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Polyvinylsiloxanes in Dentistry: An Overview

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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, [email protected]

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

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

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 H. Surapaneni, P.S. Yalamanchili, R.S. Yalavarthy, S. Attili

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
Fig 1: Polydimethyl siloxane amorphous polymers of distinguish the base and catalyst pastes and to aid
silicone and oxygen atoms 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

Fig 2: Amorphous polymers of silicone and oxygen atoms and vinyl groups (Fig 3). There is crosslinking of a vinyl
which are randomly coiled like spaghetti 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
These oligomers are double-bond-functional silicones
of gypsum dies poured immediately from polyvinyl
which become polymerized by free radicals from
siloxane impressions [3, 13]. Hydroxide groups in many
chloroplatinic acid.
products produce hydrogen gas, resulting in small bubbles
The base material contains a polymethyl hydrogen on the model surface (Fig-4) if pouring is not delayed by
siloxane copolymer, which is a moderately low molecular 30-60 minutes. Many of these addition silicones contain
mass polymer with silane terminal groups [6, 7]. The catalysts like palladium that absorb this hydrogen.
accelerator material contains the vinyl-terminated Manufacturers have now eliminated the possibility of this
polydimethyl siloxane. This is also a moderately low side reaction by proper purification and accurate
molecular mass polymer but has vinyl terminal groups proportioning of the materials, and by the addition of
[6, 7]. The accelerator material also contains palladium to the pastes as a hydrogen absorber [9, 10]. It
chloroplatinic acid as a homogeneous metal complex is no longer necessary to wait for one hour before pouring
catalyst [8-10]. The mixture is filled with silica because these impressions.
that is the only thing with the right degree of
Retardation of the setting reaction of addition silicones
hydrophilicity to be blended into the material.
can occur if they come into contact with latex gloves or
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 Fig 3: Reaction: Ionic Polymerization

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 Polyvinylsiloxanes in Dentistry: An Overview

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
Fig 4: Hydroxide groups in many products produce
inhibitors. Jones et al [21] were able to show that
hydrogen gas, resulting in small bubbles on the model provisional luting agents did not interfere with the
surface if pouring is not delayed by 30-60 minutes. 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
other rubber products. This was first encountered when siloxane to cause a delay or total inhibition of
putty consistency addition silicones were mixed with polymerization [15, 19, 22] reported that even in
gloved hands. Slowing of the setting time may even result concentrations as low as 0.005 per cent, total inhibition
from contact of the impression material with the patient’s of polymerization of polyvinyl siloxane can be observed.
teeth after the operator has touched the teeth with his It is also believed that the compound can remain on a
gloves. It is theorized that residual sulfur in the gloves previously gloved hand, and so washing gloves or
(which serves as an accelerator and/or surfactant in the washing hands after glove use is not recommended as a
manufacture of rubber latex) inhibits the action of the means of avoiding contamination. Interestingly, not all
platinum salt catalyst [14]. Some researchers believe that latex gloves will cause an inhibition of set. It has been

Fig 5: Polyvinylsiloxane materials and equipment

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 medium, high and very high. The viscosity of the material
phenomenon, while some natural latex gloves do [18, 19, increases with the proportion of filler present. Viscosity
23]. is also affected by the shear force placed on the material.
The mixed base and catalyst pastes exhibit a decrease in
Advantages and Disadvantages their relative viscosities in response to high shear stresses.
This is termed shear thinning. Thus a medium body
Advantages: Excellent dimensional stability, good tear
impression material can possess sufficient viscosity to
strength, good working and setting times, excellent
wettability, automixed system(Figure-5), short setting avoid excess flow if loaded into an impression tray, yet it
time, adequate tear strength, extremely high accuracy, can also exhibit an apparent lowered viscosity suitable
minimal distortion on removal, dimensionally stable even for intrasulcular impressions, when it is expressed through
after 1 week, If hydrophilic, good compatibility with an impression syringe tip. [7, 48].The higher the viscosity
gypsum. There are no reports of patient sensitivity to the of the material, the more pronounced is the effect of shear
addition silicones. thinning. This phenomenon is suggested to be due to the
Disadvantages: Hydrogen gas release, inhibition of setting extremely small filler particle size. [48]
by sulfur-containing materials, expensive, Hydrophobic
& hence requires a very dry field. Working and setting times

