Dent Mater 11:354-358, November.

1995

Properties of heat-treated composites

after aging in water

Jack L. Ferracane, Joel K. Hopkin, John R. Condon

ABSTRACT
composite inlays ils compared with direct fill restoralion~. It I\
Objectives. Post-cure heat treatments have been shown to Increase the
also believed that these restorations may be more durable
fracture toughness and elastic modulus of composites. The objective of
because of an enhanced cure produced by the application of
this study was to determine if the increase remained after the
heat to initiate curing or to further the reaction ot’ 3 light-cured
composites were aged in water.
restoration. i (2.. post-cure heat treatment. However. 1)11t‘
Methods. The fracture toughness (K,,), flexural modulus and flexural
clinical study reported no difference in the wear rates tor ;t
strength of four experimental and one commercial composite (Z-100,
light-cured inlay and an inlay given an additional heat
3M Dental Products) were tested after 1.7.30,60 and 180 d of aging in
37°C water. The four experimental composites were made with a treatment for IO min at 1?O”C. although marginal integrity
and post-op sensitivity were improved (Wendt and Lxinfelder.
BisGMAiTEGDMA resin and were characterized as follows: Micro =
1990).
38 ~01% silane-treated silica, Fine = 65 ~01% silane-treated quartz of
Numerouh studies have reported on rhe ettcct ot ~W;II
1-2 pm average size, Hybrid = 65 ~01% silane treated quartz of a
treatments on the mechanical properties of dental compoite>
mixture of 1-2 pm average and 8 ym average size, and Large =
which shov.ed increases in diametral tensile strength.
65 ~01% quartz of 8 pm average size (of which only 75% were silane-
hardness. ellthtic modulus. :tbrasion rc\i\liuicc’. flcsurai
treated). All specimens were light-cured (normal-cured:Triad II - 80 s).
strength. and t’rxture toughness (Wendt I YX7:r: lYX7b: I YXY‘
One set of each composite was further heat-cured at 120°C for 10 min
Keinhardt. IYXY: Asmussen and Peutrt‘eldt. IYYO: Cook anti
(heat-cured). A third set of the Hybrid was heat-cured with
Johannson. 19X7: De&e rf cl/ IYYO: FLl,jishlma 0: ~11 IV)!
simultaneous light exposure (Elipar, Espe) for the first 3 min.
McCabe and Kagi. 19YI: Ferracane and (‘ondon. 1992). III
Results. By 30 d, normal-cured and heat-cured specimens showed
contrast, compressive strength and compressive modulus ‘reem
significant (ANOVAiTukey’s test; p s 0.05) reductions in fracture
to be only minimally increased or remain unaffected (Wendt
toughness (avg. 16% and 22%, respectively), flexural modulus (avg. 11%
1987x 1987b) The increase in certain properties has beeli
and 1I%, respectively) and flexural strength (avg. 25% and 29%.
shown to be related to an increase in degree of curt’ hCook mi
respectively). Further aging had little effect. The use of additional light-
Johannson. 19x7. Ferracane and (‘ondon. IQV i
curing during heating did not affect the properties more than heat-curing
Earlier result\ in the present laboratory ~i~(~cv~*cI I~;II
alone.
experimental composite\ made with ;1 BisGM.4/TEGDMA resin
Significance. The tmprovements in some of the properties of
filled with quartc particles experienced a reciuc-tion tn fracturr
composites produced by heat-treating are of only short-term benefit.
toughness during agin, (r in water. even aIter beins g~\en ;i
and are for the most part negated due to an alteration of the resin matrix
post-light-cure heat treatment ikrracane and ~‘ondon. I QYl )
as the composite equilibrates with water.
Therefore. the ob,jectives of’ this study \ttlre IO e\.tluate the
htabilitv ot’ the mechanical propertles f~rr St ,crie\ 01’
INTRODUCTION
composites cured with light energy alone or light tollowed b! .i
Composite inlays have become popular due to the difficulties heat treatment. Fracture toughness. t‘lexurai rnodulu\ .tnci
encountered in placing direct posterior composite restorations. tlexural strength were cvalunted after asing the composite-. in
The major benefit to be derived from the inlay is an improve- water for several time periods LIP lo 6 mon. The hypotheG< to
ment in the fit at the margins due to the minimization 01 hc tested was lhul water sorption ~vould L‘~III~K .I greater
contraction stresses, Hailer et trl. ( 1990) reported improved reduction in the mechanical properties for the Irgh-cured (VII\

