VISVESVARAYA TECHNOLOGICAL UNIVERSITY

GENERATION AND PROPERTY EVALUATION OF NANOFLUIDS

PROJECT REPORT
SUBMITTED IN PARTIAL FULFILLMENT FOR THE AWARD OF

BACHELOR OF ENGINEERING IN MECHANICAL ENGINEERING

2007
Pavan R Lohit Raghavendra N Rahul R Anil R G (1MS03ME104) (1MS03ME113) (1MS03ME118) (1MS03ME195)

UNDER THE GUIDANCE OF

Mr. RAJI GEORGE

DEPARTMENT OF MECHANICAL ENGINEERING M.S. RAMAIAH INSTITUTE OF TECHNOLOGY BANGALORE - 560054

VISVESVARAYA TECHNOLOGICAL UNIVERSITY

GENERATION AND PROPERTY EVALUATION OF NANOFLUIDS

PROJECT REPORT
SUBMITTED IN PARTIAL FULFILLMENT FOR THE AWARD OF

BACHELOR OF ENGINEERING IN MECHANICAL ENGINEERING

2007
Pavan R Lohit Raghavendra N Rahul R Anil R G (1MS03ME104) (1MS03ME113) (1MS03ME118) (1MS03ME195)

UNDER THE GUIDANCE OF

Mr. RAJI GEORGE

DEPARTMENT OF MECHANICAL ENGINEERING M.S. RAMAIAH INSTITUTE OF TECHNOLOGY BANGALORE - 560054

M.S. RAMAIAH INSTITUTE OF TECHNOLOGY

M.S.R.I.T POST, BANGALORE-560054

DEPARTMENT OF MECHANICAL ENGINEERING

CERTIFICATE
This is to certify that the project work entitled Generation and property evaluation of nanofluids, is a bonafide work carried out by Rahul R (1MS03ME118), Pavan R Lohit (1MS03ME104), Raghavendra N (1MS03ME113) and Anil RG (1MS03ME195) in partial fulfillment for the award of degree of Bachelor of Engineering in Mechanical Engineering of the Visvesvaraya Technological University, Belgaum during the year 2007. It is certified that all corrections /suggestions indicated for internal assessment have been incorporated in the report deposited in the department library. The project report has been approved as it satisfies the academic requirement in respect to project work prescribed for the Bachelor of Engineering degree.
(RAJI GEORGE) Assistant professor Department of Mechanical Engineering, M.S. Ramaiah Institute of Technology, Bangalore560054 (Dr. R. CHANDRASHEKAR) Head of the Department of Mechanical Engineering, M.S. Ramaiah Institute of Technology, Bangalore560054

(Dr. K. RAJNIKANTH) Principal, M.S. Ramaiah Institute of Technology, Bangalore560054

Pavan R Lohit (1MS03ME104)

Raghavendra N (1MS03ME113)

Rahul R (1MS03ME118)

Anil R G (1MS03ME195)

External Viva Name of the examiners

1. 2.

Signature with date

1. 2.

ABSTRACT
Carbon nanotubes both multiwalled nanotubes (MWNT) and singlewalled nanotubes (SWNT) have been successfully synthesized by the arc discharge method. The nanotubes were puried by the solvent approach and the purity of MWNT was found to be 95%. These nanomaterials were dispersed in SAE40 diesel oil to generate the nanouid. To improve the uniformity in distribution of MWNTs in the base oil, Sodium Dodecyl Sulphate was used as the dispersant. It was experimentally determined that 1 weight% of SDS was required to uniformly distribute 0.1 wt% of MWNT. The wear resistant properties of the nanouid was tested using a four ball wear testing machine. For a given weight percentage of nanoparticle, the wear resistance of nanouids was assessed for varying loads (100-500N) and temperatures (40o C, 70o C and 100o C) at a constant rpm of 1200. Each test was carried out for a period of 60 minutes after which the wear scar diameter formed on the steel balls was measured using a microscope. At low load and temperatures, the nanouid was found to exhibit huge decrease in Coecient of friction (upto 45%).

ACKNOWLEDGEMENT
We would like to extend our heartfelt thanks to, 1. Parents, relatives and friends for being a constant source of encouragement in all our endeavors. 2. Management of M.S. Ramaiah Institute of Technology. 3. Teaching and non teaching sta of the Department of Mechanical Engineering, M.S. Ramaiah Institute of Technology. 4. Teaching and non teaching sta of the Chemistry Department, M.S. Ramaiah Institute of Technology for extending their equipments to help in our project work. 5. Teaching and non teaching sta of the Department of Biotechnology, M.S. Ramaiah Institute of Technology for providing us with microscopic facilities. 6. Teaching and non teaching sta of the Department of Electrical Engineering, M.S. Ramaiah Institute of Technology for extending their kelvin bridge apparatus. 7. S.K. Sharma, Manager - Sales, Ducom Pvt. Ltd. for guiding us. 8. Dr (Ms) Jayashree Bijwe, Professor, Industrial Tribology machine Dynamics and Maintenance Engineering Centre (ITMMEC), Indian Institute of Technology, Delhi for guiding us and referring us to Dr. Satish V Kailas. 9. Dr. Satish V Kailas, Professor Department of Mechanical Engineering, Indian Institute of Science for guiding us and for extending the four ball wear testing facility free of charge. 10. Jagdeesh, Senior Research Scientist, Tribology lab, Department of Mechanical Engineering, Indian Institute of Science for guiding us.

11. Cental Power Research Institute, Bangalore for providing Thermogravimetric Analysis facility.

Contents

1 INTRODUCTION 1.1 1.2 Nanouids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Base uids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.2.1 1.2.2 1.2.3 1.2.4 1.3 1.4 1.5 1.6 Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Mineral oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Vegetable (natural) oils . . . . . . . . . . . . . . . . . . . . . . Synthetic oils . . . . . . . . . . . . . . . . . . . . . . . . . . .

4 4 4 5 5 5 6 6 6 7 7 7 7 8 8 8 8 10 10 11 11 12 14

SAE classication of Lubricants . . . . . . . . . . . . . . . . . . . . . Selection of Base uid . . . . . . . . . . . . . . . . . . . . . . . . . . Selection of Nanomaterial . . . . . . . . . . . . . . . . . . . . . . . . Nanouids- Synthesis and property evaluation . . . . . . . . . . . . . 1.6.1 1.6.2 1.6.3 Synthesis of Multiwalled Carbon Nanotubes . . . . . . . . . . Generation of Nanouids . . . . . . . . . . . . . . . . . . . . . Property evaluation of Nanouids . . . . . . . . . . . . . . . .

1.7

Properties of uids . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.7.1 1.7.2 1.7.3 1.7.4 1.7.5 1.7.6 1.7.7 1.7.8 Oil Viscosity . . . . . . . . . . . . . . . . . . . . . . . . . . . . Dynamic viscosity . . . . . . . . . . . . . . . . . . . . . . . . . Kinematic viscosity . . . . . . . . . . . . . . . . . . . . . . . . Viscosity - Temperature relationship . . . . . . . . . . . . . . Viscosity index . . . . . . . . . . . . . . . . . . . . . . . . . . Viscosity-pressure relationship . . . . . . . . . . . . . . . . . . Thermal Conductivity . . . . . . . . . . . . . . . . . . . . . . Flash point and Fire point . . . . . . . . . . . . . . . . . . . .

1.7.9

Additive Compatibility and Solubility

. . . . . . . . . . . . .

15 16 20 21 21 21 22 24 24 24 25 26 27 27 29 29 30 30 32 37 37 38 40 40 40 42 42 44 44

1.7.10 Lubricant Additives . . . . . . . . . . . . . . . . . . . . . . . . 1.8 Wear . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.8.1 1.8.2 1.8.3 1.9 Abrasive wear . . . . . . . . . . . . . . . . . . . . . . . . . . . Erosive Wear . . . . . . . . . . . . . . . . . . . . . . . . . . . Adhesive Wear . . . . . . . . . . . . . . . . . . . . . . . . . .

SCOPE OF PRESENT WORK . . . . . . . . . . . . . . . . . . . . .

2 LITERATURE REVIEW 2.1 Nanouids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1.1 2.1.2 2.1.3 Preparation of Nanoparticles and Nanouids . . . . . . . . . . Thermally enhanced Nanouids . . . . . . . . . . . . . . . . . Carbon nanotube based Nanouids . . . . . . . . . . . . . . .

3 EXPERIMENTATION 3.1 3.2 3.3 3.4 3.5 Preparation of MWNT by arc-evaporation technique . . . . . . . . . Purication of MWNTs . . . . . . . . . . . . . . . . . . . . . . . . .

Preparation of SWNT by arc-evaporation technique . . . . . . . . . . Purication of SWNTs . . . . . . . . . . . . . . . . . . . . . . . . . . Characterization of Nanotubes . . . . . . . . . . . . . . . . . . . . . . 3.5.1 3.5.2 Electron Microscopy . . . . . . . . . . . . . . . . . . . . . . . Thermogravimetric analysis (TGA) . . . . . . . . . . . . . . .

3.6 3.7

Generation of Nanouids . . . . . . . . . . . . . . . . . . . . . . . . . Four Ball Wear Test . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.7.1 3.7.2 3.7.3 3.7.4 3.7.5 Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Cleaning Fluids . . . . . . . . . . . . . . . . . . . . . . . . . . Test Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . Procedure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Measuring wear scar diameter . . . . . . . . . . . . . . . . . .

