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Radiation curable polysiloxane: synthesis

to applications
Cite this: Soft Matter, 2021,
17, 6284
Muthamil Selvan T. and Titash Mondal *

Received 20th February 2021,
Accepted 4th June 2021
DOI: 10.1039/d1sm00269d
rsc.li/soft-matter-journal
Among the different types of specialty polymers, polysiloxane finds its position in the pyramid’s apex in
terms of its performance attributes. Its unique structural features result in it having superior performance
benefits over wide operational conditions. Hence, polysiloxanes are used in various industries. Like other
polymers, to effectively use polysiloxanes, curing is a non-negotiable fact. Therefore, polysiloxanes are
cured using different chemistries such as addition, condensation, and peroxy-mediated methods, etc.
However, recently, it has been noted that there is a strong impetus towards developing radiation-
curable polysiloxanes. A faster turnover time, higher yield, and marginal involvement in the release of
any toxic by-products has resulted in the widespread acceptance of radiation curing techniques. This
review article provides insight into the various facets of polysiloxane chemistry, the synthesis of radiation
curable polysiloxane, and the curing methodology of polysiloxane using radiation sources such as
ultraviolet, electron beam, and gamma radiation. We further provide an account of the various
applications of such radiation-curable polysiloxanes.

1. Introduction structural aspect, polysiloxanes have Si–O (siloxane bonds)

Polysiloxanes are gaining widespread popularity in different
application areas due to their unique structural attributes.
The latest research has highlighted the astounding pursuit of
polysiloxanes in areas such as healthcare, the automotive industry,
personal care, aerospace, construction industry, etc.1–10 From a
Rubber Technology Centre, Indian Institute of Technology Kharagpur, Kharagpur,
West Bengal 721302, India. E-mail: titash@rtc.iitkgp.ac.in, titash786@gmail.com;
Tel: +91 3222-283182
repeating units in their backbones and are connected to organic
group(s) such as methyl, phenyl, or vinyl groups. Due to the
presence of such unique structural features, polysiloxanes
demonstrate attractive functional attributes. Typically, a partial
double bond character is demonstrated by the polysiloxanes.11
This is because the Si–O has a shorter bond length than the sum
than the covalent radii of the individual atoms.
Additionally, functional groups, such as methyl and ethyl
groups, protrude out of the plane. This induces a significant
deviation from the orthodox tetrahedral angle noted for similar

Muthamil Selvan T. completed Titash Mondal received his

his MTech in Polymer Science MTech degree in 2011 in Rubber
and Technology from the Technology from the Indian
University of Calcutta, India in Institute of Technology
2020. Currently, he is a PhD Kharagpur, India, and his PhD
student at the Rubber degree in 2015 jointly from the
Technology Centre at the Indian Indian Institute of Technology of
Institute of Technology Patna, India, and University of
Kharagpur, India, currently Houston, USA. From 2016 to
working with soft materials 2020, he worked as a scientist in
based printed electronics. the US-based silicone industry.
Since 2020, he has been working
Muthamil Selvan T. Titash Mondal as an Assistant Professor at the
Indian Institute of Technology
Kharagpur, India. His expertise focuses on the development of
composites based on soft materials and printed electronics.

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variants.12 Apart from that, a lower barrier of rotation and
linearization further contribute toward the inherent flexibility of
polysiloxanes. The glass transition temperature of polysiloxanes is
also low due to their weak intermolecular interactions.13
Additionally, such structural attributes result in high permeability
to oxygen, nitrogen, and water vapor.14,15 Due to the attachment
of organic groups to a chain of inorganic atoms, polysiloxanes
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demonstrate unique properties such as improved flexibility, heat,
cold, and ultraviolet (UV) resistance.16 Their flexibility, stress-
absorbing properties, and durable dielectric insulation over a
wide range of conditions results the widespread usage of silicones
over traditional organic polymers.
It is worth mentioning that, like other organic polymers, the
crosslinking of polysiloxanes is by and large needed for their
applications as coatings, self-healing elastomers, thermally
stable polymers, etc.17–20 Although, there are a few examples
where polysiloxane fluids are added into several formulations
wherein the crosslinking of the polysiloxanes is not achieved.21,22
Apart from these specific fluids, most polysiloxanes are cross-
linked using four different techniques, namely (i) the peroxy
route, (ii) addition curing, (iii) condensation curing, and (iv)
radiation curing. Each of the techniques has their uniqueness
as well as their shortcomings. For instance, peroxide and
condensation curing gives by-products and those by-products
remain in the material even after curing.23,24 Similarly, the efficacy
of the addition curing (Pt catalyzed) process is compromised in
the presence of contaminants such as elemental tin, sulfur, or
amine compounds.25 Hitherto, it can be unequivocally suggested
that despite the first three crosslinking methodologies being
essential in polysiloxane chemistry, they are associated with
particular challenges. The usage of a radiation curing process
can address such shortcomings.
Radiation curing can be carried out by leveraging photon
sources like UV and gamma irradiation or using electron
sources like electron beam curing. The radiation curing process
is preferred over the other methodologies due to the multiple
advantages associated with the same. Some of the critical
facets, like a faster throughput time in processability, low heat
generation associated with the process, and economical route,
make radiation curing the preferred process. Industrially, the
contribution of radiation-curable polysiloxanes is peerless.
This is reflected in a series of granted patents in the domain.26–30
In fact, the development of radiation curable polysiloxanes is
becoming more pressing due to the advent of various market
sectors, such as wearable and flexible devices.31,32
It is worth mentioning that the appropriate design of polysilox-
ane molecules (via an appropriate selection of monomers) plays a
critical role in developing a radiation-curable variant. Such an effect
is more pronounced, especially in the UV curing technique. Owing
to the inorganic nature of polysiloxanes, they often demonstrate
poor solubility in various organic solvents. Additionally, the
photoinitiators used for curing also have poor solubility in
polysiloxanes.33 Thus, the appropriate selection of functional
groups of polysiloxanes is critical towards materials development.
