Hostname: page-component-586b7cd67f-tf8b9 Total loading time: 0 Render date: 2024-11-23T12:24:04.187Z Has data issue: false hasContentIssue false
  • English
  • Français

Glass transformation in vitreous As2Se3 studied by conventional and temperature-modulated differential scanning calorimetry

Published online by Cambridge University Press:  31 January 2011

S. O. Kasap  and
D. Tonchev
S. O. Kasap*
Affiliation:
Materials Research Laboratories, Department of Electrical Engineering, University of Saskatchewan, Saskatoon, S7N 5A9 Canada
D. Tonchev*
Affiliation:
Materials Research Laboratories, Department of Electrical Engineering, University of Saskatchewan, Saskatoon, S7N 5A9 Canada
*
a)[email protected]
b)[email protected]
Get access

Abstract

We have studied the glass transition behavior of vitreous As2Se3 by carrying out temperature-modulated differential scanning calorimetry (TMDSC) and conventional differential scanning calorimetry (DSC) experiments to measure the glass transition temperature Tg. In TMDSC experiments we have examined the reversing heat flow (RHF), that is the complex heat capacity CP in the glass transition region as the glass is cooled from a temperature above the glass transition temperature (from a liquidlike state) and also as the glass is heated starting from room temperature (from a solidlike state). The RHF, or CP versus T, in TMDSC changes sigmoidally through the glass transition region without evincing an enthalpic peak which is one of its distinct advantages for studying the glass transformations. The Tg measurements by TMDSC were unaffected by the amplitude of the temperature modulation. We have determined apparent activation energies by using Tg-shift methods based on the Tg-shift with the frequency (ω) of temperature modulation in the TMDSC mode and Tg-shift with heating and cooling rates, r and q, respectively, in the DSC mode. It is shown that the apparent activation energies ∆h* obtained from ln ω versus 1/Tg and ln q versus 1/Tg plots are not the same, but nonetheless, they are approximately the same as the apparent activation energy ∆hn of the viscosity over the same temperature range where the empirical Vogel expression of Henderson and Ast, η = 12.9 exp[2940/(T - 335)], was used for the viscosity. The latter observation is in agreement with the assertion that the structural relaxation time Ʈ is proportional to the viscosity h. The apparent activation energy ∆hr obtained from the ln r versus 1/Tg plot during heating DSC scans is lower than ∆h* observed during cooling scans. The results are discussed in terms of a phenomenological Narayanaswamy type relaxation time. It was observed that Tg obtained from TMDSC cooling experiments did not depend on the underlying cooling rate for q ≤ 1 °C min-1; and for temperature amplitudes 0.5–5 °C. The transition due to the temperature modulation was well separated from the transition due to the underlying cooling rate. Further, the apparent activation energies obtained from ln ω versus 1/Tg during cooling and heating scans for q and r ≤ 1 °C min−1 are approximately the same as expected from Hutchison's calculations using a single relaxation time model of TMDSC experiments.

Type
Articles
Information
Journal of Materials Research , Volume 16 , Issue 8 , August 2001 , pp. 2399 - 2407
Copyright
Copyright © Materials Research Society 2001

