A brief history of discovery
During the Stone Age, people were already utilizing manganese oxide (pylurite) as a pigment in cave paintings. This practice dates back a staggering 17,000 years and was particularly popular among individuals during the late Paleolithic period. Remarkably, the ancient Greek Spartans even incorporated this versatile element into their weaponry. Their innovative use of manganese truly showcased its potential. Furthermore, both the ancient Egyptians and Romans recognized the value of manganese ore in the realm of glassmaking. They employed it to decolorize or dye glass, further highlighting its significance in ancient societies.
For centuries, pyrolusite had been utilized by people, yet Western chemists held a misconception about its composition until the 1870s. They mistakenly believed that pyrolusite contained tin, zinc, and cobalt. In the late 18th century, a Swedish chemist named T.O. Bergman dedicated his studies to pyrolusite, considering it to be a novel metal oxide. However, all his attempts to isolate the metal failed. Another Swedish chemist named Scheler also faced the same difficulty in extracting the metal from pyrolusite. Desperate for a breakthrough, Scheler sought help from his friend and Bergman's assistant, Gunn. In 1774, Gunn performed an experiment using Scheler's purified pyrolusite powder and charcoal, heating them together in a crucible for an hour. The remarkable outcome was a solid block of metallic manganese in the shape of a button [1]. It was Bergman who subsequently gave this newly obtained metal the name "manganese."
Development history abroad
During the early 19th century, the study of manganese's application in steel production captured the attention of British and French scientists. In 1799 and 1808, respectively, Britain and France acknowledged the potential of manganese. A significant breakthrough occurred in 1816, when a German researcher unveiled that manganese enhances the hardness of iron without compromising its ductility and toughness. Following this discovery, in 1826, Piege from Germany successfully created manganese steel using 80% manganese in a crucible.
The year 1840 saw J.M. Hitz achieve the production of manganese metal in England, further advancing the understanding of this element. A substantial milestone occurred in 1841, when Passa initiated industrial-scale manufacturing of mirror iron. The year 1875 marked the commencement of commercial production of ferromanganese by Passa, containing an impressive 65% manganese content.
These sequential developments demonstrate the progressive exploration and utilization of manganese's properties in the steel industry within the mentioned timeframe.
In the early industrial revolution, a significant milestone was achieved in the history of metallurgical development with the advent of the Bessemer method in 1860. Named after its creator, Bessemer, this steel-making process faced a challenge of excessive oxygen and sulfur retention in the steel. Fortunately, in 1856, Mahit proposed a brilliant solution - the addition of mirror iron (ferromanganese with lower manganese content) to the molten steel, effectively eliminating the sulfur. This breakthrough marked the transition from the "iron age" to the "steel age," marking a new era in industrial progress. The utilization of manganese in this context demonstrated its crucial role in steel production, cementing its significance in the advancement of metallurgy.
Patent applications made by William Siemens in 1866 marked the beginning of the use of ferromanganese in controlling phosphorus and sulfur levels in steel production. Following this, Leclanché invented the first dry battery in 1868, using manganese dioxide as a cathode depolarizer. The rising demand for manganese dioxide in the battery field was a significant factor in the growth of the manganese dioxide market.
In the years that followed, European countries began using blast furnaces to produce mirror iron containing 15% to 30% manganese, and ferromanganese containing up to 80% manganese. The electric furnace process for producing ferromanganese was first introduced in 1890, while the aluminothermic method of producing metal manganese came into existence in 1898. Later, the electric furnace desiliconization refining method was used to produce low-carbon ferromanganese.
In 1939, the process of producing metal manganese through electrolysis began. With the continuous advancements in technology, the annual output of manganese continues to increase. According to the US Geological Survey's data from 2015, the global manganese ore production in 2013 was approximately 18 million tons.
Apart from its predominant use in the steel industry, manganese has found its way into diverse fields such as batteries, the chemical industry, electronics, agriculture, and medicine, among others. This highlights the growing consumption of manganese in various sectors and the significant role it plays in modern society.
Domestic development history
In my country, the exploration of manganese ore started in 1886 [4], with the initial discovery of manganese ore occurring in Xingguo Prefecture (now Yangxin) in Hubei in 1890. Following the establishment of New China, extensive geological exploration for manganese ore began. As of the end of 2012, a total of 213 mining areas had been identified with confirmed reserves in my country.
