Header Page of 89 I HC HU TRNG I HC KHOA HC Lời -cảm ơn Trớc tiên, xin by tỏ lời cảm ơn chân thnh v tri ân sâu sắc đến ThầyLấGiáo TS Phan Đình Giớ tận IPGS VNG tình hớng dẫn v truyền đạt cho nhiều kiến thức quý báu, giúp thực tốt đề ti luận án ny NGHIấN Tôi CU TOcảm VơnCC TNH CHT xin CH chân thnh quí thầy cô giáo VT Khoa Lí VậtGM Lý, Trờng Đại học Khoa học Huế dạy tạo V CA H A THNH PHN TRấN C dỗ, SvPZT điềuVT kiện LIU thuận lợiST cho IN trongCHUYN trình thực hiệnNHềE đề ti CC PHA Bên cạnh nhận đợc quan tâm tạo điều kiện v giúp đỡ Trờng Cao đẳng Công nghiệp Huế, Khoa Công nghệ Hóa - Môi trờng v động viên bạn bè Chuyờn ngnh: Vt lý Cht rn đồng nghiệp Mó s: 62.44.01.04 Cuối cùng, lòng biết ơn trân trọng dnh cho Gia đình đặc biệt l B Nội, Vợ Con v ngời thân bên tôi, Nviên TIN VTgiúp Lí thực tốt hỗ trợ vật chấtLUN v động tinhSthần, đề ti luận án.Ngi hng dn khoa hc: PGS TS Phan ỡnh Gi Huế, 2014 Lê Đại Vơng HU, 2014 i Footer Page of 89 Header Page of 89 Lời cảm ơn Trớc tiên, xin by tỏ lời cảm ơn chân thnh v tri ân sâu sắc đến Thầy Giáo PGS TS Phan Đình Giớ tận tình hớng dẫn v truyền đạt cho nhiều kiến thức quý báu, giúp thực tốt đề ti luận án ny Tôi xin chân thnh cảm ơn quí thầy cô giáo Khoa Vật Lý, Trờng Đại học Khoa học Huế dạy dỗ, v tạo điều kiện thuận lợi cho trình thực đề ti Bên cạnh nhận đợc quan tâm tạo điều kiện v giúp đỡ Trờng Cao đẳng Công nghiệp Huế, Khoa Công nghệ Hóa - Môi trờng v động viên bạn bè đồng nghiệp Cuối cùng, lòng biết ơn trân trọng dnh cho Gia đình đặc biệt l B Nội, Vợ Con v ngời thân bên tôi, hỗ trợ vật chất v động viên tinh thần, giúp thực tốt đề ti luận án Huế, 2014 Lê Đại Vơng ii Footer Page of 89 Header Page of 89 LI CAM OAN Tụi xin cam oan õy l cụng trỡnh nghiờn cu ca tụi, c thc hin ti Phũng thớ nghim Vt lý cht rn, Khoa Vt lý, Trng i hc Khoa hc Hu di s hng dn ca PGS TS Phan ỡnh Gi Cỏc s liu v kt qu lun ỏn l trung thc v cha tng cụng b bt c cụng trỡnh no khỏc Tỏc gi lun ỏn Lờ i Vng iii Footer Page of 89 Header Page of 89 DANH MC CC Kí HIU V CH VIT TT PT PbTiO3 PZ PbZrO3 PZT PbZr1-xTixO3 PZN Pb(Zn1/3Nb2/3) PMnN Pb(Mn1/3Nb2/3) PNN Pb(Ni1/3Nb2/3) PZT-PZN Pb(Zr,Ti)O3 Pb(Zn1/3Nb2/3) PZT-PMnN Pb(Zr,Ti)O3 Pb(Mn1/3Nb2/3) PZT-PMnS Pb(Zr,Ti)O3 Pb(Mn1/3Sb2/3) PZT-PSN-PMnN Pb(Zr,Ti)O3 Pb(Sb1/2Nb1/2) Pb(Mn1/3Nb2/3) PZT-PZN-PMN Pb(Zr,Ti)O3 Pb(Zn1/3Nb2/3) Pb(Mg1/3Nb2/3) PZT-PZN-PMnN Pb(Zr,Ti)O3 Pb(Zn1/3Nb2/3) Pb(Mn1/3Nb2/3) TC Nhit Curie (oC) Tm Nhit ng