YInMn Blue

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Short description: Inorganic blue pigment
YInmn Blue
 
YInMn Blue - cropped.jpg
YInMn Blue powdered pigment
About these coordinates     Color coordinates
Hex triplet#306AC0
Source[1][2][lower-alpha 1]
ISCC–NBS descriptorDeep blue
YInMn Blue
YMnO3 P63mmc Wiki Image.png
Crystal structure of YInMn Blue
Identification
FormulaYIn
1−xMn
xO
3
Crystal systemHexagonal
Crystal symmetryP63cm
Unit cella = 6.24 Å; c = 12.05 Å
ColorLight to dark blue

YInMn Blue (/jɪnmɪn/; for the chemical symbols Y for yttrium, In for indium, and Mn for manganese), also known as Oregon Blue or Mas Blue, is an inorganic blue pigment that was discovered by Mas Subramanian and his (then) graduate student, Andrew Smith, at Oregon State University in 2009.[1][3] The pigment is noteworthy for its vibrant, near-perfect blue color and unusually high NIR reflectance.[2] The chemical compound has a unique crystal structure in which trivalent manganese ions in the trigonal bipyramidal coordination are responsible for the observed intense blue color. Since the initial discovery, the fundamental principles of colour science have been explored extensively by the Subramanian research team at Oregon State University, resulting in a wide range of rationally designed novel green, purple, and orange pigments, all through intentional addition of a chromophore in the trigonal bipyramidal coordination environment.[4][5]

Historical pigments

The discovery of the first known synthetic blue pigment, Egyptian blue (CaCuSi
4O
10) was promoted by the Egyptian pharaohs who sponsored the creation of new pigments to be used in art.[6] Other civilizations combined organic and mineral materials to create blue pigments ranging from azure-blue like the Maya blue[1] to the Han blue (BaCuSi
4O
10), which was developed by the China Han dynasty and manipulated to produce a light or dark blue color.[7]

Currently, a number of pigments are used to impart the blue color. Cobalt blue (CoAl
2O
4) was first described in 1777; it is extremely stable and has been traditionally used as a coloring agent in ceramics.[1][8][9][10] Ultramarine (Na
7Al
6Si
6O
24S
3) was made by grinding the forbiddingly expensive lapis lazuli into a powder until a cheaper synthetic form was invented in 1826 by the French industrialist Jean Baptiste Guimet and in 1828 by the German chemist Christian Gmelin.[11] Prussian blue (Fe
4[Fe(CN)
6]
3) was first described by the German polymath Johann Leonhard Frisch and the president of the Prussian Academy of Sciences, Gottfried Wilhelm Leibniz, in 1708.[12][13] Azurite (Cu
3(CO
3)
2(OH)
2) is a soft, deep-blue copper mineral produced by weathering copper ore deposits; it was used since ancient times and was first recorded by the first century Roman writer Pliny the Elder.[14] Phthalocyanine Blue BN was first prepared in 1927 and has wide range of applications.

Most known pigments have detrimental health and environmental effects and/or durability issues. Cobalt blue causes cobalt poisoning when inhaled or ingested.[15] Prussian blue is known to liberate hydrogen cyanide under certain acidic conditions.[16] Ultramarine and azurite are not stable particularly in high-temperature and acidic conditions; additionally, ultramarine production involves the emission of a large amount of the toxic sulfur dioxide.[1] The newer Phthalocyanine Blue BN is non-biodegradable and has been found to cause neuroanatomical defects in developing chicken embryos when injected directly into incubating eggs.[17][18]

Inorganic blue pigments in which manganese (in the pentavalent oxidation state and in a tetrahedral coordination) is the chromophore have been employed since the Middle Ages (e.g., the fossil bone odontolite, which is isostructural to the apatite structure).[19][20] Synthetic alternatives, such as barium manganate sulfate (or Manganese Blue, developed in 1907 and patented in 1935), have been phased out industrially due to safety and regulatory concerns,[21][22] hence YInMn Blue fills the niche of an inorganic, environmentally safe alternative to the traditionally used blue pigments, and offers a durable intense blue color.[1]

Discovery

In 2008, Subramanian received a National Science Foundation grant to explore novel materials for electronics applications. Under this project, he was particularly interested in synthesizing multiferroics based on manganese oxides. He guided Andrew E. Smith, the first graduate student in his lab, to research an oxide solid solution between YInO
3 (a ferroelectric material) and YMnO
3 (an antiferromagnetic material) at 1,093 °C (2,000 °F). The resulting compound Smith synthesized was by coincidence a vibrant blue material. Because of Subramanian's experience at DuPont, he recognized the compound's potential use as a blue pigment and together they filed a patent disclosure covering the invention. After publishing their results, Shepherd Color Company successfully contacted Subramanian for possible collaboration in commercialization efforts.[23][24] For his outstanding contributions to inorganic color pigment chemistry, Subramanian was awarded the Perkin Medal from the Society of Dyers and Colourists in 2019.[25]

