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Polyvinylsiloxanes in Dentistry: An Overview

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Trends Biomater. Artif. Organs, 27(3), 115-123 (2013) http://www.sbaoi.org/tibao

Review Article

Polyvinylsiloxanes in Dentistry: An Overview

Hemchand Surapaneni1*, Pallavi Samatha Y2., Ravi Shankar Y., Sirisha Attili
Department of Prosthodontics1, Department of Periodontics2, Drs.Sudha &Nageswara Rao Siddhartha Institute of Dental
Sciences, Chinaoutpalli, Gannavaram Mandal,Vijayawada, Krishna District 521286 Andhra Pradesh, India
Department of Prosthodontics, GITAM Dental College and Hospital, Gandhi Nagar Campus, Rushikonda,
Visakhapatnam 530045, Andhra Pradesh, India
Department of Prosthodontics, St.Joseph Dental College, Eluru,West Godavari District 521286 Andhra Pradesh, India
*Corresponding author, Dr. Hemchand Surapaneni, hemchand_18@yahoo.co.in

Received 27 December 2012; Accepted 16 June 2013; Available online 21 July 2013

Polyvinylsiloxanes are elastomers that remain in an elastic or flexible state after they have been removed from the mouth. The
elastic impression materials are most generally used for the making of impressions for removable partial dentures, immediate
dentures, and crowns and fixed partial dentures when tooth and tissue undercuts and surface detail must be recorded with
accuracy. Today, their use far exceeds the use of all other impression materials in general dental practice because of their
hydrophilicity, ability to record accurate impressions because they reproduce fine surface detail, and have excellent elastic
recovery, adequate tear strengths, and exceptional dimensional stability. In this review, the chemistry and important physical
properties of polyvinylsiloxanes are summarized, and recent clinical questions of improved hydrophilics, tray adhesives,
disinfection, and glove-induced polymerization inhibition are addressed.

Introduction rubber consistency. Polyvinyl siloxane (PVS) impression

Historically, various impression materials are used to
record intraoral structures for the fabrication of definitive
restorations. Impression materials too have gone through
a tremendous phase of development. Knowing the
physical and biological properties as well as the
advantages and disadvantages of different impression
materials, is a prerequisite for adequate practical
application of dental materials and contributes to the
success of prosthetic therapy. In the 1950s the rubber
base materials, first in the form of the polysulfide and
later the silicone, polyether began to be used as dental
impression materials [1]. Elastomers are a group of
elastic impression materials. General reviews of rubber
impression materials by Craig (1977), Harcourt (1978),
and McCabe and Storer (1980) have been published, as
have a status report on polyethers (Council on Dental
Materials and Devices, 1977) and an appraisal of addition
silicone impression materials (McCabe and Wilson,
1978).There are four groups of Elastomers: polysulfides,
polyethers, condensation and addition silicones. Addition
silicones (polyvinylsiloxanes) have a moderately low-
molecular weight silicone that contains silane groups that
bind together in a network of chains that give material a
materials represent the state of the art in elastomeric
impression materials in prosthodontics and restorative
dentistry [2-5] used for recording the impressions of
dentulous and edentulous arches, duplication of casts and
bite registrations. Recently, new elastomeric impression
materials with very high elastic recovery and high tear
strength have been introduced.
Composition and chemistry of
Polyvinylsiloxane
Polyvinylsiloxane (or PVS) is often called ‘viny
polysiloxane’ (or VPS) as well. Since it is based on
silicone chemistry, it has sometimes been referred to as
an addition-silicone. Amorphous polymers of silicone
and oxygen atoms (Fig 1) which are randomly coiled
like spaghetti, (Fig 2) translucent or transparent because
of the lack of crystallinity, tend to be flexible rather than
brittle. Polyvinyl siloxane materials are a modification
of the original condensation silicones. Both are based
on the polydimethyl siloxane polymer; however the
presence of differing terminal group’s accounts for their
different curing reactions [6] .Elastic properties can be
obtained by cross linking and addition of the long chains.

115
 H. Surapaneni, P.S. Yalamanchili, R.S. Yalavarthy, S. Attili
Fig 1: Polydimethyl siloxane amorphous polymers of
silicone and oxygen atoms
Fig 2: Amorphous polymers of silicone and oxygen atoms
which are randomly coiled like spaghetti
These oligomers are double-bond-functional silicones
which become polymerized by free radicals from
chloroplatinic acid.
