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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 r t i c l e
Article history:

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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 20–30% 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 Clearfil 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 Clearfil

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 artificial saliva covered the surfaces of the resins with mineral crystallites. Significance. 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: (S. Ito). 0109-5641/$ – see front matter © 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved. doi:10.1016/

disk diameters were 10 mm and 0. 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. Uniform absorption was seen as isolated individual silver grains. the specimens were placed in desiccators and transferred to a preconditioning oven at 37 ◦ C. rounded to the nearest 0.02 mm thick. If this water is not evaporated. When dentin bonded with adhesive resins was stored in water for 12 months. While in the dark. They were dry polished to a thickness of 0. 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. for 30 min to insure that all volatile solvents had been removed prior to light curing.e. The weight of plasticplate with the bonding resin was successively remeasured every minute for the first 5 min. placed on a tared slide. The Teflon slide was weighted before and immediately after depositing the drop of bonding resin.14].02 mm. highly polar functional groups substituted on methacrylates. the Teflon well containing the solvated comonomers was exposed to the same air-stream used to evaporate the solvents in the previous section. a similar light exposure was applied to the lower disk surface. 10–30 wt% [8–10] 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. Clearly. This could explain why resin–dentin bonds made with hydrophilic resin monomers significantly degrade over time in vitro [15–20] and in vivo [21–24]. the commercial comonomers/solvent mixtures were placed in a circular well made in Teflon to form disks 10. The weight of residual adhesives at each time (B) was determined by subtracting the weight of the plastic-plate.0 ± 0. the plastic-plate with the unpolymerized adhesive mixture was stored in the dark for 60 min at room temperature (25 ◦ C). the distribution of absorbed water changed dramatically [27]. to match the dimensions of specimen molds. All-in-one adhesives and self-etching primers are intrinsically hydrophilic owing to the presence of acidic. Water absorption into polymers is assumed to be directly related to the hydrophilicity of the polymers [31–34]. To allow the volatile dentin bonding components to spontaneously evaporate. Even in self-etching adhesives that are applied to dry smear layer-covered dentin. Japan) operated at 600 mW/cm2 . The null hypothesis tested was that none of the adhesive resins tested will have different water sorption/solubility values. The specimens were repeatedly weighed after 24 h intervals until a constant mass (m1 ) was obtained (i. FB II. Thickness and diameter of the specimens were measured using a digital caliper. Using ammoniacal silver nitrate to trace the distribution of absorbed water. Water sorption was measured following the method outlined in ISO 4049 (12-1998). Introduction In 2003.2. Specimen dimensions to the nearest 0. and these measurements were used to calculate the volume (V) of each specimen (in mm3 ).1.2 mg in any 24 h period).01 mm were measured using a digital micrometer. Water sorption/solubility 2. They rapidly absorb water. 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. Five specimens were prepared per adhesive.0 ± 0.50 ± 0. and the resin was light-cured for 30 s using a dental curing light (Morita. while the non-uniform water uptake resulted in the formation of liner. The degree of spontaneous evaporation of volatile solvents (Ep in wt%) at room temperature was followed for 60 min. branched. 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. forming a flat surface. every 5 min from 10 to 30 min and every 10 min for the rest of the time. After removing the disk from the mold. 2. and may interfere with bonding [11. Materials and methods 2. 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 fibrils collapsing [2]. it will dilute the comonomers. with the tip held 1 mm from cover slip. Kyoto. have shown both uniform and non-uniform water uptake into commercial adhesive resins [25–27]. The resin disks were then individu- . Tay et al. a 3-way air-water syringe was clamped 15 cm from the adhesive and the control button depressed half-way to produce an air flow of 20 L/min for 30 min in the dark.13.01 mm. variation was less than 0. enabling the weight of the bonding resin (A) from the difference of the two weights to be calculated (0-min storage time). but can water also causes phase changes when dimethacrylates encounter too much water [3–7].618 d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 617–626 1. water sorption by dental resins and the hybrid layer is more complex than expected [1]. which results in polymer swelling. Immediately after polymerization. and the presence of water and ethanol solvents. 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 Teflon slide. Ten resin disks were made for each of the commercial resins. For two-step adhesive. When an air-stream was used to evaporate solvents.5 mm in thickness. However.1 mm in diameter and 1. The water sorption and solubility of newly developed adhesives needs to be fully investigated. plasticizing [28–30] and weakening of the polymer network [28–30]. Water sorption within polymer matrices created by contemporary hydrophilic dentin adhesives is not always uniform.12] and lower the mechanical properties of the resin [6. water-filled channels [26]. The surface of the comonomers was covered with a glass cover slip to exclude atmospheric oxygen.

