2020 Surface Modification of Polymeric Substrates with Photoand Sonochemically Designed Macromolecular Grafts

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10
Surface Modification of Polymeric Substrates with Photo-

and Sonochemically Designed Macromolecular Grafts
Fatima Mousli 1,2 , Youssef Snoussi 3 , Ahmed M. Khalil 4 , Khouloud Jlassi 5 ,
Ahmed Mekki 6 , and Mohamed M. Chehimi 7
1
Université Mouloud Mammeri, Laboratoire de Physique et Chimie des Matériaux (LPCM), Faculté des Sciences,
département de chimie, Tizi-Ouzou 15000, Algeria
2 Université Paris Diderot, Sorbonne Paris Cité, UMR CNRS 7086, 75013 Paris, France
3
Institut Préparatoire aux Etudes Scientifiques et Techniques (IPEST), University of Carthage, Sidi Bou Said
Road, B.P. 51, La Marsa 2070, Tunisia
4
Photochemistry Department, National Research Centre, 33 El-Buhouth Street, Dokki, 12622, Giza, Egypt
5 Center for Advanced Materials, Qatar University, Doha 2713, Qatar
6
Ecole Militaire Polytechnique, BP 17, Bordj El Bahri, Algiers, 16111, Algeria
7
CNRS and Université Paris Est (UMR 7182), 2 Rue Henri Dunant, 94320 Thiais, France
10.1 Introduction
10.1.1 Context
Despite the global concern of plastic wastes and their impact on the envi-
ronment, polymers continue to serve as functional materials in our everyday
life, therefore responding to numerous of our needs: packaging, automobile,
protective coatings, separation science and technology as well as biomedical
diagnostics, implants, structural composites, new power sources, and flex-
ible and wearable electronics to name but a few. However, most plastics or
thermosets are hydrophobic with substantial chemical inertness, while several
applications require specific implementation of reactive species at the surface
without altering the desired bulk properties.
To the frequently asked question why do we need surface modification, the
answer is (i) to tune wetting properties so that a surface is more hydrophilic or
in contrast superhydrophobic [1], (ii) to impart reactive functional groups for
further modification and steps [2], (iii) to impart molecular recognition ability
[3, 4], (iv) to make polymer substrates selective adsorbents of metal ions [5], (v) to
design anti-inflammatory and antibacterial polymeric implants [6], (vi) to design
smart plastic or paper with thermoelectric top polymer coating [7], etc.
The main aim of the book is to report on timely plethora of polymer surface
modifications; in this chapter we concentrate on the attachment of ultrathin
polymer grafts by photo- and sonopolymerization. The domains of photo-
and sonopolymerizations are vast, and for this reason we will tackle only the
essential findings. The reader is referred to a list of important recent reviews and
Surface Modification of Polymers: Methods and Applications, First Edition.

Edited by Jean Pinson and Damien Thiry.
© 2020 Wiley-VCH Verlag GmbH & Co. KGaA. Published 2020 by Wiley-VCH Verlag GmbH & Co. KGaA.
274 10 Surface Modification of Polymeric Substrates with Photo- and Sonochemically Designed
papers from the last decade. We will select some eye-catchy applications that
refer to the surface and interface chemistry underlying the polymeric substrate
modification and uses thereof.
By “polymer substrates” we mean conventional, insulating organic polymers
(e.g. PE or PET), thermosets (epoxy), biobased polymers such as cotton, inorganic
polymers such as polysiloxanes and eventually mesoporous silica, and finally con-
jugated conductive polymers.
10.1.2 Scope of the Chapter

The present chapter is dedicated to surface modification of polymer substrates
with macromolecular grafts using radiation-induced methods (UV, visible, and
sonowaves). It is split into two main sections:
– Surface modification using traditional, insulating monomers and polymers
where radical polymerization is the main object of the study.
– Attachment of inherently conductive polymer coatings by photo- and
sonopolymerization.
In the first main part (Section 10.2), the emphasis is on in situ radical polymer-
ization methods (termed “grafting from”) that consist in modifying the “plastic”
surface by:
– Radical photopolymerization.
– Cationic-induced radical photopolymerization.
– Photoinduced controlled radical polymerization (CRP) such as photo-ATRP
(atom transfer radical polymerization)
There are only few examples of polymer attachment to polymeric substrates
by photoinduced “grafting onto,” and we will not detail them in this chapter.
Instead, one can read about light-induced grafting of diazonium-functionalized
polymers to polymeric substrates [8] and the attachment of proteins to benzophe-
none (BP)-functionalized polypyrrole [9] among other strategies [10].
In the second main part of the chapter (Sections 10.3 and 10.4), we will tackle
surface modification of polymeric materials surfaces by in situ photo- and sono-
chemically induced polymerization methods for the attachment of thin func-
tional conductive polymer top layers. This area of research is important whenever
electrical conductivity is required for designing new electrode materials, super-
capacitors or any flexible electronics devices.
10.2 Surface-confined Radical Photopolymerization

of Insulating Vinylic and Other Monomers
Surface-initiated photopolymerization using UV or visible light is a facile and
smart method to prepare ultrathin reactive and functional polymer coatings
attached to surfaces with covalent bonds [11, 12]. As briefly mentioned above, the
attached polymeric adlayers impart surface reactivity, hydrophilic/hydrophobic
10.2 Surface-confined Radical Photopolymerization 275
character, or antifouling/biocidal properties. The rationale for triggering

photopolymerization or grafting isolated macromolecules using light lies in the
simplicity and particularly spatiotemporal character as time has effect on the
thickness of the coating, whereas light can be combined with photomasks to
create original patterned and gradient polymeric coatings.
Using light to build up continuous, patterned, or complex polymer coatings
has been the subject of numerous studies, and it is impossible to summarize
the past and present knowledge in a short section. Instead, Table 10.1 reports
handpicked review papers from the period 2006–2017 where the reader will cer-
tainly find classical and new routes for attaching thin functional polymer coating
to natural and synthetic polymeric substrates, e.g. flat substrates, porous mem-
branes, woven, and nonwoven fibers. The aim is rather to report the most applied
approaches, keeping in mind new innovative trends of designing reactive and
functional thin polymeric coatings. Actually, besides references [11, 12] and to a
lesser extent references [14, 18], the other entries are comprehensive and permit
to deepen the knowledge of making bulk polymers. Note, however that most of
approaches could be amenable to surface-initiated light-induced polymerization.
In this section, we will summarize some simple and efficient strategies to make
ultrathin polymer coating on either natural or synthetic polymeric substrates.
Examples are taken from the literature and the authors’ work.
10.2.1 Type I and Type II Photoinitiation Systems

Classical free radical photopolymerization (see also Chapter 7) can be initiated
with Type I and Type II Norrish initiators [21, 22] (Figure 10.1).
Type I such as benzoin (and several similar compounds [24]) cleaves to provide
radicals that trigger the polymerization; it is used in industrial applications [25]
owing to its high efficiency [22]. Benzoin-functionalized polymers are easily
cross-linked under UV or serve for making graft copolymer network by pho-
topolymerization [26]. Benzoin-functionalized multiwalled carbon nanotubes
(MWCNTs) were proposed for surface-confined radical photopolymerization
of styrene to generate multiwalled carbon nanotube-polystyrene (MWCNT-PS)
nanocomposites [23]. There are also azo types such as azobisisobutyroni-
trile (AIBN) that is frequently employed for photopolymerization despite its
lower efficiency [22]. Interestingly, for surface confined photopolymerization
AIBN-bearing silanes were used by Prucker and Rühe [27]. As they give two
radicals, one that is attached to the surface and the other in solution both grafted
chains, and free macromolecules are obtained. The method has also been adapted
to gold surface using a dithiol AIBN derivative for making PS grafts [28] and to
clay intercalated by AIBN type-functionalized quaternary ammonium [29].
Type II photoinitiators consist of bimolecular system: a hydrogen donor and a
molecule, which upon excitation by light, abstracts hydrogen to provide a radical
that initiates polymerization. Under UV, BP and derivatives are the most popu-
lar Type II initiators acting by hydrogen abstraction. The generated ketyl radical
from BP after hydrogen abstraction is less prone to trigger photopolymerization.
For this reason, BP is popular for Type II photopolymerization confined to sur-
faces. As we discuss here polymer surface-confined photopolymerization, Type
Table 10.1 Running titles, scopes, publication year, and references of selected reviews
focusing on free radical/controlled radical and other polymerizations to generate polymers in
bulk and ultrathin polymer grafts.
Running Publication
title Scope of the review year References
Photoinitiated Summary of various photopolymerization 2006 [11]

