Bi 2 O 3 Sb 2 O 3 Æ ZnO Ô Ø

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1 Ù 10 Vol. No Ú ACTA METALLURGICA SINICA Oct. 00 pp Bi O 3 Sb O 3 Æ ZnO Ô Ø 1,) 1) 1) 1) 1) Ludwig J. Gauckler ) 1) Ç ( Ñ), Ñ 03 ) Department of Materials Science, Nonmetallic Inorganic Materials, Swiss Federal Institute of Technology Zurich, Zurich CH 093, Switzerland À ( º Bi O 3 Sb O 3 º Ó) ZnO ³. µ, Bi ± (%, Â ), Sb ± ( ) ²È, «Æ ZnO Î, ±Ó²È, ³ ¹ Ü ÈÓÞÖ Ú²È; Sb ± (3%, Â ), Bi ± ²È, «Æ ZnO ²È ± ÓÎ, ³ ¹ Ü ÈÓÞÖ ÚÎ. ÀÈ ³ ÊÃ : Ë ¹ 11 GPa, Ï ¹ 115 GPa, Ü ÈÓ 10 MPa, Ö 1.7 MPa m 1/. Ð ZnO, Bi O 3, Sb O 3, º, ÆÃ, Ð Ó TB Đ Ü A Đ Ï (00) INFLUENCE OF Bi O 3 AND Sb O 3 DOPING ON MECHAN- ICAL PROPERTIES OF ZnO BASED COMPOSITES PENG Zhijian 1,), YANG Yiyong 1), WANG Chengbiao 1), FU Zhiqiang 1), MIAO Hezhuo 1), Ludwig J. Gauckler ) 1) School of Engineering and Technology, China University of Geosciences, Beijing 03 ) Department of Materials Science, Nonmetallic Inorganic Materials, Swiss Federal Institute of Technology Zurich, Zurich CH 093, Switzerland Correspondent: PENG Zhijian, professor, Tel: (010)3055, pengzhijian@cugb.edu.cn Supported by the Scientific Research Foundation for the Returned Overseas Chinese Scholars, Ministry of Education, and Cooperation Foundation for Industry, University and Research Institute, Guangdong Province and Ministry of Education (No.007A03010) Manuscript received , in revised form ABSTRACT Three series of ZnO based varistor materials with different doping levels of Bi O 3 and Sb O 3 were prepared, and their mechanical properties were measured. Under %Bi (atomic fraction), with increasing amount of Sb in an appropriate range, the ZnO grain size decreases, the porosity almost has no change, and the relative density increases. As a result, the modulus, bending strength and fracture toughness increase. Under 3%Sb (atomic fraction), with increasing amount of Bi, the grain size and porosity increase, thus the relative density decreases, which results in the decrease of modulus, bending strength and fracture toughness. The optimum ZnO based composite has elastic modulus of 11 GPa, flexure modulus of 115 GPa, bending strength of 10 MPa, and fracture toughness of 1.7 MPa m 1/. KEY WORDS ZnO, Bi O 3, Sb O 3, dopant, composite ceramic varistor, mechanical property ZnO ÇÄ ¹ Ô ZnO Õ ( Bi, * ± ÞÑÂÑ ³ ÐÞ ±¼ Ñ Í ½ 007A03010 Á ÅÏ : , ÅÏ : ÌºÍ : É,, 19 Û,, Sb, Co, Mn, Ni, Cr, Al ß À ) Õ¾ Å Ü ± ÆÎ Ä, ÀÅ ³½ È Ð³ ( ohm ) ß Å. À Î ßÅ³½ Ð Ü Ðßß³É, ÜË¼ Đ ß, À, ZnO ÇÄ ½ È Äß Ã Ä À

