Preparation and Characterization of Barium Titanate

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ScienceDirect Materials Today: Proceedings 4 (2017) 3300–3307

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5th International Conference of Materials Processing and Characterization (ICMPC 2016)

Preparation and Characterization of Barium Titanate Composite Film Sudhanshu Singh1, Subhrangsu S. Dey2, Sheshamani Singh2, Neeraj Kumar2* 1

Department of Electronics & Communication Engineering, Amity School of Engineering & Technology (ASET), Amity University Rajasthan, NH-11C, Jaipur-Delhi National Highway, RIICO Industrial Area, Kant Kalwar, Jaipur (Rajasthan), 302006, India 2

Department of Physics, Amity School of Applied Sciences (ASAS), Amity University Rajasthan, NH-11C, Jaipur- Delhi National Highway, RIICO Industrial Area, Kant Kalwar, Jaipur (Rajasthan), 302006, India

Abstract Present investigations devoted to the performance of the composite films of Barium Titanate (BaTiO3) with Titanium Dioxide (TiO2) and Poly (methyl methacrylate) (PMMA) at room temperature. The composites were prepared by simple solution casting technique. Different wt. % concentrations of BaTiO3 have been choose to find out the best optimal condition for further investigations. The preparation and characterization have been carried out at room temperature using X-ray diffraction (XRD). The average crystallite size of the BaTiO3 particles in the composite films has been found to be lies in between ~ 20 -70 nm. It has been found that the peak intensities increase with increasing the wt. % of BaTiO3 in the composite films at room temperature (RT). The XRD analysis revealed that the addition of TiO2 has played a crucial role to enhance the crystalline nature of the composite films at room temperature. Efforts have been made to correlate the results with investigated XRD results of pure BaTiO3 and its composites as observed by other workers at room temperature. © 2017 Published by Elsevier Ltd. Selection and peer-review under responsibility of Conference Committee Members of 5th International Conference of Materials Processing and Characterization (ICMPC 2016). Keywords: BaTiO3, Poly (methyl methacrylate), Solvent caste, TiO2 and XRD

1. INTRODUCTION Barium Titanate: Barium Titanate is an inorganic compound, having chemical formula BaTiO3. It is very well good ferroelectric ceramic material [1, 3, 4]. There are numerous applications of BaTiO3 in electronics industry because of its high dielectric constant and low tangent losses [2, 5]. BaTiO3 is highly stable with excellent mechanical, electrical and chemical properties [4, 6, 7, 9]. *Corresponding author. E-mail address: [email protected]

2214-7853 © 2017 Published by Elsevier Ltd. Selection and peer-review under responsibility of Conference Committee Members of 5th International Conference of Materials Processing and Characterization (ICMPC 2016).

Sudhanshu Singh et al. / Materials Today: Proceedings 4 (2017) 3300–3307

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It exhibits these properties above the room temperature, which makes it important for various devices such as ferroelectrics and piezoelectric. BaTiO3 has been widely used in many fields, such as semiconductor, embedded capacitors, nonlinear optics, microphones, solar cells, microwave transducers and its unique applications as Piezoelectric and Photorefractive materials [2, 3, 6, 10]. It can used to improve brain imaging and spectroscopy at 7T in radiology. High cost and low v/v ratio of BaTiO3 are some of the drawbacks of BaTiO3 [10, 12]. BaTiO3 is a perovskite structured materials which exhibit variety of crystal structures. It also exhibit phase transformations above room temperature [16, 19], Fig. 1. Cubic

Tetragonal 130˚C

Hexagonal 1432˚C

Liquid 1625˚C

Fig. 1. Crystal Structure of Barium Titanate

Polymethyl methacrylate: Polymethyl methacrylate (PMMA) is a plastic material with excellent transparency with processing ability, and low mechanical properties [3, 10, 18]. It was developed in 1928 in various research laboratories. It is useful because of high fabric, transparency, chemical resistant (both acidic and alkaline), dimensional stability, good weatherbility, protection against Ultraviolet (UV) radiation and good mold ability [5, 7, 18]. PMMA has wide range of applications from long years with good industrial and consumer demand due to the low cost and direct finishing material. Today, it is used in various applications like laser disc, CDs, DVDs, TFTLCDs, semiconductor research and industry such as in Lucite and most of plastics materials [9, 18]. PMMA is a very good light sensitive, pressure sensitive, and surface/spin coating capacitive to composite films which resist the films in nanofabrication process and may be highly applicable to electronics devices [5, 9, 18], Fig 2.

