Journal of Analytical Chemistry

, Volume 55, Issue 5, pp 405–416 | Cite as

Chemical derivatization techniques in the determination of functional groups by X-ray photoelectron spectroscopy

  • V. I. Povstugar
  • S. S. Mikhailova
  • A. A. Shakov


The fundamentals of chemical derivatization techniques as applied to the quantitative analysis of ultrathin surface layers of various organic compounds via functional groups were considered. Using X-ray photoelectron spectroscopy as an example of the most informative and almost nondestructive technique for characterization of thin layers, the general requirements imposed on the selective chemical reactions and possible artifacts were discussed. The validity of the technique was illustrated by the examples of analyses of surface layers of organic polymers with known concentrations of surface functional groups, plasma-modified polymers, and carbon fibers. It was noted that selective chemical reactions are successfully used in other techniques for studying material surfaces. The surface analysis of organic materials via functional groups can be performed with a simultaneous increase in the sensitivity of the corresponding spectral technique.


Carbon Fiber Chemical Derivatization Hydroxypropyl Methacrylate TFAA Bromination Reaction 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    Adamson, A.,The Physical Chemistry of Surfaces, New York: Wiley, 1976. Translated under the titleFizicheskaya khimiya poverkhnosti, Moscow: Mir, 1979, p. 568.Google Scholar
  2. 2.
    Nefedov, V.I. and Cherepin, V.T.,Fizicheskie metody issledovaniya poverkhnosti tverdykh tel (Physical Methods of Studying Solid Surfaces), Moscow: Nauka, 1983, p. 296.Google Scholar
  3. 3.
    Electron and Ion Spectroscopy of Solids, Fiermans, L., Vennik, J., and Dekeyser, W., Eds., New York: Plenum, 1978. Translated under the titleElektronnaya i ionnaya spektroskopiya tverdykh tel, Moscow: Mir, 1981, p. 467.Google Scholar
  4. 4.
    Methods of Surface Analysis, Czanderna, A., Ed., Amsterdam: Elsevier, 1975. Translated under the titleMetody analiza poverkhnosti, Moscow: Mir, 1979, p. 582.Google Scholar
  5. 5.
    Practical Surface Analysis by Auger and X-ray Photoelectron Spectroscopy, Briggs, D. and Seah, M.P., Eds., New York: Wiley, 1983, p. 533.Google Scholar
  6. 6.
    Nuzzo, R.G. and Smolinsky, G.,Macromolecules, 1984, vol. 17, p. 1013.CrossRefGoogle Scholar
  7. 7.
    Sirota, A.G.,Modifikatsiya struktury i svoistva poliolefinov (Structure Modification and Properties of Polyolephines), Leningrad: Khimiya, 1984, p. 152.Google Scholar
  8. 8.
    Kestel’man, V.N.,Fizicheskie metody modifikatsii polimernykh materialov (Physical Methods of Modification of Polymer Materials), Moscow: Khimiya, 1980, p. 224.Google Scholar
  9. 9.