In this article, we aim to discuss the general strategies
involved in the synthesis of polysiloxanes. Furthermore, we
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diverge our discussion on the synthesis strategy of specialized
radiation-curable polysiloxanes. The processes involved in
curing such functional polysiloxanes using radiation sources
like UV, electron beam (EB), and gamma irradiation are
reviewed. The properties demonstrated by such cured materials
as a function of radiation doses and types of radiation used are
reviewed. The article also detailed the applications of such
radiation-curable polysiloxanes.
2.General synthesis of polysiloxanes
Generally, the polysiloxanes structure can be represented as
–[Si(R2)–O]–, where R represents alkyl groups or other phenyl,
vinyl, or fluoro functional groups. Invariably, the typical routes
involved in synthesizing polysiloxanes are classified as (i) via a
direct process involving the Rochow–Mueller pathway, (ii)
using organolithium reagents (Grignard Process),34–38 and (iii)
hydrosilylation chemistry.39–44 The diverse family of silicones
includes reactive silanes, silicone fluids, and silicone polymers.
Among the different synthesis pathways, the key synthesis
routes for developing polysiloxanes are listed below.
2.1 Direct process assisted synthesis of polysiloxanes
The synthesis of polysiloxanes involves the use of hydrolyzable
functional silanes. The functional groups are selected from Cl,
–OR, –OC(O)R, –NR2; where the R groups are alkyl groups or
hydrogen. The generic formula for the representation of such
hydrolyzable silanes is: R4nSiXn, wherein X represents the
functional groups. Dimethyldichlorosilane (DDS) is the most
widely used precursor for the synthesis of polydimethylsiloxanes,
and the process is known as a ‘‘direct process’’.45–49 The direct
process involves a reaction in a fluidized- or stirred-bed at 250–
300 1C. Typically, gaseous methyl chloride is passed through the
fluidized bed in the presence of silicon and a copper catalyst.
Depending on the synthesis conditions, DDS is obtained as the
product in the highest fraction (70–90%). Apart from DDS, a few
other crude silanes of the generic formula: MenSiCl4n, with
n ranging from 0 to 4, and hydride-containing silanes are
produced. Further, hydrolysis and methanolysis are also lever-
aged to synthesize a variety of linear and cyclic polysiloxanes.
2.2 Synthesis of polysiloxanes via hydrolysis and
polycondensation
Briefly, the preparation of polysiloxanes from chlorosilanes involves
two important steps: (a) a functional silane precursor undergoes
hydrolytic polycondensation via hydrolysis or methanolysis. As a
result, a mixture of linear and cyclic oligomeric siloxanes is formed.
Silanols are considered to be the most critical intermediates
obtained in this step. The silanols further undergo a condensation
reaction with many functional silanes. The silanols are also known
to self-condense under ambient conditions. The reactivity of
silanols depends on the number of hydroxyl groups they contain,
and typically the reactivity order of the different silanols can be
noted as R3SiOH o R2Si(OH)2 o RSi(OH)3. Homofunctional silanol
condensation occurs if the reaction contains excess water, and
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SiOH protonation is well maintained. Heterofunctional polycon-
densation occurs if moisture is present at a lower level in the
reaction. Protonic acids also assist the self-condensation of silanols.
Ideally speaking, in a polycondensation reaction, a catalytic amount
of Lewis acids, phosphonitrile chlorides, weak uncharged bases
(amines), strong charged bases, protic acids, and stannous salts
are often used. Siloxanes prepared from chlorosilanes following a
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non-hydrolytic pathway involves dimethyl sulfoxide (DMSO) as an
oxygen source.
The other step involves (b) converting these cyclic oligomeric
siloxanes into a high molecular weight polymer via the ring-
opening polymerization (ROP) method. Compared to the cyclic
oligomeric siloxanes, the molecular weight of the ring-opened
product is higher due to its polymeric nature.50–53
2.3 Ring-opening polymerization (ROP) for the synthesis of
polysiloxanes
Another important synthesis route of polysiloxanes is ROP.54–57
The polysiloxanes obtained from the ring-opening process
result in high molecular weight polymers than the variants
obtained using the condensation route. The commonly used
cyclo-structured siloxane monomers are octamethylcyclotetra-
siloxane (Me2SiO)4 or D4 and hexamethylcyclotrisiloxane
(Me2SiO)3 or D3. Both anionic or cationic initiator-based routes
can be used for ROP. Typically in an anionic ROP process,
strong inorganic, organic, or organometallic-based initiators
are used. A silanolate active center is formed, thereby leading to
the propagation of the polymerization step upon the further
addition of cyclosiloxane monomers.58 Similarly, strong acids
or acidic resins can be used for cationic ROP.59 Further ROP of
cyclic oligomeric siloxanes can be classified as: (i) thermo-
dynamically controlled (mostly for D4 and higher analogs; both
linear polysiloxanes and cyclic oligomeric siloxanes are formed
in parallel)60–62 and (ii) kinetically controlled (mostly for D3;
Fig. 1 Synthesis of functionalized polysiloxanes using hydrosilylation chemistry.81 Adapted with permission from the Royal Society of Chemistry,
Copyright 2014.
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high molecular weight linear polysiloxanes are formed followed
by equilibration).63–65
2.4 Functionalization of polysiloxanes using hydrosilylation
The polysiloxanes synthesized using the above methodologies
demonstrate complete inorganic characteristics. As a result, the
solubility of these siloxanes in typical organic solvents is
compromised. Hence, incorporating organic functional groups
at the terminal position or as pendant groups becomes
essential to impart better solubility in a wide variety of solvents.