synthesis of methods initiated at the surface of organic
grafted polymers polymers, silicon oxide and gold
UV-induced Advances in UV light-induced surface graft 2009 [12]
surface graft polymerizations (mostly radical) for
polymerizations modification of natural and synthetic
polymeric materials surfaces
Photo-irradiation The review summarizes the synthesis and 2009 [13]
for polymeric post-modification of polymeric membranes by
membranes photopolymerization and uses thereof
Polymer brushes Review on surface-initiated controlled radical 2009 [14]
via SI-CRP polymerization methods. The review
summarizes SI-PIMP
Brushing up from Review on universal SI-polymerization from 2015 [15]
“anywhere” under polydopamine-coated surfaces using visible
sunlight light to photoinitiate grafting from
polymerization
Photoinduced Review on photoinduced electron transfer 2016 [16]
electron transfer reactions in polymer synthesis by free radical,
reactions for cationic polymerizations, and step-growth
macromolecular polymerizations involving electron transfer
syntheses processes
Photomediated Summary of recent existing knowledge on the 2016 [17]
controlled radical fundamentals and applications of
polymerization photomediated CRP techniques for preparing
block and graft copolymers,
sequence-controlled polymers, and hybrid
materials via SI-polymerization
SI-CRP: surface Summarizes recent advances in SI-CRP and 2017 [18]
and interface other non-CRP methods with emphasis on
engineering with novel architectures
polymer brushes
Surface Tutorial review describing various methods of 2017 [19]
functionalization surface modification of polymers, including
of polymers plasma and UV irradiation, electrochemistry,
oxidation, reduction, hydrolysis, and “grafting
onto”/“grafting from” of polymers
Polymer brushes: A review on the historical development of 2017 [20]
novel surfaces for polymer brushes
future materials
Light-induced Short review on surface-initiated 2019 [21]
grafting-from photopolymerization as a method to
strategies for functionalize any type of surface
surface
modification
CRP, controlled radical polymerization; SI, surface-initiated; PIMP, photoinferter-mediated

polymerization; SI, surface initiated.
Type I Type II
+ DH
R
O
O
hν
hν
+ D
+ R
OH
O
hν DH
S0
hν
S1 T1 R + R′ S0 S1 T1 R + D
CH3
O
O OH H3C
*
C C C O O
O
H S
H3C O
m
Benzoin MWCNT-benzoin Isopropylthioxanthone Camphorquinone
Figure 10.1 Photoactivation of Norrish Type I and Type II initiators. Examples of Type I
initiators are benzoin and MWCNT-benzoin hybrid [23], while isopropylthioxanthone and
camphorquinone are examples of Type II photoinitiators. S0 , singlet ground state; S1 , lowest
singlet excited state; T1 , lowest triplet state; R• , radical; DH, hydrogen donor; D• , donor radical.
II photoinitiation process is depicted in Figure 10.2 [30]. The process takes place
in one step (Equations 1–7) or in two steps (Equations 8–9).
BP is excited by light to be in a triplet state; it abstracts hydrogen from the sur-
face and changes to ketyl radical, while the surface (noted P for polymer) turns
to a macro-radical that initiates the polymerization and growth of the grafted
chains until termination by attaching the ketyl radical. In a two-step process, the
ketyl binds again to the polymer surface to form substrate-C(Phenyl)2 -OH that
is cleaved again by UV to provide a polymer substrate radical that initiates poly-
merization [31].
The system can be applied to free polyethylene oxide (PEO) chains; the group
of Yagci [32] demonstrated that this biocompatible polymer is a good hydrogen
donor for building up interesting polymer architectures (Figure 10.3).
As far as polymeric materials are concerned, several groups have used
BP and related ketones to abstract hydrogen from the polymer surface and
initiate photopolymerization on flat polypropylene (PP) [31, 33], electrospun
biosourced polymers for drug delivery [34], polyethersulfone membranes [35],
and poly(dimethyl siloxane) (PDMS) microfluidic channels [36]. Particularly,
with the two-step photoinitiation process, adsorption of BP followed by pho-
topolymerization on the inner wall of the microchannel, a thin polymer coating
was designed, specifically in the part of the channel exposed to light (Figure 10.4).
For the attachment of thin polymer coating to polymeric substrates in aque-
ous medium, it is necessary to use water-soluble Type II photoinitiator such as
anthraquinone-2-sulfonate sodium salt that could be employed to graft linear or
cross-linked polymers such as polyacrylamide on PP [37].
Excitation [BP]T hν
[BP]s [BP]T
(Eq. 1)
OH
Photoreduction [BP]T + H C + P (Eq. 2)
Initiation + CH2 CH CH2 CH (Eq. 3)
R R
Polymerization M
CH2 CH + nCH2 CH (Eq. 4)
R R
Termination
(Eq. 5)
CH2 CH + CH2 CH
R R
+
OH
H
CH2 CH + C CH2 C C OH (Eq. 6)
R R
OH
OH OH
C
C + C (Eq. 7)
C
OH
O R1 R2 OH R1 OH
R2 R1
UV Recombination R2
C C C
H
(Eq. 8)
Polypropylene
H H H H
Grafted surface initiator

R2 OH R1 R2 OH R1
C C
(Eq. 9)
UV Reactive monomer
H H
Grafted chains
Figure 10.2 Mechanism of one-step photopolymerization at a hydrogen donor surface

(equations 1–7). The process is depicted for polyethylene (PE) and polypropylene (PP) and any
other surface from which benzophenone is able to abstract a hydrogen. The lower panel
depicts a similar mechanism but in two steps, first the attachment of ketyl radical to the
surface followed by Type II surface confined-free radical photopolymerization. Source:
Adapted from Deng et al. 2009 [12] and Yang and Rånby 1996 [30].
O O O
1 * 3 *
hν ISC
O OH
3 *
+ O + O
n n
O
O O
m n–m
O
O p
Figure 10.3 Photoinitiated free radical photopolymerization using PEO as hydrogen donor.
Source: Tasdelen et al. 2009 [32]. Reproduced with permission of Springer.
The same system can be adapted to metallic, ceramic, or clayous materials

surfaces provided a hydrogen donor moiety is attached to the surface. The group
of Fouassier [38] has demonstrated that in solution, Type II photoinitiation
system is efficiently performed with N,N-dimethylaniline. For this reason, it
has been adapted to surfaces by attaching N,N-dimethylamino-functionalized
thiol to gold [39] or N,N-dimethyl aminosilane to clay, thus generating a
macro-hydrogen donor for surface-confined photopolymerization providing
reactive filler for epoxy type polymer matrices [40]. Similarly, Gam-Derouich
et al. [2] grafted poly(2-hydroxyethyl methacrylate) (PHEMA) by photopoly-
merization of hydroxyethyl methacrylate (HEMA) on gold grafted with
N,N-dimethylaminophenyl groups from the electroreduction of the parent
diazonium salts. The final surface gold-PHEMA exhibited dual properties:
antifouling with pure PHEMA grafts, or after activation by carbonyldiimida-
zole, it covalently attached bovine serum albumin (BSA) therefore providing
polymer/protein bioconjugate-grafted gold [2]. Other interesting combinations
of grafted hydrogen donors by diazonium electroreduction routes and BP or
isopropylthioxanthone were proposed for Type II surface-confined photopoly-
merization initiation [41]. Of particular interest, the same kind of initiation
can be performed in order to graft polymers under visible light to naturally
donating surface like woven cotton fabric1 or montmorillonite intercalated
by N,N-dimethylamino-functionalized diazonium cation [42] in order to
make ion imprinted clay–polymer nanocomposite by photopolymerization.
Figure 10.5 displays the mechanisms of photoinitiation under visible light with
the example of clay or any other surface grafted with –N(CH3 )2 and patchy
coatings of PHEMA on cotton fabric prepared through a mask. Both examples
use camphorquinone (CQ) as Type II photoinitiator active under visible light.
1 F. Mousli, M.M. Chehimi, 2018, unpublished results.

(a)
Top PDMS Adsorb

Photoinitiator
(c)
Lumen
Bottom
Photoinitiator
(b) Add monomer
Monomer
Photopolymerize
Polymer
Detach
top half
Stain with
toluidine blue
(d) 30 μm (e) 30 μm
120 μm
(f)
Figure 10.4 (a) Pristine microfluidic channel; (b) principle of photopolymerization using Type
II photoinitiator benzophenone in one setp; (c) Type II photopolymerization in two steps that
is after attachment of ketyl radical to the inner wall of the channel; (d) cross section of the
channel after one step photopolymerization; (e) thin polymer coating prepared by
photopolymerization on inner wall of the channel grafted with benzophenone; (f ) spatially
localized photografting of a microchannel using a mask placed over the left portion of the
channel that was coated with poly(acrylic acid) by the two-step method. Source: Hu et al. 2004
[36]. Adapted with permission of ACS.
3 *
O O
hν
O ISC
O
OH
+ N
O
Monomer
N Polymer
(a)
(b)
Figure 10.5 Type II photoinitiating system with substrate serving as hydrogen donor for the
photosensitizer camphorquinone. (a) Mechanism of surface-confined visible light-induced
radical photopolymerization. (b) Woven cotton textile serving as hydrogen, donor for
camphorquinone and subsequent formation of PHEMA patches on the fabric using
photomask. High resolution C1s spectra are assigned either to PHEMA patches or to pristine
cotton sites that were unexposed to the visible light (Lower panel: Mousli, F. and Chehimi,
M.M. Unpublished results).
Although examples are numerous, the photopolymerization with Norish
Type II photoinitiator was applied in very elegant ways to provide micro-
spherical instead or continuous polymer coatings. For example, Wang et al.
[43] have demonstrated the versatility of Type II photoinitiator in making
not only linear and cross-linked coatings but also microspherical coatings.
In the case of microspheres, the method was coined in situ polymerization
stringed assembly (SPSA); both solid and hollow, microscale spherical par-
ticles were designed by radical photopolymerization of microemulsions of
Poly(PEGMA)
H H H H
O O O O
UV
O O O OO OO O
H2O
O O
O O O O
20 μm O 10 μm
O
PET
Figure 10.6 Modification of PET fibers by PPEGMA particles prepared by Type II free radical
photopolymerization. Source: Regev et al. 2019 [44]. Reproduced with permission of Elsevier.
MMA/DVB (methylmethacrylate/divinylbenzene, hydrophobic phase) and NVP

