Cau Truc Perovslite Cua Vat Lieu Ceramic

7/15/2019 Cau Truc Perovslite Cua Vat Lieu Ceramic

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Trnh by:Ng Trng Ngc MaiB Mn Cng Ngh Ha Hc01-2011

Bo co seminar


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Vt liu ceramic l g? Vt liu v c phi kim loi (thnh phngm cc vt cht c

cha oxy hoc khng

cha oxy): cc khong vt silicate, ZrSiO4

,Al2

O3

, 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 corundumth (oxit nhm)

Chi tit my zirconia Corundum sau gia cng


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Phn loiVt 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!


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5Cc nghin cu v ng dng quan trng

Cc phng php sn xut

Tnh cht ca cc perovskite

Cu trc perovskite

Lch s

pht hin perovskite


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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 lnu 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 sa dng v tnh cht

cc nhit

khc nhau.

Perovskite l tri tim ca vt l cht rn (nh vt lngi n Rao)


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- Cubic SrTiO3

0,10,1

0,1

0,1

1/2 1/2

1/2

1/2

1/2 Oxygen

B site

A site

0,1 0,1

0,1

0,1

(a) (b)

(c)

ABO3

- SrTiO3


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- Cubic SrTiO3

OO

SrSr

TiTi

Bt din BO6 (TiO6

)

S phi tr ca B (Ti): 6 S

phi tr

ca A (Sr): 12

rA ~ rO, rA > rB , tngin tchcation A v B = 6

ABO3

(ti l

hng bt din)


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- n gin v phc tp-n gin: ABO3

-Phc tp: A: 2+, B: hn hp vi cation c

tng ha tr

4

-Vd: (3+ + 5+)/2=4+; (1x2+ +2x5+)/3=4+

Loiperovskite

Ha tr

cation AV

d

A Ha tr

cation BV

d

B Hp cht ABO3

2, 4-Ph

bin,

quan trngnht

2 Ba2+, Ca2+,Mg2+, Zn2+,

Cd2+, Ni2+,

Sr2+, Pb2+

4 Ti4+, Mn4+,Ce4+, Sn4+,

Zr4+

CaTiO3

, BaTiO3

,

SrMnO3

, PbZrO

3,

PbTiO3Vt liu stin

3, 3- 3 La3+, Y3+,

Gd3+, Nd3+,

Bi3+

3 Sc3+, Fe3+,

Ga3+, Ni3+,

Fe3+,

LaNiO3

, YFeO

3

,

LaAlO3

1, 5-Quan trng

th

hai

1 K+

, Na+

5 Mn5+

, Nb5+

,

Ta5+KNbO3

, KTaO3

Vt liu ha inv quangin


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Phc tp: hp cht 1/2:1/2 v 1/3:2/3-Hp cht 1/2:1/2: A2

BBO6

hoc AB1/2

B1/2

O3

Loi :

Hatr

A

Hatr

B

V

d

B Ha

tr

B

V

d

BHp cht

3,5 2 3 Sc, Nd, La,

Y, Gd, In

5 Nb, Ta Pb2

ScTaO6

,

Ba2

YTaO6

2,6 2 2 Co, Sr, Mg 6 W Pb2

CoWO6

1,7 2 1 Na, K 7 Os Ba2

NaOsO6

Pb2

ScTaO6


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Phc tp: hp cht 1/2:1/2 v 1/3:2/3-Hp cht 1/3:2/3: A3

BB2

O9

hoc AB1/3

B2/3

O3

-Thng 2+ (Zn, Mg), 5+ (Nb, Ta): Ba3

MgTa2

O9

, Pb3

MgTa2

O9

Pb3

ZnTa2

O9

Pb

Zn

Ta


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- Cubic SrTiO3

TiO6

Nu A qu nh hay qu ln

hn kch thc

l hng, iug s

xy ra?

