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FROM AFFF TO F3 Part 1 : History

Modern chemistry has created many hundreds of thousands of chemical compounds, which we encounter as part of our daily lives. Indeed, it would be very hard to spend a day without being in contact with a class of molecules – perfluoroalkyl substances or PFAS – which have been commercially exploited since the end of WWII over the last 75 years.

Even if we could qualify chemistry as a miracle of science, it is worth knowing that chemistry has been approached by the Egyptian 3000 years BC, and was later on studied by the Ancient Greeks which described the combination of the 5 elements: earth, air, fire, water and ether. This theory was largely accepted for more than 1000 years.

The basis of the modern chemistry, as we now understand it, was established over the last three hundred years. The nature of the atom, the identification of atomic compounds, the first modern synthesis was achieved.

In 1906, Frédéric Henri Moissan (1852-1907), a French chemist working in Paris at the École Supérieure de Pharmacie, isolated for the first-time elemental fluorine gas, F2, a discovery for which he was awarded the Nobel Prize in Chemistry in 1906. Hydrogen fluoride obtained from fluorspar had been identified by the renowned Swedish chemist Karl Wilhelm Scheele some years earlier.

The post war years after WWI In the mid 1930s, were the heyday the German chemical industry, especially as regards new synthetic dyes. Fluorine chemistry started to have a commercial role – a red dye Naphthol AS, used as the official red colour the Nazi flag, and Indanthrene Blue used as a component of ‘Flieger Grau’ or Pilot Grey, the blue-grey colour of Luftwaffe uniforms, both contained a fluorinated methyl group, CF3, which helped prevent fading. Carothers working for DuPont produced the first industrial wholly synthetic fabric, the polymer Nylon. From this point chemists have never stopped to inventing new compounds!

When we think about chemicals, it is important to realise that many, if not most of the synthetic compounds now commercially available are produced by the petrochemical industry. Since the invention of the internal combustion engine, petrol (gasoline) and petroleum products have been become increasingly important around in for many human activities but are associated with a high fire risk.
The nature of this risk highlighted the necessity of addressing these often-catastrophic fires. In the early 40’s, protein foam made from ‘horn and hoof’, a slaughterhouse waste, was developed to control Class B hydrocarbon fires, e.g., those involving oil, gasoline, aircraft fuel and solvents.
In 1949, the 3M Company Minnesota industrialized the Simons electrochemical fluorination (ECF) process for making perfluoro-compounds (PFC) such as perfluorinated amines, carboxylic and sulphonic acids in which the hydrogens of the alkyl carbon chain had been totally replace by fluorine. Joseph Simons had discovered the ECF process whilst working at Pennsylvania State College in the 1930s but was unable to publish his work until after WWII because fluorine chemistry was essential for uranium purification as part of the Manhattan Project.

In 1953 the structure of Scotchgard was accidentally discovered by Patsy Sherman and Sam Smith working for the 3M Company whilst working on a rubber for jet fuel lines. Three years later in 1956, the 3M Company launched Scotchguard on the market. This fabric, textile and leather treatment is based on a PFOS-derivative containing N-ethyl-PFOSA and gives water, oil, and other liquids and stain-protection to the treated fibre.
Interestingly, N-ethyl-PFOSA known as Sulfluramid, was originally developed to kill ants, cockroaches and termites, and is still used to this day as the insecticide sulfluramid against leaf-cutting ants in Brazil. The lithium salt of PFOS was developed to kill wasps and hornets but is highly toxic to honey bees.

PFOS, perfluoro-octane sulphonic acid, and its derivatives subsequently become crucial for the development of Class B aqueous film-forming foams (AFFFs) effective against liquid hydrocarbon and solvent fires.

Figure 1. The structure of PFOS, perfluoro-octane sulphonic acid.

During the 1960s the US Department of the Navy Naval Research Laboratory in collaboration with the 3M Company began developing PFOS-based firefighting foams. A patent for AFFF firefighting foam was awarded in June 1996 for extinguishing liquid hydrocarbon fires.

