2325 Journal of Applied Sciences Research, 8(4): 2325-2334, 2012 ISSN 1819-544X This is a refereed journal and all articles are professionally screened and reviewed

ORIGINAL ARTICLES

Dielectric Properties and Conductivity of Some Alkali Borate Doped With Cobalt Oxide

1S.Y. Marzouk, 2L.I. Soliman, 3M.S. Gaafar, 4H.A. Zayed, 5A.H. Serag El-Deen

1Arab Academy of Science and Technology, P. O. Box 2033, Al- Horria, Heliopolis, Cairo, Egypt. 2National Research Center, Dokki, Cairo Egypt. Solid state Physics Dept. 3Ultrasonic Laboratory, National Institute for Standards, Tersa Str., P. O. Box 136, El-Haram, El-Giza 12211, Egypt. 4Professor of Solid State Physics, Ain Shams University, Faculty of Women, Solid state physics dept. Cairo, EGYPT. 5Modern Academy for Engineering and Technology in maadi.

ABSTRACT

Glass samples of a mixed alkali borate glasses doped with cobalt oxide have been prepared by the melt quenching technique in air atmosphere. The glassy state of the samples is characterized using X-ray diffraction. -transition temperatures are measured using differential scanning calorimetery (DSC). A.C. Conductivity (σa.c), real and imaginary parts of the impedance of the prepared samples have been measured in the frequency range (42Hz-5MHz). The measurements were carried out in the temperature range (303-468K). The total conductivity as well as the frequency exponent, S, were determined from the dielectric spectrum, also the activation energy was calculated and discussed.

Key words: Dielectric Properties, Alkali Borate Glasses, Cobalt Oxide

Introduction

Boric oxide (B2O3) is an important constituent of a wide range of glasses. Glass wool for thermal and acoustic insulation, textile fibres for the reinforcement of plastics, enamels, ceramic glasses (for example tiles and tableware), optical glass and a diverse range of technical glasses for lighting laboratory, cookware, medical and LCD screens. B2O3 is one of the most important glass formers incorporated into various kinds of glassy stems as a flux material, in order to attain materials with specific physical and chemical properties suitable for high- technological applications. The boron atom in borate crystals and glasses usually coordinated with either three or four oxygen atoms, forming [BO3) or (BO4) structural units (Nagaraja et al., 2008; Dutta et al., 2005; Dutta et al., 2005; Dutta et al., 2006). Alkali borate glasses are highly useful materials for vacuum ultraviolet (VUV) and semiconductors lithography owing to the presence of stable glass forming range and transparency from the near UV to the middle infrared region. Alkali/alkaline earth borate glasses containing various transition metal ions have been under extensive investigation in recent years in view of their technological applications especially in phosphors, lasers, solar energy converters and in a number of electronic devices. The reason is that, in the glasses the transition metal ion can exist in more than one valence state (Chakradhar et al., 2000). These glasses are relatively resistant to atmospheric moisture and are capable of accepting large concentrations of transition metal ions, rare earth ions and can be composed of structural groupings (boroxol, tetraborate, diborate, metaborate, pyroborate and orthoborate) that are present in the various crystal structures of the alkali borate compounds. The addition of alkali oxides modifies the boroxol rings, which are complex borate groups with one or two four- coordinated boron atoms (Roling, 1999). M. Shapaan and F .M. Ebrahim (Shapaan et al., 2010) studied the AC conductivity on the glass system as (80-X) - B2O3 - XBi2O3 - 20Fe2O3 (X, 10, 15 and 20 mol%). From the electric–dielectric measurements, it is found that σdc, σac(ω) decrease and (θD/2), increases with increasing Bi2O3 content. K. H. Mahmoud et al. (Mahmoud et al., 2011) studied the dielectric constant (έ) dielectric loss tangent tan δ and electric modulus behaviour as a function of temperature on glass system as (xBi2O3-(75-x) B2O3-25Li2O with, x= 0, 5, 20, 25, 30, 35, 40 mol %). The detailed analysis of the results showed that the dielectric consists of both dipolar and interfacial polarization. The activation energy of the dielectric relaxation process from the electric modulus measurements was calculated. Measurements of the ac conductivity as a function of Corresponding Author: S.Y. Marzouk, Arab Academy of Science and Technology, P. O. Box 2033, Al- Horria, Heliopolis, Cairo, Egypt.

