THE SENSITIVITY OF SPECIFIC HEAT CAPACITY AND HEAT TRANSFER COEFFIECIENT ON NANOPARTICLE GROWTH IN PLASMA CHEMICAL REACTOR Oluranti

Sadiku1 and Emmauel Rotimi Sadiku Department of Mechanical Engineering, Faculty of Engineering and the Built Environment, Tshwane University of Technology, Pretoria, South Africa. CSIR Campus Building 14D Postnet Suit # 186, Private Bag x025 Lynnwoodridge 0040, Republic of South Africa. e-mail1: rantisadiku@yahoo.com; funmi2406@gmail.com Cell Phone No: +27783572455 Abstract A mathematical model is developed to simulate the comprehensive systems of nanoparticle growth. The model developed is the detailed population balance equation (PBE). The thermophysical properties of nanoparticles, especially specific heat capacity, overall heat transfer coefficient were investigated. This article presents a study on the sensitivity of overall heat transfer coefficient and the specific heat capacity during nanoparticle growth with the simultaneous chemical reaction, nucleation, condensation and coagulation under high temperature. The influence of the overall heat transfer coefficient and specific heat capacity on modeling of nanoparticle growth for the understanding of thermal stability on particle growth was investigated. Keywords: Population balance equation, Particle size distribution, Average particle diameter, Thermal conductivity, overall heat transfer coefficient and specific heat capacity.

1. Introduction
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Nanotechnology is mainly defined by size and comprises the visualisation, characterisation, production and manipulation of structures which are smaller than 100 nanometers (nm). They are particles with one or more dimensions on the nanoscale. When the particle size is decreased to the nanoscale range, fundamental physical and chemical properties appear to change, often resulting in completely new and different physical/chemical property than before. For example, titanium dioxide particles lose their white colour and become colourless at decreasing size ranges below 50 nm. Other particle types, known for their electrical insulating properties, may become conductive at the nanosize scale, or low soluble substances can increase their solubility when their sizes are below 100 nm 1, 2. The behaviour of nanoparticles is similar to the behaviour of a gas or a vapour and it is related to the size of the particles, which depends on their formation mechanism and the diffusion forces. Air diffusion is the principal mode of transport of particles smaller than 100 nm. The speed at which particles diffuse is determined by their 'coefficient of diffusion', which is inversely proportional to their diameter. Coagulation of very small particles quickly leads to the formation of larger particles in lower concentration. Particles ranging from 1 to 100 nm tend to agglomerate quickly to form larger diameter particles. When they reach a size of ~100 nm, they grow at a slower pace, up to 2,000 nm. This zone of slow growth, between 100 and 2, 000 nm, is called the 'accumulation mode'. The primary aerosol particles that come into contact with each other adhere together, due to short distance forces (a few atoms diameter) to form loosely larger particles or agglomerates. The aerosol coagulation process is caused by the relative motion among the particles. When the movement is due to the Brownian effect, the process is called Brownian or thermal coagulation; this is a spontaneous and it is an ever-present phenomenon for aerosols. If the relative motion is caused by external forces (such as gravity, electrical or aerodynamic forces), the process is called kinematic coagulation.3
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Nanostructured or nanophase materials are nanometre-sized solid substances engineered on the atomic or molecular scale to produce either new or enhanced physical properties not exhibited by conventional bulk solids. Therefore, particles less than 100nm in diameter exhibit properties differently from those of conventional solids. Properties that mostly determine the thermal performance of materials for heat transfer applications are the thermal conductivity, viscosity, specific heat capacity, overall heat transfer coefficient and density. The transfer of heat is normally from a high temperature object to a lower temperature object. Heat transfer changes the internal energy of both systems involved, according to the First Law of Thermodynamics. This is the application of conservation of energy principle to heat and the thermodynamic process. Thermal conductivity is the quantity of heat transmitted during a given time, through a material in a direction normal to a surface area of the particle. This is due to the temperature difference under steady state conditions, when the heat transfer is dependent only on the temperature gradient. Fluids such as air, water, ethylene glycol, and mineral oils are typically used as heat transfer media in applications such as power generation, chemical production, automobiles, computing processes, air conditioning and refrigeration. However, their heat transfer capabilities are limited by their very low thermal conductivity. These fluids have almost two orders of magnitude lower in thermal conductivity when compared to metals, resulting in low heat removal efficiencies.4 Many studies involving suspension in mill and microsized particle in various fluids have been done. Ahuja5, 6 did show that by suspending 50-100 m sized polystyrene particles in glycerine, the thermal conductivity is lowered below that of glycerine. The lower thermal conductivity followed the existing heterogeneous mixed media models, like that of Hamilton and Crosser 7. However, convective heat transfer rate of the mixture in the laminar flow increased by a factor of 2, without any increase in friction losses. The same work also
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investigated, from the theoretical standard point, the effect of varying the particle size, density and other factors that might influence this enhancement. Ahuja suggested that the physical mechanisms of heat transfer enhancement for this mixture are due to centrifugal fantype churning, due to rotation of particles in the shear gradient and a good dispersion of particle in the flow thereby creating more of this churning. Application of such coolants to real systems has proved difficult due to the inherent inability to keep these particles dispersed in fluids and the resultant settling and clogging potential. Therefore, these fluids are hardly considered for industrial applications. 5, 6 Over the years, a significant amount of data has been gathered on the thermal conductivity of nanofluids. Typical materials used for nanoparticles include metals such as copper, silver, and gold and metal oxides such as alumina, titania, and iron. Carbon nanotubes have also been used to enhance the thermal conductivity of liquids. Experimental data on the thermal conductivity of nanofluids varies widely and the mechanisms responsible for the thermal conductivity enhancement are under debate. Masahide et al 8 experimentally investigated the thermal performance of a new type of self-rewetting fluid heat pipe containing aqueous 1butanolic solution with microwave-assisted synthesis of very dilute polyvinylpyrrolidone (PVP)-capped silver nanoparticles (nano-self-rewetting fluid). This was done by investigating the temperature dependencies of surface tension and viscosity of 1-butanol containing chemically synthesized PVP-capped silver nanofluids. Zhang et al 9 employed homogeneous atomic chain to demonstrate atomistic green function approach with one degree of freedom per atom in order to determine the thermal conductance. Yulong et al
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worked on the heat

