SOME APPLICATIONS OF INFRARED SPECTROSCOPY IN THE EXAMINATION OF PAINTING MATERIALS
Richard Newman
REFERENCES
K�hn, H. “Verdigris and Copper Resinate.” St. in Cons.15 (1970): 12–36
K�hn, H. “A Study of the Pigments and the Grounds used by Jan Vermeer.” National Gallery of Art Report and Studies in the History of Art 1968, pp. 154–202
Hofenk-de Graaff, J.H.Natural Dyestuffs: Origin, Chemical Composition, Identification, ICOM Plenary Meeting, 1969 (Amsterdam: Central Research Laboratory for Objects of Art and Science, 1969)
Masschelein-Kleiner, L.; Heylen, J.B. “Analyse des laques rouges anciennes.” St. in Cons.13 (1968): 87–97
Flieder, F. “Mise au point des techniques d'identification des pigments et des liants inclus dans la couche picturale des enluminures de manuscrits.” St. in Cons.13 (1968): 49–86
K�hn, H. “Detection and Identification of Waxes, Including Punic Wax, by Infra-red Spectrography.” St. in Cons.5 (1960): 71–79
Birstein, V.J. “On the Technology of Central Asian Wall Paintings: The Problem of Binding Media.” St. in Cons.20 (1975): 8–19
Masschelein-Kleiner, L.; Heylen, J.; Tricot-Marckx, F. “Contribution � l'analyse des liants, adhesifs et vernis anciens.” St. in Cons.13 (1968): 105–121
Low, M.J.D.; Baer, N.S. “Applications of Infrared Fourier Transform Spectroscopy to Problems in Conservation. I. General Principles.” St. in Cons.22 (1977): 116–128
Low, M.J.D.; Baer, N.S. “Dammar and Mastic Infrared Analysis.” Preprints, ICOM Committee for Conservation, 5th Triennial Meeting, Zagreb, 1978: 78/16/5
Low, M.J.D.; Baer, N.S. “Advances in the Infrared Spectroscopic Examination of Pigments.” Preprints, ICOM Committee for Conservation, 5th Triennial Meeting, Zagreb, 1978: 78/20/3
Grissom, C.A. “A Literature Search for a Pigment Study.” Preprints, ICOM Committee for Conservation, 4th Triennial Meeting, Venice, 1975:75/21/5
Siesmayer, B.; Giebelhausen, A.; Zambelli, J.; Riederer, J. “Beitrag zur Anwendung der Infrarotspektroskopie f�r Untersuchungen von Farberden kulturhistorischer Objekte im Vergleich mit rezenten europ�ischen Lagerst�tten.” Z. Anal. Chem.277 (1975): 193–196
Riederer, J. “Infrarotspektrographische Untersuchung der gelben und roten Eisenoxidpigmente.” Deutsche Farben-Zeitschrift23 (1969): 569–577
Afremow, L.C.; Vandeberg, J.T. “High Resolution Spectra of Inorganic Pigments and Extenders in the Mid-Infrared Region from 1500 to 200 cm−1.” J. Paint Tech. 38 (1966): 169–202. Spectra of most of the types of pigments discussed in this paper are included in this article.
Afremow, L.C.; Isakson, K.E.; Netzel, D.A.; Tessari, D.J.; Vandeberg, J.T.Infrared Spectroscopy. Its Use in the Coatings Industry. Philadelphia: Fed. Soc. Paint Tech., 1969. Spectra of many of the pigments discussed in this paper may be found in this publication.
Two excellent recent reviews are:
(a) Estep-Barnes, P.A. “Infrared Spectroscopy,” in Physical Methods in Determinative Mineralogy, ed.J.Zussman (London: Academic Press, 1972, 2nd ed.), pp. 529–604
(b) Farmer, V.C. (ed.). The Infra-red Spectra of Minerals. London: Mineralogical Society, 1974, Mineralogical Society Monograph 4.
Some applications in this area have also been recently reviewed in: Laver, M.E.; Williams, R.S., “The Use of a Diamond Cell Microsampling Device for Infrared Spectrophotometric Analysis of Art and Archaeological Materials,” J. IIC-Canadian Group3 (1978): 34–39
The catalog numbers given in the captions of the Figures for the “Forbes Collection” pigments refer to bottles in the wall case displays in the Center of Conservation and Technical Studies, Fogg Art Museum. Several Museums, including the Fogg, own samples from a second and not identical “Forbes Collection,” which is catalogued in a different manner.
Low, M.J.D. “Fourier Transform Spectroscopy,” in Encyclopedia of Chemical Analyses (N.Y.: Interscience, 1971), Vol. 13, pp. 139 ff.
Perkin-Elmer Corp., Norwald, Conn.: Instructions, Combination Accessory for Perkin Elmer Infrared Spectrophotometers 186–0373 (1972)
Located in the Chemistry Department, Harvard University, Cambridge, Massachusetts
Duyckaerts, G. “The Infra-red Analysis of Solid Substances: A Review.” Analyst84 (1959): 201–214
Meloche, V.W.; Kalbus, G.E. “Anomalies in the Infrared Spectra of Inorganic Compounds Prepared by the Potassium Bromide Pellet Technique.” J. Inorg. Nucl. Chem.6 (1958): 104–111
Gettens, R.J.; Stout, G.L.Painting Materials: A Short Encyclopaedia. N.Y.: Dover, 1966, reprint of original 1942 edition with some revisions
Venkataraman, K. (ed.). The Analytical Chemistry of Synthetic Dyes. N.Y.: Wiley, 1977
Pamer, T. “Modern Blue Pigments.” Preprints, AIC Annual Meeting, Ft. Worth, Texas, 1978, pp. 107–118
Knudsen, B.I. “Copper Phthalocyanine: Infrared Absorption Spectra of Polymorphic Modifications.” Acta Chem. Scand20 (1966): 1344–1350
Shurvell, H.F.; Pinzuti, L. “Sur les spectres infrarouges des phthalocyanines.” Can. J. Chem.44 (1966): 125–136
Miller, R.K. “Infrared Spectroscopy,” in Ref. 26, pp. 197–216
See, for example: McClure, A.; Thomson, J.; Tannahill, J. “The identification of pigments,” J. Oil Col. Chem. Assoc. 51 (1968): 580–635
Ref. 17(b), pp. 54 ff.
