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Hygroscopic and hydrolytic effects in dental

polymer networks
Jack L. Ferracane
*
Division of Biomaterials and Biomechanics, Department of Restorative Dentistry, Oregon Health & Science
University, 611 S.W. Campus Drive, Portland, OR, USA
Received 21 March 2005; accepted 11 May 2005
KEYWORDS
Dental resins;
Polymer network;
Hydrolytic;
Hygroscopic;
Sorption;
Solubility;
Degradation;
Dental composites
Summary Objectives. The objective of this manuscript is to outline the factors
associated with hygroscopic and hydrolytic effects in dental polymer networks, and
to review the literature generated over the past thirty years or more in this area.
Methods. Information was gathered from nearly 90 published articles or abstracts
appearing in the dental and polymer literature. Studies were predominantly
identied through a search of the PubMED database.
Results. Studies were included that provided direct evidence for the uptake of
solvent by a polymer network and its subsequent physical or chemical effect, or the
loss of molecular species into solvents. An attempt was made to select articles that
spanned the timeframe from approximately 1970 to today to ensure that most of the
classic literature as well as the latest information was included.
Conclusions. Dental polymer networks have been shown to be susceptible to
hygroscopic and hydrolytic effects to varying extents dependent upon their chemistry
and structure. The importance of these effects on the clinical performance of
polymer restoratives is largely unknown, though numerous investigators have alluded
to the potential for reduced service lives.
Signicance. While the physical and mechanical properties of these materials may
be signicantly altered by the effects of solvent uptake and component elution,
what may constitute the greatest concern is the short-term release of unreacted
components and the long-term elution of degradation products in the oral
cavity, both of which should be strongly considered during restorative material
development.
Q 2005 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
Introduction
Many polymer networks are considered to be largely
insoluble structures with relatively high chemical
and thermal stability. However, these networks
Dental Materials (2006) 22, 211222
www.intl.elsevierhealth.com/journals/dema
0109-5641/$ - see front matter Q 2005 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.dental.2005.05.005
* Corresponding author. Tel.: C1 503 494 4327; fax: C1 503
494 8260.
E-mail address: ferracan@ohsu.edu.
may absorb water and chemicals from the
environment. In turn, the network may release
components to its surroundings. The phenomena of
sorption and solubility may serve as precursors to a
variety of chemical and physical processes that
create biological concerns as well as producing
deleterious effects on the structure and function of
the polymeric material. These effects may include
volumetric changes such as swelling, physical
changes such as plasticization and softening, and
chemical changes such as oxidation and hydrolysis
(Fig. 1). The properties of the network may be
permanently altered by these events, and the
performance of the polymer may be compromised.
It is generally accepted that all polymers degrade to
some extent, and in this light, it is appropriate to
suggest that the greatest difference between
degradable and non-degradable polymers may be
temporal. There are many applications in which
the degradation of polymers is acceptable and even
required. In any case, this manuscript will only be
concerned with non-degradable polymers, dened
as those requiring a much longer time to degrade
than their expected time of service [1].
There is concern that the effects of solvent
uptake and hydrolytic degradation may lead to a
shortened service life of dental restorations. But an
even greater concern is the possibility of biological
effects elicited by the species evolved from
polymeric dental restoratives, thus requiring the
effects of hygroscopic and hydrolytic phenomena to
be investigated and explained. There are a variety
of polymers used in dentistry, but the concerns over
sorption and solubility mainly are limited to
restorative and prosthetic materials residing semi-
permanently within the oral cavity. While sorption
and solubility do occur with other polymers, such as
impression materials, these will not be addressed
here. The objective of this manuscript is to outline
the factors associated with hygroscopic and
hydrolytic effects in dental polymer networks, and
to review the literature generated over the past
thirty years or more in this area.
