8 6 Ø Vol.8 No.6 6 67 677 ACTA METALLURGICA SINICA Jun. pp.67 677 (Y, Gd) O Eu + ÆÅ ³ º ½ Á ÞÐÜ ) ÓØÔ ) Ù Ò ) Ö ) Ó Ò,) Ú Õ ) ) Ä Ë Ä ÆË ½, ) ¾ ¼ ¾ ( ) ½, 6 ) Õ Ë, 89 ¹Ì Ó² Ñ (Y, Gd) O Eu + Þ, ²ßÚ ±, Í (Y, Gd) O Eu + Ǿ, Ì XRD SEM ß Ò Á Ù; Ì TG DTA Í Ò ² ßÉ Ð. ß Ì, Þ ± Å Ú ÝÜ, Ì Doyle Ozawa Kissinger Ì ÇÝÜ ¹ËÅ, ÚÔ Ú 9.5, 557.5 6.58 kj mol, Ö» ¹ ; (Y, Gd) O Eu + ž² ËÅ 5.58 kj mol, Ǿ ž ÌÏÅĐ³. ¼ (Y, Gd) O Eu + Ǿ, ¹, ËÅ, Ö¹ Á Ê TQ Ì µéã A Ì 96()6 67 7 SYNTHESIS KINETICS OF (Y, Gd) O Eu + NANO POWDERS DURING PROCESS OF PREPARATION ZHU Hongyan ), MA Weimin ), WEN Lei ), GUAN Renguo ), MA Lei,), WU Nan ) ) Key Laboratory for Rare earth Chemical and Applying of Liaoning Province, School of Material Science and Engineering, Shenyang University of Chemical Technology, Shenyang ) Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 6 ) Institute of Metallurgy and Materials, Northeastern University, Shenyang 89 Correspondent: MA Weimin, professor, Tel: ()85886, E-mail: maweimin56@6.com Supported by Natural Science Foundation of Liaoning Province (No.6), Science & Technology Program of Shenyang (No.F 5 ) Manuscript received 7, in revised form 6 ABSTRACT Using NH H O and NH HCO blended solution as a complex precipitation agent, (Y, Gd) O Eu + nano particles were synthesized by co precipitation reaction. XRD and SEM were applied to analyze the crystallization and morphology of the sample. The thermal decomposition curves of samples were analysed by TG DTA at different heating rates. Results showed that under the conditions of ph= and reverse titration, the change process of (Y, Gd) O Eu + precursors is divided into three steps. The apparent activation energy of each step was calculated by using the Doyle Ozawa and Kissinger methods. The calculated results are 9.5, 557.5 and 6.58 kj mol. The dynamic equations have been also established. The activation energy of (Y, Gd) O Eu + grain growth is 5.58 kj mol, indicating that grain growing is primarily controlled by interfacial reaction during process of preparation. KEY WORDS (Y, Gd) O Eu + nano particle, synthesis kinetics, activation energy, micro morphology º Ï Å GE ±È ± º * ¹ 6 ± à F 5 Ù : 7, ² Ù : 6 ÔÐ :,, 987 ², Å ² DOI:.7/SP.J.7..75 X CT Í ± Í Æ Å Y. Gd.6 O (Eu, Pr).6, Ñ YGO, ¾ Eu Pr Y O Gd O Í Å [,], Å Æ ¼ Å. ß (Y, Gd) O Eu + Å Ú Ú Ñ Æ ³ Ò Â [ 7]. Ü, ³ Ò Ä ÂÑ Ã ½ ÈÍ. Í Å
