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SPECIAL REPORT

Next Generation Ultra Polymer Technology for Offshore Oil and Gas Applications Facing the Extreme Challenges of Aggressive Offshore Environments with Ultra-High Performance Polymers Preparing for Deep Water and Harsh Environments Selecting the Next Generation of Polymers Gaining NORSOK Certification Ultra Polymers and the Future of Oil Production

Sponsored by

Published by Global Business Media


SPECIAL REPORT

Next Generation Ultra Polymer Technology for Offshore Oil and Gas Applications Facing the Extreme Challenges of Aggressive Offshore Environments with Ultra-High Performance Polymers

NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

Contents

Preparing for Deep Water and Harsh Environments Selecting the Next Generation of Polymers Gaining NORSOK Certification Ultra Polymers and the Future of Oil Production

Foreword 2 Tom Cropper, Editor

Facing the Extreme Challenges of Aggressive Offshore 3 Environments with Ultra-High Performance Polymers Solvay Specialty Polymers Sponsored by

Advanced Materials for Critical Offshore Requirements Published by Global Business Media

Superior Sour Resistance at High Temperatures Published by Global Business Media

High Wear and Fatigue Strength for Dynamic Seals

Global Business Media Limited 62 The Street Ashtead Surrey KT21 1AT United Kingdom

Reliable Floating Production

Switchboard: +44 (0)1737 850 939 Fax: +44 (0)1737 851 952 Email: info@globalbusinessmedia.org Website: www.globalbusinessmedia.org

One-Stop Shop for All Offshore Specialty Polymer Needs

Publisher Kevin Bell

Tom Cropper, Editor

Editor Tom Cropper Business Development Director Marie-Anne Brooks Senior Project Manager Steve Banks Advertising Executives Michael McCarthy Abigail Coombes Production Manager Paul Davies For further information visit: www.globalbusinessmedia.org The opinions and views expressed in the editorial content in this publication are those of the authors alone and do not necessarily represent the views of any organization with which they may be associated. Material in advertisements and promotional features may be considered to represent the views of the advertisers and promoters. The views and opinions expressed in this publication do not necessarily express the views of the Publishers or the Editor. While every care has been taken in the preparation of this publication, neither the Publishers nor the Editor are responsible for such opinions and views or for any inaccuracies in the articles.

Cost-Effective Alternatives to Corrosion Resistant Alloys

Preparing for Deep Water and Harsh Environments 10 Deep Water Concerns Deeper, Further and More Extreme

Selecting the Next Generation of Polymers

12

Jo Roth, Staff Writer

Identifying Solutions Testing

Gaining NORSOK Certification

14

James Butler, Staff Writer

Finding the Next Generation Proving Value

Ultra Polymers and the Future of Oil Production

16

Tom Cropper, Editor

Tapping Harsh Climates Nanotechnology Testing Conditions

References 18 Š 2015. The entire contents of this publication are protected by copyright. Full details are available from the Publishers. All rights reserved. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical photocopying, recording or otherwise, without the prior permission of the copyright owner. WWW.OFFSHORETECHNOLOGYREPORTS.COM | 1


NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

Foreword A

S DEEP water exploration takes the industry

a safe, sustainable and effective manner. Extreme

into increasingly hostile environments, the

environments go far beyond the toleration limits of

industry needs a new generation of technologies

conventional plastics. A new generation of advanced

to cope with the challenges of modern oil and

high performance materials must emerge.

gas exploration.

However, awareness of these materials and the

One of the key areas of development comes in the

benefits they can offer remains low. Jo Roth will

form of plastic and elastomers. Extreme environment

offer a guide to the available polymer compounds

exploration and drilling takes companies into

and technology before we highlight the importance

conditions which exceed the capacity of conventional

of testing. James Butler looks at the race to achieve

materials. However, these are now making way for

NORSOK certification and how this can widen the

ultra polymers – hard wearing compounds uniquely

choice of materials for end buyers.

qualified to function in the harshest of environments.

Finally, we’ll take a look to the future. The market is

Our opening article comes from one of the leading

evolving rapidly, with new production techniques and

manufacturers of ultra polymers. Solvay Specialty

technologies creating new, more advanced polymer

Polymers has developed a range of compounds

compounds. We’ll assess the key trends and look at

offering high strength, corrosion and heat resistance

where this technology is heading over the next few

suitable for offshore applications. In their article they

years and decades.

outline the rise in deep water drilling and some of the key areas in which ultra polymers are making their presence felt. We then look more closely at the future of deep water exploration and the role ultra polymers can play in helping oil and gas producers tap these sources in

Tom Cropper Editor

Tom Cropper has produced articles and reports on various aspects of global business over the past 15 years. He has also worked as a copywriter for some of the largest corporations in the world, including ING, KPMG and the World Wildlife Fund.

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NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

Facing the Extreme Challenges of Aggressive Offshore Environments with Ultra-High Performance Polymers Solvay Specialty Polymers

A

right polymer choice that can deliver significant cost advantages in terms of both capital and operational expenditures (CAPEX/OPEX) thereby helping to increase system longevity and reduce maintenance needs. Trends in offshore operations are governed above all by temperatures exceeding 200°C and higher, as well as -60°C and lower, such as in cryogenic extraction and processing applications for natural gas. Deeply buried reservoirs in high-temperature fields are also associated with pressures up to 2,000 bar (29,000 psi) and exceedingly sour (H2S, H2SO4) conditions. In addition, Enhanced Oil Recovery (EOR) techniques – which provide significantly higher extraction rates and yields than conventional primary or secondary recovery processes – are increasingly using super-critical carbon dioxide (scCO2) as a

600

300

HPHT

150°C

200 100 0 0

10,000 20,000 30,000 Static reservoir pressure [psi]

Specialty Polymers

241 MPa

400

Ultra-HPHT

205°C

138 MPa

500

HPHT-hc

260°C

69 MPa

Static reservoir temperature [°F]

