Metallurgical and Refractory Minerals The minerals, which stand high temperature sat above 15000C, may be moulded

into bricks or other forms, resist cracking under temperature change, and are nonreactive with materials being melted are refractory materials. The metallurgical process involves high temperature, need refractory minerals for furnace lining. The important refractory minerals should have a high melting point and resistant to heat. Refractory Products Refractory materials are used in linings for furnaces (used for heating), kilns (oven), incinerators (waste to energy) and reactors (nuclear). They are also used to make crucibles. The important minerals are: Fire clay Graphite bauxite Chromite Dolomite Magnesite Sillimanite group of Minerals Pyrophyllite Quartz and quartz schist Zircon

1. Fire clay Fire clays are sedimentary mudstones that occur as the seatearths that underlie almost all coal seams. Fire clays are high alumina clays with some non-plastic refractory flint (mineral quartz) and with some moderately refractory plastic clays, which withstand temperature rise of 27140 F to 29840 F. The term fireclay was derived from their ability to resist heat and their original use in the manufacture of refractories for lining furnaces. Properties Fireclays are typically thin (normally <1 m, although rarely >3m) and are composed of the clay minerals kaolinite and hydrous mica (illite), together with fine-grained quartz in varying proportions; kaolinite is the key component. The impurities present are carbon, sulphur and iron, greatly influences their refractory properties. Fireclays are similar in basic composition to ball clays. Uses : Fire clay is chiefly consumed in refractory industry. Several kinds of fireclay bricks are manufactured: This kind of bricks are utilized in different industries, like iron and steel, ferroalloys, cement, glass etc. The other uses of fireclay are in the ceramics, sanitary ware products, sugar manufacture, abrasive, chemical, rubber, textile, etc.

Specifications Iron oxide contents should normally be less than 2.5% Fe2O3 and carbon and sulphur are common impurities and should normally be less than 1.5% and 0.1% respectively. Mode of origin and occurrence: Fireclays occur mainly as underlying the coal seams. The beds are small, lens-shaped and exhibit little lamination. They are considered to have originated from suspended matter carried by lowgradient streams into coal seams. Distribution: A number of opencast coal sites operated by companies such as UK Coal and H J Banks in England, and The Scottish Coal Company in Scotland have the potential to produce fireclay. In Britain economically important coals principally occur within the Coal Measures Group of Carboniferous age. Fireclay distribution in Tanzania: Coal deposits at Mchuchuma which is near the border with Malawi and Mozambique are estimated at 125.3 million tones. 2. Graphite Graphite is a hexagonal structure of carbon, one of the two crystal modifications of pure carbon, (C), the other being diamond. Properties: Graphite has properties of both metals and non-metals, which makes it suitable for many industrial applications depending on the specific grade. Graphite which is black, very soft, and greasy mineral is very typical for metamorphic rocks whose organic content has been metamorphosed to graphite. It has excellent electrical and thermal conductivity; outstanding lubricity, high thermal shock resistance, high temperature resistance up to >3,000C in O2-free atmosphere. It is also resistant to acids and oxidising agents. It is soft (harness 1 to 2 ) and iron-grey to steel grey in colour with black shining streak and sp.gr. of 2 to 2.3, depending upon its purity . It has a metallic lustre and fells cold like metal and owing to its being a good conductor of heat. Distribution The world graphite production is 1.13 m.tonnes, the main producing countries being China, India, Brazil, North Korea and Canada. Graphite is the second largest input material by volume used in Li-ion batteries, and it has been estimated that an additional 1m. tonnes graphite will be needed by 2020, a figure which still remains controversial in the industry.

Leading graphite producers include: China, India, Brazil and Canada. According to the United States Geological Survey (USGS), world production of natural graphite in 2008 was 1,110 thousand tonnes, of which the following major exporters are: China (800 kt), India (130 kt), Brazil (76 kt), North Korea (30 kt) and Canada (28 kt). Distribution is Graphite in Tanzania: In Tanzania graphite deposits are numerous. Only two deposits have been mined: 1. Small Nambiranje deposit in the Lindi region and 2. Big Merelani deposits. Merelani is the name of the village in the northern foothills of the leltema mountains About 16KM SW of Kilimanjaro International Airport, which is hlaf way between arusha and Moshi. In southern Tanzania graphite deposits are distributed in Lindi, Mtwara regions. Graphite also has been reported from eastern Uluguru mountains. Mode of occurrence and Origin In nature graphite occurs in metamorphic rocks (gneisses, schists, marble, quartzite and altered coal beds) and is divided in three types: (1) Amorphous: 70-85% C, most abundant, lowest price, (2) Flake: 85-90% C, less common and (3) Vein/lump: 90-96% C, rarest, the most valuable. Minerals associated with graphite include quartz, calcite, micas and tourmaline. 3. Bauxite Bauxite is an aluminium ore and is the main source of aluminium. This form of rock consists mostly of the minerals gibbsite Al(OH)3, boehmite [AlO(OH)], and diaspore [AlO(OH)]. Diaspore is grouped under high alumina refractory. It is distinguishes by its hardness(6.5 to 7) and pearly lustre on cleavage faces. The chemical composion of diaspore shows Al2O3 =56 to 62%, Fe2O3 = 1 to4 % TiO2 =0.8 to 1.5. Mode of occurrence and origin: It commonly occurs associated with corundum or emery as alteration product of the oxide. It occurs similarly in bauxite deposits and some of the bauxite may be diaspore. It has been noted as an accessory mineral in metamorphic limestone and dolomite. It has been found in the form of geodes and lenses associated with pyrophillite and quartz-reef.

