(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.

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.

Ceramics International. 0272-8842/95/$9.50 0 Elsevier Science Limited, England and Techna S.r.1. Printed in Great Britain

as the reference material. 21. 1. and 3.18 C3 C. The glass transition and dilatometric softening temperatures were obtained from the thermal expansion curves by the usual techniques. varies from 525 to 635°C for samples with different compositions.114 Table 1.22 1. with a resolution of 2 cm-‘. Thermal expansion coefficients were measured in a horizontal vitreous silica dilatometer (SETARAM High Temperature Dilatometer). Fourier transform infrared spectra were measured in the 400-1200 cm-’ region using a Nicolet 800 system. The glass transition temperature (7”).97 AI. Chemical composition of g&SeJS Oxides Samples Na.61 3.O C. Effect of Nap addition on the Tg.4 Refractive index measurement The refractive index of these were polished for adjacent was measured as a function wavelengths nd = 587. and also two melting endotherm temperatures.61 0 CaO 12. 1.3 /&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. In Fig.O. = glass samples which perpendicular faces of Na.O content at nf = 486.56 nm. These glass samples showed the two stage crystallization temperatures.27 nm. DTA curves of the germanate glasses heating at a rate of 10Wmin. Specimen temperature was measured by an X-type thermocouple in contact with the specimen surface.5 mm thick.18 59.2 Thermal property measurement Differential thermal analysis (DTA) on a 200 mg powder sample (67.83 3.) and the first I I I I I I 350 550 750 950 1150 1350 Temperature ('Cl Fig. C.51 21. c2 bivt%o) M. 656. H. which corresponds to the glass transition point. . KBr pelletized disks were fabricated containing 2 mg of the glass sample and 600 mg KBr.83 6. dilatometric softening temperature (M. Typical thermal expansion specimens were 25 mm long.51 21.97 12. 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.44 2. 2.22 4.44 4.18 59. Wang.18 59. S. The first endotherm.5 mm wide. 2.13 nm and 500 L 0 I I 2 Na20 I I 4 (wt%) I I 6 1 Fig. J. 640 2.51 21. YE. M. 2. C5 0 1.18 59.51 GeO.97 12. The infrared spectra were recorded with a Hitachi Infrared Spectrometer Model 29030.97 12. Wang. for the germanate glass samples.” The typical DTA curves obtained from the asquenched glasses are shown in Fig.48 pm) at lO”C/min in air was conducted by SETARAM TAG24 Simultaneous Symmetrical Thermoanalyzer with powdered AlzO. 1 the single glass transition temperature suggests the existence of compositionally homogeneous amorphous state in the as-quenched glass.51 21. were polished for parallel faces. Hon 3 RESULTS L&O 6. MB and T. 59.97 12.

density for the glass samples. This type of behaviour found in other glass-forming systems is often indicative of phase separation.are raised as L&O decreased and Na.16 The T. 3. changes from a rigid to a plastic structure. the replacement of L&O by Na. The changes of the difference of the first crystallization temperature and transition temperature (T. The hypotheses suggested the consistence with the behaviour of Tg as a function of glass composition.) of these glasses are also shown in Fig.” The difference of the glass transition and dilatometric softening temperature (M. on .1 nm I f 1. . LY values from 70 to 400°C are 9.3 nm 114 587.) of these glass samples are shown in Fig. The variation of thermal expansion coefficients and 4.O lie in a region of immiscibility. 5.72 0 2 4 6 0 2 4 Nan0 twt%) 6 Na.Eflect of Na.61% to 644%.O content is to increased from 1.O increased.6 nm 1. Effect of Na.O/Na. 4. . Mazurin et aZ. The effect of Na20 addition on the thermal expansion coefficients (a) and density of these glass samples is shown in Fig.O = 1.T.18.6 X lO-‘?‘C as Na.O has a considerable concentration of continuous highviscosity phase which gradually loses the continuity between the composition of 644% and 1.54 M-656. l6 The Tg corresponding to the temperature at which the network acquires mobility.m-e 486. Fig. In general.of these glasses is around 531 f 6°C which suggests that the tetrahedra are the same mobile components of glasses. Effect of NazO content and wavelength variation the refractive index for the germanate glasses.17 Mazurin et a1. 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. except C.O content on the difference between Mg and Tg. The density of these germanate glasses is a function of composition and the maximum in Fig. 2 indicates that the glass sample containing 644% Na. 3.20 pointed out that in the Na20-Ge02 system.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.and TEfor the germanate glass samples.T.is It seems reasonable to suggest that this also occurs here and that the glasses containing >6-44% Na.83 wt% Na20 addition as shown in Fig. Mg and T.74 1.th the ratio Li. On this basis. 3.O (wt%) Fig. the Mg in Fig. It is seen that the Tg.) decreases sharply at about 4. 2.O content.61% Li20. .2 X 104/oC 10.u ro 1-78 I 1 13.76 . and T.O in glasses with the same other contents. the expansion coefficient of the glass in this system increases almost linearly with increasing Na.O addition on germanate glass 115 crystallization temperature (T. glass at 635”C. The maximum point in the Tc-T curve corresponds to the glass composition w.

