6.

REFRACTORIES
6.1 INTRODUCTION Refractories are materials that can withstand high temperatures without softening or deformation in shape. Refractories are mainly used for the construction of lining in -furnaces, kilns, converters, etc. The main function of a refractory is to withstand and maintain high temperatures and to resist the abrasive and corrosive action of molten metals, slags and gases. Objective of a refractory The main objective of a refractory is to resist heat losses and also to resist the abrasive and corrosive action of molten metals, slags and gases at higher temperatures, without softening or deformation in shape. 6.2 DEFINITION Refractories are materials that can withstand high temperatures without softening or deformation in shape. 6.2.1 Uses of Refractories 1. Refractories are mostly used for the construction of the lining of the furnaces, tanks, converters, kilns, crucibles, ladles, etc. 2. They are employed for the manufacture of cement, glass, ceramics, paper, metals (both ferrous and non-ferrous), etc. CHARACTERISTICS OR REQUISITES OF A GOOD REFRACTORY (i) It should be infusible at the operating temperatures.

(ii)

It should be chemically inert towards the corrosive gases, metallic slags and liquids.

(iii) (iv)

It should resist the abrading action of flue gases, flames, etc. It should not crack and suffer loss in size, at the operating temperatures.

(v)

It

should

expand

and

contract

uniformly,

with temperature

rise and fall respectively. (vi) It should be able to withstand overlying load of structure, at operating temperatures. (vii) It should have high refractoriness. 6.4 CLASSIFICATION OF REFRACTORIES Refractories are classified in the following two ways (i) (ii) According to their chemical properties. According to their refractoriness.

1. According to their chemical properties According to the chemical properties, refractories are classified into three main types Refractories

Acidic Refractories

Basic Refractories 2

Neutral Refractories

Examples (i) Silica (ii) Alumina

Examples (i) Magnesite (ii) Dolomite

Examples (i) Graphite (ii) Carborundum

(i) Acidic Refractories Acidic refractories consist of acidic materials like alumina (A1 203) and silica (Si02). They are not attacked by acidic materials, but easily attacked by basic materials. Examples Silica, Alumina, Fire clay refractories. (ii) Basic Refractories Basic refractories consist of basic materials like CaO, MgO, etc. They are not attacked by basic materials, but are easily attacked by acidic materials. Examples Magnesite, Dolomite refractories. (iii) Neutral Refractories Neutral refractories are made from weakly acidic and basic materials like Carbon, Chromite, Zirconia, etc. They are not attacked by both acidic and basic materials. Examples Graphite, Chromite, Zirconia, Carborundum refractories. II. According to their refractoriness 3

According to the refractoriness, refractories are classified into four types.

Sl. No Type of Refractories . 1. Low heat duty refractories 2. Intermediate heat duty refractories 3. High heat duty refractories 4. Super heat duty refractories

PCE Refractoriness Valu (oC) e 19-28 1520-1630 28-30 30-33 >33 1630-1670 1670-1730 >1730

Examples Fireclay bricks Chromite bricks Magnesite bricks

6.5 PROPERTIES OF REFRACTORIES 1. Refractoriness It is the ability of a material to withstand very high temperature without softening or deformation under particular service condition. How to measure refractoriness Since most of the refractories are mixtures of several metallic oxides, they do not have a sharp melting points. So the refractoriness of a refractory is generally measured as the softening temperature and is expressed interms of Pyrometric Cone Equivalent (PCE). Pyrometric Cone Equivalent (PCE) Pyrometric cone equivalent is the number, which represents the softening temperature of a refractory specimen of standard dimension (38 mm 4

height and 19 mm triangular base) and composition. Some examples are given in the table. PCE Number 32 36-38 38 Softening temperature 1710C 1800- 1850 C 1850 C

Refractory (i) Silica bricks (ii) Alumina bricks (iii) Magnesite bricks Objectives of PCE Test

1. To determine the softening temperature of a test refractory material. 2. To classify the refractories. 3. To determine the purity of refractories. 4. To check whether the refractory can be used at the particular servicing temperature. Measurement Refractoriness is determined by comparing the softening temperature of a test cone with that of a series of segar cones. Segar cones (also called pyrometric cones) are pyramid'shaped standard refractory of definite composition and dimensions and hence it has a definite softening temperature. A test cone is prepared from a refractory, for which the softening temperature to be determined, as the same dimensions of segar cones. Then the test cone is placed in an electric furnace along with segar cones (Fig. 6.1).

Fig 6.1 Segar cone-test The furnace is heated at a standard rate of 10 C per minute, during which softening of segar cones occur along with test cone. The temperature at which the apex of the cone touches the base is taken as its softening temperature. A good refractory should have high refractoriness. 2. Refractoriness under load (RUL) (or) strength Refractories, used in industries and in metallurgical operations, should bear varying loads. Hence refractories should have high mechanical strength under operating temperatures. Generally softening temperature decreases with increase of load. The load bearing capacity of a refractory can be measured by RUL test. RUL Test RUL test is conducted by applying a constant load of 3.5 or 1.75 kg/cm2 to the test refractory specimen of size base 5 cm2 and height 75 cm and heating in a furnace at a standard rate of 10 C per minute. The temperature at which the refractory deforms by 10% is called refractoriness under load (RUL). A good refractory should have high RUL value. 6

3. Porosity It is defined as the ratio of its pore volume to the bulk volume. Thus,
Porosity ( P ) = W D x 100 W A

where W = Weight of saturated specimen (with water) in air. D = Weight of dry specimen. A = Weight of saturated specimen (with water) in water. Porosity is an important property of refractory bricks, because it affects many other characteristics like chemical stability, strength, abrasion-resistance and thermal conductivity. Disadvantages of high porosity refractory (i) (ii) (iii) It reduces the strength. It reduces resistance to abrasion. It reduces the resistance to corrosion.

Advantages of high porosity refractory (i) Highly porous refractory possess lower thermal conductivity. This is due to presence of more air voids, which act as insulators and hence it can be used for lining in furnaces, ovens, etc. (ii) Highly porous refractory reduces thermal spalling.

