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Gamma Irradiation of Silicones

Article in Journal of Inorganic and Organometallic Polymers and Materials · January 2008
DOI: 10.1007/s10904-008-9205-0

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J Inorg Organomet Polym (2008) 18:207–221
DOI 10.1007/s10904-008-9205-0

REVIEW

Gamma Irradiation of Silicones

Aniruddha S. Palsule Æ Stephen J. Clarson Æ
Christopher W. Widenhouse

Accepted: 5 February 2008 / Published online: 1 April 2008

Ó Springer Science+Business Media, LLC 2008

Aniruddha S. Palsule completed his Bachelor of Engineering degree

from the University of Pune, India in the field of Polymer Engineering in
2004. He commenced his doctoral thesis work with Dr. Steve Clarson at
the University of Cincinnati in 2004. His research work has focused on the
evaluation of permeation and biocompatibility of biomedical grade sili-
cone elastomers. This work has been supported by the NSF Membrane
Applied Science and Technology (MAST) center. He is also working on
the development of enzyme based ‘green’ catalytic routes to silicone
polymers.

Stephen J. Clarson obtained his doctoral degree in Chemistry at the Uni-

versity of York, England in 1985. He then spent the summer of 1985 at the
Institute of Macromolecular Chemistry in Prague, Czechoslovakia before tak-
ing up a postdoctoral appointment with James Mark. In 1988 he joined the
faculty of the Department of Materials Science and Engineering at the Uni-
versity of Cincinnati. He is currently the Director of the NSF I/UCRC
Membrane Science and Technology Center. He is the North American Editor of
European Polymer Journal. In January, 2000, he was elected Fellow of the Royal
Society of Chemistry (FRSC). Dr. Clarson has published over 200 technical
articles and co-authored four books. The research carried out in his group has led
to several inventions and he holds five US patents and two Japanese patents. His
current scientific research interests include materials chemistry, polymer syn-
thesis, silicon-based chemistry, biomaterials, biomineralization, biocatalysis,
optoelectronic materials, thin films and surface science.

A. S. Palsule
Department of Chemical and Materials Engineering,
University of Cincinnati, 400 Rhodes Hall, ML 0012,
Cincinnati, OH 45221, USA

S. J. Clarson (&)
Department of Chemical and Materials Engineering,
University of Cincinnati, 601B ERC, ML 0012, Cincinnati,
OH 45221, USA
e-mail: Stephen.Clarson@UC.Edu

C. W. Widenhouse
Ethicon Endo-Surgery, 4545 Creek Road, Cincinnati,
OH 45242-2839, USA

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208 J Inorg Organomet Polym (2008) 18:207–221

Christopher W. Widenhouse received his doctoral degree from the

Materials Science and Engineering Department of the University of
Florida at Gainsville. He worked as Staff Engineer-New Product Devel-
opment at Cordis Corporation. He is currently based in Cincinnati at
Ethicon Endo-Surgery, a Johnson & Johnson company, where his work
focuses on developing surgical tools and techniques.

Abstract Silicones in various forms have been utilized in
biomedical applications over the past several decades.
While silicone elastomers are currently the most common
silicone biomaterial, low molar mass cyclic silicones, low
molar mass linear silicones, silicone oligomers, silicone
polymers and silicone gels have each found applications as
biomaterials. For the biomedical applications of silicones,
it is required that the materials be sterilized prior to
application or implantation. Common methods of sterili-
zation include steam sterilization, ethylene oxide
sterilization, electron beam sterilization and gamma ster-
ilization. In this review we will describe the behavior of
various silicones upon exposure to gamma radiation.
Keywords Silicones
Polysiloxanes
PDMS

Gamma irradiation
Gamma sterilization
1 Introduction
Silicones are synthetic polymers whose skeletal backbone
is made up of silicon–oxygen bonds. The basic repeating
unit of a linear polysiloxane molecule has the structure—
(RR0 SiO)n–. The most common member of the siloxane
family is polydimethylsiloxane (PDMS) i.e. when both R
and R’ are methyl groups. Since their development in the
early 1940s [1–8], dimethylsiloxane has been the work-
horse of the silicone industry. Siloxane units are also
utilized that have various functional and non functional
groups attached to silicon. The silicon atoms can be bonded
to organic groups such as phenyl and vinyl groups. Other
important materials include those where silicones are
copolymerized with a wide variety of organic repeat units.
The presence of organic groups attached to an inorganic
backbone gives silicones a set of properties which are
different from the corresponding organic compounds. Sil-
icones can be grouped into compounds based on fluids,
resins and elastomers with the elastomer field accounting
for about 50% of the applications in extremely diverse
fields [9]. Current sales of silicones are estimated to be
about 10 billion dollars per year [10]. Their excellent
thermal and electrical stability has resulted in their use in
the aerospace industry and as insulating materials. Sili-
cones have excellent low and high temperature properties.
They can be used as sealants, adhesives and for waterproof
coatings due to their durability and low surface tension.
Another major application of the silicones is in the medical
field where their excellent biocompatibility makes them
ideal for use in numerous personal care products and
medical devices [11–19]. Silicones in the form of low
molar mass cyclic silicones, low molar mass linear sili-
cones, silicone oligomers, silicone polymers, silicone gels
and silicone elastomers have all found applications.
The biocompatibility and the biodurability of silicones is
a result of other material properties such as hydrophobicity,
low surface tension, elastic nature and chemical and thermal
stability. The range of use of silicones in the medical field
covers applications such as orthopedics, catheters, heart
valves, pacemakers and breast, chin and testicular implants
[11–19]. A couple of familiar examples are the use of sili-
cone fluids for lubricating hypodermic syringes and silicone
elastomers as catheters. Silicone elastomers can also be fil-
led with silica to enhance the mechanical properties. Some
implants also utilize swollen and lightly crosslinked sili-
cones, referred to as silicone gels, for soft tissue mimicry.
The implantable materials must be sterilized before use.
Sterilization can be defined as ‘‘any process which results
in the total destruction or death of all forms of micro-
bial life (bacteria, spores, fungi and viruses) on the
devices.’’ [20]. The commonly used techniques for steril-
izing implants are steam autoclaving, treatment with
ethylene oxide and exposure to high energy ionizing radi-
ation [21]. A comparison of the sterilization methods for
implants has been presented by Park and Lakes and by
Kowalski and Morrissey [22, 23]. They also include ster-
ilization technologies such as application of gluteraldehyde
solutions, gaseous chlorine dioxide, low-temperature gas
plasma, vapor-phase hydrogen peroxide and machine-
generated X-rays. Sterilization by irradiation can be
achieved by irradiating the implantable material either by

