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1 s2.0 S1878535221004950 Main
1 s2.0 S1878535221004950 Main
REVIEW ARTICLE
a
Department of Chemistry, University of Agriculture Faisalabad, Pakistan
b
Department of Pharmaceutical Sciences, College of Pharmacy, QU Health, Qatar University, P.O. Box 2713, Doha, Qatar
c
Biomedical and Pharmaceutical Research Unit (BPRU), QU Health, Qatar University, P.O. Box 2713, Doha, Qatar
d
Department of Polymer Engineering, National Textile University, Faisalabad, Pakistan
e
Department of Textile Engineering, School of Engineering and Technology, National Textile University, Faisalabad, Pakistan
f
Environmental Science Centre, Qatar University, PO Box 2713, Doha, Qatar
KEYWORDS Abstract In the modern age, the most important and prevailing issue is the monitoring of human
Smart sensors; health. To address this, several devices have been developed and a need new materials investigated.
Wearable textile; The idea of textile-based smart sensors is emerging rapidly. In this regard, ICPs and ECPs have
Conductive polymers; attracted the attention of researchers due to their mechanical adaptability to suit the characteristics
Polymerization; of textile fabric. The lighter weight, stretchability and wearability, etc. are considered an advantage
Health monitoring while selecting the material for developing sensors not only in health monitoring but also in biomed-
ical, sports, and military fields. The idea behind wearable sensing devices is to enable easy integra-
tion of the sensor device into daily life routines. Such wearable sensors also have the potential for
real time and online monitoring of human health and integrate with smart monitoring devices. The
purpose of this review is to discuss the recent developments in smart monitoring sensors.
Ó 2021 The Author(s). Published by Elsevier B.V. on behalf of King Saud University. This is an open
access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
* Corresponding authors.
E-mail addresses: [email protected] (Z. Ahmad Rehan), [email protected] (I. Shahid).
Peer review under responsibility of King Saud University.
https://doi.org/10.1016/j.arabjc.2021.103480
1878-5352 Ó 2021 The Author(s). Published by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
2 M. Zahid et al.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Conducting polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Intrinsically conductive polymers (ICP). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.2. Extrinsically conductive polymers (ECP) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3. Most commonly used ICPs in smart sensors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.1. Polyacetylene (PA) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.2. Polyparaphenylene (PPP). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.3. Polypyrrole (PPy) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.4. Polythiophene (PT) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.5. Polyaniline (PANI) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4. Methods of preparing intrinsically conducting polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.1. Electrochemical polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
4.2. Doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
5. Applications of conducting polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
6. Textile or clothing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
7. Methods of coating textile . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
7.1. In situ polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
7.2. Two-step polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
7.3. Chemical vapor deposition (CVD) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
8. Smart sensors and their applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
8.1. Movement and postures monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
8.2. Strain and stretch sensing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
8.3. Pressure monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
8.4. For electrocardiogram monitoring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
8.5. Detection of ballistic penetration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
9. Future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
10. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
Unlike ceramic and metals, polymers can be molded into a 2.2. Extrinsically conductive polymers (ECP)
variety of complex structures. Before the discovery of conduct-
ing polymers, these are mostly used in non-electronic applica- Another class of polymers is also synthesized by the blending
tions. After that, researchers from multiple disciplines (melt mixing or solvent mixing) of thermosetting plastic, ther-
contributed to research in this field and improved the conduct- moplastic or insulating polymer materials with conductive fil-
ing polymers. The conducting polymers can conduct electricity lers. This class of polymers is referred to as conductive
in a broad range like metals whereas at the same time they can polymer composites (CPCs), or extrinsically conductive poly-
also retain their polymeric mechanical properties (Burr et al., mers (ECPs). Filler family include: ICP, Metal (Silver, stainless
2008; Fomo et al., 2019). steel), Carbon (CB, CNT), oxide /non-organic (ITO, CuS).
Conducting polymers are an essential component in the ‘‘However, they have much lower conductivity values then
development of smart textiles, exhibiting a conductive or a the ICPs (Grancarić et al., 2018)” but equal mechanical prop-
semiconductive behavior, and are capable of conducting elec- erty (flexibility elongation). If we use CPC with 97% silver and
tricity and therefore, they are also referred to as organic poly- 3% PU, conductivity will be close to conductivity of silver bulk
mers (Mattana, 2011). Till now, more than 25 conducting but the CPC will be brittle.
polymers have been discovered like polyacetylene, polyur-
ethane, polyaniline, etc. (Benhamou and Hamouni, 2014).
