d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 617626

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Water sorption/solubility of self-etching dentin bonding agents

Shuichi Ito a, , Tomohiro Hoshino a , Masahiro Iijima b , Naohiro Tsukamoto a , David H. Pashley c , Takashi Saito a
Health Sciences University of Hokkaido, Division of Cariology and Endodontology, Department of Oral Rehabilitation, School of Dentistry, 1757 Tobetsu, Hokkaido 0610293, Japan b Health Sciences University of Hokkaido, Division of Orthodontics and Dentofacial Orthopedics, Department of Oral Growth and Development, Tobetsu, Hokkaido, Japan c Medical College of Georgia, Department of Oral Biology, Augusta, GA, USA
a

a r t i c l e
Article history:

i n f o

a b s t r a c t
Objectives. The purpose of this study was to compare the water sorption/solubility, percent conversion and microtensile bond strength of three single-step self-etching adhesives with those of a two-step self-etching primer adhesive system. Methods. Solvent evaporation from the adhesives was determined gravimetrically. After removal of volatile solvents, the resins were cast into disks and polymerized. One-half of the disks were incubated in water while the other half were incubated in hexadecane. Repeated measurements of water sorption were made for 10 days followed by drying for 2.5 days to a

Received 12 September 2008 Received in revised form 13 November 2009 Accepted 5 March 2010

Keywords: Water sorption Water solubility Dentin bonding Percent conversion

constant weight. Percent conversion was done using FTIR spectroscopy. Microtensile bond strengths were measured 24 h after bonding. Results. All of the adhesives lost 2030% of their weight after 4 min of forced air except for Fluorobond II which lost no weight. All resins stored in water exhibited a time-dependent increase in water sorption and solubility. The resins stored in hexadecane showed very low sorption and solubility. Water sorption was highest for Absolute 2 (20.7%), intermediate for Fluorobond Shake One (10.2%) and lowest for Clearl 3 S (8.9%) and Fluorobond II (7.5%). Percent conversions ranged from a low of 68.3% for Absolute 2 to a high of 87.4% for Clearl
3

S. The two-step self-etching primer adhesive (Fluorobond II) gave the lowest water sorp-

tion and lowest solubility of any of the tested adhesives. SEM observations of resin disks incubated in hexadecane looked similar to unincubated controls. Incubating resin disks in articial saliva covered the surfaces of the resins with mineral crystallites. Signicance. Single bottle self-etching adhesives show higher water sorption/solubilities than two-step self-etching adhesives. The former products would not be expected to function as well as the latter products. 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Corresponding author. Tel.: +81 133 23 1423; fax: +81 133 23 1423. E-mail address: shu@hoku-iryo-u.ac.jp (S. Ito). 0109-5641/$ see front matter 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.dental.2010.03.001

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1.

Introduction

In 2003, Tay and Pashley [1] asked the question have dentin adhesives become too hydrophilic? It has become clear that water left on acid-etched dentin surfaces in the wet bonding technique is necessary to keep collagen brils collapsing [2], but can water also causes phase changes when dimethacrylates encounter too much water [37]. Even in self-etching adhesives that are applied to dry smear layer-covered dentin, 1030 wt% [810] water is added to the hydrophilic formulations to ionize the carboxylic or phosphate methacrylates and to solubilize calcium and phosphate ions liberated from the action of self-etching adhesives with dentin. If this water is not evaporated, it will dilute the comonomers, and may interfere with bonding [11,12] and lower the mechanical properties of the resin [6,13,14]. Manufacturers seem to concentrate on how rapidly their materials can create a bond rather than determining the optimum application time and evaporation time for maximum bond strength. It has been reported that reduction in mechanical strength [2] and modulus of elasticity [3] are associated with increasing hydrophilicity of the copolymer blends after water storage. This could explain why resindentin bonds made with hydrophilic resin monomers signicantly degrade over time in vitro [1520] and in vivo [2124]. Water sorption within polymer matrices created by contemporary hydrophilic dentin adhesives is not always uniform. Using ammoniacal silver nitrate to trace the distribution of absorbed water, Tay et al. have shown both uniform and non-uniform water uptake into commercial adhesive resins [2527]. Uniform absorption was seen as isolated individual silver grains, while the non-uniform water uptake resulted in the formation of liner, branched, water-lled channels [26]. When dentin bonded with adhesive resins was stored in water for 12 months, the distribution of absorbed water changed dramatically [27]. Clearly, water sorption by dental resins and the hybrid layer is more complex than expected [1]. All-in-one adhesives and self-etching primers are intrinsically hydrophilic owing to the presence of acidic, highly polar functional groups substituted on methacrylates, and the presence of water and ethanol solvents. They rapidly absorb water, which results in polymer swelling, plasticizing [2830] and weakening of the polymer network [2830]. Water absorption into polymers is assumed to be directly related to the hydrophilicity of the polymers [3134]. The water sorption and solubility of newly developed adhesives needs to be fully investigated. The null hypothesis tested was that none of the adhesive resins tested will have different water sorption/solubility values.

