The first patent for AFFF and maybe fluoroprotein foams was by Tuve & Jablonski at the Naval Research Laboratory in the early 1960’s. The Naval Research Laboratory has played a major role since then is extensively testing fire fighting foams for US military applications.
National Foam had the first fluoroprotein on the market in 1964.
Non aspirated AFFF application became relatively common by the mid 1980’s after a number of test series by Mobil and the US Navy.
In the early 1980’s the first alcohol resistant AFFF’s were developed.
In the mid 1980’s FFFP and AR-FFFP products were developed
In the late 1980’s low viscosity AR-AFFF’s became available.
The US Navy and the oil industry have conducted many large scale tests over many decades. The US Navy has published many performance evaluations of their AFFF systems over the decades also.
In the 1990’s non-aspirated foam application for tank fire fighting became more common, though with higher than normal application rates.
Since their development there have been thousands of technical articles published on fluorine containing foams. In the References section of these pages you can find a small selection of them. These pages all have reference sections of their own and a web search can find even more (a search for “Tuve, R.L., & E.J. Jablonski. Aqueous Film Firefighting Foam“ will find quite a few links to some of the research that has been published).
Patent – AFFF. Tuve RL, J.Jablonski E., Method of extinguishing liquid hydrocarbon fires. U.S. Patent 3,258,423. 1966 Jun 28
Patent – ARAFFF. Peter J. Chiesa, Jr., Edward C. Norman, Preparing fire-fighting concentrates. US Patent 4,464,267 Aug 7, 1984