Bauxite is a mixture of hydrated aluminium oxides. It is most favorably formed under near surface conditions in humid rain forests in tropical and subtropical regions. More than 90% of the bauxite mined in the world is used for the production of aluminium metal. Bauxite is no longer recognised as a mineral species, but is considered as a mixture of several aluminium oxides with considerable variations in alumina content. Iron oxides, halloysite, kaolinite, and nontrolite are invariably present as impurities.

Specifications of typical bauxite A typical bauxite contains 55 to 65 % Al2O3, 2 to 10% SiO2, 2 to 20% Fe2O3, 1 to 3 % TiO2, and 10 to 30% combined water. But a typical aluminium ore (bauxite) should contain at least 50% Al2O3, and less than 6% SiO2, 10% Fe2O3, and 4% TiO2. Specifications of bauxite for different uses ------------------------------------------------------------------------------------------------------------------------------Uses chemical composition of bauxite (% by weight) Al2O3 SiO2 Fe2O3 TiO2 ------------------------------------------------------------------------------------------------------------------------------Metallurgical 52 4.5 6.5 Chemical 52 3.0 Refractories 50 3-6 3-5 2.4-4 Abrasives 40-60 3-5 3-5 2.4-4 -----------------------------------------------------------------------------------------------------------------------------Occurrence Commercial bauxite occurs in three forms: (i) Pisolites or oolites, (ii) Porus sponge ore and (iii) amorphous or clay ore Other types of occurrence of bauxite and origin 1) Blanket at or near the surface 2) Interstratified bedded deposits lying on erosional unconformities 3) Pocket deposits or irregular masses in limestone or dolomite and 4) Transport deposits Occurrence of bauxite in Tanzania In Tanzania bauxite material is reported from Amani and west of Mombo towards the Lwengera valley in the Usambara mountains. Chemical analysis of bauxite material from different places -----------------------------------------------------------------------------------------------------------------------------Location chemical composition of bauxite (% by weight) Al2O3 SiO2 Fe2O3 TiO2 H2O Total -----------------------------------------------------------------------------------------------------------------------------Amani nodules 57.72 10.53 1.15 1.66 26.80 97.86 Mombo nodules(1) 35.14 26.35 7.40 1.54 22.49 93.92 Mombo nodules(2) 33.04 43.80 0.72 0.83 16.97 95.36 Western Uluguru 34.2 39.3 7.2 1.0 18.3 100 mountains -----------------------------------------------------------------------------------------------------------------------------4. Dolomite (CaMgCO3) : Dolomite is a double carbonate of calcium and magnesium (CaCO3=54.35% and MgCO3=45.65%) and is of great industrial importance. Some of the magnesium in the dolomite is replaced by iron or manganese, and with lesser proportion of magnesium carbonate, it is dolomitic

