Open Access

Structural characterization and colour of MgxCu3-xV2O8 (0 ≤ x ≤ 3) and MgyCu2-yV2O7 (0 ≤ y ≤ 2) compositions

SpringerPlus20154:163

https://doi.org/10.1186/s40064-015-0908-8

Received: 22 November 2014

Accepted: 26 February 2015

Published: 3 April 2015

Abstract

In this study, MgxCu3-xV2O8 (0 ≤ x ≤ 3) and MgyCu2-yV2O7 (0 ≤ y ≤ 2) compositions were synthesized by the chemical coprecipitation method and characterized by X-ray diffraction, UV–vis-NIR spectroscopy and CIE L* a* b* parameters measurements. Melting points of compounds Cu3V2O8 and Cu2V2O7 are 780°C and 790°C, respectively. The addition of small amounts of Mg (II), MgxCu3-xV2O8 (x < 1.0) and MgyCu2-yV2O7 (y < 0.5) fused compositions, was not sufficient to stabilize structures at 800°C. For the Mg2CuV2O8 (x = 2.0) composition fired at 800°C, Mg (II) incorporated into the monoclinic Cu3V2O8 structure stabilizes this crystalline phase. At 1000°C, orthorhombic Mg3V2O8 structure from this composition was obtained. Solid solutions with orthorhombic symmetry were detected from the prepared compositions fired at 1000°C when 1.0 ≤ x ≤ 3.0. The difference of coloration of Cu, Mg vanadates might be explained by the presence of a strong charge transfer band in visible spectra.

Keywords

Orthovanadate Divanadate Solid solutions Structure Colour

Background

The preparation of materials with applications on ceramic pigments industry by the conventional ceramic method presents some drawbacks. Thus, the necessary high temperatures and long soaking times give rise to loss of volatile reagents and consequently to deviation of the stoichiometric conditions of the initial systems. Some improvements were obtained with alternative synthesis methods (García et al. 2001, Tena et al. 2003). For example, no desirable brown materials were obtained from oxide mixtures in VxTi1-xO2 (x < 0.10) rutile solid solutions with potential usefulness as gray ceramic pigments but only bluish gray colorations were obtained from gels (Tena et al. 2003). However, the ceramic pigments industry tends towards cheap and simple processing. The synthesis from mixtures of solid starting materials with addition of halides as flux agents is habitual (Sorlí et al. 2004). Alternative synthetic methods are used exceptionally. The choice of precursors materials is a possibility to obtain desired final industrial product. The bright colours of vanadates could be considered from ceramic industry to development ceramic pigments but their melting points are low. These melting points can be modified by the formation of solid solutions (West 1984). Solid solutions are very common in crystalline materials. A solid solution is basically a crystalline phase that can have variable composition.

Cu3V2O8 and Mg3V2O8 compounds melt incongruently at 780°C and 1212°C respectively (Fleury 1966, Clark and Morley 1976). Mg2V2O7 melts incongruently at 1132°C (Clark and Morley 1976) and Cu2V2O7 melts at 790°C (Fleury 1966). Considering these melting points, Mg (II) orthovanadate and Mg (II) divanadate structures can be more suitable for ceramic industry than Cu (II) orthovanadate and Cu (II) divanadate structures.

Colour is often, but not always, associated with transition metal ions. In molecular chemistry, colour can arise from two possible common causes. The d-d electronic transitions within transition metal ions give rise to many of the familiar colours of transition metal compounds, e. g. the various shades of blue and green associated with different copper (II) complexes. Charge transfer effects in which an electron is transferred between an anion and a cation are often responsible for intense colours as in, for example, permanganate (purple) and chromates (yellow). In solids, there is an additional source of colour; it involves the transition of electrons between energy bands. Colour may be measured in a quantitative way by spectroscopic techniques. At higher frequencies than the infrared, electronic transitions associated with d-level splitting, impurity ions, crystal defects, etc., are possible. Many of these occur in the visible region and are responsible for colour.

Most of divalent metal orthovanadates of small ionic radius have orthorhombic symmetry. Copper orthovanadate presents triclinic symmetry at atmospheric pressure (Coing-Boyat 1982). A monoclinic form of this compound prepared under pressure at high temperature (4 GPa, 1173K) was described (Shannon and Calvo 1972). The structure of Cu3V2O8 compound with monoclinic symmetry and space group P121/c1 is similar to the orthorhombic structure of Mg3V2O8 compound with space group Cmca (Krishnamachari and Calvo 1971). Most of divalent metal divanadates, M2V2O7, are polymorphic. Copper divanadate, Cu2V2O7, presents orthorhombic (Calvo and Faggiani 1975), monoclinic (Mercurio-Lavaud and Bernard Frit 1973) and triclinic crystalline forms and Mg2V2O7 presents monoclinic and triclinic symmetries (Gopal and Calvo 1974). Information about these crystal structures is included in an Additional file 1.

In this study, structural characterization of MgxCu3-xV2O8 (0 ≤ x ≤ 3) and MgyCu2-yV2O7 (0 ≤ y ≤ 2) compositions was made to investigate the possible formation of solid solutions with orthovanadate or divanadate structure. Coloration of these materials was also measured and related with structure in prepared compositions. A partial substitution of Cu (II) by Mg (II) ions might increase the melting point of materials with orthovanadates and divanadates structures. These potential solid solutions could be applied in ceramic industry.

Methods

MgxCu3-xV2O8 (0 ≤ x ≤ 3) and MgyCu2-yV2O7 (0 ≤ y ≤ 2) compositions were synthesized by the chemical coprecipitation method. The starting materials were Cu(NO3)2 · 2.5H2O (Sigma-Aldrich, 98%), MgCl2.6H2O (Panreac) of reagent grade chemical quality, and NH4VO3 (Sigma-Aldrich, 99%). The stoichiometric amount of NH4VO3, Cu(NO3)2 · 2.5H2O and MgCl2 · 6H2O was added on 200 mL of water with vigorous stirring at room temperature. These starting materials were added in solid state and the concentration of the various cations is different in each prepared composition. After that, a solution of ammonium hydroxide was added dropwise until pH = 8. The obtained precipitates were dried by an infrared lamp and dry samples were fired at 300°C for 12 hours, 600°C for 12 hours, 800°C for 1 hour and 1000°C for 1 hour.

The resulting materials were examined by X-ray diffraction with CuKα radiation to study the development of the crystalline phases at different temperatures. A structure profile refinement was carried out by the Rietveld method (Fullprof.2 k computer program) (Rietveld 1969, Rodriguez-Carvajal 2012, Chapon and Rodriguez-Carvajal 2008). Unit cell parameters and interatomic distances (M-O and V-O) in divanadates and orthovanadates structures were obtained from MgxCu3-xV2O8 (0 ≤ x ≤ 3) and MgyCu2-yV2O7 (0 ≤ y ≤ 2) fired compositions to investigate the possibility of formation of solid solution in these synthetic conditions. The diffraction patterns were collected running from 5 to 110 o2θ, using monochromatic CuKα radiation, a step size of 0.02 o2θ and a sampling time of 10 s. The initial structural information was obtained of the Inorganic Crystal Structure Database (Inorganic Crystal Structure Database ICSD 2013). Table 1 includes the reference ICSD to every structure. This initial structural information also appears in the references (Coing-Boyat 1982, Shannon and Calvo 1972, Krishnamachari and Calvo 1971, Calvo and Faggiani 1975, Mercurio-Lavaud and Bernard Frit 1973, Gopal and Calvo 1974) for the main structures of this study. Dicvol program (Boultif and Loüer 2007) was used to obtain initial cell parameters in some compositions.
Table 1

