Fullerenes

What are Fullerenes? Fullerenes are a group of polymorphic form of pure carbon compounds whose discrete molecule consists of hollow spherical cluster of a large number of carbon atoms.

Characteristics of Fullerenes: Each molecule is composed of groups of carbon atoms that are bonded to one another to form both hexagon (6-membered ring) and pentagon (5membered ring) geometrical configurations. But no two pentagons share a common side. Fullerene cages are about 7-15 angstroms in diameter ( 1A = 10-10m). In atomic terms, their sizes are enormous. But fullerenes are still small compared to many organic molecules. Chemically, they are quite temperatures of over 10000 C. stable; breaking the balls requires

At much lower temperatures (a few hundred oC) fullerenes will "sublime which means vapour will form directly from the solid. Fullerene-20 (C20) is the smallest number of carbon atoms containing fullerene. Giant fullerene with at least 600 Carbon atoms have been discovered.

Properties of Fullerene- C60

The material composed of 60 carbon atoms is known as Buckminsterfullerene (C60) as its shape resembles the geodesic domes designed by R. Buckminster Fuller. Pure C60 consists of 60 carbon atoms arranged as 12 pentagons and 20 hexagons. It is a yellow powder, which appears brown to black with increasing film thickness. In toluene (1g/L), turns to magenta colored solution. When exposed to strong ultraviolet light, they polymerize, forming bonds between adjacent balls. Its crystalline form is cubic. As a pure solid, it is electrically insulating. On reaction with good inorganic electron donors (alkali metals), electrical conductivity is increased several times. Stoichiometry of the alkali fullerides is M3C60. On reaction with organic electron donor like tetrakis (dimethyl amino) ethylene (TDAE), ferromagnetic material is formed.

Comparison between C70 and C60

Fullerene C70 Fullerene C60

Pentagon (C5)

The rugby-ball shaped C70has 12 pentagons and 25 hexagons Gives red color with dichlorobenzene

Hexagon (C6)

The soccer-ball shaped C60 has 12 pentagons and 20 hexagons Gives pink color with toluene

(i) preparation of superconductors, (ii) electronic devices, (iii) micro-electronic devices, (iv) preparation of ferromagnetic materials, and (v) as charge carriers in batteries.

Applications:

Preparation of fullerene by DC-Arc Method

It is basically a DC arc chamber reactor chamber with (a) Reactor chamber, (b) Electrode assembly (anode & cathode), (c) cooling system for the reactor chamber, (d) cooling system for the electrode assembly (e) vacuum system, (f) electrical and electronics system. The operating conditions are: (i) diameter of the electrodes: 6 mm; (ii) discharge voltage: 25 V (iii) current on the electrodes: 60 A (iv) cooling water flow of the discharge chamber: 300L/h (v) cooling oil flow of the electrodes: 60L/h; (vi) control gas pressure(helium): 100 to 200 mmHg.

Set-up Assembly: The main part is the extra-pure spectroscopic grade graphite rods of 6 mm dia and 150 mm length fixed in copper holders. The facing sides of both the graphite rods are parallel. The arc chamber has a cooling coil attached to remove the heat produced. The power to the generator is a high current, low voltage power supply. Working method: The chamber is evacuated to 10-3 torr using a vacuum pump. The pump is disconnected and the chamber is now filled with 99.99% pure Helium gas to a pressure of 100 to 200 mm Hg. An arc is strike between two graphite electrodes kept at a distance of 2 mm apart by maintaining a voltage of 25 V. At the end of the reaction, the chamber is cooled down and the soot is collected from the inner walls.
Composition and separation of the soot from the DC Arc method
The soot contains (a) Carbon clusters mixture = 25-30%; and b) C60 and C70 fullerenes = 1.2-2.5%. Fullerenes can be separated from the carbon mixture by Soxhlet extraction with toluene followed by separation in a ultrasonicator bath. The obtained C60+C70 mixture is further separated by column chromatography using neutral alumina as the stationary phase and hexane as the mobile phase..

