Crystal structure and thermal characteristics of Mn modified ultra-high curie temperature (>800 °C) Bi2WO6 piezoelectric ceramics

Accepted Manuscript Crystal structure and thermal characteristics of Mn modified ultra-high curie temperature (>800 °C) Bi2WO6 piezoelectric ceramics Qingwei Liao, Lirong Zheng, Zhao An, Haining Huang, Chao Yan, Lei Qin, Likun Wang, Shasha Peng PII:

S0925-8388(16)32879-1

DOI:

10.1016/j.jallcom.2016.09.126

Reference:

JALCOM 38960

To appear in:

Journal of Alloys and Compounds

Received Date: 29 May 2016 Revised Date:

8 September 2016

Accepted Date: 11 September 2016

Please cite this article as: Q. Liao, L. Zheng, Z. An, H. Huang, C. Yan, L. Qin, L. Wang, S. Peng, Crystal structure and thermal characteristics of Mn modified ultra-high curie temperature (>800 °C) Bi2WO6 piezoelectric ceramics, Journal of Alloys and Compounds (2016), doi: 10.1016/j.jallcom.2016.09.126. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT Crystal structure and thermal characteristics of Mn modified Ultra-high Curie temperature (> 800°C) Bi2WO6 piezoelectric ceramics

Qingwei Liao1, 2*, Lirong Zheng2, Zhao An3, Haining Huang3, Chao Yan4, Lei Qin1, Likun Wang1, Shasha Peng 5 1

Wuhan University, Wuhan, 430072, China

RI PT

Research Center of Sensor Technology, Beijing Information Science & Technology University, Beijing 100192, China 2 Insitute of High Energy Physics Chinese Academy of Sciences, Beijing, Beijing 100049, China 3 Institute of Acoustics, Chinese Academy of Sciences, Beijing 100190, China 4 School of Electronics and Information Engineering Tianjin Polytechnic University, Tianjin 300387, China 5 Key Laboratory of Artificial Micro- and Nano-structures of the Ministry of Education, School of Physics and Technonogy,

SC

* Corresponding author, E-mail: [email protected], Tel: 0086-10-8217-8521

Abstract: Searching low sintering temperature material with ultra-high Curie temperature (> 800°C) is urgent to

M AN U

seafloor hydrothermal vents detection. Bi2WO6 was first improved to possess ultra-high Curie temperature and ultra-high depolarization temperature by experiment. The MnCO3 was selected as dopant materials due to its excellent effect on improvement of sintering abilities and piezoelectric properties. The density test shows that Mn addition can obviously improve the density of Bi2WO6 ceramics from 93.6 % to 97.76 %, and the grains

TE D

also changed from round to layered. The crystal structure change with Mn addition was tested by synchrotron radiation and calculated by ab initio and Rietveld refinement. The symmetry group of ultra-high Curie

EP

temperature Bi2WO6 is Aba2 (41). The XAFS results show that Mn atom more likely at the Bi-site in the crystal structure of Bi2W1-xMnxO6 and the Mn ion has the valence alternation. The Curie temperature of Bi2W1-xMnxO6

AC C

with increasing x are 997 °C, 915 °C, 890 °C, 729 °C, respectively, and the depolarization temperatures are around 940 °C, 895 °C, 825 °C, and 700 °C, respectively. The results show that Bi2W1-xMnxO6 (x≤0.01) ceramics are suitable for the ultra-high temperature applications of sensors or transducers on seafloor hydrothermal vents detection. Keywords: Piezoelectric materials; Crystal structure; Synchrotron radiation; Thermal characteristic; Seafloor hydrothermal vents

1

ACCEPTED MANUSCRIPT Introduction Seafloor hydrothermal activities and hydrothermal vents area involved in Meteorology, Geology, Geochemistry, Metallogeny and some important scientific issues of Marine biology, and become one of the great

RI PT

frontier hot research field in the world. However, because of the special structure of the seafloor hydrothermal chimneys, extreme high temperature (often up to 350 ~ 450 °C) and highly corrosive of fluid, it is difficult to obtain long time series of in situ velocity data by conventional observation methods [1,2]. In 2010, Crone et al.