Structural information of Cu and Mg orthovanadates and divanadates

Structure

ICSD* reference

Crystalline system

Standard unit cell* (Å and degrees)

Standard space group

Z

Cu3V2O8

27184

Triclinic

a = 5.196 (4), b = 5.355 (1), c = 6.505 (4), α = 69.22 (3), β = 88.69 (4), γ = 68.08 (3)

P −1

1

Cu3V2O8

27310

Monoclinic

a = 6.2493 (9), b = 7.9936 (9), c = 6.378 (1), β = 111.49 (1)

P 1 21/c 1

2

MgCu2V2O8

404852

Monoclinic

a = 6.453 (1), b = 8.342 (2), c = 11.517 (2), β = 90.44 (2)

P 1 21/c 1

4

Mg2CuV2O8

404851

Monoclinic

a = 6.167 (3), b = 8.172 (5), c = 6.400 (3), β = 116.22 (3)

P 1 21/c 1

2

Mg3V2O8

156155

Orthorhombic

a = 6.0814 (7), b = 11.469 (1), c = 8.337 (1)

C m c a

4

α-Cu2V2O7

34756

Orthorhombic

a = 8.411 (5), b = 20.68 (1), c = 6.448 (5)

F d d 2

8

β-Cu2V2O7

158375

Monoclinic

a = 7.6890 (8), b = 8.0289 (9), c = 10.1065 (8), β = 110.252 (7)

C 1 2/c 1

4

γ-Cu2V2O7

171028

Triclinic

a = 5.087 (1), b = 5.823 (1), c = 9.402 (2), α = 99.780 (3), β = 97.253 (3), γ = 97.202 (3)

P −1

2

Cu1.5 Mg0.5V2O7

69731

Monoclinic

a = 7.660 (6), b = 8.089 (8), c = 10.117 (9), β = 110.6 (1)

C 1 2/c 1

4

Cu1.33 Mg0.67V2O7

69732

Monoclinic

a = 7.645 (4), b = 8.095 (3), c = 10.119 (3), β = 110.54 (3)

C 1 2/c 1

4

α-Mg2V2O7

93603

Monoclinic

a = 6.599 (1), b = 8.406 (1), c = 9.472 (2), β = 100.6085 (4)

P 1 21/c 1

4

Mg2V2O7

2321

Triclinic

a = 4.912 (2), b = 5.414 (3), c = 10.669 (7), α = 100.36 (4), β = 102.82 (4), γ = 98.58 (4)

P −1

2

* Inorganic Crystal Structure Database (ICSD) (2013).

UV–vis-NIR spectroscopy (diffuse reflectance) allows the Cu (II) site and the V (V)-O and Cu (II)-O charge bands in samples to be studied. A Jasco V-670 spectrophotometer was used to obtain the UV–vis-NIR (ultraviolet visible near infrared) spectra in the 200 to 2500 nm range. X-Rite spectrophotometer (SP60, an illuminant D65, an observer 10°, and a reference sample of MgO) was used to obtain CIEL*a*b* colour parameters on fired samples: L* is the lightness axis (black (0) → white (100)), a* the green (−) → red (+) axis, and b* is the blue (−) → yellow (+) axis (CIE 1971).

Results and discussion

Tables 2 and 3 show crystalline phase evolution with composition and temperature in MgxCu3-xV2O8 (0 ≤ x ≤ 3) and MgyCu2-yV2O7 (0 ≤ y ≤ 2) compositions. XRD patterns from MgxCu3-xV2O8 and MgyCu2-yV2O7 compositions are shown in Additional files 2 and 3.
Table 2

Evolution of crystalline phases with temperature in Mg x Cu 3-x V 2 O 8 (0 ≤ x ≤ 3) samples

x

T (°C)

Crystalline phases

0.00

300

C2(s), C1(vw)

0.50

300

C2(s), MT(w), C1(vw)

1.00

300

CM(m), M(w), C2(vw)

1.50

300

CM(m)

2.00

300

M(m), CM(w)

2.50

300

M(m), MT(w)

3.00

300

M(m), MT(w)

0.00

600

CT(s), C1(m), C2(m)

0.50

600

CT(m), C2(w), M(vw), C1(vw)

1.00

600

CT(m), M(m), C2(w), MO(w), CM(vw)

1.50

600

CM(m)

2.00

600

CM(m), MO(w)

2.50

600

MO(m), M(vw)

3.00

600

MO(m), M(w)

1.00

800

MC(s)

1.50

800

CM(s), MC(s), C2(vw)

2.00

800

CM(s)

2.50

800

MO(s), M(vw)

3.00

800

MO(s), MT(w)

1.00

1000

MO(m), CM(w), M(vw)

1.50

1000

MO(m), CM(w), M(w)

2.00

1000

MO(m), M(w), MC(vw), CT(vw)

2.50

1000

MO(s), MT(vw)

3.00

1000

MO(s), MT(w)

Crystalline phases: CT = Cu3V2O8 (triclinic), CM = Cu3V2O8 (monoclinic), MC = MgCu2V2O8 (monoclinic), MO = Mg3V2O8 (orthorhombic), C1 = α-Cu2V2O7 (orthorhombic), C2 = β-Cu2V2O7 (monoclinic), C3 = γ-Cu2V2O7 (triclinic), M = α-Mg2V2O7 (monoclinic), MT = Mg2V2O7 (triclinic).

Diffraction peak intensity: s = strong, m = medium, w = weak, vw = very weak.

Table 3

Evolution of crystalline phases with temperature in Mg y Cu 2-y V 2 O 7 (0 ≤ y ≤ 2) samples

y

T (°C)

Crystalline phases

0.00

300

C2(m), CT(m), M2(m), C1(w), CM(w), C3(vw)

0.25

300

C2(m), C3(m), M3(m)

0.50

300

C3(m), M2(m), M1(m), C2(w), M3(w), C1(vw)

0.75

300

CM(s), M2(m), C2(w), C3(w)

1.00

300

C3(w), M1(w), CM(vw)

1.25

300

CM(s), N(s), C2(vw)

1.50

300

C3(m), CM(vw), M3(w)

1.75

300

N(s), CM(m), C2(vw)

2.00

300

N(s), MT(w)

0.00

600

C1(s)

0.25

600

C2(s), C1(w)

0.50

600

C2(s), C2’(m), M3(w)

0.75

600

M3(s), C2(m), C2’(m)

1.00

600

M3(m), C2(m)

1.25

600

C2(m), M4(m), M3(w)

1.50

600

C2(m), M4(m), M1(w)

1.75

600

M1(s), C2(w), M4(w)

2.00

600

M1(s), M2(w)

0.50

800

C2(s), M4(m), M2(w)

0.75

800

C2(s), M3(m), C3(w)

1.00

800

M4(s), C2(w)

1.25

800

M4(s), C2(w), M3(w)

1.50

800

C1(s), M4(m), MT(vw)

1.75

800

MT(m), M4(m)

2.00

800

MT(m), M4(m)

1.50

1000

M1(m), MT(m), C2(w)

1.75

1000

M1(s), MT(w), C2(vw)

2.00

1000

MT(m), M1(w), MO(w)

Crystalline phases: C1 = α-Cu2V2O7 (orthorhombic), C2 = β-Cu2V2O7 (monoclinic, C2: β < 110.6o, C2’: β > 110.6°), C3 = γ-Cu2V2O7 (triclinic), CT = Cu3V2O8 (triclinic), CM = Cu3V2O8 (monoclinic), M = α-Mg2V2O7 (monoclinic, M1: β =100.6-102.0°, M2: β = 98.0-99.6°, M3: β = 94.5-97.0°, M4: β = 88.0-92.0°), MT = Mg2V2O7 (triclinic), N = α-Mn2V2O7 (triclinic, P Ῑ, Z =4 with all atoms in 2i sites, ICSD-81993), MO = Mg3V2O8 (orthorhombic).

