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Non-invasive methods in the identification of selected writing fluids from late 19th and early 20th century

Agata Kłos

Résumés

Cette contribution presente la recherche menée dans le cadre de la thèse de maîtrise. L'objectif de la recherché fut d’évaluer l'efficacité de certaines méthodes d'identification non-invasives pour les analyses d'encres d'écriture introduites pendant la Révolution Industrielle. Un autre bur relevant de la recherche fut le développement d’une méthodologie d'analyse des encres de la fin de 19ème et début de 20ème siècle dans les documents historiques qui pourrait faciliter le choix d’une méthode optimale du traitement de conservation-restauration de ces documents.

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Introduction. Production of writing inks in late 19th and early 20th century

1The Industrial Revolution brought changes to all fields of human activity: industry, economy, technology and culture. It was the time of innovations that changed people’s lifestyles forever. Papermaking and writing materials manufacturing processes developed due to democratization, industrialization, modernization of industry and the widening participation in education. A growing need for inexpensive materials to satisfy the emerging markets was arising. In effect, many new writing fluids were invented and introduced to the market. These inventions were found to be very useful in everyday life and thus we have inherited a large amount of records written with these new inks. Their identification is now one of the most difficult analytical tasks for paper conservators as they possess different properties to traditional writing materials.  

Objects of the study

2The article presents the results of research conducted for a master degree dissertation entitled “Non-invasive methods in the identification of writing inks from late 19th and early 20th century” performed under the guidance of Jarosław Rogóż, PhD, in the Department of Technology and Painting Techniques of the Institute for the study, Conservation and Restoration of Cultural Heritage, Nicolaus Copernicus University in Toruń, Poland. The work described here was undertaken in order to assess the efficacy of selected non-invasive identification methods in the analyses of writing inks from the late 19th and early 20th century and their practical use during research. The project included the creation of an ink standards database that would help to develop a new procedure to be used in practical conservation research.

A short history of writing fluids in the late 19th and early 20th century

  • 1  Guthke, B., op. cit., pp. 22-23; Janik, L.A, Skarbnica wiedzy – podręcznik chemiczno-techniczny do (...)
  • 2  Davids, T., The History of Ink Including its Etymology, Chemistry and Bibliography, New York, Thad (...)

3Writing inks from the late 19th and early 20th century varied greatly according to their production, composition, color and use. They were sold in two main forms: ready-made writing fluids and inks in solid form that needed to be dissolved prior to writing. The very basic components of a standard writing ink were a colorant and a water-dissolved binder. Natural or synthetic dyes and pigments were used as colorants. The composition of inks varied according to its future use1. Modern inks from the 19th and 20th century had chemical characteristics of solutions and were called writing fluids2.

  • 3  Guthke, B., Wyrób atramentów (tuszów, taśm kopjowych i t. d.), Łódź, Księgarnia Ludwika Fiszera, 1 (...)
  • 4  Davids, T., op. cit., p. 16.
  • 5  Carvalho, D.N.,Forty Centuries of Ink [online], URL: http://www.gutenberg.org/cache/epub/1483/pg14 (...)
  • 6 At that time, those substances also became popular as additives to iron gall ink.
  • 7  Martuscelli, E., I coloranti naturali nella tintura della lana. Arte, storia, tecnologia e “Archeo (...)
  • 8  United States, op. cit., p. 5.
  • 9  Carvalho, D. N., op. cit.
  • 10  Guthke, B., op. cit., p. 45; Carvalho, D. N., op. cit.
  • 11 Good water-solubility was at that time considered an advantage because it facilitated ink preparati (...)

4In the second half of the 19th century, the most common European writing materials were still tannin inks, the most popular of which was iron gall ink introduced in the 5th century3. Its production was nevertheless expensive and time consuming4. Growing demand for widely accessible writing materials had led to experiments with the composition of traditional inks. Researchers worked on a permanent, cheap ink that could also be used in reservoir pens5. As a result, in the second half of the 19th century a brand new concept of ink had been introduced along with new recipes, many of which enabled people to prepare their inks at home. In 1847, a German scientist F. J. Runge introduced logwood (or chrome) ink. This invention is now widely appreciated as the first modern ink. Its basic composition was a mixture of hematoxylin and potassium chromate6. In 1855, A. Leonhardi from Dresden created a formula of alizarin ink. In its basic form it was prepared with tannin solution, iron (II) sulfate, iron (III) nitrate and haematein. An important breakthrough in ink production took place in 1856 when W. H. Perkin discovered the first aniline dye, mauveine7. In 1860, for the first time a synthetic dye, novein, was used as an additive colorant to iron gall ink. Soon the first fully synthetic ink based on methyl violet went into production8. In the second half of the 20th century, synthetic inks have replaced pigments and natural dyes in book-printing9. They were cheap, convenient and had a wide range of beautiful intense colors10. They could be easily prepared at home. Their main disadvantage was their light fastness and very good water solubility11. The most popular aniline dyestuffs used in the late 19th and early 20th century were nigrosine, eosin, fuchsine, methyl violet, crystal violet, indigo carmine, malachite green, methylene blue, phenol blue and induline.