SC

with a pair of hydrophone of seafloor hydrothermal noise measurement system in Juan De Fuca Ridge

M AN U

hydrothermal vent has the continuous measurement, and the equipment damage after only 48 hours [3]. Therefore, acoustic equipment and the key materials which can bear the high temperature is of great significance for the related detection of seafloor hydrothermal research. The material which can function at temperature above 450 °C stably require it have the ultra-high Curie temperature above 800 °C due to the operation

TE D

temperature always at the half of Curie temperature. In addition, studies have shown that the optimal frequency range of seafloor hydrothermal vents detection is 15 to 25 KHz. Hence, the lower frequency higher power is also one of the design concept of hydrothermal detection equipment. The array and the multilayer structure is an

EP

effective way to improve the output power. Low temperature co-firing ceramic technology provide a new way to

AC C

solve the limitations of the traditional Array and Multi-layer transducer process, and improve the flexibility of the transducer design. Searching low sintering temperature material with ultra-high Curie temperature is urgent to seafloor hydrothermal vents detection. The Aurivillius (Bi-layer) family piezoelectric ceramic as one of most famous ultra-high temperature ceramic, is reported to have Curie temperature range of 400~950 °C [4-6]. Bi2WO6 is the simplest member of the Aurivillius family which possesses many interesting physical properties such as ferroelectricity associated to a large spontaneous polarization, a high Curie temperature (~ 950°C), and piezoelectricity making it a potential

2

ACCEPTED MANUSCRIPT alternative to BaTiO3 and PbZr1-xTixO3 solid solutions for applications at ultra-high temperatures [7]. However, the relative reports are all about the theory calculation [7, 8] or phase transition [9]. It is rare to see the experiment research maybe because of difficult of testing in the ultra-high temperature ranges. Therefore, in this

RI PT

paper, we reported an ultra-high Curie temperature (> 800°C) and ultra-low sintering temperature piezoelectric ceramics Bi2W1-xMnxO6 (x=0, 0.005, 0.01, 0.02) for the application of seafloor hydrothermal vents detection. The MnCO3 was selected as dopant materials due to its excellent effect on improvement of piezoelectric

SC

properties [10,11]. Crystal structures of ultra-high Curie temperature phases of Bi2WO6 and Mn-doped Bi2WO6

M AN U

were determined and compared by synchrotron radiation diffraction analysis. Curie temperature and thermal depoling were tested in the temperature range up to 1000 °C. The piezoelectric properties and dielectric properties also were investigated. Experimental section

TE D

The Bi2W1-xMnxO6 (x=0, 0.005, 0.01, 0.02) ceramics were prepared by the solid-state reaction method. The starting materials were high-purity oxide powders (＞ 99.9%) of Bi2O3, WO3, MnO2. They were milled using de-ionized water and zirconia balls for 10 h. The dried powders were calcined at 550°C for 2.5 h, and then

EP

pressed into pellets with 12 mm in diameter and 1mm in thickness with addition of appropriate amount PVA

AC C

(5 %). The green body was sintered at 700 °C for 4 h. The theoretical density was calculated from the atomic weight and crystal structure by Eq. (1):

ρ theory =

ZA Vc N A

(1)

where Z is number of atoms in unit cell, A is atomic weight (g/mol), Vc is volume of unit cell (cm3), NA is Avogadro number (mol-1). The relative density was calculated by Eq. (2):

ρ relative =

3

ρ bulk ρ theory

(2)

ACCEPTED MANUSCRIPT The polished samples after thermal etching were prepared, and then were observed using a Scanning Electron Microscope (Hitachi, S-4800, Japan). The powder X-ray diffraction analysis of Bi2W1-xMnxO6 (x=0, 0.005, 0.01, 0.02) was carried out at the 1W1A beamline at the Beijing synchrotron radiation facility (BSRF)

RI PT

with an X-ray wave length of 0.1547 nm. The crystal structure of Bi2WO6 and Bi2W0.98Mn0.02O6 was determined by ab initio and Rietveld refinement [12]. The X-Ray Absorption Fine Structure (XAFS) analysis of Bi2W0.98Mn0.02O6 was carried out at the 1W1A beamline at the Beijing synchrotron radiation facility (BSRF).