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

REFERENCES

1Wunderlich, B., Thermal Analysis (Academic Press, Boston, MA, 1990) and references therein.CrossRefGoogle Scholar
2Sauerbrunn, S., Crowe, B., and Reading, M., Am. Lab. August, 44, (1992).Google Scholar
3Reading, M., Elliott, D., and Hill, V.L., J. Therm. Anal. 40, 949 (1993).CrossRefGoogle Scholar
4Reading, M., TRIP 1, 248 (1993).Google Scholar
5Reading, M., Luget, A., and Wilson, R., Thermochim. Acta 238, 295 (1994).CrossRefGoogle Scholar
6Sauerbrunn, S. and Thomas, L., Am. Lab. January, 19 (1995).Google Scholar
7Thomas, L., NATAS Notes (North American Thermal Analysis Society, Sacramento, CA, 1995), Vol. 26, p. 48.Google Scholar
8Jones, K.J., Kinshott, I., Reading, M., Lacey, A.A., Nikopoulos, C., and Pollosk, H.M., Thermochim. Acta 304/305, 187 (1997).CrossRefGoogle Scholar
9Hassel, B., NATAS Notes (North American Thermal Analysis Society, Sacramento, CA, 1995), Vol. 26, p. 54.Google Scholar
10Wunderlich, B., Jin, Y., and Boller, A., Thermochim. Acta 238, 277 (1994).Google Scholar
11Boller, A., Schick, C., and Wunderlich, B., Thermochim. Acta 261, 97 (1995).CrossRefGoogle Scholar
12Wagner, T. and Kasap, S.O., Philos. Mag. B 74, 667 (1996).CrossRefGoogle Scholar
13Kasap, S.O., Wagner, T., and Maeda, K., Jpn. J. Appl. Phys. 35, 1116 (1996).CrossRefGoogle Scholar
14Wagner, T. and Kasap, S.O., J. Mater. Res. 12, 1892 (1997).CrossRefGoogle Scholar
15Feng, X., Bresser, W.J., and Boolchand, P., Phys. Rev. Lett. 78, 4422 (1997).CrossRefGoogle Scholar
16Boolchand, P., Feng, X., Bresser, W.J., Zhang, M., and Goodman, B., J. Non-Cryst. Solids 222, 137 (1997).CrossRefGoogle Scholar
17Wagner, T., Kasap, S.O., and Petkov, K., J. Mater. Sci. 32, 5889 (1997).CrossRefGoogle Scholar
18Schawe, J.E.K., Thermochim. Acta 260, 1 (1996).CrossRefGoogle Scholar
19Hutchinson, J.M. and Montserrat, S., Thermochim. Acta 304–305, 257 (1997).CrossRefGoogle Scholar
20Hutchinson, J.M. and Montserrat, S., J. Therm. Anal. 47, 103 (1996).CrossRefGoogle Scholar
21Hutchinson, J.M., Thermochim. Acta 324, 165 (1998).CrossRefGoogle Scholar
22Schick, C., Merzlyakov, M., and Hensel, A., J. Chem. Phys. 111, 2696 (1999).CrossRefGoogle Scholar
23Henderson, D.W. and Ast, D.G., J. Non-Cryst. Solids 64, 43 (1984).CrossRefGoogle Scholar
24Doremus, R.H., Glass Science, 2nd ed. (Wiley Interscience, New York, 1994).Google Scholar
25Kasap, S.O. and Yannacopoulos, S.Y., Phys. Chem. Glasses 31, 71 (1990).Google Scholar
26Webber, P.J. and Savage, J.A., J. Mater. Sci. 16, 763–766 (1981).CrossRefGoogle Scholar
27Moynihan, C.T., Easteal, A.J., DeBolt, M.A., and Tucker, J., J. Am. Ceram. Soc. 59, 12 (1976).CrossRefGoogle Scholar
28DeBolt, M.A., Easteal, A.J., Macedo, P.B., Moynihan, C.T., J. Am. Ceram. Soc. 59, 16 (1976).CrossRefGoogle Scholar
29Mazurin, O.V., J. Non-Cryst. Solids 25, 131 (1977).CrossRefGoogle Scholar
30Moynihan, C.T., Easteal, A.J., and DeBolt, M.A., J. Am. Ceram. Soc. 54, 491 (1971).CrossRefGoogle Scholar
31Sasabe, H. and Moynihan, C.T., J. Polym. Sci. 16, 1447 (1978).Google Scholar
32Avramov, I., Grantscharova, E., and Gutzow, I., J. Non-Cryst. Solids 91, 386 (1987) and references therein.CrossRefGoogle Scholar
33Yannacopoulos, S. and Kasap, S.O., J. Mater. Res. 5, 789 (1990).CrossRefGoogle Scholar
34Avramov, I., Avramova, N., and Fakirov, S., J. Polym. Sci. 27, 2419 (1989).CrossRefGoogle Scholar
35Avramov, I., Gnappi, G., and Montenero, A., Phys. Chem. Glasses 33, 140 (1992).Google Scholar
36Moynihan, C.T., Macedo, P.B., Motrose, C.J., Gupta, P.K., DeBolt, M.A., Dill, J.F., Dom, B.E., Drake, P.W., Easteal, A.J., Elterman, P.B., Moeller, R.P., Sasabe, H., and Wilder, J.A., Ann. N.Y. Acad. Sci. 279, 15–35 (1976).CrossRefGoogle Scholar