Polymer networks
Polymers used in the fabrication of dental compo-
site restorative and prosthetic materials are typi-
cally composed of mono- or di-methacrylates,
though molecules with higher functionality are
also used. Most prosthetic polymers are composed
of polymethylmethacrylate, used as a linear poly-
mer or lightly cross-linked by the addition of a small
amount of difunctional methacrylate, such as
ethylene glycol dimethacrylate. Because their
chemical structure is nearly identical, the reaction
of prosthetic polymers to an aqueous environment
is similar to that of the composite restoratives. The
other commonly used polymeric networks are made
from polyacrylic acid and its copolymers, which are
used in glass ionomers and adhesives, and from
polydimethylsiloxane, which is used in soft denture
liners. This manuscript will concentrate on degra-
dation of the composite restorative and prosthetic
materials, as these are likely to have the greatest
consequence due to their high frequency of use.
Dental restorative materials are exposed to a
service environment, saliva, containing water,
histatins, statherins, lysozyme, proline-rich
proteins, carbonic anhydrases, amylases, peroxi-
dases, lactoferrin, mucin and sIgA, which provides
many functions including buffering, digestion,
lubrication, tissue coating, mineralization and
anti-viral and anti-bacterial action [2]. In addition,
Figure 1 Overview of factors affecting the hygroscopic and hydrolytic properties of polymer networks.
J.L. Ferracane 212
the materials are exposed to exogenous substances
that contain a variety of chemicals, including acids,
bases, salts, alcohols, oxygen, etc. that enter the
oral environment during eating and drinking. The
chemistry and duration of exposure are important
determinants of what if any inuence a molecule
may have on the materials polymer network.
Several factors relating to the chemistry and
structure of the polymer network are important in
determining the extent to which the material will be
affected by an aqueous environment. Important
chemical characteristics include the hydrophilicity
of the polymer, and the differences in solubility
parameter between the polymer and the solvent.
Important structural parameters include the cross-
linking density and the porosity of the network. In
addition, the presence of reinforcing ller may
signicantly inuence the solubility and sorption of
the structure. These factors need to be addressed
individually.
Hydrophilicity
The hydrophilic nature of a polymer is in large
part a function of the chemistry of its monomers
and its polymerization linkages. The three most
common monomers used in dental composites are
Bis-GMA (2,2-bis[4-(2
0
-hydroxy-3
0
-methacryloxy-
propoxy)phenyl]propane), UDMA (urethane
dimethacrylate), and TEGDMA (triethyleneglycol-
dimethacrylate) (Fig. 2), but commercial
composites have been formulated with many
other monomers including Bis-EMA (2,2 bis[4-(2-
methacrylyloxyethoxy)phenyl]propane), Bis-MA
(2,2 bis[4-(2-methacrylyloxy)phenyl]propane, Bis-
PMA (2,2 bis[4-(3-methacrylyloxypropoxy)phenyl]-
propane, EGDMA (ethyleneglycol dimethacrylate),
DEGDMA (diethyleneglycol dimethacrylate),
TE-EGDMA (tetraethyleneglycol dimethacrylate),
and other dimethacrylates, including several with
cyclic structures [3].
An examination of the structure of the most
popular monomers reveals that they are heteroatom
polymers, having carbon and oxygen or nitrogen in
their backbones. In addition, their structure shows
the presence of hydrolytically susceptible groups,
such as ester, urethane, and ether linkages, as well
as hydroxyl groups. While these monomers and their
resultant polymers are not considered to be
extremely hydrophilic, they certainly absorb water
and to a potentially damaging extent. Venz and
Dickens [4] reported differences in long term water
sorption (6 months) for polymer networks composed
of various monomers, showing sorption to be in the
following order: TEGDMAOBis-GMAOUDMAO
HMDMA. This difference was explained by the
presence of hydrophilic ether linkages in TEGDMA,
hydroxyl groups in Bis-GMA, urethane linkages in
UDMA, and the presence of ester groups in all,
including the HMDMA. Water enters the polymer
network through porosity and intermolecular
spaces. The extent and rate of water uptake is
Figure 2 Common monomers used to produce cross-linked dental resins.
