Welcome to the Presentation

on

Application of Chromic
Colourants in Textiles
Presented by

Md. Ershad Khan

ID: 2013-2-3-001
M.Sc. in Textile Engineering
Department of Wet Processing Engineering
Bangladesh University of Textiles

What is Chromic Colourant?

Chromic colourants may be dened as dyes and
pigments that exhibit a distinct colour change when
exposed to an external stimulus, especially when the
change is reversible and controllable.
A wide range of materials that exhibit colour change
effects have been investigated in recent decades
and numerous products have been introduced
commercially.

Although these colorants have not been developed

specically for textiles, there is growing interest in
their potential for applications in technical and smart
textile products.
2

An overview of chromic materials

Over the last 150 years, a comprehensive range of synthetic
dyes have been introduced industrially for the purpose of
dyeing the different textile bre types with the complete gamut
of colours.
Any variation in the colour of a coloured fabric, for example
when exposed to a change in temperature or to light, would
normally be regarded as highly undesirable, i.e. a defect.
However, it has been recognised in recent decades that there
are potential important commercial niche applications for dyes
and pigments that exhibit a distinct colour change when
exposed to an external stimulus, especially when that change
is controllable and reversible. Such colorants are collectively
referred to as chromic materials
3

An overview of chromic materials

A wide range of chromic phenomena are now well
known and the underlying physical and chemical
principles have been established.
An extensive range of materials that exhibit the
colour change effects have been investigated and,
where appropriate, introduced commercially.
The industrial applications which have emerged
are generally in high technology areas, for
example in thermometry,
ophthalmics,
electronics and
biomedicine, where the
particular colour change (chromic) effect produced
by the stimulus is specically exploited.
4

list of chromic phenomena & the stimuli involved

Chromic phenomenon

Stimulus

Thermochromism

Heat

Photochromism

Light

Ionochromism

Ion

Electrochromism

Electric current ow

Solvatochromism

Solvents

Vapochromism

Solvents

Mechanochromism

Mechanical action

Chronochromism

Time

Radiochromism

Ionising radiation

Magnetochromism

Magnetic eld

Biochromism

Biological sources

Indeed, the list in the table is not exhaustive.

Chromic phenomena for textile applications

Four chromic phenomena which have been most
extensively studied for textile applications

1. Thermochromism (colour change due to a

change in temperature)
2. Photochromism (UV-light induced colour
change)
3. Ionochromism (especially halochromism
where the colour change is related to pH
variation)
4. Electrochromism (colour change due to
electric current ow)
6

Thermochromism
Thermochromic systems provide a change of
colour as the temperature changes, commonly
reversibly, by either heating or cooling. The main
applications of thermochromism involve a colour
change
to
indicate
temperature
variation.
Thermochromics may be categorised into two broad
types:
1. Intrinsic systems in which heating is the direct
cause of the colour change

2. Indirect systems in which heating causes

changes in the environment in which the
chromophore is located, which in turn results in a
colour change.
7

Types of Thermochromic Colourants

There is a wide variety of thermochromic
materials. Many of such materials commonly
operate at high temperatures and are thus not
normally appropriate for textile applications.
There
have
been
interesting
recent
developments in organic polymers that show
reversible intrinsic thermochromism. Two types
of thermochromic system have been applied to
textiles: (The term system is used advisedly as
neither are dyes in the conventional sense.)
1. Leuco dye
2. Liquid crystal types
8

Thermochromics Leuco dyes

The most widely used industrial thermochromic system is the leuco dye
type. The term leuco describes a dye which can acquire two forms, one
of which is colourless. This microencapsulated composite system relies
on colour formation from the interaction of three materials:
1. An organic colour former (the leuco dye)
e.g. Crystal violet lactone (CVL), a diarylphthalide
which is colourless in its ring-closed form (Fig.
1.1(a)).
2. A developer (proton donor)
e.g. )). The most common acid developer is
Bisphenol A. Other weak acids which are
appropriate
include
alkylgallates,
hydroxybenzoates, hydroxycoumarins and
1,2,3-triazoles.
3. A low-melting, nonvolatile hydrophobic solvent
e.g. The most common hydrophobic solvents are aliphatic alcohols of
varying chain lengths.
9

Thermochromics Leuco dyes

Figure: Schematic representation of the mechanism of colour change in a

microencapsulated organic leuco dye thermochromic system.

