Raman spectroscopy for Art. Instruments

I started working on cultural heritage science with a bench-top Horiba Jobin Yvon Raman Spectrometer  in 1999. I did keep working on other Raman systems from time to time. A lot has been written on this technique  and its applications for Art and Archaeology.So, this post just provides – as usual – my personal insights.

Raman

My first Raman spectrometer, a bench-top Horiba Jobin Yvon Raman Spectrometer in 1999.

An  affordable Raman system

There are plenty of systems for Raman spectroscopy. I’m interested to mobile solutions which can be used for on site examination. Among the “mobile” systems there are some that are pretty heavy; the spectrometer and power laser are hosted in a luggage – such the one I worked with for the Leonardo’s project for the Battle of Anghiari in 2010.

Raman Anghiari

This mobile Raman system has an heavy spectrometer and power laser hosted in a luggage. Even if mobile, it’s still too heavy for practical art examination on site.

For on site art examination we need a mobile and lightweight. I worked with the DeltaNu Inspector 785. This is a very low cost Raman system, probably the cheaper, and really light. I tested it on my collection of historical pigments painted with gum Arabic. So, basically this is the case if you plan to work on manuscripts. I got acceptable Raman spectra from the pigments listed below (a “Y” means a characterizing Raman spectrum could be acquired).

cadmium red
red ochre Y
burnt umber
Sienna
burnt Sienna
Vermilion Y
Red lead Y
Yellow ochre Y
Naples yellow
Realgar Y
Orpiment Y
Cadmium yellow
Cobalt yellow Y
Malachite
Green earth
Cobalt green Y
Verdigris
Cadmium green Y
Phtalo green Y
Chrome green Y
Viridian
Azurite
Cobalt blue Y
Indigo Y
Ultramarine natural Y
Phtalo blue Y
Egyptian blue
Prussian blue
Smalt Y
Ultramarine synth Y
Cobalt blue
Cobalt violet
Van dyke brown
Asphalthum
Ivory black
Vine black Y
Lead white Y
Zinc white
Lead Tin yellow Y
alizarin
massicot Y
gypsum Y
titanium white Y


pigments checker v2 vsPigments Checker is for photographers, conservators and scientists interested in technical documentation of paintingss. It has 54 swatches of historical pigments designed for infrared photography, ultraviolet photography and other technical photographic methods for art examination. Check it out!

Pigments Checker is a collection of 54 swatches of his­tor­i­cal pig­ments that have been applied using gum ara­bic as a binder on a cel­lu­lose and cot­ton water­color paper, acids and lignin free. This paper is not treated with opti­cal bright­en­ers, it’s slightly UV flu­o­res­cent, and it reflects IR. Two cross-hair lines, 0,2 mm (ver­ti­cal) and 0.4 mm (hor­i­zon­tal) are printed on each swatch of paper before the appli­ca­tion of paint, in order to have a means to eval­u­ate the pig­ments’ trans­parency in the IR and IRR imag­ing. Among all the pig­ments and their vari­eties ever used in art these pig­ments col­lec­tion select the most used ones from antiquity to early 1950’.


When it comes to oil painting the instrument performance is much worse. I didn’t try the system on oil painted test swatches but on an old oil painting. I could see peaks just from the strongest Raman scatterers; vermilion and lead white. The linseed oil fluorescence is really strong even if with the 785 nm laser in the DeltaNu Raman Inspector.

DeltaNu Raman Inspector

DeltaNu Raman Inspector. The most compact, lightweight and affordable Raman (785 nm laser) on the market.

Prussian blue

This system can get Raman Spectra until 2000 cm^-1. Prussian blue has its strongest emission at 2154 cm^-1, so, unfortunately this system misses to identify this important pigment.

References on Raman Spectroscopy for Art

This topic has been extensively covered by a number of publications. You can find many on the internet.

My PhD Thesis on Raman Spectroscopy for Art. Unfortunately, it’s just in Italian and it’s a bit outdated, 2004.