Solvent effects on polymer networks 213
dependent upon the density of the polymer network
and the potential for hydrogen bonding and polar
interactions. The latter is expressed in the solubility
parameter (d), which is represented as the cohesive
energy of the solvent molecules in a given volume,
and is typically measured by swelling. The extent of
solvent uptake by the polymer is a function of the
differences in solubility parameter between the
polymer and the solvent, being greatest when this
difference is small.
Network characteristics
The quality of the network that forms during
polymerization also will dictate the extent to
which molecular uptake and swelling occur when a
polymer is submerged in a solvent. Networks with
high cross-linking density, which is typical of dental
composites, have reduced solvent uptake and
swelling due to the reduced free volume in the
network, as well as to the covalent cross-links that
maintain the close proximity of the polymer chains.
As will be described later, swelling can be used to
measure relative cross-linking density. It is generally
held that highly crosslinked polymers are more
resistant to degradative reactions, based on the
more limited space and pathways available for
solvent molecules to diffuse within the structure
(Fig. 3). Arima et al. [5] has shown a strong
correlation between increasing the concentration
of cross-linking agents and the reduced solubility of
polyethylmethacrylate polymers. However, their
study also showed that when the cross-linker
containedhydrophilic ether linkages, water sorption
actually increased with cross-linker concentration,
suggesting that the chemical nature of the cross-
linking agent may supercede the effect of higher
molecular density. A high level of porosity or
microvoids has also been shown to facilitate uid
transport into and out of the polymer by serving as
sites for molecules to be sequestered and leading to
enhanced solvent uptake and elution [6]. Other
factors that likely inuence water sorption include
the degree of conversion of the polymer, as well as
the quantity of pendant molecules existing within
the network.
Filler effects
The presence of llers in a polymer network can
greatly affect solvent uptake and dissolution,
possibly in direct relation to its proportion as it
reduces the overall volume of the absorbing polymer
[7,8]. However, water also serves as a weak acid and
may cause the erosion of the surface of ller
particles, as has been shown for a variety of dental
ceramics [9]. Whereas, composites with pure silica
or quartz llers are comparatively inert in water,
many composites containing radiopaque glasses
have been shown to undergo greater dissolution in
water and saline solutions [7,1012]. This potential
deterioration of the glass is one of the reasons that it
is so important to form an organic layer, typically of
silane molecules, on the surface of the ller to
protect it from the environment [4,13]. There is
some evidence that the quality of this interface
inuences the extent to which the composite
material is affected by solvents, as a poor, non-
bonded interface may provide a lowenergy pathway
for solvent molecules and elutable species [14].
Solvents
The chemistry of the environment surrounding a
polymer network, in particular the chemical compo-
sitionof theconstituents, inuences thenatureof the
interaction between the two. Saliva is composed of a
variety of molecules in an aqueous environment.
Studies of the effect of storage conditions on the
stability of dental polymer networks have exposed
the materials to water, articial saliva, alcohol, and
acidic or basic solvents in an attempt to study the
agingprocess. Theeffect of thesechemicals is varied,
but typically involves an elution of unreacted
components and some degradative effect on the
polymer network. Solutions of 5075%ethyl alcohol in
water have beenshowntobe among the best solvents
for dental composite networks [15]. Studies have
shown that the solubility parameter of the solvent is
the most important consideration, the solvent effect
being greatest when there is minimal solubility
parameter mismatch between the solvent and the
polymer itself [1517]. Thus, like dissolves like. In the
case of a network, the polymer is not dissolved, but
High X-link density =
denser structure
vs. Low X-link density =
more open structure




Figure 3 Schematic depicting differences in the open-
ness of networks with low vs high cross-linking density.
J.L. Ferracane 214
swells when placed into a good solvent as the forces
of attraction between the polymer chains are
exceeded by the forces of attraction between the
solvent molecules and the components of the chains.