vi hng s in mụi cc i (oC) BX Bin t ỏp in dng xuyn BG Bin t ỏp in Langevin Cs in dung ca mu ER Ergodic relaxor NER Non ergodic relaxor TB Nhit Burn Tf Nhit ụng cng HWHM bỏn rng ca vch Raman BO Phng phỏp trn cỏc ụxớt v trớ B iv Footer Page of 89 Header Page of 89 % kl Phn trm lng kp H s liờn kt in c theo phng bỏn kớnh kt H s liờn kt in c theo phng b dy Qm H s phm cht c hc d31 H s ỏp in theo phng ngang P phõn cc Pr phõn cc d Ps phõn cc t phỏt E in trng EC in trng khỏng t Tha s xp cht Zm Giỏ tr cc tiu ca tng tr nhũe Hng s in mụi Gúc nhiu x tan Tn hao in mụi v Footer Page of 89 Header Page of 89 MC LC M U CHNG 1: TNG QUAN Lí THUYT V CC VN NGHIấN CU 1.1 Cu trỳc perovskite ABO3 1.2 c trng st in thụng thng 1.2.1 Hin tng tn ti phõn cc t phỏt cỏc tinh th st in 1.2.2 Nhit Curie v s chuyn pha 10 1.2.3 ng tr st in 12 1.2.4 Cu trỳc ụmen st in 16 1.3 c trng st in chuyn pha nhũe 18 1.4 Tng quan tỡnh hỡnh nghiờn cu gm ỏp in trờn c s PZT 24 1.4.1 Vt liu PZT pha n 24 1.4.2 Vt liu PZT pha phc 27 1.5 Ph tỏn x Raman 31 1.6 Kt lun chng .33 CHNG 2: TNG HP VT LIU, CU TRC V VI CU TRC CA H GM PZT PZN PMnN 34 2.1 Tng hp h vt liu PZT PZN PMnN .34 2.2 Cu trỳc v vi cu trỳc ca h vt liu PZT PZN PMnN 41 2.2.1 Cu trỳc v vi cu trỳc ca nhúm vt liu MP 41 2.2.2 Cu trỳc v vi cu trỳc ca nhúm vt liu MZ 44 2.3 Cỏc phng phỏp nghiờn cu tớnh cht ca vt liu 49 2.3.1 Phng phỏp nghiờn cu tớnh cht in mụi 49 2.3.2 Phng phỏp nghiờn cu tớnh cht ỏp in 51 vi Footer Page of 89 Header Page of 89 2.3.3 Phng phỏp nghiờn cu tớnh cht st in 55 2.4 Kt lun chng 57 CHNG 3: NGHIấN CU TNH CHT IN MễI, ST IN V P IN CA H GM PZT-PZN-PMnN 58 3.1 Tớnh cht in mụi ca h vt liu PZT- PZN-PMnN 59 3.1.1 Hng s in mụi ca cỏc nhúm mu MP, MZ nhit phũng 59 3.1.2 S ph thuc ca hng s in mụi theo nhit 60 3.1.3 S ph thuc ca tớnh cht in mụi vo tn s ca trng ngoi 64 3.2 Tớnh cht st in ca h vt liu PZT- PZN-PMnN 68 3.2.1 nh hng ca nng PZT v t s Zr/Ti n tớnh cht st in ca h vt liu PZT PZN PMnN ti nhit phũng 68 3.2.2 nh hng ca nhit n tớnh cht st in ca h vt liu PZT PZN PMnN 70 3.3 Tớnh cht ỏp in ca h vt liu PZT- PZN-PMnN 73 3.4 Kt lun chng .79 CHNG 4: NGHIấN CU NH HNG CA Fe2O3, CuO N CC TNH CHT CA H GM PZT-PZN-PMnN 81 4.1 nh hng ca Fe2O3 n cỏc tớnh cht ca h gm PZT-PZN-PMnN 81 4.1.1 nh hng ca Fe2O3 n cu trỳc, vi cu trỳc ca h gm PZTPZNPMnN 81 4.1.2 nh hng ca Fe2O3 n tớnh cht in mụi ca h gm PZT-PZN-PMnN 84 4.1.3 nh hng ca Fe2O3 n tớnh cht ỏp in ca h gm PZT-PZN-PMnN 