Unit-V Engineering Materials

Unit-V Engineering Materials
5. 1 UNIT-V ENGINEERING MATERIALS Introduction: Engineering materials are those materials which are usually used in engineering applications in the field of science and technology. These materials are used in check abrasives, adhesives, lubricants, refractories, ceramics, glasses, metals, polymers, semiconductors and other multiphase systems. Engineering materials play an important roles in mechanical and civil engineering fields, where very specific requirements are needed. Refractories Definition Refractories are the materials that can withstand high temperature without softening, melting or deformations in shape. Refractories are chemically inert and hard in nature. The major function of a refractory is to withstand high temperatures and to resist the abrasive and corrosive action of molten metals, slags and gases. Characteristics of a Refractory It should be infusible at high temperature. It should be chemically inert towards corrosive gases, metals and slags produced in the furnaces. It should resist the abrasive action of gases. It should withstand the applied load of structure at operating temperatures. It should have uniform expansion and contraction. It should not get cracked at operating temperature. It possesses low permeability. It should have high refractoriness. It should be able to withstand overlying load of structure, at operating temperature. Uses of Refractories 1. They are used in making crucibles for processing materials at high temperature. 2. They are mostly used for the construction of lining of furnaces, kilns etc., 3. They are also used in the manufacturing of cement, glass, ceramics, paper, metals.(both ferrous and non-ferrous) etc., Classification of Refractories Refractories are mainly classified into two ways on the basis of chemical properties of their constituent substances and their refractoriness.
Department of Chemistry, Annapoorana Engineering College, Salem
5. 2 According to their chemical properties REFRACTORIES
Acidic Refractories Ex: Silica Alumina
Basic Refractories Ex: Magnestie Dolomite
Neutral Refractories Ex:Graphite Carborundum
Acidic Refractories: They contain acidic materials like alumina (Al2O3) and silica (SiO2) and are not attacked by acidic materials. They are easily attacked by basic materials. Ex.: Alumina, Silica, fire clay refractories. Basic Refractories They are basic materials like CaO, MgO etc., and not attacked by basic materials. They are easily attacked by acidic materials. Ex.: Magnsite, Dolomite, Chrome magnsite. Neutral Refractories: They are made from weakly acidic / basic materials like carbon, chromite, zirconia, etc., but remain unaffected by acidic or basis materials. Ex: Graphite, Chromite, Zirconia, Carborundum refractories. According to their refractoriness: S.NO 1 2 3 4 TYPE OF REFRACTORIES Low heat duty refractories Intermediate heat duty refractories High heat duty refractories Super heat duty refractories PCE VALUE 19-28 28-30 30-33 >33 REFRACTORINESS(0C) EXAMPLES 1520 1630 1630 1670 1670 1730 >1730 Silica bricks Fireclay bricks Chromite bricks Magnesite bricks
5. 3 Based on the oxide content, they are also classified as. 1) Single oxide refractories Ex.: Alumina, Magnesia, Zirconia 2) Mixed oxide refractories Ex.: Spinel, Mullite 3) Non-oxide refractories Ex.: borides, Carbides, Silicates Properties of Refractories 1. Refractoriness It is the ability of the refractory materials to withstand the heat without softening or deformation under the working conditions. Usually refractoriness of materials are measured by measuring its softening or fusion temperature higher than the operating temperature of the industries. Ex.: Fire clay bricks (1600 1750C) Bauxite bricks (1730 1850C) Chromite bricks (1950 2200C) Zirconia bricks (2200 2700C) The refractoriness is determined by means of the standard PCE (Pyrometric Cone Equivalent) Test. Pyrometric Cone Equivalent (PCE) Pyrometric Cone equivalent is the number, which represents the softening temperature of a refractory specimen of standard dimension (38mm height and 19mm triangular base) and composition. Ex: S.No. 1 2 3 Refractory Silica bricks Alumina bricks Magnesite bricks PCE. Number 28.32 36.38 38 Softening temperature 17100C 1800-18500C 18500C
Objectives of PCE Test: (i) To determine the softening temperature of a test specimen material (ii) To classify the fire clay refractories. (iii)To check and determine the purity of the refractories. (iv) To check the uniformity of the composition of the materials.
5. 4 Measurement of PCE
The Rafractoriness is commonly measured by comparing the softening temperature of a test cone with the softening temperatures of the pyrometric cones. Pyrometric cones are pyramid shaped standard refractories of definite composition and dimensions and also having definite softening temperatures. A test cone is prepared from a refractory material, similar to pyrometric cones. The test cone is placed on an electric furnace along with pyrometric cones. The furnace is heated at a standard rate of 100C per minute; during which softening of pyrometric cones occurs along with test cone. The temperature at which the apex of the cone touches the base is taken as it softening temperature. A good refractory should have high refractoriness. 2. Refractoriness Under Load (RUL) The temperature at which the refractory deforms by 10% is called refractoriness under load (RUL) A good refractory material must possess high mechanical strength to withstand compressive loads, tension and stress without deformation at high temperature. Generally softening temperature decreases with respect to increase of the load. The capacity of load bearing character can be measured by RUL Test. RUL Test: It is conducted by applying a constant load of 1.75 kg/cm2 on test material of size 5cm2 and height 75 cm and heating on a carbon resistance furnace at a standard rate of 100C per minute. A good refractory should have high RUL value.
5. 5 3. Dimensional stability It is the resistance of a refractory material to change in volume due to its prolonged exposure to high temperatures. These dimensional changes could be reversible or irreversible. Irreversible changes may lead to contraction or expansion. These changes take place because of variations in the extent of vitrification or because of transformation from one crystalline form into other having different density as below Examples a. Magnesite bricks ( contraction) Magnesite Periclase Amorphous Crystalline Sp.gr = 3.05 Sp.gr = 3.54 b. Silica bricks ( expansion) 870C Quartzite (crystalline) Tridymite ( form) 1470C Cristobalite ( form)
4. Porosity A good refractory should have the low porosity. Porosity may be defined as the ratio of its pore volume to the bulk volume. Porosity P = W - D W -A X 100
Where W - weight of saturated specimen D - weight of dry specimen in air A - weight of saturated specimen submerged in water Porosity is an important property of a refractory. It decreases the strength, resistance to abrasion, chemical stability and thermal conductivity. Advantages of high porosity refractory (i) High porous refractory increases resistance to thermal spalling. (ii) High porous refractory materials possess lower thermal conductivity due to the presence of more voids.
5. 6 Disadvantages of high porosity refractory (i) It reduces the strength of the material. (ii) It also reduces resistance to abrasion. (iii)It reduces the resistance to corrosion. A good refractory should have low porosity. 5.Thermal spalling Thermal spalling is the property of breaking, cracking, peeling off a refractory material under high temperatures. A good refractory must show a very good resistance to thermal spalling. Thermal spalling is mainly due to, i) Rapid change in temperature: This causes uneven expansion and contraction within the mass of the refractory which leads to the development of internal stress and strain that leads to spalling ii) Slag penetration into the refractory brick: This causes the variations in the coefficient of expansion and leads to spalling. A good refractory material should have low co-efficient of expansion.
Spalling can be reduced by Using high porosity, low coefficient of expansion and high thermal conductivity refractory bricks. Avoiding sudden temperature changes. By modifying the furnace design so that stress is not setup, when the furnace is heated. Preventing slag penetration. Over firing the refractories at high temperatures for sufficiently long time, that making the material less susceptible to uneven expansion and contraction, when heated. Properties like Permeability, Bulk density, Thermal conductivity, Chemical inertness, Thermal expansion, Electrical conductivity, Texture, Resistance to abrasions and Heat capacity are other important factors of a refractory. Manufacture of Refractories: Manufacture of a refractory consists of the following steps: 1. Crushing: The raw materials in the form of big lumps are crushed to about 25mm in size. 2. Grinding: The crushed materials are ground down into 200 meshes in size by using crushers, pulverizers, hammer mills, ball mills, and screens. The ratio of coarse to fine particles should be even.