123
J Inorg Organomet Polym (2008) 18:207–221
gamma rays (Co-60 source) or by a high energy beam of
electrons. Broadly speaking, sterilization by irradiation is
an efficient method and offers the advantage of being able
to sterilize a packaged article with little or no thermal
effect on the device. The penetrating power of gamma
radiation is higher than that of electrons but it is more
costly to install, and sterilization typically takes a longer
time [20]. However certain plastics degrade when irradi-
ated, and chemical changes can be induced in the article on
a molecular level depending on the chemical structure
involved.
Sterilization of polymers can induce either crosslinking or
degradation in the polymer depending upon the chemical
structure. Crosslinking is usually manifested by an increase
in the molecular weight of the polymer with radiation dose,
giving rise to a branched structure; and finally, a network is
formed. On the other hand degradation can give rise to main
chain scission and a drop in the molecular weight. In actu-
ality, both crosslinking and degradation are known to occur
in most polymeric systems with one or the other effects
predominating. Examples of the systems where degradation
is predominant are PMMA and polyisobutylene, while
polyolefins are known to crosslink when irradiated [20].
Silicones or polysiloxanes and polyurethanes are elas-
tomers that are approved by the Food and Drug
Administration (FDA) for use in the form of biomedical
devices. Thus, they are used in a wide variety of biomed-
ical devices as stated above. All these devices need to be
sterilized before implantation. Sterilization by gamma
radiation is fast becoming the preferred technique in the
United States, replacing ethylene oxide or autoclaving [21].
Thus, as this sterilization technique grows, it is extremely
important to have knowledge about the effects of the
exposure of silicones to gamma irradiation.
The purpose of this review is to compile the available
literature on this subject and present an overview in a
concise fashion. The effects of gamma irradiation on the
three different forms of silicones
(1) Linear chains of polysiloxanes,
(2) Crosslinked polysiloxane elastomers (filled and
unfilled), and
(3) Cyclic siloxanes
are described in detail. The effects of irradiation on the
crosslinking and curing of the linear polymer, changes in
the mechanical properties of elastomers and polymeriza-
tion of cyclic species have all been given due consideration
in this review.
While the various investigations of gamma irradiation of
silicones reported in the literature and discussed herein have
been carried out under a variety of experimental conditions,
some of the important variables have been identified and
evaluated. Of particular importance are the exposure times or
209
total dose, the dose rate, the presence of additives (solvents,
fillers, antioxidants, pigments, etc.), the ‘equation of state’
variables (temperature, pressure, etc.) and the atmosphere
(air, oxygen, nitrogen, hydrogen, argon, vacuum, etc.).
2 Linear Polysiloxanes
Linear polysiloxanes are available as fluids whose viscosity
depends on their molecular weight. They consist of Si–O
bonds in the main chain of the polymer. Therefore, it is
easier to determine the difference between main chain and
side chain chemistry when the polymer is exposed to
radiation. In the case of main chain fracture, fractions
containing silicon or oxygen may be obtained. Thus, it is
possible to study the effects of radiation by irradiating
siloxane liquids of different viscosities and monitoring the
molecular weight changes for an indication of crosslinking.
Polymers containing carbon in the main chain are
known to crosslink when irradiated. However, the presence
of carbon in the backbone of the chain was not a pre-
requisite for crosslinking to occur. PDMS can also be
crosslinked when exposed to high energy gamma radiation
and electrons, giving rise to a material with elastomeric
properties. The extent of crosslinking is a function of the
radiation dose and can be deduced from solubility studies
carried out on the crosslinked elastomer [24–26]. Linear
silicones are readily soluble in solvents such as benzene
and xylene. In a typical crosslinking process some of the
molecules get tied together with covalent bonds between
chains. This results in the increase in viscosity of the fluid.
However the solubility is still retained. Adjacent chain
segments come together and connect to form a network
structure which is of an infinite extent. All the initial
molecules taking part in this reaction now form one single
molecule which loses solubility in any of the aforemen-
tioned organic solvents. Some molecules remain which are
not crosslinked to any portion of the network. These mol-
ecules can be dissolved out of the gel upon swelling in a
solvent and are referred to as the sol fraction. The cross-
linking efficiency should therefore be inversely related to
the sol fraction. Thus solubility studies on the gel are a
good indication of the extent of crosslinking occurring as a
function of different doses of radiation.
Early studies by Charlesby and Miller established that the
degree of crosslinking was a function of the radiation dose.
Charlesby obtained this by extracting the sol fraction for the
crosslinked polymer [24]. Miller observed the increasing gel
content with electron irradiation dose [26] (Fig. 1).
Gel formation commences when there is on average one
crosslinked monomer unit per weight average molecule
and further crosslinking will just increase the amount of gel
produced. Charlesby measured the radiation dose required
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210 J Inorg Organomet Polym (2008) 18:207–221

