Australian Dental Journal 1998;43:(6):428-34
Polyvinyl siloxane impression materials: An update
on clinical use
Michael N. Mandikos, BDSc, MS*
Abstract
Polyvinyl siloxane impression materials have
applications in a variety of indirect procedures in
prosthodontics and restorative dentistry. Favourable
handling properties, good patient acceptance and
excellent physical properties have resulted in their
popularity in today’s practice. In this review, the
chemistry and important physical properties of
polyvinyl siloxanes are summarized, and recent
clinical questions of improved hydrophilics, tray
adhesives, disinfection, and glove-induced
polymerization inhibition are addressed.
Key words: Polyvinyl siloxane, elastomer, impression
materials, hydrophilic, polymerization inhibition.
(Received for publication November 1997. Revised
March 1998. Accepted April 1998.)
Introduction
The polyvinyl siloxane impression materials are
addition reaction silicone elastomers which were
first introduced in the 1970s. Since that time and
especially in the past decade, these materials have
gained in their acceptance and account for a large
share of the impression material market. Polyvinyl
siloxanes have applications in fixed prosthodontics,
operative dentistry, removable prosthodontics and
implant dentistry.1,2 The materials are presented in
the form of two pastes (a base and an accelerator)
which can be hand spatulated or autodispensed from
a dual cartridge, and mixed in equal quantities for
use. They have achieved a high level of dentist and
patient acceptance as they are clean, odourless and
tasteless.
Chemistr y
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 groups accounts for
*Advanced Education Program in Prosthodontics, State University
of New York at Buffalo, New York, USA.
428
their different curing reactions.3 As the dimensional
stability of the polyvinyls is so much improved and
the setting reaction is sufficiently different from the
condensation curing silicones, the polyvinyl siloxanes
warrant classification as a separate category of
material.4
The base material contains a polymethyl hydrogen
siloxane copolymer, which is a moderately low
molecular mass polymer with silane terminal
groups.3,5 The accelerator material contains the
vinyl-terminated polydimethyl siloxane. This is also
a moderately low molecular mass polymer but has
vinyl terminal groups.3,5 The accelerator material
also contains chloroplatinic acid as a homogeneous
metal complex catalyst.6-8 On mixing, an addition
reaction occurs between the silane and vinyl groups
(Fig. 1). There is minimal dimensional change during
this polymerization and there are no by-products.
Several authors have reported hydrogen gas
bubble formation on the surface of gypsum dies
poured immediately from polyvinyl siloxane
impressions.1,2,6 A side reaction of the hydrides on
the base polymer can produce hydrogen gas if
moisture or residual silanol groups are present.
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.7,8 It is no longer necessary to wait for one
hour before pouring these impressions.
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 a
cross-linker. 6 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.9
Australian Dental Journal 1998;43:6.
 Fig. 1. – The accelerator polymer is terminated with vinyl groups which cross-link to the silane
terminal groups on the base polymer when activated by a platinum salt catalyst. Note that this is an
addition reaction and there are no by-products.
Properties
a. Viscosity
Polyvinyl siloxanes are available in viscosities ranging
from very low (for pouring, syringing or wash use),
to 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.5,10 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.10
Thixotropy is the property of certain gels to
liquefy when subjected to vibrating forces (for
example, ultrasonic waves) and then to solidify when
left to stand again. Polyvinyl siloxanes behave
similarly to this but have not been sufficiently
investigated to be classified as thixotropic materials.
Australian Dental Journal 1998;43:6.
b. Working and setting times
Modern polyvinyl siloxanes have a working time
of two minutes and a setting time of six minutes
(with slight variation). 1,2 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.2
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 retarder was used by
two dental schools in the USA to provide students
with extended working times in a teaching
429
environment. It has become less commonly used
since the polyvinyl siloxanes became available in
automix dual cartridges.
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. 2,11
c. 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. 5,12,13
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 Ibbetson14 reported that heavy body and
wash impressions were more accurate than putty and
wash impressions. Frederick and Caputo15 further
showed that the putty and wash technique was
significantly less accurate than polyether (heavy and
light body) or reversible hydrocolloid impressions.
d. 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. All rubber
polymers must contract slightly during polymerization
as a result of reduction in spatial volume as they
cross-link. If the setting reaction produces a by-
product or if accelerator components are liberated,
then the set volume is further decreased. Some
impression materials like the polyethers are less
hydrophobic and can absorb and then even lose
water if they are placed in wet or varying humidity
environments. Changes in temperature can also lead
to varying changes in the final dimensions.
