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1 Journal of the Korean Ceramic Society Vol. 48, No. 1, pp. 63~68, DOI: /KCERS Effects of Substituting B 2 O 3 for P 2 O 5 on the Structure and Properties of SnO-P 2 O 5 Glass Systems Dong-Hwan Kim, Cha-Won Hwang, Nam-Jin Kim, Sang-Hyeok Im, Dong-Gun Gwoo, Tae-Hee Kim, Jae-Min Cha*, and Bong-Ki Ryu Division of Materials Science and Engineering, Pusan National University, Pusan , Korea *Departmet of Materials Science and Engineering, Kyushu University, Fukuoka , Japan (Received November 11, 2010; Revised November 26, December 7, 2010; Accepted December 20, 2010) SnO-P 2 O 5 P 2 O 5 B 2 O 3 ey e w ½ yáy Á½û Á xá Á½k Á *Á» w œw *j w œw ( ; , 12 7 ; ) ABSTRACT The investigation is directed to lead free (Pb-free) frits that can be used for organic light emitting diode, plasma display screen devices and other sealing materials. P 2 O 5 -SnO system glasses have been prepared for Pb-free low temperature glass frit. Structure and properties of the glasses with the composition SnO-xB 2 O 3 -(60-x)P 2 O 5 (x=0, 5, 10, 15, 20, 25, 30, 35, 40 mol%) were characterized by infrared spectra (IR), X-ray diffraction(xrd), Density, Molar volume, Thermo mechanical analysis(tma) and weight loss after immersion test. Glass transition temperature(t g ), dilatometric softening temperature(t d ) and chemical durability increased, and coefficient of thermal expansion(α) decrease with the substitution of B 2 O 3 for P 2 O 5 in the range of 0~25 mol%. Key words : Glass, Pb-free, P 2 O 5 -SnO, Sealing materials 1. Glass frit v ƒÿ š OLED (organic light emitting diode) seal, PDP(plasma display panel), LCD(liquid crystal display) VFD (vacuum fluorescent display) seal w š,» t paste š. 1) w Glass frit p k» w û y (T d ) ƒ, PbO ƒ š. w û w y w w 2,3) w, PbO w» w w ƒ w š, t Bi 2 O 3, P 2 O 5, 4-6) 7) BaO-B 2 O 3. P 2 O 5 p Corresponding author : Bong-Ki Ryu bkryu@pusan.ac.kr Tel : Fax : y ƒ š ƒ w, SiO 2» ¾ yƒ ƒ w. w p P 2 O 5 y (T d ) û» w. p SnO P 2 O 5 ƒ y y w y ù x w w. 8) w SnO-P 2 O 5 PbO w ƒ ƒ š, û yw w w š. 9) SnO-P 2 O 5 üyw j» w, P 2 O 5 B 2 O 3 eyw, eyz mw. y p, üyw, mw, y, FT-IR spectroscopy w mw. 2. x 2.1. xsno-(100-x)p 2 O 5 63