The base material contains a polymethyl hydrogen
siloxane copolymer, which is a moderately low molecular
mass polymer with silane terminal groups [6, 7]. The
accelerator material contains the vinyl-terminated
polydimethyl siloxane. This is also a moderately low
molecular mass polymer but has vinyl terminal groups
[6, 7]. The accelerator material also contains
chloroplatinic acid as a homogeneous metal complex
catalyst [8-10]. The mixture is filled with silica because
that is the only thing with the right degree of
hydrophilicity to be blended into the material.
Polyvinylsiloxanes (PVS), used as dental impression
materials, were formulated with the variation of loading
combination of six types of fillers including nano-sized
fumed silica. The fillers were blended with three types of
silicone polymers together with cross-linker and inhibitor
in base paste and with plasticizer and platinum catalyst
in catalyst paste. By replacing parts of crystalline quartz
with other fillers, the setting time became much faster.
The test group in which quarter of quartz was replaced
with fumed silica showed the most ideal working and
setting time for clinical use. There was a negative
correlation between pH and setting time (p < 0.05).
Combining the fumed silica was effective in increasing
the viscosity, tensile strength and maximum% strain.
Combining the diatomaceous earth reduced the setting
time and maximum% strain, and dramatically increased
the viscosity and tensile strength. The best modulation of
physical properties of PVS material was possible by
116
combining fillers during the formulation. The base and
accelerator pastes also contain fillers. Amorphous silica
or fluorocarbons are used as fillers to add bulk and
improve the properties of the paste. The filler is also
normally silanated to increase the bond strength between
filler and polymer, which better allows it to function as
across – linker [11]. Colouring agents are added to
distinguish the base and catalyst pastes and to aid
evaluation of mixing. More recently, intrinsic surfactants
have also been added in an attempt to negate the
hydrophobicity of these materials[12].Compositions are
proprietary however they are usually supplied in two
equal-size tubes, often in cartridges for use in an automix
dispenser gun. The base-to-catalyst ratio is 1:1. Newer
addition silicones have been formulated to be more
hydrophilic. Shelf life is usually about 2 years but is
reduced by warm conditions.
Setting Reaction
Poly vinyl siloxane + silane siloxane —–Pt, Salt —–> silicone rubber
On mixing, an addition reaction occurs between the silane
and vinyl groups (Fig 3). There is crosslinking of a vinyl
terminated polydimethyl siloxane catalyzed by a platinum
salt (chloroplatinic acid). Hydrogen gas is a byproduct
of the polymerization reaction. Several authors have
reported hydrogen gas bubble formation on the surface
of gypsum dies poured immediately from polyvinyl
siloxane impressions [3, 13]. Hydroxide groups in many
products produce hydrogen gas, resulting in small bubbles
on the model surface (Fig-4) if pouring is not delayed by
30-60 minutes. Many of these addition silicones contain
catalysts like palladium that absorb this hydrogen.
Manufacturers have now eliminated the possibility of this
side reaction by proper purification and accurate
proportioning of the materials, and by the addition of
palladium to the pastes as a hydrogen absorber [9, 10]. It
is no longer necessary to wait for one hour before pouring
these impressions.
Retardation of the setting reaction of addition silicones
can occur if they come into contact with latex gloves or
Fig 3: Reaction: Ionic Polymerization
 Polyvinylsiloxanes in Dentistry: An Overview
Fig 4: Hydroxide groups in many products produce
hydrogen gas, resulting in small bubbles on the model
surface if pouring is not delayed by 30-60 minutes.
other rubber products. This was first encountered when
putty consistency addition silicones were mixed with
gloved hands. Slowing of the setting time may even result
from contact of the impression material with the patient’s
teeth after the operator has touched the teeth with his
gloves. It is theorized that residual sulfur in the gloves
(which serves as an accelerator and/or surfactant in the
manufacture of rubber latex) inhibits the action of the
platinum salt catalyst [14]. Some researchers believe that
Fig 5: Polyvinylsiloxane materials and equipment
it is the powder on gloves that is the source of the problem,
but others question this [15]. In addition, sulfur-
containing retraction cord additives such as ferric sulfate
(found in Astringent) and aluminum sulfate may also
produce this effect. Gloves and the inhibition of
polymerization occasionally an inhibition or retarding
effect is seen on polyvinlsiloxanes when they are used in
a clinical setting. This phenomenon can occur after direct
contact between the impression material and latex gloves,
or a region of the mucosa previously touched by latex
gloves [15, 16, 17, 18, 19].