5. 7 3. Screening: It involves the purification of the refractory raw materials. It is essential to remove the unwanted materials from the raw materials for producing better refractories. This is done by (a) setting (b) magnetic separation and (c) chemical methods. 4. Storage: After screening and mineral operating dressing, the pure materials are stored in storage bins with bucket elevators. 5. Mixing: It is done for the proper distribution of the plastic materials throughout the mass. This makes moulding easier. 6. Moulding: Moulding can be done by hand or mechanically. Mechanical moulding produces refractories having more density and strength than that produced by handmoulding. De-moulding of the refractory material is essential for increasing the density and the strength of the refractory by mechanical moulding. 7. Drying: Slow drying is employed to remove the moisture from the Refractories which help to avoid voids and high shrinkage. So drying mobilizes the strength of the refractory and making it safe for subsequent handling. 8. Firing: The Refractories are fired in kiln at a temperature as high as or higher than their use temperature to stabilize and strengthen their structure. Depending upon the nature of the bricks the firing temperature will be different. Firing helps (a) to remove water of hydration (b) to impart high crushing strength (c) to facilitate development of stable mineral forms to the finished products. Manufacture of common Refractory: Alumina Bricks (or) Fire Clay Bricks: Alumina bricks contain 50% or more of Al2O3. They are generally manufactured by mixing calcined bauxite (Al2O3) with clay binder. Note: Calcination: Heating the ore in the absence of air Manufacturing: 1. Grinding and Mixing: The raw materials (calcined bauxite & SiO2) and calcined fire clay are ground to fine powder and are mixed with required amount of water to convert it into pasty material. 2. Moulding: The pasty material is converted into bricks by the general moulding technique like machine pressing or slip casting. 3. Drying and firing: The bricks after moulding are dried slowly to remove the moisture and then fired in a continuous kiln or tunnel kiln to about 1200 14000C for 6-8 days. Properties: Alumina bricks are acidic refractories. They posses very high coefficient of expansion.
5. 8 They also posses high porosity, and high temperature load-bearing capacity. They are inert to the action of gases like CO2, H2 and natural gas. They are also very stable to both in oxidizing and reducing conditions. They posses better resistance to thermal spalling. Uses: Medium-duty bricks (containing 50 to 60% Al2O3), are used in linings of cement rotary kilns, soaking pits, reheating furnaces and walls etc., which are subjected to high abrasion. High-duty bricks (containing 75% Al2O3) are used in hottest zones of cement rotary kilns, lower parts of soaking pits, brass melting reverberatories, aluminium melting furnaces, etc., Fire clay refractories are largely used in steel industries.
MAGNESITE BRICKS Magnesite bricks contain mainly MgO. They are generally manufactured by mixing calcined Magnesite with caustic magnesia or iron oxide as binding materials. Manufacturing of Magnesite Bricks 1. Grinding and mixing: The raw materials (calcined Magnesite) and binding materials (caustic magnesia (or) iron oxide) are ground to fine powder and mixed with water to a pasty material. 2. Moulding: Moulding is usually done by machine pressing to a required shape. 3. Drying and firing: Drying is carried out at ordinary temperature to remove the moisture. Firing is done in a kiln at 15000C, for 8 hours and then cooled slowly. Properties: Magnesite bricks are basic refractories. Magnesite bricks can be used up to 20000C without load and up to 15000C under a load of 3.5kg/cm2. They have good resistance to basic slags, but combine with H2O and CO2. They possess good strength, little shrinkage. They have poor resistance to abrasions. They are used in steel industry for the lining of basic converters and open-hearth furnaces. They are also used in hot mixer linings, copper converters and reverberatory furnaces.
5. 9 ZIRCONIA BRICKS Manufacture: They are prepared by mixing zirconite mineral (ZrO2) with colloidal Zirconia or alumina as binder and finally heating to 17000C. A small amount of MgO or CaO is added as stabilizer because mineral zirconite undergoes volume changes on heating and cooling. Properties: Zirconia bricks are neutral refractories. Though Zirconia bricks are neutral, they are affected by acidic slags. They can be used up to 20000C and up to 15000C under a load of 3.5kg/cm2. They are also quite resistant to thermal shocks. Their thermal expansion is low. Uses: They are used only where very high temperature is maintained, e.g., high frequency electric furnaces.
ABRASIVES Abrasive are hard substances, used for polishing, shaping, grinding operations. They are characterized by high melting point, high hardness and chemical inertness. Characters of abrasives: Characteristics of an abrasive are as follows They are very hard. They are chemically inert. They have high melting point. They possess high refractoriness. They should not be affected by the frictional heat. They should be resistant to mechanical shock. They should resist the abrading action.
5. 10
Mohs scale of hardness Hardness is the most important property of an abrasive. It is the ability or capacity of an abrasive to grind away another substance. Mineralogist has suggested a scale for determining the hardness of abrasive substances known as Mohs scale or Vickers scale.
Scale In this scale, the hardness of common abrasives are given in the increasing order. According to this scale, talcum power is having the hardness of one and it is the softest material and the diamond is having the hardness of 10 and it is considered as the hardest material. The hardness of any material on Mohs scale therefore falls between 1 and 10. Name of the abrasives Talc Gypsum Calcite Fluorine Apatite Feldspar Quartz Topaz Corundum diamond Chemical formula 3MgO.4SiO2.H2O CaSO4.2H2O CaCO3 CaF2 CaF2.3Ca3(PO4)2 K2O.Al2O3.6H2O SiO2 AlF3.SiO2 Al2O3 C Mohs number 1 2 3 4 5 6 7 8 9 10
5. 11 Abrasives having their hardness 1 to 4 in Mohs scale are called soft abrasives. E.g., talc, gypsum, calcite, etc. Properties of abrasives: Hardness It is the ability of an abrasive to grind or scratch away other materials. The harder the abrasive the quicker will be its abrading action. Hardness of the abrasive is measured on Mohs scale or Vickers scale. Measurement of hardness using mohs scale: Mohs scale is a scale in which common abrasives (natural or artificial) are arranged in the order of increasing hardness. Talc, quartz, diamond have got 1,7,10 in mohs scale. Abrasive having their hardness 1-4 in Mohs scale are known as soft abrasives. Toughness: Abrasives are generally hard and brittle, which is otherwise known as toughness. Abrasive power: It is the strength of an abrasive to grind away another material. It depends on hardness, toughness and refractoriness. Classification of abrasives: Natural abrasives Non-siliceous abrasives: Diamond: It is pure crystalline carbon. It is the hardest known substance. It is chemically inert and not affected by acids or alkalies. The off-color diamond is called borts and black color diamond is called carbonado. Uses: It is used in drill points, cutting rocks, stones and grinding wheels. Corundum: It is pure crystalline alumina (Al2O3). Its hardness on mohs scale is 9. Uses: It is used for grinding glasses, gems, lenses, metals, etc. Emery: It is a fine grained, opaque, black colored mineral. It consist of I. 55-75% crystalline alumina II. 20-40% magnesite III. 12% other minerals
5. 12 Uses: It is used in the tip of cutting and drilling tools, and also it is used in making abrasive paper and cloth. Siliceous abrasives: Quartz: It is pure crystalline silica (SiO2) .Its hardness is 7 on Mohs scale. Uses: It is used for grinding pigment in the paint industry and also used as granules in grinding machines. Garnet: It is a mixture of trisilicates of alumina, magnesia and ferrous oxide. Its hardness ranges from 6-7.5 on Mohs scale. Uses: It is used in making abrasive paper and abrasive cloth, it is also used in glass grinding and polishing and polishing metals. Synthetic abrasives Silicon carbide or carborundum (SiC) Manufacture: Silicon carbide is manufactured by heating sand (60%) and coke (40%) with some sawdust and a little salt in an electric furnace to about 1500C. Saw-dust evolves gases during burning, which on circulation increases the porosity of the charge. Salt reacts with iron and other similar impurities present in the raw materials, forming volatile chlorides. This also increases the porosity of the final products. SiO2+ 3C SiC + 2CO at (1500C)
The silicon carbide, removed from the furnace is then mixed with bonding agent (like clay silicon nitride) and then shaped, dried and fired. Properties: Silicon carbide possesses thermal conductivity, low expansion and high resistance to abrasion and spalling. They are mechanically strong and withstand loads in furnace up to 1650C. Heat conductivity of SiC is intermediate between metals and ceramic materials.
5. 13 Uses: Silicon carbides are used as heating elements in furnaces in the form of rods and bars. They are also used for partition walls of chamber kilns, coke ovens, muffle furnace, and floors of heat-treatment furnaces. SiC bonded with tar are excelled for making high conductivity crucibles.