4 RESULTS and DISCUSSIONS 4.1 Characterization of Carbon Nanotubes . . . . . . . . . . . . . . . . .

4.1.1 4.1.2 4.1.3

Transmission Electron Microscopy . . . . . . . . . . . . . . . . Thermogravimetric Analysis . . . . . . . . . . . . . . . . . . . Coding of nanouid samples . . . . . . . . . . . . . . . . . . .

44 44 44 63

5 CONCLUSION

6 CHALLENGES FACED DURING EXECUTION OF THE PROJECT 64 6.1 6.2 6.3 6.4 6.5 6.6 Selection of suitable base oil . . . . . . . . . . . . . . . . . . . . . . . Non uniform dispersion of MWNT in base oil . . . . . . . . . . . . . Determination of method used to test wear resistant properties of oil Searching for Four ball wear testing facility . . . . . . . . . . . . . . . Diculty in obtaining slots for testing . . . . . . . . . . . . . . . . . Diculty in producing 4 grams of puried Carbon nanotubes . . . . . 64 64 65 65 65 65

Chapter 1

INTRODUCTION

1.1

Nanouids

Nanouids are engineered colloidal suspensions of nanoparticles in a base uid. In general the size of these nanoparticles vary from 1-100nm. The type of nanoparticle used is directly dependent on the enhancement of a required property of the base uid. All physical mechanisms have a critical length scale, below which the physical properties of materials are changed. Therefore particles <100 nm exhibit properties that are considerably dierent from those of conventional solids. The noble properties of nanophase materials come from the relatively high surface area to volume ratio that is due to the high proportion of constituent atoms residing at the grain boundaries. The thermal, mechanical, optical, magnetic, and electrical properties of nanophase materials are superior to those of conventional materials with coarse grain structures [1].

1.2

Base uids

Liquid lubricants may be characterized in many dierent ways. One of the most common ways is by the type of base oil used. Following are the most common types: 1. Water 2. Mineral oil 3. Vegetable (natural oil) 4

4. Synthetic oils 5. Others

1.2.1

Water

Water can be used on its own or as a major component in combination with one of the other base oils.

1.2.2

Mineral oil

This term is used to encompass lubricating base oil derived from crude oil. API designates several types of lubricant base oil identied as: Group I - Saturates < 90% and / or Sulfur > 0.03% and Viscosity Index 80 to <120 Group II - Saturates 90% and Sulfur 0.03% and Viscosity Index 80 to <120 Group III - Saturates 90% Sulfur 0.03% and Viscosity Index 120 Group IV - Poly alpha olens (PAO) Group V - All others not included above The lubricant industry commonly extends this group terminology to include: Group I+ with a Viscosity Index of 103 - 108 Group II+ with a Viscosity Index of 113 - 119 Group III+ with a Viscosity Index of 140

1.2.3

Vegetable (natural) oils

These are primarily triglyceride esters derived from plants and animals. For lubricant base oil use the vegetable derived materials are preferred. Common ones include high oleic canola oil, palm oil, sunower seed oil and rapeseed oil from vegetable and Tall 5

oil from animal sources. Many vegetable oils are often hydrolyzed to yield the acids which are subsequently combined selectively to form specialist synthetic esters.

1.2.4

Synthetic oils

1. Poly alpha-olen (PAO) 2. Synthetic esters 3. Poly alkylene glycols (PAG) 4. Phosphate esters 5. Alkylated naphthalenes (AN) 6. Silicate esters 7. Ionic uids

1.3

SAE classication of Lubricants

The Oils used in the combustions and power transmission are graded according to SAE J300 and SAE J306 classications respectively. A recent SAE classication establishes eleven engine oil grades and seven transmission oil grades. Table 1.1: SAE Automotive oil specication SAE number Viscosity range, SUS At 18o C At 99o C Min Max Min Max 5W 4000 39 10W 6000 12000 39 20W 12000 48000 39 20 45 58 30 58 70 40 70 85 50 85 110

1.4

Selection of Base uid

The main criteria in the selection of base oil for generating nanouids were as follows:6

1. The base oil had to have minimum amount of additives so that there would be no adverse eects resulting in destabilization of nanouid when nanomaterials were added to it. 2. The lubricating oil had to be easily available and common in use. A monograde oil is designed to work at higher temperatures and lacks the polymer additives that multigrade oil commonly posses in order to perform at a wider range of temperatures. Hence commonly available monograde diesel oil (SAE40) manufactured by Shell was chosen as the base uid.

1.5

Selection of Nanomaterial

The prime focus of the project was to improve the lubrication properties of the base uid. Multiwalled carbon nanotubes possessing a tubular structure seemed an outright choice and hence was chosen to enhance the wear resistant behavior of the lubricant.

1.6
1.6.1

Nanouids- Synthesis and property evaluation

Synthesis of Multiwalled Carbon Nanotubes

Carbon Nanotubes were discovered by Sumio Iijima in 1991, since then numerous procedures have been developed to produce Multiwalled carbon nanotubes. However arc evaporation process is one of the simplest methods which produces a yield of high purity, defect free MWNTs. MWNTs were prepared inhouse using a stainless steel arc discharge chamber and were puried using solvent approach.

1.6.2

Generation of Nanouids

Nanouids were prepared by dispersing puried MWNTs (95% purity) in SAE 40 diesel oil using ultrasonic energy. Sodium Dodecyl Sulphate (SDS), a commonly used surfactant, was employed as a dispersing agent to enchance uniformity in dispersion of MWNTs.

1.6.3

Property evaluation of Nanouids

The enhancement in wear reduction property of the nanouid was evaluated using a four ball wear tester at the Tribology lab, Department of Mechanical Engineering, Indian Institute of Science (IISc), Bangalore. The tests were conducted at varying loads (100-500N) and temperatures (40o C, 70o C and 100o C); each test was carried out for 60 minutes and the spindle speed was constant at 1200rpm.

1.7
1.7.1

Properties of uids
Oil Viscosity

The parameter which plays a fundamental role in lubrication is oil viscosity. Dierent oils exhibit dierent viscosities. In addition, oil viscosity changes with temperature, shear rate and pressure and the thickness of the generated oil lm is usually proportional to it. So, at rst glance it appears that the more viscous oils would give better performance, since the generated lms would be thicker and a better separation of the two surfaces in contact would be achieved. This unfortunately is not always the case since more viscous oils require more power to be sheared. Consequently the power losses are higher and more heat is generated resulting in a substantial increase in the temperature of the contacting surfaces which may lead to the failure of the component. For engineering applications the oil viscosity is usually chosen to give optimum performance at the required temperature. Knowing the temperature at which the oil is expected to operate is critical as oil viscosity is extremely temperature dependent. The viscosity of dierent oils varies at dierent rates with temperature. It can also be aected by the velocities of the operating surfaces (shear rates). The knowledge of the viscosity characteristics of a lubricant is therefore very important in the design and in the prediction of the behaviour of a lubricated mechanical system.

1.7.2

Dynamic viscosity

Consider two at surfaces separated by a layer of uid of thickness h as shown in gure 1.1 The force required to move the upper surface is proportional to the wetted

Figure 1.1: Schematic representation of the uid separating two surfaces area A and the velocity u, i.e.,

F = Au

(1.1)

Assume that the uid lm separating the surfaces is made up of a number of innitely thin layers. Compare now two uid lms of dierent thickness made up of equispaced layers. If the surface velocity remains unchanged in these two cases then a single layer in the thicker lm will undergo less relative sliding than in the thinner lm. The velocity gradients for these two layers will be dierent. Since the thicker lm contains more single layers, less force will be needed to shear a single layer so the
1 viscous resistance will vary as the reciprocal of the lm thickness h . The force needed

to move the upper surface is thus proportional to: u h

F A

(1.2)

This relationship is maintained for most uids. Dierent uids will exhibit a dierent proportionality constant , called the dynamic viscosity given by u h

F = A or =
u h

(1.3)

(1.4)

Where: is the dynamic viscosity (Pas); is the shear stress acting on the uid 9

Table 1.2: Commonly used equations to determine viscosity-temperature relationship Name Equation Comments Early equation; accurate only for a Reynolds = beaT very limited temperature range Reasonable; useful in numerical a Slotte = b+T c analysis 1 Forms the basis of the ASTM Walther + a = bd T c viscosity-temperature chart b Most accurate; very useful in engiVogel = ae T c neering calculations (Pa);
u h

is the shear rate, i.e., velocity gradient normal to the shear stress s1 .

1.7.3

Kinematic viscosity

Kinematic viscosity is dened as the ratio of dynamic viscosity to uid density:

(1.5)

where: is the kinematic viscosity (m2 s1 ); is the dynamic viscosity (Pas); is the uid density (kg/m3 ). The most commonly used kinematic viscosity unit is the Stoke (S). This unit, however, is often too large for practical applications, thus a smaller unit, the centistokes (cS), is used. The SI unit for kinematic viscosity is (m2 s1 )

1.7.4

Viscosity - Temperature relationship

There are several viscosity-temperature equations available; some of them are purely empirical whereas others are derived from theoretical models. The most commonly used equations are summarized in Table 1.2. Among them the most accurate is the Vogel equation. Three viscosity measurements at dierent temperatures for a specic oil are needed in order to determine the three constants in this equation. The oil viscosity can then be calculated at the required temperature, or the operating temperature can be calculated if the viscosity is known. Apart from being very accurate the Vogel equation is useful in numerical analysis.

10

1.7.5

Viscosity index

The viscosity index is an inverse measure of the decline in oil viscosity with temperature. High values indicate that the oil shows less relative decline in viscosity with temperature.

