d e n t a l m a t e r i a l s 2 5 ( 2 0 0 9 ) 852856

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Polymerization contraction stress in resintooth bonds under hydrated and dehydrated conditions
Masanori Hashimoto a, , Kouichi Nakamura b , Albert J. Feilzer c
a

Division of Biomaterials and Bioengineering, Health Sciences University of Hokkaido, School of Dentistry, 1757 Kanazawa, Ishikari-Tobetsu, Hokkaido 061-0293, Japan b Division of Pediatric Dentistry, Hokkaido University, Graduate School of Dental Medicine, Sapporo, Japan c Department of Dental Materials Science, Academic Center for Dentistry Amsterdam (ACTA), The Netherlands

a r t i c l e
Article history:

i n f o

a b s t r a c t
Objective. This study hypothesizes that, with enamel or dentin as a bonding substrate, intrinsic water affects the development of polymerization contraction stress in the bonds of self-etching adhesives during bonding. Materials and methods. The inuence of the water content in dentin and enamel (wetness with water as control and acetone-dried specimens) on the stress development in self-etching adhesives was determined with a tensilometer. Thin layers of self-etching primer and/or adhesive resins were created between a glass plate and a at enamel or dentin surface.

Received 7 April 2008 Received in revised form 17 September 2008 Accepted 12 January 2009

Keywords: Polymerization Contraction stress Self-etching adhesive Dentin Enamel Water pH

Results. After an initial maximum shortly after light curing for 30 min, the contraction stress was decreased in the dentin (3070%) and enamel (approximately 20%). In the acetone-dried specimens, the stress was continuously increased for 2050%. Signicance. The intrinsic water content of tooth tissue inuences the initial polymerization of polymers. This effect is favorable for stress relief in resin restoration but causes unwanted nanoleakage channel formation in resintooth bonds. 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

It has been shown that presently used adhesive resins contain relatively high concentrations of water or solvent which may induce water sorption into the resin from the tooth tissue which in turn results in accelerating hydrolysis of bonds [18]. Fluid movement study [9] has shown displacement of water in resindentin bonds during bonding procedures such as air-blasting and light irradiation. Further, a recent study showed that water sorption of bonding resins results in softening of the resin matrix and polymerization contraction stress relief [10]. This effect occurs in resins bonded to dentin as well as to enamel [11]. A TEM study [12], using silver nitrate as a

tracer, has shown that transparent carious dentin containing mineral dentinal tubules prevented water movement from the dentinal tubules to the adhesive interface. Therefore, the presence of water during polymerization may create an expanded polymer network that offers greater swelling potential, and lead to un-desirable long-term effects [18]. However, it is not clear at what level of intrinsic water content the characteristics of adhesives is signicantly affected and whether the risk is dependent on the type of hard tooth tissue (enamel or dentin) and its condition (wet or dry). The rst aim of this study was to evaluate the effect of the water content of the bonding substrate (hydrated vs. dehydrated) on the development of contraction stress during initial

Corresponding author. Tel.: +81 133 23 1211; fax: +81 133 23 1669. E-mail address: masanori-h@mue.biglobe.ne.jp (M. Hashimoto). 0109-5641/$ see front matter 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.dental.2009.01.005

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Table 1 Two self-etching adhesive system investigated. Material (manufacturer)

Two-step self-etching adhesive Imperva FL-Bond (Shofu Inc., Kyoto, Japan) All-in-one self-etching adhesive Xeno III (Dentsply deTrey, Konstanz, Germany)

Primer
4-AET, HEMA, ethanol, water

Adhesive
4-AET, UDMA, HEMA, ller

Pyro-EMA-SK,PEM-F, UDMA, BHT, EDAB, HEMA, ethanol, water

Abbreviations: 4-AET, 4-aeryloxythyltrimellitic; UDMA, urethane dimethacrylate; HEMA, 2-hydroxylethyl methacrylate; Pyro-EMA-SK, tetramethacryl-ethyl-cyclo-phosphazen-monouride; BHT, 2,6-di-tert-butyl-p-cresol; EDAB, ethyl 4-dimethylaminobenzoate and pyrophosphate.

bonding. The second aim was to evaluate the effect of the pH of self-etching primers on the dynamic stress development within resintooth bonds. To monitor the effect on the stress development when the bonding substrates are dried, specimens were divided into two groups, control and acetone-dried (24 h of acetone storage) enamel or dentin. The null hypothesis tested is that there are no signicant differences in the stress development for hydrated and dehydrated substrates.

for 24 h at room temperature to remove water. Subsequently, the cores were air-blasted and then left in air for 2 h. For the wet groups, the cores were stored in water and air-blasted prior to bonding.

2.4.

Surface treatment prior to bonding

2.
2.1.