4. Thermal Spalling Thermal spalling is the property of breaking, cracking or peeling off a refractory material under high temperature. 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 a refractory, thereby leading to development of uneven stresses and strains. (ii) Slag penetration This causes variation in the co-efficient of expansion and leads to spalling. Thermal spalling can be decreased by (i) Using high porosity, low co-efficient of expansion and good thermal conductivity refractory. (ii) (iii) Avoiding sudden temperature changes. By modifying the furnace design.

5. Dimensional stability It is the resistance of a refractory to any volume changes, when exposed to high temperature over a prolonged time.

These dimensional changes are of two types. (i) (ii) Reversible or Irreversible.

(i) Reversible dimensional changes This may result due to the uniform expansion and contraction of a refractory material. So the dimensional changes of a good refractory must be reversible. (ii) Irreversible dimensional changes This may result either in the contraction or expansion of a refractory. Example - 1 Magnesite bricks shrink in service. Magnesite is an amorphous material (specific gravity is 3.05). On heating it is gradually converted into more dense crystalline form of periclase (Sp. gravity = 3.54) Magnesite
(Amorphous)

-------------->

Periclase
(Crystalline)

Sp.gr.-3.05 Example 2

Sp.gr.= 3.54

Silica bricks expand in service. Silica bricks expand on heating due to the transformation of one form to another forms. This is accompanied by a considerable increase in volume.

C Quartz 870 Tridymite 1475 Cristobali te Crystalline ( form) ( form)

oC

6.6 GENERAL METHODS OF MANUFACTURE OF REFRACTORIES The manufacture of refractories involve the following steps. 1. Grinding Raw materials are crushed and ground to fine powder using crushers, pulverisers, ball mills. 2. Mixing In order to alter the chemical properties of the refractories, two or more powdered raw materials are throughly mixed with a suitable binding material, which, makes moulding easier. 3. Moulding Moulding can be done either manually or mechanically by the application of high pressure. Hand-moulding produces refractories of low strength and low density. Mechanical-moulding produces refractories of high strength and high density. 4. Drying Drying is carried out slowly to remove the moisture from refractories. 5. Firing It is done at a temperature as high as. or higher than their use temperature. Firing is generally carried out in kilns.

10

The refractories are fired, (i) (ii) (iii) to stabilize and strengthen their structures. to remove water of hydration. to facilitate development of stable mineral form to the finished products.

6.7 SOME IMPORTANT REFRACTORY BRICKS 6.7.1 Alumina bricks (or) Fire clay bricks Alumina bricks contain 50% or more of A1203. They are generally manufactured by mixing calcined bauxite (A1203) with clay binder. Manufacture 1. Grinding and mixing The raw materials (calcined bauxite & Si02) and grog (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 is dried slowly to remove the moisture and then fired in continuous kiln or tunnel kiln to about 1200 - 1400C for 6-8 days.

11

Properties (i) (ii) (iii) Alumina bricks are acidic refractories. They posses very low coefficient of expansion. They also posses high porosity, and high temperature load-

bearing capacity. (iv) They are inert to the action of gases like C0 2, H2 and natural gas. (v) (vi) Uses 1. Medium-duty bricks (containing 50 to 60% AI2O3) It is used in linings of cement rotary kilns, soaking pits, reheating furnaces, hearths and walls, etc., which are subjected to high abrasion. 2. High-duty bricks (containing 75% A1203) It is used in hottest zones of cement rotary kilns, lower parts of soaking pits, brass melting reverberatories, aluminium melting furnaces, etc., 3. Fire clay refractories are largely used in steel industries. 6.7.2 Magnesite bricks Magnesite bricks contain mainly MgO. They are generally They are also very stable to both in oxidizing and reducing conditions. They posses better resistance to thermal spalling than silica bricks.

manufactured by mixing calcined magnesite with caustic magnesia or iron oxide (or) sulphite lye as binding material. 12

Manufacture 1. Grinding and mixing The raw materials (calcined magnesite) and binding materials (caustic magnesia (or) iron oxide (or) sulphite lye) 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 1500C for 8 hours and then cooled slowly. Properties 1. Magnesite bricks are basic refractories. 1. Magnesite bricks can be used upto 2000C without load and upto 1500C under a load of 3.5 kg/cm2. 2. They have good resistance to basic slags, but combine with H 20 and C023. They possess good strength, little shrinkage and have lot of spalling. 2. They have poor resistance to abrasions.

13

Uses 1. They are used where high temperature is required to be maintained, together with great resistance to basic materials. 2. They are used in steel industry for the lining of basic converters and open-hearth furnaces. 3. They are also used in hot mixer linings, copper converters and reverberatory furnaces. 6.7.3 Zirconia bricks Manufacture They are prepared by mixing zirconite mineral (Zr0 2) with colloidal zirconia or alumina as binder and finally heated to 1700C. Small amount of MgO or CaO is added as stabilizer because mineral zirconite undergoes volume changes on heating and cooling. Properties 1. Zirconia bricks are neutral refractories. 2. Though zirconia bricks are neutral, they are affected by

acidic slags. 3. They can be used upto 2000C and upto 1500C under a load of 3.5 kg/cm2. 4. They are also quite resistant to thermal shocks. 5. Their thermal expansion is low.

14

Uses They are used only where very high temperature is maintained, e.g., high-frequency electric furnaces. 6.8 ANNA UNIVERSITY QUESTIONS 1. Discuss in detail about any three properties of refractories [AT. Jan 2003] 2. Classify refractories into different' types and give one example for each type porosity and thermal conductivity, of refractories? [May -2003] 4. What is meant by refractoriness of refractories? How is it determined? [May-2004] 5. What are refractories? How are they classified? Give examples for each type. Explain the terms refractoriness and thermal spalling [Dec-2004] 6. Give the preparation and application of any one acid refractory. (June 2006) 7. Define refractoriness and explain thermal spalling and porosity of refractories. (June 2006) (June 2006) 9. What are the important properties required for a good refractory. (June 2005) 10. What are the characteristics of a good refractory? Name the stages in, the manufacture of a refractory. (AM. Dec. 2006) 11. Explain any five important properties of refractories. (AM. Dec 2006) 15 8. Discuss the properties and uses of high alumina and zirconia bricks. [May 2003] 3. What are the significance of the three characteristics, refractoriness,