placed on a tared slide. The Teon slide was weighted before and immediately after depositing the drop of bonding resin, enabling the weight of the bonding resin (A) from the difference of the two weights to be calculated (0-min storage time). To allow the volatile dentin bonding components to spontaneously evaporate, the plastic-plate with the unpolymerized adhesive mixture was stored in the dark for 60 min at room temperature (25 C). When an air-stream was used to evaporate solvents, a 3-way air-water syringe was clamped 15 cm from the adhesive and the control button depressed half-way to produce an air ow of 20 L/min for 30 min in the dark. Five specimens were prepared per adhesive. The weight of plasticplate with the bonding resin was successively remeasured every minute for the rst 5 min, every 5 min from 10 to 30 min and every 10 min for the rest of the time. The weight of residual adhesives at each time (B) was determined by subtracting the weight of the plastic-plate. The degree of spontaneous evaporation of volatile solvents (Ep in wt%) at room temperature was followed for 60 min. The rate of evaporation of volatile solvents in response to an airstream was calculated as follows: Ep = (A B) 100 A

with A the initial weight of the adhesive mixture and B the weight of the mixture after each storage time.

2.2.

Water sorption/solubility

2.

Materials and methods

2.1. Evaporation of dentin bonding resin components by storage in room temperature and by air-drying
Forty microliters of unpolymerized adhesive were placed on a tared Teon slide. For two-step adhesive, FB II, equal volumes of primer and adhesive were rapidly (5 s) mixed together and

After the time required for spontaneous or air-streaminduced solvent evaporation was known, the commercial comonomers/solvent mixtures were placed in a circular well made in Teon to form disks 10.0 0.1 mm in diameter and 1.0 0.02 mm thick. While in the dark, the Teon well containing the solvated comonomers was exposed to the same air-stream used to evaporate the solvents in the previous section, for 30 min to insure that all volatile solvents had been removed prior to light curing. The surface of the comonomers was covered with a glass cover slip to exclude atmospheric oxygen, forming a at surface, and the resin was light-cured for 30 s using a dental curing light (Morita, Kyoto, Japan) operated at 600 mW/cm2 , with the tip held 1 mm from cover slip. After removing the disk from the mold, a similar light exposure was applied to the lower disk surface. Specimen dimensions to the nearest 0.01 mm were measured using a digital micrometer. Ten resin disks were made for each of the commercial resins. They were dry polished to a thickness of 0.50 0.02 mm. Water sorption was measured following the method outlined in ISO 4049 (12-1998). However, disk diameters were 10 mm and 0.5 mm in thickness, to match the dimensions of specimen molds. Immediately after polymerization, the specimens were placed in desiccators and transferred to a preconditioning oven at 37 C. The specimens were repeatedly weighed after 24 h intervals until a constant mass (m1 ) was obtained (i.e. variation was less than 0.2 mg in any 24 h period). Thickness and diameter of the specimens were measured using a digital caliper, rounded to the nearest 0.01 mm, and these measurements were used to calculate the volume (V) of each specimen (in mm3 ). The resin disks were then individu-

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Table 1 Composition of the adhesive used. Material (Manufacture)

Single-step Absolute 2 (AB2) (Dentsply Sankin, Tokyo, Japan Single-step Clearl Tri-S Bond (3 S) (Kuraray Medical, Osaka, Japan) Single-step Fluoro Bond Shake One (SO) (Shofu, Kyoto, Japan) Two-step Fluoro Bond II (FB II) (Shofu, Kyoto, Japan)

Composition
Acetone, pyro-EMA, PEM-F, 4-MET, CQ, nanollers, UMDA MDP, Bis-GMA, HEMA, microller, initiator, water ethanol Bottle A: Glass ller, acetone water; Bottle B: HEMA, 4-AET, Bis-GMA, initiator Primer: Carboxylic acid Monomer, Phosphonic acid Monomer, Water, Solvent, Initiator; Bond: S-PRG ller, UDMA, TEGDMA, HEMA, Initiator

