Document j7m9DJQZv83Rqwjbek8rxvdZ

American Petroleum Institute European Chemicals Agency (ECHA) Telakkakatu 6, 00150 Helsinki, Finland September 11, 2023 RE: ECHA Annex XV Restriction Report: Per- and Polyfluoroalkyl substances (PFAS) Dear Sir or Madam: As a follow up to the July 31, 2023, submission of the American Petroleum Institute (API) to the European Chemicals Agency (ECHA) on its proposed restriction on per- and polyfluoroalkyl substances (PFAS), API respectfully offers a second submittal which provides exceptional analysis by Arcadis U.S. Inc (Arcadis). The attached Arcadis report further demonstrates the critical uses of certain PFAS, particularly fluoropolymers that researchers have shown meet the Organisation for Economic Co-operation and Development (OECD) criteria for "polymers of low concern," 1 in the oil and natural gas industry. API is the U.S. national trade association representing all facets of the oil and natural gas industry, which supports nearly 10 million U.S. jobs and 8% of the U.S. economy and provides critical energy to the European continent. While API represents North American-based companies, API membership includes multinational corporations with business in Europe and U.S. companies that trade with the European Union (EU), both of which would be significantly affected by the proposed PFAS restriction. API's approximately 600 members include large integrated companies, as well as exploration and production, refining, marketing, pipeline, marine businesses, and service and supply firms. Additionally, API is the global leader in convening subject matter experts across segments to develop, maintain, and distribute consensus standards and safety programs for the oil and natural gas industry. API's goal is to enhance operational safety, environmental protection, and sustainability across the industry, especially through the global adoption of standards. API standards are developed under the American National Standards Institute (ANSI) accredited process, ensuring the standards are recognized not only for their technical rigor but also for their thirdparty accreditation. This accreditation facilitates the incorporation of API standards into regulations by state, federal, and international regulators. API's July 31, 2023, submission to ECHA provided a thorough examination of API standards that specifically reference the direct use of PFAS in equipment and operations or require the use of PFAScontaining equipment to meet certain safety criteria -- indicating their essential use in various equipment and materials to ensure operational safety and integrity across all segments of the industry. In a separate undertaking, to better understand the extent of fluoropolymer use in the upstream (exploration and production), downstream (petroleum refining), and associated segments of the industry (e.g., transportation and storage), API contracted with Arcadis in early 2023 to evaluate the published literature and patents to identify the nature, volumes, and timing of PFAS use in these key segments. This search considered linings that might be present in piping, valves, flowmeters, and tanks; materials used in high-temperature and high-pressure applications such as gaskets, seals, rings, liners, and packer elements; cable and wiring insulation, including communication at the bottom of a well; and other applications necessary for safe operations. Additionally, attention was given to whether the fluoropolymers that are in use today can readily be replaced by alternative chemistries or techniques. 1OECD 'Data Analysis of The Identification Of Correlations Between Polymer Characteristics And Potential For Health Or Ecotoxicological Concern"; Joint Meeting Of The Chemicals Committee And The Working Party On Chemicals, Pesticides And Biotechnology. January 27, 2009: https://www.oecd.org/enviehs/riskassessment/42081261.pdf 200 Massachusetts Avenue NW, Suite 1100, Washington, DC 20001-5571 USA api.org ECHA Annex XV Restriction Report: Per- and Polyfluoroalkyl substances (PFAS) Page Two September 11, 2023 As the attached Arcadis summary report and accompanying detailed slide deck describe, Arcadis reviewed 18 fluoropolymers that researchers2 determined fit the OECD criteria of "polymers of low concern" and identified solid fluoropolymer and equipment applications for 17 of the 18 fluoropolymers; no applications were identified for ionomer fluoropolymers. Of the 17 fluoropolymers with identified oil and natural gas applications, the upstream sector had more applications than the downstream sector, and PVDF (homopolymer) and FFKM exhibit the widest range of applications in the industry. A timeline tracking the introduction of these chemicals to the oil and natural gas industry was created based on patent data, stretching from 1997 to 2019. Benefits, patents, and applications of each fluoropolymer were researched and categorized as one of three fluoropolymer subtypes (fluoroplastics, fluoroelastomers, and specialty fluoropolymers). Specifically, within Appendix 1 of the Arcadis report, slide number 9 provides an extensive overview of uses in the oil and natural gas industry and slide number 13 illustrates that different polymers are suitable for various fluids and temperatures, emphasizing the benefits of fluoropolymer performance in extreme conditions. Under the section Research Findings, beginning on slide number 16, a review of each of the 17 fluoropolymers includes a description of its uses in the industry and the benefits provided. On slide number 48, limited alternatives for a few fluoropolymers were identified, including cautions on those applications. The Arcadis review and findings further supports API's previous recommendations to ECHA to reconsider components of the restriction, including the broad classification of all PFAS and applying the restriction to fluoropolymers, particularly those that meet the criteria for "polymers of low concern." API additionally recommends inclusion of risk-based approaches. Finally, API urges ECHA to grant a permanent derogation for the essential uses of particular PFAS and fluoropolymers of low concern for all segments of the oil and natural gas industry, emphasizing that public exposure to these chemicals is minimal. PFAS-containing equipment and materials in the oil and natural gas industry do not have viable alternatives that effectively and consistently meet the unique, combined criteria of corrosion resistance, thermal tolerance, durability, excellent sealing properties, lubricity, dielectric strength, flexibility, and low flammability that are necessary to meet industry operational demands. API appreciates the opportunity to provide additional supporting material for ECHA's consideration as it reviews public input on the Annex XV Restriction Report: Per- and Polyfluoroalkyl substances (PFAS). Please feel free to contact us if you have questions or require additional information. Sincerely, Holly Hopkins Vice President, Upstream Policy @api.org RittOrnerA.,__ Will Hupman Vice President, Downstream Policy 2Korzeniowski, S.H., Buck, R.C., Newkold, R.M., Kassmi, A.E., Laganis, E., Matsuoka, Y., Dinelli, B., Beauchet, S., Adamsky, F., Weilandt, K., Soni, V.K., Kapoor, D., Gunasekar, P., Malvasi, M., Brinati, G. and Musio, S. (2023), A critical review of the application of polymer of low concern regulatory criteria to fluoropolymers II: Fluoroplastics and fluoroelastomers. Integr Environ Assess Manag, 19: 326-354. https://doi.org/10.1002/ieam.4646 ARCADIS Fluoropolymers in the Oil and Gas Industry Literature Review August 29, 2023 Prepared By: Arcadis U.S., Inc. 10205 Westheimer Road, Suite 800 Houston Texas 77042 Phone: Fax: Our Ref: 30172078 Prepared For: American Petroleum Institute This document is intended only for the use of the individual or entity for which it was prepared and may contain information that is privileged, confidential and exempt from disclosure under applicable law. Any dissemination, distribution or copying of this document is strictly prohibited. www.arcadis.com Contents Executive Summary................................................................................................................................................. ii 1 Introduction ...................................................................................................................................................... 