Diffraction peak intensity: s = strong, m = medium, w = weak, vw = very weak.

In MgxCu3-xV2O8 (0 ≤ x < 1.0) compositions the major crystalline phase is the triclinic Cu3V2O8 polymorph at 600°C. Cu3V2O8 compound melts incongruently at 780°C. This fact can explain the melting of samples with a presence higher than 50% in Cu3V2O8 triclinic crystalline phase (small amount of Mg in compositions). This crystalline phase with triclinic structure is not detected in samples fired at 800 and 1000°C.

A crystalline phase with Cu3V2O8 structure and monoclinic symmetry was obtained at 300 and 600°C in compositions with 1.0 ≤ x ≤ 2.0. This crystalline phase with monoclinic Cu3V2O8 structure is also present when 1.5 ≤ x ≤ 2.0 at 800°C. The crystalline phase with the structure of MgCu2V2O8 compound (β = 90.44 (2) and Z = 4) is detected when 1.0 ≤ x ≤ 2.0 at 800°C but the crystalline phase with the ordered metal distributions in Mg2CuV2O8 compound (β = 116.22 (3), Z = 2, Cu1 in 2a sites and Mg1 in 4e sites, ICSD-404851) is not detected in conditions of this study. In the prepared Mg2CuV2O8 composition (MgxCu3-xV2O8 with x =2.0), crystalline phase with Cu3V2O8 structure and monoclinic symmetry (Z = 2 and M1 (M1 = Mg, Cu) in 2b sites and M2 (M2 = Mg, Cu) in 4e sites) is the only crystalline phase detected at 800°C. Figure 1 shows the major crystalline phase detected in MgCu2V2O8 (x = 1.0), Mg2CuV2O8 (x = 2.0) and Mg2.5Cu0.5V2O8 (x = 2.5) compositions fired at 800°C.
Figure 1

Diffractograms from Mg x Cu 3-x V 2 O 8 compositions at 800°C. Diffraction maxima from the major crystalline phase in : (a) x = 1.0, MgCu2V2O8; (b) x = 2.0, Mg2CuV2O8 and (c) x = 2.5, Mg2.5Cu0.5V2O8 compositions. Crystalline phases: MC (MgCu2V2O8, monoclinic), CM (Cu3V2O8, monoclinic) and MO (Mg3V2O8, orthorhombic).

Crystalline phase with orthorhombic Mg3V2O8 structure is obtained when 2.0 ≤ x ≤ 3.0 at 600°C and when 2.5 ≤ x ≤ 3.0 at 800°C. At 1000°C, this phase is the major crystalline phase in the unfused samples (x ≥ 1.0). Figure 2 shows the positions of diffraction lines and their intensities from MgxCu3-xV2O8 compositions with x = 1.0, x = 2.0 and x = 2.5 fired at 1000°C. The orthorhombic Mg3V2O8 crystalline phase is the major phase in them.
Figure 2

Diffractograms from Mg x Cu 3-x V 2 O 8 compositions at 1000°C. Diffraction maxima from the major phase in: (a) x = 1.0, MgCu2V2O8; (b) x = 2.0, Mg2Cu2V2O8 and (c) x = 2.5, Mg2.5Cu0.5V2O8 compositions. MO: orthorhombic Mg3V2O8 crystalline phase.

Cu divanadates and Mg divanadates are present together with Cu and Mg orthovanadates in some samples.

Crystalline phase with α-Cu2V2O7 structure (orthorhombic symmetry) is only present in MgyCu2-yV2O7 compositions when y < 0.5 at 600°C. These compositions melt at 800°C. Diffraction peak intensity associated with this crystalline phase is weak or very weak at 300°C.

Presence of crystalline phase with β-Cu2V2O7 structure (monoclinic symmetry) is more extended than the crystalline phase with α-Cu2V2O7 structure in the prepared compositions. At 300°C, crystalline phase with β-Cu2V2O7 structure is present when y < 0.5 with diffraction peaks of medium intensity. This crystalline phase is present when 0.25 ≤ y < 1.50 at 600°C and when 0.50 ≤ y ≤ 0.75 with diffraction peak of strong or medium intensity. Figure 3 shows graphical result of the diffraction profile refinement by Rietveld’s method from the Mg0.25Cu1.75V2O7 composition fired at 600°C.
Figure 3

An example of the diffraction profile refinement. The diffraction profile refinement by Rietveld’s method from Mg0.25Cu1.75V2O7 composition fired at 600°C. Crystalline phases: α-Cu2V2O7 (C1) and β- Cu2V2O7 (C2).

Crystalline phase with γ-Cu2V2O7 structure (triclinic symmetry) is present in compositions when 0.25 ≤ y ≤ 0.50 at 300°C but its intensity of diffraction peak is weak at 600 and 800°C (Table 3).

In MgyCu2-yV2O7 compositions fired at 300°C, the assignation to α- Mn2V2O7 structure of a crystalline phase detected when y ≥ 1.25 might be explained by the existence of a polymorph of Mg2V2O7 compound with this structure. It was not detected any match with the existing single-crystal related in the bibliography. Synthesis of single-crystal is the most used method in synthesis of vanadates.

Crystalline phase with α-Mg2V2O7 structure (monoclinic symmetry) is detected in a compositional range more extended than the crystalline phase with triclinic Mg2V2O7 structure from MgyCu2-yV2O7 prepared compositions. Crystalline phase with monoclinic α-Mg2V2O7 structure is identified when 0.75 ≤ y ≤ 2.00 at 600°C, when 0.50 ≤ y ≤ 2.00 at 800°C, and when 1.50 ≤ y ≤ 2.00 at 1000°C.

Crystalline phase with triclinic Mg2V2O7 structure is observed when 1.5 ≤ y ≤ 2.00 in compositions fired at 800°C and only when y = 2.0 at 300°C.

