SYNOPSIS OF

CARBON NANOCOMPOSITES: SYNTHESIS AND APPLICATIONS IN ELECTRON FIELD EMISSION, NANOFLUID AND BIOSENSOR
A THESIS to be submitted by

TESSY THERES BABY

for the award of the degree of

DOCTOR OF PHILOSOPHY

DEPARTMENT OF PHYSICS INDIAN INSTITUTE OF TECHNOLOGY MADRAS CHENNAI 600 036, INDIA MARCH 2011

1. Introduction Theres Plenty of Room at the Bottom was the title of a lecture given by famous physicist Richard Feynman in 1959, which motivated many scientists to probe the concept of nanomaterials theoretically and experimentally. Carbon nanomaterials are an interesting class of nanomaterials with excellent properties like high surface area, high mechanical strength, good electrical conductivity, high thermal conductivity etc. Hence, they find applications in various fields such as chemical and bio-sensing, fuel cells, solar cells, batteries, energy storage, electronic applications etc. This present research work is mainly focused on synthesis and some of the applications of multiwalled carbon nanotubes (MWNT) and graphene, which are 1D and 2D allotropes of carbon, respectively.

2. Objective and scope of the work Graphene is the basic building block for many of the carbon allotropes. Though the theoretical concept of single layer graphene was proposed long back, researchers believed that this 2-dimensional structure would not be thermodynamically stable. But in 2004, Geim and Novoselov (Novoselov et al., 2004) successfully synthesized single layer graphene by micromechanical cleavage technique. Since then, single layer and few layer (<5 layer) graphene have been synthesized by a variety of techniques (Schniepp et al., 2006; Somani et al., 2006; Wei et al, 2009). The quality of few layer graphene depends on the synthesis procedure. Accordingly, in the present work, few layer graphene has been synthesized by the well known thermal exfoliation technique and the novel hydrogen induced exfoliation technique developed during the course of the work. The emission of electrons from the surface of a material to vacuum by the application of an external electric field is an interesting phenomenon known as electron field emission. Carbon based nanomaterials such as carbon nanotubes (CNT) have been extensively studied for the last ten years for field emission applications. Few layer exfoliated graphene are also attractive candidates for field emission studies because of its wrinkled morphology (Eda et al., 2008; Zhang et al., 2010). Hence, it is interesting to investigate the field emission properties of graphene and its composites using an in-house fabricated setup.

In the present scenario of energy conservation, cooling systems have tremendous applications. Nanofluids or nanocoolants are nanomaterials dispersed in base fluids (Choi et al., 2001). Since the conventional heat transfer fluids like water, ethylene glycol and transformer oil have very low thermal conductivity, these fluids are not very effective for cooling applications. In 1904, Maxwell theoretically suggested that solid materials dispersed in base fluids can improve the thermal conductivity of the base fluids (Maxwell, 1904). But the use of micro and macro sized particles dispersed in base fluids created problems such as clogging, sedimentation, and high pump power. Nanomaterials can avoid these problems to some extent because of their small size. Graphene and MWNT are proved to have high thermal conductivity. Therefore, in the present work, graphene/graphene nanocomposites dispersed nanofluids have been synthesized and their heat transfer properties have been studied. A heat transfer setup has been designed and fabricated for convective heat transfer study of the synthesized nanofluids. Magnetic nanofluids are used for many applications such as dynamic mechanical seals, airborne seals for protection of optical devices and sensitive electronic instrumentation in military and surveillance aircraft, stimulant for enhancing chemical reactions and medical diagnostics and therapy. In the present work, thermal properties of Fe3O4/MWNT and Fe3O4@SiO2/MWNT magnetic nanofluids consisting of magnetic nanoparticles decorated on the surface of MWNT in deionized water have been investigated. Biosensors are becoming increasingly important due to their applications in biological and chemical analyses, clinical detection, and environmental monitoring. The immobilization of enzymes on electrode is generally the first step in fabrication, and thus, has attracted significant important since enzymes are highly selective and quickly responsive to specific substrates. Nanomaterials are advantageous for immobilizing enzymes as they retain their bioactivity due to the desirable microenvironment (Wang et al., 2009). These materials can also increase the direct electron transfer between the enzymes active sites and the electrode. Among all the enzymebased biosensors, glucose biosensor is widely studied because of its importance in the monitor of blood glucose for the treatment and control of diabetes. CNT and graphene have gained considerable attention for sensing applications in recent years because of their remarkable electronic and mechanical properties which have made them extremely attractive for a wide range of sensing applications from structural materials to nanoelectronic components. In the