energy absorption per crosslink was 32 eV [24]. Based on

Fig. 1 (a) plot showing the drop in the sol fraction with radiation
dose (gamma) for different viscosities of silicone fluids [24] and (b)
plot showing the increase in gel fraction with radiation dose
(electrons) for 30,000 cs PDMS oil (Mw = 85,000) irradiated at
25 °C and 13.8 Mr/min [26]
for incipient gelation for linear polymers of different
molecular weights and viscosities and used the data to
estimate the percentage of monomers crosslinked due to
radiation (Table 1). He concluded that the density of
crosslinking is independent of the starting molecular
weight of the polymer. We see that it varies within the
range of experimental error around the mean value of
2.2%. However the radiation dose required for incipient
gelation is a function of the starting molecular weights.
Charlesby deduced a crosslinking yield of 2.2% and the
the same criteria, Miller calculated a crosslinking yield of
3.0% for irradiation by electrons [26].
Thus irradiating a linear silicone polymer by gamma rays
results in the formation of a crosslinked network polymer
and the degree of crosslinking is related to the radiation dose.
Irradiation of polymers results in the evolution of gases. The
total gas yield should correspond to the crosslinking
occurring in the polymer as long as there are no intramo-
lecular crosslinking or backbiting reactions occurring.
PDMS structure precludes the formation of unsaturation in
the main chain. This is a major difference between the
behavior of silicones and that of the corresponding paraffins.
Sterilization of a silicone article packaged in a polyolefin
film results in the packaging material darkening after irra-
diation. However the silicone itself remains clear and
transparent after sterilization. This is attributed to the ability
of the paraffins to form C=C double bonds in its backbone.
Thus we can expect the total gas yield to match with the
degree of crosslinking in the structure. Miller observed that
this correlation was obeyed up to 100 °C. But for higher
temperatures there was divergence between the gas
yields and the degree of crosslinking [26]. He attributed
this to main chain scission occurring at the elevated
temperatures.
Mass spectrometric analysis of the evolved gases
revealed that hydrogen, methane and ethane gases were
produced [24, 26]. This led to the idea that fracture
occurred at the C–Si or C–H bonds giving rise to methyl
radicals. These radicals could then combine with hydrogen
gas or other methyl radicals to give methane or ethane.
Ethane was observed in a very low yield which is rea-
sonable (Fig. 2).
2.1 Radical Formation Upon Irradiation
Radiation induced crosslinking reactions in most organic
polymers proceed through the formation of radicals.

Table 1 Calculations for the crosslink density [24]

Bulk Weight No. of Minimum Rgn 100/Rgn
viscosity average monomers per radiation
(cS, 25 °C) mol. Wt. weight dose for gel
(Mw) average formation
molecule (n) (Rg)

1,00,000 1,06,000 1,430 .037 53 1.9

30,000 80,000 1,080 .051 55 1.8
12,500 62,000 840 .07 59 1.7
1,000 26,400 360 .12 43 2.3
50 3,900 53 .72 38 2.6 Fig. 2 Proposed crosslinking mechanism based on gas yields after
irradiation [24, 26]