limestone. Chemically pure dolomite has a composition of 30.4wt% CaO. 21.9 wt% MgO and 47.7wt% LOI. Properties: It is yellowish-white or brownish-white in colour and some times tinged with red, green or black. The cleavage is perfect and lustre is vitrious including pearly in crystals, but massive types are dull and opaque. It shows conchoidal or uneven fracture and has hardness of 3.5 to 4 and sp.gr. 2.8-2.9.It is distinguished from calcite in that it does not bubble readily in cold acid. Refractory Specifications of dolomite For refractory usage, dolomite should have an equimolecular proportion of CaCO 3, and MgCO3. It must be low in SiO2, Fe2O3 and Al2O3 (together less than 3%). For calcined dolomite, the specifications are very rigid and SiO2 and Al2O3 should not exceed 1% each. Origin of Dolomite The origin of dolomite is one of the major unsolved problems in geology. Debate has raged for decades over whether dolomite is of "primary" origin (i.e. precipitated directly from sea water), or "secondary" origin (post-depositional changes of calcitic carbonates), and if secondary by what mechanism dolomitization occurs. No universal solution to this problem yet exists but most dolomite beds have been formed by the alteration of limestone, the calcite of which replaced by dolomite. Dolomitisation is often related to joints and fissures through which the solutions penetrated and thick beds of limestone may be changed to dolomite. The solutions are mainly from the sea, and an example of this change is seen in the conversion of the calcite and aragonite of coral reefs into dolomite by reaction with magnesium-salts contained in sea water. Distribution in Tanzania Neither exact locations nor reserves have been reported on nay of the dolomite occurrences in Tanzania with the exception of Chafukwa in Chimala area with 10 m thick massive band of dolomite distributed in several km. 5. Magnesite (MgCO3 ) Magnesite is magnesium carbonate. It forms commonly from the alteration of magnesium-rich rocks during low grade metamorphism while they are in contact with carbonate-rich solutions. Magnesite has the same crystal structure of calcite, hence its inclusion into the calcite mineral group. physical characteristics: Color is white or gray, also tinted yellow or brown. Luster is vitreous. Transparency crystals are translucent to transparent only in individual crystals. Crystal System is trigonal; Crystal Habits are usually massive forms such as lamellar, fiberous and course to fine grained rocks. Crystals are extremely rare, but when found are in the form of rhombohedrons or hexagonal prisms with a pinacoid termination. Cleavage is perfect in three directions forming

rhombohedrons. Fracture is conchoidal to uneven. Hardness is 4 - 4.5. Specific Gravity is approximately 3.0 (average) , Streak is white. Associated Minerals calcite, dolomite, aragonite, strontianite and serpentine. Origin Magnesite occurs as veins in and an alteration product of ultramafic rocks, serpentinite and other magnesium rich rock types in both contact and regional metamorphic terranes. Magnesite can also be formed via the carbonation of magnesian serpentine via the following reaction: Serpentine + carbon dioxide Talc + magnesite + Water 2Mg3Si2O5(OH)4 + 3CO2 Mg3Si4O10(OH)2 + 3MgCO3 + H2O 6. Alumino silicate (Sillimanite )group of minerals : The sillimanite group consists of : Andalusite Sillimanite Kyanite are naturally occurring aluminosilicate minerals that have the composition Al2SiO5 or Al2O3 SiO2. All three minerals convert at high temperature, 100 to 1650 degrees centigrade to mullite (crystobalite), which is also an excellent high temperature insulator. Andalusite is a polymorph with two other minerals; kyanite and sillimanite. One outstanding feature of sillimanite is that the volume porosity of grains hardly exceeds 6% after heating. They all contain 63.2% Al2O3 and 36.8% SiO2.

Properties Andalusite Orthorhombic Crystal system Colour Form Hardness Sp. Gravity Refractive Index Pink,Red,Grey, Brown Stout,prismatic crystal, grain size 7.5 3.15 1.629 - 1.647

Alumino-silicate minerals Kyanite Triclinic Blue, Green, White Sillimanite Orthorhombic White,Grey, Brown, Yellow Mullite Orthorhombic -

Bladed, Accicula,needle like Elongated, enlongated, tabular needle like 4-7 3.6 1.712 - 1.729 6-7 3.23 1.657 - 1.684 7 3.16 1.659 - 1.692

Decomposition Volume change

1380 -1400C

1350 - 1380C

1550 - 1650C Slight increase

1810C Stable

Very slight increase Notable increase

Physical properties of alumino-silicate minerals Uses: The main consumers of these refractories are iron and steel, glass, ceramic and cement industries. Because of the change in refractory technology, andalusite has greater demand and better market. Kyanite is easily distinguished from sillimanite or andalusite by its tabular, long bladed, acicular form and by bluish colour; and slightly lower hardness than sillimanite and andalusite. Another important property is its double hardness. Its specific gravity is 3 to 3.7. Distribution Kyanite can be found in a wide variety of locations around the world including: Brazil ,India, Kenya, Mozambique, Nepal, Russia, Serbia, Switzerland, Tibet Mode of Occurrence and Origin The sillimanite group of minerals occurs in metamorphic rocks, mostly of argillaceous composition. Andalusite is formed under conditions of high temperature and low stress in regional metamorphism. Sillimanite occurs as slender prisms in argillaceous crystalline rocks. It is produced high temperature and moderate stress, and is found in the rocks of innermost zone of thermal metamorphosed or in regional metamorphism of high grade. Kyanite is characteristic of argillaceous rocks, metamorphosed under high stress and moderate temperature, as in many gneisses and schists, pegmaties and also in eclogites. 7. Pyrophillite (Aluminum Silicate Hydroxide [(AlSi2O5OH)] Pyrophyllite resembles talc in physical properties, through differs in chemical composition.The laminae is flexible, but not elastic. It has greasy feel with hardness 1 to 2 and sp.gr. 2.8 to 2.9. Field indicators are crystal habit, color, cleavage, softness, aluminum test and feel. Pyrophyllite containing 28.3% Al2O3, 66.7% SiO2 and 5% H2O. In appearance it looks like talc and in physical properties also it is identical to talc. However, it differs in chemical composition, as talc is a hydrous magnesium silicate whereas pyrophyllite is hydrous aluminum silicate. Mode of occurrence and origin: It occurs as foliated masses in crystalline schists. It is found in gangue for kyanite minerals. It also occurs in slates and tuffs with inter-bedded breccias and flows, all of which have been metamorphosed.