12. Explain the general methods of manufacture of refractories. (AM. Dec 2006) 13. Classify the refractories based on their chemical composition. Write about the manufacture of fire clay bricks. refractoriness under load. (AM. May 2007) 15. Discuss the manufacture and properties of alumina and magnesite bricks. (AM. May 2007) 16. What are the characteristics of a good refractory? Write a note on carborundum. 17. Explain the characteristics of refractories. (May 2008) (Dec 2008) (Dec 2008) (ii) Other University Questions: 1. What are refractories? How are they classified? Discuss the requisites of refractory materials. (Mds. Oct. '96; Apr. '98; BDU; Nov. '96) 2. What are the characteristic properties of good refractory materials? Give the specific application of acidic, basic and neutral refractory materials? (BU. No. '94, Apr. '96; MSU. Nov. '94; Mds. Oct.'95) 3. Explain the manufacture, properties and uses of any one of acidic and basic refractories. 4. Write the preparation, properties and uses of high alumina bricks. 5. Bring out a detailed discussion on magnesite bricks. What are the general methods of Preparation of refractories? (AM. Dec 2006) 14. What are refractories? Explain the followings, refractoriness and

18. Discuss the manufacture and properties of zirconia bricks.

16

7. ABRASIVES
7.1. DEFINITION Abrasives are hard substances, used for polishing, shaping, grinding operations. They are characterised by high melting point, high hardness and chemically inactive. 7.2 PROPERTIES OF ABRASIVES 1. Hardness It is the ability of an abrasive to grind or scratch away other materials. The harder the abrasive quicker will be its abrading action. Hardness of the abrasive is measured on Moh's scale or Vicker's scale. Measurement of hardness using Moh's scale Moh's scale is a scale, in which common abrasives (natural or artificial) are arranged in the order of increasing hardness. The Moh's scale of hardness is given in the table 7.1. Table 7.1 Moh's scale Name of the abrasives Gypsum Calcite Fluorite Apatite Feldspar Quartz Topaz Corundum Diamond Chemical formula CaS04.2H20 CaC03 CaF2 CaF2. 3Ca3(P04)2 K20 . A1203 . 6H20 Si02 A1F3 . Si02 A1203 C Mohs number (or) Hardness 2 3 4 5 6 7 8 9 10

17

Soft abrasives Abrasives having their hardness 1-4 in Moh's scale are known as soft abrasives. 2. Toughness Abrasives are generally hard and brittle, which is otherwise

known as toughness. 3. Abrasive power It is the strength of an abrasive to grind away another materials. It depends on hardness, toughness and refractoriness. 7.3 CHARACTERISTICS 0F ABRASIVES The followings are the important characteristics of an abrasive. (a) It should be very hard. (b) It should resist the abrading action. (c) It should be chemically inactive. (d) It should possess high refractoriness. (e) It should have high melting point. (f) It should not be affected by frictional heat. 7.4 CLASSIFICATION OF ABRASIVES Abrasives are classified into two types 1. Natural abrasives (a) Non-siliceous abrasives (b) Siliceous abrasives 18

2. Artificial or synthetic abrasives. Abraisves

Natural Abraisves

Natural Abraisves Examples (i) Carborundum (ii) Alundum (iii) Boron Carbide

Non-siliceous Abrasives Examples (i) Diamond (ii) Corundum (iii) Emery

Siliceous Abrasives Examples (i) Quartz (ii) Garnets

7.4.1. Natural abrasives (a) Non-Siliceous Abrasives 1. Diamond It is a pure crystalline carbon. It is the hardest known substance. Its hardness is 10 on Moh's scale. It is chemically inert and not affected by acids or alkalis. The off-colour diamond is called borts and black colour diamond is called carbonado. Uses: It is used in drill points, cutting rocks, stones and grinding wheels. 2. Corundum It is a pure crystalline alumina (A1203). Its hardness on Moh's scale is 9. Uses: It is used for grinding glasses, gems, lenses, metals, etc.

19

3. Emery It is a fine-grained, opaque, black coloured mineral. It consists of (i) (ii) (iii) 55-75% crystalline alumina 20-40% magnesite 12% other minerals. Its hardness is 8 on Moh's scale.

Uses: It is used in the tip of cutting and drilling tools, and also it is used in making abrasive paper and cloth. (b) Siliceous abrasives 1. Quartz It is a pure crystalline silica (Si02). Its hardness is 7 oh Moh's scale. Uses: It is used for grinding pigments in the paint industry and also it is

used as granules in grinding machines. 2. Garnet It is a mixture of trisilicates of alumina, magnesia and ferrous oxide. Its hardness ranges from 6-7.5 on Moh's scale. Uses: It is used in making abrasive paper and abrasive cloth, and also it is

used in glass grinding and polishing metals. 7.4.2. Synthetic abrasives 1. Silicon carbide or carborundum (SiC) Manufacture

20

Silicon carbide is manufactured by heating sand (60%) and coke (40%) with some saw-dust 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 product. 1500C Si02 + 3C -------------------------> SiC + 2CO The silicon carbide, removed from the furnace, is then mixed with bonding agent (like clay, silicon nitride) and then shaped, dried and fired. Properties 1. Silicon carbide possess a high thermal conductivity, low expansion and high resistance to abrasion and spalling. 2. They are mechanically strong and withstand loads in furnaces upto 1650C. 3. Heat conductivity of SiC is intermediate between metals and ceramic materials. 4. They are electrically intermediate between conductors and insulators. 5. The strength, density, abrasion-resistance, chemical bonded

resistance softening temperature of the various refractories will be in the following order.

21

Self - bonded product > silicon nitride bonded product > clay - bonded product. Uses 1. Silicon carbides are used as heating elements in furnaces in the form of rods and bars. 2. They are also used for partition walls of chamber kilns, coke ovens, muffle furnaces, and floors of heat-treatment furnaces. 3. SiC bonded with tar are excellent for making high conductivity crucibles. 2. Norbide or Boron carbide (B4C) Manufacture It is prepared by heating a mixture of boron oxide (B 203) and coke (carbon) in an electric furnace to about 2700C. 2700C 2B203 + 7C -----------------------> B4C + 6COT Properties 1. Its hardness is 9 on moh's scale. 2. It is light weight and black coloured compound. 3. It is highly resistant to chemical attack and erosion. 4. It resist oxidation much better than diamond. Uses

22

(i)

It is used as hard materials for making grinding dies, and for cutting and sharpening hard high-speed tools.

