Looking for a new color for a billion dollars

We have never had a truly safe, stable and bright red pigment. His invention can start with YInMn, the first blue pigment created over two centuries.

Mas Subramanian , the largest star in the little-known world of pigment research, looks at a cluster of wide-necked jars containing powders of all colors of the rainbow, except for one. There are orange, yellow, green, blue, blue and purple. “We are close to the goal,” he says optimistically. And points to a jar with red-brown dust, smoky and with a hint resembling paprika. Nice color, but not the one he is looking for.

During the nine years of his temporary stay in the sophisticated world of colors, Subramanian, a professor of materials science at the University of Oregon at Corvallis, was completely fascinated by the world of chemistry, which he, like many of his colleagues, had previously considered a low-tech field. He gained fame thanks to the random creation of a new pigment in 2009, a substance capable of imparting color to another material. YInMn blue (read "Yingmin") - a mixture of yttrium, indium oxide and manganese, elements of the periodic table, which, when put together, produce something unique. YInMn was the first blue pigment to be discovered in more than 200 years.

The color industry was struck not only by the exotic blue of the pigment, but also by the other shades that it is capable of producing. Subramanian soon realized that by adding copper, you can make a green pigment. Adding iron - orange. Zinc and titanium - muffled magenta.

Studying his creations, scattered around the workbench, as if he were testimony to Willie Wonka's revelry, he frowns. “We made other colors,” he says, “but did not find red.”

The world lacks perfect red. And always lacked. We were interrupted by all sorts of options, from toxic to unpleasant. Gladiators smeared faces with vermillion, a dye based on mercury. Titian painted using realgar mineral containing arsenic. The red uniform of the British army was created with the help of the dye extracted from the beetle " Mexican cochineal ". For several decades, red Lego cubes contained cadmium, which turned out to be a carcinogen.

Today, there are more than 200 natural and artificial red pigments, but each of them has problems with security, stability, color and opacity. The pigment is red 254, it is also the “red Ferrari”, for example, popular and safe, but based on carbon, which makes it dull in the rain or in the heat. “It’s contraindicated for us to be in the sun,” says Narayan Khandekar, director of the Harvard Ostrich Center for Conservation and Technical Research, and curator of the Forbes pigment collection. "The same is true for most organic systems." One red pigment is stable, non-toxic and eternal: iron oxide, or red ocher, reddish clay, which was found in the Paleolithic rock art. “But it’s not as bright as people need,” says Handkar.

The new pigment can annually bring hundreds of millions of dollars, affecting all categories of products, from plastic and cosmetics to machines and construction. The most commercially successful blue pigment, phthalocyanine , can be found in eye shadows, hair gel and even on the wagons of British railways. Subramanian's blue pigment seems to be superior to him, but this does not mean that he made the scientist rich. What began in the form of scientific research has revealed a whole set of new problems related to the approval of YInMn, its production and market launch.

Having launched this process, Subramanian, being more a scientist than a general director, now hunts for the equally safe, inorganic red color originating from YInMn - something that can leave a red Ferrari, bringing in $ 300 million annually, far behind. Mark Ryan, a marketing manager for Shepherd Color Co., located in Cincinnati, says that those who can find such a red color "can no longer go to work the next day."

Subramanian, learning about the promises of Ryan, grins. “I would go to work anyway,” he says. “I like what I do.”

Subramanian is 64 years old, he is short, a little plump, and wears dark whiskers bent down the corners of his mouth. He grew up in the city of Chennai [ex. Madras / approx. trans.], located on the southeastern coast of India, and his passion for what constitutes objects, was born in the study of the beautiful shells, which the sea threw ashore. “How does nature do such things?” He asked himself. And only much later, he began to ask questions about how shells acquire their color.

Technically speaking, colors are the visual perception of a color that is refracted and scattered, or reflected from the atomic composition of an object. Modern computers are capable of displaying 16.8 million different colors — much more than people can see or print printers. To transform a digital or invented color into something tangible, a pigment is required. “Let's say you come up with a beautiful blue color,” says Laurie Presman, vice president of the Pantone Color Institute, who helps companies develop color strategies for brands and products. “But can you really make such a color and put it on velvet, silk, cotton, viscose or coated paper?”

“It's not just color,” she adds. - The point is the chemical composition of color. Is it possible to actually implement this composition in the material on which you want to apply it? "

These features limit the range of pigments available for clothing, construction, technology and other industries. A single titanium oxide occupies nearly two thirds of the international pigment market; It is estimated at $ 13.2 billion and is responsible for the fresh whiteness of road marking lines, toothpaste and donuts in powder. Historically, obtaining other colors has been associated with the inclusion of hazardous inorganic elements or substances - lead, cobalt, or even cyanide. In recent years, rules related to health and the environment have generated an active shift towards more favorable organic pigments, with the result that researchers discover many new black, yellow and green flowers. But blue is a completely different thing.