Fig 2. Structure of Polymethyl methacrylate

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Titanium Dioxide: Titanium dioxide (TiO2) is a multifaceted compound. It was discovered in 1791 by William Gregor in England. TiO2 is also a potent photo catalyst that can break down almost any organic compound when exposed to sunlight [14, 18, 23]. Due to the nanodimensions (several nanometers) of TiO2, it is used in various research field and semiconductor materials with a wide range of application including dye sensitized solar cells, paints, rubber, printing inks, coated fabrics & textiles, catalyst systems, ceramics, floor coverings, coatings, adhesives, paper, paperboard, plastics roofing materials, cosmetics, pharmaceuticals, water treatment agents, food colorants and in automotive products, etc [14, 19]. TiO2-the oxide of the metal titanium, occurs naturally in several kinds of rock and mineral sands. TiO2 is typically thought as being chemically inert [3, 18, 23]. Titanium dioxide (TiO2) is a white solid inorganic substance that is thermally stable, non-flammable, poorly soluble, and it is classified as non-hazardous material oxide according to United Nation (UN) and Globally Harmonized System of Classification and Labeling of Chemicals (GHS). Research work also done on Polyaniline (PANI)-TiO2-Poly (vinyl alcohol) (PVA) and TiO2 as Metal Matrix Composites (MMC) which exhibit the same behavior as investigated by us in our BaTiO3:TiO2: PMMA work. [24, 25, 26]. In the recent studies, Nano particles and quantum dots show a tremendous growth in thin films formation [9, 11, 18, 22]. Also some Nano particles and quantum dots doped semiconductor compound plays a vital role in defining well structural growth of composites with TiO2, BaTiO3 & polymers, Fig 3.

Fig 3. Structure of TiO2

BaTiO3: PMMA Based Composites: In recent trends Barium Titanate uses for composite preparation with conjugate of various polymer including PMMA and PVDF etc, due to high dielectric constant and various applications [5, 9, 11, 15, 18]. It was reported by several workers that the dielectric measurements of BaTiO3: PMMA composite films in the range of 100 Hz -10MHz, it depends on the frequency, the temperature and filter fraction [3, 5, 11, 15, 19]. Dissipation factors influenced by frequency and temperature but slightly influenced by the filter fraction. It was found that in a lower concentration of BaTiO3 composite film, had the lowest dielectric constant of 3.58 and dielectric loss tangent of 0.024 at 1 MHz and 25˚C [3, 10, 12, 18].As a result, it is widely useful to Multi-layered ceramic capacitors (MLCC), Micro-Electro mechanical systems (MEMS), Dynamic Random Access memory (DRAM) (Setter and waser 2000), waveguides, ferroelectric sensors, and luminescent materials [2, 17, 19]. Dielectric Properties of BaTiO3: PMMA Composite films [18, 19] can be summarised as: Frequency Dependence (at Room Temperature): Dielectric constant (έr) and Tangent loss (D) decreases with increasing frequency from 100 Hz to 1MHz in Composite films. The permittivity of combined BaTiO3: PMMA composites decrease with increasing frequency. Temperature Dependence: Dielectric constant (έr) and Tangent loss (D) increases with increasing temperature in the frequency range 100 Hz to 1MHz. Filter Concentration Dependence: Dielectric constant (έr) increases with increasing filter concentration but Tangent loss (D) not much affected with filter concentration.


