1.

INTRODUCTION
A metal matrix composite (MMC) is a type of composite material with at least two constituent parts, one being a metal. The other material may be a different metal or another material, such as a ceramic or organic compound [1].

Copper is widely used because of a high thermal conductivity, ease of fabrication and a good erosion-resistance. On the other hand, copper has low hardness and yield strength. Therefore, particles like oxides, carbides and borides are dispersed to improve mechanical properties such as strength and hardness [2, 6]. Those dispersing particles must have high strength, high melting point and low solubility in the metal matrix. Especially TiB2 particles are excellent candidates for dispersoids of Cu alloys because of their high melting point, high hardness, low resistance and excellent thermal conductivity [4]. The combination of high electrical and hardness is particularly attractive for welding electrodes and sliding contact. Copper and copper-based alloys are widely used as electric and electrode materials due to their good conductivity. However, in the case of precipitation hardened copper alloys (such as Cu-Zr and Cu-Cr) with high strength, there is a problem that the mechanical property decreases rapidly due to the presence of a coarse precipitate phase at high temperature. This problem limits the application of copper alloy in electrical and resistance welding applications. There have been several efforts to develop copper alloys which exhibit good mechanical properties even at elevated temperatures. Copper-base metal matrix composites (MMC) with reinforcing ceramic particles such as oxides, borides and carbides were developed as electrode materials because the ceramic particles are stable at high temperatures. TiB2 was also found to be a potential candidate for reinforcement of the copper alloy because of its high melting point, hardness, thermal conductivity as well as electrical conductivity [2, 4-5]. Powder metallurgy is a method of consolidation of metal powder (non-metallic powder or metal powder mixture) into finished product. The advantages of powder metallurgy technology have made it the key to solve the problem of new materials, whose development plays an important role in todays world. It can be used to prepare materials having excellent electrical, magnetic, optical, mechanical properties and having very high
1

Melting point without segregation; can easily achieve a variety of types of complex, give full play to the characteristics of each group element, is a low-cost production of high performance metal matrix and ceramic composite materials; Can achieve near net shape forming and automated mass production, and thus, can effectively reduce the production of resources and energy consumption. Titanium carbide and TiB2 have high melting points, very high hardness and strength, and high chemical stability. These compounds also have large absolute values of heat of formation and are normally produced by high-temperature processes such as the selfpropagating high-temperature synthesis (SHS).

2. Literature Survey
One of the current problems facing Material Science is the production of bulk materials with fine nano-level microstructure. Methods of mechanical alloying and mechanical treatment are widespread and well known for making it possible producing a great variety of composite powders with nano-level grains or inclusions. But it is understood that when nanocomposite is in powder form it becomes very important to find an appropriate method of consolidation to obtain high-density material and not to sacrifice its fine microstructure [15]. Copper matrix composites are promising candidates for applications in electrical sliding contacts such as those in homopolar machine and railway overhead current collection system [13], where good wear resistant properties and high thermal and electrical conductivity are needed. Addition of non-metallic second phase particles such as oxides, carbides and borides can dramatically improve mechanical properties and wear resistance of metal matrix composites [16]. A COPPER-BASED composite formed by dispersion strengthening with TiB2 is a leading candidate for applications where an excellent combination of high thermal and electrical conductivity and high-temperature mechanical strength are required [3].Unlike the precipitation strengthens copper alloys like Cu-Zr and Cu-Cr, Cu-TiB2 maintains its strength upto very high temperatures because TiB2 particles have excellent thermal stability [2 ,15]. Titanium diboride is a hard high-melting ceramics with high stiffness and wear resistance. Thermal and electrical conductivities of titanium diboride are higher compared to other ceramics. The behaviour of TiB2 particles during of heat treatment of mechanically alloyed TiB2-Cu mixtures has been studied in a number of works [3, 4-15]. Due to the TiB2 nanoparticles, tensile strength and hardness of the Cu-TiB2 composite improved. But the electric conductivity of the nanocomposites decreases with increasing the TiB2 content [4]. Various methods have been employed to manufacture Copper Titanium diboride composites namely SHS, SPS, Coated filler method etc. each having its own advantages. Powder metallurgical fabrication of a metal-matrix composite conventionally involves mixing the discontinuous reinforcement and matrix metal powder and subsequent sintering. This conventional method of powder metallurgy is called the admixture method. A less conventional method of powder metallurgy is the coated filler method, which involves coating the discontinuous reinforcement with the matrix particle and then sintering. The
3