Phosphonic acid Monomer. Each surface of mid-coronal dentin was ground with 320-grit silicon carbide paper under running water for 30 s just prior to bonding. Microtensile bond test 2.5 L/s) for 10 min or until there was no further weight loss. The specimens were washed in running water. Briefly. Japan) Single-step Fluoro Bond Shake One (SO) (Shofu. water ethanol Bottle A: Glass filler. Conversion was calculated by using the following equation: % Conversion = 1− C U × 100 2. Initiator Resin application Apply to tooth for 5 s with Agitation. 2. Japan Single-step Clearfil® Tri-S Bond (3 S) (Kuraray Medical. gently wiped with a soft absorbent paper. (mg) before water immersion. Woodstock. Flat dentin surfaces were created in mid-coronal dentin perpendicular to the tooth’s longitudinal axis using a slowspeed diamond saw (Isomet. the hole provided a convenient “well” into which was placed 5 L of each evaporated resin blends. Inc.4. Shofu. Multiple scans were made before and after light exposure at 2 cm−1 resolution between 1680 and 1550 cm−1 at a rate of one scan/s for 305 s. MDP = 10methacryloyloxydecyldihydrogen phosphate. 7 and 10 days of storage. the specimens were dried inside a desiccator containing fresh silica gel and weighed daily for 2. 4. The degree of conversion was calculated using changes in the molar ratios (represented as peak absorbance height) of aliphatic (1636 cm−1 )/aromatic (1608 cm−1 ) carbon double bonds on the cured (C) and uncured (U) states. that was placed directly over the 2 × 2 mm diamond crystal of a horizontal attenuated total reflectance unit (Golden GateSPECAC. Bond: S-PRG filler. Following the 10 days of storage. weighed in an analytical balance (m2 ) and returned to the vials containing 10 mL of fresh distilled water. acetone water. GA). resin disks were removed from the hexadecane and blotted dry of excess hexadecane before weighing. UMDA MDP.3. Kyoto. Bis-GMA. The fluid was covered with a thin Mylar film which. 5. Tokyo. The values (%) for water sorption (WS) and solubility (SL) were calculated WS = M2 − M3 /V. in turn. ally placed in sealed glass vials containing 10 mL of distilled water (pH 7. Gentle air-blast. according to the method of Rueggeberg et al. HEMA. Buehler. Repeat this Procedure 2 times during 15 s.5 days until a constant mass (m3 ) was obtained (as previously described). PEM-F. After obtaining an initial weight. After fixed time intervals of 1. Lake Bluf. Resin disks were also immersed in hexadecane as an example of a water-free pure oil with a viscosity similar to water. Leave 10 s Abbreviations: Pyro-EMA = tetramethacryloyloxyethyl pyrophosphate. UDMA. IL. the vials were removed from the oven and left at room temperature for 30 min. nanofillers. Solvent. Then 5 L of the solvent-free blend was placed in a 6-mm hole was punched in a piece of single side Scotchtape. PEM-F = pentamethacryloyloxyethyl cyclohexaphosphazene monofluoride. 4-AET = 4-acryloxyethyltrimellitic acid. Kyoto. using a 120s exposure. TEGDMA = triethyleneglycol dimethacrylate. The teeth were collected after obtaining the patients’ informed consent under a protocol approved by the Health Sciences University of Hokkaido Institutional Review Board.. using a Fourier Transform Infrared spectrophotometer (IR Prestige-21. Japan). Osaka. UMDA = urethane dimethacrylate. following drying in a sealed chamber filled with anhydrous calcium sulfate [35]. The resin was cured as described above. 4-MET = 4-methacryloxyethyltrimellitic acid. CQ = camphorquinone. 4-MET. Leave 20 s. where M1 is the initial dry constant mass as SL = M1 − M3 /V. Japan) Composition Acetone. TEGDMA. [37]. microfiller. dispense equal volumes of liquid from bottle A and bottle B. was covered by a glass slide. The commercial adhesives were Fluoro Bond II (FB II. initiator. Disk volume was determined by measuring diameter and thickness before and after water exposure. 4-AET. 3. the monomer conversion of the commercial resins was measured using infrared spectroscopy. 