It was initially suspected that the corn starch powder used
as a lubricant in the gloves was interacting [17] while
other authors suggested atmospheric oxygen inhibition,
or interactions with haemostatic agents were the cause.
Several haemostatic agents were tested before
DeCamargo et al [20] concluded that they were not the
inhibitors. Jones et al [21] were able to show that
provisional luting agents did not interfere with the
polymerization. A sulphur compound has since been
identified as being responsible for the retarding effect on
polymerization. Zinc diethyl dithiocarbamate is an
accelerator used in the manufacture of the latex gloves.
It reacts with the platinum catalyst in the polyvinyl
siloxane to cause a delay or total inhibition of
polymerization [15, 19, 22] reported that even in
concentrations as low as 0.005 per cent, total inhibition
of polymerization of polyvinyl siloxane can be observed.
It is also believed that the compound can remain on a
previously gloved hand, and so washing gloves or
washing hands after glove use is not recommended as a
means of avoiding contamination. Interestingly, not all
latex gloves will cause an inhibition of set. It has been
117
 H. Surapaneni, P.S. Yalamanchili, R.S. Yalavarthy, S. Attili
Fig 6: Maxillary arch impression with Stock tray
observed that synthetic latex gloves do not produce this
phenomenon, while some natural latex gloves do [18, 19,
23].
Advantages and Disadvantages
Advantages: Excellent dimensional stability, good tear
strength, good working and setting times, excellent
wettability, automixed system(Figure-5), short setting
time, adequate tear strength, extremely high accuracy,
minimal distortion on removal, dimensionally stable even
after 1 week, If hydrophilic, good compatibility with
gypsum. There are no reports of patient sensitivity to the
addition silicones.
Disadvantages: Hydrogen gas release, inhibition of setting
by sulfur-containing materials, expensive, Hydrophobic
& hence requires a very dry field.
Each group of material has its advantages and
disadvantages [24].Their main advantages are low
polymerization shrinkage, long-lasting dimensional
stability and endurance, and an absence of toxic or
allergenic behaviors [25-29].Impression detail (Figure
6&7)is influenced by factors such as viscosity, wettability
[30-35], handling properties [36-38], and the presence
of voids [39-43] .Two principal characteristics of the
impression material are accuracy and dimensional
stability [44-47].
Properties
Viscosity
Polyvinyl siloxanes are available in viscosities ranging
from very low (for pouring, syringing or wash use), to
118
medium, high and very high. The viscosity of the material
increases with the proportion of filler present. Viscosity
is also affected by the shear force placed on the material.
The mixed base and catalyst pastes exhibit a decrease in
their relative viscosities in response to high shear stresses.
This is termed shear thinning. Thus a medium body
impression material can possess sufficient viscosity to
avoid excess flow if loaded into an impression tray, yet it
can also exhibit an apparent lowered viscosity suitable
for intrasulcular impressions, when it is expressed through
an impression syringe tip. [7, 48].The higher the viscosity
of the material, the more pronounced is the effect of shear
thinning. This phenomenon is suggested to be due to the
extremely small filler particle size. [48]
Working and setting times
Modern polyvinyl siloxanes have a working time of two
minutes and a setting time of six minutes (with slight
variation) [3, 13]. They are more sensitive to temperature
than polysulfide, can be extended by cooling or adding
retarder. Ratio of base: Accelerator does not change
working & setting time.These times are considered to be
adequate if not ideal. Occasionally, situations will present
which require extended working times and some methods
of altering working and setting times have been reported
in the literature. Alteration of the proportion of catalyst
is to be avoided as this leads to variable results and has
been suggested to facilitate the side reaction which
produces hydrogen gas. Some manufacturers supply a
retarder that can be incorporated into the mix to provide
additional working time without compromising other
properties [3].