In the late 60’s, a series of major fuel fires happen on board US Navy ships causing extensive loss of life and damage:
(i) 1966: USS Oriskany – fire kills 44 sailors.
(ii) 1968: USS Forrestal – whilst on active service in the Gulf of Tonkin during the Vietnam War, malfunction and accidental firing of a fighter Zuni rocket on the flight deck of this super-carrier led to a catastrophic aviation fuel fire claiming the lives of 134 crew, injuring many more, destroying nearly 50 aircraft, doing $72 million worth of damage, and leaving the vessel unfit for active service.

(iii) 1969: USS Enterprise – a shipboard fire kills 28 sailors.

These major fires prompt the US Department of the Navy to mandate the use of the recently developed AFFF firefighting foam, which the 3M Company was manufacturing for the US military.

Perfluorocompounds had been successfully used to create AFFF, and 3M’s PFOS-based LightWater® and alcohol-resistant ATC® brands became the staple for liquid hydrocarbon fuel fires from the 1970s until May 2000 when the Company announced that it was phasing out PFOS-based chemistry on environmental grounds. AFFF had indeed conquered the world of firefighting and was seen for decades as the ultimate answer to extinguishing large hydrocarbon (oil and gasoline) fires both for military and civilian use especially by the aviation and petrochemical industries.

In the 70’s, an alternative technology was developed based on the telomerization process. This technology provided an alternative to the ECF process and introduced a new class perfluorochemicals on the market. Whereas the ECF process produced mainly PFOS contaminated with odd and even numbered homologues of PFOS such as PFHxS (~5-8 % w/w), perfluorohexane sulphonic acid, as well as branched chain isomers, telomerisation produced only even number linear alkyl carbon chains. The characteristic of fluorotelomer derivates is a perfluoroalkyl moiety linked by a dimethylene group -CH2-CH2- to a functional group which could be negatively (anionic), positively (cationic) or both negatively and positively charged (amphoteric).

Most modern fluorotelomer-based AFFF firefighting foams, known as ‘pure C6 foams’, are based on derivatives of 6:2 fluororelomer sulphonic acid (6:2FTS), or a thioether analogue, containing a C6 perfluoroakyl chain linked through -(CH2)2- to a charged functional group. 6:2FTS contains a C8 chain and its structure is shown below. Its similarity to PFOS is clear but the CH2 groups cause it to behave very differently in terms of its PBT profile. All perfluoroalkyl moieties or their breakdown products are extremely environmentally persistent (vP), but with differing bioaccumulation or toxic potential.

Figure 2. Structure of 6:2FTS

Early fluorotelomer foams, however, contained both 6:2FTS and often substantial amounts of 8:2FTS derivatives. This was a problem as the 8:2FTS could be degraded to a stable end product perfluoroctanoic acid or PFOA which had substantial toxicity. This problem has now been essentially resolved as a result of the industry PFOA Stewardship Program 2010-2015, with residual PFOA or its precursors reduced to less than 25 parts perbillion (ppb).

Figure 3. 8:2FTS breakdown to PFOA

From the 1970s to the late 1990s, many manufacturers of firefighting foam appeared in the market, developing and offering a wide range of different foams for end-users. These included Class B AFFF, AFFF-AR (alcohol resistant), film-forming-protein (FFFP) and fluoro-protein (FP) foams. Class A foams specifically intended for solid carbonaceous fires such as structural building or wildland (bush) fires were also developed in this period.