(ii)

It is used to prepare scratch and wear resistant coatings.

3. Alundum (A1203) 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. Uses (i) It is used in grinding of hard steels and other materials of high tensilestrengths. (ii) It is also used in the manufacture of abrasive wheels.

7.5 APPLICATIONS OF ABRASIVES Abrasives are used in three forms. 7.5.1 As loose powder To clean the surface prior to coating, abrasive powders are used. Examples Quartz and Garnet. 7.5.2 As abrasive paper or cloth Manufacture of abrasive paper and cloth

23

The roll of paper or cloth is made to pass through a series of rollers, and a thin coating of glue is applied on its upper side. It is then passed under a hopper (Fig. 7.1), from which the grit 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.

Fig. 7.1 Manufacture of abrasive paper or cloth Uses: It is used to prepare smooth wood, metal and plastic surfaces. Examples Alumina and silicon carbide. 7.5.3 As grinding wheels Manufacture of grinding wheel Grinding wheel is manufactured by mixing abrasive grains with binder. The mixture is moulded into desired shape and heated and cured. Uses: It is used for the removal of scales from iron surfaces, cutting tool sharpening.

24

7.6 QUESTIONS (i) Anna University Questions 1. How are silicon carbide bricks prepared? Give it's important

properties and uses?

(Nov. 2003; May 2003)

2. What are garnets and carborundum. Give the properties of Boron carbide. (June, 2006) 2. Write notes on artificial abrasive. 3. Explain the preparation and uses of silicon carbide (June 2006) (ii) Other University Questions 1. What are abrasives? How are they classified? Give their uses. (MSU. Apr. '96, '97; Mds. Apr. '97; Oct. '98, Apr. 2001) 2. Write a note on synthetic abrasives. 3. (BDU. Nov. '95) What are the different types of abrasives? Describe a process of manufacture of carborundum. Mention its uses. (Mds. Apr. '96, Apr. 2001) 4. How is SiC manufactured? 5. (Mds. Apr. 2001) (Dec. 2005)

What are abrasives? How are they classified? Write briefly on grinding wheels. (Mds. Oct. 2000)

6.

How is abrasive paper or cloth manufactured?

25

8. LUBRICANTS
8.1 INTRODUCTION In all type of machines, the moving surfaces rub against each other. Due to this rubbing, a resistance is offered to their movement. This resistance is known as Friction. This friction will cause a lot of wear and tear of surfaces of moving parts. Due to the friction large amount of energy is dissipated in the form of heat, thereby the efficiency of machine gets reduced. 8.2 DEFINITIONS Lubricant Lubricant is a substance used in between two moving surfaces to reduce the friction. Lubrication Lubrication is a process of reducing friction and wear between two moving surfaces by adding lubricant in between them. 8.3 FUNCTIONS OF A LUBRICANT 1. It prevents the direct contact between the moving surfaces and reduces wear, tear and surface deformation of the concerned parts. 2. It reduces wastage of energy so that efficiency of the machine is enhanced. 3. It reduces the factional heat and thus prevents the expansion of metals.

26

4. It acts as a coolant by removing the frictional heat generated due to the rubbing of surfaces. 5. At sometime, it acts as a seal preventing the entry of dust and leakage of gases at high pressure. 6. It reduces the maintenance and running cost of the machine. 7. It minimizes corrosion. 8.3.1. Requirements (or) Characteristics of a lubricant 1. A good lubricant should not undergo any decomposition, oxidation, reduction at high temperature. 2. A good lubricant should have higher flash and fire points than the operating temperature. 3. A good lubricant should have high oiliness, viscosity index, aniline point. 4. A good lubricant should not corrode the machine parts. 8.4 CLASSIFICATION OF LUBRICANTS Lubricants are classified on the basis of their physical state as follows : 1. Liquid lubricants (a) Vegetable oils - (e.g): Palm oil, castor oil, etc. (b) Animal oils - (e.g): Whale oil, tallow oil, etc. (c) Mineral oils - (e.g): Petroleum fractions. (d) Synthetic lubricants - (e.g): Silicones, polyglycol ethers, etc.

27

(e) Blended oils (or) Compounded oils - (e.g) Mineral oils with various additives. 2. Semi-solid lubricants (e.g): Greases, vaselines, etc. 3. Solid lubricants (e.g): Graphite, molybdenum-disulphide, etc, 4. Emulsions (a) Oil in water type - (e.g): Cutting emulsions. (b) Water in oil type - (e.g): Cooling liquids. 8.5 LIQUID LUBRICANTS (or) LUBE OILS 8.5.1 Vegetable and Animal oils These are glycerides of higher fatty acids and have very good oiliness. However, these oils cannot be used effectively, because (i) They undergo oxidation at higher temperature and forms gummy and acidic products. (ii) Also, they get hydrolysed easily under moist conditions. Actually, they are used as "blending agents" with other lubricating oils. 8.5.2 Mineral oils (or) Petroleum oils It is obtained by fractional distillation of crude petroleum oil. The length of the hydrocarbon chain varies from Ci2toC5Q. It is cheap and quite stable under normal operating condition. But, it possess poor oiliness. The oiliness of which can be improved by mixing it with animal (or) vegetable oils. 28

The mineral oil obtained cannot be used as such, because it contains a lot of impurities such as wax, asphalt, oxidisable impurities etc. These impurities have to be removed from the mineral oil before using it as a lubricant. The impurities are generally removed by the following methods. (a) Removal of waxes Waxes get separated at lower temperatures and interfere with lubricating properties. The wax can be removed by dewaxing process, in which the petroleum oil is mixed with a suitable solvent (propane, trichloroethylene etc.,) and then cooled. The wax crystallises out and is removed by filtration. (b) Removal of asphalt Asphaltic and naphthenic materials tend to leave carbon deposits on the engine parts. These materials can be removed by acid refining process, in which the dewaxed oil is treated with con. H 2S04 and then agitated. Some of the unwanted impurities get dissolved in acid while others are converted into sludges. The sludges are removed by filtration. The filtrate is neutralised with calculated quantity of NaOH to neutralise the acid. (c) Removal of sulphur Sulphur can be removed from the oil by desulphurisation process, in which the oil is treated with hydrogen in the presence of nickel as catalyst. During this process the unsaturated compounds are converted to saturated compounds. (d) Removal of coloured substance

29

The coloured substances and micro - crystalline waxes can be removed by filtration through Fuller's earth.