354 Ferracane et a/./Aging of heat-treated composites

 mold. The protocol outlined in IS0 3049 (ISO. 1988) for
resin-based filling materials was followed. The samples (n = 6)
were initially light-cured as described above and were tested
in three-point bending on a span of 20 mm at a crosshead speed
of 0.254 mm/min. The crosshead iravel of the universal
Micro 38 SiO, 0.04 pm 0.01 - 0.2 pm testing machine was synchronized with the motion of the strip
PPRF* 17.00 pm 1.0 - 60 ym chart. The slope of the linear portion of the load vs. time curve
was used in the calculation of the modulus according to the
Fine 65 quartz 1.60 pm Of - 5pm specification. Specimens were aged in water at 37°C for 1 d
and 30 d before testing.
Hybrid 65 quartz 1.60 pm (55 wt%) 0.1 - 5 pm Within S min after the initial light-curing. a second set of
800pm(45wt%j l.O- f5pm specimens was heated for IO min in an oven at 120°C. These
heat-cured specimens were then placed in water at 37°C for
large 65 quartz 8.00 pm+ 1.0 - 15 pm periods of I d. 7 d, 30 d, 60 d and I80 d before testing. For the
Hybrid composite (Table I ), a third set of specimens was made
z-100 66 zircon/a 0.60 pm O.f- 5ym by subjecting the specimens to additional light-curing using
silica direct illumination from the exposed bulb of a disassembled
curing light (Elipar, Espe, Germany). The bulb was positioned
against the glass door of an oven set at 120°C and illuminated
the composites at a distance of IS mm during the first 3 min of
composites because the increased cure in the heat-treated a IO min post-light-curing heat treatment. This experiment
composites would make their polymer networks more was performed to determine if light application during the heat-
resistant to degradation. The degree of cure (DC) for one of the treatment could further the polymcrlration reaction by the
composite\ was evaluated by Micro-FTIR (XAD Micro-FTIR production of additional free radicals.
module/RFX 30 FTIR. KVB/Analect. Irvine, CA. USA) to Degree of conversion was detennined for samples from the
determine if changes in properties during aging could be Micro composite for both the normal-L,ured and heat-cured
attributed to a change in conversion. groups at I d and 30 d. Conversion of carbon double bonds
during the polymerization reaction was evaluated using
MATERIALS AND METHODS transmission Micro-FTIR from chips removed with a scalpel
from the surfaces of the specimens used in the fracture
Four experimental light-cured composites with different filler
composition5 were made with a 50% BisGMA / 50% TEGDMA toughness test. The chips were norrnall~ 20-30 pm thick and
(triethyleneglycol dimethacrylate) resin l(K) pm or so in length. Because the surface of each bar was
containing
campl-loroquinone and a tertiary amine reducing agent lightly ground prior to testing. the chips were removed from an
(Table I ). The resin wa\ the same as that used in Silux Plus area that was 20-30 pm below the actual light-cured surface
t3M Dental Products. St. Paul. MN, USA). The composites which had been covered by a plastic matrix. The uncured pastes
were synthesized for the study by a dental manufacturer were first examined in transmission and the ratio of C=C/C...C
(3M Dental Products) using quartz and fumed silica silanated before and after curing was determined using techniques
with methacryloxypropyl trimethoxysilane (5% by weight of previously described in detail (Ferracane and Marker, 1992).
filler and 20% hq weight of filler, respectively). These formula- Two-way ANOVA and Tukey’s test for making multiple
tions were chosen to provide a spectrum of materials in terms comparisons between means were used to compare the
of filler size and filler/matrix coupling. In addition. one fracture toughness, modulus and ttrength results for the
commercial material was evaluated. Z- 100 (3M Dental different time periods and curin g modes for each composite
Products) is 21 light-cured, small particle composite containing (p i 0.05).
66 ~01% of ;I synthetic Lirconia silica with an average size of
0.6 pm and ;I BisGMA/TEGDMA resin matrix. RESULTS
Fracture toughnes\ (K,,) was evaluated using single edge The fracture toughness values for the experimental
notch specimens (2.5 mm x 5.0 mm x 2.5 mm) prepared in steel composites subjected to the normal-cure and the heat-cure are
molds with a r;1zor blade insert to provide an a/w of 0.5. where presented in Table 2. As previously shown, the heat-
a = notch length and u = specimen width. The specimens treatment initially produced a significant increase in fracture
(n = 6) were initially cured in a light-curing unit (Triad II, Caulk/ toughness ranging from IO-25% for each composite (Ferracane
Dentsply. Milford, DE, USA) with 40 s exposures of both the and Condon, 1992). Aging in water for 7 ld did not significantly
top and bottom surface\. These specimens, representative of a change the K,‘ for any of the experimental composites, except
normal-cured composite, were then soaked in deionized Micro, which showed a significant reduction for the normal-
water at 37°C’ for periods of I d. 7 d. 30 d, 60 d and I80 d before cured specimens. Continued aging In water beyond 7 d
testing. The Z- 100 specimens were aged for 1 d, IO d and 40 d. generally caused a significant reduction in the K,‘ for each
Specimens were tested on :I universal testing machine (Model composite. The average reduction I‘or the normal-cured
TT-B, Instron Corp.. Canton, MA, USA) in bending on a span specimens was 185%at 30 d, IX% at 60 d and 19%) at 180 d. The
of 20 mm at a crosshead speed of 0. I27 mm/min. K,, was average reduction in K,L for the heat-cured specimens was 23%
calculated as previously described (Ferracane Ct ~1.. 1987). at 30 d, 25% at 60 d and 22% at I80 d. There was no significant
Flexural modulus and flexural strength were evaluated reduction in K,L for any composite after the 30 d aging period,
using bars (35 mm x 2 mm x 2 mm) produced in a split steel with the exception of Micro at IX0 cl. In general, the normal-

