Basic ResearchTechnology

Comparison between the Effect of Plasma and Chemical Treatments on Fiber Post Surface
Marta Cla Costa Dantas, DDS, MSc,* Mara do Prado, DDS, MSc, Vinicius Silva Costa, DDS,* e Mauro G. Gaiotte,* Renata A. Sim~ o, MSc, PhD,* and Fernando Luis Bastian, PhD* a
Abstract
Introduction: The aim of the present study was to evaluate the ber post surface after plasma and usual treatments and the adhesion between treated ber posts and Rely X Unicem resin cement (3M ESPE, St Paul, MN). Methods: Flat ber posts were divided into 6 groups according to surface treatment: silane, hydrouoric acid, hydrouoric acid plus silane, plasma polymerization with argon, ethylenediamine plasma (EDA), and the control group. A goniometer was used to measure the contact angle between the groups with water or resin cement. Scanning electron microscopy and electron dispersive spectroscopy were used to examine the topography and chemical changes in the post surfaces after treatment. Push-out tests were performed using a universal testing machine to evaluate the adhesion strength between treated ber posts and resin cement. Results: In the contact angle with water, the most hydrophilic surface was observed in samples treated with argon plasma, followed by treatments with silane and hydrouoric acid plus silane. The hydrophobic characteristic was observed with EDA and hydrouoric acid. The contact angle with dual resin cement showed lower values with argon and EDA, followed by silane and hydrouoric acid plus silane. Electron dispersive spectroscopy analyses showed chemical modications in the surface after different treatments although topographic changes were veried only with EDA plasma compared with the control. Push-out results did not show differences between groups compared with the control, except for EDA plasma treatment. Conclusions: Plasma treatment favored the wettability of the post surface by modifying it chemically. Adhesion improvement was only observed after EDA treatment. (J Endod 2012;38:215218)

iber posts are widely used and accepted for the restoration of endodontically treated teeth as a viable alternative to cast post (1, 2). Fiber post retention depends on the strength of the chemical and micromechanical interaction between ber-reinforced material and composite resin (3). Several surface pretreatments for posts have been used to optimize the bond between post and resin cement (310). The contact angle technique evaluates the interaction between 2 surfaces: a liquid and a solid. To calculate the contact angle, the following Youngs equation is applied: gif cosq = gsf - gsl, where contact angle qYoung is uniquely determined by the 3 interfacial tensions gif, gsf, and gsl, functioning as an equilibrium property of the system (11). This technique is able to measure wettability and surface free energy (12). According to Asmussen and Peutzfeldt (13), the contact angle between surface and liquids, polar and apolar, with known density are used to calculate the surface free energy, calculated from the equation gs= gsd+ 2(gs+gs_)1/2. These authors analyzed both contact angle and surface free energy and showed that the bond strength between polymerized composites and fresh dentin was inuenced by the mechanical properties of the former and by the compatibility between composite and adhesive. Asmussen et al (14) determined the surface energy characteristics of 3 variously treated post materials and 2 resin cements and investigated whether previously measured bond strengths between cements and treated posts could be related to the surface energy characteristics of both materials. The authors concluded that factors other than surface energy characteristics of adherent and adhesive surfaces play a role in determining the bond strength. Chemical vapor deposition is a plasma technique. This technique yields neither waste product during reaction nor modies the chemical and physical properties of the substrate surface, allowing bond strength between dissimilar materials without modifying their bulk properties. The changes caused by plasma technology are characterized by the deposition of ions and molecules resulting from the vaporization of different substances, which modies physically and chemically the deep surface depth at micrometric and submicrometric scales (1522). Yavirach et al (23) evaluated the effects of treatment on the adhesion between ber posts and composite core materials, observing that plasma treatment increased the tensile-shear bond strength between post and composite. The aim of the present study was to evaluate the ber post surface after plasma and usual treatments as well as the adhesion between treated ber posts and Rely X Unicem resin cement (3M ESPE, St Paul, MN).

