Potential safer substitutes for PFAS (Forever Chemicals)

Author: Gayathri Rajendran

PFAS is an acronym for per- and polyfluoroalkyl substances. These are man-made group of synthetic organofluorine chemical compounds that have multiple fluorine atoms attached to an alkyl chain.

These PFAS have unique characteristics such as:

1. Water resistance
2. Oil resistance
3. Scuff Resistance
4. Dirt Resistance
5. Heat stability
6. Chemical stability

Owing to these characters, they are widely used in various applications where oil, water and dirt resistance are required, such as non-stick cookware, water-repellent clothing, stain resistant fabrics and carpets, cosmetics, firefighting foams etc.

Due to their chemical structure, PFAS are not easily degradable. Also, they are highly persistent and bio accumulative in nature, and they result in various health problems like kidney and liver damage, cancer, impaired fertility and immunity, and adverse pregnancy outcomes in humans.

There has been an increasing regulation to phase out non-essential uses and production of PFAS globally (Please refer to Beroe’s article on Recent Regulation on PFAS). A global level of awareness is spreading on the harmful effects of PFAS on humans and the environment. This article covers why PFAS has such a key role in the industry, potential impacts and identified the safer substitutes for these PFAS specific to various industries.

Why PFAS are so special:

These compounds are made up of carbon and fluorine. The bond between carbon and fluorine is a strongest covalent bond. This bond gets even stronger when more fluorine atoms are attached to the same carbon. For example, the bond strength of tetrafluoro methane (4 fluorine is attached to one carbon) is high compared to fluoroalkane (one fluorine is attached to carbon atom).

This chemistry is the reason they are called forever chemicals as they cannot be broken down by the environment when the effluent is exposed to the water bodies or by human body when consumed along with lipsticks (lipsticks also have these harmful PFAS).

PFAS are, in general, used to give repellence from oil, water, and grease. This particular property of these PFAS makes them so inevitable that these chemicals are used in mascara to medical devices.

One Magical Substitute

Nearly 70% of the PFAS produced by volume are four chemicals namely PFOS, PFOA, PTFE and PFHxS; and the remaining 30% accounts for nearly 4000 PFAS which are used in various sectors. Hence, the first idea was to find where these PFAS are used and what can be the potential substitutes for these PFAS.

An interesting insight in our research process was one of the PFAS chemical called Perfluorooctanoic acid (PFOA) is used in various applications like textiles, paints, coatings, firefighting foams, non-stick coatings, cosmetics, electronics, aerospace, automotive and chemicals. One magical alternative chemical is not available currently to replace PFOA in all the above-mentioned applications. For example, a replacement like acrylic based resin named HIGUARD NF-184 from Hi-Chem can give oil and water repellency on textile fibres but cannot be used on a firefighting foam or on a mascara to provide the same characteristics provided by PFOA.

So, PFOA cannot be replaced with a single substitute for all applications and the focus shifted from PFAS types to industries. We studied what property the PFAS chemicals are imparting which makes them so inevitable and studied other chemistry which can substitute these PFAS in terms of technical and safety parameters.

Can a substitute be regrettable in future?

While studying the safer substitutes, we should be diligent enough to understand the concept called regrettable substitutes. When a chemical is under scrutiny, it will be replaced by another chemical without being analysed completely on all levels and eventually the replacement is nearly harmful or sometimes more harmful than the first chemical.

The so-called replacement GenX produced by Chemours (one of the largest producers of PFAS) is an ammonium salt of hexafluoropropylene oxide dimer acid (HFPO-DA) or in short-term, it is an organofluorine chemical. Thus, the same law on C-F bond is applicable here.

So, we did not include any substitutes which are organofluorine in nature in our study.

Textiles: 

Until recent years, there were no alternatives commercially available which can impart oil and water repellence on textile fibres but certain commercial products like HIGUARD NF-184 (Hi-Chem) a non-fluoro, Eco friendly acrylic resin which can provide excellent water and oil repellency on natural and synthetic fibres.

