èƵ

New blues: The quest to make the world’s rarest colour

Natural blue pigments to colour paints, inks and plastics are so hard to find that people will go to the depths of Earth to discover new ones
Starry Night painting
Fade to grey: Van Gogh’s The Starry Night would once have been bluer
The Starry Night, June 1889 (oil on canvas), Gogh, Vincent van (1853-90)/Museum of Modern Art, New York, USA/Bridgeman Images

YOU have probably seen The Great Wave off Kanagawa – the Japanese woodblock print of a huge, foaming wave about to engulf a group of small boats. It’s no surprise that the picture is mostly blue; it is a wave after all.

However, it is part of a series of images called Thirty-six Views of Mount Fuji by the artist Hokusai, and if you flick through them, you will notice that nearly every one is predominantly blue. That might seem strange, until you realise that in 1830, when Hokusai began printing these works, blue was rather a new thing. The Prussian blue he used had been introduced into Japan just a few years earlier, giving artists their first blue pigment that was bright, attractive and lasting.

“Historically, blue has been a big issue for artists; there are very few natural blue colours,” says materials scientist . These days, we have plenty of blue dyes, which, being soluble, are ideal for colouring materials uniformly. But the insoluble blue pigments needed for paints, printing inks, ceramics and plastics are still rare. That is why, when Dobson realised that he might be able to create a new one based on a mineral that can exist only at the immense pressures found 500 kilometres beneath Earth’s surface, he was very much up for the challenge.

“The ancient Greeks didn’t even have a word for blue – hence Homer’s famous ‘wine-dark’ sea”

The colour blue has proved such a problem to recreate that most ancient cultures don’t seem to have had a word for it – Homer famously describes the “wine-dark” sea. , and it’s probably no coincidence that they alone were able to produce a blue pigment. Egyptian blue was used widely until the Middle Ages when the recipe was lost and artists had to resort to either azurite or ultramarine (see “True blue“). Both were made from naturally occurring minerals, the latter from lapis lazuli. This was exorbitantly expensive, explaining why blue tended to be reserved for high-ticket items such as the Virgin Mary’s robes.

Dobson, who is an artist as well as a scientist, has a long-running collaboration with Jo Volley at UCL’s Slade School of Fine Art. However, he was unaware of just how rare blue pigments are until a few years ago. His epiphany came when he attended a meeting of artists to describe his work with one of Volley’s students hunting for new pigments in coal-mine sludge. The conference was abuzz with the discovery of a pigment called YInMn blue. Volley explained that everyone was excited about it because blues are so rare. That got Dobson thinking about another blue he had seen – a mineral that had been discovered deep in the bowels of our planet.

It’s not easy to know exactly what rocks deep inside Earth are like because they exist under extreme pressures and change when brought to the surface as the minerals become distorted. However, sometimes diamonds are dug up that bear “inclusions” – minerals within them that are trapped at the pressures they experience during formation. In 2014, Graham Pearson at the University of Alberta, Canada, . Geologists were fascinated because it addressed a long-running debate about where Earth’s water came from; it is thought that ringwoodite in the mantle contains enough water to fill the surface oceans three times over. But Pearson’s discovery intrigued Dobson for an entirely different reason: the mineral was blue.

The Milkmaid painting
Vivianite, the blue used by Vermeer in The Milkmaid (above) and azurite (below) both turn green in time
The Milkmaid, Vermeer, Jan (Johannes) (1632-75)/Rijksmuseum, Amsterdam/Bridgeman Images Azurite

UIG-3524518

Now, ringwoodite’s structure would collapse and lose its intense colour at normal surface pressures, but Dobson wondered if it might be possible to capture its blueness by engineering a crystal that mimicked it at surface pressure.

You can think of a crystal a bit like a 3D version of the colourful, tessellated tiling often seen in Islamic buildings. Each atom in the crystal structure is like a tile that must fit snugly next to its neighbours. Dobson made an educated guess that the key to ringwoodite’s blueness was the iron atoms. These were in a tetrahedral configuration, in which each is surrounded by four other atoms. “If you could put an iron ion into a tetrahedral coordination, it should end up going blue,” he says.

“Unfortunately, a student recently blew up my furnace, so that’s hampering progress”

In January 2017, Dobson got a chance to test this idea when he became the first scientist in residence at the Slade School. What he needed was a mineral that would interact with iron ions to give a crystal with the characteristic tetrahedral configuration found in ringwoodite. First he looked at a series of minerals called spinels, which have a cubic crystalline structure. One of these, magnesium aluminate (MgAl2O4), seemed perfect because its aluminium ions have the same charge as the iron ions in ringwoodite. But when he tried baking it in an oven with a source of iron, he found the iron kept slipping into the wrong size gaps – surrounding itself with eight oxygen atoms rather than four. “It ended up just brown,” says Dobson.

Then he hit on two other compounds, zinc silicate (ZnSiO4) and zinc germanate (ZnGeO4), which contain zinc in just the right configuration. When he tried substituting the zinc for iron, lo and behold he got two new blues. The silicate is a soft, greenish blue that Dobson describes as “duck egg”. The germanate gives a richer “deep water blue”.

A manufacturer of fine-art products has already shown interest in commercialising his blues. But there is still a hurdle to overcome. At the moment, when the compound Dobson has created is ground into a fine powder to suspend into a liquid paint, its colour dims. That’s because it contains too little iron. But if he adds too much, the blue will disappear. The balance of iron and zinc in the compound needs to be just right.

“That’s what I’m working on now: trying to see how much iron I can dissolve into these structures and so how intense I can get the blue,” says Dobson. “Unfortunately, a student recently blew up my furnace, so that’s hampering progress.”

But then, no one said making a new blue would be easy.

True blue

Azurite

The first blue pigment. Originally made by grinding up the mineral azurite, a copper carbonate. Synthesised artificially from the 17th century. Can dehydrate into malachite, another copper carbonate, which is green.

Ultramarine

Made as early as 7000 BC in Afghanistan from lapis lazuli. Famously used on Tutankhamun’s death mask, illuminated manuscripts and Italian panel paintings. In the Renaissance it was more expensive than gold. First synthesised in 1826.

Prussian blue

The first modern synthetic pigment. Discovered by accident in 1706, and produced by the oxidation of ferrous ferrocyanide salts. Exemplified by Hokusai’s The Great Wave off Kanagawa and Van Gogh’s The Starry Night. It fades to grey over time.

Cobalt blue

A mixture of cobalt, aluminium and oxygen. Discovered by French chemist Louis Jacques Thénard in 1802. Famously used in Bristol blue glass. The pigment is very stable but costly, and cobalt is toxic when inhaled or ingested.

Yinmn blue

Discovered by Mas Subramanian at Oregon State University in 2009. An inorganic pigment, prepared by heating oxides of yttrium, indium and manganese to around 1200°C. It is chemically stable, non-toxic and does not fade.

This article appeared in print under the headline “Blue dye thinking”

Topics: Art / Festive science / geology