SC

The ceramic pellets for electrical characterization were polished and coated with Ag74-Pd26 electrodes, and

M AN U

then were poled at ~ 70 °C for 30 min under an electric field of ~ 4 kV/mm in a silicone oil bath. The piezoelectric properties were measured after 24 h aging at room temperature. Temperature dependence of dielectric properties were measured using a computer controlled TH2826 (Changzhou, China) high frequency LCR meter from room temperature to 804~1073 °C. Temperature dependence of resistivity were measured

TE D

using a computer controlled Agilent 4294A (CA, United States) high frequency LCR meter from room temperature to 900 °C. The planar electromechanical coupling factor kp and Qm were derived by the resonance and anti-resonance method. The piezoelectric constant d33 was measured by a quasistatic piezoelectric ZJ-3D d33

EP

meter produced by Institute of Acoustics, Chinese Academy of Sciences. Thermal depoling experiments were

AC C

conducted by annealing the poled samples at various temperatures for 240 h, and d33 values were measured after cooling down to room temperature. Results and Discussions

Fig. 1 shows the densities and SEM photographs of Bi2W1-xMnxO6 (x=0, 0.005, 0.01, 0.02) ceramics samples. Fig. 1(a), (b), and (c) show the theory densities (ρtheory), and the bulk densities (ρbulk), and the relative densities (ρrelative) of each Bi2W1-xMnxO6 samples. Fig. 1 (d)~(g) show the SEM photographs of each Bi2W1-xMnxO6 samples. The theory densities of Bi2W1-xMnxO6 are calculated from X-Ray Powder Diffraction

4

ACCEPTED MANUSCRIPT patterns, and in the range of 9.440~9.625 g/cm3. With increase of Mn addition, the value of theory densities decreased. On the contrary, the bulk densities and relative densities of Mn doping samples are increasing with increase addition of Mn. It can be indicated that Mn addition can obviously improve the density of Bi2WO6

RI PT

ceramics. From the SEM photographs of ceramic surface which was thermal etched after polished, it can be seen that pure Bi2WO6 has the round grain, but with Mn addition, the grains became layered. From density test results, it can be seen that the layered grains have more large density that round grains. In addition, when the Mn

SC

doping from 0 to 0.02mol, the relative density increased from 93.6 % to 97.76 %.

M AN U

Fig. 2(a) shows the synchrotron radiation patterns of Bi2W1-xMnxO6 (x=0, 0.005, 0.01, 0.02) ceramics. It can be seen that with increase of Mn addition, the relative intensity changed obviously from x= 0 to x= 0.02. This indicated that the crystal structure changed significantly due to the large difference between W6+ ion radius (0.74 Å) and Mn2+ ion radius (0.81 Å). In order to get a more particular knowledge, the patterns of x= 0 and x=

TE D

0.02 were selected to contrast the detail crystal structure data. First of all, the symmetry group and lattice constant were calculated by ab initio method with DICVOL (Reliability factor M≤10) [13], and then the results were refined by Fullprof [12]. The atom sites were determined by Fourier maps calculation and Rietveld

EP

refinement, and the final crystal structures were shown in Table 1. The symmetry group of ultra-high Curie

AC C

temperature Bi2WO6 is Aba2 (41). And it can be seen that the lattice volume has obvious expansion from

481.5456 Å3 to 489.1866 Å3 with Mn addition. The visual crystal structure of Bi2WO6 (x= 0, 2×2×2 supercell) and Bi2W0.98Mn0.02O6 (x= 0.02, 2×2×2 supercell) was shown in Fig. 2(b) and Fig. 2(c), respectively. Further calculation shows that the volume of WO6-octahedra expanded from 7.096 Å3 to 7.293 Å3 when x increased from 0 to 0.02. The more information about the side length of WO6-octahedra was also shown in Fig. 2(a) and (b).

