The Journal of Adhesive Dentistry, 01/2020

This literature-based OPINION PAPER reflects in an introductory historical perspective on the rapid advancement of dental adhesive technology. Past and current techniques to bond to tooth tissue, in particular to dentin as the most challenging bonding substrate, are critically appraised. Including the historical perspective in (1), this paper focuses on fourteen items thought to be of primary importance with regard to the current status of dental adhesive technology. In (2) the primary mechanisms involved in adhesion to enamel and especially dentin are dealt with having (3) also revisited the previously introduced adhesion-decalcification concept (AD concept) as basis of biomaterial-hard tissue interaction; the worldwide accepted classification of today's adhesives into etch&rinse (E&R) and self-etch (SE) adhesives are presented in (4), along with presentation of their respective PLUS-MINUS balances in (5) and (6); nomination of the GOLD-STANDARD E&R (7) and SE (8) adhesives is based on evidence of successful laboratory and long-term clinical performance, resulting in a recommended 3-step full E&R bonding route in (9) and the preferred 3-step combined selective enamel E&R with 2-SE bonding route in (10); (11) description of the main bond-degradation pathways and eight strategies to preserve bond stability; (12) coverage of the PROS and CONS of the newest generation of UNIVERSAL adhesives. Looking into the future, some expected future developments in dental adhesive technology have been suggested in (13), along with (14) a first status determination of the latest research-and-development towards self-adhesive restorative materials that no longer require any pre-treatment. Keywords: review, bonding, dentin, adhesion, self-adhesive

Purpose: The aim of this review article was to provide an overview of the scientific and patent literature on the different synthesis pathways of modified polyacids suitable for application in a new class of restorative dental materials. Methods: The literature based on patents and publications from 2009 to 2018 of Dentsply Sirona in cooperation with Heinrich Heine University, Düsseldorf, was reviewed and summarized. Results: Multiple approaches towards the development of polymerizable acid polymers have been introduced and their strength and weaknesses were discussed. A target structure and the respective synthesis were developed allowing the formulation of a restorative dental material with unique properties, such as high mechanical strength paired with good adhesion properties. Conclusion: From a variety of hydrolytically stable acidic polymers, the most promising versions were selected and used for the product development of Surefil one (Dentsply Sirona). Keywords: additive coupling, copolymerization of acrylic acid with amine derivatives, modified polyacrylic acid, polymer- analogous modification, restorative materials

Purpose: The development of a novel material requires a comprehensive pre-clinical assessment of clinical longevity before any market release. This study aimed to investigate the mechanical performance of a novel self-adhesive restorative material (ASAR MP4). Materials and Methods: Fracture strength (FS), flexural fatigue strength (FFS) and fracture toughness (KIc) were measured for the experimental material ASAR MP4 in self-cure (SC) and light-cure (LC) mode. ASAR MP4 was processed in capsules. Three direct resin composites (CeramX mono+, DentsplySirona; Heliomolar, IvoclarVivadent; Filtek Supreme XTE, 3M) and two glass-ionomer-cement (GIC) based materials (Equia Forte, GC; Fuji II LC, GC) were selected for comparison with ASAR MP4. FS specimens (n = 15) were tested in a 4-point bending configuration according to ISO 4049 and 9917. FFS specimens (n = 25) were additionally stressed for 104 loading cycles using the staircase approach. The single-edge-notch beam (SENB) configuration was selected for determining KIc according to ISO 13586. All specimens were stored for 14 days at 37°C. Data were analyzed using Weibull statistics (FS), ANOVA (FS, KIc), and the non-parametric Mann-Whitney U-test (FFS). Results: The FS, FFS and KIc data of the ASAR MP4 material reveal a mechanical performance in the range of the successful permanent direct resin composites CeramX mono+ and Heliomolar. The results for ASAR MP4 in SC mode were superior to the LC mode. A fine-grained and pore-free microstructure was observed. Conclusion: Within the limitations of this study we conclude that the novel self-adhesive restorative material ASAR MP4 exhibits mechanical performance close to that of the resin composites Heliomolar and CeramX mono+, both indicated for permanent use in the load-bearing posterior region. Processing the material in either self-cure or light-cure mode led to superior performance over glass-ionomer cements. Keywords: flexural strength, cyclic fatigue, fracture toughness, self-adhesion, resin composite, glass-ionomer cement