    Briggs, D.,Surface Analysis and Pretreatment of Plastics and Metals, Brewis, D.M., Ed., London, 1982.Google Scholar
  10. 10.
    Povstugar, V.I., Kodolov, V.I., and Mikhailova, S.S.,Stroenie i svoistva poverkhnosti polimernykh materialov (Structure and Properties of the Surface of Polymer Materials), Moscow: Khimiya, 1988, p. 192.Google Scholar
  11. 11.
    Briggs, D.,Polymer, 1984, vol. 25, no. 10, p. 1379.CrossRefGoogle Scholar
  12. 12.
    Povstugar, V.I., Tyurin, S.A., and Kodolov, V.I.,Vysokomol. Soedin. Ser. A, 1985, vol. 37, no. 1, p. 3.Google Scholar
  13. 13.
    Pijpers, A.P. and Meier, R.J.,J. Electron Spectrosc. Relat. Phenom., 1987, vol. 43, p. 131.CrossRefGoogle Scholar
  14. 14.
    Batich,C.D., Appl. Surf. Sci., 1988, vol. 32, p. 57.CrossRefGoogle Scholar
  15. 15.
    Andrade, J.D.,Surface and Interfacial Aspects of Biomedical Polymers, vol. 1:X-Ray Photoelectron Spectroscopy, New York: Plenum, 1985, ch. 4, p. 105.Google Scholar
  16. 16.
    Everhart, D.S. and Reilley, C.N.,Anal. Chem., 1981, vol. 53, p. 665.CrossRefGoogle Scholar
  17. 17.
    Knapp, D.R.,Handbook of Analytical Derivatizaton Reactions, Wiley, 1979, p. 741.Google Scholar
  18. 18.
    Critchfield, F.,Organic Functional Group Analysis, Oxford, 1963. Translated under the titleAnaliz osnovnykh funktsional’nykh grupp v organicheskikh soedineniyakh, Moscow: Mir, 1965, p. 207.Google Scholar
  19. 19.
    Siggia, S. and Hanna, J.G.,Quantitative Organic Analysis via Functional Groups, New York: Wiley, 4 ed., 1980. Translated under the titleKolichestvennyi organicheskii analiz po funktsional’nym gruppam, Moscow: Khimiya, 1983, p. 672.Google Scholar
  20. 20.
    von Brecht, H., Mayer, F., and Binder, H.,Macromol. Chem. Phys., 1973, vol. 33, p. 89.Google Scholar
  21. 21.
    Dwight, D.W. and Riggs, W.M.,J. Coll. Interface Sci., 1974, vol. 47, p. 656.Google Scholar
  22. 22.
    Millard, M.M.,Ind. Appl. Surface Anal. Symp. 181st Meeting American Chemical Society, New York, 23–28 Aug. 1981, Washington, D.C., 1982, p. 143.Google Scholar
  23. 23.
    Riggs, W.M. and Dwight, D.W.,J. Electron Spectrosc. Related Phenom., 1974, vol. 5, no. 3, p. 447.CrossRefGoogle Scholar
  24. 24.
    Amemiya, T., Hayashi, T., and Nihei, Y.,Bunseki Kagaku, 1988, vol. 37, no. 9, p. 481.Google Scholar
  25. 25.
    Briggs, D., Brewis, D.M., and Konieczo, M.B.,J. Mater. Sci., 1977, vol. 12, no. 3, p. 429.CrossRefGoogle Scholar
  26. 26.
    Reilley, C.N. and Everhart, D.S.,Applied Electron Spectroscopy for Chemical Analysis, Windawi, H. and Ho, F.F.-L., Eds., New York: Wiley, 1982.Google Scholar
  27. 27.
    Briggs, D., Rance, D.G., Kendall, C.R., and Blythe, A.R.,Polymer, 1980, vol. 21, p. 895.CrossRefGoogle Scholar
  28. 28.
    Ohmichi, T., Tamaki, H., Kawasaki, H., and Tatsuta, S., inPhysicochemical Aspects of Polymer Surfaces, Mittal, K., Ed., New York: Plenum, 1983, p. 793.Google Scholar