conduction, convective heat transfer under both natural and forced flow conditions, and boiling heat transfer in a nucleate regime. Syam Sundar and Sharma
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developed flow heat

transfer coefficient and friction of Al2O3 nanoparticles dispersed in water and ethylene glycol in circular tube. The heat transfer coefficient and friction factor characteristics of Al 2O3
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nanofluid in circular tube were numerically studied. The thermo-physical properties of the nanofluid are considered for heat transfer coefficient and friction factor by assuming that nanofluid is a single-phase fluid. Sami et al
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studied situations in which nanoparticles in a

fluid are strongly heated, thereby generating high heat fluxes. The situation they studied is relevant to experiments in which a fluid is locally heated by using selective absorption of radiation by solid particles. They explored the phenomenon of heat transfer in the vicinity of strongly heated nanoparticles, using molecular dynamics simulations of atomically realistic models or of more coarse-grained LJ monoatomic fluids. Garg et al 4 developed a technique for chemical synthesis of copper in ethylene glycol nanofluid and measured its thermal conductivity and viscosity. Yang et al.
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studied the convection heat transfer performance of

the graphite nanofluids in laminar flow through a circular tube. The experimental results show that the nanoparticles increase the heat transfer coefficient of the fluid system in laminar flow, but the increase is significantly less than that predicted by current correlation, based on static thermal conductivity measurements. Afshar et al
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analytically solved the