coated filler method is more effective than the admixture method when reinforcement volume fraction is high [3, 14]. Cu-TiB2 nanocomposites may be fabricated through combination of mechanical alloy, SHS and SPS [4, 15]. Recently, an in situ technique has been developed to fabricate ceramic particle-reinforced metal matrix composites an improved reinforcementmatrix interface bond could be achieved because the reinforcement surfaces generated in situ tend to remain free of contamination, such as gas absorption, oxidation and other detrimental surface reactions [16]. Often mechanical alloying has been combined with other techniques to create dispersion-strengthened copper alloys [17]. Cu-TiB2 composites with high volume content of titanium diboride introduce a potential for a new kind of composite structures with both matrix and reinforcement forming 3D interpenetrating networks [8]. Particle connectivity and spatial distribution of networks define the properties of these composites [15]. The strengthening effect has been analyzed by various hardening models such as shear-lag model [7], Orowan-looping mechanism [8,9], and the empirical Hall petch relationship [10]. Nardone and Prewo suggested a modified shearlag model [11] which considered the load transfer by normal stress at the reinforcement ends. The entire strengthening, effect was described to the load-bearing feature of the hard reinforcements. This model, however, is irrelevant in explaining the strengthening of the TiB2 particulate reinforced Cu composite since the continuum mechanics model does not take into account the obvious influence of size, distribution, and properties of the reinforcement. The Orowan mechanism is not suitable either for explaining the strengthening of the alloys containing coarse hard particles. Dislocation generation at the reinforcement and matrix interface, due to a local stress concentration, is expected instead of Orowan looping. This assumption is in agreement with the observation of the many dislocation tangles in the vicinity of the coarse particles reported previously [12]. In all the study so far parameters like sintering temperature ,sintering time and porosity and the size and shape of particles have been found to affect the properties of the composite drastically. Porosity is the dominant factor which affects almost all properties of the compact, though the critical porosity levels may be different for different compositions and samples prepared by different mechanisms. The sintering time and temperature are also important as they determine the extent of interaction between the matrix and reinforcement which will affect the harness and other mechanical properties.
4

3. Experimental Procedure
To fabricate Cu-TiB2 composite we have followed a procedure similar to that of the admixture method. First the TiB2 powder was prepared by Self propagating High Temperature synthesis followed by leaching and pure copper powder was taken and they were mechanically alloyed and pressed to obtain the pellets. The pellets were then sintered and were characterized. The details of the various processes have been discussed in detail below.

3.1 Self Propagating High Temperature Synthesis Of all the intermetallics of titanium and boron system, TiB2 is the most stable compound. It has properties such as high melting point (2970C), high hardness (1800 Knoop), wear resistance in acid environment and chemical inertness. These excellent properties of TiB2 make it desirable for many applications such as ballistic armor, reinforced magnesium matrix composites and cutting tools [22]. Recently, the process for synthesis of TiB2 have attracted much attention and the successful process to synthesized TiB2 were preferred such as the mechanical alloying of titanium (Ti) and boron (B) powders, carbothermal reduction of the titanium dioxide (TiO2) and Boric acid (H3BO3), solid-state reaction of the TiCl4, Mg and MgB2. The selfpropagating high-temperature synthesis method has been developed to produce ceramics, intermetallics, catalysts and magnetic materials at low cost. This method exploits selfsustaining solid-flame combustion which develops very high temperature inside materials over a short period. It therefore offers many advantages over traditional methods, such as a much lower energy lost, a lower environmental impact, a convenient many fracturing process and unique properties of the product. In the present study, TiB2 powders were synthesized by SHS method [22]. In the SHS process, once the combustion reaction is ignited, extremely high temperatures can be achieved within a very short time. The outstanding features of SHS such as the internal heat release and the high-burning velocity make it a highly productive and resource-saving manufacturing technique for various materials. New advanced materials such as, nano-composite powders, ceramic foams, ceramic containing number of activators for sintering, anisotropy ceramics and oxygen free single crystal are developed using SHS
5

techniques. Special attention is also paid to the development of macro-inhomogeneous structure, multilayer and functionally graded materials, etc. [20]. The SHS has several advantages that include less processing times, low processing temperatures, simple operation and generation of fine microstructures due to high cooling rates. In the SHS process, volatilization of impurities in the reactant powder takes place; this improves the purity of the product. The SHS technique has the capability to synthesize ultrafine microstructures; the particle size grows due to high adiabatic temperatures and enhanced mass transfer during combustion reaction propagation [20].

Experimental The raw materials used in this paper were TiO2, H3BO3 and Mg powders whose properties are listed in Table Reactant TiO2 H3BO3 Mg Purity (%) 99.5 99.5 99.8

TiO2, H3BO3 and Mg powder were weighted as stoichiometric ratio and mixed manually for long enough to ensure homogenisation of the mixture. The mixture was pyrolysed in a tubular (resistance heating) furnace with continuous flow of argon gas. After the combustion synthesis, the by-product MgO was leached out from the synthesized powder by boiling in dilute HCl. The residue is filtered using the filter paper and allowed to dry in the oven for 2 hour at 80C Here after, the final powder prepared. In the combustion synthesis technique, the self-sustainability of the exothermic reaction and the propagation wave front mostly depends upon the enthalpy change associated with the reaction. Since there is very little time for the heat dissipation to the surrounding, it can be assumed that a thermally isolated exothermic system exists. Therefore, the maximum

temperature that can be attained during the combustion is assumed to be the adiabatic temperature. The overall chemical reactions can be expressed as: TiO2(s) + H3BO3(s) +5Mg(s) = TiB2(s) + 5MgO(s) + 3H2O (g)
(1)