Thus, there is an exchange of secondary bond
interactions leading to an increase in the volume of
the network and potentially a softening due to fewer
chain-chain interactions and increased plasticizing.
Other solvent degradative effects may be experi-
enced by the ller particles of a composite structure,
for instance whenexposedtoacidic solutions, suchas
an acidulated phosphate uoride gel [1819].
Another very important aspect of the interaction
between thepolymer network andits environment is
the presence of enzymes that can degrade the
polymer through attacks on the side chains,
producing both potentially harmful by-products
as well as a deterioration of the properties of
the network [20]. Numerous studies have shown
the effect of esterases, those that may be present
in the saliva or those that may react like those
present in the saliva, on dental composites [2124].
These studies have shown a reduction in wear
resistance as well as the loss of molecules from the
surface of the composite. Due to the large size of the
proteins and their limited mobility within a polymer
network, it is unlikely that the effects of enzymes
would be experienced deep within the structure of
the polymer, away from the surface. However,
surface effects such as wear may continue to erode
the material, in time exposing more of the material
to the enzymes. The chemistry of the polymer will
again signicantly inuence the enzymatic degra-
dation of the material, as evidenced by the fact that
urethane modied bis-GMA/TEGDMA networks have
been shown to be more stable in the presence of
cholesterol esterase than unmodied bis-GMA/
TEGDMA networks [25].
An interaction between oral microbes and the
polymer network also may occur, though little
current information exists regarding this possibility.
In vitro studies have shown that bacteria can colonize
on compomer surfaces, and that the surface
roughness of the material increased after incubation
with bacteria, suggesting some surface degradative
effect [26]. It is likely that this surface degradation is
a result of acids produced by the bacteria.
Sorption
Quantity
Dental polymer networks based on dimethacrylate
monomers absorb aqueous solvents to the extent of
several percent of their total weight [27]. Studies
with experimental composite formulations show
water uptake of 1.01.6%, with only a minimal
relationship between sorption and the degree of
conversion of the polymer network [8]. Other
studies show water uptake in commercial dental
composites and compomers to vary between 1.0
and 3.5 mg/mm
3
, with the level of sorption being
much higher (67 mg/mm
3
) for resin modied glass
ionomers [28]. Musanje et al. [29] also showed
higher water sorption for resin-modied glass
ionomers (7.0%) compared to compomer (1.2%)
and composite (0.17%) after 9 months in articial
saliva. There is a general trend for the sorption of
ethanol/water solutions to be greater than that of
water alone [30].
Water sorption has been shown by several
authors to follow Fickian diffusion kinetics
[3133]. Ortengren et al. [34] compared the
water uptake of a variety of composites and
resin cements for up to 6 months. Most of the
materials reached saturation within 760 days,
except for one composite which continued to
absorb water throughout the experiment. Ferra-
cane [8] presented similar results for experimen-
tal composites, showing water sorption to be
lower for more highly lled materials, but the
rate of uptake and time to reach saturation being
essentially equivalent. Therefore, one might
expect a typical polymeric dental restoration to
become saturated with its solvent environment
within one to two months after placement.
Obviously, the water sorption is highly dependent
upon the chemistry of the monomers. Studies
have shown water sorption to be greater for Bis-
GMA-based resins compared to urethane resins
[35], and lowest for ethoxylated Bis-GMA
(Bis-EMA) resins that do not contain the hydroxyl
groups of Bis-GMA or the urethane linkages of
UDMA [36]. Furthermore, water uptake is greater
for Bis-GMA resins containing higher concen-
trations of TEGMDA due to the hydrophilic ether
linkages contributed by the TEGDMA [32,37].
