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1 Jurnal f the Krean Ceramic Sciety Vl. 44, N., pp. 110~115, 007. Micrwave Dielectric Prperties f BaNd - BaO-B -K O-SiO -xtio Glass Cmpsites Dng-Eun Kim,*, ** Sung-Min Lee,* Hyung-Tae Kim,* and Hyung-Sun Kim** *Krea Institute f Ceramic Engineering and Technlgy, Seul , Krea **Schl f Materials Engineering, Inha University, Inchen , Krea (Received December 4, 006; Accepted January 10, 007) BaO-B -SiO -K O-xTiO Glass ƒ w BaNd -Glass w j q p ½ *, **Á * Á½xk*Á½x ** * ( )»» q ** w w œw ( ; ) ABSTRACT The effects f TiO in the glasses n the shrinkage and dielectric prperties f BNT-glass cmpsites have been investigated. Withut TiO additin, BNT-glass cmpsite shwed tw humps in the shrinkage curve, which are related with crystallizatin f BaTi(B and Bi 4. Hwever, the increase f TiO additin resulted in the decrease f nd hump in the shrinkage. The increased dielectric cnstant with TiO additin might be due t the reduced crystallizatin f Bi 4. A dielectric cnstant f 5, a quality factr f 5088 GHz, and a temperature cefficient f resnant frequency f 0.16 ppm/ C were btained fr a specimen cntaining TiO -added glasses, withut sacrificing the benefits f high ε r and lw TCF f BNT ceramics. Key wrds : LTCC, Micrwave, Dielectric prperties, Glass, TiO 1. m t xy, š y, ƒ y v wš, e w t m l w w w t š. wz m l GHz lq w m t xy yƒ v w, w w» w d ƒ ƒ w (lw temperature c-fired ceramic, LTCC)». xy w 1-10) t j» w x w w w. 1) x š ƒ BaO-TiO, pk yw, w r e p w, p BaO-TiO Crrespnding authr : Sung-Min Lee smlee@kicet.re.kr Tel : Fax : BNT) m ƒ BaO-Nd -TiO ( w l w œ q (τ f =6.) (ε r =90) ƒ LTCC y w ƒ. -5) w, BNT ƒ 1300 C LTCC Ag(961 C) ù Cu(1083 C) w». j q p w BNT» p w Ag (900 C w) j û» w v ƒw š. ù 6-9) 900 C w 50 š w p glass y mw p e w w w. 6-10) BNT w p y w LTCC w wš w TiO w y g» p y š w. TiO w p w, w BNT w w p š w. w w p, mw 110

2 BaO-B -SiO -K O-xTiO Glass ƒ w BaNd -Glass w j q p 111 p w w š wš w.. x x BaC, B, SiO, K C, TiO ( 99%, Kjund Chemical Labratry C. Ltd., Japan) w š, BNT p w» w BaO Bi ƒ ey (MBRT-90, Fuji Titanium Industry C. Ltd., Japan) w (Table 1). x» 30BaO-40B -0K O- 10SiO (ml%) kw TiO BaO 0~1.0 j Table 1. Cmpsitin and Prperties f MBRT-90 Cmmercial Ceramic Pwder frm Fuji Titanium Industry C. Ltd. Chemical frmula BaTi +Nd (Ti +Bi (Ti Ingredients Micrwave characteristics (at 0 C) BaTi Nd (Ti Bi (Ti MnO, Al, SiO H O ε r 90 Q f 0 (GHz) 6140 τ f (ppm/ C)+0~+80 C 6. 5 wt% 59 wt% 15 wt% Max. 1 wt% Max. 0. wt% Table. Chemical Cmpsitins f Glasses Used in This Experiment Cmpsitin (ml%) BaO B SiO K O TiO TiO /BaO (Glass cde) (00T) (0T) (04T) (06T) (08T) (10T) Table 3. DTA Analysis Results Item ƒ k ù yww w (Table ). ƒƒ yw ƒ w» ü 1300 C g. q þ k z e, g p g planetary mill w 1 w s³ 0.8 µmƒ w.» w (0 wt%) BNT (80 wt%) k g wì yww 4 w,» w yw. yw 10 mm, Ì 5mm ƒ xw z, CIP mw 00 MPa x w. x 5 C/min 800 C, 850 C, 900 C, 950 C w. j (Archimedes) w w. w r SiC w 3µm r p wš FE-SEM(JSM-6700F, JEOL, Japan) w w. p w» w e(differential Thermal Analysis, Q600, TA, USA), dilatmeter(l76, Linseis, Germany) w 10 C/min» 1000 C¾ d w. X- z»(d/max-500/pc, Rigaku, Japan) w θ=10~70 4 /min z ql w. š q p netwrk analyzer(870es, Agilent, USA) w d w š, Hakki- Cleman 11) sx q (pst resnatr methd), t (Q f) (Tcf) œ œ» (transmissin cavity methd) d w. 3. m 3.1. p Table 3 ƒ (T g ) y ùkü. T g TiO (T p ), (T l ) T g T p T Activatin l energy (Kcal/mle) Heating rate( C/min) Glass cde T T T T T T «y(007)