The pigment is noteworthy for its vibrant, near-perfect blue color and unusually high NIR reflectance.[1][2] The color may be adjusted by varying the In/Mn ratio in the pigment's base formula of YIn
1−xMn
xO
3, but the bluest pigment, YIn
0.8Mn
0.2O
3, has a color comparable to standard cobalt blue CoAl
2O
4 pigments.[2]

Properties and preparation

YInMn Blue is chemically stable, does not fade, and is non-toxic. It is more durable than alternative blue pigments such as ultramarine or Prussian blue, retaining its vibrant color in oil and water, and is safer than cobalt blue, which is a suspected carcinogen and may cause cobalt poisoning.[26]

The pigment is resistant to acids such as nitric acid, and is difficult to combust. When YInMn Blue does ignite, it burns a violet color attributed to the indium atoms.[27]

Infrared radiation is strongly reflected by YInMn Blue, which makes this pigment suitable for energy-saving, cool coatings.[28] It can be prepared by heating the oxides of the elements yttrium, indium, and manganese to a temperature of approximately 1,200 °C (2,200 °F).[29]

Commercialization

In popular culture

After Subramanian, Smith, and other colleagues published their results, companies began inquiring about commercial uses. Shepherd Color Company eventually won the license to commercialize the pigment in May 2015.[23][24][28][30] Many companies such as AMD and Crayola rushed to use the new pigment name in product announcements and press releases. It is unclear when the first commercial application of YInMn blue reached the consumer market.

AMD announced in July 2016 that the pigment would be used on new Radeon Pro WX and Pro SSG professional GPUs for the energy efficiency that stems from its near-infrared reflecting property.[31][32]

The American art supplies company Crayola announced in May 2017 that it planned to replace its retired Dandelion color (a yellow) with a new color "inspired by" YInMn. The new color does not contain any YInMn.[30] Crayola held a contest for more pronounceable name ideas, and announced the new color name, "Bluetiful", on 14 September 2017.[33][34][35] The new crayon color has been made available in late 2017.

In artists' pigments

In June 2016, an Australian company, Derivan, published experiments using YInMn within their artist range (Matisse acrylics),[36] and subsequently released the pigment for purchase.[30]

As of April 2021, Golden Paints has commercially licensed and sourced the pigment from Shepherd Color Company. According to Golden, the supply of the raw pigment is extremely limited.[37] Shephard Color Company received the required environmental and safety approvals to sell the pigment in the U.S. in 2020.[38]

See also

Notes

  1. ↑ The color coordinates were obtained from Smith et al. 2016 for the optimal blue pigment, which has the composition YIn
    0.8    Mn
    0.2    O
    3    . The CIELAB coordinates (L = 34.6, a = 9.6, b = −38.9 in table 1) were converted using an online tool.

