Bo co seminar

Trnh by:

Ng Trng Ngc Mai

B Mn Cng Ngh Ha Hc 01-2011
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Vt liu ceramic l g? Vt liu v c phi kim loi (thnh phn

gm cc vt cht c cha oxy hoc khng cha oxy): cc khong vt silicate, ZrSiO4, Al2O3, ZrO2, SiO2, SiC, SiN, BaTiO3, Sn xut bng phng php nung kt khi nhit cao (gm s) hoc nu chy (thy tinh)
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Bi nghin oxit nhm

Khong vt corundum th (oxit nhm)

Chi tit my zirconia

Corundum sau gia cng3

Phn loi
Vt liu ceramic: - Truyn thng (traditional ceramics) - K thut (industrial ceramics) Vt liu ceramic k thut: - Cu trc/kt cu (structural ceramics) - Chc nng (functional ceramics)

Cu trc ph bin nht ca functional ceramics l PEROVSKITE!

Lch s pht hin perovskite Cu trc perovskite Tnh cht ca cc perovskite Cc phng php sn xut Cc nghin cu v ng dng quan trng
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 Perovskite l tn gi chung ca cc vt liu c cu trc tng t khong vt CaTiO3 Khong perovskite c nghin cu v pht hin ln u tin vng ni Uran ca Nga bi Gustav Rose vo nm 1839 v c t tn theo nh khong vt hc L.A Perovski (1792-1856) C trong rt nhiu dng khong vt t nhin cc vng ni Uran v Thy S, Cu trc c quan tm nghin cu do s a dng v tnh cht cc nhit khc nhau. Perovskite l tri tim ca vt l cht rn (nh vt l ngi n Rao) 6

- Cubic SrTiO3
1/2 0,1 0,1 1/2 0,1 B site 1/2 0,1 0,1 0,1 1/2 0,1 (a) 0,1 (b) 1/2 Oxygen

A site

ABO3 - SrTiO3

(c)

- Cubic SrTiO3 Ti

O
Bt din BO6 (TiO6) S phi tr ca B (Ti): 6

ABO3

S phi tr ca A (Sr): 12 rA ~ rO, rA > rB , tng in tch 8 cation A v B = 6

Sr (ti l hng bt din)

- n gin v phc tp
-n gin: ABO3
Loi perovskite 2, 4Ph bin, quan trng nht 3, 3Ha tr cation A 2 V d A Ba2+, Ca2+, Mg2+, Zn2+, Cd2+, Ni2+, Sr2+, Pb2+ La3+, Y3+, Gd3+, Nd3+, Bi3+ K+ , Na+ Ha tr cation B 4 V d B Ti4+, Mn4+, Ce4+, Sn4+, Zr4+ Sc3+, Fe3+, Ga3+, Ni3+, Fe3+, Mn5+, Nb5+, Ta5+ Hp cht ABO3 CaTiO3, BaTiO3, SrMnO3, PbZrO3, PbTiO3 Vt liu st in LaNiO3, YFeO3, LaAlO3 KNbO3, KTaO3 Vt liu ha in v quang in

1, 5Quan trng th hai

-Phc tp: A: 2+, B: hn hp vi cation c tng ha tr 4

-Vd: (3+ + 5+)/2=4+; (1x2+ +2x5+)/3=4+
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Phc tp: hp cht 1/2:1/2 v 1/3:2/3 -Hp cht 1/2:1/2: A2BBO6 hoc AB1/2B1/2O3
Loi : Ha Ha V d B Ha V d tr A tr B tr B B 3,5 2 3 Sc, Nd, La, 5 Nb, Ta Y, Gd, In 2,6 2 2 Co, Sr, Mg 6 W 1,7 2 1 Na, K 7 Os Hp cht Pb2ScTaO6, Ba2YTaO6 Pb2CoWO6 Ba2NaOsO6

Pb2ScTaO6
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Phc tp: hp cht 1/2:1/2 v 1/3:2/3 -Hp cht 1/3:2/3: A3BB2O9 hoc AB1/3B2/3O3
-Thng 2+ (Zn, Mg), 5+ (Nb, Ta): Ba3MgTa2O9, Pb3MgTa2O9
Pb Zn Ta

Pb3ZnTa2 O9
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- Cubic SrTiO3

TiO6
A qu nh: bt din BO6 b nghing A qu ln: lin kt Ti-O b ko dn, Ti b lch khi v tr trung tm gia 2 nguyn t O

Nu A qu nh hay qu ln hn kch thc l hng, iu g s xy ra?