BORON CARBIDE (B4C) or NORBIDE Manufacture: It is prepared by heating a mixture of boron oxide (B2O3 ) and coke (carbon) in an electric furnace to about 2700C. 2B2O3+7C B4C + 6CO (at 2700C)
Properties: Its hardness is 9 on Mohs scale. It is light in weight and black colored compound. It is highly resistant to chemical attack and corosion. It resists oxidation much better than diamond. Uses: It is used as hard material for making grinding dies, and for cutting and sharpening hard high-speed tools. It is used to prepare scratch and wear resistant coatings. It is used in the nozzles for sand blasting ALUNDUM (Al2O3) Manufacture: It is prepared by heating a mixture of calcined bauxite, coke and iron in an electric furnace to about 4000C. It is an artificial corundum. It is not as hard as carborundum but is less brittle and tougher. 4Al + 3O2 2 Al2O3 Properties: i. It is not as hard as carborundum but it is brittle and tougher ii. It is stable at high temperature iii. It is very hard iv. It is resistant to hydration and to attack by acid
5. 14 Uses: It is used in grinding of hard steels and other materials of high tensile strength. It is also used in the manufacture of abrasive wheels
APPLICATIONS OF ABRASIVES Abrasives are used in three forms. 1. as loose powder Example: quartz and garnet 2. as abrasive paper or cloth Manufacture of abrasive paper and cloth: The roll of paper or cloth is made to pass through a series of rollers, and a thin coating glue is applied on its upper side. It is then passed under a hopper from which the gravel of abrasive is allowed to fall and spread evenly on the glued paper or cloth. Then it is dried in warm drying room. Finally it is allowed to age for few days, so that the glue sets firmly. Uses: It is used to prepare smooth wood, metal and plastic surfaces. Example: alumina and silicon carbide. 3. as grinding wheels Manufacture of grinding wheels: Grinding wheel is manufactured by mixing abrasive grains with binder. The mixture is molded into desired shape and heated and cured. Uses: It is used for the removal of scales from iron surfaces, cutting tool sharpening
LUBRICANTS Lubricant: Lubricant is a substance used in between two moving surfaces to reduce the friction. Lubrication: Lubrication is a process of reducing the friction and wear and tear between the two moving surfaces. Functions of lubricant 1. They reduce friction, wear and tear between the moving surfaces. 2. They are acting as an anti corrosion agent. 3. They reduce energy wastage and are cost effective. 4. They reduce the expansion of metal parts by local frictional heat.
5. 15 5. They prevent the entry of dirt, dust and moisture between the moving parts. 6. In certain engines like internal combustion (IC) engines, the lubricant acts as a fuel gasket and in aircraft, lubricant is used as a hydraulic fluid to change the pitch of the propellant. Important requirements of a good lubricant: A good lubricant should not undergo any decomposition, oxidation, reduction at high temperature. A good lubricant should have higher flash and fire points than the operating temperature and low ash content. A good lubricant should have higher flash point and low ash content. A good lubricant should have high oiliness, viscosity index, aniline point. A good lubricant should not corrode the machine parts. It should not be harmful to the operator. It should be cheap and easily available. It should be chemically and thermally resistant.
Classification of lubricants: Lubricants can be classified on the basis of their physical state and consistency. i. Solid lubricants: Ex: graphite, molybdenum, disulphide, etc ii. Semi solid lubricants: Ex: greases, Vaseline, etc iii. Liquid lubricants ( or) lube oil (or)lubricating oil Ex: a) vegetable oils: olive oil, palm oil, castor oil, etc. b) Animal oils: whale oil, shark oil, tallows oil, etc. c) Mineral oils or petroleum oils or blended oils: petroleum fractions and petroleum oils d)synthetic oils: silicones, poly glycol, ethers, etc. e) Blended oils (or) compounded oils: mineral oils with various additives. iv. Emulsions a) Oil in water type: Ex cutting emulsions. b) Water in oil type: Ex cooling liquids. V. Gases: Used in fans, compressors, etc Ex: air, H2 Features of lubricants: Liquid lubricants or lubricating oils or lube oils
5. 16 Animal and vegetable oils These are glycerides of higher fatty acids and have very good oiliness. These oils cannot be used effectively due to the following reasons. They undergo oxidation at higher temperature and forms gummy and acidic products. They get easily hydrolysed under moist condition. So they are used as blending agents with other lubricating oils. Mineral oils and petroleum oils They are obtained by fractional distillation of crude petroleum oils, having carbon chain length varing from C12 to C50. It possesses poor oiliness, which can be improved by mixing with animals or vegetable oils. These oils are cheap and quiet stable under normal conditions. Usually the mineral oils are contaminated with lot of impurities such as wax, asphalt, oxidisable impurities etc. These impurities are generally removed by following methods. A. Removal of waxes The wax can be removed by dewaxing process. In this process the petroleum oil is mixed with a suitable solvents such as propane, trichloroethylene etc and then cooled. The wax crystallises out and is removed by filtration. B. Removal of asphalt Asphaltic and naphthenic material can be removed by acid refining process, in which the dewaxed oil is treated with con.H2SO4 and then agitated. Some of the unwanted impurities get dissolved in acid, while others converted in to sludges. The sludge is removed by filtration. The filtrate is neutralized with calculated quantity of NaOH to neutralize the acid. C. Removal of sulphur Sulphur can be removed from the oil by desulphurization process, in which the oil is treated with hydrogen in the presence of nickel as a catalyst. During this process, the unsaturated compounds are converted to the saturated compounds. D. Removal of colored substances These substance and micro crystalline waxes can be removed by filtration through Fullers earth. Blended oils By the addition of suitable additives like castor oil, coconut oil, oleic acid, palmitic acid, phenols, polyester, n-hexanol etc., the various properties of the lubricating oils cans be
5. 17 improved. Such lubricating oils having improved properties are called Blended oils (or) compounded oils. Some of the important additives and their functions S.No Name of the additive Examples Aromatic amino compounds. Phenolic compounds Organic Pb and Sb compounds functions To avoid oxidation of the oil and prevent the formation of gum like substance They are adsorbed on metal surface, thereby protecting the surface from attack of moisture. They react with metal surface forming surface film of lower shear strength and high melting point. They prevent foreign particles and carbon deposits in engines which block the passage of oil. They prevent separation of wax from the lubricating oil They prevent the oil from thinning at higher temperatures and thickening at lower temperatures Reduces foaming They increase the oiliness or adhering property of the lubricants. They increase the viscosity of the lubricants
1.
Antioxidants
2.
Corrosion inhibitors
3.
Extreme pressure additives
Organic compounds having S,P,Cl etc
4.
Detergents or deposit inhibitors
Salts of phenols or salts of carboxylic acid, sulphonates Phenols ,poly alkyl benzene ,chlorinated wax with naphthalene n-hexanol, poly iso butylene ,poly alkyl benzene, poly metha acrylates Methyl silicone polymers Fatty acids such as stearic acid ,palmitic acid ,oleic acid Polyesters, polystyrene
5.
Pour-point depressants
6.
Viscosity index improvers Foam inhibitors (or) antifoaming Oiliness carriers
7.
8.
9.
thickeners
5. 18 c) Silicone oils (Or) liquid silicones (or) silicone fluids Silicone oils are relatively low molecular weight silicones or silicon polymers. Dimethyl silicones or methyl and phenyl silicones are commonly available silicone oils. Hydrolysis of chlorotrimethyl silane with water yields monohydroxy compounds, which spontaneously condenses to form hexamethyl disiloxanes Hydrolysis of dimethyl dichlorosilane gives a linear polymer, whereas, hydrolysis of trichloromethsilane gives a network polymer. Properties: 1. They are odourless, tasteless, inert and possess constant physical properties over a wide range of temperature (-70C to 200C). 2. The viscosity of silicone oils ranges from 5 to 106 m pas. 3. They exhibit pour points between -60C to 35C, its viscosity is weaken depends on temperature. 4. In comparison with hydrocarbons oils, they are more stable to high temperatures, stress and oxidative degradation. 5. Silicone oils containing phenyl groups exhibit the highest thermal stability. These can be used for months at 250C in air and up to 300C in closed systems. Uses: 1. Silicone oil is used as a very good lubricant without softening. 2. Silicone oil is used as polish additives in polishes for cars, furnitures and cosmetics, because of its water repelling property. 3. They are used as flow and gloss improvers in paint industry. 4. They can be used as water repellant finishes for large number of natural and synthetic textiles. 5. Silicone oil is used as a release agent in moulds, in the manufacture of rubber tyres, plastics and also in the casting of metals. (e) Synthetic lubricants Synthetic lubricants can meet any requirements, under drastic and severe conditions .In air craft engines, synthetic lubricants (e.g. organic amines, imines or amides) can be used in the temperature range of -50C and 250C. These lubricants should have low freezing point, high viscosity index and they should be non inflammable. Such lubricants that can be synthesized and successfully utilized in severe operating conditions (-50oC to -250oC) are called synthetic lubricants. Eg. Silicones, polyglycol, ethers, organic amines.