Nyquist, K.; Kagel, R.Infrared Spectra of Inorganic Compounds(3800–45 cm−1). N.Y.: Academic Press, 1971
Hornig, D.F. “The Vibrational Spectra of Molecules and Complex Ions in Crystals. I. General Theory.” J. Chem. Physics16 (1948): 1063–1076
Adler, H.H.; Kerr, P.F. “Infrared Absorption Frequency Trends for Anhydrous Normal Carbonates.” Am. Mineral. 48 (1963): 124–137
Adler, H.H.; Kerr, P.F. “Infrared Spectra, Symmetry and Structure Relations of Some Carbonate Minerals.” Am. Mineral. 48 (1963): 839–853
Adler, H.H.; Kerr, P.F. “Variations in Infrared Spectra, Molecular Symmetry and Site Symmetry of Sulfate Minerals.” Am. Mineral. 50 (1965): 132–147
The infrared spectral features of several carbonates are discussed (often with spectra reproduced) in the following: (a) Calcite and other Group II anhydrous carbonates; cerussite: Gettens, R.J.; Fitz-Hugh, E.W.; Feller, R.L. “Calcium Carbonate Whites,” St. in Cons.19 (1974): 157–184 (b) Cerussite and hydrocerussite: K�hn, H. “Bleiweiss und seine Verwendung in der Malerei,” Farbe und Lack73 (February, 1967): 99–105; (March, 1967): 209–213
(c) Malachite: Gettens, R.J.; FitzHugh, E.W. “Malachite and Green Verditer,” St. in Cons.19 (1974): 2–23
The absorption bands reproduced in the Figures are those in the mid-infrared range which are caused by the polyatomic ions contained in the compounds, but are not necessarily the only ones which would occur in the full spectra. For example, the water of hydration in gypsum causes bands at 3554, 3408, and 1690 cm−1. The hydroxyl groups in the basic carbonates also cause absorptions: in azurite, at 3425, 1035, and 952 cm−1; in malachite, at 3400, 3320, 1045, and 875 cm−1; and in hydrocerussite, at 3535, 1047, and 1040 cm−1. See Ref. 17(b) for a discussion of these.
Bearn, J.G.The Chemistry of Paints, Pigments & Varnishes. London: Ernest Benn, 1923.
Ref. 25, pp. 105–106
Campbell, J.A. “Spectral evidence for interionic forces in crystals—chromates and dichromates.” Spectrochim. Acta21 (1965): 1333–1343.
Ref. 37
Ref. 17(b), pp. 365 ff.
Ref. 17(b), pp. 340 ff.
Farmer, V.C.; Russell, J.D. “The infrared spectra of layer silicates.” Spectrochim. Acta20 (1964): 1149–1173
Ref. 25, p. 117
Hendricks, S.B.; Ross, C.S. “Chemical Composition and Genesis of Glauconite and Celadonite.” Am. Mineral. 26 (1941): 683–708
Deer, W.A.; Howie, P.A.; Zussman, J.Rock-Forming Minerals. London: Longmans, 1962, Vol. 3: Sheet Silicates.
Ref. 49, pp. 216 ff
Carroll, D.Clay Minerals: A guide to their X-ray identification. Boulder, Colorado: Geological Society of America, 1970, Geol. Soc. of America Special Paper 128.
Stubiĉan, V.; Roy, R. “Isomorphous Substitution and Infra-red Spectra of the Layer Silicate Minerals.” Am. Mineral46. (1961): 32–51
Launer, P.J. “Regularities in the Infrared Absorption Spectra of Silicate Minerals.” Am. Mineral. 37 (1952): 764–784
Ref. 46
Manghnani, M.H.; Hower, J. “Glauconites: Cation Exchange Capacities and Infrared Spectra. II. Infrared Absorption Characteristics of Glauconites.” Am. Mineral. 49 (1964): 1631–1642
R-OH stretching and librational bands, where R = octahedrally-coordinated ions, are discussed in Ref. 46 and: Russell, J.D., Farmer, V.C., Velde, B. “Replacement of OH by OD in layer silicates, and identification of the vibrations of these groups in infra-red spectra,” Min. Mag.37 (1970): 869–879.
Ref. 25, p. 107 and pp. 173–174
Ref. 27
Ref. 17(b), Ch. 3 & 10
Ref. 15, 16
McDevitt, N.T.; Brown, W.L. “Infrared absorption study of metal oxides in the low frequency region (700–240 cm−1).” Spectrochim. Acta20 (1964): 799–808
Ref. 17(b), pp. 188–189
ACKNOWLEDGEMENTS
THE AUTHOR would like to thank Eugene Farrell (conservation scientist, Center for Conservation and Technical Studies, Fogg Art Museum) who prepared some of the samples and helped the author with acquiring the spectra. This study would not have been possible without the use of the Nicolet 7199 FT-IR spectrometer, and for allowing us to use this instrument and training us in its operation, I gratefully acknowledge Dr. Gregory Exarhos and particularly Barry Nelson (both Chemistry Department, Harvard University).
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