Using the thermodynamic data from a recent compilation, the heat of formation was calculated to be 220 kcal/mol [20] and the adiabatic temperature was found to be 2831.8C [22]. During the process of SHS, TiO2, H3BO3, and Mg may be interacted to form some possible compounds as following intermediate chemical reactions below: 4Mg(s) + 2TiO2(s) = 2Ti(s) + 4MgO(s) 2H3BO3 = B2O3(s) + 3H2O (g) 3Mg(s) + B2O3(s) = 2B(s) + 3MgO(s) Ti(s) + 2B(s) = TiB2(s) Equilibrium composition of TiO2- H3BO3-Mg system in Ar gas atmosphere
(2) (3) (4) (5)

Fig 3 It can be seen from Figure 3 that it is thermodynamically feasible to synthesis composites by heat up the system of reaction. As accepted that the reaction can be self-sustained combustion when adiabatic temperature of the reaction higher than 1800C [22].
7

3.2 Mechanical alloying and Compaction After preparing the TiB2 powder the next step is making the pellets. In order to make the pellets pure copper (99.99%) and the TiB2 powder were weighed and were taken in a ceramic bowl where they were grinded and mixed long enough to ensure that the TiB2 has been evenly distributed. This is very important as this is not done properly it may lead to nonuniform distribution of the reinforcement in the matrix and hence will not improve the mechanical properties. Once the alloying is completed the mixture was the compacted into cylindrical pellets, using a 10 mm die set and a pelletizer, by applying load of 2 ton for 30 sec. It should be noted that the die surface should be clean and smooth else the pellet surface will be rough and also Zinc Stearate was also applied for lubrication. About 4 set of pellets, each set having 5 compositions of 0%, 5%, 10%, 20% and 30% TiB2 respectively, were prepared. Table 3.1.1 The table shows the amount of TiB2 added to produce different samples.
Composite Copper (%weight) Sample I Sample II Sample III Sample IV Sample V 100 95 90 80 70 TiB2 (%weight) 0 5 10 20 30 TiB2 (weight in gm) 0 0.15 0.30 0.60 0.90

3.3 Sintering After the pellets were prepared the next step was sintering. Stability and growth of nanoparticulate reinforcements in metal matrix composites during heating are widely studied, which contain several volume percent of reinforcing phase. When high volume content of nanoparticles distributed within a matrix is concerned results of particles aggregation and growth as well as crystallization mechanisms are evident [13]. In this experiment we have used pressureless sintering to sinter the pellets. A set of pellets was taken in a alumina boat
8

and kept inside a tube furnace, an inert atmosphere was also maintained to prevent the sample from being oxidized. The heat cycle consisted of the various sintering temperatures with a heating rate of 12.5oC/min and a soaking time of 30 min was also given so as to allow the sample to homogenize and then cooled in the furnace itself. The sintering was carried out at temperatures of 700oC, 750oC, 800oC, 900oC each for a set of pellets and the pellets were carefully stored after cooling. The soaking or holding time for the 750oC set was 1 hour. 3.4 Analysis of Microstructure Microstructure of as obtained composites were studied in an optical microscope and the corresponding images were obtained using an image analyzer. To study the sample they were etched using FeCl3-H2O-ethyl alcohol and dried and then viewed under microscope. All the sample were viewed at 100x in order to study the connectivity of the TiB2 skeleton and the changes that occur during the sintering in the skeleton because the connectivity affects the final properties of the sample. Microstructure of sample sintered at various sintering temperatures 1. Microstructure of sample sintered at 700oC

Fig 3.1 Microstructure of 5% TiB2 composite (100x)

Fig 3.2 Microstructure of 10% TiB2 composite (100x)

Fig 3.3 Microstructure of 20% TiB2 composite (100x)

Fig 3.4 Microstructure of 30% TiB2 composite (100x)

2. Microstructure of sample sintered at 750oC

Fig 3.5 Microstructure of 5% TiB2 composite (100x)

Fig 3.6 Microstructure of 10% TiB2 composite (100x).

Fig 3.7 Microstructure of 20% TiB2 composite. (100x)

Fig 3.8 Microstructure of 30% TiB2 composite (100x).

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3. Microstructure of sample sintered at 800oC

Fig 3.9 Microstructure of 5% TiB2 composite (100x).

Fig 3.10 Microstructure of 10% TiB2 composite (100x).

Fig 3.11 Microstructure of 20% TiB2 composite (100x)

Fig 3.12 Microstructure of 30% TiB2 composite (100x)

4. Microstructure of sample sintered at 900oC

11

Fig 3.13 Microstructure of 5% TiB2 composite (100x).