present work, the glucose sensing properties of metal oxide nanoparticles decorated MWNT, graphene and metal nanoparticles decorated graphene have been studied by electrochemical measurements to investigate the electron-transfer reactions between the MWNT/graphene modified electrodes and biomolecules. 3. Summary of research work MWNT were prepared by catalytic chemical vapor deposition (CCVD). The synthesis and purification procedures are described elsewhere (Shaijumon and Ramaprabhu, 2003). Graphene was synthesized by two different exfoliation techniques, namely, the well known thermal exfoliation technique (Schniepp et al., 2006) and the novel hydrogen exfoliation technique (Kaniyoor et al., 2010). Graphite oxide (GO) was prepared by Hummers method (Hummers and Offeman, 1958). Thermal exfoliated graphene (TEG) was synthesized by treating GO in Argon atmosphere at 1050 C for 30 s. Hydrogen exfoliated graphene (HEG) was synthesized by treating GO in hydrogen atmosphere at 200 C for 1 min. The TEM image of MWNT figure 1 (a) shows that the outer diameter varies between 30-50 nm, while TEM images of TEG and HEG show the presence of folding and wrinkles figure 1 (b,c).

Figure 1. TEM images of (a) multiwalled carbon nanotubes (MWNT), (b) thermal exfoliated graphene (TEG) and (c) hydrogen exfoliated graphene (HEG).

3.1 Field emission Field emission is the quantum mechanical tunneling of electrons from the surface of the emitter to vacuum on the application of sufficiently high external electric field. There have been some attempts to investigate the field emission properties of graphene films, recently. A spin coated graphene composite thin film showed a threshold field of 4 V m1 with a field 3

enhancement factor () of 1200 (Eda et al., 2008). The quantitative description of the process was first suggested by the Fowler-Nordheim (F-N) theory (Fowler and Nordheim, 1928). This theory relates current density to field strength (E) and work function () with the formula:
I= ( aA 2 E 2 )
3

exp ( B 2 / E )

--------------- (1)

where a = 1.54 10-6 A eV V-2 and B = 6.83 107 eV3/2 V cm-1 respectively. A is emission area and is the field enhancement factor which is given by
B 2 d = slope
3

----------------- (2)

where d is the distance of the anode from the emitting surface.

3.1.1 Field emission study of graphene The current density-electric field (J-E) plots for HEG and metal decorated HEG field emitters are shown in Figure 2 (a & b) and the results are summarized in table 1. The significantly good performance of HEG can be due to the following reasons. The folding and wrinkles on the surface of graphene help the electron emission. The defects on the graphene sheet lower the electron affinity that provided a low-energy barrier and enhanced electron emission. The considerably good turn-on voltage and threshold voltage of HEG can also be due to the residual hydrogen atoms present in the graphene. According to Lu et al. (2010), the hydrogen atoms adsorbed on the surface and edges of graphene aggregate to form the localized states near the Fermi level, which is responsible for the emission. The enhancement of electric current at low electric field is due to the charge distribution on carbon and hydrogen atoms and the resulting surface dipoles, which are expected due to the difference in electro negativity of carbon and hydrogen. At low fields, a large dipole moment is created between positive hydrogen and negative carbon. The direction of the field is such that it assists in the extraction of electrons from graphene sheets effectively by reducing the work function. The improved performance of metal oxide nanoparticles decorated graphene is due to the low work function and surface roughness of these materials.

