Effect of Na2O Addition on the Properties and Strcture of Germanate Glasses | Glasses | Refractive Index

CeramicsInternational

(1995) 113-118

Effect of Na,O Addition on the Properties and Structure of Germanate Glass
M. C. Wang,
Department of Mechanical Engineering, National Kaohsiung Institute of Technology, Kaohsiung, 80782, Taiwan

J. S. Wang & M. H. Hon
Department of Materials Science and Engineering, National Cheng Kung University, Tainan, Taiwan (Received 21 January 1994; accepted 26 April 1994)

Abstract: The L&O (Na,O)-CaO-Al@-GeO,

system, was prepared for infrared transmitting germanate glasses. The properties and structure of these glasses have been studied. The transition and crystallization temperatures are raised as L&O concentration is decreased and Na,O concentration is increased. The refractive index and Abbe number are increased with increasing Na20 content. The vibration modes observed in the high wave number regions of the FTIR spectra are from the symmetrical and antisymmetrical stretching and bending motions of GeO, tetrahedra.

1 INTRODUCTION The vitreous solidification of GeO, melt was first reported by Dennis and Laubengayer.’ In Imaoka’s experiments, the visible immiscibility gaps were observed in the systems CaO-GeO, St-O-GeO, and BaO-GeO,. 2 Relatively wide areas of glass formation were found in the R20-A1203-Ge02,3’4 R20-B203-Ge02,5,6 Pb0-Sb203-Ge027 and ZnOBa0-Ca0-Al@-Ge0~8 systems. There have been a large number of studies concerning the properties and structure of R20-Al, O,-GeO, (or R20-A1203-SiO,-GeO& g1asses,3,4,9-‘3 and the corresponding MO-A120,-Ge02.8~14. However, an extensive literature search showed that details of the structure, thermal and optical properties related to the addition of Na,O to the Li,O-CaO-Al,O,-GeO, glass system have not been elaborated. In the present paper, the thermal, optical properties and structure of Li,O(-Na,O)-CaO-A 12O3Ge02 glasses were studied. The refractive index of these glasses was measured as a function of Na,O content in the visible region of the spectrum.
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The purposes of this investigation are two-fold: (1) to evaluate the effect of composition on the therma1 and optical properties of these germanate glasses, (ii) to determine the effect of Na,O content on the structure of these glass samples. 2 EXPERIMENTAL PROCEDURE 2.1 Materials Specimens were prepared from materials of electronic grade Ge02 and analytical grade Li2C0,, Na,CO,, Al,O,, and CaCO, in 20 g quantities by melting at 1420°C in a platinum crucible for 2 h. After homogenizing, the melt was quenched in water, dried, crushed, and remelted at 1420°C for another 2 h, cast onto a 400°C hot stainless steel plate and transferred to an annealing furnace held for 1 h. Finally, a clear, transparent and colourless glass was obtained. The glass compositions are listed in Table 1, which are formulated on the basis of weight percent of the constituents of the glasses. The Na,O was introduced in 1.61 wt% stepwise substitutions for the L&O.

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. Effect of Nap addition on the Tg.18 59. Specimen temperature was measured by an X-type thermocouple in contact with the specimen surface. = glass samples which perpendicular faces of Na.56 nm.61 3. Wang.18 59. S. Each specimen was heated to the softening temperature in a dilatometer at a heating rate of 3Wmin and thermal expansion coefficients are reported for the temperature range from 70 to 400°C.18 59. 640 2. J.97 12. C. 2. 1.” The typical DTA curves obtained from the asquenched glasses are shown in Fig. Hon 3 RESULTS L&O 6. MB and T.O content at nf = 486. with a resolution of 2 cm-‘.3 /&fared and Fourier transform spectra measurement infrared 850 H M 0+3 Crystallization tmature Softening temperature Tcansition tenqerat The glass samples (about 2-O mm thick) for optical absorption measurement.44 2.48 pm) at lO”C/min in air was conducted by SETARAM TAG24 Simultaneous Symmetrical Thermoanalyzer with powdered AlzO.61 0 CaO 12.44 4. and also two melting endotherm temperatures.114 Table 1. 21. were polished for parallel faces.O. which corresponds to the glass transition point.2 Thermal property measurement Differential thermal analysis (DTA) on a 200 mg powder sample (67. The first endotherm.13 nm and 500 L 0 I I 2 Na20 I I 4 (wt%) I I 6 1 Fig.51 GeO. KBr pelletized disks were fabricated containing 2 mg of the glass sample and 600 mg KBr.51 21. DTA curves of the germanate glasses heating at a rate of 10Wmin.97 12. C5 0 1. dilatometric softening temperature (M.) and the first I I I I I I 350 550 750 950 1150 1350 Temperature ('Cl Fig.51 21. Wang.5 mm thick. as the reference material. varies from 525 to 635°C for samples with different compositions. YE. The infrared spectra were recorded with a Hitachi Infrared Spectrometer Model 29030. Thermal expansion coefficients were measured in a horizontal vitreous silica dilatometer (SETARAM High Temperature Dilatometer). for the germanate glass samples. Typical thermal expansion specimens were 25 mm long. These glass samples showed the two stage crystallization temperatures.22 1.83 6. H. The glass transition and dilatometric softening temperatures were obtained from the thermal expansion curves by the usual techniques. In Fig.51 21.97 AI.18 59.22 4.83 3.O C.5 mm wide. Chemical composition of g&SeJS Oxides Samples Na.97 12. 2. c2 bivt%o) M.51 21. Fourier transform infrared spectra were measured in the 400-1200 cm-’ region using a Nicolet 800 system. M.27 nm. 1.97 12.18 C3 C. The glass transition temperature (7”). 59.4 Refractive index measurement The refractive index of these were polished for adjacent was measured as a function wavelengths nd = 587. 656. 2. 1 the single glass transition temperature suggests the existence of compositionally homogeneous amorphous state in the as-quenched glass. and 3.