Fig 3.14 Microstructure of 10% TiB2 composite (100x)

Fig 3.15 Microstructure of 20% TiB2 composite (100x).

Fig 3.16 Microstructure of 30% TiB2 composite (100x).

5. Microstructure of non-sintered Sample

Fig 3.17 Microstructure of 5% TiB2 composite (100x).

Fig 3.18 Microstructure of 10% TiB2 composite (100x).

12

Fig 3.19 Microstructure of 20% TiB2 composite (100x).

4. Results and observations

Various tests were carried out to characterize the composite and to evaluate the effect of sintering on the properties of the compact. 4.1 Porosity: Since the powder is consolidated to form a specimen by compaction and sintering, it is expected to have a good amount of pores in it. The specimen is not subjected to any further thermo mechanical treatment and hence found to have large amount of porosity. The micro structural images obtained from image analyzer were observed for pore distribution on the surface of specimen. Size of the pores was not consistent throughout the surface. Pore distribution on the surface was quiet uniform. As the amount of TiB2 in the specimens increased, the porosity also increased. It can also be noted that the porosity has been found to decrease as the sintering temperature increases. Similarly the porosity increases with the amount of TiB2. The porosity can be calculated by considering the following equations: Consider a composite of mass Mc and volume Vc. The total mass of the composite is the sum total of the masses of reinforcement and matrix, that is,
(6)

The volume of the composite, however, must include the volume of voids Vv. Thus,
(7)

Dividing the equation 1 by Mc and equation 2 by Vc and denoting the mass and volume fractions by MR, MM and VF, VM, VV, respectively, we can write MR + MM =1 VF +VM +VV = 1
13 (8) (9)

The composite density Dc

is given by
(10)

Dc = DrVR + DmVM

(11)

Representing the Previous equations in terms of mass fractions we get

Hence using this formula we can calculate the volume fraction of voids and find the porosity.

Table 1 Porosity for different pellets obtained after sintering to 700oC S No Percentage Composition 0 5 10 20 30 Theoretical Density(g/cm3) 8.96 8.54 8.15 7.49 6.92 Observed Density (g/cm3) 6.11 6.12 5.71 4.60 4.34 Porosity

1 2 3 4 5

0.31 0.28 0.29 0.38 0.39

Table 2 Porosity for different pellets obtained after sintering to 750oC S No Percentage Composition Theoretical Density(g/cm3) Observed Density (g/cm3) Porosity

14

1 2 3 4 5

0 5 10 20 30

8.96 8.54 8.15 7.49 6.92

6.37 6.50 6.04 4.9 4.37

0.29 0.24 0.25 0.33 0.37

Table 3 Porosity for different pellets obtained after sintering to 800oC S No Percentage Composition 0 5 10 20 30 Theoretical Density(g/cm3) 8.96 8.54 8.15 7.49 6.92 Observed Density (g/cm3)
6.20 6.31 5.63 4.67 4.43

Porosity

1 2 3 4 5

0.30 0.25 0.26 0.373 0.38

Table 4 Porosity for different pellets obtained after sintering to 900oC S No Percentage Composition 0 Theoretical Density(g/cm3) 8.96 Observed Density (g/cm3)
6.00

Porosity

0.33

15

2 3 4 5

5 10 20 30

8.54 8.15 7.49 6.92

6.42 5.74 4.90 4.44

0.24 0.25 0.34 0.36

Porosity 750 degrees 0.45 0.4 0.35 0.3

Porosity 800 degrees

Porosity

0.25 0.2 0.15 0.1 0.05 0 0% 5% 10% 15% 20% 25% 30% 35%

Percentage of TiB2 Graph 1 The graph shows the variation of porosity with percentage of TiB2 at different sintering temperatures

This graph depicts the effect of holding time on the porosity. The sample which was sintered to 750 oC had a holding time of 1 hour while that of 800 oC had a holding time of 30 min. So it can be concluded that as the holding time at mximum temperature increases the porosity decreases. This may be because more time is available for homogenization and hence the entrapped air leaves the composite thereby creating pores at the surface as was seen in the microstucture. The other point woth noting is that even though the second sample was help at a higher temperature the porosity was not reduced by much extent, this shows the importance of holding time. Moreover indirectly affects the mechanical properties too as they depend on the extent of porosity.Hence optimum holding time is very important.

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Porosity 700 degrees 0.45 0.4 0.35 0.3

Porosity 800 degrees

Porosity 900 degrees

Porosity

0.25 0.2 0.15 0.1 0.05 0 0% 5% 10% 15% 20% 25% 30% 35%

Percentage of TiB2 Graph 2 The graph shows the variation of porosity with percentage of TiB2 at different sintering temperatures

This graph depicts the importance of sintering temperature on porosity. It can be clearly concluded from the graph that as the temperature of sintering is increased the porosity decrease. It is because at higher temperature it becomes easier for the entrapped gases to come out resulting in lesser porosity of the composite.

