Special Report – Next Generation High Performance Fluoropolymer and Cross Linkable Compound Solu

Special Report

Next Generation High Performance Fluoropolymer and Cross-Linkable Compound Solutions Fluoropolymers and Cross-Linkable Compounds for Oil and Gas Versatility and Durability The Market for Fluoropolymers A Developing Technology Challenges, Solutions and Considerations

Sponsored by

Published by Global Business Media

SPECIAL REPORT

Next Generation High Performance Fluoropolymer and Cross-Linkable Compound Solutions Fluoropolymers and Cross-Linkable Compounds for Oil and Gas

SPECIAL REPORT: NEXT GENERATION HIGH PERFORMANCE FLUOROPOLYMER AND CROSS-LINKABLE COMPOUND SOLUTIONS

Contents

Versatility and Durability The Market for Fluoropolymers A Developing Technology

Foreword

Challenges, Solutions and Considerations

2

John Hancock, Editor

Fluoropolymers and Cross-Linkable Compounds for Oil and Gas

3

Marie Schmidt, Global Market Manager for Oil and Gas, Solvay Specialty Polymers Sponsored by

Published by Global Business Media

Published by Global Business Media Global Business Media Limited 62 The Street Ashtead Surrey KT21 1AT United Kingdom Switchboard: +44 (0)1737 850 939 Fax: +44 (0)1737 851 952 Email: info@globalbusinessmedia.org Website: www.globalbusinessmedia.org Publisher Kevin Bell Business Development Director Marie-Anne Brooks Editor John Hancock 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 organisation with which they may be associated.

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A Broad Choice of Materials Material Selection for Oil and Gas Applications A Long Track Record About Solvay Specialty Polymers

Versatility and Durability

7

John Hancock, Editor

What Makes a Fluoropolymer?

The Properties of Fluoropolymers Applications and History Cross-Linking Offshore Oil and Gas A Happy Accident

The Market for Fluoropolymers

9

Peter Dunwell, Correspondent

Function Drives the Market Main Markets Demand and Growth A Range of Sectors It’s Also a Green Issue

A Developing Technology

11

Francis Slade, Staff Writer

Corrosion Accretion and Fouling Other Uses

Challenges, Solutions and Considerations

13

John Hancock, Editor

Durability Safety Environmentally Friendly Chemical Resistance

References 15

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SPECIAL REPORT: NEXT GENERATION HIGH PERFORMANCE FLUOROPOLYMER AND CROSS-LINKABLE COMPOUND SOLUTIONS

Foreword F

or all of their skills, modern scientists

describe the broad choice of materials supplied by

sometimes achieve something more

the company, their properties and typical applications

incredible by accident than even when they meet

in the oil and gas industry.

the objectives of their project. Those ubiquitous

Not only can fluoropolymers slip easily passed

Post-it™ notes that serve for extended memory

each other, but, also, they are exceptionally resistant

in the modern world, on refrigerators, around

to abrasion or adhesion by external elements. This

computer monitors, on walls and sometimes on

makes them the perfect material for lining pipes

the documents for which they were intended, use

both internally, to resist the corrosive and abrasive

a gum that was a failed part of a programme to

characteristics of the mix of crude oil and chemicals

develop a new adhesive. Fluoropolymers were

to be transported from the wellhead, and externally, to

also discovered by accident in 1938 and today

resist the corrosive and abrasive effects of salt water

have grown into another ubiquitous family of

and the adhesion of fouling organisms.

coatings and materials that can be found in

When used to coat nuts and bolts and components,

products as diverse as non-stick frying pans

the same fluoropolymers can not only resist corrosion

and aerospace assemblies where durability,

and fouling, but also retain their necessary separation

resistance and dry lubrication are essential

that make it possible to undo and reassemble

performance characteristics.

parts during maintenance. In fact the range of their

In this Special Report, we will be most concerned

capabilities is impressive.

with applications in the offshore energy sector

We look at the products, consider the markets for

where the enormous and exceptional capabilities of

them, take an overview of where they are going in

fluoropolymers make them the ideal solution for many

the future and review the challenges they are used to

of the industry’s greatest challenges.

address and how they address them.

The opening article in the Report looks at Solvay Speciality Polymers, the leading supplier of hightech solutions, offering the largest portfolio of high-performance polymers to a significant number of oil and gas operators. The article goes on to

John Hancock Editor

John Hancock joined as Editor of Offshore Technology Reports in early 2012. A journalist for nearly 25 years, John has written and edited articles and papers on a range of engineering, support services and technology topics as well as for key events in the sector.

Subjects have included aero-engineering, testing, aviation IT, materials engineering, weapons research, supply chain, logistics and naval engineering.

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SPECIAL REPORT: NEXT GENERATION HIGH PERFORMANCE FLUOROPOLYMER AND CROSS-LINKABLE COMPOUND SOLUTIONS

Fluoropolymers and Cross-linkable Compounds for Oil and Gas Marie Schmidt, Global Market Manager for Oil and Gas, Solvay Specialty Polymers

T

he Oil & Gas industry continuously poses new challenges for most polymeric materials used in onshore and offshore applications, combining a variety of properties whilst providing long-term reliability.

With over 1500 products across 35 brands, Solvay Specialty Polymers offers the largest portfolio of high-performance polymers to the market and has become the leading supplier of high-tech solutions to a significant number of Oil and Gas operators. Amongst many other products, Solvay Specialty Polymers offers a family of melt-processable fluoropolymers and silane-based cross-linkable compounds with unique capabilities.

Solvay’s fluoropolymers consist of two product families: partially-fluorinated polymers like Solef® PVDF (polyvinylidene fluoride) and Halar® ECTFE (ethylene-chlorotrifluoroethylene), and fullyfluorinated polymers like Hyflon® PFA (copolymers of tetrafluoroethylene perfuoroalkoxyvinylethers).