Hydrosilylation chemistry involves a reaction between a silicone
hydride fluid and vinyl- or allyl-containing organic moiety in the
presence of a transition metal-based catalyst. The mechanism is
referred to as the Chalk–Harrod pathway.66 In this case, oxidative
addition and complexation between the silicon hydride and
transition metal occur. The allyl or vinyl groups are inserted
further into the metal hydride complex, followed by the reductive
elimination of the hydrosilylated product. In most cases,
Karstedt’s catalyst or platinum-based catalysts are preferred.
However, owing to the high cost of platinum, researchers have
also investigated several complexes based on iron, cobalt, nickel,
etc.67 A typical example of the functionalization of silicone
hydride using hydrosilylation is shown in Fig. 1. Apart from
augmenting their solubility, polysiloxanes are often modified to
induce their functional attributes.68–81 Similarly, to prepare
radiation-curable polysiloxanes, the functionalization of polysi-
loxanes using reactive groups becomes essential.
3 Synthesis and crosslinking of
polysiloxanes using radiation sources
Radiation curing is a technique in which high-intensity radiation
energy from photonic or electronic sources are used to cure the
materials. Such radiation sources can be broadly classified as UV
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irradiation, accelerated electron beams, or gamma rays. Radiation-
curable systems contains some reactive sites in the polymer and are
specially formulated to be cured using radiation energy. Generally,
radiation curing involves the ionization of radiation-sensitive
functional groups using high energy. Curing starts with ionic or
free radical intermediates decomposed via a radiation-sensitive
resin. Radiation curing leads to improved resin stability, fast
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curing, handling flexibility, and energy efficiency compared to
thermal curing systems. The radiation curing technique has
evolved a lot over the last decade. In this part of the review,
details about curing polysiloxanes using various radiation sources
are given.
3.1 UV light assisted photochemical reaction of
photopolymerizable polymers
In UV curing, the crosslinking is initiated via a photochemical
reaction with the help of UV light and photoinitiators. In the
photochemical reaction, the photoinitiators absorb light energy
and this absorbed energy further assists in the formation of
reactive intermediates like free radicals and reactive cations.
These free radicals/reactive cations react with the allyl, vinyl
ether, epoxy, acrylates, or methacrylate functional groups of the
polymer, among others, thereby leading to the curing of the
system. These reactive species further initiate polymerization
and crosslinking. Free radical curing and cationic curing
systems are two types of UV curing. It is generally noted that
the rate of crosslinking in the cationic route is slower than that
of the free radical pathway. Challenges like chain termination,
which occurs during the cationic pathway, often slow down the
process. Usually, the UV visible spectral range between 250–
550 nm can be absorbed by photoinitiators. UV curing can be
employed for printing, coating, and other specialty techniques
like stereolithography. UV curing can be done at low temperatures,
and it is typically known for its fast curing process.
Generally, in light-induced curing systems, one of the
commonly associated limitations is the depth of penetration
of light. Minimal light is absorbed when a small amount of
photoinitiator is used, and apparently, a slower cure rate is
achieved. Photoinitiators may become poisoned by the
presence of moisture in the air. Norish type I and II initiators
are two types of free radical initiators employed in UV curing
systems. Type I photoinitiator curing involves homolytic
bondage cleavage and generates two highly reactive radical species.
Typically, type I initiators have benzoyl groups. 2-Hydroxy-2-methyl-
1-phenylpropanone and 1-hydroxycyclohexylphenyl-ketone are the
most common type I initiators. Alcohol or amine as a co-initiator is
used along with photoinitiators in type II systems, which generally
abstracts hydrogen from this initiator and forms free radicals.
Photoinitiators absorb UV light and form excited molecules,
followed by hydrogen atom abstraction from the co-initiators. 2-
Ethyl-(4-N,N-dimethylamino)benzoate and 2-ethylhexyl-(4-N,N-
dimethyl amino)benzoate are the two commonly employed aro-
matic amine co-initiators.
3.1.1 Synthesis, crosslinking and applications of UV curable
polysiloxanes. In polysiloxane chemistry, mostly acrylated,
methacrylated, vinyl ether and epoxy-functional polysiloxanes
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are used in the UV curing system. Further, based on the type of
functional group present in the polysiloxane chain, it can
classified based on the UV curing route it adopts. Typically,
polysiloxanes that contains acrylate, methacrylate, maleate,
fumarate, thiol, and vinyl type functionalities undergo cross-
linking via free radical UV curing, whereas epoxy and vinyl ether
functional groups containing polysiloxanes are crosslinked via a
cationic route.
3.1.1.1 Free radical reaction mediated UV curing. Acrylated or
methacrylated polysiloxanes are industrially important polymers
that can have acrylate or the methacrylate functionalities at the
terminal of the chain or as pendant groups. Typically, the
synthesis of acrylated or methacrylated polysiloxanes is achieved
using hydrosilylation chemistry or via the condensation of
2-hydroxyethyl methacrylate along with silanol. Wang et al.82
studied the synthesis and properties of a UV curable silicone-
containing methacrylate monomer. Typically, dichloromethyl
disiloxane was taken as the starting material. It was subjected
to treatment with triethylamine in the presence of THF as
the solvent. 2-Hydroxyethyl methacrylate dissolved in THF was
introduced into the system and was further allowed to react with
a siloxane derivative. It is worth mentioning that a low reaction
temperature facilitated higher product yield. The methacrylated
polysiloxanes so obtained were used as a coating and were cured
under a low-pressure mercury lamp for 30 min (light intensity
of around 30 mW cm2). 2-Isopropylthioxanthone (ITX) and
2-methyl-4-(methylthio)-2-morpholinopropiophenone (Irgacure
907) were used as a photoinitiator. Photo differential scanning
calorimetry (DSC) was further utilized to evaluate the UV curing
kinetics. The DSC results demonstrated that higher final
conversions and curing rates were noted for silicon-containing
monomers than silicon-free ones (control sample). From the
results, it was noted that with an increase in the silicon content,
the contact angle of the UV cured film increased; hence a
decrease in the surface free energy was observed. Similar to
methacrylates, acrylates demonstrate strong affinity towards UV
curing. Kim et al.83 studied the characterization of UV-cured
polyester acrylate films containing acrylate functionalized
polydimethylsiloxane (AF-PDMS). The formulation involved the
use of the tri acrylate of trimethylolpropane triacrylate (TMPTA),
the diacrylate of tri(propylene glycol) diacrylate (TPGDA) and 1,6-
hexanediol diacrylate (HDDA), with 2-hydroxy-2-methyl-1-phenyl-
propane-1-one used as a photoinitiator. The influence that the
AF-PDMS content and the impact of the UV curing have on the
polyester acrylate properties was also reported. The results
showed that 1 wt% of AF-PDMS leads to an increase in pencil
hardness.