Figure 2. Current density-electric field plots of (a) hydrogen exfoliated graphene (HEG) and (b) metal oxide decorated HEG (CuO/HEG and RuO2/HEG). Inset on both figures shows the corresponding Fowler-Nordheim plot. Table 1. Field emission characteristics of different graphene nanocomposites Sample code Turn on voltage for current density 10 A/cm2 (V/m) TEG HEG CuO/HEG RuO2/HEG 1.82 1.18 1.1 0.91 Threshold voltage for current density 0.2 mA/cm2 (V/m) 1.92 1.43 1.32 1.41 3677 4907 6935 7621 Field enhancement factor

3.2 Nanofluids 3.2.1

Thermal and electrical conductivity Another important area in which carbon based nanomaterials can be of extensive use, is

the coolant technology. Recently, Balandin et al., (2009) reported a thermal conductivity of about 5000 W/mK for a suspended single-layer graphene at room temperature. This extremely high value of thermal conductivity suggests that graphene dispersed nanofluids can perform better as nanocoolants. The proper functionalization of HEG (f-HEG) helps one to disperse it in

base fluids like de-ionized (DI) water. Figure 3a shows the normalized thermal conductivity (Kn/Kf) of f-HEG dispersed DI water based nanofluid as a function of temperature for different fHEG volume fractions. The percentage enhancement in thermal conductivity was calculated using the relation ((Kn - Kf) 100)/Kf, where Kf is the thermal conductivity of base fluid and Kn is that of nanofluid. Figure 3b shows the normalized electrical conductivity (n/f) for three different volume fractions at varying temperature in DI water based nanofluid, where n represents the electrical conductivity of nanofluid and f is that of base fluid. The graphs show that both thermal and electrical conductivity increase with increase in volume fraction and increase in temperature. The enhancement in thermal conductivity at high temperature can be due to the Brownian like motion of nanoparticles.

Figure 3. (a) Thermal conductivity and (b) electrical conductivity of functionalized hydrogen exfoliated graphene (f-HEG) dispersed de-ionized water nanofluid for different volume fractions at different temperatures. 3.2.2 Experimental study of convective heat transfer using f-HEG nanofluid The heat transfer coefficient, h, is a macroscopic parameter describing heat transfer when a fluid is flowing across a solid surface of different temperature and is defined as
h= q (Ts ( x) T f ( x ))

---------------------- (3)

where x represents axial distance from the entrance of the test section, q is the heat flux, Ts is the measured wall temperature, and Tf is the fluid temperature. A new convective heat transfer setup has been fabricated. The photograph of the setup is shown in figure 4a. The validity of the 6

Figure 4. (a) Photograph of the convective heat transfer setup. (b) Heat transfer measurement in terms of Nusselts number (Nu) and ratio of position (x) to diameter of the tube (D) of f-HEG dispersed DI water based nanofluid. Black dotted lines, blue solid lines and red dashed lines are for DI water, 0.005% of f-HEG and 0.01% of f-HEG respectively. Symbols corresponds to Re=4500 (), Re=8700 () and Re=15500 (). experimental setup has been check for laminar flows by Shah correlation (Shah, 1975) and turbulent flow by Dittus-Boelter equation (Dittus and Boelter, 1930) using DI water as the base fluid. The experimental results of thermal conductivity and heat transfer coefficient of f-HEG dispersed DI water based nanofluids for different volume fractions and Reynolds number (Re) respectively are shown in figure 4b. The performance has been improved by using silver or copper oxide nanoparticles decorated HEG. It is expected that these nanoparticles avoid the stacking of graphene layers and thereby increase the surface area. The results are summarized in table 2. Table 2. Thermal conductivity and heat transfer coefficient of different materials Sample code Enhancement in thermal conductivity in DI water 14% (0.05%) 25% (0.05%) 28% (0.05%) 7 Heat transfer coefficient in DI water for a volume fraction of 0.005 % Re=15500 108% 157% 259%

f-HEG Ag/HEG CuO/HEG

3.2.3 Magnetic nanofluid Magnetic nanofluids find potential applications in both energy related and biomedical fields. The chain formation of magnetic nanomaterials in a base fluid in the presence of magnetic field is anticipated to increase the thermal conductivity of magnetic nanofluids. Since MWNT are known to have high thermal conductivity, the use of MWNT and magnetic nanoparticles can give anomalous thermal properties for nanofluid. The photograph used for thermal conductivity in presence of magnetic field is shown in figure 5a. The thermal conductivity of Fe3O4@SiO2/MWNT dispersed DI water based nanofluids with and without magnetic field is shown in figure 5b. Fe3O4@SiO2/MWNT dispersed DI water based nanofluids with a volume fraction of 0.03 % shows a thermal conductivity enhancement of 24.5 % in the presence of magnetic field. The enhancement in thermal conductivity is due to the chain formation of magnetic material in the direction of magnetic field. When the magnetic field is removed, the thermal conductivity starts decreasing due to the aggregation of magnetic nanomaterials.

