Acta Materialia 51 (2003) 25692576 www.actamat-journals.

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Temperature dependence of effective thermal conductivity and effective thermal diffusivity of Ni-Zn ferrites
G.P. Joshi, N.S. Saxena , R. Mangal
Condensed Matter Physics Laboratory, Department of Physics, University of Rajasthan, 5-6, Vigyan Bhawan, Jaipur-302004, India Received 6 August 2002; accepted 24 December 2002

Abstract Measurement of thermal transport properties of nanocomposites of Ni-Zn ferrite in a copolymer matrix of anilineformaldehyde has been made using transient plane source (TPS) technique. In the temperature range from room temperature to 140 C both effective thermal conductivity (le) and effective thermal diffusivity (ce) increase with increase in temperature and become maximum at a particular temperature which is a characteristic temperature for a given material. For further increase of temperature the le and ce decreases slowly. An effect has also been made to predict theoretically these values by an empirical model. Addition of zinc concentration in the composite decreases the value of le and ce over the entire range of temperature under investigation. It has also been found that the temperature at which a structural and bond strength change occurs depends on zinc concentration. 2003 Published by Elsevier Science Ltd on behalf of Acta Materialia Inc.
Keywords: Nanocomposites; Transient plane source technique; Effective thermal conductivity; Effective thermal diffusivity

1. Introduction In the past few years nanocomposite materials have become one of the most extensively studied materials. Nanocomposite materials composed of oxides and conducting polymers have brought out more elds of applications such as smart windows, toners in photocopying, rechargeable batteries [1], etc. Thermal transport properties of oxides have wide ranging applications, such as in supercon-

Corresponding author. Tel.: +1-91-141-511239; fax: +191-141-515828. E-mail address: nFsFsaxena@hotmail.com (N.S. Saxena).

ducting materials, nuclear reactor etc. It is observed that in powder systems the values of effective thermal conductivity and effective thermal diffusivity vary with the variation of particle size [2] and porosity of the system. Nanomaterials, particularly with magnetic properties, have their applications in color imaging, ferrouids, bioprocessing, medical diagnosis and electromagnetic wave absorption [3,4] etc. The nanocomposites are one of the class of nanomaterials. The nanomaterials can be amorphous in nature and they can be distinguished from the nanocrystalline and nanophase materials as only one phase exists. Physical properties of nanophase materials are presently of great scientic interest [5]. Thus nanocomposites are formed

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by combining conducting polymers and inorganic nanoparticles. The properties of nanocomposite of such kind are strongly dependent on concentration of polymer [6]. Optical properties such as optical band gaps have been done in these samples. Nanocomposites of aniline formaldehyde have been found to have direct band gap which increases with the concentration of zinc in the composite [7]. So the present study is aimed at studying the variation in thermal properties of these nanocomposites materials over a temperature range from 30 to140 C and at normal pressure using transient plane source (TPS) technique.
Fig. 1. Sample holder.

2. Experimental details Nanocomposites of Ni-Zn ferrite in a copolymer matrix of aniline-formaldehyde were synthesized at room temperature by using a novel chemical method reported elsewhere [8]. The nanocomposities of Ni1-x ZnxFe2O4 ferrites with x = 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0 were synthesized in a copolymer matrix (containing three different monomers) of aniline-formaldehyde. As a typical preparation, sample S1 (x = 0) was synthesized by treating the aqueous solution of aniline (0.10 mole), hydrochloric acid (0.12 mole), formaldehyde (0.10 mole) and nickel (0.189 mole) taken according to the stoichiometry. The resulting solution was stirred thoroughly and added to 10% solution of alkali. The precipitated composite was washed repeatedly with the distilled water till the ltrate was free of alkali (pH = 7.5) and then dried in air. Similarly, the samples S2S6 (x = 0.2, 0.4, 0.6, 0.8 and 1.0) were synthesized using the same procedure by varying the quantities of nickel and zinc according to the stoichiometry. Pellets of thickness 2 mm and diameter 12 mm were prepared from the powdered materials by a pressure of 4.33 108 Pascal. The sample holder (Fig. 1) containing these samples is placed in a furnace having sensitivity of 1 K. After achieving the isothermal conditions in the sample, a constant current pulse of width 15 s and height 0.0792 Amp is passed through the heating element. The measurements reported in this paper were performed with a TPS element of the type shown in Fig. 2. It is made of 10 m-thick nickel foil with

Fig. 2.

Schematic diagram of TPS sensor.

an insulating layer made of 50 m-thick kapton, on each side of the metal pattern. Evaluation of these measurements was performed in a way that was outlined by Gustafsson [9]. No inuence could be recorded from electrical connections, which are shown in Fig. 3. These connecting leads had the same thickness as the metal pattern of the TPS

Fig. 3. Schematic diagram of electrical circuit for simultaneous measurements of effective thermal conductivity and effective thermal diffusivity.