Additionally, making a hybrid of acrylated polysiloxanes with
urethane also induces the additional benefits of polyurethane
in the matrix. Typically, such hybrids demonstrate improved
toughness, adhesion to multiple substrates, etc.84 Yu et al.85
studied the synthesis and properties of photosensitive silicone-
containing polyurethane acrylate. The reaction of hydroxyl-
terminated polysiloxane (Si), isophorone diisocyanate (IPDI)
and 2-hydroxyethyl acrylate (HEA) was carried out and was cured
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Fig. 2 Schematic pathway for the curing of polysiloxane-urethane arylate derivatives using UV radiation.85 Reprinted (adapted) with permission from
American Chemical Society, Copyright 2014.
using photopolymerization. Typically, in the first step of
the reaction, the silanol groups were made to react with the
isocyanate group of the IPDI using a tin catalyst. The product so
obtained was further made to react with hydroxyethyl acrylate.
The film was cured by UV irradiation for 60s. The results showed
that the thermostability, glass transition temperature (Tg),
tensile strength, hardness, modulus, and dispersion surface
energy increased upon UV curing. The mechanism of cross-
linking using UV radiation is shown in Fig. 2. The developed
material was further utilized as a leather finishing agent.
Similarly, Park et al.86 studied the synthesis of a silicone
urethane acrylate (SiUDMA) oligomer to improve the adhesion
properties of a silicone acrylic pressure-sensitive adhesive
(SPSA). The SiUDMA synthesis involved polydimethylsiloxane
(PDMS), IPDI and 2-hydroxyethyl methacrylate (HEMA), and
a dibutyltin dilaurate (DBTDL) catalyst was employed in
the system. Pressure-sensitive tapes were further cured using
a 0–2000 mJ UV dose. Results showed that the addition of
SiUDMA increased the peel strength.
3.1.1.2 Cationic reaction mediated UV curing. Epoxide functional
group-containing polysiloxanes can be UV cured by leveraging
the cationic technique. The cationic system has the advantage
that while curing, the need for an inert atmosphere is marginal.
Wang et al.87 studied the synthesis of UV-curable epoxy
silicone. Two different types of epoxy silicones were
synthesized, namely: carbazole-bound epoxy tetramethylcyclo-
tetrasiloxane (Ep-Cz-Si) and carbazole-bound epoxy methyl
hydrogen silicone oil (Ep-Cz-SiO). The functional siloxanes were
further treated with a photoinitiator. They were then irradiated
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with a UV lamp from a distance of 10 cm and a light intensity of
1 mW cm1 using a high-pressure mercury lamp. The cationic
photoinitiators employed were diphenyl(4-(phenylthio)phenyl)-
sulfonium hexafluorophosphate (P–S) and di-p-tolyliodonium
hexafluorophosphate (P–I). Carbazole bound Ep-Cz-Si shows
high reactivity, and carbazole acts as an efficient group for
cationic polymerization. The results also proved that a higher
carbazole content increases the refractive index of the system.
Zhu et al.88 synthesized a cationic UV curable cycloaliphatic
epoxy/silicone hybrid using a similar route. A series of hybrid
polymers were synthesized by varying the ratio of 3,4-epoxy-
cyclohexyl-methyl methacrylate (METHB), methyl methacrylate
(MMA) and butyl acrylate (BA), with azodiisobutyronitrile
(AIBN) used as an initiator. Further, epoxycyclohexyl-modified
polydimethylsiloxane (PDMS-VCH) was synthesized using a
Pt catalyst. 3,4-Epoxycyclohexylmethyl-3 0 ,4 0 -epoxycyclohexyl
carboxylate (CE) was also employed to synthesize MMB-CE
and MMB-CE/PDMS-VCH. Two separate UV curable systems
using triarylhexafluoroantimonate sulphonium salt as a cationic
photoinitiator were prepared thereof. The surface performance,
mechanical properties, and thermal behavior of cationic UV
cured coatings prepared using the synthesized materials were
reported further. As shown in Fig. 3, Kowalewska et al.89 reported
the synthesis of tris(trimethylsilyl)hexyl and reacted glycidoxy-
propyl with polysiloxanes. The reaction was carried via hydro-
silylation, and the formed polymer was further crosslinked
by UV radiation in the presence of a diaryliodonium salt.
The thermal properties of the UV cured film were noted to
depend on the ratio of [tris-(trimethylsilyl)hexyl](methyl)-
siloxane to (glycidoxypropyl)(methyl)siloxane. Thermal resistance
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Fig. 3 Schematic diagram of the pathway for the synthesis and curing of
epoxidized polysiloxane using UV radiation.89 Reprinted (adapted) with
permission from American Chemical Society, Copyright 2014.
offered by the bulky tris- (trimethylsilyl)hexyl group and cross-
linking expand via reactive glycidoxypropyl. Fluid separating
membranes were made using this kind of material. Chen
et al.90 prepared cationic UV-curable epoxy-siloxane and used it
further for application as a release coating. An epoxy-siloxane
oligomer was copolymerized to di-functional oxetane monomer
(DOX) for toughened fouling-release coatings. Impact resistance
was found to increase by using DOX. Additionally, improved algae
fouling and marine bacteria release performance of systems with
10 and 20 wt% DOX toughened coatings were also observed.