91 4.1.4 nh hng ca Fe2O3 n tớnh cht st in ca h gm PZT-PZN-PMnN 94 4.2 nh hng ca CuO n hot ng thiờu kt v cỏc tớnh cht in ca h gm PZTPZNPMnN 96 4.2.1 nh hng ca CuO n hot ng thiờu kt ca h gm PZTPZNPMnN 96 4.2.2 nh hng ca CuO n tớnh cht in ca h gm PZTPZNPMnN 101 vii Footer Page of 89 Header Page of 89 4.3 Th nghim ch to mỏy siờu õm trờn c s bin t ỏp in PZT-PZNPMnN 112 4.4 Kt lun chng 115 KT LUN V KIN NGH 116 DANH MC CC CễNG TRèNH NGHIấN CU 118 TI LIU THAM KHO 120 viii Footer Page of 89 Header Page of 89 DANH MC CC BIU BNG Bng 1.1 Giỏ tr ca tha s xp cht t i vi mt s hp cht kiu perovskite Bng 2.1 Cỏc kt qu tớnh toỏn kớch thc ht, hng s mng v mt gm trung bỡnh ca nhúm mu MP t vic phõn tớch SEM v nhiu x Tia X 42 Bng 2.2 Cỏc kt qu tớnh toỏn kớch thc ht, hng s mng v mt gm trung bỡnh ca nhúm mu MZ t vic phõn tớch SEM v nhiu x tia X 46 Bng 2.3 Cỏc h s a thc ca (2.14) v (2.15) 54 Bng 3.1 Cỏc giỏ tr trung bỡnh ca hng s in mụi v tn hao in mụi tan ca cỏc nhúm mu MP, MZ nhit phũng ti tn s 1kHz 59 Bng 3.2 Cỏc giỏ tr ca hng s in mụi cc i max, nhit ng vi hng s in mụi cc i Tm v nhũe ca cỏc nhúm mu MP, MZ o ti tn s 1kHz 63 Bng 3.3 Cỏc thụng s thu c t vic lm khp s liu vi cỏc h thc Vogel Fulcher 68 Bng 3.4 Cỏc thụng s c trng cho tớnh cht st in ca gm PZT-PZNPMnN ti nhit phũng: phõn c d Pr, in trng khỏng EC 69 Bng 3.5 Cỏc thụng s c trng cho tớnh cht st in ca gm PZT-PZNPMnN theo nhit : phõn c d Pr, in trng khỏng EC 72 ix Footer Page of 89 Header Page 10 of 89 Bng 3.6 Cỏc giỏ tr trung bỡnh ca h s liờn kt in c kp, k31, kt, h s ỏp in d31 v h s phm cht c hc Qm ca gm PZT-PZN-PMnN 76 Bng 3.7 So sỏnh cỏc tớnh cht ca gm ó ch to vi gm ca cỏc cụng trỡnh khỏc 79 Bng 4.1 Cỏc kt qu tớnh kớch thc ht v mt gm ca nhúm mu MF t vic phõn tớch SEM 83 Bng 4.2 Cỏc giỏ tr trung bỡnh ca hng s in mụi v tn hao in mụi tan ca cỏc mu MF nhit phũng ti tn s 1kHz 84 Bng 4.3 Cỏc giỏ tr ca hng s in mụi cc i max, nhit ng vi hng s in mụi cc i Tm v nhũe ca cỏc mu MF ti tn s 1kHz 88 Bng 4.4 Cỏc giỏ tr trung bỡnh ca h s liờn kt in c kp, kt, k31, h s ỏp in d31 v h s phm cht c hc Qm ca gm PZT-PZN-PMnN pha Fe2O3 92 Bng 4.5 Cỏc thụng s c trng cho tớnh cht st in ca gm PZT-PZNPMnN pha Fe2O3: phõn c d Pr, in trng khỏng EC 95 Bng 4.6 So sỏnh cỏc tớnh cht ca gm ó ch to vi gm ca cỏc cụng trỡnh khỏc cú cựng loi Fe2O3 95 Bng 4.7 Mt gm, hng s in mụi, tn hao tan, h s kp ca mu M01150 97 Bng 4.8 Cỏc kt qu tớnh toỏn kớch thc ht, thụng s