1

INTRODUCTION

Colour has been part of our daily life. It provide a lot of benefit and it define the beauty
of the thing itself. The colour has been imply in the smart material where it define as the
chromic material. In this study will be learn about chromic material and it application.

1.0 Chromic Material

Changing colour material are termed as chromogenic and was describe as chameleonic
as it can change colour back to its original form and it depends on the environmental
phenomena. The act of changing colour is term as Chromism. Generally chromism is based on
change of electron state of molecules. It involve Π and d electron state. Each stimuli will alter
the electron density of each compound. Chromism contain several stimuli that act on the
compound and change it from colourless to colour compound. Chromism changing colour
phenomena contain several type with different stimuli. Here all the type in chromic material.

 Photochromism - colour change caused by light.

 Thermochromism - colour change caused by heat.
 Electrochromic - colour change caused by an electric current.
 Gasochromism- colour change caused by a gas - hydrogen/oxygen redox.
 Solvatochromism - colour change caused by solvent polarity.
 Concentratochromism - colour change caused by changes in the concentration in
the medium
 Rigidichromism - colour change caused by changes in the rigidity of the medium.
 Vapochromism - colour change caused by vapour of an organic compound due to
chemical polarity/polarisation.
 Ionochromism - colour change caused by ions.
 Halochromism - colour change caused by a change in pH.
 Metallochromism - colour change caused by metal ions.
 Mechanochromism - colour change caused by mechanical actions.
 Tribochromism - colour change caused by mechanical friction.
 2

 Piezochromism - colour change caused by mechanical pressure.

 Cathodochromism - colour change caused by electron beam irradiation.
 Radiochromism - colour change caused by ionising radiation.
 Magnetochromism - colour change caused by magnetic field.
 Biochromism - colour change caused by interfacing with a biological entity.
 Amorphochromism - colour change caused by changes in crystalline habitat.
 Cryochromism - colour change caused by lowering of temperature.
 Hydrochromism - colour change caused by interaction with bulk water or humidity.
 Chronochromism - colour change indirectly as a result of the passage of time.
 Aggregachromism - colour change on dimerization/aggregation of chromophores.
 Crystallochromism - colour change due to changes in crystal structure of a
chromophore.
 Sorptiochromism - colour change when a species is surface adsorbed.

Each stimuli given a different reaction to the compound and each stimuli using different
polymer that can satisfy it need to change from colourless to coloured form. In this study we
will focus on five chromic material that usually used in the industry and widely known to the
people which are:

TYPE EXTERNAL STIMULI

Photochromic Light
Thermochromic Temperature
Piezochromic Pressure/stress
Electrochromic Electric/electron movement
Solvatochromic Solvent
 3

1.1 Term used in this study

Term Definition
Heterocyclic Compound or ring structure is a cyclic
compound that has atoms of at least two
different elements as members of its ring(s)
Heterolytic cleavage Bond breaking in which the bonding
electron pair is split unevenly between the
products
Visible spectrum The portion of the electromagnetic spectrum
that is visible to the human eye
Sp3 hybridization Tetrahedral shape (109.5⁰)

Sp2 hybridization Overlap of 1S orbital and 2P orbitals to form

three orbitals (planar)
Covalent bond A chemical bond that involves the sharing of
electron pairs between atoms. It is known as
shared pairs or bonding pairs, and the stable
balance of attractive and repulsive forces
between atoms
Bathochromic shift (red shit) A change of spectral band position in the
absorption, reflectance, transmittance, or
emission spectrum of a molecule to a longer
wavelength (lower frequency)
Hypsochromic shift (blue shift) A change of spectral band position in the
absorption, reflectance, transmittance, or
emission spectrum of a molecule to a shorter
wavelength (higher frequency)
Hydrogen bond A primarily electrostatic force of attraction
between a hydrogen (H) atom which is
covalently bound to a more electronegative
atom or group
Excited state Any quantum state of the system that has a
higher energy than the ground state (that is,
more energy than the absolute minimum)
Conjugated system A system of connected p orbitals with
delocalized electrons in a molecule, which in
general lowers the overall energy of the
molecule and increases stability.
solvent polarity Determination of what type of compounds it
is able to dissolve and with what
other solvents or liquid compounds it is
miscible.
 4