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TiO2: BaTiO3 and its Polymer Based Composites: Titanium Dioxide is a semiconductor material. Polymermatrix insulating materials are widely used in electrical and electronics engineering owing to their excellent mechanical properties, thermal and dielectric properties [6, 18] (Table 1). During last few decades, TiO2 takes an important role in semiconductor devices [14, 18]. In this study, we performed TiO2: PMMA and BaTiO3 composite films for high performance. TiO2 was well dispersed in composite films and minimized the porosity. TiO2 may take a crucial role to influence the dielectric properties [14, 18]. Table 1. Physical properties of BaTiO3, TiO2 and PMMA [6, 18, 19] M.P. (˚C)

Density (gm/cm3)

BaTiO3

1625

6.02

Electrical/Thermal

Dielectric

Conductivity

constant

5.5-6W/m.K

at

100-1250

Tc (˚C)

Permittivity Constant

120

300K

1200-10000 20˚C-120˚C

TiO2

1843

4.23

1.6-2.7 W/m.K

100

230-427

86-173

PMMA

160

1.18

0.19-0.24 W/m.K

2.8-4

65

4.9 at 100 Hz

2.

EXPERIMENTAL METHODS

2.1 Materials For the formation of composite solution all materials were of analytical grade and were used without further purifications. To prepare the BaTiO3 : TiO2 : PMMA nanostructure composite films, we have used Barium Titanate (BaTiO3) in Nano powder form (Sigma Aldrich –USA), Titanium Dioxide (TiO2) in powder form (Fisher Scientific, India) and the granules of PMMA (C5O2H8)n – Aldrich USA. Chloroform (Sigma Aldrich) an organic compound with formula CHCl3 have been used as a solvent for the composites preparation.

2.2 Preparation of BaTiO3-TiO2-PMMA composite films The investigated composite films were prepared on the basis of varying wt. % of BaTiO3 Nano powder with TiO2 nanoparticles embedded in the PMMA polymer matrix. The granules of PMMA – Aldrich USA (20 mg by wt.) were dissolved in 15 ml of Chloroform in the ultraclean borosil beaker and stirred well at room temperature until the granules of PMMA were completely and homogeneously dissolved in chloroform [4, 9, 18]. Further to prepare the 50-50 wt.% the equal quantity of Titanium Dioxide (50 wt.%) was then added to the solution of PMMA and the solution was then placed on magnetic stirrer (2NLH magnetic stirrer manufactured by Remi Equipment Pvt. Ltd) for 1 hours at the speed of 300 rpm (revolution per minute). Then BaTiO3 was poured into the composite solution on the basis of varying wt. % of the total quantity of TiO2: PMMA. After then the solution was placed on magnetic stirrer for another 1 hours at the speed of 300 rpm with constant temperature at 60 deg C. A glass slide of dimensions (75 × 25 × 1.25 mm) was ultra cleaned with acetone and then carefully poured in the composite solution of BaTiO3, TiO2 and PMMA. After five seconds, the glass slide of composite solution was

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separated from the solution and then placed horizontally in the enclosed environment with a bell jar to prevent the excessive moisture. After 24 hours, the thin composite films were carefully removed from the glass slide. The thin composite film of BaTiO3 (10 wt. % of the total quantity of PMMA: TiO2) was formed. This procedure was adopted to make thin composite films of different wt. % of BaTiO3 with 50-50 wt. % of TiO2 and PMMA as shown in Fig 4. fig 4.

Fig 4. Flow chart of Experimental procedure

2.3 Instrumentation Techniques The prepared composite films were characterized using X-ray diffractometer (XRD) PANalytical X' Pert Powder (Netherlands) with Cu-Kα radiation source (λ = 1.54059 Å) for structural and phase analysis. Digital data is collected with a counting rate 2°/minutes in the scanning range of Bragg angle (2θ) from 10° to 60° as shown in Fig 5(a) [18, 19]. The Digital microscopy images were recorded using Transmitted light routine laboratory microscope (Motic BA300) with phase contrast slider Ph10x and aperture of 1.25 for particle distribution study is shown in Fig 6 (b). 3. RESULTS AND DISCUSSION XRD pattern of various weight percentages of BaTiO3 with TiO2: PMMA nanocomposite films of concentration 10wt. %, 30wt. %, 70wt. % and 90wt. % combined graph are shown in Fig 5 as a individual graph. The XRD analyses are taken very carefully where PMMA is amorphous in nature with clear peak intensities. It was observed that the prominent peak intensity v/s 2θ increased with increasing of concentration of Barium Titanate [13, 15, 21].


