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YInMn Blue

YInMn Blue is a synthetic inorganic with the YIn1-xMnxO3, where x typically ranges from 0.002 to 0.03, discovered in by a team led by Mas Subramanian at . This , also known as Oregon Blue or Mas Blue, derives its vibrant turquoise-blue hue from the trigonal bipyramidal coordination of trivalent (Mn3+) ions within a hexagonal , marking the first new blue inorganic developed in over 200 years since the invention of in 1802. It stands out for its exceptional stability, non-toxicity, resistance to heat, UV light, acids, and alkalis, as well as its near-100% reflectance in the near-infrared () spectrum, which qualifies it as a "cool " for reducing heat absorption in applications exposed to . The discovery occurred serendipitously during research on manganese oxide materials for potential use in transparent oxide electronics and high-temperature superconductors. A graduate student, Andrew E. Smith, heated a mixture of yttrium oxide (Y2O3), indium oxide (In2O3), and (Mn2O3) to approximately 1,200 °C (2,200 °F) in a , expecting a or powder but instead producing a striking blue . calculations later confirmed that the intense blue color results from a symmetry-allowed electronic transition between Mn 3d and O 2p states, absorbing light in the red and green wavelengths while transmitting and reflecting blue. The color intensity can be tuned by varying the indium-to-manganese ratio, with optimal vibrancy at low concentrations. YInMn Blue's unique properties surpass those of traditional blue pigments like or in durability and environmental safety, avoiding toxic such as or . Its high solar reflectance—up to 98%—enables it to keep surfaces cooler, potentially reducing costs for cooling in buildings and vehicles by reflecting while maintaining aesthetic appeal. The is produced via high-temperature , ensuring chemical inertness and weather resistance suitable for exterior use. Following its patenting in 2012 (U.S. 8,282,728), the technology was exclusively licensed to The Shepherd Color Company in 2015 for commercialization under the trade name Blue 10G513. Initial limited approvals allowed industrial applications starting in 2017, with full U.S. Environmental Protection Agency (EPA) approval under the Toxic Substances Control Act (TSCA) granted in May 2020, enabling broader use including in artists' paints and materials. As of 2024, it has become available in limited quantities for artists through companies such as Golden Artist Colors. Key applications now include energy-efficient coatings for pre-painted metals, roofing granules and tiles, glass enamels, plastics, and media such as watercolors and oils, where its and permanence are highly valued.

Historical Context

Traditional Blue Pigments

The earliest known synthetic blue pigment, , was developed around 3000 BCE in as a calcium copper silicate compound known as cuprorivaite (CaCuSi₄O₁₀). This vibrant pigment, produced by heating a mixture of silica, , compounds, and , marked the first intentional creation of an artificial colorant and was widely used in murals, sculptures, and jewelry across ancient , , and civilizations for its stability and intense hue. Its production process, involving high-temperature firing, enabled consistent application in . Prior to the dominance of synthetic options, natural blue pigments derived from minerals played a central role in artistic and decorative traditions. , a (Cu₃(CO₃)₂(OH)₂), served as one of the earliest mineral-based , mined and ground for use in ancient Mediterranean and Asian artworks, though it often darkened to green upon exposure to air. , extracted from the semi-precious stone sourced primarily from , emerged around the CE and became the most prized blue during the and in . Renowned for its deep, saturated color, natural was extraordinarily costly—often more expensive than —due to arduous and across routes, restricting its use to high-status commissions like illuminated manuscripts and religious icons. Synthetic , achieved through heating kaolin, sulfur, soda ash, and charcoal, was not developed until 1828 by French chemist Jean-Baptiste Guimet, dramatically reducing costs and enabling broader accessibility. The advent of modern synthetic inorganic blues began in the with , discovered accidentally in 1706 by pigment maker Johann Jacob Diesbach through a reaction involving iron salts and , yielding ferric ferrocyanide (Fe₄[Fe(CN)₆]₃). As the first stable, affordable synthetic blue, it revolutionized painting by providing a deep shade suitable for landscapes and shadows, quickly spreading across and influencing artists like and . Nearly a century later, in 1802, French chemist Louis Jacques Thénard synthesized (cobalt aluminate, CoAl₂O₄) by calcining and alumina, creating a transparent, lightfast that addressed the opacity and variability of earlier cobalt-based colors like smalt. This innovation built on 18th-century experiments with cobalt ores, offering a reliable alternative for ceramics, , and oils. Despite these advances, traditional blue pigments faced significant limitations that underscored the scarcity of viable inorganic options. , while inexpensive, exhibited fading and discoloration in alkaline oil media due to interactions with , compromising long-term durability in paintings. , prized for its permanence, posed health risks from toxicity, including respiratory issues and potential carcinogenicity of compounds during mining and handling, alongside environmental concerns from ore extraction. Natural and suffered from high costs and instability— price stemmed from limited lapis sources, while faded under light and humidity—driving reliance on organic alternatives like , which bleached rapidly in . These challenges persisted into the , with no new stable inorganic blue pigments emerging after , highlighting a two-century gap in innovation amid growing demands for non-toxic, durable colors in industry and art.