These products can be best described as high performance thermoplastics with an outstanding balance of properties, combining thermal stability at high and low temperatures with chemical and permeation resistance. Fluoropolymers are intrinsically UV and weather resistant, hydrolytically stable, and non-flammable.

Cross-linkable compounds provide an excellent and competitive alternative to Polyethylene and Polyamides in specific applications, offering good thermal and chemical stability up to 90°C. Both fluoropolymers and silane-based crosslinkable compounds can be processed by conventional techniques such as extrusion, injection or compression molding, rotomolding and powder coating. In some cases, the use of corrosion-resistant processing equipment is required.

A Broad Choice of Materials Cross-linkable compounds XLPE, also referred to as PEX, is a cross-linked Polyethylene. Through one of several processes,

links between polyethylene macromolecules are formed to create bridges between PE molecules. The resulting molecule becomes more durable under temperature and chemical attack and demonstrates higher resistance to creep deformation.

Polidan® XLPE materials were introduced to the market in the early 1990s. They are silane cross-linkable polyethylene compounds which have been specifically designed to combine high pressure resistance with long-term performance at high temperature. The Sioplas® cross-linking process offers many advantages over other technologies: the polymer is processed as a standard Polyethylene, no specific equipment nor tools are required, no limitation in screw speed nor in pipe diameter. Curing is achieved through hot water circulation or steam or a combination of both. The cross-linking process can be delayed to suit the requirements of each customer/application, so that pipes and parts can be first installed and welded before the curing process begins.

Typical properties are: •T emperature resistance up to 90°C in hydrocarbon service •V ery high environmental stress crack (ESCR) and notch resistance • Very good chemical resistance, no hydrolysis •V ery high resistance towards rapid crack propagation (RCP) • Excellent creep and long term strength • High abrasion resistance • Excellent resistance to supercritical CO2 Typical applications in the Oil and Gas industry: • Pressure sheath in flexible risers and RTPs • Umbilical hoses • Internal liners of rigid pipelines • Cable jacketing •S elf-supported pipes and fittings for district heating and chemical transport www.offshoretechnologyreports.com | 3

SPECIAL REPORT: NEXT GENERATION HIGH PERFORMANCE FLUOROPOLYMER AND CROSS-LINKABLE COMPOUND SOLUTIONS

With over 1500 products across 35 brands, Solvay Specialty Polymers offers the largest portfolio of high-performance polymers to the market and has become the leading supplier of high-tech solutions to a significant number of Oil and Gas operators

Fluoropolymers Solef® PVDF is perhaps the best known partiallyfluorinated fluoropolymer used in the Oil and Gas industry for a variety of reasons including its safety credentials and the extensive use in flexible risers and flowlines since the 1990s. Solef® PVDF offers a unique combination of mechanical, thermal and chemical properties and is best-in-class for corrosion protection in hydrocarbon service pipelines and flowlines that carry significant amounts of CO2, H2S, and free water.

Solef® PVDF is available as a homopolymer and copolymer, as pellets or powder, and can be processed by extrusion, injection molding, rotomolding and powder coating. It is also available as a foam with excellent insulation properties at high and low temperatures.

Typical properties are: • Thermal stability from -30°C to 150 °C • Excellent chemical resistance •G ood mechanical properties and impact strength •V ery low permeability to most gases and liquids including water and H2S • High abrasion resistance •E xcellent resistance to Rapid Gas Decompression (RGD) up to 140°C and 1000 bar (API 17J) Typical applications in the Oil and Gas industry: •F lexible risers: pressure sheath, antiwear tapes, thermal insulation • HP/HT injection hoses in umbilicals • I nternal liners of new rigid flowlines and rigid risers •C oatings for internal and external corrosion protection • Electrical insulation in subsea pumps Halar ® ECTFE is a partially-fluorinated fluoropolymer that is very well established wherever corrosion protection is required in challenging conditions. It combines mechanical properties, abrasion resistance, chemical and permeation resistance with fire properties and electrical insulation performance, and outstanding low temperature performance.

Since its market introduction in the 1970s, Halar® ECTFE has been extensively used for direct powder coating on metal surfaces. Coated parts exhibit an outstanding surface smoothness, on top of all other properties. It is also widely used in downhole cable applications and can be processed by extrusion.

Typical coatings properties are: • Thermal stability up to 150 °C

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• Brittleness temperature < –76°C • High coating hardness • Good adhesion to substrate • Excellent barrier properties • Low wettability • Excellent abrasion resistance • Non-flammability • Exceptional surface smoothness Typical applications in the Oil and Gas industry: •P owder coating of metals for corrosion protection • Encapsulation of downhole cables • Cable jacketing • Tank liners Hyflon® PFA is a fully-fluorinated, meltprocessable fluoropolymer offering chemical inertness with extremely high and low thermal stability. It can be processed by extrusion and as a powder coating.

Typical properties are: •M echanical properties and dimensional stability from -200 °C to +260 °C • Excellent long-term aging resistance •G ood flexibility and ductility even down to -100 °C •U niversal chemical resistance combined with good permeation resistance •E xcellent electrical properties and fire resistance •G ood resistance to rapid gas decompression at 185°C and 1000 bar (API 17J) Typical applications in the Oil and Gas industry: •E lectro-mechanical cable jacketing and encapsulation • Heater cables • Internal liners for OCTG tubing •P owder coating of metals for corrosion protection • Tank and valve liners

Material Selection for Oil and Gas Applications Selecting the right material is critical, especially in offshore applications where maintenance can be very challenging. A thorough review of all the technical requirements is necessary. The variation in the properties of the resin over time, processing and installation of the final part and an analysis of all potential failure modes in the specific application must be considered. Selection of the correct resin during the design stage can not only prevent early failure but also considerably reduce monitoring, maintenance and repair activities thereby saving time and money.