Polyvinyl siloxanes show the smallest dimensional
changes on setting of all the elastomeric impression
materials. The majority of this shrinkage is due to
continued polymerization occurring within the first
three minutes of removal of the impression from the
mouth.2 Reductions in volume due to polymerization
have been reported to be as low as 0.1 to 0.05 per
cent.5,7 This linear contraction is well matched to the
setting expansion of modern type III and type IV die
stones and results in a slightly larger replication of
the preparation.5,13,16
430
Long term dimensional stability of polyvinyl
siloxanes 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.1-3,5,16-18 Polyvinyl siloxane
impressions may be repoured to produce stone dies
which are as accurate as the original, as many as
seven days later.1,16,19
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 their
lower filler content.16,17 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.11,17
e. Tear energy, elastic recovery and
deformation
Impression materials must have sufficient strength
to allow removal from a gingival sulcus without
tearing. Tear energy is that energy required to
sustain a tear through a material, and is of obvious
importance in thin intrasulcular or interproximal
areas.
Elasticity is inherent to all the elastomeric
impression materials as they are polymers with
highly flexible kinked segments that allow freedom
of movement. Under a load, the flexible kinked
segments of these polymers will uncoil allowing
movement. Upon removal of the load, an ideal
elastomer will exhibit complete elastic recovery and
return to its prestressed configuration. The degree
to which this occurs is a measure of the elastic
recovery of the material. Permanent deformation
occurs when a polymer is elongated beyond the
point where elastic recovery is possible. Permanent
deformation is related to the degree of cross-linking
of the polymer strands, temperature, and the rate of
applied stress.20
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.20 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),
Australian Dental Journal 1998;43:6.
they rebound to only 0.6 per cent permanent
deformation.16,20
f. 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.5 Polyvinyl siloxanes
have the least viscoelastic qualities thus requiring the
least time for recovery from viscoelastic deformation.
Blomberg et al.21 reported that polyvinyl siloxanes
have sufficient elastic recovery to allow an impression
to be poured only six minutes after removal from the
mouth.
g. 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 poly-
sulphide materials exhibit significant radiopacity due
to their lead dioxide content.
Shillingburg et al.22 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.
h. The hydrophilic question
According to O’Brien,8 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. 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 a gypsum slur ry.
Polyvinyl siloxanes are inherently hydrophobic.3,7
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
nonylphenoxypolyethanol homologues.7,23 Research
Australian Dental Journal 1998;43:6.
in this area has involved observations of the wetting
of set surfaces of polyvinyl siloxanes. The conclusion
then is that the ‘hydrophilic’ statements refer to the
newer materials being more readily poured up with
a gypsum-based die stone than the previous
generation materials. There is no scientific evidence
to indicate that polyvinyl siloxanes advertised as
‘hydrophilic’ can be syringed into a wet sulcus for an
accurate impression.2,9,12,23
This has been confirmed by Takahashi and
Finger,24 who demonstrated that under a simulated
clinically dry field, both the hydrophilic and original
formulations of polyvinyl siloxane wet tooth structure
with equal results. 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.9,23
The application of an extrinsic surfactant to the
surface against which an impression is to be made
has also been suggested. Millar and co-workers25
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.
Impression trays and adhesives
Tray spacing and tray design have often been cited
as potential sources of error in impressions for fixed
prosthodontic procedures. When only polysulphide
materials were available, even tray spacing was
critical to minimize distortion due to uneven poly-
merization shrinkage in areas of greater impression
material bulk. The improved physical properties of
modern elastomers and particularly polyvinyl
siloxanes have diminished this concern and now the
use of stock trays for impressions has become common
practice for reasons of cost and convenience.26
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.27 Wassell and Ibbetson14 and Payne
and Pereira 28 identified poor fitting stock trays and
consequent tray wall flexure as the greatest concern
for inaccuracy.
Whether custom or stock trays are used for
impressions, another potential source of error may
arise if the material is not adequately retained in the
impression tray when it is removed from the mouth.
The use of adhesives in trays has been shown to
achieve higher material bond strengths for polyvinyl
siloxanes than has mechanical retention.28,29 The
adhesives used are usually polydimethyl siloxane and
ethylsilicate. The adhesive reacts with the surface of
431
the tray material and forms a chemical bond to the
tray and to the impression material. It is generally
recommended to wait ten to fifteen minutes after
application of the adhesive before making the
impression.29 This allows time for the solvent to
react with the tray material.
