Journal of Thermal Analysis and Calorimetry

, Volume 104, Issue 2, pp 439–450 | Cite as

The use of thermal analysis methods for authentication and conservation state determination of historical and/or cultural objects manufactured from leather

  • P. BudrugeacEmail author
  • Andrei Cucos
  • Lucreţia Miu


Leather products have been useful materials since the dawn of human history. Many leathers objects are valuable treasures due to the history they represent, and their preservation challenges museum custodians and private collectors alike. In this article, the applications of thermal analysis methods (Micro Hot Table (MHT), thermogravimetry/derivative thermogravimetry (TG/DTG), dynamic scanning calorimetry (DSC), differential thermal analysis (DTA), and dynamic mechanical analysis (DMA)) for the characterization of the recently manufactured and old leathers are presented. These methods can be used for the assessment of deterioration degree of leathers, and, therefore, the data obtained by these techniques could be useful for achievement of the suitable preservation procedures as well as the effects of conservation treatments. In addition, it was pointed out that these methods are suitable for qualitative distinction between the recently manufactured leathers and heritage items.


Thermal analysis Leathers Historical objects Damage assessment 


  1. 1.
    Forbes RJ. Studies in ancient technology, vol. V. Leiden, The Netherlands: Technology and Engineering; 1966. p. 22.Google Scholar
  2. 2.
    Guideline for the conservation of leather and parchment bookbindings, Chapter 4. National Library of the Netherlands. 1995.
  3. 3.
    Haines B. Natural ageing of leather in libraries. In: Calnan C, Haines B, editors. Leather, its composition and changes in time. Northampton: The Leather Conservation Centre; 1991. p. 66–74.Google Scholar
  4. 4.
    Calnan CN. Ageing of vegetable tanned leather in response to various climatic conditions. In: Calnan C, Haines B, editors. Leather, its composition and changes in time. Northampton: The Leather Conservation Centre; 1991. p. 44–50.Google Scholar
  5. 5.
    Florian M-LE. The mechanism of deterioration in leather. In: Kite M, Thomson R, editors. Conservation of leather and related materials, Chapter 5. Amsterdam: Elsevier; 2006.Google Scholar
  6. 6.
    Thomson R. Leathers. In: May E, Jones M, editors Conservation science—heritage materials, Chapter 5. Cambridge: RSC Publishing; 2006.Google Scholar
  7. 7.
    Stuart BH. Analytical techniques in materials conservation, Chapter 9. Chichester: John Wiley and Sons, Ltd.; 2007Google Scholar
  8. 8.
    Mackenzie RC. Nomenclature in thermal analysis. In: Kolthoff IM, Elving PJ, Murphy CB, editors. Treatise on analytical chemistry, Part 1, vol. 12, 2nd ed. New York: Wiley; 1983. pp. 1–16.Google Scholar
  9. 9.
    Mackenzie RC. IUPAC technical reports and recommendations—nomenclature for thermal analysis. Pure Appl Chem. 1985;57:1737–40.CrossRefGoogle Scholar
  10. 10.
    ICTAC Nomenclature Committee (W. Hemminger (chairman)). Recommendations for names and definitions in thermal analysis and calorimetry. ICTAC News. 1998;13(2):107–22.Google Scholar
  11. 11.
    Hemminger W, Sarge SM. Definitions, nomenclature, terms and literature. In: Gallagher PK, Brown ME, editors. Handbook of thermal analysis and calorimetry, Chapter 1, vol. 1. Amsterdam: Elsevier; 1998.Google Scholar
  12. 12.
    van Humbeech J. Simultaneous analysis. In: Gallagher PK, Brown ME, editors. Handbook of thermal analysis and calorimetry, Chapter 11, vol. 1. Amsterdam: Elsevier; 1998.Google Scholar
  13. 13.
    Menard KP. Dynamic mechanical analysis: a practical introduction, Chapter 1, 2nd ed. Washington: CRC Press; 2008.Google Scholar
  14. 14.
    Witnauer LP, Wisnewski AJ. Absolute measurement of shrinkage temperature by differential thermal analysis. J Am Leather Assoc. 1964;59:598–612.Google Scholar
  15. 15.
    Chahine C. Acid deterioration of vegetable tanned leather. In: Calcan C, Haines B, editors. Leather, its composition and changes with time. Northampton: The Leather Conservation Centre; 1991. p. 75–87.Google Scholar
  16. 16.