Tables 4, 5, 6, 7, 8 and 9 show the unit cell parameters and weight fractions in crystalline phases with weight fractions higher than 8% from samples fired at 600, 800 and 1000°C. The variation of these parameters with composition confirms the formation of solid solutions.
Table 4

Unit cell parameters in crystalline phases with weight fractions higher than 8% from Mg x Cu 3-x V 2 O 8 (0 ≤ x ≤ 3) compositions fired at 600°C/12 h

x

Crystalline phases (weight fractions)

Unit cell parameters (Å and degrees)

0.00

CT (75.02 %)

a = 5.18451(7) b = 5.34518(8) c = 6.51005(7)

α = 69.261(1) β = 88.644(1) γ= 68.99(1)

C1 (12.83 %)

a = 8.4016(3) b = 20.666(1) c = 6.4433(2)

α = 90.00 β = 90.00 γ = 90.0

C2 (12.16 %)

a = 7.6982(6) b = 8.0361(9) c = 10.112(1)

α = 90.00 β = 110.29(1) γ = 90.00

0.50

CT (64.09 %)

a = 5.1861(2) b = 5.3448(2) c = 6.5457(2)

α = 69.039(3) β = 88.500(4) γ = 68.036(3)

C2 (21.23 %)

a = 7.6404(7) b = 8.1244(9) c = 10.116(1)

α = 90.00 β = 110.66(1) γ = 90.00

M (11.41 %)

a = 6.611(1) b = 8.314(2) c = 9.483(1)

α = 90.00 β = 100.54(2) γ = 90.00

1.00

CT (23.62 %)

a = 5.1925(3) b = 5.3492(3) c = 6.5674(3)

α = 68.997(5) β = 88.449(6) γ = 67.980(5)

C2 (19.24 %)

a = 7.6147(5) b = 8.1294(6) c = 10.1159(6)

α = 90.00 β = 110.374(6) γ = 90.00

MO (18.80 %)

a = 6.0533(5) b = 11.098(1) c = 8.4009(8)

α = 90.00 β = 90.00 γ = 90.00

M (26.46 %)

a = 6.5954(4) b = 8.3555(4) c = 9.4997(6)

α = 90.00 β = 100.520(5) γ = 90.00

CM (13.71 %)

a = 6.1842(7) b = 8.084(1) c = 6.3181(9)

α = 90.00 β = 111.38(1) γ = 90.00

1.50

CM (100 %)

a = 6.3729(1) b = 8.1626(2) c = 6.1790(1)

α = 90.00 β = 115,608(2) γ = 90.00

2.00

CM (73.01 %)

a = 6.5984(3) b = 8.1901(3) c = 6.1459(3)

α = 90.00 β = 119.656(2) γ = 90.00

MO (26.99 %)

a = 6.0787(3) b = 11.4674(8) c = 8.2078(5)

α = 90.00 β = 90.00 γ = 90.00

2.50

MO (92.55 %)

a = 6.0975(1) b = 11.4523(2) c = 8.2555(2)

α = 90.00 β = 90.00 γ = 90.00

3.00

MO (80.94 %)

a = 6.0613(3) b = 11.4395(5) c = 8.3115(4)

α = 90.00 β = 90.00 γ = 90.00

M (19.06 %)

a = 6.6051(5) b = 8.4106(6) c = 9.4815(8)

α = 90.00 β = 100.626(8) γ = 90.00

Crystalline phases: CT = Cu3V2O8 (triclinic), CM = Cu3V2O8 (monoclinic), MO = Mg3V2O8 (orthorhombic), C1 = α-Cu2V2O7 (orthorhombic), C2 = β-Cu2V2O7 (monoclinic), M = α-Mg2V2O7 (monoclinic).

Table 5

Unit cell parameters in crystalline phases with weight fractions higher than 8% from Mg x Cu 3-x V 2 O 8 (0 ≤ x ≤ 3) compositions fired at 800°C/1 h

x

Crystalline phases (weight fractions)

Unit cell parameters (Å and degrees)

1.00

MC (100%)

a = 6.4444 (1) b = 8.2992 (1) c = 11.4842 (2)

α = 90.00 β = 90.61 γ = 90.00

1.50

CM (55.49%)

a = 6.3869 (3) b = 8.1575 (4) c = 6.1600 (3)

α = 90.00 β = 116.308 (3) γ = 90.00

MC (40.82%)

a = 6.4472 (1) b = 8.2960 (2) c = 11.4933 (2)

α = 90.00 β = 90.479 (2) γ = 90.00

2.00

CM (100%)

a = 6.6120 (1) b = 8.1901 (1) c = 6.1525 (1)

α = 90.00 β = 119.795 (1) γ = 90.00

2.50

MO (92.55%)

a = 6.0963 (1) b = 11.4581 (2) c = 8.2556 (1)

α = 90.00 β = 90.00 γ = 90.00

3.00

MO (76.55%)

a = 6.06485 (6) b = 11.4416 (1) c = 8.31576 (8)

α = 90.00 β = 90.00 γ = 90.00

 

MT (23.45%)

a = 4.9304 (2) b = 5.4199 (2) c = 10.6787 (4)

α = 100.321 (3) β = 102.808 (3) γ = 98.640 (3)

Crystalline phases: CM = Cu3V2O8 (monoclinic), MC = MgCu2V2O8 (monoclinic), MO = Mg3V2O8 (orthorhombic), C2 = β-Cu2V2O7 (monoclinic), MT = Mg2V2O7 (triclinic).

Table 6

Unit cell parameters in crystalline phases with weight fractions higher than 8% from Mg x Cu 3-x V 2 O 8 (0 ≤ x ≤ 3) compositions fired at 1000°C/1 h

x

Crystalline phases (weight fractions)

Unit cell parameters (Å and degrees)

1.00

MO (84.55%)

a = 6.0999 (2) b = 11.4633 (4) c = 8.2642 (3)

α = 90.00 β = 90.90 γ = 90.00

CM (12.12%)

a = 6.4805 (9) b = 8.458 (1) c = 6.2031 (8)

α = 90.00 β = 117.29 (1) γ = 90.00

1.50

MO (66.10%)

a = 6.0850 (2) b = 11.4556 (4) c = 8.2858 (2)

α = 90.00 β = 90.90 γ = 90.00

CM (17.35%)

a = 6.5138 (7) b = 8.590 (1) c = 6.2116 (8)

α = 90.00 β = 117.495 (9) γ = 90.00

M (16.54%)

a = 6.5786 (6) b = 8.4263 (7) c = 9.5107 (9)

α = 90.00 β = 100.49 (1) γ = 90.00

2.00

MO (78.31%)

a = 6.0826 (1) b = 11.4538 (3) c = 8.2864 (2)

α = 90.00 β = 90.00 γ = 90.00

M (9.13%)

a = 6.1867 (6) b = 8.2179 (7) c = 6.3129 (5)

α = 90.00 β = 112.016 (8) γ = 90.00

2.50

MO (96.02%)

a = 6.0775 (1) b = 11.4473 (2) c = 8.2813 (1)

α = 90.00 β = 90.00 γ = 90.00

3.00

MO (77.73%)

a = 6.06118 (5) b = 11.4365 (1) c = 8.31278 (7)

α = 90.00 β = 90.00 γ = 90.00

MT (22.27%)

a = 4.9278 (2) b = 5.4169 (2) c = 10.6733 (4)

α = 100.326 (2) β = 102.779 (3) γ = 98.632 (2)

Crystalline phases: CM = Cu3V2O8 (monoclinic), MO = Mg3V2O8 (orthorhombic), M = Mg2V2O7 (monoclinic), MT = Mg2V2O7 (triclinic).