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J Inorg Organomet Polym (2008) 18:207–221
Knowledge about the nature and the yield of these radi-
cals can provide an insight into the mechanism of
crosslinking involved. It is possible to react these radicals
with some radical scavengers such as iodine in very small
concentrations. The scavenger will stabilize the radicals.
Thus these radicals will no longer be available for
crosslinking. Consequently the dose of radiation required
for incipient gelation will increase in that proportion. This
increased dose can then be correlated with the additive
concentration. Radical scavengers used this way can
protect the linear silicone from crosslinking. Iodine, sul-
phur and benzophenone have been shown to prevent
crosslinking in linear silicones either by reacting with the
polymer radical and stabilizing it or by reacting with the
hydrogen atom which would otherwise be available for
abstraction [27, 28].
Miller was able to identify and determine the yields of
–SiH, –SiCH2Si–, and –SiCH2CH2Si– groups through FTIR
study of the irradiated samples. He also established the
presence of Si–Si crosslinks [26]. The observation of
Fig. 3 Proposed reaction
mechanism to explain the
observed radicals by Miller and
Menhofer [31]
211
Si–OH functionalities, for irradiation in the presence of
mercaptan, by the infrared analysis, led Miller to speculate
that main chain scission was occurring and the H atom was
abstracted by the Si–O functionality [29]. These observa-
tions were then corroborated by an electron spin resonance
(ESR) study of PDMS in which the –(CH3)2–O–Si* radicals
were clearly identified at room temperature and at low
temperature such as 77 K [30]. The radicals at low tem-
peratures disappeared after subsequent annealing. However,
the –Si* radical at room temperature was positively iden-
tified. This verified Miller’s conclusion that crosslinking
was occurring through –Si* and –Si–CH2* radicals.
The direct measurement of the trapped radicals at low
temperature is not a very efficient technique. These radicals
disappeared at slightly higher temperatures. ESR tech-
niques using spintrap measurements indicated the presence
of H3C* and –Si* radicals at room temperature. Keeping in
mind the nature of the observed radicals it is possible to
propose a reaction mechanism explaining their formation
[31] (Fig. 3).
123
212
2.2 Effect of Oxygen
Charlesby observed that the gelation dose required for
PDMS exposed to the atmosphere was approximately
double that of the dose required for degassed samples of
the same viscosity and molecular weight [27]. For electron
irradiation, Miller observed that the crosslinking yield
decreased from G(X) = 3 to G(X) = 1 in the presence of
oxygen [29]. He postulated that, in the presence of oxygen,
the –Si–CH2* and the –Si* polymer radicals produced
upon irradiation are converted into their peroxy derivatives
which are unable to directly participate in crosslinking.
Oxygen interferes with the formed radicals which is
manifested by the decrease in the yield of the dimers
formed upon irradiation and an increase in the oxidation
products [32]. The oxygenated products were identified as
carboxylic acid and two peroxides of the type Si–OOC–. In
the case of polyolefins, the presence of oxygen during
irradiation inhibits the crosslinking process. However, in
the case of polysiloxanes, it was not possible to completely
inhibit crosslinking. The residual crosslinking is attributed
to the existence of small amounts of dimers and also to the
rearrangement of the oxygenated products [29, 32]. Evo-
lution of carbon monoxide and carbon dioxide is also
observed upon irradiation in the presence of oxygen [33].
2.3 Protective Effect of the Phenyl Group
Oxygen acts as an external agent for the prevention of
crosslinks in siloxane polymers exposed to radiation. How-
ever, this protection can be internal as well with the
incorporation of phenyl groups on the PDMS chains by
copolymerizing with small amounts of phenylmethylsilox-
ane. The phenyl group is capable of protecting as many as six
adjacent siloxane units on the main backbone chain. The
phenyl group is a resonant structure. An electron knocked out
of the side chain by ionization or irradiation can be easily
replaced by another electron from the Si–O backbone. The
energy in this process can be dissipated in the various reso-
nant forms of the phenyl group which has a delocalized p
electron structure. The extent of protection increases for
biphenyl groups and so on. However, saturation in protection
is observed for a phenyl content of more than 40 mole %.
Details of copolymers are beyond the scope of this review
work; however readers are referred to more comprehensive
studies on the same subject [34, 35].
The crosslinking mechanism proposed by Charlesby and
Miller (Fig. 2) considers that crosslinking occurs through
C–Si and C–H scission with essentially no main chain scis-
sion. This was corroborated by the positive identification of –
CH2, –CH3 and –Si radicals both at low temperatures and
high temperatures by spin trapping studies. However, the
existence of other structures occurring primarily due to main
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J Inorg Organomet Polym (2008) 18:207–221
chain scission has not been elaborated upon in any of the
studies described above. Based on some indirect evidence in
cases where the gas yield did not agree fully with the cal-
culated degrees of crosslinking, Miller alluded to the idea of
main chain scission occurring in irradiated PDMS.
In a series of subsequent studies involving solid state
and solution state 29Si–NMR, 13C –NMR, solvent extrac-
tion studies and GPC studies for molecular weight
determination, Hill et al. provided the first direct evidence
of the occurrence of main chain scission [36–38]. These
studies were carried out at 303 K in an inert atmosphere.
With the use of 29Si NMR they were able to identify the
presence of three membered, four membered and five
membered cyclic structures of PDMS. The only way these
structures could occur was through main chain scission of
the chain upon irradiation. Backbiting was the postulated
mechanism for the formation of these cyclics (Fig. 4).
After assignment of the various structures formed after
irradiation to NMR peaks, the authors were successful in
verifying the existence of new types of crosslinks formed
due to main chain scission along with the H-type crosslink
described by Charlesby and Miller which was based on
side chain scission. The existence of two different types of
crosslinks, i.e. one based on main chain scission (Y-type)
and the other based on side scission (H-type), was proven
for the first time. Figure 5 shows the different types of
crosslinks as postulated by Hill.
Calculation of the degrees of crosslinking for these new
types of crosslinks revealed that crosslinking occurred
principally through the Y-type crosslinks described by Hill.
The G values (yield, gaseous or otherwise, per 100 eV of
energy absorbed) calculated by Hill were G(Y) = 1.7 and
G(H) = 1.45 along with a G value for scission of
G(S) = 1.15. Thus, crosslinking is predominant for irra-
diation under vacuum as well as in air, although the net
yield of crosslinking in air is slightly lower [38].
Fig. 4 Mechanism for the formation of low molecular cyclics upon
irradiation of PDMS [36]
J Inorg Organomet Polym (2008) 18:207–221 213

