NaF. Study on the Crystallization of NaF using Quartz Crystal Analyzer

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1 HWAHAK KONGHAK Vol. 40, No. 6, December, 2002, pp NaF * ** Hiroshi Muramatsu * *, ** ( , ) Study on the Crystallization of NaF using Quartz Crystal Analyzer Sung-Woong Han, Se-Young Son, Seong-Hun Song, Jong-Min Kim*, Woo-Sik Kim**, Hiroshi Muramatsu* and Sang Mok Chang Department of Chemical Engineering, Dong-A University, Pusan , Korea *R&D Center, Seiko Instruments Inc., Chiba , Japan **Department of Chemical Engineering, Kuyng-Hee University, Yongin , Korea (Received 2 April 2002; accepted 6 September 2002) NaF.! "# NaF $ % NaF & '( NaF )*+,- NaF.* / *01. NaF $ 2.* / *0 3 ' :% ;<=>?@A (cysteamine hydrochloride; 2-mercaptoethylamine hydrochloride)- self-assembly B C D* EF. G&.*H NaF ;<=>?@A :% 6 IJ% IJH K LM NO 3 5 PQ NO 3 R- S TU,- NaF VWX YZ. N[\ 1-5 ml 3 =]- S $ ^ )* NaF _ 3=` NZ-a, ;<=>?@A bc d1 NO 3 VWR- S N[\ ef NaF &WX YZ. g g G 1 NaF VW DR YZ. Abstract The crystallization of NaF driven by adding ethanol was monitored using quartz crystal analyzer (QCA). Adding ethanol to NaF solution reduced the solubility of NaF and consequently led to nucleation and growth of NaF crystals. To investigate the crystallization behavior of NaF, a gold electrode of QCA was modified by anchoring with 2-mercaptoethylamine hydrochloride based on a self-assembly method. Frequency of QCA varied with the amount of NaF adsorbed on the selfassembled layer of 2-mercaptoethylamine hydrochloride, and thereby the process of NaF crystallization could be analyzed indirectly by monitoring the frequency change of QCA. To change the extent of supersaruration of NaF, the amount of ethanol added to the solution was varied from 1 to 5 ml. Then, the effect of the extent of the supersaturation on the crystallization was examined by analyzing the frequency changes of QCA coated with 2-mercaptoethylamine hydrochloride. It was shown that the QCA technique could be well applied for the characterization and analysis of the crystallization behavior of NaF. Key words: Crystallization, NaF, QCA, Metastable, Nucleation 1.!"!# $"%, &'"%, ( ')*%, +,,-./, 0"%, 12, 3, 4"$,!5 $ %: ; +2 <!./ )* =7 >2 To whom correspondence should be addressed. BC DE F. )* =G HI "! JKL = 7! -M N OP QR?!-1S 1T, -S UV <! OW XYW 6 ZG OP [V\] ^_ A. `!: ab cdg dfa. # e fg R,, ] P+?hA. :! N K- =: 3i ` 1j k GA. lm `:!n o?pj q A. R rb sy# o?pj q]t u v# 1jw 659