1 2 Methodology .................................................................................................................................................... 2 3 Key Findings .................................................................................................................................................... 2 4 Areas of Additional Study..........................................................................................................3 5 References ....................................................................................................................................................... 4 Tables Table 1 Fluoropolymers included in the literature review................................................................................... 1 Appendix Appendix 1 Literature Search Slides Executive Summary Arcadis identified solid fluoropolymer applications for 17 of the 18 fluoropolymers of low concern; no applications were identified for ionomer fluoropolymers. Of the 17 fluoropolymers with identified oil and gas applications, the upstream sector had more applications than the downstream sector, and PVDF and FFKM exhibit the widest www.arcadis.com ii range of applications. A timeline tracking the introduction of these chemicals to the oil and gas industry was created based on patent data, stretching from 1997 to 2019. Benefits, patents, and applications of each fluoropolymer were researched and presented as one of three fluoropolymer subtypes (fluoroplastics, fluoroelastomers, and specialty fluoropolymers). Alternatives to select fluoropolymers were identified. www.arcadis.com iii 1 Introduction Arcadis U.S., Inc. (Arcadis) has prepared this report summarizing the methodology and findings of the literature review conducted on fluoropolymer use in the oil and gas industry for the American Petroleum Institute (API). Applications of solid fluoropolymers and equipment pre-coated with fluoropolymers (hereafter referred to as `solid fluoropolymers') relevant to upstream and downstream oil and gas applications were the focus of this review. The list of fluoropolymers of interest in this review included four fluoropolymers identified in the peer-reviewed journal article by Henry et al. (2018) and 14 fluoropolymers identified in the peer-reviewed journal article by Korzeniowski et al. (2022). Collectively, the two articles identified the following 18 fluoropolymers as fluoropolymers of low concern, based on criteria established by the Organization for Economic Co-operation and Development (OECD). Table 1 Fluoropolymers included in the literature review. Fluoropolymer Abbreviation Fluoropolymer Name Amorphous Amorphous fluoropolymers CPT Chlorotrifluoroethylene-tetrafluoroethylene ECTFE copolymer Ethylene-chlorotrifluoroethylene copolymer ECTFE terpolymer Ethylene-chlorotrifluoroethylene terpolymer EFEP Ethylene-tetrafluoroethylene-hexafluoropropylene ETFE Ethylene tetrafluoroethylene FEP Fluorinated ethylene propylene FEPM Trifluoroethylene-propylene copolymer FEVE Fluoroethylene-vinyl ether FFKM Tetrafluoroethylene-trifluoromethyl trifluorovinyl ether (TFE-PMVE) perfluoroelastomer FKM Hexafluoropropylene-vinylidene fluoride (HFP-VF2) polymer and hexafluoropropylene-vinylidene fluoride-tetrafluoroethylene (HFP-VF2-TFE) polymers Ionomer Fluorinated ionomers PCTFE Polychlorotrifluoroethylene PFA Tetrafluoroethylene copolymers with perfluoroalkyl vinyl ethers (e.g., perfluoroalkoxy polymer, PFA) PTFE Polytetrafluoroethylene PVDF copolymer Polyvinylidene fluoride copolymer PVDF homopolymer Polyvinylidene fluoride homopolymer THV Tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride (TFE-HFP-VF2) terpolymer www.arcadis.com 1 Detailed upstream and downstream applications for each of these solid fluoropolymers are presented in the accompanying slides (Appendix 1). An overview of the literature review methodology, findings, data gaps, and conclusions are presented in the text below. 2 Methodology The literature search included journal articles, textbooks, databases, patents, and manufacturer/supplier websites. These sources were screened for relevance to research-specific keywords and search strings. In addition to the names and acronyms of the individual fluoropolymers identified for research in Table 1, the following list shows examples of keywords that were used in various combinations to search for known uses of fluoropolymers in the oil and gas industry: PFAS perfluoro fluoro fluoropolymers fluorinated polymers oil and gas petroleum perfluoroelastomer seals oil and gas wells oil production heat exchangers Though many references were identified based on the searches performed, further screening to ensure that sources were relevant to the 18 fluoropolymers of focus and that they yielded a focused list of final references relevant to the literature review. Detailed citations are provided for each of the references in Appendix 1. Findings for each of the 18 fluoropolymers were categorized by upstream and downstream use, fluoropolymer type, trade name(s), year of invention, years of active use, related patents, product types, and standards. Arcadis identified 26 ASTM International (ASTM) standards, 12 International Organization for Standardization (ISO) standards, and 22 API standards related to fluoropolymer use. 3 Key Findings The 18 fluoropolymers of interest (Table 1) are high-performance polymers known for their thermal and chemical resistance, as well as their mechanical strength. These qualities make them well-suited for oil and gas applications, particularly in upstream applications, where durability, safety, and protection are crucial factors. Variations of these properties dictate which of the 18 fluoropolymers are used for specific oil and gas applications. Arcadis identified solid fluoropolymer applications for 17 of the 18 fluoropolymers; no applications were identified for ionomer fluoropolymers. Four main uses for these 17 fluoropolymers were identified: cable insulations, pipe linings, sealing materials (such as in valves, pumps, and O-rings), and equipment coatings. The fluoropolymers www.arcadis.com 2 have more upstream applications than downstream applications. Furthermore, the literature suggests that PVDF and FFKM are used in the widest range of applications. Arcadis constructed timelines to track the invention and usage of the 18 fluoropolymers within the oil and gas industry (Appendix 1). Specific dates of invention or market introduction were identified for 15 of the fluoropolymers. Only a general timeframe was determined for the remaining three: amorphous in the 1980s; ionomer in the mid-1960s; and FFKM in the mid-1970s. The timeline spans from 1937, when PCTFE was invented, to 2005, when the Neoflon CPT product line was launched. Published patents were used to identify dates of invention specific to the oil and gas industry when possible. The following eight fluoropolymers were identified in such patents: FEP PFA PTFE/Expanded PTFE (ePTFE) ETFE CPT PVDF ECTFE Amorphous The patent timeline starts in 1997 with the publication of Schlumberger's patent US 5,894,104 A, which patented a downhole cable insulated with fluoropolymer PFA. The timeline extends to 2019, when two patents were published: one for a multi-use oil and gas PVDF pipeline and another for a multi-layer tube/industrial pipe containing CPT, FEP, and PFA. Most patents identified were related to downhole cables or oil and gas pipelines. Further details are provided in Appendix 1. Specific fluoropolymer benefits, patents, and applications for each of the 18 fluoropolymers are presented in Appendix 1, where they are organized by three fluoropolymer subtypes (fluoroplastics, fluoroelastomers, and specialty fluoropolymers) as categorized by Korzeniowski et al. (2022) and Henry et al. (2018). In addition to the 18 fluoropolymers, Xylan is included. Xylan is a brand-name fluoropolymer coating line composed of fluoropolymers such as PTFE, PFA, and FEP, combined with a reinforcing binder. Although not part of the original scope, Xylan is included due to the presence of PTFE, PFA, and FEP in its composition and its widespread use in offshore drilling equipment. 