Journal of Alloys and Compounds 693 (2017) 792e798

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Investigation and characterization on crystal structure of ixiolite

structure ATiNb2O8 (A ¼ Mg, Zn) ceramics at microwave frequency
based on the complex chemical bond theory
H.L. Pan, L. Cheng, Y.X. Mao, H.T. Wu*
School of Materials Science and Engineering, University of Jinan, Jinan, 250022, China

a r t i c l e i n f o a b s t r a c t

Article history: Ixiolite structure ATiNb2O8 (A ¼ Mg, Zn) microwave dielectric materials were prepared via the con-
Received 11 August 2016 ventional solid state reaction method. The crystal structure was researched by X-ray diffraction. Rietveld
Received in revised form refinement was used to analyze the crystal structure and the lattice parameters were obtained. Based on
21 September 2016
the complex chemical bond theory and lattice parameters, intrinsic factors such as the bond ionicity,
Accepted 24 September 2016
lattice energy, bond energy and coefficient of thermal expansion were calculated. The relationships
Available online 28 September 2016
between structures and properties of ATiNb2O8 (A ¼ Mg, Zn) ceramics were researched. The microwave
properties were strongly dependent on intrinsic factors. The dielectric constant (εr) was strongly
Keywords:
ATiNb2O8
dependent on the bond ionicity of NbeO bonds. The quality factor (Q·f) was mainly affected by the lattice
Conventional solid state reaction method energy of NbeO bonds. The temperature coefficient of resonant frequency (tf) could be mainly influenced
Microwave dielectric properties by the bond energy and coefficient of the thermal expansion of NbeO bonds.
Complex chemical bond theory © 2016 Elsevier B.V. All rights reserved.

1. Introduction et al. [8] reported that ZnTiNb2O8 exhibited good microwave

The rapid progress of the mobile and wireless communication
technology has stimulated the fast development of the microwave
dielectric ceramics, which are widely used for microwave compo-
nents including oscillators, antennas, resonators and filters [1,2].
Generally speaking, microwave dielectric ceramics possess three
significant parameters: the quality factor (Q·f), dielectric constant
(εr) and temperature coefficient of resonant frequency (tf) [3,4].
ATiNb2O8 (A ¼ Mg, Zn) ceramics had received a lot of attentions due
to their excellent microwave dielectric properties [5e11] (see
Table 1). Mei et al. [5] reported that MgTiNb2O8 ceramics exhibited
the microwave dielectric properties of εr ¼ 33.8, Q·f ¼ 26, 260 GHz
and tf ¼ 19.2 ppm/ C by the aqueous sol-gel process. As for
ZnTiNb2O8, there were a lot of research about the system, most of
which were prepared through the solid state method. Kim et al. [6]
firstly reported that ZnTiNb2O8 ceramics sintered at 1250  C
exhibited the properties of εr ¼ 34, Q·f ¼ 42, 500 GHz and
tf ¼ 52 ppm/ C. Later, Liao et al. [7] reported that microwave
dielectric properties with εr ¼ 34.4, Q·f ¼ 56, 900 GHz and
tf ¼ 47.94 ppm/ C were obtained for ZnTiNb2O8. In addition, Lei
* Corresponding author.
E-mail address: mse_wuht@ujn.edu.cn (H.T. Wu).
properties of εr ¼ 34.2, Q·f ¼ 28, 696 GHz and tf ¼ 75.841 ppm/ C
at the sintering temperature of 1150  C. Tseng et al. [9] also reported
that microwave properties with εr ¼ 37.4, Q·f ¼ 194, 000 GHz and
tf ¼ 58 ppm/ C were obtained. The aqueous sol-gel process and
reaction sintering method were also used to prepare the ZnTiNb2O8
ceramics. For instance, Mei et al. [10] reported that excellent mi-
crowave properties with εr ¼ 35.3, Q·f ¼ 66,700 GHz and
tf ¼ 55.4 ppm/ C were obtained by an aqueous sol-gel process.
Barzegar Bafrooei et al. [11] reported that ZnTiNb2O8 exhibited
properties of εr ¼ 36.7, Q·f ¼ 54,000 GHz and tf ¼ 70.4 ppm/ C by
the reaction sintering method.
However, until now, the influences of the intrinsic factors such
as the bond ionicity, lattice energy, bond energy and coefficient of
thermal expansion on the microwave dielectric properties have not
been reported. The concept of the chemical bond ionicity was
widely used in many areas and very important for explaining many
basic properties [12,13]. It could be evaluated by generalized P-V-L
theory, which was applied to complex crystals [14e16]. Based on
the chemical bond ionicity and lattice parameters of the crystal, the
lattice energy and coefficient of thermal expansion were calculated,
which acted an important role in diverse stability and thermody-
namic analyses of complex ionic crystals. Based on the electro-
negativity and complex chemical bond theory, the bond energy of a
complex crystal could be calculated to evaluate the stability. In the