Key Words
Argon plasma, ethylenediamine plasma, ber post, hydrouoric acid, silane, wettability

Materials and Methods

Sample Preparation Cylindrical ber epoxy resin posts (FGM, Santa Catarina, Brazil) of 1.6 mm in diameter and 20 mm in length were used. Fiber posts were wet grinded with carborundum sandpapers (400, 600, and 1,200 grits) to obtain a at surface before being

From the *Department of Metallurgic and Materials Engineering, Federal University of Rio de Janeiro, Rio de Janeiro, Rio de Janeiro, Brazil; and Department of Restorative Dentistry, Endodontic Division, State University of Campinas, UNICAMP, Piracicaba, S~o Paulo, Brazil. a Address requests for reprints to Dr Ma do Prado, Department of Restorative Dentistry, Piracicaba Dental School State University of Campinas, Avenida Limeira, ra 901, Piracicaba, SP, Brazil 13414-018. E-mail address: mairapr@fop.unicamp.br 0099-2399/$ - see front matter Copyright 2012 American Association of Endodontists. doi:10.1016/j.joen.2011.10.020

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attached to a metal matrix along their long axis by using beeswax. Next, the posts were polished with aluminum oxide paste and submitted to an ultrasonic bath for 15 minutes in distilled water and acetone PA (Vetec Chemical, Duque de Caxias, Brazil) so that any supercial contaminant could be removed. The resulting samples were divided into 6 groups according to surface treatment: silane (G1), hydrouoric acid (G2), hydrouoric acid plus silane (G3), argon plasma polymerization (G4), ethylenediamine plasma (G5), and control group (G6). Ram-Hart software calculated the energy parameters and surface e energy.

Surface Treatments The surface modication was performed by using Monobond-S silane (3-methacryloxypropylmethoxysilane; Vivadent, Barueri, SP, Brazil) and 4% hydrouoric acid gel (Frmula & Ac~o, S~o Paulo, o a a SP, Brazil). In G1, silane was applied with a microbrush for 60 seconds. In G2, the samples were treated with hydrouoric acid for 60 seconds and then rinsed with running water for 10 seconds. In G3, the samples were treated with hydrouoric acid for 60 seconds, rinsed with running water for 10 seconds, and dried before further silane application for 60 seconds. Surface modication through chemical vapor deposition was performed by using a cathode of glow-discharge reactor operating at 13.56 MHz. The vacuum chamber was pumped down to 0.1 Pa, and monomer vapor or gas was allowed to ll the reactor up to 15 Pa. Surfaces were then modied by argon plasma polymerization (G4) (White Martins, Rio de Janeiro, RJ, Brazil) and 99% ethylenediamine plasma polymerization (G5) (Sigma Chemicals by Tedia, Rio de Janeiro, RJ, Brazil) with 280 V self-bias voltage (VB) for 5 minutes. At the end of the process, radiofrequency was turned off and the system allowed to cool down before exposure of the samples to air. Contact Angle Analyses A Ram-Hart goniometer (Ram-Hart Instrument Company, e e Netcong, NJ) was used to measure the contact angle. A total of 10 analyses were made per group: 5 in contact with water (n = 5) and 5 in contact with Rely X Unicem resin cement (n = 5). Twenty measurements were obtained for each analysis, totaling 100 measurements per group. The data were analyzed using one-way analysis of variance and Fisher post hoc test (P < .05). To measure the surface free energy of the Rely X Unicem resin cement, the material was placed in a rectangular mold (25 mm 2 mm 2 mm) covered on both sides with transparent matrices and light cured for 40 seconds with a light-emitting diode unit. After 1 day, the matrices were removed, and the contact angle was measured for each of the 3 test liquids with known surface energy parameters: water, ethylene glycol, and diiodomethane. With these data, the

