1930s: A Happy Accident and the Discovery of the Father of Fluorinated Polymers
In 1938, a young chemist at DuPont, Roy J. Plunkett, was conducting research on new refrigerants to replace Freon when he stumbled upon something completely unexpected. One candidate – tetrafluoroethylene (TFE) gas – was being stored in a pressurized metal cylinder awaiting use in his experiments, but when he tried to release it, the gas stopped flowing before the container was empty. Curious, he cut the cylinder open and discovered that a mysterious waxy white substance had formed inside.
Surprisingly, the TFE molecules had polymerized spontaneously inside the cylinder to form a novel compound – polytetrafluoroethylene (PTFE) – which would become one of the most important materials of the 20th century (Gardiner, 2014). This is the origin of Teflon™ – as PTFE is more commonly known today – the frictionless coating that keeps eggs from sticking to your frying pan. PTFE consists solely of carbon and fluorine atoms arranged in a semicrystalline order, making it extremely hydrophobic, chemically inert, and heat and corrosion resistant – properties that turned out to be extraordinarily useful for applications in industries ranging from aerospace to electronics (Kořínek, 1994).
1960s to 1970s: From PTFE to Melt-Processable Fluoropolymers – Introducing FEP and PFA
While PTFE was a remarkable material, its major drawback was that it could not be manipulated using melt processing techniques like injection molding and extrusion, the dominant ways to shape plastics into useful products. Because PTFE decomposes before reaching its melting point, it has to be molded via more costly and less efficient methods like powder sintering, where it is compressed into the desired shape and then heated to just below its decomposition temperature. Because of this limitation, scientists began developing other semicrystalline fluoropolymers, such as fluorinated ethylene propylene (FEP) and perfluoroalkoxy (PFA), which offered better processing properties while retaining PTFE’s durability (Teng, 2012).
FEP and PFA improved upon PTFE in several important ways:
| Property | PTFE (Teflon™) | FEP | PFA |
| Melt-Processable | No, must be sintered as a powder | Yes, can be extruded, injection molded | Yes, can be extruded, injection molded |
| Thermal Stability | ~500oC | ~400oC | ~400oC |
| Chemical Resistance | Excellent | Excellent | Excellent |
| Flexibility | Rigid and more brittle | Most flexible | More flexible |
| Transparency | Opaque | Transparent | Translucent |
As you can see in the table above, FEP and PFA retained the most desirable properties of PTFE but allowed manufacturers to use conventional thermoplastic processing techniques, opening new applications in wire insulation, coatings, tubing, and semiconductor manufacturing (Teng, 2012).
1980s: The Birth of Amorphous Fluoropolymers – Teflon™ AF and CYTOP®
PTFE, FEP and PFA are semicrystalline materials, meaning they have both ordered (crystalline) and disordered (amorphous) regions. The degree of crystallinity affects their transparency across the ultraviolet (UV) to near-infrared (IR) spectrum. PTFE, having the highest crystallinity, is opaque. FEP and PFA have good transparency, but their crystallinity can cause some light scattering, degrading their optical clarity.
By the late 1970s, cutting-edge applications were driving the need for fluoropolymers that were completely amorphous – without any crystalline regions – to enable:
- Superior optical clarity (for photonics and waveguides)
- Solubility in fluorinated solvents (for making coatings and films)
- Low refractive index (for optical and sensing fibers)
- Superior gas permeability and selectivity (for gas separation applications)
- Lower dielectric constants (for next generation microelectronics)
- Electrowetting and insulating properties (for digital microfluidics) (Seyrat, Hayes, 2001)
This led to the development of amorphous fluoropolymers, starting with:
- Teflon™ AF (DuPont) – Developed in the 1980s as the first fully amorphous fluoropolymer.
- CYTOP (Asahi Glass, AGC) – Commercialized soon after and widely used in optical, electronic, and bioimaging applications.
Being fully amorphous – with no crystallites and absorbing functional groups – significantly enhances the optical properties of these materials, enabling minimal light scattering and high transparency across a broad wavelength range. Learn more about high-performance amorphous fluoropolymers in our previous blog post.
2020s: Modern Innovations – CyclAFlor® and the Era of Tailored Amorphous Fluoropolymers
Chromis Technologies (Chromis) was founded in 2004 to commercialize technology developed at Bell Laboratories to extrude high-bandwidth, low-attenuation graded-index polymer optical fibers (GI-POF) from AGC CYTOP for use in high-speed digital communications. Many years later, the company was looking to create new types of GI-POF with properties that CYTOP and other existing polymeric materials could not provide. Driven by a need for specialty polymers innovation, Chromis developed the ability to synthesize cyclic ring fluoromonomers and amorphous fluoropolymers. This new capability enables Chromis to produce custom amorphous fluoropolymers with specific properties for emerging challenges in high-tech industries.