Each group of material has its advantages and Modern polyvinyl siloxanes have a working time of two
disadvantages [24].Their main advantages are low minutes and a setting time of six minutes (with slight
polymerization shrinkage, long-lasting dimensional variation) [3, 13]. They are more sensitive to temperature
stability and endurance, and an absence of toxic or than polysulfide, can be extended by cooling or adding
allergenic behaviors [25-29].Impression detail (Figure retarder. Ratio of base: Accelerator does not change
6&7)is influenced by factors such as viscosity, wettability working & setting time.These times are considered to be
[30-35], handling properties [36-38], and the presence adequate if not ideal. Occasionally, situations will present
of voids [39-43] .Two principal characteristics of the which require extended working times and some methods
impression material are accuracy and dimensional of altering working and setting times have been reported
stability [44-47]. in the literature. Alteration of the proportion of catalyst
is to be avoided as this leads to variable results and has
Properties been suggested to facilitate the side reaction which
produces hydrogen gas. Some manufacturers supply a
Viscosity
retarder that can be incorporated into the mix to provide
Polyvinyl siloxanes are available in viscosities ranging additional working time without compromising other
from very low (for pouring, syringing or wash use), to properties [3].

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 Polyvinylsiloxanes in Dentistry: An Overview

Fig 7: Maxillary arch impression with custom tray

The retarder is a small, reactive, tetracyclic vinyl molecule heavy body and wash impressions were more accurate
that polymerizes preferentially to the siloxane than putty and wash impressions. Frederick and Caputo
copolymers. This small molecule is cyclic and does not [54] further showed that the putty and wash technique
form a chain. It is thus a chain stopper, and temporarily was significantly less accurate than polyether (heavy and
prevents polymerization of the linear siloxane molecules. light body) or reversible hydrocolloid impressions.
The retarder continues to polymerize until it is completely
consumed and then the linear siloxane molecules Dimensional stability
polymerize causing the impression material to set. The
most convenient and widely advocated method for The accuracy of an impression material is dependent on
extending working time is to refrigerate the materials the dimensional stability. There are a number of possible
before mixing. Gains of up to 90 seconds have been causes for dimensional changes in elastomeric impression
reported when the materials are chilled to 2°C [3, 49]. It materials. The major factors affecting the dimensional
is a good idea to store the addition silicones in a change of the impression are thermal contraction,
refrigerator and use them immediately after removal polymerization shrinkage, and contraction due to the loss
because the cool storage conditions act to lengthen the of volatile by products [55]. Polyvinyl siloxanes show
working time by about 1.5 minutes without adversely the smallest dimensional changes on setting of all the
affecting the material’s accuracy. elastomeric impression materials. Long term dimensional
stability of polyvinylsiloxanes is reported in the literature.
Reproduction of detail This is because they are not susceptible to changes in
humidity, and they do not undergo any further chemical
Polyvinyl siloxanes are currently considered to reproduce reactions or release any by-products.
the greatest detail of all the impression materials. The [3,6,7,13,52,56,57,58]. Tjan et al [59] evaluated the
international standard for dental elastomeric impression accuracy of monophase polyvinyl silicones and found that
materials1 states that a type III (light body) impression repeat pour at later time periods, did not affect the
material must reproduce a line 0.020 mm in width. With dimensional accuracy and stability of impression made
the exception of the very high viscosity putty materials, with these materials. Polyvinyl siloxane impressions may
all polyvinyl siloxanes (light, medium and heavy body) be repoured to produce stone dies which are as accurate
achieve this. Very low viscosity materials can reproduce as the original, as many as seven days later [58].The linear
lines 1-2 μm wide [7, 50, 51]. Further, PVS materials coefficient of thermal contraction is relatively high for
have the best fine detail reproduction and elastic recovery all elastomers. When an impression is removed from the
of all available materials.[52]. It should be noted that the mouth, there is an element of shrinkage due to the decrease
literature does not tend to support the use of putty and in temperature that occurs as the material moves from
wash impression techniques for greatest accuracy in the mouth to the bench. Lower viscosity materials show
impressions. Wassell and Ibbetson [53] reported that 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 Shillingburg et al [63] tested an experimental polyvinyl
37°C before pouring has been demonstrated to improve siloxane material containing 20 per cent barium sulphate
the accuracy of the resultant die; however it is doubtful to improve radiopacity. Although they were able to