Fig. which is a measure of optical dispersion. S.21 The refractive index of a glass. respectively. 8. but also for some applications.n. varies with wavelength. and n. respectively. 1500 1c 1200 800 Wavenumber (cm-l) 400 Wavenumber Fig. 2500 . M. and C. 486.O content is shown in Fig. The glass begins with a relative broad absorption in the region of 2. and transmission in the near infrared is thus restricted.9 and 7. are refractive indexes at wavelengths 587. The infrared transmittance of C2 and C. glasses is shown in Fig. C. Wang.116 M..22 The infrared cut-off is at about 6. 6. 2000 (cm-') . ITIR spectra for glass samples. The infrared transmittance 7. which may be suggested to be due to the O-H bond bending and stretching vibration. = (nd .13 nm and 656. in the near infrared and ultraviolet regions.g2nUn I 4000 3500 I I 3000 I . . For Figs 5 and 6. Hon this curve is related to the change of coordination number of germanium from six to four. This variation can be considerable and it is necessary for the application of glass in optical system to have accurate information on the variation. H.85m (C2)'1. The measured index of refraction as a function of Na20 content and wavelength for these germanate glasses is shown in Fig. The ability 57 0 I 2 t I 4 I I 6 Na20 (wt%) Fig.O addition on the variation number for the glass samples. The 67 I- 65 - Abbe number.5 pm for C. Effect of Na. the refractive index and vd of these germanate glasses are increasing as Na20 content is increased. of C2 and C5 glasses. J.27 nm. as of other materials. which are longer than that of 5. may be estimated from the refractive index by V.56 nm.0 pm for silicate glass.6. of Abbe Wavelength 2. Wang. 5. The variation of vd with Na. glass samples. V. 7. .5 100 L 3 4 (pm) 5 I I 1 0 10 . . where nd.l)/(n.9 pm. not only in the visible part of the spectrum.). . n. 30 Thickness 20 Thickness (C5)=1.

61% to 6.26. they are linked to two silicon atoms.e. only for those alkaligermanate glasses in which the density and refractive index are increasing with the addition of alkali oxide. the tetrahedra do not share corners. i. The FTIR spectra of analysed glasses have shown that the glasses have a three-dimensional. i. respectively. 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. This is true. Na.61% to 644%.23m26 The second strong region of absorption lies between 500-600 cm-‘.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.e.’ 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.O(-Na. as Na. the transition. 5 CONCLUSIONS By a progressive weight percent substitution of Na. however. 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.* FTIR spectra of these germanate glass samples have two regions of absorption as shown in Fig.. The most intense absorption band is in the 800900 cm-’ region.O)CaO-A1203-Ge02 system was prepared for infrared transmitting germanate glasses.9T23-26 4 DISCUSSION In fused silica there is a continuous random network of Si04 tetrahedra and all the oxygens are doubly bonded. but are linked through the apices. as Na20 content increased from 1. random network structure consisting of Ge04 tetrahedra as their most fundamental units. Larger cations and anions with lower field strength will move the infrared transmittance to longer wavelengths. Similarly. each of the six oxygen apices of the GeO.’ 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.6 X lO?‘C. The observed results in the FTIR spectra of analysed glasses have shown that the glasses have .27 Murthy et ~1. germanate tetrahedra.O content increased from 1.O for Li.9.e.~pointed out that when an M20 oxide is added to fused germanate.O content decreased and Na. dilatometric and first crystallization temperatures are raised as Li.e.25.03 f 4.07. i.26 Vibrational spectra of the studied germanate glasses exhibit bands which are characteristic for the networkforming. For these glass samples. and GeO.3 The bonds in spectra of germanate glasses are consistent with the similar assignment of corresponding bonds in the silicate glasses. but is also governed by the frequency of vibration of cation-anion bonds resulting in the infrared absorption cut-off. the refractive indexes are from I.44%. 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. fused germania consists of a continuous random network of Ge04 tetrahedra.). The thermal expansion coefficients from 70 to 400°C are 9. In this study. The infrared cut-off for C2 and C. the species of L&O.2 X 10-6/“C to 10. and that no non-bridging oxygen is present. however. 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. the Li.O content increased.5 pm. with the formation of singly bonded non-bridging oxygens as in the case of alkali-silicates.* Bond strengths and lengths tend to vary depending on the particular glass composition. Ge-0-Ge bond) and non-bridging (i.9.O at constant ratio of concentration of CaO.’ The high-frequency bands in the FTIR of these germanate glasses are narrower than their counterparts in silicate glasses. respectively. octahedra is shared by neighbouring tetrahedra (GeO. a continuous network of tetrahedra and octahedra exists. For these glasses. and may be related to mixed stretching-bending motions. germanate glass samples are about 6. 8. which are longer than that of 5-O pm for silicate glasses.e.9. The Abbe number for the glass samples is about 62. 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.769. two things can happen.703 to 1.3 There is no direct evidence in the present spectra that these glasses contain higher than four-fold coordination of Al cations. Al2O3.bonding) oxygens.9 and 7. act as the glass network modifier cations of lower field strength. Ge-O. the coordination number of the Ge4’ ions can remain the same (four).O and CaO.