Challenges in Modern Pigment Development

The development of new blue pigments in the late 20th and early 21st centuries faced significant hurdles due to the limitations of traditional inorganic and organic options. Cobalt-based pigments, such as aluminate (CoAl₂O₄), while offering vibrant color and thermal stability, pose health risks including potential carcinogenicity and toxicity upon inhalation or prolonged exposure, prompting efforts to minimize content without compromising intensity. Additionally, mining contributes to through and pollution in resource extraction regions. blue pigments, in contrast, often exhibit instability under light and heat, leading to fading or degradation in applications like coatings and textiles, as elevated temperatures accelerate molecular breakdown and reduce color retention. Furthermore, many conventional blue pigments suffer from low near-infrared () reflectivity, causing excessive heat absorption in exterior coatings and increasing energy demands for cooling in buildings. Broader industry demands amplified these challenges, as there was a growing need for non-toxic, durable pigments suitable for diverse uses in paints, plastics, and sustainable applications like eco-friendly coatings. Regulatory pressures, particularly the Union's REACH framework, imposed strict restrictions on such as , lead, and in chemical substances, including pigments, to mitigate environmental and health risks, thereby limiting the viability of legacy materials. These regulations required manufacturers to demonstrate compliance through testing for impurities and , often necessitating costly reformulations or substitutions. Pre-2009 research trends reflected a shift toward oxide-based materials, initially driven by applications in and ceramics, which occasionally spilled over into pigment development but yielded limited success in producing vibrant, stable blues. Efforts focused on modifying structures like those in cobalt aluminates to reduce , yet achieving intense coloration without environmental drawbacks proved elusive, with most innovations failing to match the performance of established . This scarcity underscored the need for breakthroughs in to meet modern sustainability standards.

Discovery and Early Research

Accidental Synthesis

In 2009, researchers in Mas Subramanian's laboratory at were investigating transparent conductive s, particularly variants of indium , for potential applications in such as flat-panel displays and solar cells. The team's work focused on the electronic properties of manganese-containing s, aiming to develop materials with specific conductivity and transparency characteristics. During an experiment in 2009, graduate student Andrew E. Smith prepared a mixture of yttrium oxide (Y₂O₃), indium oxide (In₂O₃), and manganese oxide (Mn₂O₃). He ground the powders together and heated them in a at temperatures between 1,000 °C and 1,200 °C for several hours, expecting to produce a with conductive properties akin to dark-colored materials like or black oxides commonly observed in such syntheses. Upon removing the sample from the furnace and allowing it to cool, Smith observed a striking vibrant powder instead of the anticipated dark material, an outcome that immediately caught the attention of the research group. This serendipitous result deviated entirely from the project's objectives, as the team had no intention of synthesizing pigments and was solely focused on functionalities. Subramanian later described the moment as one of pure , noting that the blue hue emerged unexpectedly from routine materials exploration.

Initial Scientific Analysis

Following the accidental synthesis of a vivid blue compound during experiments aimed at developing materials for transparent conductors, the research team at conducted immediate analyses to characterize its properties. Initial investigations employed to examine the crystalline phases, revealing a hexagonal structure akin to that of YInO₃ with incorporated in trigonal bipyramidal coordination sites. UV-Vis spectroscopy was used to assess color absorption, showing strong bands in the red and green wavelengths (approximately 550–700 nm) that result in the observed intense reflection due to a symmetry-allowed d-d transition involving Mn³⁺. Basic stability tests, including immersion in acids, demonstrated the material's resistance to dissolution, while its synthesis at 1200°C indicated inherent thermal durability. These findings confirmed a perovskite-like framework with Mn incorporation as the basis for the novel blue chromophore, marking the first such inorganic in over two centuries. The team quickly recognized the shift in potential from electronics applications to use, leading to the publication of their results in the Journal of the in 2009 and the filing of a provisional (US 61/268,479) on June 11, 2009, followed by a full in 2010 (granted as US 8,282,728 B2 in 2012).