NavierStokes and energy equations for fluid flow in a microchannel in slip flow regime during which time, temperature and velocity profiles were evaluated. They concluded that the key to improve the heat transfer is to add nanoparticles so that part of heat is being transported from the microchannel without any additional pressure drop. Wen et al
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employed the molecular dynamics simulations with the quantum corrected SuttonChen type of the many-body force field to investigate the energetic and structural evolution of platinum nanoparticles with different shapes during the heating process. The shapes of nanoparticles include cube, octahedron, truncated octahedron, and sphere. Their study addresses the shape effects on thermal characteristics of platinum nanoparticles; however the modeling of process sensitivity of overall heat transfer coefficient and specific heat capacity for the understanding of thermal stability on particle growth has not been investigated. In this article, the objective
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is to investigate the sensitivity of the overall heat transfer coefficient and specific heat capacity on modeling of nanoparticle growth for the understanding of thermal stability on particle growth. Thermal conductivity is possibly the most important element in this study because it points out the nanoparticle with high heat transfer potential. 2.0 Process description 2.1 Population balance model The population balance equation consists of the following nonlinear partial integrodifferential equation.
(G (v, z , x ) n) n n + + cz - I (v ) (v v ) t z v

=1

~, v v ~ , x ) n( v ~, z , t ) n( v v ~, z , t ) dv ~ n (v , z , t ) ( v

~ ) n( v ~ , z , t ) dv ~ ( v, v

(1) The first term on the left hand side of equation (1) describes the change in the number concentration of particle volume interval v, v+dv and in the spatial interval, z. z+dz, n (v, z, t) denotes the particle size distribution function, v is particle volume, t is time, z

[0, L] is the

spatial coordinate, L is the length of the process. The second term on the left hand side gives the loss or gain of particles by condensational growth, the third term on the left hand side
n corresponds to the convective transport of aerosol particles at fluid velocity z

which is c z

c z and the fourth term on the left hand side accounts for the formation of new particles of

critical volume v by nucleation rate I . I (v ) (v v ) , also accounts for gain and

~, v v ~, ~ x ) are the loss of particles by condensation. G (v, z , x ) , I (v * ) and (v

nonlinear scalar functions and is the standard Dirac function. The nucleation rate I (v * ) is
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assumed to follow the classical Becker-Doring theory, given by the expression below (Pratsinis). 16

I = n s2 s1 (k BT / 2m1 )1 / 2 S 2 (2 / 9 )1 / 3 1 / 2 exp( k * InS / 2),

(2) Where s1 is the monomer surface area and k * which is the number of monomer in the critical nucleus and is given by:

4 k= 6 InS

3
, Where = v12 / 3 / k B T and is the surface tension. (3)

The mathematical equation that describes the dimensionless temperature is given by Kalani and Christofides 17 thus:
dT dT = c zl + BC1C 2T + ET (Tw T ) d dz

(4)

The term on the left hand side describes the dimensionless temperature with dimensionless time. The first term on the right hand side describes the dimensionless temperature with dimensionless distance due to convection by chemical reaction. The second term on the right hand side gives the temperature change in the concentration of reactants due to energy release in the chemical reaction. The last term on the right hand side describes the temperature change in the heat transfer. Heat transport and heat release due to chemical reactions leads to spatial and temporal temperature distributions in chemical reactors. This prediction is based on the first law of thermodynamics which says that the total energy of a

given system obeys a conservation law. Table 1 and 2 gives the dimensionless variable and process parameters used for the simulation respectively.

2.2 THE LAW OF HEAT CONDUCTION The law of heat conduction states that the time rate of heat transfer through a material is proportional to the negative temperature gradient and the area in the right angles, to that gradient, through which heat is flowing. This law is also known as Fouriers law. The differential form of this law will be considered which look at the heat flow rate intensity (flow of energy per unit area per unit time). The differential form of Fourier's Law of thermal conduction shows that the heat flow rate intensity is equal to the product of thermal conductivity k, and negative local temp gradient. The heat flow rate is the amount of energy that flows through a particular surface per unit area per unit time. Fourier law for one dimensional form in its x direction is given as:
q x = k dT dx

(5)

Table 1: Dimensionless Variables by Kalani and Christofides 17 N= M 0 / n s , V= M 1 / n s v1