The polyether systems have the greatest bond
strengths while the polyvinyl siloxanes show great
variability between manufacturers with some being
very poor, and others rivalling the polyether
systems.27 Bond strengths will also vary depending
on the tray material. In contrast to the polyethers
and polysulphides, Chai et al.27 reported that
adhesive strength to acrylic resin (custom trays) was
significantly lower than polystyrene or metal stock
trays for the polyvinyl siloxanes.
Visible light-cured tray materials based on urethane
dimethacrylate have found recent acceptance.
Investigations into their bond strengths with
polyvinyl siloxane adhesives indicate that they bond
better than polymethyl methacrylate mat e ri a l s
provided that the air inhibited non-polymerized
layer is removed with isopropyl alcohol or a carbide
bur.28,30 Sulong and Setchell31 demonstrated that
roughening the surface of the impression tray will
significantly improve the effectiveness of polyvinyl
siloxane adhesives.
It is important to note that although other
elastomers have stronger bonding adhesives, these
cannot be substituted for use with polyvinyl
siloxanes. Also, polyvinyl siloxane putties are reported
to show no chemical adhesion to their adhesive and
so the use of putties requires mandatory mechanical
retention in the impression tray.27
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.32
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.
Extended periods of immersion can risk distorting
impressions by liquid uptake and subsequent
swelling of the material. Consequently, procedures
currently used to control the transmission of
pathogens from impressions have tended to be
disinfecting and not sterilizing due to concern for
the accuracy of the impression.
432
Herrera and Merchant33 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.34 agreed with the findings
of Herrera and Merchant. Johansen and Stackhouse35
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.36 measured the dimensional stability
of polyvinyl siloxanes 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.37
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.†
Compatibility with die materials
The hydrophobicity of polyvinyl siloxanes is well
established, however, as mentioned previously, the
introduction of newer materials with intrinsic
surfactants or the conjunctive use of extrinsic
surfactants topically, can greatly improve wettability.
This makes polyvinyl siloxanes compatible with
gypsum, epoxy resin, and polyurethane resin
materials.9,12,38
Gypsum stones cannot reproduce detail much
smaller than 20 µm because their crystal size ranges
from 15 to 25 µm. Epoxy and polyurethane resins
can reproduce detail down to 1 to 2 µm making
them highly compatible with the detail capture
possible with polyvinyl siloxane impressions.12
Polyvinyl siloxanes can also be silver electroplated.
This procedure can be facilitated by soaking the
† Baier RE. Written communication, September 1996.
Australian Dental Journal 1998;43:6.
impressions in water for 24 hours before application
of the silver powder. It is thought that this alters the
concentration of surfactants in the surface layers of
the impression.‡ Crispin et al.39 reported that silver
dies recovered from polyvinyl siloxane impressions
are the most accurate dies.
The ability to pour duplicate dies from one
impression is highly advantageous. Morgano et al.40
reported that the removal of dies and subsequent
repouring of polyvinyl siloxane impressions produced
clinically accurate duplicate models.
Gloves and the inhibition of polymerization
Occasionally an inhibition or retarding effect is
seen on polyvinyl siloxanes 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.41-45 It was initially suspected
that the corn starch powder used as a lubricant in
the gloves was interacting,41 while other authors
suggested atmospheric oxygen inhibition, or inter-
actions with haemostatic agents were the cause.
Several haemostatic agents were tested before de
Camargo et al.46 concluded that they were not the
inhibitors. Jones et al.47 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 poly-
merization. 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.44,45,48 Baumann44 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 observed that synthetic
latex gloves do not produce this phenomenon, while
some natural latex gloves do.42-44 One’s own testing
and subsequent use of a non-retarding glove is
recommended.
Conclusions
The results of investigations into polyvinyl siloxane
impression materials indicate that they produce
highly accurate impressions because they reproduce
fine surface detail, and have excellent elastic recovery,
‡Garlapo DG. Written communication, February 1996.
Australian Dental Journal 1998;43:6.
adequate tear strengths, and exceptional dimensional
stability. They are compatible with all common die
materials, can be disinfected or sterilized, and can be
repoured after delayed periods. They are dispensed
in convenient automixing dual cartridges or single
tubes and are available in several viscosities. If
handled appropriately, polyvinyl siloxanes can be
applied in almost any indirect procedure.
Acknowledgements
The author would like to thank Dr J. Malcolm
Carter, Associate Professor Biomaterials, Department
of Restorative Dentistry, State University of New
York at Buffalo, for his advice in preparing this
manuscript.
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Address for correspondence/reprints:
Dr Michael N. Mandikos,
1st Floor, Loyal House,
245 Albert Street,
Brisbane, Queensland 4000.
Australian Dental Journal 1998;43:6.