 Polyvinylsiloxanes in Dentistry: An Overview
Fig 7: Maxillary arch impression with custom tray
The retarder is a small, reactive, tetracyclic vinyl molecule
that polymerizes preferentially to the siloxane
copolymers. This small molecule is cyclic and does not
form a chain. It is thus a chain stopper, and temporarily
prevents polymerization of the linear siloxane molecules.
The retarder continues to polymerize until it is completely
consumed and then the linear siloxane molecules
polymerize causing the impression material to set. The
most convenient and widely advocated method for
extending working time is to refrigerate the materials
before mixing. Gains of up to 90 seconds have been
reported when the materials are chilled to 2°C [3, 49]. It
is a good idea to store the addition silicones in a
refrigerator and use them immediately after removal
because the cool storage conditions act to lengthen the
working time by about 1.5 minutes without adversely
affecting the material’s accuracy.
Reproduction of detail
Polyvinyl siloxanes are currently considered to reproduce
the greatest detail of all the impression materials. The
international standard for dental elastomeric impression
materials1 states that a type III (light body) impression
material must reproduce a line 0.020 mm in width. With
the exception of the very high viscosity putty materials,
all polyvinyl siloxanes (light, medium and heavy body)
achieve this. Very low viscosity materials can reproduce
lines 1-2 μm wide [7, 50, 51]. Further, PVS materials
have the best fine detail reproduction and elastic recovery
of all available materials.[52]. It should be noted that the
literature does not tend to support the use of putty and
wash impression techniques for greatest accuracy in
impressions. Wassell and Ibbetson [53] reported that
heavy body and wash impressions were more accurate
than putty and wash impressions. Frederick and Caputo
[54] further showed that the putty and wash technique
was significantly less accurate than polyether (heavy and
light body) or reversible hydrocolloid impressions.
Dimensional stability
The accuracy of an impression material is dependent on
the dimensional stability. There are a number of possible
causes for dimensional changes in elastomeric impression
materials. The major factors affecting the dimensional
change of the impression are thermal contraction,
polymerization shrinkage, and contraction due to the loss
of volatile by products [55]. Polyvinyl siloxanes show
the smallest dimensional changes on setting of all the
elastomeric impression materials. Long term dimensional
stability of polyvinylsiloxanes is reported in the literature.
This is because they are not susceptible to changes in
humidity, and they do not undergo any further chemical
reactions or release any by-products.
[3,6,7,13,52,56,57,58]. Tjan et al [59] evaluated the
accuracy of monophase polyvinyl silicones and found that
repeat pour at later time periods, did not affect the
dimensional accuracy and stability of impression made
with these materials. Polyvinyl siloxane impressions may
be repoured to produce stone dies which are as accurate
as the original, as many as seven days later [58].The linear
coefficient of thermal contraction is relatively high for
all elastomers. When an impression is removed from the
mouth, there is an element of shrinkage due to the decrease
in temperature that occurs as the material moves from
the mouth to the bench. Lower viscosity materials show
the greatest change (0.02-0.05 per cent shrinkage) due to
119
 H. Surapaneni, P.S. Yalamanchili, R.S. Yalavarthy, S. Attili
their lower filler content[56].Reheating an impression to
37°C before pouring has been demonstrated to improve
the accuracy of the resultant die; however it is doubtful
that this is clinically significant. [49,56] The addition
silicones have excellent dimensional stability with
shrinkage over 24 hours of only 0.05%.
Tear energy, elastic recovery and deformation
Polyvinyl siloxanes are frequently reported to be the most
ideally elastic impression materials because they exhibit
better elastic recovery and less permanent deformation
than the other elastomers. They can absorb over three
times more energy up to the point of permanent
deformation than other elastomers, and if elongated to
over 100 per cent (strain at tear), they rebound to only
0.6 percent permanent deformation [60]. Permanent
deformation is related to the degree of cross-linking of
the polymer strands, temperature, and the rate of applied
stress. The ideal impression material should exhibit
maximum energy absorption with minimal distortion.
However, it is also desirable that the material tears rather
than deforms past a critical point such as a margin.
Polyvinyl siloxanes deform at much slower rates and tear
at points of less permanent deformation than do the other
elastomeric materials [60]. Blomberg et al [61] reported
that polyvinyl siloxanes have sufficient elastic recovery
to allow an impression to be poured only six minutes after
removal from the mouth.
