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

IPC2012-90185
NOVEL HIGH PERFORMANCE ELASTOMERS: NEW, RECYCLABLE MATERIALS FOR OIL & GAS FROM IN-LINE INSPECTION TO PIPE COATING
Michael Magerstdt ROSEN Swiss AG Stans, Switzerland
1

Holger Schmidt ROSEN Technology and Research Center Lingen, Germany Frank Schellbach ROPLAST GmbH Lingen, Germany

Gunther Blitz ROSEN Swiss AG Stans, Switzerland

Contact Author

Ralf Dopieralla ROPLAST GmbH Lingen, Germany ABSTRACT Starting out from the need for polyurethanes with higher abrasion and tear resistance for pipeline inspection, an entire class of new high performance elastomers were developed. Within a few years materials were synthesized which did not only extend the mechanical properties of polyurethane elastomers, but also led to the development of completely new products. Applications range from intelligent plastic solutions combining elastomers and electronics via highly abrasion resistant pipe coatings to a new process for recycling and reuse of crosslinked polyurethanes. Fundamental to these successful developments is the building-block chemistry of polyurethanes. A very high number of permutations of the up to 7 components used in the synthesis of a polyurethane elastomer is possible. By choosing the right combinations and the right reaction conditions, specific material properties can be designed. Materials exhibiting the following material properties, hitherto not found in polyurethanes, were developed: An operating temperature range from 50 to + 135C. Chemical resistance to highly acidic and alkaline media, e.g., pure ammonia. Significantly higher abrasion and tear resistance than standard polyurethanes.

Exactly adjustable visco-elastic damping (rebound resilience). Adhesion to steel higher than reported with any other polyurethane elastomer. A novel polyurethane elastomer with more than 90% share of recycled material reaching mechanical properties in the same range as virgin material

This presentation will detail the materials and their properties and give application examples from pipeline cleaning, pipe protection, and pipe coating to mechanical protection devices made from recycled polyurethane elastomer. 1. THE ROLE OF POLYURETHANES IN PIPELINE CLEANING AND IN-LINE INSPECTION Polyurethane elastomers (PURs) have been used in pipeline cleaning and pipeline inspection for decades. Discs and cups of pipeline inspection tools and cleaning tools are made from such PUR elastomers. 1.1 Polyurethanes and their properties

The reason is that PUR elastomers exhibit the right ratio of mechanical strength and elasticity to efficiently create a seal between the tool and the pipe wall. This creates the pressure drop propelling the tool forward. In addition, in cleaning tools, there are also discs and cups that serve as

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scrapers to clean the pipe wall. These scraper discs need to be much harder than the sealing / propelling discs. This means in turn that elastomers to be used in pipeline pigging need to come in different hardness grades. This is one reason why polyurethanes are employed because the chemistry of polyurethanes is a tool box in which up to 7 components that make up the eventual polymer can be combined in a large number of variations. FIGURE 1 SHOWS THE VARIOUS BASIC TYPES OF POLYURETHANES AND THEIR APPLICATIONS:

and further components that can be employed is large. This allows a vast number of possible combinations. By selecting the right combination, properties of the finished polyurethane can be modified to fit the requirements of the application. This relates to all material properties from shore hardness to abrasion resistance, to temperature resistance and chemical resistance. Even properties like visco-elastic damping can be custom designed. FIGURE 3 SHOWS A SELECTED NUMBER OF GRADES OF HIGH PERFORMANCE POLYURETHANE ELASTOMERS. IT ALSO LISTS SOME TYPICAL APPLICATIONS OF THESE MATERIALS:

All these products exhibit properties outside the range of commonly available polyurethane elastomers, hence the designation high performance. FIGURE 2 SHOWS THE FUNDAMENTALS OF POLYURETHANE CHEMISTRY IN A SCHEMATIC WAY AND EXPLAINS THE INFLUENCE OF THE COMPONENTS ON THE PRODUCT PROPERTIES: By utilizing grades with very high abrasion resistance and very high tear resistance, pipeline inspection and cleaning tools are able to perform much longer runs than pigs with standard polyurethanes. The material resists the abrasion by the pipe wall much longer. Examples from the field will be given under 1.2. 1.2 Why use polyurethanes for pigging? Standard polyurethane elastomer discs have been used in pigging operations for decades. On land pipelines, the average distance between launchers and receivers is approx. 50 miles / 80 km. To perform pigging of subsea pipelines, tools need to be equipped with such PUR elastomers that exhibit a much higher abrasion resistance. Tear propagation resistance is another highly important property of disc / cup materials because a tear, e.g., caused by a piece of metal sticking into the pipe interior, e.g., at a weld seam, can propagate during the pipeline tool run. This would slow down the tool and could even lead to a stuck tool. If a tool gets stuck in a subsea pipeline, huge losses occur due to the loss of product