mng v mt gm ca nhúm mu MC t vic phõn tớch SEM v nhiu x tia X 104 x Footer Page 10 of 89 Header Page 135 of 89 nú th hin tn hao in mụi gim; h s phm cht Qm tng, bờn cnh ú Fe2O3 cng lm gia tng kớch thc ht gm ci thin ỏng k cỏc tớnh cht in mụi, ỏp in v st in ca vt liu Chỳng tụi ó xỏc nh c nng Fe2O3 ti u l 0,25 % kl Ti nng ny gm cú tớnh cht in mụi, st in v ỏp in tt nht: = 1400; max = 24920; tan = 0,003; d31 = 155 pC/N; kp = 0,64; kt = 0,51; Pr = 37 àC/cm2 v Qm = 1450 - Vi mc ớch lm gim nhit thiờu kt, chỳng tụi ó thnh cụng vic pha CuO vo h vt liu PZT PZN PMnN v ó gim ỏng k nhit thiờu kt ca vt liu Vi nng 0,125 % kl CuO, nhit thiờu kt ca gm ó gim t 1150 oC xung cũn 850 oC Nh vy nhit thiờu kt ca gm ó gim 300 oC so vi mu khụng cú CuO Cỏc thụng s c trng cho tớnh cht in mụi, ỏp in ca vt liu t giỏ tr tt nht ng vi mu cú nng CuO l 0,125 % kl, thiờu kt ti nhit 850 oC: mt gm l 7,91 g/cm3, hng s in mụi = 1179, tn hao in mụi tan = 0,006, h s liờn kt in c kp= 0,55 Chỳng tụi ó ch to thnh cụng mỏy siờu õm cú cụng sut trung bỡnh (40 W), tn s lm vic ca mỏy l 40,26 kHz da trờn cỏc bin t c ch to t h gm PZT PZN PMnN + 0,10 % kl CuO - Mc dự chỳng tụi ó thnh cụng vic ch to bin t ỏp in dng xuyn ghộp theo kiu Langevin s dng cho mỏy siờu õm, nhng cỏc kt qu cng ch dng li mc th nghim Lnh vc ny cn phi c nghiờn cu sõu hn, rng hn cho nhiu loi ng dng hn Bờn cnh ú, vic thay th cỏc nguyờn t khỏc (K, Na, Ba, Bi) vo v trớ A ca cu trỳc ABO3 thay cho Pb l cng l hng mi ca ti nhm xõy dng mt h vt liu mi thõn thin vi mụi trng v ngi 117 Footer Page 135 of 89 Header Page 136 of 89 DANH MC CC CễNG TRèNH NGHIấN CU 1) Phan ỡnh Gi v Lờ i Vng (2011), Tớnh cht in mụi, st in ca gm PZT-PZN-PMnN Tp khoa hc, i hc Hu, S 65, tr 53-61 2) Phan ỡnh Gi v Lờ i Vng (2011), nh hng ca nng PMnN n cu trỳc v cỏc tớnh cht ỏp in ca gm PZT-PZN-PMnN Tp khoa hc, i hc Hu, S 65, tr 63-71 3) Phan ỡnh Gi, Nguyn Th Bớch Hng, Lờ i Vng (2012), nh hng ca t s nng Zr/Ti n cỏc tớnh cht vt lý ca h gm PZT-PZN-PMnN Tp Khoa hc v Cụng ngh 50 (1A),tr 112-118 4) Phan ỡnh Gi, Nguyn Vn Quý, Lờ i Vng (2012), S ph thuc nhit ca mt s tớnh cht vt lý ca h gm PZT-PZN-PMnN Tp Khoa hc v Cụng ngh 50 (1A), tr 235-240 5) Phan ỡnh Gi, Lờ i Vng, Nguyn Th Trng Sa (2013), nh hng ca thi gian thiờu kt n mt s tớnh cht ca h gm ỏp in PZT-PZN-PMnN thiờu kt nhit thp, Tp khoa hc, i hc Hu, Tp 87, S 9, (2013), tr 45-51 6) Phan ỡnh Gi, Lờ i Vng v Nguyn Quang Long (2013), Nghiờn cu, ch