(N-vinylpyridine, hydrophilic phase). The particles were tightly attached to the
surface of biaxially oriented polypropylene (BOPP), a polymer that is prone to
hydrogen abstraction by adsorbed BP. Recently, this approach was conducted on
flat polyethylene terephthalate (PET) fibers in order to graft stable and strongly
adherent 1–10 μm-sized particles of poly[poly(ethylene glycol) methacrylate]
(PPEGMA) monomers prepared by UV-induced photopolymerization in aque-
ous solutions of (see Figure 10.6) [44]. The particle-decorated PET fibers served
as filters with enhanced performance and better dust removal capacity. These
fibers have potential for coarse filtration of water used for agriculture and other
purposes.
10.2.2 Simultaneous Photoinduced Electron Transfer and Free Radical

Polymerization Confined to Surfaces
In a series of papers, Yagci and coworkers [45] have proposed an interesting pro-
cess for the one-pot preparation of metal nanoparticle/polymer nanocomposites
by photopolymerization. The method is versatile and proceeds under either UV
or visible light (Figure 10.7). In short, upon light excitation, the photoinitiator
in the cationic state produces a radical R• that reacts with the metal salt MX:
An electron transfer occurs between R• and M+ to give the metal M∘ as metallic
nanoparticles (for example, Ag or Au) and R+ as (R+ X− ). The photoinitiator also
initiates polymerization. In a recent collaboration with the group of Yagci [46],
we have adapted the protocol devised in Figure 10.7 to the surface of biaxially
oriented PET (BOPET) in order to graft ultrathin antibacterial Ag/polymer
nanocomposite coating (Figure 10.8). To avoid degradation of BOPET by UV
light, we have selected surface-confined photopolymerization in the visible
light using CQ to abstract hydrogen from the surface. BOPET was grafted with
dimethylaminophenyl groups by reduction of in situ generated diazonium pre-
cursor. The surface bound –C6 H4 –N(CH3 )CH2 • (after hydrogen abstraction by
CQ) triggers polymerization and monomers attaches one by one to the surface;
therefore polymer chains grow from the surface. Simultaneously, the CQ radical
donates an electron to Ag+ and the latter reduce to Ag (Figure 10.8a). The system
Reduction
• + – 0
R + M tX R X + M t
MtX: metal salt
0
hν •
M t
PI R
Polymerization
• • Polymer
R + M RM
M: monomer Metal–polymer nanocomposites
Figure 10.7 Principle of simultaneous photoinduced electron transfer and free radical
photopolymerization. Source: Yagci et al. 2010 [22]. Adapted with permission of ACS.
O
O
hν
ISC
O O
O O
N + N +
O HO
BOPET
surface
•
R + AgNO3 R+NO3– + Ag
HEMA
HEMA
N N
(a)
N N
O PEMA or PPGL/silver
Aryl layer nanocomposite layer
(DMA) , AgNO3
OH Nanocomposite-coated
BOPET fexible substrate
HEMA BOPET flexible substrate
or
OH
O
O
n
(b) PGL
Figure 10.8 (a) In situ, reduction of silver salts and polymerization of HEMA on the BOPET
films by photopolymerization. (b) Schematic illustration of the multilayered structure of
BOPET-aryl-polymer/Ag substrates. After polymer/Ag coating, the color of the flexible sheet
remains the same. Source: Samanta et al. 2014 [46]. Adapted with permission of Ingenta.
functions very well for the photopolymerization of either HEMA or the polygly-
cidol macromonomer (PGL) at the surface of the diazonium-modified BOPET
(see dark yellow color induced by the grafted aryl groups to the transparent
BOPET, Figure 10.8b).
10.2.3 Surface-initiated Photoiniferter

Iniferter (initiator–transfer–terminator) is a well-known controlled polymer-
ization method based on a reversible chain transfer process. Iniferter can be
triggered by either heat or light; in the latter case it is called photoiniferter.
Provided a dithiocarbamate molecule is attached to a surface, one can trigger
a photoiniferter process. In this way, silica [20] on the one hand, and gold [47]
and copper [48] on the other hand, were grafted with silane and diazonium salt
bearing dithiocarbamate moieties, respectively. Interestingly, a copper surface
was grafted with a diazonium salt substituted with a photoiniferter in order
to polymerize acrylic acid to polyacrylic acid (PAA); in a second step, this
modified surface is patterned by conventional free radical photopolymerization,
under UV, with hydrophobic perfuorinated polymethacrylate for effective
anti-icing properties [48]. Concerning layered aluminosilicate clay, intercalation
of iniferter-diazonium proceeds by cation exchange of sodium by the diazonium
salt; the final diazonium-intercalated clay served as macro-photoinitiator
for the in situ radical photopolymerization of glycidyl methacrylate [49].
Similarly, polymer surfaces can be equipped with dithiocarbamate for con-
ducting surface-confined photoinferter. For example, poly(4-vinylbenzyl
chloride-co-styrene) particles can be reacted with diethyldithiocarba-
mate (DEDTC), therefore providing particle with surface bound iniferter
moiety: PS—CH2 —S—C(=S)—N(C2 H5 )2 for the in situ controlled radical
co-photopolymerization of acrylamide-co-N,N-methylenebisacrylamide [50].
The strategy could be simplified with poly(vinyl chloride) (PVC) beads the C—Cl
bond of which was reacted with DEDTC to provide dithiocarbamate-PVC sur-
face bound groups [51]. The so-activated beads served for the surface-confined
photoiniferter to attach poly(acrylamide-co-bisacrylamide) imprinted with
lysozyme, a small model protein (Figure 10.9a). The molecularly imprinted
polymer (MIP) coated beads recognized lysozyme to a much higher extent
than the non-imprinted polymer (NIP)-coated beads (Figure 10.9b). More
importantly, the lysozyme-imprinted beads selectively recognized this protein
over cytochrome and myoglobin (Figure 10.9c).
10.2.4 “Brushing Up from Anywhere” Using Polydopamine Thin

Adhesive Coatings
Polydopamine (PDA) bioinspired adhesive is the subject of a growing number of
studies owing to the remarkable interfacial properties of this kind of molecular
glues. The rationale for the interest raised by PDAs lies in the fact that these
adhesives combine amine and catechol functional groups, a unique combination
and salient feature of mussel [52]. For these reasons, and given the versatility of
PDAs, they found timely applications such as environment friendly dyeing of
S
Et
DEDTC N
Cl S C
Et
PVC PVC-I
hν = 365 nm
AA, MBAA
lysozyme
H2N O
H2N O
Rebinding H H
Imprinted N
cavity
Remove
template
O O NH2
NH2 PVC-MIP
(a)
MIP Lysozyme
25 25
Adsorbed lysozyme (mg/g)
Adsorbed lysozyme (mg/g)
NIP Cytochrome
Myoglobin
20 20
15 15
10 10
5
5
0
0
0 10 20 30 40 50 0 10 20 30 40 50 60 70
(b) Equilibrium concentration Ce (102 mg/ml) (c) Equilibrium concentration Ce (102 mg/ml)
Figure 10.9 (a) Schematic illustration of the preparation procedure of lysozyme-imprinted

polymer coated PVC beads by photoiniferter. (b) Adsorption of lysozyme onto imprinted (MIP)
and non-imprinted PVC beads (NIP) showing the importance of the imprinting technique to
recognize the protein; (c) selectivity of lysozyme-imprinted PVC beads for lysozyme over
cytochrome and myoglobin. Source: Ayadi et al. 2016 [51]. Adapted with permission of John
Wiley & Sons.
silk, carbohydrate-based biosensor, and PDA-coated boron nitride nanosheets

for energy storage [53]. Returning to the object of this chapter, a recent review
summarized the current knowledge on visible light-induced grafting from
photopolymerization confined to any surface that has been precoated with a
thin PDA adhesive layer [15]. The general process is schematically illustrated in
Figure 10.10a and the effect of post-grafted polymer nature on the wettability
of the substrate is displayed in Figure 10.10b. PDA can be coated by UV-graft
photopolymerization of dopamine, whereas the post surface-confined pho-
topolymerization is performed under visible light. Clearly, PDA sticks to metals,
mica, and even polytetrafluoroethylene (PTFE) as judged from the similar
contact angles obtained after its deposition on these different materials. The
top 70–90 nm thick polymer layer imparts the final wettability depending on
the chemical nature of the polymer. PS top coating is hydrophobic in nature
with water contact angle (𝜃 w ) in the 67–87∘ when one considers all substrates;
in contrast on all substrate–PDA surfaces, attachment of poly(3-sulfopropyl
methacrylate) (PSPMA), imparts highly hydrophilic character with 𝜃 w < 10∘ .
HO NH2
NH NH
HO UV or
HO OH n HO OH n
Any substrate pH 8.5 PDA
Surface-bound ht
nlig
radicals Su
Monomer
(a)
PDA PSPMA PS
Al
Fe
Ti
PDMS
Pl
PTFE
Mica
(b)
Figure 10.10 (a) Principle of surface-initiated polymerization from polydopamine-coated