Materials and methods

Adhesives resin systems and pH measurements

Two commercially available self-etching primer systems (Xeno III, Dentsply de-Trey, Konstanz, Germany and Imperva FLBond, Shofu Inc., Kyoto, Japan) were used in this study (Table 1). The pH values of the adhesive resin systems were measured with a pH meter (Delta 350, Metter-Toledo, Tiel, The Netherlands, pH surface electrode: Orion Ross model 8135, Thermo Electron Corporation, Breda, The Netherlands). The measurements were performed at 23 C in a dark room with special red light on approximately 10 drops of each liquid and values were read for 15 s when the pH was stable (n = 5 for each group).

For Xeno III (all-in-one self-etching adhesive), the enamel or dentin surfaces were covered with the self-etching adhesives (mixture of adhesive A and B), left undisturbed for 20 s and then air-dried for 3 s to remove the volatile solvents. For FLBond (two-step self-etching adhesive), the enamel or dentin surfaces were covered with the self-etching primers (mixture of primer A and B), left undisturbed for 20 s, and then air-dried for 3 s. The bonding resin was then applied at the primeddentin surface.

2.5.

Contraction stress measurements

2.2.

Preparation of enamel and dentin specimens

Eighty cylindrical cores of dentin, 7.0 mm in diameter were cut from the roots of central bovine incisors, normal to the at ground mesial or distal root surface, using a hollow diamond drill with copious water cooling (Diamant Boart Nederland B.V., Vianen, The Netherlands). Enamel cores were made from the crowns of central bovine incisors, using the same diamond drill. Each enamel or dentin core was mounted at the free end of a rotatable rod with the central axes aligned. A 1.0 mm length of the free end of each dentin core was trimmed to a diameter of 6 mm using a diamond bur in an air-rotor with water spray (Fig. 1). The at end of each core was nally wet ground with SiC-paper up to 600 grit at the bonding site.

The polymerization contraction stress was determined in a universal testing machine (ACTA Intense, ACTA, Amsterdam, The Netherlands) [10,11]. The cores were xed in a specially machined steel cylindrical specimen holder, from which 0.5 mm of the 6 mm diameter part of the cores could protrude, and connected to the crosshead with the load-cell of the universal testing machine. The specimens with adhesivesapplied were lowered toward the glass plate and adjusted to a position to form an adhesive layer of approximately 15 m. Adhesion to the glass plate was ensured by sandblasting and silanizing. The adhesive layer was then light cured from underneath the glass plate for 20 s (600 mW/cm2 ) using a light-curing unit (Astralis 10, Ivoclar-vivadent). The contraction stress development was recorded continuously from the start of light curing up to 30 min. The relative polymerization contraction stress was calculated by the following equation: (stress value after 30 min/stress value after 1 min) 100 (%). One-way ANOVA and Tukeys post hoc tests were used to analyze differences (p < 0.05) in the ratio of polymerization contraction stress. Differences between the maximum and 30 min values within each group were analyzed with paired ttests (p < 0.05). The number of experiments was n = 10 for each group.

2.3.

Test groups 2.6. Tensile bond test

The specimens were divided into two groups; wet (control group) and dry (experimental group). For the dry group, the enamel or dentin cores were stored in 100% acetone solution

After 30 min of contraction stress measurements, a tensile load was immediately applied with a universal testing

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Fig. 1 Polymerization contraction stress for each group as a function of time (1, 5, 10, 15, 20, 25 and 30 min) after light curing. Vertical lines stand for standard deviations. n = 10 for each group.

machine in the same test set-up with the same material at a crosshead speed of 1.0 mm/min. The mean bond strengths were evaluated by two-way ANOVA and Fishers PLSD test (p < 0.05, n = 10 for each group).

3.

Results

The results of the pH measurements (mean S.D.) of the various components of resin systems are shown in Table 2. The development of stress showed a maximum at approximately 1 min after the start of light curing followed by a clear decline

for the control group (Fig. 1). For the group of acetone-dried specimens, the stress increased continuously after light curing for 30 min (Fig. 1). Paired t-tests showed a statistically signicant difference (p < 0.05) between the maximum and 30 min value for all groups (not shown). One-way ANOVA and Tukeys post hoc tests showed statistically signicant differences (p < 0.05) in relative contraction stresses between all control groups and the acetone-dry group. The relative contraction stress (%) of Xeno III (control, dentin) was signicantly smaller than that of the other groups (p < 0.05). There were no signicant differences in the tensile bond strengths of all groups (p > 0.05).

Table 2 Components, pH values of the investigated adhesive. Resin adhesive

Two-step self-etching adhesive Imperva FL-Bond

Components
Liquid A and B (printer) Adhesive

pH
1.8 0.03 (mixed) 2.6 0.01 1.1 0.02 (mixed)

All-in-one self-etching adhesive Xeno III

Liquid A and B (adhesive)

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4.