SPECIAL REPORT: NEXT GENERATION HIGH PERFORMANCE FLUOROPOLYMER AND CROSS-LINKABLE COMPOUND SOLUTIONS

Hydrogen sulfide permeability

Permeability [ml mil/day 100 in 2 atm]

10,000

1,000

100 Halar ® ECTFE Solef ® PVDF HDPE 10 0

20

40

60 Temperature [°C]

A Long Track Record Flexible risers and flowlines In 2013, Solvay Specialty Polymers is celebrating its 15th anniversary as the global supplier of Solef® 60512 PVDF resin to the Oil and Gas industry.

Solef® 60512 was developed in the mid-1990s specifically for offshore applications. It contains no plasticizer and thereby ensures safe, long-term performance as no migration nor loss of additives will occur over time.

NOV Flexibles also marks 15 years of producing flexible pipes made of Solef® 60512 with no service failures ever reported. This unbroken track record dates back to 1998 when NOV Flexibles installed its first pipe in the BANFF field in the North Sea. Solef® PVDF is a key component of the company’s deep-water riser concepts, withstanding high pressure and high

80

100

120

Umbilicals Umbilical hoses supply wells with chemicals and fluids and must resist methanol and ethanol. Thanks to its very low permeability to such fluids, Solef® PVDF was selected by high pressure hose manufacturer SPIR STAR® for their HP/HT pressure hoses, for use up to 150°C and 1,125 bar.

Polidan® XLPE is also widely used in umbilicals, typically as a competitive alternative to PA11.

Flexible Riser. Courtesy of NOV Flexibles.

temperatures. NOV Flexibles uses Solef® 60512 in single-layer extrusion over the metallic carcass, a unique safety benefit in risers to prevent gas accumulation between polymeric layers.

Solvay’s track record with Polidan® XLPE for pressure sheathing in flexible pipes dates back to 1991. Silane-based XLPE has been traditionally positioned between HDPE and PA11 in flexible risers for years and is now seeing increasing demand thanks to its outstanding resistance to supercritical CO2, an emerging technical challenge linked to Enhanced Oil Recovery.

Polidan® XLPE is a competitive and popular alternative to PA11 and PA12 in low to mid pressure pipe applications.

Umbilicals. Courtesy of SPIR STAR®

Polymeric liners Solvay Specialty Polymers have recently joined their material expertise with Swagelining® installation technologies to enable the rehabilitation of existing pipelines for lining of new carbon steel pipelines. This technology protects the internal surface from corrosive hydrocarbon or other media, especially where sulfate reducing bacteria (SRB) is one of the principal sources of corrosion activity. www.offshoretechnologyreports.com | 5

SPECIAL REPORT: NEXT GENERATION HIGH PERFORMANCE FLUOROPOLYMER AND CROSS-LINKABLE COMPOUND SOLUTIONS

In 2013, Solvay Specialty Polymers is celebrating its 15th anniversary as the global supplier of Solef® 60512 PVDF

Polymeric liners. Courtesy of Swagelining®

resin to the Oil and

Solef® PVDF or crosslinked polyethylene Polidan® PEX liners can be used to protect the internal pipe bore from corrosion, which may also offer some secondary containment capability in the event of a rupture or damage to the outer steel pipeline.

Gas industry

Application matrix Application

PEX

PVDF

●

●

ECTFE

PFA

About Solvay Specialty Polymers

Flexible risers Pressure sheath Anti wear tapes

Solvay Specialty Polymers supplies over 1500 products across 35 brands of high-performance polymers – fluoropolymers, fluoroelastomers, fluorinated fluids, semi-aromatic polyamides, sulfone polymers, aromatic ultra polymers, high-barrier polymers and cross-linked high-performance compounds – for use in Oil and Gas, Aerospace, Alternative Energies, Automotive, Healthcare, Membranes, Packaging, Plumbing, Semiconductors, Wire and Cable, and other markets. Learn more at www.solvayspecialtypolymers.com.

Solvay is an international chemical Group committed to sustainable development with a clear focus on innovation and operational excellence. It is realizing over 90% of its sales in markets where it is among the top 3 global leaders. The Group is headquartered in Brussels and its companies, which employ about 29,000 people in 55 countries, generated EUR 12.4 billion in net sales in 2012. Solvay SA (SOLB.BE) is listed on NYSE Euronext in Brussels and Paris (Bloomberg: SOLB.BB – Reuters: SOLBt.BR).

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Umbilicals

●

●

Pipe liners

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●

RTPs

●

●

Coatings

●

Control line encapsulation Power cables

●

Tubing

●

●

●

●

●

●

●

●

●

●

●

●

An internal liner can extend the service life of a carbon steel pipeline beyond the period of operation for which it was originally designed.

Unforeseen operational parameters such as CO2 or SRB corrosion can often lead to early shut down and abandonment for safety and/ or environmental reasons. Routine internal inspections typically show that corrosion is often greater than anticipated and is the main cause of pipeline failures. Identified applications for the technology are transportation of hot sour hydrocarbon product and use in elevated temperature Water Injection service.

Following a comprehensive R&D programme, pipes made of Solef® PVDF have been confirmed as suitable for installation by Swagelining® into the host pipes, and can be butt-welded for long-length installations. Tests on Polidan ® PEX materials are now well under way and it is anticipated that similar confirmation will be achieved in the very near future. These developments further support the case for seriously considering polymer lined carbon steel flowlines as an alternative to CRAs, resulting in cost and scheduling advantages.