8.5.3. Synthetic lubricants Under severe operating condition (-50C to 250C) for example; in air craft the lubricants are pumped at -50C, but during take off and landing they get heated upto 120 150C petroleum oils cannot be effectively used, because they tend to get oxidised at higher temperatures while wax separation will occur at lower temperatures. So synthetic lubricants have been developed which can be used effectively in the temperature range of (-50C to 250C). Examples Silicones, polyglycot, ethers, etc. 8.5.4. Blended (or) Compounded oils (or) Additives for lubricating oils To improve the properties of the lubricating oils, certain substances called additives are added to the lubricating oils. The oils thus prepared are known as "Blended oils (or) Compounded oils". Some of the important additives used to enhance the property of lubricants are listed below (Table 8.1)

30

Table 8.1: Important additives and their functions Name of the additive (i) Oiliness carriers. Examples Fatty acids such as stearic acid, palmatic acid, oleic acid. Functions They increase the oiliness or adhering property of lubricants. They react with metal surface forming surface film of lower shear strength and high melting point. They prevent the oil from thining at higher temperatures and thickening at lower temperatures. They prevent separation of wax from the lubricating oil. They increase the viscosity of the lubricants. They retard the oxidation of the oil and prevent the formation of gum-like substances.

(ii) Extreme Organic chlorine pressure additives. compounds, organic sulphur compounds, organic phosphorous compounds. (iii) Viscosity index improvers. n-hexanol, poly isobutylene, poly alkyl benzene. Phenols, benzene. poly alkyl

(iv) Pour-point depressants. (v) Thickeners

Polyesters, polystyrene.

(vi) And oxidants Aromatic ammo compounds, phenolic compounds.

(vii) Deflocculents Salts of phenols, salts of They prevent foreign particles and detergents carboxylic acids, and carbon deposits in engines (or) Deposit sulphonates. which block the passage of oil. inhibitors. (viii) Corrosion preventors (or) Corrosion inhibitors. Tricresyl phosphates, organic compounds of phosphorous (or) antimony. They are adsorbed on metal surfaces there by protecting the surface from attack by moisture.

31

8.6 SEMI-SOLID LUBRICANTS (GREASES) Preparation Greases are semi - solid lubricants obtained by thickening of lubricating oil by the addition of metallic soaps. Soaps are prepared by saponification of vegetable oils (or) fats with alkali (like NaOH, Ca(OH) 2, etc.) usually Na, Ca, Li soaps are used as thickener (or) gelling agents. CH2COOR CH2-OH I I CHCOOR + 3 MOH > CH - OH + 3 R COOM I | metallic soap CH2COOR CH2-OH Examples Preparation of Lithium grease I Step Lithium soap is prepared by the saponification of vegetable oils (or) fats with lithium hydroxide. II Step Lubricating oil is thickened by adding lithium soap. The nature of the soap determines, (a) The temperature upto which the grease can be used. (b) It acts as a thickener. (c) Its water and oxidation resistance. (d) It enables the grease to stick to the metal surface firmly.

32

Different greases, their properties and uses are listed below (Table 8.2). Table 8.2: Different greases, their properties and uses Type of greases 1. Sodium soap grease (soda - base grease). 2. Calcium soap greases (lime - based grease, cup grease). Properties (i) Slightly soluble in water. (ii) Dropping point of it is very high. (i) It is water resistant. (ii) Beyond 70C the grease separates into soap and oil. (iii) Lesser dropping point than soda - base grease. . Uses It can be used upto 175C in ball bearings. It is a general purpose grease, used for lubricating water pumps, tractors, etc.,

3. Barium soap greases. (i) It is water resistant. (ii) Possesses good adhesiveness. 4. Lithium soap grease. (i) It is a resistant to water and heat. (ii) Expensive and superior to all other types. 5. Aluminium -soap grease. (i) It possess very high adhesiveness. (ii) Expensive and water resistance. It is cheap and water resistant.

Used for lubricating automotives. It is used at lower temperatures; used for lubricating engines. Used for lubricating chains and oscillating surfaces. Used for less delicate equipments under high load and low speed.

6. Axle - grease (Resin grease).

Greases are used under the following situations (i) Where oil is squeezed out due to heavier load or low speed.

33

(ii)

Where

the

bearings

and

gears

that

work

at

high

temperature. (iii) Where the bearings need to be sealed against the entry of dirt, grit, dust, etc. (iv) Where frequent application of lubricant is inconvenient, as in automobile wheel bearings. 8.7 SOLID LUBRICANTS Solid lubricants are used under the following situations. (i) (ii) Where the operating temperature and load is too high. Where contamination of lube oils or greases by the entry of dust or grit particles are avoided. (iii) Where combustible lubricants must be avoided. The most widely used solid lubricants are graphite and molybdenum disulphide. 8.7.1. 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 vanderwalls forces (Fig. 8.1). Since the distance between the adjacent layers is high (3.41 A), the layers can slide easily one over the other with little friction. As a result graphites possess very low co-efficient of friction. This property makes use of graphite as a lubricant.

34

Graphite is very soapy to touch and non - inflammable, It can be used upto 375C and above this temperature it gets oxidised. Graphite is used either as a dry powder or as a colloidal dispersion. A dispersion of graphite in water is called Aqua dag and a dispersion of graphite in oil is called Oil dag.

Fig. 8.1 The structure of graphite Uses

i. ii.

Oil dag is used in internal combustion engines. Aqua dag is used in air compressors and in food processing equipments.

iii.

Graphite is, as a lubricant, generally used in lathes, machine shop works, railway track joints, open gears, chains.

8.7.2. 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 vanderwaals forces of attraction. (Fig. 8.2).

