An in vitro investigation of a poly(vinyl phosphonic acid) based cement

with four conventional glass-ionomer cements. Part 1: exural strength

and uoride release
V.H.W. Khouw-Liu, H.M. Anstice, G.J. Pearson
*
Departments of Paediatric Dentistry and Biomaterials Science, Eastman Dental Institute, University of London, 256 Grays Inn Road, London WC1X 8LD, UK
Received 10 March 1998
Abstract
Objective: To investigate the exural strength and uoride release of four conventional glass-ionomer cements: Ketac-Molar (KM), HiFi
(HF), Vivaglass Fil (VF), Ketac-Fil (KF) and a newly developed glass polyphosphonate cement, Diamond Carve (DC).
Method: Disc specimens (10 mm diameter, 1 mm thick) were prepared and mould stored at 37C. After one hour, the specimens were
removed from their mould and immersed in 20 ml of deionised water until required for testing. Biaxial exural strength was determined at 1
hour and at 1, 7, 30 and 90 days after the start of mixing. Measurements of uoride release from the specimens were carried out at 2 hours and
at 1, 3, 7, 14, 30, 60 and 90 days after the start of mixing using a uoride ion selective electrode. The results were analysed using ANOVAand
student t tests.
Results: All the materials displayed different exural strength patterns. KM and DC became stronger whilst KF and VF plateaued in
strength with time. HF peaked in strength and then became weaker. At 90 days, the mean exural strengths in decreasing order was as
follows: KMVF DC HF KF. An initial fast rate of uoride release followed by a slower but steady release of uoride was observed
in each of the materials. The mean cumulative uoride release in decreasing order was as follows: VF KF HF DC KM. VF released
signicantly higher level and KM signicantly lower level of uoride than the other materials.
Conclusions: The acid used to form the cement could not be used to predict changes in cement strength behaviour with respect to time. DC
increased in strength with time and its exural strength at 90 days was comparable to that of HF and VF. The cumulative and rate of uoride
release varied for the materials. DC had a low uoride release consistent with a fast setting material with good early resistance to water.
1999 Elsevier Science Ltd. All rights reserved.
Keywords: Glass-ionomer cements; Glass polyalkenoate cements; Strength; Fluoride
1. Introduction
First introduced in the early 1970s by Wilson and Kent
[1], glass-ionomer cement (GIC) is now established as an
important restorative material. Its inherent qualities of adhe-
sion to tooth structure and anticariogenic properties through
its ability to release and uptake uoride have encouraged
much research and development over the years [2,3]. Like
all dental materials, glass-ionomer cement has certain draw-
backs; chiey its susceptibility to water and its low initial
strength [4,5]. Since the development of the original glass-
ionomer cement, efforts have been made to improve these
properties and changes have been made in both the glass
powder component and the polycarboxylic acid. As a result,
there are signicant differences in the composition and
properties of commercial materials for the various applica-
tions.
Glass-ionomer cements are acidbase reaction cements
[6] whereby the basic component is an acid-degradable
glass and the acidic component, an aqueous solution of a
polymeric acid. Setting of the cement occurs by slow
neutralisation of the acidic polymer leading to the formation
of a polysalt matrix. This takes place through 3 stages that
overlap each other: dissolution, gelation and hardening. The
nature of the GIC setting reaction causes the strength of the
material to develop with time. Glass-ionomers reach an
initial peak strength by 24 hours after mixing suggesting
that the rst 2 stages of the setting reaction (dissolution
and gelation phase) have already occurred [79]. Any
further increase in physical properties is thought to be due
Journal of Dentistry 27 (1999) 351357
Journal
of
Dentistry
0300-5712/99/$ - see front matter 1999 Elsevier Science Ltd. All rights reserved.
PII: S0300-5712(98)00061-X
* Corresponding author. Tel.: 44-171-915-1019; fax: 44-171-915-
1019.
E-mail address: gpearson@eastman.ucl.ac.uk (G.J. Pearson)
to an increase in the number of ionic cross-links during the
hardening stage [4] and more recently has been attributed to
the slow build-up of the silica matrix during the setting
process [10].