SPIE Emerging Optical Mater. Non-Cryst. 93 (1987) 155.. GLASSENER. New York 1982. & MOWBRAY. SAKKA. SHELBY. D. 145 (1962) 797. Vol. B19 (1979) 4292. Transformation oxide glass. Phys. SNOWDEN. D. Wang. 13. E... MAZURIN. New York 1982. A. Rev. M. 10. Commun.. A. 17.. & MOWBRAY. H. M. J. Non-Cryst. J. J. Phys. 633 (1971). J. ACKNOWLEDGEMENT This work was supported by the National Science Council of the Republic of China under Contract No. Cerum. K. 28. 69 (1982) 81. The Properties of Glass and Glass-forming Melts.... J. 9. J... S. J. 119 K. Non-Cryst.. 30 (1926) 1519. Solids. MURTHY. Non-Cryst. H. 122 (1990) 1. . 3. 9th Znt. Solids. J. 27. Sci. 1. J. Mineral. Appl. L. Mineral. STREL’TSINA. MAZURIN. SHARMA.. Non-Cryst. H. LIPINSKA-KALITA. B. Solids. Chem. 112 (1989) 282. Sot. & NAKASHIMA. A. Glasses. & ROUSH. SSSR. T. & KAMITSOS. F.. Jpn. DUMBAUGH. Chemistry of Glass. MYSEN. & YESTROPIEW. Wang. 58 (1975) 306. K.. PAUL. 19. I. random network structure consisting of Ge04 tetrahedra as their most fundamental units. J. MATSON. & TOTESH.. PHILPOTTS.... J. J. J. & PASH.. Akad. Chem. W.. Glass. Izdutel’stvo Nauka Leningradshoe Odelenie.. temperature of inorganic 16. & VIRGO. 8. B. J. Chem. Sot. RAY. 30. (1990) 41. Nature (Lond. J. I. 22... K. 0. 23. T.. Leningrad 1975. 12 (1971) 82. M. 11 (1972) 199. V. Non- Cryst. A. SHARMA. 7. Cerum.. & YODER JR. 68 (1983) 1113. Dokl. S. NSCXl-0115-E-151-01 which is gratefully acknowledged. S. SIMMONS. DENNIS. IVANOV. S.. 79 (1971) 428. 4. H. LIPINSKA-KALITA. 14. NonCryst. Chemistry of Glasses. Solids. LIPINSKA-KALITA. 119 K. Chem. (1990) 310. 219 (1990) 107. 297 (1981) 80. W. Solids. KISHIOKA. K. M. Nauk.). A. p. & SCROGGIE. Glasses. L. SEIFERT. A. & LAUBENGAYER. S. & MATSON. P. Struct.. V. H... SHARMA. MORINAGA. OYAMADA. J. Yogyo-Kyokai-Shi. Vol. D. M. 67 (1982) 696. 26. D. 0. Hon a three-dimensional. V. 0. Solids. Non-Cryst. 49 (1976) 5885. J. W. Am. 6 (1965) 162. K. MAZURIN. N. Am. STREL’TSINA. G. W. Solids. D.. A. & IHARA. VOGEL. 21.. M. M. Phys. Phys. 12.. 11. H. K. S. R. V. E. F. C. K. SAKAMURA. E. J. 201 (1964) 285. 103 (1988) 154. Glasses. 100 (1992) 27. 2. YOSHIMURA. K.. A.. Am. W. S. 25. E. 10 (1969) 63. 24. J. & SUMI. J. J. D. & STREL’TSINA... Congr.. 6. REFERENCES 1. 85 (1977) 299... 2. 15. B. Chapman and Hall. 0. & YASUI. MURTHY. 5.. Solids.118 M. 20. T. E. V. FUKUNAGA. URNES. Phys. 18. V. & IP. CHYRSSKIOS. K. S. 68 (1984) 99. K. 0.. K... J. W. E. Molec. L. S. LIPINSKA-KALITA.. Solids. Chapman and Hall. NonCryst. & SHVAIKA-SHVAIKOVSKYA. Phys. Technol.. Yogyo-Kyokai-Shi..