2 660 Hiroshi Muramatsu x! g jm rb \]! N Ky ^ ]w Rx! g GA. e8p g z{! # }A. `n ~# rb! NL o] ^ d* L m ƒ! syj q rbn A. v# : x! G 1j L x! g GA. x! ˆ # Š:! NL 1Kj qjm Œ :! )"Žp, ~ ; rb!n ^ A. ^!ht +s-(quartz crystal analyzer; QCA) G # ;2\ $\ ] + y ^ A. ^! ;2\ ˆ G ^! ; š f "hœ ^ ] ;2\ # œ ^! ;2\ ˆ G ] žÿ CPU ht,, 6L ^ A. $\ # ^!ht : o?p ; šp \ 6 G "hœ ^ G ] n [1, 2], `![3], u u 3 G 3 [4, 5],!, ª 3 +s[6], 0 3 s [7], s, 0-$ 3 s[8, 9] 6L ^ A. ^!ht «G : Kh j ql «G : Kh n A Nomura Nagamura[3] 6 : h ±, ² e³ 7 -*!+s, µ2 0-cV+s[10, 11], + 0 N +s[12] 6 ¹=, OP A. ^ c: ^!ht KhL 7 $ y rb, ^!ht ; š ºš NL rb ; rb p» ^ A. ^!ht ; š ºš NL G ¼ \ ] 0-$ \! A. ½W p L ^!ht sy :, f ^!ht Khœ ^!¾] s YÀ ÁL 9 A. ÂG 0Ã3 f ^!ht cá!¾] 0Ã &, 0cVÄ ÅÆ} Ç +s A. ; È ÉÄ! ¼G # ÃÊ BC OP Ë jm ¹=G ÌK ÍÎ A. ÉÄ! j : "hœ ^ Œ "hzug HI JÏ? ÀA.!¾] Š KÐ; o[ ÑÒ +sp Ó 3 s,!p j 6 + ÔÄ 0 +s 6L y ^ A[13]. ² OP: x! NaF Dn) ÕÖ L Dn 7 NaF ; ¼G ~Ø? NaF!L Ù, À NaF!L Ú9 ÛÜ self-assemblyà ^!ht = šý] NaF! ¼G +s n L ÍÎG A. 2. Fig. 1# ^!ht Þ& htþi pßà A. ^!ht á 0Ã RF(Radio-Frequency) 0 L â?œ ^!h T ^ ãä] 0 å?j ^!ht 0 ^ ^æãä] ht ÀA. ç, ^æãä] ht ^!h T 0Ã = ˆ! ; š htèjn éf, \] šà ; á êë7 ^!ht œ ^n éf ÀA. Z È, cá "hœ ^ Z & Sauerbrey 1ìA[14]. c: í ãä] É htl rb «G ^!h Fig. 1. Conceptual diagram of quartz crystal analyzer to detect vibration change with adsorption of NaF on self-assembly layer of cysteamine hydrochloride. (a) AT-cut quartz crystal analyzer system and (b) shear vibration model of quartz crystal. A; quartz crystal, B; electrode, C; lead wire. T Khœ ^ ˆ ZG &# Kanazawa 6 1ìA [15]. c: ^!ht "hzu# ^!ht 0-\ 6n î $\ 6n î Þï "h : l ^!ht "h zu JÏ# Muramatsu FJì A[16-18]. 8G OP L Î¼ ^!ht "h œ ^n Ej šg ; á ðm }g ^!ht œ ; : GA ñò óa. È, "- c: ht ^!ht ôe ^!ht 0E hty ç $\ zu L õ htèjn éf ÀA. $\ zu G htèj éf G o[ Á ö 7 "hœ ^ GA[19, 20]. 3. ² òø ñà 9MHz ^!ht ^!ù á r 5mm ½ 0Ã å? A. W: òø n ú Gû m «ú Fig. 2 v ) G ^!ht ül ñ Fig. 2. Schematic diagram of quartz cell for monitoring vibration change with adsorption of NaF on self-assembly layer of cysteamine hydrochloride.