  • 12  Guthke, B., op. cit., pp. 56-59.

5One of the most popular inventions of the 19th century was copying ink – concentrated ink mixed with an additive such as glycerin that slowed down its drying. It was used to produce quick copies. For this purpose such instruments as copying pencils, copy paper, copy tape as used in typewriters and hectograph could be used. Also rubber stamp inks were at this time usually manufactured from synthetic inks mixed with glycerin and gum arabic12.

  • 13  Dube, L., “The Copying Pencil: Composition, History and Conservation Implications“ [in:] The Book (...)

6Copying pencils were very popular during the second half of the 19th century. The idea of a copying pencil was to create a writing instrument that would combine the most significant advantages of a pen and a pencil – permanence and ease of writing. Text written on damped paper with a copying pencil can be easily mistaken for pen writing. The writing core of a copying pencil consisted of concentrated dyestuff solution, graphite and clay – mainly kaolin. The colorant of a copying pencil was usually a synthetic dyestuff: methyl violet, methylene blue or nigrosine. The most common in everyday use were violet, blue and red pencils13.

  • 14  Sakayanagi, M., Komuro, J., Konda, Y.,  Watanabe, K., Harigaya, Y., “Analysis of ballpoint inks by (...)
  • 15  Vide: no 1, 4, 8, 9, 14, 17, 18 - 21, 24, 25 in attached Bibliography.   

7The analysis of ink writings is used in forensic science for authentication of documents and crime analysis14. In conservation determining the source and nature of a colorant is an essential step in the process of conservation research and treatment. More and more technologically advanced analytical tools are being used for this purpose15. Nevertheless written records from the 19th and 20th century are still extremely difficult to identify and analyze since they are usually written with very thin layers of chemically similar substances.

Methodology of the study. Introducing non-invasive techniques to ink identification

8The research was performed with non-destructive optical techniques (near-infrared reflectography, ultraviolet fluorescence, false-color infrared photography technique) and two spectroscopic techniques: Fourier transform Infrared spectroscopy (FTIR) and Raman scattering spectroscopy. These methods were selected because of their efficacy in analyzing the composition and chemical structure of organic substances. During the development of the procedure consideration was given to such characteristics as cost and duration of analyses and also availability. Methods were modified in order to provide specific results. A key point of the study was the creation of a reference database containing information of analyzed substances obtained during our research:

  • results of external synthetic dyestuff analyses – the most common components of inks in the late 19th and early 20th century;

  • results of ink analyses (standard ink solutions prepared according to original formulas from the firsthalf of the 20th century);

    • 16 Analyzed copying pencils were produced by L. & C. Hardmuth-Lechistan and “St. Majewski i S-ka” Poli (...)

    results of ink analyses of copying pencils16.   

Preparation of reference material

9Ten standard inks were prepared for the examination: six ink prepared with synthetic dyestuffs and four inks with natural and synthetic components. Synthetic inks were prepared with water-soluble nigrosine (black ink), methylene blue (blue ink), crystal violet (violet ink), malachite green (green ink), fuchsine (red ink), indigo carmine (indigo ink) (Tab. 1). Four inks based on natural components were:

  • alizarin ink: gallic acid, iron (II) sulfate, gum arabic, acetic acid, water, indigo carmine, oxlid acid;

  • “Leonhardi’s patented ink”: gallic acid, alizarin, water, indigo carmine, iron (II) sulfate, acetic acid, water;

  • logwood ink: haematein, water, potassium chromate;

  • iron-gall ink with logwood: gallic acid, haematein, iron (II) sulfate, gum arabic, water.

  • 17  Guthke, B., op. cit., pp. 34-37, 41, 43-44, 49, 54; Janik, L.A, op. cit., pp. 145, 149, 151, 156.

10Both permanent and copying form of each ink were prepared according to original formulas17. Color shade tables were created by applying prepared ink samples to high quality cellulose filter paper .