Table 7

Unit cell parameters in crystalline phases with weight fractions higher than 8% from Mg y Cu 2-y V 2 O 7 (0 ≤ y ≤ 2) compositions fired at 600°C/12 h

y

Crystalline phases (weight fractions)

Unit cell parameters (Å and degrees)

a / b / c // α / β / γ

0.000

C1 (100%)

8.40244 (8) / 20.6701 (2) / 6.44418 (5) // 90.00 / 90.00 / 90.00

0.250

C2 (87.6%)

7.67549 (8) / 8.0734 (1) / 10.1196 (2) // 90.00 / 110.437 (1) / 90.00

 

C1 (12.4%)

8.3703 (3) / 20.6942 (8) / 6.4551 (3) // 90.00 / 90.00 / 90.00

0.500

C2 (63.1%)

7.6554 (1) / 8.1002 (1) / 10.1168 (2) // 90.00 /110.550 (1) / 90.00

 

C2’(26.8%)

7.6219 (4) / 8.0881 (6) / 10.1139 (6) // 90.00 / 110.655 (5) / 90.00

 

M3 (10.1%)

6.7623 (6) / 8.4212 (7) / 9.3331 (9) // 90.00 / 95.61 (1) / 90.00

0.750

M3 (50.51%)

6.7701 (5) / 8.4666 (5) / 9.3134 (7) // 90.00 / 96.577 (7) / 90.00

 

C2’(29.1%)

7.6322 (4) / 8.0720 (5) / 10.1722 (7) // 90.00 / 111.164 (5) / 90.00

 

C2 (20.4%)

7.6410 (4) / 8.1202 (5) / 11.1141 (5) // 90.00 / 110.629 (5) / 90.00

1.000

M3 (54.4%)

6.8418 (4) / 8.4116 (4) / 9.3644 (5) // 90.00 / 95.904 (5) / 90.00

 

C2 (45.6%)

7.6091 (4) / 8.0465 (3) / 10.1275 (5) // 90.00 / 110.048 (5) / 90.00

1.250

C2 (36.4%)

7.6115 (2) / 8.0629 (2) / 10.1148 (3) // 90.00 / 109.804 (3) / 90.00

 

M4 (40.0%)

6.8263 (2) / 8.0816 (3) / 9.3090 (3) // 90.00 / 88.438 (3) / 90.00

 

M3 (23.6%)

6.8846 (3) / 8.4130 (4) / 9.2537 (5) // 90.00 / 95.778 (4) / 90.00

1.500

C2 (37.4%)

7.5684 (3) / 8.0539 (3) / 10.1486 (4) // 90.00 / 109.879 (4) / 90.00

 

M4 (42.3%)

6.8291 (2) / 8.0591 (3) / 9.3291 (3) // 90.00 / 88.249 (3) / 90.00

 

M1 (20.3%)

6.5895 (5) / 8.3913 (6) / 9.4963 (7) // 90.00 / 100.397 (7) / 90.00

1.750

M1 (73.1%)

6.58498 (9) / 8.3914 (1) / 9.4872 (1) // 90.00 / 100.462 (1) / 90.00

 

M4 (15.1%)

6.8308 (4) / 8.0534 (4) / 9.3113 (5) // 90.00 / 88.705 (6) / 90.00

 

C2 (11.8%)

7.5662 (5) / 8.0592 (5) / 10.1427 (6) // 90.00 / 109.864 (6) / 90.00

2.000

M1 (83.9%)

6.60534 (6) / 8.41437 (8) / 9.48264 (9) // 90.00 / 100.6104 (8) / 90.00

 

M2 (16.1%)

6.6639 (2) / 8.4361 (3) / 9.5745 (3) // 90.00 / 99.446 (3) / 90.00

Crystalline phases: C1 = α-Cu2V2O7, C2 = β-Cu2V2O7 (monoclinic, C2: β < 110.6°, C2’: β > 110.6°), M = α-Mg2V2O7 (monoclinic, M1: β = 100.0-100.6°, M2: β = 98.0-99.6°, M3: β = 94.5-97.0°, M4: β = 88.0-92.0°).

Table 8

Unit cell parameters in crystalline phases with weight fractions higher than 8% from Mg y Cu 2-y V 2 O 7 (0 ≤ y ≤ 2) compositions fired at 800°C/1 h

y

Crystalline phases (weight fractions)

Unit cell parameters (Å and degrees)

a / b / c // α / β / γ

0.500

C2 (56.8%)

7.6430 (3) / 8.1076 (3) / 10.1147 (4) // 90.00 / 110.589 (4) / 90.00

 

M4 (26.3%)

6.719 (1) / 8.553 (1) / 9.846 (2) // 90.00 / 91.33 (2) / 90.00

 

M2 (16.9%)

6.936 (1) / 8.423 (1) / 9.793 (2) // 90.00 / 98.32 (1) / 90.00

0.750

M3 (48.4%)

6.9060 (4) / 8.3131 (5) / 9.5450 (5) // 90.00 / 95.346 (7) / 90.00

 

C2 (36.0%)

7.6308 (4) / 8.1127 (5) / 10.0542 (7) // 90.00 / 110.389 (6) / 90.00

 

C3 (15.1%)

4.9809 (5) / 5.8341 (6) / 10.933 (1) // 101.554 (8) / 96.517 (7) / 95.032 (8)

1.000

M4 (91.3%)

6.7766 (4) / 8.4899 (4) / 9.1447 (6) // 90.00 / 88.294 (5) / 90.00

 

C2 (8.7%)

7.542 (2) / 8.083 (2) / 10.0574 (2) // 90.00 / 110.59 (2) / 90.00

1.250

M4 (79.9%)

6.81447 (7) / 8.11262 (8) / 9.30424 (9) // 90.00 / 88.444 (1) / 90.00

 

C2 (13.9%)

7.6192 (3) / 8.0576 (4) / 10.1113 (4) // 90.00 / 109.689 (4) / 90.00

1.500

C1 (63.8%)

8.3392 (1) / 20.8256 (3) / 6.44642 (9) // 90.00 / 90.00 / 90.00

 

M4 (32.1%)

6.7458 (3) / 7.8414 (3) / 9.2234 (3) // 90.00 / 90.890 (3) / 90.00

1.750

M4 (59.3%)

6.7825 (3) / 8.0761 (3) / 9.3084 (4) // 90.00 / 89.448 (4) / 90.00

 

MT (40.7%)

4.9343 (4) / 5.4102 (5) / 10.7164 (9) // 99.866 (7) / 102.996 (5) / 98.743 (7)

2.000

M4 (59.3%)

6.7823 (1) / 8.0669 (2) / 9.3201 (2) // 90.00 / 89.345 (2) / 90.00

 

MT (40.7%)

4.9354 (2) / 5.4094 (2) / 10.7145 (5) // 99.874 (3) / 102.959 (3) / 98.756 (3)

Crystalline phases: C1 = α-Cu2V2O7, C2 = β-Cu2V2O7 (monoclinic, C2: β < 110.6°, C2’: β > 110.6°), C3 = γ-Cu2V2O7 (triclinic), M = α-Mg2V2O7 (monoclinic, M1: β = 100.0-100.6°, M2: β = 98.0-99.6°, M3: β = 94.5-97.0°, M4: β = 88.0-92.0°), MT = γ-Mg2V2O7 (triclinic).