Fig. 5 (a) Silmethylene

crosslink (H-type) formed by a
combination of a side chain
methylene radical and an in-
chain silicon radical [37] (b)
Y-type crosslink formed by the
reaction of methylene radicals
and silicon radicals formed by
main chain scission [37]

3 Silicone Elastomers Sheets of similar formulation were also exposed to

Silicone polymers can be easily transformed into three
dimensional networks through a number of different
crosslinking reactions. They include the use of a tri or
tetra functional siloxane comonomer, using thermal initi-
ators such as a peroxide which abstract a hydrogen atom
from the siloxane or by the use of high energy radiation.
Most of the commercially useful applications of the
polymer are in its elastomeric form which makes it
extremely vital to understand the effect of gamma radia-
tion on the properties of these materials. Most of the
elastomers are filled with silica or titania filler for rein-
forcement purposes. The effect of filler in the interactions
with radiation is also of interest.
3.1 Enhancement in Mechanical Properties
e-beam radiation. The effect on the tensile properties, shore
hardness and percent elongation are shown in the table
below. In this case, based on the tensile properties, the
optimum cure seems to be around 10 Mrep (Table 3).
With an increase in the crosslinking, the hardness of the
cured polymer also goes up. It is safe to assume that the
hardness increase is proportional to the radiation dose.
Comprehensive data for Durometer A type hardness, pro-
vided by Basfar for different formulations of curing agent
in silicone rubber, is shown in Fig. 6. Different formula-
tions are represented as 0/10 (parts of curing agent/parts of
silicone rubber), 0.5/10, 0.25/10 and 1/10 for Si, Si-1, Si-2
and SiC respectively [40]. A 300–400 kGy dose was
required for optimum cure.
The improvements in the tensile properties, modulus
and ultimate properties for PDMS elastomers blended with

For most polymers, crosslinking results in the formation of Table 2 Effect of gamma radiation on silicone rubber [39]
a dense network with an enhancement in mechanical Dose (Mrep) Shore Tensile (psi) % Elongation
properties such as modulus, hardness and tensile properties.
25 53 916 158
Thus, these properties, especially the modulus, can be
5 27 1,180 750
monitored as an indication of crosslinking in a sample.
1.25 18 135 550
Warrick, in 1955 [39], provided a comparative study of
the effects of gamma ray and electron-beam (e-beam)
Table 3 Effect of e-beam radiation on silicone rubber [39]
irradiation on the mechanical properties of a silicone
elastomer filled with 35% SiO2 filler loading. The vulca- Dose (Mrep) Shore Tensile (psi) % Elongation
nization of silicone rubber was carried out by gamma rays
2 15 153 780
from a Cobalt-60 source, and the tensile strength, %
6 26 742 605
elongation and shore hardness were studied as functions of
10 29 876 580
the radiation dose. Based on the tensile properties and the
20 43 679 250
% elongation values, the optimum cure for the silicone
40 52 561 117
sample was somewhat above 5 Mrep (Table 2).

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214 J Inorg Organomet Polym (2008) 18:207–221

Fig. 6 Shore A hardness measurements as a function of the dose for

formulations of silicone rubber [40]

silica filler and cured by gamma radiation have been

studied as a function of the radiation dose [41]. Swelling
studies revealed that the presence of filler slightly
improved the crosslinking efficiency in PDMS and caused
a drop in the soluble fraction in the elastomer after
extraction in toluene. Mooney–Rivlin plots for the elasto-
mer revealed an increase in the tensile properties with
higher doses (Fig. 7).
For most polymeric systems, an increase in the ultimate
strength of the material at rupture is synonymous with a
decrease in the ultimate elongation. However, this was not
observed for unfilled PDMS cured by gamma radiation,
where the ultimate strength increased with an increase in the
radiation dose along with a concurrent increase in the ulti-
mate elongation. For filled systems the reinforcing effect of
the colloidal silica completely masks that of radiation.
However, both the filler as well as the radiation have a
cumulative effect on the strength enhancement (Fig. 8).
3.2 Effects of Filler Loading
Silica filler plays an important role in PDMS by contrib-
uting to the overall increase in crosslink density by forming
hydrogen bonds between the silicone polymer chain and
the surface silanol groups on the silica filler. These are
often termed as apparent crosslinks and the resultant
increase in the crosslink density is the apparent crosslink
density. It is possible to disrupt this hydrogen bonding on
the surface of the filler by swelling in ammonia to obtain
Fig. 7 (a) Soluble fraction after extraction v/s radiation dose for
filled and unfilled systems and (b) Mooney–Rivlin stress–strain plots
for filled and unfilled elastomers for different radiation doses [41]
the actual crosslink density of the elastomer. Studies
revealed that silica reinforcement contributed about 67% to
the apparent crosslink density of the filled elastomer [42].
It was also observed that filled silicone copolymer samples
irradiated in air showed an initial drop in the apparent
crosslink density due to a disruption of the hydrogen bonds
on the filler surface. There was no drop observed for
samples irradiated in a vacuum and the crosslink density
showed steady increase (Fig. 9).
NMR and GC-MS studies also revealed the formation of
degradation products in the form of low molecular weight
cyclics formed as a result of backbiting [42]. The yield of
these degradation products was higher in the vacuum
environment as opposed to those irradiated in atmospheric
conditions, thus highlighting the role of oxygen as a radical