Although there are only 3 isocyanates that are used in PUR manufacturing, the number of polyols, crosslinkers,

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transport revenues, but also due to the very high cost of 1 locating and recovering the tool in a subsea environment . In a real-life example, tools equipped with materials of grades 1200 and 1100 from figure 3 hold the world record in pipeline inspection and pipeline cleaning. Both the Langeled pipeline from Norway to the UK and the NordStream pipeline through the Baltic Sea, both ranging between 1100 km and more than 1200 km without any launcher/receiver, were successfully inspected and cleaned with tools bearing discs made from these materials. See figure 4. In fact, the NordStream pipeline construction plans originally included an intermediate station on an island in the middle of the Baltic Sea. Besides allowing additional compressors, which were not really needed for the pipeline, the main purpose of this station would have been pigging launchers and receivers. The operator instructed two pipeline inspection companies to evaluate the possibility to do pig runs on the entire length of the pipeline without the intermediate station. The result of this study was that pigging is possible in one run if high performance PUR elastomer are used. This saved the 2 operator millions in construction and maintenance cost . FIGURE 4 SHOWS TOOLS WITH HIGH PERFORMANCE PUR ELASTOMERS COMING OUT OF THE RECEIVER AFTER A 1200 KM GAS PIPELINE RUN:

1.4 High temperature applications As table 3 shows, there are temperature limits to PUR elastomers. Whilst standard PURs can withstand operating temperatures up to 80C, there are now high performance grades (like 1500 and 5500 in figure 3) that can operate at 100 C and above. An offshore operator had a subsea well from which a product was transported to a platform. Product temperature exiting the well as 125C and when reaching the platform, the product had close to sea water temperature due to cooling by the sea water when passing through the pipe. This line needed to be cleaned quite frequently. A detailed qualification program by the operator showed that standard PURs were able to withstand the temperature near the well. A high performance PUR elastomer, however, was the only PUR material that did pass these tests and that was consequently qualified and applied by the operator. As described under 1.1., the only reason that such an application can be covered by cleaning pigs at all is the tool box chemistry of polyurethanes. Only be formulating the right polyurethane recipe and reaction conditions, a material can be obtained that meets the specific requirements of this high-temperature application without compromising mechanical properties at the lower 4 temperature end of the run . 1.5 CO2 pipelines / CCS For pipeline inspection / pipeline cleaning in supercritical CO2, there are a number of concerns when polymeric materials are involved. Swelling of discs or cups during a pigging run can lead to tool damage, but also to tools getting stuck. But more importantly in supercritical CO2 (theoretically possible in any compressed gas) is the danger of explosive decompression. If the elastomer has absorbed gas (swollen) under pressure, the rapid release of the gas from the polymer can literally blow the polymer to pieces. High performance elastomers exhibit close to zero uptake of CO2 and therefore neither are deformed nor are posing any threat of explosive decompression. High performance PUR elastomers have already been successfully used as disc material in CO 2 pipeline 5 pigging . 1.6. Tool vibration induced damage prevention

1.3 PURs for extreme pH and corrosive media Obviously, pipelines do not only transport oil and gas. Pipelines transporting chemicals like ammonia, acids, and corrosive salt brines are pigged with discs made from high performance polyurethane elastomers. Standard PURs disintegrate e.g., in ammonia. High performance types 3 like grade 1306 survive multiple runs in pure ammonia .

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In certain pipeline geometries, particularly when uneven pipe surfaces prevail, in-line tools can start vibrating. Basically, the PUR sealing discs or cups scrape along the pipe-wall in a stop-and-go kind of motion. In such cases, vibration will start heating up the elastomer. Standard polyurethanes will start losing their mechanical strength in the range around 80 C. Vibration-induced heating of the polyurethane can have two consequences which both can cause major damage: The first consequence is heat deformation of the discs or cups. If the elastomer heats up so strongly that it softens, the discs or cups will lose their shape, thereby adjusting to the exterior forces acting on them. In essence, this means that discs or cups will turn into lumps of plastic that do not seal to the pipe wall anymore so that in turn the tool may get stuck. The second consequence is similarly dangerous. Since the discs and cups are bolted to the steel body of the pipeline pig, vibration-induced heating becomes dangerous when the PUR elastomer heats up so much that the area around the bolts softens and tears start propagating from there. Discs or cups can completely tear apart or parts come off, again leading to the pig getting stuck. A material was designed that exhibits strongly reduced vibration-induced heating can be obtained by using a specific isocyanate that also leads to polyurethanes in which the kinetic energy of a dynamic load is absorbed by a process in between the intertwined polymer chains which leads to significantly less heating than what would be observed with standard PUR elastomers. In cases where standard PURs have disintegrated in operation due to vibration-induced heating, these materials allow multiple pig runs with discs and cups lasting as long as 3 they would in non-vibrating applications . 1.7 Hazardous environments Pipeline inspection and cleaning tools for hazardous area application need to be explosion proof. The steel and electronics parts of a tool need to be intrinsically safe; the polyurethane elastomers need to be conductive so that any static charges are avoided which could lead to spark generation. High performance PUR elastomers can be equipped with conductive particles thereby reaching conductivity that 6 correspond to an electrical resistance in the range of 10 9 10 Ohm. This allows certification by the respective ATEX directive 94 / 9 / EC and by similar standards.

