Fusion Engineering and Design 81 (2006) 321325

Thermal conductivity of ceramics during irradiation

M. Akiyoshia, , I. Takagia , T. Yanob , N. Akasakac , Y. Tachic
c a Kyoto University, Yoshida-Honmachi, Sakyo-ku, Kyoto 606-8501, Japan Tokyo Institute of Technology, 2-12-1 O-okayama, Meguro-ku, Tokyo 152-8550, Japan Japan Nuclear Cycle Development Institute, 4002 Narita-cho, O-arai-machi, Ibaraki-ken 311-1393, Japan b

Received 29 January 2005; received in revised form 19 August 2005; accepted 19 August 2005 Available online 18 January 2006

Abstract Thermal conductivity is one of the most important parameters for the design of fusion reactors using ceramic materials. Thermal diffusivity of ceramics decreases by phonon scattering and specic heat increases slightly as the temperature rises to 1300 K. The amount of point defects during neutron irradiation changes with the irradiation temperature. In this work, -Al2 O3 , AlN, -Si3 N4 and -SiC specimens were irradiated in the experimental fast reactor JOYO at 775, 835 and 1039 K to high neutron uence. Thermal diffusivity was measured at elevated temperatures in vacuum via the laser ash method. Using an approximation function, the thermal diffusivity at the irradiation temperature was determined for each specimen, and the one during irradiation was estimated with additional assumptions. Thermal diffusivity of ceramics during irradiation was found to be almost temperature independent, and the thermal conductivity has a slight increase with temperature. 2005 Elsevier B.V. All rights reserved.
Keywords: Thermal conductivity; Thermal diffusivity; Ceramics; Neutron irradiation

1. Introduction Ceramic materials have many superior properties, and some of them are expected to be used in several nuclear applications, such as blanket materials for future fusion reactors where they would be exposed to high uence of 14 MeV neutrons at temperatures up to 1300 K [1,2]. High neutron uence irradiation induces many defects and resulted in physical property changes,
Corresponding author. Tel.: +81 75 753 4837; fax: +81 75 753 4837. E-mail address: akiyoshi@nucleng.kyoto-u.ac.jp (M. Akiyoshi).

like swelling, degradation of mechanical strength, corrosion resistance, electrical conductivity, thermal diffusivity and thermal conductivity. Thermal conductivity is one of the most important factors for the solid breeder of fusion reactor blanket design and other nuclear applications. It has also been reported that thermal diffusivity and conductivity showed signicant decrease after neutron irradiation [38]. But in most previous works, post-irradiation measurements were operated at room temperature (even after annealing, the measurement itself was performed at room temperature). Generally, thermal diffusivity of ceramics decreases as measurement temperature rises

0920-3796/$ see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.fusengdes.2005.08.084

322

M. Akiyoshi et al. / Fusion Engineering and Design 81 (2006) 321325

Table 1 Properties of non-irradiated ceramic specimens Specimen Thermal diffusivity Density (103 kg/m3 ) Specic heat (103 J/kg K) Thermal conductivity (W/m K) (104 m2 /s) -Al2 O3 0.077 3.96 0.789 36.9 AlN 0.616 3.25 0.738 238 -Si3 N4 0.257 3.33 0.636 53.0 -SiC 0.334 3.20 0.697 91.4