On 16 May 2000 the 3M Company abruptly announced the phasing-out of its activity in PFOS-based chemistry for producing fluorochemicals, affecting not only firefighting foams but also a wide range of domestic and commercial products. This announcement was justified on company responsibility for environment, as it was confirmed that the C8 perfluoroalkyl substances (PFAS) made using ECF technology posed a threat to the environment, with pollution that had spread worldwide affecting a wide range of environmental compartments as well as biota including man.
Over the next 2-3 years, the company had stopped all activities involving PFOS-based chemistry, with a total withdrawal from the firefighting foam market, replacing it with mitigated success by a shorter chain PFBS-based (perfluorobutyl sulphonate) chemistry. However, some production of PFOS and PFHxS derivatives using the ECF process did continue in both China and India.
With 3M’s phase-out of PFOS-chemistry and withdrawal from the firefighting foam market, other major manufacturers of PFAS fluorochemicals and firefighting foam stressed that they considered fluorotelomer chemistry was ’safe’ and indeed environmentally friendly as it had nothing to do with ECF chemistry and products could not contain either PFOS or PFOA. The firefighting foam market transitioned to AFFF products based on fluorotelomers over the next few years 2000-2010.

From 2002 onwards a lively and sometimes acrimonious debate took place between manufacturers of PFAS and AFFF – under the auspices of a trade association, the Fire Fighting Foam Coalition (FFFC), funded mainly by the fluorochemical industry – and independent manufacturers especially of nascent fluorine-free foams (F3), regulators and scientific experts from academia. This discussion gave rise to a series of international seminars, conferences as well as hundreds of publications in the peer-reviewed literature about the environmental consequences of substituting fluorotelomers for PFOS-based products. At this time the main international forum for discussing developments in firefighting foam technology turned out to be the Reebok series of foam conferences, held in Manchester and Bolton in the UK, 2002, 2004, 2007, 2009 and 2013.

Starting as early as 2002 a number of the smaller independent foam manufacturers started to offer first generation experimental Class B liquid hydrocarbon fluorine-free foams (F3) as more environmentally sustainable alternatives to PFAS -containing foams. During the following 10 years the debate raged on driven by published scientific studies which concluded that telomer chemistry posed a threat to the environment. Early telomer formulation were mixtures of 6:2 and 8:2 derivatives. The 8:2 material was shown to be a potential precursor for the generation of environmentally extremely persistent PFOA (perfluorooctanoic acid or C8) through breakdown, subsequently associated with long-term health effects. At the time this was vigorously contested by representatives advocating the fluorochemical industry attending Reebok conferences.
However, as a result of pressure from the US EPA many large feedstock manufacturers adopted the PFOA Stewardship Program 2010-2015 aimed at reducing the use of PFOA or its precursors. Improvements in purifying the fluorotelomer derivatives resulted in a reduction of PFOA related material to less than 25 ppb providing so-called ‘pure C6’ fluorotelomer derivatives. The Stewardship Program led to a change in foam formulations formerly containing C6/C8 fluorotelomers to a so-called ‘drop in’ replacement containing predominantly C6 fluorotelomer.
Unfortunately, this change was not as simple as it was supposed to be and foam manufacturers had to reformulate and increase the total fluorochemical content to achieve a similar performance compared with previous C6/C8 formulations. Unfortunately, end-users were not even made aware of this change!

Around the same time, scientific studies accumulated evidence that even hyper-pure C6 was NOT a suitable alternative, but a ‘regrettable substitution’ and the debate went to another level. 2015 marked a sea-change in the PFAS debate. The toxicity of PFOA was no longer denied by the fluorochemical industry or regulators and the issue was brought to the attention of the public by scientific journalists.

A series of public statements signed by scientists worldwide – the Helsingǿr Statement 2014, the Madrid Statement 2014 and the Zürich Statement 2018 – raised concerns about the continuing use of PFAS and as major planetary pollutants and their long-term impact on the environment. A major publication in 2020 raised the issue that all PFAS should be treated as a chemical class because of their common environmental problems rather than individual chemicals.

The United Nations Stockholm Convention and their Persistent Organic Pollutants Review Committee (POPRC) has added PFOS, PFHxS and PFOA to the appropriate Annexes banning or restricting use (2018-2022).

Countries such as Germany and Norway, or individual states such Queensland in Australia, have been at the forefront in regulating the use of PFAS, especially for highly dispersive use such as firefighting foams.