5

ACCEPTED MANUSCRIPT Fig. 3 (a)~(d) show the X-Ray Absorption Fine Structure (XAFS) analysis of Bi2W0.98Mn0.02O6. Fig. 3 (a) shows the comparison of XAFS for Bi2W0.98Mn0.02O6, Mn-foil, MnO, Mn2O3 and MnO2. Fig. 3 (b) shows the R-space of them. From the inset of Fig. 3 (a) and Fig. 3 (b), it can be seen that the absorption curve of

RI PT

Bi2W0.98Mn0.02O6 is the most close to the curve of Mn2O3. The first main peak of Bi2W0.98Mn0.02O6 and Mn2O3 were fitted and the results were shown in Fig. 3 (c) and Fig. 3 (d), respectively. The bond length of Mn-O in Bi2W0.98Mn0.02O6 and Mn2O3 is 1.874 Å and 1.913 Å, respectively. The valence state is between +2 and +3.

SC

Therefore, the Mn atom more likely at the Bi-site in the crystal structure of Bi2W1-xMnxO6 and the Mn4+ ion has

M AN U

the valence alternation when doped in Bi2WO6. These also can explain the variation of reflections (002)/(200), (062)/(260), and (082)/(280). The Mn3+ ion replace the Bi3+ ion cause the variation of F factor in the relative crystal face.

Fig. 4 (a)~(d) shows the temperature dependences of dielectric constant (left Y) and dielectric loss (right Y)

TE D

of the Bi2W1-xMnxO6 (x=0, 0.005, 0.01, 0.02) ceramics. The dielectric constant peaks of Bi2W1-xMnxO6 with increasing x are 997 °C, 91 5°C, 890 °C, 729 °C, respectively. The dielectric loss peaks of Bi2W1-xMnxO6 with increasing x are located at 944 °C, 898 °C, 827 °C, 700 °C, respectively. It can be seen that with increasing Mn

EP

addition, the phase transition temperatures are decreased. Fig. 4 (e) shows the thermal depoling effects on

AC C

piezoelectric constant of Bi2W1-xMnxO6 (x=0, 0.005, 0.01, 0.02) ceramics. It can be seen that when the annealing temperature increasing, the piezoelectric constant shows highly stability that always keeps value constant and then drop to zero rapidly, and the depolarization temperatures are around 940 °C, 895 °C, 825 °C, and 700 °C, respectively. It can be seen that Bi2W1-xMnxO6 (x≤ 0.01) ceramics are suitable for the ultra-high temperature applications. Fig. 5 shows the temperature dependence of resistivity of Bi2W1-xMnxO6 ceramics. It shows that there is a peak around 150 °C. With doping of Mn element, the peak value decreased and peak position move to the higher

6

ACCEPTED MANUSCRIPT temperature slightly. The inset shows the details of resistivity above 600 °C. It can be seen that when temperature increase to 600 °C, the resistivity still above 70000 Ω*cm. Table 2 shows the piezoelectric and dielectric properties of Bi2W1-xMnxO6 (x=0, 0.005, 0.01, 0.02)

RI PT

ceramics. It shows that the addition of Mn can improve the piezoelectric properties of Bi2WO6. With increase of Mn addition, the piezoelectric constant increased. It can be explained by the valence alternation of Mn from +4 to +3, the ceramic become more “soft”. The other properties, like Qm, K33, tanδ have no obvious trend because

SC

that there are lots of factors effect on the dielectric properties and Qm, the variation trend of them are more

M AN U

complicated .The highest piezoelectric constant (d33 =18 pC/N) is obtained at x=0.02. The typical properties are as follows: Curie temperature Tc = 890°C, depolarization temperature Td = 825°C, mechanical quality factor Qm = 439.2, d33 =15 pC/N , K33=92.0, tanδ=0.168×10-2 with x value of 0.01. Conclusions

TE D

In summary, Bi2W1-xMnxO6 (x=0, 0.005, 0.01, 0.02) ceramics with ultra-high Curie temperature, and ultra-high depolarization temperature were tested. The density test shows that Mn addition can obviously improve the density of Bi2WO6 ceramics from 93.6 % to 97.76 %, and the grains also changed from round to

EP

layered. The crystal struc ture change with Mn addition was calculated by synchrotron radiation diffraction with

AC C

ab initio and Rietveld refinement. The symmetry group of ultra-high Curie temperature Bi2WO6 is Aba2 (41). The lattice volume has obvious expansion from 481.5456 Å3 to 489.1866 Å3, and the volume of WO6-octahedra expanded from 7.096 Å3 to 7.293 Å3 with Mn addition. The Curie temperature of Bi2W1-xMnxO6 (x=0, 0.005, 0.01, 0.02) with increasing x are 997 °C, 915 °C, 890 °C, and 729 °C, respectively, and depolarization temperatures of them are around

940 °C, 895 °C, 825 °C, and 700 °C, respectively.