4.2 Density: The dimensions of specimens of different compositions were measured with the help of vernier callipers. After calculating the average values of diameter and length of the specimen, volume of specimen is found. The Specimen being cylinder, following formula is used
(13)

After finding out the volume, weight of each sample is measured using a micro balance. Density of the specimen is calculated using the obtained values of weight and volume.
(14)

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All the values are noted in different tables. Each table has density values of specimens with a common sintering temperature. The density values obtained are as follows.

Table 1: density values of 0%, 5%, 10%, 20%, and 30% by weight Cu-TiB2

S. No.

Type of sample % TiB2 Added

Diameter Length

Weight

Volume mm3

Density g/cm3

mm

mm

1 2 3 4 5

0% 5% 10% 20% 30%

14.98 9.99 9.99 10.02 10.18

7.23 4.46 6.68 7.37 8.9

8 2.24 3.05 2.94 2.98

1273.59 349.41 523.33 580.86 724.02

6.00 6.05 5.52 4.56 4.11

Table 2: density values of 0%, 5%, 10%, 20%, and 30% by weight Cu-TiB2 composites at 700C sintering temperature.

S. No

Type of sample % TiB2 Added

Diameter Length Weight

Volume mm3

Density g/cm3

mm

mm

1 2 3 4 5

0% 5% 10% 20% 30%

14.97 10.1 10.08 10.16 10.04

7.37 6.01 6.76 8.39 8.66

7.926 2.95 3.08 3.13 2.98

1296.52 481.26 539.18 679.85 685.25

6.11 6.12 5.71 4.60 4.34

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Table 3: density values of 0%, 5%, 10%, 20%, and 30% by weight Cu-TiB2 composites at 750C sintering temperature.

S. No

Type of sample % TiB2 Added

Diameter Length Weight

Volume mm3

Density g/cm3

mm

mm

1 2 3 4 5

0% 5% 10% 20% 30%

14.98 9.95 10.01 10.1 10

7.06 5.89 6.62 7.52 8.76

7.926 2.978 3.15 3.01 3.01

1243.64 457.75 520.70 602.18 687.66

6.37 6.50 6.04 4.99 4.47

Table 4: density values of 0%, 5%, 10%, 20% and 30% by weight Cu-TiB2 composites at 800C sintering temperature.

S. No

Type of sample % TiB2 Added

Diameter Length

Weight

Volume mm3

Density g/cm3

mm

mm

1 2 3 4 5

0% 5% 10% 20% 30%

14.95 10.1 10.08 10.3 10.03

7.3 5.75 6.85 7.97 8.65

7.95 2.91 3.08 3.1 3.03

1280.78 460.44 546.36 663.74 683.10

6.20 6.31 5.73 4.67 4.40

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Table 5: density values of 0%, 5%, 10%, 20% and 30% by weight Cu-TiB2 composites at 900C sintering temperature.

S. No

Type of sample % TiB2 Added

Diameter

Length

Weight

Volume mm3

Density g/cm3

Mm

mm

1 2 3 4 5

0% 5% 10% 20% 30%

15.09 10.03 10.1 10.16 9.98

7.51 5.83 6.98 7.72 8.97

8.0557 2.96 3.21 3.07 3.05

1342.41 460.40 558.94 625.56 701.33

6.28 6.42 5.84 4.90 4.44

Graphs were plotted between the sintering temperature and the density of Specimen of a given composition.
6.4 6.35 6.3 6.28 6.37

Density [g/cm3]

6.25 6.2 6.2 6.15 6.1 6.05 6 6 5.95 0 100 200 300 400 500 600
oC

6.11

700

800

900

1000

Temperature [

Fig 1: Graph plotted between sintering temperature and density for 0% TiB2 sample

20

6.55 6.5 6.45 6.4

6.5 6.42

Density [g/cm3]

6.35 6.3 6.25 6.2 6.15 6.1 6.05 6 0 100 200 300 400 500 600
oC

6.31

6.12 6.05

700

800

900

1000

Temperature [

Fig 2: Graph plotted between sintering temperature and density for 5% TiB2 sample

6.1 6 5.9

6.04

Density [g/cm3]

5.84

5.8 5.71 5.7 5.6 5.52 5.5 5.4 0 100 200 300 400 500 600
oC

5.73

700

800

900

1000

Temperature [

Fig 3: Graph plotted between sintering temperature and density for 10% TiB2 sample

21

5.05 5 4.95 4.9 4.99

4.9

Density [g/cm3]

4.85 4.8 4.75 4.7 4.65 4.6 4.56 4.55 4.5 0 100 200 300 400 500 600
oC

4.67 4.6

700

800

900

1000

Temperature [

Fig 4: Graph plotted between sintering temperature and density for 20% TiB2 sample.