LTHOUGH OIL prices have dropped in recent months and there is even an excess of oil and gas, global energy demands will continue to rise given that many traditional wells are drying up. As a result, the oil and gas industry is turning to sites increasingly hard to explore. Most of these new sources are located in extremely aggressive offshore environments and can only be accessed under very harsh operating conditions. While this places new demands on materials used for applications such as downhole components, seals and pipe liners, it also offers a wide range of attractive opportunities for ultra-high performance polymers in longer lasting and more sustainable solutions over traditional metals or corrosion-resistant alloys (CRAs). Therefore, an important consideration is the

40,000

FIGURE 1. IN RECENT YEARS, THE OFFSHORE ENVIRONMENT HAS BEEN ADVANCING RAPIDLY INTO THE ULTRA-HIGH

Reliable Long-Term Performance

PRESSURE AND TEMPERATURE RANGE. GRAPHIC COURTESY SOLVAY SPECIALTY POLYMERS (BASED ON INFORMATION PROVIDED BY SCHLUMBERGER OILFIELD TECHNOLOGIES)

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NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

An important

Torsional DMA of various Solvay products

consideration is the

1,00E+10

right polymer choice that can deliver significant of both capital and operational

1,00E+09

G' [GPa]

cost advantages in terms

1,00E+08

expenditures (CAPEX/ OPEX) thereby helping to increase system

1,00E+07

longevity and reduce

30

70

110 150 190 230 Temperature [°C]

Torlon® 4203L AvaSpire® AV-630 NT KetaSpire® KT-820 NT

maintenance needs

270

310

Solef ® PVDF Halar ® ECTFE Hyflon® PFA

FIGURE 2. TORSIONAL DYNAMIC-MECHANICAL ANALYSES (DMA) OF NEAT KETASPIRE® PEEK AND AVASPIRE® PAEK OIL AND GAS GRADES SHOW EXCELLENT STIFFNESS RETENTION EVEN AT TEMPERATURES ABOVE 200°C. GRAPHIC COURTESY SOLVAY SPECIALTY POLYMERS

more efficient, low-toxicity and environment-friendly extraction fluid, which adds another dimension to the chemical resistance to be met by materials in this increasingly high-pressure, high-temperature (HPHT) environment (Fig. 1).

Advanced Materials for Critical Offshore Requirements “The property profile required for next-generation offshore oil and gas applications exceeds the capabilities of most engineering plastics and is more readily offered by what we call

Ultra Polymers, especially polyketones and polyamide-imides,” says Bruno Langlois, Global Marketing, Oil & Gas, for Solvay Specialty Polymers. “Our range of Spire® Ultra Polymers is leading the market with solutions addressing the most demanding needs of the offshore industry in terms of thermal and chemical resistance, chemical permeation resistance, mechanical strength and toughness, without compromising efficient processability and productivity.” Among these advanced polymers, KetaSpire® polyetheretherketone (PEEK) delivers excellent

Elastomers in Oil & Gas temperature range Tecnoflon® PFR FFKM Tecnoflon® FKM TFE/P HNBR LT HNBR – 50

0

50

100 150 200 Temperature [°C]

250

300

FIGURE 3. TECNOFLON® PERFLUOROELASTOMERS PROVIDE THE WIDEST SERVICE TEMPERATURE RANGE OF ALL ELASTOMERS. GRAPHIC COURTESY SOLVAY SPECIALTY POLYMERS

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350


NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

mechanical properties and outstanding chemical resistance at elevated temperatures, while specific grades of novel AvaSpire® polyaryletherketone (PAEK) chemistry can provide even higher ductility, stiffness and temperature performance (Fig. 2). Another family in Solvay’s Spire® portfolio of ultrahigh performance polymers, Torlon® polyamideimide (PAI) resins combine the highest strength and stiffness of any thermoplastic material up to 275°C with superior resistance to chemicals, creep and wear. The PEEK, PAEK and PAI portfolio of Ultra Polymers is complemented by Tecnoflon ® fluoro/perfluoroestastomers (FKM/FFKM) wherever there is a need for superior elastomer performance in offshore applications. The product family includes peroxide-curable FKM grades that offer the best chemical resistance of all FKM in the market and are specifically designed to resist the harsh alkaline solutions routinely used in the oil and gas industry. Tecnoflon® PFR FFKM grades provide exceptional resistance to nearly any chemical class as well as extremethermal reaching up to and beyond 300°C (Fig. 3). The scope of critical offshore uses where these materials have an ideal fit comprises both sealing and non-sealing applications, and ranges from compressor plates, O-rings and labyrinth seals to jackets and cables, from pipes and tubing for risers to umbilicals and flowline rehabilitation. Some examples and specific requirements follow below.

One of the most apparent offshore application areas for Ultra Polymers is sealing components, including back-up structures and valve seats, in sour service where hydrogen sulfide (H2S) is present. Particularly high levels of H2S are found in oil extraction, where the aggressive chemical is formed by sulphate-reducing bacteria in the

crude, which can speed internal corrosion and premature failure of flowlines and systems. Besides offering high continuous-use temperatures, Solvay’s PEEK and PAEK materials are characterized by their outstanding resistance to organics, acids and bases. In order to establish a more reliable way of predicting the life of sealing components and other applications in sour environments, the company embarked on an ambitious long-term study together with Element Hitchin, formerly known as Materials Engineering Research Laboratory Limited (MERL, UK). Test samples of both aromatic polyketones were exposed to a multi-phase sour fluid with 20 mole percent H2S in the gas phase, which is ten times the specified level of the NORSOK M-170 standard for non-metallic sealing materials for use in oilfields, and was refreshed every two weeks. For tensile testing at defined intervals, the liquid phase consisted of NORSOK oil with 70/20/10 percent of heptane/cyclohexane/toluene. After 330 to 360 days of exposure at a temperature of 170°C and further accelerated testing at 200°C and 215°C, no chemical aging was observed. Both neat (unfilled) and 30 percent carbon fiber filled PEEK and PAEK samples showed excellent retention of tensile strength, modulus and elongation (Fig. 4). Linear regressions provided by the researchers based on the 170°C aging test indicated that these materials offer robust performance in highly sour environments, with at least 5, and up to 17 years required for properties to drop below 50 percent of their initial values. In almost all cases, the mass and volume change due to fluid uptake was less than 5 percent. Element Hitchin also evaluated KetaSpire® PEEK according to NORSOK M-710 multi-phase sour service conditions in a fluid mixture of 10 percent hydrogen sulfide, 5 percent carbon dioxide and 85 percent methane at 100 bar (1,450 psi). The test confirmed the material’s compliance with the