that this is clinically significant. [49,56] The addition demonstrate qualities of radiopacity equal to that of the
silicones have excellent dimensional stability with polysulphides, there were associated physical property
shrinkage over 24 hours of only 0.05%. drawbacks including hydrogen bubble formation in dies
poured from the impressions, and evidence of long term
Tear energy, elastic recovery and deformation breakdown limiting the shelf life.
Polyvinyl siloxanes are frequently reported to be the most Wettability
ideally elastic impression materials because they exhibit
better elastic recovery and less permanent deformation An impression material should have intimate contact with
than the other elastomers. They can absorb over three the tooth and underlying soft tissues and should not form
times more energy up to the point of permanent bubbles or voids. Wettability is best with a hydrophilic
deformation than other elastomers, and if elongated to material. Material should possess ability to displace
over 100 per cent (strain at tear), they rebound to only moisture. According to O’Bri e n, wetting describes the
0.6 percent permanent deformation [60]. Permanent relative affinity of a liquid for a solid. It is the degree to
deformation is related to the degree of cross-linking of which a drop will spread on a solid surface, and can be
the polymer strands, temperature, and the rate of applied quantified by observing the contact angle. High angles
stress. The ideal impression material should exhibit (greater than ninety degrees) indicate poor wetting, whilst
maximum energy absorption with minimal distortion. a zero angle would indicate perfect wetting of the surface.
However, it is also desirable that the material tears rather Early forms of the addition silicones were hydrophobic,
than deforms past a critical point such as a margin. however most now available are hydrophilic because of
Polyvinyl siloxanes deform at much slower rates and tear inclusion of surfactants which reduce their contact angles
at points of less permanent deformation than do the other with gypsum from approximately 90 to 50 degrees. This
elastomeric materials [60]. Blomberg et al [61] reported makes their contact angles with gypsum similar to those
that polyvinyl siloxanes have sufficient elastic recovery of the hydrophilic polyethers. [64]
to allow an impression to be poured only six minutes after
When discussing the wetting characteristics of impression
removal from the mouth.
materials, it is important to distinguish between the ability
Marcinak and Draughn[62] evaluated the dimensional of the material to flow around the soft and hard tissues of
change in addition silicones by delaying the pouring of the mouth, and the ability of the material to be wet by
impressions from 2 h to one week. They concluded that gypsum slurry. Polyvinyl siloxanes are inherently
these materials remained remarkably accurate even after hydrophobic, however in recent times; new ‘hydrophilic’
one week, with the greatest change at any time being polyvinyl siloxanes have been introduced with
0.3%. Lacy et al [27] investigated the time dependant manufacturer claims that they better wet moist dental
accuracy of elastomeric impression materials and surfaces. These new formulations have intrinsic
concluded that polyvinyl siloxanes were the most stable surfactants added. Typically these are non-ionic
of elastomers. surfactants of phenoxypolyethanol homologues [65-69].
There is no scientific evidence to indicate that polyvinyl
Creep compliance siloxanes advertised as ‘hydrophilic’ can be syringed into
a wet sulcus for an accurate impression [50, 65, 66]. It
All elastomers are viscoelastic materials, implying that has also been shown that the newer hydrophilic materials
deformation and elastic recovery are time dependent as perform no better than the original formulations of
well. Therefore, the longer the material is deformed (as polyvinyl siloxane in wettability for pouring dies, if a
occurs when impressions are removed slowly from the compatible, extrinsic, spray-on surfactant is applied
mouth or separated slowly from a poured model), then before pouring[ 65,66].
the longer time it takes for elastic recovery and the
possibility of permanent deformation becomes higher. This has been confirmed by Takahashi and Finger [70]
Polyvinyl siloxanes have the least viscoelastic qualities who demonstrated that under a simulated clinically dry
thus requiring the least time for recovery from viscoelastic field, both the hydrophilic and original f ormulations of
deformation. polyvinyl siloxane wet tooth structure with equal results.
The application of an extrinsic surfactant to the surface
Radiopacity against which an impression is to be made has also been
suggested. Millar and co-workers [71] reported a
Radiopacity of impression materials is important for significant reduction in the number of voids and an overall
radiographic identification of excess material which may increased quality of polyvinyl siloxane impression when
be accidentally swallowed, aspirated or left in gingival a modified polydimethyl siloxane wetting agent was
tissues. Presently, only the polysulphide materials exhibit applied to the prepared tooth surfaces before impressions
significant radiopacity due to their lead dioxide content. were made.
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 Polyvinylsiloxanes in Dentistry: An Overview