FIGURE 5 SHOWS AN ATEX CERTIFIED CLEANING TOOL WITH CONDUCTIVE DISCS. NOTE THE BLACJK COLOR CAUSED BY CONDUCTIVE GRAPHITE PARTICLES:

IMPROVEMENT OF POLYURETHANE PROPERTIES

As discussed in chapter 1, the tool box chemistry of polyurethanes allows specific improvement of one or more than one mechanical property. Grades with the following improved properties that were developed are examples for the extent to which such improvement is possible: Higher abrasion resistance (factors of 2 to 5) vs. standard polyurethanes Higher tear propagation resistance vs. standard polyurethanes Temperature resistance up to +125 C Chemical resistance to acids and alkaline materials (entire pH range) Adjustable visco-elastic damping down to a rebound elasticity of 8% Extremely high adhesion to steel Extremely low swelling and high barrier function against liquids and gases Intrinsic fire retardation and smoke inhibition in case the elastomer is exposed to fire Higher dynamic load absorption capacity (less vibration-induced heating) vs. standard polyurethanes 6 9 Conductivity (resistivity 10 to 10 Ohm)

2.1 Abrasion and Tear Propagation Resistance By combining the right base compounds plus optimizing the casting process, PUR elastomers with vastly improved abrasion resistance and tear propagation resistance were created. As shown as examples under 1.2., these

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properties make it possible to perform very long ILI runs. These properties also make high performance PUR elastomers ideal protective materials for other high abrasion applications, e.g. in mining. See also chapter 3. FIGURE 6 GIVES A STANDARDIZED OVERVIEW OF ABRASION RESISTANCE AND TEAR PROPAGATION ESISTANCE (EXPRESSED AS TENSILE STRENGTH) COMPARING RUBBER, COMMERCIALLY AVAILABLE STANDARD POLYURETHANES, AND HIGH PERFORMANCE PUR ELASTOMERS FROM THE LIST IN FIGURE 3: 2.2 Adjustable visco-elastic damping Elastomers normally have a low rebound resistance. In essence, things that impact the elastomer are rebounded very much like a rubber ball that hits the ground. By a rather complicated combination of recipe and manufacturing conditions, materials can be created that show only a reduced rebound or almost none at all. The highest rebound resistance reached is in the range of 8%, i.e., the impacting mass receives only 8% of the kinetic energy back which it brought into the elastomer by hitting it. Such materials are ideally suited for vibration damping applications like pipe supports, feet for compressors, valves, and other installations; see 3. FIGURE 8 SHOWS THE PRINCIPLE CUSTOMIZABLE VISCO-ELASTIC DAMPING: OF

spring functionality

damper functionality

FIGURE 7 SHOWS A SUMMARY OF ABRASION TESTS BY VARIOUS INTERNATIONAL STANDARDS, ALL PERFORMED BY INDEPENDENT PARTIES:

2.3 Increased adhesion to steel Polyurethane elastomers can protect steel from mechanical impact, abrasion, and even corrosion. This includes pipelines, but also vessels, mining equipment, and other equipment. Applications will be described under chapter 3.