Figure 1.2: Viscosity-temperature characteristics of selected oils

1.7.6

Viscosity-pressure relationship

Lubricant viscosity increases with pressure. For most lubricants this eect is considerably larger than the eect of temperature or shear when the pressure is signicantly above atmospheric. This is of particular importance in the lubrication of heavily loaded concentrated contacts which can be found, for example, in rolling contact bearings and gears. The pressures encountered in these contacts can be so high and the rate of pressure rise so rapid that the lubricant behaves like a solid rather than a liquid. The phenomenon of viscosity increasing with pressure and the possibility 11

of lubricant failure by fracture rather than viscous shear is often observed but not always recognized. The best known equation to calculate the viscosity of a lubricant at moderate pressures (close to atmospheric) is the Barus equation [2, 3]. The Barus equation is of the form:

p = o ep

(1.6)

where: p is the viscosity at pressure p (Pas); p is the atmospheric viscosity (Pas); is the pressure-viscosity coecient (m2 N 1 ), which can be obtained by plotting the natural logarithm of dynamic viscosity versus pressure p. The slope of the graph is ; p is the pressure of concern (Pa). For higher pressures Chu et al. [7] suggested that the following formula can be used: p = o (1 + Cp)n (1.7)

where: C, n are constants, n is approximately 16 for most cases and C can be obtained from the diagram shown in gure 1.3 [7].The pressure-viscosity coefcient is a function of the molecular structure of the lubricant and its physical characteristics such as molecular interlocking, molecular packing and rigidity and viscosity-temperature characteristics.There are various formulae available to calculate the pressure-viscosity coecient. One of them is

= (0.6 + 0.965log1 0o )108

(1.8)

where: is the pressure-viscosity coecient (m2 N 1 ); p is the atmospheric viscosity (cP); i.e. 1(cP ) = 103 (P as)

1.7.7

Thermal Conductivity

Thermal conductivity also varies linearly with the temperature and is aected by polarity and hydrogen bonding of the molecules. The thermal conductivity of most of the mineral and synthetic hydrocarbon based lubricants is in the range between 0.14 [W/mK] at 0C to 0.11 [W/mK] at 400C. For a rough estimation of a thermal 12

Table 1.3: Dynamic viscosity and pressure-viscosity coecients of some commonly used lubricants Lubricants Dynamic viscosity Pressure-viscosity o measured at at- coecient mospheric pressure (x109 m2 N 1 ) (103 P aS) 30o C 60o C 100o C 30o C 60o C 100o C High VI oils Light machine oil 38 12.8 5.3 18.4 13.4 Heavy machine oil 153 34 9.1 23.7 20.5 15.8 Heavy machine oil 250 50.5 12.6 25 21.3 17.6 Cylinder oil 810 135 26.8 34 28 22 Medium VI Oils Spindle oil 18.6 6.3 2.4 20 16 13 Light machine oil 45 124 13.9 28 20 16 Medicinal white oil 107 23.3 6.4 29.6 22.8 17.8 Heavy machine oil 122 26.3 7.3 27 21.6 17.5 Cylinder oil 171 31 7.5 28 23 18 Low VI Oils Spindle oil 30.7 8.6 3.1 25.7 16 15.4 Heavy machine oil 165 30 6.8 33 22.8 16 Heavy machine oil 310 44.2 9.4 27 34.6 19.5 Cylinder oil 2000 180 24 28 41.5 25 Other uids and lubricants Water 0.8 0.48 0.28 0 0 0 Ethylene oxide - propylene 204 62.5 22.5 17.6 14.3 12.2 oxide copolymer Castor oil 360 80 18 15.9 14.4 12.3 Di(2-ethylehexyl)phthalate 43.5 11.6 4.05 20.8 16.6 13.5 Glycerol(glycerine) 535 73 13.9 5.9 5.5 3.6 Polypropylene glycol 750 82.3 17.8 Polypropylene glycol 1500 177 17.4 Tri-aryl phosphate ester 25.5 31.6 -

13

Figure 1.3: Evaluation of viscosity index conductivity the following formula can be used: 0.12 (1 1.667104 ) s

K=

(1.9)

where; K is the thermal conductivity (W m1 K 1 ); is the temperature of interest (o C); s is the specic gravity at 15.6o C.

1.7.8

Flash point and Fire point

The ash point of the lubricant is the temperature at which its vapour will ignite. In order to determine the ash point the oil is heated at a standard pressure to a temperature which is just high enough to produce sucient vapour to form an ignitable mixture with air. This is the ash point. The re point of an oil is the temperature at which enough vapour is produced to sustain burning after ignition.

14

1.7.9

Additive Compatibility and Solubility

The additives used in the lubricants should be compatible with each other and soluble in the lubricant. These additive features are dened as additive compatibility and additive solubility.

Additive Compatibility Two or more additives in an oil are compatible if they do not react with each other and if their individual properties are benecial to the functioning of the system. It is usually considered that additives are compatible if they do not give visible evidence of reacting together, such as a change in colour or smell. This also refers to the compatibility of two or more nished lubricants. Lubricants should also be compatible with the materials of the components used in a specic application. For example, mineral oils are incompatible with natural rubber, and phosphate esters are incompatible with many dierent rubbers. Mineral oils give very poor performance with red hot steels because they produce carburization whereas with rape-seed oil this problem is avoided. In most industries these problems can be overcome by careful selection of lubricants. On the other hand, in some industries like pharmaceutical and foodstus where any lubricant leaks are not acceptable, process uids might be used as lubricants. For example, in sugar rening high viscosity syrups and molasses can be used, if necessary, to lubricate the bearings, but they are in general poor lubricants and their use may lead to severe problems.

Additive Solubility The additive must dissolve well in petroleum products. It must remain dissolved over the entire operating temperature range. Separation of an additive in storage or in service is highly undesirable. For example, elemental sulphur could be used as an additive in extreme conditions of temperature and pressure but it is insoluble in oil and it would separate during storage and service

15

1.7.10

Lubricant Additives

A large number of additives are used to impart performance characteristics to the lubricants. The main families of additives are: 1. Antioxidants 2. Viscosity index improvers 3. Anti-wear 4. Metal deactivators 5. Corrosion inhibitors 6. Rust inhibitors 7. Friction modiers 8. Extreme Pressure 9. Demulsifying / Emulsifying

Antioxidants Antioxidants are molecules that slow or prevent the oxidation of other chemicals. Oxidation is a redox chemical reaction that transfers electrons from a substance to an oxidizing agent. Oxidation reactions can involve the production of free radicals, which can form dangerous chain reactions. Antioxidants can terminate these chain reactions by removing radical intermediates and can inhibit other oxidation reactions by being oxidized themselves. As a result, antioxidants are often reducing agents such as thiols or phenols.

Anti-wear AW additives, or antiwear additives, are additives for lubricants to prevent metal-tometal contact between parts of gears. EP additives are usually used in applications such as gearboxes, while AW additives are used with lighter loads such as bushings. AW additives typically contain zinc and phosphorus compounds. 16

Some popular AW additives are: zinc dithiophosphate (ZDP) zinc dialkyl dithio phosphate (ZDDP), probably the most widely used in formulated engine oils, also acts as a corrosion inhibitor and antioxidant Tricresyl phosphate (TCP), used for high-temperature operation, often used as an AW and EP additive in turbine engine lubricants, and also in some crankcase oils and hydraulic uids Halocarbons (chlorinated parans), for extreme pressure operations Glycerol mono oleate Stearic acid, adhering to surfaces via reversible adsorption process under 150 C, which limits its use to mild contact conditions.

Metal deactivators Metal deactivators are fuel and lubricant additives used to stabilize uids by deactivating (usually by sequestering) metal ions, mostly introduced by the action of naturally occurring acids in the fuel and acids generated in lubricants by oxidative processes with the metallic parts of the systems. Metal deactivators inhibit the catalytic eects of such ions, especially copper, retarding the formation of gummy residues (eg. gels containing copper mercaptide). An example of a metal deactivator used for gasoline and jet fuels is N,N-disalicylidene-1,2-propanediamine. It is used in turbine and jet fuels, diesel, heating oil, and greases. It is approved for military and commercial aviation fuels. Benzotriazole and its various derivatives are also common in lubricant formulas.

Corrosion inhibitors A corrosion inhibitor is a chemical compound that, when added in small concentration, stops or slows down corrosion of metals and alloys. A typical good corrosion inhibitor will give 95% inhibition at concentration of 80 ppm, and 90% at 40 ppm.

17

Some of the mechanisms of its eect are formation of a passivation layer (a thin lm on the surface of the material that stops access of the corrosive substance to the metal), inhibiting either the oxidation or reduction part of the redox corrosion system (anodic and cathodic inhibitors), or scavenging the dissolved oxygen. Some corrosion inhibitors are hexamine, phenylenediamine, dimethylethanolamine, sodium nitrite, cinnamaldehyde, condensation products of aldehydes and amines (imines), chromates, nitrites, phosphates, hydrazine, ascorbic acid, and others. The suitability of any given chemical for a task in hand depends on many factors, from the material of the system they have to act in, to the nature of the substances they are added into and their operating temperature.