Chemical Composition and Structure

Molecular Formula

The molecular formula of YInMn Blue is YIn_{1-x}Mn_xO_3, where yttrium (Y) remains fixed at a stoichiometry of 1, while the ratio of indium (In) to manganese (Mn) varies through the substitution parameter x, and oxygen (O) completes the perovskite-like oxide structure. This composition consists of yttrium oxide acting as a structural stabilizer, indium oxide serving as the primary host lattice, and manganese oxide providing the chromophoric Mn^{3+} ions responsible for the blue coloration, forming a non-toxic, rare-earth-based inorganic pigment. The value of x typically ranges from 0.05 to 0.5 to achieve hues, with specific ratios influencing the and ; for instance, x = 0.05 yields a , while x = 0.2 produces a bright , as detailed in the patent. Adjusting x within this range shifts the color from lighter s at lower manganese doping (e.g., x = 0.05) to deeper or blues at higher levels (e.g., x = 0.35), with further increases beyond 0.75 resulting in darker, non- tones.

Crystal Structure and Coloration Mechanism

YInMn Blue crystallizes in a hexagonal structure derived from the YInO₃ host lattice, which features a distorted perovskite arrangement with layers of corner-sharing trigonal bipyramids formed by (Y, In, Mn)O₅ polyhedra, separated by yttrium layers. The Mn³⁺ ions, with a 3d⁴ electronic configuration, occupy indium sites in a rare trigonal bipyramidal (TBP) coordination geometry, surrounded by five oxygen atoms. This TBP environment exhibits significant distortion, characterized by asymmetric axial Mn–O bond lengths, such as 1.891 Å and 2.045 Å in compositions with x ≈ 0.08 in YIn_{1-x}Mn_xO₃, which breaks the symmetry and influences the electronic properties. The vibrant blue coloration stems from allowed d–d electronic transitions within the Mn³⁺ ions, facilitated by the non-centrosymmetric TBP coordination that lacks an inversion center, thereby relaxing Laporte selection rules and intensifying the optical absorption. The crystal field of the TBP geometry splits the Mn orbitals into multiplets, with occupied d states lying within the broader O 2p–In 5s of approximately 4 . These transitions produce strong absorptions in the visible range, peaking broadly from ~1.2 to 2.5 (corresponding to wavelengths of ~500–1000 , absorbing , , and light) and a narrower feature at ~3 (~413 , absorbing light), selectively reflecting around 450 nm. This mechanism contrasts sharply with the more common octahedral coordination of Mn³⁺ in oxides, where weakens d–d transitions and leads to broader absorptions across the , often resulting in tan, brown, or purple hues rather than a pure . The in the TBP sites of YInMn Blue is crucial, as it introduces the higher-energy ~3 absorption peak absent in symmetric TBP environments, enhancing the selectivity and intensity of the blue color.

Physical and Chemical Properties

Optical Characteristics

YInMn Blue displays an intense coloration, characterized by high opacity and tinting strength comparable to that of (CoAl₂O₄), yet with enhanced brightness that results in a more vivid appearance. This pigment's visual properties stem from its selective light interaction, producing a pure, non-metallic suitable for diverse applications. In terms of spectral behavior, YInMn Blue exhibits a in the 450–500 range, allowing strong of while featuring absorption bands around 550–650 that target and wavelengths, contributing to its characteristic hue. Furthermore, it shows notably high near-infrared () , typically around 70-80% across 700–2500 , exceeding that of traditional like aluminate. Relative to established blue pigments, YInMn Blue offers superior vibrancy over (Na₈₋₁₀Al₆Si₆O₂₄S₂₋₄), appearing less reddish-purple, and is less greenish than , providing a cleaner spectral profile in the visible range. Its color remains consistent under varied lighting conditions, exhibiting minimal metamerism due to the broad reflectance in the blue region.

