A brief history of refractories (1)
  • Time:Nov 17, 2022
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      Refractories become necessary materials only after humans understand the use of fire, so it can be said that the history of fire is the history of refractories. It can be shown that on many occasions pottery occurred by applying clay to woven or wooden containers to make them resistant to fire, probably everywhere. Soon after, it was discovered that molded clay could be used in this way, without the need for internal containers. It can be seen that humans began to use clay as refractories about 15,000 years ago. Ruins of sun-dried brick dwellings dating from around 6000 BC have been discovered in Jordan. In addition, it is confirmed that sun-dried bricks were already widely used throughout Western Asia around 4500 BC. These unburned bricks were used to build pyramids and palaces. Around 2000 BC, fired bricks were made in the Indus Valley of Misopotalaia and Pakistan. It is said that from the Bronze Age in 3000 BC to the Iron Age in 1200 BC, these bricks began to be used in the furnace structure of fire, and by the 3~4th century AD, the furnace furnace using brick laying in alchemy has been very developed, and various small reflex furnaces, rotary furnaces, muffle furnaces, etc. have been designed.

      Accounts by the ancient Egyptians and Assyrians indicate that making clay bricks was one of the first industries to be established. However, early refractory manufacturing was not separated from the manufacture of metallurgical furnaces and did not become an important independent industry until later periods. In the 16th century, the British used sandstone furnaces to promote the development of the metal industry. The origin of refractory products dates back to 1615; The British made clay bricks from Stourbridge clay and Kayla clay from Conwall for masonry furnaces; Make crucibles from clay to melt glass.

      Bristol, England, successfully applied clay bricks to copper refining furnaces and spread to continental Europe. Russia used sandstone masonry to build the first iron-melting furnace in the 30s of the 17th century, and various metallurgical furnaces have long been built using natural materials. In the United States, iron furnaces and uncovered blast furnaces were built of stone. The first use of clay refractories in the United States was in glass melting furnaces and clay crucibles, and the clay refractories used were imported from Germany.

A brief history of refractories (1)

      Bricks are made from refractory clay or kaolin, and blast furnaces appear after the start of production. In 1810, Germany organized for the first time specialized in the production of clay refractories. The first production of clay bricks in the United States was in 1812, the first clay brick factory in Russia was built in 1865, in 1869 the Osaka Mint in Japan failed to manufacture refractory materials, and in 1873, the Ministry of Works Provincial Iron and Steel Bureau successfully manufactured clay bricks from Yunshan clay.

      The first manufacture of siliceous refractories was in 1822 by the Englishman W.W. Young, who first used the Dinas sandstone of Vale of Neatn in South Wales as raw material and lime bonding to make silicon bricks. The first silicon bricks to be made in the United States were made in Akron, Ohio, in 1866. Russia in the 80s of the 19th century organized the production of silicon bricks such as the O6yxOBCKOM plant in Petersburg, and the first factory specializing in the production of silicon bricks was built in 1889 by the Gekohckull silicon brick factory in Donbass. Japan discovered silica in 1892 at Sarutoyama Mikawa, and then began producing silicon bricks at the Shinagawa Refractory Company.

      Magnesia refractories first appeared in Austria in 1860. In 1866, Carnon, France, reported on the method of making magnesia bricks. Industrial production began in 1882. However, the United States did not successfully use it until 1888. Russia built a "magnesia" factory in Catka in the Urals in 1900. Japan discovered magnesite near the White Tiger Mountain in the northeast of China in 1918 and began to produce magnesia refractories. American Yongman made chemically bound magnesia bricks in 1928.

      In 1878, S.G. Thomas and DGilchrist used tar combined with dolomite as a converter lining and added lime to make calcium phosphate residue to dephosphorize the molten iron of high phosphorus into steel. The Thomas Alkaline converter steelmaking method was also extended to open-hearth furnaces. As a result, alkaline open-hearth furnaces with regenerative chambers were developed. In 1884, an alkaline open-hearth furnace with tar combined with dolomite bricks was built in England.

