABS

The environment was prepared by purging three times with helium gas to remove oxygen and scavenge impurities, and subsequently purged three times with 99.999% pure hydrogen gas to remove the helium. An intensifier was then used to pressurize to 3,000 psig hydrogen. The specimens were progressively loaded and unloaded by approximately 50% of the current force until achieving a maximum load, and an appreciable permanent change in COD value was reached. At this point, the test was stopped and the specimen was removed from the pressure vessel. Following testing, the samples were heat tinted at 250 oC for 30-60 minutes to thermally color the fracture surface. In doing so, the crack propagation occurring during fracture toughness testing can be easily distinguished from the fatigue precrack and the fracture of the remaining ligament. After heat tinting, the samples were immersed in liquid nitrogen and then loaded to failure to fracture the remaining ligament in a flat brittle fashion. The fractured specimens were placed in isopropyl alcohol until they warmed to room temperature to prevent corrosion of their fracture surfaces. To calculate KEE, a load value PE is determined by extending the linear portion of the load-displacement curve until the area under the linear portion equals the area to the maximum load. The procedure is graphically represented in Figure 4. Using the same function of a/W provided in Equation 3, the equivalent energy fracture toughness is then calculated as per Equation 4. Here, a was obtained from physical measurements of distance from the load line to the tip of the fatigue precrack following the tests.

MICROSTRUCTURAL CHARACTERIZATION Microstructure plays a role in a given steels ability to perform in the presence of hydrogen. Therefore it was important that the microstructures of each steel studied by characterized. Optical microscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) techniques were used to identify major microstructural phases and to estimate the volume fraction of each phase. The main microstructural phases in the steels studied were polygonal ferrite, pearlite, upper bainite and acicular ferrite (a low carbon form of bainite). Alloys A-F microstructure characterizations were completed and reported in previous work. Alloys G-P Nind was completed in this work. Figure 5 shows all of the microstructural volume fractions from the previous work and current work. It can be seen that a wide range of different volume fractions of the microstructural phases were covered in the study. Volume fractions of polygonal ferrite and acicular ferrite ranging from 100% to 0% along with various volume fractions of intermediate microstructural phases of pearlite and upper bainite were part of the study.

FIGURE 5: VOLUME FRACTION RANGES OF MICROSTRUCTURAL PHASES STUDIED

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Example microstructures of the alloys in the study not published previous can be seen in Figure 6.

FIGURE 6: OPTICAL, SEM AND TEM MICROSTRUCTURAL CHARACTERIZATION OF ALLOYS NOT PREVIOUSLY PUBLISHED

Alloy A 92% Polygonal Ferrite, 8% Upper Bainite (Red Arrows)

As an observation, it appears that the induction bending process did alter the microstructure of alloys PInd and PNind with a slight reduction in acicular ferrite after induction bending. The samples from the induction bend pipe are from the same mother pipe so that the starting base microstructure (PNind) could be compared to that after induction bending (PInd). The presence of obviously banded microstructures is of interest as it relates to fracture appearances after the fracture toughness testing in hydrogen has been completed. This will be discussed later. FRACTURE TOUGHNESS RESULTS Fracture toughness testing was conducted on the alloys at 800 psig (5.5 MPa) and 3,000 psig (21 MPa). During the analysis of this fracture testing it was observed that the presence of abnormal crack prorogations (separations) during the test. The presence of these separations made calculations of fracture toughness as per ASTM E1820/E992 somewhat challenging. As the severity of the separations increased, the calculated fracture toughness also increases. This of course gives one a false sense that the steel has excellent fracture toughness characteristics in hydrogen but in fact the steel fracture toughness is most likely much lower if the crack propagation in hydrogen would have been normal and as expected. This is something that has been seen by others in conducting ASTM E1820 fracture toughness testing. These separations can be seen in fracture toughness testing in air and in hydrogen and appear to increase in severity with increasing pressure. Examples of this can be seen in Figure 7.