Swelling
The uptake of water or solvent by a dental
composite may cause swelling that affects the
dimensions of the restoration. As previously
mentioned the solvent diffuses into the polymer
network and separates the chains, creating an
expansion. However, since the polymer network
contains porosity and free volume between chains,
especially in the region near crosslinks, it is
theoretically possible for water to be absorbed
Solvent effects on polymer networks 215
without creating a change in volume. In addition,
water uptake is accompanied by a loss of unreacted
components that would cause a reduction in
volume. Thus, the dimensional change of a polymer
network in a solvent is somewhat complex and
difcult to predict, and is very material dependent
[32,38]. One study showed that composite core
materials undergo an increase in volume during
water storage averaging 0.41.0% over two months
[39]. This is much less than the 5 or 8% that occurs
for resin-modied and conventional glass ionomers.
Another study showed a 0.5% volumetric expansion
for a dental composite after two years in water,
compared to a value of 1.1% for a composite
cement and 2.26% for a compomer [40]. In a rigid
material, this expansion may produce stresses on
the interfacial bonds with the cavity wall, and may
even lead to dislodgement from the cavity. The
effect of this volumetric increase is tempered
signicantly by the fact that the volumetric
shrinkage accompanying the polymerization
process leaves the material initially undersized,
and volumetric expansion from sorption is typically
insufcient to completely counter the
contraction [41].
Plasticization
The effect of solvent on the polymer network have
been described as plasticizing. The reduction in
hardness and other properties is a product of the
separation of the polymer chains by a molecule that
does not form primary chemical bonds with the
chain, but simply serves as a space occupier (Fig. 4).
Thus, the main effect of the solvent is to reduce
interchain interactions, such as entanglements and
secondary bonding. The rate of this softening
matches the rate of solvent uptake, which begins
immediately and reaches a maximum within one or
two months when the network is fully saturated
[42]. The effect initially would be greatest for
surface properties, such as hardness and wear,
and at a slower pace involve more of the network
and be reected in bulk properties.
Solubility
Species
The free radical polymerization of dimethacrylate
monomers produces a highly crosslinked polymer
network, but also leaves unreacted monomers,
polymerization promoters and oligomers. In lled
polymers, ions from the ller particles may also be
released. These components are all capable of
being dissolved from the network, and may
constitute a biological concern. Studies also have
identied degradation by-products, such as
methacrylic acid, formaldehyde, and specic
methacrylate molecules that are capable of being
leached from dental resins.
Techniques such as UV, IR, HPLC, GC, and MS
have been used to identify Bis-GMA, TEGDMA,
HEMA, other dimethacrylates and catalysts as
being leached from dental restorative resins,
adhesive resins, and sealants (Table 1). It should
be noted that several studies have concluded that
any component present in a composite or adhesive
resin is capable of being leached from the set
material [50,66]. Generally, extraction is more
complete in alcohol or organic solvents compared
to water. But even studies in water have shown
elution of components present in very small
concentration, such as the photoinitiators used to
cure the material [6263].
It is also interesting to note that of the 25 or so
studies cited over the past 20 or more years, only
three have shown the release of Bis-Phenol A (BPA)
or Bis-Phenol A dimethacrylate from composites or
sealants [54,65,68], despite the fact that several of
these studies were conducted for the expressed
purpose of identifying these molecules as well as
other potentially estrogenic molecules as elution
products [5556,67,69]. Since BPA is not purposely
added to any dental sealant or composite, one
would not expect to identify it as a leachable
component unless it was the result of a
degradation reaction or impurity. Schmalz et al.
[70] analyzed a commercial source of Bis-GMA and
found no BPA, despite treating the Bis-GMA
monomer with extreme acidic and basic conditions
as well as exposing it to porcine liver esterase.
Schmalz did nd that BPA could be extracted
from the commercial monomer Bis-Phenol A
dimethacrylate (Bis-DMA). He concluded that the
estrogenic effect attributed to a specic dental
stiffer
spongier
Figure 4 Schematic of the physical effect of a
plasticizer molecule in separating polymer chains and
producing softening by reducing the effectiveness of
entanglements.