http://dx.doi.org/10.1016/j.jallcom.2016.09.281
0925-8388/© 2016 Elsevier B.V. All rights reserved.
 H.L. Pan et al. / Journal of Alloys and Compounds 693 (2017) 792e798 793

Table 1 According to the lattice parameters, atomic positions and oc-

Summarized microwave dielectric properties of ATiNb2O8 (A ¼ Mg, Zn) ceramics. cupations, the schematic representation of the ATiNb2O8 (A ¼ Mg,
Material STa ( C) εr Q·f (GHz) tf (ppm/ C) References Zn) (3  3  3) supercell was shown in Fig. 2, which showed that
MgTiNb2O8 1000 33.8 26,260 19.2 [5]
MgTiNb2O8 and ZnTiNb2O8 were constituted by Mg/Ti/Nb and Zn/
ZnTiNb2O8 1120 34.3 42,500 52 [6] Ti/Nb oxygen octahedrons, respectively. In the crystal structure of
ZnTiNb2O8 1120 34.4 56,900 47.94 [7] ATiNb2O8 (A ¼ Mg, Zn), A/Ti/Nb cations occupied 4c Wyckoff po-
ZnTiNb2O8 1150 34.2 28,696 75.841 [8] sitions and O anions occupied 8d Wyckoff positions. O1, O2 and O3
Zn0.5Ti0.5NbO4 1100 37.4 194,000 58 [9]
were used to distinguish oxygen atoms with different bond lengths.
ZnTiNb2O8 1050 35.3 66,700 55.4 [10]
ZnTiNb2O8 1075 36.7 54,000 70.4 [11] The bond length between the cations and O anion were 1.9381 Å,
a
1.9956 Å and 2.118 Å for MgTiNb2O8, and 1.9412 Å, 2.0115 Å and
ST: sintering temperatures.
2.1202 Å for ZnTiNb2O8, respectively.
Microwave dielectric properties of ceramics were dependent on
present study, ATiNb2O8 (A ¼ Mg, Zn) ceramics were prepared both extrinsic factors and intrinsic factors. The secondary phase,
successfully through the solid state reaction method. Subsequently, grain size and density played an important role in extrinsic factors,
Rietveld refinement was used to analyze the crystal structure and while the intrinsic factors were mainly affected by the lattice de-
the lattice parameters were obtained based on X-ray diffraction. fects and crystal structure [18e20]. In our researches, a dense state
According to the complex chemical bond theory and refinement and no other secondary phases were obtained for ATiNb2O8
results, the chemical bond ionicity, lattice energy, bond energy and (A ¼ Mg, Zn) ceramics, which meant that the extrinsic factors could
coefficient of thermal expansion were calculated to character the be ignored. Thus, intrinsic factors such as the bond ionicity, lattice
correlations between the intrinsic factors and microwave dielectric energy, bond energy and coefficient of thermal expansion should
properties of ATiNb2O8 (A ¼ Mg, Zn) ceramics. be considered. Kapustinskii et al. and Xue et al. reported that the
chemical bond ionicity could explain many basic properties in
diverse areas [12,13], which could be evaluated by P-V-L theory.
2. Experimental procedure
Zhang et al. improved the P-V-L theory and made it possible for
application in complex crystals [14e16]. Based on the lattice pa-
High-purity powders of ZnO (99.9%, Aladdin), MgO (99.99%,
rameters and complex chemical bond theory, the complex crystals
Aladdin) Nb2O5 (99.9%, Aladdin) and TiO2 (99.9%, Aladdin) were
ATiNb2O8 (A ¼ Mg, Zn) were decomposed into the sum of binary
used as starting materials to prepare ATiNb2O8 (A ¼ Mg, Zn) ce-
crystals as follows.
ramics by the solid state reaction method. Firstly, chemical pow-
ders were weighed in accordance with the chemical formula and
ATiNb2 O8 ¼ AO2 þ TiO2 þ Nb2 O4
milled in a teflon jar with ZrO2 balls as the medium for 24 h. The
slurry was then dried in an oven at the temperature of 80  C. ¼ A1=3 O12=3 þ A1=3 O22=3 þ A1=3 O32=3 þ Ti1=3 O12=3
Secondly, the mixed powders were calcined at selected tempera-
þ Ti1=3 O22=3 þ Ti1=3 O32=3 þ Nb2=3 O14=3 þ Nb2=3 O24=3
tures and then re-milled for 6 h. Thirdly, the powders were mixed
with 8 wt% paraffin and then pressed into pellets with 5 mm in þ Nb2=3 O34=3
thickness and 10 mm in diameter under the pressure of 200 MPa.
(1)
Finally, these pellets were sintered at 1100  C for MgTiNb2O8 and
1250  C for ZnTiNb2O8 in air at a heating rate of 5  C/min. Fig. 3 showed the coordination number and charge distribution
Phase analysis of the samples was conducted with the help of a of ions in ATiNb2O8 (A ¼ Mg, Zn) crystal. The coordination numbers
Rigaku diffractometer (Model D/MAX-B, Rigaku Co., Japan) using Cu of A, Ti, Nb and O were 6, 6, 6 and 3, respectively. The valence
Ka radiation (l ¼ 0.1542 nm) at 40 kV and 40 mA settings. electron numbers of cations in these bonds were ZA ¼ 2, ZTi ¼ 4 and
ZnTiNb2O8 reported by Baumgarte et al. [17] was adopted as the ZNb ¼ 5, while the effective valence electron numbers of anions
starting model of Rietveld refinement. Some parameters such as were ZO ¼ 1 in the A-O bond, ZO ¼ 2 in the TieO bond and
the background, zero point, half width, unit-cell parameters, atomic ZO ¼ 2.5 in the NbeO bond. The difference effective valence
position, asymmetry parameters, etc. were refined gradually using electron number of oxygen atoms were mainly due to the charge
Fullprof software. The reliability of the results was judged by the balance for each sub-formula.
pattern R factor (Rp), weighted pattern R factor (Rwp) and good- According to the generalized P-V-L theory [14e16], the bond
ness of fit indicator (c2). ionicity (fi) of an individual bond m could be calculated as follows.