because of phonon scattering and specic heat slightly increases. In addition, if a material is annealed above the irradiation temperature, irradiation defects will be recovered and show higher thermal diffusivity and conductivity. If measurements are performed at elevated but below the irradiation temperature, the specimen would just keep the amount of defects that were induced at the irradiation temperature. It is clear that the irradiation temperature changes the amount of defects during irradiation, but a post-irradiation measurement of thermal diffusivity and conductivity at an elevated temperature could show different results from the one in the reactor. On the other hand it is very difcult to measure thermal conductivity during irradiation. To resolve this problem, we used only one measurement temperature for each specimen, which is the irradiation temperature. Using an approximation function, thermal diffusivity at the irradiation temperature was estimated for each specimen, and the relation between the irradiation temperature and the thermal diffusivity and conductivity during irradiation was assessed. 2. Experimental The -Al2 O3 , AlN, -Si3 N4 and -SiC specimens were irradiated in the experimental fast reactor JOYO enclosed in the same capsule. The capsule was irradiated to different neutron uence at different temperature, e.g. 5.3 1026 n/m2 at 775 K (T52), 7.3 1026 n/m2 at 835 K (T54) and 6.9 1026 n/m2 at 1039 K (T58), respectively. Properties of each specimen before irradiation are listed in Table 1 and other details were reported in previous paper [9]. The dimension of the specimens was 3 mm in diameter and 0.5 mm in height. In this study, thermal diffusivity was measured by the laser ash method (ULVAC TC-7000, laser

power 2.6 kV) and analyzed with the t1/2 method. AlN and -Al2 O3 specimens were coated by carbon spray and baked on a hot plate at about 373 K because of their translucence property. Measurements at elevated temperature were performed in vacuum (<0.01 Pa) up to 1073 K with an increase temperature rate of 10 K/min. During the measurement the temperature was kept stable within 1 K/min. After that, the specimen was cooled and the thermal diffusivity was measured at room temperature to estimate the recovery by annealing. Thermal conductivity K(W/K m) was obtained from the equation K = Cp where (m2 /s) is the thermal diffusivity, Cp (J/K kg) the specic heat and (kg/m3 ) the density. In this work, specic heat and density of non-irradiated specimens were used to calculate the thermal conductivity. These parameters were changed by neutron irradiation, but it was reported that these changes were very small as compared with that of the thermal diffusivity. At an elevated temperature, the change in density due to thermal expansion was estimated to be below 1%, so that this changes was ignored [10]. 3. Result Fig. 1 shows the temperature-dependent thermal diffusivity and thermal conductivity of neutron irradiated ceramics. The small dots with solid lines show the thermal diffusivity. In the previous works, thermal diffusivity of neutron irradiated ceramics began to recover above 873 K [68]. So, the thermal diffusivity at 1073 K was modied via 1073 0 /an where 1073 is the thermal diffusivity measured at 1073 K (plotted with outline symbols), 0 the one measured at room temperature before annealing (as-irradiated) and an the one at room temperature after annealing at 1073 K.

M. Akiyoshi et al. / Fusion Engineering and Design 81 (2006) 321325

323

Fig. 1. Thermal diffusivity and conductivity of neutron irradiated ceramics at elevated temperatures. Solid lines represent thermal diffusivity, and broken lines thermal conductivity. Symbols , , and show the result for T52, for T54 and for T58, respectively. Thermal diffusivity at 1073 K measurements contained recovery effect by annealing (plotted with outline symbols) and the values were reduced with measurement at room temperature after annealing for each specimen: (a) -Al2 O3 , (b) AlN, (c) -Si3 N4 and (d) -SiC.

It should be noted that these values were not measured during the irradiation, but post-irradiation measurement at elevated temperatures. Thermal diffusivity controlled by phonon scattering is expressed by = 1 3 where (m) is the mean free path and (m/s) the mean phonon speed. The mean phonon speed does not change without serious damages or change of the crystal structure [10], but the mean free path decreases with the increasing of point defects, especially due to voids. Neutron induced point defects keep a certain bal-

ance of creation and recombination, which was shifted with the irradiation temperature. At a lower temperature, point defects had a shorter recombination radius and therefore the density of defects was higher. After the irradiation, specimens were cooled and frozen with the same density of point defects as in the reactor unless annealed to above the irradiation temperature. But at each measurement, the point defects density was different from the balance during the irradiation at that temperature.