References

  1. ↑ 1.0 1.1 1.2 1.3 1.4 1.5 1.6 Smith, Andrew E. et al. (2 December 2009). "Mn3+ in Trigonal Bipyramidal Coordination: A New Blue Chromophore". Journal of the American Chemical Society 131 (47): 17084–17086. doi:10.1021/ja9080666. ISSN 0002-7863. PMID 19899792. 
  2. ↑ 2.0 2.1 2.2 2.3 Smith, Andrew E. et al. (October 2016). "Spectral properties of the UV absorbing and near-IR reflecting blue pigment, YIn1−xMnxO3". Dyes and Pigments 133: 214–221. doi:10.1016/j.dyepig.2016.05.029. 
  3. ↑ Cascone, Sarah (20 June 2016). "The Chemist Who Discovered the World's Newest Blue Explains Its Miraculous Properties". Artnet News. https://news.artnet.com/art-world/yinmn-blue-to-be-sold-commercially-520433. 
  4. ↑ Li, Jun; Subramanian, M. A. (April 2019). "Inorganic pigments with transition metal chromophores at trigonal bipyramidal coordination: Y(In,Mn)O3 blues and beyond". Journal of Solid State Chemistry 272: 9–20. doi:10.1016/j.jssc.2019.01.019. Bibcode: 2019JSSCh.272....9L. 
  5. ↑ Li, Jun et al. (13 September 2016). "From Serendipity to Rational Design: Tuning the Blue Trigonal Bipyramidal Mn3+ Chromophore to Violet and Purple through Application of Chemical Pressure". Inorganic Chemistry 55 (19): 9798–9804. doi:10.1021/acs.inorgchem.6b01639. PMID 27622607. https://ws680.nist.gov/publication/get_pdf.cfm?pub_id=921441. 
  6. ↑ Jaksch, H. et al. (November 1983). "Egyptian blue — Cuprorivaite a window to ancient Egyptian technology". Naturwissenschaften 70 (11): 525–535. doi:10.1007/BF00376668. ISSN 1432-1904. Bibcode: 1983NW.....70..525J. 
  7. ↑ Berke, Heinz (18 April 2007). "The Invention of Blue and Purple Pigments in Ancient Times". ChemInform 38 (19). doi:10.1002/chin.200719227. 
  8. ↑ Parmelee, Cullen Warner; Harman, Cameron Gerald (1973). Ceramic Glazes. Cahners Books. pp. 491. ISBN 978-0-8436-0609-6. https://books.google.com/books?id=7FFQAAAAMAAJ. 
  9. ↑ Needham, Joseph et al. (2004). Science and Civilisation in China. Cambridge University Press. p. 659. ISBN 978-0-521-83833-7. https://books.google.com/books?id=mabcHwmAD5oC. 
  10. ↑ Maerz, A.; Paul, M. Rea (1930). A dictionary of color. New York: McGraw-Hill Book Co.. OCLC 1150631. https://www.worldcat.org/oclc/1150631. 
  11. ↑ Gmelin, C. G. (1828). "Ueber die künstliche Darstellung einer dem Ultramarin ähnlichen Farbe" (in de). Naturwissenschaftliche Abhandlungen. Herausgeben von Einer Gesellschaft in Würtemberg (Scientific Essays. Published by a Society in Würtemberg) 2 (10): 191–224. doi:10.1002/andp.18280901022. Bibcode: 1828AnP....90..363.. https://books.google.com/books?id=ZjArAAAAcAAJ&pg=PA191. 
  12. ↑ Woodward, John (1724). "IV. Præparatio cærulei prussiaci ex germaniâ missa ad Johannem Woodward, M. D. Prof. Med. Gresh. R. S. S.". Philosophical Transactions of the Royal Society of London 33 (381): 15–17. doi:10.1098/rstl.1724.0005. 
  13. ↑ Frisch, Johann Leonard et al. (1976) (in de). Der Briefwechsel mit Gottfried Wilhelm Leibniz. Hildesheim: G. Olms. ISBN 978-3-487-06071-2. OCLC 3303263. https://www.worldcat.org/oclc/3303263. 
  14. ↑ Zigan, F.; Schuster, H. D. (1972). "Verfeinerung der Struktur von Azurit, Cu3(OH)2(CO3)2, durch Neutronenbeugung" (in de). Zeitschrift für Kristallographie 135 (5–6): 416–436. doi:10.1524/zkri.1972.135.5-6.416. ISSN 0044-2968. Bibcode: 1972ZK....135..416Z. 
  15. ↑ Prescott, Eva; Netterstrøm, Bo; Faber, Jens; Hegedüs, Laszlo; Suadicani, Poul; Christensen, Jytte M. (April 1992). "Effect of occupational exposure to cobalt blue dyes on the thyroid volume and function of female plate painters". Scandinavian Journal of Work, Environment & Health 18 (2): 101–104. doi:10.5271/sjweh.1605. ISSN 0355-3140. PMID 1604269. 
  16. ↑ Tuorinsky, Shirley D., ed (2008). Medical Aspects of Chemical Warfare. Textbook of Military Medicine. Washington, D.C.: Office of The Surgeon General, Borden Institute. ISBN 978-0-16-081532-4. OCLC 271597882. https://medcoe.army.mil/borden-tb-med-aspects-chem-warfare. 
  17. ↑ Sandor, S. et al. (Jul–Sep 1985). "Sulphonated phthalocyanine induced caudal malformative syndrome in the chick embryo". Romanian Journal of Morphology and Embryology 31 (3): 173–181. PMID 2931590. 
