Effect of Combined Additives of CaF 2 -Y 2 O 3 on Microstructrue and Thermal Conductivity of AlN-BN Composite Ceramics

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1 23 Â 3 µ ¾ Û Vol. 23, No À Journal of Inorganic Materials May, 2008 Ê Æ : X(2008) ¹ ¼ CaF 2 -Y 2 O 3 AlN-BN ¹Ã ÍÇ Đ (ÞÕÙÓÐ ÚÒÖß ÝÔØ ÑÛÐÜ ÞÕ ) ¼ Ø AlN-BN ¼ ¾Û CaF 2 Y 2O 3 ² Å Ø ² ÅÐ Ô Ñ ¼ ¾ÛÐÄ Å ² Ø Ð ¼ Å (1 3)wt%Y 2O 3-3wt%CaF 2 ÐÐ Ä Ê Õ ÒØ¼ ¾ÛÐ Ø¼ ¾ÛÕ AlN ÞÞØ Ð AlN-BN ¼ ÑÆ CaF 2 ÅÐÐ ¼ ÅÐÐ Ðº Ø Í ¼ Å (1 3)wt%Y 2O 3-3wt%CaF 2 Õ Y 2O 3 ÔÐÉ AlN-BN ¼ Ð Ø ¼ Å 3wt%Y 2O 3-3wt%CaF 2 ÐÐ Ä 1850 C Í 3h ÞÞÐ Ø 132.7W m 1 K 1. ² ¾ AlN-BN; ² Ø ¼ Å CaF 2-Y 2O 3 Æ TQ174 Ê Á A Effect of Combined Additives of CaF 2 -Y 2 O 3 on Microstructrue and Thermal Conductivity of AlN-BN Composite Ceramics ZHAO Hai-Yang, WANG Wei-Min, FU Zheng-Yi, WANG Hao (State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Science & Technology, Wuhan , China) Abstract: AlN (Aluminum nitride)-bn (Boron nitride) ceramic composites were prepared by hotpressing in nitrogen atmosphere at 1850 C. Different contents of CaF 2 and Y 2 O 3 were added as sintering additives. The effects of sintering additives and soaking time on crystalline phase, microstructure, and thermal conductivity of AlN-BN composite were explored. The experimental results show that the AlN-BN composites with combined sintering additives CaF 2 -Y 2 O 3 are pure AlN and BN phases, and the grain boundaries evaporate at high sintering temperature. The dielectric properties of the AlN-BN composites with combined sintering additives Y 2 O 3 -CaF 2 decrease little, comparing with that of the AlN-BN composites with CaF 2 additive. The thermal conductivity is increased with Y 2 O 3 contents increasing in the combined sintering additives of Y 2 O 3 -CaF 2. When AlN-BN ceramic composites with 3wt%Y 2 O 3-3wt%CaF 2 is sintered at 1850 C for 3h, its thermal conductivity of reaches 132.7W m 1 K 1. Key words: AlN-BN; thermal conductivity; microstructure; combined sintering additive; CaF 2 -Y 2 O 3 1 Õ Ó Å Þ ÝË Þ «AlN-BN ½ À Ò» Ù Þ Ø ½¼ ÙĐ µ¹µ Ý [1,2]. Ö AlN Õ Á ÅÎ Ã ÁÙ Ì [3]. Ò BN ¹ Õ Å ² Ø ³ Å ßß AlN-BN ½ Ö ÙĐ «ß ß ³ ÇÉ¾ ÓÅ ¾½ Đ ÓÅ ³ «««AlN Al 2 O 3 BN Ö B 2 O 3 Õ Ù Ø Ó ÐÝ Â Æ , Â Æ » Æ ¼ÍÒ Đ (PCSIRT0644); ÒÛ ¾ÚÀ Đ (NCET ); ¼ Ú ¼ ( ) ½ Æ ÍÍ (1981 ), Ú Å zhyxx2008@sina.com Å Ì Æ «Å wangwm@hotmail.com