Friction modiers Friction modiers are added to lubricants to reduce the surface friction of the lubricated parts. Typically thes are polar chemical compounds having high anity for metal surfaces and possessing long alkyl chains.Glycerol mono-oleate is a common example of a friction modier Extreme Pressure additives EP additives, or extreme pressure additives, are additives for lubricants with role to decrease wear of the parts of the gears exposed to very high pressures. They are also added to cutting uids for machining of metal. EP additives are usually used in applications such as gearboxes, while AW additives are used with lighter loads such as bushings. EP additives typically contain organic sulfur, phosphorus or chlorine compounds which chemically react with the metal surface under high pressure conditions. Under such conditions, small irregularities on the sliding surfaces cause localized ashes of high temperature (300-1000 C), without signicant increase of the average surface temperature. The chemical reaction between the additive and the surface is conned to this area. Some of the EP additives are: Dark inactive sulphurized fat Dark active sulphurized fat Dark active sulphur hydrocarbon

18

 Short and medium chain chlorinated alkanes (see chlorinated hydrocarbons and chlorinated parans) Esters of chlorendic acid Polymer esters Organophosphates (phosphoric acid esters), eg. tricresyl phosphate, TCP) Zinc phosphates (zinc dialkyl dithio phosphate, ZDDP) Polysuldes Molybdenum compounds

Anti-foaming The main task of foam inhibitors is to destabilize foam generated during the operation of the machinery. Usually long chain silicone polymers are used in very small quantities of about 0.05% to 0.5% by weight. The amount of additive used is quite critical, i.e. excessive amount of this additive is less eective.

Viscosity improvers These are additives which arrest the decline in oil viscosity with temperature and they are commonly known as viscosity index improvers. Viscosity improving additives are usuallyhigh molecular weight polymers which are dissolved in the oil and can change shape from spheroidal to linear as the temperature is increased. This eect is caused by a greater solubility of the polymer in the oil at higher temperatures and partly osets the decline in base oil viscosity with temperature. The linear or uncoiled molecules cause a larger rise in viscosity in comparison to spheroidal or coiled molecules. Typical viscosity improvers are polymethacrylates in the molecular weight range between 10,000 and 100,000. It seems that linear polymer molecules with only a small number of side chains are the most eective. These additives are used in small concentrations of a few percent by weight in the base oil. They have been used for many years as an active ingredient of multigrade oils. The main problem

19

associated with these additives is that they are easily degraded by excessive shear rates and oxidation. Under high shear rates viscosity improvers can suer permanent or temporary viscosity loss. Temporary viscosity loss results from the alignment of the polymer molecules under high shear rates and is reversible. On the other hand, permanent viscosity loss involves the breakdown of large polymer molecules under high shear rates and is irreversible. Viscosity improvers can usually raise the viscosity index of an oil from 110 to 150, but only at moderate shear rates and for a limited period of time. Oil oxidation can also contribute to the degradation or breakdown of the polymer molecules. Pressure-viscosity coecients are not signicantly aected by polymer viscosity improvers although some minor eects have been reported in the literature.

1.8

Wear

Wear [4] is a damage to a solid surface, generally involving progressive loss of material due to relative motion between that surface and a contacting substance or surface. There are basically three types of wear viz., 1. Abrasive wear 2. Erosive wear and 3. Adhesive wear Wear by abrasion and erosion are forms of wear caused by contact between a particle and solid material. Abrasive wear is the loss of material by the passage of hard particles over a surface. Erosive wear is caused by the impact of particles against a solid surface. Adhesive wear occurs when there is surface interaction and welding at localized contact areas when one material is sliding over another. Abrasion and erosion in particular are rapid and severe forms of wear, which when not adequately controlled can result in signicant costs.

20

Figure 1.4: Adhesive Wear

1.8.1

Abrasive wear

Abrasive wear occurs whenever a solid object is loaded against particles of a material that have equal or greater hardness. Any material, even if the bulk of it is very soft, may cause abrasive wear if hard particles are present.

1.8.2

Erosive Wear

Erosive wear is caused by the impact of particles of solid or liquid against the surface of an object. In common with other forms of wear, mechanical strength does not guarantee wear resistance and a detailed study of material characteristics is required for wear minimization. The properties of the eroding particle are also signicant and are a relevant parameter in the control of this type of wear.

1.8.3

Adhesive Wear

Adhesive wear [5] is the second most common form of wear in industry. It is dened as: The action of one material sliding over another with surface interaction and welding (adhesion) at localised contact areas Adhesive wear may be between metallic materials, ceramics or polymers, or combinations. It is dependent on adhesion between the materials and that in turn depends on surface lms like oxides or lubricants, as well as the mutual anity of one material for another. If loads are light and the natural spontaneous oxidation of a metal can keep up with the rate of its removal by wear, then that wear rate will be relatively low (the oxide acting as a lubricant) and is known as Mild Wear. If loads are high and the protective oxide is continually disrupted to allow intimate metallic contact 21

and adhesion, then the wear would be classied as Severe Wear With materials which have thin, brittle oxides, notably stainless steel, aluminium alloys and titanium, the protective oxide is easily disrupted and the consequent massive adhesion and wear is called Galling. The terms Mild wear, Severe wear and Galling are used with specic meanings. They are in relation to unlubricated sliding. Mild wear is characteristic of dry sliding metals where the conditions are such that the naturally protecting oxide can continuously reform at the slidng contact, so acting with a degree of dry lubrication and reducing the wear rate. It also occurs with hardened alloys (usually steels) when, even under high contact loads and speeds, the underlying substrate can support the oxide and prevent its disruption by deformation below it. Severe wear occurs (generally in soft metals or alloys) when the conditions are such that the oxide is disrupted at a greater rate than which it can reform, so that clean metal is exposed below and massive adhesion occurs between the mating surfaces. It is not uncommon for soft materials to show sudden transitions between these two wear regimes. With mild steel at low load, mild wear results. As the load is increased, a point is reached when the oxide cannot keep pace and there is a sudden 100 fold increase in wear rate. At even higher loads, the frictional heating is such that the oxidation rate rapidly increases and can again form a protective layer; and mild wear is re-established. The use of a lubricant is to separate the surfaces and to eliminate contact and wear. This is achieved by the generation of a wedge of oil as the lubricant is drawn into the contact region by the motion of the parts.

1.9

SCOPE OF PRESENT WORK

Nanouids are engineered colloidal suspensions of nanoparticles in a base uid. The enhancement in a particular property of nanouids is dependent on the dispersed nanomaterials. Carbon nanotubes have a thermal conductivity of 6000W/mK and a cylindrical structure which makes it an outright choice for generation of nanouids.

22

In the present work, an attempt is made with some degree of success to uniformly disperse MWNTs in the SAE40 diesel oil with the aid of Sodium Dodecyl Sulphate. The wear resistant property of the nanouid is studied extensively using a four ball wear testing machine. Reduction in coecient of friction (upto 45%) was observed.

23

Chapter 2

LITERATURE REVIEW

2.1

Nanouids

Nanouids are engineered colloidal suspensions of nanoparticles in a base uid. In general the size of these nanoparticles vary from 1-100nm. The type of nanoparticle used is directly dependent on the enhancement of a required property of the base uid. The research work on nanouids until now has focused mainly on the improvement of thermal properties of the base uid. All physical mechanisms have a critical length scale, below which the physical properties of materials are changed. Therefore particles <100 nm exhibit properties that are considerably dierent from those of conventional solids. The noble properties of nanophase materials come from the relatively high surface area to volume ratio that is due to the high proportion of constituent atoms residing at the grain boundaries. The thermal, mechanical, optical, magnetic, and electrical properties of nanophase materials are superior to those of conventional materials with coarse grain structures [1].

2.1.1

Preparation of Nanoparticles and Nanouids

There are many methods that are used to prepare nanoparticles for dispersion in base uids. Current nanophase technology can produce large quantities of powders with average particle sizes of about 10-nm. Several modern nanophase materials have been prepared by physical gas-phase condensation or chemical synthesis techniques [6]. The gas-phase condensation process involves the evaporation of a source material and

24

the rapid condensation of vapor into nanometer-sized crystallite or loosely agglomerated clusters in a cool, inert, reduced pressure atmosphere [7, 8]. A chemistry-based solution-spray conversion process starts with water-soluble salts of source materials. The solution is then turned into an aerosol and dried by a spray-drying system. Rapid vaporization of the solvent and rapid precipitation of the solute keeps the composition identical to that of the starting solution. The precursor powder is then placed in a uidized-bed reactor to evenly pyrolyze the mixture, drive o volatile constituents, and yield porous powders with a uniform homogeneous ne structure [9]. A third technique is to generate nanophase materials by condensation of metal vapors during rapid expansion in a supersonic nozzle [10, 11, 12] Nanouids are generally prepared by dispersing nanosized particles (10-100nm) in a base uid. However nanouids with uniformly dispersed nanoparticles are very dicult to prepare as the particles agglomerate over time due to mutually attractive Van der waals forces. Hence some kind of dispersant is generally added for this purpose. The choice of the dispersant depends on the type and the properties of the base uid. The most commonly used dispersant for aqueous solution of carbon nanotubes is Sodium Dodecyl Sulphate (SDS). Lian Gao et al. [13] have conducted extensive stability analysis on aqueous suspension of carbon nanotubes using UVSpectrophotometric measurements. It was found that the optimum concentration of SDS to disperse 0.5wt% of CNTs was 2wt%. Addition of higher percentages of SDS results in the formation of micelles which hinder proper distribution of CNTs.

2.1.2

Thermally enhanced Nanouids

It is a well known fact that the thermal conductivity of solid particles is much higher than those of liquids. For example, at room temperature the thermal conductivity of copper (401 W/mK) is 691 times greater than that of water (0.58 W/mK). Therefore it is natural that addition of copper particles increases the thermal conductivity of water. However the size of these particles makes a signicant impact on the properties of the uid. Milli or micrometer sized particle suspensions have limited applications as the particles settle down or clog the lters. This is where nanouids come into picture;

25

the small size of these particles oer a unique stability and application advantage when compared with all other commercially available heat transfer uids. For example 0.3 volume percent of copper nano-particles dispersed in ethylene glycol increases its thermal conductivity by about 40% [14]. Metal oxides such as aluminum oxide or titanium oxide are also used to enhance the thermal conductivity of base uids although the amount of heat transfer increase is not as large as that seen in metal particle suspensions [15]. The eectiveness of heat transfer enhancement is known to be dependent on the amount of dispersed particles, material type, particle shape, and so on. However there has been no established mechanism for the heat transfer enhancement. The reason may arise from the diculty caused by the fact that the heat-transfer between the base uid and particles occurs while the particles are in random Brownian motion. Also, depending on the ow condition and chemical nature of particles, dispersion state can be dierent [16, 17].