3. Most commonly used ICPs in smart sensors
These materials exhibit both electrical and mechanical charac-
teristics in plastics (S. Wang et al., 2019). These polymers have
become prevailing conductive materials because they show Various types of ICPs are used in the fabrication of smart sen-
comparatively high regulating electrical conductivity, can be sors but the commonly used polymers are as follows:
customized to have sense, ease of preparation, biocompatibil-
ity, lightweight, flexibility, and relatively low cost. Conductive 3.1. Polyacetylene (PA)
polymers combined the essential properties of conventional
polymers and metals (Iqra Abdul Rashid et al., 2020). Polyacetylene is a conducting polymer due to the simplest
Conducting polymers are divided into two subgroups structure among all the other polymers. Its structure consists
(Kosack et al., 2017): of a long chain of alternate double bonds arranging themselves
in several ways to give different forms of structures like trans-
Intrinsically conductive polymers Cisoid polyacetylene or cis-Transoid polyacetylene. It can be
Extrinsically conductive polymers prepared with high conductivities as 103 S cm 1. The degree
of oxidation is a key parameter for the conductivity of poly- phenylene). When AsF5 reacts with single crystal plate of ter-
acetylene and can extend between the range of 10-9 to 103 S phenyl to develop PPP, this polymer exhibits strong electrical
cm 1 comprising the semi-conductive and metallic systems and optical anisotropy (Dias et al., 2019) (See Fig. 4).
(Mark, 2007). In the beginning, it was expected that organic
chemists can tailor a pervasive family of conducting polymers 3.3. Polypyrrole (PPy)
just by substituting the hydrogens of polyacetylene with vari-
ous functional groups and the properties could be varied sys- Polypyrrole (PPy) gained importance because of its stability in
tematically. Some derivatives of polyacetylene have also been oxidized states and highly conductive nature. It also has some
prepared by replacing the hydrogens with phenyl or methyl significant characteristics such as simple oxidation reaction
groups. However, their conductivity cannot be elevated to a and low-cost method, making it more advantageous over other
higher level due to less delocalization of electrons either by conducting polymers. However, in comparison with PANI,
reducing or oxidizing agents. Thus, the significance of solid- pyrrole monomers have higher costs than aniline monomers,
state effects is increased by this failure and helps to define therefore they become less attractive for some potential pur-
the electronic properties. Karasz and co-workers have revealed poses (Shi et al., 2021). At room temperature oxidized PPy is
that to raise the conductivities of copolymer films of methyl chemically stable relative to polyacetylene. Degradation of
acetylene and acetylene at the range of 50 S cm 1, these poly- PPy only takes place when the temperature exceeds 150–
mers can be oxidized chemically with AsF5 (Ishii et al., 2019) 300 °C (Fernandez et al., 2021). The electrical conductance
(See Figs. 1-3). of PPy ranges from 10 to 1000 S/cm depending on the presence
of counter ions (Lekpittaya et al., 2004). Electrochemical poly-
3.2. Polyparaphenylene (PPP) merization of PPy can be carried out both in aqueous media or
non-aqueous media as dichloromethane (Tamburri et al.,
Poly(p-phenylene) is another member of the family of conduct- 2009), acetonitrile (D. Wang et al., 2021), and propylene car-
ing polymers. In 1979, for the first time, Ivory et al. synthesized bonate (She et al., 2021) (See Fig. 5).
PPP. Simply, benzene rings join through a single bond to each
other to form long chains, giving rise to poly(p-phenylene). 3.4. Polythiophene (PT)
Ivory et al. were able to oxidize PPP using AsF5 to raise its
conductivity from 10-14 S cm 1 to 500 S cm 1 (Chow and Both polythiophene and pyrrole have similar structures, but in
Someya, 2020). N-type poly(p-phenylene) can also be prepared polythiophene, the amine group of pyrrole is substituted by
using alkali metals as reducing agents. Biphenyl, terphenyl, Sulphur. It has been stated that polythiophene particles syn-
and tetraphenyl are the oligomers of poly(p-phenylene), react thesized by chemical polymerization, possess poor electrical
with AsF6 in an instantaneous oxidative polymerization, conductivity (2 10-2 S/cm) (Ahmadian-Alam et al., 2021).
which leads to the formation of conducting poly(p- However, the electrical conductivity of electrochemically poly-
merized polythiophene (PT) is comparable with PPy (Iqra sides are generated. Therefore, PANI is always polymerized in
Abdul Rashid et al., 2020). Facchetti (Facchetti, 2011) have the presence of an acidic environment. If polyaniline is pre-
demonstrated the mechanism of electrochemical synthesis of pared in neutral, basic, or weak acidic media then the conduc-
polythiophene. As thiophene has a similar structure to the pyr- tivity of the final product decreases (Bashir, 2013; M. F. Shakir
role therefore method to prepare it, is also comparable to PPy. et al., 2020) (See Fig. 7).
For electrochemical polymerization of polythiophene, a non-
aqueous media is used. The most commonly used electrolytes 4. Methods of preparing intrinsically conducting polymers
for polymerization are benzonitrile (Sapurina and Shishov,
2012), Acetonitrile (Balint et al., 2014; Tamburri et al., 4.1. Electrochemical polymerization
2009), and propylene carbonate (Ramanathan et al., 2007).
