Materials Research Bulletin 41 (2006) 19721978 www.elsevier.

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Effect of V2O5 additive to 0.4SrTiO30.6La(Mg0.5Ti0.5)O3 ceramics on sintering behavior and microwave dielectric properties
ZhongHua Yao, HanXing Liu *, ZongYang Shen, ZhiZheng Chen, ZhaoHui Wu, HongTao Yu, MingHe Cao
State Key Laboratory of Advanced Technology for Materials Synthesis and Processing, Wuhan University of Technology, 122 Ruo Shi Road, Wuhan 430070, PR China Received 6 October 2005; received in revised form 25 February 2006; accepted 9 March 2006 Available online 31 March 2006

Abstract The effect of V2O5 addition on the microwave dielectric properties and the microstructures of 0.4SrTiO30.6La(Mg0.5Ti0.5)O3 ceramics sintered for 5 h at different sintering temperature were investigated systematically. It was found that the sintering temperature was effectively lowered about 200 8C by increasing V2O5 addition content. The grain sizes, bulk density as well as microwave dielectric properties were greatly dependent on sintering temperature and V2O5 content. The 4ST6LMT ceramics with 0.25% V2O5 sintered at 1400 8C for 5 h in air exhibited optimum microwave dielectric properties of er = 50.7, Q f = 15049.6 GHz, Tf = 1.7 ppm/8C. # 2006 Elsevier Ltd. All rights reserved.
Keywords: A. Ceramics; C. X-ray diffraction; D. Dielectric properties

1. Introduction With the recent progress in the microwave communication system, microwave dielectric materials of a high quality factor, a good stability of the temperature coefcient of resonant frequency and a high dielectric constant have been extensively studied because of their applications to microwave devices such as lters, duplexers, voltage-controlled oscillators, and antennas [15]. The present trends are the miniaturization of microwave devices and narrowing channel bandwidth. To meet the demands of microwave circuit designs, each dielectric property should be precisely controlled. Recently, attempts have been made to satisfy microwave needs by using ATiO3Ln(B1/2Ti1/2)O3 (A = Ca, Sr; Ln = La, Sm, Nd; B = Zn, Mg) ceramics which have low dielectric loss and reasonable dielectric constant with adjustable temperature coefcient of resonant frequency [69]. Seabra et al. [10] studied the microstructure and dielectric properties of ySrTiO3(1 y)La(Mg0.5Ti0.5)O3 ceramics with a near-zero temperature coefcient of resonant frequency when y = 0.36 by theoretical calculation and y = 0.42 by practical research results,

* Corresponding author. Tel.: +86 2787854681; fax: +86 2787879468. E-mail address: lhxhp@mail.whut.edu.cn (H. Liu). 0025-5408/$ see front matter # 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.materresbull.2006.03.003

