microwave synthesis using microwave transparent metal oxides: … · 2011. 12. 12. · 11 microwave...
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11
Microwave Plasma Synthesis of Lanthanide Zirconates From Microwave Transparent Oxides
Yi-Hsin Choua, Nicole Hondowb, Chris I. Thomasa, Robert Mitchella, Rik Brydsonb and Richard E Douthwaitea
aDepartment of Chemistry, University of York, Heslington, York, YO10 5DD, UK
b Leeds Electron Microscopy and Spectroscopy (LEMAS) Centre, Institute of Materials Research , University of Leeds, Leeds LS2
9JT, UK
Supplementary Information
Pages
PXRD comparison of microwave and furnace prepared Ln2Zr2O7 and Ln4Zr3O12 2-11
SEM comparison of microwave and furnace prepared Ln2Zr2O7 and Ln4Zr3O12 11-13
Microwave apparatus diagrams 14
Heating profiles of microwave prepared Ln2Zr2O7 and Ln4Zr3O12 15-20
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is © The Royal Society of Chemistry 2012
22
Y2Zr2O7
0
100
200
300
400
500
5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
2 Theta
coun
ts
1550 °C, 10+10+10 hours
microwave, 900W, O2=10ml/min, 10+10 min
111
002
022
311
222 004
Furnace Microwave Reference [9a] Space Group
Fm3m
Fm3m
Fm3m
Lattice Parameter a
5.201(8) Å
5.175(9)Å
5.211 Å
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33
La2Zr2O7
0
100
200
300
400
500
600
700
5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
2 Theta
coun
ts
1550 °C, 10+10 hours
microwave, 900W, O2=10ml/min,10+10 min
222
004
404
226
111 313 115444
008
[&] M. E. Björketuna, C. S. Knee, B. J. Nymana and G. Wahnströma, Solid State Ionics, 2008, 178, 1642-1647.
Furnace Microwave Reference [&] Space Group
Fd3m
Fd3m
Fd3m
Lattice Parameter a
10.73(2) Å
10.77(2)Å
10.882 Å
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44
Gd2Zr2O7
0
100
200
300
400
5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
2 Theta
coun
ts
1550 °C, 10+10 hours
microwave, 900W, O2=10ml/min,10+10 min 111
002
022311
Furnace Microwave Reference [9a] Space Group
Fm3m
Fm3m
Fm3m
Lattice Parameter a
5.24(2) Å
5.22 (4)Å
5.280 Å
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55
Dy2Zr2O7
0
100
200
300
400
500
600
700
5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
2 Theta
coun
ts
1550 °C, 10+10 hours
microwave, 900W, O2=10 ml/min,10+10+10 min
111
002
022311
† data from ICSD ref Kongelige Danske Videnskabernes Selskab, Matematisk-Fysike Meddelelser (1967) 35, 1-37
Furnace Microwave Reference [†] Space Group
Fm3m
Fm3m
Fm3m
Lattice Parameter a
5.210(6) Å
5.20 (5)Å
5.21Å
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66
Ho2Zr2O7
0
100
200
300
400
500
600
5 10 15 20 25 30 35 40 45 50 55 60 65 70 75
2 Theta
coun
ts
1550 °C, 10+10+10 hours
microwave, 900W, O2=10ml/min, 10+10+10min
111
002022
311
222 004
† data from ICSD ref Kongelige Danske Videnskabernes Selskab, Matematisk-Fysike Meddelelser (1967) 35, 1-37
Furnace Microwave Reference [†] Space Group
Fm3m
Fm3m
Fm3m
Lattice Parameter a
5.19(4) Å
5.19 (2) Å
5.2 Å
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77
Y4Zr3O12
0
100
200
300
400
500
600
700
800
10 15 20 25 30 35 40 45 50 55 60 65 70
2 Theta
coun
ts microwave, 500W, O2=10ml/min, 10+10+10+10+10 min
1550 °C, 10+10+10 hours
003
211
122
241 410
125 413
404
111
002022
222
311
[*] V. P. Redko and L. M. Lopato, Inorg. Mater., 1991, 27, 1609-1614.
Furnace Microwave Reference [*] Space Group
R3 (hex)
Fm3m
R3 (hex)
Lattice Parameter a
9.74(2) Å
5.232(3)Å
9.729(1) - 9.738(2) Å
c
9.06(1) Å
5.232(3)Å
9.103(2) - 9.115(3) Å
Furnace Microwave
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88
Gd4Zr3O12
0
100
200
300
400
500
10 15 20 25 30 35 40 45 50 55 60 65 70
2 Theta
coun
ts
microwave, 500W, O2=10ml/min, 10+10+10+10min
1550 °C, 10+10+10 hours
111
002 022 311222
Dy4Zr3O12
0
100
200
300
400
500
600
700
800
10 15 20 25 30 35 40 45 50 55 60 65 70
2 Theta
coun
ts
1550 °C, 10+10 hours
microwave, 500W, O2=10mL/min, 10+10+10 +10+10+10min
111
022311
002
222
Space Group
Fm3m
Fm3m
Lattice Parameter
5.275(8) Å
5.295(1)Å
Furnace Microwave
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99
Space Group
Fm3m
Fm3m
Lattice Parameter
5.22(4)Å
5.250(3)Å
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1010
Ho4Zr3O12
0
100
200
300
400
500
600
700
10 15 20 25 30 35 40 45 50 55 60 65 70
2 Theta
coun
ts
1550 °C, 10+10+10 hours
microwave, 500W, O2=10ml/min, 10+10+10+10+10+10+10 min
003
211
122
404125
413410
241
111
002 022
311
222
[*] V. P. Redko and L. M. Lopato, Inorg. Mater., 1991, 27, 1609-1614.