Wang et al.91 studied the synthesis and characterization of a
UV-curable polydimethylsiloxane epoxy acrylate (PSEA) system.
The synthesis of polydimethylsiloxane-epoxy (PSE) was carried
out via the hydrosilylation of allyl glycidyl ether with a
hydrogen-containing polymethylsiloxane. A Pt catalyst was used
along with toluene under a low stream of nitrogen, which was
continuously mixed at 130 1C until the absorption peak of Si–H
disappeared. FTIR spectra were used to monitor the progress of
the reaction. Furthermore, the PSE was modified with acrylic
acid by dissolving acrylic acid with toluene at 110 1C.
Grafting of acrylic functionalities in PES resulted in the
material demonstrating UV curability. Conversion of the
reaction was confirmed by measurement of the acid or epoxy
values. PSEA resin was further UV irradiated using a high-
pressure mercury lamp under a nitrogen atmosphere at
room temperature. The effects of catalyst, temperature, and
concentration of the reactant and the properties of the UV
cured PSEA film were also studied.
3.1.2 Applications of UV curable polysiloxanes. Hitherto, it
can be noted that UV curable functional silicones are an important
soft matter for consideration. The diverse architectures of
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functional silicones can be made using different chemistry.
The ease of preparation and curing of such diverse polysiloxane
structures resulted in their use in various applications. In the
next section of this review, we will focus on some of the specific
applications of such functional polysiloxanes. Goswami et al.92
reported the development of UV curable PDMS with multi-
walled carbon nanotubes (MWCNTs) composites. The dielectric
properties of the composites were further measured. A hyper-
branched PDMS was synthesized using short-chain vinyl
terminated PDMS with a thiol crosslinker. A 2,2-dimethoxy-2-
phenylacetophenone, (DMPA) photoinitiator was used and was
further crosslinked using UV irradiation. With an increase in
the MWCNT percentage, the permittivity of the composite
exhibited a higher value.
Ye et al.93 prepared sub-100 nm nanostructures using a
nanoimprint lithography (NIL) technique. UV-curable epoxy
siloxane was further used as a NIL resist. These systems were
fabricated to imprint resists for application in areas like
photonics, nano-devices, nano-electronics, or memory devices.
Kozakiewicz et al.94 reported conductive polymer composites
comprising poly(siloxane-urethane) (PSUR) and polyethylene
oxide (PEO) for application as UV cured separators for
lithium-ion batteries. Bakhshandeh et al.95 studied the impact
of UV curing of functionalized PDMS and polyurethane-acrylate
coatings. It was noted that with the use of UV curable fragments,
the water contact angle was improved from 72 to 1021. UV
curable PDMS three-dimensionally printed molds have also been
reported in the literature. These molds provide an upper edge as
the fabrication of such molds is cumbersome and they are
difficult to fabricate via soft lithography. These molds are
typically employed in microchannel geometries.96 Yan et al.97
proposed a technique to prepare single-layer microfluidic PDMS
devices. This was found to be a low-cost rapid prototyping
method. A PMMA mold plate has a design or channel patterns
with various ranges upon which UV curable polymers can be
used for fabrication. This method was found to be more effective
in the microfluidic and small-scale commercialization of
products. Montazerian et al.98 prepared low-cost porous
scaffolds using a fused deposition modeling (FDM) 3D printer.
A UV curable PDMS polymer was used as the model polymer.
This method can be effectively leveraged for developing biocom-
patible porous organ-shaped scaffolds for tailored tissue
regenerative applications. As shown in Fig. 4, different scaffolds
were prepared using the protocol mentioned herewith. Gelatin
methacryloyl (GelMA) used with PDMS scaffold pores was cross-
linked using UV radiation. Further, the cell viability of the
material was examined.
Xiang et al.99 studied the preparation of vinyl and thiol
functionalized polysiloxanes that can be UV cured to make 3D
printed structures with a higher level of precision and accuracy.
Reaction activation energy was found to be 23.30 kJ mol1 for the
thiol–ene type. Obata et al.100 prepared UV curable PDMS in the
2D patterning of a film via a hybrid method of aerosol jet
printing and ultraviolet (UV) laser writing. Uniform coating
and elimination of solvents were achieved using this UV
curable PDMS.
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Fig. 4 (a and b) Schematic representation of the preparation of different scaffolds. In b(I), PLA molds were prepared using 3D printing. (II) To which
PDMS was added, and (III) thereby PLA was dissolved out using dichloromethane. (c and d) Example of porous scaffolds of UV curable scaffolds.98
Reprinted with permission from Elsevier, Copyright, 2019.
3.2 Synthesis and applications of electron beam curable
polysiloxanes
Electron beam (EB) is referred to as one of the most reliable and
optimal ways of curing various polymers. The electron beam
technique can be used to crosslink polymers that are difficult to
crosslink chemically in a facile manner. Usually, electrons are
highly energetic and reactive, hence valuable in inducing
chemical reactions and augmenting the cure time. A cathode
generates electrons, which are accelerated in a vacuum by an
electric field created by a series of aligned cathodes with
increasing potential. Electrons passes through this field with
high speed or energies. EB curing makes use of high energy
electrons (between 150 and 300 keV), which strike the polymers
and stimulates electrons in the polymer-initiator mix/polymer.
As a result, crosslinks are formed. The initiation of crosslinking
starts when accelerated electrons decompose radiation-
sensitive polymers. EB curing does not usually require any
vulcanization agent and is carried out without heating. Curing
happens at high speed when the beam energy is increased. The
beam penetrates the materials to cure them uniformly and
effectively. The penetration of the EB depends on the irradiation
energy. A higher degree of crosslinking occurs due to heat
development as a result of the increase in the mobility of reactive
species. Some of the advantages of EB curing are: minimal curing
time, strong bond formation, curing at room temperature, no
blooming effect, improved aging properties, better compression
set, and high strength. Generally, EB curing can be affected by
many factors, including impurities, irradiation dose, initiator
content, thermal history, and irradiation energy. Contaminants in
the resin can reduce the activity of the curing process. This must be
taken into account, and the initiator’s critical concentration will
compensate for the effects. The curing process is also impacted by
the presence of oxygen (in a free radical approach). In most of
cases, a free radical curing system is employed in EB curing.