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respectively. However, for the compositions with 0 y 0.5, the ySrTiO3(1 y)La(Mg0.5Ti0.5)O3 ceramics to attain high densities (>95%) have very high sintering processing temperature to 1600 8C and poor sinterability which cost much. Low temperature solid-state synthesis is an approach that shows great promise for the synthesis of materials with unusual interesting properties. Generally, three methods are applied to reduction of the sintering temperature of dielectric ceramics: low melting-point addition [11], chemical processing [12], and powder with smaller particle sizes. The rst method using liquid-phase glass sintering was found to effectively lower the sintering temperature. However, it also greatly decreased microwave dielectric properties of dielectric resonators, especially quality factor. The chemical process as well as the third method often required a complicated procedure, which was expensive and time consuming. Therefore, the selection of non-glass addition with low melting point is of the utmost importance. In previous work [13], liquid-phase ux such as CuO, B2O3 and Bi2O3 were added to enhance the sinterability of ceramics and microwave dielectric properties. Since V2O5 with a 690 8C melting point is one of the ux formers and has been reported to effectively lower the sintering temperature of ceramics [14,15], it was selected as a sintering aid in present study. The effect of different amount of V2O5 addition on the sintering behavior and microwave dielectric properties of 0.4SrTiO30.6La(Mg0.5Ti0.5)O3 (hereafter referred to as 4ST6LMT) ceramics were investigated. 2. Experimental Ceramics samples were prepared by the conventional mixed oxide method. The samples were prepared by the twostage method to acquire a pure phase of perovskite. Reagent-grade materials of SrCO3, TiO2, MgO and La2O3 with higher than 99.0% purity were used as starting materials. La2O3 and MgO were rst dried at 800 8C for 5 h to eliminate absorbed moisture. In the rst stage, these powders were batched to 4ST6LMT, and then wet mixed with ZrO2 balls for 24 h in deionized water. After drying, the mixed powders were calcined for 4 h at 1250 8C. In the second stage, the above precursor was mixed with different amounts of V2O5 addition. Then the remixed powders were milled in deionized water for 12 h, using telfon pots and ZrO2-balls in a planetary mill and dried. All mixtures were granulated with the organic binder (5.0% PVA) and then sieved using a 40-mesh screen. Prepared powders were uniaxially pressed at 200 MPa into 12 mm diameter and 6 mm height disc-type pellets. After being red to remove the organic binder, these pellets were sintered at a temperature range between 1350 and 1500 8C for 5 h in air. The heating rate and the cooling rate were both set at 108C/min. Crystalline phases of the sintered specimens were identied by a Philips vertical X-ray diffractometer (PW3050/60, MPSS) using Cu Ka (l = 1.54056 A) radiation with 2u in the range of 20808 and step size of 0.028 with XPert HighScore Plus diffraction software. The ceramic pellets were rst at ground (on 2000-grade SiC paper) manually. The microstructural observations and analysis of polished and thermally etched surfaces of sintered specimens were examined using a scanning electron microscopy (SEM, Akashi Seisakusho JSM-5610LV). The bulk densities of the sintered pellets were measured by the Archimedes method. The dielectric constant (er) and the quality factor values (Q) at microwave frequencies were measured using the HakkiColeman dielectric resonator method as modied and improved by Courtney [16,17]. A system combining a HP8722ET network analyzer was employed in the measurement. An identical technique was applied in measuring the temperature coefcient of resonant frequency (Tf) of the TE01d mode. The temperature coefcient of resonant frequency (Tf) at microwave frequency was measured in the temperature range from 20 to 80 8C. The Tf (ppm/8C) can be calculated by the following equation: f2 f1 (1) Tf f1 T2 T1 where f 1 and f 2 represent the resonant frequencies at T1 and T2, respectively. 3. Results and discussion Fig. 1 shows the XRD patterns of the 4ST6LMT ceramics with 0.25% V2O5 addition and without V2O5 addition sintered at different sintering temperatures for 5 h. Fig. 2 shows XRD patterns of the 4ST6LMT ceramics doped

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Fig. 1. XRD patterns of the 4ST6LMT ceramics with 0.25% V2O5 addition at different sintering temperature for 5 h, A represents for undoped4ST6LMT ceramics.

with 0.251.0% V2O5 at 1400 8C for 5 h. Seen from Figs. 1 and 2, no secondary phases for various V2O5 addition are observed since detection of a minor phase by X-ray is extremely difcult. And even at a high amount of V2O5 addition, XRD patterns showed no difference from the 4ST6LMT sample without additive sintered at 1550 8C. According to Avdeev et al. [18], some weak peaks (marked by asterisk *) in Figs. 1 and 2 mean the presence of in- or anti-phase octahedral tilting. But there were no any other peaks of supercell reection, such as Mg/Ti ordering, antiparallel (La, Sr) displacement. The spectra were indexed according to an orthorhombic unit cell with space group Pbnm (no. 62, reference code: 01-089-5628 by PCPDF les) [19]. Previous work [8] conrmed that the 4ST6LMT system showed obviously orthorhombic structure which was similar with CaTiO3La(Mg0.5Ti0.5)O3 structure by Kipkoech et al. [7]. The SEM images of polished and thermally etched surfaces from the specimens of the 4ST6LMT ceramics with 0.25% V2O5 addition at different sintering temperature for 5 h are illustrated in Fig. 3(a)(g). As shown, the V2O5 doped 4ST6LMT ceramics were already dense at 1350 8C while the undoped 4ST6LMT ceramics with high relative density require high sintering temperature to over 1550 8C [10]. It illustrates that V2O5 addition improves the

Fig. 2. XRD patterns of the 4ST6LMT ceramics doped with various V2O5.