Figure 5. (a) Experimental Set up used and (b)Thermal conductivity measurement in presence of magnetic field for different volume fraction of Fe3O4@SiO2/MWNT nanofluid.

3.3 Biosensors Considering its importance in day to day life, the present study is concentrated on glucose biosensor. Electrochemical glucose detection has been done using an enzyme called glucose oxidase (GOD) which catalysis the oxidation/reduction reaction of glucose. GOD does not

directly transfer electrons to conventional electrodes because a thick protein layer surrounds its flavin redox center, flavin adenine dinucleotide (FAD). Such thick protein shell introduces a spatial separation of the electron donor-acceptor pair, and hence intrinsic barriers to direct electron transfer. The minimization of the electron-transfer distance (between the immobilized GOD and the electrode surface) is thus crucial for ensuring optimal performance. This problem can be overcome by the use of artificial mediators that shuttle electrons between the FAD center and the electrode surface by the following scheme:
Glu cos e + GOD( ox ) gluconicacid + GOD( red ) GOD( red ) + 2 M ( ox ) 2 M ( red ) GOD( ox ) + 2 M ( red ) + 2 H + 2 M ( ox )+2e

where M(ox) and M(red) are the oxidized and reduced forms of the mediator. Such mediation cycle produces a current dependent on the glucose concentration. By the use of these electroncarrying mediators, measurements become largely independent of dissolved oxygen and can be carried out at lower potentials that do not provoke interfering reactions from coexisting electro active species. To avoid the enzymatic difficulties researchers are now concentrating more on the fabrication of non-enzymatic biosensors. In non enzymatic biosensors, the mediators themselves help the oxidation of glucose. The above scheme can be therefore modified as
Glu cos e + 2 M ( ox ) gluconicacid + 2 M ( red ) + 2 H + 2 M ( red ) 2 M ( ox )+2e

In order to function effectively, the mediator should react rapidly, should possess good electrochemical properties, have low solubility in aqueous medium, must be nontoxic and chemically stable.

3.3.1 Amperometric study of enzymatic electrode Under the optimized experimental conditions, the biosensor was used to determinate glucose. Figure 6 (inset) shows a typical current-time response of the biosensor on successive addition of 40 M glucose in 0.1 M phosphate buffer solution (PBS, pH=7.0) at -0.4 V (vs Ag/AgCl). The subsequent addition of glucose to the stirring PBS leads to a remarkable increase in the oxidation current, and the time required to reach the 95% steady state response is less than 5 s. The proposed Nafion/GOD/ZnO/MWNT biosensor presents a linear range from 1 M to 22 9

mM (correlation coefficient R2 = 0.994) with a detection limit of 900 nM and the linear part of the calibration curve is shown in figure 6. This high sensitivity in detection of glucose suggests that the Nafion/GOD/ZnO/MWNT nanocomposite retains the electrochemical catalytic activity of enzyme by giving a biocompatible microenvironment.

Figure 6. Amperometric i-t curve obtained by adding different concentration of glucose to the buffer solution (inset) and the corresponding calibration curve for glucose biosensor using Nafion/GOD/ZnO/MWNT/GC electrode.

3.3.2 Amperometric study of non-enzymatic electrode Figure 7(A) shows a typical current-time response of the Nafion/ZnO/MWNT biosensor on successive addition of 40 M glucose in 1M NaOH solution at -0.5 V (vs Ag/AgCl). Subsequent addition of glucose to the stirring NaOH solution leads to a remarkable increase in the oxidation current, and the time required to reach 95% of the steady state response is less than 4 s. The two part of the graph shows the low and high concentration regions. The current signal of the Nafion/ZnO/MWNT/GC electrode was proportional to the concentration of glucose from 700 nM to 31 mM with the detection limit of 500 nM (S/N=3), figure 7(B). The linear regression equations are I (A) = 24.607 C (mM) 13.1032 (from 700 nM to 1 mM, R2= 0.9960) and I (A) = 4.7167 C (mM) -5.6015 (from 1 mM to 31 mM, R2 = 0.9964), respectively. This high sensitivity in detection of glucose suggests that ZnO/MWNT nanocomposite retains the electrochemical catalytic activity of both MWNT and ZnO in 1 M NaOH buffer solution.