2 1 Ù «ÄÒ [1 ]. ÄÁ Matsuoka [5] 1971 ² Ü Bi O 3, CoO, MnO, Cr O 3 Sb O 3 ZnO ± Ø È ß, ¹Û ÍÚ Å», ß Ò¼ È ; ¾Æ, ÉÛ ÒÕ ÍÒ µ Ò È Ý ¾ É ¹ ³Ó [ 11]. ZnO ÇÄ Đ, Í É ÕÐ Ì ¹ Ð, ± Ó½Ü É ± : Ç Ä ÅÐ Ö² Ý Î Ü Á,» Û ± Ô Ô Ü Áµ [1,13]. µ Ò Ü Ø¾Ô, Ø Ø Ç, Ü¾Æ¼ ³ ¹Õ [1 1]. ØÁ (» Bi O 3 Sb O 3» Ô) ZnO Å ÇÄ, ¼ÒÕ» Ú ZnO Å ± Ì. Å¾ Ô Ã, Ý ÉÔ Æ» µ 0 30 MPa, µ MPa m 1/, 5%, ÇÄĐ µ 50%. 1 Û Ô ØÁ ß : CB(º Bi ² ) CS(º Sb ² ) CZ(º ZnO ² ).» Bi O 3, Sb O 3» Ô Å ± É 1. ZnO ² Bi O 3, Sb O 3 ß, Õ¾ Ç Zn Ã ÃÅ, ZnO ZnO ² ( ) 95%. ZnO, Bi O 3, Sb O 3 ß À» Fe O 3, Co O 3, NiO, Cr O 3 Û Æ. 1 º Ö È Table 1 Compositions of the designed ZnO based varistor materials (atomic fraction, %) No. Group CB Group CS Group CZ Bi Sb ZnO Bi Sb ZnO Bi Sb ZnO µ ¼±, Æ [17]. À, Å ZnO ÐÅ Ä 1. µm; Ô Ý 0 Å/h, 0 Å/h, Ë ÔÅ 1115 Å h. ± Ô», ÒÊ» ( Æ Ò»Û 1 µm)» 3 mm mm 0 mm. É 10,. À, ÜÆ Ý ÉÔ º, ÜÆ ( ). Ð, Û«¹ ISO 1573 Â Ü³²ÆÓÜ mm Ú V. ÊÉ ²Ô Ð,». ÊÉ D/max 550 X ÖÈÓÖÝ (XRD, Cu K α ), ÀÆ Ð 10 /min. ²Ô Archimedes «¹ Â ISO 175, ÊÚ²Ô ²Ô ²Ô. À, ²ÔÁ Ð, Æ Ô Sb O 3 ² ¾ ÊÐ Ê Zn 7 Sb O 1, À Bi O 3 ZnO. LEO 1530 Ð Ó (SEM). ( Æ Ò»Û 1 µm). ÐÅÉ Lince PC Á SEM ½Ï. Û Ñ «ßÖ.1 Sb Þ Ú Õ Ù Å ½ 1 Bi» Ô ( Ã ) % º Ã,» Sb» XRD. Á½ß, Sb» ³Å, Å Ô ÊÐ Ê ( É Zn 7 Sb O 1, ÂÓ² Õ Cr, Mn, Co, Ni, Bi [1,19] ) ² ³É. ½ SEM Ï À, ½ Ñ «Bi Ê, Ñ ÅÐ, Ñ ZnO, Ç Ñ ÊÐ Ê (Ã»); ½ 3 ²Ô Sb» ¾., Sb» ³Å, Ô ZnO ÐÅ Ï, ZnO Ð ÊÐ Ê ÐÅ É [17] ; Í Sb O 3» Đ Ð, ZnO ÐÅÏ, ÜÔ ÅÐ ¼ ¾, ÊÚ²Ô ³É; Ê Í Sb» ( Ã ) 5.0% Ð, Ô ÅÐ Å ³É (½ g), ²ÔÃ (½ 3), ¼ß ÊÐ ÊÐ ÐÅ É Á. Relative intensity, a.u. z ZnO b Bi O 3 s Spinel Zn 7 Sb O 1 CB1 CB CB3 CB CB5 CB CB7 b s z z s bz z z z s z CB , deg 1 º Sb º ÓÂÖ XRD z,b Fig.1 XRD patterns of ZnO based varistor materials with %Bi (atomic fraction) and different amounts of Sb

$10 È : Bi O 3 Sb O 3 ¹ Ø ZnO «Ë 17 Apparent density, g/cm 3 5.70 5. 5. 5. 5. 5.0 5.5 5.5 Apparent density Relative density.0 99.5 99.0 9.5 9.0 97.5 97.0 5.5 9.5 1.5.0.5 3.0 3.5.0.5 5.0 5.5.0 Atomic fraction of Sb, % Relative density, % 3 ZnO ÆÃ³ ±Ó ÉÙ±Ó Sb º Ó Ë Fig.$

