RECENT ADVANCES IN THERMOCHROMIC MATERIALS’

SYNTHESIS AND APPLICATIONS

ABSTRACT
Thermochromic material is a kind of smart material whose colour will vary as the result of
the phase transition caused by the temperature change. Thermochromism is an interesting
physicochemical phenomena applied in the chemistry, health and biology fields and others.
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 this review, types of thermochromic materials, its
mechanism of discoloration, methods of synthesis and its application in various fields have
been discussed.

INTRODUCTION

Thermochromic compounds, a new type of functional materials with unique colour changing
ability, have attracted the attention of many scientists. The chemistry behind the changing
colours of these chromic materials is a virtue of the change in electronic energy states within
the molecule where the surrounding alters the electron density by changing p- or d- electronic
state. Thermochromic material contains discoloration substances and other auxiliary
components, which are also called temperature sensitive material. The colour can vary with
the change of temperature in a certain temperature range, because the visible absorption
spectrum of discoloration compounds or mixtures can be changed when heated or cooled. [1,
2]. Thermochromic discoloration often accompanies photochromic reactions to enrich the
functionality and intelligence of materials [3, 4, 5]. The applications of thermochromic
material have been explored in many fields, such as smart windows, printing technology,
textile, architectural coatings and so on [6, 7].Some thermochromic materials can be used in
toys for children. They also have a huge potential application in the field of food packaging.

LITERATURE REVIEW

Thermochromic materials can be classified into inorganic, organic and liquid crystal types.
Inorganic thermochromic materials mainly include metal iodide, double salt, transition metal
compounds, metal alloys and metal chloride. Inorganic thermochromic materials are
advantageous because of its good temperature resistance, durability, light resistance and
processability [8]. Organic thermochromic materials occupying most quantities and species
contain spiropyrans, fluoranthene, triarylmethane, ethylene with substituents and organic
complexes [9]. Their advantages include adjustable colours, low discoloration temperature,
high sensitivity of discoloration and low cost. Liquid crystal can be divided into smectic,
nematic and cholesteric types according to molecular arrangement, which have the
advantages of good stability and high thermal sensitivity, but its application is limited
because of its chemical sensitivity and high cost [10].

Now let’s see the mechanism for discolouration:

Discolouration in Organic reversible thermochromic materials occurs in various steps-

1. Intermolecular electron transfer-Such thermochromic materials are generally composed of
electron donor, electron acceptor and solvent compounds. Here the electron donor decides the
colour, electron acceptor decides the colour Chroma and solvent compounds decide the
discolouration temperature [11].
2. Structural changes in the molecules. Some thermochromic materials themselves appear
discoloration phenomenon when the temperature rises, because the molecular structures of
such materials are susceptible to temperature change.
3. Intramolecular proton transfer. When the temperature rises, the protons in the molecules
are transferred and the molecular structure of the material changes, resulting in the reversible
thermochromic phenomenon.
4. Crystal transition. Crystal transformation is a common discoloration mechanism for
inorganic thermochromic materials. However, many organic thermochromic materials also
follow this mechanism [12].
There are several methods for synthesising Thermochromic Materials. The most widely used
methods for preparing thermochromic materials are solid phase method, liquid phase
deposition method and chemical vapour deposition method.
1. Solid Phase Method: This method includes four steps of the diffusion, reaction,
nucleation and growth. This includes four steps of the diffusion, reaction, nucleation
and growth. Solid phase method has the inherent shortcomings, such as high energy
consumption, low efficiency, large particle size and impurities of the materials.
However, the particles prepared by this method have good dispersity, excellent filling
property, low cost, large output, simple preparation process [14]
2. Liquid phase deposition method: The liquid phase method includes sol-gel method
[7], hydrothermal method [15] and chemical precipitation method. The particle size
 and morphology are mainly controlled by adjusting the parameters, such as the
reagent concentration, temperature, stirring speed, pH value, reaction time [17].
Liquid phase precipitation method is usually used to prepare oxide, oxide composite
and metal ultrafine powder.
3. Vapour deposition: This includes chemical vapour deposition (CVD) and physical
vapour deposition (PVD). CVD is a common industrial technology for producing high
quality and performance films [18,19,20,21]
In addition, there are other methods for preparing thermochromic materials, such as
electrochemical method, polymer assisted deposition.
There are numerous applications of Thermochromic materials.
The most significant one is its use in Smart Windows. Windows are an essential part of a
building and play a decisive part in maintaining the temperature of the inner room. Although
windows form only a small section of the housing envelope, they control most of the sunlight
and breeze in and out of the building. A thermochromic window is also called a smart
window; ‘‘smart’’ is used because these windows cleverly control the solar transmittance
when activated by temperature, i.e., when there is a temperature increase, the solar passage
reduces to obstruct the unwanted solar radiation by reflection. In principle, as the outside
temperature is more than the transition temperature of the smart window, the allowance of
solar radiation is reduced, and thus less solar energy enters the building, reducing the in-
house temperature and hence decreasing the utilization of electrical energy used in ACs.
When the outside temperature falls below the critical temperature of the smart window, solar
radiation passing through it rises. In this way, the window controls the temperature of the
place and helps in decreasing the energy use for heating or cooling [22, 23].
The formulation of the smart windows is done by adding the following:
(1) The thermochromic dyes of transition temperature 48C, which transitions from opaque to
translucent.
(2) Saturated hydrocarbons, which change from opaque to transparent at approx. 40C.
(3) Hydrogel made from hydroxypropyl methylcellulose, which transitions from transparent
to opaque around 40C.
Thermochromic windows were reported to have the potential to save heating and cooling
energy demand from 5.0 to 84.7%, in comparison to plain glass and depending on climatic
conditions. What makes this material feasible is that this process is highly reversible.
Thermochromic materials are also used as Functional coatings. Functional coatings include
pigments, dyes, paints, printing inks, etc. Thermochromic pigment refers to the micro-
encapsulated reversible thermochromic spherical materials with an average diameter of 2–7
nm [24]. The outside layer is a transparent shell with a thickness of 0.2-0.5 m that cannot be
dissolved or melted, which can protect the discoloration material in the core from erosion.
Pigments can be encapsulated by polyethylene (PE), polypropylene (PP), polystyrene (PS),
soft polyvinyl chloride (S-PVC), acrylonitrile-styrene resin (AS), acrylonitrile butadiene
styrene (ABS) and other transparent or translucent plastic [25, 26]. Thermosensitive ink can
rapidly change its colour with the ambient temperature change, which is widely used in the
packaging field.
Thermochromic materials are also used in the manufacture of biosensors, temperature sensors
and chemical sensors. The best used thermochromic material for manufacturing these sensors
is Polydiacetylene (PDA). PDA has self-assembled function and some properties similar to
the biological cell membranes, which is used in the design of biosensors for the molecule
recognition. This kind of polymer achieves the signal transmission through the discoloration
caused by changing the skeleton structure.