Marcinak and Draughn[62] evaluated the dimensional
change in addition silicones by delaying the pouring of
impressions from 2 h to one week. They concluded that
these materials remained remarkably accurate even after
one week, with the greatest change at any time being
0.3%. Lacy et al [27] investigated the time dependant
accuracy of elastomeric impression materials and
concluded that polyvinyl siloxanes were the most stable
of elastomers.
Creep compliance
All elastomers are viscoelastic materials, implying that
deformation and elastic recovery are time dependent as
well. Therefore, the longer the material is deformed (as
occurs when impressions are removed slowly from the
mouth or separated slowly from a poured model), then
the longer time it takes for elastic recovery and the
possibility of permanent deformation becomes higher.
Polyvinyl siloxanes have the least viscoelastic qualities
thus requiring the least time for recovery from viscoelastic
deformation.
Radiopacity
Radiopacity of impression materials is important for
radiographic identification of excess material which may
be accidentally swallowed, aspirated or left in gingival
tissues. Presently, only the polysulphide materials exhibit
significant radiopacity due to their lead dioxide content.
120
Shillingburg et al [63] tested an experimental polyvinyl
siloxane material containing 20 per cent barium sulphate
to improve radiopacity. Although they were able to
demonstrate qualities of radiopacity equal to that of the
polysulphides, there were associated physical property
drawbacks including hydrogen bubble formation in dies
poured from the impressions, and evidence of long term
breakdown limiting the shelf life.
Wettability
An impression material should have intimate contact with
the tooth and underlying soft tissues and should not form
bubbles or voids. Wettability is best with a hydrophilic
material. Material should possess ability to displace
moisture. According to O’Bri e n, wetting describes the
relative affinity of a liquid for a solid. It is the degree to
which a drop will spread on a solid surface, and can be
quantified by observing the contact angle. High angles
(greater than ninety degrees) indicate poor wetting, whilst
a zero angle would indicate perfect wetting of the surface.
Early forms of the addition silicones were hydrophobic,
however most now available are hydrophilic because of
inclusion of surfactants which reduce their contact angles
with gypsum from approximately 90 to 50 degrees. This
makes their contact angles with gypsum similar to those
of the hydrophilic polyethers. [64]
When discussing the wetting characteristics of impression
materials, it is important to distinguish between the ability
of the material to flow around the soft and hard tissues of
the mouth, and the ability of the material to be wet by
gypsum slurry. Polyvinyl siloxanes are inherently
hydrophobic, however in recent times; new ‘hydrophilic’
polyvinyl siloxanes have been introduced with
manufacturer claims that they better wet moist dental
surfaces. These new formulations have intrinsic
surfactants added. Typically these are non-ionic
surfactants of phenoxypolyethanol homologues [65-69].
There is no scientific evidence to indicate that polyvinyl
siloxanes advertised as ‘hydrophilic’ can be syringed into
a wet sulcus for an accurate impression [50, 65, 66]. It
has also been shown that the newer hydrophilic materials
perform no better than the original formulations of
polyvinyl siloxane in wettability for pouring dies, if a
compatible, extrinsic, spray-on surfactant is applied
before pouring[ 65,66].
This has been confirmed by Takahashi and Finger [70]
who demonstrated that under a simulated clinically dry
field, both the hydrophilic and original f ormulations of
polyvinyl siloxane wet tooth structure with equal results.
The application of an extrinsic surfactant to the surface
against which an impression is to be made has also been
suggested. Millar and co-workers [71] reported a
significant reduction in the number of voids and an overall
increased quality of polyvinyl siloxane impression when
a modified polydimethyl siloxane wetting agent was
applied to the prepared tooth surfaces before impressions
were made.
 Polyvinylsiloxanes in Dentistry: An Overview
Impression trays and adhesives
VPS adhesives (blue) for polyvinyl siloxane
impression materials
The improved physical properties of modern elastomers
and particularly polyvinylsiloxanes the use of stock trays
for impressions has become common practice for reasons
of cost and convenience [59].Common stock trays made
of polystyrene or chromium plated brass are reported to
be suitably stiff to prevent flexure or distortion, although
there remains some possibility of tray wall flexure with
polystyrene trays[38,53]. The use of adhesives in trays
has been shown to achieve higher material bond strengths
for polyvinyl siloxanes than has mechanical retention [72,
73]. The adhesives used are usually polydimethyl siloxane
and ethylsilicate. The adhesive reacts with the surface of
the tray material and forms a chemical bond to the tray
and to the impression material. It is generally
recommended to wait for ten to fifteen minutes after
application of the adhesive before making the impression
[73].This allows time for the solvent to react with the
tray material.