5. 19 Gas Lubricants In gas lubrication there is negligible wear of machinery, lower chance to radiation damage, no risk of contamination and long life. In the case of gases, viscosity is low and is independent of temperature and pressure. But gases have no boundary lubricating properties. Moreover there is a chance for some wear during the starting and stopping of the machinery. Uses i. Gas lubricants are used in precision spindles and gyroscopes. ii. They are also used in compressors, fans, etc. Lubricating Emulsions Lubricating Emulsions are of two types (a) Oil in-water emulsions, (b) Water in-oil emulsions (a) Oil in-water emulsions: They are obtained by adding less quantity of an oil containing water soluble emulsifying agent (3- 20%) to a suitable quantity of water. Usual emulsifying agents are sodium soaps and salts of sulfonic acids. These emulsions are used in internal combustion engines, and marine diesel engines. In addition to the lubrication and cooling, they protect the machine parts from rust. e.g.,cutting emulsions. (b) Water in oil emulsions: They are prepared by mixing water containing 1 to 10% water soluble emulsifier with oil. Alkaline earth soaps are used as an emulsifiers. These lubricants are usually used in compressors and pneumatic tools. e.g., cooling liquid. Properties of Lubricants o viscosity o viscosity-index o flash and fire points o cloud and pour points o oiliness o emulsification o volatility o corrosion stability o decomposition stability o aniline point o sp. gravity o ash content 1. Viscosity Viscosity is measure of the internal resistance of a liquid during its flow. It is expressed in centipoises
5. 20 Viscosity is the property of a liquid or fluid by virtue of which it offers resistance to its own flow. It is the most important property since it determines the operating characteristics of the lubricant. If the viscosity of the oil is low, the oil film cannot be maintained between two moving surfaces. This results in excessive wear. If the viscosity is high, excessive friction will result. So a good lubricant should have moderate viscosity. The viscosity of a lubricant can be measured experimentally by Red wood or Say bolt or Engler or U-tube viscometers depending upon the nature of the lubricants. Viscosity-Index and the Effect of Temperature on Viscosity Lubricating oil becomes thinner when the operating temperature increases. It is due to the decrease in viscosity with increase in temperature. For a good lubricant, its viscosity should not change with change in temperature, so that it can be used continuously, under varying conditions of temperature. The rate of change of viscosity with temperature is expressed by a scale is known as viscosity-index (VI). It is defined as the average decrease in viscosity per degree rise of temperature between 100F and 210F. It is a graphical representation. If the viscosity of an oil falls rapidly as the temperature is raised, it has a low viscosityindex. Example: Gulf coast oil (naphthenic hydrocarbons) and its viscosity-index is arbitrarily fixed as zero. If viscosity of an oil is affected slightly with increase of temperature, it has high viscosity index. Example: Pennsylvanian oil (paraffinic hydrocarbons) and its viscosity index value is arbitrarily fixed as 100. Determination of Viscosity - Index (V.I) The viscosity-index of the test oil is calculated by comparing the viscosity of the test oil at 100 F (38C) with the viscosity of the zero viscosity-index Gulf coast oil and hundred viscosity index pennsylvanian oil both having the same viscosity as the test oil at 210 F (99C) (See the Fig.). There are three different steps in this measurement. Step 1 : Find out the viscosity of the test oil at 100 F and 210 F. Let 'V' be the viscosity at 100 F and 'V' be the viscosity at 210 F. If the difference between these two values is low, the oil is good and high if the oil is poor. Step 2 : Select a high-viscosity standard oil (i.e., pennsylvanian oil of V.I = 100) having same viscosity at 210o F as the test oil, and its corresponding viscosity at 100 F is found out. Let it be 'H'. Step 3 : Then select a low-viscosity standard oil (i.e. Gulf coast oil of V.I.=0) having the same viscosity at 210 F as the test oil, its viscosity at 100 F is found out. Let it be 'L', then
5. 21 Viscosity Index (V.I.) =
LU x 100 LH
Where U = Viscosity of the test oil at 100 F L = Viscosity of the low-viscosity standard oil at 100F having the same viscosity at 210F as the test oil. H = Viscosity of the high-viscosity standard oil at 100F having the same viscosity at 210 F as the test oil.
Fig. Viscosity - temperature curves for the standard oils (L & H) and the oil under test (U) 3. Flash and Fire points Flash point : It is the lowest temperature at which the oil lubricant gives off enough vapours that ignite for a moment, when a tiny flame is brought near to it. Fire point: It is the lowest temperature at which the vapours of the oil burn continuously for at least five seconds, when a tiny flame is brought near to it. Normally, fire points are 5 to 40 C higher than flash points. A good lubricant must have high flash and fire points. Significance Flash points and fire points are important when oils are exposed to high temperature service. A knowledge of flash and fire points is useful in providing safe-guards against fire hazards during use and transport. Flash point is an indication of the oil to volatilise and the level of storage of the lubricant. Paraffinic lubricants have higher flash points than that of the naphthenic lubricants. So the type of petroleum oils can be identified by the flash point determination.
5. 22 Determination The flash and fire points are usually determined by using Pensky-Marten's apparatus. The test oil is taken in the oil cup and heated by using a water bath at the rate of raising the oil temperature 5C per minute. The oil is stirred at the rate of 1 to 2 revolutions per second. The test flame is introduced for a moment at every 10o rise of temperature. The temperature at which a distinct flash appears inside the cup is noted as the flash point. The heating is continued and the temperature is again noted at which the oil ignites and continues to bum at least for 5 seconds. This temperature is taken as the fire point of the oil.
Pensky-Martens Apparatus 4. Cloud and Pour Points Cloud point: The temperature at which an oil becomes cloudy or hazy in appearance when it is cooled slowly is called the cloud point. On cooling the oil, impurities like wax. Asphalt, etc., present in the oil crystallise out, and causing the oil, turbid. Significance: Knowledge of cloud point is useful in predicting the lowest temperature up to which the machine can be operated without any risk of jamming. Pour point: It is the temperature at which the oil ceases to flow or pour when it is cooled slowly below the cloud point. Below the cloud point, the oil itself crystallises out and minute crystals of wax become interlocked and therefore the flow is arrested. Significance: A knowledge of pour point helps to fix the 1owest temperature up to which the flow of lubricant is reliable. The cloud and pour points should be low for a good lubricant. They indicate the suitability of lubricants in cold conditions. The cloud and pour points can be lowered
5. 23
by lowering the viscosity of the oil by dewaxing by adding pour point depressant like polyalkyl benzene
Determination The cloud and pour points can be determined by using an apparatus called pour-point apparatus. It consists of a flat bottomed tube enclosed in an air jacket (Fig.). The jacket is surrounded by freezing mixture taken in a jar. The tube is half filled with oil. Every degree fall of temperature of the oil is noted by taking the tube outside the air jacket for a moment by means of a thermometer introduced in the oil. The temperature at which cloudiness is noticed is taken as the cloud-point.
Cloud and Pour-Point Apparatus
The cooling is continued and the tube is taken outside after every 3C fall of temperature and tilted to observe the flow or pour of the oil. The temperature at which the oil does not flow in the tube even when kept horizontal for 5 seconds is noted as the pour-point.
5. Oiliness: Oiliness is an important property of a lubricant and it is a measure of its capacity to stick on to the metallic surfaces under the conditions of heavy pressure or load. When a machine is subjected to high pressure operation, a poor oiliness lubricant will be squeezed out of the lubricated machine parts and a good oiliness lubricant will stay in between the lubricated surfaces.
Vegetable oils have good oiliness but mineral oils have poor oiliness. By adding higher fatty acids like stearic acid, oleic acid or by adding vegetable oils, the poor oiliness of a lubricant can be improved. A good lubricant must have good oiliness.
5. 24 SOLID LUBRICANTS Solid lubricants are used under the following situations. Where the operating temperatures and load is too high. Where contamination of lube oils or greases by the entry of dust or grit particles are avoided. Where combustible lubricants must be avoided. The most widely used solid lubricants are graphite and molybdenum disulphide. Graphite Graphite consists of flat layers of hexagonal arrangement of carbon atoms. The carbon atoms in hexagons are bonded together by strong covalent bonds. The adjacent layers are held together by weak Vandar Waal forces. Since the distance between the adjacent layers in high 3.41 , the layers can slide easily one over the other with little friction. As result graphites possess very low co-efficient of friction. This property makes use of graphite as a lubricant.
Graphite is very soapy to touch and non-flammable. It can be used upto 375C and above this temperature it gets oxidized. Graphite is used either as a dry powder or as a colloidal dispersion. A dispersion of graphite in water called Aqua dag and a dispersion of graphite in oil is called Oil dag.