Acknowledgements

7

ACCEPTED MANUSCRIPT This work is supported by the National Natural Science Foundation of China (No. 11604363, 61671068, 61302015, 61471047). The project is also supported by The Importation and Development of High-Caliber

RI PT

Talents Project of Beijing Municipal Institutions (No. CIT&TCD201504053).

Reference:

[1] T. M. Kingston. Generation of seafloor hydrothermal vent fluids and associated mineral deposits. Oceanography. 20(1) (2007): 50-65.

SC

[2] T. Nozaki, J. I. Ishibashi, K. Shimada. Rapid growth of mineral deposits at artificial seafloor hydrothermal vents. Scientific Reports. 6 (2016): 22163. [3] T. J. Crone, W. S. D. Wilcock, and R. E. McDuff, Geochem. Geophys. Geosyst., 11 (2010): Q03012.

M AN U

[4] H. Yan, H. Zhang, R. Ubic, M. J. Reece, J. Liu, Z. Shen, Z. Zhang. A Lead-free high-Curie-Point ferroelectric ceramic, CaBi2Nb2O9. Adv. Mater. 17 (2005): 1261-1265. [5] A. Rosyidah, D. Onggo, Khairurrijal, Ismunandar. Atomic simulations of Aurivillius Oxides: Bi3TiNbO9, Bi4Ti3O12, BaBi4Ti4O15, Ba2Bi4Ti5O8 doped with Pb, Al, Ga, In, Ta. Journal of the Chinese Chemical Society. 55 (2008): 115-120.

TE D

[6] H. Yan, Z. Zhang, W. Zhu, L. He, Y. Yu, C. Li, J. Zhou. The effect of (Li,Ce) and (K,Ce) doping in Aurivillius phase material CaBi4Ti4O15. Materials Research Bulletin. 39 (2004): 1237-1246. [7] H. Djani, P. Hermet, P. Ghosez. First-principles characterization of the P21ab ferroelectric phase of Aurivillius Bi2WO6. Journal of Physical Chemistry C. 118 (25) (2014): 13514-13524.

EP

[8] K. S. Knight. The crystal structure of ferroelectric Bi2WO6 at 961K. Ferroelectrics. 150 (1993): 319-330. [9] Y. Yoneda, H. Takeda, T. Tsurumi. Phase transition of Bi2WO6 below 300K. JPS Conf. Proc. 1 (2014): 012103.

AC C

[10] Q. Zhang, Y. Zhang, F. Wang, Y. Wang, D. Lin, X. Zhao, H. Luo, W. Ge, and D. Viehland. Enhanced piezoelectric and ferroelectric properties in Mn-doped Na0.5Bi0.5TiO3-BaTiO3 single crystals. Appl. Phys. Lett. 95 (2009): 102904. [11] X. Li, M. Jiang, J. Liu, J. Zhu, X. Zhu, J. Zhu, and D. Xiao. Enhanced piezoelectric properties in Mn-doped .98K0.5Nb0.5NbO3-0.02BiScO3 Lead-free ceramics. J. Am. Ceram. Soc., 92 (7) (2009): 1625-1628. [12] H. M. Rietveld. A profile refinement method for nuclear and magnetic structures. J. Appl. Crystallogr, 2 (1969): 65-71 [13] A. Boultif and D. Louer. Powder pattern indexing with the dichotomy method. J. Appl. Cryst. 37 (2004): 724-731.

8

ACCEPTED MANUSCRIPT

M AN U

SC

RI PT

Figures

Fig. 1 The densities and SEM photographs of Bi2W1-xMnxO6 (x=0, 0.005, 0.01, 0.02) ceramics. (a): Relative density; (b) Bulk density; (c) Theory density; (d) SEM of x= 0 mol; (e) SEM of x= 0.005 mol; (f) SEM of x=

AC C

EP

TE D

0.01 mol; (g) SEM of x= 0.02 mol.