Raman Microscopy in art and Archaeology If you never heard about Raman Spectroscopy for art this is a nice introductory paper. H.G. M Edwards,Spectroscopy 17(2) 2002

Free Software for Raman Spectroscopy

Most Raman spectra are in the .spc format.   You can use a very simple and free software to open them from Thermo Scientific SPC Viewer.

If you want something more flexible and yet free try out Spekwin32. So far the best free Raman software.  I noticed that on Win7 you have to run it as administrator otherwise it doesn’t load the spc files.

Database of Raman spectra for Art

  • ColoRaman. Unfortunately it is not online anymore, the Raman spectra database of pigments I develop for my PhD. It showed how the Raman scattering changes with 3 different laser wavelengths.
  • e-VISART. Run by Dr Kepa Kastro, useful collection of spectra with peaks intensity noted.
  • University of Parma. This is a Raman database of minerals but since most pigments are minerals…This project springs from the passion of Dr. Danilo Bersani for minerals’ collection.
  • Romanian Database. While writing this post I checked out this website and had the pleasure to discover this group has develop a nice program, RDSS. I actually do the same thing in order to interpret a Raman spectrum. I made an Access MS Database  with, for each art material, a column for the main peak, another column for the second intense peak and so on.. Then, other columns for reference papers, pictures of the  spectra, notes,.. I’ll keep using my Access DB but I will compare my data with theirs. Nice program.
  •  RRUFF. University of Arizona  runs this outstanding database. it’s pretty unique because you can download the spc file so you can compare  – using a software such as   Spekwin32 – your spectra with these standards.
  • UCL. This is a classic you cannot miss.  Prof. R.J.H. Clark – University College London -has played a pivotal role in the development of Raman microscopy for art and this is one of the first database ever made on this topic. You can also download the spc file. Useful, clean, simple.
2016-10-17T16:34:24+00:00

11 Comments

  1. Sam May 7, 2013 at 3:31 am - Reply

    I am surprised that you didn’t mention IRUG http://www.irug.org
    Do you consider this site useful?

  2. Friedrich Menges August 26, 2013 at 10:30 pm - Reply

    Hi Antonino,

    just two comments about Spekwin32:
    – It is sufficient to install Spekwin32 in Admin mode or else run it once in Admin mode while opening a spc file. This is necessary for registering the DLL used for converting this file type.
    – Currently, Spekwin32 is able to read *.rruff files. The next version will be able to also create them. Please contact me, if interested.

  3. Bessie Smith October 4, 2013 at 4:15 am - Reply

    Wow! That was really a cool information! Glad to know that a Raman Spectroscopy are now also used in art as an instrument. I hope I could give a chance to try this for an art project maybe as I am a fan of art. Thanks! EnwaveOpt.com

  4. Juraj Lipscher January 24, 2015 at 11:42 am - Reply

    Thank you for the collection of databases.
    Juraj

    • Antonino Cosentino January 24, 2015 at 11:54 am - Reply

      Hi Juraj,
      you are welcome. Hope those databases are useful for your research and teaching in science applied for art research. I saw from your website that you have a long experience in particular in the application of art and science for education and you worked as me for “Pigments through ages”. Hope you find CHSOS website inspirational 🙂

  5. Juraj Lipscher January 24, 2015 at 2:48 pm - Reply

    Hi Antonino

    Thank you too for your kind words. If you would be willing to let me publish any of your pigment spectra on my website, it would be greatly appreciated.

    I did not know that you have also worked on ‘Pigments through the ages’. Are the Raman spectra from you?

    Juraj
    http://colourlex.com

    • Antonino Cosentino January 24, 2015 at 4:27 pm - Reply

      Yes, Juraj, you are welcome to publish my spectra on your website. As usual with this material, add the link chsopensource.org
      No, the Raman spectra are not mine.

    • Antonino Cosentino January 24, 2015 at 4:31 pm - Reply

      you can also add this reference where the database is published
      A. Cosentino “FORS spec­tral data­base of his­tor­i­cal pig­ments in dif­fer­ent binders” e-conservation Jour­nal 2, 57–68, 2014.
      http://e-conservation.org/issue-2/36-FORS-spectral-database

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