Wikipedia

YInMn 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]

YInMn Blue
 
YInMn Blue powdered pigment
About these coordinates     Color coordinates
Hex triplet#306AC0
sRGBB (r, g, b)(48, 106, 192)
HSV (h, s, v)(216°, 75%, 75%)
CIELChuv (L, C, h)(45, 80, 255°)
Source[1][2][a]
ISCC–NBS descriptorDeep blue
B: Normalized to [0–255] (byte)
YInMn Blue
Crystal structure of YInMn Blue
Identification
FormulaYIn1−xMnxO3
Crystal systemHexagonal
Crystal symmetryP63cm
Unit cella = 6.24 Å; c = 12.05 Å
ColorLight to dark blue

Historical pigments

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The discovery of the first known synthetic blue pigment, Egyptian blue (CaCuSi4O10) 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 (BaCuSi4O10), which was developed by the Chinese Han dynasty and manipulated to produce a light or dark blue color.[7]

A number of pigments are used to impart the blue color. Cobalt blue (CoAl2O4) 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 (Na7Al6Si6O24S3) 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 (Fe4[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 (Cu3(CO3)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 or durability problems. 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

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In 2008, Mas 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 YInO3 (a ferroelectric material) and YMnO3 (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 YIn1−xMnxO3, but the bluest pigment, YIn0.8Mn0.2O3, has a color comparable to standard cobalt blue CoAl2O4 pigments.[2]

Properties and preparation

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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

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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 was made available in late 2017.

In artists' pigments

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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] Shepherd Color Company received the required environmental and safety approvals to sell the pigment in the U.S. in 2020.[38]

Gamblin Artists Colors made a first Limited Edition batch of YInMn Blue in November 2020.[39]

See also

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Notes

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  1. ^ The color coordinates were obtained from Smith et al. 2016 for the optimal blue pigment, which has the composition YIn0.8Mn0.2O3. The CIELAB coordinates (L = 34.6, a = 9.6, b = −38.9 in table 1) were converted using an online tool.

References

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  1. ^ a b c d e f g 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. ^ a b c d 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. Archived from the original on 4 April 2020.
  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. Bibcode:2019JSSCh.272....9L. doi:10.1016/j.jssc.2019.01.019. S2CID 104373418.
  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.
  6. ^ Jaksch, H.; et al. (November 1983). "Egyptian blue — Cuprorivaite a window to ancient Egyptian technology". Naturwissenschaften. 70 (11): 525–535. Bibcode:1983NW.....70..525J. doi:10.1007/BF00376668. ISSN 1432-1904. S2CID 2457936.
  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. p. 491. ISBN 978-0-8436-0609-6.
  9. ^ Needham, Joseph; et al. (2004). Science and Civilisation in China. Cambridge University Press. p. 659. ISBN 978-0-521-83833-7.
  10. ^ Maerz, A. & Paul, M. Rea (1930). A dictionary of color. New York: McGraw-Hill Book Co. OCLC 1150631.
  11. ^ Gmelin, C. G. (1828). "Ueber die künstliche Darstellung einer dem Ultramarin ähnlichen Farbe" [On the artificial preparation of a pigment similar to ultramarine]. Naturwissenschaftliche Abhandlungen. Herausgeben von Einer Gesellschaft in Würtemberg (Scientific Essays. Published by a Society in Würtemberg) (in German). 2 (10): 191–224. Bibcode:1828AnP....90..363.. doi:10.1002/andp.18280901022.
  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) [1896]. Der Briefwechsel mit Gottfried Wilhelm Leibniz [Correspondence with Gottfried Wilhelm Leibniz] (in German). Hildesheim: G. Olms. ISBN 978-3-487-06071-2. OCLC 3303263.
  14. ^ Zigan, F. & Schuster, H. D. (1972). "Verfeinerung der Struktur von Azurit, Cu3(OH)2(CO3)2, durch Neutronenbeugung" [Refinement of the structure of azurite Cu3(OH)2(CO3)2 by neutron diffraction]. Zeitschrift für Kristallographie (in German). 135 (5–6): 416–436. Bibcode:1972ZK....135..416Z. doi:10.1524/zkri.1972.135.5-6.416. ISSN 0044-2968. S2CID 95738208.
  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. JSTOR 40965976. 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.
  17. ^ Sandor, S.; et al. (July–September 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". Screening Information Dataset. Organisation for Economic Co-operation and Development. August 2002. pp. 124–152. Cas No. 147-14-8.
  19. ^ "From Fossilised Mastodon Ivory to Gemstone". European Synchrotron Radiation Facility. 2001. Retrieved 14 February 2021.
  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. Bibcode:2001AmMin..86.1519R. doi:10.2138/am-2001-11-1221. ISSN 0003-004X. S2CID 55240370.
  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. Retrieved 28 January 2021.
  23. ^ a b "The Story of YInMn Blue". Oregon State University. Retrieved 28 May 2018.
  24. ^ a b "Licensing agreement reached on brilliant new blue pigment discovered by happy accident". Oregon State University. 27 May 2015. Archived from the original on 3 July 2016. Retrieved 2 July 2016.
  25. ^ "SDC awards the prestigious Perkin Medal". 14 June 2019. Retrieved 19 November 2021.
  26. ^ Li, Jun; Lorger, Simon; Stalick, Judith K.; Sleight, Arthur W.; Subramanian, M. A. (3 October 2016). "From Serendipity to Rational Design: Tuning the Blue Trigonal Bipyramidal Mn 3+ Chromophore to Violet and Purple through Application of Chemical Pressure". Inorganic Chemistry. 55 (19): 9798–9804. doi:10.1021/acs.inorgchem.6b01639. ISSN 0020-1669. PMID 27622607.
  27. ^ Yttrium (new) - Periodic Table of Videos. YouTube. Periodic Videos. 19 May 2022. Retrieved 24 August 2022.
  28. ^ a b Schonbrun, Zach (18 April 2018). "The Quest for the Next Billion-Dollar Color". Bloomberg. Retrieved 20 April 2018.
  29. ^ "YInMn blue". ColourLex. Archived from the original on 5 November 2017.
  30. ^ a b c 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. Retrieved 15 May 2019.
  31. ^ Carbotte, Kevin (25 July 2016). "Team Red Goes Blue: AMD Announces Radeon Pro WX Series". Tom's Hardware. Retrieved 15 May 2019.
  32. ^ "Radeon Pro WX Series and YInMn Blue". YouTube. AMD. 15 August 2016. Archived from the original on 11 June 2017. Retrieved 22 August 2016.
  33. ^ Bowerman, Mary (5 May 2017). "Crayola's newest crayon color is a shade of blue that was just discovered". USA Today. Archived from the original on 6 May 2017. Retrieved 5 May 2017.
  34. ^ Waugh, Rob (16 May 2017). "Chemist finds new shade of blue by mistake (and Crayola is now making a crayon of it)". Metro. Archived from the original on 17 May 2017.
  35. ^ "Crayola names new blue crayon 'Bluetiful' after retiring yellow 'Dandelion'". ABC News. 14 September 2017. Archived from the original on 14 September 2017.
  36. ^ "Product Profile: Yin Min Blue". YouTube. Derivan. 12 July 2016. Archived from the original on 5 November 2017.
  37. ^ "Update on YInMn Blue from GOLDEN's Custom Lab". 23 April 2021. Retrieved 18 August 2021.
  38. ^ "YINMN = BRILLIANT BLUE".
  39. ^ "Gamblin YInMn Blue".
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