3 10 È : Bi O 3 Sb O 3 ¹ Ø ZnO «Ë 17 Apparent density, g/cm Apparent density Relative density Atomic fraction of Sb, % Relative density, % 3 ZnO ÆÃ³ ±Ó ÉÙ±Ó Sb º Ó Ë Fig.3 Densities and relative densities of ZnO based varistor materials as a function of Sb content (Bi content is constant of % in atomic fraction) 10 (a) Flexure modulus Elastic modulus Modulus, GPa Grain size, m (g) Grain size Porosity Atomic fraction of Sb, % º Sb º ÓÂÖ Ä ÎÉ Ã ³ À Fig. SEM images and measured grain sizes and porosities 10 Porosity, % of ZnO based varistor materials with %Bi (atomic fraction) and different amounts of Sb (a) polished sample with %Sb (b) fracture sample with %Sb (c) polished sample with.5%sb (d) fracture sample with.5%sb (e) polished sample with 5.5%Sb (f) fracture sample with 5.5%Sb (g) grain sizes and porosities ½ ZnO ± Å Ì º º Ý ÉÔß Sb ² ¾. Á½ß, Sb» ³Å, Ì º, MPa m 1/ (b) Benidng strength Bending strength, MPa Atomic fraction of Sb, % ZnO ÆÃ³ Sb º Ó Ë Fig. Mechanical properties of ZnO based varistor materials as a function of Sb content (Bi content is constant of % in atomic fraction) (a) elastic and flexure moduli (b) toughness and bending strength º Ý ÉÔß Û ³É; Ê Sb» Î ÉÔÃ. ÊÐ ZnO» ÙØ Å, À¾ Å Ù, À, ¾ Ð Û, ¾» Ù Å, ¾ É.» Ð, Å Sb O 3 Û, ZnO ± Å Ô º ; Ê, Sb O 3»» ²Ô Ã Î ¾

4 1 Ù º Ï. Sb O 3» ÕÐ, Û Sb O 3 Å, Å ² ÅÐ ¾ É ZnO ÐÅÏ Ì º ³É ÊÐ ÊÐÐ¾ Ì, Ô Ý ÉÔ³É, Ê Ù³É. Ê, Í Sb O 3» Ð, Ô ÅÐ Å ³É, ²Ô Ã, Ô ÉÔÃ. À, ZnO ÐÅĐ ÝÊ À ÅÛ, Ë Þ Ð ÝÊ Û, Ô, É. Ô, ÊÐ Zn 7 Sb O 1 ¼ Í Ãß Ô Ð, ¼ ZnO Å µ.. Bi Þ Ú Õ Ù Å ½ 5 Sb» Ô 3%( Ã ) º Ð,» Bi» XRD. Á½ß, Bi» ³Å, Û «Bi ÐÐ Ê [17]. ½ SEM Ï À, ½ 7 ²Ô Bi» ¾., Bi» ³Å, ZnO ÐÅ³É, À Ô ÐÛÊ ³ÅÂ ÐÅÜ [17] ; Å Ð Ý Ç³Û ²ÔÃ, ¼ ZnO ÐÅ³ É, Ë Ð ÛÊ Ð Á Í, Ì ÅÐÜ Ã É ÅÐ [17]. À, ²Ô³É, ÊÚ²Ô Ï (½ 7). ½ ZnO ± Å Ì º º Ý ÉÔß Bi» ¾. Á ½ß, Bi» ³Å, Ì º º Ý ÉÔß Û Ï. ØÁ Bi» Đ, ËÄ : Ì º 11 GPa, º 115 GPa, Ý ÉÔ 10 MPa, 1.7 MPa m 1/. Bi O 3» ³Å, «Bi ÐÐÊ³Û, Î Ð, Ü ÔÓÙÎ ¾. À, º Ï, Ý ÉÔ ÙÊ. ÜË, ÅÐ Ý ²ÔÃ Ç Relative intensity, a.u. CS5 z z z z CS bs b s b z,bzz z z z CS , deg 5 º Bi º ÓÂÖ XRD z ZnO b Bi O 3 s Spinel Zn 7 Sb O 1 CS1 CS CS CS3 Fig.5 XRD patterns of ZnO based varistor materials with 3%Sb (atomic fraction) and different amounts of Bi Grain size, m (e) Grain size Porosity Atomic fraction of Bi, % º Bi º ÓÂÖ Ä Î Ã³ À Fig. SEM images and measured grain sizes and porosities Apparent density, g/cm Porosity, % of ZnO based varistor materials with 3% Sb (atomic fraction) and different amounts of Bi (a) polished sample with 0.5%Bi (b) polished sample with 3.5%Bi (c) fracture sample with 0.5%Bi (d) fracture sample with 3.5%Bi (e) grain sizes and porosities Apparent density Relative density Relative density, % Atomic fraction of Bi, % 7 ZnO ÆÃ³ ±Ó ÉÙ±Ó Bi º Ó Fig.7 Densities and relative densities of ZnO based varistor materials as a function of Bi (content of Sb is constant of 3% in atomic fraction)