Several groups investigating the mechanical behaviour of
GICs, have found that the strength of some materials based
on copolymers of acrylic acid deteriorates with time [9,11].
A study by Cattani-Lorente and co-workers reported obser-
ving a similar deterioration in strength but this only
occurred in a few materials and was not limited to copoly-
mer based cements [12]. Cattani-Lorente et al. attributed the
weakening to the plasticising effect of water on these mate-
rials. However, in a recent study, the loss of strength was
reported to be as a consequence of the high cross-link
density found in these copolymers and not due to hydrolysis
as previously suggested [13].
Another important property of the GIC is its long-term
uoride release and its ability to take up uoride from an
external source and subsequently release it [14,15]. The
action of this uoride clinically is a matter of some debate,
but it is thought by many to confer a cariostatic action. For
example in a recent study, when glass-ionomer and amal-
gam restorations were compared, signicantly fewer lesions
of secondary caries were found in teeth restored with GICs
[16].
In the last ve years, several new conventional glass-
ionomer cements (e.g. HiFi, Vivaglass Fil, Ketac-Molar)
have been introduced. In addition, one glass polyphospho-
nate cement has been developed and has recently become
commercially available (Diamond Carve). This cement is
based on poly(vinyl phosphonic acid), PVPA, which is the
phosphorus analogue to polyacrylic acid, PAA. PVPA,
being a stronger acid than PAA, is more reactive and is
thought to form cements that are hydrolytically more stable
[17,18] due to the rapidity of the binding of the cations to the
anions. To date, no studies have been undertaken to
compare the properties of these newer GICs. This study
therefore aimed to investigate and compare some of the
properties, in this instance strength and uoride release, of
the more recently developed materials including the new
polyphosphonate cement.
2. Materials and methods
The materials used, including details of their composi-
tion, P/L ratio, manufacturer and batch number are listed
in Table 1.
For biaxial exural strength measurements, disc specimens
were prepared using brass split rings (10 mm diameter and
1 mm thick). The materials were mixed according to the
manufacturers instructions. For the hand-mixed materials
(HiFi and Diamond Carve), the powder and liquid were
weighed out to ^ 0.001 g prior to mixing using a stainless
steel spatula on a glass slab. To formthe disc, the cement paste
was packed into a ring placed on a microscope slide. Asecond
slide was placed over the ring and light hand pressure applied
to enable the extra material to ow out of the ring through the
slit. The mould assembly was then placed in a thermostatically
controlled oven at 37C^1C. After one hour, the specimens
were removed from their moulds and then immersed in 20 ml
of deionised water in individual sealed plastic containers
before being placed in the oven again at 37C until required
for testing.
The biaxial exural strength of the materials was deter-
mined at the following time intervals: 1 hour, 1 day, 7 days,
30 days and 90 days after the start of mixing. At least six
specimens of each material were tested at each time interval.
Prior to testing, the thickness of a specimen was measured at
4 points across the disc. The disc was then placed centrally
on a knife edged annulus 8 mm in diameter and loaded at a
rate of 1 mm/min using a ball ended indentor (4 mm
diameter) in a universal load testing machine (Hounseld,
UK) with a 200 N load cell. The force at fracture of each
specimen was noted and the biaxial exural strength (FS) in
MPa calculated using the formula [19]:
FS
P
h
2
0:606 log
e
a
h
1:13 1
where:
a is the radius of the annular (mm)
h is the average thickness of specimen (mm)
P is the load at fracture (N).
1.13 is a constant derived from Poissons ratio [20].
V.H.W. Khouw-Liu et al. / Journal of Dentistry 27 (1999) 351357 352
Table 1
Materials used in this study
Material Manufacturer Batch number P/L ratio[w/w] Type
Diamond Carve Associated Dental Products Ltd L:02/97 P:R985/1 3.8:1 Glass polyphosphonate
cement (hand mixed)
HiFi Shofu Inc. P:069523-1 L:109427-1 4.5:1 Glass polyalkenoate
cement (hand mixed)
Vivaglass Fil Ivoclar-Vivadent 808131 1:1 V:V Glass polyalkenoate
cement (capsulated)
Ketac-Fil ESPE 026 12704 3.2:1 Glass polyalkenoate
cement (capsulated)
Ketal-Molar ESPE 01832039 3.5:1 Glass polyalkenoate
cement (capsulated)
The disc specimens used for measuring uoride release
were prepared using the same technique. After the 1 hour
storage period was complete, the samples were removed
from their moulds and then weighed to an accuracy of
^0.001 g. Each specimen was then stored in 20 ml of
deionised water in a sealed plastic container at 37C. The
measurement of uoride release from the samples was
carried out at the following time intervals: 2 hours, 1 day,
3 days, 7 days, 14 days, 30 days, 60 days and 90 days after
the start of mixing. 7 specimens of each material were
evaluated.