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element. Each TPS element had a resistance at room temperature of about 3.26 and a temperature coefcient of resistance (TCR) of around 4.6103K1. Owing to the change in average temperature of the sensor, the potential difference across it will change. The transient potential difference across the terminals is recorded by a digital multimeter, and the current through the TPS sensor with a digital power supply. The current in the circuit is adjusted according to the nature of the sample material. Multiple readings at appropriate intervals are taken to ensure the accuracy of the results. The TPS programme used here is capable of recording the temperature of the sample through the TPS sensor itself. In addition to this a sensitive thermometer is kept just above the sample pieces inside the furnace to monitor the temperature of the sample. 3. Transient plane source (TPS) theory The TPS method consists of an electrically conducting pattern (Fig. 2) in the form of a bilar spiral, which also serves as a sensor of the temperature increase in the sample. The sensor is sandwiched between the thin insulating layers of kapton. Assuming the conductive pattern to be in the y-z plane of a co-ordinate system inside the sample, the rise in the temperature at a point y-z at time t due to an output power per unit area Q is given by [9] T(y,z,) d 1 43/2a 0 2

R(t) R0 T()

(2)

where Ro is resistance of TPS element before the transient recording has been initiated, a is TCR and T() is the properly calculated mean value of the time-dependent temperature increase of the TPS element. During the transient event, T()can be consider to be a function of time only, where as in general it will depend on such parameters as the output power in TPS element, the design parameters [10] of the resistive pattern, and the thermal conductivity and thermal diffusivity of surroundings. T() is calculated by averaging the increase in temperature of TPS element over the sampling time because the concentric ring sources in TPS element have different radii and are placed at different temperatures during the transient recording. It is possible to write down an exact solution [9] for the hot disc if it is assumed that the disc contains a number m of concentric rings as sources. From the ring source solution [11] we immediately get T() where Ds() [m(m 1)]2 P D () 3/2a s (3)

d 2 0
m m

k exp

I1

k1

(l2 k2) lk L 42m2 0 22m2

(4)

s2a2 (yy)2(zz)2 exp 4s2a2

dydzQ(y,z,t

(1)

where (t - t) = 2 a2 , q = a2 / , and = [t / ]1 / 2. a is the radius of the hot disc which gives a measurement of the overall size of resistive pattern and q is known as the characteristic time. s is the variable parameter, l is the thermal conductivity in units of W/mK and c is the thermal diffusivity in unit of mm2/s of the sample material. The temperature increase T (y,z,t) because of ow of current through the sensor gives rise to a change in the electrical resistance R(t) which is given as

In Eq. (4), P0 is the total output power, L0 is the modied Bessel function and l, k are the dimensions of the resistive pattern. To record the potential difference variations, which normally are of the order of a few millivolts during the transient recording, a simple bridge arrangement as shown in (Fig. 3) has been used. If we assume that the resistance increase will cause a potential difference variation U(t) measured by the voltmeter in the bridge, the analysis of the bridge indicates that E(t) where Rs I R(t) Rs Ro o (5)

Rs IoaRoPo D () (Rs Ro) 3/2a s

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E(t) U(t)[1 C.U(t)]1 and C Rp RsIo 1 (Rs Ro) Rp 1

(6)

(7)

The denition of various resistances is found in Fig. 3. Rp is the lead resistance, Rs is a standard resistance with a current rating that is much higher than Io, which is the initial heating current through the arm of the bridge containing the TPS-element. g is the ratio of the resistances in two ratio arms of the bridge circuit, which is taken to be 100 in the present case.

4. Results and discussion Results of effective thermal conductivity and effective thermal diffusivity are given in Tables 1 and 2. It is interesting to note that the value of effective thermal conductivity and effective thermal diffusivity are for the glass pallets made at 5 tone of load. It has been observed [12] that the value increases slightly with the increasing pressure or load used for making the pallets. The variation of effective thermal conductivity and effective thermal diffusivity with temperature for

nanocomposities of Ni1-xZnxFe2O4 ferrites with x= 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0 is shown in Figs. 4 and 5. It is seen that the effective thermal conductivity of all the composites shows a similar trend of almost linear increase with temperature to a peak value. The peak values are observed at around 120 C for all compositions. The value of effective thermal conductivity then decreases with the increase of temperature. Experimental value of the effective thermal conductivity and effective thermal diffusivity at room temperature is 0.29 W/mK with x = 0.0 and decreases with the increase of concentration of zinc to 0.24 W/mK for x = 1.0. Nanomaterials can be polycrystalline or amorphous in nature and may belong to inorganic, organic or combinations of inorganic and organic classes of materials. Inorganic nanomaterials include metal and alloys, semiconducting oxides, magnetic oxides (ferrites, ferrouds) etc. Properties in inorganic nanomaterials arise due to contribution by individual nanoparticle as well as their combination due to peculiar structure and abnormal phase state. These samples are prepared at low temperatures by sol-gel technique, which upon heating at high temperatures gives rise to single phase crystalline or multiphasic crystalline ceramics. These materials thus exhibit properties arising due to nanometer size scale or large density of defects. On increasing the concentration of zinc,