11Table 1. Chemical structure of analyzed synthetic dyestuffs

dyestuff name

chemical structure

nigrosine

C22H14N6Na2O9S2

methylene blue

C16H18N3SCl

Agrandir Original (png, 12k)

crystal violet

C24H28ClN3 (R=H)

Agrandir Original (png, 10k)

malachite green

C23H25ClN2

Agrandir Original (jpeg, 12k)

fuchsine

C20H20N3· HCl

Agrandir Original (png, 7,0k)

indigo carmine

C16H8N2Na2O8S2

Agrandir Original (png, 14k)

12Table 2. Components of natural inks and their chemical structure

components of natural inks

Chemical structure

gallic acid

C6H2(OH)3COOH

iron (II) sulphate

FeSO4 ; FeO4S

oxalic acid

C2H2O4

haematein

C16H12O6

potassium chromate

K2CrO4

alizarin

C14H8O4

acetic acid

C2H4O2

Non-destructive optical analyses of standard synthetic inks

  • 18  Rogóż, J., Zastosowanie technik nieniszczących w badaniach konserwatorskich malowideł ściennych, T (...)
  • 19  Photos were taken by and false-color images processed by the author and MA Adam Cupa (Department o (...)

13In the first part of the research three non-destructive optical techniques18 were used: near-infrared reflectography (IR; 840-1000 nm), ultraviolet fluorescence (UV; maximum of excitation – 365 nm; image registration – 400-700 nm) and false-color infrared photography technique (VIS/IR; 500-1000 nm). Ink tables were illuminated with adequate radiation sources and photographed with FujiFilm Digital CameraFinePix S3 Pro UVIR. Adequate UV and IR filters were used. False-color images were digitally processed prior to interpretation19.

14Near-infrared reflectography allowed us to analyze the inks’ transparency characteristics to IR radiation (Ill. 1). The study has shown that synthetic malachite (green) and indigo carmine (blue) inks do not absorb IR radiation and therefore were observed as transparent. Methyl violet, methylene blue and fuchsine (red) inks were completely transparent to IR radiation. Nigrosine (black) ink showed relatively little infrared reflectance. Ultraviolet fluorescence images allowed us to analyze the fluorescence properties of inks (Ill. 2).

Fig. 1 NIR reflectography color table of standard synthetic inks

Fig. 1 NIR reflectography color table of standard synthetic inks

Comparison of standard permanent and copying synthetic inks photographed in visible (above) and NIR light.

Photo: © Agata Kłos

Fig.  2 UV fluorescence color table of standard synthetic inks

Fig.  2 UV fluorescence color table of standard synthetic inks

Comparison of standard synthetic permanent and copying synthetic inks photographed in visible light (above) and their UV fluorescence image

Photo: © Agata Kłos

15Synthetic standard inks were characterized by low fluorescence emission intensity.Fuchsine (red) ink emitted a pink red light and green ink had a characteristic light green glow. Copying inks containing glycerin showed higher fluorescence emission intensity than regular inks which did not contain glycerin. The false-color infrared photography technique allowed us to see the analyzed inks’ false colors which is the first step to their composition identification (Ill. 3). In false-color infrared photograph methylene blue ink appeared violet red, fuchsine (red) ink – light yellow, methyl violet ink – orange, malachite (green) ink – pink, black nigrosine ink gave a grayish green image and indigo carmine ink appeared red.

Fig. 3 IRC color table of standard synthetic inks

Fig. 3 IRC color table of standard synthetic inks

Comparison of standard synthetic permanent and copying synthetic inks photographed in visible light (above) and obtained through false-color infrared imaging.

Photo: © Agata Kłos

Non-destructive optical analyses of standard natural inks

16Inks based on natural components were opaque to IR radiation due to their high infrared absorbance (Ill. 4). Those inks also did not emit ultraviolet fluorescence (Ill. 5). Using false-color infrared photography technique, we have registered their false colors (Ill. 6). Haematein and potassium chromate in logwood ink, haematein mixed with iron gallates in iron-gall ink with logwood, as well as a mix of hematein, iron gallates and indigo carmine in Leonhardi’s patented ink and alizarin ink were brown-red.

Fig. 4 IR reflectography color table of standard inks based on natural components

Fig. 4 IR reflectography color table of standard inks based on natural components

Comparison of standard permanent and copying inks based on natural components photographed in visible (above) and near-infrared light.

Photo: © Agata Kłos

Fig. 5 UV fluorescence color table of standard inks based on natural components

Fig. 5 UV fluorescence color table of standard inks based on natural components

Comparison of standard synthetic permanent and copying inks based on natural components photographed in visible (above) and ultraviolet light.

Photo: © Agata Kłos

Fig. 6. IRC color table of standard inks based on natural components

Fig. 6. IRC color table of standard inks based on natural components

Comparison of standard synthetic permanent and copying inks based on natural components photographed in visible (above) and obtained through false-color infrared imaging.