One of the most widely studied polymers of today is Poly
For the preparation of conducting polymers, different proce-
(3,4-ethylene dioxythiophene) (PEDOT) because of its stability
dures are available. However, the general method to prepare
and tunable electrical conductivity. In the doped state, it shows
electrically conducting polymers is electrochemical synthesis
higher conductivity than that of the PPy, which can further be
which is the most preferred method because of its reproducibil-
improved by post-treatment or blending methods (Xu et al.,
ity and simplicity (Hsiao et al., 2018). By this method, a thin
2021). Moreover, the highly stable oxidized state facilitates it
layer of polymer can be produced, and also by altering the
to keep up with conductivity for a considerable length of time
parameters of electrochemical polymerization such as time of
even at high temperatures and thus making it an excellent
electro-polymerization and current density, the viscosity of
material for the electrode of an actuator. Besides these, the
film can be precisely controlled (Wustoni et al., 2020). The
synthesis of PEDOT by easy and simple methods like electro-
polymerization can undergo oxidative (Gerard et al., 2002)
chemical or chemical reaction, makes it more useful (Yang
as well as reductive reaction(s) (Malinauskas, 2001). During
et al., 2020) (See Fig. 6).
this method, few factors should be considered, for example,
applied voltage versus applied current and the selection of elec-
3.5. Polyaniline (PANI)
trolytes. Because, physical and electrical properties of electri-
cally conducting polymer are significantly affected by these
The most commonly conductive polymer is polyaniline factors (Gerard et al., 2002).
(PANI). PANI has considerable properties like high chemical Usually, an electrochemical cell is used for the electrochem-
stability, cheap monomers, high value of capacitance, tunable ical coating. This cell is comprised of three electrodes; one is
properties, and ease of synthesis. Due to these properties, this designated as a working electrode on which substrate is to be
polymer has high significance over other conducting polymers. coated and the other is a counter electrode and reference elec-
PANI doped with counter ions always degrades thermally at a trode made up of inert materials usually platinum and Ag/
temperature higher than 200 0C (Koncar et al., 2009). PANI AgCl or Saturated Calomel Electrode (SCE) respectively.
exhibits good electrical conductivity ranging from 10 to 100 The polymerization solution consists of supporting electrolyte,
S/cm (Lekpittaya et al., 2004). The degree of doping, oxidation solvent, and monomer. This method is further classified into
level, molecular weight, and fraction of crystallinity is consid- potentiostatic, potentiodynamic, and galvanostatic electro-
ered to be the tuning tools to control electrical conductivity. polymerization (Advincula, 2015). This method is beneficial
PANI can be transformed into two forms, either in protonated as it is simple and appropriate for practical application, and
form by reduction or deprotonated form by oxidation (A. Liu by specifying the time during polymerization, the thickness
et al., 2021). During the electrochemical polymerization pro- of the polymer film can be controlled (Zhou et al., 2021)
cess of PANI, if the value of pH of the solution is too high then (See Fig. 8).
properties like mechanical, optical, and electrochemical of the Lee in 1859 (L. Wang et al., 2021), Spinning jenny by James
doped conjugated polymers can be tailored (Scholes et al., Hargreaves around 1765, and the flying shuttle by John Kay
2017) (See Fig. 10). in 1733 (Zhang et al., 2021), which laid the foundation for
the first industrial revolution.
5. Applications of conducting polymers Textile is a porous and flexible material, prepared by knit-
ting, braiding, nonwoven or weaving synthetic, natural fibers,
Conducting polymer exhibits unique characteristics due to the or artificial fibers i.e. polyester or cotton (Shim et al., 2008).
presence of multi-components and their synergetic/combined Fabrics are fibrous materials with a hierarchical structure.
effect. Therefore, these conducting polymers are likely to find The first integration level or smaller units are known as fibers
applications in several disciplines, such as sensors, catalysis and can be characterized by a high ratio of thickness to length;
or electrocatalysis, energy, biomedicine, nano-electronic these units are intertwined to form a thread (Castano and
devices, electrorheological (ER) fluids, chemical or biological Flatau, 2014). The second integration level is the twisting of
sensors, EMI shielding, and microwave absorption (Das and thread to form yarn. The yarn then gets turned into fabric in
Prusty, 2012; Iqra A Rashid et al., 2021) (See Fig. 11). the third integration level utilizing different techniques like
knitting and weaving (Lomov et al., 2001). Fabrics being
new wafers of silicon have generated much interest owing to
6. Textile or clothing
the advent of soft computing and portable devices. Structu-
rally, woven and knitted fabrics were used for electronic cloth-
Currently, textiles have numerous applications almost in all ing that can be worn for observation. Flexibility is the main
human activities. As compared to other materials, they also advantage of textiles relating to a few extents of wearing
have various advantages i.e. strength, flexibility, and ductility. comfort.
Due to these reasons, the recent integration of multifunctional Knitted fabrics possess the advantage of being deformable
properties in such an ordinary material has become an innova- and stretchable to some extent have been employed where
tive step towards the upcoming generation of textiles the need of fabrics to be in fitting or close to the body, for
(Gorgutsa et al., 2014). Advances both in nanotechnology example, for sportswear or leotards. Woven fabrics are com-
and materials science have provided novel strategies for sys- paratively best suited where large body movements are not a
tem’s design in applications like healthcare industries significant factor and provide more dimension stability.