10

Thermochromics Liquid crystal Dye

The second type of thermochromic system that can be
applied to textiles is based on liquid crystals.
Liquid crystals, often termed the fourth state of matter,
show liquid-like behaviour but the molecules have a
tendency to line up in an ordered pattern, unlike normal
(isotropic) liquids in which there is random orientation.
The thermochromic effect provided by certain liquid
crystals is quite different from that of leuco dye types.
They provide a continuously changing spectrum of
colours over a range of temperatures (referred to as
colour-play) when observed against a dark (ideally
black) background.
11

Thermochromics Liquid crystal Dye

As the liquid crystals
heat up, the orientation
of the helices changes,
which
causes
the
helices to reflect a
different wavelength of
light. To our eyes, the
result is a change in
color. As the crystals
cool down, they reorient
themselves into their
initial arrangements and
the
original
color
returns.

Figure: Temperature dependence of

the reected wavelengths for a
microencapsulated chiral nematic
liquid crystal pigment printed on black
polyester.
12

General applications of thermochromism

Plastic strip thermometers
It is used for example to measure the
temperature of air or water (e.g., in an
aquarium).

Medical thermography
The
temperature
indicating
thermochromic devices are placed on the
forehead to monitor skin temperature.

Battery testers:
It is used to monitor lifetime based on the
heating effect produced by a live battery.
13

General applications of thermochromism

Food packaging
They are also commonly applied by
printing on food packaging, for example on
bottles, cans or cartons of drinks to
indicate correct chilling.
Architectural application
There is growing interest in the use of
thermochromics in architecture, for
examples in coatings or tiles for either
Internal or external use.
Novelty areas
There is an endless list of uses, in bath
toys, mugs, umbrellas, golf balls, jewellery
and cosmetics, to name only a few.
14

Major International Manufacturers

of Thermochromic Dyes
LCR Hallcrest (UK), now incorporating
ColorChange Corporation (USA)
Matsui (Japan).
Siltech Limited (UK)

QCR Solutions Corp (USA)

15

Textile applications of thermochromism

Colour
changeable
T-shirts:
Global
Hypercolor brand, introduced an apparel use
of thermochromic leuco dyes is in T-shirts
initially in 1991. These particular products
were
coloured
with
thermochromics,
commonly with an additional permanent colour
to provide a colour to colour change.
Baby clothes: The colour change to indicate
that the child may be too hot.
Faded indigo effect: Applications of leuco
dye systems to denim produce the blue to
colourless thermochromic effect, thus sharing
a similarity with the faded indigo effect.
Color changing flu-masks The color change
via Thermochromic ink is easily triggered be
exhaling through the mesh of such masks.
16

Photochromism
Photochromism is commonly dened as a
process in which a compound undergoes a
reversible change between two species with
different absorption spectra, i.e., with different
colours, on irradiation with light.
Most photochromic dyes acquire a colour when
exposed to irradiation by UV or low wavelength
visible light and revert to their original
colourless state when the light source is
removed.
17

Types of photochromic dyes

Photochromic dyes may be categorised into two
broad types.

1.T-type photochromic dyes

When the reverse reaction is thermally driven

2. P-type photochromic dyes

When the reverse reaction is photochemically
induced, using light of a different wavelength.

While most industrial photochromic dyes are of the

T-type, there is considerable ongoing research
interest in P-type photochromics and their potential
applications.
18

Main Chemical Classes of Photochromic dyes

1.Spiropyrans dye

2. Spirooxazines dye

3. Fulgide dye

19

Main Chemical Classes of Photochromic dyes

5. Naphthopyrans dye

4. Diarylethene dye

20

General applications of photochromism

Ophthalmic
Sunscreening:
Responsive
eyewear items include the familiar spectacles
which become sunglasses when exposed to UV
light, and also ski-goggles and motorcycle
helmet visors.
Cosmetic and Beauty Products: They are
used in nail varnishes which acquire colour in
the sun and have been proposed for other
cosmetics and personal care uses, such as in
hair dye formulations and sunscreen lotions.
Security
Printing:
The
photo-induced
coloration may be used in security printing, for
example as anti-counterfeit Markers on
banknotes and documents such as passports.
21

General applications of photochromism

Novelty Plastic Items: They have also been used
for novelty effect in plastic items such as toys,
combs, beads, drinkingstraws, cups, spoons and
drinks bottles.
Fishing Lines: Another interesting functional use of
photochromism is in shing lines which become
coloured in sunlight and thus visible to the angler,
while below the water-line where the sun cannot
penetrate, the line is colourless, thus assisting
concealment from the sh.