2 64 ½ yáy Á½û Á xá Á½k Á Á» Table 1. Compositions of Glasses Composition Batch (mol%) SnO B 2 O 3 P 2 O 5 SP SP SP SP SP SP SBP SBP SBP SBP SBP SBP SBP SBP SnO 40 mol% š jš B 2 O 3 w 0~40 mol% ¾ P 2 O 5 ey g. Junsei Chemical Co., LTD Extra Pure NH 4 H 2 PO 4, SnO, B 2 O 3 w, Sn 2+ Sn y v 4+ w» w Sucrose 1wt% ƒw. 10) ww z ù 10 yww Batch, Table 1 ùkü. B 2 O 3 ƒw SnO-P 2 O 5 SP series wš B 2 O 3 ƒw SnO-B 2 O 3 -P 2 O 5 ƒ SBP series š t w. yw Batch ù ƒ» 200 C o 2h w wš, 1100~1200 C o 1h z l q œ» w. (T g )+ 20 o C þ w. r, š yw ü x v ƒx m cutting z, t SiC paper(# ) w., XRD, FT-IR x z 325 mesh m w w d & y y v w y y w. X-Ray Fluorescence spectroscopy(xrf, PHILIPS PW2400) w d w. r n y n (Transparent), + (crystal+glass), (crystalline) w, XRD(Rigaku Corporation /Cu/30 Kv/15 ma) Pattern mw y w Ì 3 mm w sww v (T g : glass transition temperature) y (T d : dilatometric softening temperature) š q (CTE: The Coefficient of Thermal Expansion) Simadzu(Japan) TA-60H TMA(Thermal Mechanical Analyzer) w 10 o C/min, w 50 g d w & v Archimedes method AND GH-200 w d w. w d (Molar Volume, Vm) (1) w. 11) V M M = ----» M = = s³ = x i n i i = i = R m O n y üyw v üyw sƒ ƒƒ v 50 o C 12 w k z (2) w DR(Dissolution rate) w. 11)» ρ ρ x i x i n i M i n i w DR = S t w = Weight loss (g) S = Sample area (cm 2 ) before the dissolution test t = Dissolution time (min) FT-IR spectroscopy y mw» w Ÿ FT-IR spectroscopy d w. d KBr glass powder Kbr powder 1:200 yww z» 100 o C w w. d»» Spectrum GX w š, d 400~1500 cm -1 w z 20 z, w 2cm š & y y v ù ƒ e y y w» w w (1) (2) w wz

3 SnO-P 2 O 5 P 2 O 5 B 2 O 3 ey e w 65 Table 2. Componential Analysis of Glasses Composition Analyzed (mol%) SnO B 2 O 3 P 2 O 5 SP SP SP SBP SBP SBP Fig. 3. Tg, Td and CTE of the xsno-(100-x)p 2 O 5 glass Fig. 1. Glass formation region of the SnO-B 2 O 3 -P 2 O 5 glass Fig. 4. Tg, Td and CTE of the 40SnO-xB 2 O 3 -(60-x)P 2 O 5 glass Fig. 2. XRD patterns of the 40SnO-xB 2 O 3 -(60-x)P 2 O 5 glass, Table 2 ùkü. SnO-P 2 O 5, SnO- B 2 O 3 -P 2 O 5 Al 2 O 3. ù ƒ e w, w r y w. Fig. 1 SnO-B 2 O 3 -P 2 O 5 x ù kü. xsno-(100-x)p 2 O 5 SnO 30~60 mol% n w ƒ x. w SnO 30 mol% x ù ü û y w. SnO-P 2 O 5 y ƒ û SP-3(40SnO-60P 2 O 5 ) w P 2 O 5 B 2 O 3 eyw. Fig. 2 SnO 40 mol% š w SP-3 P 2 O 5 B 2 O 3 eyw XRD Pattern ùkü. B 2 O 3 0~30 mol%¾ ey k Pattern, 35 mol% vjƒ ùkû Fig. 3 xsno-(100-x)p 2 O 5 SnOƒ 40, 50, 60 mol%, y š q ùkü. SnO w ƒw y w ƒw, q w w. d ƒ û 48«1y(2011)