3 11 ½ Á Á½xkÁ½x Fig. 1. X-ray diffractin patterns f glasses heat-treated at 750 C fr h with respect t TiO additin. ƒ j 550 C w ùkü. ù y š (T p ) TiO ƒ š w. w w 3 C, 5 C, 10 C, 15 C 0 C/min T p d w š, lnβ y 1/T p š l»» y y w (Table 3). 1) 750 C g y k z X- z mw w (Fig. 1). TiO ƒw 00T BaB O 4 (JCPDS Card #38-07) ùkû. TiO ƒw 04T Ba TiSi O 8 (JCPDS Card #70-190), BaTi(B (JCPDS Card #35-085)ƒ ùkû, TiO ƒ BaTi(B ƒ yw (08T). Fig. z 10 C 1 z þw w 00T 08T j w, œ q d w. Ti/Ba ƒ ƒw ƒw ù s 1%. w % ƒƒ š œ q 58 ppm/ C 3 ppm/ C. w p Ti/Ba w - w p x» w Fig. 3 TiO ƒ BNT w y š. (0 wt%) (80 wt%) yw w 560 C ùkû. 660~740 C Fig.. Micrwave dielectric prperties f bulk glasses with respect t TiO additin. Fig. 3. Shrinkage curves f the BNT-glass cmpsites under a heating rate f 10 C/min. x ùkû. w, 00T 0T, 04T 760~840 C w x. y (T p ) yw w y (T p1, T p ) TiO ƒ ù kü (Fig. 4). - w w. 00T š, 0~10T w (Fig. 1) - w 00T~04T¾ w wz

4 BaO-B -SiO -K O-xTiO Glass ƒ w BaNd -Glass w j q p 113 Fig. 4. T c and T p frm DTA results in the mixture pwder (0 wt% glass and 80 wt% ceramic) and the glass. Fig. 6. XRD pattern f BNT_00T cmpsites sintered at varius temperatures fr h. Fig. 5. XRD pattern f BNT_00T and 08T cmpsites sintered at (a) 700 C and (b) 800 C fr 5 min. peakƒ xw š, 06~10T¾ 1 peak xw. 800 C Fig wš 700 C 5 w BNT w XRD. w BaNd š BNT_00T w 700 C w ƒ BaTi(B x š, 800 C w BNT s w Biƒ w Bi 4 ùkû. BNT_08T 700 ~800 C BaTi(B x. ù, Fig. 4. Fig. 3 w y p w. BNT_00T, 0T, 04T w ƒ ùkù, 700 C z BaTi(B x ùkùš, hump 800 C BNT ey Bi Fig. 7. XRD pattern f BNT_08T cmpsites sintered at varius temperatures fr h. w Bi 4 x ùkù., BNT_06T, 08T, 10T w BaTi(B x w hump x q. 800~950 C w r w (Figs. 6, 7). BNT_00T w BaTi(B 900 C z l w š, Bi C z ƒ û. 08T w BaTi(B x 00T w, Bi 4. TiO ƒ w - w 900 C w r w y Fig. 8 ùkü. TiO ƒ ƒw 900 C w r w ù s 1%. Fig. 9 back scattered 44«y(007)

5 김동은 이성민 김형태 김형순 114 Fig. 8. Variatins f bulk densities f BNT-glass cmpsites sintered at 900C fr h. Fig. 10. Micrwave dielectric prperties f glass-ceramic cmpsites sintered at 900C fr h. 지를 통해 보여주고 있다. TiO 첨가량에 따른 입자크기 변화는 크지 않았다. EDX 분석 결과 BNT_00T 복합체의 경우 Bi-rich 상이 다수 관찰되었고 BNT_08T 복합체의 경우 Bi-rich 상이 거의 관찰되지 않았다. 유리-세라믹 복합체에서 유리 조성에 TiO 첨가량이 많 아질수록 유전율과 품질계수, 공진주파수 온도계수는 향 상됨을 보였다(Fig. 10). BNT_10T 복합체에서의 유전율 (ε )은 5.4, 품질계수(Q*f)는 5088 GHz, 주파수 온도계수 (τ )는 0.16 ppm/ C 값을 나타내었다. Fig. 에서는 08T 유리가 00T 유리보다 17%의 유전율 향상을 보였다. 이는 유리-세라믹 복합체에서 0 wt%를 첨가한 유리 함량을 고 려하면 유전율이 높은 Ti 함유 유리를 사용한 복합체에 서의 유전율의 증가가 3.4%로 예상되지만, 실제로는 17% 의 증가를 보였다. 즉, 복합체의 유전율 증가 효과는 유 리의 유전율 증가 때문만이 아님을 알 수 있다. 밀도는 유전율과 깊은 상관 관계를 가지고 있다고 알 려져 있다. Fig. 8에서는 밀도의 변화를 나타내었는데 유리에 TiO 첨가량이 증가할수록 900 C에서 소결한 시 편의 밀도는 감소하였다. 이는 결정화제인 TiO 의 첨가량 이 많아지면서 소성과정에서 유리 프릿의 연화에 의한 수 축 속도보다도 결정화로 인하여 치밀화가 방해받는 것으 로 생각하여 볼 수 있다. X-선 회절분석과 미세구조에서 나타나듯이 BNT_00T 복합체의 경우 BNT로부터 Bi O 의 용출과 TiO 와의 반응으로 인한 Bi Ti O (밀도 :8.045 g/cm ) r f 6-11) Fig. 9. Back scattered images f samples sintered at 900C fr h: (a) BNT_00T, (b) BNT_04T, and (c) BNT_08T (A: Bi4Ti3O1, B: BaTi(BO3), C: BaTiSiO8). 한국세라믹학회지