Dental hk&rialdNovember 1995 355

 Micro Norma/-cured 1.08(0.05)' 0.83(0lOI!' 0.80(O.OS)r

Heat-cured 1.34(0.07)" 1.25(0.08) 0.98(0.51' 0.92(0.05P

Fine Normal-cured 1.62(0.04pb 1.71(0.14)a 1.40(0.09) 1.46(O0.08)hCA 1.42(0.10)""

Heat-cured 1.97(0.08) 2.01(0.14)" 1.53(0.06)b 1.50(0.07)"A

Hybrid Normal-cured 1.81(0.05) 1.86(0.16) 1.49(0.08)-' :48 (007)L:

Heat-cured 2.05(0.
IO) 2.09(0.12k 1.54(0.1op 1.53(O.OSP" 7 6! @10):'

Large Normal-cured 1.82(0.07) 1.70(0.06pb 1.55(0.08pF 1.58(0.06)hcH

Heat-cured 2.oo(O.lOfa 1.96(0.13)a 1.61(O.lOjbF 1.58(0.08)""

cured and heat-cured composites behaved identically. The the heat trcattnent. but the diflercnce v+~I\ 011i) \f:_inltlc,a11t IIN
samples subjected to the heat-cure had significantly higher Micro. Large and Z-100 [Fig. 31. There M;I\ <i \ignit‘ican~
fracture toughness than the light-cured samples at the earlier reduction in flexural strength for all cxperimcntal compo\itek
time periods, but this difference was eliminated by 30 d or 60 d as a resull of water storage for 30 d (p I 0.05 I. l’hc nzduclion ii)
for all but Micro. tlexural strength was Gtnilar for the norma-curtxd (;~verage i II