4 Areas of Additional Study Arcadis researched alternative materials for the above applications in a preliminary effort to understand how essential these 18 fluoropolymers are to the oil and gas industry. Alternatives for PTFE, PVDF, FKM and precoated equipment include well-known and frequently used materials, as well as new inventions. These alternatives are presented in Appendix 1. The performance of alternatives in comparison to the identified fluoropolymers is an area of active research and analysis. www.arcadis.com 3 5 References ASTM International. Available online at: https://www.astm.org/products-services/standards-andpublications/standards/petroleum-standards.html Henry, B. J; Carlin, J. P; Hammerschmidt, J. A; Buck, R. C; Buxton, L W.; Fiedler, H.; Seed, J.; Hernandez, O. A Critical Review of the Application of Polymer of Low Concern and Regulatory Criteria to Fluoropolymers. Integrated Environmental Assessment and Management. 2018, 14 (3), 316- 334, DOI: 10.1002/ieam.4035. International Organization for Standardization. Available online at: https://www.iso.org/standards.html. Korzeniowski S et al. 2022. A critical review of the application of polymer of low concern regulatory criteria to fluoropolymers II: Fluoroplastics and fluoroelastomers. Integrated Environmental Assessment and Management. 19 (2): 326-354. Petroleum Abstracts. The University of Tulsa. TULSA Database. Available online at https://www.pa.utulsa.edu/products/tulsadatabase. The Society of Petroleum Engineers. OnePetro. Available online at http://www.onepetro.org. URLs checked and confirmed on 29 August, 2023 www.arcadis.com 4 Appendix 1 Literature Search Slides www.arcadis.com A Arcadis U.S., Inc. 10205 Westheimer Road, Suite 800 Houston Texas 77042 Phone: Fax: www.arcadis.com Arcadis. Improving quality of life. Fluoropolymers in the Oil and Gas Industry A Literature Search for API August 21, 2023 APPENDIX 1 Our Team Stephanie Fiorenza, PhD Principal Scientist, Oil & Gas Sector Solution Lead Johnsie Lang, PhD PFAS Technical Expert Ruben Lopez Project Manager Katie Barry, PhD Emerging Contaminants Practice Area Co-Lead Andy Newcombe Vice President, Product Stewardship and Sustainability Fred Lont Library Director Agenda 1 Background 2 Research Findings: Overview of Uses 3 Research Findings: Specific Fluoropolymers 4 Research Findings: Standards that Identify Fluoropolymers 5 Final Notes Background Fluoropolymers of Low Concern Research focused on solid fluoropolymer applications and equipment pre-coated with aqueous fluoropolymers (McKeen 2017) Amorphous: Amorphous fluoropolymers CPT: Chlorotrifluoroethylenetetrafluoroethylene FKM: hexafluoropropylene-vinylidene fluoride (HFP-VF2) polymer and hexafluoropropylenevinylidene fluoride-tetrafluoroethylene (HFPVF2-TFE) polymers ECTFE copolymer: Ethylenechlorotrifluoroethylene copolymer ECTFE terpolymer: Ethylenechlorotrifluoroethylene terpolymer EFEP: Ethylene-tetrafluoroethylenehexafluoropropylene ETFE: Ethylene tetrafluoroethylene FEP: Fluorinated ethylene propylene Ionomer: Fluorinated ionomers PCTFE: Polychlorotrifluoroethylene PFA: Tetrafluoroethylene copolymers with perfluoroalkyl vinyl ethers (e.g., perfluoroalkoxy polymer, PFA) PTFE: Polytetrafluoroethylene PVDF copolymer: Polyvinylidene fluoride copolymer FEPM: Trifluoroethylene-propylene copolymer PVDF homopolymer: Polyvinylidene fluoride FEVE: Fluoroethylene-vinyl ether homopolymer FFKM: tetrafluoroethylene-trifluoromethyl trifluorovinyl ether (TFE-PMVE) perfluoroelastomer THV: tetrafluoroethylene- hexafluoropropylene-vinylidene fluoride (TFE-HFP-VF2) terpolymer References: McKeen M. 2017. Film Properties of Plastics and Elastomers. Fourth Edition. William Andrew. . Polymer Definitions Related to this Research Polymer: a large molecule composed of many smaller repeating units, known as monomers (Wade 1991) Homopolymer - polymer composed of only one type of monomer (Thomas and Weimin 2009) Copolymer - polymer composed of two or more types of monomers. Monomer units can have many arrangements (Thomas and Weimin 2009) - Terpolymer - polymer composed of three monomers (Gauthier 1995) Elastomer: polymer with elastic properties (Drobny 2009) (University of York 2023) References: Drobny, J.G. 2009. Technology of Fluoropolymers. 2nd Edition, CRC Press, Boca Raton, FL. Gauthier MM (ed.) 1995. Engineered Materials Handbook Desk Ediition. ASTM International. Thomas S and Y Weimin (eds). 2009. Advances in Polymer Processing, From macro to nano scales. CRC Press. New York, NY. University of York, Department of Chemistry. Essential Chemistry Industry. https://www.essentialchemicalindustry.org/polymers/polymers-an-overview.html. Accessed online 5 June 2023. Wade, LG. 1991. Organic Chemistry. Prentice-Hall, Inc. Englewood Cliffs, NJ. Arcadis 2022 11 September 2023 6 Literature Review Methodology Relevant Sources Reviewed Over 20 journal articles Nine textbooks Over 10 patents Over 20 supplier websites OnePetro and TULSA databases ASTM and ISO databases Google Scholar Arcadis 2023 11 September 2023 7 Research Findings: Overview of Uses Research Findings: Overview of Uses Fluoropolymer Applications in the Oil and Gas Industry Arcadis 2023 Cable Insulations: Fluoropolymers patented for cable insulations in deep drilling communications cables. Ensures reliable performance in challenging drilling environments. Pipe Linings: Fluoropolymer pipe linings used in oil pipelines, flexible tubing, and pipes. Enhances durability and resistance to corrosion. Valves, Pumps, O-Rings, and Sealing Materials: Fluoropolymers widely utilized in valves, pumps, o-rings, and sealing materials. Provides exceptional reliability and longevity in demanding oil and gas applications. Coatings for Equipment: Fluoropolymers employed in coatings for various equipment, including offshore marine uses. Offers increased performance and protection in harsh environments. 11 September 2023 9 Overview of Uses - Upstream Applications Fluoropolymer CPT ECTFE1 EFEP ETFE FEP FEVE PFA PTFE PVDF2 THV PCTFE FEPM FFKM FKM Amorphous Ionomer Drilling Applications Oil/ Gas Production Formation Evaluation Fluoroplastics No upstream uses identified. Fluoroelastomers Specialty No upstream uses identified. No upstream uses identified. Offshore Exploration General Upstream Use Applicable to Multiple Categories Footnotes: 1. Includes both the co- and terpolymer of ECTFE. 2. Includes both the homo- and copolymer of PVDF. 11 September 2023 10 Overview of Uses - Downstream Applications Fluoropolymer CPT ECTFE1 EFEP ETFE FEP FEVE PFA PTFE PVDF2 THV PCTFE FEPM FFKM FKM Amorphous Ionomer Hydrocarbon Processing Natural Gas/Oil Delivery Fluoroplastics No downstream uses identified No downstream uses identified Fluoroelastomers Specialty No downstream uses identified General Downstream Use Applicable to Multiple Categories Footnotes: 1. Includes both the co- and terpolymer of ECTFE. 2. Includes both the homo- and copolymer of PVDF. 11 September 2023 11 Overall Use Takeaways Arcadis 2023 More identified applications in the upstream sector compared to downstream Our research identified polyvinylidene fluoride (PVDF) and Kalrez (FFKM) as the fluoropolymers with the widest variety of O&G applications 11 September 2023 12 Fluoropolymers: Optimal Performance in Extreme Conditions Different polymers are suitable for various fluids and temperatures. Upstream applications (e.g., offshore and deep drilling) require higher temperature, pressure, and corrosion resistance. (Khalid et al., 2020) References: de Leon et al. 2021. High performance polymers for oil and gas applications. https://www.sciencedirect.com/science/article/pii/S1381514821000705 Khalid, H. U., M. C. Ismail, and N. Nosbi. 2020. Permeation Damage of Polymer Liner in Oil and Gas Pipelines: A Review. Polymers. 