67 8 ½ (TG DTA) Æ Ý, ½ Ð È Ø º ± È ÎÆ Â Å [8,9]. µ, Ø º ½ ¼Ø ºÅ Î ÈÞÝ ºÌÆ, Ê Î Â [,]. (Y, Gd) O Eu + Ø º, Đ Ó. ºÍ Ô ³ Ò (Y, Gd) O Eu + È, ºÍ X (XRD) ÊÐ (SEM) Á TG DTA ½ (Y, Gd) O Eu + Ø º. Í Doyle Ozawa [ ] Kissinger [5 7] Í ÈÞÝ ºÌÆ. È ÁÄÛÛ 99.99% Y O, Gd O Eu O Û, NH H O, NH HCO, HNO C H 5 (OH) ÛÆ Ä. Y. Gd.6 Eu.6 O ƺ «Ð Æ Ê, ÛÛ.5 mol/l HNO Î. Í ÛÛ. mol/l NH H O. mol/l NH HCO, Ð NH H O NH HCO ÏĐ Û Ò. ³ Ò, ÍÅ Û Ô (NSC) Ô (RSC), NSC Ù Ô Û Ò», RSC ÑÙ» Ò. Ù Ø Ò ( RSC ) Î Ò, ÔÊ Û ml min, Û 7 K, Ô µû, Þ Ò. Ù Ò Í ÂĐ 5 Ç, À, ÍĐÂÀÃĐ Ç. Ù À Ò «Ö Ð 58 K Ð h, ß Ò, Í Ä ZrO ÅÝ» ÁĐÂÀÃÛ ¹ Î h, À««, Ð 87 7 K ² h, (Y, Gd) O Eu + È. ºÍ D/max 5PC XRD Æ ³ Û ², Sherrer ± µí Ó «É. Í HITACHI S N SEM º¼ Ó Â. Í NET ZSCH STA 9C ½ / ÅÆ (DTA/TG) Î Ò ß 7 7 K TG DTA, Æ Û«Æ, ¾ Û ml min N, ºÍ µ Ê, Æ Û 5,, 5 K min. È Î. (Y, Gd) O Eu + À ¾¹ Û³ ÔÅ Î ß Æ 7 K ² h SEM. Á, NSC Î Ó ± Ò, ÉÜÍг, ÄÍ Ò È ( a); RSC Î Ó Ë ¹Ì NSC RSC Í Þ 7 K ± h SEM Fig. SEM images of precursor precipitates prepared by the normal strike co precipitation (NSC) (a) and reverse strike co precipitation (RSC) (b) after calcined at 7 K for h, Í, Æ ± ( b). dz ³, ÔÅ» Á Ç ph г, ºÍ NSC ¼, Î Ò Ò,» ph Ð µ, Y +, Gd + Eu + Æ Û³ Æ Ç Ò; RSC, Ò ph Ð (ph=),» à Y +, Gd + Eu + ¼ Ò, Æ Ê ÏÆ Ê, ÄÆ Ô ß Ò [8].. (Y, Gd) O Eu + À» Ï Û 58 K ÐÀ ß Ò Fourier È Ò (FT IR). Á, cm Á ܲ Î, È Ò H O O H Ô Ï Ø; 98 cm Á NH + N H Ô Ï Ø ; 57 cm Á CO C O Ô ³ Ï Ø ³; cm Á È CO C O Ô Ï Ø; 88, 86 686 cm C O Ô Ó Ø; O H ÔÓ Ø ³ 76 cm Á ; RE O Ô Ø 556 cm Á. ÁÐÞ, ß Ò RE +, OH, CO, «Â ÝÔÅÆ NH H O NH HCO. ß 87 7 K ² FT
6 Ø «: (Y, Gd) O Eu + ƽ Ö 67 IR. Ó, ² ÛÛ 87 K ¼, Í, 556 cm Á RE O Ø, ÄÍ Æ «; ² ÛÒ 7 K ¼, ÕÂ, Ú Û, ÕÄÍ ÆÔÅ «. Ûß ³ µ Ê TG DTA. Á, ß Æ ÆÛ ÞÝ: ÞÝÛÑÂÞÝ, Û ÙÛ 7 K, Å 8%, Û 9 K Á Å Ó ÂÆØ, 9 K ¼, ÅÊ Í, DTA, Õ ß «ÂµÆ ; ÞÝÛ Æ ÞÝ, Û ÙÛ 9 K, ÍÆ Å, Å Û 5%, DTA 89 K Á RE(OH) x (CO ) y Æ ; ÞÝ Û (Y, Gd) O Eu + ÞÝ, Û ÙÛ 9 5 K, ųÍÆ, Û 5%, DTA 7 K Á Í Ó Æ, ĐÔ Û Transmittance, % 98 57 556 88 686 86 76 5 5 5 5 Wavenumber, cm - Ë Þ Ñ 58 K FT IR Ö Fig. Fourier transform infrared (FT IR) spectrum of precursor precipitates after dried at 58 K Transmittance, % 87 K 7 K 5 5 5 5 Wavenumber, cm - Ë Þ 87 7 K ± Í FT IR Ö Fig. FT IR spectra of the samples obtained by calcined precursors at 87 and 7 K 5 K/min K/min 5 75 9 5 5 75 9 5 5 K/min K/min 5 75 9 5 5 75 9 5 Ë Þ ² ßÉ TG DTA Fig. TG DTA curves of precursors at different heating rates