9

M AN U

SC

RI PT

ACCEPTED MANUSCRIPT

Fig. 2 (a) The synchrotron radiation patterns of Bi2W1-xMnxO6 (x=0, 0.005, 0.01, 0.02) ceramics; (b) the (2×2×2)

AC C

EP

TE D

supercell crystal structure of pure Bi2WO6; (c) the (2×2×2) supercell crystal structure of Bi2W0.98Mn0.02O6.

10

M AN U

SC

RI PT

ACCEPTED MANUSCRIPT

TE D

Fig. 3 The X-Ray Absorption Fine Structure (XAFS) analysis of Bi2W0.98Mn0.02O6. (a) the comparison of XAFS for Bi2W0.98Mn0.02O6, Mn-foil, MnO, Mn2O3 and MnO2; (b) the R-space of Bi2W0.98Mn0.02O6, Mn-foil, MnO,

AC C

EP

Mn2O3 and MnO2; (c) The fit of first main peak of Bi2W0.98Mn0.02O6; (d) The fit of first main peak of Mn2O3.

11

TE D

M AN U

SC

RI PT

ACCEPTED MANUSCRIPT

Fig. 4 (a)~(d): The temperature dependences of dielectric constant (left Y) and dielectric loss (right Y) of the

EP

Bi2W1-xMnxO6 (x=0, 0.005, 0.01, 0.02) ceramics. (a): x=0; (b) x=0.005; (c): x=0.01; (d): x=0.02. (e): The

AC C

thermal depoling effects on piezoelectric constant of Bi2W1-xMnxO6 (x=0, 0.005, 0.01, 0.02) ceramics.

12

M AN U

SC

RI PT

ACCEPTED MANUSCRIPT

AC C

EP

TE D

Fig. 5 The temperature dependence of resistivity of Bi2W1-xMnxO6 (x=0, 0.005, 0.01, 0.02) ceramics

13

ACCEPTED MANUSCRIPT

Table 1 The crystal structure parameters of Bi2WO6 and Bi2W1.98Mn0.02O6 ceramics.

Lattice parameters b( Å)

c( Å)

Vol(Å3)

Rp

Rwp

GOF

5.2480

16.3675

5.4202

481.5456

0.139

0.273

2.586

Atom

x

y

z

Occupancy

W

0

0

0

Bi

0.4869

0.1728

0

O

0.75

0.24761

0.24943

O

0.75

0.49561

0.17653

1.00

O

0

0.08842

0

1.00

b( Å)

5.4628

16.4394

Atom

x

W

0

Bi

0.5030

O O

1.00

Reliability factors

Vol(Å3)

Rp

Rwp

GOF

5.4472

489.1866

0.132

0.278

2.677

y

z

Occupancy

0

0

0.50

0.1721

0.006

1.00

0.6459

0.3212

0.2878

1.00

0.7970

0.4996

0.1700

1.00

0

0.0884

0

1.00

AC C

EP

O

1.00

c( Å)

TE D

Bi2W0.98Mn0.02O6

a( Å)

0.50

M AN U

Lattice parameters

RI PT

a( Å)

SC

Bi2WO6

Reliability factors

14

ACCEPTED MANUSCRIPT Table 2 The piezoelectric and dielectric properties of Bi2W1-xMnxO6 (x=0, 0.005, 0.01, 0.02) ceramics.

d33 (pC/N)

Kp

Qm

K33*

tanδ * (10-2)

0

7

0.055

418.2

92.47

0.130

0.005

12

0.061

377.5

103.30

0.760

0.01

15

0.065

439.2

92.00

0.168

0.02

18

0.110

384.2

113.59

0.340

AC C

EP

TE D

M AN U

SC

* Polarized, measured at 1 KHz

RI PT

Value of x (mol)

15

ACCEPTED MANUSCRIPT Highlights

1、 Bi2WO6 was improved to possess ultra-high Curie temperature by experiment. 2、 The highest depolarization temperature is around 940 °C.

RI PT

3、 The symmetry group of ultra-high Curie temperature Bi2WO6 is Aba2 (41).

AC C

EP

TE D

M AN U

SC

4、 The structure change with Mn doping was studied by ab initio and refinement calculations.