  29. 29.
    Dickie, R.A., Hammond, Y.S., de Vries, J.E., and Holubka, J.W.,Anal. Chem., 1982, vol. 54, p. 2045.CrossRefGoogle Scholar
  30. 30.
    Gerenser, L.J., Elman, J.F., Mason, M.G., and Pachan, J.M.,Polymer, 1985, vol. 26, no. 8, p. 1162.CrossRefGoogle Scholar
  31. 31.
    Pennings, J.F.M. and Bosman, B.,Coll. Polym. Sci, 1980, vol. 258, p. 1099.CrossRefGoogle Scholar
  32. 32.
    Briggs, D. and Kendall, C.R.,Int. J. Adhes. Adhes., 1982, no. 1, p. 13.Google Scholar
  33. 33.
    Hammond, J.S.,Polym, Preprint Am. Chem. Soc., Div. Polym. Chem, 1980, vol. 21, no. 1, p. 149.Google Scholar
  34. 34.
    Polymer Blends, Paul, D. and Newman, C., Eds., New York: Academic, 1979. Translated under the titlePolimernye smesi, Moscow: Mir, 1981, p. 540.Google Scholar
  35. 35.
    Clark, D.T. and Feast, W.Y.,J. Macromol. Sci., Rev. Macromol. Chem., 1975, vol. 12, no. 2, p. 191.Google Scholar
  36. 36.
    Fryling, M., Zhao, J., and McCreery, L.,Anal. Chem., 1995, vol. 67, no. 5, p. 697.CrossRefGoogle Scholar
  37. 37.
    Whitesides, G.M., Rasmussen, J.R., and Tredronsky, E.R.,J. Am. Chem. Soc., 1977, vol. 99, p. 4736.CrossRefGoogle Scholar
  38. 38.
    Briggs, D. and Kendall, C.R.,Polymer, 1979, vol. 20, p. 1053.CrossRefGoogle Scholar
  39. 39.
    Bradley, A. and Czuha, M., Jr.,Anal. Chem., 1975, vol. 47, no. 11, p. 1838.CrossRefGoogle Scholar
  40. 40.
    Denison, R., Jones, F.R., and Watts, J.F.,J. Mater. Sci., 1985, vol. 20, no. 12, p. 4647.CrossRefGoogle Scholar
  41. 41.
    Batich, C.D. and Wendt, R.C.,Am. Chem. Soc. Symp. Ser, 1981, vol. 162, p. 221.Google Scholar
  42. 42.
    Deldime, M., Dewez, J.-L., Schneider, Y.-J., and March-and-Brynaert, J.,Appl. Surf. Sci., 1995, vol. 90, no. 1, p. 1.CrossRefGoogle Scholar
  43. 43.
    Clark, D.T.,Pure Appl. Chem., 1982, vol. 54, no. 2, p. 415.CrossRefGoogle Scholar
  44. 44.
    Millard, M.M. and Masri, M.S.,Anal. Chem., 1974, vol. 46, no. 12, p. 1820.CrossRefGoogle Scholar
  45. 45.
    Dang, T.A. and Gnanasekaran, R.,Surf. Interface Anal., 1990, vol. 15, p. 113.CrossRefGoogle Scholar
  46. 46.
    Pochan, J.M., Gerenser, L.J., and Elman, J.F.,Polymer, 1986, vol. 27, no. 7, p. 1058.CrossRefGoogle Scholar
  47. 47.
    Gombotz, W.R. and Hoffman, A.S.,J. Appl. Polym. Sci: Appl. Polym. Symp., 1988, vol. 42, p. 285.Google Scholar
  48. 48.
    Zeggane, S. and Delamar, M.,Appl. Surf. Sci., 1988, vol. 31, no. l, p. 151.CrossRefGoogle Scholar
  49. 49.
    Dickie, R.A. and Hammond, J.S., de Ries J.E., Holubka J.W,Anal. Chem., 1982, vol. 54, p. 2045.CrossRefGoogle Scholar
  50. 50.
    Everhart, D.S. and Reilley, C.N.,Surf. Interface Anal., 1981, vol. 3, no. 6, p. 258.CrossRefGoogle Scholar
  51. 51.