●

Temperature ranking & limitations PFA

ECTFE

PVDF

PA-11

Contact Details XLPE 100 % Water 0 % Water

HDPE – 100

– 50

0

50

100 Temperature [°C]

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150

200

250

300

Marie Schmidt Solvay Specialty Polymers Global Market Manager – Oil & Gas +49 40 5377 9731 www.solvay.com

SPECIAL REPORT: NEXT GENERATION HIGH PERFORMANCE FLUOROPOLYMER AND CROSS-LINKABLE COMPOUND SOLUTIONS

Versatility and Durability John Hancock, Editor Fluoropolymers and cross-linkable compound solutions are game changers in many walks of life

general more resistant to heat and chemical attack than other materials. They have strong electrical insulation, lubrication, non-stick, temperature resistance, transparency, and other properties.

Different fluoropolymers have different properties.

Type one fully fluorinated polymers, in which fluorine atoms replace all of the hydrogen atoms, generally emphasise the properties mentioned above. Type two partially fluorinated polymers, in which fluorine atoms replace only some of the hydrogen atoms, are useful for applications in which mechanical toughness greater than that available to fully fluorinated polymers is required, special processing or manufacturing conditions are desirable or resistance to specific chemicals is useful.”

The Properties of Fluoropolymers

F

luoropolymers and associated compound materials are a remarkable group of plastics whose versatility and allround durability are making them useful across a range of engineering applications, not least among in the offshore oil and gas sector.

Operators face particularly harsh conditions and equipment needs to maintain operating integrity, in environments that challenge engineering and materials. But before we consider what these materials can do and how fluoropolymers as well as cross-linkable compound solutions might be applied in the offshore oil and gas industry, we should understand what they are and what they do.

What Makes a Fluoropolymer?

The Plastics Portal1 offers a succinct description of how fluoropolymers are constructed, explaining that they “… are fluorinated plastics.

Most plastics are chains of carbon atoms with hydrogen or other atoms attached to them. In fluoropolymers, fluorine atoms replace some or all of the hydrogen atoms. Substituting fluorine for hydrogen creates a high binding energy among atoms within the plastic molecules, making the plastics highly stable and giving them unique and valuable properties. Fluoropolymers are in

The Zeus Technical White Paper ‘Introduction to Fluoropolymers’2 offers a good summary of the properties that make fluoropolymers such remarkable materials in the pantheon of working plastics. “[These] high performance semi-crystalline thermoplastics tend to have the following properties (in comparison to amorphous plastics): • Higher specific gravity; • Higher tensile strength and tensile modulus; • Lower ductility; •T end to be translucent or opaque rather than transparent; • Higher fatigue resistance; •M ore difficult to bond using adhesives and solvents.

These plastics also tend to have the following properties (in comparison to other plastics): • Outstanding temperature resistance; • Outstanding electrical properties; • Outstanding chemical resistance; • Lower coefficient of friction; • Better toughness.”

Part of their robust reputation and versatility stems from the fact that, “All fluoropolymers are normally regarded as completely insoluble.

Only perfluorocarbons, perfluorocarbon www.offshoretechnologyreports.com | 7

SPECIAL REPORT: NEXT GENERATION HIGH PERFORMANCE FLUOROPOLYMER AND CROSS-LINKABLE COMPOUND SOLUTIONS

Sometimes, even the considerable properties of a fluoropolymer can be enhanced by cross-linking with another product whose characteristics complement even those of the fluoropolymer

ethers, perhalocarbons, sulphur hexafluoride and carbon dioxide are known to dissolve fluoropolymers and only under the right conditions of temperature and pressure. Fluoropolymers resist chemical attack from virtually all acids, bases, and solvents. A complete chemical resistance chart is available. Because of the size of fluorine molecules, Fluoropolymers also have low chemical permeability.” This, again, from The Plastics Portal3.

Applications and History However, for all of these characteristics, it would be wrong to assume that fluoropolymers are only applied in high-tech and challenging situations. The Plastics Portal continues to explain that, “The best known member of this [fluoropolymer] family is called PTFE. PTFE is one of the smoothest materials around, and very tough! You can find it in most kitchens as a coating on pots, pans and many other utensils.

Fluoropolymers are also used to improve the performance and safety of racing cars and aircraft. They help protect big buildings from fire.

They can also be found in the coatings of the cabling for telephones and computers.”

Despite these very modern applications, fluoropolymers have been with us for well over half a century. Wise Geek4 tells us that, “A fluoropolymer is a synthetic carbon-based plastic, rubber or resin used to manufacture high-performance industrial coatings. Strong, lightweight, nonstick and durable, fluoropolymers are often valued for their resistance to heat, water, salt and chemicals in some of the most extreme environments. Developed in 1938 by accident, Teflon™ fluoropolymers were first used in 1945 for military purposes. Later, the unique properties of this cost-effective synthetic plastic proved useful in a variety of industries including the automotive, aerospace, and telecommunication industries. In fact, most people have come into contact with a product that was made from a fluoropolymer. Coated wires, semiconductors, and Teflon™ cookware include parts made from fluoropolymers. Some weatherproof clothing uses fluoropolymers for its resistance to moisture.” This is a truly versatile group of materials.

Going back to that early history, the ‘accidental’ development refers to the fact that 5, “In 1938, polytetrafluoroethylene (DuPont brand name Teflon) was discovered by accident by a recently-hired DuPont Ph.D., Roy J. Plunkett.

While working with tetrafluoroethylene gas, he noticed that a previously-pressurized cylinder had no pressure remaining. In dissecting the cylinder, he found a mass of white solid in a quantity similar to that of the tetrafluoroethylene gas. It was determined that this material was a

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new-to-the-world polymer. Tests showed the substance was resistant to corrosion from most substances and had better high temperature stability than any other plastic.

By early 1941, a crash program was making commercial quantities.

Cross-Linking Sometimes, even the considerable properties of a fluoropolymer can be enhanced by crosslinking with another product whose characteristics complement even those of the fluoropolymer.

Again there is a technical way of describing this process6, “A cross-linkable fluoropolymer dispersion… involves a polymer product of at least one polymerizable acrylic and/or vinyl containing monomer and at least one hydrolytically stable silane containing monomer… in the presence of an aqueous dispersion of at least one fluoropolymer.”