Some countries are not waiting for UN decisions to regulate the use of PFAS. In Europe, PFOS has been prohibited since 2011 and PFOA since 2018; current discussions aim to stop the use of all PFAS with C4 to C20 carbons completely with a deadline of 2025, in anticipation of these restrictions many industries are moving to fluorine-free technology. In the USA, change is being driven mainly by the cost of litigation with thousands of cases against the fluorochemical industry including foam manufacturers in the pipeline.

To be continued in Part 2

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About the authors : Dr Thierry BLUTEAU et Dr Roger A. Klein

Dr Thierry BLUTEAU
Managing Director
3F Americas – Panamá

Dr. Thierry BLUTEAU, French, studied at University of Paris XI, where he achieved a Master in Biochemistry and a PhD in Organic Chemistry.

In 1983, He is nominated as Professor of Biology at French Lycée in Montevideo in Uruguay for two years.

He starts to work in firefighting industry in 1992, where he is Technical Manager in Croda Fire Fighting Department.

6 years later, he funds the company Bio-EX, where he stands as Site Manager. He creates a range of firefighting foams and additives, and develops a wide network of international distributors, with presence in Asia, Australia, Africa and Latino America.`

In 2012, he keeps developing new foams independently in collaboration with LEIA Laboratories, and achieves the creation of two lines of innovative products : the firdt line is Smart Foam, foam products with no solvents and green profile. In 2020, a full line of FREGEN F3 is launched, fluoro-free products to be discovered on our website www.3fff.co.uk

Still active at R&D department in LEIA, he manages also our subsidiary 3F Américas in Panama City.

 

Dr. Roger A. Klein trained as a medical doctor and as a PhD physical chemist at the University of Cambridge. His academic research interests have covered tropical diseases, fundamental drug research, and more recently theoretical quantum chemistry (IUPAC Task Group on redefining hydrogen bonding) He has nearly 50 years experience advising and working with the Fire Service both in the UK and internationally, in areas that include hazardous materials (Hazmat and CBNRE) and decontamination issues, personal protective equipment (PPE), risk assessment and management, incident command and control, and the impact of fire service operations on the environment, having acted as Principal Scientific Adviser and Radiation Protection Adviser to Cambridgeshire Fire & Rescue Service until 2000. In the late 1990s he was asked by HM Fire Services Inspectorate to produce the first draft of UK guidance on risk assessment and management for the Emergency Services, which later became part of the Fire Service Manual. In 2002 he was involved in the McKinsey report on New York Fire Department (FDNY) operations at the 9/11 WTC incident in New York.

Following on from the 3M Company’s announcement on 16 May 2000 that it was withdrawing from PFOS-based chemistry he became heavily involved in the environmental chemistry of perfluorochemicals, especially as it affected the environment and human health through widespread contamination. In particular, he was concerned with the environmental impact of the dispersive use of firefighting foams, especially fluorosurfactant containing AFFF, and the transition to fluorine-free (F3) Class B foams. He has published extensively in the technical literature and co-organised a series of international seminars on the environmental impact of firefighting foams held at the Reebok Centre, Bolton, UK, in August 2002, December 2004, September 2007, July 2009 and March 2013, as well as the 1st Australian National Forum on Firefighting Foam held in Adelaide in 2011. More recently he has acted in an advisory capacity as a technical advisor to the Environment, Natural Resources and Rural Development Committee (ENRRDC) of the Parliament of Victoria (Australia) as part of the Inquiry into the legacy PFC contamination at the CFA Training College Fiskville, as well as accompanying the Committee on a study trip to Germany in December 2015.