Purification of Fullerenes by Chromatography

The Soot (C60+C70+impurities) extracted with Toluene using the Soxhlet method is deep Red in color.
o o o o The column is first filled with carbon granules. Toluene is filled into the column until the level of toluene equals to the height of carbon granules. Then the solution containing C60& C70 in toluene is added into the column through a dropper flask. The initial solution coming out of the column is collected separately in a conical flask and thrown into waste. o o o o o o o Color starts to change to magenta after 20 to 25 minutes the fraction is collected as C60. After 20 to 30 minutes the solution with magenta color stops coming out. At this stage, dichlorobenzene is added to the column. A red color separation will be seen for C70 fraction will appear. This fraction C70 is collected separately in a flask. From both the flasks, the solvent is evaporated to obtain pure C60 and C70 fractions separately. The characterization of purified C60 and C70 are carried out using XRD,
13C-NMR,

Crude soot solution (in organic solvent)

Alumina Carbon granules

C70 Band C60 Band impure band-1 impure band-2

1. pure C60 (magenta) in Toluene 2. pure C70 (Red) in C6H4Cl2

Mass spectra and FTIR.

Applications of fullerene C60 Superconductivity in C60

When doped with alkali metals, the solid C60 becomes a super conductor (A3C60 where A = Alkali metal). Resistance of a substance tends to be zero at the critical temperature (Tc). Eg.: for K3C60 the Tc is 18 K. C60 - Non conducting K3C60 - Insulating at RT K3C60 - Super conducting at below Tc ~18 K K3C60 exhibit super conductivity due to the partial filling of conduction band. It retains the basic FCC structure of C60 and lattice constants to accommodate the alkali ions. K3C60 has only a single stable superconducting phase with a Tc of 19 K. RbC60 has maximum Tc of 28 K.

Resistance

Temp. (K)

Superconductivity of Doped C60

When K3C60 is cooled to well below room temperature, its resistivity begins to drop sharply at about 19 K indicating the onset of superconductivity. As larger Alkali Metal Cations are incorporated into the C60 lattice,, the superconducting temperature (Tc) also increases. For example, compared to K3C60 (19 K), Rb3C60 exhibit Tc of 28 K. This rise may be related to an increase in the density of states at the Fermi level with increasing lattice constant. Hence, higher Tc could be obtained by incorporating larger alkali metal cations into the C60 lattice.

HIV Protease Inhibition by C60

o Derivatives of C60 are currently being investigated as potential inhibitors of the protease enzyme, which is specific to the HIV (virus) generation. o Active site of the HIV enzyme roughly described as an open-ended cylinder structure, which is lined almost exclusively by large hydrophobic amino acids. o The C60 has approximately the same radius as the cylinder of the active site of HIVP. o Since C60 and its derivatives are primarily hydrophobic, a strong hydrophobic vander Waals interaction between the non-polar active-site surface and the C60 surface which can able to block the active side and hence, reduce the HIV (virus) generation. o There is also an opportunity to increase the binding energy by the introduction of specific electrostatic interactions in the C60.

Hydrophobic sites

C60 (as inhibitor)

al eric d ylin C

HIV protease site

Diagram for the C60 HIV protease inhibition.

LUBRICANTS
Friction:
Resistance observed between two moving or sliding surfaces creating wear and tear.

Lubricant:
Any substance introduced between two moving or sliding surfaces with a view to reduce the frictional resistance between them is know as a lubricant.

Lubrication:
The process of introducing lubricant between moving/sliding parts is known as lubrication

Functions of Lubricant
o To reduce frictional resistance between surfaces and
reduce deformation, wear and tear between moving/sliding surfaces. To reduce loss of energy in the form of heat (Coolant). To reduce waste of energy i.e., to increase efficiency of machines. To reduce irregular expansion of metals. To reduce welding of the two surfaces. To reduce or avoid rough relative motions of moving / sliding parts. To reduce running and maintenance cost of the machine. To reduce the leakage of gases under high pressure like a seal or Teflon.

o o o o o o o

Mechanisms of Lubrication
1. Fluid-film (or) Thick-film (or) Hydrodynamic lubrication 2. Boundary lubrication (or) Thin-film lubrication 3. Extreme pressure lubrication

1. Fluid Film/Thick-Film/Hydrodynamic

Lubrication (~ 1000 )
Characteristics:
o The surfaces are separated by a thick-film (at least 1000 thick) and hence there is no direct surface to surface contact. o No welding of junctions. o Since thick film lubricant covers/fills the irregularities on the both surfaces, there is no direct contact between material surfaces and so the wear is reduced.