Resin application
Apply to tooth for 5 s with Agitation. Repeat this Procedure 2 times during 15 s. Gentle air-blast for 5 s Apply to tooth for 20 s. Strong air-blast for 5 s Shake bottles, dispense equal volumes of liquid from bottle A and bottle B. Leave 20 s. Gentle air-blast Apply primer to tooth for 10 s. Gentle air-blast. Apply bonding agent to tooth. Leave 10 s

Abbreviations: Pyro-EMA = tetramethacryloyloxyethyl pyrophosphate; PEM-F = pentamethacryloyloxyethyl cyclohexaphosphazene monouoride; 4-MET = 4-methacryloxyethyltrimellitic acid; UMDA = urethane dimethacrylate; HEMA = 2-hydroxyethyl methacrylate; MDP = 10methacryloyloxydecyldihydrogen phosphate; Bis-GMA = bisphenyl A diglycidylmethacrylate; TEGDMA = triethyleneglycol dimethacrylate; CQ = camphorquinone; 4-AET = 4-acryloxyethyltrimellitic acid.

ally placed in sealed glass vials containing 10 mL of distilled water (pH 7.2) at 37 C. After xed time intervals of 1, 2, 3, 4, 5, 6, 7 and 10 days of storage, the vials were removed from the oven and left at room temperature for 30 min. The specimens were washed in running water, gently wiped with a soft absorbent paper, weighed in an analytical balance (m2 ) and returned to the vials containing 10 mL of fresh distilled water. Following the 10 days of storage, the specimens were dried inside a desiccator containing fresh silica gel and weighed daily for 2.5 days until a constant mass (m3 ) was obtained (as previously described). The initial mass determined after the rst desiccation process (m1 ) was used to calculate the change in mass after each xed time interval, during the 10 days of storage in water calculated as the difference in dry mass before immersion and after reaching the water sorption plateau, following drying in a sealed chamber lled with anhydrous calcium sulfate [35]. Disk volume was determined by measuring diameter and thickness before and after water exposure. Dry weight measurements were followed daily for 10 days. The values (%) for water sorption (WS) and solubility (SL) were calculated WS = M2 M3 /V, where M1 is the initial dry constant mass as SL = M1 M3 /V, (mg) before water immersion; M2 is the mass (mg) after water immersion; M3 is the mass (mg) after drying specimens that had reached their maximum water sorption and V is the specimens volume in mm3 . Net water uptake was calculated as the sum of water sorption and solubility [36]. Resin disks were also immersed in hexadecane as an example of a water-free pure oil with a viscosity similar to water. At each time period, resin disks were removed from the hexadecane and blotted dry of excess hexadecane before weighing. These specimens were run in parallel with the water immersed specimens as controls.

blends were placed in a small tared vessel on an analytical balance. After obtaining an initial weight, the vessel was removed from the balance and evaporated with an air-stream (0.5 L/s) for 10 min or until there was no further weight loss. Then 5 L of the solvent-free blend was placed in a 6-mm hole was punched in a piece of single side Scotchtape, that was placed directly over the 2 2 mm diamond crystal of a horizontal attenuated total reectance unit (Golden GateSPECAC, Inc., Woodstock, GA). As the tape was 50 1 m thick, the hole provided a convenient well into which was placed 5 L of each evaporated resin blends. The uid was covered with a thin Mylar lm which, in turn, was covered by a glass slide. The resin was cured as described above, using a 120s exposure. Multiple scans were made before and after light exposure at 2 cm1 resolution between 1680 and 1550 cm1 at a rate of one scan/s for 305 s, using a Fourier Transform Infrared spectrophotometer (IR Prestige-21, Shimazu, Tokyo, Japan). The degree of conversion was calculated using changes in the molar ratios (represented as peak absorbance height) of aliphatic (1636 cm1 )/aromatic (1608 cm1 ) carbon double bonds on the cured (C) and uncured (U) states. Conversion was calculated by using the following equation: % Conversion = 1 C U 100

2.4.

Microtensile bond test

2.3.