Alloy G 90% Polygonal Ferrite, 10% Upper Bainite

Alloy H 70% Polygonal Ferrite, 30% Upper Bainite

Alloy I 85% Polygonal Ferrite, 15% Pearlite, Banded

Alloy J 92% Polygonal Ferrite , 5% Acicular Ferrite, 3% Pearlite

Alloy A air fracture Alloy L 40% Polygonal Ferrite, 60% Pearlite, Banded

Alloy A 800 psig H2 fracture

Alloy A 3,000 psig H2 fracture

Alloy P Ind 95% Polygonal Ferrite, 5% Acicular Ferrite Alloy I air fracture Alloy I 800 psig H2 fracture Alloy I 3,000 psig H2 fracture

Alloy P NInd 90% Polygonal Ferrite, 10% Acicular Ferrite

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Alloy G air fracture

Alloy G 800 psig H2 fracture

Alloy G 3,000 psig H2 fracture

Alloy E 800 psig H2 fracture

Alloy E 3,000 psig H2 fracture

Alloy E 15,000 psig H2 fracture

microstructural differences starts with the solidification process which controls the which microstructure will form for a given cooling rate. One possible theory to the presence of these separations might lie with the presence of macro and micro microstructural difference/banding formation during rolling and cooling as a result of the presence of macro and micro chemical segregation during the solidification process in casting. It is known that banded microstructures can be potential hydrogen trapping sites9. Macro banding usually can be seen optically as in Alloys I and L, however micro banding would require a more detailed investigation to decipher. It would appear from the fractures that the severity of the separations increases with increasing pressure which may be due to a high potential of hydrogen collection aggravating microstructural inconsistencies. It is known from the microstructural characterizations some obvious macro banding could be seen optically, Figure 6. Not all of the steels exhibited separations in the fractures in air or hydrogen under pressure. In fact, Alloy L which definitely shows microstructural banding did not show any separations at either hydrogen pressure, however, it did have significantly lower fracture toughness in hydrogen than the others. A summary of the fracture toughness and noted separation severity is seen in Table 2. It should be noted that testing of Alloy E, F and J at 3,000 psig was done in prior published work and was reported as KJC and not KEE. In this study Alloy E, F and J were also tested at 800 psig to keep continuity.
TABLE 2: SUMMARY OF FRACTURE TOUGHNESS RESULTS
Fracture Toughness in Air Single Specimen (MPa-m1/2) and Separation Severity Rating 327.83 1 NA NA 236.1 341.7 192.8 173.3 394.73 211.3 265.0 325.2 342.3 312.4 264.8 NA NA 2 2 2 0 1 0 0 0 0 0 0 800 psig Fracture Toughness KEE/KJQ (MPa-m1/2) and Separation Severity Rating 140.7 117.9 86.6 129.21 155.6 128.61 150.2 133.41 141.2 85.6 133.3 113 136.3 145.9
1

Project Code

3,000 psig Fracture Toughness KEE/KJQ (MPa-m1/2) and Separation Severity Rating 2 0 0 2 0 2 0 0 0 0 0 0 0 0 94.51 114.8 85.3 711 75 127.61 91.61 81.81 107 94.8 123.7 139.4 113.5 147.4 2 0 0 3 0 3 1 2 0 0 0 0 0 0 95.1 115.7 117.7 127.4 144.51 0 0 0 0 1 961 118.7 85.3 821 85 87.6 1591
1

Alloy F 800 psig H2 fracture

Alloy F 3,000 psig H2 fracture

Alloy F 15,000 psig H2 fracture

A B

0 1 0 2 0 2 0 1 0 0 0 0 0 0

138.51 128.8 89.2 153.41 159.6 122.81 155.4 140.3 141.8 100.3 120.4 142.2 196.5 143.3

2 1 0 3 0 2 0 3

FIGURE 7: EXAMPLES OF SEPARATIONS IN AIR AND INCREASING H2 PRESSURE

D E F G H I J L P Ind P Ind IR2 P Ind OR2 P Nind

Separations in traditional steel Charpy fracture toughness testing has always been related to microstructural banding associated from the macro chemical segregation found at the centerline of a continuous cast slab. The severity of the banding/macro chemical segregation is related to the alloy design and several casting processing parameters. The macro chemical segregation tendencies in a continuously cast slab can be from 5-10 mm on either side of the exact centerline of the slab thickness. In addition to this, micro chemical segregation that can form at the dendrites during solidification can be found in the thickness region of the slab and can even go out near the slab surface depending on the alloy content and casting processing parameters that control the solidification. The resultant macro/micro chemical segregation results in different continuous cooling transformation characteristics and subsequent different microstructure formation upon final rolling and cooling temperature/rate. The bottom line is that the root cause of final cross sectional