22

Major International Manufacturers of

Photochromic Dyes
Vivimed Labs (formerly James Robinson,
UK) and
PPG Industries (USA).
Corning (France)

Shanghai Zhuerna High-Tech Powder

Material Co. Ltd. (China)

Textile applications of Photochromism

There have been comparatively few reports of the
application of photochromic compounds on textiles,
although recent papers indicate growing interest,
with applications envisaged in creative and intelligent
design, and in functional or smart textile products.
There are a number of reports of investigations of
exhaust dyeing of synthetic fabrics using simple
photochromic spirooxazine dyes. Photochromic
textiles were obtained converting from colourless
or weakly coloured to blue on exposure to UV
radiation.
24

Textile applications of Photochromism

Photochromic dyes may be applied to textiles by
screen printing. A series of publications have been
aimed
at
establishing
how
commercial
photochromic dyes are capable of performing on
fabric screen-printed using a pigment printing
method, following optimisation of the formulations
and application conditions.
The use of photochromics in novelty printing is a
signicant commercial outlet. Because of their
ability to show resistance to thermal fade rates
fulgides have been the class most commonly used
for this application. Typical uses are on childrens
toys and for logos on T-shirts.
25

Ionochromism
Ionochromism is the phenomenon in which a reversible
colour change is caused by interaction with an ionic
species. A wide range of colour changes are available
which can be either from colourless to coloured or from
one colour to another.
The most common ionochromic materials, arguably the
longest-established useful group of chromic materials,
are pH-sensitive dyes, used for decades as analytical pH
indicators.
These dyes are sensitive to the hydrogen ion
are referred to as halochromic. Another
ionochromism involves a colour change
interaction with metal ions, referred
metallochromism.

(H+) and
form of
due to
to as
26

Mechanism of ionochromic dyes

The main chemical classes of technically important pH-sensitive
dyes are phthalides (exemplied by the well-known pH indicator,
phenolphthalein), triarylmethines and uorans.
However, many other chromophores can undergo halochromism,
including a number of simple azo dyes, such as methyl orange (Fig.
(a) which provides a colour change from orange to red with the
formation of the species in Fig. (b) due to protonation as the pH is
lowered.

Figure: The halochromism of methyl orange (a) and red (b).

27

Mechanism of ionochromic dyes

Crystal violet lactone (CVL), a diarylphthalide which is colourless in
its ring-closed form (Fig. 1.1(a) ). A ring-opened protonated species
(Fig. 1.1(b) ) is formed as the pH is lowered. This species is highly
conjugated, although not coplanar (it is propeller-shaped), and is
thus coloured, reddish-blue in the case of CVL.

Figure: Protonation of crystal violet lactone (a, b)

28

General applications of ionochromic dyes

pH indicators
Halochromic dyes have been used extensively over the years
in analytical chemistry as reversible pH indicators in detecting
the endpoint of acidbase titrations and in spot papers, such
as litmus.

Optical sensors
Halochromic dyes are used, for example, in absorbance-based
ion-selective optical sensors, which have applications in
chemical process control, medical diagnostics and
environmental monitoring.

Carbonless copy paper

A familiar application of CVL and related halochromic dyes is
as colour formers in carbonless copy paper and direct thermal
printing where an irreversible change from colourless to
coloured is exploited.
29

Textile applications of ionochromic dyes

In spite of the fact that they are the longest established class of chromic
materials, ionochromic dyes have been largely neglected for textile
applications. However, there has been recent renewed interest in their
potential for functional textile applications in which a visual indicator of pH
change is required.

The fabric dyeing with water-soluble disazo dye Brilliant Yellow

changes colour reversibly from yellow (pH 34) through orange (pH
56) to red (pH 79).

Figure: Halochromic dyes: Brilliant Yellow (CI Direct Yellow 4)

Textile applications of ionochromic dyes

Textile sensors
In a subsequent investigation, Brilliant Yellow and Bromocresol
Purple were successfully incorporated by electrospinning from
solution into non-woven nanobrous polyamide 6.6 structures to give
halochromic properties which were assessed as suitable for use in
textile sensors. It is envisaged that such sensors have potential for
application in medical textiles.
Healing indicating bandage
It has been reported that the pH of the skin of burn patients changes
during the healing process. It is thus conceivable that a colour
change on a wound dressing as a result of a localised change in pH
might be used to monitor the healing process without the need to risk
damaging the wound by removing the dressing.
Technical textiles
There are also potential applications for halochromic textiles in
protective clothing and geotextiles.
31

Electrochromism
Electrochromism involves a reversible
colour change resulting from a ow of
electric current. The colour change is due
to electron transfer reactions, i.e.,
oxidation/reduction, occurring at an
electrode oxidation at an anode and
reduction at a cathode.