2.1.3

Carbon nanotube based Nanouids

Carbon nanotubes exhibit exotic properties. Their extraordinary stiness and strength combined with their thermal and electronic properties have grabbed the attention of researchers worldwide. Multiwalled nanotubes have a stiness of 1.8TPa [18, 19, 20]while their thermal conductivity is around 6600W/mK at room temperature [21] which are higher than those of graphite and diamond. Nanotube based nanouids have been studied extensively by various research groups for its thermally enhanced properties [22, 23, 24, 25, 26], however there has been very little research done in the area of lubrication property enhancement of nanouids. Carbon nanotubes which are one of the allotropic forms of carbon resembles the shape of a roller bearing at the nanolevel, besides carbon graphite is also a good solid lubricant; hence CNTs might show some extraordinary lubrication properties. Very few research groups have explored this area [27, 28].

26

Chapter 3

EXPERIMENTATION

3.1

Preparation of MWNT by arc-evaporation technique

A stainless steel vertical chamber with a viewing port was used as the basic arc evaporation setup. The chamber has an inlet port for Helium and an outlet port connected to a vacuum pump as shown in gure 3.1. The chamber consists of a copper cathode ( 12mm) and a consumable graphite anode ( 7mm and length 3in). The entire chamber is cooled by passing water through anode and cathode supports, chamber walls and through copper tubes surrounding the electrodes. Carbon nanotubes are produced by evaporating the graphite anode in a helium atmosphere at 500torr vacuum. A cylindrical deposit is formed on the cathode with a diameter greater than that of the initial graphite anode evaporated. Consequently, an anode feed mechanism is employed to maintain a constant arc gap of 1mm between the electrodes. The arc struck between the electrodes is sustained with a DC voltage of 20V and current of 100A. The process takes about an hour to complete producing soot on the inside walls of the chamber and a cathode deposit. The soot contains amorphous carbon and minute quantities of fullerenes. The cathode deposit (gure 3.2) has a cigar like structure and contains MWNTs, amorphous carbon and polyhedral particles in its core. MWNTs along with impurities are extracted from the deposit.

27

Figure 3.1: Schematic view of arc-evaporation apparatus

28

Figure 3.2: A photograph of the cathode deposit

3.2

Purication of MWNTs

MWNTs are extracted by the solvent approach. The impure MWNTs obtained from the cathode deposit is dispersed in ethanol and is sonicated (gure 3.3) at 150V for 20 minutes. Nanotubes get separated from the surrounding debris as the graphite impurities being of relatively higher density settle down in the beaker. The solution is then decanted and the process is repeated several times. Finally the residue containing mainly graphite particles is discarded. The decanted solution is left undisturbed for a day to allow the MWNTs to agglomerate and settle at the bottom. Around 75 percent of the ethanol is recovered by decantation. The remaining ethanol containing settled MWNTs is evaporated to obtain a residue of pure MWNTs.

3.3

Preparation of SWNT by arc-evaporation technique

SWNTs are produced in the same arc evaporation chamber shown in gure 3.1 by co -vaporization of graphite and bimetal catalyst (Co and Ni) in a composite anode. The graphite rod is 6mm in diameter and 150mm in length. A hole of 4mm is drilled axially and densely packed with mixture of cobalt, nickel and graphite powder. The helium pressure is maintained at 500 torr. A stable arc is formed at 20V and 75A. The gap between electrodes is maintained around 2mm.

29

SWNTs are formed as a web like structure in the chamber (gure 3.4) and also as a collaret around the cathode. It should be noted that cylindrical deposit also grows at the cathode, consisting of a hard gray shell and a soft core. The soft core has poorly developed columnar structure and contains MWNTs and polyhedral particles.

3.4

Purication of SWNTs

The mixed carbon and metal vapour that escapes the electrode gap then condenses and deposits on the reactor surface. The product obtained can be divided in to three structural types; a spongy soft belt called collaret is formed around the cylindrical deposit while relatively a strong cloth like soot is found on the chamber walls and nally a web like structure is suspended in the chamber volume between cathode and walls. The above three type contains varying amount of SWNTs, Fullerenes and amorphous carbon. To extract SWNTs, the soot is heated at 450o C for 20 minutes to vaporize volatile impurities. The residue is then treated with HN O3 to dissolve metal catalyst particles. The soot, free from volatile impurities and catalyst particles is ltered to separate it from HN O3 and the residue thus obtained is dissolved in ethanol followed by sonication for 20 minutes. The decanted solution is nally heated to vaporize ethanol to obtain pure SWNTs.

3.5

Characterization of Nanotubes

The basic tools used to characterize Carbon Nanotubes are: 1. Electron microscopy (a) Transmission Electron Microscopy and (b) Scanning Electron Microscopy (SEM) 2. Raman Spectroscopy and 3. Thermogravimetric Analysis

30

Figure 3.3: Photograph of Ultrasonicator used for sonication

Figure 3.4: Schematic view of arc-evaporation apparatus 31

3.5.1

Electron Microscopy

Optical microscopes have been used from centuries together, to magnify objects. However, even compound optical microscopes are limited in their ability to resolve ne details by the properties of light and the refractive materials used to manufacture lenses. A lens magnies by bending light by refraction. Optical microscopes are restricted in their ability to resolve features by a phenomenon called diraction which, based on the numerical aperture (AN ) of the optical system and the wavelengths of light used (), sets a denite limit (d) to the optical resolution. Assuming that optical aberrations are negligible, the resolution (d) is given by: 2An

d=

(3.1)

If = 550 nm is assumed corresponding to green light and with air as medium, the highest practical An is 0.95, and with oil, up to 1.5. This limits the resolution to around 0.2. In order to increase the resolution of microscopes so as to observe nanomaterials, light of lower wavelength () than visible light must be used. This is the basic principle employed in Electron Microscopes. Electron Microscopes use electrons in order to examine a given specimen. The wavelength of an electron can be given by debroglie equation: h h = p 2me Eb

(3.2)

where h is Plancks constant. The electron has rest mass me and energy Ee = me c2 = 511keV . If an electron with charge qe is accelerated from rest by an electrical potential U , to the electron beam energy Eb = qe U , it will have a wavelength of 1 nm at 1 eV decreasing to 1 pm at 100 keV where it will be travelling with 50% the speed of light. There are two general types of electron microscopes: 1. Scanning Electron Microscope that scans an electron beam over the surface of an object and measures how many electrons are scattered back and 32

Figure 3.5: A very simple sketch of a Transmission Electron Microscope (TEM) and Scanning Electron Microscope (SEM) compared to an optical transmission microscope and a cathode ray tube (CRT) TV screen - both systems have many things on common with the electron microscope. The optical microscope uses lenses to control the lights pathway through the system and is in many ways built up like a TEM only the TEM uses electromagnetic lenses to direct the beam of electrons. The CRT uses electromagnetic lenses as the TEM and SEM to control the electron beam, and generates an image for the viewer by scanning the beam over a uorescent screen - in the same way the a SEM generates an image by scanning the electron beam over a small sample. 2. Transmission electron Microscope that shoots electrons through the sample and measures how the electron beam changes because it is scattered in the sample. Electrons are easily scattered by gases and hence the microscopes must be used in a vacuum or very low pressure environment which makes the instruments larger and expensive. The electron optical system sets limitations to the achievable primary beam current and radius. The expected image resolution set by the primary beam cannot be reached if the signal detected for imaging is caused by electrons scattered far in the sample. The trajectory of an electron penetrating a bulk solid is a complex trajectory due to multiple elastic and inelastic collision events. As the primary electron (PE) 33

penetrates into the sample it will gradually change direction and loose energy in collisions. The mean free path due to elastic and inelastic collisions, mf p , depends on the atomic number of the material and the PE energy. At 100 keV mf p = 150nm for carbon and 5 nm for gold. For samples thinner than mf p the main part of the PE will pass relatively unaected through the sample, which is the basis for TEM. The PE are scattered within the interaction volume, dened the electron range in the material. The range is longer than the mean free path mf p . The SE have a very short range, and only those created within that range from the surface can escape the material. This denes the SE escape depth. SEM can be used for thicker specimens. The electrons that escape from the sample in a new direction compared to the PE due to elastic collisions are called backscattered electrons (BSE). The electron range is about 1 m at 10 keV for carbon, decreasing with higher atomic number for the material. Both the high energy PE and BSE generate secondary electrons (SE) by inelastic scattering events. The SE are generally dened as having energy below 50 eV while the BSE have energies up to the PE energy. The range of SE is typically 1 nm for metals and about 10 nm for insulators

Scanning Electron Microscope (SEM) In a scanning electron microscope a beam is scanned over the sample surface in a raster pattern while a signal is recorded from electron detectors for SE or BSE. The PE energy is kept relatively low (1-30 keV) to limit the interaction volume in the specimen that will contribute to the detected signal. Especially low energy PE will provide high sensitivity to surface composition as they cannot penetrate far into the sample. The gure 3.6 above showed the eect of PE penetration depth of a carbonaceous nanostructure with a gold core, where only the surface is visible at low PE energies, while the carbon becomes increasingly transparent and the core visible at high PE energies. The low energy SE can easily be attracted and collected by a positively charged detector and are hence an ecient source for an image signal. The standard SE detector is an Everhart-Thornley (ET) detector where a positively charged grid attracts 34

Figure 3.6: The electron range increases with beam energy. The internal structure of the EEBD deposits can be examined at high electron beam energies in SEM. At 5 kV with shallow penetration depth, the surface of the tips is clearly visible while at higher energies a core of more dense material becomes increasingly visible. At 100 keV and above, TEM images can achieve atomic resolution where the lattice planes in nanocrystals such as the gold nanocrystal in (c). The gold crystal is embedded in amorphous carbon with no clear lattice pattern [29]. the SE and accelerates them to suciently high energies to create a light pulse when striking a scintillator. The light pulse is then amplied by a photomultiplier. Despite the complex construction, the ET detector is remarkably ecient.

