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
18 59.5 mm thick.3 /&fared
and Fourier transform spectra measurement
850 H M 0+3 Crystallization tmature Softening temperature Tcansition tenqerat
The glass samples (about 2-O mm thick) for optical absorption measurement.83 3. 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. YE. were polished for parallel faces. 2. Fourier transform infrared spectra were measured in the 400-1200 cm-’ region using a Nicolet 800 system.
. In Fig. Wang.”
The typical DTA curves obtained from the asquenched glasses are shown in Fig.44
2.18 59.61 0
CaO 12. KBr pelletized disks were fabricated containing 2 mg of the glass sample and 600 mg KBr. The glass transition temperature (7”). C.
M.97 12. Specimen temperature was measured by an X-type thermocouple in contact with the specimen surface.56 nm. dilatometric softening temperature (M.114 Table 1.61 3. MB and T.5 mm wide.O. and 3. Thermal expansion coefficients were measured in a horizontal vitreous silica dilatometer (SETARAM High Temperature Dilatometer).27 nm.18 59. 1. DTA curves of the
germanate glasses heating at a
rate of 10Wmin.
C3 C.51 21.2 Thermal property measurement
Differential thermal analysis (DTA) on a 200 mg powder sample (67. 1.97 12.48 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.22 1. The infrared spectra were recorded with a Hitachi Infrared Spectrometer Model 29030. 59. which corresponds to the glass transition point. varies from 525 to 635°C for samples with different compositions.51 21. J.18 59. = glass samples which perpendicular faces of Na.83 6.
2.44 4. C5
0 1.O C. H.97 12.51
GeO. The first endotherm. 656. with a resolution of 2 cm-‘. as the reference material. 21. These glass samples showed the two stage crystallization temperatures. The glass transition and dilatometric softening temperatures were obtained from the thermal expansion curves by the usual techniques.51 21. Wang.4 Refractive index measurement The refractive index of these were polished for adjacent was measured as a function wavelengths nd = 587. for the germanate glass samples. Hon 3 RESULTS
L&O 6.) and the first
Fig.22 4.51 21.13 nm and
Fig. and also two melting endotherm temperatures. Typical thermal expansion specimens were 25 mm long.97 12.97
AI. 2.O content at nf = 486. M. Effect of Nap addition on the Tg. Chemical composition of g&SeJS
Oxides Samples Na.
” The difference of the glass transition and dilatometric softening temperature (M.20 pointed out that in the Na20-Ge02 system.O content.) decreases sharply at about 4.O lie in a region of immiscibility.O addition on germanate glass
crystallization temperature (T.6 nm 1.
4 Nan0 twt%)
Na. Effect of NazO content and wavelength variation the refractive index for the germanate glasses.O/Na. 3. The density of these germanate glasses is a function of composition and the maximum in
Fig.83 wt% Na20 addition as shown in Fig.61% Li20.and TEfor the germanate glass samples.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. the expansion coefficient of the glass in this system increases almost linearly with increasing Na. 3. Effect of Na.18.O
Fig.Eflect of Na.O in glasses with the same other contents. and T.54
M-656. 3. In general. 4. The variation of thermal expansion coefficients and 4. 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.
. On this basis.O has a considerable concentration of continuous highviscosity phase which gradually loses the continuity between the composition of 644% and 1. Mg and T.are raised as L&O decreased and Na.u
13.T. The hypotheses suggested the consistence with the behaviour of Tg as a function of glass composition.1 nm
1. except C. the replacement of L&O by Na.17 Mazurin et a1.16 The T.61% to 644%.) of these glasses are also shown in Fig.76 .) of these glass samples are shown in Fig. The maximum point in the Tc-T curve corresponds to the glass composition w.O content on the difference between Mg and Tg.O content is to increased from 1. the Mg in Fig. This type of behaviour found in other glass-forming systems is often indicative of phase separation.is It seems reasonable to suggest that this also occurs here and that the glasses containing >6-44% Na. 5. The changes of the difference of the first crystallization temperature and transition temperature (T.3 nm 114 587.of these glasses is around 531 f 6°C which suggests that the tetrahedra are the same mobile components of glasses. density for the glass samples. 2. . changes from a rigid to a plastic structure.74
1. It is seen that the Tg.6 X lO-‘?‘C as Na. . with a rather abrupt
1 1190 6
change as the continuity of that phase disappears. LY values from 70 to 400°C are 9.O increased.O = 1.T.th the ratio Li.
. l6 The Tg corresponding to the temperature at which the network acquires mobility.2 X 104/oC 10.m-e 486. glass at 635”C. Mazurin et aZ.