Stability and Durability

YInMn Blue exhibits exceptional , remaining inert across a wide range from acidic to basic conditions. It resists degradation in strong acids such as 10%–50% (HNO₃), (HCl), and (H₂SO₄), showing negligible changes in weight or color after prolonged exposure. Similarly, the pigment is stable in alkaline environments, with no reported structural alterations or color shifts. This inertness extends to common solvents, preventing leaching of constituent metals like , , or , which underscores its suitability for demanding chemical environments. In terms of physical durability, YInMn Blue withstands high temperatures up to and beyond 1,300°C, the approximate condition, without or color loss, surpassing many traditional inorganic . It demonstrates superior UV , with color changes below ΔE = 0.5 after 5,000 hours of accelerated UV exposure testing, far exceeding standard benchmarks for fading resistance. For weather resistance, the performs exceptionally in outdoor exposure, maintaining integrity with color shifts under ΔE = 1.4 after 48 months of natural weathering, outperforming cobalt aluminate () in UV , heat buildup, and overall durability. Beyond these properties, YInMn Blue is non-toxic, lacking such as or found in some conventional pigments, and has received full U.S. EPA approval for commercial applications, including consumer products. Its low migration in matrices enables reliable incorporation into plastics without or performance degradation over time. Additionally, the pigment's high near-infrared results in low heat buildup—reaching only 27–30°C under simulation compared to 37°C for —making it ideal for cooling applications like energy-efficient coatings, though its inherent thermal conductivity supports in composite materials.

Synthesis Methods

Laboratory Procedures

The laboratory synthesis of YInMn blue (YIn1-xMnxO3) typically employs a conventional solid-state reaction, which is straightforward and yields high-purity phases suitable for research applications. This method relies on the thermal decomposition and reaction of metal oxide precursors without requiring fluxes, as the process proceeds via diffusion in the solid state. Stoichiometric ratios of the starting materials are crucial, with the manganese content (x) generally ranging from 0.005 to 0.1 to achieve the characteristic intense blue hue; for example, a ratio of Y:In:Mn = 1:0.995:0.005 produces a bright turquoise blue, while higher Mn doping shifts the color toward deeper navy tones. The procedure begins with the selection of high-purity precursors: yttrium oxide (Y2O3, >99.9%), indium oxide (In2O3, >99.9%), and manganese(III) oxide (Mn2O3, >99%). These are weighed according to the desired stoichiometry—for a 5 g batch of YIn0.995Mn0.005O3, approximately 2.25 g Y2O3, 2.75 g In2O3, and 0.01 g Mn2O3 are used—and thoroughly mixed to ensure homogeneity. Mixing is achieved by grinding the powders in an agate mortar and pestle for 30–60 minutes or, preferably, by ball-milling in a planetary or vibratory mill with zirconia media for 2–4 hours at 200–300 rpm to achieve sub-micron particle uniformity without contamination. The homogeneous mixture is then uniaxially pressed into pellets (typically 10–13 mm diameter, 2–3 mm thick) at 50–100 MPa using a hydraulic press to facilitate uniform heating. The pellets are placed in an alumina crucible and calcined in a muffle furnace under ambient air atmosphere. Heating is ramped at 5–10°C/min to 1000–1200°C, held for 4–12 hours depending on the scale and desired phase purity, and then slowly cooled to room temperature at 5°C/min to minimize thermal stress. For optimal results in solid-state synthesis, multiple cycles are often employed: after initial calcination (e.g., 1200°C for 12 hours), the product is ground, re-pressed, and calcined again (e.g., 1300°C for 12 hours) to achieve higher phase purity (>95%) with minimal secondary phases. Post-calcination, the brittle pellets are ground in a mortar or ball-milled for 1–2 hours to produce a fine pigment powder with particle sizes of 1–5 μm, suitable for spectroscopic analysis or dispersion testing. Phase purity and structure are confirmed using on a (e.g., Cu Kα , 10–80° 2θ range), where the characteristic hexagonal peaks at ~30.5° and ~33.5° 2θ indicate successful formation of the trigonal bipyramidal Mn3+ . Variations in the procedure include adjusting the Mn content (x = 0.001–0.2) to tune the hue from to , or incorporating minor substitutions (e.g., 5–10% for In) to modify stability, though these require recalibration of times to maintain phase purity. No additional fluxes are needed, distinguishing this from flux-mediated syntheses, and the process is scalable to gram quantities in standard lab furnaces while avoiding hazardous reagents.