J.L. Ferracane 216
sealant by Olea et al. [54] was in fact due to the
presence of Bis-DMA in the sealant, which Schmalz
et al. [70] showed was capable of being hydrolyti-
cally degraded to BPA. This conclusion is supported
by the study of Tarumi et al. [69], in which BPA
itself was not identied in 3 sealants and 5 dentin
adhesives, but Bis-DMA was found in two sealants
which had conrmed estrogenic activity using a
reporter gene assay. In contrast, Noda et al. [71]
evaluated the pastes of ve uncured dental
composites and showed by HPLC that BPA or its
derivatives, was present in each of them, likely as
an impurity. An impurity would be present in very
small concentrations (probably less than 0.10.2%
of the weight of the material). It is important to
note that Noda et al. [71] needed to use a strong
organic solvent, acetonitrile, to extract and ident-
ify the BPA. Therefore, it seems unlikely that
impurity levels of Bis-Phenol A that might be
present in some composites or sealants would likely
constitute a signicant concern, despite its known
estrogenic effects. While Wada et al. [67] has
demonstrated that at least two leachable catalyst/
inhibitor components of commercial dental compo-
sites do have in vitro estrogenic activity, they
concluded that in vivo problems were unlikely due
to the low levels released.
Other monomers and products of degradation
reactions may pose signicant concerns however,
and it is important to identify them and their ability
Table 1 Identied components eluted from composites, sealants and adhesives.
Study Solvent Method Eluted components
Braden and Pearson (1981) [43] Water IR Monomer, oligomer
Inoue and Hayashi (1982) [44] Water HPLC Bis-GMA, monomers
Thompson et al. (1982) [45] Ethanol UV Monomers
Okamoto et al. (1986) [46] Water HPLC Bis-GMA, TEGDMA, HQ
Tanaka et al. (1991) [47] Water GC/MS Bis-GMA, TEGDMA
Rathbun et al. (1991) [48] Organic solvents FTIR, GC/MS Bis-GMA, ketone stabilizer, phenyl
ester of benzoic acid
Ferracane et al. (1990) [49] Water, ethanol FTIR Bis-GMA and/or TEGDMA
Spahl et al. (1991) [50] Methanol GC/MS all monomers and catalysts found in
uncured
Lee et al. (1995) [51] Saliva, ethanol FTIR Monomers (ethanol only)
Eliades et al. (1995) [52] Ethanol HPLC Bis-GMA and TEGDMA
Hume and Gerzina (1996) [53] Water HPLC/GC-MS Bis-GMA, TEGDMA, HEMA and BPO
Olea et al. (1996) [54] Saliva HPLC/GC-MS Bis-Phenol A, Bis-Phenol A dimeth-
crylate, Bis-GMA and Bis-Phenol A
diglycidylether
Hamid and Hume (1997) [55] Water HPLC Bis-GMA, TEGDMA
Nathanson et al. (1997) [56] Ethanol HPLC/GC-MS Bis-GMA, TEGDMA, UDMA, Bis-DMA
Muller et al. (1997) [57] Water GC TEGDMA
Lee et al. (1998) [58] Ethanol, acetic
and proprionic
acid
GC/MS TEGDMA, silane, catalysts
Pelka et al. (1999) [59] Water HPLC TEGDMA, methacrylic acid
Spahl et al. (1998) [60] Water, methanol GC/MS; LC/MS All monomers and catalysts in
methanol; TEGDMA in water
Hamid et al. (1998) [61] Water HPLC HEMA
Guertsen et al. (1999) [62] Water GC/MS TEGDMDA, other monomers, ethyl-
ene glycol, HEMA, catalysts
Lygre et al. (1999) [63] Water GC/MS TEGDMA, EGDMA, catalysts
Munksgaard et al. (2000) [64] Methanol HPLC Bis-GMA, TEGDMA
Mazzaoui et al. (2002) [65] Ethanol/water Ionization/MS Bis-GMA, TEGDMA, HEMA, UDMA,
BisPhenol A
Michelsen et al. (2003) [66] Ethanol, Ringers GC/MS All monomers (and decomposition
products) and catalysts (more in
ethanol)
Finer and Santerre (2004) [25] Esterase HPLC, UV, MS TEGDMA, BisHPPP, E-bisPA, TEGMA,
methacrylic acid
Wada et al. (2004) [67] Water HPLC HMBP, BHT, DMPA
Solvent effects on polymer networks 217
to be leached from these cross-linked resins. This
topic has been extensively reviewed by Santerre
et al. [24]. A degradation reaction would undoubt-
edly require time to produce signicant quantities
of any by-product, suggesting that elution studies
may need to examine several time points. It should
also be noted that many studies have also reported
on the leaching of monomers and plasticizers from
denture base, reline, soft liner and tissue con-
ditioning materials, most of which are not cross-
linked polymers.