2 3 µ ÌÌÆ ¼ Å CaF 2-Y 2O 3 AlN-BN ¼ ² ØØ Ð 497»ÅĐ Ö Û Ï Ý ÙĐ [4]. ¼ µ Ã ± Þ Ý Ù ÂÓ Ç Õ [5 8] ; Ò Å ³ËÀÖ BN Ó [8 10]. Ï [11], CaF 2 «Í AlN-BN ½ Ý ÙĐ«Æ ß ³ «Þ AlN-BN ½ Ý ÙĐ ß ½ «Å AlN BN ÝÖ CaF 2 Y 2 O 3 ³ «½ ³ Ð AlN-BN ½ Ý Ù½ ³ «Ò ÝÅ «³ ÙĐ ¹ «2 À Ô ½ Â Tokuyama AlN (grade F, 3.31m 2 /g), Í Û BN (± Ä 0.34µm, >98.5%), Î Ó «CaF 2 ( >98.5%), Æ Ó «Y 2 O 3 ( 99.99%). AlN É Đ Õ Ä Á BN Å Õ «85wt%AlN-15wt%BN ÙÕ Ý ¹ Õ CaF 2 Y 2 O 3 «ZrO 2 Á Ï»Ó ÅÅ Ø Ü 24h ÎÞ Ü Ý À ÅÕ»» Ö «Đ 10 C/min, 1850 C 30MPa Î ³ 3h ßÚ φ50 (5±0.5)mm ÖÙ «Archimedes Å«Ö ½ TC-7000H Laser Flash Thermal Constant Analyzer Ã Å ÌË Ë ßÅ ÙĐ«³ È Ö ½ D/MAX-R Ó X ««Ö½ SEM(JSM-5460LV, JEOL) EDX TEM (JEM-2010FEF, JEOL) È ³ «3 ³ Ä 3.1 AlN-BN º ± Ë ½ «(0 3)wt%Y 2 O 3-3wt%CaF 2 Ä ßßÙ ß Ä 3.00g cm 3. ¼ 1 ¹ «AlN-BN ½ X «¼ «È 3wt%CaF 2 Í ßß AlN-BN ½ Ý (Y0). Þ Ç CaF 2 AlN É Al 2 O 3 Ù AlF 3 Ca-N Ó Å Ö AlF 3 Å Î Ð Ca 3 N 2 Å ÎÀ Ø Ù [11 14]. 3wt%Y 2 O 3 (Y1) Ö É YAG(Y 3 Al 5 O 12 ) ¹ AlN Ö Y 2 O 3 Y-Al-O Ó Å Ü ¼ Ö [15] Ö Ü YBO 3 Y 3 BO 6 Ó Å Í Þ Õ Ë Å ³ ËÀÖ µø ³È«½ «(1 3)wt%Y 2 O 3-3wt%CaF 2 (Y2 Y3 Y4) Ä AlN BN, Å 1850 C ³ Î ½ «Ç Í Ö µø «¼ 2 ½ «3wt%Y 2 O 3-3wt%CaF 2 Å 1850 C ³ Ò Ò ³ ½ ÝÅ «¹ «Í 1h Ö É CaYAlO 4 YCaAl 3 O 7 ¹ Þ «CaF 2 Y 2 O 3 AlN Ö Al 2 O 3 Õ Y Ca Al O [12, 13] Ü «Å Ò Ú 3h Ò ßß AlN BN. Å ËÀÖ CaYAlO 4 YCaAl 3 O 7 Å Õ» ÖÜ µø «² AlN-BN ½ Ö Ç½ «CaF 2 - Y 2 O 3, Å 1850 C Î ³² 3h Ó«3.2 AlN-BN º ÎÈ ± Ë ¼ 3 (0 3)wt%Y 2 O 3-3wt%CaF 2 ½ ³ «AlN-BN ½ ³ ¹ «Í ÇÅ Ò CaF 2 (¼ 3(a)) ½ «CaF 2 -Y 2 O 3 Ç Ù AlN-BN ½ Ý Ó AlN BN É Õ BN» AlN É Ê«Y 2 O 3 Õ Ê É AlN É Ü ÏÕ ³ É È Þ Ê Ð «¼ 4 ¹ Ø ³ «AlN-BN ½ Ý Ï SEM Ì «Í ÇÅ Ò 3wt%Y 2 O 3 AlN-BN Ö Û Y Å ÄÁ» AlN É Ë Ê ³ XRD Å È Í Y 2 O 3 Í AlN Ö Al 2 O 3 Y-Al-O Ó Å ³ Ó Ã AlN Ö AlN É ÌÙÖ Ì ÙĐ [16]. ÖÅ ³ Ø Y-Al-O Ó ÅÜ É Ê Ç¹ ÙÙ «Å ½ «Y 2 O 3 -CaF 2 AlN-BN Ö Ö Y Å Å (¼ 4(b)), ³ Å È (¼ 1 ¼ 2) Í CaF 2 Ç Ù Y Å ³ Ø Ù ÓÙ ÙÉ È«²