At each test interval, the specimen disc was removed
from the solution and transferred to a new container with
20 ml of fresh deionised water. The new container was then
replaced in the oven until the next test interval. The concen-
tration of uoride in the storage water from the original
container was measured using a uoride ion selective elec-
trode, calibrated using standard solutions of 1, 10 and
100 ppm uoride. Recalibrations were performed every
23 hours to compensate for any variation caused by
changes in the temperature and humidity. To measure
uoride concentration, 0.5 ml of the sample was mixed
with 1.5 ml of 0.1 M HCl in order to decomplex any
bound uoride that might be present in the solution. Once
thoroughly mixed, the concentration of uoride in ppm of
the sample solution was measured. Between all readings, the
electrodes were thoroughly washed and dried before being
placed in the next test solution.
Statistical analysis of all the results was carried out using
ANOVA and student t tests.
3. Results
The results of the exural strength measurements for all
materials are summarised in Table 2 and Fig. 1. They show
the mean values of exural strength (and standard deviation)
in MPa for the different test materials at the different test
intervals.
As can be seen from the results, there was no single trend
in the change of measured strength with time. HiFi
increased in strength up to day 30 but from day 30 to day
90 showed a signicant decrease in exural strength.
Diamond Carve increased its strength with time. The great-
est increase in exural strength for this material occurred
from 1 hour to 1 day after which the rate of increase was
more gradual. The difference in exural strength from 1
hour and day 90 was highly signicant but that from day
30 to day 90 was not. Vivaglass Fil reached its maximum
exural strength earlier at around day 7. It was interesting to
note that the material did not show any signicant change in
strength from day 1 to day 90. Although there was a slight
decrease in exural strength between day 7 and day 90, this
was not statistically signicant. Ketac-Fil demonstrated a
V.H.W. Khouw-Liu et al. / Journal of Dentistry 27 (1999) 351357 353
Table 2
Flexural strength of each material over the test period (MPa). Results
expressed as mean (standard deviation) n 6
Day HiFi Diamond Carve Vivaglass Fil Ketac-Fil Ketac-Molar
1/24 31.7(3.6) 27.7(3.1) 39.6(5.4) 26.6(3.0) 34.5(10.5)
1 40.4(6.7) 36.5(2.9) 44.3(5.2) 33.0(3.6) 44.7(6.0)
7 40.8(3.2) 38.7(5.0) 51.7(3.0) 37.0(2.6) 46.5(8.5)
30 49.0(2.9) 43.3(10.6) 48.6(6.0) 36.5(3.7) 46.3(4.1)
90 43.3(4.3) 44.8(4.4) 48.9(7.0) 37.4(5.3) 54.3(4.4)
Fig. 1. Comparison of mean exural strengths of each material at different time intervals. Note: Error bar is ^ 1 standard deviation.
rapid increase in strength initially. The exural strength
reached its maximum measured strength at day 7 after
which there was no change in strength for the remainder
of the experiment. Although Ketac-Molar showed a rapid
early increase in exural strength from 1 hour to 1 day, the
material also increased in strength throughout the test
period, the increase in strength between day 30 and day
90 was highly signicant.
Whenthe measuredstrengths of the materials at 1 hour were
compared, Vivaglass Fil was found to be signicantly stronger
than Diamond Carve, Ketac-Fil and HiFi although there was
nostatisticallysignicant difference instrengthbetweenViva-
glass Fil and Ketac-Molar. However, Ketac-Molar had a high
standard deviation representing 30%of its mean value. By day
30, the properties of the materials had changed such that the
exural strengths of Vivaglass Fil, Ketac-Molar and HiFi were
not statistically different. Ketac Fil was signicantly weaker
than all other materials except Diamond Carve although it
should be noted that Diamond Carve had a high standard
deviation (25% of the mean value) at that time interval.