Subramanian entered the annals of pigment studies, although he did not look for pigment and did not even mix the ingredients that could produce some particular color. He and his colleagues were engaged in electronics - specifically, multiferroics , materials that are both polarized both magnetically and electrically, which can be useful for creating computers. Yttrium looks like dull white, indium oxide is black, and manganese is yellowish. Andrew Smith, one of the graduate students under the leadership of Subramanian, crushed them to gray, put the mixture on a plate and put it in the oven at 1200 ° C. Twelve hours later, they got a deep, energetic, intoxicating blue from the stove. It was so bright, so amazing, that it seemed almost extraterrestrial — the freshest Venusian blueberry, cleaned, polished and glowing from the inside.

“What the hell happened?” Asked Subramanian when he saw him.

“I did exactly what you asked for!”

“Are you sure you cooked everything correctly?”

"Yes".

"Let's try again."

Subramanian knew something about discoveries. After receiving a doctorate in chemistry from the Indian Institute of Technology in Madras, he spent three decades researching the chemistry of solid materials at DuPont Co., in essence, studying the composition of everything that was not liquid. He registered 54 patents, mainly related to superconductors, thermoelectric materials, and other esoteric topics, interesting only to a narrow circle of electronics chemists. Nothing colorful. But Subramanian realized that something interesting had happened here.

He got in touch with colleagues from the University of California at Santa Barbara. “You have to see it in order to believe,” he said. They did not share his optional enthusiasm.


Different concentrations of manganese give different shades and densities of color.

“In life, I have not seen such a color,” he recalls. - I made so many oxides. Superconductors are always black, brown, sometimes yellow. This I have never done. " It's as if he crossed tomatoes with onions and got a melon. “I was constantly worried - is it real or is it dreaming of me?”

Blue is one of the most common colors in nature, but it turned out that it is very difficult to create for man. When the ancient Egyptians tried to reproduce the deep, oceanic shade of ultramarine to decorate tombs, papyrus, and drawing, they got a turquoise color. In the Renaissance, ultramarine could cost more than gold, because lapis lazuli , from which this pigment was made, was mined in far-off Afghanistan. (And, nevertheless, Michelangelo managed to get it enough to paint the ceiling of the Sistine Chapel.) The first modern synthetic pigment, Prussian blue , a mixture of hexacyanoferrates, was discovered only at the beginning of the 18th century by a German chemist who tried to create a red color. Since then, many common blue pigments (azure, midnight, aquamarine, smalt) contained traces of cobalt, which is probably carcinogenic.

Subramanian and Smith began testing their mixture, dipping it into acid. They liked that it did not dissolve. YInMn also proved to be inert, non-dimming and non-toxic. It was more reliable than ultramarine and Prussian blue, safer than cobalt blue , lighter than phthalocyanine blue, darker than Victorian blue. It reflected the heat quite well, which probably would have allowed an object covered with such a dye to remain cold under the sun. Subramanian put two wooden birdhouses under a pair of lamps on the office table. The roof of one of them was painted in half with black chrome oxide and cobalt blue; the other is black mixed with YInMn blue. The nesting box, painted with YInMn, remained at 55 degrees [° F; about 11 ° C / approx. transl.] colder than the other.

Subramanian wrote a scientific paper describing his blue pigment, and published it in the Journal of the American Chemical Society, and then filed a patent application (No. 8,282,728, October 2012). The fact that he became the father of a new type of blue pigment attracted the attention of the media, and then of corporations. Subramanian was surprised by his interest and quickly applied for new grants from the government. “I thought that in this area everything is already known,” he says. “Who would give me money for pigment research?”


Mixing yttrium, indium and manganese to obtain YInMn

But more was at stake than he thought. The research company Ceresana estimates the volume of the pigment industry at $ 30 billion, headed by such large chemical companies as Lanxess, BASF, Venator (a branch of Huntsman), and Chemours (a branch of DuPont). The best pigments - the brightest, stable and reliable - represent a fast-growing segment of the market, and were responsible for the sixth part of its volume in 2016, according to a study by Smithers Rapra Ltd. The demand for pigments is growing as lead-based dyes gradually disappear, and new markets use dyes for industrial and construction purposes.