    Chahine C, Rottier C. Changes in thermal stability during artificial ageing with pollutants: a DSC study. In: Postprints of the ICOM interim symposium. London: ICOM; 1992. pp. 6–10.Google Scholar
  17. 17.
    Chahine C. Changes in hydrothermal stability of leather and parchment with deterioration: a DSC study. Thermochim Acta. 2000;365:101–10.CrossRefGoogle Scholar
  18. 18.
    Thomson R. Testing leathers and related materials. In: Kite M, Thomson R, editors. Conservation of leather and related materials, Chapter 6. Amsterdam: Elsevier; 2006.Google Scholar
  19. 19.
    Williams JMV. IULTCS (IUP) “Test methods”. J Soc Leather Technol Chem. 2000;84:359–62.Google Scholar
  20. 20.
    Larsen R. Experiments and observations in the study of environmental impact on historical tanned leathers. Thermochim Acta. 2000;365:85–99.CrossRefGoogle Scholar
  21. 21.
    Miu L, Vîlsan M, Plăvan V. Leather evaluation by optical microscopy methods. Leather Footwear J. 2009;9:75–86.Google Scholar
  22. 22.
    Font J, Espejo J, Cuandros S, Reyes MR, Bacardit A, Buti S. Comparison of IUP 16 and Microscopic Hot Table methods for shrinkage temperature determination. SLTC J. 2010;94:59–64.Google Scholar
  23. 23.
    Williams SL, Beyer SR, Khan S. Effect of freezing treatments on the hydrothermal stability of collagen. J Am Inst Conserv. 1995;34:107–12.CrossRefGoogle Scholar
  24. 24.
    Young GS. Microscopical hydrothermal stability measurements of skin and semi-tanned leather. ICOM Committee for Conservation Preprints, 9th Triennial Meeting, Dresden: ICOM; 1990. pp. 626–31.Google Scholar
  25. 25.
    Larsen R, Vest M, Nielsen K. Determination of hydrothermal stability (shrinkage temperature) of historical leather by the Micro Hot Table technique. J Soc Leather Technol Chem. 1993;77:151–6.Google Scholar
  26. 26.
    Williams SL. Variability in measurements resulting from microscopic analyses of collagen shrinkage temperature. Collect Forum. 1991;7:53–63.Google Scholar
  27. 27.
    Badea E, Miu L, Budrugeac P, Giurginca M, Masić A, Badea N, Della Gatta G. Study of deterioration of historical parchments by various thermal analysis techniques complemented by SEM, FTIR, UV-VIS-NIR and unilateral NMR investigations. J Therm Anal Calorim. 2008;91:17–27.CrossRefGoogle Scholar
  28. 28.
    Vest M. White tawed leather—aspects of conservation. 9th International Congress IADA, Copenhagen, Aug 1999.Google Scholar
  29. 29.
    Bernath A, Miu L, Guttmann M. Identifications, microanalyses, evaluations and diagnosis of an ethnographical leather object. 9th International Conference on NDT of Art, Jerusalem, May 2008.Google Scholar
  30. 30.
    Budrugeac P, Miu L. The suitability of DSC method for damage assessment and certification of historical leathers and parchments. J Cult Herit. 2008;9:146–53.CrossRefGoogle Scholar
  31. 31.
    Budrugeac P, Miu L. Effect of accelerated thermal ageing on the thermal behaviour of the recently made parchments. J Therm Anal Calorim. 2008;94:335–42.CrossRefGoogle Scholar
  32. 32.
    Budrugeac P, Miu L, Soukova M. The damage in the patrimonial books from Romanian libraries. Thermal analysis methods and scanning electron microscopy. J Therm Anal Calorim. 2007;88:693–9.CrossRefGoogle Scholar
  33. 33.
    Plăvan V, Giurginca M, Budrugeac P, Vîlsan M, Miu L. Evaluation of zje phzsico-chemical characteristics of leather samples of some historical objects from Kiev. Rev Chim (Buchar). 2010;61:627–31.Google Scholar
  34. 34.
    Budrugeac P. TG/DTG, DTA and DSC analyses of the patrimonial leathers from the tomb of Hagi Gherai Khan. In: Gavriliuk NA, Ibraghimova AM, editors. The tomb of Hagi Gherai Khan (in Russian). Kiev-Zaporojie, 2010. pp. 111–117.Google Scholar
  35. 35.
    Okamoto Y, Saeki K. Phase transition of collagen and gelatin. Kolloid-Zeitshrift und Zeitshrift fűr Polymere. 1964;Band 194-Heft 2:124.Google Scholar
  36. 36.
    Nguyen AL, Vu BT, Wilkes GL. The dynamic mechanical, dielectric, melting behaviour of reconstructed collagen. Biopolymers. 1974;13:1023–37.CrossRefGoogle Scholar
  37. 37.
    Samoillan V, Dandrirand-Lods J, Lamure A, Maurel E, Lacabanne C, Gerosa G, Venturini A, Casarotto D, Gherardini L, Spina M. Thermal analysis characterization of aortic tissues for cardiac valve bioprostheses. J Biomed Mater Res. 1999;46:531–8.CrossRefGoogle Scholar