Tensile strength retention of unfilled resins in 200 °C and 215 °C environment

Tensile strength retention of fiber reinforced resins in sweet and sour environment

Superior Sour Resistance at High Temperatures

Tensile strength [MPa]

100 14

95 90

13

85 80

12 0

5

10

15

20 25 30 35 40 45 Time [days] AvaSpire® AV-621 200 °C KetaSpire® KT-820 200 °C KetaSpire® KT-820 215 °C AvaSpire® AV-621 215 °C

200 °C samples tested at 5 mm/min (0.2”/min) 215 °C samples tested at 50 mm/min (2”/min)

180

26

170

24

160 150

22

140

20

130

18

120

16

110 100

0

5

10

15

Tensile strength [kpsi]

15

Tensile strength [kpsi]

105

Tensile strength [MPa]

190

110

20 25 30 35 40 45 Time [days] KetaSpire KT-820 GF30 200 °C AvaSpire® AV-621 CF30 200 °C KetaSpire® KT-820 GF30 215 °C AvaSpire® AV-621 CF30 215 °C ®

Samples tested at 5 mm/min (0.2”/min)

FIGURE 4. TENSILE STRENGTH RETENTION OF UNFILLED AND FIBER REINFORCED KETASPIRE® PEEK

Specialty Polymers Reliable Long-Term Performance

AND AVASPIRE® PAEK RESINS AT 200°C AND 215°C IN NORSOK OIL WITH 20 MOLE % H2S. GRAPHICS COURTESY SOLVAY SPECIALTY POLYMERS

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NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

Innovative labyrinth seal designs based on Ultra Polymers such as KetaSpire® PEEK and Torlon® PAI have shown superior durability while also permitting smaller clearances and optimized tooth profiles when properly redesigned

oil and gas standard for a sour gas resistance rating of up to 200°C. A typical sealing application that benefits from this superior sour resistance is that of anti-extrusion rings manufactured by CDI Energy Products using KetaSpire® PEEK. “PEEK is a unique polymer that offers features not found in traditional high performance polymers and makes an excellent anti-extrusion ring for HPHT applications. Offering excellent chemical resistance combined with high strength makes it the preferred choice when pressure and temperature exceeds the capability of traditional anti-extrusion rings such as PTFE. The other outstanding feature of PEEK is ductility or flexibility. Most high performance thermoplastics have very low elongation whereas unfilled PEEK has 20 to 40 times the elongation of most traditional high performance polymers. This allows the rings to be split and installed into a piston groove without breaking the ring,” says Brian James, Senior Technical Advisor at CDI Energy Products. “PEEK can be formulated with fillers to offer high creep resistance and good tribological properties. This is very important in oil and gas applications given that they need excellent chemical resistance and load bearing capability. These applications range from stacked packing adapters to bushings/ bearings,” he added. H2S resistance can also be critical in compressor applications. This is confirmed by KB Delta, a North American manufacturer of high-performance sealing components for reciprocating compressor valves. The company uses 30 percent glass-filled KetaSpire® PEEK for extrusion molded blanks that are then machined into compressor plates, rings and poppets designed for high service

temperatures of up to 250°C. “Compared to competitive materials such as steel, PEEK is much more resistant to the high levels of sour gas concentration and hydrogen sulfide often found in oil and gas processing, and also gives our compressor parts the required fatigue resistance to withstand an average of 500 million cycles,“ states Alexandra DeCarlo, Vice President of Manufacturing & Operations for KB Delta.

High Wear and Fatigue Strength for Dynamic Seals Another sealing application with challenging requirements in chemically aggressive hightemperature environments is that of labyrinth seals for use in centrifugal compressors. In an efficient compressor, these seals must reliably minimize the leakage of hot compressed gas. Otherwise, the gas may have to be recompressed at the cost of additional energy input. Labyrinth seals have rotating or stationary teeth or an interlocking combination of both to seal off against a smooth surface. This requires high wear and fatigue resistance to maintain the desired sealing performance as the teeth are frequently bent and returned to their initial position. Moreover, traditional designs made from aluminum tend to gall when rubbing on other metals, i.e. they can melt, stick, pull apart and cause surface damage, resulting in additional wear. More recently in contrast, innovative labyrinth seal designs based on Ultra Polymers such as KetaSpire® PEEK and Torlon® PAI have shown superior durability while also permitting smaller clearances and optimized tooth profiles when properly redesigned (Fig. 5).

