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

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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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1313

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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1414

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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1700

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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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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

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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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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

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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

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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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1400

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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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