74 1.54 M-656. changes from a rigid to a plastic structure.2 X 104/oC 10. on . .) of these glasses are also shown in Fig. 3. .18.6 nm 1.” The difference of the glass transition and dilatometric softening temperature (M. .72 0 2 4 6 0 2 4 Nan0 twt%) 6 Na. Effect of Na.16 The T. density for the glass samples. The changes of the difference of the first crystallization temperature and transition temperature (T.O content on the difference between Mg and Tg. The effect of Na20 addition on the thermal expansion coefficients (a) and density of these glass samples is shown in Fig. 2 indicates that the glass sample containing 644% Na. Fig.and TEfor the germanate glass samples.) decreases sharply at about 4.1g discussed the effect of dilatometric softening temperature on the morphology of phase-separated glasses and found that IMg is controlled by the higher-viscosity phase as long as that phase is continuous.O has a considerable concentration of continuous highviscosity phase which gradually loses the continuity between the composition of 644% and 1. Effect of NazO content and wavelength variation the refractive index for the germanate glasses. except C. 4.) of these glass samples are shown in Fig.O/Na. The variation of thermal expansion coefficients and 4.O in glasses with the same other contents. The density of these germanate glasses is a function of composition and the maximum in Fig. the replacement of L&O by Na.of these glasses is around 531 f 6°C which suggests that the tetrahedra are the same mobile components of glasses. The hypotheses suggested the consistence with the behaviour of Tg as a function of glass composition.61% to 644%.1 nm I f 1. 3. On this basis. LY values from 70 to 400°C are 9.Eflect of Na.O increased.T. In general. 3.76 .17 Mazurin et a1. l6 The Tg corresponding to the temperature at which the network acquires mobility. and T. the Mg in Fig.83 wt% Na20 addition as shown in Fig. 2.6 X lO-‘?‘C as Na.O content is to increased from 1. Mazurin et aZ.3 nm 114 587.O (wt%) Fig.m-e 486.th the ratio Li.O lie in a region of immiscibility.20 pointed out that in the Na20-Ge02 system.O = 1. glass at 635”C. The maximum point in the Tc-T curve corresponds to the glass composition w.O content.T.is It seems reasonable to suggest that this also occurs here and that the glasses containing >6-44% Na. the expansion coefficient of the glass in this system increases almost linearly with increasing Na.O addition on germanate glass 115 crystallization temperature (T. Mg and T.u ro 1-78 I 1 13. It is seen that the Tg. This type of behaviour found in other glass-forming systems is often indicative of phase separation.are raised as L&O decreased and Na. 5. with a rather abrupt lIz’” 331 0 I I 2 Nil20 I I 4 0 1 1190 6 (wt%) change as the continuity of that phase disappears.61% Li20.

2000 (cm-') . respectively. . S. 5.85m (C2)'1.5 pm for C. = (nd . The infrared transmittance of C2 and C.O addition on the variation number for the glass samples. as of other materials. glasses is shown in Fig.g2nUn I 4000 3500 I I 3000 I . where nd. which may be suggested to be due to the O-H bond bending and stretching vibration. of C2 and C5 glasses.5 100 L 3 4 (pm) 5 I I 1 0 10 . and n. The ability 57 0 I 2 t I 4 I I 6 Na20 (wt%) Fig.n. glass samples. . For Figs 5 and 6. J. which are longer than that of 5.13 nm and 656. and transmission in the near infrared is thus restricted.22 The infrared cut-off is at about 6.116 M. This variation can be considerable and it is necessary for the application of glass in optical system to have accurate information on the variation. The glass begins with a relative broad absorption in the region of 2. Wang.6. 486. M. respectively. not only in the visible part of the spectrum.). C. The variation of vd with Na. are refractive indexes at wavelengths 587. The 67 I- 65 - Abbe number. the refractive index and vd of these germanate glasses are increasing as Na20 content is increased. in the near infrared and ultraviolet regions. of Abbe Wavelength 2. 1500 1c 1200 800 Wavenumber (cm-l) 400 Wavenumber Fig. ITIR spectra for glass samples. Effect of Na. .21 The refractive index of a glass.l)/(n. Hon this curve is related to the change of coordination number of germanium from six to four.O content is shown in Fig. and C. 8. which is a measure of optical dispersion.9 and 7. V. 7. Wang. 30 Thickness 20 Thickness (C5)=1.9 pm.27 nm. n. Fig. The measured index of refraction as a function of Na20 content and wavelength for these germanate glasses is shown in Fig. varies with wavelength. 6. 2500 .. H. The infrared transmittance 7. may be estimated from the refractive index by V.0 pm for silicate glass.56 nm. but also for some applications. .