498 ¾ Û 23 Â» 1 ÅÐ AlN-BN ¼ 1850 C 3h Ð XRD»³ Fig.

3wt%Y 2 O 3 ; Y2, 1wt%Y 2 O 3-3wt%CaF 2 ;Y3, 2wt%Y 2 O 3-3wt%CaF 2 ; Y4, 3wt%Y 2 O 3-3wt%CaF 2 )» 2 3wt%Y 2O 3-3wt%CaF 2

2 XRD patterns of AlN-BN composites with 3wt%Y 2O 3-3wt%CaF 2 sintered at 1850 C for different sintering times» 3 Y 2O 3

3 Effect of Y 2O 3 contents on the microstructure of the AlN-BN composites sintered at 1850 C for 3h (a) 3wt% CaF 2 ;

3 498 ¾ Û 23 Â» 1 ÅÐ AlN-BN ¼ 1850 C 3h Ð XRD»³ Fig. 1 XRD patterns of AlN-BN composites with different sintering additives sintered at 1850 C for 3h (Y0, 3wt%CaF 2 ; Y1, 3wt%Y 2 O 3 ; Y2, 1wt%Y 2 O 3-3wt%CaF 2 ;Y3, 2wt%Y 2 O 3-3wt%CaF 2 ; Y4, 3wt%Y 2 O 3-3wt%CaF 2 )» 2 3wt%Y 2O 3-3wt%CaF 2 Ð AlN-BN ¼ Ä 1850 C Ñ Ð XRD»³ Fig. 2 XRD patterns of AlN-BN composites with 3wt%Y 2O 3-3wt%CaF 2 sintered at 1850 C for different sintering times» 3 Y 2O 3 ² Å AlN-BN ¼ ¾Û ( 1850 C 3h) ² Ð Fig. 3 Effect of Y 2O 3 contents on the microstructure of the AlN-BN composites sintered at 1850 C for 3h (a) 3wt% CaF 2 ; (b) 1wt%Y 2 O 3-3wt%CaF 2 ; (c) 2wt%Y 2 O 3-3wt%CaF 2 ; (d) 3wt%Y 2 O 3-3wt%CaF 2»Ð ÆÌ ± Ñ Ñ Æ µð AlN-BN»½Ú TEM µ ÆÙ º 5. ºÔÌÆÄ Ô Ç ¾ Ó µº Ê É Æ» ±Ð TEM Î ÔÌ Â <50nm (º 5(b)). EDX ²µÆ Ô Y Ca O Ó È Ý Al N Ð Æ Y 2 O 3 TEM EDX µæ±ç (º 5(a) (c)), Ì CaF 2 ³Æ Ô Y Ã Ö ± µ Ö Ñ»½Ú [17] ²É XRF µæ 1650 C É Ô Æ (CaY)F 3 AlN ± Ô Ca Y Ö [12 14] Ä Ì AlN Ô Y-Al-O Ca-Al-O ÑÃµ Ö

3 µ ÌÌÆ ¼ Å CaF 2-Y 2O 3 AlN-BN ¼ ² ØØ Ð 499» 4 Y 2O 3+CaF 2 ² ÅÕ CaF 2 Ô AlN-BN ¼ ¾Û ( 1850 C 3h) ² Ð

at 1850 C for 3h (a) 3wt%Y 2 O 3 ; (b) 3wt%CaF 2-3wt%Y 2 O 3» 5 AlN-BN ¼ ¾Û ( 1850 C 3h)TEM Ç Fig.