2326 J. Appl. Sci. Res., 8(4): 2325-2334, 2012 frequency at different temperatures indicated that, the correlated barrier hopping (CBH) model is the most suitable mechanism for the ac conduction behaviour. In the present investigation, a mixed alkali borate glasses doped with cobalt oxide samples were prepared and then they characterized by DSC and XRD. The electrical properties were studied through impedance spectroscopy in view of the fact that, this technique is a powerful tool for characterizing the electrical properties of glass materials as a function of frequency and temperature (Gedam et al., 2006; Rao et al., 2008).

2. Experimental methods:

2. 1 Sample Preparation:

A different borate glass samples have been prepared by rapid-quenching method. Batches of each glass composition are listed in Table 1. The analytical-grade materials of purity more than 99.9% of K2CO3, Li2CO3, Na2CO3, H3BO3, and CoO chemicals were used to prepare the glass samples. The homogeneity of the chemicals mixture was achieved by repeated grinding using an agate mortar. The mixture was preheated in porcelain crucible at 673K for 60 min to remove H2O and CO2. The mixture then melted in a muffle furnace at temperature 1323K for 2h with stirring to gain bubble-free liquid. The molten mixture was poured in a cuboidal- shaped split mold made of mild steel then, it preheated at about 675 K then at 723 K for 2h. Bulk glass samples of about 1.5_0.5_0.3 cm3 were obtained.

2. 2 Sample identification and structure characterization:

Identification of the structural phase is accomplished to the eight different compositions in the glass system. A successive experiment can be performed to study whether the glasses under investigation could contain crystalline structure or it is of amorphous nature. The XRD patterns of the considered borate glasses are shown in Fig. (1), For X-ray diffraction (XRD) analysis, small pieces of the prepared glasses were grounded in an agate mortar to obtain very fine powder. The structure of the samples have been investigated by using a computerized X-ray system, model: Philips EXPERT-MPDUG PW-1710 diffractometer with Cu-Kα radiation source and a copper target with a nickel filter to obtain Cu-Kα radiation of a wavelength λ = 1.542 Ǻ. The samples in a powder form are measured at the same operating conditions. The powder sample was obtained by grinding to be in a fine powder form. The XRD pattern that is recorded in the diffraction range 2θ =4-70o. The XRD patterns of each glass sample indicating an amorphous nature of the glass sample under investigation.

2. 3. Differential scanning calorimetry (DSC):

The temperatures Tg of the samples were determined by a standard Shimadzu differential- scanning calorimeter (DSC). The values of Tg for each glass sample under investigation were listed in Table (2).

Results and Discussion

AC measurements:

The ac conductivity was measured as a function of frequency by using computerized Lock-in amplifier (model: HIOK 3532-50 LCR HI-TESTER) in the frequency range of 42 Hz : 5 MHz with accuracy 0.001 Hz. This Lock-in amplifier can detect and measure very small AC signals (down to nano-volts). So, accurate measurements can be made even when the small signal is obscured by noise sources many thousands of times larger. Lock-in amplifiers use a technique known as phase-sensitive detection to signal out the component of the signal at a specific reference frequency and phase. The frequency dependent measurements of capacitance, C, and dissipation factor, tan, were obtained and temperature from 303 to 468K. The dielectric constants (' and "), dielectric loss factor (tan δ) and conductivity () were determined as per the following expressions (Kumar et al., 2006);

Cd     (1)  o A

    tan (2)

2327 J. Appl. Sci. Res., 8(4): 2325-2334, 2012

The temperature dependence of the ac conductivity, ac(), dielectric constant, ', and the loss factor, tan , are studied at various frequencies (42 Hz to 5 MHz) for the as quenched glass samples. The temperature range of measurements is from 303 to 468K. The ac conductivity, ac(), is calculated using the relation (Dyre, 1991)

   o tan (3)

where o is the permittivity of free space, is the frequency of the input signal, The measured total conductivity in terms of frequency is generally expressed as (Dyre, 1991).

s Total = dc + ac =dc + A (4)

where dc is the frequency-independent component, A is a temperature dependent constant, S is the s frequency exponent and ac( = A ) represents ac or dissipative contribution to the total conductivity, which depends on frequency, temperature and composition of the sample (El. Mkami et al., 2000). Using the sigma plot graphics (version 11), Eq.(4) was fit to the data and shown in Fig. (2) for the glass samples under investigation. This Figure illustrates the plot of AC conductivity, ln(AC), versus ln() for the glass samples under study. Using equation (1) and (2) we can represent these parameters as in Fig. (3) which representing the dependence of ' and " on the applied frequency to the glass samples under investigation. The dependence of lnσAC on the applied temperature to the glass samples under study given in Fig. (4).