(Paradiso et al., 2005), sports training (Tang and Stylios, Exploring the functions of duality, weft and warps interlacing
2006), working wear and military (Libertino et al., 2018). Tex- within woven fabrics have been discovered as electrical cir-
tile innovation about 27,000 years ago can be considered as the cuit’s network along with supporting material for the inte-
first of humanity’s inventions of material (Y. Ma et al., 2021). grated electron (Dhawan et al., 2004). The fabric’s nature
Humanity’s need for textiles has been consolidated in the pas- makes them an ideal tool for designing sensors that have direct
sing millennia either for protection against the environment or contact with humans. An important role is played by the origin
his desire to convey a message about them themselves; whether or nature of fiber units such that natural, regenerated, or syn-
it would be wealth-related, stylistic, or artistic. The textile crea- thetic which decides the final fabric characteristics. Synthetic
tion has been therefore closely coupled with key innovations fibers have less absorption of water thus they are more
that shaped the society i.e. the knitting frame by William hydrophobic in nature compared to natural ones which are
8 M. Zahid et al.
hydrophilic and also exhibit better mechanical agreement on many types of fiber capable of generating good conductivity
(Koe, 2017). Various fiber types like acrylic, polyester, nylon considerably without alteration of existing properties of the
and natural fibers have been reported in the manufacturing substrate like handling, flexibility, and density (Meoli, 2002).
of fabrics by several methods (Lam Po Tang, 2007). Among The coating of polymer is usually carried out with a conductive
the methods, we list knitting, sewing, non-woven textile coating paste. (CPC).
(Castano and Flatau, 2014), embroidering (Tognetti et al., Coating methods for conductive textiles can be attained via
2006), braiding (Castano and Flatau, 2014), spinning, weaving
(Langereis et al., 2013), printing, laminating/coating, and che- 7.1. In situ polymerization
mical treatments (Gu, 2021), and providing significant features
like controlled hydrophobic behavior. While employing in situ polymerization, all the reagents and
fiber materials are added at a time. Chemical polymerization
7. Methods of coating textile takes place within the bulk solution and polymers so produced,
either precipitate out as insoluble entities or deposit impul-
The coating is a method of applying a formulated compound sively on immersed fiber’s surface as shown in figure 12
or viscous fluid (liquid) on a textile substrate. It can be applied (Sasso et al., 2011). Bulk polymerization has to be carried on
to fabrics, yarns, or surface of fibers to develop electrically the surface of the fabric as much as possible for a better result
conductive textiles. Such a method is appropriate for applying of coating. Usually, this can be attained by selecting an opti-
Textile backing
Plastic
Powder
Proof
Raw Material Final Product
Melting Cooling
mal condition for reaction i.e. ratio and concentration of reac- ment for promoting the reagent’s penetration into their struc-
tants, the temperature of the reaction, and suitable treatment ture. The surface undercoating process should be enriched with
of the surface of the material for coating (Qu and oxidizing agents or with monomers; the main distinctive pur-
Skorobogatiy, 2015). Besides these, in situ polymerization also pose of such processes is the polymerization exclusively takes
has various advantages such as ease to mechanize, use of cost- place at the surface and possibly within the structure of the
effective materials, and the capability to assimilate with several fiber. This process however is not suited for a few textile mate-
other curing and heating methods. Such polymer composites, rials that are not enriched sufficiently with either oxidants or
which cannot be processed by melt and solution processing monomers layer in a separate step preceding the polymeriza-
due to their insolubility and thermal instability, can easily be tion of the surface (Malinauskas, 2001). Due to several kinds
prepared by this method. This method also gives very good of conducting polymers along with their innumerable molecu-
miscibility with almost any types of polymer (Iqra Abdul lar differences, specific conditions of polymerization of simple
Rashid et al., 2020) (See Figs. 12 and 13). monomers modification allows the textiles coated with conduc-
tive polymer to suit various application (See Figs. 14).
7.2. Two-step polymerization
7.3. Chemical vapor deposition (CVD)
In this method, fiber materials firstly adsorb certain reagents
and then initialize polymerization reaction by adding the rest CVD is another process for coating conducting polymers. This
of the reagents. In the first step, textiles are subjected normally process comprises of two stages for coating polymers to
to agitation, heating, padding, or ultrasonic vibration treat- develop electro-conductive materials. The CVD process, being
10 M. Zahid et al.
economical, allows the unreacted monomers as well as oxidant skin conductivity, body temperature, etc., and location infor-
and dopant solutions to be easily recovered. Fabrics coated mation, by satellite services (Goulev et al., 2004). Various tra-
with the vapor phase deposition method exhibit a uniform ditional sensors have been made depending on their
coating on the fiber’s surface as the oxidant and dopant have requirements and size. Conducting materials like carbons or
been evenly applied on the surface of fiber in polymerization. metals can be integrated into smart textile sensors. However,
This method produces nanoparticles having low aggregation, recent study inclinations are making use of the new array of
increasing the coverage of the surface area, and also causes polymers to build up flexible sensors from textile materials,
better connection among polymeric chains. Hence results in due to their varying properties with the environmental condi-
increased conductivity of conducting polymers as compared tions, i.e. change in temperature, pressure, and moisture, etc.