Please find the commercially available safer substitutes, the chemistry behind them, the technical and environment toxicology data given below:

Fire Fighting Foam

PFOA and PFOS are mainly used in firefighting foams. As per EPA guidelines, from July 2025, the usage of PFOA in firefighting foams are prohibited. There are various alternative chemistries available in this segment. However, a non-fluorinated foam is necessary in larger volume when compared to the PFAS based for a similar performance. Though it seems expensive, this cost is nothing when compared to the clean-up and treatment cost when using PFAS based firefighting foams.

Coatings

The PFAS materials are coated to give protection from water, dirt and heat. In certain applications like solar panel, the PFAS coatings are self-cleaned (protection against dust).
There are wide variety of chemistry in this sector which can substitute PFAS in various aspects but not all at once. No alternative can give protection against fire/weather/dust/temperature, non-sticking, non-wetting, high dielectric performance properties at the same time.

Electronics and Semi-Conductor

PTFE is mainly used in this sector. This fluoropolymer fundamental characteristics such as hydrophobicity, flame retardancy, dielectric strength and chemical inertness along with cost effectiveness is the major reason for its growing demand in this application.

Printing Inks

Rub resistance is an essential criterion for printing inks. The material should not be smudged or scuffed when applied on a material when it's in moving. PTFE and PFOA are usually added to improve the scuff resistance in printing inks.

Paints

Fluro surfactants are added to the paints to improve the adhesion and to impart dirt and chemical resistance.

Packaging

PFAS materials gives grease resistance to packaging material. The usage of PFOA and PFOS are restricted in food packaging material. There are variety of safer substitutes commercially available in this sector.

Cosmetics

The oil and water resistance property of PFAS helps give a long-lasting effect on skin when added to a make-up/skin care product. Mascaras, lipsticks and foundations are tested to show elevated level of fluorine as these products require high water-resistance property. 
Leading brands like L’Oreal faced lawsuits as their mascara had PFAS but the ingredient list will be silicones and acrylates. In order to increase the water repellency and high gloss the fluorinated versions of methicone and dimethicone, acrylate, methacrylate and silicone polymers are used which were detected during the test.

Chemicals

PFAS are mainly used in Industrial surfactants and heat transfer fluids applications. These PFAS have a unique nature that they are both hydrophobic (water-resistance) and oleophobic (oil-resistance) and has high resistance property. The commercially available alternatives for PFAS in industrial surfactants and heat transfer fluids are given below.

Non-stick Coating for Utensils

A non-stick pan which we use in our daily life is the simplest application of PTFE (trade name Teflon). Research shows that when these Teflon-coated pans are heated over 348 °C, the coating can begin to deteriorate and the fumes when inhaled causes lung injury which results in fever commonly called as Teflon flu. 
When we analyse the cost of the alternative non-stick coatings for pan, the fusion coated aluminum non-stick pan costs around USD 37 mostly in comparable price range to Teflon coated pans which cost around USD 30 but the NanoBond™ coated pans are expensive and the titum pan costs around USD 200.

Automobiles

Fluoropolymers are used in brake lines, fuel lines, shaft seals, valves etc currently there are no effective technologies that can replace these PFAS, but certain available options are listed below.

Medical Device

Certain critical applications like high dielectric insulators which are used in pacemakers and MRI imaging devices may not be replaced at once as there are no workable alternatives available currently, but dental floss can be rid of PFAS.

Fuel cells

PTFE and ionomers are mainly used in fuel cells and PEM membranes. Till date, there are no alternatives to perfluorinated membranes which gives minimum acceptable levels of function.

Conclusion

Nothing can be changed until its faced. Now the industry and environment are facing the challenge and it is advisable to shift to PFAS-free alternatives which are commercially available in the market. 
Sometimes the combination of alternatives may even give superior results. For example, in firefighting foam application a hydrocarbon-based foam in combination with a detergent based foam can exceed the performance of PFAS based foam.

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