Transmission electron microscopy (TEM) is an imaging technique whereby a beam of electrons is transmitted through a specimen, then an image is formed, magnied and directed to appear either on a uorescent screen or layer of photographic lm (see electron microscope), or to be detected by a sensor such as a CCD camera. The contrast in a TEM image is not like the contrast in a light microscope image. A crystalline material interacts with the electron beam mostly by diraction rather than absorption, although the intensity of the transmitted beam is still aected by the volume and density of the material through which it passes. The intensity of the diraction depends on the orientation of the planes of atoms in a crystal relative to the electron beam at certain angles the electron beam is diracted strongly from the axis of the incoming beam, while at other angles the beam is largely transmitted. Modern TEMs are often equipped with specimen holders that allow the user to tilt the specimen to a range of angles in order to obtain specic diraction conditions, and apertures placed below the specimen allow the user to select electrons diracted in a particular direction.

35

A high contrast image can therefore be formed by blocking electrons deected away from the optical axis of the microscope by placing the aperture to allow only unscattered electrons through. This produces a variation in the electron intensity that reveals information on the crystal structure, and can be viewed on a uorescent screen, or recorded on photographic lm or captured electronically. This technique (known as Bright Field or Light Field) is particularly sensitive to extended crystal lattice defects in an otherwise ordered crystal, such as dislocations. As the local distortion of the crystal around the defect changes the angle of the crystal plane, the intensity of the scattering will vary around the defect. As the image is formed by the distortion of the crystal planes around the defect, the contrast in these images does not normally coincide exactly with the defect, but is slightly to one side. It is also possible to produce an image from electrons deected by a particular crystal plane. By either moving the aperture to the position of the deected electrons, or tilting the electron beam so that the deected electrons pass through the centred aperture, an image can be formed of only deected electrons, known as a Dark Field image. In the most powerful diraction contrast TEM instruments, crystal structure can also be investigated by High Resolution Transmission Electron Microscopy (HRTEM), also known as phase contrast imaging as the images are formed due to dierences in phase of electron waves scattered through a thin specimen. Resolution of the HRTEM is limited by spherical and chromatic aberration, but a new generation of aberration correctors has been able to overcome spherical aberration. Software correction of spherical aberration has allowed the production of images with sucient resolution to show carbon atoms in diamond separated by only 0.89 A and atoms in silicon at 0.78 A (78 pm) at magnications of 50 million times. Improved resolution has also allowed the imaging of lighter atoms that scatter electrons less eciently lithium atoms have been imaged in lithium battery materials. The ability to determine the positions of atoms within materials has made the HRTEM an indispensable tool for nanotechnology research and development in many elds, including heterogeneous catalysis and the development of semiconductor devices for electronics and photonics. 36

Figure 3.7: A Perkin-Elmer TGA7

3.5.2

Thermogravimetric analysis (TGA)

Thermogravimetric analysis (TGA) is an analytical technique used to determine a materials thermal stability and its fraction of volatile components by monitoring the weight change that occurs as a specimen is heated. The measurement is normally carried out in air or in an inert atmosphere, such as Helium or Argon, and the weight is recorded as a function of increasing temperature. A derivative weight loss curve can also be used to tell the point at which weight loss is most apparent.

3.6

Generation of Nanouids

Nanouids were prepared by dispersing MWNTs (nanoparticle) in SAE40 diesel oil (baseuid). However ensuring uniform dispersion of nanotubes in the base oil has been a serious challenge. The nanotubes tend to aggregate, form agglomerates and separate from the dispersion under the inuence of strong Vanderwaals forces. In order to reap maximum property enhancement from the nanouid, the MWNTs need to be dispersed uniformly, which was accomplished to a certain extent by the addition of a dispersing agent. The use of dispersion agents, such as surface-active agents, to disperse ne particles of hydrophobic materials in aqueous solution have been reported in literature [30, 31]. Sodium Dodecyl Sulphate (SDS) is one of the commonly used surfactant to disperse carbon nanotubes in aqueous solution and hence was adopted 37

to disperse MWNTs in oil medium. In order to determine optimum concentration of SDS to uniformly disperse MWNTs, varying weight percentages of SDS was used to disperse 0.1wt% of MWNT in SAE 40 oil. The mixture was sonicated for 30 minutes and analyzed under a microscope of 40x magnication to nd any trace of agglomerates. The photographs of agglomerates with dierent weight fractions of SDS is shown in gure 3.8 From gure 3.8 it can be seen that the nanotubes are dispersed quite uniformly in the oil for 1wt% of SDS which leads to the conclusion that the optimum concentration of SDS for 0.1wt% CNT is 1wt% SDS. Any amount lower or higher than this will lead to large aggregation as can be seen in gure 3.8. Insucient surfactant cannot produce an ecient coating that will induce electrostatic repulsion and counterbalance the Vanderwaals attractions. At higher SDS concentrations, the clusters become larger and denser. Such a behavior can presumably be ascribed to the reduction of electrostatic repulsion forces between MWNTs due to the large ionic strength and the increasing concentration of surfactant aggregates, known as micelles [13]. Micelles cannot t in between two CNT bundles that are close to each other. As a result, the osmotic pressure of the micelles around bundles creates an eective attraction. In classical colloidal suspensions and in multiwall nanotube dispersions, this attraction is known as a depletion attraction. It was inferred that the concentration of SDS has to be roughly 10 times the concentration of MWNT assuming linear variation. Therefore to prepare 0.25wt% MWNT nanouid, 2.5wt% of SDS was added. However some portion of SDS always settled at the bottom even after sonication time reaching 5 hours. Therefore the assumed linear variation was incorrect. For preparing other weight fractions of MWNT nanouid, 1.25 wt% of SDS was used and the dispersion was found to be adequate.

3.7

Four Ball Wear Test

The Four Ball Wear Test method [32] can be used to determine the relative wear preventive properties of lubricating uids in sliding contact. This test puts one rotating ball against three xed balls under specic conditions of pressure, temperature,

38

(a) 0.25 wt% SDS

(b) 0.50 wt% SDS

(c) 0.75 wt% SDS

(d) 1 wt% SDS

(e) 2 wt% SDS

(f) 3 wt% SDS

(g) 4 wt% SDS

(h) micelle

Figure 3.8: Dispersion analysis for 0.1 wt% of CNT

39

Figure 3.9: Schematic of a four ball wear test machine revolutions per minute and duration gure 3.9. The test may be used to evaluate the friction and wear control ability of liquid lubricants or greases in sliding contact gure 3.10.

3.7.1

Materials

Test Balls are of chrome alloy steel, made from AISI standard steel No. E-52100, with diameter of 12.7 mm [0.5 in.] Grade 25 EP (Extra Polish). However the Rockwell C hardness should be between 64 to 66, a closer limit than is found in the ANSI requirement.

3.7.2

Cleaning Fluids

Cleaning Fluids for preparing balls and apparatus for the test should be those approved as nontoxic, capable of removing antirust coatings from the balls, eliminating test-oil carryover from one test to the next, and not contribute to wear or antiwear of the test lubricant. When the uid is ammable, appropriate precautions should be taken. In our tests we used Hexane as a cleaning uid.

3.7.3

Test Conditions

The testing parameters for the base oil and 0.25wt% MWNT nanouid is given in table 3.1

40

Figure 3.10: Four Ball Wear Tester

Base Oil 100N 200N 300N 400N 500N

40o C 2 2 2 2 2

70o C 2 2 2 2 2

100o C 2 2 2 2 2

Table 3.1: Parameters for testing of base oil and 0.25 wt% MWNT nanouid

41

3.7.4

Procedure

1. The four test balls, clamping parts for upper and lower balls and the oil cup are thoroughly cleaned with hexane and nally wiped using a fresh tissue paper. It is to be noted that no trace of solvent must remain when the test oil is introduced and the machine assembled. 2. One of the clean balls is tightened onto the spindle of the test machine. 3. The remaining three clean test balls are assembled in the test-oil cup and hand tightened using the supplied wrench gure 3.12. 4. The oil to be evaluated is poured into the test-oil cup to a level at least 3 mm above the top of the balls. It has to be noted that this oil level still exists after the test-oil lls all of the voids in the test-oil cup assembly. 5. The test-oil cup with the three balls is installed in the machine and the normal load and coecient of friction is tared to zero. 6. The test conditions are set properly and the load is applied slowly to avoid shock gure3.13. 7. The heaters have to establish the given temperature 2o C while the variation in rpm can be 60 8. The test is conducted for 60 1 minutes after which the heaters and drive motors are switched o and the test-oil cup and three-ball assembly is removed.