Uses: The Pyrophyllite finds the same use as talc, that is why most of the countries combine the production figures of talc, steatite, etc. and pyrophyllite together. But it is not utilised for making body and face powders. Besides refractory, it is used in ceramic industry. 8. Quartzite and Quartz-schist Quartize and quartz schist are largely for use in refractory industry. They have high refractoriness and, hence, are used in the manufracture of acid-silica bricks. Silica sand of metamorphic origin is better than that of sedimentary origin. Physically, quartzite should be fine grained, compact and crypto-crystalline. Chemical properties: SiO2 95-97%, Iron (Fe2O3) 0.5%-1.5%, Alumina (Al2O3) 1 to 1.5%, Soda (Na2O) & Potash (Kro) Less then 1%, Lime (CaO) Less then 0.5%, Magnesia (MgO) Less then 0.5% and Loss On Ignition (LOI) Less then 0.5%. Mode of occurrence and Origin: Quartzite and quartz-schist occur in the form of beds, pocket, lenses etc. They usually form hillocks or mounds and resistant o alteration and may reach only the cataclastic stage of metamorphism under a given intensity. Sedimentary quartite also occur in nature. Uses Besides refractories, quartzite has been used in decorative items. Quartzite is the raw material for the glass and ceramics industries. Distribution in Tanzania: Rock crystals of small sizes were first rep psorted from gravels and surface detrital deposits near Mbirira north of Kasulu in Kigoma district. Marketable grade quartz crystal was made in the Rubeho area of the Kisola district. Large crystals of pegmatite quartz are found Uluguru mountains. 9. Zircon (Zirconium Silicate-Zr.SiO4 ) During the Middle Ages, zircon was believed to contain remedial power, protecting the wearer from diseases and banishing insomnia. The name "zircon" is believed to have derived from the Arabic words, "zar", meaning gold, and "gun", meaning color. Zircon is the chief mineral of zirconium is obtained in crystals or in the power form. It has a specific gravity of 4.08 with melting point of 13000C. The chief zirconium minerals are zircon and Baddeleyite (ZrO2). Properties

Zircon shows reddish brown, light yellow, greenish grey, or colorless with adamantine lustre, hardness of 7.5 and sp.gr. 4.7. Whereas the beddeleyite shows colourless to yellow, brown to black, H=6.5 and sp.ge.5.5-to 6. Distribution :Economic deposits are occurs in the beach sands of Australia, USA, South Africa, West Africa and India. Uses: Zircon, baddeleyite or manufactured zirconia are all useful refractory materials. They are valued for the preparation of special moulds and refractory bricks. High-grade zircon melts at about 2190C, softens between 1600C and 1800C and shows little shrinkage upto 1750C. Prepared zirconia and also zircon are extensively used in the glass and ceramic industry for enamels, porcelain and glazes. Mode of occurrence and origin The zircon is a common accessory mineral of igneous rocks, which is derived from magmas containing much soda, such as syenite, diorite etc. It is one of earliest minerals to crystallise from the cooling magma. It occurs as larger crystals in pegmatitic bodies. It is also found in metamorphic rocks such as gneisses and crystalline limestones etc. It is resistant to weathering, is a common constituent in placers concentrated along the beach sands and found in association with ilmenite, rutile, monozie, sillimanite etc. 10. Chromite (Feo. Cr2O3) Chromite is the only source of chromium metal, required by the alloy steel industry. It with stand temperature about 2000 degrees centigrade. Chromite is iron black or brownish black in color with brown strak, failt submetallic luster, and uneven brittle fracture and is having hardness of 5.5 and sp.gr. 4.5 to 4.8. The chemical composition of chromite contains 68% Cr2O3 and 32% FeO, but Al2O3, fe2O3, Mgo CaO and SiO2 replace some Cr2O3, reducing Cr2O3 content to as little as 40%. Refractory specification: Chrome-ore should be SiO2 6% (max), FeO 18% (max) and CaO 1%. Cr2O3 ans Al2O3 contents combined should be atleast 58-60%. Origin and occurrence: The chromite deposits are characterized by their close relationship with ultrabasic rocks ( deep seated intrusive igneous rocks) and have originated from concentration of early magmatic crystallization. It will occur in banded, massive crystalline and disseminated forms. So far no chromite deposits are reported in Tanzania.