3 ý òø þ ^!ht +s-(qca917, Seiko EG&G) ñ ýa. ^!ht òø? 0Ã 0ÿ2!# z piranha solution(hydrogen peroxide:sulfuric acid=1:3)] 10-15M! etchingl Ž A É, e2 Fn *Ù!L ŽA[21, 22]. DMF(N,N-dimethylformamide) 3 : Lancaster: PG 0.01 M Ú9 ÛÜL 7 selfassembly!l ËA. 7-: Ú9 ÛÜ ) ^ ] ) y ç k- OH(hydroxide)- 3 ] 3 \# DMF ñýa. self assembly G A ^!ht DMF ] 2-3î G ±, Fn * A ^ 7 *ýa. ² òø NaF ^: _jw ^ G A 3i *7k GA. ^ NaF 3.5%(Vol%) 7 x! NaF L m ) ül 7 ^! ht œ ^ ¼G 3 äl BF òøýa. ± 3L : x! NaF ^ ÕÖ L 1 ml, 3 ml, 5ml E \] œ7 NaF â NaF!L å ƒa. åà NaF! ^!ht ½0Ã Ú9 Û Ü self-assembly Ä ¼G š7 ÍÎý ^!ht +s- œ ^!7 NaF!! +s n L ÍÎýA. ^!ht ñ 1-; šy rb, ^!ht œ ^ šà ; É\ ˆ j¼g äl A. 3 ^!ht,-+n šy rb, š ŽT# 0\] É \ š] ^!ht œ ^ šà ; É\ ˆ Ž äl œj q A. 8G 1 ² òø: Ú9 Û Ü self-assembly!l +sy ç ^!ht œ ^ "h zu T +sýjm NaF!! +s òø: ^! ht œ ^ m!7 +sýa. 4. Fig. 3# ^!ht ½0Ã L Ú9 ÛÜ] self-assembly Tx œ ^!G A. Fig. 3: self-assembly ^!ht œ ^n ( 200 Hz! éf e ± ^!htn x!à L Ö ^ A. Sauerbrey & ( 200 ng Ú9 ÛÜ ^!ht self-assembly À ] 9 ÀA[14]. Fig. 3(a) Ë Ú9 ÛÜL œ ^!ht œ ^n Ê éfýan ::Ê n : x!?n L Ö ^ A. Fig. 3(b) Ë "hzu# "hœ ^ ËA *½ M r S: Ã¼L pßšan é F7 x!?n L ^ A. ÿ Ú9 ÛÜ L œ S\] ^!ht = Ú9 ÛÜ Þ7 ìan 3 0 o +- ç] ñ/à A. e2 180 Hz! œ ^n ý "hzuäl j q ^ Ú9 ÛÜself-assembly G g n!ga ( 180 ng Ú9 ÛÜ ^!ht selfassemblyà ] 9ÀA. # \ Ú9 ÛÜ + kinetic diameter 3.8Å(Aungstrom)L ] 9G \ 9Á ( 6X GA[23-25]. 7 åg ^!ht ½ L 7 1ö \ \ \ 5-6X! ÀA Qg Ú9 ÛÜ 180 ng ^&ìa # ^!ht ½0Ã L Ú9 ÛÜ 03\] ^& A n! 7,ãy A. Fig. 4 ^G ^ ÕÖ!L 1ml E \] : Ú9 ÛÜ ^&À ^!ht "hœ ^!G NaF 661 Fig. 3. (a) Typical frequency responses during self-assembly process of cysteamine hydrochloride on the gold electrode of quartz crystal, (b) Typical resistance responses during self-assembly process of cysteamine hydrochloride on the gold electrode of quartz crystal. Fig. 4. Frequency response of quartz crystal in pure water as ethanol was injected. At each injection, 1 ml of ethanol was A. Fig. 4: ^ ÕÖ!L 1ml ÿ 6î "j G# ç$a ( 20 Hz œ ^n éfan e ± œ ^ n %L Ö ^ A. ñò# ^ ÕÖ! Dn ^!ht 0Ã ; ¾ T ^!ht 0Ã ÕÖ! š? ^!ht ht^n éfàa ÀA. Ú9 ÛÜL ^&j q# ½0Ã ^!ht ñ7 ê HWAHAK KONGHAK Vol. 40, No. 6, December, 2002

4 662 Hiroshi Muramatsu Fig. 5. Frequency response of quartz crystal in 3.5% NaF solution as ethanol was injected. At each injection, 1 ml of ethanol was &G 'L ^ ìa. e2 3.5% NaF : ÕÖ!L : ê òøl 7 Ú9 ÛÜ ^&j q# ½0 Ã ^!ht rb, œ ^ n ^G ^ ÕÖ!L ýl ç Ž ê&ýa. È 3.5% NaF : ÕÖ! L x! :!L â NaF! jm ½0Ã À NaF! šj q Ej ÕÖ! äm pßp ] ÀA. e8p Ú9 ÛÜ ^ &À ^!ht ñ7! 