Methodology for DSC calibration in high heating rates

Braga, Carlos Isidoro; Rezende, Mirabel Cerqueira; Costa, Michelle Leali

doi:10.5028/jatm.2011.03021911

Abstract

Despite the large use of differential scanning calorimetry (DSC) technique in advanced polymer materials characterization, the new methodology called DSC in high heating rates was developed. The heating rate during conventional DSC experiments varying from 10 to 20ºC.min^-1, sample mass from 10 to 15mg and standard aluminum sample pan weighting, approximately, 27mg. In order to contribute to a better comprehension of DSC behavior in different heating rates, this work correlates as high heating rate influences to the thermal events in DSC experiments. Samples of metallic standard (In, Pb, Sn and Zn) with masses varying from 0.570mg to 20.9mg were analyzed in multiples sample heating rate from 4 to 324ºC. min^-1. In order to make properly all those experiments, a precise and careful temperature and enthalpy calibrations were performed and deeply discussed. Thus, this work shows a DSC methodology able to generate good and reliable results on experiments under any researcher choice heating rates to characterize the advanced materials used, for example, for aerospace industry. Also it helps the DSC users to find in their available instruments, already installed, a better and more accurate DSC test results, improving in just one shot the analysis sensitivity and resolution. Polypropylene melting and enthalpy thermal events are also studied using both the conventional DSC method and high heating rate method.

Keywords:
DSC; High heating rate; Calibration; Thermal analysis; Polymers

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REFERENCES

ASTM D3418-08, Association Standards Testing Materials, 2008, ASTM D3418-08: "Test method for transition temperatures of polymers by differential scanning calorimetry", Philadelphia, USA.
ASTM E793, Association Standards Testing Materials, 2006, ASTM E793: "Test method for enthalpies of fusion and crystallization by differential scanning calorimetry", Philadelphia, USA.
ASTM E794, Association Standards Testing Materials, 2006, ASTM E794: "Test method for melting and crystallization temperatures by thermal analysis", Philadelphia, USA.
ASTM E928, Association Standards Testing Materials, 2008, ASTM E928: "Test method for purity by differential scanning calorimetry", Philadelphia, USA.
ASTM E967, Association Standards Testing Materials, 2008, ASTM E967: "Standard practice for temperature calibration of differential scanning calorimetry and differential thermal analyzers" ,Philadelphia, USA.
ASTM E968, Association Standards Testing Materials, 2008, ASTM E968: "Standard practice for heat flow calibration of differential scanning calorimeters" Philadelphia, USA.
Braga, C. I., 2009, "Desenvolvimento de metodologia para análises de DSC em altas taxas de transferência de calor" (in Portuguese), Master Thesis, Instituto Tecnológico de Aeronáutica, S.J.Campos, S.Paulo, Brazil.
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Chagas, A. P., 1999, "Termodinâmica Química", Editora da Unicamp, Campinas, São Paulo, Brazil.
Gill, P. S.; Sauerbrunn, S. R. & Reading, M., 1993, Journal of Thermal Analysis and Calorimetry, Vol. 40, pp. 931-939.
Gramaglia, D., Conway, B.R., Kett, V.L., Malcolm, R. K., Batchelor, H. K. 2005, "International Journal of Pharmaceutics", Vol. 301, pp. 1-5 .
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Ionashiro, M.; Giolito, E. I.,1980, "Nomenclatura, Padrões e Apresentação dos Resultados em Análise Térmica", Parte II. Cerâmica, Vol. 34, pp. 225-230.
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Mathot, V. B. F., 1994, "Calorimetry and Thermal Analysis of Polymers", Hanser Publishers, New York.
Nascimento, M. L. F., 2000, "Condutividade elétrica de vidros de boratos, silicatos e sílico-sulfatos de íons alcalinos" (in Portuguese), Master Thesis, Universidade de São Paulo, Physics Institute, São Paulo, Brazil.
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Wendlandt, W. W., 1986, "Thermal Analysis", Wiley, edition3, New York, USA.
Wunderlich, B., 1990, "Thermal Analysis", Academic Press Inc., Boston, USA.

Publication Dates

Publication in this collection
May-Aug 2011

History

Received
16 May 2011
Accepted
04 July 2011

This is an Open Access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

[1] ASTM D3418-08, Association Standards Testing Materials, 2008, ASTM D3418-08: "Test method for transition temperatures of polymers by differential scanning calorimetry", Philadelphia, USA.

[2] ASTM E793, Association Standards Testing Materials, 2006, ASTM E793: "Test method for enthalpies of fusion and crystallization by differential scanning calorimetry", Philadelphia, USA.

[3] ASTM E794, Association Standards Testing Materials, 2006, ASTM E794: "Test method for melting and crystallization temperatures by thermal analysis", Philadelphia, USA.

[4] ASTM E928, Association Standards Testing Materials, 2008, ASTM E928: "Test method for purity by differential scanning calorimetry", Philadelphia, USA.

[5] ASTM E967, Association Standards Testing Materials, 2008, ASTM E967: "Standard practice for temperature calibration of differential scanning calorimetry and differential thermal analyzers" ,Philadelphia, USA.