Quantity
Most of the unreacted methacrylate groups in
dental restorative resins, sealants and adhesives
are not capable of being leached into aqueous
environments, because they are part of dimetha-
crylate molecules that have reacted on one end
and are therefore covalently bonded to the main
polymer chain. Despite this, a signicant amount
of unreacted monomer or small chain polymer is
released. Studies show elution of as little as
0.05% to as high as 2.0% of the weight of the
specimen, with elution into alcohol and other
organic solvents being generally higher (26%)
(Table 2). Inoue and Hayashi [44] have suggested
that only 10% of the unreacted monomer in
dental composite is elutable. This conclusion is in
good agreement with Ferracane [30] who
suggested that about 8% of the total remaining
carbon-carbon double bonds are elutable as
unreacted monomers, and Tanaka et al. [47]
who suggested that only 27% of the unreacted
monomer was elutable. Elution from set resins is
rapid for most species, essentially reaching
completion within 13 days. One study shows
Bis-GMA continuing to leach in very small
concentrations for more than one week [47].
Elution has been shown to be dependent upon
surface area, as demonstrated with milled
composites [59]. Munksgaard et al. [64] veried
much higher elution when the composite was not
adequately light-cured. However, the results
suggest that none of these resins provides a
signicant, long-term source of monomer eluates
due to the small concentrations available and the
rapid rate of release.
Hydrolytic degradation
Polymers may be degraded in aqueous solutions
through two primary mechanisms: passive
hydrolysis and enzymatic reaction [75]. Reviews
of polymer degradation mechanisms have been
published [1,24]. Studies have shown dental
polymer networks to be degraded to produce
small molecules through oxidation, attack of
functional groups, and chain scission. Studies
further show that methacrylates can undergo
degradation reactions over time, producing for-
maldehyde via oxidation and methacrylic acid
and other molecules, such as bis-HPPP, which is
Table 2 Studies measuring the quantity of elutable species and their rate of release.
Study Solvent Quantity Rate
Inoue and Hayashi (1982) [44] Water 0.050.12% Nearly all eluted within
3 days
Thompson et al. (1982) [45] 8090% within hours
Pearson and Longman (1989) [72] Water 0.250.85%
Ferracane and Condon (1990) [49];
Pham and Ferracane (1989) [73]
Water and ethanol 1.52.0% 5075% of total elutes
within 3 h and 90C%
within 24 h
Rathbun et al. (1991) [48] Organic solvents 47%
Tanaka et al. (1991) [47] Water 0.21.5% Most of TEGDMA elutes
in 12 days; Bis-GMA
elutes for weeks
Ferracane (1994) [30] Water and ethanol 0.253%; 17% EtOH
Hume and Gerzina (1996) [53] Water (in dentin) 630 mg Mostly complete by
1 day
Pelka et al. (1999) [59] Water TEGDMA Rate at 24 h !10% of
1 h
Munksgaard et al. (2000) [64] Methanol 0.20.6%
Hofmann et al. (2002) [74] Water (1 d); 50% (3 d)
methanol
0.30.8% water;
0.35.2% methanol

J.L. Ferracane 218


the dialcohol left after splitting methacrylic acid
from bis-GMA by hydrolysis or esterication
(Table 3). Oxidation reactions, and potentially
transesterication, can occur in water or ethanol.