The fracture toughness of the commercial composite, Z-100, 25% ) and heat-cured (average of ZY/c ) samples. ‘T‘~c reduction
was significantly increased by the heat-cure. However, there for Z- 100 w a 74% for the specimen subjected IO the ~totmxtl

was a significant 1.5% reduction in K,‘ for both the norma- cure and 37’1; t’or the heat-cured specimen\
cured and heat-cured Z- 100 specimens after 10 d (Fig. I ). The Fig. 4 demonstrates that approximately 71 ( ~I,~IY ot tll~>
K,‘ was further reduced by a total of 45% for both sets of available carbon-carbon double bonds in the Micrct comp(~Gl~
specimens after 40 d in water. had reacted a\ a result 01’the heat treatment. c,ontrlbuting to ,.I
The Hybrid composite specimens subjected to the post- significant increase in con\ er\ton (17 5 0.05 1. Tlici-v i\ ;I\ II,%

light-cure heat treatment with a simultaneous exposure to light difference in degree of con\,erjion tor the \p~c~mcn~ w

had an initial fracture toughness of 2.17 -f: 0. I I MPa.m”‘. which tneasured after 30 d ot aging in eater
was about 5% higher, but not significantly different from the
heat-cured material. After 30 d of aging in \;ater, these DISCUSSION
specimens had a K,( of 1.56 f 0.04. which was the same as the The result\ ot thih htudy dcmon\trate thal the ~n~ttai IIICIYXW

specimens subjected to the heat treatment without an in mechanical properties of composites \ub,jectetl to ;I po+lighl--
additional simultaneous light curing. curing heat treatment i\ transient. Recauht’ ~Jrni’ of the initial
The flexural moduli of the experimental composites was properties of the composite\ arc‘ Itnprovc’d ;I\ ;I rc,\ult ot‘ 111~’
significantly increased by S- 10% after the heat-treatment heat-curing process. the final properties cjftcn rcsmained hi&cl
(Fig. 2). The modulus of Z- 100 was increased by 20% after the than those of the composites that were light-cut-cd onI>. Tht,
heat-cure. Each experimental composite experienced a slight fact that the composite\ sub,jccted to the Norma-curIIlg
but significant reduction in flexural modulus after aging in experienced 21 reduction in propertie\ which ~~lo~l! paralleled
water for 30 d (p 5 0.05). The average reduction for the four the reduction experienced by the hca-L.urcd \perimcnh
composites exposed to the normal-cure was IO%. and suggests that the reduction ha\ ;t similar ctiologh III both GISC\

essentially the same as for those exposed to the heat-cure (i.c~. The reason for thij reduction in propertic\ i\ predominanti\
I I%,). The flexural modulus of Z- 100 did not change related to the uptake of‘ water hy the polymer-. which likeI>
significantly during aging. causes a swelling of the croa\linked polymer nctworh thaw

The initial flexural strength was increased by approximatel) reduces the frictional forces between the polvmrr chains. ()nc~~
10% for the experimental composites and Z- IO0 as a result of the polymer network \aturate\ \bith Mater. ~hr‘ ~o~nposrtt~

356 Ferracane et a/./Aging of heat-treated composites

 m NORMAL CURE

m NORMAL CURE HEAT CURE

2.50

1 30 1 30 1 30 I 30 1 30
MICRO FINE HYBRID LARGE Z-100

TIME (days)

Fig. 1. Graph of fracture toughness vs. time for 2.100 comparing the normal-cured Fig. 2. Graph comparing the flexural modulus for the normal-cured and heat-cured
and heat-cured specimens. specimens at the two time periods. Bars connect values at 1 d and 30 d that were
not significantly different. Asterisks denote values of normal-cured and heat-cured
specimens that were not significantly different for a given composite.

- NORMAL CURE HEAT CURE m NORMAL CURE i@% HEAT CURE

200 80
--
--
*I *

60 ’
1 30 1 30 1 30 1 30 1 30 1 day 30 days
MICRO FINE HYBRID LARGE Z-100
TIME
Fig. 3. Graph comparing the flexural strength for the normal-cured and heat-cured Fig. 4. Graph of degree of conversion vs. time for Micro comparing the normal-
specimens at the two time periods. Bars connect values at 1 d and 30 d that were cured and heat-cured specimens.
not significantly different. Asterisks denote values of normal-cured and heat-cured
that were not significantly different for a given composite.