1000

700

10% BaTiO3

500

Intensity

600

Intensity

30% BaTiO3

600

800

400 200

400 300 200 100 0

0

10 10

20

30

40

50

60

70

20

30

80

700

40

50

60

70

2Theta

2Theta

70% BaTiO3

90% BaTiO3

400

600 500

300

400

Intensity

Intensity

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300 200

200

100

100 0

0 10

20

30

40

50

60

70

80

2Theta

10

20

30

40

50

60

70

80

2Theta

Fig 5. XRD pattern of BaTiO3 with TiO2+PMMA nanocomposite film with different weight fractions of BaTiO3

The width of nanowires or Crystallite size was increased as increase in concentration of BaTiO3 which is determined by using Scherer’s formula that’s simplified by Bragg’s law

βcrystallinesize =

9λ BCosθ

(1)

Where λ is the wavelength of Cu Kα radiation, and B is the full-width at half-maximum (FWHM). The average crystallite size of the BaTiO3 particles in the composite films has been found to be lies in between ~ 20-70nm is shown in Fig 6. The Digital Microscopic image of different wt. % BaTiO3 nanoparticles embedded in PMMA: TiO2. As a resultant, the particles are well dispersed in the matrix of PMMA, is shown in Fig 7. The Stability of crystal structure of Barium Titanate was unaltered during and after preparation of nanocomposite thin films. It has been found that the peak intensities increase with increasing the wt. % of BaTiO3 in the composite films. The relative intensity of different composite films was estimated from Fig 5, it was shown that the intensity ratio increased as increasing of concentration BaTiO3 (The ratio of 2θ= 22: 31). The XRD analysis revealed that the addition of TiO2 has played a crucial role to enhance the crystalline nature of the composite films at room temperature. Efforts have been made to correlate

the results with investigated XRD results of pure BaTiO3 and its composites as observed by other workers at room temperature.


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2Theta=22 2Theta=31

100

100

80

80

60

60

40

40

20

20

0

0

20

40

60

80

70

Crystalline Size

INTENSITY RATIO

B 80

60 50 40 30 20

0

100

0

WT.% 0F BaTiO3

20

40

60

80

100

Wt.%

Fig 6. Intensity v/s Bragg angle and in (b) Intensity Ratio (I2θ=22)/(I2θ=31) v/s wt.% of BaTiO3 and Crystallite size v/s wt. % of BaTiO3

Fig 7. The Digital Microscopic images of 70 wt. % of Barium Titanate The Current voltage measured at room temperature, it was shown ( Table 2) that the dielectric constant is very high with very low tangent loss for the composite film of BaTiO3: PMMA composite film rather than PMMA. As a result it can be uses wide range of electrical application. Table 2. Current Voltage Data Measured at Room Temperature and 1 MHz for BaTiO3 and BaTiO3: PMMA composite PMMA

BaTiO3 :PMMA composite

Dielectric constant

3.42

21.6

tan δ

0.02

ΔCmax/C0 V (%)

0.016 0

0.14

Maximum electric field intensity was about ± 20 V/mm. CONCLUSION Nanocomposite films of Barium Titanate with TiO2 and PMMA polymer were prepared with eco-friendly solvent cast method which is an inexpensive method. The TiO2 has played a crucial role to enhance the crystalline nature of the composite films at room temperature. The Digital Microscopic image of different wt. % BaTiO3 nanoparticles embedded in PMMA: TiO2 is also taken. As a resultant, the particles are well dispersed in the matrix of PMMA. While studying the structural properties of Barium Titanate, it was observed that the crystallite size was increased as increasing the concentration of Barium Titanate.