Scanning Electron Microscopic and Electron Dispersive Spectroscopy Analyses The surface morphology of ber posts regarding each treatment and those of the control group was investigated. For this purpose, the samples were prepared and analyzed by using a scanning electron microscope (SEM) (JSM 6460 LV; JEOL, Tokyo, Japan). For each group, 5 samples were used (n = 5), and microphotographs were obtained at 100 magnication. Next, electron dispersive spectroscopy (EDS) was used to verify the chemical composition of the samples. Push-out Test and Failure Pattern Analysis Treated posts and controls were cut into 2 pieces of 10 mm in length and cemented within a central hole of 1.8 mm in diameter made in a composite core of a 6-mm height and a 10-mm diameter. Following the manufacturers instructions, the encapsulated dualcured resin cement was manipulated in Amalgam II (3M ESPE) for 15 seconds. The resin cement was applied with appropriate syringe into the hole of the composite core, and the post was properly positioned. Each sample was polymerized for 40 seconds with a lightemitting diode unit (Radi Call, SDI, Australia). After storage for 24 hours, each specimen of 6 mm was sectioned perpendicularly to its long axis by means of a precision saw machine (Isomet 1000; Buehler Ltd, Lake Bluff, IL) to obtain 2 slabs of (2.5 0.3) mm in thickness. These slabs were wet grinded with carborundum papers (400, 600, and 1,200 grits) to obtain a at surface. A total of 8 samples were prepared for each group (n = 8). Bond strength was analyzed through the push-out test by using a universal testing machine (Emic DL 10000, S~o Jos dos Pinhais, PR, Brazil) at a cross-head speed of 1 mm/min a e and a cylindrical post of a 1.6-mm diameter and a 20-mm length with 200-kgf load cell. To express the bond strength in megapascals (MPa), the load value recorded in newtons (N) was divided by the area (mm2) of the bonded interface. It was calculated as follows (24): A 2prh, where pi is equal to 3.14, r is the post radius, and h is the thickness of the slice in millimeters. Means and standard deviations of bond strength were calculated, and data were analyzed by using one-way analysis of variance and the Fisher post hoc test (P < .05). The fractured specimens were prepared and analyzed by an SEM at 50 magnication to classify the failure pattern into 3 types: (1) adhesiveness between post and composite core with adhered cement, (2) adhesiveness between post and composite core without adhered cement, and (3) cohesiveness in composite core.

Figure 1. A graph with the contact angle values between the treated surfaces and water or resin cement.

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TABLE 1. The Contact Angle ( ) between the Treated Surfaces and Water or Resin Cement Treatment
Control Silane Hydrouoric acid Hydrouoric acid + silane Argon EDA

Water contact angle ( )

92.3 (5.9)d 56.1 (2.4)a,b 71.2 (5.7)c 59.4 (1.2)b 50 (12.8)a 72.1 (3.5)c

Resin cement contact angle ( )

75.8 (10.9)b,c 66.2 (6.5)b 76.9 (11.3)b,c 73.3 (19.1)b 43.4 (10.0)a 51.0 (15.1)a

*Mean value (standard deviation). The values with the same superscript letter do not differ (P < .05).

Results
Figure 1 and Table 1 show the contact angle analyses between treated surfaces and water or resin cement. As for the contact angle with water, the most hydrophilic surface was observed in the samples treated with argon plasma because they showed the lowest contact angle values followed by silane-treated samples, which showed no signicant difference compared with the treatment with hydrouoric acid plus silane. Hydrophobic characteristic was observed in samples submitted to ethylenediamine plasma (EDA) and hydrouoric acid treatments because the contact angle obtained was higher than that of controls. As for the contact angle with dual resin cement, lower values were found for samples treated with argon and EDA plasma, followed by treatments with silane and hydrouoric acid plus silane. Similarly, treatments with silane and hydrouoric acid plus silane showed no differences compared with the control group. As for the resin cement surface

energy parameters, the Rely X Unicem resin cement showed a hydrophobic characteristic with low surface energy values (6 1 mJ/m2). Figure 2 shows representative topographic images of the different groups and their corresponding EDS. EDS analysis showed chemical modications in the surface of the samples after different treatments. Scanning electron microscopic analysis showed topographic changes only in the EDA plasma group. Table 2 shows bond strength results and fracture surface morphology for all groups. The bond strength value of the EDA plasma group (17.3 MPa) was signicantly higher compared with all other groups, ranging from 10.9 to 13.9 MPa (P < .05). Scanning electron microscopic images from fracture morphologies showed that fracture occurred mainly because of adhesive failure, with no resin cement adhered to the post surface. Only EDA group had fractures in composite core because of cohesive failure.

