American Journal of Analytical Chemistry
Vol.05 No.16(2014), Article ID:51723,8 pages
10.4236/ajac.2014.516121
IR and Raman Spectra Properties of Bi2O3-ZnO-B2O3-BaO Quaternary Glass System
Feng He1*, Zijun He2, Junlin Xie1, Yuhui Li1,2
1State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan, China
2Department of Materials Engineering, Monash University, Melbourne, Australia
Email: *he-feng2002@163.com
Copyright © 2014 by authors and Scientific Research Publishing Inc.
This work is licensed under the Creative Commons Attribution International License (CC BY).
http://creativecommons.org/licenses/by/4.0/
Received 17 September 2014; revised 3 November 2014; accepted 18 November 2014
ABSTRACT
Among new low-melting-point glasses, bismuth ate glass is deemed to have the most potential as an environmentally friendly replacement for polluting Pb-containing glasses. Current studies of boro-bismuthate glasses focus on the structural influence of the additional oxide in the context of low-melting-point electronic sealing applications. In this study, the structure of quaternary Bi2O3- ZnO-B2O3-BaO glasses was investigated spectroscopic ally, with Fourier-transform-infrared (FT-IR) and Raman spectra recorded for glasses with different main oxide contents. Signals in the FT-IR are mainly observed around
Keywords:
IR and Raman spectra, Bi2O3-ZnO-B2O3-BaO quaternary glass system, structure
1. Introduction
The special properties of bismuth glass have been investigated mainly in the Bi2O3-B2O3 [1] [2] and Bi2O3- ZnO-B2O3 systems [3] . Greater information is becoming available on its structure and properties [4] - [6] . Bi glass benefits from a low melting point, below 1100˚C, and could therefore be developed as a new type of lead-free low-melting-point sealing glass.
Bismuth borate glass has gradually been drawing interest among researchers as a new kind of lead-free material, leading to greater information becoming available on its structure and performance. Raman and infrared (IR) spectroscopy provide important information on the local structure of vitreous and ceramic materials [7] [8] . Shashidhar Bale et al. [2] studied the role of Bi2O
In this study, the spectroscopic properties of the quaternary Bi2O3-ZnO-B2O3-BaO glass system were studied by Fourier transform (FT)-IR and Raman spectroscopy. Variations in the glass structure were investigated on the basis of the spectra to understand the relationship between the atomic-level structure and the bulk properties of the glasses.
2. Experimental procedure
Glass samples of compositions (65 − x)Bi2O3-xZnO-5BaO-30B2O3 (3 ≤ x ≤ 15 mol%) and (80 − y)Bi2O3- yB2O3-15ZnO-5BaO (20 ≤ y ≤ 40 mol%) were prepared by melt quenching using reagent grade Bi2O3, ZnO, and H3BO3. The precursor chemicals were mixed in porcelain crucibles, calcined at 450˚C for 1 h and then melted at 1100˚C - 1200˚C depending on the glass composition. The melts were stirred for 1 h to homogenize the mixtures. The clear melts (free of bubbles) were quickly cast in stainless steel molds kept at 250˚C and pressed with another steel disc maintained at same temperature. The resulting samples were transparent and their color varied from yellow to light brown with increasing bismuth content. The glasses were then annealed at 300˚C for about 8 h to remove thermal stress and strain. In the following, the glass samples with x = 3, 6, 9, 12, and 15, are named A1, A2, A3, A4 and A5, respectively. Similarly, the glass samples with y = 20, 25, 30, 35, and 40, are named B1, B2, B3, B4, and B5, respectively.
Infrared spectra of the powdered glass samples were recorded at room temperature in the wavelength range 400 - 2000 cm−1 using a Nicolet-60-SXB FT-IR spectrometer. These measurements were performed on glass powder dispersed in KBr pellets.
Room-temperature Raman spectroscopy was performed in the 100 - 1700 cm−1 wavelength range using a Renishaw inVia micro-Raman spectrometer. The incident laser was focused to a diameter of 1 - 2 μm and a notch filter was used to suppress Rayleigh light. Raman shifts were measured to a precision of ~
3. Results and Discussion
3.1. Structure of the Bi2O3-ZnO-B2O3-BaO glasses
Figure 1 shows the FT-IR spectrum of the x = 9 glass sample, for which absorption bands are clearly observed around 500, 720, 840, 980 - 1080 and 1200 - 1500 cm−1. The corresponding assignments are listed in Table 1.