In Fluid Film Lubrication, the Lubricating properties depend on:

o Viscosity of lubricant (Lubricant should be

of low viscosity). o Thickness of lubricant layer. o Relative velocity and area of moving/sliding surfaces.

Example: Shaft running (Journal bearings)

Lubricant oil covers the irregularities of the shaft as well as the bearing surfaces.

o Examples where fluid film lubrication is used are :

i) Sophisticated instruments ii) Light machines like watches, guns, sewing machines etc. o Examples for fluid-film lubricants are: Hydrocarbon oils are considered to be satisfactory lubricants. To maintain viscosity throughout lifecycles long chain polymers are used as blenders with normal hydrocarbons oils. Small amount of unsaturated hydrocarbons present in hydrocarbon oils produced from petroleum fractions, which causes oxidation and produce gummy like products. Hence, anti-oxidant like aminophenol are used in journal bearings with lubricant

Mechanism of fluid film lubrication

2. Boundary Lubrication/Thin-film Lubrication

Characteristics of thin film lubrication are:
o High viscosity-index. o Resistance to heat and oxidation. o Good Oiliness. o Low pour-point.

Mechanism of Boundary Lubrication/Thin-film Lubrication This Lubrication takes place due to:
o Adsorption of lubricating oils to both surfaces by physical/chemical means. o The adsorbed layers on the both metal surfaces carry the applied load. o Co-efficient of friction, f = 0.05 - 0.15 and distance between surfaces is to be the order of the distance of the asperities.

For boundary lubrication, molecule should have:

the

lubricant

(i) Long hydrocarbon chain with polar groups. (ii) Polar groups promote spreading and orientation over the metallic surfaces at high pressure. (iii) Lateral attraction between the chains. (iv) Active groups or atoms, which can form chemical linkages with metal or other surfaces.

Examples of Boundary lubrication

Vegetable and animal oils (glycerides of higher fatty acids & their soaps).
o These oils either physically adsorbed to metal surfaces or react chemically at the metal surfaces. o Although these oils posses greater adhesion property, yet they tend to breakdown at high temperatures. Hence, fatty acids are added to improve the oiliness.

Graphite and Molybdenum disulphide alone or oil suspension may be used because:
o They have Low internal friction o They can bear/withstand compression o They are thermally stable

Mechanism of Boundary Lubrication

3. Extreme-pressure Lubrication
When moving/sliding surfaces are under very high pressure and speed, a high local temperature is attained. In such conditions, liquid lubricants fail to stick and may decompose and even vaporize. To avoid this, special additives are added to mineral oils. These are called extreme-pressure additives.

Mechanism
The extreme-pressure additives form on metal surfaces more durable films, capable of withstanding very high loads and high temperatures. Examples:
Organic compounds containing chlorine, sulphur and phosphorus. o These compounds react with metallic surfaces, at prevailing high temperatures, to form metallic chlorides, sulphide or phosphides. o These metallic compounds possess high melting points.

CLASSIFICATION OF LUBRICANT
Based on Physical state, lubricants are classified as: a) Lubricating oils or liquid lubricants
b) Semi solid lubricants or greases c) Solid lubricants

1. Lubricating oils or liquid lubricants

Purpose:
o o o o Provide a continuous fluid film. Provide a cooling between the surfaces. Act as a sealing agent. Act as corrosion preventing materials.

Properties of liquid lubricants:

o Low pressure i.e., high boiling point. o Adequate viscosity for particular service conditions. o Low freezing point. o Heat stability. o Stability to decomposition at the operating terms. o High oxidation resistance. o Non-corrosive properties.

Types of Liquid Lubricants

a) Animal and Vegetable oils:
- Usable under very high temperature and heavy load. Disadvantages of its usages are 1. Costly 2. Undergo oxidation easily in contact with air and forms gummy and acidic products, and get thickened. 3. Tendency to hydrolyze in contact with moist-air or aqueous medium. So, they are used as blending agents with other mineral oils.

b) Mineral oils or petroleum oils:

- They are obtained by distillation of petroleum.
o o Length of hydrocarbon chain varies between 12 to 50 carbon atoms. Shorter- chain oils have lower viscosity than the longer- chain hydrocarbons.