0 pm for silicate glass. which are longer than that of 5.21 The refractive index of a glass. Wang. n.. 6. 7. the refractive index and vd of these germanate glasses are increasing as Na20 content is increased. The measured index of refraction as a function of Na20 content and wavelength for these germanate glasses is shown in Fig. H. = (nd .9 and 7. C. The glass begins with a relative broad absorption in the region of 2.O addition on the variation number for the glass samples. 5. which is a measure of optical dispersion. ITIR spectra for glass samples. glasses is shown in Fig. which may be suggested to be due to the O-H bond bending and stretching vibration.6. The variation of vd with Na.g2nUn
Abbe number.13 nm and 656. as of other materials.). where nd. The infrared transmittance 7.
. The infrared transmittance of C2 and C.85m (C2)'1.
. not only in the visible part of the spectrum. are refractive indexes at wavelengths 587.
of C2 and C5 glasses. Effect of Na. and n. V. Hon
this curve is related to the change of coordination number of germanium from six to four.
800 Wavenumber (cm-l)
Fig. This variation can be considerable and it is necessary for the application of glass in optical system to have accurate information on the variation.
30 Thickness 20 Thickness (C5)=1.56 nm. S.O content is shown in Fig. respectively.
.9 pm. glass samples. in the near infrared and ultraviolet regions.116
Fig. For Figs 5 and 6.22 The infrared cut-off is at about 6. but also for some applications. of Abbe
Wavelength 2. The ability
Na20 (wt%) Fig.5 100 L 3 4
. Wang. 8. M. respectively. and C.l)/(n. and transmission in the near infrared is thus restricted.27 nm. . may be estimated from the refractive index by V. J.5 pm for C. varies with wavelength. 486.
The infrared cut-off for C2 and C.769.61% to 644%.. the tetrahedra do not share corners. 5 CONCLUSIONS By a progressive weight percent substitution of Na. This is true.’ 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.61% to 6.Efect
of NazO addition on germanate glass
of a material to exhibit a long wavelength transmittance is dependent not only on the material possessing a large band gap. and that no non-bridging oxygen is present.O at constant ratio of concentration of CaO. only for those alkaligermanate glasses in which the density and refractive index are increasing with the addition of alkali oxide. random network structure consisting of Ge04 tetrahedra as their most fundamental units.). germanate glass samples are about 6.703 to 1. Larger cations and anions with lower field strength will move the infrared transmittance to longer wavelengths. i. Al2O3.26 Vibrational spectra of the studied germanate glasses exhibit bands which are characteristic for the networkforming.26. germanate tetrahedra.2 X 10-6/“C to 10.e. i.O content decreased and Na.9.~pointed out that when an M20 oxide is added to fused germanate. the coordination number of the Ge4’ ions can remain the same (four). they are linked to two silicon atoms. The observed results in the FTIR spectra of analysed glasses have shown that the glasses have
. 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.03 f 4. Na. In this study.3 The bonds in spectra of germanate glasses are consistent with the similar assignment of corresponding bonds in the silicate glasses.6 X lO?‘C. 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. but is also governed by the frequency of vibration of cation-anion bonds resulting in the infrared absorption cut-off. however. respectively.bonding) oxygens. The Abbe number for the glass samples is about 62. Similarly.’ 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. the refractive indexes are from I. and GeO.e.O and CaO. two things can happen.O)CaO-A1203-Ge02 system was prepared for infrared transmitting germanate glasses.O content increased.9 and 7. dilatometric and first crystallization temperatures are raised as Li. the Li.25. For these glass samples. as Na.e. a continuous network of tetrahedra and octahedra exists. 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.27 Murthy et ~1. the transition. as Na20 content increased from 1.07. The FTIR spectra of analysed glasses have shown that the glasses have a three-dimensional.e. i. but are linked through the apices. Ge-O. and may be related to mixed stretching-bending motions. the species of L&O.O for Li. 8.e.3 There is no direct evidence in the present spectra that these glasses contain higher than four-fold coordination of Al cations. with the formation of singly bonded non-bridging oxygens as in the case of alkali-silicates. 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.* 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.’ The high-frequency bands in the FTIR of these germanate glasses are narrower than their counterparts in silicate glasses.O content increased from 1.5 pm.23m26 The second strong region of absorption lies between 500-600 cm-‘. each of the six oxygen apices of the GeO.9. respectively.* Bond strengths and lengths tend to vary depending on the particular glass composition. Ge-0-Ge bond) and non-bridging (i. fused germania consists of a continuous random network of Ge04 tetrahedra.9. The most intense absorption band is in the 800900 cm-’ region. 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.9T23-26 4 DISCUSSION In fused silica there is a continuous random network of Si04 tetrahedra and all the oxygens are doubly bonded. which are longer than that of 5-O pm for silicate glasses. octahedra is shared by neighbouring tetrahedra (GeO. For these glasses. The thermal expansion coefficients from 70 to 400°C are 9.44%.
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