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H s dung sai(Tolerance factor)

a = 2 (RO + RB
A

2 a = 2 ( RO + RA )
B

Mong mun:

( RO + RA ) = 1 = 2 ( RO + RB )

Thc t: 0.88 < t < 1.02 Nu t khc 1: cu trc b bin dng hoc, khng hnh thnh perovskite Nu t <1: A qu nh cu trc nghing t=1: A c kch thc l tng t > 1 : A qu ln cu trc lch

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Cubic Lin kt Mn-O-Mn thng

CaMnO3

Orthorhombic Mn-O-Mn cong

Mn

Mn

Mn

Mn
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LaMnO3
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 WO3 Ba5Nb4O15 YBa2Cu3O7

ABO3 1 l trng v tr A, W6+ v tr B 5(ABO3) 1 l trng B 3(ABO3) Y3+, Ba2+ v tr A, 2 l trng O 2Cu2+ v 1 Cu3+ v tr B

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 Tnh st in v st t (ferromagnetic): trn c s BaTiO3 Tnh ha in (pyroelectricity) Tnh p in (piezoelectricity) Tnh t tnh (magnetic property) Tnh siu dn (superconductivity): c s Ba2YCu3O7 Tnh dn in (electrical conductivity) Tnh dn ion v electron (ion conductivity): SOFC Tnh xc tc (catalytic property)
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Thnh phn CaTiO3

BaTiO3 Pb(Zr1-xTix)O3 (Ba1-xLax)TiO3 (Y1/3Ba2/3)CuO3-x NaxWO3 SrCeO3 RE*TM**O3-x AMnO3-x Li0,5-3xLa0,5+xTiO3

Tnh cht
Cch in (dielectric) St in (ferroelectric) p in (piezoelectric) Bn dn (semiconductor) Siu dn (superconductor), dn ion O2Dn ion v electron (mixed conductor), quang in (electrochromic) Dn proton Dn ion v electron (Mixed conductor) Hiu ng in tr t khng l (giant magnetoresistance effect) Dn ion Li+
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* Rare Earth-Nguyn t t him, ** Transition metal-Kim loi chuyn tip

 Tnh st in (ferroelectricity): tnh cht hng ng mnh di in trng ngoi do c s sp xp cc lng cc in theo cng mt hng (ng dng: t in, TB lu tr thng tin, th RFID) http://www.doitpoms.ac.uk/tlplib/ferroelectrics/index.php * Tnh p in (piezoelectricity): Khi tc dng lc ln vt liu s sinh ra dng in v ngc li do gi tr moment lng cc thay i khi cu trc b nn p (ng dng: cc sensor).

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 Tnh ha in (pyroelectricity): khi gia nhit, dng in xut hin trong vt liu do gi tr ca moment lng cc b thay i khi cu trc b t nng (ng dng: sensor) Tnh siu dn: tnh cht tn ti nhit cc thp, khi dng in chy qua, vt liu khng c khng tr

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Phng php tng hp t phn ng pha rn

- Sn phm ceramic dng khi - Sn phm ceramic dng mng (film)

Kch thc ht tng i ln (micron)

Phng php tng hp t phn ng pha lng

Kch thc ht rt nh (c nano) - Sn phm ceramic dng khi - Sn phm ceramic dng mng (film)
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Phng php tng hp t phn ng pha rn

Nguyn liu Cn ng t l Nghin trn Sy Ry Hn hp cc oxide Nung
Oxide, mui carbonat dng bt Nc/dung mi hu c

Sn phm dng khi

Sn phm dng bt Sn phm dng film Ry Sy Nghin Hp cht perovskite

Nc/dung mi hu c

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Sn phm dng bt

Sn phm dng bt
Dung mi hu c

p kh/bn kh Nung kt khi

To huyn ph To mng mng Nung kt khi

-Kt ta in di - In

Sn phm dng khi (bulk ceramics)

Sn phm dng mng (ceramic films) Sn phm dng mng

Sn phm dng khi

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Phng php tng hp t phn ng pha lng

Mui kim loi, alkoxide kim loi, hp cht c kim

Nguyn liu

Dung mi Bay hi Dung dch Kt ta/gel ha Tc nhn kt ta/ to phc/ gel ha

Phn ng c th
(thy nhit,)

Gia nhit

Sn phm
(kch thc ht rt nh)
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Phng php tng hp t phn ng pha lng Phn loi Phng php thc hin

Nhit phn t pha hi/sng, phn Nhm 1 hy nhit, sy lnh, sng siu Bay hi hoc kt ta c iu m, nc siu ti hn, khin Nhm 2 S dng l xp c micron Antimicelle keo

Cht trung gian hydroxide, sol-gel, Nhm 3 phn hy, phng php phc S dng hp cht trung gian EDTA, (hu c)
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Knh thng minh: smart window, E-glass

Gm p in: piezoelectric ceramics

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Knh thng minh: smart window, E-glass

Tt (~99,4% nh sng)

- L loi thy tinh c th iu chnh lng nh sng v nhit truyn qua n khi cho dng in chy qua: electrically switchable glass - gim s dng iu ha khng kh 28 - gim si m, chiu sng