Offshore Oil and Gas Because of their remarkable qualities, it is not surprising that fluoropolymers have found applications within the offshore oil and gas industry. There are many functions for which equipment with a fluoropolymer coating will be able to perform better for longer without the need for maintenance interventions.

For instance, cables sheathed with the material will be safer and able to operate effectively for longer; equally, pipes can employ the characteristics of fluoropolymers both outside (to shield against the elements and corrosive environments) and inside to ease the passage of products whilst resisting abrasion and chemical damage. Also, hoses and a whole range of fixtures and fittings benefit from being able to function for more time in the challenging environments that typify an offshore oil and gas installation.

A Happy Accident Fluoropolymers sit at the pinnacle of materials development and without their use much of what we take for granted in the modern world, let alone the world of engineering, might simply not exist. With incredibly low levels of friction and adhesion to other materials plus a resistance to threats likely to be encountered in even the most challenging offshore operations, this group of plastics can ensure that your fried egg slips effortlessly onto the plate or that abrasive and corrosive product being pumped from a deep sea oil well can travel unhindered along its pipe to the processing plant, or that the pipe can sit for years under hundreds of feet of salt water or in a constant salt spray… and all from the unintended consequence of an accidental outcome.

SPECIAL REPORT: NEXT GENERATION HIGH PERFORMANCE FLUOROPOLYMER AND CROSS-LINKABLE COMPOUND SOLUTIONS

The Market for Fluoropolymers Peter Dunwell, Correspondent

What has made these plastics such ubiquitous ingredients in almost every market there is and what do they add?

Function Drives the Market The markets for fluoropolymers are very much a function of the material’s exceptional and unusual characteristics such as its, “high resistance to solvents, acid, and bases. Fluoropolymers have… non-stick and friction reducing properties about them. They are often used to line the interior of large metal and non-metal containers.”7 Those qualities have created applications from non-stick cookware to the automotive industry and aerospace industries and a whole range of engineering applications where fluoropolymers’ resistance to chemicals, climate and other environmental challenges as well as the fact that it is often referred to as ‘the slippery substance known to man’ has not only made established processes better, but have also made new processes possible.

It all springs from what Fluorotherm8 calls, “The chemical structure of fluoropolymers (also called fluoroplastics) [which] primarily consists of carbon and fluorine.”

In continuing to explain the success of fluoropolymers and their superior performance compared to other plastics, Fluorotherm adds, “In general, the chemical resistance of these materials is superior to most other families of plastics. This ‘chemically inert’ characteristic is closely allied to their superior performance in ultrapure environments. The chemical inertness varies between the fluoropolymers. The fully fluorinated resins such as PTFE, FEP, PFA and MFA exhibit chemical inertness to a wider range of chemicals than do the partially fluorinated polymers such as CTFE (or PCTFE) and ECTFE. A better property in one or two areas is accompanied by a diminished property in others (for example PTFE is better than PVDF in chemical resistance but it has lower mechanical properties at normal ambient temperatures. Fully fluorinated polymers (Perfluoropolymers) such as PTFE, FEP and PFA offer better thermal (higher use temperature) and chemical resistance properties than their partially fluorinated counterparts like ECTFE or PCTFE.

However, partially fluorinated resins possess better mechanical properties, such as tensile strength, toughness, abrasion and cut-through resistance at ambient temperatures.”

Main Markets As has already been suggested, many of the markets for fluoropolymers are mundane, even domestic, including roof coatings, plastic siding finishes, wood composite decking finishes and particularly consumer house paints.9 “The performance properties that accompany a PVdFcontaining coating are excellent weatherability and color fade resistance, dirt pickup resistance, and mildew resistance.” But it isn’t only in the domestic market that fluoropolymers have found a valued place. In the opening paragraph of the PaintSquare article quoted above, the author, Bob Parker of AGC Chemicals Americas, cites “Fluoropolymer on the Tsurumi Tsubasa Bridge over Yokohama Bay in Japan” and that, “The Akashi-Kaikyo Bridge has fluoropolymer protection against the aggressive environment of Japan’s Akashi Strait.” www.offshoretechnologyreports.com | 9

SPECIAL REPORT: NEXT GENERATION HIGH PERFORMANCE FLUOROPOLYMER AND CROSS-LINKABLE COMPOUND SOLUTIONS

Fluoropolymer resins, through the highperformance of the applications for which they are used, their durability and longevity are intrinsically ‘green’ materials from the outset

Demand and Growth According to Wikipedia10, “The global demand on fluoropolymers was estimated at approximately 7.25 billion USD in 2011. Driven by new developments of products, applications, and processes, as well as strong demands in new markets, the demand is expected to grow by 5.8% in the following years.” Putting that into volumes, The Plastics Portal estimates “… that the world market for fluoropolymers is between 80,000 and 90,000 tons per year. Although fluoropolymers represent just 0.1% of all plastics, their outstanding performance characteristics have made them a valuable catalyst in improving the quality of our lives.”

The Market Report ‘Global Fluoropolymer Market’11 from Acmite Market Intelligence adds that, “The fluoropolymer market presents strong growth driven by the development of new applications and products, advancement of application processes, and new technological developments, as well as strong demands in new markets.” Confirming the financial values of the market (see above) the report continues with, “Petrochemical & chemical processing presents the largest application market, and North America and Western Europe are the largest production and consumption markets of fluoropolymers. With unique properties, distinct performance characteristics, and many new developments in processes and technologies, fluoropolymers provide a market with opportunities and potential.”

A Range of Sectors The sectors in which the characteristics of fluoropolymers are valued are many and varied.

