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Usage of Smart Polymer Coatings in The Textile Applications
Usage of Smart Polymer Coatings in The Textile Applications
Abstract
In past few decades, revolutionary advancements in clothing and textile industry have occurred
in an unprecedented rate. Smart materials and structures brought tremendous advances in the
field of smart textile. They are divided into passive smart, active smart and very active materials
and are the materials that sense and react to stimuli and surrounding environment sources like
from, electrical, magnetic and thermal source etc. The current demand in the textile industry is
of the materials with high functionality and high material smartness. For high performance of
garments, shape memory polymers are used in film, foam and fibre form. One aspect of smart
clothing is that the clothing should be compatible with the skin temperature (30.4 - 36.4℃) and
any sort of environment either hot or cold. Since last 30 years new research is done to
manufacture and get suitable and desired properties for thermo-regulated and heat storage
clothing. This includes various Phase Change Materials also known as latent heat storage
materials. Ultraviolet, near IR, far IR rays absorbing clothing have been manufactured that
provides heating or cooling effects. Smart Nano-textile is also developed having some special
features like self-cleaning and it also has the ability to sense and to actuate. Different conductive
polymers, composites of CNTs and polymers are coated on fiber in textile field to improve the
mechanical and thermal properties and methodologies used for the coating purpose in which
most prominent are continuous wet spin coating, continuous knife over role coater, vapor and
spray methods of polymerization. Several methods are or characterization techniques were used
to test the coating adhesion and resistivity and other functionalities. This new class of textile
which is coated with conductive polymer brought tremendous changes in the field of ordinary
clothing and textile.
Keywords: conductive polymers, Smart polymers, textile, composite of CNTs and polymer, high
material smartness
1
Outline
Abstract-----------------------------------------------------------------------------------1
1. Introduction--------------------------------------------------------------------------4
2. Overview of smart textile----------------------------------------------------------5
2.1 History--------------------------------------------------------------------------------------------5
2.2 Classification of smart textile----------------------------------------------------------------5
2.2.1. Passive smart textile---------------------------------------------------------------------5
2.2.2. Active smart textile----------------------------------------------------------------------5
2.2.3. Ultra-smart textile------------------------------------------------------------------------5
2.3 Working of smart textile----------------------------------------------------------------------5
3. Conductive polymers---------------------------------------------------------------6
3.1 Inherently conductive polymers-------------------------------------------------------------6
3.2 Commercially conductive polymers--------------------------------------------------------7
3.2.1. Polyaniline (PANI) ---------------------------------------------------------------------7
3.2.2. Poly-pyrrole-------------------------------------------------------------------------------8
3.2.3. poly-Thiophene---------------------------------------------------------------------------8
4. Polymer composites-----------------------------------------------------------------8
4.1 Applications of polymer composites--------------------------------------------------------8
4.1.1. Carbon black and polyaniline composite----------------------------------------------8
4.1.2. CNT and thermoplastic polyurethane conductive polymer composite------------8
4.1.3. Macro structured carbon black and polymer composite----------------------------9
4.1.4. Thiophene based intrinsically conductive polymer composites-------------------9
5. Coatings of conductive polymer--------------------------------------------------9
5.1 Polymer based conductive coatings------------------------------------------------------10
5.1.1. Poly-pyrrole----------------------------------------------------------------------------10
5.1.2. polyethylene-dioxythiophene--------------------------------------------------------11
5.2 Coating methods-----------------------------------------------------------------------------11
5.2.1. Vapor deposition polymerization----------------------------------------------------11
5.2.2. Direct coating--------------------------------------------------------------------------11
5.2.3. Transfer coating-----------------------------------------------------------------------12
5.2.4. Screen printing------------------------------------------------------------------------12
5.2.5. Knife-over-roll------------------------------------------------------------------------12
6. Applications of smart textiles---------------------------------------------------12
6.1 Health-----------------------------------------------------------------------------------------12
6.2 Military/defense-----------------------------------------------------------------------------13
6.3 Fashion/entertainment---------------------------------------------------------------------13
6.4 Sports------------------------------------------------------------------------------------------14
7. Characterization-----------------------------------------------------------------14
8. Future direction------------------------------------------------------------------15
9. Problems---------------------------------------------------------------------------15
2
10.Conclusion-------------------------------------------------------------------------15
11.References-------------------------------------------------------------------------16
3
1. Introduction
Smart polymers are those which can be used in various smart applications because of their
stimulus responsive behavior. They go through changes when come in contact with any sort of
change in the environment. They are also called intelligent polymers and environmental effective
polymers1.Now a days smart polymers are one of the most researched topics because of their
wide applications in different fields. In military, sports, textile and medical fields smart polymers
are widely used2. The application of smart materials are extended from heat generating and
storage clothing, optical fiber sensors in fabrics to monitor the buildings and bridges, in space
programme, the biggest development is the manufacturing of wearable motherboards capable of
detecting any health issue and injury and also transmitting this information to the hospital3.
