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

IPC2012-90488

THE EFFECT OF LOW SULFUR CONTENT ON THE WELDABILITY OF LINEPIPE STEEL

Kimberly K. Cameron, Ph.D., P.E. Engineering Systems Inc. (ESI) Sunnyvale, CA USA Alfred M. Pettinger, Ph.D., P.E. Engineering Systems Inc. (ESI) Foothill Ranch, CA USA

ABSTRACT Over time, the demand for high-strength linepipe has increased significantly. One of the challenges for developing higher strength linepipe has been maintaining an appropriate level of fracture toughness, yield to tensile strength ratio, and weldability. Fortunately, significant progress has been made in the production of high strength line pipe steel. A major improvement in steel making has been the utilization of secondary steel treatments to refine the steel and accurately control alloy additions to achieve a higher level of steel cleanliness. In particular, these refining treatments have enabled the achievement of extremely low sulfur levels. For most purposes, restricting sulfur content is desirable to help prevent a reduction in mechanical properties such as fracture toughness of the steel. Fortunately, steelmaking and desulfurization technologies have advanced to the point where pipeline steel with sulfur contents less than the requirements by API 5L are available on a large scale. Extremely low sulfur contents, however, can lead to other problems when welding steels. These weldability problems are related to the fact that sulfur is a known surface active agent for steels. Low sulfur concentrations lead to a reversal of the Marangoni convection in the weld pool, which is responsible for the large differences in weld penetration on otherwise identical steels. Additionally, when welding heats of unmatched sulfur concentrations, the arc will tend to deviate towards the low sulfur heat and axially shift the root of the weld if one of the heats was below a critical value for the sulfur content and the other was above this value. Although this phenomenon has been primarily observed in stainless steels, the increasing ability to produce linepipe steel with extremely low sulfur contents has led to the possibility that this phenomenon could also occur in low carbon pipeline steels. One pipeline system utilizing cellulosic

consumables for shielded metal arc welding (SMAW) of X70 steel with sulfur contents an order of magnitude below that permitted by API 5L and with widely varying sulfur contents shows evidence of this effect. The profiles of the welds in this system exhibited a tendency for lack of penetration, asymmetric weld roots, and concave welds. One approach to ameliorate this would be the specification of a lower permissible amount of sulfur. INTRODUCTION Steel pipe has long been used to transport natural gas. Advances in metallurgy and welding that occurred after the First World War made pipeline construction more economical and allowed the construction of the first natural gas pipelines. After the Second World War, during the 1950s and 1960s, pipeline companies in the United States constructed thousands of miles of pipeline. By the 1970s, much of the framework of the pipeline infrastructure of the United States had been put into place. Over time, construction of high-pressure gas transmission lines became more focused on the greatest possible transport efficiency. This is achieved by minimizing both the cost of pipeline construction and gas transportation. Larger pipes and higher operating pressures can be used to increase the volume of gas transported. Without other adjustments, however, larger wall thicknesses would need to be used to maintain the same level of safety. Larger wall thicknesses are typically undesirable because they are accompanied by higher material costs and pipe transport costs and are more time consuming to weld. In order to avoid the larger wall thicknesses that would be needed to accommodate the higher operating pressures, higher strength steel grades began to be developed.

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The development of higher grade steel required advances in pipe mill technology and pipe chemistry. The early pipeline steel was typically grade X42, X52 or X60 and was manufactured by hot rolling and normalizing. The subsequent development of pipeline steel was very much dependent on the individual pipe mills and occurred over a period of time. Overall the process started in the 1970s, when hot rolling and normalizing was replaced by thermomechanical rolling. This enabled reduced carbon content steels that were microalloyed with niobium and vanadium to be produced in grades up to X70. In the 1980s, further improvements in processing came from thermomechanical rolling followed by accelerated cooling. This method allowed the development of X80 steels with even further reduced carbon content. Typically, further control with additions of elements such as nickel, copper and molybdenum allowed the production of grade X100 steel [1]. One of the challenges of producing high strength steel is to ensure that the toughness, yield to tensile strength ratio, and weldability is not compromised. For example, while dislocation hardening, precipitation hardening and solid solution hardening can increase the strength, they can also be accompanied by a reduction in fracture toughness. Likewise, reduced pearlite content can improve the toughness but also reduces the strength. Grain refinement, on the other hand, is able to both increase the strength and toughness. Typically, to achieve improvements in strength without compromising toughness or weldability, the steel microstructure and chemistry must be better understood and precisely controlled. Many technical innovations have also been attained over time to improve pipeline safety beyond the development of steels with higher strength and significantly higher fracture toughness. In particular, welding inspection techniques have greatly contributed to improved pipeline safety over time. Likewise, in the days of pipeline construction when hydrostatic testing at levels that were close to or slightly above yield strength first began, many material and weld anomalies were removed. For example, in 1972, the Texas Eastern Transmission Corporation, who had at this time over 5,000 miles of hydrostatically tested transmission pipelines in service, reported that hydrostatic testing at a pressure sufficient to induce a hoop stress close to the specified minimum yield strength (SMYS) of the pipeline steel removed 129 defects over a span of 3,424 miles of pipe. Of these 129 defects, 10 were plate defects, 16 were defects in the girth welds, and the remainders were defects at the longitudinal welds [2]. Nowadays, pipe leakage during hydrostatic testing only occurs occasionally. This is evidence of the significant progress made in pipe steel technology, and the design and construction of modern pipelines. However, the rupture of circumferential welds on a recently constructed gas distribution pipeline, utilizing X70 pipeline steel and cellulose consumables for the shielded metal arc welding (SMAW) process has raised some interesting questions. This paper attempts to highlight the