Monomer conversion

To ascertain that the increase in water sorption of the more hydrophilic resin blends was not caused by their lower extent of cure, the monomer conversion of the commercial resins was measured using infrared spectroscopy, according to the method of Rueggeberg et al. [37]. Briey, 25 L of solvated

Sixteen extracted noncarious human third molars were used in this study. The teeth were collected after obtaining the patients informed consent under a protocol approved by the Health Sciences University of Hokkaido Institutional Review Board. Flat dentin surfaces were created in mid-coronal dentin perpendicular to the tooths longitudinal axis using a slowspeed diamond saw (Isomet, Buehler, Lake Bluf, IL, USA) to remove occlusal enamel and supercial dentin. Each surface of mid-coronal dentin was ground with 320-grit silicon carbide paper under running water for 30 s just prior to bonding. One two-step and three one-step self-etching adhesives were used in this study (Table 1). The commercial adhesives were Fluoro Bond II (FB II, Shofu, Kyoto, Japan), Clearl Tri-S

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Bond (3 S, Kuraray Medical Inc., Tokyo, Japan), Absolute 2 (AB, Dentsply-Sankin, Tokyo, Japan), Fluoro Bond Shake One (SO, Shofu, Kyoto, Japan). Each bonding resin was applied on the dentin surface according to the manufactures instruction. That means their solvents were not completely removed as they were in the water sorption/solubility specimens. All adhesives were subsequently light-cured for 10 s with the light-curing unit (Morita, Kyoto, Japan) operated at 600 mW/cm2 . Following adhesive treatment, ve 1-mm increasements of a resin composite (Beautil, Shofu, Kyoto, Japan) were built up and individually light-activated for 60 s. After the bonded specimens had been stored in water at 37 C for 24 h, the built-up teeth were sectioned perpendicular to the adhesive interface to remove the peripheral 3 mm from each side of the tooth, yielding a cube-like specimen that represents the center of the tooth. This central cube was cut into 0.9-mm-thick slabs. Each slab, in turn, was sectioned into 1.0-mm-wide beams (adhesive area: approximately 0.9 mm2 ) with a diamond saw under water cooling/lubrication. Although 9 beams were produced, only the 6 with the greatest dentin thickness were selected for testing. Four teeth were used for each group. Beams were attached to a testing apparatus with a cyanoacrylate adhesive (Model repair 2, Dentsply-Sankin, Tokyo, Japan). A tensile load was applied with a material tester (EZ test, Shimazu, Kyoto, Japan) at a crosshead speed of 1.0 mm/min until failure. The load (N) at failure divided by the cross-sectional area of each failed beam measured with a digital micrometer permitted calculation of the microtensile bond strength that was expressed in MPa. Four teeth were used per bonding material. As each tooth yielded 6 beams, there were 24 beams per material. The mean microtensile bond strengths of each tooth were calculated separately and then averaged. There were no pretesting failures.

Fig. 2 Evaporation of solvated adhesives using a continuous gentle air-stream over time. The solvated adhesives of AB, SO, and 3 S rapidly lost weight during the rst 5 min. The weight of FB II did not change during the 30 min of exposure to a continuous air-stream.

(2-hydroxyethl) piperazine-1-ethanesulfonic acid (HEPES, 20), pH = 7.4. After storage, resin discs were immediately xed in 2.5% glutaraldehyde buffered in 0.1 M cacodylate titrated to pH 7.2, for 72 h. The specimens were then rinsed several times with 0.1 M sodium cacodylate buffer. The resins disks were dehydrated in increasing concentrations of ethanol (40, 50, 60, 70, 80 and 90%) for 30 min each and in 100% ethanol for 24 h. Final chemical drying was conducted according to the protocol of Perdigo et al. [38] using hexamethyldisilazane (Kyowa chemicals, Tokyo, Japan). The dry resin disks were sputtercoated with gold for 200 s and then examined with a scanning electron microscope (SSX-550, Shimazu, Tokyo, Japan).

2.5.

SEM examination

3.

Results

Resin disks were stored in an articial saliva for 10 days. The composition of the buffer solution (mmol/L) was: NaCl (130), CaCl2 (0.7), MgCl2 (0.2), KH2 PO4 (4.0), KCl (30), NaN3 (3), 4-

3.1. Evaporation of volatile adhesive components by storage at room temperature for 60 min and by an air-stream for 30 min
The degree of spontaneous evaporation of the volatile solvents of the solvated adhesives was measured at room temperature for 60 min (Fig. 1). The rate of evaporation induced by a stream of air over 30 min is graphically presented in Fig. 2. The weights of adhesives SO, 3 S and AB2 adhesive mixtures gradually decreased 1933% during dark storage at room temperature. In contrast, the weight of FB II showed no change during the 60-min storage period (Fig. 1). Fig. 2 shows similar evaporation of volatile adhesive components induced by an air-stream. The weight loss of AB2, SO and 3 S reached a plateau in 35 min. However, there was no weight loss in FB II specimens over the 30 min of a directed air-stream.

