alum & lake pigments

In the last post, we discussed the quantity of alum necessary to marble with watercolor and acrylic pigments on paper. There is another class of pigments that can be used for marbling, and was historically an important source of particular hues. These are lake pigments, made from natural dyes. As both a marbler and a natural dyer myself, these pigments are of great interest.

What are lake pigments?

Natural dyes (with the exception of vat dyes including indigo) are water soluble. This means they cannot be used for marbling, as they simply dissolve into the size. In order to make these beautiful organic colors, many of which have no counterpart among mineral colors, useful for  marbling they must be converted into pigments. A lake pigment is made when dissolved dye is precipitated onto an inert substrate - often potash alum. The precipitate is then filtered, washed, and ground. For marbling it can be mixed or mulled with a binder, usually watercolor medium, and used like any other watercolor paint.

If you've ever used the all-in-one dyeing method of mixing mordant, dye, and fiber in one pot, you may have noticed some of the dye spontaneously settling to the bottom. This means the dye and alum have bonded together, making a lake pigment.

mulling watercolor

What role does alum play in lake pigments?

As we learned about alum, it readily bonds to dye molecules, making it a substrate well suited to the formation of lake pigments. Other mineral mordants can function the same way, such as tin and copper salts. Each of these mordant substrates acts to stabilize the dye compound, improving its lightfastness. And just as with natural dyes applied to fabric, the choice of mordant and pH can strongly affect the shade of a lake pigment.

The example below is a lightfastness test of homemade lake pigments( yes, I need to practice patience in grinding pigments). On top is madder lake with copper; below it is weld lake with a little indigo, mixed as watercolors. The left side was exposed to direct southerly sunlight for one month, and the results I think are quite promising. Unfortunately lake pigments suffer from a bad reputation because they are not as permanent as their modern synthetic replacements or mineral pigments. Some lake pigments are certainly fugitive, and care should be taken to keep artwork made with them out of direct sunlight. The most lightfast pigments are made from the most lightfast dyes, such as madder, buckthorn, and weld.

 Lightfastness test of madder lake and weld lake. Left side exposed to sunlight for one month

Lightfastness test of madder lake and weld lake. Left side exposed to sunlight for one month

Marbling with lake pigments

Because lake pigments contain a mordant within them, paper does not need to be pre-mordanted before marbling! I have read this in multiple sources, and the test below confirms it.

  • A: Unmordanted paper

  • B: Paper pre-mordanted with 1.5 teaspoons alum/pint water

The mordanted paper absorbs the marbled print a bit more quickly with a slightly sharper quality, but this shows that pre-mordanted paper is not a requirement.

Lakes are prepared for marbling just like any other watercolor pigment: each color is thinned to a good consistency and mixed with the appropriate amount of surfactant. You don't need to go through the trouble of grinding your own pigments to enjoy working with lakes, any 'genuine' watercolor lake such as rose madder or carmine will work. It can be difficult to know just what manufacturers put in their paints, and whether they are synthetic pigments simply bearing the names of historical shades, so it's worth seeking high quality paints if you want the real thing.

If you are marbling with a mixture of genuine lakes and pigments from other/unknown sources, pre-mordanting the paper is advisable.

testing alum mordant with lake pigments

In addition to lake pigments, I've read that any genuine earth pigment may be used for marbling without a mordant, as earth pigments are composed of minerals. It is clear from natural dyeing that ferrous salts are a very effective mordant, so the iron present in earth pigments should work the same way. I hope to test this in future, and make a comparison of the lightfastness of these samples.

Update: After 1 month of exposure to direct sunlight, no fading has been observed in samples printed on mordanted and unmordanted paper. The alum and chalk present within the lake pigments appears to stabilize the dye colorants admirably.

Please feel free to contact me with any insights or sources for historical pigments!

alum quantity

When preparing paper for marbling, it is pre-mordanted with an alum solution. We discussed the role and varieties of alum in the last post, and let's continue with the question:

How much alum to use?

Marbling instructions vary greatly in the strength of the alum solution recommended to mordant paper. I've seen measurements ranging from 1.5 teaspoons to 5 tablespoons per pint of water. Let's investigate just how much is enough to make a successful print.

What can go wrong?

If too little alum is used, marbled designs made with watercolor or acrylic pigments cannot bond to the paper. Western-style papers used in the European marbling tradition are sized to improve their durability and slow their absorbency. Alum bonded to the surface of mordanted paper is the chemical helping hand essential for linking marbling pigments to the paper fiber, and stabilizing the colors for lightfastness in the long term. Any marbler who has accidentally printed on the unmordanted back side of a sheet is familiar with the disappointment of watching their design wash down the drain with the rinse water, having no alum to hold it fast.

However, if too much alum is used, crystals may build up on the surface of the paper without actually adhering to to the paper fibers. In this case a bit of the excess alum will dissolve into the size as each print is made. If the size becomes polluted with alum, it causes the paint to clump together in a very frustrating way, and must be replaced with fresh size.* If you can feel a buildup of powder on the surface of your paper or see white streaks on colored papers, you are using too much alum.