substrates. (b) Water drop contact angle results on various pristine or modified substrates
coated PDA or PDA-polymer bilayers. Source: Sheng et al. 2015 [15]. Adapted with permission
of RSC.
PDA adhesive patterned coatings can be deposited by photopolymerization

using photomask [15] or alternatively by microcontact printing (μCP) [54] using
PDMS stamp on Piranha-cleaned silicon substrate (𝜃 w = 14∘ ). The PDA patches
(𝜃 w = 57∘ , 15 nm thick) could further be coated via self-initiated photografting
and photopolymerization (SIPGP) [55] with the hydrophobic PS (𝜃 w = 94∘ ,
320 nm thick) or the hydrophilic poly(N,N-dimethylaminoethyl methacrylate),
PDMAEMA (𝜃 w = 28∘ , 44 nm thick).
A similar SIPGP protocol was adapted to PDA nanosheets (12 nm, pre-
pared using 1 g dopamine/l at pH 8.3, for 0.5–18 hours.) that were prepared
on Si/SiO2 substrate then lifted off by HF etching and coated with a series
of polymers (SIPGP conditions: 𝜆 = 350 nm, power density = 5 mW/cm2 ,
18 hours) [56]. All organic materials were tested by wettability, 𝜃 w = 45,
35, 105, 78, 62, 54, 12, and 90∘ for PDA-coated Si, PDA nanosheets,
PS, poly(2-dimethylaminoethylmethacrylate) (PDMAEMA), poly(methyl
methacrylate) (PMMA), poly(4-vinyl pyridine) (P4VP), PSPMA, and
poly(tert-butylacryalte) (PtBuA), fairly in line with the chemical structure
and with fair agreement with published wettability data. Importantly, PDA
coating, PDA nanosheet and PDA–PSPMA carpet attached ∼130, 190, and
∼50 mouse embryonic fibroblasts cells per mm2 therefore demonstrating the
non-fouling character of PSPMA compared with the opposite sticky PDA.
10.2.5 Recent Trends in Surface-confined Photopolymerization (CRP)

While the 1995–2015 period has witnessed skyrocketing number of publications
on CRP methods and their confinement to surfaces [14, 57], the new trend is to
facilitate these procedures by conducting polymerizations in air and to use pho-
tosensitive nanoparticles or metal complexes to trigger or enhance CRP such as
ATRP using light. These aspects are thoroughly discussed in [17, 18] and will
simply be tackled very briefly in the following text. Figure 10.11a shows a series
of photosensitizers employed to trigger photo-ATRP. Interestingly, both classi-
cal Type I and Type II Norrish photoinitiators can induce electron transfer upon
excitation by either UV or visible light (Figure 10.11b). TiO2 photocatalyst per-
mits to trigger ATRP at the surface provided it has a grafted halogenated ester
or aryl initiator; light excites the nanoparticles that release an electron that is
trapped by Cu(II) complex, which in turn reduces to Cu(I) ATRP catalyst; ATRP
is then triggered and polymer brush grows (Figure 10.11c). Photo-ATRP can be
used to control the growth of the brushes by periodically switching “on” and “off”
the UV or visible light (Figure 10.11d). Despite the numerous developments in
photo-ATRP, a few examples were reported for the modification of silicon [60]
and gold [58] surfaces by this process. As far as polymeric substrates are con-
cerned, photo-mediated ATRP using Ir(ppy)3 complex as a photo-redox catalyst
under low intensity blue LED light strips (10 W, 460–470 nm) in dimethylfor-
mamide permitted to graft poly(pentafluorophenyl methacrylate) (PFMA) and
poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) that exhibits
opposite wettability properties on PVC (hydrophobic and hydrophilic, respec-
tively) characteristic [59]. In this process, the photo-redox catalyst Ir(ppy)3 acti-
vates the structural defects of allyl chloride and tertiary chloride groups of PVC,
O O
O
OH
HO O
O
Irgacure 2959 2,2-Dimethoxy-2-phenyl
O acetophenone
O
Benzophenone Camphorquinone
O
O
O COOH
I I Br O Br
(a) HO O OH HO O OH
I I Br Br
Erythrosin B Eosin Y
e–
UV light Cu(II)/(Bipy)2
ZnO TiO2 NbCl5 hv
h+
TiO2 UV Air Si-ATRP
Zinc Titanium Niobium(V)
oxide dioxide chloride
OC CO CO
CO Cu(I)/(Bipy)2
OC Mn Mn CO
Au substrate
OC CO OC CO
(c)
Dimanganese decacarbonyl
25
Ka
Pn–X + CuIX/L CuIIX2/L + Pn Off On
Kd 20
M
Pm
Conversion (%)
15
CuIIX2/L + Pn–Pm
10
R–X
5
hv hv
Pl 2R or R + PS PS
R-H 0
Unimolecular system Bimolecular system 0 5 10 15 20 25 30 35
Time (h)
(b) (d)
Figure 10.11 (a) Selected Type I, Type II, dyes, nanoparticles, and organometallic complex
sensitizers for photo-ATRP. Source: Pan et al. 2016 [17]. Adapted with permission of Elsevier. (b)
Mechanism of photo-ATRP triggered by Type I and Type II photosensitizers. Source: Pan et al.
2016 [17]. Adapted with permission of Elsevier. (c) Mechanism of photo-ATRP using TiO2
nanoparticles as photosensitizers. Source: Yan et al. 2013 [58]. Reproduced with permission of
ACS. (d) Effect of light “On” and “Off” on the monomer conversion kinetics in photo-ATRP.
Source: Huang et al. 2016 [59]. Reproduced with permission of RSC.
10.3 Surface-confined Photopolymerization of Conjugated Monomers 289
460 nm
light
Without Ir(ppy)3
Mask
With Ir(ppy)3
PVC
(a) (b)
Figure 10.12 (a) Schematic illustration of patterned polymer brushes on the surface of the
PVC sheet and (b) optical images of the PVC sheets after polymerization with and without the
addition of the Ir(ppy)3 photo-redox catalyst. Source: Huang et al. 2016 [59]. Reproduced with
permission of RSC.
along with some of the secondary chlorides of vinyl chloride repeated units, into
initiating sites (resulting from C—Cl bond homolysis) for photo-mediated ATRP.
This process can yield patterned polymethacryalte coatings on PVC using pho-
tomask as displayed in Figure 10.12. Concerning natural polymeric substrates,
photo-ATRP based on copper (II) was applied to modify cellulose by polymer
brushes but without any photosensitizer [61, 62]. As a matter of fact, it was dis-
covered a while ago [63], in 2000, that visible light has a remarkable effect on
ATRP as it accelerates the dynamic equilibrium of chlorine atom transfer thus
promoting the polymerization. There is a total monomer conversion, better con-
trol with narrower size distribution of the chains and minimal consumption of
copper catalyst.
Other new trends are based on the use of dyes and the reader is referred to [64]
for details.
10.3 Surface-confined Photopolymerization

of Conjugated Monomers
Conjugated polymers are usually prepared as thin films by electropolymerization
[65] or in bulk powders via oxidative chemical polymerization. Both methods
permit to synthesize nanostructured materials as demonstrated in several papers
and reviews [66]. In this regard, photopolymerization has less been explored
although it offers several advantages like providing diverse structures, enabling
the preparation of patterned surfaces and finally metallic nanoparticles can
be embedded in the growing conjugated polymer during its photochemical
synthesis. In this section, we first summarize the fundamental aspects of
photopolymerization of conjugated polymers, and then we will tackle their

preparation on plastic substrates.
10.3.1 Polypyrrole
10.3.1.1 Mechanisms of Photopolymerization of Pyrrole
The photopolymerization leads to the preparation of conductive polymers in dif-
ferent shapes and textures, by exposing the corresponding monomer to a light
source [67]. This technique can be adopted according to two types of processes:
(i) Direct photopolymerization (photo-excitation of the monomer) that does
not necessarily lead to the expected results in terms of quality (disordered
polymeric chain) and quantity (low yield).
(ii) Photopolymerization in the presence of an initiator or photosensitizer
[67, 68]. This approach is by far the most adopted one owing to the impor-
tant yield of the reaction and reduced synthesis time. Its principle is based
on the generation of active radical species capable of causing the monomer
oxidation and forming the polymer [67, 69, 70]. The creation of these
active species (free radicals, cations, ...) takes place using photosensitizer in
the formulation: photoinitiator such as AgNO3 , AuCl3 , CuSO4 [69] or Ru
complex, or even cationic photoinitiator such iodonium salts. The process of
photoinduced polymerization is depicted in Figure 10.13. It is a very advan-
tageous method offering the possibility of preparing a variety of conductive
polymers while controlling their shape, size, and physical properties [67].
Herein, we will mostly tackle the synthesis of conductive polymers by pho-
topolymerization using photosensitizers for the inclusion of metallic nanostruc-
tures.
Figure 10.14 describes a possible mechanism of pyrrole photopolymer-
ization: UV light decompose nitrates to provide hydroxyl radicals • OH [71]
that trigger pyrrole oxidative polymerization. Meanwhile Ag+ can oxidize
resulting oligomers due to their low oxidation potentials and yield Ag NPs.
The simultaneous reactions impart nitrate-doped PPy chains with embedded
Ag NPs.
Light source
* *
*
Reactive species
Photoinitiator * *
Monomer * Polymer
*
Figure 10.13 General schematic diagram of the photopolymerization process.
– UV – •
NO3 NO2 + O–
•
O– + OH2 • OH + OH–
•
OH + + OH–
•
N NH+
H
H
H –2H+ N
2 NH+
. NH+ N
NH+ H H
–ne–
–nH+
PPy
N
H H
nAg+ + N PPy + nAg
N
H –ne–, –nH+
NH+ • NH+ H
N •
NH+
N
• –2H+ N
H NH+
H N N
H H
Figure 10.14 Pyrrole photopolymerization mechanism in the presence of silver nitrate

