Saturday, October 29, 2011

Better Know the Historic Palette:
What's the Matter with Madder?



J.G. Vibert  -  The Preening Peacock


In examining the working methods and materials of oil painters of the past, a pigment which frequently appears on the palettes of these artists is an ancient color called madder lake. It is a historically important pigment, and artists such as Bouguereau, Hals, Carolus-Duran, Alma-Tadema, Bonnat, David, Gérôme, Ingres, Millet, and Dagnan-Bouveret are just a few among the many who employed some variant of this pigment in their paintings. Today, the color is still often used, though what is seen on contemporary palettes is a synthetic replacement of madder lake, better known as alizarin crimson permanent, and is now chemically derived from compounds like quinacridone. 

 (In this article, “madder lake” refers to two different, but related artists’ colors: true organic madder lake, which Franz Hals would have used, and what, throughout most of the nineteenth century, was referred to variously as madder lake, laque de garance, garance foncée, laque alizarine, rose madder, pink madder, madder carmine, Rubens’ madder, krapplack, lacca di robbia, rubric, et al.. This latter pigment, by whichever name it was called, was actually madder lake which had been refined to produce true alizarin.)

The reasons why chemists and paint-makers eventually replaced madder lake were multiple. Not only was madder lake more expensive to produce as an oil paint than its synthetic version, it was, disappointingly, also a fugitive color. The fears that this pigment, in the presence of light, would eventually completely fade away were so pervasive and strongly expressed, that today, many artists even avoid the permanent, and synthetic, approximation of the color. 

Why then do paint manufacturers still produce madder lake, and why would contemporary painters still consider using it? Admittedly, the market for such antique colors is somewhat limited, but there is a growing number of artists who wish to experiment with older palette arrangements to emulate their favorite painters of the past, and there is nothing invalid in that desire. Despite any warnings and concerns over using madder lake, and despite observable evidence that in some ancient paintings, the color has faded badly, there are still many, many paintings in museums throughout the world in which madder lake was used to great effect and without detriment. 


J.G. Vibert  -  A Marvelous Sauce


How have some paintings containing madder lake survived, while others have faded? The difference is in the knowledge possessed by the artist who used the pigment, and in the knowledge of the colourman who produced the paint. By the end of the nineteenth century, madder lake had been used for half-a-millennia as an oil color. Years of experimentation and observation had led to successful methods of improving the color and then employing it properly. And such understanding was widely dispersed. But by the middle of the twentieth century, the new generation of artists found such material knowledge irrelevant to their art-making, and the expertise was practically lost. To make enduring work, that knowledge must be regained. To merely know that a favorite artist of the past used the color, is not enough; it must also be known how they used the color if one is to try and recreate their results. 


Lake Pigments

Lake pigments are manufactured by precipitating a dye with an inert binder, usually a metallic salt.¹  In other words, the dye, whether organic or synthetic, must first stain a material which has enough substance to enable grinding with oil to make an oil paint; the dye alone simply does not have enough body to do so. Practically any color is available as a lake, with the exception of white and a true black, and, generally, to achieve a variety of tone, increasing the ratio of the metallic oxide to the colorant will produce a paler lake, while the reverse would produce a darker lake.²  Sadly, most organic lakes, whether of vegetable or animal origin, are useless as artists materials; ultimately, most will drastically fade on the canvas. 

When prepared according to historic processes, some lake colors to be avoided include: Dutch Pink, a yellow lake prepared from the buckthorn berry; Indian Yellow, made from the urine of cows fed upon mango leaves; Carmine Lake, made from crushed cochineal insects; Florentine Lake, also made from cochineal, but cheaper in quality than Carmine; Indigo Lake, from the tropical indigo plant; Sap Green, made from unripe Persian berries; Vandyke Brown, made from peat moss; Asphaltum††, made from coal tar; and Sepia, made from the ink of cuttlefish. 

 ††(Asphaltum, though prepared in a similar manner to lakes, may not be strictly considered a lake pigment. Some artists swore by the color, and their works have not exhibited damage due to the inclusion of asphaltum on their canvas. These artists who successfully used the pigment claimed it was proper technique that prevented the harm to their works. This is likely only partly true. There were different qualities of asphaltum, different methods of manufacture, and even different source materials. Toward the end of asphaltum’s popularity, the majority of the pigment available was made from coal tar, and this version faded in light, melted in heat, caused cracking, and was liable, after appearing to set, to soften and run.³)  