Photo: © Agata Kłos

Non-destructive optical analyses of copying pencil inks

17In the next part of the study we conducted analyses of copying pencil inks dating back to the first half of the 20th century. For this purpose, pencil shade tables were created by applying pencil markings to filter paper. For comparison purposes, an additional set of markings was applied to the paper and dissolved with a drop of water. Near-infrared reflectography allowed us to analyze pencil inks’ transparency characteristics to IR radiation (Ill. 7). The ink of a modern reference pencil was completely  transparent to infrared light. In ultraviolet fluorescence photographs of dry inks, we registered medium violet-blue fluorescence emission intensity in comparison with water dissolved inks whose fluorescence emission intensity appeared extinguished (Ill. 8).

Fig. 7 IR reflectography color table of copying pencils’ inks

Fig. 7 IR reflectography color table of copying pencils’ inks

Visible light photography of original dry and water-dissolved copying pencils’ inks (above) in comparison with their NIR image.  

Photo: © Agata Kłos

Fig. 8 UV fluorescence color table of copying pencils’ inks

Fig. 8 UV fluorescence color table of copying pencils’ inks

Visible light photography of original dry and water-dissolved inks of copying.

Photo: © Agata Kłos

18The false color of copying pencil’s markings depends on its colorant which allowed us to pre-determine their chemical composition. In some cases the false color depended strongly on the percentage of other components such as kaolin and graphite. For example, a high content of graphite was responsible for the pencil’s grayish false color. The same pencil’s ink dissolved by water gave a characteristic violet-red false color of methyl violet (Ill. 9).

Fig. 9 IRC color table of copying pencils’ inks

Fig. 9 IRC color table of copying pencils’ inks

Visible light photography of original dry and water-dissolved inks of copying pencils (above) in comparison with their false-color image.

Photo: © Agata Kłos

Micro-Raman and FTIR examination

  • 20  All FTIR and Raman spectra obtained in this research were described and interpreted by the author (...)

19Conditions of measurements20:

    • 21  InVia (Renishaw, Gloucestershire, UK); measurements performed by MA Agnieszka Górska in the Instit (...)

    Micro-Raman analyses: MicroRaman spectrometer21 with a laser source emitting at 488 nm and laser spot of 1,5 μm (maximum power 100mW); time of measurement: 2-3 minutes;

    • 22  FT-IR ALPHA-P BRUKER; measurements performed by PhD Andrzej Balawski in the Department for Conserv (...)

    FTIR analyses: FTIR spectrometer22 with ATR table; spectral resolution: 4 cm-1 (128 scans); spectra recorded in the range 4000 – 400 cm-1; time of measurement: 43 seconds.

Spectroscopic analyses of reference dyestuffs

  • 23  Barańska H., Łabudzińska A., Terpiński J., Laser Raman spectrometry: analytical applications, Wars (...)

20The first step of spectrometric analyses was spectral measurement of 6 reference synthetic dyestuffs used for preparation of standard inks (Tab. 3). Each dry dyestuff was placed on microscope slide, dissolved with a drop of water and left to dry prior to spectroscopic examination. The spectra obtained in this part of the study were used as a reference database for the next steps of the research.We were able to measure all the Raman and FTIR spectra except for the Raman spectrum of fuchsine due to extremely high fluorescence emission intensity of the colorant. In the FTIR spectra the most intense bands were found at a wide range between 548 – 3427 cm-1. In Raman spectra the significant bands were found between 550 – 2882 cm-1 range. At this stage the spectra were described in reference to the characteristics of bands related to known specific molecular structure properties, i.e. functional groups (Tab. 1), vibrational modes, molecular bonds23.

Results of spectroscopic analyses of synthetic inks

21The next step was the analyses of 6 standard synthetic inks. A drop of each ink was placed on separate microscope slide and left to dry prior to examination.

22The obtained FTIR and Raman spectra were compared with reference spectra of synthetic dyestuffs and external spectra from online databases, i.e. IRUG Database24. In this group the significant bands in FTIR spectra were found between 546 and 3360 cm-1 range. Most intense Raman bands were found in the range of 548 – 2878 cm-1. Interpretation of the spectra allowed us to identify the chemical composition of all the prepared inks by comparing properties of bands of previously analyzed dyestuffs with bands found in the spectra of inks. For example in the FTIR spectrum of blue ink (Tab. 4) sets of peaks characteristic for the molecular structure of the methylene blue colorant were found (882 cm-1, 1025 cm-1: C-H aromatic; 1334 cm-1: C-H strech; 1393 cm-1: anthracene ring) as well as set of peaks related to the binder of this ink – gum arabic (1247 cm-1: C-O; 1597 cm-1: C=C aromatic; 3284 cm-1: O-H)25. In the Raman spectrum all observed peaks were assigned to methylene blue (Tab. 3), with the highest one found at 1626 cm-1 related to C=N stretch.