structure reaches a stable state. and no further reduction in monomer or oligomers which appears to be completed within
properties occurs. This limited reduction in properties several days (Ferracane and Condon. 1090). Simultaneously,
provides evidence that further degradation, such as filler/ water is absorbed by the composite.. predominantly by
matrix inter-facial hydrolysis or polymer matrix crazing, does diffusion into the polymer matrix. Water swells the polymer
not occur to a significant degree as long as the composite and occupies space between the main chains and crosslinks.
remains moist. Also. results from a previous study in this as well as filling microvoids created during the polymerization
laboratory in which specimens aged dry for 30 d did not process (Soderholm, 1984). The uptake of water is a
experience a reduction in properties (Ferracane and Condon, diffusion-controlled process. requtring weeks to reach
I99 1). emphasizes that a weakening of the polymer due to completion. This slow uptake of water c~orrelates with the fact
water uptake is primarily responsible for the decreases seen in that for the majority of the composites, the properties werp not
the present study. Finally, the fact that no change in degree of reduced until the polymer matrix was essentially saturated
conversion occurred during aging for 30 d shows that an with water. This required about 30 d of soaking.
alteration in cure state did not contribute to a reduction in the The fact that the properties were essentially the same at
properties. 7 d as they were initially is not surprising. As leachable
When a light-cured resin composite is soaked in water, two components are removed from the composite during the first
phenomena occur. There is a rapid elution of uncured few days. water is absorbed to replace them. The net effect is

Dental Materi’aMVovember 1995 357

minimal and the properties are not affected. However, once
the majority of the elutable components are extracted, uatel
uptake continues to swell and alter the polymer matrix. It is
possible that at the same time the water may cause \ome
hydrolysis of the filler/matrix interfaces and/or a crazing of the
polymer matrix which would contribute to the reduction in
properties. However, imaging of the fracture surfaces by
scanning electron microscopy did not show an)’ evidence ot
such events.
The simultaneous light curing for the initial 3 min of the
heat-treating process for the Hybrid composite had no
significant effect on the fracture toughness after 30 d of aging.
The heat treatment. alone or in combination with the
additional light exposure, was expected to increase the degree
of conversion of the polymer. However, it was thought that the
additional application of light energy during the hear
treatment tnight generate more free radicals to participate tn
the polymerization process. thus driving the curing reaction
further than was possible with the additional heat treatment
alone. This material might then be more resistant to the
degradative effects of the water solvent. No evidence for this
was revealed. though this is a technique used in at least one
commercial curing system. The lack of a significant difference
suggests that the degradative effects of water are independent
of cure state. However. another possibility is that the light \~‘a>
significantly attenuated by the distance to the specimen. a\
well as the glass plate of the oven and, therefore. had no et’t’ect
on increasing the number of free radicals. Although the extent
of this attenuation was not measured. it should bc pointed OLIN
that in the Triad II curing unit which provides the initial light
exposure. the specimen rehts a similar distance from the light
source and the light must pass through a mall plate of glas\
in front of the bulb to reach the specimen.
The results of this study jhow that for BiaGMA-based
composites. the initial increase in some mechanical
properties (especially the fracture toughness and flexural
strength) that is produced by the post-light-curing heat
treatment is transient. Though the final properties of the hcat-
cured materials often remained higher than those that were
light-cured only, both materials experienced similar reduction\
as a result of aging in water. This conclusion support5 ;I
clinical study which reported no difference in wear resistance
for inlays that were tight-cured only I’.\. those that were
exposed to a heat treatment after the initial light-curing (Wendt
and Leinfelder. 1990). In addition. the results of this stud!
also support the reduced i/r ritzy wear resistance reported tar
heat-treated composite inlays after aging in water (DeGce
ctt (11.. 1990). Though the heat treatment may not produce a
long-term improvement in properties, it does appear lo be an
effective mechanism for increasing the degree of conversion in
dental composites and, therefore. may still ha\#c merit.

ACKNOWLEDGMENTS
The authors would like to thank 3M Dental Products. St. P~LII.
MN. USA. for providing the composite materials used in thiz
htudy. This work was supported in part by Research Grant DE
07079 from the National Institute of Dental Research, National
Institutes of Health, Bethesda, MD. LJSA.

358 Ferracane et a/./Aging of heat-treatedcomposrtes