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3.2.1 Free radical reaction mediated EB curing. Similar to
the UV curing methodology, the EB curing technique also
leverages free radical chemistry to induce crosslinks in the
polysiloxane system. Hence, it can be unequivocally suggested
that the presence of similar functional groups will aid in the
crosslinking via the free radical mechanism under an EB.
Kokko et al.101 synthesized EB curable silicone acrylate via the
hydrosilylation of polyacryloyloxy functional monomers with
copolymers of dimethylsiloxane and hydrogen methylsiloxane
(PDMHMS). The monomers used were 1,6-hexanediol diacrylate
(HDDA) or trimethylolpropane triacrylate (TMPTA). Pt-catalyzed
hydrosilylation of the above monomers was used for hydrosilylation
with PDMHMS. The synthesized materials were cured using an EB
and further used as a release liner for paper. Batten et al.102 studied
the EB curing of silicone acrylates. By reacting a chlorosilane with
either 2-hydroxyethyl acrylate or 4-hydroxybutyl acrylate, a silicone
series containing mono, di, tri, and tetra acrylates were prepared.
The results showed that the order of reactivity follows the following
trend: diacrylate 4 triacrylate 4 monoacrylate by measuring the
gel content after irradiation of the film at 20 kGy. Properties
pertaining to the different compounds obtained by irradiation
with different EB dosages were also reported in that study.
Naggar et al.103 prepared two different blends containing poly-
dimethylsiloxane (PDMS) in polystyrene (PS) or poly(methyl
methacrylate) (PMMA). These blends were further coated in various
synthetic fabrics, followed by EB treatment of their surfaces.
The acrylate types and the types of the fabric were found to also
influence the adhesion of polysiloxane. Compared with PDMS/
PMMA, the PDMS/PS formulation led to better results in both
polyester and nylon-6 fabrics. PDMS/PS showed less compatibility
with cotton/polyester blend when compared to PDMS/PMMA.
The effects of the styrene and methyl methacrylate monomer ratios,
the polymethylsiloxane ratio, the EB irradiation dose and the
surface morphology of the waterproof finished textiles were
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studied. Xiang et al.104 demonstrated the modification of
polydimethylsiloxane via an electron beam irradiation source.
The properties of the treated polymer were characterized by
swelling degree, using a universal testing machine, X-ray photo-
electron spectroscopy (XPS), contact angle measurements and
thermogravimetric analysis (TGA). The PDMS samples were
prepared using different ratios of PDMS and cross-linker. The
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strength, modulus, elongation, and hardness. Voká et al.110
investigated silicone rubber cured using thermal and radiation
methods. The parameters selected for irradiation were: an
accelerating EB with a dose of 50 kGy, an electron energy of
about 4 MeV, and a power output 1.2 kW. On the other contrary,
thermal curing was performed using 2,4 dichlorobenzoyl
peroxide (10 minutes at 150 1C). The tensile strength, modulus,

samples were further irradiated with a linear electron accelerator elongation, hardness, degree of swelling and sol content
with an energy of 10 MeV, a current density of about 1 Ma cm2, percentage were determined for both processes. Samples
and an absorbed dose in the range of 20 to 200 kGy. The effect of prepared using the radiation methodology demonstrated
irradiation caused the PDMS sheet to demonstrate a reduction improved properties.
in its swelling degree. Similarly, the strength and thermal
decomposition temperature were also found to be positively 3.3 Crosslinking of functional silicones with gamma
impacted by EB curing. Aksüt et al.105 carried out comparative irradiators and their applications
studies on the mechanical and relaxation properties of vinyl-
Compared to the EB technique, gamma irradiation exhibits
methyl-polysiloxane and phenyl-vinyl-methylpolysiloxane when
very high penetration. Generally, gamma ray photon energy is
exposed to EB radiation. The authors synthesized a series of
usually higher than 100 KeV, whereas energies of X-ray photons
silicone-containing peroxide (2,5-bis(tert-butylperoxy)-2,5-
are in the range of 100 to 100 000 eV. Due to this, gamma rays
dimethylhexane) using a Type I (ZDA) or Type II (Triallyl iso-
can penetrate different materials. Gamma radiation is produced
cyanurate) co-agent. The samples were irradiated with an EB
by the gamma radiator cobalt-60. Similar to UV and EB, gamma
with a dose in the range of 0–80 kGy. The results showed that the
rays are also used to effectively cure different functional
crosslinking density increased with EB irradiation and was
polysiloxanes. In the case of the crosslinking induced by gamma
further confirmed by gel fraction measurements.
irradiators, the curing happens mostly via a free radical
3.2.2 Cationic reaction mediated EB curing. Cationic reaction
mechanism. Examples of cationic pathways are few and far
mediated EB curing of functionalized polysiloxanes is not
between. For instance, Satti et al.111 investigated the effect that
commonly utilized. However, specialty polymers with vinyl
gamma radiation has on the room temperature vulcanization of
ethers or epoxy functionalities are often cured via the EB
silicone rubber (RTVSR). Nanocomposites were prepared by
technique using the cationic method with the use of iodonium
mixing RTVSR and montmorillonite nanoclay, nano fumed silica
salts. This is similar to the observations made in the UV curing
and their hybrids. The samples were then irradiated using
method. Typically, the EB dose rate depends on the type of
cobalt-60 gamma rays with a dosage rate of around 1 kGy h1.
resin and the concentrations of the initiators. Faster curing
With an increase in the radiation (up to 100 kGy), the tensile
occurs for a high initiator concentration with the same dose
strength, thermal, fire retardancy and electric insulation
rate. The selection of the resin formulation requires different
properties of the materials were found to improve. However, it is
initiator concentrations and mostly ranges from 1 to 3 wt%.
worth mentioning that at a dosage of 150 kGy, some of the
For instance, Itoh et al.106 reported the electron beam-
properties were found to decline. Similarly, Xinfang et al.112
photoinitiated polymerization of a silicon-containing vinyl
synthesized a non-random crosslinked polysulphone-polysiloxane
ether. The team reported properties such as softness, creasing
segmented copolymer under gamma radiation. The samples were
and wrinkle resistance, with special reference to the water
repellency in textiles. Crivello et al.107 synthesized a
1-propenylether functionalized siloxane with the use of an EB.