2.0 Chromic Material with Different Stimuli

2.1 Photochromic

Photochromic is the reversible transformation of a chemical species between

two forms by the absorption of electromagnetic radiation (photo isomerization), where the
two forms have different absorption spectra. In simpler context, photochromic is a change
in colour when there is a light with a certain wavelength react with the polymer. Change
in colour usually based on the longer wavelength and each polymer has its own wavelength
that can satisfy the need in photochromic.

2.1.1 Application

Photochromic material has been used widely in around the world. We can see it
usually used in a glass in order to block the shade of the sun. It were majorly apply in
ophthalmic as the ability for it to maintain correct colour, and it density in the lens. In
ophthalmic it was applied in spectacle lens where it will turn darken to protect the user
from the ray. The spectacle will slowly darken until it maximum optical density and
maintain it shade until the source of the light or photo being remove or gone then it turn
back to its original state. Figure 2.1 below shows the example of the application of the
photochromic on the ophthalmic.

Figure 2.1: Ophthalmic application of photochromic

 5

Other than ophthalmic, photochromic also applied in novelty printing and

textile. It is use for commercial as it mostly applied in children toy, and logos on t-shirt.
The esthetical value increase with the existence of photochromic material in the product
as it gives a reason why it more valuable compare to normal toy or shirt. Figure 2.2
below shows the example of t-shirt that can change colour in the existence of light.

Figure 2.2: Change colour T-shirt

The t-shirt above, change it printed picture to a coloured picture when it exposed to the
sunlight while when it in indoor, and doesn’t expose to the light source it turn to
colourless picture.

2.1.2 Properties of Photochromic Material

Photochromic material has five main important properties that need to be

achieve by the chemical compound. If it not satisfy one of this properties, it will can
achieve a photochromism. The five main properties are:
 6

 Colour development. The material must develop rapidly a strong colour

upon irradiation with UV light
 Control of return back to colourless state. The fade rate back to the
colourless state must be controllable
 Wide colour range. The range of colours must be across the visible
spectrum
 Long life. The response must be constant through many colouration cycles
 Colourless rest state. The colourless rest state must have as little colour as
possible, preferably colourless

There are five main compound that can achieve this ideal criteria to achieve
photochromism which are spiropyrans, specifically spiroindolinobenzopyrans,
spironaphthoxazines, naphthopyrans, fulgides and diarylethenes. In this study we will
focus one compound which is spiropyrans and see how the light influence the comping
in changing the it from colourless to coloured compound and then return to its original
state.

Spiropyran is widely used and study in the photochromism. They consist

structurally of a pyran ring, usually a 2H-1- benzopyran, linked via a common Spiro
group to another heterocyclic ring, e.g. (1.1). Irradiation of the colourless
spirobenzopyran (1.1) with UV light causes heterolytic cleavage of the carbon–oxygen
bond forming the ring-opened coloured species, often called the ‘merocyanine’ form,
which can be either cis-(1.2) or trans-(1.3), and (1.4) where the extra electron O- form
the double bond and the double bond at N+ move to the N+ and complete the electron
arrangement. Figure 2.3. In fact the structure of the ring-opened form is probably best
represented by a delocalised system with partial charges on nitrogen and oxygen atoms.
 7

