Manganese compounds were in use in prehistoric times; paints that were pigmented with manganese dioxide can be traced back 17, 000 years. The Egyptians and Romans used manganese compounds in glass-making, to either remove color from glass or add color to it. Manganese can be found in the iron ores used by the Spartans. Some speculate that the exceptional hardness of Spartan steels derives from the inadvertent production of an iron-manganese alloy. In the 17th century, German chemist Johann Glauber first produced permanganate, a useful laboratory reagent (although some people believe that it was discovered by Ignites Kaim in 1770). By the mid-18th century, manganese dioxide was in use in the manufacture of chlorine (which it produces when mixed with hydrochloric acid, or commercially with a mixture of dilute sulfuric acid and sodium chloride). The Swedish chemist Scheele was the first to recognize that manganese was an element, and his colleague, Johan Gottlieb Gahn, isolated the pure element in 1774 by reduction of the dioxide with carbon. Around the beginning of the 19th century, scientists began exploring the use of manganese in steelmaking, with patents being granted for its use at the time. In 1816, it was noted that adding manganese to iron made it harder, without making it any more brittle. In 1837, British academic James Couper noted an association between heavy exposure to manganese in mines with a form of Parkinson's Disease. In 1912, manganese phosphating electrochemical conversion coatings for protecting firearms against rust and corrosion were patented in the United States, and have seen widespread use ever since. In the 20th century, manganese dioxide has seen wide commercial use as the chief cathodic material for commercial disposable dry cells and dry batteries of both the standard (carbon-zinc) and alkaline type.