Frequency exponent, S:

The temperature dependence of frequency exponent, S, obtained from the non-linear fits made to Eq.(4) for our glass samples and found to be lying between 0.25 and 1 in the studied range of temperature indicating no systematic variation of S with composition. According to the Correlated Barrier Hopping (CBH) model, the value of exponent S, take values between 0.5 and 1 at room temperature and decreased with increasing temperature which represented by samples BLANK, BNKL1, BNKL2 and 0.1Co as shown in Fig. (5). According to Quantum Mechanical Tunneling (QMT) model (Ghosh, 1990), the exponent S was between 0.95 and 1 with a slight increase with temperature or independent of temperature as seen happened in samples BKL5 and 0.025Co. According to the Overlapping Large Polaron Tunneling (OLPT) model the exponent S, is depends on both temperature and frequency that can be seen clearly in the same Figure which expressed by samples BLNK3 and BNKL4 and the exponent S lying between 0.25 and 0.9. However, the decreasing trend of S with temperature can be noticed. This kind of variation of S with temperature has been observed in different (Transition metal ion) TMI/ alkali doped borate (Raistrick, 1987) and phosphate (Cutroni et al., 1996) glasses. The observed variation of S with temperature may be due to different contributions from conducting and dielectric losses at different temperatures (Raistrick, 1987; Cutroni et al., 1996). The theoretical models (Ghosh, 1993; Jain et al., 1987) such as (CBH), (QMT) and (OLPT) predicted the temperature dependence of frequency exponent, S. Also the activation energy of the glass samples under study has been determined from the plot of ln σac versus ln ω and have the values between 0.45 eV and 0.59 eV Table (3).

Table 1: Chemical compositions of the prepared glass systems and mol %.

Glass number Glass system B2O3 Na2O K2O Li2O CoO 1 BLANK 62 10 7 21 _ 2 BNKL1 62 10 7 21 0.05 3 BNKL2 62 13 7 18 0.05 4 BNKL3 70 18 12 _ 0.05 5 BNKL4 57 15 _ 28 0.05 6 BKL5 60 _ 10 30 0.05 7 0.1Co 62 10 7 21 0.1 8 0.025Co 62 10 7 21 0.025

Table 2: Values of the glass transition temperatures (Tg) for the different borate glasses under investigation. Glass 1 2 3 4 5 6 7 8 number BLANK BNKL1 BNKL2 BNKL3 BNKL4 BKL5 0.1Co 0.025Co Tg, K 727 721 724 694 726 739 741 746

2328 J. Appl. Sci. Res., 8(4): 2325-2334, 2012

Fig. 1: XRD patterns of the freshly borate glass systems as prepared.

2329 J. Appl. Sci. Res., 8(4): 2325-2334, 2012

Fig. 2: The dependence of ln AC on the applied frequency to the glass samples under study.

2330 J. Appl. Sci. Res., 8(4): 2325-2334, 2012

2331 J. Appl. Sci. Res., 8(4): 2325-2334, 2012

Fig. 3: The dependence of ' and " on the applied frequency to the glass samples under study

2332 J. Appl. Sci. Res., 8(4): 2325-2334, 2012

2333 J. Appl. Sci. Res., 8(4): 2325-2334, 2012

Fig. 4: The dependence of lnAC on the applied temperature to the glass samples under study.

Fig. 5: The dependence of exponent S on the applied temperature to the glass samples under study.

2334 J. Appl. Sci. Res., 8(4): 2325-2334, 2012

Table 3: The values of the activation energy of the investigated glass samples. Glass 1 2 3 4 5 6 7 8 number BLANK BNKL1 BNKL2 BNKL3 BNKL4 BKL5 0.1Co 0.025Co

Eac, ev. 0.541 0.535 0.584 0.458 0.571 0.532 0.566 0.544

Conclusions:

Glass samples of a mixed alkali borate glasses doped with cobalt oxide have been prepared by the melt quenching method. The XRD technique were applied to the glass samples as prepared to test the amorphously of the samples under study. The glass transition temperature have been determined to be sure that the applied temperature still under Tg (in the amorphous range). The dielectric properties of the glass samples have been studied for over a wide range of frequency (42 Hz to 5M Hz) and temperature (303K to 468k). The ac conductivity have been determined and discussed. The dielectric properties as a function of frequency and temperature have been investigated. The exponent, S, has values lying between 0.25 and 1 according to the three models (CBH), (QMT) and (OLPT) for all samples. Also, the calculated values of the activation energy found to be lying between 0.45 and 0.59 eV.