UV

Figure 2.3: Reaction of Spiropyran with the UV light

From the figure we can conclude that after irradiation with UV light, the bond
between the Spiro-carbon and the oxazine breaks, the ring opens, the Spiro carbon
achieves sp² hybridization and becomes planar, the aromatic group rotates, aligns its π-
orbitals with the rest of the molecule, and a conjugated system forms with ability to
absorb photons of visible light, and therefore appear colourful. When the UV source is
removed, the molecules gradually relax to their ground state, the carbon-oxygen bond
reforms, the Spiro-carbon becomes sp³ hybridized again, and the molecule returns to its
colourless state. Another requirement of photochromism is two states of the molecule
should be thermally stable under ambient conditions for a reasonable time. All
photochromic molecules back-isomerize to their more stable form at some rate, and this
back-isomerization is accelerated by heating. Isomerize means that it is a process where
one molecule transfer to one molecule that has same atom but different arrangement.
For photochromic it is thermally stable.
 8

2.1.3 Photochromic Sculpture by Tomoko Hashida, Yasuaki Kakehi and

Takeshi Naemura, University of Tokyo, 2011

A photochromic sculpture is created by several layers of transparent plates

coated with photochromic spiropyran granules. Their coloration bleaching cycle can be
repeated up to 1000 times. When UV radiation hits the stacked layers, coloured pixels
appear within seconds. When the UV radiation is blocked, the colours gradually fade
away until the layers become transparent.

Figure A: Photochromic Sculpture

 9

2.2 Thermochromic

Thermochromic behaviour was term as thermochromism. Thermochromism is

means that a compound or material that change depending to environmental behaviour. It
reversible to its original state is easily to be notice. The change is brought up to its boiling
point depending it form. In different temperature, it acquire different colour.
Thermochromism is a phenomenon common in many chemical systems, both organic and
inorganic, including metal oxides that transform into conductors at a specific temperature.
So it can be said that it stimuli is temperature from the surrounding. Thermochromic
material usually in dye or ink form where it is thermal sensitive compound that was first
develop in 1970.

2.2.1 Application

Commonly, thermochromic application can be seen in a gift shop or baby stuff.

The colour changing mug that change colour when hot water is added one of biggest
application in thermochromic. There are also some application on baby product where
it apply in baby spoon or bottle where the change when the food or the milk is hot.
Figure 2.4 below shows the colour changing mug and baby product that has
thermochromic material.

Figure 2.4: Example of Thermochromic product.

 10

As the world more advance a lot of application for thermochromic can be found.
The most interesting one and the latest invention in term of thermochromic is the colour
changing shower where the shower will change colour depends on its temperature.
Figure 2.5 below shows the colour changing shower.

Figure 2.5: Colour changing shower

Each colour has it temperature for blue the temperature will be below 31℃. For green
and red the temperature will be between of 32℃-43℃ and between 44℃- 50℃. The
Led built in the shower will change colour when it detect the change in temperature
exceed the certain specification.

2.2.2 Properties of Thermochromic Material

Thermochromic doesn’t need to depend any agent to change it colour. It

depends completely in heating alone causing the change in colour of a chromophore,
and on removal of the source of heat the colour reverses to its thermally more stable
state. The colour change is linked to changes in the electronic properties (energy levels,
populations) of the materials. There are certain classification of systems and molecule
which are:
 11

 Molecular rearrangement of molecules by the breaking of covalent bonds

 Stereoisomerism in molecules; interchange between stereoisomers that have
different colours
 Macromolecular systems

For the molecular rearrangement by breaking the covalent bond is usually exist
in spiropyrans where it also exhibit photochromic. The ring opening was induced by
heating will produce highly coloured merocyanine form. The reaction occur in
spiropyrans during heating is almost the same as photochromic but the electron
movement and molecular arrangement is different. From figure 2.6 we can see the
different when the spiropyrans react with UV and react with the heat.

Figure 2.6: Different in movement of electron and molecular arrangement

From the figure above we can see that when the compound is treat with the UV
light, the electron at N will react first and moving to the single bond forming the double
bond and N+ and the single bond at the O will move toward the O and causing the bond
 12

to break and forming O-. Meanwhile, when it treated with the heat, the single bond
connecting the O move and break the bond forming a double bond with the O and the
double bond in the benzene ring delocalize and move toward the single bond outside
benzene ring and causing the next electron to move to the next position. The different
is that when it treated with UV light it can’t directly break the bond at the O where it
will move the electron at N first then the bond will be break.