12, 2307. Arcadis 2023 (de Leon et al., 2021) 11 September 2023 13 Chronology of Fluoropolymer Invention and Manufacturing Ionomer Use Begins in the mid-1960's FFKM Introduced in the mid1970's Amorphous Polymer Use Begins in the 1980's 1937 1938 1948 1955 1956 1970 1972 1973 1975 1980 1996 2003 2005 PCTFE Discovered PTFE Invented PDVF Invented Viton-A (FKM) Developed by DuPont FEP First produced by DuPont ECTFE Invented ETFE Invented PFA Invented AGC Begins Selling Aflas (FEPM) FEVE Developed THV Use Begins Daikin Begins to Market Neoflon EFEP Neoflon CPT Product Line Launched Arcadis 2023 11 September 2023 14 Chronology of Fluoropolymers O&G Related Patents WO2006058270: Linings for oil pipes (includes FEP and PFA) WO2012019066: Cable insulation (includes PTFE, FEP, ETFE) US20140255 703A1: Downhole cables (includes ETFE copolymer) US9994371: break seals for shipping and dispensing systems (includes PTFE bonded to LDPE) JP2019006005A: Multi-layer tube/industrial pipe (includes CPT, FEP, and PFA) 1997 2006 2009 2012 2013 2014 2016 2018 2019 US5894104A: Cable insulation (Includes PFA) US20090277837A1: Fluoropolymer Coated Membrane (Includes Amorphous Fluoropolymer) US20130164441A1: Downhole cables (includes ETFE, ECTFE, PVDF, and FEP) US20160245042A1: Check valve (includes ePTFE) WO2019055670A1: multi-use oil and gas PVDF pipeline Arcadis 2023 (US9994371) Earliest patent use identified in 1997 Fluoropolymers patented for O&G: - FEP - PFA - PTFE/ePTFE - ETFE - CPT - PVDF - ECTFE - Amorphous 11 September 2023 15 Research Findings: Specific Fluoropolymers Fluoroplastics Fluoroelastomers Specialty Fluoroplastics CPT (chlorotrifluoroethylene-tetrafluoroethylene) Trade names include: Neoflon CPT, Neofron CPT Uses in the O&G industry: Patented Use (Japan): Multilayer industrial tube with an inner layer and an outer layer are constituted by a fluorine resin (Onoda et al. 2017) Benefits of this fluoropolymer: Good flexibility and excellent permeation resistance to organic solvents, water, vapor and gasoline Hot melt adhesion to the other plastics such as polyamide with its reactive group (Daikin 2018) Development: Developed specifically by Daikin (NEOFLON product launched in 2005) Terpolymer of chlorotrifluoroethylene, tetrafluoroethylene, and perfluoroalkyl-vinyl-ether. (Korzeniowski et al. 2022) (PubChem 2023) References: Daikin. 2012. Business Overview Daikin Fluorochemical Products. January. Daikin, "Neoflon CPT LP-1000," tds-lp-1000-E_ver01, March 2018. Korzeniowski S et al. 2022. A critical review of the application of polymer of low concern regulatory criteria to fluoropolymers II: Fluoroplastics and fluoroelastomers. Integrated Environmental Assessment and Management. 19 (2): 326-354. OnAordcaa, dKi.s, O20ko2d2a, T., and Hosoya, A., inventors; AOI Co Ltd, assignee. Glide flex tube. Japanese Patent JP 2019-006005 A. 17 Jan 2019. PubChem. National Institutes of Health. https://pubchem.ncbi.nlm.nih.gov/. Accessed online 5 June 2023. 11 September 2023 18 ECTFE terpolymer (ethylene chlorotrifluoroethylene terpolymer) Trade names include: No names specific to the terpolymer identified Uses in the O&G industry: No uses specific to the terpolymer identified Benefits of this fluoropolymer: Semicrystalline and fully-fluorinated melt processable fluoropolymer Better mechanical, abrasion, and radiation resistance compared to PTFE and other perfluoropolymers (Ebnesajjad 2013) Terpolymer of ethylene, chlorotrifluoroethylene, and hexafluoroisobutylene (Korzeniowski et al. 2022) Development: No development information specific to the terpolymer identified (PubChem 2023) References: DeLeon et al. 2021. High performance polymers for oil and gas applications. https://www.sciencedirect.com/science/article/pii/S1381514821000705 Ebnesajjad S (editor). 2013. Introduction to Fluoropolymers: Materials, Technology, and Applications. William Andrew KorzAernciaodwissk2i S02e2t al. 2022. A critical review of the application of polymer of low concern regulatory criteria to fluoropolymers II: Fluoroplastics and fluoroelastomers. Integrated Environmental Assessment and M11anSaegpemteemnbt.e1r92(022):3326-354. 19 PubChem. National Institutes of Health. https://pubchem.ncbi.nlm.nih.gov/. Accessed online 5 June 2023. ECTFE copolymer (ethylene chlorotrifluoroethylene copolymer) Trade names include: Halar Uses in the O&G industry: Halar ECTFE is used for cable jacketing and insulation in downhole cables (Solvay 2017) Powder-coated tanks and ducts (Drobny 2009; Solvay 2017) Benefits of this fluoropolymer: Hardness/toughness Transparent Resistant to most chemicals except hot polar and chlorinated solvents It does not stress, crack or dissolve in any solvents Better barrier to SO2, Cl2, HCl, and water than FEP and PVDF. Development: Partially fluorinated polymer developed by Solvay in 1970 (Ebnesajjad 2013) References: DeLeon et al. 2021. High performance polymers for oil and gas applications. https://www.sciencedirect.com/science/article/pii/S1381514821000705 Drobny, J.G. 2009. Technology of Fluoropolymers. 2nd Edition, CRC Press, Boca Raton, FL. Ebnesajjad S (editor). 2013. Introduction to Fluoropolymers: Materials, Technology, and Applications. William Andrew SoAlvracyaSdpisec2ia0l2ty2Polymers. 2017. High Performance Polymers for Oil & Gas. R05/2017/Version 2.5. Teng, H. 2012. Overview of the Development of the Fluoropolymer Industry. Applied Sciences. 2, 496-512. (Teng 2012) Example of Halar ECTFE used for cable jacketing (Solvay 2017) 11 September 2023 20 EFEP (ethylene tetrafluoroethylene hexafluoropropylene) Trade names include: Neoflon EFEP Uses in the O&G industry: Used in thermoplastic umbilicals, tubing extrusion and injection molding, extrusion of thin-walled tubing (Berger et al. 2014) Benefits of this fluoropolymer: Can be coextruded with other resins such as polyamides and can form strong bonds between the layers Can bond to non-fluoropolymers (Daikin 2022) Development: Developed by Daikin, and first marketed in 2003 (History of Daikin Innovation 2023) Terpolymer of ethylene, tetrafluoroethylene, and hexafluoropropylene (Korzeniowski et al. 2022) (PubChem 2023) References: Berger, J., Franosch, J., and Dowe, A. 2014. Direct bonding, adhesive-free Multilayer Thermoplastic Systems for Oil & Gas Pipelines, Risers and Umbilicals. In Proceedings of the Offshore Technology Conference, Houston, Texas. Daikin, "Neoflon EFEP RP-5101," TDS-EFEP-RP-004 REV 0, November 2022. History of Daikin Innovation. 2023. Available online at: https://www.daikin.com/air/daikin_achievements/innovation. Retrieved June 7, 2023. Korzeniowski S et al. 2022. A critical review of the application of polymer of low concern regulatory criteria to fluoropolymers II: Fluoroplastics and fluoroelastomers. Integrated Environmental Assessment and Management. 19 (2): 326-354. PubACrhceamd.isN2a0tio2n2al Institutes of Health. https://pubchem.ncbi.nlm.nih.gov/. Accessed online 5 June 2023. 11 September 2023 21 ETFE (ethylene tetrafluoroethylene) Trade names include: Chemours Tefzel, Asahi Glass Fluon, 3M Dyneon Uses in the O&G industry: Benefits of this fluoropolymer: Patented Use: Downhole cables for deep drilling (especially in colder climates) (Lahijani 2012) Can withstand extreme temperatures, ranging from -200 to 150C Good for low temperature storage Exhibits excellent resistance to various chemicals Development: Invented in 1972 (Ebnesajjad 2013) Demonstrates strong mechanical properties, including high tensile strength and elongation, surpassing many other fluoropolymers Highly resistant to weathering and aging processes Excellent dielectric properties, making it suitable for electrical applications Possesses nonstick characteristics, making it resistant to sticking and adhesion (Teng 2012) Higher tensile strength than PTFE, FEP, and PFA because its molecular chains adopt a planar zigzag configuration (Drobny 2009) References: Drobny, J.G. 2009. Technology of Fluoropolymers. 2nd Edition, CRC Press, Boca Raton, FL. Ebnesajjad, S. (editor). 2013. Introduction to Fluoropolymers: Materials, Technology, and Applications. William Andrew. LahAirjacnai,dJis.,2in0v2e2ntor; E. I. Du Pont De Nemours And Company, assignee. Downhole well communications cable. International Patent WO 2012/019066 A1. 9 Feb 2012. Teng, H. 2012. Overview of the Development of the Fluoropolymer Industry. Applied Sciences. 2, 496-512. 11 September 2023 22 FEP (fluorinated ethylene propylene) Trade names include: Dyneon FEP, F46, Fluororesin-46, Neoflon FEP, Niflon FEP, Teflon FEP Uses in the O&G industry: Benefits of this fluoropolymer: Lined tanks Lined pipes and fittings Oil pipe lining (patented use) Down-hole cables (patented uses) Cable insulation (patented use) Over braided hose Retains most of the favorable properties of PTFE, but its melt viscosity is low enough for conventional melt processing Resists most chemicals and solvents, even at elevated temperatures and pressures Gases and vapors permeate at a rate that is lower than for most plastics Component parts of valves Resists the effects of weather, extreme heat, Gaskets and UV radiation (Drobny 2009) Heat exchangers Development: (Drobny 2009; Aten et al. 2014; Lahijani 2009; Magner First produced by DuPont in 1956 (TeflonTM et al. 2013;McKeen et al. 2006; Onodoa et al. 2019) FEP) to reduce PTFE's high crystallinity and melt viscosity (Ebnesajjad 2013) (Teng 2012) (Drobny 2009) References: Aten, R.M., Burch, H.E., Turner, J.F., Young, R.T., Campbell, K.L., inventors; Chemours Co FC LLC, assignee. Adhesion of Fluoropolymer to Metal. United States Patent US 2014/0255703 A1. 