67 8 «; 5 K ÁÀ, ³ Å. Ä ÞÝ È È Å : Re(OH) x (CO ) y nh O Re(OH) x (CO ) y (T < K) () Re(OH) x (CO ) y Re O CO +H O+CO ( K < T < 9 K) () Re O CO Re O (9 K < T < 5 K) (), x, y n Æ Û ÍÆ»Á; T Û º Û. ß Æ È Û Ù Á, ºÍ Doyle Ozawa [9,] Kissinger [,] Æ Í (Y, Gd) O Eu + ºÌÆ E. Doyle Ozawa Ü, Ô È Æ α( TG DTA Æ Á Î ), lgβ(β Ûµ Ê ) /T Þ È ± «, Ðß Û.567E/R(R ÛÏĐÝ Á). lgβ /T, ß Í È ºÌ Æ. 5 ³ È Æ ³ È lgβ /T, 5 ß Í ºÌ Æ. Ü, ß Æ ÞÝ È Õ ºÌÆÆ Û 6., 57.88.9 kj mol. Kissinger, ln(β/t m) /T m (T m Û Ð Û) È ± «, ß Û ( E/R), ln(β/t m) /T m, È ÌÆ. 6 Û È ln(β/t m ) /T m. 6 ß Í Þ 9 K, 86 9 K 97 5 K È ºÌÆÆ Û.9, 5. 7.5 kj mol. Ü Ü, Doyle Ozawa Kissinger Í ºÌƽ Ü, ÛÒ Í ½ Å Õ ÐÀ, 9 K, 86 9 K 97 5 K Û Ù Õ ºÌÆÆ Û 9.5, 557.5 6.58 kj mol. Õ ºÌÆ Ô Û Ê ß ÞÝ È Ã Û, ³ (Y, Gd) O Eu + ÞÝ ºÌÆ Í, Û 557.5 kj mol, lg(, K/min)......9.8.7.6 (a), % 5 7 9 Linear fitting curve..5..5.5.55..65.7.75. lg(, K min - )......9.8.7.6.5 (b)..5 lg(, K min - )......9.8 (c).7.6.5.95..5 Ë 5 Doyle Ozawa Í ² Ç Å ² ßÇ lgβ /T Fig.5 lgβ /T plots of different endothermic peaks at different conversions (α) obtained by the Doyle Ozawa method (β) (a) the endothermic peak between 9 K (b) the endothermic peak between 86 9 K (c) the endothermic peak between 97 5 K
6 Ø «: (Y, Gd) O Eu + ƽ Ö 675 ÄÍÆÞÝ È Ü, È ¾ ÞÝ ¼.. Ç¾Í Ï 7 Ûß Ò Æ ³ Û ² h À XRD. Á, 87 K, ß Ã ² Å ßÇ Ô ËÅ Table Activation energies of the endothermic peaks at different α α, % E, kj mol E, kj mol E, kj mol 7. 5. 8.6.6 5. 9. 9.9 58.85.69 56.9 57. 5.9 5 5. 657..57.5 59.5.5 7. 66.87. 68.6 58.8.85 9 8.6 5.7 9. 9.86 55..8 Average 6. 57.88.9 Note: E activation energy of the endothermic peak between 9 K, E activation energy of the endothermic peak between 86 9K, E activation energy of the endothermic peak between 97 5 K Æ, RE O CO, ÍÆ ; 97 K ¼ ; Æ 7 K ² À ÕÂ, Û Y O «(PDF No. 6) ; 7 7 K ², Æ ² Ó, Í. Y +, Gd + Eu + Æ, Æ Û.89,.98.95 nm, (Y, Gd) O Eu + Õ, Eu + ¾ Å Ü«, Ó Ü Y O. Scherrer ±, 7 XRD Í ««É D, lnd /T «8. «³ ÌÆ Í± [,] : d[lnd] d(/t) = E R (7) 8, (7) Í (Y, Gd) O Eu + È«³ ÌÆÜ, Û 5.58 kj mol, Í«É̱Ü, (Y, Gd) O Eu + È ³ ÛÆ «É.. Ǿ Ä Ï 9 ß Ò 7 K ² ³ ¼ SEM. Á, ÝƲ, È ÍÆ ( 9a); 7 K ² h À, ln( /T m, min - K - ) ln( /T m, min - K - ) -9. (a) -9. -9.6-9.8 -. -. -. -.6 -.8....6.8. -9. (b) -. (c) -9.6 -. -9.8 -. -. -.6 -. -.8 -. -. -.6 -. -.8 -. -..88.9.9.9.96.98.6.7.8.9.5.5.5.5.5 Ë 6 ²ßÚ Ø ßÇ ln(β/tm) /T m Fig.6 ln(β/t m) /T m plots of the endothermic peaks between 9 K (a), 86 9 K (b) and 97 5 K (c) ln( /T m, min - K - )