Liquid lubricants are most widely used lubricants because they are
1. Cheap 2. Available in abundance 3. Quite stable under service conditions.

o But they have poor oiliness character compared to

animal and vegetable oils. o So, high molecular weight compounds like oleic acid, stearic acid are used to over come this problem.

c) Blended oils: o No single oil serves as the most satisfactory lubricant

for many of the modern machines. Hence, additives are used to improve the properties. These blended oils give desired lubricating property required for a machinery.

Additives used are:

a) Oiliness- carriers: o Coconut oil, caster oil, and palmitic, stearic and oleic acids. b) Extreme-Pressure additives such as: o Fatty esters or acids which form oxide film with metal surface. o Organic materials containing sulphur. o Organic chlorine compounds. o Organic phosphorous compounds. o Some times lead (Pb) compounds could be used as high pressure lubricants. c) Pour-point depressing additives: o Phenol, condensation product of chlorinated wax with naphthalene.

d) Viscosity index improvers : hexanol e) Thickeners : Polystyrene or polystyers

f) Antioxidants or inhibitors : Aromatic phenolic or amino compounds g) Corrosion preventers : Phosphorous or Antimony organic compounds h) Abrasion inhibitors i) Antifoaming agents j) Emulsifiers k) Deposit inhibitors : tricresyl phosphate : glycols and glycerol : sodium salts of sulphonic acid : detergents such as salts of phenol and carboxylic acids

2. Semi-Solid Lubricants or Greases

o Semi solid consisting of a soap dispersed throughout a liquid lubricating oil. - May be Petroleum oil or synthetic oil with a specific additive. Preparation:
Saponification of fat (such as tallow or fatty acid) with alkali (like lime, caustic soda etc.,) Addition to hot lubricating oil under agitation

o To increase the heat resistance of grease, inorganic solid

thickening agents ( like finely divided clay, bentonite, colloidal silica, carbon block etc.,) are added. o Have higher shear or frictional resistance than oils and hence support much heavier load at lower speeds.

Applications of Greases:
o o o o When oil cannot remain in place due to high load, low speed, intermittent operation, sudden jerks etc. Work at high temperature When external contamination may create problem When dripping or spurting of oil is undesirable

Types of greases:
o

o o o o o

Calcium based greases or cup-greases Soda-based greases Lithium-based greases Axle- greases lime with resin and fatty acids Graphite greases Soap stone

3. SOLID LUBRICANTS
Solid lubricants are used when:
o Other lubricants can not be used o Contamination undesirable o Too high temperature or load are involved o Combustible lubricants not acceptable

Examples of solid lubricants used are:

a) Graphite (or) b) Molybdenum disulphide

Examples of Solid Lubricants

1.Graphite:

o Very soapy in touch

o o o o Non inflammable Not oxidized in air below 375C Oil + graphite oildag Water + Graphite aquadag - Emulsifying agent (tannin) o Grease + graphite graphite -greases

Examples of Solid Lubricants

2. Molybdenum disulphide:
o o Low coefficient of friction Stable in air up to 400 C

Soapstone, talc or mica are also used as solid lubricants.

Properties of Lubricants
1. Viscosity: The property of a liquid or fluid by virtue of which it offers resistance to its own flow . - Viscosity should not be too low or too high.

(viscosity is inversely proportional to temperature)

2. Flash - Points and Fire - Points :

Flash Point:
The lowest temperature at which the oil lubricant gives off enough vapour that ignites for a moment, when a tiny flame is brought near it. Fire Point: The lowest temperature at which the vapour of the oil burn continuously for at least five seconds, when a tiny flame is brought near it.

3. Oiliness: A measure of its capacity to stick on to the surfaces of machine parts under conditions of heavy pressure or load.
o For high pressure

high oiliness oil should be used.

o Important for extreme Pressure lubrication

4. Cloud and Pour points:

When an oil is cooled slowly, the temperature at which it becomes cloudy or hazy in appearance, is called its CLOUD POINT. The temperature at which the oil ceases to flow or pour, is called its POUR POINT.

5. Volatility:
o Good lubricant should have low volatility.

o It is measured by vaporimeter.