Wool, hemp, cotton, polyamide, polyester and polyacrylic fibre are the conventional heat
insulation materials and they provide a level of protection from body warm misfortune which is
controlled by the number of air takes (holes) present in the texture. In the late 1980s a textile
capable of absorbing near infrared ray from sun rays and converting it into heat has been
manufactured and also far infrared absorbing textile was also manufactured in this same era. In
the beginning of 1990s cool fabric with a cool feeling and ultraviolet absorbing fabric was
developed, they absorb ultraviolet rays from the sunlight and reflect back the near IR rays and in
turn reduce the temperature of the fabric. The most frequently used material in production of
thermo-regulated and heat storage fabric is Phase Change Materials (PCM) or Latent Heat
Storage Materials that with slight temperature change absorbs or releases the heat. The example
of PCM materials to be used in smart textile are hydrated inorganic salts, polyhydric alcohol,
PEG and PTMG, PET-PEG block copolymer, linear chain hydrocarbon and alcohol and ethers
etc3.
The main focus of our research is smart textile, they are called smart textiles because they
enhances the functionality and usage of simple fabric, different polymer based sensors are added
to the textile to increase their application area, for the insertion of these Nano-techs in daily
outfits it is necessary that they should be wearable, flexible and cost effective4.
Conductive polymers are one of the smart polymers which are coated on fiber in textile field to
improve the mechanical and thermal properties. Different polymers are used as conductive
polymer like polyaniline (PANI), poly-thiophene, poly-pyrrol (PPy) these are also called
inherently conductive polymers and some composites of polymer and CNTs are also being used
for the coating purpose but in the first 2 some binders are also needed to be added for good
adhesion5, 6.
A large number of present models of fibers which are used are very tiresome, ungainly and they
also wear. The use of these models is not appropriate for practical applications. For more easy to
use and understanding new type of material, structure and textures are needed to be developed2.
Smart Nano-textile is also developed for wide applications it has some special features like it is
self-cleaning and it also has the ability to sense and to actuate. This is because of the new
technologies like use of conductive polymers, CNTs and antimicrobial coatings in the textile
field. Different methodologies can be used for the coating purpose in which most prominent are
4
continuous wet spin coating, continuous knife over role coater, vapor and spray methods of
polymerization can also be used for the fabric or textile coating while coating the thickness of the
coating is very important if it is below the certain limit it will cause changes in the conductivity
or resistivity 7. The conductivity and resistivity can be measured by using A.m meter and for
characterization SEM (scanning electron microscopy) can be used. And adhesion can also be
checked by using some characterization techniques2.
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(SMPs) and conductive polymers. Each material has some specific features according to
which they respond to the external stimuli. They also transfer energy while accepting stimuli
and showing response. The amount of energy transfer is dependent on the properties of the
chosen material. Smart materials acts as brains, they accept signals in the form of stimuli
then analyze the signal and show response according to the change in the environment13.
3. Conductive polymers:
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Smart textiles are made by combination of smart materials, PCMs, shape memory polymers,
communication equipment and sensing elements and they analyze, process and respond to
external stimuli 2. All of these are complex and integrated materials. Due to their special
properties ICPs have applications in the field of composite membranes, sensing devices,
mechanical actuators, electrochromic displays, controlled drug release, rechargeable batteries,
sensing and communication technology, environmental sensing etc15.
Table1. Intrinsically conductive polymers with resistivity16.