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2.4. Low swelling, high barrier function Generally, standard PUR materials do not adhere to steel as strongly as coatings like FBE or other epoxies do. A number of measures have been devised in the past to overcome this problem. Approaches include placing a neoprene rubber layer underneath the polyurethane or employing polyureas, a class of compounds where the hydroxyl groups of the polyols used in polyurethane formation are replaced by amine groups. The resulting polyureas adhere to steel quite strongly but there are some other tradeoffs in these products property profile, e.g., lower hydrophilicity. Once again, by creation of new recipes in combination with a specific manufacturing process, we were able to create polyurethanes that exhibit an extremely high adhesion to steel, allowing for the first time the application of a polyurethane interior pipe abrasion coating. Numerous standard tests from the European standard EN 10290 to ASTM standards and operators standards were performed by independent laboratories. FIGURE 9 IS A SUMMARY OF EN 10290 ADHESION TESTION. IT NEEDS TO BE NOTED THAT THE PULLOFF TESTS WERE PERFORMEC UP TO A FORCE WHERE THE GLUE CONNECTING THE SAMPLE TO THE PULLING DOLLY RUPTURED EVERY TIME: THIS MEANS THAT THE MEASURED FORCES (TEST PASSED BY FAR) ARE ACTUALLY LOWER THAN THE STRENGTH OF THE PUR ADHESION. With elastomers, there is a chance that they take up liquids or gases; as described under 1.5, this can have serious consequences. Independent laboratory testing of the high performance PUR elastomers shown in figure 3 proved that these materials exhibit an unusually high barrier function even against gases. In some applications, hot streams are led through uninsulated pipelines in very cold environments. A very critical point for interior pipe coatings in these cases is the so-called cold wall effect: If a coating of a steel pipe allows water diffusion, water from the hot product stream (e.g., oil sand tailings) will penetrate the coating and reach the steel wall. If this steel wall is at a temperature below freezing, the water will freeze, thereby expand and cause blisters and disbondment of the coating. The Atlas Cell test, performed by an oil sands operator, simulates this situation. Elastomers from the list in figure 3 were coated onto steel plates and evaluated in the Atlas Cell test with an inside (coating side) temperature of +70C and an outside (steel side) temperature of -20C. Over 17 weeks, no effects were observed. 2.5 Fire retardation and other specific properties For applications particularly in transportation, very high demands are placed on the flame retardation and smoke behavior of materials. Again, high performance elastomer with these properties can be designed. FIGURE 10 IS A TABLE SHOWING TEST RESULTS BY A CERTIFIED LABORATORY OF A PUR ELASTOMER THAT IS SUITED FOR VIBRATION DAMPING ATTACHMENTS: TEST FAR 25.853 IS A TYPICAL STANDARD TEST FOR SUCH MATERIALS: Sample Burn length After burning After burning mm time sample (s) time drops (s) 1 14 0 0 2 17 0 0 3 15 0 0 Result: passed passed passed For smoke density and smoke toxicity, the test was passed as well. Although not directly used in pipeline pigging, these materials can play an important role in hazardous areas of refineries, pump stations, etc. 2. FROM NEW PROPERTIES TO NEW APPLICATIONS

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With the experience gathered from the application of the high performance PUR elastomers in pipeline pigging and with the material property improvements resulting from R&D based on this experience, new applications were developed. In most of these applications, the use of such materials is either resulting in significant cost savings for the operator or it is even an enabling technology for certain applications. 3.1 Applications demanding high abrasion and tear resistance and high steel adhesion Besides pipeline pigging, classic applications capitalizing on the abrasion resistance of PUR elastomers are snow plow blades, heavy duty rollers, conveyors, and cladding of equipment with ore contact in mining and in concrete mixers. With the high performance PUR elastomers developed, expansion into the following key applications lead to either commercialization or advanced field trials to date. Examples will be given under 4. Mining: lifters in ball mills Slurry pipelines and tailings: Interior abrasion coating Protection of cement mixing equipment Traffic and infrastructure: highly resilient and intelligent wheel chocks and buffers Pipe protection and security systems for pipeline 6 construction requiring adjustable visco-elastic

Outside pipelines, many other applications exist, but these lie outside the scope of this presentation. 3.3 Applications requiring low swelling / high barrier function The following applications were entered; field trials or commercial use are in progress. Pipeline inspection and cleaning of CO2 lines Interior abrasion protection in oil sands tailings and hydrotransport lines with high temperature streams and freezing outside Interior corrosion protection in salt brine lines and in high or low pH mining slurries

3. APPLICATION EXAMPLES Slurry pipelines and tailings: Interior abrasion coating

In Canadian oil sands tailings lines in Northern Alberta, test spools coated with High Performance PUR are in field test operation since 2 years. FIGURE 11 SHOWS A TEST SPOOL (1 COATING THICKNESS FOR ABRASION PROTECTION) BEFORE THE FIELD TRIAL:

3.2 Applications damping

A typical application is described below; field trials on other pipelines from Canada to Europe are in progress. A typical application on pipelines: Damping of vibrations and even shifting of the vibration frequency of a corrosioncracking causing vibration. At an Eastern European gas pipeline; a compressor, via a flange connection, introduced a vibration into the main pipe which was right at the resonance frequency of the main pipe. A hydraulic damper system was installed and clamped to the pipeline. The amplitude of the vibration was reduced, but the problem persisted endangering the pipeline. Finally only a thin small strip of a high performance PUR material with extremely high rebound resilience placed underneath the clamp did not only reduce the amplitude of the vibration introduced into the main line, but also it shifted the vibration frequency away from the pipes resonance frequency. The rebound resilience, in essence, slowed down the pipes vibration.