A safe, reliable, environmentally friendly blue pigment must be extremely profitable. This is, by a large margin, the favorite color of Americans, according to Presman of the Pantone Institute of Color. “Blue is a concept of hope, promise, reliability, stability, calmness and confidence,” she says. - We believe that this is the color of constancy and truth. This is one of the most attractive and comfortable colors. ” Blue - the main center of brands such as Ikea, Ford, Walmart and Facebook. It is found on the shelves of refrigerators, on walls and clothes. Two-thirds of the highest league baseball teams wear blue uniforms. Blue color can be found everywhere.

The companies that called Subramanian had a lot of ideas about YInMn. HP wanted to know if ink could be made from it. Chanel was interested in its use in cosmetics. Merck - about skin care. Nike wondered if it could be used to dye leather sports shoes to keep feet cool. The subcontractors of the companies working on the roboMOBs believed that the reflective abilities of YInMn could improve sensor performance.

Pigment traders were also interested. Shepherd Color Co. sent its representatives to the University of Oregon within a week after the publication of the work, and then spent two years testing YInMn for environmental impact, regulatory compliance, and cost. The next step is licensing. The patent belonged to Subramanian, but the university was credited with deductions, since the discovery was made in a laboratory belonging to it. Shepherd received an exclusive license in 2015, and immediately began to prepare for the production of lots in half a ton for the market, which, from her point of view, was the most valuable: industrial siding and roof coverings. Last September, eight years after the discovery of Subramanian, the US Environmental Protection Agency finally approved YInMn for commercial use for industrial coatings and plastics. Shepherd quickly entered the market.



The next natural step for the company was to apply for the inclusion of toxic substances in the list, which would allow the dye to be applied everywhere - potentially and in those cases in which Nike and others were interested. But so far Shepherd has not filed such an application. So far, YInMn has made other exits to the market with the help of Crayola LLC, whose first new pencil in a decade, Bluetiful, has allegedly been “inspired” by YInMn - Shepherd does not indicate whether the company pays deductions - and Derivan, the paint manufacturer that turned acrylic pigment, which she offers to artists at several retail stores.

The market available to Shepherd is limited by the high cost of the pigment, due to the cost of indium, a metal mainly used in the production of transparent, thin and conductive layers of touch screens of smartphones. For these purposes, it must be extremely clean, which, coupled with high demand, means its cost is $ 720 per kg at the end of 2017 (manganese costs $ 1.74). As a result, Shepherd's YInMn costs $ 1,000 per kg, and is the most expensive pigment. Ryan, a Shepherd marketing manager, jokes that unless a meteor from india falls anywhere in southwest Ohio, the cost will remain high.

But this does not mean that it can not earn. Jeffrey Peak, Shepherd's research and development manager, says that YInMn and other complex inorganic pigments are the most reliable positions among the company's products. As a paint, they can be given a guarantee of up to 50 years - and this is worth the investment in a metal roof or facades for skyscrapers. Other applications and lower prices will appear no sooner than researchers from Shepherd or the University of Oregon can replace indium without deteriorating blue.

The slow progress of inspections and approval by regulators, deductions to lawyers and other licensing costs mean that almost nine years after opening, Subramanian has not yet seen any deductions. And yet, YInMn revived his career and asked her a new direction. “If we can create a beautiful red pigment, stable and non-toxic, it will be a big hit,” he says. - I hope so".

Patent No. 8,282,728 is in principle something much more valuable than YInMn itself. There only briefly referred to as "rich blue". Subramanian's true invention is the crystal structure (organization of atoms) of a material called trigonal bipyramidal consistency. Manganese gives a blue color, and by adjusting its proportion in the mixture, you can make the shade lighter or darker. But, as the banks of Subramanian with lilac and marsh green color demonstrate, this structure is capable of absorbing (and reflecting) other colors. This discovery was similar to the discovery of a secret door in a bookshelf.

Jun Lee, a junior researcher at Subramanyana, says that they thought at first that simply reducing the amount of indium would lead to red. But it was not so easy. Most red dyes are semiconductors, and different tricks are required to maintain their conductivity. One approach is to adjust the distance between the atoms of the mixture, which changes the absorption energy of electrons to which the light falls, because of which the composition absorbs the blue color and reflects red. But such an approach can with the same success return to the material its original light gray color. “You can try to predict the result,” she says. “But you will not know for sure.”

Reducing the proportion or replacing indium would make the new red dye cheaper (and would potentially lead to the YInMn variant of blue without indium). The inability to compare cost and demand sank the most promising red dye of the last decades, a rich hue, discovered in the late 1990s by two German researchers. They were looking for a replacement for cadmium, the natural heavy metal present in the earth's crust. In paints, cadmium has long been considered safe and reliable; his brightness enlivened the work of Monet, Van Gogh and Munch. But he gained notoriety because of his ability to seep into the environment from production and pollute food. 1997 , . ( , «»).

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