O 3 ; (c) and (d) EDX spectra at the triple grain junctions of point a and b in (a) and (b) ± Ä µ Ó Ô

Y-Ca-Al-O Ñ Ã Ô Ô Ñ Ö µ AlN-BN» ½ ÚÔ Ý Y-Ca-Al-O ÑÃ YCaAl 3 O 7 CaYAlO 4, Ã»Ì Ì Ö» É Ì»ÑÐ (1) (2) Å µð

4 3 µ ÌÌÆ ¼ Å CaF 2-Y 2O 3 AlN-BN ¼ ² ØØ Ð 499» 4 Y 2O 3+CaF 2 ² ÅÕ CaF 2 Ô AlN-BN ¼ ¾Û ( 1850 C 3h) ² Ð Fig. 4 Effect of CaF 2 contents on the microstructure of the AlN-BN composites with 3wt% Y 2O 3 sintered at 1850 C for 3h (a) 3wt%Y 2 O 3 ; (b) 3wt%CaF 2-3wt%Y 2 O 3» 5 AlN-BN ¼ ¾Û ( 1850 C 3h)TEM Ç Fig. 5 TEM micrograph of AlN-BN composites sintered at 1850 C for 3h (a) 3wt%Y 2 O 3 ; (b) 3wt%CaF 2-3wt%Y 2 O 3 ; (c) and (d) EDX spectra at the triple grain junctions of point a and b in (a) and (b) ± Ä µ Ó Ô EDX º ² (º 5) µæ (º 4) XRD º ² (º 2) µæ Æ»Ð Ã 1850 C É Ô Y-Ca-Al-O Ñ Ã µ 3h ÌÝÝ AlN-BN» Ì ÝÃ Ôº³Ì Y-Ca-Al-O Ñ Ã Ô Ô Ñ Ö µ AlN-BN» ½ ÚÔ Ý Y-Ca-Al-O ÑÃ YCaAl 3 O 7 CaYAlO 4, Ã»Ì Ì Ö» É Ì»ÑÐ (1) (2) Å µð YCaAl 3 O 7 Ì Ôº ÃÒÖ Ä (3): YCaAl 3 O 7 (l)+n 2 (g)+3c(g) CaYAlO 4 (l)+2aln(s)+3co(g) (1) 3CaYAlO 4 (l)+4n 2 (g)+12c(g)