J.G. Vibert  -  The View


Many nineteenth century artists left themselves at the mercy of professional colourmen for the production of their pigments, and often, the artists did not know if what they were buying was what they were getting. In London alone, there were nearly 200 colourmen at the end of the seventeenth century, and it is assured that all of their products were not of genuine quality; madder lake, for instance, was often sold adulterated with the powder of tinctorial woods, substances infamous for their fugacity.⁴  Jehan Georges Vibert, in his book, The Science of Painting, described the situation thusly: “It is true that as soon as a colour is reputed bad, conscientious artists dismiss it from their palette: but it quickly reappears disguised, like swindlers who change their name to make new dupes, and it becomes very difficult to recognise those bad materials in the clever mixtures in which they are concealed.”⁵  In reaction to the possibility of unknowingly re-adding a bad pigment to their palettes, many artists came to be more cautious about the colors they used. 

Lakes, because of their poor record of performance, were, of course, distrusted, and many artists eschewed them in their works. As a consequence, madder lake, the one lake which was relatively permanent, suffered a bad reputation through “guilt by association,” which has lasted to the current day.



rubia tinctorum



Madder Lake

Madder red is an important dye extracted from the root of the madder plant (rubia tinctorum). It has been used as a colorant since as early as 1500 BC, when the Egyptians developed several techniques for producing a lake pigment from the madder, but their pigment was rather weak, and extremely fugitive. Still, examples of it have survived on Egyptian tomb walls, and fabric stained with madder root dye was found in the burial chamber of the Pharaoh Tutankhamun.⁶ 


Turkish madder roots (Kremer Pigmente)


During the fifteenth, sixteenth, and seventeenth centuries, madder lake was in wide use throughout Europe, but by the middle of the eighteenth century, the recipes for its production were relatively lost. As interest grew in reproducing the red colors seen in fabrics imported from Greece and Turkey, European dye-makers and colourmen began a renewed search for a brilliant, and less costly, red colorant of their own. Then, in 1771, German chemist Andreas Sigismund Marggraf was handed a small sample of red pigment and was asked to duplicate it; the recipe for its manufacture had been lost with the death of its original maker. Marggraf deciphered that the pigment was based on an alumina substrate, and after failing to match the color using the then more-common sources of red dyes, found success with matter extracted from Färber röthe (madder root). His analysis garnered him credit as being the first to prepare, or at least re-discover, the process for making madder lake pigment.⁷ 


unground dried madder lake (Kremer Pigmente)


In the early nineteenth century, several additional advancements were made in the process of laking madder red, and making of it an artist’s oil color. Both the scholar Sir Henry Englefield and the colourman George Field have variously been assigned the distinction of developing a system of using pressure to extract dye from madder, heating the resulting red liquid, and then precipitating it with potassium or sodium carbonate to make madder lake. Despite that Field, who was already famous for his lakes, possessed notebooks showing earlier record of this process, it was Englefield in 1804 who was awarded a silver medal by the Society of Arts in London for his approach. Two years later, Field won his own silver medal from the Society of Arts for the invention of a madder-drying stove, and then, in 1816, he went on to receive a gold medal for his creation of a percolator which used air pressure to produce lakes. The biggest breakthrough, however, came in 1826, when French chemists Pierre-Jean Robiquet and Jean-Jacques Colin isolated the primary red coloring agents in madder - purpurin, a fugitive red-yellow dye, and alizarin, a more-stable, deep, blue-red colorant. With their color, called garance†††, a madder lake formed purely from alizarin, Robiquet and Colin had finally produced a dark red pigment which was relatively as permanent as any of the best colors then available to artists.⁸ 

†††(Not all artists were quick to replace true madder lake with Robiquet and Colin’s garance. Though the alizarin derived pigment was more lightfast, it did not possess the brightness and complexity of the original.) 


Using Madder Lake 

Though alizarin was relatively permanent, only certain techniques would lead to guaranteed longevity.

Contemporary colourman, George O’Hanlon of Natural Pigments, offers the following information on the proper use of madder lake on the company’s website:

Although assigned to lightfastness category II (ASTM D 4302), madder lake may be considered as a permanent color under certain conditions. Franz Hals was well aware of the correct way in which to use this lake in order to produce vivid flesh tints. The ruddy noses and rosy cheeks portrayed by him which after a lapse of centuries have shown that this color, when intelligently used, is permanent. According to Maximilian Toch (Toch, 1911), if madder lake is used as a glaze over a color which has been allowed to dry thoroughly, it will remain permanent, but if mixed with any mineral pigment, such as ochre, lead, sienna, etc., it is altered and loses color. This Toch based on his observation of Rembrandt's use of the color in works like the Anatomy Lesson, in which 'upon close examination the flesh tones have suffered very likely due to the fact that the lake used in glazing was mixed with the under-coat.' Based on this observation it is, therefore, reasonable to assume that alizarin or madder lakes should be used as glazing colors over a properly dried surface. Alizarin or madder lakes will not decompose when mixed with various blacks such as bone black, lamp black and carbon black. 
Vermeer more than once placed a glaze of madder lake over vermilion. He first modeled the object to be represented in various tones of vermilion using white to lighten the tone and black to darken them. Once the area was dry he glazed over it with madder lake. 
Madder lake may be mixed with iron oxide pigments that have been calcined, such as Indian red, which when mixed with this pigment forms a color known as Tuscan red. It may also be mixed with burnt sienna, burnt ochre, burnt umber, etc., but is fugitive when mixed with raw ochre, raw sienna or raw umber. The chemical colors like lead white, zinc oxide, chrome yellow, Naples yellow and chrome green cause it to fade, but colors like vermilion, cadmium yellow, and all of the blacks do not affect it. 

The safest way in which to use it is as a glaze over a ground that is thoroughly dry. Madder lake deepens considerably when placed in a dark place, but is revived when subjected to bright sunlight.⁹ 

Modern Alizarin

In 1869, patents were filed, only one day apart, for a synthetic replacement for alizarin, by both William Perkins of England, and by the team of Carl Gräbe and Carl Theodore Liebermann of the German company, Baden Aniline and Soda Factory. Gräbe and Liebermann, whose good timing secured the patent for their employer, BASF, had observed transformations of alizarin under the action of certain chemical reagents which led them to connect the dye with anthracene, a coal-tar dye.¹⁰ 

Practically overnight, this artificially derived color, which was chemically identical to alizarin but cost half-as-much to produce as the natural product, decimated the market for madder. The import of madder into Britain, valued at £1.25 million a year leading up to Gräbe and Liebermann’s discovery, became unnecessary, and large areas of France, which had been thought to cultivate the finest madder, returned to regular agricultural production.¹¹ 

Through most of the twentieth century, the artificial version of alizarin was the primary replacement for madder lake. Then, in 1955, William S. Struve at E.I du Pont de Nemours and Company recognized in quinacridone, a dye first synthesized in 1896 by Polish chemist Stefan Niementowski, a source for high quality and extremely durable pigments. In 1958, DuPont commercially released quinacridone for use in such things as plastics, printing inks, and paints, including a replacement for the pigment alizarin.

Conclusion

Artists should always be concerned with producing the best artwork they can, and this includes using materials which have proven themselves to be permanent. Though there have been concerns about the fugacity of madder lake, the alizarin-based version of the pigment, when used properly, can confidently be expected to last without color loss. Whether or not an artist includes alizarin on their palette, as opposed to a synthetic substitution for the color, should be based upon personal color preference, and not on fear that the archival nature of this particular pigment is poor. 

When a past master is known to have used madder lake in their paintings, and the works have survived to this day without fading or other problems in the deep reds, it can be assumed that they used the pigment properly.†††† For a contemporary artist wishing to replicate the work of this past master, the same technique should be observed. In the case of an artist trying to emulate William Adolphe Bouguereau, for example, madder lake should be confined to glazes, or as an addition to calcined iron oxide pigments, as described earlier. 


William Adolphe Bouguereau  -  Moissoneuse (1868)  -  85 X 106.5 cm


The madder lake used toward the end of the nineteenth century is comparable to the genuine alizarin (1,2-dihydroxyanthraquinone), still available for purchase today. Natural Pigments produces one such madder lake, which is ground only in a pale and well-aged linseed oil, without use of stearates or other additives. A pigment chemically identical to this, called alizarin crimson (1,2-dihydroxyanthraquinone lake), is produced by Winsor & Newton. 

Prior to 1827, the madder lake used by artists would have included a naturally occurring secondary dyestuff, purpurin (1,2,4-trihyroxyanthraquinone), which would have increased not only the pigment’s intensity, but also its fugacity. Winsor & Newton still produces a genuine rose madder, based upon recipes found in the notebooks of George Field; it has been in constant production at Winsor & Newton’s facility in Harrow, England since 1835.¹²  As the purpurin in true madder lake is highly fugitive, it might be advisable to use a modern, synthetic substitute of alizarin for madder lake instead;  the highly chromatic modern red dyes may actually be closer in color to the original madder lake than is pure alizarin.

††††(Not all paintings showing damage are resultant upon poor decisions of the artist who created the work. In some cases, over-zealous restorers have actually removed layers of glazing while attempting to clean a painting, and in these cases, the madder lake did not fade, but was instead removed from the surface of the canvas.)