  • 26  The complete set of the interpreted spectra illustrating the method and the results remains in the (...)

23The method here described was applied in the identification of all inks analyzed in this study26. At this stage of the research we have identified all components of examined synthetic inks: fuchsine, crystal violet, glucose and fructose, oxalic acid, malachite green, nigrosine and indigo carmine. Only the Raman spectra of malachite green ink and crystal violet ink were unanalyzable due to their extremely high fluorescence emission intensity.

Results of spectroscopic analyses of natural inks

24Four samples of standard inks based on natural components were placed on separate microscope slides and left to dry prior to examination. In this group the significant bands in FTIR spectra were found between 582 and 3299 cm-1 range. Most intense Raman bands were found in the range of 553 – 3496 cm-1. Basing on the knowledge of their molecular structure (Tab. 2) we were able to assign the bands appearing in the spectra of each ink to functional groups and stretches characteristic for each of ink’ component. For example peaks of bands found in the logwood ink FTIR spectrum at 876 cm-1, 1076 cm-1, 1279 cm-1 were assigned to C-H aromatic stretch and peak at 1481 and 1570 cm-1 to C=C aromatic stretch, both of haematein, the dye extracted from logwood. The Raman spectrum of the same ink showed an intensive band at 845 cm-1 related to the presence of potassium chromate in the composition of ink. In the FTIR spectrum of iron-gall ink with logwood bands at 593, 1065, 1644 and 3299 cm-1 were due to SO42 group in iron gallates (salts of gallic acid and iron (II)sulphate) whereas bands at 1174 and 1559 cm-1 were assigned to the molecular structure of haematein. The reference spectra from the external dyestuff examination were used to distinguish indigo carmine in the composition of Leonhardi’s patented ink. The results of all analyses are presented in Table 7.

Results of spectroscopic analyses of copying pencil inks

25Measurements of eight copying pencils were performed. A sample of writing core of each pencil was placed on a separate microscope slide, dissolved by water and left to dry. In this group the significant bands in FTIR spectra were found between 423 and 3734 cm-1 range. Intense Raman bands were found in the range of 502 – 3296 cm-1. There was strong evidence of presence of kaolin binder in all the spectra of copying pencil inks discernible by many peaks assigned to Si-O stretching band. The other identified substances were colorants such as methylene blue, methyl violet, Prussian blue and aniline yellow. The reference spectra of Prussian blue and aniline yellow identified in the copying pencil no3 were obtained from IRUG Database. Methylene blue and methyl violet were distinguished through comparison with their reference spectra recorded in the first stage of spectrometric examination.    

Optical and spectroscopic analyses of historic documents

  • 27  Cyprian Kamil Norwid (1821–1883) was a Polish poet, dramatist, painter, sculptor and philosopher. (...)

26The object of the final stage of the research was to assess the efficacy of our procedure in the identification of inks on paper documents from the last quarter of the 19th century belonging to the Cyprian Norwid Library in Elbląg, Poland27 (Ill. 10, 11). For this purpose we utilized all the data collected in previous steps of the research, both optical and spectrometric.

Fig. 10 Non-invasive optical excamination of a paper manuscript

Fig. 10 Non-invasive optical excamination of a paper manuscript

One of historic documents belonging to Cyprian Norwid Library in Elbląg, last quarter of the 19th century. Clockwise from left: VIS photography, IR reflectography image, false-color image and UV fluorescence image. Visible transparency characteristics to IR radiation, false colors and ultraviolet fluorescence emission intensity.

Photo: © Agata Kłos

Fig. 11 Procedure and results of the historic ink investigation

Fig. 11 Procedure and results of the historic ink investigation

Table represents procedure and results of optical (VIS, NIR, UV and IRC) and spectrometric (FTIR and Raman) examination  of an ink writing found on a paper manuscript from the Cyprian Norwid Library in Elbląg, last quarter of the 19th century.     

Photo: © Agata Kłos

27A set of four documents was chosen for the examination. Each of them contained one or more unidentified writing material. As in the first part of the research, three non-destructive optical techniques were used: near-infrared reflectography, ultraviolet fluorescence and false-color infrared photography technique. Documents were illuminated with adequate radiation sources and photographed with adequate UV and IR filters. False-color images were digitally processed prior to interpretation.

28Spectroscopic methods have been used in-situ, without sample collection. For the FTIR measurement documents were placed on the ATR table and during micro-Raman analyses documents rested safely on the microscope table.