4.5 4.45

4.47 4.44 4.4

4.4

Density [g/cm3]

4.35 4.3 4.25 4.2 4.15 4.1 4.05 0 100 200 300 400 500 600
oC

4.34

4.11

700

800

900

1000

Temperature [

Fig 5: Graph plotted between sintering temperature and density for 30% TiB2 sample. Density of the specimens is found to decrease with an increase in percentage of TiB2. This is because TiB2 has very less density when compared to that of copper. Sintering

22

temperature variation was not found to have an orderly effect on the density. For four samples out of five, leaving out 30% TiB2 sample, are found to have maximum density at 750C sintering temperature (because of greater holding time). Whereas 30% TiB2 sample has its maximum density value at 800C. 4.3 Microhardness: The five Cu-TiB2 specimens with compositions ranging from 0% to 30% TiB2 by weight, sintered at different temperatures, have been checked for their micro hardness. The specimens were first viewed through the eye piece to select an area of interest to carry out indentation. Load 300 gms have been used for different specimen. A Vickers harness test indenter is used. Once a dent is made in the specimen, the indenter is flipped around to bring lens on to area of indentation of specimen. Specimen is viewed for indentation and the lines in eye piece are adjusted to coincide with the horizontal diagonal ends and then button provided on the viewing equipment is clicked to allow the equipment feed in the value of diagonal length. The eye piece is turned by 90 and the same procedure is repeated in vertical direction. After repeating this on both the sides, length is read by equipment and a micro hardness value is given. This test has been carried out at four different areas of specimen at different radial distances to ensure an accurate average micro hardness value. Once the values are obtained average hardness values at different sintering temperatures are calculated for specimen of different compositions.

Table 6: Microhardness values 0% TiB2 sample at different sintering temperatures.

Micro hardness values S.No Temperature 1 Green sample 700C 750C 800C 900C Hv 1 Hv 2 Hv 3 Hv 4 Hvavg

18.6 21.6 23.9 28.7 35.4

18.4 21.9 24.3 29.1 35.7

18.7 22 24.2 28.9 35.9

18.8 22.1 24 29.3 36

18.625 21.9 24.1 29 35.75

2 3 4 5

23

Table 7: Microhardness values 5% TiB2 sample at different sintering temperatures.

Micro hardness values S.No Temperature Hv 1 Hv 2 Hv 3 Hv 4 Hvavg 1 2 3 4 5 Green sample 700C 750C 800C 900C 20 24.6 32 41.6 56 20.4 24.2 31.3 41.7 55.6 20.6 24.3 31.4 42 55.2 20.2 24.3 31.6 41.9 55.9 20.3 24.35 31.575 41.8 55.675

Table 8: Microhardness values 10% TiB2 sample at different sintering temperatures.

Micro hardness values S.No Temperature 1 2 3 4 5 Green sample 700C 750C 800C 900C Hv 1 21.4 25.6 36.8 43 61.9 Hv 2 21.7 25.1 37.1 43.5 62.3 Hv 3 21.9 25.5 37.3 43.1 62.4 Hv 4 21.6 25.3 36.9 43.4 62.7 Hvavg 21.65 25.375 37.025 43.25 62.325

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Table 9: Microhardness values 20% TiB2 sample at different sintering temperatures.

Micro hardness values S.No Temperature 1 2 3 4 5 Green sample 700C 750C 800C 900C Hv 1 23.4 26.8 42.6 46.3 66.2 Hv 2 23.2 26.9 42.1 46.5 66.4 Hv 3 23.1 26.7 42.5 46.3 66.1 Hv 4 23 26.8 42.7 46.7 66.5 Hvavg 23.175 26.8 42.475 46.45 66.3

Table 10: Microhardness values 30% TiB2 sample at different sintering temperatures.

Micro hardness values S.No Temperature Hv 1 1 2 3 4 5 Green sample 24.5 700C 36.4 750C 48.3 800C 52.7 900C 76.4 76.1 76.5 76.3 76.325 52.9 52.7 52.8 52.775 48.1 48.4 48.6 48.35 36.3 36.1 36.2 36.25 24.6 24.4 24.9 24.6 Hv 2 Hv 3 Hv 4 Hvavg

25

Graphs were plotted between the Hardness values obtained and the sintering temperatures for different specimen compositions.

40 35 30 29 24.1 21.9

35.75

Hardness (Hv)

25 18.625 20 15 10 5 0 0 100 200 300 400 500 600

700

800

900

1000

Temperature (C)
Fig 6: Graph plotted between hardness value and sintering temperature for 0% TiB2 composite

60

55.675

50 41.8

Hardness (Hv)

40 31.575 30 20.3 20 24.35

10

0 0 100 200 300 400 500 600 700 800 900 1000

Temperature (C)
Fig 7: Graph plotted between hardness value and sintering temperature for 5% TiB2 composite

26

70 62.325 60 50

Hardness (Hv)

43.25 37.025

40 30 21.65 20 10 0 0 100 200 300 400 500 600

25.375

700

800

900

1000

Temperature (C)
Fig 8: Graph plotted between hardness value and sintering temperature for 10% TiB2 composite.