Industrial Production Techniques

The industrial production of YInMn Blue relies on a solid-state reaction process, where stoichiometric mixtures of oxide (Y₂O₃), oxide (In₂O₃), and (Mn₂O₃ or MnO₂) are intimately blended, typically via ball milling, before undergoing high-temperature . This , conducted at temperatures between 700°C and 1500°C for 2 to 20 hours, forms the trigonal bipyramidal YIn₁₋ₓMnₓO₃ phase essential for the 's intense blue coloration and stability. The Shepherd Color Company, which licensed the technology from in 2015, employs this method in commercial manufacturing, emphasizing careful control to produce an inert suitable for demanding applications. Post-calcination, the material is milled to reduce , typically to 1–5 μm, and classified to ensure uniformity, which enhances dispersibility and optical performance in end-use formulations. The process occurs under controlled atmospheric conditions, often in air, to promote complete reaction and minimize impurities, with the high temperatures contributing to the pigment's exceptional chemical inertness and durability. Commercial scaling has addressed challenges such as achieving consistent phase purity and batch-to-batch through optimized mixing and firing protocols, building on laboratory solid-state procedures but adapted for larger volumes. Since the 2009 discovery, key advancements include regulatory approvals enabling full commercialization: limited use in Europe and under U.S. TSCA Low Volume Exemption in 2017, followed by unrestricted U.S. approval in 2020, allowing Shepherd Color to expand production for industrial and artistic markets. These developments have focused on process reliability to meet high-purity standards (>99% for the target phase, as verified in scaled trials) while maintaining the pigment's NIR-reflective properties.

Applications and Commercialization

Industrial and Technical Uses

YInMn Blue has found significant application in industrial coatings, particularly those designed for near-infrared () reflectance to enhance in buildings and vehicles. Its high solar reflectance, often exceeding 70%, allows formulations for cool roof coatings and automotive paints that reflect a substantial portion of heat, reducing surface temperatures by up to 20°C compared to traditional blue pigments like . This property contributes to lower cooling energy demands in urban environments, with studies on similar NIR-reflective systems indicating potential reductions in building cooling loads. Additionally, the pigment's supports its use in durable, anticorrosive coatings for pre-painted metals and architectural surfaces. In plastics and ceramics, YInMn Blue serves as a non-migrating colorant due to its inorganic nature and thermal resilience. Engineering plastics such as (PVC) and (PP) incorporate the for vibrant blue coloration in components requiring high durability and heat reflection, such as exterior automotive parts or building panels. In ceramics, it is applied in high-temperature glazes for roofing tiles and glass enamels, where its stability under firing conditions up to 1,200°C maintains color integrity without or degradation. Beyond these core uses, YInMn Blue offers environmental advantages as a non-toxic alternative to cobalt-based blues, which contain hazardous heavy metals. Its integration into eco-friendly paints and additives for and textiles further promotes sustainable manufacturing by minimizing toxic emissions and enhancing overall material longevity.

Artistic and Cultural Applications

YInMn Blue has been integrated into various artist s since its commercialization, offering painters a durable option in multiple . In 2024, Golden Artist Colors launched special edition formulations incorporating the pigment, including Heavy Body , QoR Watercolor, and Williamsburg paints, available in limited U.S. quantities. The Shepherd Color Company's Blue 10G513 variant has been available for incorporation into professional-grade artist supplies since full U.S. Environmental Protection Agency approval in 2020, marketed as a high-tint-strength, red-shade . These pigments exhibit favorable mixing properties, with moderate tinting strength that behaves predictably in blends; notably, tints with white reveal red undertones, producing soft lavender hues, while the opacity ranges from semi-opaque to fully opaque, akin to . Artist feedback on YInMn Blue has been mixed but generally positive, emphasizing its reliability over vibrancy and viewing it as a complementary option to established like phthalo. The pigment earns the highest ASTM rating of I (excellent), ensuring minimal fading under prolonged exposure, which supports its appeal for long-term artworks. Culturally, YInMn Blue has garnered significant media attention as the "newest blue" pigment since 2016, with coverage spanning scientific journals and design outlets through 2025, often celebrating its accidental and unique properties. It inspired Crayola's "Bluetiful" color, introduced in as a product milestone. Its adoption extends to , influencing interior and packaging through its NIR-reflective qualities that enhance visual appeal while promoting . Although no major pop culture icons beyond such integrations have emerged, its non-toxic, stable composition positions it for growth in sustainable practices, where durability reduces and environmental impact.

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