In thermochromic, we can change the colour by its temperature, where when it

achieve certain temperature it will turn different colour from the previous temperature.
In this case the polymer that we use will be bis-spiropyrans where it produce sequential
colour changes. The colourless bis-spiropyrans (1.60) in Figure 2.7, when heated to 60
°C, it changes to a red colour, due to the formation of the mono-merocyanine (1.61),
and at 70 °C it becomes blue as the bis-merocyanine (1.62) appears.

Figure 2.7: Sequential colour changes

 13

For the stereoisomer in molecule, it occur in different type of polymer, which is

bianthrylidene systems. In bianthrylidene it consist of bianthrones polymer (1.64)
where it undergo reversible thermochromic colour change, due to two distinct and
interconvertible A and B forms. In the parent bianthrones (1.64; R = H), the A species
existing at room temperature is yellow (λmax 380 nm) and this is partially converted
into the green B form (λmax 680 nm) on heating in solution. The A form adopts a folded
and the B form a twisted conformation as in figure 2.8. At certain point the bulky R
will increase in energy until it reach a maximum absorption and it will not exhibit a
thermochromism and maintain it colour until the temperature drop down.

Figure 2.8: Example of polymer that undergo isomerism in thermochromic

For macromolecular system, the polymer that exhibit this properties are poly(3-
alklythiophene)s and poly(3-alkoxythiophene)s. The colour change, which is
reversible, is blue-shifted or hypsochromic, a phenomenon that is known as ‘negative
thermochromism’. For instance poly[3-oligo(oxyethylene)-4-methylthiophene] at
 14

room temperature has an absorption band at 550 nm, when it is heated to a higher
temperature a new band appears at 426 nm, becoming the sole absorption at over 100
°C. The change in colour is describe that at low temperatures the polymers form planar,
highly conjugated assemblies (violet coloured) that upon heating become disordered
and either twisted or non-planar and hence less conjugated (yellow coloured), as shown
in Figure 2.9. The temperature range of the solid-state thermochromic effect can also
be altered by changing the length and flexibility of the side chains.

Figure 2.9: Macromolecular change in polymer

2.2.3 In Heat by Jürgen Mayer, Installation with Thermosensitive Surfaces,

HUA Gallery New York, 2005

In heat is a gallery where it concept based on thermosensitive. This is an

installation, exhibited at the Henry Urbach Architecture (HUA) Gallery, New York, in
2005. Certain parts of the walls and seats in this installation of thermochromic paint,
which reacts to touch or body heat by losing colour. The thermosensitive surfaces
represent a three-dimensional painting where “the viewer, creating a temperature
shadow by touching, melts into the overall exhibition design”. The idea is to remove
 15

the boundaries of the wall, the floor, the ceiling, and merge them into a seamless,
endless surface and space. It give an exciting experience to the viewers.

Figure B: “In Heat” exhibition using thermochromic application

 16

2.3 Piezochromic

Piezochromic is describes as a tendency for the material to change colour due

to the pressure that was applied on the compound. The stimulus will be mechanical as
example pressure, stress and etc. back then this material hasn’t been studied or apply in
industry. Now a lot of study has been conduct as it can be apply in stress detection,
particularly for in situ failure monitoring due to fracture, corrosion, fatigue, or creep.

2.3.1 Application

Piezochromic labels or surfaces can be used to indicate an overload condition

in the box or package. Common situations where overload might occur include stacking
of many boxes in warehouses or supermarkets, which might cause damage to the
lowermost box, and overloading of an individual box which, when lifted may cause
breakage or tearing of a box, resulting in injury to the person who lifts it. Example
shows in the figure 2.10 below.

Figure 2.10: Stacking of box where Piezochromic was apply

Other application that has been apply using piezochromic was smart toothbrush.
The toothbrush body incorporates a piezochromic liquid crystal cholesterol ester
 17

whereby the user is informed whether correct or excessive force is being applied during
brushing. The main intention of this product is to prevent damage caused to teeth and
gums due to brushing too hard.