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Different MWNT and graphene nanocomposites were studied for the detection glucose. The detection limit and linearity of these nanocomposites is given in table 3.

Figure 7. (A) Amperometric i-t curve for Nafion/ZnO/MWNT (B) calibration curve of the fabricated non-enzymatic electrode. Table 3. Detection limit and linearity range of different MWNT and graphene nanocomposites for glucose biosensor. Material f-graphene Pt-Au/grapheme Au/grapheme Fe3O4@SiO2/MWNT CuO/MWNT Fe2O3/MWNT ZnO/MWNT *Fe3O4@SiO2/MWNT *ZnO/MWNT * Non-enzymatic Detection limit 10M 1 M 1 M 800nM 10 M 10M 900nM 1 M 500 nM Linear Range 15 M-10mM 3 M-25mM 1 M-30mM 1 M-30mM 50 M-18mM 8 M- 25mM 1 M-22mM 3 M -14 mM 700 nM - 31 mM

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4. Conclusions Hydrogen induced exfoliation of graphite oxide results in the synthesis of few layer graphene in large scale. HEG and HEG nanocomposites have been demonstrated as excellent candidates for electron field emission. The better electron field emission performance of these nanocomposites is due to the presence of surface roughness and residual hydrogen in HEG which lowers the work function of the material. The enhanced thermal conductivity and convective heat transfer coefficient for low volume fractions of f-HEG and f-HEG nanocomposites based nanofluids suggest that these materials are potential candidates for coolants applications. The enhancement in thermal conductivity of Fe3O4@SiO2/MWNT magnetic nanofluids in presence of magnetic field is due to alignment of magnetic materials in the direction of magnetic field suggesting their use in biomedical applications. MWNT and graphene based nanomaterials have been used for fabrication bio-electrodes for glucose detection with enzyme and without enzyme. These nanomaterials have a very low detection limit and better linear range of glucose detection.

References Balandin, A. A., S. Ghosh, W. Bao, I. Calizo, D. Teweldebrhan, F. Miao and C. N. Lau, (2008) Superior Thermal Conductivity of Single-Layer Graphene. Nano lett. 8, 902-907. Choi, S. U. S., Z. G. Zhang, W. Yu, F. E. Lockwood and E. A. Grulke, (2001) Anomalous thermal conductivity enhancement in nanotube suspensions. Appl. Phys. Lett. 79, 2252-2254. Dittus, F.W. and L.M.K. Boelter, (1930) Heat Transfer in Automobile Radiators of the Tubular Type. Uni. of California Pub.in Eng. 2, 443-461. Eda, G., H. E. Unalan, N. Rupesinghe, G. A. J. Amaratunga and M. Chhowalla, (2008) Field emission from graphene based composite thin films, Appl. Phys. Lett. 93, 233502-3. Fowler, R. H. and L. M. Nordheim, (1928) Electron emission in intense electric fields, Proc. R. Soc. London, Ser. A 119, 173. Hummers, W. S. and R.E. Offeman, (1958) Preparation of graphitic oxide. J. Am. Chem. Soc. 80, 1339. 12