Additionally, alum is acidic, and using a lot will both waste alum and make the paper overly acidic. Over time, this causes the paper fibers to become brittle and crack apart.

 Watercolor Pigments

Watercolor Pigments

Testing Alum Quantity

These samples, excepting sample A, were coated with a wash of aluminum sulfate dissolved in warm water:

  • A no mordant

  • B 1.5 teaspoons/pint

  • C 1 tablespoon/pint

  • D 2 tablespoons/pint

  • E 3 tablespoons/pint

As can be seen in both the watercolor and acrylic tests, unmordanted sample A is comparatively very pale. This was not a surprise, as it has no mordant at all. I was surprised, however, to find no discernible difference the in strength of the colors in samples  B-E. Any quantity of alum from 1.5t - 3T per pint acts as a successful mordant.

 Acrylic Pigments

Acrylic Pigments

My recommendation: 1.5 teaspoons alum per pint water

I will continue using 1.5t/pint to mordant papers in future, the amount recommended in the first marbling class I took with Stephen Pittelkow. As alum is slightly acidic, I prefer to put as little as needed on my paper to get the job done. Pre-nineteenth century marblers used potash alum, but nowadays you can mordant with either potassium aluminum sulfate or aluminum sulfate - just mix it with warm tap water to ensure the crystals are fully dissolved. Some marblers soak their paper in a mordant bath, some apply the alum solution with a natural sponge or a spray bottle; I use a wide foam brush. As each sheet is coated I flip it over and pencil an X on the back. The whole stack of wet papers is weighted with a heavy board to stay flat. They can be printed in about half an hour when still slightly damp, or kept up to 4 days. I prefer to print papers within one day of mordanting.

If you've prepared your papers with mordant but the marbled design doesn't adhere, you may be using archival paper coated with calcium. Choose a different paper stock and try again.

*Of course, any mistake can become an interesting pattern when repeated intentionally! Mixing a little bit of alum into your gall water or one color of paint can give an intriguing, crunchy texture to a marbled design.

on alum

I’ve recently undertaken a series of tests, as scientific as I can make them, to answer some questions I commonly receive from students and satisfy my own curiosity.

Firstly:  What is the difference between the various types of alum?

If you have done any natural dyeing or marbling, you have most likely used alum as a mordant. Alum is a metallic salt which bonds to both the fiber substrate and the coloring agent, creating an insoluble bridge linking them together.  Whether you are using dyes or paints on fabric or paper, an alum mordant will increase the amount of color that can latch on, and improve the washfastness and lightfastness of the finished piece. Alum is the most commonly used mordant because it is inexpensive, colorless, permanent, and toxic only in large doses.

I, like many marblers and dyers, am in the habit of using the term ‘alum’ to refer to two different compounds: potassium aluminum sulfate and aluminum sulfate. These two metallic salts function essentially the same way for mordanting, but it's worthwhile to consider their differences. I will not include aluminum acetate in this discussion, as it is always specified by name and is not in common use for marbling paper.

marbling tools.jpg

Potassium Aluminum Sulfate
Historically called potash alum, potassium aluminum sulfate is a translucent white crystalline powder.  It is naturally occurring, and has been extracted from alunite in volcanic areas since at least 1500 BC for purifying water, as a styptic, and a mordant. Today it can be refined from bauxite or alunite, or made in a laboratory by adding potassium sulfate to aluminum sulfate. Potash alum is the historical mordant called for in traditional dye and marbling instructions, and in making lake pigments from natural dyes.

Aluminum Sulfate
Aluminum sulfate can be made in a laboratory or refined from various types of stone. In appearance its crystals are jagged, with an opaque white dustiness. Since its introduction as an industrial product in the 19th century, it has replaced potash alum in many applications such as water purification and paper sizing, and is sometimes called papermaker's alum.

What's the difference?

  • Potash alum and aluminum sulfate may be used interchangeably as a mordant on both cellulose and protein fibers.
  • Potash alum is slightly more expensive.
  • Some dyers claim that potash alum gives clearer colors, but I have not noticed any difference between the two. If you have trouble with muddy colors, make sure your alum is from a reputable vendor. Any impurities, such as iron, will sadden your colors.
  • If you are forging historical artwork, using aluminum sulfate to mordant is a dead giveaway.
  • Both potash alum and aluminum sulfate are acidic. Whichever you use, follow mordanting instructions to avoid making your artwork overly acidic and brittle.
  • Most important for practical purposes: Aluminum sulfate is more water-soluble at room temperature. When mordanting paper, most historic manuals call for heating the water before adding potash alum (they don’t specify which alum, but potash alum is implied). Heating the water will allow the potash alum to dissolve quickly.
alum solubility chart

I made this chart from what scant data I could find, showing the solubility of both sorts of alum in one pint of water. Paper marblers generally use between 1-4 tablespoons of alum per pint, or about .5-2 ounces. Though both potash alum and aluminum sulfate are soluble at room temperature in that amount, in my experience warm tap water helps to speed up the dissolution of the crystals.

Please be in touch if you have any information to contribute, or reading to recommend! The alums and their history are a big topic.