Figure 2.11: Smart toothbrush with piezochromic application

2.3.2 Properties of Piezochromic

In Piezochromic, the compound that exhibit piezochromism is Poly(3-

alkylthiophenes). It will undergoes a bathochromic shift as the pressure is increased,
reaching a maximum absorption of 520 nm at 8 kbar. The shift in wavelength is thought
to be due to an increase in the length of conjugation in the chain as the packing is
improved, compensating for conformational changes. Bathochromic shift is a change
of spectral band position in the absorption, reflectance, transmittance, or emission
spectrum of a molecule to a longer wavelength (lower frequency). This effect
commonly called red shift because red colour has the longer wavelength compared to
other as shown in figure 2.12 below. Figure 2.13 shows the graph of red shift and blue
shift.
 18

Figure 2.12: Visible spectrum and its wavelength

520 nm

Figure 2.13: UV visible Spectroscopy (red shift and blue shift)

 19

2.4 Electrochromic

Electrochromic material is a compound that capable of reversibly changing

colour when an electrical current is applied to it. This change of colour is caused by
controlled redox reactions. When an electroactive species undergoes a change in colour
upon electron transfer or oxidation/reduction the process is known as electrochromism.
This process normally involves the passage of an electric current or potential and is
reversible. Electrochromic materials are used to control the amount of light and heat
allowed to pass.

2.4.1 Application

Electrochromic application has been widely use in electrically switchable rear-

view car mirrors for anti-dazzle, in glazing units for temperature and light control and
in visual displays. The application also has been apply to plane mirror where it give
comfort to the passenger if they want to open the mirror and see the views outside.
Figure 2.14 below shows the glaze mirror in the plane.

Figure 2.14: Glaze mirror in plane

 20

The latest and advance application in electrochromic it the application on smart

window where it glaze the high transmission and it can be control by the user. The
properties of the mirror was altered when voltage is applied. It will changes from
translucent to transparent by using a remote. Figure 2.15 below shows the application
of the smart window while figure 2.16 shows how the smart window works.

Figure 2.15: Smart window application using electrochromic material

Figure 2.16: Application on Smart window

In a recent development, one company has develop bag where it can change
design using a smartphone by using the electrochromic application. The using a
 21

ChroMorphous fabric where ChroMorphous can display fixed patterns or changing

patterns depend on the designer or user itself. ChroMorphous technology is the first of
its kind and it is an innovative textile that changes colour and appearance on demand.
Figure 2.17 below shows the ChroMorphous bag.

Figure 2.17: ChroMorphous bag

2.4.2 Properties of Electrochromic Material

Electrochromic material consist of two type of material which are coloured

electrode and coloured electrolyte. The most common used is coloured electrode in
which the electrodes are coated with an organic or inorganic polymer which becomes
coloured on passing a charge through the cell. Polymer that was usually used in coated
the electrode is tungsten trioxide. If both electrodes change colour they must display
complementary electrochromism which means that the colour change that occurs by
oxidation at the first electrode is the same as that occurring by reduction at the second
electrode. The degree of colouration can be controlled by the amount of charge passing
through the cell or also by switch. When the colour is formed by reduction at a negative
electrode it is called cathodic coloration. Conversely, the anode it is anodic coloration.
The figure 2.18 below shows the example of coloured electrode.
 22

Figure 2.18: Coloured electrode

For the coloured electrolyte, the two complementary electrochromes are

dissolved in the electrolyte between the transparent electrodes. One becomes coloured
by oxidation and the other by reduction and consequently the electrolyte becomes
coloured. It remain colour when there is a current pass through but it turn colourless
when the charge or electric source was remove. The figure 2.19 shows the coloured
electrolyte.

