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High-Pressure Route to Irreversible Thermochromic Materials
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2024-06-10 , DOI: 10.1021/acs.jpcc.4c01297
Masaya Oshita 1 , Hidenobu Murata 1 , Hajime Yamamoto 2 , Shintaro Kobayashi 3 , Shogo Kawaguchi 3 , Isaac Oda-Bayliss 4 , Wencong Wang 4 , Shunsuke Yagi 4 , Kenta Kimura 1
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Irreversible thermochromic materials change color when heated but do not return to their original color when cooled. This property enables the permanent storage of temperature history and can serve as a temperature marker. However, irreversible thermochromism in solids is usually based on chemical changes, leading to potential drawbacks such as low durability. Additionally, irreversible thermochromic materials operating at high temperatures above 1000 °C often contain toxic elements. Here, we propose a material design that achieves high-temperature irreversible thermochromism without chemical changes, which is applicable to inorganic materials containing no toxic elements. The design utilizes high-pressure (HP) synthesis to obtain a metastable HP phase of an inorganic material consisting of transition-metal (TM) and rare-earth (R) ions. The color is dominated by d–d transitions of the TM ions. When heated under ambient pressure (AP), a metastable HP phase sample can undergo an irreversible structural phase transition to a stable AP phase due to thermally activated diffusion of constituent ions. The resulting change in the local environment around the TM ions can induce the color change. Additionally, the R ions are likely to be difficult to diffuse, thus increasing the transition temperature. Therefore, high-temperature irreversible thermochromism is expected. We demonstrate this proposal by observing irreversible thermochromism above 1000 °C in a perovskite family RIn0.9Mn0.1O3 (R = Y, Dy, Tb, Gd, and Eu). Furthermore, the operating temperature can be tuned by changing the R-site ions. Our proposal is not limited to this perovskite family and provides a useful guideline for exploring new thermochromic materials.

中文翻译:


不可逆热致变色材料的高压路线



不可逆热致变色材料在加热时会改变颜色,但在冷却时不会恢复到原来的颜色。此属性可以永久存储温度历史记录,并可以用作温度标记。然而,固体中的不可逆热致变色通常基于化学变化,导致潜在的缺点,例如耐久性低。此外,在 1000 °C 以上高温下工作的不可逆热致变色材料通常含有有毒元素。在这里,我们提出了一种无需化学变化即可实现高温不可逆热致变色的材料设计,适用于不含有毒元素的无机材料。该设计利用高压(HP)合成来获得由过渡金属(TM)和稀土(R)离子组成的无机材料的亚稳态HP相。颜色主要由 TM 离子的 d-d 跃迁决定。当在环境压力 (AP) 下加热时,由于成分离子的热激活扩散,亚稳态 HP 相样品会经历不可逆的结构相变到稳定 AP 相。由此产生的 TM 离子周围局部环境的变化会引起颜色变化。此外,R 离子可能难以扩散,从而提高转变温度。因此,预计会出现高温不可逆热致变色现象。我们通过观察钙钛矿族 RIn 0.9 Mn 0.1 O 3 (R = Y, Dy, Tb, Gd ,和欧盟)。此外,可以通过改变 R 位离子来调节工作温度。我们的建议不仅限于这个钙钛矿家族,还为探索新的热致变色材料提供了有用的指导。
更新日期:2024-06-10
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