Discussion

During the 30 min experiments of the investigation here, the polymerization stress reached a maximum value soon after completion of the exposure to the curing light, and after the maximum the polymerization stress decreased steadily for wet-dentin substrates, while it increased for the dry condition (Fig. 1). The present test set-up is commonly used for measurements of polymerization stress of resin composites [1316], and the general experience with resin composites is that the initial polymerization stress of the resin composite continues to increase up to 24 h after polymerization. In a previous study where tooth-specimens were used instead of steel, the stress development in the resin composites showed a similar behavior, it stops increasing soon after light curing has ended and then starts to decrease [10]. Of particular interest among the ndings in the present study is that the results were different for the hydrated and dehydrated samples (Fig. 2). Clearly, the surface status of the substrate, in terms of water content, plays an important role in the initial stress development, but the extent of stress development depends on the adhesive system or type used. With the phosphoric acid in total-etch systems, the smear layer demineralizes, and makes the orices of dentinal tubules wider, making it possible for water to penetrate into the adhesive interface during the polymerization of the bonding [9]. The interfacial microstructure of self-etching adhesives varies and depends on the pH of the primer or adhesive [17,18]. Recent studies have shown that three types of selfetching adhesives can be classied based on the acidic effect of the primer or adhesive: mild (pH > 2), intermediate (pH 12), and strong (pH < 1) [19]. It has been recommended to apply a separate acid pretreatment for enamel bonding, especially for non-instrumented enamel, since the etching depth of enamel self-etching primer is not sufcient to obtain micromechanical interlocking with a low-viscosity resin into micro-porosities because of the weak etching effect [20,21]. Moreover, the mild etching effect of the acidic-monomer (pH 12) leaves parts of the smear layer intact within the adhesive

Fig. 3 Tensile bond strengths for each group. A tensile load was applied with a universal testing machine after 30 min of contraction stress measurements in the same test set-up of the same material. No statistically signicant differences were found between the bond strengths of each group (p > 0.05). n = 10 for each group. A: acetone-dried specimen and C: control.

Fig. 2 Average relative polymerization contraction stress (%): (stress value after 30 min/stress value of polymerization after 1 min) 100. Horizontal bar represents signicant difference between the groups covered by the bar (p < 0.05). n = 10 for each group. A: acetone-dried specimen and C: control.

interface, when thick smear layers are created [2224]. The strong acidic effect of the Xeno III primer (pH 1.1) opens the orices of dentinal tubules that create a pathway for water invasion from the tubules even after light-irradiation. This effect of Xeno III is less than that with total etching, however, stronger than with the self-etching primer of FL-Bond (pH 1.8). The different pH of self-etching primers caused the differences in the results of stress development after light curing, due to the water sorption because the smear layer and tubule plugs act as a barrier for water invasion to the interface. However, this effect of the pH of the adhesive in stress behavior remains speculative. Further research is needed to clearly establish the effect of the adhesive pH on the reaction rate, network structure, and polymer stability. The stress increased continuously after light curing for both the dentin substrate and for the two adhesive systems tested. Acetone removes water even in the deeper dentinal structure, mainly due to the presence of dentinal tubules. Apparently, the stress did not decrease due to lack of water under dry conditions. Even with a few seconds of air-blast applied to the dentin surface by air-syringe, sufcient water remained in the tubules to affect the polymerization stress development. This could also occur in the enamel substrate, though no clear structural voids onto the bonding surface appear to be present, even when using microscopic examination. The more hydrophilic nature of the resin of Xeno III than of FL-Bond may be a reason for the differences in the stress development behavior as this may enhance water sorption of the adhesive from the dentin. However, internal water or other solvents such as acetone or ethanol may also cause the stress relief after light curing, due to their network plasticization properties [3,25]. With enamel as the bonding substrate there were no big differences between the two systems. Based on these ndings, water sorption of adhesive from the tooth substrate may be the main factor in the stress development under this test condition. The bond strength results (Fig. 3) showed no statistically signicant correlations was between bond strength and extent

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of stress development for the different groups. This suggests that the stress relief is not caused by de-bonding or fracture of the test specimens. A previous study showed that the bond strength of resin on a dry-dentin substrate is higher than with wet-dentin (normal bonding substrate), using a microtensile bond test after 24 h of bonding [26]. However, the test set-up of the present study for bond strength testing was a conventional tensile bond test where tooth and glass are bonded together by adhesives without a covering resin composite, while in a usually applied bond strength test set-up (e.g. conventional shear or tensile bond test), the adhesive interface is localized between the two parallel planes of resin composite and teeth. Moreover, 30 min of continuing stress development has already acted on the resin-bonded specimens at the time of the measurements of the polymerization stress by the testing machine before the bond testing. Therefore, a careful comparison is needed between the previously gathered bond strength results and the bond strength results of this study. Based on this, the null hypothesis that no signicant differences would be found in the stress development after light curing of hydrated and dehydrated specimens as a bonding substrate, must be rejected. Even when short-air-blasts were applied to the surface of the bonding substrate, sufcient water may remain on the surface to affect the initial stress during and after bonding during the 30 min after light curing. Such a phenomenon also occurs with enamel specimens. Water may be an important factor in polymerization contraction stress relief, but it may also induce nanoleakage formation within the bonds.

Acknowledgements
This study was nancially supported by the Netherlands Institute for Dental Research (IOT). The adhesive systems (Xeno III, Dentsply de-Trey and Imperva FL-Bond, Shofu Inc.) used in this study were generously supplied by their manufacturers.

references

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