70 60 50 46.45 42.475

66.3

Hardness (Hv)

40 30 23.175 20 10 0 0 100 200 300 400 500 600 700 800 900 1000 26.8

Temperature (C)
Fig 9: Graph plotted between hardness value and sintering temperature for 20% TiB2 composite.

27

90 80 70 60 50 40 30 24.6 20 10 0 0 100 200 300 400 500 600 700 800 900 1000 76.325

Hardness (Hv)

52.775 48.35

36.25

Temperature (C)
Fig 10: Graph plotted between hardness value and sintering temperature for 30% TiB2 composite.

From the above collected data it can be concluded that the hardness is directly proportional to the sintering temperature. At higher temperatures various interactions occur between the matrix and the reinforcing material resulting in the formation of various intermediate phases which are formed near the interface and also the reduction in porosity occurs as a result of which the composite becomes more and more harder.

4.4 Electrical Resistivity

To calculate the electrical resistivity two terminals were connected to either side of the sample and then the resistance offered was measured. Then the electrical resistivity was found by using the formula:
(15)

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Once the resistance was found the resistivity values were calculated and the graph was plotted for the sample sintered at 900oC.

3.5

3.2 2.86 2.388 2.5

Electrical Resistivity (x 108 ohm/m)

3 2.5 2 1.79 1.5 1 0.5 0 0 5 10 15

20

25

30

35

Percentage of TiB2
Fig 10: Graph plotted between Electrical Resistivity and different composite.

The above graph shows the variation of electrical resistivity(x 108 /m) with percentage composition .This is due to the formation of the nanocomposites. These nanocomposites increase the scattering surfaces for the conduction electrons in the copper matrix. So the electrical conductivity of the copper matrix composite was reduced. When the content of TiB2 particles is more, the electric conductivity decreases sharply [4]. Moreover the porosity also increases within increase in amount of reinforcement and this also reduces the conductivity. Further studies have also shown that after reaching a critical porosity level the resistivity increases sharply [14]. 4.5 Microstructure and SEM The pellets were observed under microscope and also under SEM the images obtained by the image analyzer have already been produced. The temperature of sintering is rather low and equal to 0.7 times melting point of copper and 0.3 titanium diboride melting point. At this temperature diffusion processes in copper matrix are accelerated. It appears that titanium diboride nanoparticles move in solid copper matrix. We assume this moving as an anomalous

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mass transfer in non-uniform field of stresses. Non-uniform field of stresses in the composite powders is due to high-energy mechanical treatment used in the synthesis processing. Annealing of vacancies in metal matrix may lead to situations when a plane of matrix at one side of particulate inclusion disappears and appears at the other side [18]. These processes result in moving of the inclusion as a whole. Crystallization by formation of aggregates from nanoparticles is known for systems with liquid as a matrix [19]. It is proposed that so called heterogeneous events in crystallization are favoured at high concentrations of solids and low solubility in the matrix. Drawing the analogy to our system, these conditions are satisfied in our case by very low solubility of titanium diboride in copper and by high content of nanoparticles in copper matrix. Association of nanoparticles in aggregates becomes clear when high diffusion activity in dispersed systems and increased sinterability of nanoparticles are taken into account [18]. The Img.1shows an interface between the TiB2 and copper matrix and the other images show the distribution of TiB2 in the matrix after sintering one can also see some micro crack appearing which may be due to mechanical loads during the storage period.

Fig 11 SEM image of Cu-30%TiB2 showing the presence of minute cracks and the surface porosity

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5. Conclusions

Fig 12 SEM Fig 13 image SEM of image Cu-20% of Cu-20% TiB2 sintered TiB2 sintered at 900oC at 900oC showingshowing an interface distribution betweenof Cu TiB matrix and inthe CuTiB matrix and the. 2 phase 2 phase. Porosity and the TiB can be observed. TiB2 network can be observed. 2 network

The following conclusions can be drawn from the present study: 1. Pressureless Sintering leads to densification of samples but the extent of porosity is high. 2. The porosity increases with increase in the amount of TiB2 and decreases with the increase in sintering temperature. Porosity also decreases with increase in holding time at maximum temperature. 3. The TiB2 phase is well distributed in the matrix resulting in formation of a TiB2 network with small amount of agglomeration at places. The TiB2 phase may be considered to be moving as a whole in the bulk matrix during sintering and diffuse through appearing on the other side of pellet, as is evident from the samples at 700oC and 800oC (5% TiB2 ).
Fig 14 SEM image of Cu-20% TiB2 sintered at 700oC showing distribution of TiB2 phase in Cu matrix and the high level of porosity can be seen. Fig 15 SEM image of Cu-30% TiB2 sintered at 900oC showing distribution of TiB2 phase in Cu matrix and the agglomeration can be seen in the image.