Uses: a. Oil dag is used in internal combustion engines b. Aqua dag is used in air compressors and in food processing equipments. c. Graphite is, as a lubricant, generally used in lathes, machine shop works, railway track joints, open gears, chains Molybdenum disulphide Molybdenum disulphide has a sandwich like structure in which a layer of Molybdenum atoms lies between two layers of sulphur atoms. The atoms in the layer are bonded together by strong covalent bonds but the layers are held together by weak Vandar Waal forces of attraction. The molybdenum layers and sulphur layers slide over one another. As a result MoS2 possess very low co-efficient of friction. It is also used either as a dry powder or as a colloidal dispersion. It gets oxidizes above 800C. It is mainly used in heavy machineries working under heavy load and high temperatures.
5. 25 Uses: a. Pure MoS2 is used in the vacuum of outer space. b. It is also used in heavy machinery working at higher temperature.
Mechanism of lubrication (types of lubrication) Fluid film or thick film or hydrodynamic lubrication: Condition: under low load and high speed Under the conditions of low load and high speed, a thick fluid of lubricant is maintained between the two solid surfaces. The thickness of fluid film is at least 1000. Since the thick fluid film separates the two solid surfaces. This reduces wear and tear. The co-efficient of friction in such cases is as low as 0.001 to 0.03
Example Consider the rotation of a shaft with respect to a stationary bearing When a lubricant is added to the system, it occupies the annular space between the shaft and the bearing and forms a hydrodynamic wedge so long as the shaft rotates, the hydrodynamic wedge so long as the shaft rotates, the hydrodynamics wedge will remain and prevents contact between the two solid surfaces. When the load becomes very high, the lubrication will be sequeezed out of the wedge and friction will occur.
5. 26 Condition under high load and slow speed Under the conditions of high load and slow speed, a continuous fluid film cannot be maintained between the moving surfaces. Under such conditions, the thickness of the fluid film should be less than 1000 A. such a thin film consists of 2 or 3 molecules thick. To form a thin film the lubricant has to be adsorbed on the metal surface by physical or chemical forces. In some cases, the lubricant will react chemically with the metal surface forming a thin film of metal soap, which will act as a lubricant. This thin film is knows as boundary film. The coefficient of friction in such is around 0.05 to 0.15
The effectiveness of boundary depends on the oiliness of the lubricant. Oiliness is the ability of a lubricant to stick on to the surface. Vegetable oils and their fatty acids have more oiliness. (e.g) Oleic acid (C17H33COOH), stearic acid(C17H35COOH) etc. the polar carbonyl group(-COOH) of these oils reacts with the metal surface to form a continuous thin film of lubricant. Hydrocarbon chain of the fatty acids gets oriented outwards in a perpendicular direction as shown in figure.
Extreme pressure lubrication Under the condition of high load (high pressure) and high speed, more heat is generated between the moving surfaces. As a result of this, the liquid lubricant fails to stick and undergoes decomposition or evaporation. Under these conditions, for effectives lubrication, special additives known as extreme pressure additives are used along with the lubrications. Important extreme pressure additives are organic compound having active radicals or groups such as chlorine (e.g sulphurized oils) etc. these compounds react with metallic surfaces to form metallic chlorides, sulphides etc. these metallic compounds posses high melting points and serve as good lubricant under extreme pressure conditions. NANO MATERIALS
Nano science is the revolutionary science and art of matter at the atomic, molecular or macro molecular scale that has cut across disciplines, such as chemistry, physics, biology and engineering. Nano technology is the design, characterisation, production and application of structures, devices and systems by controlling shape and size at the nanometer scale. A nanometer is one thousand millionth of a meter. For comparison, a single human hair is about 80,000 nm wideand a red blood cell is approximately 7,000 nm wide. Nano materials are materials with very small dimensions consisting of atomic or molecular aggregates commonly called as nano particles possessing sizes of the order of 1 to 100 mm.
5. 27 CARBON NANOTUBES (CNTs) In 1991, Sumio Iijima discovered carbon nanotubes (CNTs). A carbon nanotube is a cylindrical rolled up sheet of graphene, which is a single layer of graphite atoms arranged in a hexagonal pattern. The chemical bonding of nanotubes is compressed entirely of sp2 carbon bonds. This bonding structure, which is stronger than the sp3 bonds found in diamond, provides the molecules with their unique strength. Their hexagonal structure gives them great tensile strength and elastic properties. They also transfer heat very efficiently. CNT is 100 times stronger than steel but 6 times lighter weight. Based on the way in which graphite sheets are rolled , two ways of CNTs are formed. I Single-walled carbon nanotubes (SWCNT) It is a single cylinder with diameter 1-2 nm and a length of 100 m, making it effectively a one dimensional structure.
Single-walled carbon nanotubes
(i) Armchair Nanotubes Here a carbon-carbon covalent bond is parallel to the axis of the nanotube.
Armchair Nanotubes
5. 28 (ii) Zig-zag nanotubes In this carbon-carbon covalent bonds down the centre.
Zig-Zag nanotubes
(iii) Chiral Nanotubes It exhibit a twist or spiral around the nanotube. This orientation helps to determine the electrical properties of the nanotube. II Multi-Walled Carbon Nanotubes (MWCNT) It consists of multiple concentric nanotube cylinders. Production of Carbon Nanotubes There are four different methods to produce CNT in bulk quantities and at a lower cost. (a) Carbon arc method (b) Chemical vapour deposition method (c) Laser evaporation method (d) Pyrolysis of hydrocarbon (a) Carbon arc method It involves passing a current of about 50 amps between two graphite electrodes in an atmosphere of helium. This causes the graphite to vapourise, some of it condensing on the walls of the reaction vessel and some of it on the cathode. It is the deposit on the cathode, which contains the carbon nanotubes. Single walled nanotubes are produced when cobalt, nickel or iron is incorporated as a catalyst in the central region of the anode. If no catalysts are used, multiwalled nanotubes are formed. (b) Chemical Vapour Deposition Method Carbon nanotubes can also be made by passing a carbon-containing gas, such as a hydrocarbon, over a catalyst. The catalyst consists of nano-sized particles of metal, usually iron, cobalt or nickel. These particles catalyse the breakdown of the gaseous molecules into carbon,
5. 29
and a tube then begins to grow with a metal particle at the tip of a tube. The perfection of carbon nanotubes produced in this way has generally been poorer than those made by arc evaporation.
(c) Laser evaporation method This is an important method for making carbon nanotubes. Nanotubes of 10 to 20 nm in diameter and 100 m long can be made by this method. A quartz tube filled with argon gas and a graphite target are heated at high temperature. The graphite target contains catalysts like cobalt or nickel in small amounts. An intense pulsed laser beam at higher temperature (1200oC) is incident on the target and evaporating carbon from the graphite. The argon gas then drives the carbon atoms from the high temperature zone to the water cooled copper collector on which they condense into nanotubes. (d) Pyrolysis of hydrocarbon They can be synthesized by the pyrolysis of hydrocarbons like acetylene at about 700C in the presence of Fe-silica or Fe-graphite catalyst under inert conditions. Applications of carbon nanotubes 1. Storage Devices In batteries, some charge carriers can be stored in nanotubes (i) Fuel Cells : Hyrogen can be stored in CNTs which can be used in the development of fuel cells. Carbon nanotubes are able to store hydrogen and could provide the safe, efficient, and costeffective means to achieve this goal. Hydrogen atoms bond to the carbon atoms of the nanotube, and can be later released with slight changes in temperature and pressure. (ii) Lithium/Nickel Battery: Lithium atoms are very good charge carriers and can be stored inside the carbon nanotubes. Normally one Li atom can be stored within six carbon atoms. 2. Protective Shields CNTs are poor transmitter of electromagnetic radiation and hence can be used as light weight shielding materials for protecting electronic equipment against electromagnetic radiations. 3. Sensors of gases (Chemical sensors) Gases like NO2 an NH3 can be easily sensed / detected when they flow over CNTs. The electrical conductivity of CNTs increases when the gases are passed through them. When the gas molecule bind on to the CNTs, the concentration of holes in CNTs increases as the charge is transferred from CNTs to NO2 Semiconducting carbon nanotubes display a large change in conductance (i.e, ability to store charge) in the presence of these gases (i.e. NO2 and NH3).
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Researchers have detected minute amounts of sarin gas in 4 seconds using a prototype nanotube gas sensor (previous sensors took over a minute to detect the same amount). In the future, nanotube sensors could be used for security and environmental applications.