Figure 2.19: Coloured electrolyte

2.4.3 Tungsten Trioxide

Tungsten trioxide is one of the polymer that can be use in coating the electron
to get the colour change needed. Figure 2.20 below shows how the reaction occur in
tungsten trioxide that make it change colour.
 23

Figure 2.20: Reaction occur in Tungsten trioxide

Colour change in tungsten trioxide involves partial reduction of the pale yellow
WVI to the blue WV state. This reduction requires partial insertion of a balancing cation,
as shown schematically in figure 2.20, where M is usually lithium or hydrogen. Pure
tungsten trioxide WO3, is the pale yellow and usually colourless in thin film. The
reflected colour of the reduction product is, MxWVI(1–x)WVxO3, is proportional to the
charge injected. When the electron in contact with the tungsten trioxide, the colour
changes from blue (x = 0.2), through purple (x = 0.6) and red (x = 0.7) to bronze (x =
0.8–1.0).

2.4.4 Fabrication Bag by Hanna Landin & Linda Worbin, 2005

Linda Worbin, researcher in Textiles and Interaction Design at the Swedish

School of Textiles has been exploring smart materials for some time to create
interactive textile. The Fabrication Bag may be defined as an investigation on a pattern
of static forms that change colour, or an investigation on a dynamic textile pattern of
static form, by digital information. This project is a combination of thermochromic and
electrochromic material. It will detect the smartphone if it get message or call and turn
the colour of bag in a pattern for telling there is a call or message.
 24

Figure C: Fabrication bag

 25

2.5 Solvatochromic

Solvatochromic effect was term as solvatochromism. Solvatochromism is the

phenomenon observed when the colour due to a solute is different when that solute is
dissolved in different solvents. It changes colour in existence of solvent and its colour
depends of the solvent because each solvent give different emission spectra of molecule.
More specific solvatochromic the phenomenon whereby a compound changes colour,
either by a change in the absorption or emission spectra of the molecule, when dissolved in
different solvents.
.

2.5.1 Application

The application of the solvatochromic has been slow as not many people interest
in it. But in the last few decades a lot of study and implementation has been made.
Before solvatochromic application become more advance, it has been used to determine
the existence of a solvent and the polarity of the solvent. This application has been
suggest since 1951. Then on 1958 a scientist name Kosower was the first to set up a
real spectroscopic solvent polarity scale. Figure 2.21 below shows the colours of
solutions of Reichardt’s betaine (ET-30).

Figure 2.21: Colours of solutions of Reichardt’s betaine (ET-30). From left: n-

butanol, n-propanol, ethanol, methanol, acetophenone, acetonitrile, and acetone.
 26

For the advance application, solvatochromic material has been applied in

detecting a cancer cell. It is use in a biological probes and sensor where it will detect
the cancer cell.

Figure 2.22: Application of solvatochromic in medical device

2.5.2 Properties of Solvatochromic Material

Criteria that affect the change of the solvatochromic material are the solvent
polarity and the solvatochromic shift. The observed shifts in the maxima of the
absorption or emission spectra of molecules are due to differences in the solvation
energies of the ground (ES 0 ) and excited states (ES 1 ) as the nature of the solvent is
varied, as shown in Figure 2.23.

Figure 2.23: Difference in solvation energy of each compound

 27

The figure below shows that the when the excited state is more polar than the ground
state, its stabilisation is favoured by more polar solvents. There is a decrease in
transition energy and a bathochromic shift in the spectrum. Conversely, a more polar
ground state leads to the opposite effect and a hypsochromic shift in the spectrum. The
variations in the absorption energies of various dyes have been used to characterise the
polarity of various media and create empirical scales and the dyes that has been widely
use is negatively solvatochromic betaine known as Reichardt’s dye, where it has it has
high energy transition which is ET(30).

2.5.3 Reichardt’s dye

Reichardt's dye is an organic dye belonging to the class of azomerocyanine

betaines. This dye is notable for its solvatochromic properties, meaning it changes
colour depending on the solvent in which it is dissolved.

Figure 2.24: Polymer use in Reichardt’s dye (2,6-Diphenyl-4-(2,4,6-triphenylpyridin-

1-ium-1-yl)phenolate)