FIGURE 5. LABYRINTH SEALS IN KETASPIRE® PEEK OR TORLON® PAI CAN BE OPTIMIZED TO HIGHER TOLERANCES FOR SMALLER CLEARANCES AND MORE EFFICIENT TOOTH PROFILES, REPLACING TRADITIONAL ALUMINUM DESIGNS. PHOTO COURTESY QUADRANT EPP

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NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

Torlon® PAI

Units

–196 ºC

MPa

218

192

117

66

Break Elongation

%

6

15

21

22

Flexural Strength

MPa

287

244

174

120

Flexural Modulus

GPa

7.9

5.0

3.9

3.6

Tensile Strength

23 ºC 135 ºC 232 ºC

TABLE I. TORLON® PAI SHOWS ROBUST MECHANICAL PERFORMANCE FROM CRYOGENIC -196°C TO OVER 230°C TABLE COURTESY SOLVAY SPECIALTY POLYMERS

“The choice of PEEK or PAI depends essentially on the specific operating conditions of the seals, the design and the proper installation in the equipment,” explains Frank Olmos, Global Marketing Manager, Oil & Gas at Quadrant Engineering Plastic Products. “Both materials offer significantly higher temperature and chemical resistance than engineering plastics, along with better dimensional stability. As a rule, PEEK will be our choice when the highest chemical compatibility is required, and PAI will be selected where higher heat must be handled.” Torlon® PAI is an amorphous polymer that exhibits exceptional strength and stiffness, excellent wear and creep resistance (non-galling) as well as outstanding toughness and tensile strength from cryogenic -196°C up to 275°C (Table I). Conforming to the most demanding thermomechanical requirements for dynamic sealing applications, it provides superior gas decompression properties and is an excellent candidate for cost-effective metal replacement in this market segment. It also offers broad chemical resistance, including strong acids

and most organics. Cryogenic applications include components in liquid natural gas and arctic environments where high thermal insulation, flexibility and mechanical integrity are required at very low temperatures. Furthermore, as fracking operations are moving into subsea fields, PEEK and PAI are also considered ideal materials for “frac balls” that are used in various different sizes to seal off sections of downhole and horizontal oil and gas wells, allowing pressure to build up for a fracturing effect in the target section. This environment is considered one of the most severe and challenging in the industry, and operations are subject to increasingly higher ecological and safety regulations. Next to high thermal and chemical resistance, Solvay’s Ultra Polymers offer the compressive strength and isotropy required to help ensure a consistently safe and efficient fracking process.

Reliable Floating Production Maximum reliability is also crucial for the supply, offloading and monitoring of floating production systems, especially when operating in deeper

Specialty Polymers Reliable Long-Term Performance FIGURE 6. HIGH-PERFORMANCE FPSO SWIVEL MADE OF KETASPIRE® PEEK WITH TECNOFLON® FKM SEAL. SCHEMATIC COURTESY SOLVAY SPECIALTY POLYMERS

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NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

The trends and challenges in the

5 4

offshore industry have opened a wide field of opportunities for ultra-high performance polymers in extremely aggressive operating environments demanding long-term

Hyflon ®

3

Solef ®

2 1 0

AvaSpire ® (0) H2S

FIGURE 7. ZERO PERMEATION: COMPARISON OF ACCUMULATED H2S (PPM) PRESENCE MEASURED FOR SOLEF® PVDF, HYFLON® PFA AND AVASPIRE® PAEK FILM SAMPLES AFTER “LOCK-IN” FOLLOWING EXTENSIVE PERMEABILITY, DIFFUSION AND SOLUBILITY TESTING WITH A SUPER-CRITICAL CO2 GAS MIXTURE. GRAPHIC COURTESY SOLVAY SPECIALTY POLYMERS

reliability under HPHT and multi-phase sour conditions.

waters and harsh weather. These systems rely on individual fluid, utility and electrical/optical swivels – or combined Floating Production Storage & Offloading (FPSO) swivel stacks – that permit the continuous transfer of oil, gas, air and water as well as electrical power, control and video signals without restricting the freedom of movement of the weathervaning vessel around its mooring. The diameters of these swivels and appropriate seals can easily exceed 2 m. Swivel stacks can be over 20 m high and weigh several hundred tons. Solvay’s NORSOK M-710 approved grades of KetaSpire® PEEK and AvaSpire® PAEK as well as Tecnoflon® FKM/FFKM have successfully entered the segment of offshore swivel applications (Fig. 6) due to their outstanding HPHT performance and corrosion resistance in the presence of sour gas and other aggressive chemicals. They also show excellent low temperature resistance, as required e.g. for liquid natural gas transport swivel connectors and seals, and allow rapid gas and explosive decompression. In particular, the supplier’s fluoroelastomers provide a wide formulation window for fine-tuning the polymer structure to the specific cost/performance requirements of customers. Altogether, these Ultra Polymers can significantly extend the life of complex swivel stack applications, maximizing oil and gas operators’ CAPEX/OPEX benefits.

Cost-Effective Alternatives to Corrosion Resistant Alloys For applications in the non-sealing offshore market, such as pipes and tubing for risers and umbilicals, Solvay’s aromatic polyketones combine excellent strength, stiffness and dimensional stability at high temperatures with broad chemical resistance and low 8 | WWW.OFFSHORETECHNOLOGYREPORTS.COM

permeation of gases as well as oilfield chemicals. In extensive super-critical CO2 testing at The Welding Institute (TWI, UK), AvaSpire® PAEK for instance showed zero permeability, zero diffusion and zero solubility vs. CH4 and H2S over weeks of exposure at 626 bar (9,080 psi) and 100°C. Likewise, no H2S permeation could be measured after a “lock-in” phase following those tests (Fig. 7). Moreover, KetaSpire® PEEK and AvaSpire® PAEK also share long-term oxidative stability as well as high steam and hydrolytic resistance. Both materials provide a cost-effective alternative to CRAs and – with 25 percent lower density than established polyvinylidene fluoride (PVDF) resins – can meet the need for further light-weighting of flexible risers in deep and ultra-deep water areas. Other technical solutions, e.g. increasing the subsea buoyancy of modules or using composite technologies, are far more expensive. Rapid gas decompression tests of KetaSpire® PEEK oil and gas grades at 125°C, 690 bar (10,000 psi), a gas mix of 97/3 percent of CH4/ CO2 and a decompression rate of 20 bar/min (290 psi/min) over 10 cycles showed only few or no blisters. AvaSpire® PAEK in turn is available in competitive grades that offer slightly higher ductility and better stiffness retention than PEEK at 160°C to 190°C (Fig. 2).