4. Drug delivery vessels (Drug delivery with buckyballs) Drug molecules can be attached to fullerene. The medicine loaded fullerene can then be attached to an antibody. Antibodies are V-shaped proteins that can recognize and attach to things in the body called antigens. Disease producing organisms Viruses, bacteria have unique antigens. The antibody finds the antigens in the body and then the attached fullerene delivers the appropriate medicine. Just like magnetic nanoparticles, medicine can be sent only to place where it is needed, leaving healthy cells alone. 5. Atomic Force Microscopy (AFM) Probe Tips CNTs attached to the tips of scanning probe microscope have been used to image biological and industrial specimens. Single-walled carbon nanotubes have been attached to the tip of an AFM probe to make the tip sharper. This allows much higher resolution imaging of the surface under investigation; a single atom has been imaged on a surface using nanotube-enhanced AFM probes. Also, the flexibility of the nanotube prevents damage to the surface and the probe tip if the probe tip happens to "crash" into the surface. 6. Nano Composite Materials Nylon can be mixed with carbon fibers (100-200 nm diameter threads made in a similar manner to nanotubes), creating a nanocomposite material that could be injected into the smallest gear mold. The carbon fibers have excellent thermal conductivity properties that cause the nanocomposite material to cool slowly and evenly allowing for better molding characteristics of the nanocomposite. Composites of aluminium powder mixed with 5% CNTs possess a greater tensile strength compared to pure aluminium sheets. 7. Actuators / Artificial muscle An actuator is a device that can induce motion. In the case of a carbon nanotube actuator, electrical energy is converted to mechanical energy, causing the nanotubes to move. Two small pieces of "buckypaper", paper made from carbon nanotubes, are put on either side of a piece of double -sided tape and attached to either positive or a negative electrode. When current is applied and electrons are pumped into "One piece of buckypaper and the nanotubes on that side expand causing the tape to curl in one direction. This has been called an artificial muscle, and it can produce 50 to 100 times the force of a human muscle the same size. Applications include robotics, prosthetics.
5. 31 8. Nanoscale Electronics The mechanical and electrical properties of carbon nanotubes can be used to produce molecular electronic devices. Semi conducting nanotubes could be used as compact, more efficient alternatives to conventional transistors. The integrated memory circuits made of nanotube composites with conducting polymer are found to be effective devices. 9. Quantum wires Quantum wires are made of carbon nanotubes have high electrical conductivity. 10. Catalysts They can be used as good catalysts in some chemical reactions. (i) Reduction of NiO : Nickel oxide (NiO) can be readily reduced to Ni metal.
NiO Ni
(ii) Reduction of AlCl3 AlCl3 can be reduced to its base metal.
CNT
AlCl3 Al
CNT in Fuel Cell Carbon nanotube has applications in battery technology. Lithium, which is a charge carrier in some batteries, can be stored inside nanotubes. It is estimated that one atom can be stored for every six carbons of the tube. Storing hydrogen in nanotubes is another possible application, one that is related to the development of fuel cells as sources of electrical energy for future automobiles. Principle A fuel cell consists of two electrodes separated by a special electrolyte that allows hydrogen ions, but not electrons, to pass through it. Hydrogen is sent to the anode, where it is ionized. The freed electrons travel through an external circuit wire to the cathode. The hydrogen ions diffuse through the electrolyte to the cathode, where electron, hydrogen and oxygen combine to form water. The system needs a source of hydrogen. One possibility is to store the hydrogen inside carbon nanotubes. It is estimated that to be useful in this application, the tubes need to hold 65% hydrogen by weight. At present only about 47% hydrogen by weight has been successfully put inside the tubes. Working of fuel cell with CNT An elegant method to put hydrogen into carbon nanotubes employs the electrochemical cell.
CNT
5. 32
Carbon Nanotubes In Fuel cell
Single walled nanotubes in the form of paper are the negative electrode in a KOH electrolyte solution. A counter electrode consists of Ni(OH)2. The water of the electrolyte is decomposed into positive hydrogen ions (H+) that are attracted to the negative single walled nanotube electrode. The presence of hydrogen bonded to the tubes is indicated by a decrease in the intensity of a Raman active vibration.
CATALYSIS Chemical catalysis benefits especially from nanotubes due to the extremely large surface to volume ratio. Example (a) Nested nanotubes with ruthenium metal bonded to the outside have been demonstrated to have a strong catalytic effect in the hydrogenation reaction of cinnamaldehyde. C6H5CH= CHCHO in the liquid phase compared with the effect when the same metal ruthenium is attached to other carbon substrates.
(b) Chemical reactions have also been carried out inside nanotubes. Nickel-oxide (NiO) is reduced to base metal Ni and Aluminium chloride (AlCl3) is reduced to base metal Al. A steam of hydrogen gas at 475C partially reduces MoO3 to MoO2 with the accompanying formation of steam H2O, inside the multi walled nanotubes. Cadmium Sulphide (CdS) crystals have been formed inside nanotubcs by reacting Cadmium Oxide (CdO) crystals with H2S gas at 400C.
5. 33 REFRACTORIES
1. What is the objective of refractory? The main objective of a refractory is to resist heat losses. The refractories also resist the abrasive and corrosive action of molten metal, slags and gases at higher temperatures without softening or deformation in shape. 2. Write any two uses of refractories. a. Refractories are mostly used for the construction of the lining of the furnaces, tanks, kilns, converters, crucibles, ladles etc. b. Refractories are also employed for the manufacture of cement, glass, ceramics, paper, metals etc.
3. What are refractories? (AU,2005, MKU,'95) Refractories are inorganic materials which can withstand high temperature without softening, melting or deformation in shape.
4. How are refractories classified? Give examples. (UM 2001, MKU, '95, BU, '95, '97) Refractories are classified into the following three types a. Acidic refractory - fire clay, alumina b. Basic refractory - dolomite, magnesite c. Neutral refractory - zirconia, graphite
5. Mention the requisites of a good refractory. (UM,2001, MKU, '96) A good refractory should a. be strong. b. have high fusion point. c. have high refractoriness. d. be chemically inert at high temperatures. e. be able to withstand sudden changes of temperature. f. resist the abrading action of flames, slags etc. g. possess low permeability. h. not crack and suffer loss in size at the operating temperature. 6. What is softening temperature? The minimum temperature at which a solid begins to soften and loses its shape and size is known as softening temperature.
7. What is the prime requisite of a material to be used as refractory? Its softening temperature must be higher than the operating temperature. 8. What is meant by refractoriness of a refractory? (UM, '99) It is the property of a material by virtue of which it can withstand high temperatures without appreciable softening or deformation under working conditions. It is expressed in terms of pyrometric cone equivalent (PCE).
9. What is meant by pyrometric cone equivalent of a refractory? (AU-CBE10,UM, '98)
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The refractoriness or fusion point of a refractory is commonly determined by means of the standard pyrometric cone equivalent (PCE) test. PCE test is a number which indicates the softening temperature of a refractory material. 10. Mention the objectives of PCE test. a. To determine the softening temperature of a refractory. b. To check the uniformity of composition of refractory raw materials and finished products. c. To classify the fire clay refractories d. To determine the contamination of the refractories. 11. PCE values of bricks A, B and C are 29, 32 and 35 respectively. 'Arrange them in the order of their increasing refractoriness. Brick A < B < C. 12. What is meant by refractoriness under load (RUL)? The temperature at which the refractory deforms by 10% is called refractoriness under load (RUL). 13. How is RUL test conducted? (AU, 2005) RUL test is conducted by applying a constant load of 1.75 kg/cm2 on test specimen of size base 5 cm2 and height 75 cm and heating in a furnace at a standard heating rate of 10C per minute. It is expressed in terms of temperature at which 10% deformation occurs on the test specimen . 14. What is meant by dimensional stability? It is the resistance of a refractory material to change in volume due to its prolonged exposure to high temperatures. 15. Explain why silica bricks expand on heating. Silica bricks expand on heating because of phase changes from one crystalline form into other having different densities. 1470C . 870C Quartzite Tridymite Cristobalite (crystalline) ( form) form) 16. Define porosity of a refractory. Porosity of a refractory material is given by the ratio of its pore volume to that of its bulk volume. 17. Mention the importance of porosity of a refractory. Materials with high porosity has less strength, poor resistance to abrasion and corrosion. 18. How is thermal conductivity of a refractory related to its porosity? Higher the porosity of a refractory, lesser is its thermal conductivity.