observations made on the circumferential welds and attempts to provide some explanations and recommendations. ALLOYING AND MICROALLOYING ELEMENTS The continual challenge has been to develop a combination of chemistry and processes that lead to an adequate combination of strength, toughness, yield to tensile strength ratio, weldability and resistance to hydrogen induced cracking. In order to improve both the economics and viability of particular high strength linepipe steels, the trend has been toward close compositional control, reduced carbon content, increasingly complex combinations of microalloying elements, improved cleanliness, more sophisticated processing, more uniform properties, minimal heat treatment, improved shape and surface appearance, higher strength, improved fracture properties, better weldability and better weld toughness. Several alloying elements can be used to increase the strength of the steel. For example, carbon, silicon, manganese, vanadium, niobium, titanium, aluminum, nickel, copper, chromium and molybdenum can all contribute to an increase in strength. Carbon, silicon, vanadium and copper, however, also typically decrease the toughness as well. Furthermore, the addition of copper, silicon, sulfur, vanadium, niobium, copper, nickel, chromium, molybdenum typically decreases weldability, or the ease of making a weld with adequate mechanical properties. Due to the spiraling cost of particular alloying elements such as molybdenum and vanadium, efforts focused on elimination, replacement or reduction of these elements [3]. Increasing the manganese content is one of the more economical ways to increase the strength of pipeline steel. Unfortunately, manganese also increases the susceptibility to hydrogen induced cracking and leads to an increase of the yield to tensile strength ratio as manganese increases the tendency of segregation and anomalous microstructures with high strength but low toughness [3]. When manganese is an alloying element, the sulfur forms manganese sulfides, which are elongated by rolling and cause anisotropic properties and increased risk of lamellar fracture. Therefore when manganese is used as an alloying element, the sulfur content should be reduced. THE EFFECT OF SULFUR API limits the sulfur content of Grade X70 steel to 0.015% (150 ppm) but prescribes no minimum content. For most purposes, less sulfur is more desirable to help prevent a reduction in mechanical properties of the steel. In addition, sulfur typically reduces both the toughness and impact energy significantly. Therefore, efforts are typically undertaken to desulfurize the steel or fix the retained sulfur as sulfides that do not deform easily. Extremely low sulfur contents, however, can lead to other problems when welding steels. In stainless steels, for example, it is well known that low sulfur concentrations in the base metal as well as welding low sulfur heats to heats that are in the mid-range or higher with respect to the sulfur

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concentration can cause weldability problems. Under these conditions, the low and widely varying sulfur content can dramatically affect the weld pool. During welding, the liquid weld pool of melted steel is subjected to a wide range of physical phenomena like gravity, buoyancy, electromagnetic, and surface tension forces. The well established Heiple-Roper model provides a satisfactory explanation of the effect of sulfur concentration on the behavior of weld pools [4]. Surface tension of the weld pool depends on the existence or lack of surface active agents with free sulfur being a known surface active agent for steels. Figure is a diagram of the Marangoni flow pattern per Heiple and Roper for two identical steels with different sulfur concentration levels. Fig. 1 (a) illustrates the typical flow pattern for steel with low sulfur content and Fig. 1 (b) illustrates the typical flow pattern for steel with high sulfur content.

identical steels. The weld pool widens and has less penetration as less heat is carried to the pool bottom. This causes a large difference in weld penetration and the ability of the pool bottom to melt the surrounding metal [6]. Similarly, joining pipe material with differing amount of sulfur causes the weld pool to favor the lower sulfur side of the joint, axially shifting the root of the pipe joint (see Fig. 2). This leads to asymmetrical weld deposition and a wandering weld pool, particularly when the pipe chemistry also varies circumferentially.