11 Sep 2014. Drobny, J.G. 2009. Technology of Fluoropolymers. 2nd Edition, CRC Press, Boca Raton, FL. Ebnesajjad S (editor). 2013. Introduction to Fluoropolymers: Materials, Technology, and Applications. William Andrew Lahijani, J., inventor; E. I. Du Pont De Nemours And Company, assignee. Downhole well communications cable. International Patent WO 2012/019066 A1. 9 Feb 2012. Magner, S., inventor; RSCC Wire and Cable LLC, assignee. Down-Hole Cable Having a Fluoropolymer Filler Layer. United States Patent US 2013/0164441 A1. 27 Jun 2013. McKeen, L.W., Mohan, P.K., Mestemacher, S.A., Farnsworth, K.D., and Obal, W.D., inventors; E.I. DuPont De Nemours And Company, assignee. Coated pipes for harsh environments. International Patent WO 2006/058270 A1. 6 Jan 2006. OnodaA, rKc.a, dOisko2d0a2, 2T., and Hosoya, A., inventors; AOI Co Ltd, assignee. Glide flex tube. Japanese Patent JP 2019-006005 A. 17 Jan 2019. 11 September 2023 23 Teng, H. 2012. Overview of the Development of the Fluoropolymer Industry. Applied Sciences. 2, 496-512. FEVE (fluoroethylene vinyl ether) Trade names include: Lumiflon (PFEVE) Uses in the O&G industry: Coatings for offshore and marine structures like oil rigs, tanks, and vessels (Darden et al. 2007; AGC 2018) Development: Developed in the early 1980's, primarily used in architectural markets because of FEVE's gloss and color retention properties (Ebnesajjad 2013) (Chemical Retrieval on the Web 2023) Benefits of this fluoropolymer: Curable at ambient temperatures Low permeability to oxygen, water and chloride, which offers high degradation resistance when exposed to airborne pollutants and other environmental conditions Easily repairable and often used as a restorative product to repair previously degraded PVDF applications. Can last for up to 30 to 60 years (FEVE vs. PVDF 2021; Drobny 2009) References: AGC: FEVE-Based Coatings Protect Offshore, Marine Structures. 2018. Available online at: https://www.coatingsworld.com/contents/view_breaking-news/2018-05-29/agc-feve-based-coatings-protect-offshore-marine-structures/. Retrieved June 7, 2023. Chemical Retrieval on the Web. 2023. "FLUOROETHYLENE VINYL ETHER (FEVE)". https://polymerdatabase.com/Polymer%20Brands/FEVE.html. Accessed 1 June 2023. Darden, W., Takayanagi, T., Masuda, S., and Kimura, I. 2007. Fluoroethylene Vinyl Ether Resins for Applications in Marine Environments. In Proceedings of the NACE International Corrosion Conference and Expo, Nashville, Tennessee. Drobny, J.G. 2009. Technology of Fluoropolymers. 2nd Edition, CRC Press, Boca Raton, FL. Ebnesajjad S (editor). 2013. Introduction to Fluoropolymers: Materials, Technology, and Applications. William Andrew FAlurocraoedtihsy2le0n2e2Vinyl Ether (FEVE) Versus Polyvinylidene Fluoride (PVDF): A Exploration Of The Benefits Of FEVE Resin Technology. 2021. Available online at: https://lumiflonusa.com/technical/fluoroethyle1n1e-Sveinpytl-eemthbeer-rfe2v0e2-v3ersus- 24 polyvinylidene-fluoride-pvdf-a-exploration-of-the-benefits-of-feve-resin-technology/. Retrieved June 7, 2023. PFA (tetrafluoroethylene copolymers with perfluoroalkyl vinyl ethers) Trade names include: Hyflon PFA (Solvay Solexis) Uses in the O&G industry: Cable insulation (patented use; US5894104A) Linings for oil pipes (patented use; WO2006058270) Downhole cables (patented use; US20140255703A1) Downhole cables and control lines Multi-layer tubes (patented use; JP2019006005A) Corrosion protection on steel pipes (Hedberg 1999; McKeen et al. 2006; Aten et al. 2014) (Onoda et al. 2019; Solvay 2017) Benefits of this fluoropolymer: Melt processible Continuous use temperature of 260 C (Drobny 2009; Ebnesajjad 2013) Development: Introduced in 1973 (Ebnesajjad 2013) (Teng 2012) References: Aten, R.M., Burch, H.E., Turner, J.F., Young, R.T., Campbell, K.L., inventors; Chemours Co FC LLC, assignee. Adhesion of Fluoropolymer to Metal. United States Patent US 2014/0255703 A1. 11 Sep 2014. Drobny, J.G. 2009. Technology of Fluoropolymers. 2nd Edition, CRC Press, Boca Raton, FL. Ebnesajjad S (editor). 2013. Introduction to Fluoropolymers: Materials, Technology, and Applications. William Andrew. Hedberg, H., inventor; Schlumberger Technology Corporation (Schlumberger NV), assignee. Coax-slickline cable for use in well logging. United States Patent US 5,894,104 A. 13 Apr 1999. McKeen, L.W., Mohan, P.K., Mestemacher, S.A., Farnsworth, K.D., and Obal, W.D., inventors; E.I. DuPont De Nemours And Company, assignee. Coated pipes for harsh environments. International Patent WO 2006/058270 A1. 6 Jan 2006. Onoda, K., Okoda, T., and Hosoya, A., inventors; AOI Co Ltd, assignee. Glide flex tube. Japanese Patent JP 2019-006005 A. 17 Jan 2019. ASorclvaadyisSp2e0c2ia2lty Polymers. 2017. High Performance Polymers for Oil & Gas. R05/2017/Version 2.5. Teng, H. 2012. Overview of the Development of the Fluoropolymer Industry. Applied Sciences. 2, 496-512. 11 September 2023 25 PTFE (polytetrafluoroethylene) Trade names include: Teflon (DuPont/Chemours), Dyneon PTFE, Daikin Polyflon Uses in the O&G industry: O-rings and sealants Ex: Teflon Lip Seal in Centrifugal Pump Coatings on stud bolts and threaded fasteners Coatings for oil and gas well tubulars (n) (Ebnesajjad 2013) ePTFE check valve (patented use; US20160245042A1) Cable insulation (patented use; WO2012019066) Linings for oil pipes Tank linings Shoe for oil pipeline (Dhami 2018; Gluge et al. 2020; Lahijani et al. 2012; Napier et al. 2016) (Products: Fluoropolymer Tank Lining 2023; Habonium 2018; Centrifugal Pump 350.205-11.25) (StreaMax Coating Systems 2023; Trans-Alaska Pipeline 2019) References: Available on next slide. Arcadis 2022 Benefits of this fluoropolymer: One of the lowest surface energies among the organic polymers Most chemically resistant organic polymer One of the most thermally stable among the organic polymers Melting point and specific gravity are more than double those of PE Insoluble in common solvents (Ebnesajjad 2013; 2017) Development: PTFE was discovered in 1938 by Roy Plunkett of DuPont Patent issued to DuPont in 1941 to recognize its rights to the invention In 1950, DuPont scaled up the commercial production of Teflon (Ebnesajjad 2013; 2017) 11 September 2023 26 PTFE (polytetrafluoroethylene) Trade names include: Teflon (DuPont/Chemours), Dyneon PTFE, Daikin Polyflon References: Dhami, K.R. 2018. High Performance Corrosion Resistance - Fluoropolymer / PTFE Coated Fasteners for Valves and other Equipments used Offshore and Oil Gas Industries - Coatings for 21 Centaury. In Proceedings of the International Conference and Expo on Corrosion, Jaipur, India. Ebnesajjad S (editor). 2017. Expanded PTFE Applications Handbook. William Andrew Ebnesajjad S (editor). 2013. Introduction to Fluoropolymers: Materials, Technology, and Applications. William Andrew. Glge, Juliane et al. "An overview of the uses of per- and polyfluoroalkyl substances (PFAS)." Environmental science. Processes & impacts vol. 22,12 (2020): 2345-2373. doi:10.1039/d0em00291g. Lahijani, J., inventor; E. I. Du Pont De Nemours And Company, assignee. Downhole well communications cable. International Patent WO 2012/019066 A1. 9 Feb 2012. Napier, W.J., Harp, G.P., inventors; L Gore and Associates Inc, assignee. Fluoropolymer article for downhole applications. United States Patent US 2016/0245042 A1. 25 Aug 2016. Products: Fluoropolymer tank lining. 2023. Available online at: https://www.nichias.co.jp/en/products/detail/167. Retrieved June 7, 2023. Habonium. 2018. Three piece ball valves. 04/18 REV2.04. Centrifugal Pump 350.205-11.25. 2022. Available online at: http://www.drillingsolutionsltd.com/halliburton-centrifugal-pump-parts-list.html. Retrieved June 7, 2023. StreaMaxTM Coating Systems. 2023. Available online at: https://www.teflon.com/en/industries-and-solutions/solutions/productivity-efficiency-flow/streamax-coatings. Retrieved June 7, 2023. Trans-Alaska Pipeline. 