Just a few are cited in the Product Knowledge Network article ‘What are fluoropolymers used for?’12 “Because of their unique qualities (which include great strength, versatility, durability and heat resistance), fluoropolymers improve the performance and safety of such things as aircraft and automobiles, reduce risk of fire in high-rise buildings, and reduce air, water, industrial and automotive pollution.”

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With applications in aerospace and the military, automotive and transportation sectors, chemical and petrochemical processing, semiconductor and electronics manufacturing, telecommunications, and power generation and pollution control, fluoropolymers have penetrated most significant industrial markets.

To summarise the conclusions of SPI, the plastics industry trade association, because of their inherent durability and qualities of resistance, fluoropolymers protect13.

It’s Also a Green Issue Of course, with any overview of the market these days, we cannot ignore the green agenda. Fluoropolymer resins, through the high-performance of the applications for which they are used, their durability and longevity are intrinsically ‘green’ materials from the outset. This is a summary of the conclusion of the PaintSquare article ‘A green evolution in fluoropolymer chemistry’14, which sets out the green credentials for the products.

At the other end of the timeline, The Plastics Portal looking at ‘Recovery and Disposal of Fluoropolymer Waste’ 15 explains…

“Fluoropolymers are usually employed in small components in specific complex applications such as electronic equipment, transport (cars, trains and airplanes) or as very thin layer coatings on fabrics and metals. Where sufficient quantities of fluoropolymers can be recovered and may be sufficient to warrant recycling then they should be shipped to specialist recyclers.

A very substantial market exists for recovered fluoropolymers as low friction additives to other materials. For example PTFE is typically ground into fine powders and used in such products as inks and paints.

“Fluoropolymer waste should be incinerated in authorised incinerators. Preferably, nonrecyclable fluoropolymers should be sent to incinerators with energy recovery. Disposal in authorised landfills is also acceptable.”

From outset to end of life, fluoropolymers are a useful group of products.

SPECIAL REPORT: NEXT GENERATION HIGH PERFORMANCE FLUOROPOLYMER AND CROSS-LINKABLE COMPOUND SOLUTIONS

A Developing Technology Francis Slade, Staff Writer Fluoropolymer technology has found aplications across the industrial landscape

I

n an environment such as offshore oil and gas, protection is very important in the design and manufacture and finish of any component in the system. Whether through corrosion or accretion, wear to the smallest component can bring a multimillion dollar operation to halt.

Corrosion Corrosion risks are categorised at five levels: • Buried in soil; • Under water zone (UZ); • Intermediate zone (IZ); • Splash zone (SZ); • Atmosphere zone (AZ).

According to Shield Products’ paper, ‘fluoropolymers for offshore and oil-and gas industries’16 “The highest level of corrosion is found in the UZ, IZ and SZ areas of any offshore structure. Corrosion protection is done via Active Protection, Passive Protection and Temporary Protection. Active Protection is controlled at the design stage by means of Material and Construction Details. Temporary Protection is done where the equipment is not critical and changing design is possible.

Passive Protection is done via the means of Coatings and Surface Protection Methods.”

Fluoropolymers and cross-linkable compound solutions can be utilised at any of these protection levels. As the paper concludes, “[Their] properties frequently make Fluoropolymer the product of choice when metals and less expensive plastics fail or where long term reliability is required. Fluoropolymers are often used to solve existing problems or to develop new technology. Despite a relative extra cost, Fluoropolymers have frequently been used to substantially reduce overall system cost.”

These views are supported in PaintSquare’s article, ‘Fluoropolymers for High-Performance Applications’17. “In the increasingly complex world of protective finishes, fluoropolymerbased coatings have gained a respectable position in today’s marketplace... The common thread of their performance is their resistance to degradation caused by the ultraviolet (UV)

rays of the sun.” The article continues to explain that, “The barrier that they [fluoropolymers] form on the surface of the metal structure will outlast other coatings by a factor of 4 to 5.

One exposure test in a marine environment showed a surface erosion of only 0.2 mils after 16 years of exposure. One mil of an acrylic polyurethane finish, exposed at the same time, eroded away in 13 years. Secondly, the presence of fluorine atoms is a deterrent to water migration through the film. Less water migration means less corrosion.”

Accretion and Fouling If the application of fluoropolymer-based coats can resist corrosion it can also deter accretion, fouling by the accumulation of slime. As soon as a structure enters the water, slime begins to cultivate anywhere it can get a grip which, on a conventional metal structure, will be almost everywhere. The problem with using specific and active chemicals to combat slime is that18, “The make-up of Marine slime or biofilms is so diverse that samples from one part of a [structure] could be completely different to biofilms from a few metres away.” Also, any chemicals will have undesirable side-effects in their impact on the environment in which they are used. The strength of using fluoropolymer-based coating is that it is not formulated to combat the slime but rather, through its own high level of slipperiness (a passive quality) simply releases the slime from the structure.

Also, these days, any articles of any intricacy or shape can be processed. This is all down to what fluoropolymer coatings are. According to Kirtan R Dhami in his article ‘High Performance Corrosion Resistance – Fluoropolymer/PTFE Coated Fasteners for Offshore and Oil Gas Industries – Coatings for the 21st Century’19 “… [they are] blends of high-performance resins and Fluoropolymer lubricants. Most of the useful properties of fluoropolymer are due to fluorine, the most electro-negative element and the most reactive non-metal. Its atomic radius is the smallest next to hydrogen, and it forms extremely strong bonds with other elements.

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SPECIAL REPORT: NEXT GENERATION HIGH PERFORMANCE FLUOROPOLYMER AND CROSS-LINKABLE COMPOUND SOLUTIONS

Properties frequently make fluoropolymer the product of choice when metals and less expensive plastics fail or where long term reliability is required.

Fluoropolymers are often used to solve existing problems or to develop new technology

the extremely strong, tight bond produces an extraordinary combination of properties.”

Other Uses As well as helping to prevent corrosion and fouling, fluoropolymer coatings can extend maintenance periods and lifetimes of equipment.