FUTURE SCOPE IN THE AREA OF THERMOCHROMIC MATERIALS

It has been reported that PDA/ZnO nanocomposites can exhibit reversible thermochromic
properties and the discoloration temperature was controllable [27, 28]. The colour changing
time can be controlled by changing the photo polymerisation time and the thermochromic
behaviour is controlled by varying the length of the alkyl chain of the PDA-based materials.
These properties are very important to realize its applications.
A novel microencapsulated phase change material (micro-PCMs) is being innovated [29],
which could achieve thermal discoloration when the temperature exceeded the target value.
Phase change materials are widely used for regulation of building temperature and energy
storage [31]. Their disadvantages are evaporation at higher temperatures, inflammability, and
phase separation. These can be overcome by microencapsulation. Microencapsulation of
PCMs is crucial to secure the PCMs from the working environment and for its proper
functioning at the required stage. Microencapsulation of PCMs can be done via various
techniques like interfacial polycondensation, suspension polycondensation, in situ
polycondensation
Along with the organic thermochromic materials, the inorganic, nanotechnology-based
thermochromic materials are also promising in achieving efficient and sustainable building
envelopes. Similar to the microencapsulated thermochromic dyes, the inorganic
nanotechnology-based thermochromic blazing possesses temperature-dependent properties
and helps in controlling the quantity of solar heat entering the building by changing its optical
properties, thus reducing energy consumption[32].
Smart windows can help the buildings to maintain high energy levels by increasing the heat
gain in cold weather and decreasing it in hot weather dynamically. When it comes to
thermochromic materials based on nanotechnology, the VO2-based materials are dominant.
Across a critical transition temperature (Tc), VO2 undergoes a structural transformation from
a semiconducting to a metallic state. Nano-sized materials, especially transition metal oxides
(TMOs) have great scientific interests due to their various applications in lithium-ion
batteries, sensors, transistors, photocatalysis, supercapacitors and electrochromic devices.
Among these TMOs, vanadium compounds have been widely used in various applications.
These compounds have good activity, noticeable thermal resistance, accessibility and high
stability in the catalytic processes and can be synthesized easily. Vanadium as an element can
exist in different stable valence states and hence can form various oxides e.g. VO, V 2O3,
VO2 and V2O5. Due to their novel physical and chemical properties, vanadium pentoxide
(V2O5) and vanadium dioxide (VO2) have received much attention in materials science,
electrical engineering and physics communities [19]. They are applicable as thin coatings or
nanoparticle composites and hence are a promising field for further research.

CONCLUSION
Even though the emergence of thermochromic technology and materials date back to the
1960s, there is a slow advancement in the study of these materials due to their intricate
mechanism and environmental vulnerability. In the recent decade, scientists have curiously
investigated these materials and found considerable scope for application in different fields.
Building materials perform a significant part in the thermal performance of the building and
hence are essential to help in establishing a thermally comfortable internal environment. The
recent research in the optical construction materials/coatings opens a new door in minimizing
the energy utilized, enhancing the thermal solace inside and outside of the building, and
reducing the heat island effect. Considering the rising energy demand, the development of
thermochromic technology is essential for developing green technology.
At present, micro encapsulation is an important technology for the application of
thermochromic materials. Thermochromic materials play an important role in the
development of modern society, and it is necessary to develop new methods for making full
use of these materials. Packaging, especially food packaging is a potential application of
these materials. People in modern society pay more attention to food safety, and
thermochromic materials will play an important role in food quality testing and shelf life
indication in future.
Thermochromism has a significant repercussion in academia and industry, but very few
developments that exploit these phenomena for bio recognition assays have been reported.
Nonetheless, Thermochromism advances in chemical sensing, biology, medical applications
and technological systems provide a fertile scenario for raising new bio analytical systems.

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