FT-IR spectra of glasses are generally interpreted using the method proposed by Tarte [12] and Condrate [13] , by comparing the experimental data with those of related crystalline compounds. In this study, the characteristic absorption bands for vitreous Bi2O3 [14] [15] and B2O3 [16] [17] were used. The absorption band centered at ~
Figure 1. FT-IR spectrum of a 56Bi2O3-9ZnO-30B2O3-5BaO glass.
Table 1. Assignments for the FT-IR absorption bands of Bi2O3-ZnO-B2O3-BaO glass.
meta- and ortho-borate groups [19] [21] . The broad shoulder present in the spectrum at ~
For all samples, FT-IR absorption bands for vitreous B2O3 were identified at ~720, ~1260, and ~
The assignments in Table 1 suggest that [BiO6], [BiO3], [BO3], and [BO4] units may be present in the Bi2O3-ZnO-B2O3-BaO quaternary glasses.
Further information on the structure of the glass can be gathered from the absorption peaks around 990 - 1080 cm−1,
Figure 2 shows a typical Raman spectrum for these glasses, consisting of broad peaks in the 100 - 1600 cm−1 range. For the x = 9 glass sample, peaks are observed around
The vibrational Raman and infrared spectra of the investigated glasses with 45 - 65 mol% bismuth oxide concentrations are dominated by bands associated with structural units built around the heaviest cation, Bi3+. The Raman bands arising from heavy metal oxides, such as Bi2O3, can be classified into four groups: 1) low wavenumber Raman modes (<
The presence of a band around
Figure 2. Raman spectrum of a 56Bi2O3-9ZnO-30B2O3-5BaO glass.
polyhedra [25] . In the spectrum shown in Figure 2, this band is observed at
Figure 2 and Table 2 show that [BO3], [BiO6] and [BiO3] units may be present in these boro-bismuthate glasses, but the characteristic peak for [ZnO4] units around 254 cm−1 is not clearly visible in Figure 2, suggesting that ZnO acts as a network modifier in this glass system.
Based on the FT-IR and Raman spectra obtained for this glass, the main network forming units are trigonal [BiO3] and [BO3] groups with a smaller number of [BO4] tetrahedrons. However, [BiO6] units are not incorporated in the glass network. Bi-O− NBOs may be present as well as some Bi-O-Bi and bonds between [BiO3] and [BiO3] or between [BiO3] and [BiO6] groups. The connections between [BO3] groups, and between [BO3] and [BO4] groups, may occur via B-O-B bonds or B-O− links. ZnO acts as a network modifier and is not integrated in the glass network.
3.2. Effect of Bi2O3 contents on the structure of Bi2O3-ZnO-B2O3-BaO glasses
Bi2O3 plays a unique role in the structure of these glasses. The presence in large proportions of the two network formers, Bi2O3 and B2O3, leads to the formation of a vitreous structure with exceptional properties. Figure 3 shows the FT-IR spectra obtained for glasses in this system with different Bi2O3 contents, with the corresponding Raman spectra shown in Figure 4. Both the FT-IR and Raman curves shift slightly with increasing Bi2O3 contents.
The IR absorption spectra obtained from glasses in the Bi2O3-ZnO-B2O3-BaO system with different Bi2O3 contents are shown in Figure 3. The peak around
Table 2. Assignments for the Raman scattering bands measured in Bi2O3-ZnO-B2O3-BaO glasses [3] [4] [29] [30] .
Figure 3. FT-IR spectra of (65 − x)Bi2O3-xZnO-5BaO-30B2O3 (3 ≤ x ≤ 15 mol%) glasses.
Figure 4. Raman spectra of (65 − x)Bi2O3-xZnO-5BaO-30B2O3 (3 ≤ x ≤ 15 mol%) glasses.