2019. Available online at: https://www.underwater.org/mermaid/passage/pipeline/index.html. Retrieved June 7, 2023. Arcadis 2022 11 September 2023 27 PVDF homopolymer (polyvinylidene fluoride homopolymer) Trade names include: KF, Hylar, Kynar, Solef Uses in the O&G industry: Benefits of this fluoropolymer: Flexible risers and flowlines Highest flexural modulus among the known commercial fluoropolymers Pipes: Mechanically stronger than perfluorinated polymers like PTFE Pipe liners Resistance to abrasion Flexible pipe (Ebnesajjad 2013) Resists both creep under long-term stress and fatigue during cyclic loading Multi-layer coated flexible pipeline (use starting in 1970s) Good thermal stability, making it suitable for high-temperature applications Resistant to ultraviolet (UV) and higher energy radiation Umbilicals Excellent resistance to most chemicals and solvents Liners in choke and kill lines Not hygroscopic, meaning it does not absorb significant amounts of water Downhole wire & cables Adsorbs less than 0.05% of water at room temperature Downhole cable (patented use; US20130164441A1) (Berger et al 2014; Magner 2013) (Ebnesajjad 2013; Drobny 2009) Development: (Solvay 2017; Extreme materials 2023) The first successful aqueous polymerization of vinylidene fluoride was reported in 1948. In 1960, a manufacturing process was developed, and PVDF was first introduced to the market (Ebnesajjad 2013; Drobny 2009). References: Berger, J., Franosch, J., and Dowe, A. 2014. Direct bonding, adhesive-free Multilayer Thermoplastic Systems for Oil & Gas Pipelines, Risers and Umbilicals. In Proceedings of the Offshore Technology Conference, Houston, Texas. Drobny, J.G. 2009. Technology of Fluoropolymers. 2nd Edition, CRC Press, Boca Raton, FL. Ebnesajjad S (editor). 2013. Introduction to Fluoropolymers: Materials, Technology, and Applications. William Andrew. Extreme materials for extreme environments Offshore. 2023. Available online at: https://hpp.arkema.com/en/markets-and-applications/oil-and-gas/offshore/. Retrieved June 7, 2023. MaAgrnceard, iSs.,2i0nv2e2ntor; RSCC Wire and Cable LLC, assignee. Down-Hole Cable Having a Fluoropolymer Filler Layer. United States Patent US 2013/0164441 A1. 27 Jun 2013. Solvay Specialty Polymers. 2017. High Performance Polymers for Oil & Gas. R05/2017/Version 2.5. 11 September 2023 28 PVDF copolymer (polyvinylidene fluoride copolymer) Trade names include: KYNAR Uses in the O&G industry: No uses of the copolymer specifically identified Benefits of this fluoropolymer: Higher flexibility, chemical resistance, elongation, solubility, impact resistance, optical clarity, and thermal stability during processing than PVDF homopolymer (Ebnesajjad 2013; Drobny 2009) Resists creep (deformation of the product) Can be irradiated (used in biopharma industry) Development: The first successful aqueous polymerization of vinylidene fluoride was reported in 1948 In 1960, a manufacturing process was developed, and PVDF was first introduced to the market (Ebnesajjad 2013; Drobny 2009) (Example from Mao et al. 2011) References: Drobny, J.G. 2009. Technology of Fluoropolymers. 2nd Edition, CRC Press, Boca Raton, FL. Ebnesajjad S (editor). 2013. Introduction to Fluoropolymers: Materials, Technology, and Applications. William Andrew. Mao, D. & Gnade, Bruce & Quevedo-Lopez, Ma. (2011). Ferroelectric Properties and Polarization Switching Kinetic of Poly (Vinylidene Fluoride-Trifluoroethylene) Copolymer. 10.5772/17147. Arcadis 2022 11 September 2023 29 THV (THV-HFP-VF2) tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride terpolymer Trade names include: Dyneon THV, Nowoflon THV, Altafluor 350 (THV FLEX) Uses in the O&G industry: Downhole cables (patented use; US20140255703A1) Flexible tubing Tank lining (Altafluor 2023; Aten et al 2014; Dyneon 2000) Benefits of this fluoropolymer: Low processing temperature Ability to bond to elastomers and hydrocarbon-based plastics Flexibility Optical clarity (Ebnesajjad 2013; Drobny 2009; Dyneon 2000) Development: Use begins in 1996 - predominantly used for thin film technology (Teng 2012) Applications Low Temp. Processing Chemical & Permeation Resistance Flexibility Optical Clarity Bondability & Weldability E-beam Curable Weatherability Self-Extinguishing (Teng 2012) Wire/Cable & Heat Shrink Tubing Tank & Pipe Liners References: Altafluor 350 THV Flex Tubing. 2023. Available online at: https://www.altaflo.com/products/thv-flex-altafluor-350/. Retrieved June 7, 2023. Aten, R.M., Burch, H.E., Turner, J.F., Young, R.T., Campbell, K.L., inventors; Chemours Co FC LLC, assignee. Adhesion of Fluoropolymer to Metal. United States Patent US 2014/0255703 A1. 11 Sep 2014. Drobny, J.G. 2009. Technology of Fluoropolymers. 2nd Edition, CRC Press, Boca Raton, FL. Dyneon. 2000. Dyneon Fluorothermoplastics Product Information. Issued 12/00. EbAnercsaajdjaisd 2S0(2e2ditor). 2013. Introduction to Fluoropolymers: Materials, Technology, and Applications. William Andrew. Teng, H. 2012. Overview of the Development of the Fluoropolymer Industry. Applied Sciences. 2, 496-512. 11 September 2023 30 PCTFE (polychlorotrifluoroethylene) Trade names include: Kel-F 81, Kel-F 300, Hostaflon C2, Fluon, Halon, Aclar, Neoflon-PCTFE, Voltalef Uses in the O&G industry: Seals Gaskets (especially for liquefied natural gas applications) Seat, anti-abrasion rings in three-piece ball valves (Habonium 2018) Benefits of this fluoropolymer: Exceptional barrier properties and chemical resistance Sensitive to organic solvents Low thermal stability, requires careful processing (Ebnesajjad 2013; Drobny 2009) Can be made into transparent sheets Good in cryogenic environments Development: Developed in 1937, one year before PTFE (Ebnesajjad 2013) References: Ebnesajjad S (editor). 2013. Introduction to Fluoropolymers: Materials, Technology, and Applications. William Andrew. Drobny, J.G. 2009. Technology of Fluoropolymers. 2nd Edition, CRC Press, Boca Raton, FL. HaAbrocnaiudmis. 22001282. Three piece ball valves. 04/18 REV2.04. (Ebnesajjad 2013) 11 September 2023 31 Fluoroelastomers FEPM (trifluoroethylene propylene copolymer) Trade names include: AFLAS FEPM, Viton Extreme Uses in the O&G industry: O-rings, seals, gaskets, wire and cable coating (AGC 2018) Benefits of this fluoropolymer: Resistant to acids and bases, low dielectric constant (AGC 2018; McKeen 2017) Development: Manufactured in Japan, marketed in US, differs from Viton and Fluorel by adding polypropylene to the fluorine monomer (tetrafluoroethylene) AGC begins to market AFLAS FEPM in 1975 (AGC 2018) References: AGC Chemicals Inc. 2018. Aflas Fluoroelastomers. CA011E. Chemical Retrieval on the Web. 2023. "FEPM - TETRAFLUOROETHYLENE PROPYLENE". https://polymerdatabase.com/Elastomers/FEPM.html. Accessed 1 June 2023. McAKreceandMis. 2202172. Film Properties of Plastics and Elastomers. Fourth Edition. William Andrew. (Chemical Retrieval on the Web 2023) 11 September 2023 33 FKM (Fluorine Kautschuk Material; HFP VF2 polymer and HFP VF2 TFE polymers) Trade names include: Viton, Viton-A, Viton-B, "fluoro-rubber" Uses in the O&G industry: O-rings Expansion joints Diaphragms Blow-out preventers Valve seats Gaskets Benefits of this fluoropolymer: Temperature and fuel resistant (McKeen 2017; DuPont 2023) Development: Viton-A (FKM) developed by DuPont in 1955 (Uschold 1985; Byrdson 1994) Hose Safety clothing and gloves Stack and duct coatings Tank linings Drill bit seals V-ring packers (DuPont 2023; 2021; Fluorocarbon O-Ring 2023; Habonium 2018; Kalrez Parts 2023) (VitonTM Fluoroelastomers for Oil and Gas Exploration and Production 2023) FKM fluoroelastomers contain vinylidene fluoride (VDF) as a monomer combined with a variety of other fluoromonomers (Korzeniowski et al. 2022) VDF Monomer (PubChem 2023) Viton (Departamento de Cincia e Tecnologia Aeroespacial, Brazil) References: Available on next slide. Arcadis 2022 11 September 2023 34 FKM (Fluorine Kautschuk Material; HFP VF2 polymer and HFP VF2 TFE polymers) Trade names include: Viton, Viton-A, Viton-B, "fluoro-rubber" References: Brydson J. A. 1994. Specialty Rubbers. Smithers Rapra. DuPont. 2023. DuPontTM KalrezPerfluoroelastomer Parts: In Energy/ Oil & Gas. KZE-A40128-00-B0123 CDP. DuPont. 