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19. What is meant by thermal spalling? (AU-07,AU-TVL10) Thermal spalling is breaking, cracking, peeling off or fracturing of a refractory brick or block under high temperature. 20. How will you minimise thermal spalling? Thermal spalling can be minimised by avoiding sudden temperature change and by avoiding slag penetration, by using high porosity refractory. 21. Mention two causes of thermal spalling. i) Rapid change in furnace temperature. ii) Slag or molten metal penetration into the pores of the refractory bricks. 22. Define permeability. It is a measure of rate of diffusion of gases and molten solids through a refractory material. Permeability depends upon the size and number of connected pores. 23. What is meant by bulk density? Bulk density is defined as the ratio of the weight of a specimen to its volume. An increase in bulk density increases the strength and resistance to spalling. 24. Name the stages in the manufacture of refractory. (i) Crushing (ii) Grinding (iii) screening (iv) Mixing (v) Moulding (vi) drying (vii) Firing 25. Mention the important properties of alumina bricks. They possess High porosity. Great resistance to slag. Excellent wear resistance. Very little tendency to ;spall. Very low coefficient of expansion. High RUL (1350C) value. Stability in both in oxidising and reducing conditions. 26. Why is fire clay refractory most widely used? This is because fire clay bricks are cheap and well suited for most of the applications. 27. Name two refractories which should not be placed in direct contact with fire clay refractory. Give reasons. Magnesite and dolomite refractories. Because these are basic refractories and can easily combine chemically with acidic refractory, fire clay. Such chemical reaction can lead to failure of the refractory structure. 28. Mention the name of one neutral refractory. Write its method of preparation. Zirconia bricks are neutral refractories. These are prepared from micronised zircon (Zr02) mixed with finely ground clay
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or alumina and heated to 1700C. 29. What are cermets? They are the combination of refractories (ceramics) and metals. They have high refractoriness and high thermal conductivity. They are used in rockets and jet engine parts.
ABRASIVES
1. What are abrasives? (BU & UM. '94) Abrasives are the hard substances used for grinding, cutting, sharpening, polishing or drilling purposes. They are used in the form of granules or powder. They are characterised by high hardness, high melting point and chemical inertness. 2. How are abrasives classified? Give examples. (UM, '94) Abrasives are classified into two types as below: i) Natural abrasives Diamond, Quartz ii) Artificial abrasives Carborundum, Boron carbide. 3. What is hardness of an abrasive? What is its unit? (SU & UM'96) It is the capacity of an abrasive to grind away (or scratch or make marks) another surface. It is measured in Moh's (Vicker's) scale. 4. What is Moh's scale? Name the hardest substance known. Moh's scale measures the hardness of an abrasive. Diamond is the hardest substance known.
(AU,2006) 5. Explain Moh's scale for different abrasives. Moh's scale is a comparative scale used to measure the hardness of abrasives. Standard materials are chosen according to the increase of hardness and assigned values. 6. What are soft abrasives?
Abrasives having values between I and 4 in Moh's scale are known as soft abrasives. Examples: talc, gypsum, calcite, fluorite. 7. Mention the characteristics of abrasives. It should be very hard. It should possess high refractoriness. It should be resistant to mechanical shock. It should not be affected by the frictional heat. 8. What is abrasive power? (UM, '95) It is the capacity of a particular abrasive to grind away another surface. It depends upon the hardness, toughness and refractoriness of the abrasive. 9. How are abrasives used? Abrasives are used in the following three forms: as grinding wheels as abrasive paper or cloth
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as loose powder.
10. Write some applications of abrasives. (MKU, '95) Abrasives are used for making abrasive paper or cloth which is used to prepare smooth wood, metal and plastic surfaces. grinding wheels to remove the scales from iron surfaces. abrasive powder to clean the metal surface prior to coating. 11. Arrange norbide, carborundum, garnet in the increasing order of hardness. Garnet < norbide < carborundum 12. Which abrasive is used in drilling bits? Borts (industrial or faulty diamonds) are used in drilling bits. 13. What is carborundum? How is it prepared? Silicon carbide is known as carborundum. It is manufactured by using a mixture containing sand (54%), coke (34%), saw dust (10%) and common salt (2%). The mixture is heated in an electric furnace at 2000C for 36 hours. Si02 + 3 C SiC + 2 CO.
14. Mention few important properties of carborundum. Pure carborundum is a colourless crystalline solid. It is an extremely hard substance. It is very inert to the action of many chemicals. It can withstand high temperature without any damage. It has very low coefficient of expansion. It has high resistance to abrasion and spalling. 15. Give the uses of silicon carbide. Due to its extreme hardness, SiC is used as an abrasive. It is used as refractory material. It is used as a high temperature semiconductor in transistor diode rectifiers. It finds application in atomic reactors. SiC is used as heating elements in furnaces in the form of rods and bars. 16. Write an explanatory note on emery. Emery is a fine grained, opaque, massive mineral. It is found chiefly in Greece. It is an aggregate of 55 to 75% Alumina (Al203) 20 to 40% Magnetite (Fe304) about 12% Other minerals Its hardness is about 8 in Moh's scale.
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17. Mention the uses of emery. Emery is used as tips for cutting and drilling tools etc. It is used in the production of sand paper (emery paper) and abrasive cloth for polishing purposes. 18. What are garnets? Write its uses, Garnets are the trisilicate of alumina, magnesia and ferrous oxide. Its hardness ranges from 6 to 7.5 in Moh's scale. Garnets when glued to paper or cloth, they are used for finishing woods. They are also used for bearing pivots in watches, glass grinding and polishing metals. 19. Mention the uses of abrasive paper and cloth. Abrasive paper and cloth are used for polishing furnitures, for removing rusts and for cleaning and polishing different types of materials. 20. Write in brief on norbide (84C) Boron carbide is known as norbide. It is the hardest (9.7 in Moh's scale) material ever synthesisd. It is made by heating boron oxide (B203) with coke in an electric furnace for 24 hours at about 2700C. B4C + 6 CO 2 B203 + 7C Norbide can resist oxidation much better than diamond. It is used on hard materials for making grinding dies and for cutting and sharpening high speed tools. 21. Give two examples Natural abrasive - Diamond, quartz. Synthetic abrasive - Carborundum, boron carbide
LUBRICANTS 1. Define the terms lubricant and lubrication. Lubricant is a substance used to reduce the friction between two moving surfaces. The process of reducing friction between two moving surfaces with respect to one another by introducing lubricant between them is called lubrication.
(A U, '2003; UM, '95) 2. What are the functions of a lubricant? It reduces surface deformation, wear and tear. It reduces loss of energy in the form of heat. It reduces the maintenance and running cost of the machine. It prevents the entry of moisture, dust and dirt between the moving parts It acts as a coolant.
3. Write some important characteristics of a lubricant.
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A good lubricant should not undergo any decomposition, oxidation, reduction at high temperature. A good lubricant should have higher flash and fire points than the operating temperature. A good lubricant should have high oiliness, aniline point, viscosity index etc. A good lubricant should not corrode the machine parts.
4. Why is lubricant required? During the motion of the sliding/rubbing/moving surfaces, a lot of frictional heat is generated, which results in local high temperature. This may even lead to melting of surfaces and finally formation of welded junctions. To avoid wear and tear, melting and seizure of the surfaces, a lubricant is introduced in between them. The lubricant reduces frictional resistance between surfaces, thereby minimizing the destruction of material composing sliding/rubbing/moving surfaces. 5. Define viscosity index. (UM, '99, 2001) The average decrease in viscosity per degree rise of temperature between 100 and 210 F is called viscosity index. 6. What are viscosity index improvers? Give example. (MKU. '95, '96) They are the substances added to lubricants to reduce the rate of change of viscosity with temperature. Example: n - hexanol, polyisobutylene. 7. How are viscosity and viscosity index inter related? If the viscosity of the oil falls rapidly as the temperature is raised, it has low viscosity. If oil is only slightly lowered on raising the temperature, the viscosity index is high. 8. Define the terms flash point and fire point. (AU-CBE10,BU, '96; MKU, '97) Flash point: It is the lowest temperature at which the oil gives off enough vapours that will flash if a small flame is brought near to it. Fire point: It is the lowest temperature at which the oil gives off enough vapours that must burn continuously for at least 5 seconds ~hen a small flame is brought near to it. 9. What should be the value of flash point of a good lubricant? Flash point must be atleast above the temperature at which the lubricant is to be used; otherwise there is every risk of fire during its use. 10. Define the terms cloud point and pour point. The temperature at which the oil becomes cloudy or hazy is called its cloud point.