35

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 oxidised above 800C. It is mainly used in heavy machinaries working under heavy load and high temperatures.

36

Fig. 8.2 The structure of molybdenum disulphide Uses (i) (ii) Pure MoS2 is used in the vacuum of outer space. It is also used in heavy machinery working at higher temperatures.

8.8 MECHANISM OF LUBRICATION (TYPES OF LUBRICATION) 8.8.1. Fluid film (or) Thick film (or) Hydrodynamic lubrication Under the conditions of low load and high speed, a thick fluid film of lubricant is maintained between the two solid surfaces. The thickness of fluid film is atleast 1000 A. Since the thick fluid film separates the two solid surfaces there is no direct contact between the 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 (Fig. 8.3).

37

Fig. 8.3 Fluid film formation in bearing 'A' at rest 'B' at running 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 will remain and it prevents contact between the two solid surfaces. When the load becomes very high, the lubricant will be sequeezed out of the wedge and friction will occur. 8.8.2. Boundary lubrication (or) Thin - film lubrication 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 known as boundary film. The co-efficient of friction in such cases is around 0.05 to 0.15. The effectiveness of boundary lubrication 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

38

film of lubricant. Hydrocarbon chain of the fatty acid gets oriented outwards in a perpendicular direction as shown in figure (8.4).

Fig. 8.4 Boundary lubrication 8.8.3. Extreme Pressure lubrication Under the conditions 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 effective lubrication, special additives known as Extreme Pressure additives are used along with the lubricants. Important extreme pressure additives are organic compounds 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 possess high melting points and serve as good lubricant under extreme pressure conditions. 8.9 PROPERTIES OF LUBRICANTS 8.9.1 Viscosity Viscosity is a measure of the internal resistance of a liquid during its flow. It is expressed in centipoise. The viscosity of an oil is the time in seconds for a given quantity of oil to pass through a standard orifice under the specified conditions. 39

Determination The viscosity of an oil is determined by (i) Red wood viscometer. (ii) Say bolt viscometer. The time required for 50 ml of the liquid to pass through the orifice of a red wood viscometer is called as Red wood seconds. The time required for 60 ml of the liquid to pass through the orifice of a say bolt viscometer is called as Say bolt universal seconds. Significance A good lubricating oil must have moderate viscosity. (i) If the viscosity of the lubricating oil is too high, the movement of the machine is restricted due to excessive friction. (ii) If the viscosity of the lubricating oil is too low, the liquid oil film can't be maintained and excessive wear will take place. 8.9.2 Viscosity Index The viscosity of an oil decreases with increase in temperature. The rate of change of viscosity with temperature is indicated by viscosity temperature curves (Fig. 8.5) or by a scale known as viscosity index (V.I). Viscosity index is defined as, "the average decrease in viscosity of an oil per degree rise in temperature between 100F and 210F".

40

Fig. 8.5 Viscosity - temperature curve (i) If the viscosity of an oil decreases rapidly with the increase in temperature it has low V.I. Examples Gulf coast oil (consist of naphthenic hydrocarbons) exhibit a larger change in viscosity with a increase in temperature and its V.I value is arbitrarily assigned as zero. (ii) If the viscosity of an oil is slightly affected with the increase in temperature, it has higher V.I. Examples Pennsylvanian oil (consist of paraffinic hydrocarbons) exhibits a relatively a smaller change in viscosity with a increase in temperature and its V.I value is arbitrarily assigned as 100. Determination The V.I of a test oil is calculated by comparing with the above two standard oil. The test oil is compared at 38C(100F) with zero V.I oil (Gulf

41

coast oil) and 100 V.I oil (Pennsylvanian oil) both having the same viscosity as the test oil at 99C(210F) (Fig. 8.5). The V.I of the test oil is given by the following formula L-U V.I---------------------------x l00 L-H where, U is the viscosity of the test oil at 38C. JL is the viscosity of the low V.I oil at 38C. H is the viscosity of the high V.I oil at 38C. The viscosity temperature curve is flatter for the oil of high V.I than the oil of low V.I. A good lubricant should have minimum change in viscosity for a wide range of temperature and also it should have a high V.I. V.I of a lubricant can be increased by the addition of linear polymers such as polyisobutylene, n-hexanol, etc. 8.9.3 Flash Point and Fire Point Flash Point It is the lowest temperature at which the oil gives off enough vapour that ignite for a moment, when a small flame is brought near it. Fire Point It is the lowest temperature at which the vapour of the oil burns continuously for atleast 5 seconds, when a small flame is brought near it. Generally the fire point is 5-40C higher than flash point. 42

Significance A good lubricating oil should have flash and fire points higher than the operating temperature of the machine. A knowledge of flash and fire point is useful in providing protection against fire hazard during transport and storage. Lubricating oils of paraffinic base possess higher flash points than those of naphthenic base. Hence the determination of flash and fire points is helpful in identifying the type of lubricating oil. Determination Flash and fire points can be determined using the same apparatus. An oil is heated at a prescribed rate in an open cup (Cleve land's) apparatus or closed cup (Pensky Martin's) apparatus of standard dimensions. A small test flame is periodically applied over the surface of the oil. The temperature at which a distinct flash is seen is the flash point. The heating and periodical application of test flame are continued. The temperature at which the oil vapour catches fire and bums continuously for 5 seconds is noted as the fire point. 8.9.4 Cloud and Pour Point Cloud Point When an oil is cooled slowly the temperature at which the oil becomes cloudy in appearance is called its cloud point. Pour Point The temperature at which the oil ceases to flow or pour is called its pour point.