  38. 38.
    Pietrucha K. Changes in denaturation and rheological properties of collagen-hyaluronic acid scaffolds as a result of temperature dependencies. Int J Biol Macromol. 2005;36:299–304.CrossRefGoogle Scholar
  39. 39.
    Popescu C, Budrugeac P, Wortmann FJ, Miu L, Demco D, Baias M. Assessment of collagen-based materials that are supports of cultural and historical objects. Polym Degrad Stab. 2008;93:976–82.CrossRefGoogle Scholar
  40. 40.
    Budrugeac P, Miu L, Bocu V, Wortmann FJ, Popescu C. Thermal degradation of collagen-based materials that are supports of cultural and historical objects. J Therm Anal Calorim. 2003;72:1057–65.CrossRefGoogle Scholar
  41. 41.
    Popescu C, Budrugeac P, Miu L, Idiţoiu C, Wortmann FJ. Thermal analysis of patrimonial leather objects. 30th Aachen Textile Conference, Aachen, Germany, 2003.Google Scholar
  42. 42.
    Budrugeac P, Miu L, Popescu C, Wortmann FJ. Identification of collagen-based materials that are supports of cultural and historical objects. J Therm Anal Calorim. 2004;74:975–85.CrossRefGoogle Scholar
  43. 43.
    Lim JJ, Shannon MH. Evaluation of kinetic parameters of thermal decomposition of native collagen by thermogravimetric analysis. Biopolymers. 1974;13:1791–807.CrossRefGoogle Scholar
  44. 44.
    de Simone G, Naviglio B, Tomaselli M, Bianchi L, Sannino D, Chiambelli P. Study of tanning mechanism of leathers utilizing natural tannins. XXIII IULTCS Congress, Friedrichshafen, 1995, Paper 21.Google Scholar
  45. 45.
    Kaminska A, Siokowska A. The effect of UV radiation on the thermal parameters of collagen degradation. Polym Degrad Stab. 1996;51:15–8.CrossRefGoogle Scholar
  46. 46.
    Odlyha M, Cohen NS, Foster GM, Campana R. Thermophysical and thermochemical analysis of microsamples. In: Larsen R, editors. Microanalysis of parchments, Chapter II. Archetype London Publication; 2002.Google Scholar
  47. 47.
    Lozano LF, Pena-Rico MA, Herein Ocotlan-Flores J, Gomez-Cortes A, Velazquez R, Belio IA, Bucio L. Thermal analysis study of human bone. J Mater Sci. 2003;38:4777–82.CrossRefGoogle Scholar
  48. 48.
    Budrugeac P, Miu L. The effect of accelerated thermal ageing on the thermal behaviour of the recently made parchments. J Therm Anal Calorim. 2008;94:335–42.CrossRefGoogle Scholar
  49. 49.
    Vasile C. Degradation and decomposition. In: Vasile C, editor. Handbook of polyolefins, Chapter 17. New York: Dekker; 2000.Google Scholar
  50. 50.
    Cohen NA, Odlyha M, Foster G. Measurement of shrinkage behaviour in leather and parchment by dynamic mechanical thermal analysis. Thermochim Acta. 2000;365:111–7.CrossRefGoogle Scholar
  51. 51.
    Odlyha M, Foster GM, Cohen NS, Larsen R. Characterisation of leather samples by non-invasive dielectric and thermomechanical techniques. J Therm Anal Calorim. 2000;59:587–600.CrossRefGoogle Scholar
  52. 52.
    Jeyapalina S, Attenburrow GE, Covington AD. Investigation of leather drying by dynamic mechanical thermal analysis (DMTA). J Soc Leather Technol Chem. 2007;91:102–7.Google Scholar
  53. 53.
    Jeyapalina S, Attenburrow GE, Covington AD. Dynamic Mechanical Thermal Analysis (DMTA) of leather, Part 1: effect of tanning agent on the glass transition temperature of collagen. J Soc Leather Technol Chem. 2007;91:236–242.Google Scholar
  54. 54.
    Cucos A, Budrugeac P. The suitability of DMA method for the characterization of recent and historical parchments and leathers. Int J Conserv Sci. 2010;1:13–8.Google Scholar
  55. 55.
    Cucos A, Budrugeac P, Miu L, Mitrea S, Sbarcea G. Dynamic mechanical analysis (DMA) of new and historical parchments and leathers. Correlations with DSC and XRD. Thermochim Acta. in press.Google Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2011

Authors and Affiliations

  1. 1.National Institute for Research and Development in Electrical Engineering ICPE-CABucharestRomania
  2. 2.National Research and Development Institute for Textile and Leather—Division Leather and Footwear Research Institute031215Romania

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