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J Inorg Organomet Polym (2008) 18:207–221
Fig. 8 (a) Ultimate strength as a function of radiation dose for filled
and unfilled elastomeric systems and (b) Ultimate elongation as a
function of the radiation dose for filled and unfilled systems [41]
Fig. 9 Plot of percent change in crosslink density against radiation
dose (crosslink density increases in the downward direction) [42]
215
scavenger. This is analogous to some of the studies
described for linear polysiloxanes described above
involving main chain scission and subsequent degradation
products [36–38].
Dynamic mechanical analysis of filled PDMS-PDPS
copolymer systems has revealed the apparent hardening and
the decrease in the segmental mobility of the elastomer by
monitoring the equilibrium storage modulus with increasing
radiation dose. As expected, a direct dependence is
observed due to a predominant crosslinking reaction [43].
3.3 Effects on Crystallization Behavior
Crosslinking on irradiation leads to a dramatic change in
the segmental dynamics of the elastomer, reducing the free
motion of the polymer chains. This has to manifest itself in
the crystallization behavior of the material because seg-
mental motion is vital for the polymer chains to reach the
crystallization nucleus and contribute to the overall degree
of crystallinity in the material.
Crystallization studies on irradiated silicone rubbers
indicated that the degree of crystallinity and the rate of
crystallization decreases with an increasing radiation dose
and a dose of 100 Mrads almost entirely eliminates crys-
tallization. There was observed to be a drop of about 20 °C
in the melting point for doses up to 40 Mrads. However,
changes in Tg were insignificant [44]. This impairment in
crystallization is to be expected on account of the observed
crosslinking in the rubber and was corroborated by several
later studies [43, 45, 46].
3.4 Toxicity Studies
It is clear from this discussion so far that silicones upon
irradiation primarily undergo crosslinking with minor
amounts of degradation products being formed as a result
of main chain scission. However the degradation products
happen to be cyclic siloxanes of low molecular weight in
extremely small amounts, trapped inside the matrix. Thus
they are expected to be equally benign to a cellular envi-
ronment. According to the Silicones Environmental, Health
and Safety Council of North America (SEHSC), there is no
evidence of toxicity issues or adverse health effects when
D4 and D5 are used as intended in personal care products.
In vitro cytotoxicity studies on irradiated silicone rubbers
further confirmed this observation [45].
Cells were cultured in the presence of irradiated silicone
samples and viability was measured by the neutral red
uptake assay in the presence of positive and negative con-
trols. Phenol was used as a positive control and PVC pellets
were used as a negative control. The behavior of the silicone
samples mimicked that of the negative control indicating
that no cytotoxicity occurs upon irradiation (Fig. 10).
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Fig. 10 Cell viability curves by neutral red uptake assay for silicones
irradiated at 50 kGy [45]
4 Cyclic Polysiloxanes
This class of compounds has the general structural formula
(RR0 SiO)n, where values of n up to 500 have been observed in
well equilibrated mixtures. When R=R0 =CH3, the rings can
simply be labeled as D (D5, D6 and D7). Some of the most
commonly prepared compounds in this series include cyclic
poly(dimethylsiloxane) [(CH3)2SiO]n, cyclic poly(vinyl-
methylsiloxane) [CH2=CH(CH3)SiO]n and cyclic poly
(phenylmethylsiloxane) [C6H5(CH3)SiO]n. The primary use
of cyclic siloxanes is in the synthesis of linear polysiloxanes
through ring-chain equilibration reactions and ring-opening
polymerization. Ring-opening polymerization requires a
break in the backbone Si–O bonds of the cyclic structure.
Thus, cyclic structures such as D3 and D4, with inherent
strain in them due to strained bond angles, are preferred for
polymerization.
4.1 Radiation Polymerization of Cyclic Siloxanes
Polymerization of cyclic siloxanes requires ionic initiators
for siloxane bond rearrangement reactions to occur. High
energy radiation can generate both ions as well as radicals
in the monomeric materials and thus there was a possi-
bility of initiating polymerization in cyclic siloxanes by
ionizing radiation. However, early attempts to polymerize
the cyclic trimer (D3) by high energy electrons gave poor
yields [47]. Also, the polymerization could be carried out
only in the solid state and as soon as the monomer
transformed to above its melting point, the polymerization
yield reduced to zero. This hinted towards a terminating
agent in the liquid state or the absence of proper propa-
gating species in the liquid state. Also the mechanism
could not be established and the dependence of the yield
on the radiation dose rate led to speculation that the
mechanism was free radical based. However, the kinetics
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J Inorg Organomet Polym (2008) 18:207–221
of polymerization in the solid state are complex, making
this an over-simplified assumption.
Attempts made to polymerize the cyclic tetramer by
gamma radiation led to a mixture of dimeric products and
high molecular weight linear and cyclics components [48].
The dimers were produced in very small yields along with
gases like hydrogen, methane and ethane. These dimers were
produced through Si–Si, Si–CH2–Si and Si–CH2–CH2–Si
linkages. There was correspondence between the gas yields
and the yield of dimers which confirmed the mechanism.
However for the polymer to form, siloxane ring rear-
rangement had to occur. This would involve the opening of
a ring which would lead to subsequent opening of other
rings to be incorporated into the polymer chain. Since most
ring opening catalysts are ionic, it was speculated that
radiation produced an ion of the nature shown in Fig. 11.
Starting from the silicenium ion, a reaction sequence for
the formation of linear PDMS would then be represented as,
M ! Mþ þ CH3 þ e
Mþ þ C ðinhibitiorÞ ! P (unreactive species)
Mþ ! Rþ (rearrangement to radical ion)
Rþ þ M ! RMþ
RMþ þ M ! RMþ
2 ðpropagation stepÞ
RMn1 þ M ! RMþ
n
RMþ
n þ e ! RMn ðcharge neutralization termination stepÞ
Chawla and St. Pierre reported that gamma irradiation
initiated liquid state polymerization of both D3 and D4 [49].
The previously known polymerization of D3 was in the
solid state. Appreciable yields were obtained when both the
monomers were in the ‘ultra pure’ and ‘ultra dry’ states.
To determine the nature of the propagating species
(anionic or cationic), it is necessary to use electron scav-
engers. If the propagating species is cationic, then it will be
terminated by an anionic species in the reaction. Thus, if we
Fig. 11 Silicenium ion produced as a result of gamma irradiation of
the cyclic tetramer [48]
J Inorg Organomet Polym (2008) 18:207–221 217