to aqueous coating (Cucchi et al., 2009). The bonding among Thus, for use in textile and smart clothing, new flexible sensors
conducting fibers and polymers determines the actual coating have especially been prepared (Lam Po Tang, 2007).
tendency of the polymer on the substrate. Fibers of animals, In smart clothing, sensors work as sensory nervous system
such as wool, can also be a good option as substrate material that detects the signals and transmits the data to the processor.
for conductive polymers to get attached on its surface, owing Conductive polymers are proficient in responding electrically
to functional group abundance, to which dopant anion and to changes in their molecular structure that are caused by
polymer molecules can attach by bonds like ionic or hydrogen ambient radiations, changes in temperatures, or disclosure to
bonds. Also, the wool fibers’ surface morphology provides volatile substances (Zubair et al., 2021). Baby pajamas to sup-
adsorption sites for conductive polymers (Huynh and Haick, port in averting cot death, an electronic bra to detect breast
2018). This method also has various advantages like a wide cancer, and the LifeShirt system (monitoring physiological
variety of substances can be deposited with high purity, has measurements) are modern examples of textile integrated sen-
a high deposition rate, and enables uniform coating. Other sors. The implication of such types of accessories or garments
than these, CVD does not require high vacuum process and covers several fields such as the military, sports, rescue, clini-
is therefore economical in production, since many parts can cal, or healthcare, where the detection of crucial signs is indis-
be coated at the same time (Achard et al., 2020) (See Figs. 15). pensable. In the medical sector, for continuous long-term
observation of patients’ conditions, smart monitoring gar-
ments can be used. They also provide latent assistance to fight
8. Smart sensors and their applications against cot death in babies (Hibbert, 2004; H. F. Shakir et al.,
2019). Various smart sensors and their applications are briefly
Sensors are the key component for monitoring applications in described in Table 1.
wearable electronic systems, that collect information from the Real-time information about the physiological actions and
wearer and transmit it to a processer. Innovations in monitor- conditions of a person can be monitored and recorded via
ing have developed garments and vests, incorporated with var- these wearable sensory devices. Sensor-based wearable health
ious sensors which provide physiological data like heart rate, monitoring devices may consist of various sorts of flexible
Recent developments in textile based polymeric smart sensor for human health monitoring: A review 11
sensors that can either be incorporated into clothes, elastic neurological, cardiovascular, and pulmonary diseases at their
bands, and textile fibers or directly attached to the human early stage can be detected and diagnosed with continuous
body. The sensors are proficient in computing physiological monitoring of physiological signs. Also, these sensory devices
signals such as blood pressure (BP), body temperature, respira- are very feasible in real-time monitoring of an individual’s
tion rate (RR), heart rate (HR), arterial oxygen saturation activities, proving very helpful in posture analysis, gait pattern,
(SpO2), electromyogram (EMG), electro-dermal activity sleep assessment, and fall detection. The sensory gadgets con-
(EDA) and electrocardiogram (ECG) (Nemati et al., 2012; nected in a wireless Body Sensor Network (BSN) (Al Ameen et
Pantelopoulos and Bourbakis, 2009). Several diseases such as al., 2012; Dementyev et al., 2013), firstly collect data and con-
12 M. Zahid et al.
vey it to the processing unit using an appropriate communica- 1999). Such materials have been found to have transducing
tion protocol, preferably a short-range and low-power wireless properties i.e. strain gauges, topology change, and exhibit a
media, such as ANT+ (Coskun et al., 2013; Mehmood and decrease in the value of electrical resistance as physical defor-
Culmone, 2015), Bluetooth (Chintala et al., 2020; Suzuki et mation occurs. In 2005, De Rossi et al., described gauge fac-
al., 2013), Near Field Communications (NFC) (Lam Po tors of sensors comparable to gauge factor of nickel.
Tang, 2007; Pang et al., 2015) and ZigBee (Valchinov et al., Although, they have also described that with time sensor also
2014). Various pressure sensors and their fabrication methods shows a strong variation in resistance, and the response time of
are briefly described Table 2. material alters (Anwary et al., 2021; Tao et al., 2017).
Flexible wearable sensors are gaining more attention with
8.1. Movement and postures monitoring the advancement of wearable sensing tools. In this search,
one more textile-based polymer-coated sensor was prepared.