One recent innovation includes CyclAFlor® Separator, a novel copolymer of perfluoro(butenyl vinyl ether) and perfluoro(2,2-dimethyl-1,3-dioxole) (PBVE-co-PDD) that demonstrates superior separation properties for mixed industrial gases, including a capability to remove carbon dioxide (CO2) from methane (CH4) in natural gas production (El-Okazy et al., 2022), and extract high global warming potential (GWP) refrigerants from azeotropic hydrofluorocarbon (HFC) blends (Harders et al., 2023). Separator is an example of how Chromis is working to address industrial needs as well as environmental concerns, positioning CyclAFlor tailored amorphous fluoropolymers at the forefront of specialty materials to support sustainable innovation.
Conclusion: From Accidental Discovery to High-Tech Marvels
From the accidental discovery of PTFE in 1938 to the development of amorphous fluoropolymers and their modern engineered variants, fluoropolymers have enabled new technologies and shaped multiple industries. Each breakthrough has addressed a technical challenge – whether improved processability with FEP and PFA, greater optical clarity with Teflon™ AF and CYTOP®, or optimized performance with CyclAFlor® – and expanded the applications of these unique materials. As industries continue pushing for cutting-edge solutions in high-tech applications like semiconductors and electronics, optics and photonics, and clean energy, specialty fluoropolymers will remain in the vanguard of advanced materials science, enabling further progress toward the next generation of technology innovations.
Learn More About Amorphous Fluoropolymers with Chromis Technologies
Chromis Technologies developed our CyclAFlor® family of amorphous fluoropolymers to meet the emerging demands of high-tech industries. Visit our website if you’d like to learn more about our expertise and how these unique materials can deliver the performance needed for your application.
References
- Gardiner, J. (2014). Fluoropolymers: Origin, production, and industrial and commercial applications. Australian Journal of Chemistry, 67(8), 1–13. https://doi.org/10.1071/CH14165
- Korínek, P. M. (1994). Amorphous fluoropolymers—a new generation of products. Macromolecular Symposia, 82(1), 61–65. https://doi.org/10.1002/masy.19940820108
- Teng, H. (2012). Overview of the development of the fluoropolymer industry. Applied Sciences, 2(2), 496–512. https://doi.org/10.3390/app2020496
- Seyrat, E., & Hayes, R. A. (2001). Amorphous fluoropolymers as insulators for reversible low-voltage electrowetting. Journal of Applied Physics, 90(3), 1383–1386. https://doi.org/10.1063/1.1383583
- El-Okazy, M. A., Liu, L., Abdellah, M. H., Goudeli, E., & Kentish, S. E. (2022). Gas sorption and diffusion in perfluoro(butenyl vinyl ether) based perfluoropolymeric membranes. Journal of Membrane Science, 644, 120095. https://doi.org/10.1016/j.memsci.2021.120095
- Harders, A. N., Sturd, E. R., Wallisch, L., Schmidt, H., Mendoza-Apodaca, Y., Corbin, D. R., White, W., Junk, C. P., & Shiflett, M. B. (2023). Solubility, diffusivity, and permeability of HFC-32 and HFC-125 in amorphous copolymers of perfluoro(butenyl vinyl ether) and perfluoro(2,2-dimethyl-1,3-dioxole). Industrial & Engineering Chemistry Research, 62(9), 4054–4063. https://doi.org/10.1021/acs.iecr.2c04518
Other Sources
- Cardoso, V. F., Correia, D. M., Ribeiro, C., Fernandes, M. M., & Lanceros-Méndez, S. (2018). Fluorinated Polymers as Smart Materials for Advanced Biomedical Applications. Polymers, 10(2), 161. https://doi.org/10.3390/polym10020161
- Obata, K., Hanzawa, M., Sima, F., Kawano, H., Ozasa, K., Hanada, Y., Miyaji, G., Miyawaki, A., & Sugioka, K. (2024). Fabrication of 3D microfluidic biochip using two-photon polymerized mold for high-resolution live bioimaging. 2024 Conference on Lasers and Electro-Optics Pacific Rim (CLEO-PR), Technical Digest Series. Optica Publishing Group. Paper Th1I_2.