V2 = M 2 / n s v1 2

Aerosol concentration and volume Second aerosol moment Characteristic time for particle growth

'

m1 /k B T ) 1 / 2 n s s1 =(2

K=(2
I = I /( n s / )

k B T /3 ) n s , Coagulation coefficient and Nucleation rate Knudsen number Dimensionless geometric volume Dimensionless geometric radius
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K n1 = / r1
' vg = v g / v1

rg' = rg / r1

z = z/L
c zl = c z / L , = t /

Dimensionless distance Dimensionless velocity and time Dimensionless time

= t/

Table 2: Process model parameters for the simulation study

L=1.5m D=0.1m P 0 =101000 pa T 0 =2000 K y 10 = 0.4 y 20 = 0.6 U=160 J m 2 s 1 K 1
1 R = 88000 J mol 1 1 C P = 1615.25 J mol K

Reactor length Reactor Diameter Process pressure Inlet temperature Inlet mole fractions of O 2 Inlet mole fractions of TiCl 4 Overall coefficient of heat transfer Heat of reaction Heat capacity of process fluid Mol wt. of process fluid Reaction rate constant Viscosity of process fluid PVT relation

MW g =14.0 10

1 kg mol

1 K=11.4m 3 mol s 1 1 1 = 6.7 10 5 kg m s

log Ps ( mmHg ) = 4644 / T + 0.906 log T 0.00162T + 9.004

1 = 0.08 N m

Surface tension Monomer volume

1

v1 = 5.33 10 29 m 3

N av = 6.023 10 23 # mol
1 1 R=8.314 J mol K

Avogadros constant Universal gas constant Boltzmanns constant Sigma Geometric radius Monomer radius

1 k B = 1.38 10 23 J K

= 0.5

rg =1.5e06 m

r1 = 0.5e06 m
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v g = dp 3 / 6
s 0 = 1.1587 E 19m

Geometric volume Monomer surface area Wall temperature Reynolds number

Tw = 1600K

Re = 2000

3.0 RESULTS AND DISCUSSION The mechanisms that govern the effective thermal conductivity of nanoparticles suspensions may be associated with many factors that include heat transport within the individual particles and the Brownian motion of individual particles. The thermal conductivity is often treated as a constant; however, this is not always true. For this investigation, the thermal conductivity increases slightly with dramatic increase in average particle diameter. Figure 1 shows the steady state profile of the average particle diameter as a function of the thermal conductivity. The thermal conductivity of a material generally varies with temperature; the variation can be small over a significant range of temperatures for some common materials. Figure 2 shows the variation of the thermal conductivity with dimensionless temperature.

Fig. 0. The steady state profile of the average particle diameter against the thermal conductivity.

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Fig. 2. The steady state profile of the thermal conductivity against the dimensionless temperature. The maximum diameter of particles is determined by the competition between the heating of the particles due to the energy released in the reactor and the heat dissipation (loss of energy over time) from the particles surface to the surroundings. The average particle diameter increases with increase in the residence time. It can be seen from Figure 3 below, that when the particles are nucleated, a primary particle with diameter of ~2nm is produced at constant time. After a certain number of particles have been produced, the frequency of biparticle collision increases due to the heating of particles, resulting in a sharp increase in particle diameter. The particles gain heat from their surrounding as they approach the heated surface, and when they leave the thermal region, they give up their heat to the bulk.

Fig. 3. The steady state profile of the average particle diameter against time
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Particles established a large local temperature gradient due their lateral motion, resulting from their contact and rebound to the heat transfer surface. Figures 4 and 5 show the average particle diameter and particle volume as functions of the overall heat transfer. The average particle diameter and the particle volume increase with increasing overall heat transfer.

Fig. 4. The steady state profile of the average particle diameter against overall heat transfer

Fig. 5. The steady state profile of the particle volume against overall heat transfer The steady state profile of the average particle diameter against the heat capacity of the process fluid is given in figure 6 below. The result shows that the average particle diameter increases steadily with heat capacity in the region between 1700-1730 J/mol.K and
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thereafter remains constant. The heat capacity does not have much influence on the average particle diameter as the average particle diameter approaches a limiting value of 11.82nm. The heat capacity has significant effect on the wall temperature. The wall temperature increased with increasing heat capacity as shown in figure 7.