Lu, Z., W. Wang, X. Ma, N. Yao, L. Zhang and B. Zhang, (2010) The Field Emission Properties of Graphene Aggregates Films Deposited on Fe-Cr-Ni alloy Substrates J. Nanomaterials 2010, 148596. Maxwell-Garnett, J. C., (1904) Philos. Trans. R. Soc. A 203, 385. Novoselov, K. S., A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V. Dubonos, I. V. Grigorieva and A. A. Firsov, (2004) Electric field effect in atomically thin carbon films, Science 306, 666-669. Philip, J., P. D. Shima and B. Raj, (2008) Nanofluid with tunable thermal properties. Appl. Phy. Lett. 92, 043108-3. Schniepp, H. C., J. L. Li, M. J. McAllister, H. Sai, M. Herrera- Alonso, D. H. Adamson, R. K. Prudhomme, R. Car, D. A. Saville and I. A. Aksay, (2006) Functionalized Single Graphene Sheets Derived from Splitting Graphite Oxide. J. Phys.Chem., B 110, 8535-8539. Shah, R.K., (1975) Thermal entry length solutions for the circular tube and parallel plates, in: Proc. 3rd National Heat Mass Transfer Conference. Indian Institute of Technology, Bombay, 1, Paper no. HMT-11-75. Shaijumon, M. M. and S. Ramaprabhu, (2003) Synthesis of carbon nanotubes by pyrolysis of acetylene using alloy hydride materials as catalysts and their hydrogen adsorption studies. Chem. Phys. Lett. 374, 513-520. Somani, P.R., S.P. Somani and M. Umeno (2006) Planer nano-graphenes from camphor by CVD. Chem. Phys. Lett., 430, 56-59. Wang, Y. T., L. Yu, Z. Q. Zhu, J. Zhang, J. Z. Zhu and C. Fan (2009) Improved enzyme immobilization for enhanced bioelectrocatalytic activity of glucose sensor. Sens. Actuators, B 136, 332-337. Wei, L., T. Dai-Ming, H. Yan-Bing, Y. Cong-Hui, S. Zhi-Qiang, C. Xue- Cheng, C. ChengMeng, H. Peng-Xiang, L. Chang and Y. Quan- Hong (2009) Low-temperature exfoliated graphenes: vacuum-promoted exfoliation and electrochemical energy storage. ACS Nano 3, 3730-3736 Zhang, S., Y. Zhang, S. Huang, H. Liu, P. Wang and H. Tian (2010) First-Principles Study of Field Emission Properties of Graphene-ZnO Nanocomposite. J. Phys. Chem. C 114, 1928419288.

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Proposed contents of the thesis Chapter 1. Introduction Chapter 2. Experimental techniques Chapter 3. Synthesis and electron field emission study of graphene nanocomposites Chapter 4. Synthesis and thermal propeorties of Nanofluids Chapter 5. Carbon based materials for glucose detection Chapter 6. Conclusions

Conferences attended 1. Tessy Theres Baby, T. Arockiadoss, R.B. Rakhi, and S. Ramaprabhu, Magnetic bionanoparticles modified Multi walled carbon nanotubes based Glucose biosensor, International conference on Functional Materials (FM-2008), IIT Madras, Chennai, November, 2008. 2. Tessy Theres Baby, S.S. Jyothirmayee Aravind, R.B. Rakhi, T. Arockiadoss and S. Ramaprabhu, Fabrication of Amperometric glucose biosensor using two Chennai, December, 2008. 3. Tessy Theres Baby and S. Ramaprabhu, Metal Oxide coated Carbon Nanotubes for the Amperometric study of Glucose biosensor, Second International Conference on Frontiers in Nano Science and Technology (Cochin nano-2009), CUSAT, Cochin, January, 2009. 4. Tessy Theres Baby, N. Nandhini Devi and S. Ramaprabhu, Tin oxide coated Carbon Nanotubes for the amperometric study of Glucose biosensor, Annual Research Symposium (Chemference09) IIT Madras, Chennai, 22-23 August 2009. 5. Tessy Theres Baby and S. Ramaprabhu, A novel enzyme based zinc oxide nanoparticles decorated multi walled carbon nanotube for amperometric glucose biosensor, 20th Anniversary World Congress on Biosensors (Biosensors 2010), Glasgow, UK, 26-28 May 2010. 6. Tessy Theres Baby, R.B. Rakhi, N. Ravi and S. Ramaprabhu, Cerium Oxide Dispersed Multiwaleed Carbon Nanotubes as Cathode Material for Flexible Field Emitters, 3rd dimensional Graphene, International Symposium of Research Scholars (ISRS-2008), IIT Madras,