One-Stop Shop for All Offshore Specialty Polymer Needs Further high-performance specialty polymers that have demonstrated their excellent fit in demanding offshore applications include Hyflon® perfluoroalkoxy polymers (PFA) for jackets and cables, Solef® polyvinylidene fluoride (PVDF) resins for insulation structures and flowline rehabilitation, Halar® ethylene chlorotrifluoroethylenes (ECTFE) for


NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

FIGURE 8. TAPE MADE FROM KETASPIRE® PEEK OFFERS A HIGH BALANCE OF TENSILE, TEAR, IMPACT AND CHEMICAL RESISTANCE FOR FLEXIBLE RISERS. SCHEMATIC COURTESY OF WELLSTREAM.

coatings and linings, Amodel® polyphthalamides (PPA) for rod guides and downhole components, Ryton® polyphenylsulfide (PPS) compounds for piping, Polidan® cross-linkable polyethylenes (PEX) for pipes and fittings as well as Ajedium™ anti-wear tapes (Fig. 8) and insulation films based on PEEK, PAEK or other polymers. This comprehensive portfolio is complemented by Fomblin ® perfluoropolyether (PFPE) HPHT hydraulic fluids and an extensive range of additive solutions for drilling, extraction and installation protection, including gelling agents, friction reducers, fluid loss preventers, non-emulsifiers and emulsion breakers, biocides, acidizers, corrosion inhibitors and H2S scavengers.

The trends and challenges in the offshore industry have opened a wide field of opportunities for ultra-high performance polymers in extremely aggressive operating environments demanding long-term reliability under HPHT and multi-phase sour conditions. “We are determined to provide our customers a one-stop shop in this market segment with the most diversified and advanced materials offering, helping them to stay in the lead as they enter new fields, from deeper than ever to arctic reservoirs,” summarizes Brian Stern, Global Marketing Manager Ultra Polymers at Solvay Specialty Polymers. Ongoing developments explored with oil and gas industry leaders are actively supported at Solvay’s Research and Innovation Centers around the world.

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NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

Preparing for Deep Water and Harsh Environments Tom Cropper, Editor New highly resistant polymers pave the way for affordable and reliable deep water exploration.

The Macondo disaster focused public and government minds on the environmental credentials of the oil and gas movement

F

OR ALL the concern about declining oil prices, deep water exploration continues to be prevalent for oil and gas exploration companies. Profitability may have been reduced and the time in which fields start to repay on the considerable investment may have been prolonged, nevertheless oil companies are determined to push out into new and uncharted territories. Doing so, though, represents an enormous challenge. They will need to equip rigs to withstand the harshest of environments; to comply with increasingly stringent environmental regulations and to do so on a smaller budget. Delivering deep water oil extraction that is effective, safe and environmentally sustainable represents the big challenge of the 21st century – one which could determine just how long the world’s oil resources last.

Deep Water Concerns Determining the exact point at which we reach peak oil is a difficult task. The famous Hubbert Curve formulated in 1956 predicted peak oil to hit in 1970. However, the discovery of US shale and the possibilities of new oil discoveries push the date further forward. Predicting demand and supply is a difficult business. In 2010 a report predicted a 10 million barrels per day shortfall by 20151. Today we have a surplus. The difficulty stems from the challenge in predicting how much oil is out there and how much can be recovered. Technology is constantly evolving. Companies can reach further out to sea and tap sources which might previously have been considered out of reach. Enhanced oil recovery techniques including fracking, gas and fluid injection have extended the life expectancy of existing oil fields by many decades. As a result, the date at which the world runs out of oil continues to be pushed back. At the same time, plenty of factors inhibit growth. Seismic surveys in the Arctic regions suggest 10 | WWW.OFFSHORETECHNOLOGYREPORTS.COM

vast potential resources. US Geological surveys predict the Arctic could contain 30% of the world’s remaining natural gas supplies and 13% of all undiscovered oil2. Even so, a recent drilling and exploration expedition by Shell came back empty handed. This was after a previous mission ended with nothing but fines for contraventions of environmental regulations. The troublesome issue of the oil price is also a factor. At the time of writing, the oil price has just recovered from a sub $30 per barrel dip spurred by reports of high stockpile levels and a strong dollar3. For all the predictions of a bounce-back, the price has stayed resolutely in the doldrums for several months. Ever since the Chinese Stock Market crash of the summer 2015, oil has hovered around the $40 per barrel mark. That’s a fraction of the heady plus $100 per barrel days and still a long way short of the $60 to $70 per barrel enjoyed shortly before the events in China.

Deeper, Further and More Extreme So, what does this mean for deep water exploration? On the face of it, not a great deal. At the end of 2014, with oil markets in freefall, Chevron christened a massive $8bn oil platform in the Gulf of Mexico4. For all the weakness in the market, deep water projects are going ahead and this raises a host of new considerations. Installations will be further from the shore. Delivering replacement parts will be more challenging and expensive. Likewise, the consequences of any release of hydrocarbons will be that much more severe. The Deepwater Horizon oil spill clearly demonstrated the difficulties of plugging a leak at extreme depth. Conditions will be more extreme. Just as a spill will be more difficult to clear up, so the likelihood of one happening will be higher. Deep water places equipment under unprecedented levels of strain – extreme pressures, high temperatures and extreme cold. Storms, rain, wind, rough seas – all


NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

these make for an environment which goes well beyond the capabilities of many current materials. Added to this mix are increasingly tough and stringent environmental regulations. The Macondo disaster focused public and government minds on the environmental credentials of the oil and gas movement. Since the disaster, there has been a series of new guidelines on safety and emissions. Significant progress has been made in the reduction of hydrocarbon leaks from offshore installations. Even so, more needs to be done, especially considering some of the potential new explorations, such as the Arctic or the Great Australian Bight fall into delicate ecosystems. Offshore companies must tread lightly. Their reputation and that of the industry depends upon it. To cope with challenges, the industry has been developing a range of materials designed for life in the harshest of climates. The number of extreme resistance plastics is growing rapidly as developers seek to cater for growing demand in a range of industries. These plastics, including materials such as polyetheretherketone and

polyamide-imide, exhibit toughness, high strength and durability in temperatures of 240 degrees and more. They do not corrode as quickly as metals or metal alloys and offer a longer lifespan with a lower requirement for maintenance and replacement. Glass fiber and carbon fiber reinforcement can be added to basic neat polymers to increase their strength and durability. Different compounds will offer different properties. Some will be resistant to chemical corrosion; some will withstand extremely high pressures, while others will continue to function in the highest of temperatures. Given the wide range of conditions and challenges found in the most extreme of offshore installations, these materals represent a crucial addition to the oil driller’s inventory. The many and disparate challenges of deep water oil exploration raise serious challenges for the oil and gas market. To withstand the rigours of deep water oil, manufacturers need tougher and more flexible materials. Extreme plastics play an important role in keeping infrastructure intact in even the harshest of environments.

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NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

Selecting the Next Generation of Polymers Jo Roth, Staff Writer How offshore oil and gas companies can get the best out of the next generation of advanced plastics for extreme environments.

Testing can offer an insight into how materials will perform in extreme environments and over a prolonged period of time, but they are not fool-proof

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DVANCED PLASTICS offer a number of exciting possibilities for offshore oil and gas installations. However, with technology still at a relatively early stage, their market penetration remains small. Understanding about the true capabilities and limitations of the next generation of polymer technology is relatively low. Building up knowledge is important in helping buyers select the right option for their requirements.

Identifying Solutions New techniques have opened the door to a range of advanced polymers with enhanced capabilities. These can include heat or pressure resistance, insulation, strength or rigidity. They come at a time when the oil and gas industry in changing – pushing forward into new and more dangerous territory, which places strains on equipment that existing polymers are not able to withstand. The range of applications is many and varied including seals, pipe insulation, pipes, compressor rings and much more. One of the more common materials being used is polyetheretherketone (PEEK), which offers a superb resistance to chemical corrosion and fatigue. It can also operate at temperatures of more than 200oC making it suitable for downhole operations. It is strong, flexible and is being seen as a viable replacement for metals in many industries, including oil. Polyaryletherketone (PAEK), meanwhile, can offer superior toughness and stiffness to PEEK. It can be produced in neat grades or reinforced with glass fibers to improve performance. Torlon (PAI) is seen as the industry’s highest performance plastic, offering high stiffness up to 275oC. It has higher impact resistance and strength than other advanced plastics and can perform well in some of the most inhospitable environments in the world. However, not all compounds are created equally. Much depends on the production

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process and the expertise and experience of the manufacturing company. The challenge for buyers is to distinguish between grades which offer the best performance and will be suitable for the very particular requirements of the extreme environment of oil and gas exploration.

Testing Rigorous testing and evaluation of materials is crucial to ensure that they can cope with extreme offshore conditions. However, because use remains relatively limited, accumulated experience has not built up with which to evaluate compounds’ performance in the field. A recent study into the evaluation of long term polymer behaviour5 identified the following key issues which need to be addressed with testing: •S  election of age acceleration material: Components will need to be in place for several decades and more. For this reason, acceleration mediums can be introduced at the testing phase which introduce heightened wear and tear. Selecting this material represents a difficult balancing act. On the one hand it should achieve accelerated ageing, but on the other it should not go so far that it introduces degradation factors which would not be there in the real world. • H ydrostatic degradation: Hydrostatic pressure can also be an issue. Mechanical loading has been shown to affect the chemical makeup of polymers in the past. A porous material can allow water to be forced into the microstructure, which might affect the weight or harm the quality of the material. •T  hermal insulation: Under certain conditions of temperature and pressure, solid gas hydrates can appear within the pipeline. This can in turn lead to interruption of flow and production. Understanding how polymers will function for several decades is an important component of a test. Water diffusion needs to be assessed as water can impair the thermal insulation


NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

properties of polymers. Equally, polymers can react with water or oxygen over time leading to a change in the chemical composition of the material and a degradation of performance. Age accelerating testing can use higher temperatures to predict how a material will endure over a period of several decades. Testing can offer an insight into how materials will perform in extreme environments and over a prolonged period of time, but they are not fool-proof. Even the most comprehensive test will be unable to account for all possible variables in the real world environment. To assess a component, buyers will need to understand as much as possible about the testing processes. NORSOK certification offers a widely recognized global standard. It is designed to assess the durability of components in extreme environments. The race to achieve NORSOK certification is an important step in making certain any new material is rated to cope with the most extreme of deep water environments. For many, this will be enough to install trust. Even so, it pays to know as much as possible about the nature of any tests being carried out. Not only will it help assess the quality and accuracy of any test, but it will also help in the assessment of how and where any polymer should be deployed. The more open communication there is between buyer and developer, the more likely it is that new products will be able to handle all the pressures which come with them. In making the final decision, much will also depend on how much trust a buyer has in the company delivering the work. Those offering significant scale and a good track record in the development of extreme plastics will be at a

natural advantage over any new players. Equally, those which dedicate time and resources to formulating products specifically for the offshore environment will be more likely to have delivered compounds capable of fulfilling the specific requirements of the industry. Oil and gas operations face a range of challenges as they move into deep water. Different installations will need compounds with a certain set of qualities. It is difficult to find a one size fits all solution without accepting compromise in certain areas. For example, a compound may be extremely tough and durable, but could struggle to perform at high temperatures. An effective back and forth discussion is essential between all sides to ensure developers understand what the end goal of their product must be and that buyers get the product which fully delivers on their requirements. The stakes could not be higher. The next generation of plastics is charged with a profoundly difficult task – to facilitate deep water oil production; to make it possible and ensure it can continue in a volatile market. Advanced plastics will be required to function in extremely inhospitable environments for several decades. Get it wrong and the impact can be felt in expensive replacements, leaks and production delays. Buyers need to be educated on the types of plastic compounds being produced, their properties and performance value. In a rapidly developing market, new advances are being made which means future generations of plastic technologies will offer even more. This is a subject which may not be easy for many professionals to instantly understand, but doing so can determine whether it is possible to exploit adequately deep water oil reservoirs.