Chai et al. [38] reported that adhesive strength to acrylic
resin (custom trays) was significantly lower than
polystyrene or metal stock trays for the polyvinyl
siloxanes. Investigations into their bond strengths with
polyvinyl siloxane adhesives indicate that they bond better
than polymethyl methacrylate materials provided that the
air inhibited non-polymerized layer is removed with
isopropyl alcohol or a carbide bur [72,74]. Sulong and
Setchell [75] demonstrated that roughening the surface
of the impression tray will significantly improve the
effectiveness of polyvinyln siloxane adhesives.. In many
clinical situations, the impression tray must be tried in
the mouth prior to impression making and this leads to
saliva contamination. If the tray has already been painted
with adhesive, then subsequent application is
recommended to maintain bond strengths. Contaminated
adhesives have shown a drop in bond strength to one-
fifth of their original amount.
Disinfection
Disinfection is the inhibition or destruction of pathogens
and can be achieved by immersion of an impression into
antimicrobial chemical solutions for 3 to 90 minutes
depending on the agent. Sterilization is the total
elimination of all micro-organisms and spores and
requires immersion periods of 6 to 10 hours. Herrera and
Merchant [76] tested the dimensional stability of different
impression materials following immersion disinfection
for thirty minutes. They observed that polyvinyl siloxane
and polysulphide were unaffected after immersion in
sodium hypochlorite, 2 per cent glutaraldehyde, 0.5 per
cent povidone-iodine and 0.16 per cent halogenated
phenol whilst polyethers were significantly unstable. Even
after extending the immersion times to sixty minutes, Del
Pilar Rios et al [77] agreed with the findings of Herrera
and Merchant. Johansen and Stackhouse [78]
demonstrated that polyvinyl siloxanes were able to be
immersed in 2 per cent glutaraldehyde for 16 hours
without any observed dimensional changes, whilst
polyether materials showed dramatic distortions under
the same conditions. Holtan et al. [79] measured the
dimensional stability of polyvinylsiloxanes after
sterilization procedures using a conventional steam
autoclave, and an ethylene oxide gas autoclave. They
determined that sterilization in ethylene oxide gas resulted
in gas inclusions into the impression material which then
formed bubbles in dies poured immediately from them.
Waiting to pour dies for 24 hours after gas autoclaving
prevented this problem. Impressions sterilized in the steam
autoclave did undergo distortion that would have been
significant enough to prevent a casting from seating. It
was concluded that steam autoclaving was a suitable
sterilization method if the impressions were not to be used
for fixed prostheses.
Most recently, radiofrequency glow discharging has been
advocated for use as a disinfecting procedure for polyvinyl
siloxane impressions [80]. Whilst this procedure is
claimed to clean and improve the wettability of the
impression surface, it is not clear if glow discharging
results in sterilization.
In Future
Continued efforts will be made to develop more effective
single-viscosity addition silicone systems, probably by
controlling the filler particle size and wettability of the
filler by the silicone. Hydrophilic addition silicones
should be developed further in order to improve the taking
of impressions and pouring of casts. Because of the
convenience and reduction in the number of voids,
development of automatic mixing systems, static and/or
mechanical, will continue. With the development of
information on the visible curing composites of the BIS-
GMA and urethane diacrylate, the commercial availability
of visible-curing rubber impression materials is almost a
certainty; the essentially unlimited working time at
constant viscosity would be a major advantage for this
type of system. The increased emphasis on disinfection
of impressions will stimulate the development of systems
that will disinfect polyethers without causing problems
with dimensional change.
Conclusion
Polyvinyl siloxane impression materials are routinely used
to record the impressions of dentulous and edentulous
mouths. The composition has been changing from time
to time to improve the clinical performance. It is evident
that all materials change dimensionally over time. The
present review suggests that addition silicones to a certain
extent were helpful in improving their clinical
performance and extending the use of the material in
various dental applications.
121
 H. Surapaneni, P.S. Yalamanchili, R.S. Yalavarthy, S. Attili

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