After 90days storage, Ketac-Molar was the strongest material;
Vivaglass Fil, HiFi and Diamond Carve were all similar in
strength and Ketac-Fil remained signicantly weaker than
all the other materials.
The cumulative uoride release results (mg F/g cement)
from the 5 glass-ionomer cements are summarised in Table
3 and Fig. 2.
All the materials showed a measurable uoride release
with time. Two phases of uoride release were observed in
each of the material, an initial rapid uoride washout
V.H.W. Khouw-Liu et al. / Journal of Dentistry 27 (1999) 351357 354
Table 3
Cumulative uoride release of each material over the test period (mg F/g cement). Results expressed as mean (standard deviation) n 7
Day HiFi Diamond Carve Vivaglass Fil Ketac-Fil Ketac-Molar
2.24 0.10(0.03) 0.03(0.01) 0.25(0.3) 0.09(0.01) 0.01(0.00)
1 0.55(0.18) 0.16(0.05) 1.22(0.22) 0.55(0.04) 0.09(0.01)
3 0.71(0.25) 0.24(0.08) 1.60(0.29) 0.88(0.07) 0.15(0.02)
7 0.93(0.32) 0.34(0.12) 2.03(0.36) 1.21(0.10) 0.22(0.02)
14 1.16(0.39) 0.46(0.16) 2.48(0.42) 1.57(0.13) 0.29(0.03)
30 1.50(0.49) 0.65(0.19) 3.16(0.54) 2.05(0.16) 0.39(0.03)
60 1.96(0.62) 0.88(0.24) 4.03(0.61) 2.61(0.21) 0.51(0.05)
90 2.27(0.68) 1.05(0.27) 4.69(0.67) 3.04(0.24) 0.61(0.07)
Fig. 2. Mean cumulative uoride release. Note: Error bar is ^ 1 standard deviation.
followed by a slower steady elution of uoride that contin-
ued throughout the experiment.
Vivaglass Fil released the highest amount of uoride
throughout the experimental period. It had the highest initial
burst, released during the rst 24 hours and the highest
ensuing rate of release. The initial rates of uoride release
for Ketac-Fil and HiFi were similar but signicantly less
than those for Vivaglass Fil. For HiFi, the second phase of
uoride release had started by day 3 whereas for Ketac-Fil,
the initial non-linear phase lasted until about day 14. The
subsequent release rates of these two materials appeared to
be similar (Fig. 2). Diamond Carve and Ketac-Molar
demonstrated similar behaviour with initial releases and
the steady state of uoride releases substantially lower
than those observed for the other materials.
At all time intervals, the mean cumulative uoride release
in decreasing order was as follows:
Vivaglass Fil Ketac-Fil HiFi Diamond
Carve Ketac-Molar
At all times, Vivaglass Fil showed a signicantly higher
level of uoride release than all other materials. The release
from Ketac-Molar was signicantly lower than all other
materials. At 90 days, the cumulative uoride releases
from all the materials were highly signicantly different
from one another.
4. Discussion
The exural strengths of the materials were tested and the
changes in strength after ageing in water at simulated oral
temperature over 90 days were monitored. The results
obtained showed that both the exural strengths and their
variation with time were different for the selection of mate-
rials tested.
An appreciable increase in strength over the rst 24 hours
was seen with all the materials tested. This has been
observed in previous studies [4,9] and was attributed to
the completion of the rst two stages of the setting reaction
(dissolution and gelation). All the materials showed a subse-
quent increase in strength albeit at different rates up to day
7. It was after this time that they behaved differently. The
increase in mechanical properties with time has been attrib-
uted to the maturation of the cement matrix due to additional
cross-linking resulting from the formation of new calcium
and aluminium polyacrylates [4]. However, as this post-
hardening reaction continues, the matrix becomes more
rigid and the free carboxylic groups therefore become less
available to form ionic bonds and the rate of reaction slows
down. More recently, Wasson and Nicholson have attribu-
ted the additional strengthening of the materials to the slow
build-up of a silica matrix resulting from the acid degrada-
tion of the aluminosilicate glass [10].