For monitoring the movement and postures, various arche- Firstly, polyaniline (PANI) was obtained by the in-situ poly-
types have been developed that assist in rehabilitation and help merization of aniline. Then PANI was coated on cotton
to improve body postures as well as reduce sports and other knitted fabric by the method of deposition to fabricate conduc-
injuries. Previously, these devices did not get recognition tive fabric. This conductive knitted fabric gives satisfactory
because of some disadvantages such as being heavyweight, sensing performance with maximum gauge factor and high lin-
bulky to wear as well as not easy to remove, because they earity. So this device can be used for the monitoring of human
had to be directly attached to the body for data acquisition . physical signs and movement by studying the change in resis-
Recently, the concept of integrated or firmly attached sensors tance of the fabric sensor during the movement of different
within textile has changed the perception about sensors being parts of the human body, like knees, throat, fingers, and
uncomfortable. Most flexible sensors are based on the princi- elbows (Zhou et al., 2021) (See Figs. 16).
ple that stretching causes variation in the electrical resistance
of these devices. In 1986, Neilly made good efforts to develop 8.2. Strain and stretch sensing
stress and strain sensors for fabrics and became the first
researcher to explore these flexible sensors that can be pre- For the measurement of movement at different strain ranges,
pared from piezo-electric polyvinylidene fluoride (PVDF) wearable strain gauges can be applied instead of conventional
polymer films. Though, the developed films have some limita- strain gauges. These strain gauges are made up of conducting
tions for example tensile stiffness, electromagnetic interference, polymer-coated textile materials. De Rossi and co-workers
sensitivity to temperature, and transitory output signals, which investigated flexible strain gauges using conducting polymer-
limited their usage in wearable textiles. A simple, latest but coated textiles for the first time in 2009. He stated that
successful innovation, is a knee sleeve based on a fabric strain piezoresistive properties of these coated materials are due to
sensor, which acts as a biofeedback gadget and sends informa- the presence of conductive elements that facilitate in detecting
tion in the form of beeping sound after monitoring the move- local strain on textile fabric Özdemir and Kilinç (2015).
ments of the wearer’s knee during physical activity. However, Another investigation is focusing on the fabrication of wear-
these sensors have been developed as disposable devices able strain gauges prepared from conducting polypyrrole
because of having a limited lifetime (King et al., 2014). coated nylon Lycra fabric, to be able to do biomechanical
Prototypes with durable and complex accessories, and gar- monitoring; for example intelligent knee sleeve. This knee
ments i.e. leotards, gloves, and jackets having sensors attached sleeve sends a response to the player by producing an audio
to their surfaces, exhibit the ability to monitor or sense the tone and is manufactured using conducting polypyrrole coated
physical activities and positions of different parts of the human Lycra strip. When the coated textile/fabric material is stretched
body. In coated fabrics, polypyrrole has particularly been out, the resistance of the fabric varies resulting in a variation in
investigated for coating applications (Farringdon et al., the output of an electronic circuit. Therefore, according to
Recent developments in textile based polymeric smart sensor for human health monitoring: A review 13
strain produced by coated fabric, different audio tones are shape of different parts of the human body and function ide-
emitted providing a real time feedback to its user (Munro et ally as biomechanical wearable sensor, so it could be used in
al., 2008). various applications to measure the movement of different
In several fields of applications, the main area of focus is human body parts. Generally, conductive PPy-coated nylon
analyzing gesture and posture and also the monitoring of body Lycra fabric was less stable in the air because it reacts immedi-
kinematics. In 2000, the University of Pisa, Italy, developed a ately with many atmospheric chemicals, particularly oxygen.
leotard based on elastic fabric (Lycra) coated with a conduc- This novel method can be widely used for medical treatment,
tive polymer. Using a wet process, more than 20 sensors were rehabilitation, injury prevention, and for the improvement in
applied onto the fabric comprising of direct deposition of poly- sporting techniques (J. Wu et al., 2005).
pyrrole layers on fibers in an epitaxial position via a mask- In India PSG College of Technology reported that polyani-
based process for proper patterning of the sensorized areas. line coated conductive fabric was also prepared by using in situ
The coated fabrics possess significant strain sensing qualities: chemical polymerization method. Plain woven polyester fabric
0–30 Hz bandwidth, TCGF = 0.02 gauge factor’s temperature GSM 86 was used as a coating substrate and all other chemi-
coefficient, and GF = -12 gauge factor. This sensor has been cals were obtained from S.D. Fine Chemicals Ltd., India. In
used to monitor movements and postures of the trunk and sev- this process, aniline was dissolved in HCl solutions for diffu-
eral parts of the body such as elbow joints of the spine, verteb- sion. The dry pre-weight fabric sample was placed in the solu-
ral column, glenohumeral, and scapular segment (De Rossi et tion and allowed to soak well and dopant ammonium
al., 2000). persulfate was separately dissolved in HCl solution for poly-
In 2005, the Institute of Textiles and Clothing, Hong Kong merization. After that, the polyaniline-coated fabric was taken
Polytechnic University developed polypyrrole-coated fabrics out and washed in distilled water containing HCl and was
based on flexible strain sensors by both chemical vapor deposi- dried. These coated textiles are used as smart sensors to sense
tion and in situ polymerization. Flexible strain sensors pre- a stretch in the body (Muthukumar and Thilagavathi, 2012).