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NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

Gaining NORSOK Certification James Butler, Staff Writer As ultra polymers gain increasing recognition and certification, offshore oil and gas installations are becoming more comfortable with their use.

The NORSOK standards are internationally recognized testing methods developed by the Norwegian petroleum industry

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T IS a source of frustration for manufacturers of new technologies that offshore oil and gas companies tend to be highly cautious. Their wariness of innovations and the slowness to embrace new technologies and products lengthens the amount of time between development and commercial use. Ultra polymer technology is relatively new. What this means is that technology is moving forward at a pace, with new compounds being formulated regularly. The challenge is to convince end users that they can be the solution to their problems.

Finding the Next Generation The industry has a pressing need for the next generation of extreme plastics. The extension of oil and gas exploration into increasingly extreme and volatile environments goes beyond the parameters of most conventional plastics. Even in existing, more benign fields, ultra polymers can play an important role in reducing the wear on components, improving safety and bringing down maintenance times and costs. Even so, there is a danger in rushing to adopt new, but unproven materials. If they fail to perform as predicted the costs can be high. In April 2015 Solvay Speciality Polymers announced that semi-finished tubes made from its KetaSpire polymers had passed NORSOK M-710 certification, a major step towards proving usability in the extreme offshore environment. With each new product passing NORSOK’s demanding tests, the range of available products for offshore applications grows. The NORSOK standards are internationally recognized testing methods developed by the Norwegian petroleum industry. The M-710 specifically relates to non-metallic sealing, seal or back up materials relating to sub-sea applications. Here, the range of conditions they may face are immensely challenging, from extremely high temperature and pressure, 14 | WWW.OFFSHORETECHNOLOGYREPORTS.COM

to salt water and chemical corrosion, and even fire or explosions. Solvay’s KetaSpire ® PEEK materials are made from polyetheretherketone, an easy to mold semi-crystalline polymer ideally suited for offshore environments. It features extremely high chemical resistance, but combines this with a high heat endurance of up to 240oC. It is, then, ideally suited for tough downhole operations in deep water. Glass or carbon fiber can be added to neat compounds to improve strength and rigidity. The company says it can be used in a range of applications such as compressor rings and plates, back up seal rings, electrical connectors, labyrinth seals, bearings, and wear tapes for flexible risers.

Proving Value For the industry to become fully comfortable with any new product, it has to fully understand the implications of testing procedures. Only then will a group of numbers on a certificate make sense. Te s t i n g Ke t a S p i r e ® P E E K i n v o l v e d a comprehensive set of independent testing and laboratory analysis. The work was carried out by Element Hitchin, an independent testing and analytical laboratory based close to London. The material was evaluate in multi-phase sour service conditions in fluid of 10% hydrogen sulphide, 5% carbon dioxide, and 85% methane at 10 MPa Bar. Temperatures of 200oC, 210oC and 220oC, were used over a testing period of 49 days with swelling and tensile properties being measured periodically over the course of the test. The results were highly encouraging for the company. KetaSpire® PEEK delivered high resistance to sour gas and no measurable chemical deterioration throughout the testing period. The test was part of a collaboration between Solvay and ATO, a leading producer of stock


NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

shapes. Both sides were keen to hail the importance of the test: “As the sealing industry continues to specify very high performance, quality and durability, we are excited to collaborate with Solvay as an innovative global supplier of PEEK resins,” said Davide Polloni, business export manager for ATO. “Our relationship ensures access to cutting-edge new materials as well as Solvay’s industry-leading technical expertise as ATO seeks to develop advanced solutions for challenging oil and gas applications.” Solvay were equally pleased with the certification: “KetaSpire® KT-820 NT resin’s qualification under NORSOK M-170 further highlights Solvay’s commitment to work with suppliers within the sealing industry to help support and develop next-generation materials solutions,” said Art Tigera, business development manager for Ultra Polymers at Solvay Specialty Polymers. “We look forward to continued collaboration with ATO to further cultivate our advanced polymer materials into reliable, new solutions for the global oil and gas industry.” In assessing tests such as these, it’s important for buyers to understand both the value and the limitations. This NORSOK test went a long way towards emulating environments likely to be faced, but it is impossible to fully account for every variable. The oil and gas industry is breaking frontiers and venturing into new and uncharted

territory. It is not possible to be fully prepared for all the challenges these environments can throw. The potential for unexpectedly early failure is high. True value comes in sustained and demonstrable success in the real world. What tests such as these can achieve, though, is to provide companies with as much reassurance as possible. By understanding how tests are carried out, what conditions materials were subjected to and how they performed, buyers can feel as comfortable as is reasonably possible that the products will perform as expected in the real world. Information is key from both sides of the process. Buyers want to know as much as possible about a product, while sellers will benefit from an enhanced conversation and collaboration with buyers. Understanding the requirements, the conditions which will be faced and selecting the ideal products will be crucial to development. The offshore oil and gas industry is in a period of transition. The market is unstable and unpredictable, while the future is as full of challenges as opportunities. Development is moving forward quickly as the next generation of extreme plastics step up to the plate. Choosing the right one will depend on many factors including the environment and the specific needs of a drilling company. The onus is on manufacturers to collaborate with their customers and potential clients to ensure all questions are addressed adequately.

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NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

Ultra Polymers and the Future of Oil Production Tom Cropper, Editor How a new generation extreme polymer technology could hold the future for the offshore oil and gas industry.

A key trend of 2015 has been the rush to get materials certified for use in offshore environments.