photosensitizer. Source: de Barros et al. (2010) [71]. Reproduced with permission of Elsevier.
A similar situation is encountered for the incorporation of gold NPs. Indeed, in

the presence or absence of surfactant (for example, sodium dodecylsulfate, SDS)
[69],
3Py + 6AuCl4 − + h𝜈 → [Py—Py—Py]+ AuCl4 − + 3HAuCl4 + 2Au0 + 8HCl
3Py + 4AuCl3 + NaDS + h𝜈 → [Py—Py—Py]+ DS− + HAuCl4 + NaCl + 3Au0 + 7HCl
10.3.1.2 Substrates for in Situ Photoinduced Polymerization of Pyrrole

and Potential Applications
Note that coating PPyAg on synthetic (e.g. PET) and natural polymers (cellu-
lose, woven cotton fibers, wool, silk) is subject to delamination. However, pyr-
role photopolymerization process permits to make pure PPyAg or PPyAu binary
nanocomposites [69] in water or nanocomposite films on various substrates such
as woven cotton textile [72], PET plastic sheets [73, 74], and wool fibers [75]. For
example, on woven textiles, the fibers are first impregnated with the monomer
that results in tightly attached polypyrrole; according to the authors’ experience,
cross section of the fibers reveals black color, meaning that PPy is distributed
from the bulk to the surface of the cotton fibers [72]. The nanocomposite is very
well dispersed over the fibers as shown in Figure 10.15.
As stated earlier, for PET sheets, adhesion is an issue, and in this case it
was demonstrated that pretreatment of the substrate by silane coupling agents
was essential to provide PPyAg thin films very well adherent to the underlying
10 μm 1 μm
(a) (b)
Figure 10.15 SEM images of cotton fabric coated with PPy Ag at low (a) and high (b)
magnification. Initial pyrrole/cotton weight ratio = 0.9; pyrrole/AgNO3 weight ratio = 1; initial
cotton fabric mass: 0.16 g; photopolymerization time: 6 h. Source: Attia et al. 2013 [72].
Reproduced with permission of Elsevier.
Au electrodes
r PPy–Ag
film
A
(a) (b)
0.30 1 1
Resistance (MΩ)
90° peel test

Reco
0.25
g
in
nd
very
Be
0.20
2 2
0.15
0.10
PPy–Ag films on
Flat 6 4 2 Flat (1) BOPET (2) Silanised Py modified BOPET
(c) Bend radius (mm) (d)
Figure 10.16 (a) Digital photograph of PPy–Ag films (Py:AgNO3 ∼ 0.5 M : 0.5 M, 120 min)
deposited on silanized Py modified BOPET substrate. (b) The left side shows the schematic of
the bending arrangement along with the resistance measurement circuit. The right side shows
the photograph of a few pairs of gold electrodes (gap y 12 mm) deposited on the PPy–Ag
films. (c) Variation in resistance of PPy–Ag films for different bend radii. (d) The left photograph
shows PPy–Ag film prepared on pristine BOPET (1) silanized Py modified BOPET substrate (2).
The films are glued on adhesive tape under similar loads. The right photograph shows the
material detached from the films by the adhesive tape after 90∘ peel test. Source: Singh et al.
2013 [73]. Reproduced with permission of RSC.
plastic sheets that have first been treated with pyrrolyl-functionalized silane
[73]. In a first application Singh et al. [73] have designed flexible H2 S and
NH3 chemiresistive gas sensors (Figure 10.16). The films withstand adhesive
testing (Figure 10.16d) and do not fail upon bending stress (Figure 10.16a).
Interestingly, these gases are detected for concentrations as low as 5 ppm, lower
than their toxicity limits of 10 and 25 ppm, respectively. The sensing properties
are recovered after bending stress (Figure 10.16c).
Similar PPyAg-coated PET sheets served to generate flexible, organic thermo-
electric generator (TEG) materials. The figure of merit of TEGs is
ZT = (S2 𝜎) T∕𝜅
where S is the Seebeck coefficient, 𝜎 the electrical conductivity, T the absolute
temperature, and 𝜅 the thermal conductivity. For materials with similar thermal
conductivities, the power factor S2 𝜎 (in μWm−1 K−1 ) is generally used. A good
TEG inorganic material has ZT > 1, while good organic polymeric TEGs have ZT
in the 0.1–0.5 range. Thermoelectric sheets were mounted in series as displayed
in Figure 10.17; the upper panel shows how the TEGs were mounted and the
lower panel schematically illustrates the mechanism of thermoelectric behavior
of the sheets coated with PPyAg.
Series connection of PPy–Ag films Equivalent circuit

Hot (Pt wire heater)
Current (10 nA)
TEG (PPy–Ag connected in series)
PPy–Ag
films
Mica
300 kΩ
3 mV
300 kΩ
3 mV
Cold (copper block)
Load resistance
current
6 mV
(a) 5 mm
rs
a rrie
ec
PP
arg
y
Ch
ch
no
Ag Ag
ai
Ag
Ph
n
ce
rfa
Cold end
Hot end
te
Phonon
In
Ag Ag
in
Ch Ag Ag
ha
arg
ec
yc
arr
ier
PP
s
Ag Ag
Ag
(b)
Figure 10.17 (a) Schematic showing the practical demonstration of a set of PPy–Ag film
thermoelectric power generators along with its equivalent circuit. PPy–Ag films are connected
electrically in series and thermally in parallel. Inset shows the photograph of the polymer films
connected in series. (b) Schematic showing the role of PPy/Ag interface in facilitating the
charge transport but scattering phonons. Source: Bharti et al. 2017 [74]. Reproduced with
permission of Elsevier.
In the studies conducted by Singh et al., it was found that the initial concen-
tration of AgNO3 plays an important role in designing gas sensors [73] and
TEGs [74]; a too high concentration (0.5 mol/l AgNO3 for 0.5 mol/l pyrrole and
120 minutes photopolymerization time) that yield highly conductive PPyAg on
PET will not undergo significant change of resistance upon interaction with
gases, and rather lower concentration (0.1 mol/l AgNO3 for 0.5 mol/l pyrrole
and 120 minutes photopolymerization time) is needed, so that any specific
interaction leading to molecular recognition of the gas induces significant
change in resistance. In contrast, the figure of merit ZT implies that electrical
conductivity is required to obtain a good TEG, and in this case high initial
AgNO3 concentration (1.2–1.5 mol/l for 0.5 mol/l pyrrole) was found to boost
up the final conductivity of the PPyAg-coated silanized PET (∼12 S/cm), a
low thermal conductivity and highest ZT figure of merit for similar materials
(ZT = 7.4 × 10−3 at 335 K).
In another study, interdigitated gold electrode-coated flexible PET sheet was
modified by TiO2 /PPyAg hybrid composite thin layer and served as humidity
sensor. Photopolymerization using AgNO3 photosensitizer was conducted for
20 minutes under UV light (254 nm). To improve flexibility, the pre-polymer
mixture was mixed with poly[3-(methacrylamino)propyl] trimethyl ammonium
chloride (PMAPTAC) [76].
Other authors have taken advantage of flexible resins to design interdigitated
PPy humidity sensors in PDMS molds [77]. Flexibility was imparted to the
photopolymerized poly(ethylene glycol diacrylate) (PEGDA) or epoxy resin
by 1,6-hexanediol diglycidyl ether (Araldite DY-H/CH, HDGE). The formu-
lation consisted of the resin, pyrrole, and photoinitiator (4-methylphenyl)
[4-(2-methylpropyl)phenyl]–iodonium; hexafluorophosphate (Irgacure 250), a
liquid cationic photoinitiator; and 2hydroxy-2-methyl-1-phenyl-propan-1-one
(Darocur 1173, D-1173), a radical photoinitiator in liquid state. The formulation
can be cured by UV light; Irgacure 250 serves to initiate the photopolymerization
of pyrrole and HDGE, whereas Darocur 1173 photoinitiates the polymerization
of PEGDMA.
The proposed mechanism of pyrrole photopolymerization is depicted in
Figure 10.18.
Table 10.2 gathers experimental conditions for the design of conductive
polypyrrole coatings on polymeric and other substrates by means of photopoly-
merization. Besides corrosion control, all other potential applications are within
the domain of electronics.
10.3.2 Polyaniline
10.3.2.1 Mechanisms of Photopolymerization of Aniline
Polyaniline, like PPy, is one of the most studied conductive polymer; it has
received particular attention due to its remarkable physicochemical properties
(stability, color change upon doping/dedoping, high conductivity) and its variant
fields of application (corrosion resistance, energy storage, molecular recognition
of pollutants). It can be synthesized in several shapes by different methods
including the photopolymerization in the presence of an initiator.
hν + Ph
Ph2I PF6 PhI PF6
+ PhI + PhI
N N
H H
H H
2 N –2H
N
N N N
H H
H H
N
H
N H
PhI N H
N N
H N
H N N
H H
H
H N
N
and/or
N N
H H H
N
and/or hν
n
H Ph2I PF6
N
N
H
Figure 10.18 Proposed mechanism of UV-induced step-growth polymerization of pyrrole