29During spectrometric examination we have encountered some issues. One of them concerned strong signal coming from cellulose which could have been masking other bands (Tab. 6). The other problem was created by high fluorescence emission intensity of some inks which could have been due to the presence of cellulose too (Tab. 6). Due to this extremely high fluorescence emission intensity we were unable to measure Raman spectra of three documents (6 types of ink, Tab. 7). We were able to measure FTIR spectra of all documents (7 types of ink) and only one Raman spectrum of black ink on document no1 where we identified Leonhardi’s patented ink (Tab. 5). The problem of high fluorescence emission intensity may be solved in future by replacing laser source used in this study (488 nm, VIS) with an IR laser source emitting light at 788 nm. Nevertheless the comparison of the data obtained in the optical analyses of reference inks and collected FTIR and Raman spectra of reference material allowed us to identify all historic inks on analyzed documents (Tab. 7).

Conclusions and perspectives

30The conducted research led to the following conclusions:

  • Optical techniques should be used during the first stage of ink identification.

  • Near-infrared reflectography is a method for pre-determining the composition of inks based on their transparency to IR radiation.

  • False-color infrared photography technique is a valuable analytical tool which allows a preliminary identification of inks based on their false colors.

  • Results of optical analyses help us to choose the most suitable part of the document for spectroscopic examination.

  • To detail the results obtained from non-destructive optical methods and to conform the accuracy of identification, spectroscopic examination should be performed.

  • In order to increase the accuracy of identification, tables and spectra of additional ink standards are needed to develop a more comprehensive database than that which has been created in this study.

  • The developed methodology and reference material database allows fast identification of writing substances appearing on historic documents.

31The methodology developed in this study shows a strong potential for the identification of inks which have not yet been analyzed. Two of the optical methods mentioned here (ultraviolet fluorescence and false-color infrared photography technique) have been successfully applied in the author’s diploma project which consisted of conservation and restoration of 48 ukiyo-e prints from the Ogura nazorae hyakunin isshu series belonging to the National Museum in Warsaw (Ill. 12). The methods mentioned above in this case used in preliminary conservation research have greatly facilitated the identification of pigments and dyes and the following conservation treatment.

Fig. 12. Non-invasive optical methods in preliminary examination of an ukiyo-e print

Fig. 12. Non-invasive optical methods in preliminary examination of an ukiyo-e print

Example of application of non-invasive optical techniques in conservation research. Print no16 from the Ogura nazorae hyakunin isshu collection, 1845-1847, the National Museum in Warsaw. From left: VIS photography, UV fluorescence image and false-color infrared image.

Photo: Adam Cupa, MA, Department of Technology and Painting Techniques,  Faculty of Fine Arts, Nicolaus Copernicus University in Toruń. Source: unpublished documentation of “Conservation of 48 ukiyo-e prints from Ogura nazorae hyakunin isshu series from 1845-1847” master degree conservation project of Agata Kłos performed under the guidance of Mirosława Wojtczak, MA, Department of Paper and Leather Conservation, Faculty of Fine Arts, Nicolaus Copernicus University in Toruń

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Notes

1  Guthke, B., op. cit., pp. 22-23; Janik, L.A, Skarbnica wiedzy – podręcznik chemiczno-techniczny do fabrykacji artykułów pierwszej potrzeby dla chemików, drogerzystów, fabrykantów i wszystkich interesujących się tanią fabrykacją, Warszawa, Bibljoteka Dzieł Naukowch, 1938, p. 171; United states [corporate author], Inks, Typewriter Ribbons and Carbon Paper, Circular of the Bureau of Standards, March, 1925, no 95, Washington, Department of Commerce - Bureau of Standards, Government Printing Office, pp. 2-3.

2  Davids, T., The History of Ink Including its Etymology, Chemistry and Bibliography, New York, Thaddeus Davids & Co., 1856, p. 23.

3  Guthke, B., Wyrób atramentów (tuszów, taśm kopjowych i t. d.), Łódź, Księgarnia Ludwika Fiszera, 1919, pp. 7-20.

4  Davids, T., op. cit., p. 16.

5  Carvalho, D.N.,Forty Centuries of Ink [online], URL: http://www.gutenberg.org/cache/epub/1483/pg1483.html [accessed 27.12.2013].

6 At that time, those substances also became popular as additives to iron gall ink.

7  Martuscelli, E., I coloranti naturali nella tintura della lana. Arte, storia, tecnologia e “Archeo-materials chemistry”, Collana di Trasferimento e Diffusione, Programma Nazionale di Ricerca Beni Culturali (MIUR), La Conservazione dei Tessuti Antichi, vol. 2, p. 197.