Discussion
In the present study, the contact angle between treated surfaces and water was used to evaluate the hydrophilic characteristic of the surfaces. In this sense, samples treated with argon plasma showed the highest hydrophilic characteristic, presenting lower values of contact angle, without any topographic changes compared with control. Samples treated with EDA showed a hydrophobic characteristic with high values of contact angle. It can be explained by the presence of polar groups after argon treatment and nonpolar groups after EDA treatment. According to the manufacturer, the Rely X Unicem resin cement presents hydrophilic characteristics before polymerization and becomes hydrophobic after polymerization, which was observed in

Figure 2. Topographic images of the different groups and their corresponding EDS.

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TABLE 2. Bond Strength Values (MPa) and the Failure Pattern of the Experimental Groups and the Control Treatment
Control Silane Hydrouoric acid Hydrouoric acid + silane Argon EDA

with usual treatments. Adhesion improvement was only observed after EDA treatment.

Bond strength*
13.9 (1.4) 11.7 (3.1)a 10.9 (5.3)a 12.3 (5.4)a 12.4 (2.0)a 17.3 (2.7)b
a

Failure pattern
Adhesive without cement Adhesive without cement Adhesive without cement Adhesive without cement Adhesive without cement Cohesive in composite core

Acknowledgments
We would like to thank Jackson Belmiro for technical support. The authors deny any conicts of interest related to this study.

References
1. Schwartz RS, Robbins JW. Post placement and restoration of endodontically treated teeth: a literature review. J Endod 2004;30:289301. 2. DArcangelo C, DAmario M, Vadini M, De Angelis F, Caputi S. Inuence of surface treatments on the exural properties of ber posts. J Endod 2007;33:8647. 3. de Sousa Menezes M, Queiroz EC, Soares PV, Faria-e-Silva AL, Soares CJ, Martins LR. Fiber post etching with hydrogen peroxide: effect of concentration and application time. J Endod 2011;37:398402. 4. Valandro LF, Yoshiga S, de Melo RM, et al. Microtensile bond strength between a quartz ber post and a resin cement: effect of post surface conditioning. J Adhes Dent 2006;8:10511. 5. Monticelli F, Toledano M, Tay FR, et al. Post-surface conditioning improves interfacial adhesion in post/core restorations. Dent Mater 2006;22:6029. 6. Lassila LV, Tanner J, Le Bell AM, et al. Flexural properties of ber reinforced root canal posts. Dent Mater 2004;20:2936. 7. Monticelli F, Osorio R, Sadek FT, et al. Surface treatments for improving bond strength to prefabricated ber posts: a literature review. Oper Dent 2008;33: 34655. 8. Monticelli F, Toledano M, Tay FR, et al. A simple etching technique for improving the retention of ber posts to resin composites. J Endod 2006;32:447. 9. Saha A, Peutzfeld A, Asmussen E, et al. Effect of surface treatment of prefabricated posts on bonding of re sin cement. Oper Dent 2004;29:608. 10. Vano M, Goracci C, Monticelli F, et al. The adhesion between bre posts and composite resin cores: the evaluation of microtensile bond strength following various surface chemical treatments to posts. Int Endod J 2006;39:319. 11. Huntsberger JR. Surface energy, wetting and adhesion. Adhesion 1981;12:312. 12. Prado M, Assis DP, Gomes BPFA, Sim~o RA. Effect of disinfectant solutions on the a surface free energy and wettability of lling material. J Endod 2011;37:9802. 13. Asmussen E, Peutzfeldt A. Resin composites: strength of the bond to dentin versus surface energy parameters. Dent Mater 2005;21:103943. 14. Asmussen E, Peutzfeldt A, Saha A. Bonding of resin cements to post materials: Inuence of surface energy. J Adhes Dent 2005;7:2314. 15. Vassilakos N, Fernandes CP, Nilner K. Effect of plasma treatment on the wettability of elastomeric impression materials. J Prosthet Dent 1993;70:16571. 16. Ckeliler D, Erkut S, Zemek J, Biederman H, Mutlu M. Modication of glass ber to o improve reinforcement: a plasma polymerization technique. Dent Mater 2007;23: 33542. 17. Ozden N, Akaltan F, Suzer S, Akovali G. Time-related wettability characteristic of acrylic resin surfaces treated by glow discharge. J Prosthet Dent 1999;82:6804. 18. Maruo Y, Nishigawa G, Oka M, Minagi S, Suzuki K, Irie M. Does plasma irradiation improve shear bond strength of acrylic resin to cobalt-chromium alloy? Dent Mater 2004;20:50912. 19. Ramos V Jr, Runyan DA, Christensen LC. The effect of plasma treated polyethylene ber on the fracture strength of polymethyl methacrylate. J Prosthet Dent 1996;76: 946. 20. Wu GM. Oxygen plasma treatment of high perfomance bers for composites. Mater Chem Phys 2004;85:817. 21. Mandracci P, Mussano F, Ricciard C, Ceruti P, Prri F, Carossa S. Low temperatura growth of thin lm coating for the surface modication of dental prostheses. Surf Coat Technol 2008;203:247781. 22. Yenisey M, Kulunk S. Effects of chemical surface treatment of quartz and glass ber posts on the retention of a composite resin. J Prosthet Dent 2008;99:3845. 23. Yavirach P, Chaijareenont P, Boonyawan D, et al. Effects of plasma treatment on the shear bond strength between ber-reinforced composite posts and resin composite for core build-up. Dent Mater J 2009;28:68692. 24. Kececi AD, Kaya BU, Adnir N. Micro push-out bond strengths of four ber-reinforced composite post systems and 2 luting materials. Oral Surg Oral Med Oral Pathol Oral Radiol Endod 2008;105:1218. 25. Goracci C, Raffaelli O, Monticelli F, Balleri B, Bertelli E, Ferrari M. The adhesion between prefabricated FRC posts and composite resin cores: microtensile bond strength with and without post-silanization. Dent Mater 2005;21:43744. 26. Perdig~o J, Gomes G, Lee IK. The effect of silane on the bond strengths of ber posts. a Dent Mater 2006;22:7528.