Fig. 6. The steady state profile of the average particle diameter against heat capacity

Fig. 7. The wall temperature of the reactor against heat capacity

4. Summary
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In summary, modeling of the sensitivity analysis of the overall heat transfer coefficient and specific heat capacity for the understanding of thermal stability on particle growth has been investigated. The influence of the overall heat transfer coefficient and specific heat capacity on modeling of nanoparticle growth for the understanding of thermal stability on particle growth was also investigated. The heat transfer behaviour shows that nanoparticle properties have influence on the thermal conductivity in the nucleate region as particle diameter increases with increasing overall heat transfer. The sensitivity of the variation of the overall heat transfer on the average particle diameter and particle volume shows that the thermal conductivity is an important element in the growth of nanoparticle. This is because it points out the potential of high heat transfer on nanoparticle. The sensitivity of the variation of the heat capacity on the wall temperature also shows that the thermal conductivity is an important element in the growth of nanoparticle because nanoparticle formation with high wall temperature increases the growth of particle. Further work should be done experimentally on investigating the sensitivity analysis of the overall heat transfer coefficient and specific heat capacity for the understanding of thermal stability on particle growth. References 1. D.B. Warheit, Toxicol. Sci. 101, 183 (2008) 2. V. Colvin, Nature Biotechnology. 21, 1166 (2003)
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Nanoscience and Nanotechnology, 1st ed., pp. 42, New York, (Marcel Dekker) Taylor and Francis, (2004).
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B. Poudel, M. Chiesa, J. B. Gordon, J. J Ma, J. B. Wang, Z. F. Ren, Y. T. Kang, H.

Ohtani, J. Nanda, G. H. McKinley and G. Chen, J. Appl. Phys. 103, 074301, (2008) 5. A. S. Ahuja, J. Appl. Phys. 46, 3408, (1975)
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6. A. S. Ahuja, J. Appl. Phys. 46, 747, (1975) 7. R. L. Hamilton and O. K. Crosser, Ind. & Eng. Chem. Fund. 1, 187 (1962) 8. S. Masahide, A. Yoshiyuki, U. Yuki, D. P. Roberto, S. Raffaele and C. Anselmo, Thermal performance of self-rewetting fluid heat pipe containing dilute solutions of polymer-capped silver nanoparticles synthesized by microwave-polyol process. Proceedings of International Transport Phenomena VI, Volterra, Italy, paper no: ITP-09-19, pp 1-7. October 4-9, (2009) 9. W. Zhang, T. S. Fisher and N. Mingo, Numerical heat transfer, Part B. 51, 333 (2007) 10. D. Yulong, C. Haisheng, W. Liang, Y. Chane-Yuan, H. Yurong, Y. Wei, P.L. Wei, Z. Lingling, and H. Ran, Kona, 25, 23, (2007) 11. L. Syam Sundar and K. V. Sharma, Int. J. Dynamic. of fluids, 4, 121 (2008) 12. M. Samy, S. Sergei, J. Laurent, K. Pawel and B. Jean-Louis, Proceedings of the National Academy of Science, 106, 15113 (2009) 13. Y. Yang, Z. George Zhang, E. A. Grulke, W. B. Anderson and G. Wu, International Journal of Heat and Mass Transfer, 48, 1107 (2005) 14. H. Afshar, M. Sham, S. M. M. Nainian, and G. Ahmadi, International Communications in Heat and Mass Transfer, 36, 1060 (2009) 15. Y. Wen, H. Fang, Z. Zhu and S. Sun, Phys. Lett, A 373, 272 (2009) 16. S. E. Pratsinis, Journal of Collide Interface Science, 124, 416 (1988) 17. A. Kalani and D. P. Christofides, Chem. Eng. Sci. 54, 2669 (1999)

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