Figure 1.

Fluid flow in weld pool resulting from the Marangoni convection per the Heiper-Roper model for steels with a high level of sulfur on the right and a lower levels of sulfur on the left

Figure 2.

Steels with low sulfur content have a negative surface tension temperature coefficient, , while steels that have a higher sulfur content have a positive surface tension temperature coefficient. For example, experiments have shown that for steel containing only 20 ppm of sulfur, the outward surface flow carries heat from the source to the pool edge and results in a shallow and wide pool. For steel containing 150 ppm sulfur, on the other hand, the inward surface flow turns downward to deliver heat to the pool bottom and results in a much deeper pool [5]. The concentration of sulfur where the sign of the surface tension coefficient changes depends on the presence of other surface surfactants and alloying components. Research on several different steels shows the change in sign of the surface tension temperature coefficient occurs as low as 10 ppm for some steels [6]. Generally, welding steels with sulfur content below this transition can significantly change the characteristics of the welding pool, with the result that welding procedures developed on steels with higher sulfur concentration are no longer as effective for steels with very low sulfur concentrations. Low sulfur concentration leads to a reversal of the Marangoni convection in the weld pool, which is responsible for the large differences in weld penetration on otherwise

Diagram illustrating asymmetric weld pool formation resulting from different sulfur concentrations in otherwise identical steels

The direction of the fluid flow in the weld pool is also responsible for other welding problems such as, arc wander, porosity, and humping. Therefore, it has been recognized that it is necessary to consider high and low sulfur casts separately when attempting to improve penetration by changes in welding procedures [7]. PIPELINE STEEL EXAMPLES OF SULFUR EFFECT A large diameter (36) spiral welded pipeline of X70 steel for the transportation of natural gas was recently constructed and hydrostatically tested. During construction, several circumferential welds along the newly constructed pipeline were removed for further examination. The X70 pipe was welded by hand using the SMAW method and cellulosic consumables. A 5/32 inch diameter AWS E6010 electrode was specified for the root pass and a 3/16 inch diameter AWS E8010 electrode was specified for the rest of the passes. The welding procedure used had been developed for X70 steel several years prior to the construction of this pipeline on API 5L X70 pipeline steel. Figure 3 depicts a cross section of a circumferential weld of a typical shape and characteristics one would expect

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from utilizing a qualified welding procedure with API 5L compliant pipe material and qualified fire line of welders. The two welded sections of pipe have sulfur contents above 10 ppm and well below the requirements of API 5L for X70 steel. The individual welding passes are symmetric and the weld has sufficient penetration, particularly the root pass.

Figure 3.

Weld passes centered axially along the pipe.

Figure 4 shows a cross section of a circumferential weld, where the individual welding passes are shallow and the weld pool has been moved axially to some degree. The former is indicative of a reversal of the Marangoni effect, when the free sulfur is below a critical value, changing the circulation direction of the liquid weld pool. The weld pool circulates in the direction shown in Fig. 1b), where hot molten material moves first outward, causing a shallow weld pool that gives rise to a weld pass with an elongated half moon like shape. The axial displacement of the weld pool is more likely than not attributable to the slightly different sulfur concentrations of the two pipe sections. The weld pool was moved towards the pipe section with the lower sulfur content; e.g., the left section (see Fig. 4). The root pass of the weld shows a tendency for incomplete fusion as well as a shift towards the pipe section with the slightly lower sulfur content.

Excessively wide or built-up welds can restrict pipe expansion at the joint, which may contribute to premature failure. Additionally, incomplete fusion and severe undercuts can lead to the nucleation of cracks. If undetected by x-ray, which can be poor for detecting these types of planar defects, these anomalies need to be removed by the hydrostatic test. This is especially important for even higher strength steels than X70, as these steels have an even larger fracture toughness value but not a markedly different crack propagation rate. Therefore high strength pipeline material (higher than X70) tolerate larger critical crack lengths but exhibit a similar crack growth rate, making the elimination of circumferential crack like features via hydrostatic testing a challenge [8]. Figure 5 and Figure 6 show additional examples of weld profiles from welding X70 pipe with pipe sulfur contents between 3 ppm (0.0003%) and 20 ppm (0.002%). In both cases the weld pool has moved axially to varying degrees. It should be noted that, unlike with arc blow (which can also move the weld pool), the movement of the pool in this case was along the axis of the pipe rather than forward or backward along the direction of travel of the electrode. To eliminate the possibility that this effect was due to magnetism, several of the pipes were checked for magnetism and this possibility was eliminated. Care was also taken to ensure that weldability problems were not due to poor welding technique. During welding some adjustments can be made to attempt to compensate for the shallow welding passes and movement the weld pool. For example, the current can be increased or the travel speed decreased. Adjustments such as increasing the welding current, however, can lead to other problems such as hollow bead, internal undercut or concave beads.Error! Reference source not found.