3. Results and discussion ðC m Þ2

fi ¼
2 (2)
m
Eg
Fig. 1 showed the typical refinement patterns of ATiNb2O8
(A ¼ Mg, Zn) ceramics. The diffraction peaks matched well with the

m 2  m 2
ixiolite structure ZnTiNb2O8 (JCPDS No. 48-0323) and no other Eg ¼ Eh þ ðC m Þ2 (3)
phases were observed. The calculated pattern was overlaid on the
measured pattern and the difference between two profiles was  
marked along the bottom. The reliability of the results were m 2 39:74
Eh ¼ (4)
Rp ¼ 9.16%, Rwp ¼ 12.1% and c2 ¼ 3.34 for MgTiNb2O8, and ðdm Þ2:48
Rp ¼ 5.71%, Rwp ¼ 7.77% and c2 ¼ 4.41 for ZnTiNb2O8, which
proved that the measured patterns fitted well with the calculated
h n
u * i. m
m 
u *
patterns. It indicated that the results were credible. In addition, the C m ¼ 14:4bm exp  kus r0 ZA  Z r0 (5)
m B
refinement results such as the atomic coordinate, Wyckoff site, and
m
lattice parameters were also shown in Tables 1 and 2. Based on Where Eg was the average energy gap for the bond m and it could be
m
these parameters, the bond length of ATiNb2O8 (A ¼ Mg, Zn) was decomposed into homopolar Eh and heteropolar C m parts. Some
m
calculated as shown in Table 3. parameters such as expðks r0 Þ and bm in Equ. 5 could be obtained
u
794 H.L. Pan et al. / Journal of Alloys and Compounds 693 (2017) 792e798