Below are several color swatches representing madder lake, and several other, related or similar colors.  On the left side of each example is the pigment mixed with an equal amount of Michael Harding Flake White #1 (67% lead carbonate, 33% zinc oxide).  On the right is the pigment mixed with the same flake white at a value of approximately 7 on the Munsell Value Scale.  In the middle is a gradation of the pigment, from thick to thin, left to right.  No medium was added to the center section;  the paint was used straight from the tube.

Colors and values are approximate, and will vary from monitor to monitor, but this will give some indication of the variety of this hue available.


Doak Rose Madder Genuine

Winsor & Newton -  Alizarin Crimson  -  (1,2-dihydroxyanthraquinone lake)

Rublev (Natural Pigments)  -  Madder Lake -  Alizarin (1,2-dihydroxyanthraquinone)

Gamblin -  Permanent Alizarin  -  (quinacridone red b, perylene red, ultramarine blue)

Old Holland -  Alizarin Crimson Lake Extra  -  (quinacridone, anthraquinone, azo condensation)

Doak Florentine Lake

Winsor & Newton -  Permanent Alizarin Crimson  -  (anthraquinone)

Old Holland -  Scheveningen Rose Deep  -  (quincridone)

Old Holland  - Madder Geranium Lake Light Extra  -  (anthraquinone, anthathrone, azo condensation)

Old Holland  -  Rose Doré Madder Lake Antique Extra  -  (anthraquinone, anthathrone, azo condensation)

Vasari -  Ruby Red

Kremer Pigments, whose photographs of the process of creating madder lake are shown above, makes eight different historical madder lakes, and two which are alizarin based.  Long-prized by tradionalist painters, Kremer's pigments, dyes, and ready-made colors are available from their online store.


¹ Lake Pigment, retrieved October 28, 2011 from [http://en.wikipedia.org/wiki/Lake_pigment].
² Bersch, Josef, The Manufacture of Mineral and Lake Pigments, (Scott, Greenwood & Co., London, 1901), p. 343.
³ Vibert, Jehan Georges, The Science of Painting, (Percy Young, London, 1892), p. 171.
⁴ Riffault des Hêtres, Jean René Denis, Armand Denis Vergnaud, and G. Alvar Toussaint, A Practical Treatise on the Manufacture of Colors for Painting, (Henry Carey Baird, Philadelphia, 1874), p. 458.
⁵ Vibert, p. 58.
Rose Madder, retrieved October 28, 2011 from [http://en.wikipedia.org/wiki/Rose-madder].
⁷ Kirby, Jo, Marika Spring, and Catherine Higgitt, "The Technology of Eighteenth- and Nineteenth-Century Red Lake Pigments," in National Gallery Technical Bulletin, Vol. 28, 2007, (Yale University Press, New Haven, 2007), p. 76.
⁸ Kirby, Spring, and Higgitt, pp. 76-78.
⁹ O'Hanlon, George, Madder Lake, retrieved October 28, 2011 from [http://www.naturalpigments.com/detail.asp?PRODUCT_ID=820-510).
¹⁰ The History and Production of Rose Madder and Alizarin Pigments, retrieved October 28, 2011 from [http://www.winsornewton.com/resource-centre/product-articles/rose-madder-and-alizarin].
¹¹ Idem.
¹² Idem.




11 comments:

David Gluck said...

Damn good article. I would expect nothing less from "ox puncher" Innis.

scottsz said...

Absolutely amazing post. So few people appreciate the 'chemical history' of pigments and palettes.

Well done!

nystudios said...

Interesting that you used 3 Viberts as examples. Have you read Vibert's manual on painting? I think that the reason his painting retain such extraordinary color is his use of watercolor in the beginning and middle of his pieces. He isolated every layer with what he called "Watercolor Fixative" and although he gives the ingredients for every concoction he made, he never reveal the contents of the said fixative. I have tried to do some research on the matter, and I believe he bought the fixative off the shelf so to speak so there isn't anyway to determine its contents. Looking at Rockwell, Parrish, and Vibert's works, there are similarities in crack size, depth, crazing. All three have maintained the color extremely well. I know that Rockwell and Parrish used shellac extensively, could it be possible that that was part of Vibert's fixative, and thus why his colors and the integrity of of his surfaces are so pristine? Or was it that the "Fat over Lean" was so well managed by watercolor build up, and the many layers of isolating fixative? Could this be why his madders are still so resilient? Anyway, point to ponder.