Table 9

Unit cell parameters in crystalline phases with weight fractions higher than 8% from Mg y Cu 2-y V 2 O 7 (0 ≤ y ≤ 2) compositions fired at 1000°C/1 h

y

Crystalline phases weight fractions)

Unit cell parameters (Å and degrees)

a / b / c // α / β / γ

1.500

MT (41.6%)

4.9331 (2) / 5.4122 (3) / 10.7005 (5) // 100.037 (4) / 102.907 (3) / 98.777 (4)

 

M1 (39.7%)

6.6011 (4) / 8.4011 (4) / 9.5027 (5) // 90.00 / 100.394 (5) / 90.00

1.750

M1 (81.1%)

6.5951 (1) / 8.4057 (2) / 9.5075 (2) // 90.00 / 100.427 (2) / 90.00

 

MT (16.5%)

4.9318 (4) / 5.4130 (5) / 10.7219 (9) // 100.109 (8) / 102.908 (6) / 98.769 (7)

2.000

MT (69.0%)

4.9276 (2) / 5.4164 (2) / 10.6697 (4) // 100.318 (2) / 102.785 (3) / 98.617 (3)

 

MO (17.4%)

6.0832 (4) / 10.8818 (5) / 8.6212 (5) // 90.00 / 90.00 / 90.00

 

M1 (13.6%)

6.4596 (7) / 8.5135 (8) / 9.403 (1) // 90.00 / 102.00 (1) / 90.00

Crystalline phases: M = α-Mg2V2O7 (monoclinic, M1: β = 100.6-102.0o), MT = γ-Mg2V2O7 (triclinic), MO = Mg3V2O8 (orthorhombic).

From MgxCu3-xV2O8 compositions solid solutions with triclinic Cu3V2O8 structure are obtained when 0.0 ≤ x ≤ 1.0 at 600°C. At this temperature, the c unit cell parameter increases slightly with the replacement of Cu (II) ion by a slightly smaller one (Mg (II)) from MgxCu3-xV2O8 compositions when 0.0 ≤ x ≤ 1.0. Ionic radii values do not explain this fact. A slight contraction of unit cell is expected. Structural distortion might explain the c increase with incorporation of Mg (II) ions in a structure (Tena 2012).

Variation of unit cell parameters obtained from MgxCu3-xV2O8 (x ≥ 1.0) compositions fired at 800°C is noticeable in monoclinic Cu3V2O8 structure (detected when 1.5 ≤ x ≤ 2.0) and it indicates the formation of solid solutions with monoclinic Cu3V2O8 structure in 1.5 ≤ x ≤ 2 compositional range at 600°C and 800°C.

Solid solutions with orthorhombic Mg3V2O8 structure are also obtained when 2.5 ≤ x ≤ 3.0 at 600, 800°C and when 1.0 ≤ x ≤ 3.0 at 1000°C. Figure 4 shows unit cell parameters and interatomic distances in Mg orthovanadate structure (orthorhombic symmetry) obtained from MgxCu3-xV2O8 samples fired at 1000°C/1 h. At 1000°C, the a and b unit cell parameters decrease with the replacement of Cu (II) ion by a slightly smaller one (Mg (II)). Average changes of interatomic distances are very slight. Changes in intensities with composition (Figure 2) are due to changes in both the atomic coordinates and the Mg/Cu ratio in these sites in orthorhombic Mg3V2O8 structure when solid solutions are formed. These solid solutions are the most stable solid solutions obtained in this study from MgxCu3-xV2O8 compositions.
Figure 4

Cell parameters in the Mg 3 V 2 O 8 structure. Variation of unit cell parameters (a) and interatomic distances (b) in Mg orthovanadate structure with composition obtained from MgxCu3-xV2O8 samples fired at 1000°C/1 h.

From unit cell parameters values obtained in MgyCu2-yV2O7 compositions, the formation of two kinds of solid solutions with monoclinic β-Cu2V2O7 and monoclinic α-Mg2V2O7 structures can be confirmed. Two crystalline phases with the same structure (β-Cu2V2O7 or α-Mg2V2O7) are detected in some samples (Tables 7 and 8). This fact indicates that the composition of these two crystalline phase (C2: β < 110.6 o and C2’: β > 110.6° with β-Cu2V2O7 structure or two of M1: β = 100.0-100.6°, M2: β = 98.0-99.6°, M3: β = 94.5-97.0°, M4: β = 88.0-92.0° phases with α-Mg2V2O7 structure) is slightly different at 600 and 800°C in the conditions of this study. This slight difference between the two crystalline phases with the same structure is evidenced with differences in unit cell parameters values obtained. In MgyCu2-yV2O7 compositions fired at 600°C, the values of a and β parameters decrease when y increases in β-Cu2V2O7 structure (crystalline phase is obtained with a weight fraction > 35% when 0.25 ≤ y ≤ 1.5). At 800°C this crystalline phase is obtained with a weight fraction > 35% only when 0.5 ≤ y ≤ 0.75. In crystalline phase with α-Mg2V2O7 structure, β angle value is close to 100° at 300°C and it is close to 90° at 800°C. When two crystalline phases with this structure are detected in the same sample, unit cell parameters are 0.2 Å (a, b, c parameters) or 8 degrees (β parameter) longer and wider in one of them. This fact is in accordance with the formation of solid solutions in this monoclinic α-Mg2V2O7 structure with the replacement of Mg (II) ion by Cu (II) and with an important distortion structural in these formed solid solutions. Solid solutions with monoclinic α-Mg2V2O7 structure are obtained when 0.5 ≤ y ≤ 2.0 at 600 and 800°C. At 1000°C, these last solid solutions are obtained when y ≥ 1.5, including all unmelted samples (Table 9).

Coordination number of V (V) ion in Cu and Mg orthovanadate and divanadate structures is four. Coordination number of Cu (II) ion is four and five and coordination number of Mg (II) ion is six in these structures. Values obtained from samples are in accordance with literature about these structures. In distorted monoclinic structure of Cu3V2O8 obtained from Mg2CuV2O8 composition at 800°C, the coordination number of Cu (II) and Mg (II) ions are also six.

Average interatomic V-O distances is smaller than average interatomic Cu-O or Mg-O distances in all of detected crystalline phases. Figure 5 shows the average interatomic V-O and Cu-O or Mg-O distances obtained from MgyCu2-yV2O7 compositions considering all the crystalline phases in each composition and its weight fraction in samples fired at 600, 800 and 1000°C. These M-O (M = Cu, Mg) interatomic distances increase with magnesium amount (y) when 0 ≤ y ≤ 1.25. This increased average M-O distance is coincident with destabilization of structures of Cu divanadate and a change is observed when y > 1.25. Structures of Cu divanadate are unstable with temperature and structures of Mg divanadates are stable at 1000°C when 1.5 ≤ y ≤ 2.0 (Table 3).
Figure 5

Interatomic distances in Mg y Cu 2-y V 2 O 7 compositions. Average interatomic V-O (a) and M-O (b) distances in MgyCu2-yV2O7 (0 ≤ y ≤ 1) compositions fired at 600°C/12 h, 800°C/1 h and 1000°C/1 h considering weight fraction of crystalline phases.