SR.N INTRINSICALL MATRIX / TYPE OF FORM RESISTIVITY
O Y CONDUCTIVE ADDITIVES TEXTILE OF
OHM/SQ CM
POLYMER USED TEXTILE
1 Pyrrole Naphthalene Polyester Fabric 10
Sulphonic
acid & PVA
2 Aniline Aqueous Nylon Fabric 16.67
hydrochlorid
e
3 Polyethylene polyvinyl Polyester/Nylon Fabric 8000
dioxythiophene acetate
7
to occur at a proton doping level of 50%. Doping of a functionalized sulfonic acid such as
camphorsulfonic acid with Polyaniline is another method of processing of polyaniline, the result
is PAni.HCSA emerladine salt complex which is soluble in various organic acids17.
3.2.2. Polypyrrole:
Polypyrrole is an attractive conducting polymer due to its better environmental stability, stability
in air, high electrical conductivity and electroactive in both organic and aqueous electrolyte
solutions and also the chemical, electrical and mechanical property can be controlled by
switching between its reduced and oxidized states. For immobilization of biologically active
molecules (enzymes, antibodies etc.), polypyrrole is found out to be bio compatible and non-
toxic. The two synthesis method of polypyrrole includes oxidative or chemical oxidative
polymerization of pyrrole monomer in solution, and in each process anionic dopant specie is
incorporated in oxidized polymer. Electrochemical polymerization process includes the
oxidization of pyrrole monomer in an electrolyte at a suitable anode. Chemical polarization
process is achieved by mixing of pyrrole monomer with a suitable solvent18.
3.2.3. Polythiophene (PTH):
Polythiophene and its derivatives are considered as conductive polymers because they have good
electrical and optical properties. These unusual properties are because of the presence of
conjugated π electrons and overlapping of p-orbital along the backbone. Dopant is used to
achieve high electrical properties. The thiophene id used to make wearable electrical textiles19.
4. Polymer composites:
Composites are those materials which are combination of two or more materials, whose
properties are greater than both of these individual materials. Different polymers are used in
composite form to enhance the properties in place of bulky materials i.e. ceramics and metals.
Some widely used polymer composites coatings are following
Carbon black and polyaniline composite.
Thiophene based intrinsically conductive polymer composites.
CNT and thermoplastic polyurethane conductive polymer composite.
Macro structured carbon black and polymer composite.
4.1. Applications of polymer composites:
4.1.1. Carbon black and polyaniline composite:
To decrease the sheet resistance of cotton fabric carbon black and PANI composite is
coated on the surface. Sheet resistance of uncoated cotton fabric was reported as 3.57 x
1012Ω/ sq and after polymer composite coating its sheet resistance was decreased to
500Ω/sq approximately20.
4.1.2. CNT and thermoplastic polyurethane conductive polymer composite:
Carbon nano tubes are considered as Nanocomposites which are used in place of other
fiber and textile materials. Carbon nanotubes and thermoplastic polyurethane conductive
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polymer composite are used as sensing material for external stimuli in which physical
and chemical stimuli are included5.
4.1.3. Macro structured carbon black and polymer composite:
It is very difficult to make conductive textile without any compromise on the inherent
properties of a conventional textile. These flexible textiles are used in making wearable
sensors, and in EMI shielding fabric etc. Long lasting, flexible cotton fabric is made by
using natural rubber latex and polyvinyl alcohol accompanied by carbon black composite.
By coating this composite lowest resistivity level obtained was less than 60 ± 5.4 Ω/cm 2,
which was very favorable for making profitable and also water proof breathable
conductive fabric. Breathability that was achieved was up-to 4400 g/m 2/24h and water
proofness was up-to 95 cm water16.
4.1.4. Thiophene based intrinsically conductive polymer composites:
Thiophene based intrinsically conductive polymers are better than pyrrole based
composites thiophene based intrinsically conductive polymer composites were more
strong than those that were made from various other precursors. They are used in making
electrically conductive textiles. These textiles are preferred because of its contact with
humans and advanced technologies can be inserted into textile without any notable loss in
the properties21.
9
Fig.1. historical development of coatings and solid films 24.