Fig. 1 Spontaneous evaporation of solvated adhesives of dentin bonding agents over time during storage in the dark at room temperature. The mass of the solvated adhesives (SO, 3 S and AB2) gradually decreased 1933% over 60 min. The weight of FB II did not change over 60 min.

3.2.

Water sorption and solubility changes over time

When mass gain (i.e. water sorption) and mass loss (i.e. solubility) of disks made from the bonding resin were plotted against time, the lowest water sorption (72.5 g/mm3 ) was

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Table 2 Percent conversion of the dentin bonding resins. Bonding resins

Absolute 2 Clearl 3 S Bond Fluoro Bond Shake One FluoroBond II

Conversion (%)
68.3 (0.9)a 87.4 (0.5)b 86.1 (0.8)b 75.0 (0.9)c

Means values (standard deviation, n = 5) percent conversion. Resin composition is presented in Table 1. Groups identied by different superscript letters are signicantly different (p < 0.05).

found in FB II followed by 3 S, and SO with AB2 showing the highest value, 207.7 g/mm3 (Table 3). The time required to reach maximum water sorption was different among bonding resins, being the shortest for SO and 3 S, followed by AB2 and FB II. Solubility values for SO, 3 S and FB II ranged from 2.0 to 143.1 g/mm3 , while that of AB2 was about 115.6 g/mm3 (Table 3). Since water sorption and solubility occur simultaneously [26], they were added together to provide an estimate of total water uptake. These values varied from 7.5 to 32.3% among the bonding resins (Table 3). Moreover, the oil (i.e. hexadecane) sorption and solubility of dentin bonding resins were much lower than the water sorption and solubility (Table 3).

3.3.

Monomer conversion

Conversion values for the bonding resins ranged from a low of 68.3% (0.9%) for AB2 to 86.1 (0.8%) for SO. There was no signicant correlation between percent conversion and water sorption (Table 2).

3.4.

Microtensile bond test

Table 2 shows the mean bond strengths for three single-step adhesives AB2, SO, 3 S, and the one two-step adhesive FB II systems. Their bond strengths (in MPa) in descending order were: 3 S:57.9 11.5, FB II: 51.0 5.4, SO: 40.6 9.7, and AB2: 24.8 6.9 MPa. The bond strength of Absolute 2 gave a significantly lower bond strength (p < 0.05) than did 3 S, FB II or SO. Most failures were mixed. The incidence of cohesive failures in dentin was common with increasing bond strength.

3.5.

SEM observation

Fig. 3a shows a relatively smooth SEM image of the surface of an FB II specimen immediately after removal of the glass slide (not stored articial saliva or hexadecane). Crystalline clusters were found on the surface after the specimen was immersed in articial saliva for 10 days (Fig. 3b). Fig. 3c shows the surface of FB II resin immersed hexadecane for 10 days. It looked very similar to FB II resins immediately after polymerization against glass (Fig. 3a). Fig. 4a shows the control surface of SO specimens (not stored articial saliva or hexadecane). Crystalline clusters were found on dentin surfaces immersed articial saliva (Fig. 4b). Fig. 4c shows the surface appearance and SO disk immersed in hexadecane. It looked very similar to control disks immediately after polymerization.

Fig. 3 SEM photographs of FB II disks of (a) control surface that was not immersed in any storage media showing relatively smooth surface; (b) crystalline-coated surface clusters found on disks immersed in articial saliva after 10 days; (c) relatively smooth resin surface of disks immersed in hexadecane for 10 days (magnication 2400).

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Fig. 5 SEM photographs of 3 S disks of (a) control surface not immersed in storage media showing relatively rough surface; (b) surface covered by small crystals found on disks immersed in articial saliva after 10 days; (c) relatively smooth resin surface of disks immersed in hexadecane for 10 days (magnication 2400). Fig. 4 SEM photograph of SO control surface (a) immediately after polishing but before immersion in storage media. The surface was relatively rough; (b) similar resin disks showed rougher surfaces after 10 days immersed in articial saliva; (c) SO resin disks immersed in hexadecane for 10 days showed a surface roughness that was similar to control surfaces (a) (magnication 2400).