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


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H

s

dung sai(Tolerance factor)

A

B

( )O B2a R R= +

a

( )O A2 2a R R= +

( )

( )

O A

O B

1

2

R R

R R

+=

+

Mong mun:= t

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 ln cu trc lch


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MnMn OO MnMn

MnMn

OO

MnMn

CubicCubicLin kLin ktt

MnMn--OO--Mn thMn thngng

OrthorhombicOrthorhombicMnMn--OO--Mn congMn cong

CaMnO3


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LaMnOLaMnO33


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WO3

ABO3 1 l trng v tr A, W

6+ v tr B

Ba5

Nb4

O15

5(ABO3

) 1 l trng B

YBa2

Cu3

O7

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 cs

BaTiO3

Tnh ha in (pyroelectricity)

Tnh p in (piezoelectricity)

Tnh t

tnh (magnetic property)

Tnh siu dn (superconductivity): cs

Ba2

YCu3

O7

Tnh dn in (electrical conductivity)

Tnh dn ion v

electron (ion conductivity): SOFC

Tnh xc tc (catalytic property)


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* Rare Earth-Nguyn tt him,** Transition metal-Kim loi chuyn tip

Thnh phn Tnh cht

CaTiO3

Cch in (dielectric)

BaTiO3 St in (ferroelectric)

Pb(Zr1-x

Tix

)O3 p in (piezoelectric)

(Ba1-x

La

x

)TiO

3Bn dn (semiconductor)

(Y1/3

Ba2/3

)CuO3-x Siu dn (superconductor), dn ion O

2-

Nax

WO3 Dn ion v electron (mixed conductor),

quang in (electrochromic)

SrCeO3 Dn proton

RE*TM**O3-x Dn ion v electron (Mixed conductor)AMnO3-x Hiu ng in tr t

khng l

(giant

magnetoresistance effect)

Li0,5-3x

La0,5+x

TiO3 Dn ion Li

+


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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: tin, 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 lius sinh ra dng in v ngc li do gi

tr moment lng ccthay i khi cu trc b

nn p (ng dng: cc sensor).
http://www.doitpoms.ac.uk/tlplib/ferroelectrics/index.phphttp://www.doitpoms.ac.uk/tlplib/ferroelectrics/index.phphttp://www.doitpoms.ac.uk/tlplib/ferroelectrics/index.php


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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 bthay i khi cu trc bt 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 rn1

- Sn phm ceramic dng khi

- Sn phm ceramic dng mng (film)

Kch thc ht tngi ln (micron)

Kch thc ht rtnh

(c

nano)

- Sn phm ceramic dng khi

- Sn phm ceramic dng mng (film)

Phng php tng hp t

phn ng pha lng2

Ph h t h t h h 1


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Cn ng t

l

Nguyn liuOxide, muicarbonat dng bt

Nc/dung mi hu c

Sy

Hn hp cc oxide

Phng php tng hp t phn ng pha rn1

Nghin trn

Ry

Nung Hp cht perovskite

Nc/dung

mi hu c

Sy

Ry

Sn phm dng bt

Sn phm dng khi

Sn phm dng film

Nghin


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p kh/bn kh

Sn phm dng bt

Nung kt khi

Sn phm dng khi(bulk ceramics)

To huyn ph

Sn phm dng bt

To mng mng

Sn phm dng mng(ceramic films)

Dung mihu c

Nung kt khi

-Kt ta in di

- In

Sn phm dng khi Sn phm dng mng

Ph h t h t h h l2


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Dung mi

Phn ng c th(thy nhit,)

Dung dch

Gia nhit

Sn phm(kch thc ht rt nh)

Nguyn liu

Kt ta/gel ha

Bay hi

Tc nhn kt ta/to phc/ gel ha

Phng php tng hp t phn ng pha lng2

Mui kim loi, alkoxidekim loi, hp cht ckim

Ph h t h t h h l2


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Phng php tng hp t phn ng pha lng2

Phn loi Phng php thc hin

Nhm 1Bay hi hoc kt ta c iu

khin

Nhit phn t pha hi/sng, phnhy nhit, sy lnh, sng sium, nc siu ti hn,

Nhm 2S

dng l

xp c

micron

Antimicelle keo

Nhm 3S

dng hp cht trung gian(hu c)

Cht trung gian hydroxide, sol-gel,phn hy, phng php phcEDTA,


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Knh thng minh: smart window, E-glass1

Gm p in: piezoelectric ceramics2


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Knh thng minh: smart window, E-glass1