initiated by radical cations generated from the photodecomposition of the diaryliodonium
salt. Source: Razza et al. 2017 [77]. Adapted with permission of John Wiley & Sons.
Barros et al. [91] have proposed a reaction mechanism of photopolymeriza-

tion of the aniline monomer in the presence of the Ag+ cation (Figure 10.19).
According to them, the light causes the excitation of the monomer, which behaves
as an electron donor, while the silver cation acts as an acceptor of electron.
Photopolymerization of aniline has been reported but at a lesser extent
compared with that of pyrrole and concerned essentially bulk powder. As far
as photochemically prepared PANI (polyaniline) thin films are concerned,
they were achieved on rare occasions on metallic (Ti, W) and semiconduc-
tor (ITO) substrates [90, 92]. The process could be adapted to plastic and
biosourced substrates. Nanoparticles of PANI was also synthesized by pho-
topolymerization of the aniline monomer in the presence of an ionic liquid
(1-butyl-3-methylimidazolium hexafluorophosphate, [bmim]PF6 ), it is the
most used in photopolymerization processes [93]. The irradiation leads to the
photoexcitation of the ionic liquid and produces a cation radical [bmim]2 + . ;
these radicals react with the monomer and cause its oxidation and the formation
of dimers by head-to-tail coupling. Quinoid units can be formed by the oxidation
of dimers, the protonation of these quinoids leads to the formation of nitrenium
ions; they can also react with another monomer to produce trimers and finally
the polymer (Figure 10.20).
Table 10.2 Summary of synthesis conditions, physicochemical properties, and potential applications of selected photochemically prepared
polypyrrole-coated organic soft substrates and other materials.
Polymeric substrate Compounds, 𝝀 (nm) Final hybrid material Potential application References
PET-Py Py, AgNO3 PPyAg Flexible H2 S gas sensor [73]

PET Py, AgNO3 PPy NT/Ag Thermoelectric power [74]
generator
Wool fabric Py, AgNO3 PPy/Ag — [75]
Glass, PET Py, AgNO3 PPy/Ag — [78]
F-SnO2 /TiO2 MP Py, methyl viologen dichloride, Na2 SO4 TiO2 –PPy — [79]
Si wafer Py, SDS PPy-SDS — [80]
TiO2 electrode Py, Na2 SO4 PPy Au/TiO2 — [81]
PVC Py, Cp2 Fe PVC/Ppy — [68]
PET Py, AgNO3 , TiO2 NPs, PMAPTAC, 254 nm TiO2 /PPy/PMAPTAC Humidity sensors [76]
PDMS mold Py, I-250, PEGMA, D-1173; or Py, HDGE, Interpenetrated UV printable humidity [77]
I-250/UV light 70 mW/cm2 PPyPF6 /PPEGMA or sensor
PPyPF6 /Epoxy
PI, silicone, PET Py, AgNO3 PPyAg Microwiring of flexible [82]
electronic devices
Glossy premium Py, AgNO3 PPy/Ag — [83]
Nanotubular TiO2 electrode Py, SDS TiO2 /PPy — [84]
FTO Py, KCl PPy/TiO2 — [85]
Ta electrode Py, LiClO4 , MeCN Ta2 O5 /PPy Corrosion protection [86]
Single-crystal TiO2 flat sheet Py, TEAPTS TiO2 /PPy — [87]
Al Py, TiO2 , AgNO3 TiO2 /PPy Humidity sensors [88]
Glass Py, Ru(bpy)3 2+ PPyRu — [89]
Ti foil Py, SDS TiO2 /Ppy — [90]
W foil Py SDS WO2 /PPy — [90]
FTO, fluorine doped tin oxide glass; MP, mesoporous; NT, nanotube; PET-Py, PET silanized with pyrrole silane; Py, pyrrole; SDS, sodium dodecyl sulfate; PVC,
Poly(vinylchloride); PMAPTAC, poly-[3-(methacrylamino)propyl] trimethyl ammonium chloride; TEAPTS, tetra ethyl ammonium p-toluene sulfonate.
+ * +
NH+3 + Ag + hν NH+3 + (Ag)
* +–
NH+3 + (Ag+) – H NH2 + Ag0
+– H H
2 NH2 N N + nAg0
(a) H
hν
e– Polymer
LUMO
e–
Acceptor
Monomer
h+
HOMO
Sensitizer
(b)
Figure 10.19 Proposed mechanism of photopolymerization of aniline in the presence of silver

nitrate photosensitizer (a) and schematic representation of photopolymerization of
conductive polymer in the presence of a sensitizer (b). Source: de Barros et al. 2003 [91].
Reproduced with permission of Elsevier.
+
NH2 + bmim 2+ NH3 + bmim+
+ H
2 NH2 N NH2 + 2 H+
H H +
N NH2 + 2bmim
2+
N NH2 + 2bmim+
+
H + H +
N NH2 N NH + H+
+
H + H H
N NH + NH2 N N NH2 + H+
Figure 10.20 Mechanism of photoinduced polymerization of aniline in [bmim]PF6. Source:

Zhou et al. 2009 [93]. Adapted with permission of Springer.
10.3.2.2 Substrates for in Situ Photoinduced Polymerization of Aniline

There are a few examples of plastic surface modification by photochemically
prepared PANI. The reason lies in the fact that PANI synthesis is easier by
oxidative polymerization or by electrochemistry on electrode materials. So, we
are left here with one case study of PANI photochemically prepared on PET
using AgNO3 photosensitizer [94]. Adhesion was ensured by silanization of the
underlying PET; simply aminopropylsilane (APS) was used to tightly anchor the
growing chains to the substrate. Figure 10.21a shows the photochemical reaction
that provides PANI and silver NPs and the possible chemical attachment of the
growing PANI chains to APS-modified PET (Figure 10.21b). The photopolymer-
ization process results in flexible green sheet due to the conductive form of PANI
(Figure 10.21c). These sheets are selective sensors for H2 S with optimized sensing
for an initial concentration of AgNO3 of 2 mol/l (Figure 10.21d). Interestingly,
Singh and coworkers [95] have evaluated the effect of electron beam radiation
on similar PANI–Ag coated silanized PET sheets and found improvement of
adhesion for doses above 30 kGy that resulted in cross-linking of the PANI
chains (Figure 10.21e–f ). The authors have also found a positive effect on the
sensing of H2 S for higher irradiation doses (75 and 100 kGy) with quasi linear
response for 100 kGy (Figure 10.21g).
10.4 Surface-confined Sonochemical Polymerization

of Conjugated and Vinylic Monomers
10.4.1 Insights into Sonochemistry: Origin of the Phenomenon
and Mechanism of Polymer Synthesis
Historically, the first application of ultrasound dates back to 1927 when Richards
and Loomis [96] discovered the effects of high frequency sound waves on the
promotion of the reaction rates. Technically, an ultrasound is a sound with a fre-
quency greater than 20 kHz, which is the upper audible limit that human can hear,
and can reach 10 MHz [97]. The ultrasound supplies a sufficient energy to trig-
ger both chemical and physical processes [98], a typical high-intensity ultrasonic
device is schematically illustrated in Figure 10.22a. In aqueous media, ultrasonic
irradiation induces the water sonolysis and the formation of the free radicals
H• and OH• [100]. These radicals may recombine to get back to their primary
form or also to produce H2 , H2 O2 , or even HO2 , all of them are strong oxidants
and reductants [99]. The alternating rarefactive and compressive acoustic waves
results in the bubbles formation and cavities and provokes their oscillation in the
irradiated liquid [99]. The oscillating cavities get expanded by the absorption of
vapor and gas from the solution until a maximum volume, and then they col-
lapse to very shortly release stored energy inside the bubble (cooling and heating
rates > 1010 K/s) as illustrated in Figure 10.22b [97] and produce a very high local
and transient heating and pressure reaching ∼5000 K and ∼1000 bar, respectively
[99, 101].
* H
hν 0
NH3 + Ag NH3 + Ag NH3 +Ag N N + n Ag
365 nm
n
(a) Protonated monomer Excited monomer Radical cation Polymerized aniline
Growth direction
N H
NH2
(CH2)3 (H2C)3
(c)
Si Si
O O O O
600 OH
OH
NH2 NH2
450
Response (%)
(CH2)3 (CH2)3
300 Si Si
O O O O
O O
NH2
150
PANI–Ag (2 M)
+ HNO3
PANI–Ag (0.5 M)
0 BOPET BOPET
0 20 40 60 80 100 120 140
AgNO3 + UV (365 nm)
Time (min) (b)
Figure 10.21 Synthesis of PANI–Ag thin films on silanized PET: (a) mechanism of photo-polymerization of aniline in presence of AgNO3 photo-initiators and
UV light (365 nm). (b) Scheme showing the synthesis of PANI–Ag nanocomposite films on the APS-modified PET substrate by photopolymerization. The color
code distinguishes aniline (red) from APS (black) N atoms. (c) Digital photograph of the green-colored silanized PET sheet coated with PANI–Ag top layer. (d)
H2 S sensing experiments with green sheets shown in (c). Panels (e) and (f ) are digital photographs of PANI–Ag coated PET after irradiation with electron beam
the energy of which was 10 and 75 kGy (kilo Gray), respectively. (g) Effect of electron beam radiation energy on the response of the gas sensor to H2 S. Source:
(a)–(d) Mekki et al. 2014 [94]. Adapted with permission of Elsevier and (e)–(g) Chaudhary et al. 2018 [95]. Adapted with permission of Elsevier.
70 Pristine
10 kGy
60 30 kGy
50 kGy
50 75 kGy
Response (%)
100 kGy
40
30
20
10
2 mm 2 mm 0
5 10 15 20
(e) (f) (g) H2S concentration (ppm)
Figure 10.21 (Continued)