[6] ASTM E968, Association Standards Testing Materials, 2008, ASTM E968: "Standard practice for heat flow calibration of differential scanning calorimeters" Philadelphia, USA.

[7] Braga, C. I., 2009, "Desenvolvimento de metodologia para análises de DSC em altas taxas de transferência de calor" (in Portuguese), Master Thesis, Instituto Tecnológico de Aeronáutica, S.J.Campos, S.Paulo, Brazil.

[8] Canevarolo Jr, S. V., 2002, "Ciência dos Polímeros", Artliber Editora, São Paulo, Brazil.

[9] Canevarolo Jr, S. V. et al., 2004, "Técnicas de Caracterização de polímeros", Artliber Editora, São Paulo, Brazil, pp.209-285.

[10] Chagas, A. P., 1999, "Termodinâmica Química", Editora da Unicamp, Campinas, São Paulo, Brazil.

[11] Gill, P. S.; Sauerbrunn, S. R. & Reading, M., 1993, Journal of Thermal Analysis and Calorimetry, Vol. 40, pp. 931-939.

[12] Gramaglia, D., Conway, B.R., Kett, V.L., Malcolm, R. K., Batchelor, H. K. 2005, "International Journal of Pharmaceutics", Vol. 301, pp. 1-5 .

[13] Halliday, D., Resnick, R., Walker, J., 1992, "Fundamentos de Física Gravitação, Ondas e Termodinâmica" (in Portuguese), Vol. 2, São Paulo, Brazil, LCT.

[14] Hurtta, M. Pitkänen, I., 2004, "Thermochimica Acta", Vol. 419, pp. 19-29.

[15] Illers, K. H., 1974, "DSC calibration during cooling. A survey of possible compounds", European Polymer Journal, Vol. 10, pp. 911-916.

[16] Ionashiro, M.; Giolito, E. I.,1980, "Nomenclatura, Padrões e Apresentação dos Resultados em Análise Térmica", Parte II. Cerâmica, Vol. 34, pp. 225-230.

[17] Kasap, S.O.,1997, "Principles of Electrical Engineering Materials and Devices", New York, USA, Irwin Professional Publishing.

[18] McGregor, C., Saunders, M. H., Buckton, G., Saklatvala, R. D., 2004, "Thermochimica Acta", Vol. 417, pp. 231-237.

[19] Mothé, C. G., Azevedo, A. D., 2002, "Análise térmica de materiais", (in Portuguese), iEditora, Rio de Janeiro, Brazil.

[20] Mathot, V. B. F., 1994, "Calorimetry and Thermal Analysis of Polymers", Hanser Publishers, New York.

[21] Nascimento, M. L. F., 2000, "Condutividade elétrica de vidros de boratos, silicatos e sílico-sulfatos de íons alcalinos" (in Portuguese), Master Thesis, Universidade de São Paulo, Physics Institute, São Paulo, Brazil.

[22] Neuenfeld, S., Schick, C., 2006, "Verifying the symmetry of differential scanning calorimeters concerning heating and cooling using liquid crystal secondary temperature standards". Thermochimica Acta, Vol. 446, pp. 55-65.

[23] Pijpers, F.J. et al., 2000, "Metastability in polymer systems studied under extreme conditions: high pressure, scan-iso T-t ramps and high scanning rates", Proceedings NATAS (North American Thermal Analysis Society) 28th Conference, October 4-6,Orlando, USA.

[24] Pijpers, F.J. et al., 2002, "High-Speed calorimetry for the study of kinetics of (de)vitrification; crystallization and melting of macromolecules", Macromolecules, Vol. 35, pp. 3601-3613.

[25] Pijpers, F.J. et al., 2004, "Metastability In Polymer Systems Studied At Extreme Conditions,Including Low to Very High Scanning Rates", Proceedings NATAS (North American Thermal Analysis Society) 30th Conference.

[26] Poel, G. V. & Mathot, V. B. F., 2006, Thermochimica Acta, Vol. 446, pp. 41-54.

[27] Poel, G. V., Mathot, V. B. F., 2007, Thermochimica Acta, Vol. 461, pp. 107-21.

[28] Santos, W. N., 2005, "Polímeros: Ciência e Tecnologia",Vol. 15, No. 4, pp. 289-295.

[29] Saunders, M., Podluii, K., Shergill, S., Buckton, G., Royall, P., 2004, "International Journal of Pharmaceutics", Vol. 274, pp. 35-40.

[30] Turi, E., 1981, "Thermal Characterization of Polymer Materials", Editor Academic Press Inc, Boston, USA.

[31] Vasconcelos, G. C., Mazur, R.L; Botelho, E.C, Rezende, M.C, Costa, M.L. 2010, "J. Aerosp.Technol. Manag.", Vol. 2, No. 2, pp. 155-162.

[32] Wellen, R., Rabello, M., 2005, "Journal of Materials Science", Vol. 40, No. 23, pp. 6099-6102.

[33] Wendlandt, W. W., 1986, "Thermal Analysis", Wiley, edition3, New York, USA.

[34] Wunderlich, B., 1990, "Thermal Analysis", Academic Press Inc., Boston, USA.

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