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The temperature at which the oil just ceases to flow is called its pour point 11. What are the significance of cloud point and pour point?(AU06) Cloud point is useful in locating the lowest temperature upto which a machine can be operated without any risk of clogging. It is essential for fixing the lowest (pour point) temperature upto which the flow of oil is reliable. A good lubricant must have low cloud point and pour point. 12. What are pour point depressants? Give example. (BDU, '96) These are chemical substances added to lubricants to lower the pour point of the oil. They are used to prevent separation of wax from the lubricating oil. Example: Paraflow, santa pour, polyalkylbenzene. 13. Define oiliness of a lubricant? How can this be improved? (BU, '94, '95,; UM, '98;) Oiliness of a lubricant is a measure of its capacity to stick to the surface of the machine parts under heavy load or pressure. They oiliness of the lubricating oils can be increased by mixing animal or vegetable oils on fatty acids like oleic acid, stearic acid. 14. What is meant by steam emulsion number of lubrication oil? It is the time in seconds in which the given oil and water emulsion separates out in distinct layers. 15. What are extreme pressure additives? Give examples. Extreme pressure additives react with metal surface film of lower shear strength and high melting point. Example: Organic chlorine, sulphur, phosphorus compounds. 16. Give two examples each for liquid, semisolid and solid lubricants. Liquid lubricant : Olive oils, palm oil, whale oil Semisolid lubricant : Greases, vaselines Solid lubricant : Graphite, molybdenum disulphide. 17. Give two examples of synthetic lubricating oils. Silicones, polyglycol ethers, fluolubes. 18. Write a note on lithium base greases. Lithium base grease is prepared by thickening of petroleum oil with lithium soap. It is a water and heat resistant. It is expensive and superior to all other types of greases.
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It is used at low temperatures for lubrication.
19. What are solid lubricants? Mention their applications. (AU-TNV10,UM, '98,2001) Solid lubricants are used in high temperature, high load conditions and other environments which prohibit the use of oils and greases. Only those solids having laminar micro structure can be used as lubricant. Examples: Graphite, MoS2 soap stone, talc, mica. They are used in air compressors, internal combustion engines, railway track joints, food stuff industries. 20. How graphite acts as good lubricant on the surface of the moon? The temperature of' the moon is 110C during day time and -150C during nights. Hence, oil or grease cannot act as a lubricant under these conditions. On the other hand, a solid lubricant like graphite is very little affected by temperature changes. Hence, graphite is a good lubricant on the surface of the moon.
NANOTECHNOLOGY
1. Bring out the importance of carbon nanotubes. Carbon nanotube is the most versatile material with large application potential. They have unique properties like optical absorption and emission; and Young's modulus. The various aspects of science such as chemistry, physics, biology and material science are creating numerous possibilities for its application. 2. Describe single walled nanotube (SWNT) of carbon. One can think of a carbon nanotube as a sheet of graphite rolled into a tube with bonds at the end of the sheet forming the bonds that close the tube. An arm chair structure of a nanotube is formed by rolling the graphite sheet about an axis parallel to C-C bonds. A SWNT can have diameter of 2 nm and a length of 100 films. 3. What are the methods employed to produce carbon nanotubes? (i) Laser evaporation method. (ii) Carbon arc method. (iii) Chemical vapour deposition method. 4. Write in brief on the electrical properties of carbon nanotubes. Carbon nanotubes have the most interesting property that they are metallic or semi conducting, depending on the diameter and chirality of the tube. Synthesis of carbon nanotubes generally results in a mixture of tubes - two thirds of which are semiconducting and one third metallic. The metallic nanotubes have the arm chair structure. The conductivity of metallic carbon nanotubes is very high. The reason is that
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they have very few defects to scatter electrons. High currents do not heat the nanotubes. 5. What is meant by magneto resistance? Magneto resistance is a phenomenon whereby the resistance of a material is changed by the application of a DC magnetic field. Carbon nanotubes display this at low temperature. 6. Mention the fields in which CNTs find applications (AU-TNV10) Nano technology Electronics Optics Material science Architecture Catalysis 7. What are nanomaterials? List any four nano materials (AU-CBE10) Nanomaterials is the study of how materials behave when their dimensions are reduced to the nano scale i.e., 1-100 nm. Examples: proteins, DNA, inorganic nanoparticles like C, Au, Ca, Al, Alumina, Brass 8. What are the characteristics of nanomaterials? (AU-CBE10) They have unusual mechanical, electrical, vibrational, thermal and kinetic properties
PART-A 1. Define refractories. How can they be classified? 2. Give any four characteristics of refractories. 3. What is refractoriness? How is it measured? 4. What is Segar cone test (or) PCE test? 5. What is RUL test? 6. Name the stages in the manufacture of refractory? 7. What is porosity of a refractory? How can it be modified? 8. What is thermal spalling? How will you control it? 9. What are the two types of dimension change? 10. Name two refractories which should not be kept in direct contact with fireclay refractory. Why? 11. What are abrasives? 12. What is abrasive powder? 13. What is mohs scale?
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14. How is carborundum prepared? 15. What is norbide? How can it be prepared? 16. Give the applications of garnet and emery. 17. What are the applications of abrasive? 18. How can we classify the abrasives? Give one example for each type. 19. Define lubricant. Classify them. 20. What is flash and fire point. 21. Define viscosity index. 22. Define cloud and pour point. 23. What are pour point depressants? Give an example. 24. What are greases? How can they be classified? 25. What are carbon nanotubes? What are the types? 26. What are nano materials? 27. What is nano chemistry? 28. Write down the synthetic methods to prepare carbon nanotubes. 29. Write any four applications of carbon nano tube. 30. Mention the various forms of SWNT.
PART-B
1. Classify the refractories. Explain one example for each type. 2. What are the properties of refractory? Explain any three of them. 3. Write notes on alumina, Zirconia and Magnesite bricks. 4. Write a note on synthetic abrasives. 5. What is your understanding about natural abrasives? 6. How will you explain the mechanism behind the lubrication? 7. Explain any four properties of lubricants? 8. How can you classify lubricants? Explain. 9. Write notes on solid lubricants. 10. Bring out the important applications of CNT. 11. Write a note on structure and synthesis of CNT.
PART-B BIG QUESTIONS 1. Explain the characteristics or requirements of a good refractory. Infusible Inert Resistance Withstand power 2. Explain the classification of refractories. Based on their chemical properties Based on their refractoriness
5. 44 3. What is meant by refractoriness? Explain how is it measured? Definition PCE 4. Give a brief account of neutral refractories. Manufacture Properties Uses 5. Explain the general methods of manufacture of refractories. Grinding Mixing Moulding Drying Firing 6. Explain any two properties of refractories. Refractoriness RUL Porosity Thermal spalling Dimensional stability 7. Give a brief account of acidic refractories. Manufacture Properties Uses 8. Give a brief account of basic refractories. Manufacture Properties Uses 9. What are abrasives? How are they classified? Give two examples for each category with their important properties. Definition Classification Properties with examples 10. What are the characteristics of abrasives? Explain any two properties of abrasives. Characteristics Properties 1. Hardness 2. Toughness 3. Abrasive power 11. Write short notes on synthetic abrasives. Boron carbide or Alundum 1. Manufacture 2. Properties
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3. Uses 12. Write short notes on Carborundum. Manufacture Properties Uses 13. Discuss any two abrasives in detail or what are the applications of abrasives? As loose powder As abrasive paper or cloth As grinding wheels 14. Write short notes on natural abrasives. Non-siliceous abrasives 1. Diamond 2. Corundum 3. Emery Siliceous abrasives 1. Quartz 2. Garnet 15. Discuss any four important functions of a good lubricant? Write briefly on synthetic lubricants. Functions Synthetic lubricants 16. What are lubricants? Discuss the classification of the lubricants. Definition Types 1. Liquid lubricants 2. Semi-solid lubricants 3. Solid lubricants 4. Emulsions 17. Explain the types of lubrication? Fluid film Boundary lubrication Extreme pressure lubrication 18. Explain the term; viscosity index used in lubricant technology. Definition Determination Significance 19. Discuss flash point and pour point properties of lubricant? Definition of Flash point and Pour point Determination Significance 20. Explain the following properties of lubricants. Viscosity
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Cloud point Fire point Oiliness 21. What are solid lubricants? When are they used? Explain the structure of any one solid lubricant? Definition Uses Graphite or Molybdenum disulphide 22. What are greases? When are they used? Give the preparation of lithium grease. Definition Uses Preparation of lithium grease 23. Name any four additives for lubricating oils? Indicate their functions. Name of the additive Examples Functions 24. Write notes on petroleum oils? What are the methods to remove the impurities? Definition Methods 1. Removal of waxes 2. Removal of asphalt 3. Removal of sulphur 4. Removal of coloured substance 25. Explain the structures or types of CNTs. Single-walled nanotubes Multi-walled nanotubes 26. What are nanomaterials? Write short notes on carbon nanotubes. Definition Carbon nanotubes
27. Explain the properties and applications of carbon nanotubes. Properties 1. Mechanical properties 2. Electrical properties 3. Thermal properties 4. Vibrational properties 5. Kinetic properties Applications 1. Storage devices 2. Fuel cells 3. Lithium battery 4. Protective shields
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5. Sensors of gases

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Unit-V Engineering Materials

Department of Chemistry, Annapoorana Engineering College, Salem