Nguyn tc
Lp ph dn in Cc ht l lng Mng chn Lp dn bo v Thy tinh

Tt-M c

M-Trong sut
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Cc loi knh thng minh bt tt

Quang in (electrochromic)
2

Cc ht huyn ph (suspended particles)

3

Tinh th lng (liquid crystal)

4

Micro-blinds

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Knh quang in (electrochromic)

Thy tinh Lp mng quang in Cht in ly in cc Thy tinh

ITO: Indium Tin Oxide Mng quang in: hexacianoferrate, WO3 in cc: h CeO2-TiO2
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Ngun in

M t lp mng quang in - C tnh i mu theo dng in (1 chiu: ~1V), thun nghch -Thnh phn chnh: WO3 - Cu trc: perovskite C ch i mu WO3 + trong cch in Ti +
e ITO Ngun cung cp H+ WO3 e

xH+

+xe-

HxWO3 m c dn in

Sng

ITO thy tinh

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Gii thch

WO3 + cch in

xH+

+xe-

HxWO3 dn in

W:

4f145d46s2 5d06s0 5d16s0

AxWO3 : 0 x 1, Ax(Wx5+W1-x6+)O3 d1 d0
W6+

A: H+, Na+, K+, l trng thi khng chuyn tip (tr)

W6+: W5+:

W5+: c 1 e ngoi cng orbital d c tnh dn electron ging kim loi WO3 l mt perovskite trng v tr A d dn ion A+ vo l trng, ng thi s oxy ha ca W gim t +6 n +5.
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So snh: knh i mu truyn thng

Z Trn hoc m u mt lp AgCl trong sut. Z AgCl hp th nng lng ca tia cc tm trong nh sng mt tri, b phn hy thnh ht Ag rt nh lm knh chuyn mu sm hn khi ra nng. Z sm ca knh ph thuc vo cng ca tia cc tm. Z Mu sc knh do ph thm mt lp mu (xm, nu, vng, ,) Z u im: Z Tin li, khng cn thay knh Z Ngn nga tia cc tm hi mt
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ng dng knh thng minh

Z Knh mt: chng tia cc tm (Nikon) Z Knh bo v hin vt (trong vin bo tng), my bay Z Gng chng la (Schotts) Z Ca knh nh , ta nh vn phng, bnh vin (h thng NHS Anh quc) Z Mn trnh chiu

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Gm p in: piezoelectric ceramics

* Hiu ng p in: di tc dng ca lc c hc, b mt vt liu xut hin s phn cc in v do xut hin dng in. * y l hiu ng thun nghch.

Vt liu c tnh p in cao: h gm PZT (lead zirconate titanate): PbTi1-xZnxO3, perovskite.

Pb
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ng dng
Pha pha rhombohedral: gia tc k, thit b chn on hnh nh y khoa, Pha pha tetragonal: ng nghe di nc, microphone,, cm bin, b bin i siu m, b qut, ng c ( a my tnh, chc nng zoom ng knh in thoi chp nh), Hiu ng p in cao bt thng ti vng ln cn x=0,5. V d 53% PZ, 48% PT. Vng c s chuyn gia 2 pha tetragonal v 38 rhombohedral.

Chn on hnh nh bng siu m

Dng in Transducer (PZT) Xung phn x Xung dao ng Vo c th Tr khng Hnh nh c quan ni tng v m Tn hiu in

bc sng() x tn s(f) = vn tc sng m trong mi trng(v) 1mm-50m 1,5-30MHz 1500 m/s (trong c th ngi)
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Bc sng nh sc nt cao

ng dng

Chn on siu m trong y khoa Bt la, nh la gas B chuyn i dch chuyn Gia tc k B bin th p in u in kim C cu truyn ng
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Tm tt
Cu trc Perovskite c nghin cu v ng dng

nhiu nht cho vt liu ceramic chc nng (functional ceramics) D dng thay i/iu chnh tnh cht ca vt liu c cu trc perovskite bng cch thay i thnh phn, t l kt hp. Cc tnh cht c ng dng nhiu nht: tnh st in, ha in, p in, t tnh, dn ion v electron (BaTiO3, PZT, ) Tnh cht c bit: tnh siu dn nhit cao.
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References
1. Perovskite oxide for Solid Oxide Fuel Cells, T.Ishihara, Springer Science, LLC 2009 2. http://www.doitpoms.ac.uk/tlplib/ferroelectrics/index.php 3. http://www.morganelectroceramics.com 4. J. Kulawik, D. Szwagierczak, B. Groger Investigations of properties of ceramic materials with perovskite structure in chosen electronic applications, Bulletin of the Polish academy of sciences: Technical sciences, 55(3) 2007 5. Crystal structure and defect property predictions in Ceramic Materials, Thesis of Mark R. Levy, Imperial College of Science, Technology and Medicine, 2005
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