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. Initiator. Strong air-blast for 5 s Shake bottles. Bottle B: HEMA. Japan) Two-step Fluoro Bond II (FB II) (Shofu. initiator Primer: Carboxylic acid Monomer. Dry weight measurements were followed daily for 10 days. Apply bonding agent to tooth. Gentle air-blast Apply primer to tooth for 10 s. HEMA. 6. One two-step and three one-step self-etching adhesives were used in this study (Table 1). during the 10 days of storage in water calculated as the difference in dry mass before immersion and after reaching the water sorption plateau. HEMA = 2-hydroxyethyl methacrylate. Water. Japan). At each time period.d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 617–626 619 Table 1 – Composition of the adhesive used. 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 . USA) to remove occlusal enamel and superficial dentin. Gentle air-blast for 5 s Apply to tooth for 20 s. Clearfil Tri-S . Tokyo. the vessel was removed from the balance and evaporated with an air-stream (0. Net water uptake was calculated as the sum of water sorption and solubility [36]. Shimazu. CQ. blends were placed in a small tared vessel on an analytical balance. As the tape was 50 ± 1 m thick.2) at 37 ◦ C. Material (Manufacture) Single-step Absolute 2 (AB2) (Dentsply Sankin. Bis-GMA. pyro-EMA. Bis-GMA = bisphenyl A diglycidylmethacrylate. 25 L of solvated Sixteen extracted noncarious human third molars were used in this study. These specimens were run in parallel with the water immersed specimens as controls. The initial mass determined after the first desiccation process (m1 ) was used to calculate the change in mass after each fixed time interval. Kyoto.

The weight loss of AB2. Japan). The weight of FB II did not change over 60 min. Four teeth were used for each group. Japan) operated at 600 mW/cm2 . 3 S and AB2 adhesive mixtures gradually decreased 19–33% during dark storage at room temperature. Beams were attached to a testing apparatus with a cyanoacrylate adhesive (Model repair 2.5. [38] using hexamethyldisilazane (Kyowa chemicals. 1 – Spontaneous evaporation of solvated adhesives of dentin bonding agents over time during storage in the dark at room temperature. MgCl2 (0. Japan). SO and 3 S reached a plateau in 3–5 min. The mean microtensile bond strengths of each tooth were calculated separately and then averaged.5% glutaraldehyde buffered in 0. NaN3 (3). solubility) of disks made from the bonding resin were plotted against time. the built-up teeth were sectioned perpendicular to the adhesive interface to remove the peripheral 3 mm from each side of the tooth. However. only the 6 with the greatest dentin thickness were selected for testing. in turn. Water sorption and solubility changes over time When mass gain (i. for 72 h. Shofu. The solvated adhesives of AB. Fig. 2. Following adhesive treatment. 60. Dentsply-Sankin. There were no pretesting failures. SO. The weights of adhesives SO. the lowest water sorption (72.5 g/mm3 ) was . Dentsply-Sankin.2. Japan). Japan) at a crosshead speed of 1.9-mm-thick slabs. 2 shows similar evaporation of volatile adhesive components induced by an air-stream. Fluoro Bond Shake One (SO.9 mm2 ) with a diamond saw under water cooling/lubrication. In contrast. After storage. Shimazu. All adhesives were subsequently light-cured for 10 s with the light-curing unit (Morita. KCl (30). there was no weight loss in FB II specimens over the 30 min of a directed air-stream. The specimens were then rinsed several times with 0. Tokyo.620 d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 617–626 Bond (3 S. Japan). there were 24 beams per material. KH2 PO4 (4. Kyoto. Absolute 2 (AB. water sorption) and mass loss (i. Although 9 beams were produced.e. Shofu. was sectioned into 1. Japan) were built up and individually light-activated for 60 s.. 3 S and AB2) gradually decreased 19–33% over 60 min. Kyoto. Kyoto.0). That means their solvents were not completely removed as they were in the water sorption/solubility specimens. Each bonding resin was applied on the dentin surface according to the manufacture’s instruction.1 M cacodylate titrated to pH 7. Results Resin disks were stored in an artificial saliva for 10 days.2). The dry resin disks were sputtercoated with gold for 200 s and then examined with a scanning electron microscope (SSX-550. Kuraray Medical Inc. 3. SEM examination 3. pH = 7. 