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International Conference on Advanced Nano Materials (ANM-2010) held in Agadir, Morocco on 12-15 September 2010. 7. Tessy Theres Baby and S. Ramaprabhu, Graphene and Graphitic Oxide Dispersed Propylene Glycol Based Nanofluids for coolant applications, Symposium on Recent and Emerging Advances in Chemical Engineering (REACH), Indian Institute of Technology Madras, Chennai, India. December 2-4, 2010. 8. Tessy Theres Baby and S. Ramaprabhu, Investigation of thermal transport properties of exfoliated graphene based nanofluids, 4th International Symposium for Research Scholars (ISRS 2010) on Metallurgy, Materials Science and Engineering, Indian Institute of Technology Madras, Chennai, December 20 - 22, 2010. 9. Tessy Theres Baby and S. Ramaprabhu, Magnetic Nanoparticles Decorated Multiwalled Carbon Nanotubes Dispersed Nanofluids, 55td DAE Solid State Physics Symposium (DAE 2010), Manipal University, Madhav Nagar, Manipal, Karnataka, December 26 - 30, 2010. 10. Tessy Theres Baby and S. Ramaprabhu, Field Emission Study of Thermally Exfoliated Wrinkled Graphene, First International Conference on Composites and Nanocomposites (ICNC 2011), held in Mahatma Gandhi University, Kottayam, Kerala from January 7-9, 2011. Visible research output: 1. Tessy Theres Baby, S. S. Jyothirmayee Aravind, T. Arockiadoss, R.B. Rakhi and S. Ramaprabhu (2010) Metal nanoparticles decorated Graphene as immobilization matrix for amperometric Glucose biosensor. Sensors and Actuators B: Chemical, 145, 71 77. 2. Tessy Theres Baby and S. Ramaprabhu (2010) SiO2 coated Fe3O4 magnetic nanoparticle dispersed multi walled carbon nanotubes based amperometric glucose biosensor, Talanta 80, 2016-2022. 3. Tessy Theres Baby and S. Ramaprabhu (2010) Thermal and electrical conductivity studies of graphene based nanofluids, Journal of Applied Physics 108, 124308-6. 4. Tessy Theres Baby and S. Ramaprabhu (2011) Non-enzymatic amperometric glucose biosensor with zinc oxide nanoparticles decorated multi walled carbon nanotubes, Journal of Nanoscience and Nanotechnology (in press).

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5. Tessy Theres Baby, R.B. Rakhi, N. Ravi and S. Ramaprabhu (2011) Cerium oxide dispersed multi walled carbon nanotubes as cathode material for flexible field emitters, Journal of Nanoscience and Nanotechnology (in press). 6. Tessy Theres Baby and S. Ramaprabhu (2011) Enhanced convective heat transfer using graphene dispersed nanofluids, Nanoscale Research Letters (in press). 7. Tessy Theres Baby and S. Ramaprabhu (2011) Experimental investigation of thermal transport properties of carbon nanohybrid dispersed nanofluid, Nanoscale (in press). 8. Adarsh Kaniyoor, Tessy Theres Baby and S. Ramaprabhu (2010) Graphene synthesis via hydrogen induced low temperature exfoliation of graphite oxide, Journal of Material Chemistry, 20, 8467-8469. 9. S. S. Jyothirmayee Aravind, Tessy Theres Baby, T. Arockiadoss, R. B. Rakhi, S. Ramaprabhu, A cholesterol biosensor based on gold nanoparticles decorated funtionalized graphene nanoplatelets, Thin Solid Films (in press). 10. Tessy Theres Baby and S. Ramaprabhu, Synthesis and Transport Properties of Metal Oxide Decorated Graphene, Journal of Physical Chemistry B (under review). 11. Tessy Theres Baby and S. Ramaprabhu, Synthesis and nanofluid application of silver decorated graphene, Journal of Material Chemistry (under review). 12. Tessy Theres Baby and S. Ramaprabhu, Cold Field Emission from Hydrogen Exfoliated Wrinkled Graphenes, Applied Physics Letters (under review). 13. Tessy Theres Baby and S. Ramaprabhu, Amperometric study of silica coated nano iron oxide dispersed multi walled carbon nanotubes based non-enzymatic glucose and cholesterol biosensors, Journal of Nanoparticle Research (communicated).

Patents: 1. Development of SiO2 coated Fe3O4 magnetic nanoparticle dispersed MWNT nanocomposite based Glucose sensor for food industry. S. Ramaprabhu and Tessy Theres Baby (US Patent (2010)) (IN-800668). 2. Scalable and Rapid synthesis of high quality two dimensional graphene material. Ramaprabhu, Adarsh K and Tessy Theres Baby (US Patent(2010)) (IN-811389). 3. Development of carbon based nanomaterials based coolants for industries. S. Ramaprabhu and Tessy Theres Baby (Patent to be filed with TATA STEEL (2011)). 16