2021. DuPontTM Kalrez OG193 Perfluoroelastomer Parts: For Oil and Gas Applications Requiring High Rapid Gas Decompression (RGD) Resistance in a Broad Range of Temperatures, Conditions and Part Configurations. KZE A40087 00 B0921. Fluorocarbon O-Ring, 95 Shore A, Oil & Gas Applications (Prdifa Series V1238-95). Available online at: https://ph.parker.com/us/en/product-list/fluorocarbon-o-ring-95-shore-a-oil-gas-applications-praedifa-series-v123895?facet:4099276460822254724791051083238327197115,4099276460822254724791051083297110100327197115&productBeginIndex:0&facetLimit:&orderBy:&pageView:list&minPrice:&maxPrice:&pageSize:&loadProductsList:true&. Retrieved June 7, 2023. Habonium. 2018. Three piece ball valves. 04/18 REV2.04. Kalrez Parts in Natural Gas Sampling Systems and Delivery. 2023. Available online at: https://www.dupont.com/knowledge/natural-gas-delivery.html. Retrieved June 7, 2023. Korzeniowski S et al. 2022. A critical review of the application of polymer of low concern regulatory criteria to fluoropolymers II: Fluoroplastics and fluoroelastomers. Integrated Environmental Assessment and Management. 19 (2): 326-354. PubChem. National Institutes of Health. https://pubchem.ncbi.nlm.nih.gov/. Accessed online 5 June 2023. McKeen M. 2017. Film Properties of Plastics and Elastomers. Fourth Edition. William Andrew. Uschold, R. E. 1985. Fluoroelastomers: Today's Technology and Tomorrow's Polymers. Polymer Journal. 17(1): 253-263. VitonTM Fluoroelastomers for Oil and Gas Exploration and Production. 2023. Available online at: https://www.viton.com/en/industries/oil-gas. Retrieved June 7, 2023. Arcadis 2022 11 September 2023 35 FFKM (TFE PMVE perfluoroelastomer) Trade names include: Kalrez, Markez, perfluoroelastomer, AFLAS FFKM Uses in the O&G industry: (primarily used in fluid sealing environments) O-rings Mechanical and pipeline seals Pumps Compressors Christmas Trees Pipeline Valves/Ball valves Subsea Equipment Risers Monitoring/logging equipment Packers/packing elements (DuPont 2023; 2021; Kalrez Parts 2023) Benefits of this fluoropolymer: Resistant to over 1500 chemical substances Service temperature up to 316C (600F) Excellent performance as static or dynamic seals Retains resilience and low compression set Good creep resistance Outperforms metals, FKM, PTFE, and other elastomers (McKeen 2017; DuPont 2023) Development: Introduced in the mid-1970's (Uschold 1985; Byrdson 1994) FF FF FF (Chemical Retrieval on the Web 2023) n FF FO n F Br co FF F Fully fluorinated class of elastomers that are typically made up of tetrafluoroethylene (TFE), a perfluoro (alkyl vinyl ether; PAVE), and a cure site monomer(s) (CSM) (Korzeniowski et al. 2022) (DuPont 2023) References: Available on next slide . Arcadis 2022 11 September 2023 36 FFKM (TFE PMVE perfluoroelastomer) Trade names include: Kalrez, Markez, perfluoroelastomer, AFLAS FFKM References: Chemical Retrieval on the Web. 2023. "FFKM - PERFLUOROELASTOMERS'. https://polymerdatabase.com/Elastomers/FFKM.html. Accessed June 2023. DuPont. 2023. DuPontTM KalrezPerfluoroelastomer Parts: In Energy/ Oil & Gas. KZE-A40128-00-B0123 CDP. DuPont. 2021. DuPontTM Kalrez OG193 Perfluoroelastomer Parts: For Oil and Gas Applications Requiring High Rapid Gas Decompression (RGD) Resistance in a Broad Range of Temperatures, Conditions and Part Configurations. KZE A40087 00 B0921. Kalrez Parts in Natural Gas Sampling Systems and Delivery. 2023. Available online at: https://www.dupont.com/knowledge/natural-gas-delivery.html. Retrieved June 7, 2023. Korzeniowski S et al. 2022. A critical review of the application of polymer of low concern regulatory criteria to fluoropolymers II: Fluoroplastics and fluoroelastomers. Integrated Environmental Assessment and Management. 19 (2): 326-354. McKeen M. 2017. Film Properties of Plastics and Elastomers. Fourth Edition. William Andrew. Brydson J. A. 1994. Specialty Rubbers. Smithers Rapra. Uschold, R. E. 1985. Fluoroelastomers: Today's Technology and Tomorrow's Polymers. Polymer Journal. 17(1): 253-263. Arcadis 2022 11 September 2023 37 Specialty Amorphous fluoropolymers Trade names include: Teflon AF, Cytop, Hyflon-AD Uses in the O&G industry: Fluoropolymer - coated membranes used for separation of non-aqueous liquid (e.g., deep desulfurization of gasoline and diesel, H2 recovery in refineries) (Liu and Tang 2009) Benefits of this fluoropolymer: Chemical stability, thermal stability, optical clarity, high gas permeability (Korzeniowski et al. 2022) Development: Pre-1980s, all industrial fluoropolymers were semicrystalline. DuPont and Asahi Glass developed amorphous perfluoropolymers in the mid-1980s (Teng 2012). (Teng 2012) References: Korzeniowski S et al. 2022. A critical review of the application of polymer of low concern regulatory criteria to fluoropolymers II: Fluoroplastics and fluoroelastomers. Integrated Environmental Assessment and Management. 19 (2): 326-354. Liu, C and M-W Tang, inventors; Honeywell UOP, assignee. FLUOROPOLYMER COATED MEMBRANES. United State Patent US 2009/0277837 A1. 12 Nov 2009. TeAngrc, aHd. i2s02120.2O2verview of the Development of the Fluoropolymer Industry. Applied Sciences. 2, 496-512. 11 September 2023 39 Fluorinated ionomers Trade names include: Nafion, Fumapem, Flemion, Aquivion, Aciplex Uses in the O&G industry: No specific uses identified Benefits of this fluoropolymer: Highly conductive (most applications of perfluorinated ionomers involve the passage of an electric current, in the form of cations, through the ionomer) Form impermeable membranes Development: Developed in the 1960s and are critical to the chlor-alkali and fuel cell industries (Grot 2011) References: Chemical Retrieval on the Web. 2023. "Ionomers". https://polymerdatabase.com/polymer%20classes/Ionomers.html. Accessed 1 June 2023. Grot W. 2011. Fluorinated Ionomers, PDL handbook series. Second Edition. William Andrew. Arcadis 2022 Nafion (Chemical Retrieval on the Web 2023) 11 September 2023 40 Xylan - Off-Shore Oil Applications Xylan is a brand-name fluoropolymer coating line developed by the Whitford Worldwide Company, now owned by PPG. Xylan coatings are composed of fluoropolymers such as PTFE, PFA, and FEP, combined with reinforcing binder Uses in the O&G industry: Widely used in the off-shore oil industry for a variety of applications such as bolts, fasteners, valves and connectors. Benefits of this fluoropolymer: Chemical and corrosion resistance Excellent weather resistance High heat resistance UV resistance Wear resistance Development: First manufactured by the Whitford Worldwide Company in 1969 References: Teng, H. 2012. Overview of the Development of the Fluoropolymer Industry. Applied Sciences. 2, 496-512. Arcadis 2022 11 September 2023 41 Research Findings: Standards that Identify Fluoropolymers ASTM D1418-22 Standard Practice for Rubber and Rubber Latices--Nomenclature Viton (https://www.astm.org/) D3307-21 Standard Specification for Perfluoroalkoxy (PFA) Resin Molding and Extrusion Materials D3222-21 Standard Specification for Unmodified Poly(Vinylidene Fluoride) (PVDF) Molding Extrusion and Coating Materials D6867-19 Standard Specification for Perfluoroalkoxy (PFA)-Fluoropolymer Tubing D7471-19 Standard Specification for CPT-Fluoropolymer Molding and Extrusion Materials D8436-22 Standard Specification for Fluoropolymer-based Materials for Use for Encapsulation of Downhole Cable (PFA, ETFE, ECTFE, FEP) D5575-18 (2023) Standard Classification System for Copolymers of Vinylidene Fluoride (VDF) with Other Fluorinated Monomers D1710-15(2021) Standard Specification for Extruded Polytetrafluoroethylene (PTFE) Rod, Heavy Walled Tubing and Basic Shapes D6713-21 Standard Specification for Extruded and Compression Molded Shapes Made from Poly(Vinylidene Fluoride) (PVDF) D8366-21a Standard Specification for Extruded and Compression Molded Shapes Made from Unfilled Poly(Vinylidene Fluoride) PVDF D3295-20 Standard Specification for PTFE Tubing, Miniature Beading and Spiral Cut Tubing D3595-14(2019)e1 Standard Specification for Polychlorotrifluoroethylene (PCTFE) Extruded Plastic Sheet and Film Arcadis 2022 11 September 2023 43 ASTM continued... D4745-19 Standard Classification System and Basis for Specification for Filled Polytetrafluoroethlyene (PTFE) Molding and Extrusion Materials Using ASTM Methods D4894-19 Standard Specification for Polytetrafluoroethylene (PTFE) Granular Molding and Ram Extrusion Materials F477-14 2021 Standard Specification for Elastomeric Seals (Gaskets) for Joining Plastic Pipe D7472-19 Standard Specification for EFEP-Fluoropolymer Molding and Extrusion Materials D3296-14a(2019) Standard Specification for FEP-Fluorocarbon