Furnace Microwave Reference [*] Space Group
R3 (hex)
Fm3m
R3 (hex)
Lattice Parameter a
9.78(4) Å
5.233(2)Å
9.732(2) Å
c
8.94(8) Å
5.233(2)Å
9.109(3) Å
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1111
Yb4Zr3O12
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
10 15 20 25 30 35 40 45 50 55 60 65 70
2 Theta
coun
ts
1550 °C, 10+10+10 hours
microwave, 500W, O2=10mL/min, 10+10+10+10+10 min
microwave, 500W, O2=10mL/min, 10+10+10+10+10 minThen 1550 °C, 24 hours
110003
211
122
113 241410
125413
404232131021101 300 104 024
110
003
211
122
113 241410
125413
404232131012021104
110
003 211
122
404125
413410241
[*] V. P. Redko and L. M. Lopato, Inorg. Mater., 1991, 27, 1609-1614.
Furnace Microwave Anneal Low T ref [*] High T ref [11] Space Group
R3 (hex)
R3 (hex)
R3 (hex)
R3 (hex)
R3 (hex)
Lattice a
9.64(3) Å
9.659(10) Å
9.641(6) Å
9.654(1) Å
9.68(3) Å
c
9.01(7) Å
8.987(1) Å
9.009(7) Å
9.021(1) Å
8.96(7) Å
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1212
Y2Zr2O7 microwave synthesis (left); furnace synthesis (right)
La2Zr2O7 microwave synthesis (left); furnace synthesis (right)
Gd2Zr2O7 microwave synthesis (left); furnace synthesis (right)
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Dy2Zr2O7 microwave synthesis (left); furnace synthesis (right)
Gd4Zr3O12 microwave synthesis (left); furnace synthesis (right)
Dy4Zr3O12 microwave synthesis (left); furnace synthesis (right)
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Microwave apparatus used for temperature measurements and synthetic reactions. The unfocussed cavity (top) was used for the Ln2Zr2O7 systems and the focussed cavity (bottom) was used for the
Ln4Zr3O12 systems.
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1515
Y2Zr2O7 heating profile at O2=10ml/min, 900W
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2100
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
Time (second)
Tem
pera
ture
(o C)
10min
10+10min
La2Zr2O7 heating profile at O2=10ml/min, 900W
400
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0 50 100 150 200 250 300 350 400 450 500 550 600 650 700
Time (second)
Tem
pera
ture
(o C)
10min
10+10min
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1616
Gd2Zr2O7 heating profile at O2=10ml/min, 900W
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2100
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700
Time (second)
Tem
pera
ture
(o C)
10min
10+10min
Dy2Zr2O7 heating profile at O2=10ml/min, 900W
400
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0 50 100 150 200 250 300 350 400 450 500 550 600 650 700
Time (second)
Tem
pera
ture
(o C)
10min
10+10min
10+10+10min
Please note: Sudden drops in the recorded temperature early in the heating process are due to plasma interference, arising from absorption of surface emitted photons by the plasma. Visually, the plasma exhibits some instability early in the experiments but subsequently stabilises, allowing uninterrupted temperature measurement.
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1717
Ho2Zr2O7 heating profile at O2=10ml/min, 900W
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2100
0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
Time (second)
Tem
pera
ture
(o C)
10min
10+10min
10+10+10min
Yb2Zr2O7 heating profile at O2=10ml/min, 900W
400
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0 100 200 300 400 500 600 700 800
Time (second)
Tem
pera
ture
(o C)
10min
10+10min
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1818
Y4Zr3O12 heating profile at O2=10ml/min, 500W
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0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
Time (second)
Tem
pera
ture
(o C)
10min
10+10+10+10min
Gd4Zr3O12 heating profile at O2=10ml/min, 500W
400
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0 50 100 150 200 250 300 350 400 450 500 550 600 650 700
Time (second)
Tem
pera
ture
(o C)
10min
10+10+10+10min
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1919
Dy4Zr3O12 heating profile at O2=10ml/min, 500W
400500600700800900
100011001200130014001500160017001800190020002100220023002400
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 3400
Time (second)
Tem
pera
ture
(o C)
1st
1st+10min
1st+10+10+10+10+10min
Ho4Zr3O12 heating profile at O2=10ml/min, 500W
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0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800
Time (second)
Tem
pera
ture
(o C)
10min
10+10+10+10+10+10min
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2020
Yb4Zr3O12 heating profile at O2=10ml/min, 500W
400
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800
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1200
1300
1400
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1600
1700
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2000
2100
0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300
Time (second)
Tem
pera
ture
(o C)
10min
10+10+10+10+10min
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