which are longer than that of 5-O pm for silicate glasses.’ It can be assumed that in germanate glass the 0-Ge-0 (0-Ge-O-) bending vibrations and symmetric stretching motions across the Ge-0-Ge bridging oxygens are coupled because of the small difference in frequency of these vibrations.9T23-26 4 DISCUSSION In fused silica there is a continuous random network of Si04 tetrahedra and all the oxygens are doubly bonded. the species of L&O. respectively. respectively.27 Murthy et ~1.’ The coupling between these two modes produces the single broad band which is observed with an apparent frequency weighted according to the bend-stretch vibration frequencies and corresponding intensities.26. In this study.9 and 7. That the latter mechanism is the most probable one is indicated by the fact that pronounced maxima exist in the propertycomposition curves for the alkali-germanate 28 Ivanov and Yestropiev29 indicated that glasses. For these glass samples. The FTIR spectra of analysed glasses have shown that the glasses have a three-dimensional. however.O content decreased and Na.Efect of NazO addition on germanate glass 117 of a material to exhibit a long wavelength transmittance is dependent not only on the material possessing a large band gap. but are linked through the apices.bonding) oxygens.44%.3 There is no direct evidence in the present spectra that these glasses contain higher than four-fold coordination of Al cations. For these glasses.O and CaO.O for Li.769. two things can happen. the coordination number of the Ge4’ ions can remain the same (four). Ge-0-Ge bond) and non-bridging (i. the Li. as Na20 content increased from 1. i. random network structure consisting of Ge04 tetrahedra as their most fundamental units.03 f 4. but is also governed by the frequency of vibration of cation-anion bonds resulting in the infrared absorption cut-off. germanate glass samples are about 6.e. The inability to form alkali-aluminogermanate glasses with a M/Al ratio less than unity can be attributed to the fact that in these glasses some of the A13+ ions must exist in octahedral coordination but cannot do so because of the presence of octahedra which are already present in the structure. or the coordination of some of the Ge4’ ions can change from four to six without the formation of non-bridging oxygens with the alkali ions going into the interstitial position as usual. Larger cations and anions with lower field strength will move the infrared transmittance to longer wavelengths. dilatometric and first crystallization temperatures are raised as Li.. i. fused germania consists of a continuous random network of Ge04 tetrahedra. the transition.e.61% to 6.e. only for those alkaligermanate glasses in which the density and refractive index are increasing with the addition of alkali oxide.O at constant ratio of concentration of CaO. germanate tetrahedra. with the formation of singly bonded non-bridging oxygens as in the case of alkali-silicates. Al2O3. The most intense absorption band is in the 800900 cm-’ region. as Na.9.23m26 The second strong region of absorption lies between 500-600 cm-‘. and may be related to mixed stretching-bending motions. Na. the tetrahedra do not share corners. however.25. i.26 Vibrational spectra of the studied germanate glasses exhibit bands which are characteristic for the networkforming.07. each of the six oxygen apices of the GeO.O content increased from 1.61% to 644%.’ The high-frequency bands in the FTIR of these germanate glasses are narrower than their counterparts in silicate glasses.~pointed out that when an M20 oxide is added to fused germanate. Similarly.e.). the refractive indexes are from I.3 The bonds in spectra of germanate glasses are consistent with the similar assignment of corresponding bonds in the silicate glasses.O content increased. The observed results in the FTIR spectra of analysed glasses have shown that the glasses have . The infrared cut-off for C2 and C. octahedra is shared by neighbouring tetrahedra (GeO.* Bond strengths and lengths tend to vary depending on the particular glass composition.9.* FTIR spectra of these germanate glass samples have two regions of absorption as shown in Fig.O(-Na. act as the glass network modifier cations of lower field strength. 5 CONCLUSIONS By a progressive weight percent substitution of Na. and GeO. The thermal expansion coefficients from 70 to 400°C are 9. and that no non-bridging oxygen is present. indicating that Ge-0-Ge bond angles have smaller fluctuations in the germanate glasses than do the Si-O-Si bond angles in the silicate g1asses. 8.O)CaO-A1203-Ge02 system was prepared for infrared transmitting germanate glasses.e.5 pm. The strongest infrared absorption bands of these germanate glasses lie in the 8OO900 cm-’ region which may be assigned to antisymmetric stretching motions of Ge04 tetrahedra containing bridging (i.6 X lO?‘C. Ge-O. The Abbe number for the glass samples is about 62. This is true. a continuous network of tetrahedra and octahedra exists. they are linked to two silicon atoms.2 X 10-6/“C to 10.9.703 to 1.

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