Fig. 1. (a) Rietveld refinement of MgTiNb2O8 ceramics (Rp ¼ 9.16%, Rwp ¼ 12.1% and c2 ¼ 3.34). (b) Rietveld refinement of ZnTiNb2O8 ceramics (Rp ¼ 5.71%, Rwp ¼ 7.77% and
c2 ¼ 4.41).

Table 2 ceramics as a variation of the bonds were shown in Fig. 4(a) and (e),
Atomic positions and occupancies of ATiNb2O8 (A ¼ Mg, Zn) ceramics. respectively. It was found that the average bond ionicity Afi(MgeO),
Compounds Atom Wyckoff site x y z Biso. Occ. Afi(TieO) and Afi(NbeO) were 0.6370, 0.8047 and 0.8426 for
MgTiNb2O8 Mg 4c 0.0000 0.3233 0.2500 1.0604 0.2500
MgTiNb2O8, and Afi(ZneO), Afi(TieO) and Afi(NbeO) were 0.6369,
Ti 4c 0.0000 0.3233 0.2500 1.0604 0.2500 0.8045 and 0.8423 for ZnTiNb2O8, respectively. Based on the result
Nb 4c 0.0000 0.3233 0.2500 1.0604 0.5000 of Afi(AeO)<Afi(TieO)<Afi(NbeO), The dielectric constant was strongly
O 8d 0.2783 0.1165 0.4156 0.0884 2.0000 dependent on the bond ionicity of NbeO bonds for ATiNb2O8
ZnTiNb2O8 Zn 4c 0.0000 0.3227 0.2500 0.7193 0.2504
(A ¼ Mg, Zn) ceramics.
Ti 4c 0.0000 0.3227 0.2500 0.7193 0.2496
Nb 4c 0.0000 0.3227 0.2500 0.7193 0.4998 As for the lattice energy, the parameters of a single bond could
O 8d 0.2738 0.1116 0.4171 1.3170 2.1928 be constituted by the ionic and covalent parts. Based on the
chemical bond ionicity and generalized PV-L theory [14e16], the
lattice energy (U) of the ATiNb2O8 (A ¼ Mg, Zn) crystal was calcu-
from Ref. [21]. The calculated results of the bond ionicity were lated by Equs. (13e16).
listed in Table 4. The bond ionicity of MgTiNb2O8 and ZnTiNb2O8

Table 3
The lattice parameters, reliability and bond length of ATiNb2O8 (A ¼ Mg, Zn) ceramics.

Compounds a (Å) b (Å) c (Å) a¼b¼g Vm (Å3) Rp (%) Rwp (%) Rexp Atom 1 Atom 2 d1,2 (Å)

MgTiNb2O8 4.6701 5.6363 5.0132 90 131.9589 9.16 12.1 3.34 MgjTijNb O1 1.9381
O2 1.9956
O3 2.118
ZnTiNb2O8 4.6750 5.6595 5.0175 90 132.7541 5.71 7.77 4.41 ZnjTijNb O1 1.9412
O2 2.0115
O3 2.1202

Fig. 2. Schematic representation of the ATiNb2O8 (A ¼ Mg, Zn) (3  3  3) supercell and its oxygen octahedrons.
 H.L. Pan et al. / Journal of Alloys and Compounds 693 (2017) 792e798 795

Fig. 3. The coordination number and charge distribution of ions in the ATiNb2O8 (A ¼ Mg, Zn) ceramics.

Table 4
The results of the bond ionicity, lattice energy and coefficient of thermal expansion for ATiNb2O8 (A ¼ Mg, Zn) ceramics.