References

Chakradhar, R., P. Sreekanth, A. Murali, J.L. Rao, 2000. A study of electron paramagnetic resonance and optical absorption spectra of VO2+ ions in alkali calcium borate glasses. Physica., B 293: 108-117. Cutroni, M., A. Mandanici, A. Piccolo, C. Fanggao, G.A. Saunders, P. Mustarelli, 1996. Frequency and temperature dependence of a.c. conductivity of vitreous silver phosphate electrolytes Original Research Article. Soild State Ionics., 90: 167-172. Dutta, B., N.A. Fahmy, I.L. Pegg, 2005. Effect of mixed transition-metal ions in glasses. I. The P2O5–V2O5– Fe2O3 system. J. Non-Cryst. Solids., 351: 1958-1966. Dutta, B., N.A. Fahmy, I.L. Pegg, 2005. Effect of mixing transition ions in glasses. II. The P2O5–Fe2O3–MnO system. J. Non-Cryst. Solids., 351: 2552-2561. Dutta, B., N.A. Fahmy, I.L. Pegg, 2006. Effect of mixed transition-metal ions in glasses. Part III: The P2O5– V2O5–MnO system. J. Non-Cryst. Solids., 352: 2100-2108. Dyre, J.C.,1991. Some remarks on ac conduction in disordered solids. J. Non-Cryst. Solids, 135: 219-226. El. Mkami, H., B. Deroide, R. Backov, J.V. Zanchetta, 2000. dc and ac Conductivities of (V2O5)x(B2O3)1−x oxide glasses. J. Phys. Chem. Solids., 61: 819-826. Gedam, R.S., V.K. Desahpande, 2006. An anomalous enhancement in the electrical conductivity of Li2O : B2O3 : Al2O3 glasses. Solid State Ionics., 177: 2589-2592. Ghosh, A., 1990. Frequency-dependent conductivity in bismuth-vanadate glassy semiconductor. Phys. Rev. B, 41: 1479. Ghosh, A., 1993. Complex ac conductivity of tellurium cuprate glassy semiconductors. Phys. Rev. B. 47: 15537-15542. Jain, H., J.N. Mundy, 1987. Analysis of ac conductivity of glasses by a power law relationship. J. Non-Cryst. Solids., 91: 315-323. Kumar, B., T. Vijaya, Sankarappa, M. Santosh Kumar, P.J. Prashant Kumar, R. Sadashivaiah, Ramakrishna Reddy, 2006. Dielectric properties and conductivity in CuO and MoO3 doped borophosphate glasses. Physica, B 404: 3487-3492. Mahmoud, K.H., F.M. Abdel-Rahim, K. Atef, Y.B. Saddeek, 2011. Dielectric dispersion in lithium–bismuth- borate glasses. Current Applied Physics, 11: 55-60. Nagaraja, N., T. Sankarappa, M. Prashant Kumar, 2008. Electrical conductivity studies in single and mixed alkali doped cobalt–borate glasses. J. Non-Cryst. Solids., 354: 1503-1508. Raistrick, L.D., J.R. Macdonald, D.R. Franceschetti, 1987. in: J. R. Macdonald (Ed.), Impedance Spectroscopy, Wiley, New York, (Chapter 2). Rao, R. Balaji, Rosario, A. Gerhardt, N. Veeraiah, 2008. Spectroscopic characterization, conductivity and relaxation anomalies in the Li2O–MgO–B2O3 glass system: Effect of nickel ions. Journal of Physics and Chemistry of Solids., 69: 2813-2826. Roling, B., 1999. What do electrical conductivity and electrical modulus spectra tell us about the mechanisms of ion transport processes in melts, glasses, and crystals? J. Non-Cryst. Solids, 244: 34-43. Shapaan, M., M. Ebrahim, 2010. Structural and electric–dielectric properties of B2O3–Bi2O3–Fe2O3 oxide glasses. Physica, B 405: 3217-3222.