Figure 5.

Shallow and axially displaced weld passes

Figure 4.

Consecutive weld passes are shallow and displaced axially along the pipe.

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Figure 6.

Low sulfur weld passes in X70 steel.

widely varying sulfur contents. However, this approach is difficult to implement in the field. Therefore, it may be more desirable to specify in the pipe purchase agreement a minimum bound for sulfur. More research on pipeline steel is necessary to specify a reasonable lower bound for the amount of sulfur, as it is the free sulfur content that determines the impact upon the Marangoni effect. However, pipeline steels with sulfur levels less than 10 ppm will likely exhibit a reversal of the Marangoni effect and require the adjustment of the welding procedure. Lastly, the use of qualified welding procedures developed several years ago when sulfur contents were likely higher may not always yield the expected consistent quality welds for very low sulfur steels with sulfur content in the single digit ppm range. Furthermore, the overall chemistry of X70 pipe has changed fairly significantly over time. Therefore, although it is not currently required to re-qualify welding procedures for the same size and grade pipe, it may be beneficial to do so. REFERENCES [1] J. M. Gray, An independent view of linepipe and linepipe steel for high strength pipelines: how to get pipe thats right for the job at the right price, API X-80 Pipeline Cost Workshop, Hobart, Australia, Oct. 2002. [2] G.H. Ewing, The Development and Results of High Stress Hydrostatic Testing of Gas Transmission Lines in the United States, 1973, 12th World Gas Conference. [3] J. G. Williams, Advances in steels for high strength ERW linepipe application in Australia, Materials Forum Volume 31, 2007. [4] D.K. Aidun and S.A. Martin, Effect of sulfur and oxygen on weld penetration of high-purity austenitic stainless steels, Journal of Materials Engineering and Performance, Vol 6(4), August 1997. [5] Sindo Kou, Welding Metallurgy, Second edition, John Wiley & Sons, Inc., 2002 [6] R. F. Brooks, and P.N. Quested, The surface tension of steels, Journal of Materials Science 40, 2005, pps. 2233-2238. [7] K.C. Mills and B.J. Keene, Factors affecting variable weld penetration, International Material Reviews, 1990, Vol. 35, No. 4, page 185. [8] K.K. Cameron & A.M. Pettinger, Effectiveness of Hydrostatic Testing for High Strength Pipe Material, Proceedings, 8th International Pipeline Conference, October 2010.

CONCLUSIONS Low sulfur levels typically correspond to higher levels of fracture toughness. Steelmaking and desulfurization technologies have advanced to the point where pipeline steel with sulfur contents less than the requirements by API 5L are available on a large scale. Extremely low sulfur contents, however, can lead to other problems when welding steels. This phenomenon was first studied on various stainless steels but recent pipeline specific experience indicates that similar issues may start to affect pipeline steels with sulfur levels less than 10 ppm. These weldability problems are related to the fact that sulfur is a known surface active agent for steels. Low free sulfur concentrations lead to a reversal of the Marangoni convection pattern in the weld pool, which is responsible for the large differences in weld penetration on otherwise identical steels. With lower concentrations of free sulfur, the weld pool widens and has less penetration as less heat is carried to the pool bottom. This causes a large difference in weld penetration and the ability of the bottom of the weld pool to melt the surrounding metal. Additionally, when welding heats of unmatched sulfur concentrations, the arc will tend to deviate towards the low sulfur heat and axially shift the root of the weld if one of the heats was below a critical value for the sulfur content and the other was above this value. Cross sections taken from the circumferential welds of a pipeline system constructed of X70 pipe with cellulosic consumables using the SMAW method showed both of these phenomena. The X70 steel had sulfur contents an order of magnitude below that permitted by API 5L and with widely varying sulfur. The profiles of the welds in this system exhibit a tendency for lack of penetration, asymmetric weld roots, and concave welds. One approach to eliminate this issue may be to track material heats and try to match the sulfur contents on the job as closely as possible to minimize the effect of extremely low and

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