Figures 6 and 7 show UV–vis-NIR spectra of MgxCu3-xV2O8 (0 ≤ x ≤ 3) and MgyCu2-yV2O7 (0 ≤ y ≤ 2) compositions fired at 600, 800 and 1000°C. Visible spectra obtained from MgyCu2-yV2O7 (0 ≤ y ≤ 2) compositions fired at 800°C/1 h and MgxCu2-xP2O7 (0 ≤ x ≤ 1.5) compositions fired at 800°C/5d (Tena 2012) are shown in Figure 8. Most of complex with Cu (II) ion are formed with four ligands (IC = 4). The reason for the unusual behaviour is connected with the Jahn-Teller effect. Because of that, the Cu (II) ions do not bind the fifth and sixth ligands strongly. Structural distortion due to this Jahn-Teller effect can explain the asymmetry in observed bands. From Cu (II) ion (d9) a transition d-d is allowed. Experimentally electronic spectra of Cu (II) ion are often characterized by a single highly asymmetric band. In this study spectra show a strong absorbance in 700–1400 nm wavelength range with the absorption maximum at 800–900 nm. It can be associated with Cu (II) d-d transition. Bands due to d-d transitions are not expected from V (V) ion. Strong absorbance in 430–600 nm wavelength range (in visible wavelength range) with the absorption maximum depending of copper amount in the sample (x or y values) is detected in MgxCu3-xV2O8 (0 ≤ x ≤ 3) and MgyCu2-yV2O7 (0 ≤ y ≤ 2) compositions at 300°C/12 h, 600°C/12 h, 800°C/1 h and 1000°C/1 h. The strong absorbance in 350–600 nm wavelength range is not observed in MgxCu2-xP2O7 compositions (Figure 8) and in MgxCu3-xV2O8 (x = 3) and MgyCu2-yV2O7 (y = 2) compositions. It is associated with charge transfer between Cu-O in orthovanadates and divanadates when 0 ≤ x < 3 or when 0 ≤ y < 2. When x = 3 or y = 2, the charge transfer is associated with V-O charge transfer (λ < 430 nm in studied temperature range). Maximum of this band is observed at higher wavelength when copper amount is hight than when the copper amount is low. This strong absorbance in visible wavelength range explains the colour of these materials. At 600 and 800°C, coloration from samples with vanadate structures is red-brown, orange and yellow and is very different to the weak blue coloration obtained from samples with phosphate structures (Tena 2012). At 1000°C, brown-dark and black colorations are obtained when x < 3.0 or y < 2.0 and a strong absorbance in 400–1800 nm range is obtained in spectra. In the most of samples band due to d-d transition and band due to charge transfer can not be differentiated at 1000°C. Vanadate structure does not seem to be the only important factor for the presence of this charge transfer band because it is present in MgxCu3-xV2O8 (x ≠ 3) compositions and in MgxCu2-yV2O7 (y ≠ 2) compositions with different crystalline phases detected by XRD (Tables 2 and 3). The difference of coloration of Cu phosphates and Cu vanadates might be explained from differences in interatomic Cu-O distances due to the presence of bonds P-O or V-O. Interatomic Cu-O distances are smaller in vanadate structures than in phosphate structures (Cu-O bond is more strong in vanadates than in phosphates) because the V-O bond is weaker than the P-O bond (interatomic V-O distances are slightly greater than interatomic P-O distances). Table 10 shows interatomic distances in some of these compositions.
Figure 6

Variation of UV–vis-NIR spectra from Mg x Cu 3-x V 2 O 8 compositions. UV–vis-NIR spectra of MgxCu3-xV2O8 (0.0 ≤ x ≤ 3.0) samples fired at: (a) 600, (b) 800 and (c) 1000 ºC; x = 0.0 (1), x = 0.5 (2), x = 1.0 (3), x = 1.5 (4), x = 2.0 (5), x = 2.5 (6) and x = 3.0 (7).

Figure 7

Variation of UV–vis-NIR spectra from Mg y Cu 2-y V 2 O 7 compositions. UV–vis-NIR spectra of MgyCu2-yV2O7 (0.0 ≤ y ≤ 2.0) samples fired at : (a) 600, (b) 800 and (c) 1000 ºC; y = 0.0 (1), y = 0.50 (2), y = 0.75 (3), y = 1.0 (4), y = 1.25 (5), y = 1.50 (6), y = 1.75 (7) and y = 2.0 (8).

Figure 8

Visible spectra of compositions at 800°C. Visible spectra of: (a) MgyCu2-yV2O7 (0.0 ≤ y ≤ 2.0) and (b) MgxCu2-xP2O7 (0.0 ≤ x ≤ 1.5) samples fired at 800°C; y = 0.50 (2), y = 0.75 (3), y = 1.00 (4), y = 1.25 (5), y = 1.50 (6), y = 1.75 (7), y =2.00 (8).

Table 10

Interatomic distances in orthovanadates, divanadates and diphosphates of Cu and Mg

Composition

Mg 2+ -O (Å)

Cu 2+ -O (Å)

V-O or P-O (Å)

1 Cu3V2O8

-----

1.912 (4) - 1.988 (5)

1.643 (3) - 1.795 (4)

1 Cu3P2O8

-----

1.925 (3) - 1.981 (3)

1.510 (2) - 1.572 (2)

1 Mg3V2O8

2.022 (1) - 2.135 (1)

-----

1.695 (1) - 1.809 (1)

1 Mg3P2O8

1.965 (8) - 2.142 (7)

-----

1.527 (5) - 1.535 (8)

2 MgxCu3-xV2O8

1.880 (2) - 2.306 (1)

1.570 (3) -1.972 (2)

1 Cu2V2O7

-----

1.880 (5) - 2.542 (4)

1.644 (7) - 1.770 (4)

1 Cu2P2O7

-----

1.929 (1) - 2.313 (1)

1.437 (1) - 1.561 (1)

1 Mg2V2O7

1.992 (3) - 2.221 (3)

-----

1.629 (3) - 1.817 (4)

1 Mg2P2O7

1.850 (1) - 2.381 (1)

-----

1.543 (1) - 1.785 (1)

2 MgyCu2-yV2O7

1.862 (3) - 2.282 (1)

1.620 (2) - 1.904 (4)

3 MgxCu2-xP2O7

1.927 (3) - 2.282 (2)

1.495 (2) - 1.574 (1)

1 Inorganic Crystal Structure Database (ICSD) (2013).

2 MgxCu3-xV2O8 (0 ≤ x ≤ 3) and MgyCu2-yV2O7 (0 ≤ y ≤ 2) compositions prepared in this study.

3 (Tena 2012).

CIE L*, a* and b* parameters of MgxCu3-xV2O8 (0 ≤ x ≤ 3) and MgyCu2-yV2O7 (0 ≤ y ≤ 2) samples fired at 600, 800 and 1000°C are shown in Table 11.
Table 11

CIE L* a* b* colour parameters in Mg x Cu 3-x V 2 O 8 (0 ≤ x ≤ 3) and Mg y Cu 2-y V 2 O 7 (0 ≤ y ≤ 2) samples

x

Observed colour

Mg x Cu 3-x V 2 O 8 samples fired at 600°C/12 h

  

L*

a*

b*

0.00

dark brown

41.57

4.10

0.79

0.50

dark brown

43.59

5.83

6.82

1.00

orange

56.94

13.29

25.79

1.50

yellow

66.67

18.29

42.22

2.00

yellow

76.77

6.47

47.76

2.50

light brown

83.12

- 1.34

35.49

3.00

light yellow

94.76

- 2.00

13.35

y

Observed colour

Mg y Cu 2-y V 2 O 7 samples fired at 600°C/12 h

  

L*

a*

b*

0.00

dark brown

43.33

13.86

4.91

0.25

red-brown

38.34

20.54

9.80

0.50

red-brown

50.60

21.72

16.23

0.75

orange

46.88

25.71

29.13

1.00

orange

58.96

19.05

30.90

1.25

orange

57.06

19.77

46.16

1.50

brown

70.76

10.83

36.19

1.75

light brown

69.70

4.76

34.91

2.00

light yellow

92.46

- 1.35

22.95

x

Observed colour

Mg x Cu 3-x V 2 O 8 samples fired at 800°C/1 h

  

L*

a*

b*

1.00

dark brown

46.73

3.03

6.73

1.50

brown

53.37

4.77

15.20

2.00

yellow

68.97

12.02

41.84

2.50

light yellow

83.96

0.38

39.86

3.00

light yellow

95.50

- 3.57

11.54

y

Observed colour

Mg y Cu 2-y V 2 O 7 samples fired at 800°C/1 h

  