$5 1.0 1.5.0.5 3.0 3.5 Atomic fraction of Bi, % ZnO ÆÃ³ Bi º Ó Ë Fig.$

5 10 È : Bi O 3 Sb O 3 ¹ Ø ZnO «Ë 19 Modulus, GPa, MPa m 1/ 10 (a) Flexure modulus Elastic modulus (b) Bending strength Bending strength, MPa Atomic fraction of Bi, % ZnO ÆÃ³ Bi º Ó Ë Fig. Mechanical properties of ZnO based varistor materials as a function of Bi (content of Sb is constant of 3% in atomic fraction) (a) elastic and flexure moduli (b) toughness and bending strength ³Û, Ý ÉÔß Ù Ï. À, ZnO ÐÅ Bi O 3» ³ÅÜ³É, Î ÝÊ («Bi ÛÊ) Å Û, Å Ð½Ü, Ô ÝÊ Ô Õ, À, Ý ÉÔ Ï [1]..3 Ý Î (Sb Bi) Õ Ù Å Á½ ß, Bi Sb» Ú ZnO Å ± Ô Ò Å Ì; À, Ú CZ, Zn Ã 95%, ÒÕ»» (Sb Bi) Ú Ì. ½ 9 Ê XRD. ½,» (Sb Bi) ³É, Å Ô ÊÐ Ê² ³ Å. ½ 10 SEM Ï À. ½ 11 ²Ô Sb Bi ¾. ß,» Sb Bi ³É, ZnO ÐÅ Ï, ÅÐ Ï, ²Ô³É, ËÛÎ : ZnO ÐÅ.05 µm, ÅÐ.9%, ²Ô 5.5 g/cm 3, ÊÚ ²Ô 99.5%. ½ 1 ZnO ± Å Ì º º Ý ÉÔß»» (Sb Bi) ¾. Á½ß,» (Sb Bi) Ý, Å Ì º º Ý ÉÔß Relative intensity, a.u. z,b z ZnO b Bi O 3 s Spinel Zn 7 Sb O 1 CZ1 CZ CZ3 CZ z CZ5 z z b z z bs b s s z z CZ , deg 9 º º (Sb Bi) Ö XRD Fig.9 XRD patterns of ZnO based varistor materials with Grain size, m 95% ZnO (atomic fraction) and different atomic ratios of Sb to Bi (e) Grain size Porosity Sb : Bi 10 º º (Sb Bi) ÂÖ Ä 10 Porosity, % Fig.10 SEM images and measured grain sizes and porosities of ZnO based varistor materials with 95% ZnO (atomic fraction) and different atomic ratios of Sb to Bi (a) polished sample with Sb Bi=9 1 (b) polished sample with Sb Bi= 3 (c) fracture sample with Sb Bi=9 1 (d) fracture sample with Sb Bi= 3 (e) grain sizes and porosities