*Mean value (standard deviation). Values with the same superscript letter do not differ (P < .05).

the present study. Adhesive materials should come into intimate contact with the substrate to facilitate molecular attraction and allow either chemical adhesion or penetration for micromechanical surface attachment (12). The wettability contact angle with Rely X Unicem resin cement was used to measure the interaction with the treated surface. These analyses showed that plasma treatments with EDA and argon were better than the use of silane, hydrouoric acid and its association to promote the spread of cement. According to de Sousa Menezes et al (3), the use of hydrouoric acid etching increases the surface roughness of ber posts, but, on the other hand, it causes damage to glass bers, thus affecting the integrity of the posts. In the present work, topographic changes were not observed. In the case of silane, a chemical change was observed. Silane only bridges resins and OH-covered inorganic supercially exposed glass bers (25, 26). The plasma treatment provides a long-lasting surface modication and could be easily used by the manufacturer. Regarding plasma treatment, Yavirach et al (23) reported that it does not induce any new reactive functionalities on the polymer surface. Argon treatment induces free radical formation on the polymer surface through ion bombardment. Epoxy resin is considered a chemically stable polymer, and, for this reason, it should be expected to be of little signicance for the reactive layer when it reacts with the methacrylate-based matrix found in Rely X Unicem cement. This fact is evident from the low values of the push-out bond strength. According to our data, EDA plasma caused a signicant chemical modication on the surface as well as topographic changes, which was indicated by the high roughness observed qualitatively by the SEM. The Rely X Unicem cement showed an afnity with ber posts treated with EDA plasma, which was observed for the bond strength of 17.3 MPa. The chemical modications are associated with nitrogen, carbon and oxygen incorporation, and their high binding energy sides, indicating carbon-oxygen and carbon-nitrogen bonding. In this case, scanning electron microscopic images showed that all fractures occurred because of cohesive failure in the composite core. These data are in accordance with Ckeliler et al (16), who o evaluated the effect of plasma-treated E-glass ber to improve the mechanical properties of acrylic resin denture base material (polymethylmethacrylate) and observed that this treatment produced chemical and topographic changes, besides increasing the exural strength. As for the bond strength analysis, the push-out test showed that hydrouoric acid combined or not with silane did not increase the bond strength or cause modications in the fracture morphology, as well as with argon plasma, as compared with the control group. According to the ndings of the present work, plasma treatment favored the wettability of the post surface by modifying it chemically when compared

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