Compounds Bond type Bond length (Å) Eh Eg m m Ubc (kJ/mol) Ubi (kJ/mol) U (kJ/mol) a (106K1)
fi fc

MgTiNb2O8 MgeO1 1.9381 7.7008 12.6566 0.6298 0.3702 492 655 1147 9.3832
MgeO2 1.9956 7.1622 11.8602 0.6353 0.3647 474 647 1121 9.6743
MgeO3 2.1180 6.1792 10.3827 0.6458 0.3542 440 628 1068 10.3116
TieO1 1.9381 7.7008 17.2838 0.8015 0.1985 822 3334 4156 3.7597
TieO2 1.9956 7.1622 16.1791 0.8040 0.1960 794 3273 4067 3.9113
TieO3 2.1180 6.1792 14.1256 0.8086 0.1914 741 3146 3887 4.2392
NbeO1 1.9381 7.7008 19.2711 0.8403 0.1597 1906 10,925 12,831 2.0461
NbeO2 1.9956 7.1622 18.0247 0.8421 0.1579 1844 10,712 12,556 2.1603
NbeO3 2.1180 6.1792 15.7088 0.8453 0.1547 1728 10,278 12,006 2.4044
AMgeO e 7.0141 11.6332 0.6370 0.3630 468 643 1112 9.7897
ATieO e 7.0141 15.8628 0.8047 0.1953 786 3251 4037 3.9701
ANbeO e 7.0141 17.6682 0.8426 0.1574 1826 10,638 12,464 2.2036
ZnTiNb2O8 ZneO1 1.9412 7.6703 12.5996 0.6294 0.3706 492 654 1146 9.3941
ZneO2 2.0115 7.0226 11.6408 0.6361 0.3639 470 643 1113 9.7666
ZneO3 2.1202 6.1633 10.3478 0.6452 0.3548 440 627 1067 10.3243
TieO1 1.9412 7.6703 17.1981 0.8011 0.1989 822 3329 4151 3.7680
TieO2 2.0115 7.0226 15.8682 0.8041 0.1959 788 3254 4042 3.9551
TieO3 2.1202 6.1633 14.0716 0.8082 0.1918 742 3142 3884 4.2449
NbeO1 1.9412 7.6703 19.1723 0.8399 0.1601 1908 10,907 12,815 2.0526
NbeO2 2.0115 7.0226 17.6721 0.8421 0.1579 1833 10,649 12,482 2.1919
NbeO3 2.1202 6.1633 15.6463 0.8448 0.1552 1732 10,265 11,997 2.4086
AZneO e 6.9521 11.5294 0.6369 0.3631 467 641 1109 9.8283
ATieO e 6.9521 15.7126 0.8045 0.1955 784 3242 4026 3.9893
ANbeO e 6.9521 17.4969 0.8423 0.1577 1824 10,607 12,431 2.2177

Note: 1, 2 and 3are used to distinguish oxygen atoms with different bond lengths; A indicates the average value.

X m AU(NbeO) were 1112, 4037 and 12,464 kJ/mol for MgTiNb2O8,

U¼ Ub (6) respectively. As for ZnTiNb2O8, AU(ZneO), AU(TieO) and AU(NbeO)
m were 1109, 4026 and 12,431 kJ/mol respectively. Obviously, there
was the sequence of AU(AeO)<AU(TieO)<AU(NbeO), the lattice energy
m m m U(NbeO) could be predominant contribution to the Q·G value as
Ub ¼ Ubc þ Ubi (7)
intrinsic factors in the ATiNb2O8 (A ¼ Mg, Zn) ceramics.

m 1:64 It was known that the shorter bond length correlated with the
m Zþ m higher bond energy, which indicated that the crystal would be
Ubc ¼ 2100m fC (8)
ðdm Þ0:75 more stable. Sanderson reported that the bond energy could be
obtained by the chemical bond and electronegativity [22,23]. Based
m m  on the electronegativity and complex chemical bond theory, the
m ðm þ nÞZþ Z 0:4 m bond energy (E) of a complex crystal could be calculated as Eqns.
Ubi ¼ 1270 m 1  m fi (9)
d d (10e13).
m m
Where Ubc and Ubi were covalent part and ionic part of m bond,
m m were the valence states of the cation and X m
respectively. Zþ and Z E¼ Eb (10)
anion, respectively. The calculated results of the lattice energy were m
listed in Table 4. The lattice energy of MgTiNb2O8 and ZnTiNb2O8
m
ceramics as a variation of the bonds were shown in Fig. 4 (b) and (f), Where Eb was the bond energy for the m bond, which was
m
respectively. The average lattice energy AU(MgeO), AU(TieO) and decomposed into the non-polar covalence energy Ec and complete
796 H.L. Pan et al. / Journal of Alloys and Compounds 693 (2017) 792e798