The article ‘Composite materials in offshore oil and gas industry’ from Philip Medlicott Ltd20 confirms “… polymer composite materials are used to strengthen all repairs steel structures, piping, vessels and tanks as an alternative to replacement. Large cost savings are possible because the technology enables a significant reduction or even elimination of platform shut down and avoidance of hot work.”

The requirements of the offshore sector are evolving all of the time. Kirtan R Dhami (see above) explains (author’s synopsis) that cleaning and painting of bolts (or other parts) in situ is difficult to impossible and all such fixings are expected to be in water (or an 12 | www.offshoretechnologyreports.com

inhospitable atmosphere) for an extended period which, as they corrode, would make tightening or adjustment impossible even if they were accessible. And yet, some bolts and fixings are likely to need to be tightened or loosened to compensate for wear as equipment ages.

Perhaps the best expectation for the future can be found in the conclusion to the PaintSquare article (see 17 above): “It is evident that the future of protective coatings will include fluoropolymer chemistry and its diversified products. The ability of the resins present in these coatings to be used in combination with so many different raw materials and to fine-tune the properties of the coating to a specific level makes them a versatile addition to every formulator’s tool box. Newer fluoropolymer technologies are still being pursued at the development level. It will be important to keep an eye on what this technology can do to improve protective coatings down the road.”

SPECIAL REPORT: NEXT GENERATION HIGH PERFORMANCE FLUOROPOLYMER AND CROSS-LINKABLE COMPOUND SOLUTIONS

Challenges, Solutions and Considerations John Hancock, Editor

There are many challenges in offshore oil and gas: for equipment wear and tear issues, fluoropolymers often provide the solutions

C

“

orrosion is a very serious issue in oil and gas companies who are into oil exploration [and production] by means of platforms. The damage due to corrosion sometimes accounts to thousands of dollars.

For this reason, major metallic equipment and parts must be protected [with] corrosion resistance. Although commonly used methods of corrosion protection are [available], over years in the market a demand and requirements [have evolved for] coating for specific applications and saline water resistance: there is a real need for long term protection. Here emerges the market for Fluoropolymers.”21 The above words from Shield Products outline the challenge for fixings and components used in offshore oil and gas; they also point to a very practicable solution – the use of fluoropolymer based coatings and compounds. Having been around for over fifty years, fluoropolymers have grown into a family of products blending the strengths that made them so useful from the outset with more recent developments to extend the range of their applications.

In its Technology White Paper, ‘Introduction to Fluoropolymers’22 Zeus records that; “PTFE was used extensively in the Manhattan Project [to develop the atom bomb] to handle corrosive compounds such as uranium hexafluoride.

Due to its full fluorination, it still has some of the best properties of the family today. The major disadvantage with PTFE is the very high melt viscosity that makes processing difficult by the normal methods of extrusion and injection molding. Processing technologies have more similarity to those of powder metallurgy than those of traditional plastics processing. This led to a search for melt-processable fluoropolymers...”

The paper includes a family tree (reproduced below) of the fluoropolymer group and different compounds that have been developed to meet varying demands.

Durability There are reasons why traditional coating methods are being replaced by fluoropolymer coatings in many applications. Further on in the Shield Products article (see 21 above) the author explains that, “Extensive testing and field use

The fluoropolymer family Source: Zeus Technical Whitepapers

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SPECIAL REPORT: NEXT GENERATION HIGH PERFORMANCE FLUOROPOLYMER AND CROSS-LINKABLE COMPOUND SOLUTIONS

As with any product or solution in which a range of variations has been developed to suit an array of purposes, the choice of which product or solution to use can become an operational challenge in itself

have proven that the future of coated fasteners lies with Fluoropolymer Coatings. Previously, hot dip galvanized cadmium or zinc plated fasteners were considered the standard. But these coatings could not stand up to the corrosive atmospheres prevalent in many industries. After 500 hours of salt spray testing (ASTM B117), fasteners coated with these conventional methods showed severe corrosion and, in some cases, failure. Fasteners coated with… Fluoropolymer coating withstood these harsh conditions with no noticeable deterioration even after as many as 1,000 hours [and] coated fasteners still could be easily disassembled.”

A number of offshore operators are beginning to see the benefits of using high-performance fluoropolymer coatings. For instance the Scottish company, Hyspec Engineering24 make extensive use of fluoropolymer based surface treatments in the components for their deep sea drilling equipment which is frequently exposed to extreme conditions. In particular, they use the coatings on their downhole motor assemblies and drill components, improving the efficiency of the equipment and, in turn, extending the range of operations in which the equipment is capable: plus, of course, it extends the life of the equipment.

Safety

Chemical Resistance

This is important for offshore oil and gas where fixings and components are subject to harsh salt laden conditions; also, when maintenance and repairs have to be made, ease of disassembly and reassembly not only speeds the job in whatever conditions are prevalent at the time but also support the sector’s all-important health and safety ethos. Workers undertaking repairs and maintenance need not take unnecessary risks in order to disassemble a unit nor will they be exposed in a hazardous position for longer than necessary.

In addition to all of these capabilities, fluoropolymers are also resistant to most chemical attacks and that is of particular value in the offshore oil sector where the product carried through a pipe is often inherently chemically corrosive.

As with any product or solution in which a range of variations has been developed to suit an array of purposes, the choice of which product or solution to use can become an operational challenge in itself. It is critical that the correct fluoropolymer types are matched to the particular operational challenges that they will face. Likely sources of attack (corrosion, fouling, etc.) as well as actual and foreseeable technical requirements (likelihood that interventions and adjustments will be required during the operational life of any assembly) will need to be taken into account when specifying the particular fluoropolymer to be used. Also cost considerations have to be taken into account over the long- as well as the short-term. While conventionally coated fixings and components might cost less at the time of initial assembly, any savings here may be offset by an increased frequency of maintenance events or a reduced level of long-term reliability.