Table 1 Experimental and theoretical value of effective thermal conductivity (W/mK) vs. temperature Sample no. Effective thermal conductivity (W/m-K) Temperature (C)

50 S1 S2 S3 S4 S5 S6 Experimental Theoretical Experimental Theoretical Experimental Theoretical Experimental Theoretical Experimental Theoretical Experimental Theoretical 0.30 0.30 0.29 0.29 0.28 0.28 0.27 0.27 0.26 0.26 0.25 0.25

80 0.32 0.31 0.31 0.29 0.30 0.28 0.29 0.27 0.28 0.26 0.27 0.25

100 0.34 0.34 0.33 0.33 0.32 0.32 0.31 0.31 0.30 0.30 0.29 0.29

120 0.36 0.36 0.35 0.35 0.34 0.34 0.33 0.33 0.32 0.32 0.31 0.31

130 0.34 0.35 0.33 0.34 0.32 0.32 0.31 0.32 0.30 0.31 0.29 0.30

140 0.33 0.33 0.31 0.31 0.30 0.30 0.29 0.29 0.28 0.28 0.27 0.27

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Table 2 Experimental and theoretical value of effective thermal diffusivity (mm2/s) vs. temperature Sample no. Effective thermal diffusivity (mm2/s) Temperature (C)

50 S1 S2 S3 S4 S5 S6 Experimental Theoretical Experimental Theoretical Experimental Theoretical Experimental Theoretical Experimental Theoretical Experimental Theoretical 0.19 0.19 0.18 0.18 0.17 0.17 0.15 0.15 0.13 0.13 0.12 0.12

80 0.21 0.20 0.20 0.19 0.19 0.17 0.17 0.15 0.15 0.13 0.14 0.13

100 0.23 0.23 0.22 0.22 0.21 0.21 0.19 0.19 0.17 0.17 0.16 0.16

120 0.26 0.26 0.24 0.24 0.23 0.23 0.21 0.21 0.19 0.19 0.17 0.17

130 0.24 0.24 0.22 0.23 0.21 0.22 0.20 0.19 0.18 0.17 0.15 0.16

140 0.22 0.22 0.21 0.21 0.19 0.19 0.18 0.18 0.16 0.16 0.14 0.14

Fig. 4. Temperature variation of effective thermal conductivity of different zinc concentration.

Fig. 5. Temperature variation of effective thermal diffusivity of different zinc concentration.

the value of saturation magnetization increases but exchange interactions decrease between the ions on the two sites thereby causing decrease in the Curie temperature. The experimental results of temperature dependence of effective thermal conductivity and effective thermal diffusivity in the temperature range from 50 to 140 C of all the samples presented in Figs. 4 and 5. The effective value of thermal conductivity (Fig. 4) initially shows a

gradual linear increase, reaches a maximum and then a decreasing trend is observed for all the compositions with temperature. In the temperature region before and after the peak in the effective thermal conductivity vs. temperature curve, structure scattering, which is temperature independent, play an important role in the thermal resistance. The observed variation in effective thermal conductivity is explained on the basis of various phonon scattering mechanisms [13,14] viz. struc-

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tural scattering, stray scattering and chain defect scattering. It has also observed that the values of effective thermal conductivity are lower for the higher concentration of zinc in the matrix for the entire range of temperature under investigation. It has already been noted that as the concentration of the zinc increases in the sample the Curie temperature decreases. The decrease in the Curie temperature of these samples is indicative of the fact that ferromagnetic nature, which depends upon the formation of close domains of magnetic moments with rigid boundaries, decreases because of inclusion of lighter diamagnetic particles of zinc. This tends towards the randomization of magnetic moments, which produces non-rigid loose structures with higher porosity of the sample. Thus, the effective thermal conductivity decreases as we include more and more concentration of zinc in the nanocomposities of Ni-Zn ferrites. Effective thermal diffusivity vs. temperature plot for all the compositions are presented in Fig. 5. It is seen that thermal diffusivity also increases linearly but slowly with temperature before the peak of thermal diffusivity, proceeds towards a maximum, which occurs almost at the same temperature where effective thermal conductivity also shows its maximum or peak value. For further increase of temperature over the characteristic temperature T0 (where le and ce show their maxima) the effective thermal conductivity and thermal diffusivity decreases very slowly. In the low temperature region below T0 the temperature dependence of effective thermal conductivity and effective thermal diffusivity is controlled by the variation of phonon mean free paths. By means of a least squares t to the experimental data of effective l and c as a function of temperature, as plotted in Figs. 6 and 7 for sample S1 to S6, empirical relationships have been developed for the theoretical prediction of l and c. As shown in Tables 3 and 4 these are given as: e A B(TTo) C(TTo) D(TTo)3 e a b(TTo) c(TTo)2 d(TTo)
3 2

Fig. 6. Temperature variation of theoretical and experimental value of effective thermal conductivity of sample S1 and S6.