Fig. 4. The bond ionicity, lattice energy, bond energy and coefficient of thermal expansion as a variation of the bond type for ATiNb2O8 (A ¼ Mg, Zn) ceramics.

m
ionicity energy Ei parts as follows.

m m m
Eb ¼ tc Ec þ ti Ei (11) m 33200
Ei ¼ (12)
m
The ionic energy Ei was the unit charge product divided by the dm
m
bond length dm, adjusted to kcal/mol by the factor 33,200 when the For any binary crystal AmBn, the non-polar covalence energy Ec
bond length was pm. parts could be calculated as following.
 H.L. Pan et al. / Journal of Alloys and Compounds 693 (2017) 792e798 797

MgTiNb2O8 and ZnTiNb2O8 ceramics as a variation of the bonds was

m ðrcA þ rcB Þ shown in Fig. 4(d) and (h), respectively. The average coefficient of
Ec ¼ ðEAA EBB Þ1=2 (13)
dm the thermal expansion Aa(MgeO), Aa(TieO) and Aa(NbeO) were
9.7897, 3.9701 and 2.2036 106/K for MgTiNb2O8, respectively. As
Where rcA and rcB were the covalent radii, and EAeA and EBeB were
for ZnTiNb2O8, Aa(ZneO), Aa(TieO) and Aa(NbeO) were 9.8283, 3.9893
the bond energy, respectively. In this paper, EZneZn ¼ 22.2 kJ/mol,
and 2.2177 106/K, respectively. Based on the result of
EMgeMg ¼ 11.3 kJ/mol, ENbeNb ¼ 513 kJ/mol, ETieTi ¼ 117.6 kJ/mol,
Aa(NbeO)<Aa(TieO)<Aa(AeO), the temperature coefficient of reso-
and EOeO ¼ 498.4 kJ/mol could be obtained from the handbook
nant frequency would be mainly affected by the coefficient of the
[24]. The final results were obtained as shown in Table 5. The bond
thermal expansion of NbeO bonds.
energy of MgTiNb2O8 and ZnTiNb2O8 ceramics as a variation of the
The complex chemical bond theory was applied to many
bonds were shown in Fig. 4 (c) and (g), respectively. The average
ceramic systems. Xia et al. [25] established the relationship be-
bond energy AE(MgeO), AE(TieO) and AE(NbeO) were 293.2087,
tween the bond ionicity, lattice energy and microwave dielectric
293.2087 and 577.0811 kJ/mol for MgTiNb2O8, respectively. As for
properties of Zn(Ta1xNbx)2O6 ceramics using the generalized P-V-L
ZnTiNb2O8, AE(ZneO), AE(TieO) and AE(NbeO) were 270.9666,
theory based on the crystalline structure refinement. Later, Zhang
380.3183 and 575.0371 kJ/mol, respectively. Based on the result of
et al. [26] systematically investigated the correlations among the
AE(AeO)<AE(TieO)<AE(NbeO), the NbeO bond might play an impor-
crystal structure, bond ionicity, lattice energy, bond energy and
tant role in Q·G values of ATiNb2O8 (A ¼ Mg, Zn) ceramics.
microwave dielectric properties of Li2Mg(Ti1xMnx)3O8 ceramics.
Based on the complex chemical bond theory, the coefficient of
The theory was also applied in Nd(Nb1xSbx)O4 [27]. In our previ-
thermal expansion (a) could be written as Equ. (14).
ous study, a semiempirical method based on the complex bond
X m m theory was used to calculate the bond ionicity, lattice energy, and
a¼ Fmn amn (14) coefficient of thermal expansion of AZrNb2O8 (A ¼ Zn, Co, Mg, Mn)
m
ceramics [18]. this theory was also applied in Zn1xCoxZrNb2O8
m (0  x  0.1) and Li2OeMgOeBO2 (B ¼ Ti, Sn, Zr) systems [28,29,30].
Where Fmn was the proportion of m bond in the total bonds of a
Based on the complex chemical bond theory and crystalline
supercell. For any binary crystal AmBn, the coefficient of thermal
m structure refinement, the bond ionicity, lattice energy, bond energy
expansion amn could be calculated as the following Eqs. 15e17.
and coefficient of thermal expansion of the complex crystals could
ammn ¼ 3:1685 þ 0:8376gmn (15) be quantitative calculated. The relationship between the structure
parameters and microwave dielectric properties could be estab-
m m
lished. In addition, this theory lays a theoretical foundation for the
kZA NCA future research.
gmn ¼ m bmn (16)
Ub D A