6 BaO-B -SiO -K O-xTiO Glass ƒ w BaNd -Glass w j q p 115 y w š, TiO ƒ ƒw Bi w. Fig. 9 w w y. BNT_00T w Bi-rich s y w, BNT_04T, 08T w w. BNT BaO-B -SiO - K O-xTiO yww w w e TiO w Bi 4 x w öe w w j w öe q. 4. BaO-B -K O-SiO -xtio BaNd yww yƒ LTCC p e w w. 00T BaB O 4ƒ ùkûš, TiO ƒ ƒw BaTi(B Ba TiSi O 8 ùkû. TiO ƒ ƒw ƒw. - w BNT_00T BaTi(B š, Bi 4 ùkû., BNT_08T w Bi 4 y w. TiO ƒ ƒw 900 C w - w w w ù j q p TiO ƒ w. BNT_10T 900 C w xr (ε r ) 5.4, t (Q f) 5088 GHz, š œ q (τ f )ƒ 0.16 ppm/ C. REFERENCES 1. C. Q. Scrantm and J. C. Lawsn, LTCC Technlgy: Where We Are and Where We're Ging-II, In IEEE Sympsium n Technlgies fr Wireless Applicatins, (1999).. S. Gabrscek and D. Klar, Cmpunds in the BaO-RE - TiO System, J. Mater. Sci. Lett., (198). 3. C. C. Cheng, T. E. Hsieh, and I. N. Lin, Effects f Cmpsitin n Lw Temperature Sinterable Ba-Nd-Sm-Ti-O Micrwave Dielectric Materials, J. Eur. Ceram. Sc., (004). 4. J. M. Durand and J. P. Bilt, Micrwave Characterisatin f BaO-Nd -TiO -Bi Dielectric Resnatrs, J. Mater. Sci. Lett., (1987). 5. T. Jaakla, A. Uusimaki, R. Rautiah, and S. Leppavuri, Matrix Phase in Ceramics with Cmpsitin Near BaO Nd 5TiO, J. Am. Ceram. Sc., 69 C34-35 (1986). 6. D. S. He, W. S. Lee, S. J. Jeng, J. S. Sng, F. Utsun, and B. K. Ryu, Sintering and Dielectric Prperties f BaO- Nd -TiO Micrwave Ceramics with Glass-Ceramics(in Krean), J. Kr. Ceram. Sc., 41 [6] (004). 7. O. Dernvsek, A. Naeini, G. Preu, W. Wersing, M. Eberstein, and W. A. Schiller, LTCC Glass-Ceramic Cmpsites fr Micrwave Applicatin, J. Eur. Ceram. Sc., (001). 8. S. J. Hwang, Y. J. Kim, and H. S. Kim, Micrwave Dielectric Prperties f La -B -TiO Glass-Ceramic and BaNd Ceramic System fr LTCC Applicatin(in Krean), J. Kr. Ceram. Sc., 41 [8] (004). 9. Y. S. Oh, Y. S. Lee, W. H. Kang, B. H. Jung, and H. S. Kim, Sintering and Dielectric Prperties f K O-CaO-P O 5 Glasses-BNT(BaO-Nd -TiO ) Ceramic Cmpsites(in Krean), J. Kr. Ceram. Sc., 40 [10] (003). 10. C. H. Lu and Y. H. Huang, Densificatin and Dielectric Prperties f Barium Nedymium Titanium Oxide Ceramics, Mater. Sci. Eng., B (003). 11. B. W. Hakki and P. D. Cleman, A Dielectric Methd f Measuring Inductive Capacitance in the Millimeter Range, IRE Trans. Micrwave Thery Tech., (1960). 1. A. Martta, A. Buri, and F. Branda, Surface and Bulk Crystallizatin in Nn-Isthermal Devitrificatin f Glasses, Thermchim. Acta, (1980). 44«y(007)