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material (Fig. 6b). When AB2 specimens were immersed in hexadecane for 10 days, they looked very similar to controls (Fig. 6d).

4.

Discussion

Fig. 6 SEM photograph of AB2 control surface (a) immediately after polymerization against glass. The surface was relatively smooth; (b) similar resin disks showed a rougher surface after 10 days immersed in articial saliva; (c) AB2 resin disk immersed in hexadecane for 10 days showed a surface roughness that was similar to control surfaces (a) (ac: magnication 2400).

The SEM appearance of 3 S control surface is shown in Fig. 5a. When 3 S specimens were immersed in articial saliva, the surface became covered with crystalline material (Fig. 5b). Hexadecane-immersed specimen surfaces were not different from controls (Fig. 5c). When AB2 polymerized against glass, they gave a typical smooth SEM appearance (Fig. 6a). When they were immersed in articial saliva, they become covered with crystalline

The results of this study clearly show that water sorption of the resins tested varied signicantly from each other. Thus, the test null hypothesis that there are no differences in water sorption/solubility of single-step self-etching adhesives must be rejected. The increased water sorption of AB2 may have been due, in part, to the fact that this resin had the lowest percent conversion (Table 2). However, the lowest water sorption/solubility (Table 3) was seen in FB II even though its percent conversion was intermediate rather than the highest. Water sorption varies widely among adhesives depending on their composition [2830]. One of the most hydrophobic commercial dentin adhesives Superbond C&B (Sun Medical Co.) contains 5 vol% 4-methacryloxyethyl trimellitic anhydride (4-META) in 95 vol% methyl methacrylate. Unemori et al. [36] reported that this material had an extremely low water sorption of 0.4 wt% at 37 C. Burrow et al. [39] reported that adhesive resins commonly used in 1999 in the products Universal Bond (L.D. Caulk), All Bond 2 (Bisco) and Clearl Liner Bond II (Kuraray Medical) had maximum water sorption values of 2.0, 3.9, 4.8 and 5.5%, respectively. These values are somewhat lower than the water sorption values observed in SO, 3 S, in the current study. Conversely, AB2 exhibited a water sorption value that was much higher (ca. 21%, Table 3), and thus should be regarded as very hydrophilic. This value is similar the water sorption of Xeno III reported by Fabre et al. [40], of 26.8%. Reis et al. [41] reported water sorption of two-step self-etching primer adhesives (Clearl SE Bond and Protect Bond) of 7 and 8%, respectively. These values were similar to FB II in the current work (7.2%, Table 3). A previous study [28] showed that extensive water sorption and solubility was coupled with large reductions in resin stiffness after water sorption for the most hydrophilic resin blend. This is cause for concern, as the concentration of acidic resin monomers utilized in the most acidic resin blends in that study were similar to those employed in contemporary aggressive self-etching dentin adhesive. Figs. 1 and 2 showed that the optimal drying time for different solvated adhesives is quite different. For example, the manufacture of 3 S recommends a 5-s air-drying after 20 s of active agitation of the solvated adhesive. In the current study, evaporation of volatile solvent from the solvated 3 S adhesive after 1 min with an air syringe was only removed about one-fourth of the total weight loss achieved after 5 min of an air-blast (Fig. 2). Thus, even 1 min of evaporation, that is far in excess of manufacturers recommendations, would leave three-fourths of the solvents in the adhesive. This study revealed that the evaporation volatile solvent from self-etching of bonding resins depends largely on the amount of solvent added to the blend and the chemical composition of the adhesive blends. Complete evaporation of solvents is difcult to achieve, even by what appears to be thorough air-drying [4245].