5 500 ¾ Û 23 Â 3YN(g)+3AlN(s)+12CO(g)+Ca 3 N 2 (g) (2) 3CaYAl 3 O 7 (l)+7n 2 (g)+21c(g) 3YN(g)+9AlN(s)+21CO(g)+Ca 3 N 2 (g) (3) 3.3 AlN-BN µ Æ Y 2 O 3 Ó È Æ Æ» ± Ð AlN-BN» ½ Ú Ð È Ü Æ 3wt%CaF 2-3wt%Y 2 O 3 Ý Ý Ð 132.7W m 1 K 1. Masahiko Tajika [18] Á Ü AlN µº AlN Ð ± Ü Ë³ ²Û AlN-BN» Ô AlN Ý Ð BN, ± AlN Î È Ç¾ ² ÝÝ Ð AlN-BN» Y 2 O 3 ³ ÆÌ CaF 2» ±Ð» ±Ð Ñ» ÕÝ Ë È ½ Ô AlN ± Ý Ð AlN Ô Ç ² È ½ ± Ñ Ô Đ Â ÎÝ AlN-BN»½Ú Ð Ý ± ½Ú ¹ Æ Ð Æ 3wt%CaF 2 AlN-BN» ½ Ú ¹ ¹ Ã 1MHz Ì µ ³ Æ» Ð 3wt%CaF 2-3wt%Y 2 O 3 AlN-BN»½Ú ¹ ¹ Ã 1MHz Ì µ Ð Æ CaF 2 Ð» Ð CaF 2 -Y 2 O 3 Æ Ã º AlN-BN»½Ú ÐÆ ½Ú ¹ Ì» 6 AlN-BN Ð Ð Ø ¼ ² ÅÕ Y 2O 3 ÔÐÀÊ Fig. 6 Effect of Y 2O 3 contents on thermal conductivity of AlN-BN composites with 3wt% CaF 2 sintered at 1850 C for 3h 4» Ã 1850 C 3h ± 85wt%AlN-15wt%BN» ½ Ú Æ Ð CaF 2 AlN BN Æ Y 2 O 3 ÔÔ Y-Al-O Æ»Ð CaF 2 -Y 2 O 3 Ã 1850 C É ÔÆ Ð Y-Ca-Al-O Ì Ö Ñ»½Ú AlN 3h ÌÝÝ AlN-BN»½Ú»Ð Ô Y 2 O 3 Ó ÈÆ Ô AlN BN È Ð ß 1850 C Ì 3h Æ» Ð 3wt%CaF 2-3wt%Y 2 O 3 ÝÝ Ð 132.7W m 1 K 1 AlN-BN»½Ú ÉÏ [1] Slack C A. J. Phys. Chem. Solids, 1973, 34 (2): [2] Karen A. Cummings., Subhash H. Risbud. Journal of Physics and Chemistry of Solids, 2000, 61 (4): [3] Virkar A V, Jackson T B, Cutler R A. J. Am. Ceram. Soc., 1989, 72 (11): [4] ÕÐ Ñ º Å ÜÊĐ 2002, 20 (2): [5] Æ ßÙ Ò (QIN Ming-Li, et al). Ä Đ (Journal of the Chinese Ceramic Society), 2003, 30 (10): [6] ± «ÅÂ ĐĐ 2006, 28 (1): 1 3. [7] Jin Hai-Yun, Wang Wen, Gao Ji-Qiang, et al. Materials letters, 2006, 60 (2): [8] Zhang Guo-Jun, Yang Jian-Feng, Motohide Ando, et al. J. Am. Ceram. Soc., 2002, 85 (12): [9] Takao Kanai, Kei Tanemoto, Hiroshi Kubo. Japanese Journal of Applied Physics, 1990, 29 (4): [10] ËÏ¾ (YE Nai-Qing, et al). Ä Đ (Journal of the Chinese Ceramic Society), 1998, 26 (2): [11] ÍÍ «¾ (ZHAO Hai-Yang, et al). À ÜĐ (Journal of Inorganic Materials), 2008, 23 (1): [12] Peter Greil, Michael Kulig, Dachamir Hotza. J. Eur. Ceram. Soc., 1994, 13 (3): [13] Ú Ú (ZHOU He-Ping, et al). À ÜĐ (Journal of Inorganic Materials), 1995, 10 (4): [14] Qiao Liang, Zhou He-Ping, Fu Ren-Li. Ceramics International, 2003, 29 (8): [15] Îµ Ú«ÅÄ ³ 2003, (2): [16] Yu Ying-Da, Aase Marie Hundere, Ragnvald Høier, et al. J. Eur. Ceram. Soc., 1994, 22 (2): [17] Ñ Ú ß Á Å Ü 2000, (10): [18] Masahiko Tajika, Hideaki Matsubara, William Rafanicllo. J. Am. Ceram. Soc., 1999, 82 (6):

» LiNi 0.5 x Co 2x Mn 0.5 x O 2 Æ º

«22 «5 Æ Ç Vol. 22, No. 5 2007 À 9 ³ Journal of Inorganic Materials Sep., 2007 Ç : 1000-324X(2007)05-0873-06» LiNi 0.5 x Co 2x Mn 0.5 x O 2 Æ º ÔÒ Ó Ð Ó Ñ ( Ï 410083) Æ Ã Ç ÊÉ É Ni 0.5 xco 2xMn 0.5 xco