Microstructure and Mechanical properties of Spark Plasma sintered

Al2O3-SiC-CNTs hybrid Nanocomposites

-N. Saheb , K. Mohammed

Dept. of Mechanical Engineering

King Fahd University of Petroleum and Minerals

Dhahran, Saudi Arabia

Review By: SHAYAAN AHMED

17BME7030
VIT-AP University
Amaravati, Andhra Pradesh
______________________________________________________________________________

ABSTRACT:

The conventional Ceramic Composites possessed very low fracture toughness and hardness and
thus hybrid nanocomposites such as Al2O3-SiC-CNTs were used which drastically increased the
fracture toughness of the ceramic composites. Al2O3-10SiC-2CNTs possessed the highest
fracture toughness, an increase of 93.95% compared to alumina. Al2O3-SiC-CNTs hybrid
Nanocomposites used different manufacturing processes such as ball milling, sonication and
spark plasma sintering at 1500 oC for 10 min. Characterization of material at all stages was done
using Field Emission Scanning Electron Microscope (FE-SEM), Transmission Electron
Microscopy (TEM), and X-Ray mapping. Final Microstructure comprised intergranular CNTs
along with inter- and intragranular SiC nanoparticles.

The addition of SiC to alumina changed its fracture mode from intergranular to a mix of
intergranular and transgranular modes. But addition of Carbon nanotubes to this Nanocomposite
mix further changed the mode to complete transgranular fracture mode.
INTRODUCTION:

o Ceramics have high hardness, high thermal stability, good chemical resistance, and low
density but they are brittle and have poor fracture toughness. Alumina is one of the most
commonly used ceramic materials for the production of cutting tools, chemical and electrical
insulators and armories.
o The properties obtained had marginal improvement or degradation of properties were
attributed to the agglomeration of the reinforcements, growth of matrix grain size and
inhibition of densification.
o Many research has been carried out in this field to improve the properties of the ceramic
composites out of which alumina-silica carbide-CNTs gave the best results.

Figure: TEM images of Al2O3-5SiC-1CNT

METHOD USED:

o Ball Milling is one of the main methods used in the synthesis of Nanocomposite powders at
solid state. It is cost efficient and gives uniform distribution of reinforcement on the
nanometer scale.
o The dispersion of the reinforcement uniformly into an Alumina matrix is very important to
fabricate Alumina based Nanocomposites.
o Spark Plasma Sintering process allows for the sintering of the Nanocomposites to an almost
full density without breaking the very fine structure of the fibers.
o As a result the ceramic Nanocomposites have much better properties than those of either
monolithic ceramic.

Figure: FE-SEM images of (a) Al2O3, (b) Al2O3-5SiC and (c) Al2O3-10SiC

MATERIALS USED:

o Alpha-AL2O3 with average size of 150 nm, of 99.85% purity index

o SiC (beta) with average size of 45-55 nm, 97.5% purity index obtained from nanostructured
and Amorphous Material.
o Carbon Nanotubes obtained using Chemical Vapor Deposition Method. CNTs must be
functionalized to generate COOH- functional groups on the surface of the tubes.
 Figure: TEM images of (a) Al2O3, (b) SiC and (c) CNT

PRODUCTION:

o Synthesis of Nanocomposite Powders: Prepared in 2 stages:

1. 1st stage – Al2O3-5SiC and Al2O3-10Si powders are prepared through sonication and ball
milling. The alumina and SiC was added to distilled water and magnetically stirred for 5
mins. The slurry was then Ultrasonicated for 2 hrs. The sonicated slurry was put in 250
mL cylindrical alumina vials together with 10-mm dia alumina balls and the powders
were milled at room temp. at 300 rpm.
2. 2nd stage – The functionalized CNTs were added to the slurries and further sonicated for
2 hrs using a high energy probe sonicator to obtain Al2O3-5SiC-1CNT, Al2O3-5SiC-
2CNT, Al2O3-10SiC-1CNT and Al2O3-10SiC-2CNT Nanocomposite powder.
o Spark Plasma Sintering - The synthesized composite powder as well as reference alumina
powder is consolidated at 50 MPa and 1500 oC for 10 min using a SPS machine with the
heating rate being kept at 100 K/min. Friction was minimized using a sheet made of graphite
placed between the die walls and the powder.
 Figure: TEM images of spark plasma sintered Al2O3-5SiC-1CNT hybrid composite