8  United States, op. cit., p. 5.

9  Carvalho, D. N., op. cit.

10  Guthke, B., op. cit., p. 45; Carvalho, D. N., op. cit.

11 Good water-solubility was at that time considered an advantage because it facilitated ink preparation. The same property is at the same time disadvantageous as it makes ink writings water-sensitive.  

12  Guthke, B., op. cit., pp. 56-59.

13  Dube, L., “The Copying Pencil: Composition, History and Conservation Implications“ [in:] The Book and Paper Group Annual [online], vol. 17, 1998, pp. 45-52, URL: http://cool.conservation-us.org/coolaic/sg/bpg/annual/v17/bp17-05.html [assessed: 27.12.2013]; Mitchell, C. A., “Copying-ink Pencils and the Examination of Their Pigments in Writing”, in Analyst, 1916, vol. 42, pp. 3-11.

14  Sakayanagi, M., Komuro, J., Konda, Y.,  Watanabe, K., Harigaya, Y., “Analysis of ballpoint inks by field desorption mass spectrometry”, in Journal of Forensic Sciences, 1999, no 44(6), p. 1204.

15  Vide: no 1, 4, 8, 9, 14, 17, 18 - 21, 24, 25 in attached Bibliography.   

16 Analyzed copying pencils were produced by L. & C. Hardmuth-Lechistan and “St. Majewski i S-ka” Polish pencil factories in the first half of the 20th century.  

17  Guthke, B., op. cit., pp. 34-37, 41, 43-44, 49, 54; Janik, L.A, op. cit., pp. 145, 149, 151, 156.

18  Rogóż, J., Zastosowanie technik nieniszczących w badaniach konserwatorskich malowideł ściennych, Toruń, Wydawnictwo Naukowe Uniwersytetu Mikołaja Kopernika, 2009.

19  Photos were taken by and false-color images processed by the author and MA Adam Cupa (Department of Technology and Painting Techniques of the Institute for the study, Conservation and Restoration of Cultural Heritage, Nicolaus Copernicus University in Toruń, Poland)

20  All FTIR and Raman spectra obtained in this research were described and interpreted by the author and PhD Paweł Szroeder of Institute of Physics, Astronomy and Informatics, Nicolaus Copernicus University in Toruń, Poland.

21  InVia (Renishaw, Gloucestershire, UK); measurements performed by MA Agnieszka Górska in the Institute of Physics, Astronomy and Informatics, Nicolaus Copernicus University in Toruń, Poland.

22  FT-IR ALPHA-P BRUKER; measurements performed by PhD Andrzej Balawski in the Department for Conservation and Restoration of Architectonic Elements and Details, Faculty of Fine Arts, Nicolaus Copernicus University in Toruń, Poland.

23  Barańska H., Łabudzińska A., Terpiński J., Laser Raman spectrometry: analytical applications, Warszawa, PWN, 1981, pp. 78-120.

24  http://www.ut.ee/katsekoda/IR_Spectra/index1.htm [accessed 30.01.2013]; http://www.irug.org/ed2k/search.asp [accessed 30.01.2013].

25  The reference spectra of gum arabic were obtained from IRUG Database.

26  The complete set of the interpreted spectra illustrating the method and the results remains in the possession of the author.

27  Cyprian Kamil Norwid (1821–1883) was a Polish poet, dramatist, painter, sculptor and philosopher. He is now considered one of the most important Polish romantic and classical poets.