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Fig. 3. SEM graphs of the 4ST6LMT ceramics with 0.25% V2O5 addition at different sintering temperatures for 5 h: (a) 1350 8C; (b) 1375 8C; (c) 1400 8C; (d) 1425 8C; (e) 1450 8C; (f) 1475 8C; (g) 1500 8C. SEM graphs of the 4ST6LMT ceramics at 1400 8C for 5 h doped with various V2O5: (h) 0.25%; (i) 0.5%; (j) 1.0%.

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Fig. 3. (Continued ).

sinterability and results in a sintering temperature 200 8C lower than that without addition. Note that the grain size as well as porosity of the ceramics increased notably with the increase of sintering temperature. However, the grain grew abnormally at temperatures above 1475 8C which may affect the microwave dielectric properties of the ceramics. Fig. 3(h)(j) shows SEM graphs of the 4ST6LMT ceramics doped with various V2O5 and sintered at 1400 8C for 5 h. With increasing V2O5, the grain size increased remarkably. It should contribute to the formation of liquid phase, which accelerated the rate of grain growth. Fig. 4 shows the plots of bulk densities of 4ST6LMTceramics with various amounts of V2O5 added as a function of sintering temperature. The bulk density slightly increased till to 1400 8C and then declined sharply at higher temperature due to abnormal grain growth and much porosity which may affect the dielectric loss of the ceramics. At 1400 8C, the ceramics with 0.25% V2O5 addition reached the optimal bulk density. Microwave dielectric properties of 4ST6LMT specimens sintered for 5 h at different temperature with various V2O5 additive were shown in Fig. 5. Seen from Fig. 5(a), dielectric constants of the 4ST6LMTceramics gradually enhanced with the increase of sintering temperature and the specimens with 0.25% V2O5 additive showed the maximum values in the studied temperature range. Many factors, such as crystal defects, grain boundary, second phases and pores, are believed to affect the microwave dielectric loss of ceramics. The abnormal grain growth occurred in sintered doped-4ST6LMT specimens with further increasing in sintering temperatures above the densied temperatures, which led to the increase of crystal defects because the more liquid phases at higher temperature resulted in the more unhomogeneity of apparent density and more porosity for much abnormal grain growth than that at densied temperature when cooling, and the decrease in the Q f value. The Q f value of ceramic specimens increased at rst till to 1400 8C and then decreased sharply at higher temperature which had the similar trend to bulk

Fig. 4. The plots of bulk densities of 4ST6LMTceramics with various amounts of V2O5 added vs. the sintering temperature.

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Fig. 5. Microwave dielectric properties of 4ST6LMT specimens sintered for 5 h at different temperature with various V2O5 addition: (a) relative dielectric constant, er; (b) quality factor, Q f (GHz); (c) temperature coefcient of resonant frequency, Tf.

density due to abnormal grain growth and the porosity in the specimens. At 1400 8C, specimens with 0.25% V2O5 addition attained the maximum Q f value, namely 15049.6 GHz. With the increasing temperature, the Tf value changed little. However, with the decrease of V2O5 addition, the Tf values decreased to negative value regularly. Therefore, at 1400 8C, the 4ST6LMT ceramics with 0.25% V2O5 addition reached the optimal microwave dielectric properties, a er value of 50.7, a Q f value of 15049.6 GHz, and a Tf value of 1.7 ppm/8C. 4. Conclusion The effect of V2O5 addition on the microwave dielectric properties and the microstructures of 4ST6LMT ceramics sintered for 5 h at different sintering temperature were investigated systematically. It was found that the sintering temperature was effectively lowered about 200 8C by increasing V2O5 addition. The grain sizes, bulk density as well as microwave dielectric properties were greatly dependent on sintering temperature and V2O5 content. The 4ST6LMT ceramics with 0.25% V2O5 sintered at 1400 8C for 5 h in air exhibited optimum microwave dielectric properties of er = 50.7, Q f = 15049.6 GHz, Tf = 1.7 ppm/8C. Acknowledgement The research work was supported by Natural Science Foundation of China (NSFC, Grant no. 50472016).

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