He was also heavily involved in assisting the Queensland Government Department of Environment and Science in their development of a fire fighting foam management policy, including helping to co-organize a major conference held by the Department in Brisbane during February 2017. More recently he has been involved in presenting the case for fluorine-free firefighting (F3) foams as viable alternatives to AFFF as well as environmental and health issues concerning PFOS, PFOA and PFHxS to the UN Stockholm Convention Persistent Organic Pollutants Review Committee (POPRC-14) which met at the UN FAO Headquarters in Rome 17-21 September 2018, the ninth Convention of the Parties to the Stockholm Convention (COP-9) in Geneva 29 April-4 May 2019, and POPRC-15 also at FAO Headquarters in Rome 1-4 October 2019; acting as coordinator for the IPEN F3 Panel which produced a series of White Papers for the Committee and COP-9, which are now referenced by regulatory bodies. Formerly of the Universities of Cambridge and Bonn, and recently affiliated as a theoretical chemist to the Department of Chemistry, University of Wisconsin, Madison, since 2009 he has been Affiliated Research Faculty at the Christian Regenhard Center for Emergency Response Studies (RaCERS), John Jay College of Criminal Justice, CUNY New York.

In summary, since 2000 when the 3M Company announced withdrawing all PFOS-based chemistry, Roger Klein has been heavily involved in advising fire services, airports and industry, as well as collaborating with environmental regulators at national and international level, especially in Australasia (e.g., Australia, New Zealand, Singapore) and Northern Europe, in the control and remediation of PFAS environmental contamination. He assisted in the development of the 2016 Queensland foam management policy, now regarded as best-practice worldwide, and gave expert evidence to the Victorian Parliament’s Fiskville Inquiry 2015. He was also on the Advisory Board of a clinical study in Australia aimed at reducing blood PFAS levels in previously exposed firefighters, with the results published in April 2022 in the Journal of the American Medical Association (JAMA). He was previously a Member of the UK Institution of Fire Engineers, a Chartered Chemist and a Chartered Scientist; he is currently both a Fellow of the Royal Society of Chemistry and a Fellow of the International Union of Pure and Applied Chemistry (IUPAC); he now works as an independent scientific consultant.

Contact details:
Dr. Roger A. Klein, tel: +44 1223 306 846 mob: +44 07555 545 070 email: rogeraklein@yahoo.co.uk

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Serie of articles to review the foam facts – 3F

3F dedicates its activity around the proposal of safe and efficient solutions to control and extinguish fires. Our role is not only to manufacture and supply firefighting foams, but to inform our customers about the past, actual and future of the foams regarding the risks, the technology and the regulation.
To bring more awareness on the market, 3F decided to publish on its website a serie of articles to review the foam facts, from AFFF to F3.

About the authors:
Dr Thierry Bluteau: Leia Laboratories, UK. PhD Organic Chemistry.
See profile in the next article
Dr Roger A. Klein: Independent Consultant UK, PhD Physical Chemistry.
See profile in the next article

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3F MEXICO is born

3F enlarges its international network and offers now a direct sales service in Mexico. 3F MEXICO is located in Querétaro where it maintains a foam stock for emergencies and immediate delivery. From Querétaro 3F MEXICO offers its products and services to all its customers in the Republic.

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BV IMO APPROVAL

3F is happy to announce that our BV certificate has been renewed for 5 years.  The list of approved products includes our F3 FREEGENs and FREEDOL, our AFFF range of CHEMEX, FLUOEX and FREESOLV and 3 protein references FP397, PROSEAL 3 and 6.

3F will be pleased to inform you in detail for your requirements to satisfy and supply foam for your shipment activities.

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MOTO-TRUCK : our new ally

3F is pleased to announce the agreement to represent MOTO-TRUCK trucks in Latin America. This is based on our first sales in Mexico for around 30 trucks.

MOTO-TRUCK is a renowned manufacturer of fire trucks established in Kielce, Poland for more than 25 years.

MOTO-TRUCK offers a complete set of light, medium and heavy vehicles mounted on most chassis on the market: MAN, RENAULT, MERCEDES, IVECO, SCANIA, etc.

MOTO-TRUCK offers the advantage of integrating the in-house production of key parts: pump, nozzles, lighting mast, tanks, winch, etc.


MOTO-TRUCK sp. o. o. With headquarters in Kielce is a Polish manufacturer operating on the market of specialized vehicles for nearly 25 years. We manufacture, among others, pumps, plots, masts, tanks and shutters. We constantly implement innovative solutions to increase the functionality and facilitate the use of our products. The superstructures offered by us are supported by the most modern control systems. We make sure that the design of our vehicles is a combination of global trends dominating in the automotive industry and traditional and proven solutions.