    Nakayama, Y., Takahagi, T., Soeda, F., Hatada, K., Nagaoka, S., Suzuki, J., and Ishitani, A.,J. Polym. Sci., Part A: Polym. Chem., 1988, vol. 26, no. 2, p. 559.CrossRefGoogle Scholar
  52. 52.
    Chillkoti, A., Castner, D.G., Ratner, B.D., and Briggs, D.,J. Vac. Sci. Technol., A, 1990, vol. 8, no. 3, p. 2274.CrossRefGoogle Scholar
  53. 53.
    Chillkoti, A., Ratner, B.D., and Briggs, D.,Chem. Mater., 1991, vol. 3, p. 51.CrossRefGoogle Scholar
  54. 54.
    Davies, C. and Munro, H.S.,Polym. Commun., 1987, vol. 29, no. 2, p. 47.Google Scholar
  55. 55.
    Andrade, J.D. and Chen, W.-Y.,Surface Interface Anal., 1986, vol. 8, no. 6, p. 253.CrossRefGoogle Scholar
  56. 56.
    Pennings, J.F.M. and Bosman, B.,Coll. Polym. Sci, 1980, vol. 258, p. 1099.CrossRefGoogle Scholar
  57. 57.
    Lanauzer, J.A. and Myers, D.L.,J. Appl. Polym. Sci., 1990, vol. 40, nos. 3–4, p. 595.CrossRefGoogle Scholar
  58. 58.
    Everhart, D.S. and Reilley, C.N.,Surf. Interface Anal., 1981, vol. 3, no. 3, p. 126.CrossRefGoogle Scholar
  59. 59.
    Elman, J.F., Gerenser, J.L., Goppet-Berarducci, K.E., and Pochan, J.M.,Macromolecules, 1990, vol. 23, p. 3922.CrossRefGoogle Scholar
  60. 60.
    Inagaki, N. and Kubokawa, Y.,J. Polym. Sci., Part A: Polym. Chem., 1989, vol. 27, p. 795.CrossRefGoogle Scholar
  61. 61.
    Denison, R., Jones, F.R., and Watts, J.F.,J. Phys. D: Appl. Phys., 1987, vol. 20, no. 3, p. 306.CrossRefGoogle Scholar
  62. 62.
    Denison, R., Jones, F.R., and Watts, J.F.,Proc. 2nd Int. Conf. Compos. Interfaces, Cleavland, Ohio, June 13–17, 1988, New-York, 1988, p. 77.Google Scholar
  63. 63.
    Takahagi, T. and Ishitani, A.,Carbon, 1988, vol. 26, no. 3, p. 389.CrossRefGoogle Scholar
  64. 64.
    Takahagi, T. and Ishitani, A.,Carbon, 1984, vol. 22, no. l, p. 43.CrossRefGoogle Scholar
  65. 65.
    Idage, S.B., Badrinarayanan, S., Vernekar, S.P., and Sivaram, S.,Langmuir, 1996, vol. 12, p. 1018.CrossRefGoogle Scholar
  66. 66.
    Deldime, M., Dewez, J.-L., Schneider, Y-J., and March-and-Brynaert, J.,Appl. Surf. Sci., 1995, vol. 90, p. 1.CrossRefGoogle Scholar
  67. 67.
    Gang, T.A. and Gnanasekran, R.,Surf. Interface Anal., 1990, vol. 15, p. 113.CrossRefGoogle Scholar
  68. 68.
    Povstugar, V.I., Shakov, A.A., Mikhailova, S.S., Voronina, E.V., and Yelsukov, E.P.,Proc. 6th European Conference on Applications of Surface and Interface Analysis, Oct. 9–13, 1995, Montreux, Switzerland, New York: Wiley, 1996, p. 695.Google Scholar
  69. 69.
    Povstugar, V.I., Lyakhovich, A.M., and Shakov, A.A.,J. Electron Spectrosc. and Related Phenom., 1994, vol. 68, p. 565.CrossRefGoogle Scholar

Copyright information

© MAIK “Nauka/Interperiodica” 2000

Authors and Affiliations

  • V. I. Povstugar
    • 1
  • S. S. Mikhailova
    • 1
  • A. A. Shakov
    • 1
  1. 1.Physicotechnical Institute, Ural DivisionRussian Academy of SciencesIzhevskRussia

Personalised recommendations