6 170 Ù Apparent density, g/cm Apparent density Relative density Sb : Bi Modulus, GPa, MPa m 1/ 10 Relative density, % 11 º º (Sb Bi) ZnO ÆÃ³ ±Ó ÉÙ±Ó Fig.11 Densities and relative densities of ZnO based varistor materials as a function of the atomic ratio of Sb to Bi (content of ZnO is constant of 95% in atomic fraction) (a) Flexure modulus Elastic modulus (b) Bending strength Bending strength, MPa Sb : Bi 1 ZnO ÆÃ³ º º (Sb Bi) Fig.1 Mechanical properties of ZnO based varistor materials as a function of the atomic ratio of Sb to Bi (content of ZnO is constant of 95% in atomic fraction) (a) elastic and flexure moduli (b) toughness and bending strength Û ³É, ÙÒÎ : Ì º 115 GPa, º 10 GPa, Ý ÉÔ 117 MPa, 1.5 MPa m 1/. ZnO ² º Í Ã, À» (Sb Bi) ³É, Ô Sb» Ôµ Ü Bi» Ô, ¼Đ ÀÔ ½Ü Û ÊÐ Ê, ÛÊ ( ÐÊ) Õ. ÁÆ³ ² ß¾, ÊÐ ÊÚ ZnO ÐÅÜ Í, Đ ZnO ÐÅÏ ; ÛÊ ÏÕ, ĐÔ ÁÍ ÛÊ«ÜÎ ÅÐ, ĐÔ ²Ôµ. À, ZnO Å º (Ì º º ) ³É, ÉÔ ( ß Ý ÉÔ) ³É. 3 ÑÖ (1) Bi ² (%, Ã ) º, Đ, Á Sb» ³É, ZnO ÐÅ Ï, ÜÔ ÅÐ ¼, ÀÊÚ²Ô³É, ± Å º ³É ÉÔ³É. () Sb ² (3%, Ã ), Á Bi» ³É, ZnO ÐÅ³É, ÅÐ ³É, Ê ± ²ÔÏ, Å º Ï ÉÔ. (3) ZnO ² (95%, Ã ), Á Sb Bi ³É, ZnO ÐÅÏ, ÅÐ Ï, ²Ô³É, ÊÚ²Ô Ï, Ò Î, Å º ÉÔÙÒ ³É. () ØÁ É Đ, ZnO ÇÄ ËÄ : Ì º 11 GPa, º 115 GPa, Ý ÉÔ 10 MPa, 1.7 MPa m 1/. ÒĐ [1] Gupta T K. J Am Ceram Soc, 19; 73: 117 [] Levinson L M, Philipp H R. Am Ceram Soc Bull, 19; 5: 39 [3] Einzinger R. Annu Rev Mater Sci, 197; 17: 99 [] Clarke D R. J Am Ceram Soc, 1999; : 5 [5] Matsuoka M. Jpn J Appl Phys, 1971; 10: 73 [] Park J S, Han Y H, Choi K H. J Mater Sci, 005; 1: 15 [7] Pfeiffer H, Knowles K M. J Eur Ceram Soc, 00; : 1199 [] Anastasiou A, Lee M H J, Leach C, Freer R. J Eur Ceram Soc, 00; : 1171 [9] Chen C S. J Mater Sci, 003; 3: 1033 [10] Ott J, Lorenz A, Harrer M, Preissner E A, Hesse C, Feltz A, Whitehead A H, Schreiber M. J Electroceram, 001; : 135 [11] Kutty T R N, Raghu N. Appl Phys Lett, 199; 5: 179 [1] Akbar M, Ahmad M. Electr Power Systems Res, 1999; 50: 79 [13] Ramirez M A, Bueno P R, Ribeiro W C, Varela J A, Bonett D A, Villa J M, Marquez M A, Rojo C R. J Mater Sci, 005; 0: 5591 [1] Balzer B, Hagemeister M, Kocher P, Gauckler L J. J Am Ceram Soc, 00; 7: 193 [15] Begum S, Hashmi M S J. J Mater Process Technol, 005; 17: 5 [1] Ferraris M, Verné E. J Eur Ceram Soc, 199; 1: 1 [17] Peng Z J, Wang C B, Gauckler L J, Miao H Z. Key Eng Mater, 00; 3 37: 79 [1] Wong J. J Appl Phys, 1975; : 153 [19] Olsson E, Falk L K L, Dunlop G L, Sterlund R O. J Mater Sci, 195; 0: 091

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