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After a long period attempting to develop a process to upgrade rubber qualities (such as including nitric acid) that almost ruined him, in 1840 Goodyear discovered vulcanization, quite by accident. An interesting fact: in 1815, a humble sawyer-Hancock-became one of the leading manufacturers in the UK.
In the 50's they were more commonly made in the calf high version and in the 60's they were both superseded by the ankle boot, except for riding. After Charles Goodyear (1800-1860) invented a vulcanisation process for rubber some American bookmakers began making rubber boots. Hiram Hutchinson saw the potential to shod agricultural workers in France and bought the patent from Goodyear in 1852.