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Acknowledgements We would like to thanks Instrumentation Lab facility proved by MNIT Jaipur and Rajasthan University Jaipur. I would also like to acknowledge the technician and faculty member who support us for these sampling and characterization. References [1] Neeraj Kumar and R. Nath, J. Appl. Phys. 97, 024105 (2005) [2] Z. Guo, S.-E. Lee, H. Kim, S.Park, H.T. Hahn, A.B. Karki and D.P. Young, Acta Materials, 57, 67-277, (2009) [3] Ravindra H. Upadhyay and Rajendra R. Deshmukh, Advances in Materials Research,Vol. 2, No. 2, 99-109, (2013) [4] Uvais Valiyaneerilakkal and Soney Varghese, AIP Advances 3, 042131 (2013) [5] Yoshio Kobayashi and Aiko Odo, J Matter Technology, 3 (4) : 290-295, (2014) [6] R.M. Radwan, S.S. Aly and S. Abd El Aal, J. Rad. Res. Appl. Sci.,11 , 9-16 (2008) [7] Ben-Hui Fan, Jun-Wei Zha, Dongrui Wang, Jun Zhao, and Zhi-Min Dang, Applied Physics Letters 100, 012903 (2012) [8] Ke Yu, Hong Wang, Yongcun Zhou, Yuanyuan Bai, and Yujuan Niu, Journal of Applied Physics 113, 034105 (2013) [9] Jung Min Park, Hee Young Lee, Jeong-Joo Kim, Eun Tae Park, and Yul-Kyo Chung, IEEE Transactions on ultrasonics, ferroelectrics, and frequency control, Vol. 55, No. 5, (2008) [10] M.R.A. Bhuiyan, M.M. Alam, M.A. Momin, M.J. Uddin and M.Islam, International Journal of Material and Mechanical Engineering, 1: 2124, (2012) [11] Wenhui Xu, Yichun Ding, Shaohua Jiang, Linlin Chen, Xiaojian Liao and Haoqing Hou, Materials Letters 135 158-161, (2014) [12] D. Olmos , G. González-Gaitano , A. L. Kholkin and J. González Benito, Ferroelectrics, 447 : 9–18, (2013) [13] Syed Khasim , S. C. Raghavendra , M. Revanasiddappa and M. V. N. Ambika Prasad, Ferroelectrics, 325:111–119, (2005) [14] Lavinia Curecheriua, Petronel Postolachea, Vincenzo Buscagliab, Nadejda Horchidana, Marin Alexec and Liliana Mitoseriua, Phase Transitions, Vol. 86, No. 7, 670–680, (2013) [15] X. F. Li , H. S. Zhao , P. L. Zhang , W. L. Zhong and C. S. Fang, Ferroelectrics, Vol. 196, pp. 39-42, (1997) [16] Liang Zhang, Dingquan Xiao and Jian Ma, Ferroelectrics, 455:77–82, (2013) [17] Jing Wang, Gang Song and Jin Qing Qi, Ferroelectrics, 355 : 165–170, (2007) [18] Kristina Brandt, Claudia Neusel, Sebastian Behr and Gerold A. Schneider, J. Mater. Chem. C, 1, 3129, (2013) [19] Liyuan Xie, Xingyi Huang, Chao Wu and Pingkai Jiang, J. Mater. Chem., 21, 5897 , (2011) [20] Z. Guo , S.-E. Lee , H. Kim , S. Park , H.T. Hahn , A.B. Karki and D.P. Young, Acta Materialia, 57, 267–277, (2009) [21] Jeżowski, J. Mucha, R. Pazik and W. Strek, Applied Physics Letters, 90, 114104 (2007) [22] Sunil Kumar, Nitu Kumari , Sudhanshu Singh, Tej Singh and Sanyog Jain, Colloids and Surfaces A: Physicochemical. Eng. Aspects 389, 1– 5, (2011) [23]Jin-Young Baek, Zhi-Cai Xing, Giseop Kwak, Keun-Byoung Yoon, Soo-Young Park, Lee Soon Park, and Inn-Kyu Kang, Journal of Nanomaterials Volume 2012, Article ID 171804, 11 pages (2012) [24] Rajeev Arora, Utam Kumar Mandal, Pankaj Sharma and Anupam Srivastav Procedia Materials Science-6, 238 – 243 ( 2014 ) [25] K. Srinivasa Vadayar, S. Devaki Rani, G. Sri Satya and V.V. Bhanu Prasad Advanced Materials Manufacturing & Characterization Vol 3 Issue 2 (2013) [26] Jung Min Park, Hee Young Lee, Jeong-Joo Kim, Eun Tae Park, and Yul-Kyo Chung ieee transactions on ultrasonics, ferroelectrics, and frequency control, vol. 55, no. 5,May 2008