As with anything in the offshore oil and gas sector, considerations are never simple but subject to a matrix of conditions, stresses and outcomes that will impact upon the equipment and decisions about it.

Environmentally Friendly As well as corrosion, fouling can as easily diminish the functionality of any component or assembly.

In their report, ‘Advances in marine antifouling coatings and technologies’23 C Hellio and DM Yebra explain that, “Items submerged in water, especially those in the littoral zone, are potential sites for the growth of marine organisms… The introduction of man-made structures (… offshore installations or renewable energy systems) presents these organisms with additional surfaces to occupy… It is normal practice to apply anti-fouling coatings (AFC) containing biocides to man-made structures in the marine environment ... However, where there is a high density of surfaces with AFC, the level of toxins could exceed sensible limits with consequences for the ecosystem. New approaches include… foul release (‘non-stick’ fluoropolymers and siloxanes) coatings...”

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SPECIAL REPORT: NEXT GENERATION HIGH PERFORMANCE FLUOROPOLYMER AND CROSS-LINKABLE COMPOUND SOLUTIONS

References: 1

The Plastics Portal, ‘What are Fluoropolymers?’ http://www.plasticseurope.org/what-is-plastic/types-of-plastics/fluoropolymers/what-are-fluoropolymers.aspx

2

Zeus Technical White Paper ‘Introduction to Fluoropolymers’

http://www.zeusinc.com/UserFiles/zeusinc/Documents/Zeus_introduction_fluoropolymers.pdf 3

The Plastics Portal, ‘Fluoropolymers’

http://www.plasticseurope.org/what-is-plastic/types-of-plastics/fluoropolymers/what-makes-fluoropolymers-so-versatile.aspx

4

Wise Geek ‘What is a Fluoropolymer?’ http://www.wisegeek.com/what-is-a-fluoropolymer.htm

5

Wikipedia http://en.wikipedia.org/wiki/Fluoropolymer

6

docstoc http://www.docstoc.com/docs/53072244/Cross-linkable-Aqueous-Fluoropolymer-Based-Dispersions-Containing-Silanes---Patent-6833414

7

Articlesbase, Uses and Advantages of Fluoropolymer

http://www.articlesbase.com/business-articles/uses-and-advantages-of-fluoropolymer-1024557.html

8

Fluorotherm, ‘Overview of Fluoropolymers’ http://fluorotherm.com/Overview.asp

9

PaintSquare, ‘Fluoropolymers for High- Performance Applications‘ http://www.paintsquare.com/archive/?fuseaction=view&articleid=4891

10

Wikipedia http://en.wikipedia.org/wiki/Fluoropolymer

11

Acmite Market Intelligence ‘Global Fluoropolymer Market’ www.acmite.com/brochure/Brochure-Global-Fluoropolymer-Market-Report.pdf

12

Product Knowledge Network article ‘What are fluoropolymers used for?’

http://www.productknowledge.com/fluoropolymers-what-are-fluoropolymers-used-for.html# 13

SPI, http://www.fluoropolymer-facts.com/Benefits/BenefitsList.cfm?navItemNumber=4038

14

PaintSquare, ‘A green evolution in fluoropolymer chemistry’

15

16

http://www.paintsquare.com/archive/?fuseaction=view&articleid=3785&CFID=10711378&CFTOKEN=86674116 The Plastics Portal, ‘Recovery and Disposal of Fluoropolymer Waste’ http://www.plasticseurope.org/what-is-plastic/types-of-plastics/fluoropolymers/recovery-and-disposal-of-fluoropolymer-waste.aspx Shield Products’ paper on ‘fluoropolymers for offshore and oil-and gas industries’ http://uk.search.yahoo.com/r/_ylt=A7x9QV7SBQ1Sp24A7hVLBQx.;_ylu=X3oDMTByNGxmazk4BHNlYwNzcgRwb3MDMQRjb2xvA2lyZAR2dGlkAw--/SIG=13lvq7ied/ EXP=1376613970/**http%3a//www.shieldproducts.com/PRODUCT%2520PDF/GENERAL%2520INFO/Off-Shore%2520Oil%2520Drilling.pdf

17

PaintSquare, ‘Fluoropolymers for High-Performance Applications’ http://www.paintsquare.com/archive/?fuseaction=view&articleid=4891

18

International Marine Coatings

19

http://www.international-marine.com/foulrelease/slime-release-coatings.aspx

Kirtan R Dhami

http://www.oilgasarticles.com/downloadattachment.php?aId=58dcd57ddadc2468d6b49b41a1425032&articleId=490 20

‘Composite materials in offshore oil and gas industry’ Philip Medlicott Ltd http://www.medlicott.uk.com/CompOilIndustry.html

21

Shield Products’ paper on ‘fluoropolymers for offshore and oil-and gas industries’ http://uk.search.yahoo.com/r/_ylt=A7x9QV7SBQ1Sp24A7hVLBQx.;_ylu=X3oDMTByNGxmazk4BHNlYwNzcgRwb3MDMQRjb2xvA2lyZAR2dGlkAw--/SIG=13lvq7ied/ EXP=1376613970/**http%3a//www.shieldproducts.com/PRODUCT%2520PDF/GENERAL%2520INFO/Off-Shore%2520Oil%2520Drilling.pdf

22

Zeus Technical White Paper ‘Introduction to Fluoropolymers’

http://www.zeusinc.com/UserFiles/zeusinc/Documents/Zeus_introduction_fluoropolymers.pdf 23

24

C Hellio and DM Yebra, ‘Advances in marine antifouling coatings and technologies’ http://www.iom3.org/book-review/advances-marine-antifouling-coatings-and-technologies Hyspec Engineering

http://www.surfacetechnology.co.uk/userfiles/hyspec_case_study.pdf

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