add a cationic species to the reaction, which will act as a

scavenger to all the anions present in the reaction, the rate of
polymerization will increase [50, 51]. Work was carried out
using nitrous oxide as a potential electron scavenger. This
led to a 4-fold increase in the rate of polymerization which,
consequently, indicates that the polymerization reaction
propagates through a cationic species [50] (Fig. 12).
Rapid advances have since been reported in a number of
other studies. With the use of ultra dry (obtained by contact
with a series of sodium mirrors) and ultra pure monomers, Fig. 13 Reaction sequence for ROP of gamma radiation initiated D4
polymerizations could be carried out both in liquid as well [54]
as in solid states with different rate dependence for both.
Molecular weight measurements indicated that linear
PDMS with molecular weight going up to several million
can be formed [51]. Polymerization of D5 in the liquid state
has also been successfully reported [52].
In all these cases, the product obtained contains a small
percentage of cyclics which are presumed to be formed by
backbiting reactions. These reactions compete with the
primary propagation reaction and originate from the same
cationic active center generated by gamma irradiation [52–
54]. The same type of active center was formed for all the
three monomers i.e. D3, D4 and D5. The initial rates, the
final leveled off conversions, the concentration of cyclics
formed by backbiting and the activation energies were
consequently the same for all three monomers [54]. These
results are completely different from chemically-initiated
species. Thus, a possible reaction sequence for polymeri-
zation of cyclic PDMS is shown in (Fig. 13).
The plot of the rate of polymerization for both D4 and
D5 and for the square root of the radiation dose rate was
linear and passed through the origin, as is the case for ionic
polymerizations in the absence of impurities. Addition of
ammonia and triethylamine inhibited the polymerization
process, further corroborating the cationic mechanism for
propagation [53] (Fig. 14).

Fig. 14 Plot of the rate of polymerization vs. square root of radiation

dose [54]

The same mechanisms of silicenium ion formation by

gamma irradiation and the subsequent ring opening poly-
merization has also been applied to co-polymerizations of
D3 with D4 and D4 with D5. For further details regarding
the same, readers are directed towards texts describing the
process in detail [55].

4.2 Irradiation of Cyclic Poly(dimethylsiloxane)

We have discussed above the investigations that have been

reported in the literature on the gamma irradiation of low
Fig. 12 Plot showing the percent yield of the polymer against molar mass cyclic siloxanes. We have also performed
concentration of nitrous oxide [50] studies on the effects of irradiation of well characterized