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Table 3 Means of water sorption and solubility of dentin bonding resin. Resin
Absolute 2 Fluoro Bond Shake One Clearl 3 S Fluorobond II

Water sorption ( g/mm3 ) (%A )

207.7 (4.5)a (20.7) 101.9 (3.8)b (10.2) 89.2 (3.6)c (8.9) 72.5 (2.3)d (7.3)

Water solubility ( g/mm3 ) (%)

115.6 (5.8)a (11.6) 143.1 (3.8)b (14.3) 127.4 (2.4)c (12.7) 2.0 (0.5)d (0.2)

Hexadecane sorption ( g/mm3 )

17.6 (1.8)a 7.8 (1.5)b 5.9 (1.3)b 13.7 (2.1)c

Hexadecane solution ( g/mm3 )

41.2 (3.4)a 21.6 (2.3)b 19.6 (1.5)b 3.9 (0.8)c

Net water uptake (%)B

32.3 24.5 21.6 7.5

Values are mean (standard deviation, n = 5) g/mm3 . Same superscript letters (ad) in the columns and rows indicates no statistical difference. Water sorption is given in absolute terms ( g/mm3 ) and in relative terms (%) to provide comparisons to literature values which include both expressions. A 207.7 g/mm3 = 0.2077 mg/mm3 100 = 20.7 mg/100 mm3 = 20.7%. B Net water uptake is the sum of water sorption and solubility (%).

Table 4 Microtensile bond strengths for self-etching adhesives. Adhesive

Tensile bond strength

AB2
24.8 (6.9)
a

3S

SO
b

FBII
b

57.9 (11.5)

40.6 (9.7)

51.5 (5.4)b

Values are means (standard deviation, n = 24) MPa. Superscript letters designate statistically signicant differences (p < 0.05).

Formulation compromises are made when creating selfetching adhesives. The inclusion of relatively high concentrations of acidic monomers and water, to permit ionization of those monomers and solubilization of calcium and phosphate, makes these polymers very hydrophilic. The advantages that these systems provide during bonding may be compromised by relatively large subsequent water sorption behavior that lowers the stiffness of adhesive layer which couples resin composites to dentin. This change may result in poor load transfer across the bonded interface during function over time, leading to catastrophic joint failure. The lack of solvent evaporation from FB II was unexpected. The only other product that has been reported not to lose weight during attempts to evaporate its solvents was a solvent-free experimental resin and the solvent-free adhesive of Clearl SE Bond [31]. In that same study, One-Up Bond F only lost 5.4% of its weight during exposure to an air-stream for 10 min. We speculate that the water used to ionize the acidic monomers and solubilize released calcium and phosphate immediately reacts with the prereacted surface of glass ller particles in FB II in an acidbase reaction that binds water to the silica gel layer that forms in the glass llers. In addition, that water likely hydrogen bonds to the polycarboxylate matrix. The net result may be no water evaporation. Since water evaporation from FB II is not possible clinically, the manufacturers directions to use gentle air-blast to evaporate volatile solvent seems to be superuous. There were no signicant differences in the microtensile bond strengths between adhesives that included the S-PRG ller (i.e. FB II) or not (Table 4). However, in the SEM observation, a crystalline structure was observed on the surface of all of the resins after incubation in articial saliva (Figs. 3b, 4b and 5b) but not when they were incubated in hexadecane or in control resin disks polymerized on glass. These crystals were much smaller than those reported by Hashimoto et al. [46] in an articial 40 m gap between the resins and dentin disks over a 1000-day period. In the current study, the smaller crystals formed on resin within 10 days from a solu-

tion of articial saliva. We speculate that water trees in the resin become saturated with the inorganic salts in the articial saliva and interact with acidic polymers in the resin to form microscopic crystals of calcium phosphates. The somewhat higher bond strength of FB II compared to SO made by the same company may be due to the fact that the hydrophilic primer of FB II is covered by a solvent-free mixture of UDMA and TEGDMA that may be more hydrophobic than the ingredients of SO. This might also be responsible for the signicantly lower water sorption of FB II compared to SO and the extraordinary low water solubility of FB II (ca. 2%). The low water sorption probably plasticitized FB II much less than those resins showing higher water sorption (Table 3). The extremely low hexadecane absorption/solubility is probably due to its hydrophobicity and its relatively large size (MW 226) making it relatively impermeable to these resins. Clearly, long-term studies on the durability of resindentin bonds are needed to provide a more realistic evaluation of the longevity of bonds made with new, more hydrophilic self-etch adhesives. This study demonstrated that the unlled phosphoric acid esters of methacrylate (Absolute 2) had the highest water sorption. Single-step self-etching dentin adhesives gave higher water sorptions and solubilities compared with the two-step self-etching primer adhesive system (FluoroBond II).

Acknowledgements
The materials (Absolute; Dentsply Sankin, 3 S Bond; Kuraray, Shake One and FL Bond II; Shofu) used in this study were generously supplied by the respective manufacturers. The authors are grateful to Michelle Barnes for secretarial support.

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