Tube D1710-15(2021) Standard Specification for Extruded Polytetrafluoroethylene (PTFE) Rod, Heavy Walled Tubing and Basic Shapes D3159-22 Standard Specification for Modified ETFE Fluoropolymer Molding and Extrusion Materials D3308-12(2022) Standard Specification for PTFE Resin Skived Tape D6585-17(2022) Standard Specification for Unsintered Polytetrafluoroethylene (PTFE) Extruded Film or Tape D7193-17(2022) Standard Specification for Unsintered Pigmented Polytetrafluoroethylene (PTFE) Extruded Film or Tape D3294-22 Standard Specification for Polytetrafluoroethylene (PTFE) Resin Molded Sheet and Molded Basic Shapes D7211-23 Standard Specification for Parts Machined from Polychlorotrifluoroethylene (PCTFE) and Intended for General Use D3275-18(2023) Standard Classification System for E-CTFE-Fluoroplastic Molding, Extrusion, and Coating Materials D4895-18(2023) Standard Specification for Polytetrafluoroethylene (PTFE) Resin Produced From Dispersion Arcadis 2022 11 September 2023 44 (https://www.iso.org/home.html) ISO ISO 23936-2:2011 Petroleum, petrochemical and natural gas industries -- Non-metallic materials in contact with media related to oil and gas production -- Part 2: Elastomers ISO 10423:2022 Petroleum and natural gas industries -- Drilling and production equipment -- Wellhead and christmas tree equipment (This document supplements API Spec 6A, 21st edition (2018), the requirements of which are applicable with the exceptions specified in this document.) ISO 13628-4:2010 Petroleum and natural gas industries -- Design and operation of subsea production systems -- Part 4: Subsea wellhead and tree equipment ISO 13628-10:2005 Petroleum and natural gas industries -- Design and operation of subsea production systems -- Part 10: Specification for bonded flexible pipe for petroleum and natural gas industries ISO 13628-15:2011 Petroleum and natural gas industries -- Design and operation of subsea production systems -- Part 15: Subsea structures and manifolds ISO 10400:2018 Petroleum and natural gas industries -- Formulae and calculations for the properties of casing, tubing, drill pipe and line pipe used as casing or tubing ISO 11960:2020 Petroleum and natural gas industries -- Steel pipes for use as casing or tubing for wells ISO 13678:2010 Petroleum and natural gas industries -- Evaluation and testing of thread compounds for use with casing, tubing, line pipe and drill stem elements ISO 15463:2003 Petroleum and natural gas industries -- Field inspection of new casing, tubing and plain-end drill pipe ISO 27914:2017 Carbon dioxide capture, transportation and geological storage -- Geological storage ISO 27916:2019 Carbon dioxide capture, transportation and geological storage -- Carbon dioxide storage using enhanced oil recovery (CO2-EOR) Arcadis 2022 11 September 2023 45 API API Spec 6A, 21st edition (2018), Specification for Wellhead and Tree Equipment (https://www.api.org/) API Spec 14A, Petroleum and natural gas industries -- Downhole equipment -- Subsurface safety valve equipment API Spec 17D, 2nd edition (2011), Design and Operation of Subsea Production Systems -- Subsea Wellhead and Tree Equipment Additional mentions of fluoropolymers: 16A, 17B, 17F, 17J, 17TR1, 17TR8, 19D, 21TR1, 5C1, 5C5, 5CT, 6FA, 6J, 15S, 551, 553, 574, 584, 588, 608, 610 Arcadis 2022 11 September 2023 46 Final Notes Potential Alternatives/ New Directions Nanofillers are being studied to improve the wear of PTFE in the form of PTFE nanocomposites (Ye et al. 2013). HDPE can be used as a substitute for PVDF pipe liners but is more prone to failure under high pressure (Khalid et al. 2020). Polyamides (PA11 And PA12) can also be used as pipe liners in similar applications to PVDF (Khalid et al. 2020). New `superhydrophobic' coatings for oil and gas pipelines have been developed in the past three years to address oil and gas pipeline explosions. While the coatings are polymer based, it is unclear if they contain any fluorinated polymers (Ijaola et al. 2020). PEEK (polyetheretherketone) is a non-fluorinated polymer that has widespread applications in the oil and gas industry and can be used as an alternative to fluorinated compounds (deLeon et al. 2021). HDPE-based products that contain nano ceramic or nano aluminum oxide (Micro Powders, 2021) and polyurethane (PU), polyvinyl chloride (PVC), polyolefin and epoxy powders for coating materials (OECD 2022). Hydrogenated nitrile butadiene rubber (HNBR) for fluoroelastomers (Viton-FKM) (New Deal Seals). References: De Leon et al., 2021. High performance polymers for oil and gas applications. Reactive and Functional Polymers, 162:104878. https://doi.org/10.1016/j.reactfunctpolym.2021.104878Get rights and content Ijaola et al, 2020. Khalid, H.U. et al, 2020.Permeation damage of polymer liner in oil and gas pipelines: a review. Polymers 12: 2307- 2338. Micro Powders (2021), PolyGlide product details, http://www.micropowders.com/ProductDetail.aspx?id=283 and Micro Powders (2021), Powder Coatings, http://www.micropowders.com/files/brochures/Powder.pdf. New Deal Seals.com Accessed 2 June 2023 https://newdealseals.com/o-rings/hnbr-o-rings-seals/#:~:text=HNBR%20has%20excellent%20abrasion%20resistance,and%20tear%20resistance%20than%20fluorocarbon. OECDA2r0c2a2d. iPse2r0- a2n2d Polyfluoroalkyl Substances and Alternatives in Coatings, Paints and Varnishes. Ye et al., 2013. Transfer film evolution and its role in promoting ultra-low wear of a PTFE nanocomposite. Wear 297:1095-1102. 11 September 2023 48 Current Scientific Consensus Indicates that Solid Fluoropolymers are Polymers of Low Concern Korzeniowski et al. 2022: "The data presented demonstrate the fluoropolymers in the study are thermally, biologically, and chemically stable, negligibly soluble in water, nonmobile, nonbioavailable, nonbioaccumulative, and nontoxic, and contain low levels of impurities." Henry et al. 2018: "Data show that fluoropolymers have thermal, chemical, photochemical, hydrolytic, and biological stability." "The data presented demonstrate that the fluoropolymer class of PFAS is well defined, meets PLC criteria, and should be considered as distinctly different from other classes of PFAS." But See: Myers et al., 2014: Thermal decomposition fragments of fluoropolymers (PCTFE e.g.) might be environmentally persistent and toxic. Lohmann et al. 2020: "The concerns we present above suggest that there is no sufficient evidence to consider fluoropolymers as being of low concern for environmental and human health. The group of fluoropolymers is too diverse to warrant a blanket exemption from additional regulatory review. Their extreme persistence and the emissions associated with their production, use, and disposal result in a high likelihood for human exposure as long as uses are not restricted. Concluding that some specific fluoropolymer substances are of low concern for environmental and human health can only be achieved by narrowly focusing on their use phase, as was done by Henry et al." References: Henry, B. J; Carlin, J. P; Hammerschmidt, J. A; Buck, R. C; Buxton, L W.; Fiedler, H.; Seed, J.; Hernandez, O. A Critical Review of the Application of Polymer of Low Concern and Regulatory Criteria to Fluoropolymers. Integr. Environ. Assess.Manage. 2018, 14 (3), 316- 334, DOI: 10.1002/ieam.4035. Korzeniowski S et al. 2022. A critical review of the application of polymer of low concern regulatory criteria to fluoropolymers II: Fluoroplastics and fluoroelastomers. Integrated Environmental Assessment and Management. 19 (2): 326-354. Lohmann, Rainer; Cousins, Ian T.; DeWitt, Jamie C.; Glge, Juliane; Goldenman, Gretta; Herzke, Dorte; Lindstrom, Andrew B.; Miller, Mark F.; Ng, Carla A.; Patton, Sharyle; Scheringer, Martin; Trier, Xenia; Wang, Zhanyun. "Are Fluoropolymers Really of Low Concern for Human and Environmental Health and Separate from Other PFAS?" Environmental Science & Technology, vol. 54, no. 20, 2020, pp. 12820-12828. DOI: 10.1021/acs.est.0c03244. PMID: 33043667. Myers, A.L. et al. 2014. Using mass defect plots as a discovery tool to identify novel fluoropolymer thermal decomposition products. J. Mass. Spectrom. 49:291-296. Arcadis 2023 11 September 2023 49 'hank You! Stephanie Fiorenza Ruben Lopez Katie Barry Johnsie Lang Andy Newcombe Arcadis 2023 @arcadis.com @arcadis.com @arcadis.com @arcadis.com @arcadis.com 11 September 2023  Arcadis 2022 Questions? 11 September 2023 51