L*

a*

b*

0.50

dark brown

48.90

4.19

10.50

0.75

dark brown

47.58

3.95

8.75

1.00

brown

49.18

10.31

11.09

1.25

orange

52.11

13.11

16.37

1.50

orange

57.13

13.67

24.55

1.75

light brown

69.05

3.87

35.70

2.00

light brown

85.00

- 5.37

22.14

x

Observed colour

Mg x Cu 3-x V 2 O 8 samples fired at 1000°C/1 h

  

L*

a*

b*

1.00

grey

52.75

0.96

0.56

1.50

dark brown

48.74

1.15

4.58

2.00

dark brown

51.37

1.46

6.09

2.50

brown

58.02

2.69

12.51

3.00

yellow

94.28

- 4.86

17.95

y

Observed colour

Mg y Cu 2-y V 2 O 7 samples fired at 1000°C/1 h

  

L*

a*

b*

1.50

black

46.85

- 0.16

3.84

1.75

black-brown

47.39

0.31

3.86

2.00

yellow-brown

67.25

- 1.12

20.11

Interesting yellow colorations are obtained when x = 1.5 and 2.0 at 600°C/12 and when x = 2.0 at 800°C/1 h. In these samples that development yellow colorations, crystalline phase with monoclinic Cu3V2O8 structure is detected. The best yellow colour is obtained from Mg2CuV2O8 (x = 2.0) solid solution with monoclinic Cu3V2O8 structure. This is the only crystalline phase detected at 800°C in conditions of this study. The Mg (II) incorporated into this structure stabilizes this crystalline phase at temperatures higher than 780°C (melting point of Cu3V2O8). In Mg2CuV2O8 composition fired at 800°C, average distances of M1-O (M1 = Cu, Mg) = 1.9587 Å and M2-O (M2 = Cu, Mg) = 2.1129 Å are obtained. Yellow colorations are not obtained from Cu, Mg divanadates.

The colour red-brown obtained from Mg0.5Cu1.5V2O7 (y = 0.5) fired at 600°C /12 h is the most noticeable colour but it is unstable at 800°C /1 h. Dark brown colour is obtained from this composition at 800°C. The major crystalline phase detected by XRD is the crystalline phase with β-Cu2V2O7 structure in this sample fired at 600°C.

Orange colour is obtained when y = 0.75, 1.00 and 1.25 at 600°C/12 h and when y = 1.25 and 1.50 at 800°C/1 h. In these orange materials, a mixture of monoclinic crystalline phases with β-Cu2V2O7 and Cu3V2O8 or β-Cu2V2O7 and α-Mg2V2O7 structures is detected by XRD.

Figure 9 shows the wavelength of charge transfer in MgyCu2-yV2O7 compositions fired at 600°C/12 h (bands in Figure 7 (a)) and the variation of average V-O and M-O distances with wavelength of charge transfer and with composition (y). Inflection point between maximum and minimum absorbance in band is considered in assignation of wavelength values. Distances are calculated considering all the crystalline phases detected by XRD in each composition and its weight fraction in this sample. When Cu (II) amount (y) decreases in samples, the wavelength of charge transfer decreases in all compositions at this temperature and colour of samples changes from red-brown to yellow. From variation of average interatomic distances at 600°C/12 h, the longest average M-O distances is detected when 0.75 ≤ y ≤ 1.25 and orange coloration is obtained in these materials (charge transfer about 550 nm). At this temperature red-brown coloration is obtained in samples with the shortest average M-O distances (charge transfer about 570 nm). The obtained colorations are different with similar average distances when Mg amount is high (y > 1.25) and when Cu amount is high (y < 1.25) because Mg (II) and Cu (II) radius are similar. Structural changes must be also considered to explain the complete evolution of colour with composition.
Figure 9

Variation of interatomic distances with wavelength and composition. Variation of wavelength of Cu-O charge transfer with composition (a), variation of average interatomic V-O and M-O (M = Cu, Mg) distances with wavelength (b) and variation of these average interatomic distances with composition (c) from MgyCu2-yV2O7 samples fired at 600°C. Solid marks: y < 1.5; Empty marks: y ≥ 1.5.

Conclusions

From MgxCu3-xV2O8 compositions solid solutions with triclinic Cu3V2O8 structure are obtained in 0.0 ≤ x ≤ 1.0 at 600°C. When x = 1.0, MgCu2V2O8 compound is detected at 800°C. When x = 2.0, Mg2CuV2O8 compound with the ordered metal distributions is not detected in the conditions of this study. From this composition, solid solutions with monoclinic Cu3V2O8 structure (Cu1 in 2b sites) are obtained. These solid solutions with monoclinic Cu3V2O8 structure are obtained when 1.5 ≤ x ≤ 2.0 at 600°C and 800°C. Solid solutions with orthorhombic Mg3V2O8 structure are obtained when 2.5 ≤ x ≤ 3.0 at 600, 800°C and when 1.0 ≤ x ≤ 3.0 at 1000°C. In this study, the most stable solid solutions are obtained with Mg orthovanadate structure (orthorhombic).

From MgyCu2-yV2O7 compositions, the formation of two kind of solid solutions with β-Cu2V2O7 and α-Mg2V2O7 structures is detected. Solid solutions with monoclinic β-Cu2V2O7 structure are obtained when 0.25 ≤ y ≤ 1.50 at 600°C and when 0.50 ≤ y ≤ 0.75 at 800°C. Solid solutions with monoclinic α-Mg2V2O7 structure are obtained when 0.5 ≤ y ≤ 2.0 at 600 and 800°C and showing an important structural distortion. At 1000°C, solid solutions with α-Mg2V2O7 structure are obtained in 1.5 ≤ y ≤ 2.0 compositional range. It is proposed the existence of a new polymorph of Mg2V2O7 compound with α-Mn2V2O7 structure detected when y ≥ 1.25 at 300°C.

Strong absorbance in visible spectra is detected in MgxCu3-xV2O8 (0 ≤ x < 3) and MgyCu2-yV2O7 (0 ≤ y < 2) compositions which is associated with charge transfer between Cu-O in orthovanadates and divanadates. Wavelength of the abrupt change in absorbance is in accordance with Cu-O interatomic distances in these structures. In this study, the best yellow colour is obtained from Mg2CuV2O8 (x = 2.0) solid solution with monoclinic Cu3V2O8 structure. The colour red-brown is obtained from Mg0.5Cu1.5V2O7 (y = 0.5) fired at 600°C /12 h and it is unstable at 800°C /1 h. This red-brown colour is obtained when the average M-O distances are the shortest from divanadates. Orange colour is also obtained from some divanadates when average M-O distance is long.

Structural changes must be also considered to explain the colour of these materials. Thus, yellow colorations are obtained from orthovanadates and red-brown and orange colorations are obtained from divanadates.

Declarations

Acknowledgements

The authors acknowledge the financial support given by the government of Spain, MAT 2008–02893, MAT 2010–15094 and MAT2013-40950-R projects.

Authors’ Affiliations

(1)
Inorganic Chemistry Area, Inorganic and Organic Chemistry Department, Jaume I University
(2)
Physical Chemistry Area, Physical and Analytical Chemistry Department, Oviedo University-CINN

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© Tena and García-Granda; licensee Springer. 2015

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