      The United Kingdom also began manufacturing chrome bricks in 1866. Chrome bricks were first adopted in Russia in 1879 at the Alexandrovsk Steel Foundry in Petersburg. The United States began to use chrome bricks in 1896 for steel mills. Japan began manufacturing chrome bricks in 1907. In 1913, Mecallim in the United States was the first to make iron-hulled non-chromium-fired magnesia bricks. In 1915, Wynam in the United Kingdom obtained a patent for the manufacture of chrome-containing ore containing 20%~80% chromium-magnesia bricks. In 1931, chrome-magnesia bricks appeared simultaneously on the markets of the United States, Germany and the United Kingdom. In 1933, Germany was successful in using chrome-magnesia bricks on all-alkaline open-hearth furnaces. In 1952, the American company Cohart obtained two patents for melting and casting magnesia bricks, which are mainly composed of 55% MgO and 45% chromium ore. In 1961, the US market sold directly combined magnesia bricks, and in 1962, the United States developed and recombined magnesia bricks.


      In 1900, H. Aharker proposed to use ZrO2 as a refractory material. The National Physical Laboratory of the University of Sherfield in the United Kingdom uses zirconia bricks to make bricks, but due to the volume changes accompanying the phase transition of ZrO2 monoclinic and tetragonal crystal systems, no usable products are made. In 1927, O. Ruff and F. Ebbert made stabilized zirconia products. In 1947, some stable ZrO2 products with good thermal shock resistance were successfully developed.

      In 1903, silicon carbide bricks were successfully developed and began to be used on zinc distillation furnaces in France and Belgium. Since the mid-60s of the 20th century, Si3N4 combined with SiC bricks, β-SiC combined with SiC bricks, and Si2ON2 combined with SiC bricks have been developed. In 1971, the United States tried silicon carbide bricks in the blast furnace air duct area. In the early 80s of the 20th century, Sialon combined silicon carbide bricks were developed.

      In 1925, Britain began to manufacture high-alumina bricks from kyanite clinker. In 1935, the Soviet Union made high-alumina bricks for the first time, and in the same year, Japan used high-bauxite produced in China as raw materials to manufacture high-aluminum bricks. The United States uses kyanite to make products close to the composition of mullite bricks, which are widely used in glass melting furnaces. Diaspore from Missouri, USA, was only recognized as a particularly good refractory material after 1917. Kyanite, sillimanite, andalusite refractories were introduced to the United States after World War I. High-alumina refractories were only developed in the 20th century.

      In 1929, carbon bricks began to be used in the bottom and belly of the German blast furnace. In 1921, the United States used Al2O368%~74%, and Fe2O3, TiO2 content is also relatively high bauxite as raw materials to make mullite cast bricks, and used for the side wall of glass melting furnace, the use effect is obviously good. In 1936, the United States manufactured zirconium mullite cast bricks containing 220% ZrO. The American Emery Company made the first cast alumina brick and named Monofrax, and in 1937 Monofrax-M containing β-Al2O3 and Monofrax-K containing a-Al2O3 were granted production licenses.


      In 1941, the American Colhart Company made Al2O3-ZrO2-SiO2 cast brick (AZS for short), that is, No. 33 AZS cast brick, which can increase the service life by 2~4 times for glass melting furnace. In 1960~1962, the French electrofused refractory company invented the oxidation method of melting zirconium corundum brick (AZS brick). In the 80s of the 20th century, the USSR developed AZS fused bricks with a ZrO2 of 45% and a ZrO2 of 50%. Japan developed ZrO293% more than 1% of cast bricks by adjusting the shape of Al2O3/SiO2 less than 1 by adding phosphorus.

      In the 80s of the 20th century, Japan developed a new type of zircon brick containing 7% silica powder. In the 90s, the United States developed dense thermally resistant zircon bricks for glass fiber melting furnaces, and at the same time developed fine-grained high-density zircon-zirconia sizing inlay tiles. In the mid-80s, Japan developed an aluminum-zirconium-zirconium carbon composite spout brick with ZrO2-C quality slag wire sleeve.

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