70. Japan). The resins disks were dehydrated in increasing concentrations of ethanol (40. (2-hydroxyethl) piperazine-1-ethanesulfonic acid (HEPES. After the bonded specimens had been stored in water at 37 ◦ C for 24 h. Japan). The weight of FB II did not change during the 30 min of exposure to a continuous air-stream. Final chemical drying was conducted according to the protocol of Perdigão et al.0-mm-wide beams (adhesive area: approximately 0. 4- 3. 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. 50. resin discs were immediately fixed in 2. Tokyo. five 1-mm increasements of a resin composite (Beautifil.2. As each tooth yielded 6 beams. Four teeth were used per bonding material.1. Tokyo. The composition of the buffer solution (mmol/L) was: NaCl (130).0 mm/min until failure. 2. Tokyo. Fig. Kyoto. yielding a cube-like specimen that represents the center of the tooth. Shimazu. Tokyo. 1). The rate of evaporation induced by a stream of air over 30 min is graphically presented in Fig. 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. Each slab. 80 and 90%) for 30 min each and in 100% ethanol for 24 h.1 M sodium cacodylate buffer. 20).e. Fig. This central cube was cut into 0.4. 2 – Evaporation of solvated adhesives using a continuous gentle air-stream over time. and 3 S rapidly lost weight during the first 5 min. 1). CaCl2 (0. A tensile load was applied with a material tester (EZ test. the weight of FB II showed no change during the 60-min storage period (Fig.7). The mass of the solvated adhesives (SO.

0 (0.05) than did 3 S.5)b 86.e. Most failures were mixed. Microtensile bond test Table 2 shows the mean bond strengths for three single-step adhesives AB2. Their bond strengths (in MPa) in descending order were: 3 S:57.9 ± 11. 3 S.1 g/mm3 . and SO with AB2 showing the highest value. SO: 40.0 ± 5.8)b 75. and AB2: 24.0 to 143. The bond strength of Absolute 2 gave a significantly lower bond strength (p < 0. 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 artificial saliva or hexadecane). Groups identified by different superscript letters are significantly different (p < 0. SEM observation Fig. 4a shows the control surface of SO specimens (not stored artificial saliva or hexadecane). 207. 3b). Crystalline clusters were found on the surface after the specimen was immersed in artificial saliva for 10 days (Fig.3% among the bonding resins (Table 3). 3. and the one two-step adhesive FB II systems. n = 5) percent conversion.8 ± 6. Crystalline clusters were found on dentin surfaces immersed artificial saliva (Fig. they were added together to provide an estimate of total water uptake. These values varied from 7. (b) crystalline-coated surface clusters found on disks immersed in artificial saliva after 10 days. 3a). FB II: 51.3. Fig.9%) for AB2 to 86. Fig. being the shortest for SO and 3 S.6 ± 9. 3c shows the surface of FB II resin immersed hexadecane for 10 days.9)a 87.05). SO. It looked very similar to FB II resins immediately after polymerization against glass (Fig. Bonding resins Absolute 2 Clearfil 3 S Bond Fluoro Bond Shake One FluoroBond II Conversion (%) 68. (c) relatively smooth resin surface of disks immersed in hexadecane for 10 days (magnification 2400×). It looked very similar to control disks immediately after polymerization. hexadecane) sorption and solubility of dentin bonding resins were much lower than the water sorption and solubility (Table 3).8%) for SO.5. 4b).1 (0.d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 617–626 621 Table 2 – Percent conversion of the dentin bonding resins. Resin composition is presented in Table 1. 3 S and FB II ranged from 2. Since water sorption and solubility occur simultaneously [26].1 (0.3 (0.5 to 32. Fig. The time required to reach maximum water sorption was different among bonding resins. 3. . There was no significant correlation between percent conversion and water sorption (Table 2).6 g/mm3 (Table 3).7. Moreover. followed by AB2 and FB II. 4c shows the surface appearance and SO disk immersed in hexadecane. Solubility values for SO.4.4. while that of AB2 was about 115. Monomer conversion Conversion values for the bonding resins ranged from a low of 68. 3 – SEM photographs of FB II disks of (a) control surface that was not immersed in any storage media showing relatively smooth surface.9 MPa. the oil (i.4 (0.7 g/mm3 (Table 3). FB II or SO. The incidence of cohesive failures in dentin was common with increasing bond strength. found in FB II followed by 3 S.5.9)c Means values (standard deviation.3% (±0. 3.