Figure 4 shows the Raman spectra obtained for glasses with different Bi2O3 contents. A clear increase in intensity is observed around
The scattering peak around
To summarize, the FT-IR and Raman spectra of these glasses suggest that bismuth is present in the form of [BiO6] and [BiO3] units, and boron as [BO3] and [BO4] units. ZnO is not incorporated in the network and provides free oxygen atoms. In the glasses with higher Bi2O3 contents, a clear increase in the numbers of [BiO6] and [BiO3] units is evidenced. The FT-IR absorption peaks at 990 - 1080 cm−1 shift to lower wavenumbers from samples A1 to A5, indicating that the [BO4] units tend to become loose in the glass network, the latter being built mainly around trigonal [BO3] groups.
3.3. Effect of B2O3 contents on the structure of Bi2O3-ZnO-B2O3-BaO glasses
Figure 5 shows the infrared spectra obtained for the glasses in group B. For all compositions, bands around
The absorption band at 980 - 1080 cm−1, attributed to stretching vibration in [BO4] groups, increases in intensity from sample B1 to B5. Higher B2O3 contents result in stronger B-O-B bond vibrations from trigonal [BO3] units, which appear around 1100 - 1400 cm−
Figure 6 shows the Raman spectra obtained for different glasses in group B, covering the spectral range of 100 - 1600 cm−1. For the B1 sample, scattering bands are clearly observed at
As they belong to the same glass system, the samples from groups A and B produce similar Raman peaks, as evidenced by comparing Figure 4 and Figure 6. However, as the B2O3 content increases, the scattering intensity at
As the B2O3 content increases from sample B1 to B5, the band around
Figure 5. FT-IR spectra of (80 − y)Bi2O3-yB2O3-15ZnO-5BaO (20 ≤ y ≤ 40 mol%) glasses.
Figure 6. Raman spectra of (80 − y)Bi2O3-yB2O3-15ZnO-5BaO (20 ≤ y ≤ 40 mol%) glasses.
Bi-O− NBO of [BiO3] units and the B-O-B stretching vibration of [BO3] units. As the B2O3 content is increased in going from sample B1 to B5, this peak weakens, indicating a relative decrease and increase in the number of [BiO3] and [BO3] units, respectively. Indeed, the decrease in the Raman peak around 1250 - 1500 cm−1 suggests that the decrease in the number of [BiO3] units is more substantial than the increase in the number of [BO3] groups.
The above analysis of the B samples suggests that [BiO6], [BiO3], [BO3], and [BO4] units are present in the glasses. With increasing B2O3 content, the relative numbers of [BO3] and [BO4] units increase with a corresponding decrease in the number of [BiO3] and [BiO6] units. It is notable however that no Raman peak assignable to [ZnO4] tetrahedrons appears in the group B glasses.
4. Conclusions
In summary, glasses in the Bi2O3-ZnO-B2O3-BaO system were prepared and investigated by FT-IR and Raman spectroscopy in terms of the structure of the glass matrix. The FT-IR data suggest that the glass network is built around trigonal [BO3] units, cross-linked or connected to [BO4] groups, while the Raman data highlight the presence of [BiO3] and [BiO6] units. The main network forming species are trigonal [BiO3] and [BO3] units, but [BO4] tetrahedrons form part of the network. The [BiO6] units do not enter the glass network.
When altering the content of the main oxide, only slight changes are observed in the FT-IR and Raman spectra. As the Bi2O3 content is increased, the absorption and scattering peaks associated with Bi3+ and B3+ increase and decrease, respectively. Contrarily, for increasing B2O3 contents, the peaks arising from [BiO3] and [BiO6] units decrease in intensity, while those from [BO3] and [BO4] units strengthen.
All the results point to the fact that introducing Bi2O3 leads to a somewhat looser structure, and this is therefore propitious for lowering the melting point of the glass. On the contrary, increasing the B2O3 content leads to a more compact structure and thus to a more stable glass system.
Acknowledgements
This work was financially supported by the National “Twelfth Five-Year” Plan for Science & Technology Support of China (2012BAA08B04). This work was also supported by a Research and Test of Material grant from Wuhan University of Technology.
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NOTES
*Corresponding author.