Separations Rating Code: 0-None, 1-Slight, 2-Moderate, 3-Severe

1 - Calculated KEE and KJQ values may be falsely high due to the presence of various severity levels of separations. Only calculated KEE and KJQ values with a 0 separations rating should be considered reasonable. 2 - OR and IR are outside and inside radius of the induction bend 3 Air testing done without side grooves machined on specimen which may yield higher values. All others specimens machined with side grooves.

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There are several observations that can be made of the data. Fracture toughness measured in air ranged between 173395 MPa-m1/2. It was expected and in general and on average the fracture toughness in air was approximately two times higher than those achieved in hydrogen at 800 psig. The separations generated in the air fracture toughness testing tended to be less in frequency and also severity than those observed at either 800 or 3000 psig hydrogen testing. Separations in There were a variety of different yield strength levels in this study from a nominal 52 ksi (360 MPa) to 80 ksi (550 MPa). As has been observed in prior work and contrary to previously published data, at the tested pressures, there is not any significant difference in fracture toughness, Figure 8. Induction bending only reduced the fracture toughness slightly regardless of test pressure. In addition, there was no appreciable difference in the outside or inside radius of the induction bend, Figure 9.

Overall on average, a polygonal ferrite/acicular ferrite microstructure performed slightly better than a polygonal ferrite/upper bainite-pearlite microstructure at each pressure, Figure 10. It should be noted that Alloy L with the highest volume fraction of pearlite did have significantly lower overall fracture toughness values at each pressure. The differences in microstructures fracture toughness performance in hydrogen depending on what role separations play in masking the actual performance.

FIGURE 10: AVERAGE FRACTURE TOUGHNESS VS. MICROSTRUCTURE

FIGURE 8: FRACTURE TOUGHNESS VS. STRENGTH AT 800 PSIG (5.5 MPa) AND 3,000 PSIG (20.7 MPa)

Regardless of microstructure, increasing hydrogen pressure does lower overall fracture toughness, Figure 11. However, in several alloy/microstructure designs it is not significant.

FIGURE 11: FRACTURE TOUGHNESS VS. HYDROGEN PRESSURE FIGURE 9: COMPARISON OF INDUCTION BEND VS. NONINDUCTION BEND FRACTURE TOUGHNESS AT 800 PSIG (5.5 MPa) AND 3,000 PSIG (20.7 MPa)

Since the presence of separations has an effect of perhaps making the calculated fracture toughness values higher than

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they should rightly be, an understanding of what might drive the presence of separations in these fractures is desirable. As discussed previous the separations may be the result of macro and micro chemical segregation from the solidification process and the resultant potential for macro and micro banded microstructures. Since chemistry plays a major role in the macro and micro chemical segregation tendencies a comparison of carbon equivalent as measured by the ItoBessyo Pcm formula might give some direction. Figure 12 shows the average separation rating versus Pcm. As can be seen, regardless of hydrogen pressure, a lower Pcm/alloy design reduces the severity of the separations. Hydrogen pressure does seem to aggravate the separation issue. However, Pcm/alloy design is just one parameter that might contribute to the separations. Numerous casting parameters along with final rolling cooling also contribute to the final level of microstructural banding.

FIGURE 13: CARBON EQUIVALENT VS. AVERAGE TOUGHNESS AT DIFFERENT HYDROGEN PRESSURES

FIGURE 12: CARBON EQUIVALENT VS. AVERAGE SEPARATIONS RATING AT 800 PSI (5.5 MPA) AND 3000 PSI (20.7 MPA) HYDROGEN PRESSURE. PCM - C+Si/30+(Mn+Cu+Cr)/20+Ni/60+Mo/15+V/10+B

Carbon equivalent as measured by Pcm seems to play a role in the average measured fracture toughness, especially with the higher 3,000 psig pressure. Lower Pcm results in a trend of higher average measured fracture toughness. However, at 800 psig hydrogen pressure the trend is less significant, Figure 13.