10.4 Surface-confined Sonochemical Polymerization of Conjugated and Vinylic Monomers 301
Power supply
Piezoelectric
transducer
Titanium Hom
Collar and O-rings
Gas inlet/outlet
Cooling
Glass cell
bath
Reaction
solution
(a)
+
pressure
Acoustic
–
density
Liquid
150
Implosion
Bubble radius (μm)
100
th
Grow
Formation
Shockwave
50
Hot Rapid
spot quenching
0
0 100 200 300 400
(b) Time (μs)
Figure 10.22 (a) A typical ultrasonic spray setup, (b) life cycle of an acoustic cavitation. Source:
Bang and Suslick 2010 [99]. Reproduced with permission of John Wiley & Sons.
The coincidence of such harsh conditions can engender a light emission, a fas-
cinating physical phenomenon that was first observed by Frenzel and Schultes in
1934 [102], the so-called sonoluminescence.
In polymer science, the as-mentioned conditions serve to promote poly-
merization. The ultrasound provides a highly efficient and particular initiator
facilitating the chemical bonds breaking as shown in Figure 10.23 [97]. It
replaces the chemical radical initiator or they can be used together [104]. The
irradiation of a solution containing vinyl monomers is an alternative strategy of
macromolecules synthesis [105].
S S
S S 1R S S
+ 1
R R2 R2
H2O n
(a)
Acoustic
20 kHz frequency 500 kHz
Physical/ Dominant
Chemical
(b) mechanical effect
R2
H2O R2
HO Pn
+
R3
H OH R3
S S R
Z
R2
R2 S S Pn
M Pm R
R3
+R
R3 Z
S S Pm S S Pn
Pn S S Pm
Kp Pn Pm
+ + +
Kt Z Z Z Kt
Main RAFT equilibrium

(c)
Figure 10.23 (i) Schematic illustration of sono-assisted reversible addition-fragmentation

chain transfer (RAFT) polymerization, (ii) force types depending on the ultrasonic frequencies,
and (iii) mechanism proposition of the sono-induced RAFT polymerization. Source: McKenzie
et al. 2017 [103]. Adapted with permission of John Wiley & Sons.
It has been demonstrated that sono-induced polymerization is not limited

to water medium, but it can take place in organic solvent. Weissler et al.
[106] have first reported the breakdown of acetonitrile under ultrasonic treat-
ment into nitrogen, methane, and hydrogen. Since then, ultrasound-assisted
polymerization in organic medium has been thoroughly investigated [105].
Several studies revealed the high efficiency of the sono-assisted route for the
preparation of acrylic hydrogels [107], polystyrene [108], poly(methyl methacry-
late) [109], and poly(n-butyl acrylate) [110] to name but a few.
Price and coworkers [104, 109, 111, 112] have extensively studied the
ultrasound-initiated polymerization and detailed very important findings: (i)
high molecular weight polymers could be synthesized at early stages of the
vinylic monomers polymerization, (ii) a prolonged ultrasonic irradiation may
degrade the fabricated polymer, and (iii) the polymer formation increases the
liquid viscosity, the bubbles formation decreases as well and induces a decrease
of the monomers conversion to polymer [113]. Kruus et al. [114, 115], when
studying the sonopolymerization mechanism of methyl methacrylate, showed
that under sono-treatment, pyrolysis of the monomer could occur and then
insoluble chars could be formed as well as linear polymers.
In this section of the chapter, we intend to highlight how the versatile sono-
chemistry served to the coating and the modification of synthetic- and biopoly-
meric surfaces for various applications.
10.4.2 Ultrasound-assisted Polymerization or Polymer Deposition

over Organic Polymeric Substrates
10.4.2.1 Sonopolymerization
The ultrasound-assisted route for polymer deposition figures as a “green” and
impressive process among the available synthetic ones. It made possible modify-
ing polymer surfaces using generated free radicals [116]. It increases the reaction
yield for a short time process.
Recently, Sanaeishoar et al. [116] introduced a sono-based method (using an
ultrasound probe) to graft polyacrylamide onto nano-fibrillated cellulose (NFC)
under mild conditions. Such material has particular physical and chemical prop-
erties motivating its application in some fields like the separation and the elec-
tronic devices. They demonstrated the high efficiency of sonication in promoting
the “grafting-from” of polyacrylamide on the backbone of a commercial NFC in
the presence of potassium persulfate (K2 S2 O8 ), used as initiator (see also Chapter
11). The energy generated from the ultrasound waves facilitates sulfate ion rad-
icals’ formation (SO4 • − ). Then, these species attack the hydroxyl groups on the
organic substrate (NFC) to form alkoxy radicals. Both of these reactions consti-
tute the initiation phase of the copolymerization process (Figure 10.24).
Hamouma et al. [117] proposed a new strategy to coat surface-modified cellu-
losic paper electrodes with polypyrrole. For that purpose, an ultrasonic tank was
used. The preparation strategy is schematically represented in Figure 10.25. The
paper surface was first modified by a layer of diazonium modified-multiwalled
carbon nanotubes (CNTs). The diazonium modification of CNTs ensures their
adhesion to the paper surface and favors coating with polypyrrole. This layer pro-
vided a very suitable platform for the in situ sonopolymerization of pyrrole. The
sonochemical deposition of the polypyrrole film took only one hour, it showed
a better electrochemical behavior than other chemical routes and produced a
nanocomposite with a particular physicochemical properties.
10.4.2.2 Ultrasonic Spray

Polymer deposition or polymer coating could be performed via the ultrasonic
spray. Fine droplets of the coating solution (polymer solution) are formed using
a spraying nozzle and then deposited over the substrate to coalesce and to form
the coating film, the setup is illustrated in Figure 10.26. The breakdown of the
liquid into droplets, the atomization, is ultrasonic [119].
The ultrasonic spray is economical and provides certain important advan-
tages like simplicity, uniformity, reproducibility and it permits to coat
Initiation
S4O82– 2SO4
–
+ SO4 + HSO4
OH O
NFC
Propagation
H2C
+ O
O H2N O CH2 CH2
O
H2N
H2C
+ n O
O CH2CH2 H2N O CH2 HC n+1
O O
H2N H2N
Termination
2 O CH2 HC n+1 O CH2 HC O

2n+2
O O
H2N H2N
Figure 10.24 Ultrasound assisted preparation of polyacrylamide modified NFC. Source:

Sanaeishoar et al. 2018 [116]. Reproduced with permission of Elsevier.
(1) (2)
(a) (b) (a) (b)
SEM SEM
SO3–
N N R
R = SO3–, NH2
Figure 10.25 General strategy for fabricating the modified cellulosic paper (1) SEM images of
CNTs modified paper electrodes (2) SEM images of the nanocomposite after the sono-coating
with polypyrrole; (a): low magnification, and (b): high magnification. Source: Hamouma et al.
2018 [117]. Adapted with permission of Elsevier.
three-dimensional micro-structured materials with planar and nonplanar

surfaces [119–121]. Several parameters are involved for the achievement of the
spraying process, namely, the polymer concentration, the used solvent, the type
of the substrate, the total amount that was sprayed, the spraying flow rate, the
speed with which the nozzle is moved, the air pressure used to vehiculate fine
droplets, and the nozzle-substrate distance [119].
(b) Liquid inlet

Solution
inlet Power connector
Ultrasonic generator
Deagglomeration
Piezoelectric
Ultrasonic transducers
nozzle
Nitrogen
inlet
Nitrogen Atomizing surface

shroud Spray
Shroud
Atomized (a) Ultrasonic atomization at the atomizing surface
solution
Vibrating ultrasonic nozzle tip