4. The presence of finely dispersed TiB2 particles is the main reason for the high micro hardness values of the Cu-TiB2 composite. The hardness has been found to increase as the amount of reinforcement and sintering temperature increase. But overall the sample have
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high porosity hence the hardness can be further increased is pellets with lesser porosity can be prepared by SPS. 5. The Electrical Resistivity was found to be good which was the main requirement but even the resistivity can be decreased further owing to the fact that the sample had porosity. The electrical resistivity was found to increase with increase in the composition of TiB2 as the porosity level increases.

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6. Reference
1. A.K. Khanra,L.C. Pathak, S.K. Mishra, M.M. Godkhindi Materials Letters 58 (2004) 733 738. 2. Mechanical, electrical and wear properties of Cu-TiB2 nanocomposites fabricated by MA-SHS and SPS Dae-Hwan Kwon, Thuy Dang Nguyen, Khoa Xuan Huynh, Pyuck-Pa Choi, Myung-Gyu Chang, Young-Jin Yuma, Ji-Soon Kim* and Young-Soon Kwon. Journal of Ceramic Processing Research. Vol. 7, No. 3, pp. 275~279 (2006) 3. Formation of a TiB2-Reinforced Copper-Based Composite by Mechanical Alloying and Hot Pressing S.J. DONG, Y. ZHOU, Y.W. SHI, and B.H. CHANG. 4. Mechanical Properties of Cu-TiB2Nanocomposite by MA/SPS Young-Jin Yum, Kyung-Sik Lee, Ji-Soon Kim et al 5. Investigation of In situ Cu-TiB2 Composite on the Copper Using Laser Melting Synthesis L.Y. Gu, G.Y. Liang, and Z.B. Zheng. 6. Strengthening Mechanism of a Spray-Formed Cu-TiB2 Composite Jongsang Lee*, J. Y. Jung, Eon-Sik Lee, Nack J. Kim* and S. Ahn 7. Load Bearing Fibre Composites, M. R. Piggott, p. 62,Pergamon Press (1980). 8. Symposium on Internal Stresses in Metals and Alloys, E. Orowan, in p. 451, Institute of Metals, London, England (lq48). 9. Micromechanisms in Particle Hardened Alloys, J. W. Martin, p. 62, Cambridge University Press, Cambridge, England (1980). 10. R. M. Aikin, Jr. and L. Christodoulou, Scripta metall.mater. 25, 9 (1991). 11. V. C. Nardone and K. M. Prewo, Scripta metall. 20, 43 (1986). 12. Strengthening Methods in Crystals M. F. Ashby (eds.,A. Kelly and R. B. Nicholson), p. 137, Applied Science Pub., London, England (1971). 13. Microstructure changes in TiB2-Cu nanocomposite under sintering D. V. DUDINA, M. A. KORCHAGIN, O. I. LOMOVSKY JOURNAL OF MATERIALS SCIENCE 39 (2004) 5325 5331 14. A comparative study of the coated filler method and the admixture method of powder metallurgy for making metal-matrix composites Pay Yih, D. D. L. Chung Journal of Materials Science 32 (1997) 2873-2882

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15. Microstucture of Spark-Plasma Sintered TiB2-Cu Nanocomposites D.V. Dudina, MA Korchagin, 0.1. Lomovsky, Y.-S. Kwon" Institute of Solid State Chemistry and Mechanochemistry, SB RAS Kutateladze 18, Novosibirsk, 630128, Russia 16. Dry sliding wear behavior of in situ CuTiB2 nanocomposites against medium carbon steel J.P. Tu a, , W. Ronga, S.Y. Guob, Y.Z. Yang aWear 255 (2003) 832 835 17. Heat-Resistant Dispersion-Strengthened Copper Alloys Joanna Groza JMEPEG91992- 1:113-121 ASM International. 18. Dispersion Strengthened Mater K. I . PORTNOY and B. N. BABICH (Metallurgiya,
Moscow, 1974, in Russian)p. 53

19. C. SURYANARAYANA and C. C. KOCH, Hyperf. Interact 130 (2000) 5. 20. Effect of NaCl on the Synthesis of TiB2 powder by self-propagation hightemperature synthesis technique, A.K. Khanra, Mishra, L.C.P., and Godkhindi, M.M. Mater. Lett., 58, 2004, pp. 733-738. 21. Fabrication of TiB2 and TiB2-TiC particulates reinforced magnesium matrix composites Wang, H.Y., Jiang, Q.C., Zhao, Y.Q., Ma, B.X. and Wang, Y. Mater. Sci. Eng. A, 372, 2004, pp. 109-114. 22. Synthesis of Titanium Diboride Powder by Self-propagating High Temperature Synthesis N. Chaichana, N. Memongkol , J. Wannasin, S. Niyomwas.

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