We make superstructures for specialized vehicles from the highest quality corrosion-resistant materials – aluminum, stainless steel and recyclable plastics. The cars we have prepared have a water and foam tank made of corrosion-resistant materials. The equipment of the vehicles we deliver is based on the latest technical solutions. As a result, the vehicles we offer will prove themselves in multi-tasking operations, even in the most difficult geographical conditions.

Confirmation of the strong position of MOTO-TRUCK sp.z o.o. in the market of suppliers of specialist cars and the high-quality products offered, the certificate was granted in 2004 in the field of “Design and construction of rescue and fire-fighting and specialist bodies”. Professional and reliable production is ensured by the Quality Management System implemented and used since 2004, compliant with the PN-EN ISO 9001: 2000 standard and ISO 14001. In 2013, the company obtained the AQAP 2110: 2009 certificate in the field of: Design and installation of rescue and fire-fighting and specialized bodies, which confirms the high level of the quality management system. During the XXIX International Defense Industry Exhibition in Kielce (MSPO 2021), the company was awarded the Golden Quality Certificate in terms of creating quality and building the potential of the armaments and defense industry of the Republic of Poland.

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3F presents FREEGEN SMART FOAM® the third generation of F3 Fluoro-Free Foam!

  • 100% Fluoro-Free : no Fluorinated Organic Compound
  • Class 1-A under EN 1568:2015 for hydrocarbon fires and polar solvents fires
  • ICAO Class B
  • Technology SMART FOAM – Solvent-Free: Chemical Oxygen Demand is significantly reduced
  • Stable as a premix solutionno settlement or decay

FREEGEN SMART FOAM® is offered under two references :

FREEGEN SF-LV

  • LV- Low Viscosity: UNIQUE Foam F3 usable with all existing dosing equipment

This foam is the perfect foam for most users, as it combines the low viscosity with highest ratings and the best environmental profile

FREEGEN ULTRA

This foam has been designed to offer a maximum efficiency on tough risks. It is highly efficient on the most difficult fires, such as crude oil, ethers, ketones,… Recommended for oil industry and chemical plants

 

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3F Américas participates in a Show in Mexico

 

 

3F Américas and its commercial partner Actwa Emergencias, are increasing their activity to improve risk prevention in the industry.

3F attended the show DATACHAIN SUMMIT 2023 named as: CHANGING TRAINING IN THE INDUSTY WITH VIRTUAL REALITY AND INNOVATION, held on 20th and 21st of April 2023 in  Queretaro – Mexico.

During his presentation, Dr. Thierry Bluteau presented the world’s move towards related goods in the protection industry, with emphasis on the new Fluorine Free Foams FREEGEN SMART FOAM. He emphasized the combination between firefighting foams and the use of new technologies, such as High expansion and the benefits of High-Pressure equipment FAS, with the aim of protecting property, public health and our environment.

 

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3F doubles the surface of its manufacturing facility in Corby U.K.

Because of the growing demand for F3 foams, 3F decided to further invest and increase its foam manufacturing capacity. The new plant will extend our operational space to 3000 sqm and include 3 new 10,000 litre blending tanks. This will increase our capacity to more than 50 tons per day. Previous investments already ensure full separation of the manufacturing between F3 foams – FREEGEN, FREEFOR and HYFEX – and AFFF foams. This additional capacity will be fully operational in May 2023.

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3F around the world

Unit B, 18 Brunel Road,
Earlstree Industrial Estate, Corby,
Northants, NN17 4JW, UK

+44 (0) 1536 202919

sales@3fff.co.uk

1002 Toa Payoh Industrial Park
#03-1447
S.319074 Singapore

+65 6356 6040

export@3fffasia.com

Edificio Abou Saad 13,
Oficina # 104,
Albrook - PANAMA

+337 6146 1665

export@3famericas.com

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