Impression trays and adhesives and Merchant. Johansen and Stackhouse [78]
demonstrated that polyvinyl siloxanes were able to be
VPS adhesives (blue) for polyvinyl siloxane immersed in 2 per cent glutaraldehyde for 16 hours
impression materials without any observed dimensional changes, whilst
polyether materials showed dramatic distortions under
The improved physical properties of modern elastomers
the same conditions. Holtan et al. [79] measured the
and particularly polyvinylsiloxanes the use of stock trays
dimensional stability of polyvinylsiloxanes after
for impressions has become common practice for reasons
sterilization procedures using a conventional steam
of cost and convenience [59].Common stock trays made
autoclave, and an ethylene oxide gas autoclave. They
of polystyrene or chromium plated brass are reported to
determined that sterilization in ethylene oxide gas resulted
be suitably stiff to prevent flexure or distortion, although
in gas inclusions into the impression material which then
there remains some possibility of tray wall flexure with
formed bubbles in dies poured immediately from them.
polystyrene trays[38,53]. The use of adhesives in trays
Waiting to pour dies for 24 hours after gas autoclaving
has been shown to achieve higher material bond strengths
prevented this problem. Impressions sterilized in the steam
for polyvinyl siloxanes than has mechanical retention [72,
autoclave did undergo distortion that would have been
73]. The adhesives used are usually polydimethyl siloxane
significant enough to prevent a casting from seating. It
and ethylsilicate. The adhesive reacts with the surface of
was concluded that steam autoclaving was a suitable
the tray material and forms a chemical bond to the tray
sterilization method if the impressions were not to be used
and to the impression material. It is generally
for fixed prostheses.
recommended to wait for ten to fifteen minutes after
application of the adhesive before making the impression
Most recently, radiofrequency glow discharging has been
[73].This allows time for the solvent to react with the
advocated for use as a disinfecting procedure for polyvinyl
tray material.
siloxane impressions [80]. Whilst this procedure is
Chai et al. [38] reported that adhesive strength to acrylic claimed to clean and improve the wettability of the
resin (custom trays) was significantly lower than impression surface, it is not clear if glow discharging
polystyrene or metal stock trays for the polyvinyl results in sterilization.
siloxanes. Investigations into their bond strengths with
polyvinyl siloxane adhesives indicate that they bond better In Future
than polymethyl methacrylate materials provided that the
air inhibited non-polymerized layer is removed with Continued efforts will be made to develop more effective
isopropyl alcohol or a carbide bur [72,74]. Sulong and single-viscosity addition silicone systems, probably by
Setchell [75] demonstrated that roughening the surface controlling the filler particle size and wettability of the
of the impression tray will significantly improve the filler by the silicone. Hydrophilic addition silicones
effectiveness of polyvinyln siloxane adhesives.. In many should be developed further in order to improve the taking
clinical situations, the impression tray must be tried in of impressions and pouring of casts. Because of the
the mouth prior to impression making and this leads to convenience and reduction in the number of voids,
saliva contamination. If the tray has already been painted development of automatic mixing systems, static and/or
with adhesive, then subsequent application is mechanical, will continue. With the development of
recommended to maintain bond strengths. Contaminated information on the visible curing composites of the BIS-
adhesives have shown a drop in bond strength to one- GMA and urethane diacrylate, the commercial availability
fifth of their original amount. of visible-curing rubber impression materials is almost a
certainty; the essentially unlimited working time at
Disinfection constant viscosity would be a major advantage for this
type of system. The increased emphasis on disinfection
Disinfection is the inhibition or destruction of pathogens of impressions will stimulate the development of systems
and can be achieved by immersion of an impression into that will disinfect polyethers without causing problems
antimicrobial chemical solutions for 3 to 90 minutes with dimensional change.
depending on the agent. Sterilization is the total
elimination of all micro-organisms and spores and Conclusion
requires immersion periods of 6 to 10 hours. Herrera and
Merchant [76] tested the dimensional stability of different Polyvinyl siloxane impression materials are routinely used
impression materials following immersion disinfection to record the impressions of dentulous and edentulous
for thirty minutes. They observed that polyvinyl siloxane mouths. The composition has been changing from time
and polysulphide were unaffected after immersion in to time to improve the clinical performance. It is evident
sodium hypochlorite, 2 per cent glutaraldehyde, 0.5 per that all materials change dimensionally over time. The
cent povidone-iodine and 0.16 per cent halogenated present review suggests that addition silicones to a certain
phenol whilst polyethers were significantly unstable. Even extent were helpful in improving their clinical
after extending the immersion times to sixty minutes, Del performance and extending the use of the material in
Pilar Rios et al [77] agreed with the findings of Herrera various dental applications.

121
 H. Surapaneni, P.S. Yalamanchili, R.S. Yalavarthy, S. Attili

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