6. Emulsification:
o The property of oils to get intimately mixed with water forming

an emulsion. o Emulsions have a tendency to collect dirt, girt, foreign material etc., causing abrasion and wearing out of the lubricating parts of the machinery. o A good lubricating oil should form an emulsion with water which breaks off quickly.

7. Carbon residue:
Normally lubricants consist of high % of carbon containing compounds.
o Lubricants decompose due to raise in temp. and deposit

carbon creating problems to : a) IC engines and b) Air compressors. o A good lubricant should deposit least amount of the carbon .

8. Corrosion stability:
Corrosion Test: o A polished copper strip is placed inside a lubricating oil for a specified time and temperature and then checked for any tarnishing . o To prevent or retard corrosion effect of lubricating oils, additives such as Phosphorous, Arsenic, Antimony, Chromium, Bismuth or Lead are added.

9. Decomposition stability:
o Lubricating oils must be stable to decomposition at the operating temperatures by : a. Oxidation: To prevent it anti oxidant or inhibitor are used. b. Hydrolysis: Moisture in oils causes hydrolysis of esters c. Pyrolysis : At high temperature

10. Aniline point: (A.P.)

o The minimum equilibrium solution temp. for equal volumes of aniline and oil sample. o A good lubricating oil should have higher aniline points (A.P) o Higher A.P means higher % of paraffinic hydrocarbons and hence lower % of aromatic HC. (Aromatic HC dissolves natural rubbers and few synthetic ones)

11. Precipitation Number:

o The percentage of asphalt present in oil. o Precipitation Number is used to differentiate the different classes of lubricants.

12. Specific Gravity:

A.P.I. ( American petroleum Institute) degree A.P.I degree = 141.5/sp. gr. at temp(60F) -131.5 where 141.5 modulus of the A.P.I scale.

13. Ash Point:

o For used oil it is important to get an idea as to how much

abrasion and wear it may cause 14. Saponification number: o Number of milligrams of KOH required to saponify 1g of oil.

15. Mechanical stability:

o At very high pressures of operation, the stability of a lubricant is judged by four balls extreme pressure lubricant test.

16. Neutralization Number: o Is a scale to determine the amount of acidic or basic constituents of an oil. o Acid Number: Amount of KOH required in milligrams to neutralize the fatty acids in 1g of oil. o Good lubricating oil acid number value < 0.1

C. Propellants
High oxygen containing fuels or mixture of fuels + oxidiser Controlled combustion Evolution of Huge volume of hot gases (temp= 3000oC & pressure: 300kg/cm2) Gases escape through a jet or nozzle at supersonic velocity.

Characteristics of a good propellant

o Have high specific impulse o Deposit low molecular weight products( H2, CO2, CO, N2) o Burn at a slow and steady rate o Have low ignition delay ( in milliseconds) o Have high density o Be Stable over a wide range of temperatures o Be Safe to handle and store at ordinary conditions i.e., under shock, heat or impact o Be readily ignitable at predictable burning rate o Be Non corrosive and non hygroscopic o Leave no solid residue after ignition o Not release any toxic products on burning o Give high temperature on combustion

Types : Mono propellants

Fuel + oxidizer are in the same molecule or in the same solution. Properties:

o Safe to store
o Burning should be smooth

Examples :

H2O2, nitro methane, ethylene oxide, hydrazine, propyl nitrate a mixture of 21.4% MeOH and 78.4% H2O2 solution

Bipropellants
Fuel and oxidiser are separate compounds and injected separately to the combustion chamber from separate compartments Fuels: Liquid hydrogen, hydrazine, ethyl alcohol, aniline, kerosene. Ethanol mixed with 25% of water

Oxidizers: Liquid oxygen, ozone, H2O2, fuming HNO3, liquid fluorine

o Liquid O2 is non toxic but need high pressure insulated container for storing. o Liquid O3 is also very good but forms toxic products and can explode at high concentration o Liquid fluorine is volatile, toxic, corrosive, very reactive, difficult to store and handle.

Comparative features of solid and liquid propellants

Solid propellants
Low specific impulse Easily handling and storing Simple engine More economical Not versatile Engine calibration difficult

Liquid propellants
High Not easy Delicate engine design Less economical Versatile Easy