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5.1.2. Poly ethylene-dioxythiophene (PEDOT):
PEDOT-PSS is a conductive polymer which is used as a coating material. To make
stretchable and wearable electro textile, spandex fabric was immersed into the PEDOT-
PSS. This coated fabric had average conductivity of about 0.1 S/cm. the conductivity
value can be increased by just increasing the no. of dips into the PEDOT-PSS. The
flexibility, softness and mechanical strength was not affected by the coating material25.
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applying polymer coating on the base cloth, to solidify the coating material cloth is
placed in the oven at 200-250 0C 27.
5.2.3. Transfer coating:
In this process a coating media is used i.e. paper carrier. Transfer media is embossed
release paper having a pattern which show on the final product. A layer of coating
material is applied on paper, material takes on emboss of paper. Number of the layers of
coating material is depends on the desired properties. At the end backer is applied on the
last layer. After this it will place in the oven and would be solidify, then paper is pulled
off and process is finished 28.
5.2.4. Screen printing:
Screen printing is a common technique of printing, begin in the last decade. It is used for
a range of materials included metal, ceramics, textile, paper, glass and wood etc. Due to
low cost and easy processing this technique is preferred over other common printing
techniques. In this technique, ink or printing media is imposed onto the substrate using
mesh containing impermeable areas. A squeegee is used to force the printing media
through the mesh onto the substrate 29.
5.2.5. Knife-over-roll:
In this technique a knife is used with a roll to impart the printing material onto the
substrate. It provides overall low processing cost due to the scrapping off the excess
material. For different weights and viscosities of printing materials the gap between the
knife and roll is adjusted to control the speed and uniform distribution of the material
over the substrate. It is a cost-effective method and can be used for a range of materials of
different weights and viscosities 30.
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Fig.3. wearable health belt
6.2. Military/defense:
To increase the safety of military personnel, people are working on the use of smart textile
into their uniforms. During warfare soldiers are exposed to severe environmental and
hazardous conditions. They need protection from those conditions for their survival. Use of
smart textile which have the ability to respond according to the external stimuli is very
helpful in this regard32.
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Fig.5. light emitting smart textile
6.4. Sports:
Sports is one of the important fields of smart textile improvements. In general various
important functions can be performed by utilizing smart gadgets or clothes. These include:
Monitoring heart rate, breathing, body temperature and other physiological parameters;
Estimating action, for instance deciding the quantity of steps taken, the complete distance
which is travelled34.
7. Characterization:
For the characterization of smart polymer coatings different techniques were used in
which SEM (scanning electron microscopy) was used to investigate the non-uniformity
and potential aggregate of PEDOT-PSS on the fabric 25. And also it was used to
investigate the surface morphology and distribution of carbon particles. The electrical
resistance was measured by using digital multi-meter and surface resistivity was
measured by placing two electrodes on a distance of 1cm on the sample. For tensile
strength testing, tensile testing machine was used according to ASTM D5035 35.
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8. Future direction:
In recent decades, smart polymers and smart polymer coatings are most researched topics
because of their high potential in soft robotics, smart surfaces, strain sensors, wearable
displays, bio-motion detectors and coatings which can also be coated on steel pipes to
make them corrosion free. In future, smart textiles will be used in the transportation and
other industries. Now the growth of this sector is slow because of the high cost of these
materials, but in near future the use of smart textiles will be increasing due to the
discovery of effective and cheap way of manufacturing these material. In transport
section they will be playing role in controlling the heating of seats, smart functioning of
seat belts and in steering wheel hold32.
9. Problems:
The major problems of conductive textiles are their manufacturing on large scale. Their
processing is very costly that is why they are not used in daily lives. It is very difficult to
maintain the inherent textile properties (softness, mechanical) while using textiles as
wearable electronics. There is another problem of adhesion of conductive polymer on the
textile surface36.
10. Conclusion:
The above discussion showed that the future of textile is smart textiles because of their
exceptional uses in many fields. Smart or conductive polymers are coated on the surface
of the fiber or textile by using different deposition methods, which include vapor
deposition, knife-over-roll, screen printing and transfer coating etc. By coating different
inherently conductive, polymer composite and commercially available conductive
polymers the surface resistivity was decreased without compromising on the inherent
properties of fibers. These smart textiles has wide applications in future but now the
production of these type of textile on larger scale is difficult that is why they are costly.
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