3.7.5

Measuring wear scar diameter

The test oil is drained from the three-ball assembly. The scar area is wiped with a tissue and the scars are marked for easy observation in microscope. The wear scar diameter gure 3.11 is measured twice once parallel to the scar and the other perpendicular to the scar. The arithmetic average of the six measurements are reported as scar diameter in millimeters.

42

Figure 3.11: Photograph of a wear scar

Figure 3.12: Three ball Assembly

Figure 3.13: Four ball wear tester software

43

Chapter 4

RESULTS and DISCUSSIONS

4.1
4.1.1

Characterization of Carbon Nanotubes

Transmission Electron Microscopy

Transmission Electron Microscopy image of the MWNT and SWNT produced by arc discharge method is shown in gure [4.1, 4.2]. The sample is quite pure and contains few amorphous carbon.

4.1.2

Thermogravimetric Analysis

Thermogravimetric analysis gauges the thermal stability and purity of a particular substance in a given sample. TGA graph for MWNT is shown in gure 4.3. Around 95% of the sample is thermally stable upto 460o C with only 5% by weight of the sample decomposing, implying the presence of amorphous impurities. The steep loss of weight at about 520o C is due to MWNT. Therefore it is concluded that the puried sample of MWNT subjected to thermogravimetric analysis was of 95% purity.

4.1.3

Coding of nanouid samples

A typical code used during testing was 1B4a. The rst letter 1 indicates 100N, similarly if the rst letter is 2, it indicates 200N. The letter B in the code signies base oil, C indicates 0.25 weight percent MWNT additive, D indicates 0.5 weight percent MWNT additive, E indicates 0.75 wt %, F indicates 1 wt%, H indicates 3 wt%, A indicates 0.1 wt% and nally Z indicates 0.05 wt% of MWNT additive. The

44

Figure 4.1: Transmission Electron Microscopy image of MWNT

Figure 4.2: Transmission Electron Microscopy image of SWNT

45

Figure 4.3: Thermogravimetric analysis of MWNT third letter stands for the temperature used: 4 stands for 40o C, 7 stands for 70o C, 10 stands for 100o C. The last letter in the code indicates the trial number: a indicate trial1 and b indicates trial2.

(a) Trial1

(b) Trial2

Figure 4.4: Variation of COF of base oil with TIME at 100N and 40o C 46

(a) Trial1

(b) Trial2

Figure 4.5: Variation of COF of base oil with TIME at 200N and 40o C

(a) Trial1

(b) Trial2

Figure 4.6: Variation of COF of base oil with TIME at 300N and 40o C

(a) Trial1

(b) Trial2

Figure 4.7: Variation of COF of base oil with TIME at 400N and 40o C

47

(a) Trial1

(b) Trial2

Figure 4.8: Variation of COF of base oil with TIME at 500N and 40o C

(a) Trial1

(b) Trial2

Figure 4.9: Variation of COF of base oil with TIME at 100N and 70o C

(a) Trial1

(b) Trial2

Figure 4.10: Variation of COF of base oil with TIME at 200N and 70o C

48

(a) Trial1

(b) Trial2

Figure 4.11: Variation of COF of base oil with TIME at 300N and 70o C

(a) Trial1

(b) Trial2

Figure 4.12: Variation of COF of base oil with TIME at 400N and 70o C

(a) Trial1

(b) Trial2

Figure 4.13: Variation of COF of base oil with TIME at 500N and 70o C

49

(a) Trial1

(b) Trial2

Figure 4.14: Variation of COF of base oil with TIME at 100N and 100o C

(a) Trial1

(b) Trial2

Figure 4.15: Variation of COF of base oil with TIME at 200N and 100o C

(a) Trial1

(b) Trial2

Figure 4.16: Variation of COF of base oil with TIME at 300N and 100o C

50

(a) Trial1

(b) Trial2

Figure 4.17: Variation of COF of base oil with TIME at 400N and 100o C

(a) Trial1

(b) Trial2

Figure 4.18: Variation of COF of base oil with TIME at 500N and 100o C

(a) Trial1

(b) Trial2

Figure 4.19: Comparison of COF of base oil and 0.25wt% additive oil with TIME at 100N and 40o C

51

(a) Trial1

(b) Trial2

Figure 4.20: Comparison of COF of base oil and 0.25wt% additive oil with TIME at 200N and 40o C

(a) Trial1

(b) Trial2

Figure 4.21: Comparison of COF of base oil and 0.25wt% additive oil with TIME at 300N and 40o C

(a) Trial1

(b) Trial2

Figure 4.22: Comparison of COF of base oil and 0.25wt% additive oil with TIME at 400N and 40o C

52

(a) Trial1

(b) Trial2

Figure 4.23: Comparison of COF of base oil and 0.25wt% additive oil with TIME at 500N and 40o C

(a) Trial1

(b) Trial2

Figure 4.24: Comparison of COF of base oil and 0.25wt% additive oil with TIME at 100N and 70o C

(a) Trial1

(b) Trial2

Figure 4.25: Comparison of COF of base oil and 0.25wt% additive oil with TIME at 200N and 70o C

53

(a) Trial1

(b) Trial2

Figure 4.26: Comparison of COF of base oil and 0.25wt% additive oil with TIME at 300N and 70o C

(a) Trial1

(b) Trial2

Figure 4.27: Comparison of COF of base oil and 0.25wt% additive oil with TIME at 400N and 70o C

(a) Trial1

(b) Trial2

Figure 4.28: Comparison of COF of base oil and 0.25wt% additive oil with TIME at 500N and 70o C

54

(a) Trial1

(b) Trial2

Figure 4.29: Comparison of COF of base oil and 0.25wt% additive oil with TIME at 100N and 100o C

(a) Trial1

(b) Trial2

Figure 4.30: Comparison of COF of base oil and 0.25wt% additive oil with TIME at 200N and 100o C

(a) Trial1

(b) Trial2

Figure 4.31: Comparison of COF of base oil and 0.25wt% additive oil with TIME at 300N and 100o C

55

(a) Trial1

(b) Trial2

Figure 4.32: Comparison of COF of base oil and 0.25wt% additive oil with TIME at 400N and 100o C

(a) Trial1

(b) Trial2

Figure 4.33: Comparison of COF of base oil and 0.25wt% additive oil with TIME at 500N and 100o C

(a) Trial1

(b) Trial2

Figure 4.34: Comparison of COF of base oil and 0.1wt% additive oil with TIME at 500N and 40o C

56

(a) Trial1

(b) Trial2

Figure 4.35: Comparison of COF of base oil and 0.50wt% additive oil with TIME at 500N and 40o C

(a) Trial1

(b) Trial2

Figure 4.36: Comparison of COF of base oil and 0.50wt% additive oil with TIME at 500N and 40o C Figure 4.1.3 shows the variation of coecient of friction of Single walled nanotube additive oil with time. There is a noticeable reduction in coecient of friction when compared to that of the base oil. The wear scar diameter for dierent weight fractions of MWNT additive is shown in gure 4.41. It can be inferred that the optimum weight fraction of MWNT additive added to the base oil for eective wear and coecient of friction reduction is 0.25 weight percent. This maybe because of failure in optimum dispersion of higher weight fractions of MWNT in the base oil. At higher temperatures and higher loads SDS seems to become ineective in dispersing MWNT. Several samples of oil after undergoing testing for one hour in the four ball tester showed separation as shown in gure 4.45. This maybe one of the reason for the poor performance of the nanouid at higher loads and temperatures. Gum arabic has been used by Xuan et al. [33] to disperse MWNT in water. It 57

(a) Trial1

(b) Trial2

Figure 4.37: Comparison of COF of base oil and 0.25wt% additive oil with TIME at 400N and 40o C

(a) Trial1

(b) Trial2

Figure 4.38: Comparison of COF of base oil and 0.50wt% additive oil with TIME at 500N and 40o C

(a) Trial1

(b) Trial2

Figure 4.39: Comparison of COF of base oil and 0.05wt% additive oil with TIME at 500N and 40o C

58

Figure 4.40: Comparison of COF of base oil and 1wt% SWNT additive oil with TIME at 500N and 40o C was found that after maintaining a proper pH and treating the solution of water and disentangled MWNTs for 30 mins in a high shear homogenizer produced nanouids with no visible sedimentation for months. Therefore to improve the performance of the nanouid at higher load and higher temperatures, gum arabic might be used as an alternative to SDS.

59

Figure 4.41: Variation of Wear Scar Diameter with dierent weight fraction of additive

Figure 4.42: Variation of Wear Scar Diameter with dierent loads at 40o C

60

Figure 4.43: Variation of Wear Scar Diameter with dierent loads at 70o C

Figure 4.44: Variation of Wear Scar Diameter with dierent loads at 100o C

61

Figure 4.45: Separation of MWNT from the base oil seen in some samples at higher loads and higher temperatures

62

Chapter 5

CONCLUSION
1. Carbon nanotubes were successfully synthesized using arc evaporation technique. 2. Multiwalled nanotubes were puried through solvent approach. Carbon nanotube purity were evaluated using Thermogravimetric analysis and was found to be 95%. 3. Nanouids were prepared successfully by dispersing puried Multiwalled Nanotubes in SAE40 diesel oil. Sodium Dodecyl Sulphate (SDS), a commonly used surfactant, was employed to disperse Multiwalled Nanotubes in the base oil. 4. The optimum weight percentage of Sodium Dodecyl Sulphate to disperse 0.1 weight percent of Multiwalled nanotube in SAE40 diesel oil was experimentally determined to be 1 weight percent. 5. The nanouid was tested for its wear resistant properties at the Tribology lab, Indian Institute of Science, Bangalore. At low load and temperatures, the nanouid was found to exhibit huge decrease in Coecient of friction (upto 45%). However at higher temperatures multiwalled nanotubes were found to agglomerate and separate from the base uid (gure 4.45). This behaviour may be attributed to the failure of Sodium Dodecyl Sulphate in dispersing carbon nanotubes. 6. To improve the performance of the nanouid at higher load and higher temperatures, gum arabic might be used as an alternative to SDS.