pared by these materials exhibit good stability and high
sensitivity. Different techniques that have been used to
8.3. Pressure monitoring
enhance the stability and sensitivity of the sensors, include:
(a) polymerization of pyrrole at low temperature, (b) strength-
ening of fabrics coated with conductive polypyrrole (c) use of Pressure sensors are used commonly as interfaces and switches
chemical vapor deposition (CVD) method for the deposition of within electronic devices for monitoring vital user signs. Var-
thin coatings of polypyrrole on the fabric surface, and (d) ious technologies have been developed to prepare pressure sen-
introduction of large anion i.e., dodecyl benzene sulfonate in sors (Ashruf, 2002; Rothmaier et al., 2008). The principle of its
polypyrrole film. operation is the variation in resonance frequency of piezoelec-
In the CVD method, plain knitted Lycra fabric was used. tric charge is created through overlaid elastic foam within the
Firstly, the fabric was immersed in sodium dodecylbenzene matrix of conductive threads under applied pressure or change
sulfonate aqueous solution and then ethanol solution of FeCl3 in capacitance. In capacitive sensors, the variation in parasitic
in sequence, and by a padding machine wet take-up was con- resistance and capacitance can be reimbursed via electronics
trolled at 100% after each immersion to prepare flexible thus wiring has a marginal influence on sensed signals.
strain sensors. The conductivity strain tests reveal that the pre- Matrix with a variety of pressure capacitive sensors has
pared sensor shows a high strain sensitivity of 80 for a defor- been developed by the Computing Wearable Lab of Zurich
mation that is as large as 50%, while by small variations in ETH for integration in textiles. With such a method, they
conductivity and sensitivity its stability can be maintained are capable to calculate the pressure on the body of humans
for more than 9 months. thus detecting muscle activity of the upper arm. Application
While in solution polymerization or in-situ polymerization, of this matrix on different areas of the body can give more
PPy-coated fabric is prepared by soaking the fabric in an aqu- details about the tracking of motion or the physical state of
eous solution of FeCl3 and then adding the pyrrole and sodium muscles (Meyer et al., 2006). The British Eleksen Limited
dodecylbenzene sulfonate aqueous solution in a flask slowly Company (formerly known as Electro-textiles) commercialized
with continuous stirring. The whole process is to take place soft and sensory fabrics based on flexible textile using a
at room temperature and at the end of the procedure the mixture of conductive nylon and fibers under Tradename
obtained fabric is to be washed with water and ethanol, , ElektexÒ (Smart Fabric Interfaces).. Such combinations result
and then dried in vacuum. The polypyrrole-coated fabric finds in 3D structures that are reasonable in price, durable, wear-
its applications in rehabilitation, wearable hardwareand sen- able, and washable.
sing garment, etc. (Li et al., 2005). A soft-touch keyboard ‘‘KeyCaseTM” had been manufac-
In 2005, Intelligent Polymer Research Institute, University tured by an American-based company known as Logitech
of Wollongong, Australia, also developed a conducting Inc. (Le Lieu; Switzerland) having the ability to wrap PDA
polypyrrole-coated textile based on nylon Lycra. This sensing (Personal Digital Assistant) for protection and storage. This
fabric was prepared using an in situ chemical polymerization keyboard is made up of textile and is light in weight. The com-
method. White nylon Lycra fabric, ferric chloride as an oxidiz- pany of U.S ‘‘Pressure Profile Systems” Inc. (Los Angeles, CA,
ing agent, and 1,5-naphthalene sulfonic acid tetra-hydrate as a USA) develops, designs, and manufactures multi-element tac-
dopant were used in the preparation of the sensor. A piece of tile and pressure sensing systems with high performance
fabric was immersed in an aqueous solution having both known as ConTacts and Tactarray. Similarly, the Centre of
dopant and pyrrole monomer, and then to initialize the poly- Design at Brunel University in the UK has prepared the sen-
merization on the surface of the fabric, FeCl3 solution was sory fabric for handicapped children to make themselves
added into the flask. The obtained fabric could acquire the understood. These fabrics are composed of two layers of elec-
14 M. Zahid et al.
tric conductive textiles separated by a non-conductive mesh attached to the skin. Finally, the mobile application was made
layer. Conductive layer comes in contact with each other when for long-term monitoring and real-time monitoring of ECG
the textile is pressurized causing the flow of electric stream signals (Zahed et al., 2020).
(Stoppa and Chiolerio, 2014). The Center team of Istituto Ita- Zhang et al., also stated a high-performance bio-potential
liano di Tecnologia for Micro-Bio Robotics in Pisa, Italy has electrode prepared by the blends (PWS) of WPU, PEDOT:
prepared three axial composite capacitive sensors completely PSS, and D-sorbitol. PWS exhibit high mechanical stretchabil-
based upon conductive fabrics (commercial) having high stabi- ity, high conductivity, and self-adhesion to skin conditions,
lity and compliance under manipulation (Viry et al., 2014). and all the substances are biocompatible. These films of
PWS are adhesive to the skin and easily adaptable to the fur-
8.4. For electrocardiogram monitoring rows of the wrinkles. They also do not cause any irritation to
the skin. By using PWS dry electrodes, long-term (maybe for a
In all forms of medical treatments, monitoring of physiological month or even longer) ECG monitoring can be obtained. The
parameters like blood pressure, heart rate variability, an elec- PWS electrodes always create a conformal contact to the skin
trocardiograph (ECG) is of vital importance. Implication of because of their self-adhesion ability. To prompt movement of
a range of signal recording devices is that it confines a patient the muscles, an electrical vibrator is used. Hence, these PWS
to bed during observation. But recent inventions in smart sen- electrodes can produce signals of high quality even under vital
sors for electrocardiograms make life more comfortable and vibration (Ouyang, 2021).