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HE OFFSHORE oil and gas industry is like a shark – it has to keep moving forward otherwise it dies. The goals are constantly shifting; oil is harder to extract, regulations are stricter and profit margins are increasingly tight. To maintain sustainable operation it must continually improve practices through the introduction of new processes and technology. The next generation of extremely advanced polymers play an important role. Offering improved durability and rigidity, they can extend the life of existing equipment, reduce the costs of downtime and continue functioning in the harshest of environments. With technology still in the relatively early stages, penetration into the market is still limited. This means the future could be interesting. Any coherent analysis of that future must take into account future trends. Although deep water projects are coming online, the development of the market over the longer term depends greatly on where prices will go in the future. The current outlook appears bleak with prices still depressed at around $40 per barrel, and even occasionally dipping into the thirties. However, in the long term, there is hope. Saudi Arabia has indicated a possible rebalancing of the market in 2016, the glut of supply from US Shale will not last indefinitely, and although demand is sluggish it is still rising. Sooner or later, the world will need more oil6. Deepwater projects are long term propositions with a planned lifespan of several decades. Even with the current market problems, these still represent a solid long term bet. The demand, therefore, will surely be there. The question is: can the industry successfully tap those oil reserves? Two issues will be key – money and the ability of technology to meet the demands.

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Tapping Harsh Climates High performance plastics are pushing the boundaries forward all over oil and gas operations. For example, polyurethane insulation can be used to insulate diving bells for inspection of infrastructure at extreme depth. Conventional polyurethane cannot function at such depths. However, mixing glass microbeads can create an enhanced ultra-polymer capable of withstanding the extreme pressures found down hole. This can also be used to protect pipelines and other subsea infrastructure. Advanced polymers, formulated to offer extreme rigidity can also be used to provide current protection. Strakes placed on risers on pipelaying vessels can dissipate current, reducing the impact of corrosion. A key area is in the formulation of advanced elastomer seals. Existing elastomeric properties are insufficient to withstand ultra high temperature and pressure environments. By formulating new and stronger compounds it is possible to produce flexible, but extremely strong plastics capable of providing a solid and complete seal in even the most difficult of environments.

Nanotechnology One of the core areas in future development is nanotechnology. This futuristic sounding technology makes use of nanoparticles to create incredibly thin, light, but tough materials. Ultra tiny particles create incredibly strong atomic bonds, making material which is far stronger than its size would suggest. The combination of light weight, high strength and low biofouling make these technologies ideal for the offshore oil and gas market. Around the world, work is under way using thin polymer films and complex structures such as nanoparticles to deliver the next generation of technologies for future offshore installations.


NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

A three year study is currently coming to an end into the use of polymer nanotubes in creating a tough but light subsea umbilical conductor for deep water operations. Conventional copper wires can’t cope with the extreme pressure or heat of deep water environments. By using a nanotube made of advanced polymer technology, the Research Partnership to Secure Energy for America hopes to produce a conductor cable that is lighter, more resistant to pressure and offers superior conductivity. The carbon nanotube is capable of operating at 37.92 MPa pressure and includes a polymer jacket made of high density polyethylene which is already used in subsea operations. The final phase of the study is yet to deliver a report, but researchers are confident that they have created an important game changing solution for offshore oil7.

Testing Conditions For all the benefits they offer, the industry has only scratched the surface of what they can do and where they can go. A key trend of 2015 has been the rush to get materials certified for use in offshore environments. Throughout the year, news has come through of new materials gaining accreditation. As the number of companies satisfying such demand increases, so too will their use in offshore oil and gas installations. At the moment, most of the potential for extreme plastics lies in the future. But that future is

moving closer quickly. It has to. The oil and gas industry is adopting new techniques and moving into new territories which promise to push existing infrastructure and materials beyond their tolerance levels. As a result, the true extent of recoverable oil lying underneath the world’s oceans depends on the industry’s ability to tap the resources. This means combining both technological and financial factors. Financially, polymers can play an important role in reducing instances of failure, risk to the environment and repair costs. In doing so they can reduce significantly the level at which oil and gas operations achieve profitability. In an environment in which operators may have to function with a price as low as $40 per barrel, that could be game changing. Technologically, ultra polymers expand the horizons of deep water drilling, allowing the industry to go further and deeper. By doing so, they open up vast potential resources. These are, then, uncertain but undeniably interesting times. The industry faces a world of challenges and problems. How it rises to the challenge will shape the nature of energy supply now and into the future. There is an immense market opportunity. Companies capable of delivering advanced plastics are in line for contracts potentially worth millions of dollars. Being the first to the market and delivering the best technologies represents a goal worth fighting for.

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NEXT GENERATION ULTRA POLYMER TECHNOLOGY FOR OFFSHORE OIL AND GAS APPLICATIONS

References: 1

US Military Warns Oil Output May Dip: http://www.theguardian.com/business/2010/apr/11/peak-oil-production-supply

2

Arctic Oil Exploration: Potential Riches and Problems: http://www.bbc.co.uk/news/business-14728856

3

4

Oil rises: http://www.reuters.com/article/2015/12/03/us-global-oil-idUSKBN0TL00T20151203 Bad Timing? Chevron Christens new $8bn Deepwater Oil Platform:

http://www.forbes.com/sites/christopherhelman/2014/12/02/bad-timing-chevron-christens-new-8b-deepwater-oil-platform/

5

Evaluation of Long Term Polymer Behaviour: http://archimer.ifremer.fr/doc/00199/30978/29356.pdf

6

Oil Price Rises: http://www.reuters.com/article/2015/12/03/us-global-oil-idUSKBN0TL00T20151203

7

Ultra High Conductivity Umbilicals:

http://www.rpsea.org/media/files/project/3bc2d648/10121-4302-01-RT-Phase_2_Final_Ultra-High_Conductivity_Umbilicals_Polymer_Nanotube_Umbilicals-07-18-14.pdf

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Notes:

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Defence Industry – Special Report on Next Generation Ultra Polymer Technology for Offshore Oil and Gas Applications