  18. ↑ "Copper Phthalocyanine". Organisation for Economic Co-operation and Development. August 2002. pp. 124–152. https://hpvchemicals.oecd.org/UI/handler.axd?id=0c04d8d1-1f9c-4312-aea2-60772d6f5874. 
  19. ↑ "From Fossilised Mastodon Ivory to Gemstone" (in en). European Synchrotron Radiation Facility. 2001. https://www.esrf.fr/UsersAndScience/Publications/Highlights/2001/chemistry/CHEM8.html. 
  20. ↑ Reiche, Ina et al. (November 2001). "From mastodon ivory to gemstone: The origin of turquoise color in odontolite". American Mineralogist 86 (11–12): 1519–1524. doi:10.2138/am-2001-11-1221. ISSN 0003-004X. Bibcode: 2001AmMin..86.1519R. 
  21. ↑ Gettens, Rutherford John; Stout, George Leslie (1966). Painting Materials: A Short Encyclopaedia. New York: Dover Publications. ISBN 0-486-21597-0. OCLC 518445. 
  22. ↑ "Spotlight on: Manganese Blue". Winsor & Newton. https://www.winsornewton.com/na/articles/colours/spotlight-on-manganese-blue/. 
  23. ↑ 23.0 23.1 "The Story of YInMn Blue". Oregon State University. https://chemistry.oregonstate.edu/content/story-yinmn-blue. 
  24. ↑ 24.0 24.1 "Licensing agreement reached on brilliant new blue pigment discovered by happy accident". Oregon State University. 27 May 2015. http://oregonstate.edu/ua/ncs/archives/2015/may/licensing-agreement-reached-brilliant-new-blue-pigment-discovered-happy-accident. 
  25. ↑ "SDC awards the prestigious Perkin Medal". 14 June 2019. https://sdc.org.uk/article/sdc-awards-the-prestigious-perkin-medal/. 
  26. ↑ Li, Jun; Lorger, Simon; Stalick, Judith K.; Sleight, Arthur W.; Subramanian, M. A. (2016-10-03). "From Serendipity to Rational Design: Tuning the Blue Trigonal Bipyramidal Mn 3+ Chromophore to Violet and Purple through Application of Chemical Pressure" (in en). Inorganic Chemistry 55 (19): 9798–9804. doi:10.1021/acs.inorgchem.6b01639. ISSN 0020-1669. PMID 27622607. https://pubs.acs.org/doi/10.1021/acs.inorgchem.6b01639. 
  27. ↑ Yttrium (new) - Periodic Table of Videos. YouTube. Periodic Videos. May 19, 2022. Retrieved August 24, 2022.
  28. ↑ 28.0 28.1 Schonbrun, Zach (18 April 2018). "The Quest for the Next Billion-Dollar Color". Bloomberg. https://www.bloomberg.com/features/2018-quest-for-billion-dollar-red/. 
  29. ↑ "YInMn blue". ColourLex. https://colourlex.com/project/yinmn-blue/. 
  30. ↑ 30.0 30.1 30.2 Cascone, Sarah (19 June 2017). "The Wild Blue Yonder: How the Accidental Discovery of an Eye-Popping New Color Changed a Chemist's Life". Artnet. https://news.artnet.com/art-world/chemist-mas-subramanian-on-the-incredible-discovery-of-yinmn-blue-973700. 
  31. ↑ Carbotte, Kevin (25 July 2016). "Team Red Goes Blue: AMD Announces Radeon Pro WX Series". Tom's Hardware. https://www.tomshardware.com/news/amd-radeon-pro-wx-series,32324.html. 
  32. ↑ "Radeon Pro WX Series and YInMn Blue". AMD. 15 August 2016. https://www.youtube.com/watch?v=GMXS1A2uBeE. 
  33. ↑ Bowerman, Mary (5 May 2017). "Crayola's newest crayon color is a shade of blue that was just discovered". USA Today. https://www.usatoday.com/story/money/nation-now/2017/05/05/newest-crayola-crayon-color-shade-blue-just-discovered/309800001/. 
  34. ↑ Waugh, Rob (16 May 2017). "Chemist finds new shade of blue by mistake (and Crayola is now making a crayon of it)". Metro. https://metro.co.uk/2017/05/16/chemist-finds-new-shade-of-blue-by-mistake-and-crayola-is-now-making-a-crayon-of-it-6641350/. 
  35. ↑ "Crayola names new blue crayon 'Bluetiful' after retiring yellow 'Dandelion'". ABC News. 14 September 2017. https://abcnews.go.com/Lifestyle/crayola-names-blue-crayon-bluetiful-retiring-yellow-dandelion/story?id=49825643. 
  36. ↑ "Product Profile: Yin Min Blue". Derivan. 12 July 2016. https://www.youtube.com/watch?v=S2PjA_COOyM. 
  37. ↑ "Update on YInMn Blue from GOLDEN's Custom Lab". 2021-04-23. https://goldenpaints.com/press_releases/new-yinmn-blue. 
  38. ↑ "YINMN = BRILLIANT BLUE". https://www.shepherdcolor.com/products/yinmn/. 

External links



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