THE SAME TEST SPOOL AFTER 5000 HRS OF OPERATION IS SHOWN IN FIGURE12:

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A novel, proprietary field joining process requiring one weld per joint only was developed for this application (and for all slurry line applications). This field joining process requires just one weld per joint and no re-coating of the field joint. This is achieved by external sleeves welded to the pipe and by insulating layers underneath the coating where the sleeve is attached to the pipe by welding in the field. This method saves significant money compared to flanges or other joining solutions for internally coated pipes. FIGURE 13 SHOWS THE FIELD JOINING PRINCIPLE:

Pipe protection and security systems for pipeline construction

As reported in another IPC lecture , for the Baltic Sea pipeline NordStream, a pipe protection system was developed and installed that protected 209000 pipe joints of 48 diameter and 40 ft length from cutback corrosion, condensation, entry of dirt, water, or animals into the pipe, third party damage, and other dangers. Using High Performance PUR Elastomer pipe caps incorporating breathing membranes and electronic sensor boxes, these pipe joints were kept secure over 5 stock yards in 3 countries for more than 3 years. FIGURE 15 SHOWS A STOCKPILE OF CAPPED PIPES:

FIGURE 14 SHOWS THE FIELD JOINT ITSELF FROM THE PIPE INSIDE: FIGURE 16 SHOWS MONITORING SYSTEM: THE SETUP OF THE

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FIGURE 17 SHOWS EXAMPLES OF PRODUCTS MADE FROM RECYCLED HIGH PERFORMANCE PUR ELASTOMERS:

4. THE LATEST MAJOR STEP: POLYURETHANE RECYCLING Although the unique properties of High Performance PUR Elastomers can only be achieved by duromeric polyurethanes, demand in the market for recyclable and thereby environmentally friendly products led us to investigate the possibility of recycling these elastomers. A duromer is a polymer that cannot be pelletized and remoulded by heating it up to a quasi-liquid phase and injection moulding that material. Duromers normally disintegrate at a temperature lower than their melting point. Our research led to two processes in which > 95 % recycled material and 100% recycled material, respectively, can be used to manufacture new product. Raw material is shredded into fine grains and process parameters are selected in a way that temperature, pressure, and other parameters remain in a range in which the polymer does not decompose. A mouldable material was obtained which exhibits mechanical properties rather close to these of new material (elongation at break is reduced, abrasion resistance is almost identical, tear propagation resistance is higher, cutting resistance is slightly lower than in virgin material. This material is competitive pricewise to standard rubbers, but almost completely retains the superior polyurethane material properties of High Performance PUR Elastomers. By the time of IPC 2012, test results from field trials will be available.

The results of this work show that our testing of High Performance PUR Elastomers has just scratched the surface of their potential. From abrasion protection in to intelligent protection systems; from pigging tools to recycled products that combine ecology and economy, the future of these materials has just begun. Based on the PUR tool box chemistry, material properties can be customized to the application. 4. CONCLUSION The results presented in this paper show that High Performance Polyurethane Elastomers can be custom designed by using the right raw materials and reaction conditions for the polyurethane toolbox chemistry. Materials with properties way beyond those of standard polyurethanes can be synthesized.

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From pipeline pigging to intelligent protection systems, from abrasion protection pipe coatings to the recycling of hitherto not recyclable polyurethanes, improvements and cost savings in and around the pipeline can be gained by applying such materials. 5. REFERENCES 1. Book: Die Bibliothek der Technik: In-Line Inspection of Pipelines, Sddeutscher Verlag onpec GmbH, Mnchen, Germany 2010 2. NordStream Press release, 2009, www.nordstream.com 3. Gunther Blitz et al., Overcoming Challenges in th Pipeline Cleaning, Proc. 7 Asian Pipeline Conference and Exhibition, Kuala Lumpur, 11. Oct. 2011 4. Private Communication by oil & gas operator; details can be obtained from author after signing an NDA. 5. Thomas Beuker et al., Inline Inspection of Dense CO2 Transmission Pipelines, paper available from author. 6. Klaus Schmidt et al.: Paper 31652, IPC 2010.

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