to mỏy siờu õm trờn c s h gm PZT - PZN PMnN, Hi ngh ton quc ln th Vt lý k thut v ng dng (CAEF-2013), Hu, 8-12 thỏng 10 nm 2013 7) Phan ỡnh Gi, Lờ i Vng, H Th Thanh Hoa, nh hng ca CuO n nhit thiờu kt ca gm ỏp in PZT-PZN-PMnN, Hi ngh Vt lý cht rn v Khoa hc vt liu ton quc ln th (SPMS-2013) Thỏi Nguyờn 46/11/2013 (ó c Tp Khoa hc v Cụng ngh 50 nhn ng 5/6/2014) 8) Lờ i Vng, Vn Qung, Phan ỡnh Gi (2013), nh hng ca nhit thiờu kt n cu trỳc v cỏc tớnh cht in ca gm PZT-PZN-PMnN pha Fe2O3, Tp khoa hc, i hc Hu, Tp 87, S 9, (2013), tr 225-231 9) Lờ i Vng, H Th Thanh Hoa, Nguyn Th Thu H, Phan ỡnh Gi (2012), nh hng ca ch n mt s tớnh cht vt lý ca h gm PZT-PZNPMnN Tp khoa hc, i hc Hu, Tp 73, s 4, tr 253-261 118 Footer Page 136 of 89 Header Page 137 of 89 10) Phan Dinh Gio, Le Dai Vuong and Nguyen Phan Nhu Y (2012), Effect of PZT content on the structure and electrical properties of PZT-PZN-PMnN ceramics The 6th International Workshop on Advanced Materials Science and Nanotechnology (IWAMSN2012) - October 30-November 02, 2012 - Ha Long City, Vietnam 11) Le Dai Vuong, Phan Dinh Gio, Truong Van Chuong, Dung Thi Hoai Trang, Duong Viet Hung, Nguyen Trung Duong (2013), Effect of Zr/Ti ratio content on some physical properties of the low temperature sintering PZT-PZN-PMnN ceramics International Journal of Materials and Chemistry, Vol 3(2), pp: 3943 12) Le Dai Vuong, Phan Dinh Gio, Nguyen Thi Kieu Lien (2013), Physical properties of PZT-PZN-PMnN ceramics were fabricated by B-site oxide mixing technique, Journal of science, Hue University, Vol 84, No.6, pp: 93-99 13) Le Dai Vuong, Phan Dinh Gio, Nguyen Truong Tho, and Truong Van Chuong (2013), Relaxor Ferroelectric Properties of PZT-PZN-PMnN Ceramics Indian Journal of Engineering & Materials Sciences, Vol 20, pp: 555-560 14) Le Dai Vuong, Phan Dinh Gio (2013) Effect of Li2CO3 addition on the sintering behavior and physical properties of PZT-PZN-PMnN ceramics, International Journal of Materials Science and Applications, Vol 2(3), pp: 8993 15) Le Dai Vuong, Phan Dinh Gio (2014), Structure and electrical properties of Fe2O3-Doped PZTPZNPMnN ceramics, Journal of Modern Physics,Vol 5, pp: 1258-1263 16) Le Dai Vuong, Phan Dinh Gio, Vo Thi Thanh Kieu (2014), Raman scattering spectra and dielectric relaxation behavior of PZT-PZN-PMnN ceramics, International Journal of Chemistry and Materials Research, Vol 2(6), pp: 48-55 17) Phan Dinh Gio, Le