Discoloration mechanism, structures and recent applications of thermochromic materials via different methods: A review

doi:10.1016/j.jmst.2018.05.016

Abstract

Abstract:

Thermochromic material is a kind of smart material whose color will vary as the result of the phase transition caused by the temperature change. The characteristics of thermochromic materials are the memory functions to the temperature, having great potential applications in aerospace, military, anti-counterfeiting technology, construction and other fields. In recent years, many kinds of thermochromic materials have been prepared by different methods and their discoloration mechanisms are various according to published literatures. In this paper, the classification, discoloration mechanism, preparation methods, application fields and development trend of thermochromic materials are reviewed.

Key words: Thermochromic materials, Discoloration mechanism, Transformation temperature, Classification

Youliang Cheng, Xiaoqiang Zhang, Changqing Fang, Jing Chen, Zhen Wang. Discoloration mechanism, structures and recent applications of thermochromic materials via different methods: A review[J]. J. Mater. Sci. Technol., 2018, 34(12): 2225-2234.

Figures/Tables 14

Fig. 1. Forms of the discoloration for thermochromic materials. (A, B and C denote different colors).

Table 1 Components and effects of organic reversible thermochromic materials [21].

Component	Sort	Effect
Electron donor	Triaryl and their phthalides, fluoran, indole phthalide, spiro-pyran, et al.	decide the color
Electron acceptor	Phenols, sulfonic acids, carboxylic acids, et al.	decide the color chroma
Eolvent compounds	Alcohols, esters, et al.	decide the discoloration temperature

Fig. 2. Structural changes in the molecules [16]: (a) electron transfer process of crystal violet alctone, (b) keto-enol tautomerizing of N-salicylideneaniline, (c) conformational change of polythiophene and (d) ring opening mechanism of spiropyrane.

Table 2 Common inorganic thermochromic materials and their discoloration principle [16].

Inorganic thermochromic materials	Discoloration principle
(1): VO, VO₂, V_nO_2n-1(n = 2-6, 8) Ti₂O₃, Ti_nO2_n-1(n = 3-6) NbO₂, Fe₃O₄, MnO₂, CuO	XM⁺ + AO_y + xe^-? → M_xAO_y (M = H, Li, Na; A = metal)
(2): Ag₂S, NiS	Still unknown
(3): Ge-Te-Sb-S	Vitreous ? Crystal transfer
(4): Ge-S-Se, As-Se-(Ag, Cu)	Metal transfer in an uncertain structure
(5): Cu₂[HgI₄] Red (T ≥ 69 °C) ? dark purple (T≤ 6 °C) Ag₂[HgI₄] Yellow (T ≥ 48 °C) ? red (T ≤ 5 °C)	Structural change

Fig. 3. Several structures for cholesteric liquid crystal: (a) constitutional formula, (b) configurational formula, (c) the spiral structure of cholesteric liquid crystal.

Fig. 4. (a) Typical low-resolution TEM and (b) field-emission SEM images of the VO2 powders, (c) snowflake-shaped VO2 structures with perfect crystallinity and (d) “growing” snowflake-shaped VO2[46].

Table 3 Radiation properties of the glazing with VO2 film and the ordinary glazing [79].

Properties	Glazing with VO₂ film		Ordinary glazing
Properties	Semiconductor state	Metal state	Ordinary glazing
Solar absorptivity	0.482	0.590	0.159
Solar reflectance	0.078	0.055	0.070
Solar transmittance	0.440	0.355	0.771
Long wave emissivity	0.880	0.880	0.840
Visible transmittance	0.435	0.421	0.837

Fig. 5. Particle morphology for hydrothermal synthesized Mo doped VO2 with the TiO2/VO2 molar ratios of 1:11 [81]: (a) and (b) without doping Mo, (c) doping Mo, (d) R phase TiO2 nanoseeds.

Table 4 Optical properties of typical samples with different W/(W + V) molar ratio [91].

W/(W + V) molar ratio (％)	Thinkness (nm)	T_lum,s (％)	T_lum,m (％)	T_sol,s (％)	T_sol,m (％)	△T_sol (％)	Tc (°C)	△Tc (°C)
0	226	80.6	79.2	81.4	72.3	9.1	56	-
0.5	234	78.9	77.8	79.5	71.2	8.3	42	14
1	392	71.6	70.1	71.7	63.2	8.6	35	21
1.5	259	74.5	74.3	76.7	70.6	6.1	32	24

Fig. 6. The surface microstructures of VO2 thin films with various W/(W + V) molar ratios: W/(W + V) = 0 (a), 0.005 (b), 0.0075 (c), 0.01 (d), 0.02 (e) and (f) the high magnification image of VO2 film with W/(W + V) = 0.02 [91].

Fig. 7. Cross-sectional SEM images of VO2 thin films with various W/V molar ratios: W/(W + V) = 0.005 (a), 0.0075 (b), 0.01 (c), and 0.02 (d) [91].

Fig. 8. Schematic representation of intercalated structure of PDA/PVP nanocomposite, chemical structures of DA monomers and PVPs with three MWs [109].

Fig. 9. TEM images of (a) PDA(8,11)/PVP10, (b) PDA(8,11)/PVP55 and (c) PDA(8,11)/PVP360 nanocomposites. The insets show local morphology of each nanocomposite which has different shapes and sizes [109].

Fig. 10. Structures of (a) Eu and (b) the complex containing Eu [123].

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