Substrate
Droplets form
(A) (B)
Figure 10.26 (A) Principle of the polymer ultrasonic spray deposition [116]. (B) (a) The
ultrasonic atomization process, and (b) droplets formation using an ultrasonic nozzle [118].
Source: (B) Stryckers et al. 2016 [118]. Adapted with permission of John Wiley & Sons.
Selgers et al. [122] reported an ultrasonic spray-based protocol to coat selective

laser sintered surfaces with a hydrophobic layer of 5% polyvinylidene fluoride in
acetone. The surfaces consist of flat tiles made of nylon 12. They showed how the
ultrasonic spray coating reduces the surface roughness of the layer-upon-layer
prepared materials (additive manufactured pieces), and how it guarantees a bet-
ter filling of the porous surface of the substrates. Selgers et al. [122] insisted on
three crucial aspects to achieve a “perfect” coating: the optimization of the whole
process (influencing parameters), the ink optimization, and the substrate prepa-
ration and pretreatment.
Gilissen et al. [123] deposited a light-emitting layer of super yellow
(poly(phenylene vinylene) copolymer) on poly(3,4-ethylenedioxythiophene)
: poly(4-styrenesulfonate) (PEDOT:PSS) surface using the ultrasonic spray. The
later was employed as a wet solution process to make a polymer light-emitting
diodes. After evaporating the dissolving solvent, a coating with low rough-
ness and notable uniformity was obtained without altering the light emission
properties.
10.4.3 Sonopolymerization over Miscellaneous Types of Surface:

Inorganic Polymeric Substrates
Snoussi et al. [113] have recently introduced a new ultrafast strategy to
sono-prepare a magnetic ternary nanocomposite, a Fe3 O4 core nanostructured
material for catalytic applications. The upper layer, the catalytically active one,
0.8 t0
Absorbance (a.u.)
0.6
15s
0.4 30s
60s
90s
0.2 120s
150s
of the ternary nanocomposite

180s
0.0
EDX elemental mapping

200 300 400 500 600 700 800
Wavelength (nm)
Absorbance (a.u.)
2 t0
1 120s
(a) (b) 180s
300s
600s
0
200 400 600

Wavelength (nm)
Figure 10.27 (a) Strategy of making Fe3 O4 @NH2 -mesoporous silica@polypyrrole/Pd; (b) (1)
monitoring of the methyl orange degradation over the nanocatalyst and (2) monitoring of the
p-nitrophenol reduction over the same nanocatalyst. Source: Snoussi et al. 2018 [113].
Adapted with permission of Elsevier.
consisting of palladium-doped polypyrrole was ultrasonically deposited over

amino modified-mesoporous silica surface (the intermediate layer). Compared
the conventional methods, the proposed ultrasound-assisted route that was
performed using an ultrasonic processor (ultrasonic probe) permitted to dras-
tically save time and energy. The deposition took one hour to be achieved. The
nanocatalyst exhibited high catalytic activities. The general process description
is shown in Figure 10.27.
Barkade et al. [124] have implemented a method based on the ultrasound assis-
tance to realize the in situ mini-emulsion polymerization of pyrrole around ZnO
nanoparticles. The polypyrrole constitutes the outer coating layer. It is worth
noting that also the spherical ZnO particles have been sonochemically synthe-
sized. Besides the uniform dispersion of ZnO nanoparticles in the polypyrrole
sono-formed matrix, the ultrasonic treatment helped in the size control of the
hybrid functional colloidal particles and in the enhancement of synergy between
ZnO and PPy. The final product denoted by PPy/ZnO was used for the sens-
ing of liquefied petroleum gas. It revealed remarkable sensing ability and notable
stability.
10.5 Conclusion
In this chapter we have laid out a fistful of strategies to modify polymeric
substrates by surface-initiated polymerization method triggered by light or
sonowaves. Classical Norrish Type I and Type II photoinitaitors continue to
receive much attention by material scientists owing to their versatility and ease
References 307
in designing polymers and polymer grafts. CRP methods have dramatically

progressed, and much is done to trigger CRP methods in bulk or at surface via
photoinduced electron transfer. In this regard, photocatalysts, metal complexes,
dyes, or even Type I and Type II photoinitiators proved efficient to conduct in a
new way ATRP and other CRP methods. The interest of radical photopolymer-
ization lies in the spatiotemporal feature as it is convenient to pattern polymer
surfaces. With a large series of acrylic monomers in hand, much can be done to
tune the surface properties of plastics by surface-initiated photopolymerization.
We have provided some interesting applications such as improved filtration,
anti-inflammatory implant, protein imprinted polymer beads, or anti-icing
surfaces.
As far as conjugated polymers are concerned, the choice of monomer is
restricted to pyrrole and aniline. However, by making nanocomposite coating
on plastic or paper substrates, it is possible to achieve ultimate performances for
future electronic devices such as TEGs, paper electrodes, supercapacitors, and
gas sensors to name but a few. Both photo- and sono-induced surface-initiated
oxidative polymerizations of conjugated monomers permit to provide acceler-
ated polymerization and unusual micro-nanostructures of conductive polymer
coatings and conductive polymer nanocomposites.
We anticipate remarkable progress of surface-confined radiation-induced poly-
merization to impart unique and unprecedented properties to plastic and paper
or cellulosic objects. With the rapidly growing domain of flexible electronics and
“elastronics” (stretchable electronics), clearly there is room for future innovative
surface confined polymerization and the development of 3D patterned surfaces.
Acknowledgments
The authors would like to thank Campus France for the provision of PROFAS
B+ fellowship to FM, North Atlantic Treaty Organization (NATO) for financial
support (CATALTEX project No. 984842), and Qatar National Research Fund for
NPRP award No 8-878-1-172.
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2020 Surface Modification of Polymeric Substrates with Photoand Sonochemically Designed Macromolecular Grafts

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273

Surface Modiﬁcation of Polymeric Substrates with Photo-

Surface Modiﬁcation of Polymers: Methods and Applications, First Edition.

10.1.2 Scope of the Chapter

10.2 Surface-conﬁned Radical Photopolymerization

character, or antifouling/biocidal properties. The rationale for triggering

10.2.1 Type I and Type II Photoinitiation Systems

Photoinitiated Summary of various photopolymerization 2006 [11]

CRP, controlled radical polymerization; SI, surface-initiated; PIMP, photoinferter-mediated

Benzoin MWCNT-benzoin Isopropylthioxanthone Camphorquinone

Initiation + CH2 CH CH2 CH (Eq. 3)

Grafted surface initiator

Figure 10.2 Mechanism of one-step photopolymerization at a hydrogen donor surface

The same system can be adapted to metallic, ceramic, or clayous materials

1 F. Mousli, M.M. Chehimi, 2018, unpublished results.

Top PDMS Adsorb

(b) Add monomer

MMA/DVB (methylmethacrylate/divinylbenzene, hydrophobic phase) and NVP

10.2.2 Simultaneous Photoinduced Electron Transfer and Free Radical

10.2.3 Surface-initiated Photoiniferter

10.2.4 “Brushing Up from Anywhere” Using Polydopamine Thin

Figure 10.9 (a) Schematic illustration of the preparation procedure of lysozyme-imprinted

silk, carbohydrate-based biosensor, and PDA-coated boron nitride nanosheets

Any substrate pH 8.5 PDA

Figure 10.10 (a) Principle of surface-initiated polymerization from polydopamine-coated

PDA adhesive patterned coatings can be deposited by photopolymerization

10.2.5 Recent Trends in Surface-conﬁned Photopolymerization (CRP)

10.3 Surface-conﬁned Photopolymerization

photopolymerization of conjugated polymers, and then we will tackle their

Figure 10.14 Pyrrole photopolymerization mechanism in the presence of silver nitrate

A similar situation is encountered for the incorporation of gold NPs. Indeed, in

3Py + 4AuCl3 + NaDS + h𝜈 → [Py—Py—Py]+ DS− + HAuCl4 + NaCl + 3Au0 + 7HCl

10.3.1.2 Substrates for in Situ Photoinduced Polymerization of Pyrrole

90° peel test

Series connection of PPy–Ag films Equivalent circuit

Figure 10.18 Proposed mechanism of UV-induced step-growth polymerization of pyrrole

Barros et al. [91] have proposed a reaction mechanism of photopolymeriza-

PET-Py Py, AgNO3 PPyAg Flexible H2 S gas sensor [73]

Figure 10.19 Proposed mechanism of photopolymerization of aniline in the presence of silver

Figure 10.20 Mechanism of photoinduced polymerization of aniline in [bmim]PF6. Source:

10.3.2.2 Substrates for in Situ Photoinduced Polymerization of Aniline

10.4 Surface-conﬁned Sonochemical Polymerization

Figure 10.21 (Continued)

Collar and O-rings

Main RAFT equilibrium

Figure 10.23 (i) Schematic illustration of sono-assisted reversible addition-fragmentation

It has been demonstrated that sono-induced polymerization is not limited

10.4.2 Ultrasound-assisted Polymerization or Polymer Deposition

10.4.2.2 Ultrasonic Spray

2 O CH2 HC n+1 O CH2 HC O

Figure 10.24 Ultrasound assisted preparation of polyacrylamide modiﬁed NFC. Source:

three-dimensional micro-structured materials with planar and nonplanar

(b) Liquid inlet

Nitrogen Atomizing surface

Atomized (a) Ultrasonic atomization at the atomizing surface

Vibrating ultrasonic nozzle tip

Selgers et al. [122] reported an ultrasonic spray-based protocol to coat selective

10.4.3 Sonopolymerization over Miscellaneous Types of Surface:

of the ternary nanocomposite

EDX elemental mapping