Lee et al. [51] used micro-FTIR analysis to
provide evidence for degradation attributable to
either hydroperoxidation or transesterication of
composites and adhesives stored in ethanol.
Various esterases that have been shown to be
present in saliva in adequate concentration can
cause esterication of methacrylates [82]. The
chemistry of these degradation reactions has
been described elsewhere [24], and is shown in
Fig. 5.
The extent of the enzymatic degradation is
probably related to the extent of cure of the
resin, because ester groups may be more
available for attack in more loosely crosslinked
networks. However, the composition of the
monomers producing the network is of primary
importance in determining the extent of
degradation, especially when enzymes are
responsible. TEGDMA has been shown to be
more susceptible to enzymatic hydrolysis than
Bis-GMA [22,83] or Bis-EMA [81]. The effect of
enzyme degradation has been manifested as a
reduction in surface hardness [8485] and wear
resistance [21].
Evidence for the hydrolytic degradation of
dental polymers has been presented in the
adhesives literature. Hashimoto et al. [86] showed
a signicant reduction in bond strengths for a
fourth generation, total etch adhesive when
placed in primary teeth and tested after
exfoliation of the teeth 13 years later. Their
subsequent study used scanning electron
microscopy to verify digestion of collagen and
degradation of the adhesive resin, primary due
to elution of unreated components, both within
the hybrid layer [87]. Further evidence for
hydrolytic degradation of the hybrid layer has
been presented by Okuda et al. [88]. Koshiro
et al. [89] also showed evidence for increased
porosity in the hybrid layer for certain total etch
adhesives, but a more stable interface at one year
for a self-etching adhesive system when tested in
monkeys.
In summary, polymers used in dental restora-
tive materials are subject to both hygroscopic
and hydrolytic effects that may inuence their
mechanical properties, dimensional stability and
biocompatibility. The extent to which these
phenomena affect the clinical performance of
polymer restoratives is unknown, though
numerous investigators have alluded to the
potential for reduced service lives. Based on
what is perceived as a general consensus that
materials related failures of dental restoratives
represent a relatively small proportion of the
total failures, the effects of solvent uptake and
polymer degradation may be of minimal conse-
quence. However, what must constitute a con-
cern are the short-term release of unreacted
components and the long-term elution of degra-
dation products in the oral cavity, and this should
be considered during restorative material
development.
Table 3 Studies assessing the degradation by-
products produced from dental resins.
Study Solvent Products
Oysaed et al.
(1988) [76]
Water Formaldehyde
Ruyter (1980) [77] Water Formaldehyde
Koda et al. (1990)
[78]
Articial saliva Methacrylic
acid
Lee et al. (1995)
[79]
Ethanol Not speci-
cally identied
Munksgaard and
Freund (1990)
[22]
Esterases Methacrylic
acid
Bean et al. (1994)
[23]
Esterases Methacrylic
acid
Pelka et al. (1999)
[59]
Acid solution Methacrylic
acid
Santerre et al.
(1999) [20]
Esterase Methacrylic
acid
Shajii and San-
terre (1999) [80]
Esterase bis-HPPP
Yourtee et al.
(2001) [81]
Esterases Methacrylic
acid
Finer and San-
terre (2004) [82]
Esterases Methacrylic
acid, bis-HPPP
Figure 5 (a) Mechanism for formaldehyde formation
via oxidation of methacrylate, after Oysaed et al. [76].
(b) Mechanism for methacrylic acid formation via
hydrolysis of TEGDMA in the presence of an enzyme,
such as cholesterol esterase, after Santerre et al. [24].
Solvent effects on polymer networks 219
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