FUTURE WORK As with any study of this nature there are still questions that have yet to be addressed. In particular from this study the presence of separations and the corresponding potential to falsely indicate higher fracture toughness than may be reasonable based on existing testing methods needs to be understood. What is the mechanism that cause the separations in these fractures when exposed to hydrogen? Does a macro/micro difference in microstructure contribute to these separations? Does the presence of hydrogen aggravate the separations as it would appear with increasing pressure? What fracture toughness is truly needed for safe operation of a hydrogen pipeline at various pressures? It is desirable to correlate the fracture and fatigue data generated in the National Laboratories in the presence of hydrogen to a more traditional testing standard such as a Charpy V-notch test, which is the subject of further study. In addition, seam and girth welds need to be part of any future work. All of this future work will be governed by availability of funding from both public and private sectors. The ultimate goal of the research will be to offer guidance, information and potential specifications to projects that will be built for gaseous hydrogen transmission. All information gained from this research work will be shared publicly in particular with the ASME B31.12 Hydrogen Piping and Pipeline codes and standards committee and other groups that need the information to evaluate hydrogen projects. CONCLUSIONS In conclusion, the test results show that commercially available pipeline and pressure vessel steels of various vintages perform differently in gaseous hydrogen at pressures relevant to gaseous transmission pipelines, namely at pressures in the range of 800 psig (5.5 MPa) and 3,000 psig (20.7 MPa). The presence of separations of various degrees of severity makes the standard calculation of fracture toughness per ASTM E1820/E992 difficult. Calculated KEE and KJQ values may be falsely higher than reasonable due to the influence of the separations on the calculation method.

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Separations may be due to the macro/micro differences in microstructures that act as potential hydrogen trapping sites thus creating the separations. Various microstructures appear to perform better than others, especially with increasing carbon equivalent and hydrogen pressure. Based on an understanding of the presence of separations in other fracture toughness tests such as the traditional Charpy and drop weight tear test (DWTT), controlling alloy design and pertinent casting parameters can minimize the formation of these separations as related to macro banding of the microstructure as seen utilizing optical microscopy techniques. This may be desirable also for steels destined for gaseous hydrogen service. This whole subject of separations needs to be investigated further to achieve a better understanding. As seen in previous studies at these pressures, yield strength does not appear to have a dominant effect on performance in gaseous hydrogen. This emphasizes the importance of the microstructure for the resistance of pipeline steels to degradation of mechanical properties in gaseous hydrogen especially with increasing pressures. Large volume fractions of pearlite as in Alloy H and Alloy L (30% and 60% respectively) resulted in no separations, but overall lower fracture toughness than the other pipeline steels studied. Overall, a polygonal ferrite microstructure coupled with a volume fraction of up to 70% acicular ferrite appears to perform the best especially at the higher pressures. Induction bending of an API X52 pipe did appear to alter the microstructure slightly which resulted in slightly lower fracture toughness KEE values. However, the decrease was not overly significant which suggests; at least for API X52 of this alloy/microstructure design does not adversely affect fracture toughness in the presence of gaseous hydrogen in pressure up to 3,000 psig (20.7 MPa). This work represents the continued effort in the development of a broader understanding of the propertymicrostructure-environmental relationships for steels used in gaseous hydrogen pipelines. Further study is necessary to understand the relationship of the observed separations in the calculation of KEE and KJQ per ASTM E1820/E992 along with their role and effect in the presence of gaseous hydrogen under pressure. Even though alloys/microstructures with a volume fraction of acicular ferrite up to 70% seemed to perform overall better in the fracture toughness testing, it does not necessarily mean that the other alloys/microstructures studied would not be suitable for hydrogen service. Whether or not the other alloys/microstructures fracture toughness resistance is adequate for service most likely would depend on the structural and operational parameters of a given transmission hydrogen pipeline design. ACKNOWLEDGEMENTS The authors want to acknowledge that the funding for testing at Powertech Labs was graciously sponsored by CBMM/Reference Metals Company and ASME ST-LLC through a work agreement with Secat, Inc. REFERENCES

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