In this study, the Ketac-Molar specimens were signi-
cantly stronger than those prepared from Ketac-Fil. In fact
the values reported for Ketac Molar are higher than those
provided by the manufacturer in their data sheet.
This is probably due to the reduced glass particle size and
increased powder to liquid (P/L) ratio in Ketac-Molar. It is
claimed that 50% of the glass particles found in Ketac-
Molar are 2.8 mm or smaller; 90% of the particles have a
diameter of less than 9.6 mm [21]. In Ketac-Molar, some of
the polymeric acid is incorporated in a dried form into the
powder. This permits higher molecular weight polymers to
be used, resulting in improved mechanical property and
increased cross-linkage. Both Ketac-Fil and Ketac-Molar
are based on a copolymer of acrylic and maleic acid, but
neither demonstrated any deterioration in exural strength
as described by some workers previously [9,11].
HiFi, which is based on polyacrylic acid, became progres-
sively stronger during the rst 30 days but thereafter dete-
riorated signicantly in strength. Although this behaviour
when rst observed was attributed to cements based on
copolymers, Cattani-Lorente and co-workers also reported
a deterioration in strength of some homopolymer glass-
ionomer materials after long-term storage in water [12].
They attributed the weakening of these materials with
time to erosion and the plasticizing effect of water although
the cement could also have become more brittle and hence
sensitive to aws due to high crosslink density as described
by Nicholson and Abiden [13].
Vivaglass Fil had the highest initial strength and the
material achieved its maximum strength early at day 7.
This observation was rather surprising considering its softer
consistency when mixed in comparison to the other materi-
als. One possible explanation could be the addition of dried
polyacrylic acid with a higher molecular weight to the
powder. This may have enhanced the exural strength [6].
Diamond Carve had low exural strength initially but it
became stronger with time. The greatest increase in strength
took place in the rst 24 hours after which, the increase was
more gradual. By 90 days, the cement was highly signi-
cantly stronger than it was at one hour and its exural
strength was comparable to that of HiFi and Vivaglass Fil.
This slow build-up of strength was consistent with the nd-
ings of Anstice and Nicholson [22]. It is surprising because
PVPA is a stronger acid than PAA and would therefore react
much faster initially causing the bulk of the ionic matrix to
be laid down in the rst 24 hours. A possible reason for this
gradual increase in strength could lie in the glass formula-
tionthe use of less reactive glasses. The subsequent
increase in strength indicated a post hardening reaction
within the set cement. The short working time and
high P/L ratio used with Diamond Carve made mixing
difcult. This can potentially lead to specimens with
more aws or inhomogeneities. This would explain the
wide scatter of results seen at day 30. Anstice and
Nicholson also found that PVPA-based materials were
very sensitive to desiccation [22] and if subjected to a
desiccating environment, a partially hydrated matrix
would occur resulting in an inferior cement.
V.H.W. Khouw-Liu et al. / Journal of Dentistry 27 (1999) 351357 355
Again a comparison with the manufacturers data shows
that these results at 24 hours are initially similar. However at
all subsequent comparable test time the manufacturers
results are substantially higher. In fact there is a difference
of between 10 and 27% at the later stages (Table 4). It is
interesting to note that the manufacturers scatter of results
is much greater than reported in this study.
All the materials released measurable quantities of uor-
ide during the experimental period. However, there was a
large variation in the rate and amount of uoride release.
The greatest amounts of uoride were released during the
rst days after which the release rate fell but continued at a
constant rate until the end of the experiment. This pattern of
release was similar to those described previously [23,24].
The rapid initial phase of uoride elution is probably due to
surface wash off and the slower prolonged phase due to
diffusion of uoride from the bulk of the material [25].
The initial high uoride release rate may have a bacterio-
static role in caries prevention whilst the continuous steady
phase may be important in the ionic exchange that occurs in
the demineralisation-mineralisation process of tooth decay
[26].