43

Significance Most of the petroleum based lubricating oils contain dissolved paraffin wax and asphaltic impurities. When the oil is cooled these impurities undergo solidification which cause jamming of the machine. So the cloud and pour points indicate the suitability of the lubricants in\ cold condition. A good lubricant must have low cloud point and pour point. Determination An oil is taken in a flat bottomed tube enclosed in an air jacket and it is cooled in a freezing mixture (ice + CaCl2). Thermometers are introduced into the oil and freezing mixture. As the cooling takes place via the air jacket temperature of the oil falls. The temperature at which the cloudiness appears is noted as the Cloud point. The cooling is further continued. The temperature at which the oil does not flow in the test tube for 5 seconds on tilting it to the horizontal position is noted as the pour point. A good lubricant should have low cloud point and pour point. Pour point of a lubricating oil can be lowered by (i) dewaxing (ii) depressant. Examples Poly alkyl benzene called 'para flow' is a commonly used pour point depressant. 8.9.5 Oiliness Oiliness is the capacity of a lubricating oil to stick on to the surface of the machine parts under heavy load or pressure. adding a pour point

44

Significance Lubricants which have high oiliness stay in between the lubricated surfaces, when they are subjected to high load and pressure. But lubricants with poor oiliness will be squeezed out of the machine parts under this condition. How to improve oiliness Mineral oils have poor oiliness where as vegetable and animal oils have high oiliness. Hence oiliness of mineral oil is improved by adding vegetable oils and higher fatty acids like oleic acid, stearic acid, etc. A good lubricant should have good oiliness. 8.10 QUESTIONS (i) Anna University Questions 1. Compare the structure of graphite and molybdenum disulphide and their use in lubrication. Lithium grease. one solid lubricant? 4. Write detailed account on the graphite. 5. Indicate the preparation and uses of lithium grease. (June 2006) 6. Discuss the importance of viscosity, flash point in selecting a lubricating oil for a particular use. 7. Write notes on flash and fire point of a lubricant. (Dec. 2005) 8. Explain the significance of solid lubricants with example. (AU Dec 2006) 45 (June 2006) [Nov 2003] [Nov 2003] [May 2003] (June 2006) 2. What are greases? When are they used? Give the preparation of 3. What are solid lubricants? When are they used? Explain the structure of any

9.

Write a detailed notes on lubricants. the following properties of their significances Flash and fire point; Cloud and pour point.

(AU Dec 2006) lubricants and give

10. Explain

(AU May 2007) solid lubricants of with action, emphasis on their and examples (Dec 2008)

11. Write

an

essay

on

classification, applications.

mechanism

(ii) Other University Questions 1. 2. Discuss four important characteristics of lubricants. (MSU - Nov. '94; MKU - Nov. '96) How are lubricants classified? Mention the additives added to the lubricants and give their functions. (MKU - Nov. '95, Mds - Apr. '99, Oct. '95, Oct. '98; BU - Nov. '95) 3. Bring out the differences between hydrocarbon lubricants and vegetable oil lubricants. (MSU - Apr. '96)

4. Explain with examples, the action of corrosion resistant, anti-oxidant and viscosity index improving additives in the case of lubricating oils. (BU-Nov. '94; Mds - Oct. '96) 5. Discuss any four important properties- of a good lubricant. Write briefly on synthetic lubricants. (Mds-Apr. '96; MSU - Apr. '97) 6. Discuss any five important properties of a lubricant. (MKU - Apr. '96; Mds - Apr. '97; BU - Apr. '96) 7. Explain the terms "Cloud and pour points" "flash and fire points". (BDU - Nov. '96; Mds - Nov. '94) 8. Explain the Term: viscosity index used in lubricant technology. (BDV - Apr. '95; Mds - Apr. '94; Apr. '97; BU Nov. '96; Apr. '97) 46

9.

Give oil.

an

account

of

the

important

properties

of

lubricating

(Mds - Oct.2000) 10. Discuss the important properties of lubricants and indicate the significance of these properties. (Mds - Apr. 2001) (Mds - Apr. 2001) 12. Explain the mechanisms of lubrication. 13. Give a comparative account of different types of lubrication. (BDU-Nov 95, 96) 11. Name any four additives for lubricating oils. Indicate their function.

47

9. NANOMATERIALS
9.1 INTRODUCTION The prefix (nano) in the word nanochemistry means a billionth (1 x 10 m). Atoms are very small and the diameter of a single atom can vary from 0.1 to 0.5 nm. It deals with various structures of matter having dimensions of the order of a billionth of meter. 9.2 DEFINITIONS 1. Nanoparticles Nanoparticles are the particles, the size of which ranges from 1-50 nm. Generally they are obtained as colloids. The colloidal particles have a tendency to remain single crystal and hence are called as nanocrystals. A large percentage of atoms in nanocrystals are present on the surface. Nanocrystals possess electronic, magnetic and optical properties. Since the nanoparticles exhibit an electronic behavior, governed by the quantum physics, they are also called as quantum dots. 2. Nanomaterials Nanomaterials are the materials having components with size less than 100 nm at least in one dimension. Nanomaterials, in one dimension, are layers such as a thin films or surface coatings. Nanomaterials, in two dimension, are tubes such as nanotubes and nanowires.

48

 Nanomaterials, in three dimension, are particles like precipitates, colloids and quantum dots. 3. Nanochemistry (or) Nanoscience Nanoscience is defined as the study of phenomena and manipulation of materials at atomic, molecular and macromolecular scales. 4. Nanotechnology Nanotechnology is defined as the design, characterization, production and applications of structures, systems and devices by controlling size and shape at 10-9 m scale or the single-atomic level. 9.3 CARBON NANOTUBES (CNT) Carbon nanotubes are attotropes of carbon with a nanostructure having a length-to-diameter ratio greater than 1,000,000, When graphite sheets are rolled into a cylinder, their edges joined and form carbon nanotubes i.e., carbon nanotubes are extended tubes of rolled graphite sheets. Nanotubes naturally align themselves into "ropes" and held together by vanderwaals forces. But each carbon atoms in the carbon nanotubes are linked by the covalent bond. 9.3.1 Structure (or) types of carbon nanotubes Carbon nanotubes are lattice of carbon atoms, in which each carbon is covalently bonded to three other carbon atoms. Depending upon the way in which graphite sheets are rolled, two types of CNTs are formed. 1. Single - walled nanotubes (SWNTs).

49

2.

Multi walled nonotubes (MWNTs)

1. Single - walled nanotubes (SWNTs). SWNTs consist of one tube of graphite. It is one-atom thick having a diameter of 2 nm and a length of 100 u,m. It forms the following three type of structures. 1. Armchair structure. 2. Zig-zag structure. 3. Chiral structure.