Further, they performed a series of hydrosilylation reactions
between various H-functional siloxanes and 1-allyloxy-4(I-
propenoxy) butane (APB). The samples were irradiated using
an EB at 165 KeV. Cationic polymerization was carried out using
a photoinitiator as a diaryliodonium salt with EB irradiation.
Kim et al.108 synthesized a polydimethylsiloxane (PDMS)-grafted
diglycidylether of bisphenol A (bis-GMA). The grafted group acts
as a group that can be cured using EB irradiation. It was noted
that surface tension was influenced more by EB irradiation with
a dosage of up to 5 Mrad.
3.2.3 EB versus conventional curing: comparison of
properties. Frounchi et al.109 reported a comparison of the
properties of silicone rubber cured using an EB and a chemical
Fig. 5 The dynamic viscosity response of irradiated and unirradiated PDMS
curing process, where the EB irradiation dosage was in the sample against variable frequencies. The experiments were carried out at
range of 50–300 kGy. Compared to the peroxide cured variant, 30 1C and were examined for different samples irradiated under different
EB cured silicone rubber demonstrated improved tensile environments.111 Reprinted with permission from Elsevier, Copyright 2018.

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irradiated using 60Co g-rays with a dose rate of around 35 KGy h1.
Menhofer et al.113 studied the impact of crosslinking polysiloxanes
using gamma radiation under different environments such as
under vacuum and in air. In the study window, the authors
reported that the crosslinking density was found to increase when
the experiment was carried out in air compared to via the vacuum
route. This is because, in air, the presence of oxygen helps to
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increase the irradiation temperature, thereby increasing the cross-
linking density. Similarly, Hill et al.114 studied the impact that the
gamma radiation environment has on the structure of the cross-
linked polysiloxanes. The number average and weight average
molecular weight were noted from the gel permeation chromato-
graphy and from the distribution curve it was noted that the overall
crosslinking increased under vacuum. This is in contrast to the
observations made by Menhofer et al.113 Further, the impact of
using different environmental conditions on the crosslinking
Fig. 6 SANS data for different hybrids prepared using gamma radiation.119 Reprinted with permission from Elsevier, Copyright, 2015.
Fig. 7 Contact angle data for different varieties of PDMS prepared via the grafting of different acrylates using gamma radiation.122 Reprinted with
permission from Elsevier Copyright, 2020.
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process of polysiloxanes using gamma radiation was studied by
Satti et al.111 Also, the viscoelastic response of the polysiloxanes was
recorded. As shown in Fig. 5, it was noted that the crosslinking
tendency of the polysiloxanes was higher when the experiments
were conducted under vacuum.
Cetina et al.115 effectively leveraged the epoxy-amine reaction
and developed different gels. Polydimethylsiloxane with a term-
inal diglycidyl ether group (PDMS-DGE) was reacted with different
amines such as 1,3-diamino-2-propanol (DAP), diethylenetriamine
(DETA), tris(2-aminoethyl)amine (TAEA) and triethylenetetramine
(TETA). The gel thus produced was then exposed to gamma
radiation. The properties of the samples exposed to radiation
were compared with the non-irradiated samples. It was noted that
residual DETA participated in further crosslinking with PDMS-
DGE. Further, it was also conjectured by the authors that upon
irradiation, the gel network became stiffer.
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Fig. 8 Plausible mechanism for the formation of H and Y crosslinks in polysiloxanes subjected to gamma irradiation.127 Reprinted with permission from
Elsevier, Copyright, 2017.
Mashak et al.116 reported the release of progesterone from
polysiloxane scaffolds. Interestingly, the authors noted that in
the traditional method of curing polysiloxane using temperature,
the drugs are often compromised. However, the use of gamma
radiation to crosslink the polysiloxane had a marginal impact
on the crystal structure of progesterone and its release rate. The
gamma irradiation doses were 50, 75, and 100 kGy.
3.3.1 Graft copolymers of polysiloxane using gamma radiation.
Apart from crosslinking, gamma radiation has been effectively
utilized to synthesize various graft copolymers of polysiloxane. For
instance, Hongfei et al.117 performed the grafting of 4-vinyl pyridine
(4-VP), acrylic acid (AA), and N-2-vinylpyrrolidone (NVP) onto a
silicone polymer using gamma radiation. The grafting of AA up to
around 8 kGy was smooth. However, at a higher dosage of gamma
radiation, the polymerization was impacted due to auto acceleration.
Similarly, for the grafting of 4-VP grafting onto silicone, a
dosage of 10 to 50 kGy was found to be optimal. While in the
case of NVP, a higher dosage of radiation was required (70 kGy).
Similarly, Uenoyama et al.118 reported the grafting of an acry-
lamide-n-isopropyl acrylamide copolymer onto silicone rubber.
Irradiation at a dose rate of around 0.68 Mrad using a cobalt-60
source was used in this process. Lancastre et al.119 reported the
development of a hybrid material based on polysiloxane-
tetraethyl orthosilicate (TEOS) and zirconium propoxide (PrZr)
using gamma irradiation. The resultant material demonstrated
good transparency and flexibility. The same group further
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extended their studies to see the impact that the variation
in molecular weight of the polysiloxanes has on the micro-
structure of the hybrid.120 The evaluation of the microstructure
was carried out using small-angle neutron scattering (SANS).