. Fig. 4 – SEM photograph of SO control surface (a) immediately after polishing but before immersion in storage media. 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 artificial saliva after 10 days. (b) similar resin disks showed rougher surfaces after 10 days immersed in artificial saliva.622 d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 617–626 Fig. The surface was relatively rough. (c) relatively smooth resin surface of disks immersed in hexadecane for 10 days (magnification 2400×). (c) SO resin disks immersed in hexadecane for 10 days showed a surface roughness that was similar to control surfaces (a) (magnification 2400×).

in part. 2). 4. of 26. 5b). Figs. the manufacture of 3 S recommends a 5-s air-drying after 20 s of active agitation of the solvated adhesive. 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.8%.9. 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. The increased water sorption of AB2 may have been due. Conversely. Caulk). respectively. respectively. (c) AB2 resin disk immersed in hexadecane for 10 days showed a surface roughness that was similar to control surfaces (a) (a–c: magnification 2400×). 5c). . 6d). These values were similar to FB II in the current work (7. they become covered with crystalline The results of this study clearly show that water sorption of the resins tested varied significantly from each other. 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. even 1 min of evaporation. 3. Hexadecane-immersed specimen surfaces were not different from controls (Fig.) contains 5 vol% 4-methacryloxyethyl trimellitic anhydride (4-META) in 95 vol% methyl methacrylate. These values are somewhat lower than the water sorption values observed in SO. Burrow et al. One of the most hydrophobic commercial dentin adhesives Superbond C&B (Sun Medical Co. they looked very similar to controls (Fig. All Bond 2 (Bisco) and Clearfil Liner Bond II (Kuraray Medical) had maximum water sorption values of 2. Table 3). For example. to the fact that this resin had the lowest percent conversion (Table 2). In the current study. Complete evaporation of solvents is difficult to achieve.D. AB2 exhibited a water sorption value that was much higher (ca. 6a).2%. [41] reported water sorption of two-step self-etching primer adhesives (Clearfil SE Bond and Protect Bond) of 7 and 8%. [39] reported that adhesive resins commonly used in 1999 in the products Universal Bond (L. Unemori et al. [40]. 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. the lowest water sorption/solubility (Table 3) was seen in FB II even though its percent conversion was intermediate rather than the highest.0. Reis et al. 6 – SEM photograph of AB2 control surface (a) immediately after polymerization against glass. When AB2 polymerized against glass. that is far in excess of manufacturer’s recommendations. This value is similar the water sorption of Xeno III reported by Fabre et al. and thus should be regarded as very hydrophilic. Discussion Fig. the surface became covered with crystalline material (Fig. When 3 S specimens were immersed in artificial saliva.d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 617–626 623 material (Fig. 3 S. 6b). 1 and 2 showed that the optimal drying time for different solvated adhesives is quite different. in the current study. This is cause for concern. The surface was relatively smooth. Thus. would leave three-fourths of the solvents in the adhesive. (b) similar resin disks showed a rougher surface after 10 days immersed in artificial saliva.5%. Thus.8 and 5. even by what appears to be thorough air-drying [42–45]. Table 3). However. 5a. The SEM appearance of 3 S control surface is shown in Fig.4 wt% at 37 ◦ C. [36] reported that this material had an extremely low water sorption of 0. When they were immersed in artificial saliva. 4. they gave a typical smooth SEM appearance (Fig. the test null hypothesis that there are no differences in water sorption/solubility of single-step self-etching adhesives must be rejected. When AB2 specimens were immersed in hexadecane for 10 days. 21%. Water sorption varies widely among adhesives depending on their composition [28–30].