4 66 ½ yáy Á½û Á xá Á½k Á Á» Fig. 5. Density and Molar volume of 40SnO-xB 2 O 3 -(60-x)P 2 O 5 glass Fig. 6. Dissolution rate of 40SnO-xB 2 O 3 -(60-x)P 2 O 5 glass x=40mol% üyw P 2 O 5 B 2 O 3 eyw. 40SnO-xB 2 O 3 -(60-x)P 2 O 5 (x=0~30 mol%) p Fig. 4 ùkþ. B 2 O 3 ey ƒw y ƒw š 25 mol% ùkü q w ùkü & 40SnO-xB 2 O 3 -(60-x)P 2 O 5 (x=0~30 mol%) w v Fig. 5 ùkü. P 2 O 5 B 2 O 3 eyw w w, P2 O 5 ( g/mol) B 2 O 3 (69.62 g/mol)» w q. w j, y dw w p eƒ w, v w. P 2 O 5 ey B 2 O 3 w ƒw v w. x SnO-P 2 O 5 ü x w w B 2 O 3 ƒw ƒ ƒ ƒw, ƒ š ƒ š yw Close structure x w üyw DR(Dissolution rate) ƒ w, 12) B 2 O 3 ƒ yw ü j š š. 9,13) Fig. 6 40SnO-xB 2 O 3 -(60-x) P 2 O 5 (x=0~30 mol%) t ù kþ. yw ü p ƒ B 2 O 3 w w ƒ š, y B 2 O 3 w 25 mol%¾ yƒ ù q. Fig. 7. Infrared spectra of 40SnO-xB 2 O 3 -(60-x)P 2 O 5 (x=0-15 mol%) glass FT-IR spectroscopy Figs. 7, 8 40SnO-xB 2 O 3 -(60-x)P 2 O 5 P 2 O 5 B 2 O 3 ey g B 2 O 3 w y FT-IR spectra. 40SnO-60P 2 O 5 ùkù 1200 ~1300 cm -1 Phosphate chain ƒ e v as (PO 2 )» wš, 890 cm -1 P-O-P w ƒ e v as (P- O-P)» w. š 720~800 cm -1 ƒ e v s (P-O-P)» w. B 2 O 3 e y ƒw q y w p v as (PO 2 ) ùkü 1200~1300 cm -1 ( ƒ e ) v as (P-O-P) ùkü 890 cm -1 (ƒ e ) r ù w. w x=0~15 ¾ v s (P-O-P) ùkü 720~800 cm -1 (ƒ e ) q q shift y w. B 2 O 3 w ƒ w wz

5 SnO-P 2 O 5 P 2 O 5 B 2 O 3 ey e w 67 Fig. 8. Infrared spectra of 40SnO-xB 2 O 3 -(60-x)P 2 O 5 (x=20-30 mol%) glass w e ƒ w w. w ƒ P 2 O 5 ƒ B 2 O 3 ƒ w ƒ x w e y w». w Fig. 8 x=20mol% l ƒ e v s (P-O-P) ùkü 720~800 cm q š -1 BO 4» e v s (O-B-O) ùkü 680 cm q -1 ùkù. phosphate ü borate ƒ, P-O-P P-O-B yw d. x=30mol% BO 3» e (B-O) as ùkü 1450 cm q -1 ƒ š. 4 BO 4 3 BO 3 w, ƒ ƒ w. SnO- P 2 O 5 P 2 O 5 B 2 O 3 ey yƒ w x ù kù y w š 40SnO-xB 2 O 3 -(60-x)P 2 O 5 x=0 40SnO-60P 2 O 5 e e ƒ ùkù. w, B 2 O 3 ey ƒ ƒw(x=0~25) e ùkü wš e ùkü ƒw. w phosphate ùkü peak intensity w ù r borate ùkü peak w. B 2 O 3 ey ƒ ƒw phosphate borate ƒ x d w. w borate x x=20mol% BO 4» e v s (O-B-O) ùkü peak m Fig. 9. Predictive model for 40SnO-xB 2 O 3 -(60-x)P 2 O 5 glass structure. w y ƒ w. B 2 O 3 ey ƒ w ƒ ƒ ƒw e, 4 boron w borate networkƒ, phosphate network, borate networkƒ y boro-phophate networks x w q. Fig. 9. w, x=30mol% BO 3» e (B-O) as ùkü peakƒ ùkù. 4 BO 4 3 BO 3 y x ù. w y y ùkü. 40SnO-xB 2 O 3 -(60-x)P 2 O 5 x=0 25 mol%¾ w phosphate networkƒ wš borate networkƒ. ƒ ƒ ƒw, w w w Highly cross-linked structure x w, üyw ƒ q. ù x=30mol% B 2 O 3 ƒ 4 3 yw x w ƒ ƒ x, ƒ y ü yw w q. 4. SnO-P 2 O 5 w p üy w x ww. x SnO-P 2 O 5 y x p q w š ƒ û ƒ 40SnO-60P 2 O 5 P 2 O 5 B 2 O 3 ey ey y mw š. (1) xsno-(100-x)p 2 O 5 2 SnO w 30~60 mol% ƒ x ù 30 mol% w x w. 48«1y(2011)