676 8 6 (Y,Gd) O :Eu + RE O CO 7 K 5..5 Intensity, a.u. 7 K 7 K 97 K 87 K Uncalcined 5 7 9, deg Ë 7 Þ Ñ ²± ßÚ ß h XRD Ö Fig.7 XRD patterns of precursor precipitates after calcined at different temperatures for h ln(d, nm)..5..5......5 Temperature, K - Ë 8 (Y, Gd) O Eu + ÇÅ lnd /T Å Fig.8 Relationship between lnd and /T of (Y, Gd) O Eu + nanocrystals (D grain diameter) Ë 9 Þ Ñ 7 K ± ²» SEM Fig.9 SEM images of precursor precipitates (a) and after calcined at 7 K for h (b), h (c) and 6 h (d), É 5 nm( 9b); ² h, Í, ± ( 9c); ² 6 h, Þ, nm( 9d). Á Í, ² ÛÛ 7 K ¼, h (Y, Gd) O Eu + È Â.  () ph ÐÛ NH H O NH HCO Ò Ô Y, Nd Eu Ë», ³³ ÒÎ ß Ò, 58 K Ð h À 7 K ² h, 5 nm (Y, Gd) O Eu +. () ß Ò µ Æ ¹ÆÑÂ Æ ³ (Y, Gd) O Eu + È«Þ Ý, ÞÝ Õ ºÌÆÆ Û 9.5, 557.5 6.58 kj mol. () (Y, Gd) O Eu + È«³ ³ ÌÆ Û 5.58 kj mol. Ì [] van Eijk C W E. Phys Med Biol, ; 7: 85 [] Hell E, Knuepfer W, Mattern D. Nucl Instrum Methods Phys Res, ; 5A: [] Jung Y S, Kim K H, Jang T Y, Tak Y, Baeck S H. Curr Appl Phys, ; : 58
6 Ø «: (Y, Gd) O Eu + ƽ Ö 677 [] Louardi A, Rmili A, Ouachtari F, Bouaoud A, Elidrissi B, Erguig H. J Alloys Compd, ; 59: 98 [5] Selvam N C S, Kumar R T, Yogeenth K, Kennedy L J, Sekaran G, Vijaga J J. Powder Technol, ; : 5 [6] Gunawidjaja R, Myint T, Eilers H. Ceram Int, ; 8: 775 [7] Taniguchi T, Watanabe T, Katsumata K, Okada K, Matsushita N. J Phys Chem, ; C: 76 [8] Chien J T, Hsu D J, Inbaraj B S, Chen B H. Int J Mol Sci, ; : 5 [9] Matiadis D, prousis K C, Markopoulou O I. Molecules, 9; : 9 [] Si W, Wang J, Wang X H, Gao H, Zhai Y C. J Inorg Mater, ; 6: 76 (Ç Ü, Õ Å, Õ²É,, Â. ¹, ; 6: 76) [] Si W, Gao H, Wang J, Jiang D, Zhai Y C. Chin J Inorg Chem, ; 6: (Ç Ü,, Õ Å, Ø, Â. Ź¹, ; 6: ) [] Jie X F, Liang G C, Wang L, Zhi X K, Gao L M. Adv Mater Res, ; 78: 7 [] Yu H Y, Ren W T, Zhang Y. J Appl Polym Sci, 9; : 7 [] Zhuang Y X, Xing P F, Duan T F, Shi H Y, He J C. J Rare Earths, ; 9: 79 [5] Wang C S, Wang R Q, Wang Y, Fu Y X. Key Eng Mater, ; 5: 9 [6] Dai J F, Ling R Q, Wang K Z. Adv Mater Res, ; 8: 8 [7] Kok M V. Fuel Process Technol, ; 96: [8] Ma W M, Wen L, Shen S F, Liu J, Wang H D. Acta Metall Sin, 9; 5: 759 (ÀÜË, Ð, ±, Å, ÕÁÙ. À¹, 9; 5: 759) [9] Ozawa T. Bull Chem Soc Jpn, 965; 8: 88 [] Doyle C D. J Appl Polym Sci, 96; 5: 85 [] Kisssinger H E. J Res Nat Bue Stand, 965; 57: 7 [] Kissingger H E. Anal Chem, 957; 9: 7 [] Zhao Y N, Zhang W L. Adv Mater Res, ; 9: 558 [] Mullaugh K M, Luther G W. J Nanopart Res, ; : 9 (Ý Ñ: Û )