4. Conclusions
mðm þ nÞ
bmn ¼ (17)
2n Ixiolite structure ATiNb2O8 (A ¼ Mg, Zn) ceramics were pre-
m
Where k was Boltzmann constant, ZA was the valence state of pared successfully by the conventional solid state reaction method.
m
the cation, NCA was the coordination number of m bond for cation. Rietveld refinement was used to analyze the crystal structure and
The calculated results of the coefficient of the thermal expansion the lattice parameters were obtained. The bond ionicity, lattice
were listed in Table 4. The coefficient of the thermal expansion of energy, bond energy and coefficient of thermal expansion were

Table 5
The results of the bond energy for ATiNb2O8 (A ¼ Mg, Zn) ceramics.

Compounds Bond type Bond length (Å) Ion coefficient Covalent coefficient Ec (kJ/mol) Ei (kJ/mol) E (kJ/mol)

MgTiNb2O8 MgeO1 1.9381 0.3550 0.6450 78.2143 716.3841 304.7646

MgeO2 1.9956 0.3550 0.6450 75.9607 695.7426 295.9833
MgeO3 2.1180 0.3550 0.6450 71.5709 655.5354 278.8783
TieO1 1.9381 0.3167 0.6833 248.5720 716.3841 396.7125
TieO2 1.9956 0.3167 0.6833 241.4098 695.7426 385.2818
TieO3 2.1180 0.3167 0.6833 227.4586 655.5354 363.0163
NbeO1 1.9381 0.3083 0.6917 547.8648 716.3841 599.8249
NbeO2 1.9956 0.3083 0.6917 532.0789 695.7426 582.5419
NbeO3 2.1180 0.3083 0.6917 501.3299 655.5354 548.8766
AMgeO e 0.3550 0.6450 75.2486 689.2207 293.2087
ATieO e 0.3167 0.6833 239.1468 689.2207 381.6702
ANbeO e 0.3083 0.6917 527.0912 689.2207 577.0811
ZnTiNb2O8 ZneO1 1.9412 0.2983 0.7017 98.0746 715.2401 282.1956
ZneO2 2.0115 0.2983 0.7017 94.6469 690.2431 272.3331
ZneO3 2.1202 0.2983 0.7017 89.7945 654.8552 258.3710
TieO1 1.9412 0.3167 0.6833 248.1750 715.2401 396.0789
TieO2 2.0115 0.3167 0.6833 239.5015 690.2431 382.2364
TieO3 2.1202 0.3167 0.6833 227.2226 654.8552 362.6396
NbeO1 1.9412 0.3083 0.6917 546.9899 715.2401 598.8670
NbeO2 2.0115 0.3083 0.6917 527.8731 690.2431 577.9372
NbeO3 2.1202 0.3083 0.6917 500.8097 654.8552 548.3071
AZneO e 0.2983 0.7017 94.1720 686.7795 270.9666
ATieO e 0.3167 0.6833 238.2997 686.7795 380.3183
ANbeO e 0.3083 0.6917 525.2242 686.7795 575.0371

Note: 1, 2 and 3are used to distinguish oxygen atoms with different bond lengths; A indicates the average value.
798 H.L. Pan et al. / Journal of Alloys and Compounds 693 (2017) 792e798

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