32

Types of electrochromic materials

1. Solid electrochromic materials: All inorganic electrochromes exist in
the solid state in both the colourless and coloured states, e.g. Prussian
Blue , cobalt oxide, nickel oxide, molybdenum trioxide, vanadium oxide
tungsten trioxide and their mixtures.

Figure: Prussian Blue produces the colourless Prussian White on reduction

2. Solution electrochromic materials: In

these systems the soluble electrochrome
undergoes an electron transfer interaction
on the surface of the appropriate electrode,
involving either anodic oxidation or
cathodic reduction, where it changes
colour and then returns back to the solution
phase, i.e. a coloured electrolyte is
produced.
Figure: The electrochromism of methyl
viologen (a) and reduction at a cathode (b).33

General applications of electrochromism

Anti-dazzle rear-view car mirrors: The mirrors contain an indium
tin-oxide (ITO) coated glass surface with the conductive side facing
inwards as one electrode and a reecting metal electrode at the
back. The gap between the electrodes consists of an electrolyte
solution or gel containing two soluble electrochromes, one of which
is oxidised at the anode and the other reduced at the cathode as
electric current ows. The devices can also incorporate sensors that
detect headlight glare from following vehicles, sending a voltage to
the electrochromic system that is proportional to the level of light
detected.
Smart windows: These are generally constructed from two
transparent sheets of glass with conductive surfaces that act as the
electrodes, on which solid-state electrochromic materials are coated,
between which is sandwiched a conducting layer of a lithium ion
polymeric electrolyte. The windows darken electrochromically
according to the level of incident sunlight.
34

Textile applications of electrochromism

The potential applications for smart textilebased electrochromic systems are immense.
The range of uses for a highly developed
system might encompass

adaptive camouage,
biomimicry,
wearable displays and
a range of fashion items which would be
capable of changing colour at the ick of a
switch.
35

Textile applications of electrochromism

The device, as illustrated in Figure, consists of electrodes based on
fabric constructed from spandex (50% nylon/50% polyurethane)
impregnated
with
poly(3,4ethylenedioxythiophene)poly(styrenesulphonate) (PEDOT-PSS). One electrode is coated with
a specically synthesised electrochromic polymer, based on a
polythiophene, and the substrates are fused together with a
transparent gel electrolyte. The device is capable of switching
electrochromically between red and blue, based on the mechanism
illustrated in Fig. 1.20.

Figure: Schematic representation of an

electrochromic textile.
36

Textile applications of electrochromism

Figure: Applying a current causes the fabric to change colour

37

Future trends
Materials that change colour have perennially attracted scientic
attention, not only for academic curiosity but also because of
perceived commercial potential.
There are now many varieties of chromic materials and a multimillion
dollar industry has developed for their manufacture and application.
Research into chromic materials shows no sign of diminishing and as
a consequence new products with enhanced properties and offering
novel colour effects may emerge, with potential for new applications.
The future may also provide developments in chromic phenomena
which are as yet either unknown or unexploited industrially. For
example, there are probably signicant opportunities for applications
of biochromism in medical textiles, where colour change might be
used to enable the monitoring of specic medical conditions or to
provide vital diagnostic information.
38

Conclusion
Research into the application of chromic materials to
textiles has generally lagged behind other applications,
although recent publication activity suggests that it is
gathering momentum.
However, in spite of considerable interest, commercial
exploitation of chromic textiles has been rather limited. This
may be due to technical difculties in application, a level of
technical performance which does not yet match that of
traditional textile dyes and pigments, and their relatively high
cost.
The most important current industrial applications of
chromic materials are in non-textile areas, and are generally
highly technical in nature. These functional applications may
provide inspiration for future uses of chromic materials on
textiles provided that the remaining technical challenges can
be met.
39

References
1. M. L. Gulrajani , Advances in the dyeing and
nishing of technical textiles, Woodhead Publishing,
UK (2013).
2. Peter Bameld, Chromic Phenomena The Royal
Society of Chemistry, UK (2001).
3. www.colourchange.com [Access date: 24-04-2013]
4. www.qcrsolutions.com [Access date: 20-04-2013]
5. www.siltechlimited.com [Access date: 21-04-2013]