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Table des illustrations

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Titre Fig. 1 NIR reflectography color table of standard synthetic inks
Légende Comparison of standard permanent and copying synthetic inks photographed in visible (above) and NIR light.
Crédits Photo: © Agata Kłos
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Titre Fig.  2 UV fluorescence color table of standard synthetic inks
Légende Comparison of standard synthetic permanent and copying synthetic inks photographed in visible light (above) and their UV fluorescence image
Crédits Photo: © Agata Kłos
URL http://ceroart.revues.org/docannexe/image/3950/img-14.jpg
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Titre Fig. 3 IRC color table of standard synthetic inks
Légende Comparison of standard synthetic permanent and copying synthetic inks photographed in visible light (above) and obtained through false-color infrared imaging.
Crédits Photo: © Agata Kłos
URL http://ceroart.revues.org/docannexe/image/3950/img-15.jpg
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Titre Fig. 4 IR reflectography color table of standard inks based on natural components
Légende Comparison of standard permanent and copying inks based on natural components photographed in visible (above) and near-infrared light.
Crédits Photo: © Agata Kłos
URL http://ceroart.revues.org/docannexe/image/3950/img-16.jpg
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Titre Fig. 5 UV fluorescence color table of standard inks based on natural components
Légende Comparison of standard synthetic permanent and copying inks based on natural components photographed in visible (above) and ultraviolet light.
Crédits Photo: © Agata Kłos
URL http://ceroart.revues.org/docannexe/image/3950/img-17.jpg
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Titre Fig. 6. IRC color table of standard inks based on natural components
Légende Comparison of standard synthetic permanent and copying inks based on natural components photographed in visible (above) and obtained through false-color infrared imaging.
Crédits Photo: © Agata Kłos
URL http://ceroart.revues.org/docannexe/image/3950/img-18.jpg
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Titre Fig. 7 IR reflectography color table of copying pencils’ inks
Légende Visible light photography of original dry and water-dissolved copying pencils’ inks (above) in comparison with their NIR image.  
Crédits Photo: © Agata Kłos
URL http://ceroart.revues.org/docannexe/image/3950/img-19.jpg
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Titre Fig. 8 UV fluorescence color table of copying pencils’ inks
Légende Visible light photography of original dry and water-dissolved inks of copying.
Crédits Photo: © Agata Kłos
URL http://ceroart.revues.org/docannexe/image/3950/img-20.jpg
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Titre Fig. 9 IRC color table of copying pencils’ inks
Légende Visible light photography of original dry and water-dissolved inks of copying pencils (above) in comparison with their false-color image.
Crédits Photo: © Agata Kłos
URL http://ceroart.revues.org/docannexe/image/3950/img-21.jpg
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Titre Fig. 10 Non-invasive optical excamination of a paper manuscript
Légende One of historic documents belonging to Cyprian Norwid Library in Elbląg, last quarter of the 19th century. Clockwise from left: VIS photography, IR reflectography image, false-color image and UV fluorescence image. Visible transparency characteristics to IR radiation, false colors and ultraviolet fluorescence emission intensity.
Crédits Photo: © Agata Kłos
URL http://ceroart.revues.org/docannexe/image/3950/img-22.jpg
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Titre Fig. 11 Procedure and results of the historic ink investigation
Légende Table represents procedure and results of optical (VIS, NIR, UV and IRC) and spectrometric (FTIR and Raman) examination  of an ink writing found on a paper manuscript from the Cyprian Norwid Library in Elbląg, last quarter of the 19th century.     
Crédits Photo: © Agata Kłos
URL http://ceroart.revues.org/docannexe/image/3950/img-23.jpg
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Titre Fig. 12. Non-invasive optical methods in preliminary examination of an ukiyo-e print
Légende Example of application of non-invasive optical techniques in conservation research. Print no16 from the Ogura nazorae hyakunin isshu collection, 1845-1847, the National Museum in Warsaw. From left: VIS photography, UV fluorescence image and false-color infrared image.
Crédits Photo: Adam Cupa, MA, Department of Technology and Painting Techniques,  Faculty of Fine Arts, Nicolaus Copernicus University in Toruń. Source: unpublished documentation of “Conservation of 48 ukiyo-e prints from Ogura nazorae hyakunin isshu series from 1845-1847” master degree conservation project of Agata Kłos performed under the guidance of Mirosława Wojtczak, MA, Department of Paper and Leather Conservation, Faculty of Fine Arts, Nicolaus Copernicus University in Toruń
URL http://ceroart.revues.org/docannexe/image/3950/img-24.jpg
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Pour citer cet article

Référence électronique

Agata Kłos, « Non-invasive methods in the identification of selected writing fluids from late 19th and early 20th century », CeROArt [En ligne], 4 | 2014, mis en ligne le 20 mars 2014, consulté le 26 mars 2017. URL : http://ceroart.revues.org/3950

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Auteur

Agata Kłos

Agata Kłos is a graduate with an MA in Conservation and Restoration of Paper and Leather in the Institute for the Study, Conservation and Restoration of Cultural Heritage, Faculty of Fine Arts, Nicolaus Copernicus University in Toruń. Her diploma project “Conservation of 48 ukiyo-e prints from the Ogura nazorae hyakunin isshu series from 1845-1847” was performed under the guidance of senior lecturer Mirosława Wojtczak, MA, in 2013. Her master degree thesis “Non-invasive methods in the identification of writing inks from late 19th and early 20th century” was performed under the guidance of professor Jarosław Rogóż, PhD, in the Department of Technology and Painting Techniques, in the same year. From January 2014 she is an intern at the Laboratorio di Restauro Della Carta dell’Istituto Superiore per la Conservazione ed il Restauro in Rome. Simultaneously she studies Japanese culture and language at the Polish-Japanese Institute of Information Technology in Warsaw.

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Licence Creative Commons
CeROArt – Conservation, exposition, restauration d'objets d'arts est mis à disposition selon les termes de la licence Creative Commons Attribution - Pas d'Utilisation Commerciale - Pas de Modification 4.0 International.

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