Dai Vuong, Ho Thi Thanh Hoa (2014), Electrical Properties of CuO-Doped PZT-PZN-PMnN Piezoelectric Ceramics Sintered at Low Temperature, Journal of Materials Science and Chemical Engineering, Vol 2, pp: 20-27 119 Footer Page 137 of 89 Header Page 138 of 89 TI LIU THAM KHO Ting Vit [1] Trng Vn Chng (2002), Ch to v nghiờn cu cỏc tớnh cht vt lý ca gm ỏp in h PbTiO3 pha La, Mn, Lun ỏn Tin s khoa hc vt liu, H Ni [2] Lờ Quang Tin Dng (2014), Nghiờn cu ch to thit b siờu õm cụng sut tng hp vt liu TiO2 cu trỳc nanụ, Lun ỏn Tin s Vt lý, HKH Hu [3] Phan ỡnh Gi (2007), Nghiờn cu cỏc tớnh cht vt lý ca gm st in hai, ba thnh phn trờn c s PZT pha La, Mn, Fe, Lun ỏn Tin s Vt lý, HKH Hu [4] Thõn Trng Huy (2014), Ch to v nghiờn cu cỏc tớnh cht vt lý ca gm ỏp in nhiu thnh phn [(1-x)Pb(Zr,Ti)O3 xPb(Mn1/3Nb2/3)O3] (PZTPMnN) pha t him, Lun ỏn Tin s khoa hc vt liu, H Ni [5] Nguyn ỡnh Tựng Lun (2011), Ch to v nghiờn cu cỏc tớnh cht vt lý ca gm ỏp in nhiu thnh phn (1-x)Pb(ZrzTi1-z)O3 - xPb[(Sb1/2Nb1/2)y(Mn1/3Nb2/3)1-y]O3, Lun ỏn Tin s Vt lý, HKH Hu [6] Nguyn ỡnh Tựng Lun, Trng Vn Chng, ng Anh Tun, Phan Thanh H, on Nam Hu, Vi cu trỳc v cỏc tớnh cht in mụi ca gm st in relaxo PZT-PMnN-PSbN, Tp Khoa hc Cụng ngh, Vin Khoa hc Vt liu, H Ni, 2012 [7] Nguyn ỡnh Tựng Lun, Thõn Trng Huy, Trng Vn Chng, Lờ Vn Hng, Nghiờn cu v biờn pha hỡnh thỏi ca h gm ỏp in PZT PbMnSbN, Tp Khoa hc Cụng ngh, Vin Khoa hc Vt liu, H Ni, 2012 120 Footer Page 138 of 89 Header Page 139 of 89 Ting Anh [8] Bau ăerle D and Pinczuk A (1976), Low Frequency Vibrational Modes and the Phase Transitions of Rhombohedral PbTi1-xZrxO3, Solid State Comm., 19,116971 [9] Beere W (1975), A unifying theory of the stability of penetrating liquid phases and sintering pores, Acta Metall 23, pp:131-138 [10] Bokov A.A, Ye Z G (2006), Recent progress in relaxor ferroelectrics with perovskite structure, Journal of materials science, pp 41 3152 [11] Burns G and Scott B A (1973), Lattice Modes in Ferroelectric Perovskites: 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Vogel Fulcher ca cỏc mu MP: MP65 (0,65 mol PZT) , MP70 (0,7 mol PZT) , MP75 (0,75 mol PZT) , MP80 (0,8 mol PZT) , MP85 (0,85 mol PZT) v MP90 (0,9 mol PZT) 67 Hỡnh 3.6 ng thc nghim v ng lm... mu MP: MP65 (0,65 mol PZT) , MP70 (0,7 mol PZT) , MP75 xiv Footer Page 14 of 89 Header Page 15 of 89 (0,75 mol PZT) , MP80 (0,8 mol PZT) , MP85 (0,85 mol PZT) v MP90 (0,9 mol PZT) 64 Hỡnh