324

M. Akiyoshi et al. / Fusion Engineering and Design 81 (2006) 321325

Table 2 Irradiation dose and temperature for each capsule and tting parameters of thermal diffusivity depend on measurement temperature T (K) with expression = k/T n Specimen -Al2 O3 AlN -Si3 N4 -SiC Parameter k 104 n k 104 n k 104 n k 104 n T52 (5.3 1026 n/m2 , 775 K) 0.15 0.40 0.06 0.29 0.19 0.31 0.23 0.37 T54 (7.3 1026 n/m2 , 835 K) 0.36 0.52 0.11 0.37 0.37 0.40 0.32 0.42 T58 (6.9 1026 n/m2 , 1039 K) 0.45 0.51 0.07 0.27 0.25 0.34 0.25 0.38 Non-irradiated 37.9 0.87 33.2 0.80

Thermal diffusivity decreased as k/T n where T (K) is the measurement temperature, k and n are the constants for each specimen. For non-irradiated perfect crystals, the parameter n is equal to 1, and it was reported that n decreases with the increase in neutron irradiation dose [4]. Fitting parameters for each specimen are listed in Table 2. In addition, the large dots with broken lines in Fig. 1 show the temperature dependent of thermal conductivity of the neutron irradiated ceramics. The specic heat Cp increases with temperature until the Debye temperature, for ceramics, about 1000 K. So in the temperature range of this experiment, specic heat increased while thermal diffusivity decreased. As the result, thermal conductivity of -Al2 O3 and AlN showed almost constant values, and -Si3 N4 and -SiC showed an increase with an increase of post-irradiation measurement temperature.

(3) degradation of thermal diffusivity with neutron dose was saturated above 3.0 1026 n/m2 . The rst assumption requires quick cooling of the irradiation reactor in order to quench the specimen. If the reactor cools slowly, the specimen will be irradiated at a lower temperature than the scheduled temperature, and therefore contains more defects and shows lower thermal diffusivity and conductivity. The second assumption is supported by the measurement of thermal diffusivity with post-irradiation isochronal annealing [68]. The last one is supported by our post-irradiation

4. Discussion Using an approximation function, thermal diffusivity of post-irradiated specimen measured at the irradin for ation temperature Tirr (K) was estimated as k/Tirr each specimen. This value represented the thermal diffusivity during the irradiation based on the following assumptions: (1) post-irradiated specimens would keep the same amount of defects as during the irradiation; (2) defects would be stabilized until being annealed to above the irradiation temperature;
Fig. 2. Estimated thermal diffusivity and conductivity of ceramics during neutron irradiation at elevated temperatures. Solid lines represent thermal diffusivity, and broken lines thermal conductivity. Symbols , , , and show the result for -Si3 N4 , for -SiC, for -Al2 O3 and for AlN, respectively.

M. Akiyoshi et al. / Fusion Engineering and Design 81 (2006) 321325

325

measurements, which will be presented in ICFRM-12, and also by other publications [3,11]. Fig. 2 shows the thermal diffusivity and conductivity of ceramics during the irradiation as a function of the irradiation temperature Tirr . The small dots with solid lines show the thermal diffusivity. During irradiation -Si3 N4 and -SiC showed a slight decrease in the thermal diffusivity as Tirr rose, while -Al2 O3 and AlN showed a slight increase. In addition, the large dots with broken lines shows the thermal conductivity, which for each specimen increased a little as Tirr rose. Usually, thermal diffusivity and conductivity of ceramics decrease as measurement temperature rises because of increasing umklapp phonon scattering, while the density of point defects decreases as irradiation temperature rises. These factors compensate each other, so these ceramics kept almost the same value of thermal diffusivity and conductivity at different irradiation temperatures. In this study, density change arising from swelling was ignored, because it was negligible. But at a far higher dose, swelling of -Al2 O3 and AlN would keep increasing [12], and it would cause a degradation of thermal conductivity, while -Si3 N4 and -SiC show saturation of swelling. In addition, in this work specimens were irradiated in a fast reactor. If specimens irradiated in a thermal reactor with a lower neutron ux, they would show higher thermal diffusivity and conductivity. Neutron ux changes defects inducing rate, and the amount of defects during an irradiation is decided by the balance between the inducing rate and the recombination rate, the latter is depending on the irradiation temperature. This balance would be a little higher than the post-irradiated specimen, so the assumption (1) is not exactly correct. We must investigate the recombination rate changes with the temperature in future works. Furthermore, measurement temperature dependence of thermal diffusivity is expressed by the k/T n function. Non-irradiated -Si3 N4 and -SiC showed n = 0.80.9, and neutron irradiated specimens showed n = 0.30.4 (-Al2 O3 showed a little larger value of about 0.5). Specimens irradiated in T54 capsule showed larger values, while T54 capsule was irradiated by higher dose and the irradiation temperature was lower than T58 (T52: 5.3 1026 n/m2 at 775 K, T54:

7.3 1026 n/m2 at 835 K, and T58: 6.9 1026 n/m2 at 1039 K). With further careful treatment, there is a possibility that it will give hint to the characterization of the induced defects [13,14].

References
[1] R. Aymar, International Team, Iter status, design and material objectives, J. Nucl. Mater. 307311 (2002) 19. [2] D. Campbell, M. Gasparotto, D. Maisonnier, K. Lackner, R. Andreani, M.A. Pick, Long-term fusion strategy in Europe, J. Nucl. Mater. 307311 (2002) 1020. [3] F.W. Clinard Jr., L.W. Hobbs, Physics of radiation effects in crystals, in: R.A. Johonson, A.N. Orlov (Eds.), Modern Problems in Condensed Matter Sciences, vol. 13, North Holland, Amsterdam, 1986, p. 387. [4] M. Rohde, B. Schulz, The effect of the exposure to different irradiation sources on the thermal conductivity of Al2 O3 , J. Nucl. Mater. 173 (1990) 289293. [5] C.S. Hazelton, J.A. Rice, L.L. Snead, S.J. Zinkle, Effect of neutron radiation on the dielectric properties of ceramics for RF transmission windows, J. Nucl. Mater. 253 (1998) 190195. [6] T. Yano, K. Ichikawa, M. Akiyoshi, Y. Tachi, Neutron irradiation damage in aluminium oxide and nitride ceramics up to a uence of 4.2 1026 n/m2 , J. Nucl. Mater. 283287 (2000) 947951. [7] T. Yano, M. Akiyoshi, K. Ichikawa, Y. Tachi, Y. Iseki, Physical property change of heavily-neutron-irradiated Si3 N4 and SiC by thermal annealing, J. Nucl. Mater. 289 (2001) 102109. [8] M. Akiyoshi, K. Ichikawa, T. Donomae, T. Yano, Macroscopic properties and microstructure changes of heavily neutronirradiated -Si3 N4 by annealing, J. Nucl. Mater. 307311 (2002) 13051309. [9] M. Akiyoshi, N. Akasaka, Y. Tachi, T. Yano, Relation between macroscopic length change and the crystal structure in heavily neutron-irradiated ceramics, J. Nucl. Mater. 329333 (2004) 14661470. [10] J.C. Corelli, J. Hoole, J. Lazzaro, C.W. Lee, Mechanical, thermal, and microstructural properties of neutron-irradiated SiC, J. Am. Ceram. Soc. 66 (1983) 529538. [11] L.R. Greenwood, D.V. Archer, D.L. Alexander, M.C. Chen, G.A. Newsome, D.J. Senor, G.E. Youngblood, Defect structure and evolution in silicon carbide irradiated to 1 dpa-SiC at 1100 C, J. Nucl. Mater. 317 (2003) 145159. [12] M. Akiyoshi, N. Akasaka, Y. Tachi, T. Yano, Interstitial atom behavior in neutron-irradiated beta-silicon nitride, J. Ceram. Soc. Jpn. 112 (2004) 14901494. [13] H.M. Rosenberg, Oxford Physics Series, The Solid State Third Edition, Oxford University Press, 1988. [14] P.G. Klemens, Theory of thermal conduction in dielectric solids: effects of radiation damage, Nucl. Instrum. Meth. Phys. Res. B1 229 (1984) 204208.