If you haven't read his book, it can be found for free on google books.

David J Teter said...

Great post. Important info not to be ignored.
I have a question, maybe it can't be simply answered in a response, if so that's ok.
Does this info also apply to watercolor and gouache pigments?

Les said...

Interesting. James Gurney's gurneyjourney blog post "Lightfastness and Alizarin Crimson" references a Handprint article which presents different conclusions:

http://www.handprint.com/HP/WCL/waterr.html

That article states in part, "The lightfastness of alizarin crimson ranges from very poor to marginal" and places it in the "Avoid" category. I like Alizarin, but switched away from it based on that article.

Further clarification would be valuable to me. Thanks much for your views and great research.

innisart said...

@ Les (and David) The website you reference is speaking specifically of watercolors, and it is my understanding that alizarin pigment does fade much more rapidly in WC (and therefore probably gouache) than it does suspended in oil.

I plan to do some tests with the swatches I made, however, to do my own comparison of lightfastness, and will report back if I find my observations run counter to the information I uncovered about madder lake oil colors.

Darren said...

Well done as always.

As I See It - Art said...

Great article! On a personal note - you may have bridged the gap between myself and my boyfriend (formerly a chemist). I have never been able to plausibly explain why some paints are $3 a tube and some are $50+ other than - I can see the difference in some colors, some are all fillers, etc. Do you have any postings reviewing the different brands? This article alone should have all the paint manufacturer's sending you samples and trying to garner your approval!

Teresa Oaxaca said...

Great article! Vibert is hilarious :) The peacock...

innisart said...

@nystudios I know of the Vibert book; I referenced it several times during the post, but I have not yet read it cover-to-cover.

Vibert's paintings seem to have retained their color well, but in thinking of the ones I have seen in person, I can't remember any damage- perhaps some very fine cracking?

Rockwell is a different story story all together. If his paintings began exploding tomorrow, he wouldn't be turning in his grave. I wonder if his paintings are in any kind of good condition because of the work of restorers.

Parrish's later works (the landscapes) were done all in glazes, with intense colors straight from the tubes. The damage I remember seeing in those was alligatoring in the blue layer. His isolation of the layers using copal varnish was to bring out the color in the previous glaze layer before beginning the next, and to allow a safety margin for removing mistakes without affecting the work done earlier.

I think perhaps if the colors in Vibert and Parrish have retained brilliance, it is not because of shellac or varnish in between layers, but because they were working on white grounds. Parrish mixed no white into any of his colors, allowing the light to reflect through the colored layers from the white ground. Vibert on the other hand, by employing an underpainting in watercolor was likely avoiding a dead-color beginning. He could have used a very chromatic rose madder watercolor and then painted in less fugitive oil colors on top of that (the oil and shellac sealing in and protecting the watercolor from major effects of light). Vibert's contemporaries were likely using dead-coloring in their starts, or dull imprimaturas; Vibert's work would have stood out.

It's an interesting idea though. If I were to try it, I'd go with copal varnish, like Parrish.

As I was writing the article, my wife suggested I write a post on Parrish's technique; it was one of the first I really got into many years ago. I think you have just made sure I follow her suggestion!

innisart said...

@As I See It - Fillers play a big role in the cost of a paint, for sure. It is amazing and saddening to compare paints some times. I remember buying a tube of color once which resembled cobalt turquoise. It was a decent price, but I always felt disappointed by the color. Then one day I bought a tube of cobalt turquoise by another manufacturer and paid 5 times as much for it. I squeezed out two nuts of white paint, and slowly mixed each of the two cobalt turqs into a nut. With the more expensive paint a small dab turned the white blue. With the cheaper paint, I had to add an amount almost the size of the white pile before it began to effect a color change. The more expensive paint was well worth it!

Labor and scarcity of material play a role in price too. Rose madder is a great example. Between growing the madder, importing it, washing it, laking it, filtering it, etc., it's quite labor-intensive. Then demand is low, and that adds to the price. Another example is ultramarine blue, which is inexpensive as paints go. But if you were to use the pigment which ultramarine blue replaced, lapis lazuli, then you are talking about grinding up a semi-precious stone to make your paint, and that isn't cheap either. Genuine ivory black, as you'd imagine, would also be expensive (and depending on the ivory source, illegal).

Of course, the other thing to keep in mind is that the art supply industry does not "drive" the pigment industry. The automobile industry plays a much larger role, for example. When a trendy color goes out of fad, bulk sales of that pigment disappear, and sometimes, so too does your new favorite tube of paint.

I envy your boyfriend's knowledge of chemistry!