3.5% NaF : ÕÖ! L ýl ç ^!ht œ ^ n ^G ^ Õ Ö!L ýl ç ^!ht œ ^ ËA () p ß*A. È ÕÖ! ] À NaF! Ú9 ÛÜ Ô Ä +,\] š-l Ö ^ ìa. Fig. 5 ½0Ã L Ú9 ÛÜ] self-assembly7 ^&G ^!ht 3.5% NaF ^? œ ^n x! 1ml ÕÖ!L OW\] : œ ^!G A. G., ÕÖ! ] À NaF! Ú9 ÛÜ selfassemblyä š j 7 ÍÎ- =7 v# * : NaF n / ^ ^!ht? œ ^n x! 1ml ÕÖ!L E \] : œ ^!G (Fig. 4) ê +sýa. Fig. 5: NaF ÕÖ!L 1ml ÿ 10î"j ÕÖ! G# ç $A ( 50 Hz! "hœ ^ éf Ë An 11î ± "hœ ^n 600 Hz! Ê éfan x! L Ö ^ A. e8p ^ ÕÖ!L 1ml ÿ 6î"j ÕÖ! G# ç$a ( 20 Hz! œ ^ n éfýa. : ÕÖ! ] À NaF! Ú9 ÛÜ ÔÄ +,\] š-l Ö ^ A. NaF 11#0 ÕÖ! "h œ ^n Ê, NaF! ::Ê An?1 S Ð $\] Rx!? NaF! - çg ÀA. Fig. 6# ÕÖ! á äl +s- =7 Fig. 5 ToG * : ÕÖ!L 3ml E \] : œ ^!G A. rb ÿ 6î"j ÕÖ! G# ç$a æ 200 Hz! œ ^ éf ËAn 7î : 1,500 Hz! "hœ ^n Ê éf¾l Ö ^ A. 3 ml Õ Ö!L G# y ç "hœ ^n 1ml ÕÖ! L y ç ËA () 2, 0\] 3ml ÕÖ!L y çn 1ml ÕÖ!L y ç ËA œ ^ n () Fig. 6. Frequency response of quartz crystal in 3.5% NaF solution as ethanol was injected. At each injection, 3 ml of ethanol was Fig. 7. Frequency response of quartz crystal in 3.5% NaF solution as ethanol was injected. At each injection, 5 ml of ethanol was L Ö ^ A. \# á ÕÖ!L x!n Ë A jw\] 1j! ::Ê o?p- ç] ñ/àa. Fig. 7 ÕÖ! á äl +s- =7 Fig. 5 ToG * : ÕÖ!L 5ml E \] : œ ^!G A. rb ÿ 5î"j ÕÖ! G# ç$a æ 250 Hz! œ ^ éf ËAn 6î ± 4,000 Hz "hœ ^n éf¾l Ö ^ A. 3 ml ê ÿ 5î "j "hœ ^ 3ml G ê&jm, 0 "hœ ^ éfá 7,000 Hz] ab 3L Ö ^ A. ê- =7 Fig. 5-7 Fig. 8 ¾4 &ýa. Fig. 8# ½0Ã L Ú9 ÛÜ] ^&G ^!ht 3.5% NaF? œ ^n x! 1, 3, 5 ml Õ Ö!L E \] : œ ^!G êg A. Fig. 8: G# ÕÖ! á 2L^ú "h œ ^ n 5%L Ö ^ ÂG Ê "hœ ^n y ç () ¾L Ö ^ A. È, ÕÖ! á \] ÕÖ!L 7 x! n ê\ jw\] 1 j? ::Ê!, Á?1! Ð $\] Rx!7 Ê!n o?6a ÀA., Õ Ö! ] À NaF! Ú9 ÛÜ ÔÄ +,\]

5 NaF 663 ² OP G:$;h<.E(KRF E00057) OPê ^ _ì- éñi=}a. Fig. 8. Cumulative change of frequency during crystallization with injection of ethanol into NaF solution. The concentration of NaF solution was fixed at 3.5% and the amount of ethanol injected at each time was varied from 1 to 5 ml. š-l Ö ^ ì NaF ä Ö ^ ìa.! ¼G Dn) á 5.!! s# œ cdjm S S!?n!L +sy ã7 /ìa. ² OP: láz8 Öh ^! ht ½0Ã L Ú9 ÛÜ ^&7 ÕÖ! ] À NaF! Ú9 ÛÜ +,\] š j 7 Dn) á! ¼G äl ÍÎG A. 3.5% NaF ÕÖ!L E \] 7 x! NaF m e2 NaF!L ƒa. ÕÖ! ] À NaF! Ú9 ÛÜ self-assemblyà ^!ht = š j ^!ht œ ^ 97!, ÍÎýA. Ú9 ÛÜ ^&À ^!ht Ú9 Û Ü ^&j q# ^!ht ñ7 ê ÍÎG, Ú9 ÛÜL ^&j q# ^!ht ½ 0Ã = ÕÖ! ] À NaF! šj qjm Ú9 ÛÜ ^&À ^!ht : ÕÖ! ] À NaF! š¾l Ö ^ ìa. e2 G # ÕÖ! á L 1, 3, 5 ml n : òøg G# 2# á ÕÖ!L "hœ ^ n 3L Ö ^ ìa. \# á ÕÖ! x! n ê\ jw\] 1j- T ::Ê!