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Rhombohedral ilmenite group nickel titanates with Zn, Mg, and Mn: synthesis and crystal structures

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Abstract

Binary, ternary, and quaternary rhombohedral ordered titanates, Ni1/2Mn1/2TiO3, Ni1/2Mg1/2TiO3, Ni1/3Zn1/3Mg1/3TiO3, and Ni1/4Zn1/4Mg1/4Mn1/4TiO3, were obtained by solid-state synthesis at 1095°C at ambient pressure in a nitrogen atmosphere. All of the compounds adopt ATiO3 (A = Ni, Mn, Zn, and Mg) stoichiometry. Crystal structures were refined by the Rietveld method from powder X-ray diffraction data. Unit cell parameters and unit cell volumes decrease with decreasing average radius of the vi A 2+ cation. All the synthetic titanates adopt the space group \(R\bar 3\) and the ilmenite structure consisting of distorted AO6 and TiO6 octahedra. The divalent cations and Ti4+ are distributed in layers of octahedra alternating along c with no evidence for disorder. In common with pyrophanite, NiTiO3, and ilmenite sensu stricto, the distortion of the AO6 octahedra is less than that of the TiO6 octahedra. The Ti4+ and A-site cations in the titanates are off-centred within the coordination polyhedra. Deviation of the z positional parameters from their theoretical values for the A and Ti atoms indicate that in the titanates with the larger A 2+ cations and Goldschmidt tolerance factors, t ≥ 0.745, the AO6 octahedral layer is more “puckered” above and below planes parallel to (001) than that of the TiO6 octahedra, and vice versa in the titanates with smaller R 2+ A for which t≤0.745. Data are given for the volumes and distortion indices of all the coordination polyhedra. This study confirms the existence and stability of complex solid solutions between ordered rhombohedral titanates of Ni and first-row transition metals at ambient conditions over a range of t from 0.786 to 0.737. These experimental data suggest that the formation of ilmenite-type titanates enriched in Ni is possible in exotic mineral-forming systems at low pressure and/or in extraterrestrial rocks.

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Acknowledgements

This work is supported by the Natural Sciences and Engineering Research Council of Canada and Lakehead University (Canada). We thank Allan MacKenzie for assistance with analytical work, and Anne Hammond for sample preparation. The authors are grateful to Dr. K. Garbev and an anonymous reviewer whose constructive criticism resulted in improvements to the initial version of this work. The authors also would like to thank Dr. Catherine McCammon for editorial care in handling of this contribution.

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Authors and Affiliations

  1. Department of Geology, Lakehead University, 955 Oliver Road, Thunder Bay, ON, P7B 5E1, Canada

    Ruslan P. Liferovich & Roger H. Mitchell

Authors
  1. Ruslan P. Liferovich
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  2. Roger H. Mitchell
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Corresponding author

Correspondence to Roger H. Mitchell.

Appendix 1

Appendix 1

Selected bond lengths (Å) and bond angles (°) of synthetic titanates at ambient conditions

 

 

 

1

2

3

4

5

6

AO6 octahedron

3×A-O1

 

Å

2.100(4)

2.085(5)

2.046(5)

2.045(5)

2.052(3)

2.059(4)

3×A-O1

 

Å

2.292(5)

2.197(6)

2.212(6)

2.197(5)

2.139(3)

2.117(4)

3×O–A–O

 

°

73.01

75.45

75.78

76.13

78.25

78.25

3×O–A–O

 

°

91.61

91.08

90.12

90.75

90.34

90.35

3×O–A–O

 

°

88.45

89.12

87.83

89.47

89.21

89.94

3×O–A–O

 

°

103.06

101.44

102.96

100.99

100.11

99.50

3×O–A–O

 

°

158.57

161.54

160.48

162.38

164.16

164.97

TiO6 octahedron

3×Ti-O1

 

Å

1.876(4)

1.862(5)

1.863(5)

1.850(5)

1.856(3)

1.858(4)

3×Ti-O1

 

Å

2.086(5)

2.084(5)

2.103(6)

2.082(5)

2.096(3)

2.079(4)

3×O–Ti–O

 

°

162.59

161.37

162.53

162.23

162.07

161.47

3×O–Ti–O

 

°

81.04

80.37

80.47

81.19

80.16

79.98

3×O–Ti–O

 

°

81.63

81.32

82.40

81.70

82.59

82.24

3×O–Ti–O

 

°

94.12

93.20

93.34

91.47

92.13

91.84

3×O–Ti–O

 

°

101.92

103.16

102.08

103.54

102.98

103.59

A–Ti

 

Å

3.035

2.945

2.960

2.917

2.867

2.843

A-A

a

Å

3.065

3.001

3.010

2.982

2.955

2.944

A-A

b

Å

3.993

4.053

3.975

4.010

4.106

4.120

Ti–Ti

a

Å

3.015

2.996

2.988

2.978

2.973

2.969

Ti–Ti

b

Å

4.223

4.076

4.077

4.030

4.010

3.985

O–O

c

Å

2.728

2.689

2.717

2.709

2.699

2.672

O–O

d

Å

3.287

3.228

3.201

3.156

3.146

3.143

O–O

e

Å

3.152

3.058

3.016

3.021

2.973

2.962

O–O

f

Å

3.066

3.006

2.955

2.988

2.944

2.952

O–O

g

Å

2.915

2.917

2.897

2.907

2.904

2.920

O–O

h

Å

2.580

2.576

2.619

2.578

2.614

2.594

O–O

i

Å

2.904

2.870

2.890

2.820

2.851

2.832

Ti–O–A

j

°

119.31

119.25

120.05

120.37

120.62

120.00

A–O–A

k

°

88.38

89.92

89.88

89.25

89.66

89.65

Ti–O–Ti

l

°

98.96

98.67

97.60

98.30

97.41

97.76

Ti–O–A

m

°

126.21

127.87

126.94

128.50

129.05

129.80

Ti–O–A

n

°

87.61

86.88

86.60

85.90

85.20

85.31

Ti–O–A

o

°

136.64

135.56

135.64

134.08

134.48

134.19

  1. 1 MnTiO3; 2 Ni1/2Mn1/2TiO3; 3 Ni1/4Mn1/4Zn1/4Mg1/4TiO3; 4 Ni1/3Zn1/3Mg1/3TiO3; 5 Ni1/2Mg1/2TiO3; 6 NiTiO3
  2. The metal–metal distances: a across shared edge between adjacent metal sites; b across vacant octahedral position
  3. The oxygen–oxygen distances: c A-Ti shared face; d A site, face opposite the shared face; e A site, shared edge; f A site, unshared edge; g Ti site, face opposite the shared face; h Ti site, shared edge; i Ti site, unshared edge
  4. Framework angles: j, m, and o at the shared vertex; k and l at the shared edge; n shared face

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Liferovich, R.P., Mitchell, R.H. Rhombohedral ilmenite group nickel titanates with Zn, Mg, and Mn: synthesis and crystal structures. Phys Chem Minerals 32, 442–449 (2005). https://doi.org/10.1007/s00269-005-0020-7

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