6 68 ½ yáy Á½û Á xá Á½k Á Á» š SnO w ƒw (T g ) y (T d ) w wš q (CTE) w w. (2) 40SnO-xB 2 O 3 -(60-x)P 2 O 5 B 2 O 3 w 0~40 mol%¾ eyw 30 mol%¾ ƒ x. ey 25 mol%¾ eyw phosphate networks e w š, BO 4 ƒ x borate, boro-phophate networksƒ x. cross-linkage yƒ w (T g ) y (T d ) wš q (CTE),, DR w. (3) B 2 O 3 ey 30 mol% BO 4 ƒ BO 3 y x ù» ƒ ƒ x ƒ y. (T g ) y (T d ) wš q (CTE), DR ƒw. (4) SnO-P 2 O 5 B 2 O 3 ey w y g üyw j ƒ yƒ ù üyw w. Acknowledgment w w (2 ) w. REFERENCE 1. Y. T. An, B. H. Choi, M. J Ji, W. S. Chang, H. Bae, and H. J. Hwang, Structure and Thermal Properties of SnO 2 -(1- X)P 2 O 5 -XB 2 O 3 Glasses(in Korean), J. Kor. Ceram. Soc., 47 [2] (2010). 2. C. J. Hudecek, Engineered Materials Handbook, Vol. 4, pp. 1069, ASM International, R. Morena, Phosphate Glasses as Alternatives to Pb-based Sealing Frits, J. Noncryst. Solids, (2000). 4. M. Busio and O. Steigelmann, New Frit Glasses for Display, GLASTECH. Ber. Glass Sci. Tehch., 73 [10] (2000). 5. B. H. Choi, Technical Development Trend for PDP Device Material, Information Display, 8 [1] 10-1 (2007). 6. R. K. Brow, and D. R. Tallant, Structural Design of Sealing Glasses, J. Noncryst. Solids, (1997). 7. E. S. Lim, B. S. Kim, J. H. Lee, and J. J. Kim, Characterization of the Low Temperature Firing BaO B 2 O 3 SiO 2 Glass : The Effect of BaO Content, J. Eur. Ceram. Soc., (2007). 8. C. Gejke and E. Zanghellini, Microscopic Structure of Tinborate Phosphate Glasses, J. Power Sources, (2003). 9. M. Kenji and F. Shigeru, Preparation and Properties of SnO-SnCl 2 -P 2 O 5 Glass, J. Noncryst. Solids, (2001). 10. J. Hong, D. Zhao, J. Gao, M. He, H. Li, and G. He, Leadfree Low-melting Point Sealing Glass in SnO CaO P 2 O 5 System, J. Noncryst. Solids, (2010). 11. N. J. Kim, S. H. Im, D. H. Kim, D. K. Yoon, and B. K. Ryu, Structure and Properties of Borophosphate Glasses, Electronic Mater. Lett., 6 [3] (2010). 12. V. S. Molchanov and N. E. Prikhid'ko, Corrosion of Silicate Glasses by Alkaline Solutions, Russian Chem. Bull, 8 [6] (1996). 13. B. C. Lee, S. W. Lee, C. W. Hwang, J. S. Lee, and B. K. Ryu, The Study on Chemical Durable Zinc-phosphate Glasses with B 2 O 3 Addition(in Korean), J. Kor. Ceram. Soc., 38 [6] (2001). w wz