ÀA L lýa. e2 E \] ÕÖ!L?1 S G œ ^ Ëý?1 S Ð $\] Ê Rx!7!n o?p- ç] ñ/àa. ² OP, [ - Ä] ^&G ^!ht 7!!L +sy ^ A L Ö ^ ìa. 1. King, W. H.: Anal. Chem., 36, 1735(1964). 2. Hlavay, J. and Guibault, G. G.: Anal. Chem., 36, 1735(1964). 3. Nomura, T. and Nagamune, T.: Anal. Chim. Acta, 131, 97(1981). 4. Shons, H., Dorman, F. and Najarian, J.: J. Biomed. mater. Res., 6, 565(1972). 5. Muramatsu, H., Dick, J. M., Tamiya, E. and Karube, I.: Anal. Chem., 59, 2760(1987). 6. Itaya, K., Ataka, T. and Toshima, S.: J. Am. Chem. Soc., 104, 4767 (1982). 7. Chang, S. M. and Muramatsu, H.: Biotechnology News, 2, 60(1995). 8. Grabbe, E. S., Buck, R. P. and Melroy, O. R.: J. Electroanal. Chem., 59, 2760(1987). 9. Bruckenstein, S. and Shay, M.: J. Electroanal. Chem. 280, 73(1985). 10. Song, S. H., Kim, J. M., Han, D. S., Park, J. Y., Park, J. S. and Chang, S. M.: J. of Korean Ind. & Eng. Chemistry, 10, 784(1999). 11. Lee, H. J., Cho, H. S., Park, J. Y., Chang, S. M. and Kim, J. M.: HWAHAK KONGHAK, 38, 443(2000). 12. Cho, H. S., Han, D. S., Park, J. Y., Lee, H. J., Park, J. S., Kim, K. and Chang, S. M.: J. of Korean Sensors Society, 9, 28(2000). 13. Jones, J. L. and Mjeure, J. P.: Anal. Chem., 41, 484(1969). 14. Sauerbrey, G., Z.: phyzik, 155, 206(1959). 15. Muramatsu, H., Suda, M., Ataka, T., Seki, A., Tamiya, E. and Karube, I.: Sensor and Actuators, A21-23, 362(1990). 16. Ye, X., Muramatsu, H., Kimura, K., Sakuhara, T. and Ataka, T.: J. Electroanal. Chem., 314, 279(1991). 17. Kanazawa, K. K. and Gordon II, J. G.: Anal. Chim. Acta, 175, 99 (1985). 18. Muramatsu, H. Tamiya, E. and Karube, I.: Anal. Chem., 60, 2142 (1988). 19. Kim, J. M., Chang, S. M. and Muramatsu, H.: Polymer, 40, 3291 (1999). 20. Landau, L. D. and Lifshitz, E. M.: Fluid Mechanics, Pentagon, Oxford, England(1959). 21. Lee, Y. J., Joen, I. C., Paik, W. K. and Kim, K.: Langmuir, 12, 5830 (1996). 22. Guo, L. H., Facci, J. S., McLendon, G. and Mosher, R.: Langmuir, 10, 4588(1994). 23. Kihara, T.: J. Phys. Soc., Japan, 6, 289(1951). 24. Hirschfelder, J. O., Curtiss, C. F. and Bird, R. B.: Molecular Theory of Gases and Liquids, John Wiley & Sons, 215(1954). 25. Stuart, H. A.: Die Strukurt des Freien Molekuls, Springer, 88(1952). HWAHAK KONGHAK Vol. 40, No. 6, December, 2002

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