EXPERIMENTATION:

o The relative density of composite is calculated as the ratio of the measured value to the
theoretical value. The theoretical density was calculated by the rule of mixtures using
theoretical densities as 3.97, 3.21 and 2 g/cm3 for alumina, SiC and CNTs respectively.
o The magnitude of the Vicker’s Hardness is determined according to: Hv =1.854 P/d2
Where P is the load applied and d is the diagonal length (in mm)
o The fracture toughness of the developed material is calculated from the crack length and
indent length. According to Antis’ equation: K1c = 0.016 (E/H)1/2 P/C3/2 where E is the
elastic modulus (GPa), H is the Vicker’s Hardness (GPa), P is the applied load (N) and C is
the diagonal crack length.
RESULTS:

POWDER SYNTHESIS

o The CNTs were treated for various reasons; remove the catalyst, open the tube caps and form
holes in the sidewalls. Finally the CNTs were oxidized so that it can generate the COOH-
functional group so that the electrostatic forces between the functionalized CNTs overcome
the weak Van-der-Waals forces to minimize the agglomeration of the CNTs.
o It is found that ball milling for 4 hrs would yield the best results for Al2O3-5SiC-2CNT and
Al2O3-10SiC-1CNT. Both of these composite compounds possess similar microstructural
features with a uniform distribution of SiC and CNTs within the Al2O3 matrix.

MICROSTRUCTURE

o High relative densities values show that fully dense monolithic Alumina and hybrid
composites can be obtained using Spark Plasma Sintering.
o In the process of SPS, a local high temperature state is momentarily generated because of
spark discharge that takes place at the contact point between the particles. This leads to
evaporation or melting on the surface of particles and formation of “necks”, which
significantly increases the diffusion rate.
o In addition to the highly localized temperature, applied pressure also contributes to the
rearrangement of particles and breakdown of agglomerates.
o The average grain size of the alumina matrix did not change significantly compared with the
average particle size of the starting powder.
o The uniform distribution of SiC particles and CNTs is obtained by ball milling followed by
the sonication process.
HARDNESS

o The monolithic Al2O3 had a Vicker’s Hardness value of 18.56 GPa.

o The addition of 5% SiC to Al2O3 increased its Hardness to 21.78 GPa. A further increase in
the SiC content to 10% slightly decreased the hardness to 20.89 GPa
o The hardness values of the Al2O3-SiC composites are higher than that of the monolithic
Al2O3.
o Further experimentation reported that the Hardness of Al2O3-SiC nanocomposites followed a
linear rule of mixtures as a function of SiC content.
o The improvement of hardness of Al2O3-SiC composite is attributed to the presence of the SiC
hard phase and the small grain size of the alumina matrix.
o The refinement of microstructure in the presence of SiC particles increases the hardness
because grain boundaries restrict dislocation movement.
o The addition of 1% CNTs to Al2O3-5SiC decreases its hardness from 21.78 GPa to 19.77
GPa and a further increase in the CNTs content to 2% further decreases the hardness to 19.11
GPa. The case is similar for Al2O3-10SiC.
o The high hardness values could be due to the amount of reinforcements used and the high
densification achieved. The hardness of the nanocomposite doesn’t only depend upon the
densification but also on the type and amount of the reinforcement used.
FRACTURE TOUGHNESS

o The addition of SiC restricted the growth of alumina matrix grains, compared with
monolithic alumina. This is due to grain boundary pinning.
o Monolithic Al2O3 had a fracture toughness of 3.61 MPa m0.5
o The addition of 5% SiC decreased its fracture toughness to 2.65 MPa m0.5.
o Further increase in SiC to 10% increased the fracture toughness to 3.64 MPa m0.5.
o The addition of 10% SiC to alumina changed the fracture mode from intergranular to mix of
intergranular and transgranular fracture modes.
o This change in fracture mode is due to the residual stresses, which result from the thermal
mismatch between Al2O3 and SiC.
o The addition of 1% CNTs to Al2O3-5SiC increased the fracture toughness to 3.89 MPa m0.5,
and a further increase in the fracture toughness to 4.2 MPa m0.5.
o The addition of 1% and 2% CNTs to Al2O3-10SiC increased the fracture toughness values to
4.58 MPa m0.5 and 6.98 MPa m0.5 respectively.
CONCLUSION:

o Al2O3-SiC-CNTs hybrid nanocomposites that have a uniform distribution of reinforcements

were successfully synthesized by ball milling, sonication, and spark plasma sintering.
o The uniform distribution of CNTs and SiC in the synthesized powders were obtained and
checked using X-Ray mapping, TEM and FE-SEM methods.
o The final microstructure comprised intergranular CNTs along with inter- and intra- granular
SiC nanoparticles.
o The addition of SiC to alumina changed the fracture mode from intergranular to mixture of
intergranular and transgranular modes.
o An almost transgranular fracture mode was obtained fro hybrid composites that is when
CNTs were added to the Al2O3-SiC composites.
o The Al2O3-10SiC-1CNTs possessed the highest hardness.