Fig. 7. Temperature variation of theoretical and experimental value of effective thermal diffusivity of sample S1 and S6.

(8) (9)

where A, B, C, D, a, b, c and d are constants calculated by experimental conditions. T is the tempera-

ture of the composite in absolute temperature units. Observed variation in le and ce with temperature can be explained by considering the effect of temperature on structural units in a phenomenological manner. In the temperature range below T0 the temperature dependence of le and ce is controlled by the variation of phonon mean free path due to structure scattering, stray scattering and chain defect scattering. For temperatures below To, struc-

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Table 3 Value of constants A, B, C, and D in Eq. 8 for the effective thermal conductivity of nanocomposites Sample no. Peak value of temperature (C) Constants for effective thermal conductivity of nanocomposites

A (W/m-K) S1 S2 S3 S4 S5 S6 120 120 120 120 120 120 0.36 0.35 0.34 0.33 0.32 0.31

B (W/m-K2) 1.0105 1.5104 1.5104 1.5104 1.5104 1.5104

C (W/m-K3) 6.2105 7.5105 7.5105 7.5105 7.5105 7.5105

D (W/m-K4) 7.2107 8.6107 8.6107 8.6107 8.6107 8.6107

Table 4 Value of constants a, b, c and d in Eq. (9) for the effective thermal diffusivity of nanocomposites Sample no. Peak value of temperature (OC) Constants for effective thermal diffusivity of nanocomposities

a (mm2/s) S1 S2 S3 S4 S5 S6 120 120 120 120 120 120 0.26 0.24 0.23 0.21 0.19 0.17

b (mm2/s-K) 1.7104 8.0104 1.5104 1.3104 1.3104 3.4104

c (mm2/s-K2) 8.7105 6.2105 7.5105 6.2105 6.2105 5.0105

d (mm2/s-K3) 10.8107 7.5107 8.6107 3.8107 3.8107 4.0107

ture scattering becomes predominant besides chain defect scattering, scattering due to defects introduced by blends and relatively smaller length of chain segments. With rising temperature the polymeric chain becomes straighter. Therefore, mean free path increases, resulting in the increase of le and ce in this temperature range. Figs. 6 and 7 also show the variation of le and ce with temperature as predicted by empirical relations 8 and 9 for sample S1 and S6. It is clear from Figs. 67 that the agreement, between the predicted values of le and ce using the empirical relation and the results of experiment, is very good.

effective thermal diffusivity of Ni-Zn ferrites in a copolymer matrix of aniline formaldehyde depend both on the temperature and the concentration of zinc in the composite. Zinc being a diamagnetic material, when added to composite in large concentrations, produces randomisation of the magnetic moments and hence loose non-rigid structures which are resposible for the observed decrease of effective thermal conductivity and diffusivity of the nanocomposite.

References
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5. Conclusions From the results of the said study it can be concluded that effective thermal conductivity and

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[4] Vadera SR, Parihar M, Negi SC, Kumar N. Smart Materials Structure and MEMS Proc SPIS 1998;369:3321. [5] Mathur R, Sharma DR, Vadera SR, Kumar N. Bulletin of Materials Science 1999;22(6):991. [6] Suri K, Annapoorni S, Tandon RP. Bulletin of Materials Science 2001;24(6):563. [7] Joshi GP, Mangal R, Saxena NS, Sharma TP. Indian Journal of Pure and Appl Physics 2002;40:297. [8] Mathur R, Sharma DR, Vadera SR, Gupta SR, Sharma BB, Kumar N. Nanostruct Mater 1999;11(5):677. [9] Gustafsson SE. Rev Sci Instrum 1991;62:797. [10] Gustafsson SE, Suleiman B, Saxena NS, Haq IU. High TempHigh Press 1991;23:289.

[11] Carslaw HS, Jaeger JC. Conduction of heat in solid. Oxford: Oxford University Press, 1959. [12] Singh K, Saxena NS. Presented in II National Conference on Thermophysical Properties, Jaipur, Sept. 1921, 2002. [13] Saxena NS, Pradeep P, Mathew G, Thomas S, Gustafsson M, Gustafsson SE. European Polymer Journal 1999;35:1687. [14] Dashora P, Saxena NS, Saksena MP, Sharma KB, Sachdev K, Pradhan PR, Ladiwala GD. Physica Scripta 1992;45:399.