Fig. 9.1 Structure of single walled carbon nanotubes (i) Armchair structure (ii) Zig-zag structure (iii) Chiral structure 2. Multi - walled nanotubes (MWNTs) MWNTs (nested nanotubes) consist of multiple layers of graphite rolled in on themselves to form a tube shape.

50

Fig. 9.2 Multiwalled carbon nanotubes 9.4 SYNTHESIS OF CARBON NANOTUBES Carbon nanotubes can be synthesized by any one of the following methods. 1. Pyrolysis of hydrocarbons. 2. Laser evaporation. 3. Carbon arc method. 4. Chemical vapour deposition. 9.4.1 Pyrolysis Carbon nanotubes are synthesized by the pyrolysis of hydrocarbons such as acetylene at about 700C in the presence of Fe-silica or Fe-graphite catalyst under inert conditions. 9.4.2 Laser evaporation It involves vapourization of graphite target, containing small amount of cobalt and nickel, by exposing it to an intense pulsed laser beam at higher temperature (1200C) in a quartz tube reactor. An inert gas such as argon is simultaneously allowed to pass into the reactor to sweep the evaporated carbon

51

atoms from the furnace to the colder copper collector, on which they condense as carbon nanotubes. 9.4.3 Carbon arc method It is carried out by applying direct current (60 - 100 A and 20 - 25 V) arc between graphite electrodes of 10-20Lim diameter. 9.4.4 Chemical vapour deposition It involves decomposition of vapour of hydrocarbons such as methane, acetylene, ethylene, etc., at high temperatures (1100C) in presence of metal nanoparticle catalysts like nickel, cobalt, iron supported on -MgO or A1 203. Carbon atoms produced by the decomposition condense on a cooler surface of the catalyst. 9.5 PROPERTIES OF CNTs 9.5.1 (a) Mechanical properties Carbon nanotubes are very strong and their elastic flexibility is indicated by young's modulus. Young's modulus of carbon nanotubes are 10 times greater than that of steel. (b) CNTs withstand extreme strain and tension. Most of the materials fracture on bending because of the presence of more defects, but CNTs possess only few defects in the structure. 9.5.2 Electrical properties The electrical properties of CNTs vary between metallic to semiconducting materials. It depends on the diameter and chirality of the nanotubes. The very high electrical conductivity of CNT is due to the minimum defects in the structure. 52

9.5.3 Thermal Conductivity The thermal conductivity of CNT is very high this is due to the vibration of covalent bonds. Its thermal conductivity is 10 times greater than the metal. The high thermal conductivity is also due to minimum defects in the structure. 9.5.4 Vibmtional properties As in normal molecules, the atoms in a CNT are continuously vibrating back and forth. CNTs have two normal modes of vibration. (i) (ii) Aig mode: It involves "in" and "out" oscillation. Ejg mode: It involves a squashing of the tube (oscillation between sphere and an ellipse). The frequencies of two modes of vibrations are Raman - active. 9.5.5 Kinetic properties The inner tubes of MWNTs can slide without any friction within the outer nanotubes leading to an atomically perfect rotational bearing. 9.6 APPLICATIONS OF CARBON NANOTUBES Due to the unusual and unique properties of CNTs, they find potential applications in the following field. 1. CNTs in storage devices Carbon nanotubes play an important role in the battery technology, because some charge carriers can be successfully stored inside the nanotubes.

53

(i) CNT in Fuel cells Hydrogen can be stored in the CNT, which may be used for the development of fuel cells. (ii) CNT in Lithium battery Lithium atoms, as a very good charge carrier, can be stored inside the carbon nanotubes. It has been estimated that one lithium atom can be stored for every six carbon atoms of the CNT and hence can be used in lithium batteries. 2. CNT as protective shields CNTs are poor transmitters of electromagnetic radiation and hence can be used as light weight shielding materials for protecting electronic equipment against electromagnetic' radiation. 3. Sensors of gases The gases like N02 and NH3 can be detected on the basis of increase in electrical conductivity of CNTs. When N0 2 or NH3 is allowed to flow over CNTs, electrical conductivity is found to increase. This is attributed to increase in hole concentration in CNTs due to charge transfer from CNTs to N02 as the gas molecules bind to the CNTs. 4. Drug delivery vessels CNTs can be effectively used inside the body for drug delivery by placing the drugs within the tubes. 5. CNT in microscope

54

CNTs, attached to the tips of scanning probe microscope, have been used to image biological and industrial specimens. 6. Reinforcing elements in composites The composites of aluminium powder, mixed with CNTs (5%), possesses a greater tensile strength compared to pure aluminium. 7. Components in integrated memory circuits The integrated memory circuits, made of nanotube composites with conducting polymers, have been found to be effective devices. 8. Quantum wires The quantum wires, made of metallic carbon nanotubes, are found to have high electrical conductivity. 9. CNT in catalysis Carbon nanotubes serves as efficient catalysts for some chemical reaction. (a) Hydrogenation reaction Nested carbon nanotubes with ruthenium (Ru) metal bonded to the outside have been proved to have a strong catalytic effect in the hydrogenation reaction of cinnamaldehyde (CgH5CH = CHCHO) when compared with the effect of the same metal Ru attached to other carbon substrates. (b) Other chemical reactions Some chemical reactions are also been carried out inside the nanotubes (i) Reduction of nickel oxide (NiO) to the base metal Ni. 55

carbon nanotube NiO------------------------------->Ni (ii) Reduction of A1C13 to its base metal. carbon nanotube AICI3----------------------------> Al (iii) A stream of H2 gas at 475C partially reduces M0O3 to Mo0 2 with the formation of steam (H20) inside the multiwalled nanotubes. (H2) 470C M0O3------------------------> Mo02 + H20 MWNT (iv)

(steam).

Cadmium sulfide (CdS) crystals have been formed inside the carbon nanotubes by reacting cadmium oxide (CdO) crystals with hydrogen sulfide gas (H2S) at 400C. 400C CdO + H2S-------------------------> CdS + H20 carbon nanotube

QUESTIONS 1. What are carbon nanotubes? Explain their types. 2. Write synthesis, properties and applications of carbon nanotubes. 3. Write notes on the followings with examples. (i) (ii) The role of CNTs in catalysis. CNTs in storage devices.

4. Explain the structures of CNTs.

56

57