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cyclic poly(dimethylsiloxane) sharp fractions (S. J. Clarson would cause a drop in the apparent crosslinking
et al., Unpublished results). One of the reasons for these density and small changes in the modulus.
studies was the idea that networks formed from large rings
The phenomena described above are occurring concur-
can have unique physical properties [56, 57]. In particular,
rently when a device is exposed to sterilizing radiation. As
these ‘model networks’ would perhaps be unique in that if
a result, the effects may compensate for each other causing
the cross-linking chemistry is solely via hydrogen
negligible noticeable changes in the structure and in the
abstraction (and therefore Si–CH2–CH2–Si linkages), then
mechanical properties of the product.
such networks would contain no dangling chain ends.
Recently, we have investigated a variety of aspects of
Another point worth noting is the susceptibility of the
the effects of gamma irradiation on the properties of
Si–H linkage in various organosilicon compounds to radi-
commercial biomedical grade silicone elastomers before
ation damage. After studying the gas yields upon exposure
and after sterilization. These investigations have included
to gamma radiation, Warrick observed that the Si–H bond
sol-fraction determination and analysis, thermal aging
is 30 times more prone to radiation rupture than the C–H or
studies, and dynamic mechanical modulus measurements
Si–C bonds. Thus, hydride terminated silicones and other
and some results from these investigations are presented
materials containing the silyl hydride functionality are
here.
particularly sensitive to radiation damage [58].
Storage modulus measurements were conducted on a
Mettler Toledo 861E Dynamic Mechanical Analyzer in a
tensile clamping mode as a function of the temperature.
5 Observations The experiments revealed an increase of about 8.3% in the
storage modulus of the gamma sterilized silicone rubber as
Silicone medical devices are sterilized in the final product shown in Fig. 15 (A.S. Palsule et al., 2006, Unpublished
form after packaging by exposing them to gamma radiation results).
or to a high energy beam of electrons. Many of the prod- Modulus measurements were accompanied by the
ucts are in a covalently crosslinked elastomeric form and quantification of extractable sol content in the elastomer.
some of them may contain a lightly crosslinked silicone The silicone sample was swollen in toluene to open up the
gel. A small fraction of uncrosslinked oligomeric fractions diffusion paths in the network. This allowed the low
of linear and cyclic polysiloxane are also known to occur in molecular weight uncrosslinked oligomeric fractions to
the elastomeric part of the device. They are trapped in the leach out of the network. The sample was then shrunk in
network elastomeric phase and several weight percent of
such materials can often be extracted from the device by
swelling in toluene or other appropriate solvents.
On the basis of the studies described above, it is rea-
sonable to make the following observations regarding the
effect of sterilizing radiation on a silicone medical implant.
(1) The implant is made up of a pre-cured elastomer with
the optimum cure having been decided by the balance
of mechanical properties. For a peroxide cured
material, additional crosslinking may occur during
sterilization. This may result in the incorporation of
the oligomeric, extractable, previously uncrosslinked
fractions in the network structure.
(2) Crosslinking dominates over main chain scission
when silicones are exposed to gamma radiation.
However, small amounts of chain scission can occur
which leads to backbiting and formation of small
amounts of low molecular weight cyclic and linear
polysiloxanes. These products are again trapped in the
network and can be subsequently crosslinked in to the
network structure.
(3) Radiation may cause breakage of the hydrogen bonds
Fig. 15 Storage modulus of gamma sterilized and unsterilized
at the filler interface between the surface silanol silicone implantable elastomer obtained by DMA measurements
groups of the filler and the siloxane polymer. This (A.S. Palsule et al., 2006, Unpublished results)

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J Inorg Organomet Polym (2008) 18:207–221
Sterilized Silicone
Unsterilized silicone
TGA of sterilized and unsterilized Silicone
4.5
4
Weight(mg)
3.5
3
2.5
0 200 400 600 800
Temperature (C)
Fig. 16 Thermogravimetric data of gamma sterilized and unsterilized
silicone (A.S. Palsule et al., 2006, Unpublished results)
methanol and the sol fraction was calculated by monitoring
the weight loss in the sample. The procedure was repeated
for both the sterilized and unsterilized samples. This
analysis revealed an average drop of 17.5% in the sol
fraction of the sterilized sample, which indicated a post
sterilization increase in the crosslinking of the elastomer as
was evident from the increase in the modulus.
Finally, thermogravimetric degradation studies of the
material did not reveal any significant changes in the
degradation characteristics of the material post steriliza-
tion. There was no observable evidence of the formation of
low molecular weight degradation products upon gamma
irradiation of the silicone and, thus, it is safe to assume that
the net effect of gamma radiation on silicones is to increase
the crosslinking in the elastomer as has been proposed
above (A.S. Palsule et al., 2006, Unpublished results)
(Fig. 16).
5.1 Different Units of Radiation Dose Used in the
Review and Their Inter-Conversions
(1) Gray (Gy, MGy) is the SI unit of absorbed dose and
one gray is equal to an absorbed dose of 1 joule/Kg
(2) Rad (Mrad) is also a unit of the absorbed dose and
one rad dose is equal to an absorbed dose of 100 ergs/
gram
(3) Rep (Mrep) is an obsolete unit of radiation dose and it
is an acronym for Roentgen equivalent physical. It is
equal to an absorbed energy dose of 93 ergs/gram
219
Thus, we can say that,
1 Rad = 0.01 Gy or 1 centigray and 1 Rep = 0.93 Rad
or 9.3 milligrays.
6 Concluding Remarks
Based on the review of the existing literature on the gamma
irradiation of silicones, it is reasonable to suggest that
sterilization of silicones by gamma irradiation has the
potential to be a more efficient and more effective tech-
nique when compared to thermal or chemical treatments.
We certainly hope that those of you who that have
reached this point in the text have found the material
presented herein and the associated bibliography compiled
to be useful to you. As the use of silicones as biomedical
materials continues to expand, we fully anticipate that we
will revisit this topic at some suitable point in the future. At
1000
that time, we will either prepare an updated article or
provide an appendix to this one. We therefore openly
welcome any comments on this text and also any sugges-
tions that you may have for material to be included in the
future.
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