easier. These sensors were designed in various forms such as
jackets, vests, sleeves, wrist bands, etc. to be worn near to 8.5. Detection of ballistic penetration
the body (Khairuddin et al., 2018).
Cetiner and his co-workers had developed a fabric-based The key investors in developing the smart monitoring textiles
smart sensor for monitoring of electrocardiogram or to are the safety and military sectors because the functionalities
observe the electrical activity of a human heart. The sensor of sensors always prove helpful in supporting the frontline per-
was fabricated by in-situ polymerization of 3,4-ethylene diox- sonnel in a combat zone. In recent years, many investigations
ythiophene (EDOT). Iron(III) chloride (FeCl3), acetonitrile, have also been carried out in the quest for smart clothing for
and p-toluene sulfonic acid monohydrate (p-TSA) were also fighters, rescue workers, policemen, fire soldiers, and other spe-
used as polymerizing reagents. While woven polyethylene ter- cial forces. To serve the military, one smart garment prototype
ephthalate (PET) fabrics were used as substrate. Development had been developed, in which a backbone based on a conduc-
of these fabric-based sensors could be an alternate for com- tive circuit of optical fibers was arranged in a network of col-
mercial sensors used in monitoring electrocardiogram and they umns and rows. As the bullet penetrates through the jacket,
could be implied for the monitoring of a long time physical sig- the conductive path of the fibers breaks down and is detected
nal without using hydrogel. These types of sensors are wash- via a processor, which then helps to detect the exact location of
able, lightweight, and appropriate to integrate into clothing the penetration. The info can then be immediately transferred
and have flexibility in terms of integrating materials, sensor to medical teams. The same concept of fabric damage can be
_
size, and sensor design (ÇETINER et al., 2017). used to develop protective garments for other types of fields
Recently, Ankhili and his co-workers fabricated a smart such as biological and chemical fields, whereby a warning sig-
sensor using polyamide as conducting material in detecting nal can be emanated when a tear or hole occurs in the fabric
the signals of the electrocardiogram. Polyamide threads were (Koe, 2017).
embroidered in the form of bands between two electrodes on Another example of this tactic includes the blending of
plain cotton fabric. Thermoplastic polyurethane films were the polyaniline with poly (ethylene oxide) (PEO). The
applied as a protective cover on these bands. The embroidered method of electrospinning is used to prepare a volatile
bands can record the electrical signals during long-term ECG organic solution based on emeraldine salt (a form of polya-
monitoring (Ankhili et al., 2019). niline) and PEO. Then this solution is used in the prepara-
Biomedical conducting gadgets are very useful in the detec- tion of conductive nanofibers. These fibers are then
tion of bio-signals. For medical diagnosis, these high- characterized electronically to show the response against
performance sensing devices play a vital role in obtaining bio- explosive reducing agents such as hydrazine as well as liquid
signals. In this scenario, Polyvinyl chloride (PVC) and Poly- and gaseous samples of bases and acids. Rapid response is
pyrrole (PPy) were used to fabricate these devices. The PPy/ an interesting feature of these high-surface-area materials
PVC sensors showed better performance in comparison to (Guo et al., 2020).
the commercially available sensors and fabricating such type Conductive optical fibers can also be prepared by a coating
of polymer-based devices can bea very helpful tool to get of conducting polymers such as polypyrrole and polyaniline.
any type of biosignal (Suaste-Gómez et al., 2019). The in-situ polymerization method is used for the deposition
Using a biocompatible polymer (poly (ethylene dioxythio- of a thick film of conductive polymer on fiber-optics. This pro-
phene): poly (styrene sulfonate), (PEDOT: PSS)), highly con- cess allowed the control of the level of doping and alsothick-
ductive and flexible dry electrodes were prepared by ness of the film. These films show chemical responses against
mechanically loading laser-induced graphene (LIG). The reductive, oxidative, acidic, and basic vapors. These strategies
LIG was coated by spraying PEDOT: PSS to enhance the are used to increase the level of protection of firefighters, med-
toughness and the electrical conductivity of the electrode. ical, law enforcement, and military personnel while dealing
Thereby, this fabricated electrode proved to be very efficient with biological and chemical threats in various environments
in obtaining the electrocardiogram (ECG) signals. Since the ranging from warfare to industrial, urban, and agricultural
electrodes were flexible and thin so it was evenly and efficiently (Nurazzi et al., 2021).
Recent developments in textile based polymeric smart sensor for human health monitoring: A review 15
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