more hydrophilic self-etch adhesives.5)a (20. Dentsply Sankin.7%. The net result may be no water evaporation. B Net water uptake is the sum of water sorption and solubility (%).9) a 3S SO b FBII b 57.5) 40.9 (11.4% of its weight during exposure to an air-stream for 10 min.3)b −19. Kuraray.8)c Net water uptake (%)B 32.6 (1.4)a −21. In the current study.3) −127.7) 51. A 207. that water likely hydrogen bonds to the polycarboxylate matrix. the smaller crystals formed on resin within 10 days from a solu- tion of artificial saliva.1 (3.4)c (12.2 (3.3)d (7.8)a −7. Adhesive Tensile bond strength AB2 24. makes these polymers very hydrophilic. Resin Absolute 2 Fluoro Bond Shake One Clearfil 3 S Fluorobond II Water sorption ( g/mm3 ) (%A ) 207.1)c Hexadecane solution ( g/mm3 ) −41. In addition.69:726–31.7 (2.624 d e n t a l m a t e r i a l s 2 6 ( 2 0 1 0 ) 617–626 Table 3 – Means of water sorption and solubility of dentin bonding resin. 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.6 (2. This change may result in poor load transfer across the bonded interface during function over time.5 (2. to permit ionization of those monomers and solubilization of calcium and phosphate. In that same study. FB II) or not (Table 4). 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.6)c (8. However.3) Water solubility ( g/mm3 ) (%) −115.3)b 13. Water sorption is given in absolute terms ( g/mm3 ) and in relative terms (%) to provide comparisons to literature values which include both expressions.6 7.6 (1. the manufacturer’s directions to use gentle air-blast to evaporate volatile solvent seems to be superfluous. Acknowledgements The materials (Absolute.2) 89. 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.7 mg/100 mm3 = 20.2077 mg/mm3 × 100 = 20. 2%). long-term studies on the durability of resin–dentin bonds are needed to provide a more realistic evaluation of the longevity of bonds made with new.7 (4. Superscript letters designate statistically significant differences (p < 0.e.5)b −5. The authors are grateful to Michelle Barnes for secretarial support. These crystals were much smaller than those reported by Hashimoto et al. n = 24) MPa.8 (1. We speculate that water trees in the resin become saturated with the inorganic salts in the artificial saliva and interact with acidic polymers in the resin to form microscopic crystals of calcium phosphates.7) −2. Single-step self-etching dentin adhesives gave higher water sorptions and solubilities compared with the two-step self-etching primer adhesive system (FluoroBond II). 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 Clearfil SE Bond [31]. 3b.8)a (11.6 (5.8)b (10.5 21.6 (9. The low water sorption probably plasticitized FB II much less than those resins showing higher water sorption (Table 3).7) 101.7 g/mm3 = 0. Since water evaporation from FB II is not possible clinically.8 (6. 4b and 5b) but not when they were incubated in hexadecane or in control resin disks polymerized on glass. Table 4 – Microtensile bond strengths for self-etching adhesives. n = 5) g/mm3 . The inclusion of relatively high concentrations of acidic monomers and water.4)b Values are means (standard deviation.2 (3.5 (5. 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 filler particles in FB II in an acid–base reaction that binds water to the silica gel layer that forms in the glass fillers. leading to catastrophic joint failure.05). Have dental adhesives become to hydrophilic? J Can Dent Assoc 2003. Pashley DH. Clearly.2) Hexadecane sorption ( g/mm3 ) −17.4 (2.0 (0. This study demonstrated that the unfilled phosphoric acid esters of methacrylate (Absolute 2) had the highest water sorption. [46] in an artificial 40 m gap between the resins and dentin disks over a 1000-day period. references [1] Tay FR. Formulation compromises are made when creating selfetching adhesives. in the SEM observation.9 (1.6) −143. a crystalline structure was observed on the surface of all of the resins after incubation in artificial saliva (Figs. Same superscript letters (a–d) in the columns and rows indicates no statistical difference.3 24.9 (0. One-Up Bond F only lost 5. . This might also be responsible for the significantly lower water sorption of FB II compared to SO and the extraordinary low water solubility of FB II (ca. Shofu) used in this study were generously supplied by the respective manufacturers. Shake One and FL Bond II. There were no significant differences in the microtensile bond strengths between adhesives that included the S-PRG filler (i. 3 S Bond.5 Values are mean (standard deviation.9 (3.9) 72. The lack of solvent evaporation from FB II was unexpected.5)b −3.8)b (14.5)d (0.

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