M Tt (~99,4% nh sng)

- L loi thy tinh c thiu chnh lng nh sng v nhittruyn qua n khi cho dng in chy qua: electricallyswitchable glass

- gim s dng iu ha khng kh- gim si m, chiu sng


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Nguyn tc

Tt-Mc M-Trong sut

Lp ph dn in

Cc ht llng

Mng chn

Lp dn bo v

Thy tinh


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Cc loi knh thng minh bt tt

1 Quang in (electrochromic)

2 Cc ht huyn ph

(suspended particles)

3 Tinh th lng (liquid crystal)

4 Micro-blinds

Knh quang in (electrochromic)


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Knh quang in (electrochromic)

Thy tinh

Lp mng quang in

ITO: Indium Tin Oxide

Mng quang in:hexacianoferrate, WO3

in cc: h

CeO

2

-TiO

2

Cht in ly

Thy tinh

Ngun in

in cc

M t lp mng quang in


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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

WO3

+ xH+

+xe- HxWO3

trong

mc

cch in dn in

Cchi mu

thy tinh

+

-

WO3

Ngun cung cp H+

ITO

ITO

Ti Sng

e

e

Gii thch WO3 + xH+ +xe- HxWO3


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Gii thch

W : 4f145d46s2

W6+:

5d06s0

W5+: 5d16s0

Ax

WO3

: 0 x

1, A: H+, Na+, K+,

Ax

(Wx

5+W1-x6+)O3

d1

d0 W6+ l trng thi khng

chuyn tip (tr)

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 oxyha ca W gim t +6 n +5.

3

x 3

cch in dn in

S h k h i h


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So snh: knh i mu truyn thng

Z Trn hoc mu mt lp AgCl trong sut.

Z AgCl hp th nng lng ca tia cc tm trong nh sng

mt tri, bphn hy thnh ht Ag rt nh lm knh chuynmu sm hn khi ra nng.

Z sm ca knh ph thuc vo cng ca tia cc tm.

ZMu sc knh do ph thm mt lp mu (xm, nu, vng,,)

Z u im:Z Tin li, khng cn thay knh

ZNgn nga tia cc tm hi mt

ng dng knh thng minh


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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

ZGng chng la (Schotts)

Z Ca knh nh , ta nh vn phng, bnh vin (h thng NHSAnh quc)

ZMn trnh chiu


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Gm p in: piezoelectric ceramics2

* Hiu ng p in: di tc dng calc c hc, b

mt vt liu xut hin s

phn cc in v do xut hin dngin.

* y l

hiu ng thun nghch.

Vt liu c

tnh p in cao: h

gm PZT (lead

zirconate titanate): PbTi1-x

Znx

O3,perovskite. Pb

ng dng


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ng dng

Pha pha rhombohedral: giatc k, thit b

chn on hnh

nh y khoa,

Pha pha tetragonal: ng nghedi nc, microphone,, cmbin, 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 rhombohedral.

Chn on hnh nh bng siu m


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Chn on hnh nh bng siu m

Dng in

Transducer (PZT)

Xung dao ng

Vo cth

Tr

khng

Xungphnx

Tn hiu in

Hnh nh cquanni tng v

m

bc sng()

x

tn s(f) = vn tc sng m trong mi trng(v)

1mm-50m

1,5-30MHz

1500 m/s (trong cth ngi)

Bc sng nhsc nt cao

Xungphnx

ng dng


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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

Ccu truyn ng

Tm tt


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Tm tt

Cu trc Perovskite c nghin cu v ng dngnhiu nht cho vt liu ceramic chc nng

(functional ceramics) D dng thay i/iu chnh tnh cht ca vt liuc

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.

References


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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.php3. http://www.morganelectroceramics.com

4. J. Kulawik, D. Szwagierczak, B. GrogerInvestigations 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
http://www.doitpoms.ac.uk/tlplib/ferroelectrics/index.phphttp://www.morganelectroceramics.com/http://www.morganelectroceramics.com/http://www.doitpoms.ac.uk/tlplib/ferroelectrics/index.php


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Cau Truc Perovslite Cua Vat Lieu Ceramic