The ranking of the different cements according to the
amount and rate of release remained unchanged throughout
the experimental period. However, a highly signicant
difference in the amount of uoride released from the
various cements was observed at the end of 90 days.
Other workers have also shown that uoride release
among various glass-ionomer cements could be signi-
cantly different [27]. This could be attributed to the many
variables that govern the release of uoride such as the type
of glass/polyacid used, its composition and proportion or the
size of the glass particles used [14,28], its P/L ratio [29],
mixing time and porosity [30].
Vivaglass Fil released the largest amount of uoride
throughout the experiment. One may speculate that this
exceptionally high uoride release could have resulted
from the incorporation of the opacifying agent, Ytterbium
triuoride (YbF
3
) into the formulation. YbF
3
has previously
been incorporated in some composite resins not only to
confer radiopacity to the material but also to provide some
measure of uoride release. Previous high releases have
been attributed to material degradation but this seems
unlikely given the maintenance of strength from 30 to 90
days.
It has been suggested that the rate of uoride release is
dependent on the maturity of the cement matrix when rst
immersed in water [31]. Davies et al. explained that when
immature cements are immersed in water, they are perma-
nently weakened, the surface area is increased by erosion
and roughening which brings about a higher level of uoride
release [31].
Vivaglass Fil and HiFi had relatively high initial rates of
uoride release which were similar to that of Ketac-Fil.
Both materials were found to set very slowly. This supports
the hypothesis that high uoride release during the initial
phase may be due to the immaturity of the cement when it
was rst immersed in water.
Ketac-Fil showed a long non-linear phase of release
lasting until day 14 suggesting a signicant surface
washout phase. Despite a short setting time, Ketac-Fil
had a prolonged high initial rate of uoride release.
This was not consistent with ndings from other studies
[3233]. Ketac-Molar released considerably less uoride
compared to all other materials. This may be explained
by its low solubility. The manufacturers had reported a
24-hour total solubility of 0.05% (Ketac-Fil 0.2%) when
samples of Ketac-Molar were placed in water after an
hour [21]. Furthermore, Ketac-Molar had a higher P/L
ratio (3.5:1) and a longer mixing time (15 seconds)
when compared to Ketac-Fil (P/L ratio of 3.2:1 and
mixing time: 10 seconds). This may explain the differ-
ence in their patterns of uoride release despite being
made by the same manufacturer.
Diamond Carve released a relatively low level of
uoride throughout the experiment. This can again be
explained by its rapid setting nature and its low solubil-
ity as well as its stiff consistency that was related to its
very high P/L ratio.
5. Conclusions
Only Ketac-Molar and Diamond Carve showed a contin-
uous increase in strength over the 90 days. The other mate-
rials showed either a plateauing effect (Ketac-Fil, Vivaglass
Fil) or a decrease in strength (HiFi) after a certain period of
time. The acids used did not predict the behaviour patterns
of the materials.
The pattern of uoride release supported the two-phase
diffusion theory postulated by previous authors, an early
rapid surface elution followed by bulk diffusion from the
core of the cement. The cumulative uoride release and the
rate of uoride release varied for the materials. Vivaglass Fil
released the highest amount of uoride throughout the
experimental period. Conversely, Ketac-Molar released
signicantly lower amounts of uoride than the rest of the
materials at all time intervals. Diamond Carve, based on
poly(vinyl phosphonic acid), had a low uoride release
consistent with a fast setting material with good early
resistance to water.
V.H.W. Khouw-Liu et al. / Journal of Dentistry 27 (1999) 351357 356
Table 4
Comparison of results for Biaxial Flexure Strength of Diamond Carve using
study and manufacturers results Manufacturers results from technical data
sheet provided by Associated Dental Products
Manufacturers Results Current study results % difference
1 day 34.5[5.8] 36.5[3.1] 5
7 days 43.3[6.2] 38.7[5.0] 10
1 month 59.7[16.2] 43.3[10.6] 27
3 months 52.2[9.0] 44.8[4.4] 15
Acknowledgements
The authors would like to thank the manufacturers: ESPE
(Germany), Shofu Inc. (UK), Ivoclar (Lichtenstein) and
Associated Dental Products Ltd (UK) for supplying the
materials used in this study.
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