The difference in the scattering length density/contrast
between the inorganic oxides, the polysiloxane chains, and
pores results in the observation of the microstructure using
SANS (as shown in Fig. 6). Similarly, Chen et al.121 reported the
development of a large scale thick polysiloxane hybrid material
using sol–gel and gamma radiation. Typically, in sol–gel
chemistry and traditional curing techniques, shrinkage and
porous structures are observed. However, the authors reported
that using gamma radiation, these issues can be addressed.
Medel et al.122 reported the grafting of acrylic acid and
acrylic acid/ethylene dimethacrylate onto polydimethylsiloxane
using gamma radiation. Introduction of the acrylate functionality
tuned the surface energetics of the graft copolymer. The
hydrophilicity of the developed polymer was found to increase
with an increase in the grafting density. Such a finding was
corroborated from contact angle measurement studies, as
shown in Fig. 7.
3.4 Impact of high energy radiation on the polysiloxane structure
During the crosslinking reaction of polysiloxanes induced by
high-energy gamma rays or EBs, gases are released. The total
yield of the gas acts as a marker to determine whether only
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crosslinking is happening or if in parallel some degree of chain
scission is also taking place. Provided there is no backbiting or
intramolecular crosslinking happening, the total yield of the
gas should correspond to the degree of crosslinking that
occurs. Incidentally, it was noted by Miller123 that gamma
radiation caused significant chain scission to occur in poly-
siloxanes. This was substantiated by mass spectroscopic
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analysis and by infrared spectroscopic studies. However, this
was true when the gamma irradiation was carried out at an
elevated temperature of above 100 1C. Further to this study, Hill
et al.124 leveraged silicon- and carbon-based NMR studies to
investigate the impact that high energy radiation has on poly-
siloxanes. They observed that a wide variety of cyclic siloxanes
were formed post irradiation. This was conjectured to happen
via a backbiting mechanism in the polysiloxanes. Further, the
same group extended the study and through silicon NMR
studies confirmed that two different types of crosslinking occur
during the polysiloxanes being placed under vacuum at
ambient temperature. Namely, crosslinking was induced in
the system, with chain scission occurring in the main chain,
while the other type of crosslinking occurred due to side chain
scission.125 Similarly, the different types of crosslinks that form
during gamma radiation exposure of polysiloxane have been a
matter of investigation by several groups.126,127 Y and H types of
crosslinks have been reported to form. A plausible mechanism
for the formation of these crosslinks is shown in Fig. 8. Satti
et al.128 studied the impact that gamma radiation (10–100 kGy,
dose rate: 10 kGy h1) has on the crosslinking and chain
scission of close to monodisperse polysiloxane (synthesized
via anionic polymerization using sec-BuLi). Negligible
chain scission was noted, whereas a predominant crosslinking
reaction occurred for the model polysiloxane. A size-exclusion
chromatographic technique was leveraged for determining the
changes that occurred.
Apart from the linear polysiloxane system, Choi et al.129 did
a comprehensive study on the EB exposure of hydrogen silses-
quioxane (HSQ) in terms of the effect that it has on chemical
structure and properties. It was noted that the chemical
structure and properties also changed after both processes.
FT-IR studies showed that redistribution of Si–H and Si–O bond
occurs upon irradiation. Despite this, such chain scission
occurs due to the exposure of polysiloxanes to high energy
radiation, as it has been experimentally proved that the degree
of crosslinking that occurs is substantially higher than that of
the chain scission in the system.
4 Concluding remarks
To summarize, polysiloxanes can be considered as one of the
most important soft materials ever discovered. Due to their
exhilarating properties such as excellent flexibility, superior
thermal properties, excellent biocompatibility, and so on,
polysiloxanes find application in different domains ranging
from healthcare to the automotive industry. By leveraging
different chemistries like hydrosilylation, ring-opening
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polymerization, and condensation, a library of structure of
polysiloxanes can be generated. Polysiloxanes can indeed be
cured using traditional techniques like heat curing, condensation
curing, or peroxy-mediated curing. However, there is a recent
impetus towards the development of radiation-curable polysi-
loxanes. A fast curing time with the marginal release of volatiles
has resulted in the widespread use of radiation curing. Various
radiation sources like UV, EB, and gamma radiation are used.
The curing can occur via a free radical mechanism or via a
cationic mechanism. The selection of the pathway is largely
guided by the type of functionalities present in the polysilox-
anes. However, it can be unequivocally suggested that the ease
of the process involved in the UV curing makes it a preferred
route over the other two methodologies. The fabrication of
polysiloxane-based complex structures using 3D printing and
lithography can be successfully developed with the help of UV
curing. The only caveat associated with UV curing is the
limitation associated with the low penetration depth and
opacity of the compounded polysiloxane composition. Such a
challenge can be addressed by EB and gamma irradiation
assisted curing. Typically, the photoinitiator in the UV curable
polysiloxane formulation is excited during the photochemical
reaction, while in the EB technique, bulk polysiloxane is excited
and ionized. Polysiloxanes demonstrate their unique properties
when they are cured using an EB or gamma rays. Unlike other
polymers, in which chain scission is a big problem commonly
associated with an EB or gamma radiation, polysiloxanes do
not face such challenges. Hence, for product profiles ranging
from release liner coatings to advanced drug delivery scaffolds,
radiation-curable polysiloxanes can be used. To the best of our
understanding, radiation-curable polysiloxanes will create a
strong footprint in sectors such as the healthcare industry,
where the application of radiation polysiloxanes will be
significant and will also play a critical role in the development
of wearable electronics for healthcare monitoring.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
T. M. acknowledges generous support of the ISIRD funding
(IIT/SRIC/RT/ESA/2020-2021/081) from IIT Kharagpur, India.
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