63

Chapter 6

CHALLENGES FACED DURING EXECUTION OF THE PROJECT

6.1

Selection of suitable base oil

At the early stages of the project, the base oil to be used for preparation of nanouid was ambiguous. It was not clear whether to use single grade oil, multigrade oil or synthetic oil for the project. However it was later decided that single grade oil with comparatively fewer additives would provide us a platform for better property evaluation.

6.2

Non uniform dispersion of MWNT in base oil

Multiwalled Nanotubes attract towards each other due to weak vanderwaals forces and agglomerate in a solution. Surfactants are generally used to coat the surface of MWNT and prevent agglomeration. However if the weight fraction of surfactant is higher than the critical micellar concentration, they begin to form micelles which dents their ability to disperse MWNTs. Sodium Dodecyl Sulphate (SDS) was used to disperse MWNT and extensive analysis was conducted to determine the optimum concentration of SDS for dispersing 0.1 weight fraction of MWNT.

64

6.3

Determination of method used to test wear resistant properties of oil

After the nanouids were generated, there was some ambiguity in choosing the method used to characterize their wear resistant property. Finally we decided to adopt four ball wear testing method as it was the standard method used in the industry for similar purposes.

6.4

Searching for Four ball wear testing facility

The major obstacle in the completion of the project was to nd a four ball tester in bangalore to characterize the nanouid. After searching in various establishments, we were successful in obtaining the facility at the Tribology lab, Department of Mechanical Engineering, Indian Institute of Science, Bangalore.

6.5

Diculty in obtaining slots for testing

The machine at IISc was overbooked by various student project groups from other projects and we were very lucky to obtain slots for testing of our nanouid. In most of the circumstances, we worked in night shifts from evening 6pm to 10am next morning.

6.6

Diculty in producing 4 grams of puried Carbon nanotubes

The yield of MWNT obtained by arc discharge was very meagre. The cathode deposits from over 10 experiments (each 40 minutes) yielded only 0.1 gram of pure MWNT (95% purity). Hence it was very dicult to produce 4 grams of puried MWNT and we almost took two and a half months to prepare the same.

65

List of Figures
1.1 1.2 1.3 1.4 3.1 3.2 3.3 3.4 3.5 Schematic representation of the uid separating two surfaces . . . . . Viscosity-temperature characteristics of selected oils . . . . . . . . . . Evaluation of viscosity index . . . . . . . . . . . . . . . . . . . . . . . Adhesive Wear . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Schematic view of arc-evaporation apparatus . . . . . . . . . . . . . . A photograph of the cathode deposit . . . . . . . . . . . . . . . . . . Photograph of Ultrasonicator used for sonication . . . . . . . . . . . . Schematic view of arc-evaporation apparatus . . . . . . . . . . . . . . A very simple sketch of a Transmission Electron Microscope (TEM) and Scanning Electron Microscope (SEM) compared to an optical transmission microscope and a cathode ray tube (CRT) TV screen - both systems have many things on common with the electron microscope. The optical microscope uses lenses to control the lights pathway through the system and is in many ways built up like a TEM - only the TEM uses electromagnetic lenses to direct the beam of electrons. The CRT uses electromagnetic lenses as the TEM and SEM to control the electron beam, and generates an image for the viewer by scanning the beam over a uorescent screen - in the same way the a SEM generates an image by scanning the electron beam over a small sample. . . . . . . 33 9 11 14 21 28 29 31 31

66

3.6

The electron range increases with beam energy. The internal structure of the EEBD deposits can be examined at high electron beam energies in SEM. At 5 kV with shallow penetration depth, the surface of the tips is clearly visible while at higher energies a core of more dense material becomes increasingly visible. At 100 keV and above, TEM images can achieve atomic resolution where the lattice planes in nanocrystals such as the gold nanocrystal in (c). The gold crystal is embedded in amorphous carbon with no clear lattice pattern [29]. . . . . . . . . . . 35 37 39 40 41 43 43 43 45 45 46 46 47 47 47 48 48 48 49 49 49 50 50

3.7 3.8 3.9

A Perkin-Elmer TGA7 . . . . . . . . . . . . . . . . . . . . . . . . . . Dispersion analysis for 0.1 wt% of CNT . . . . . . . . . . . . . . . . . Schematic of a four ball wear test machine . . . . . . . . . . . . . . .

3.10 Four Ball Wear Tester . . . . . . . . . . . . . . . . . . . . . . . . . . 3.11 Photograph of a wear scar . . . . . . . . . . . . . . . . . . . . . . . . 3.12 Three ball Assembly . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.13 Four ball wear tester software . . . . . . . . . . . . . . . . . . . . . . 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 Transmission Electron Microscopy image of MWNT . . . . . . . . . . Transmission Electron Microscopy image of SWNT . . . . . . . . . . Thermogravimetric analysis of MWNT . . . . . . . . . . . . . . . . . Variation of COF of base oil with TIME at 100N and 40o C . . . . . . Variation of COF of base oil with TIME at 200N and 40o C . . . . . . Variation of COF of base oil with TIME at 300N and 40o C . . . . . . Variation of COF of base oil with TIME at 400N and 40o C . . . . . . Variation of COF of base oil with TIME at 500N and 40o C . . . . . . Variation of COF of base oil with TIME at 100N and 70o C . . . . . .

4.10 Variation of COF of base oil with TIME at 200N and 70o C . . . . . . 4.11 Variation of COF of base oil with TIME at 300N and 70o C . . . . . . 4.12 Variation of COF of base oil with TIME at 400N and 70o C . . . . . . 4.13 Variation of COF of base oil with TIME at 500N and 70o C . . . . . . 4.14 Variation of COF of base oil with TIME at 100N and 100o C . . . . . 4.15 Variation of COF of base oil with TIME at 200N and 100o C . . . . .

67

4.16 Variation of COF of base oil with TIME at 300N and 100o C . . . . . 4.17 Variation of COF of base oil with TIME at 400N and 100o C . . . . . 4.18 Variation of COF of base oil with TIME at 500N and 100o C . . . . . 4.19 Comparison of COF of base oil and 0.25wt% additive oil with TIME at 100N and 40o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.20 Comparison of COF of base oil and 0.25wt% additive oil with TIME at 200N and 40o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.21 Comparison of COF of base oil and 0.25wt% additive oil with TIME at 300N and 40o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.22 Comparison of COF of base oil and 0.25wt% additive oil with TIME at 400N and 40o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.23 Comparison of COF of base oil and 0.25wt% additive oil with TIME at 500N and 40o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.24 Comparison of COF of base oil and 0.25wt% additive oil with TIME at 100N and 70o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.25 Comparison of COF of base oil and 0.25wt% additive oil with TIME at 200N and 70o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.26 Comparison of COF of base oil and 0.25wt% additive oil with TIME at 300N and 70o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.27 Comparison of COF of base oil and 0.25wt% additive oil with TIME at 400N and 70o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.28 Comparison of COF of base oil and 0.25wt% additive oil with TIME at 500N and 70o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.29 Comparison of COF of base oil and 0.25wt% additive oil with TIME at 100N and 100o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.30 Comparison of COF of base oil and 0.25wt% additive oil with TIME at 200N and 100o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.31 Comparison of COF of base oil and 0.25wt% additive oil with TIME at 300N and 100o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.32 Comparison of COF of base oil and 0.25wt% additive oil with TIME at 400N and 100o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68

50 51 51

51

52

52

52

53

53

53

54

54

54

55

55

55

56

4.33 Comparison of COF of base oil and 0.25wt% additive oil with TIME at 500N and 100o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.34 Comparison of COF of base oil and 0.1wt% additive oil with TIME at 500N and 40o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.35 Comparison of COF of base oil and 0.50wt% additive oil with TIME at 500N and 40o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.36 Comparison of COF of base oil and 0.50wt% additive oil with TIME at 500N and 40o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.37 Comparison of COF of base oil and 0.25wt% additive oil with TIME at 400N and 40o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.38 Comparison of COF of base oil and 0.50wt% additive oil with TIME at 500N and 40o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.39 Comparison of COF of base oil and 0.05wt% additive oil with TIME at 500N and 40o C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.40 Comparison of COF of base oil and 1wt% SWNT additive oil with TIME at 500N and 40o C . . . . . . . . . . . . . . . . . . . . . . . . . 59 58 58 58 57 57 56 56

4.41 Variation of Wear Scar Diameter with dierent weight fraction of additive 60 4.42 Variation of Wear Scar Diameter with dierent loads at 40o C . . . . . 4.43 Variation of Wear Scar Diameter with dierent loads at 70o C . . . . . 4.44 Variation of Wear Scar Diameter with dierent loads at 100o C . . . . 4.45 Separation of MWNT from the base oil seen in some samples at higher loads and higher temperatures . . . . . . . . . . . . . . . . . . . . . . 62 60 61 61

69

List of Tables
1.1 1.2 SAE Automotive oil specication . . . . . . . . . . . . . . . . . . . . Commonly used equations to determine viscosity-temperature relationship . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1.3 Dynamic viscosity and pressure-viscosity coecients of some commonly used lubricants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1 Parameters for testing of base oil and 0.25 wt% MWNT nanouid . . 13 41 10 6

70

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