Purpose: To investigate simulated localized and generalized wear of self-adhesive restorative materials. Materials and Methods: Three commercially available restorative materials and one experimental material with self-adhesive properties were evaluated. The experimental material was tested in both light-cured and self-cured conditions. Activa (A), Fuji II LC (F), and Equia Forte (E) and the experimental material ASAR-MP4 (S) were investigated. Two kinds of wear were simulated in an Alabama wear machine. Localized wear was simulated with a stainless-steel ball bearing antagonist and generalized with a flat-ended stainless-steel cylinder antagonist. The wear challenge was carried out in an aqueous slurry of polymethyl methacrylate beads. Material volume loss was measured on polyvinyl siloxane replicates of each worn surface using a Proscan 2100 noncontact profilometer in conjunction with Proscan and AnSur 3D software. Results: There were significant differences (p < 0.05) among the materials for both generalized and localized wear. The experimental material in both curing modes exhibited significantly less localized wear than F and A and significantly less generalized wear than F and E. Conclusion: Self-adhesive materials offer unique handling properties for direct placement of posterior restorations in permanent teeth. The experimental material ASAR-MP4 generated similar wear values to the other self-adhesive materials tested. Keywords: localized wear, generalized wear, self-adhesive, bulk fill, glass ionomer

Purpose: This study investigated the bonding efficacy of a new so-called self-adhesive composite hybrid onto flat (FLAT) and high C-factor class-I cavity-bottom (CAVITY) dentin. Materials and Methods: The immediate and aged (50,000 thermocycles) microtensile bond strength (μTBS) to FLAT and CAVITY dentin of the experimental self-adhesive bulk-fill restorative (K-0180 ASAR pilot [ASAR-pilot], Dentsply Sirona) was compared to that of two universal adhesives applied in self-etch mode and combined with a bulk-fill composite (Prime&Bond Elect/QuiXfil [P&Be/QuiXF], Prime&Bond Active/QuiXfil [P&Ba/QuiXF], both Dentsply Sirona), two pre-conditioned materials (Activa Bioactive-Restorative [Activa], Pulpdent; Fuji II LC Improved [Fuji2LC], GC); and one bulk-fill glass-hybrid restorative (Equia Forte Fil [EquiaF], GC). Statistically significant differences were recorded using Welch's ANOVA with Games-Howell contrast (p < 0.05). Results: No significant difference in immediate μTBS was recorded when the restorative materials were applied onto FLAT dentin, except for Activa_FLAT and EquiaF_FLAT. When bonded to CAVITY dentin, the significantly highest μTBS was recorded for Fuji2LC_CAVITY (layer filled), and was not significantly different only from P&Ba/QuiXF_CAVITY. Upon aging, the highest μTBS to flat dentin was achieved by ASAR-pilot_FLAT, which was not significantly different from P&Be/QuiXF_FLAT and Fuji2LC_FLAT. No significant difference between immediate and aged μTBS was recorded for ASAR-pilot when bonded onto FLAT or CAVITY dentin; the latter, however, was associated with low bond strength. Conclusion: Favorable bonding performance was found for the new self-adhesive bulk-fill composite hybrid ASAR-pilot when bonded to flat dentin. However, much lower bond strength was recorded when ASAR-pilot was bonded to high C-factor cavity-bottom dentin. Keywords: bond strength, bulk-fill, composite, dentin, durability

Purpose: To use shear bond strength (SBS) testing to determine the effect of surface moisture and smear layer thickness on the adhesion of self-adhesive restorative materials and a universal adhesive. Materials and Methods: One single-step self-etch universal adhesive, Prime & Bond Active (PA), was used to bond Ceram.x Spectra ST HV composite resin to dentin and enamel using the self-etching technique. Three commercially available restorative materials and one newly developed material with self-adhesive properties, Activa (A), Fuji II LC(F), Equia Forte (E), and ASAR-MP4 (S), respectively, were also bonded to enamel and dentin prepared moist and dry and to dentin prepared with a thick smear layer. Shear bond testing was performed using an Ultradent bonding apparatus. Results: The universal adhesive generated the highest SBS to dentin and enamel, followed by the newly developed material. None of the materials tested were significantly affected by the moisture conditions on enamel or dentin. The thickness of smear layer significantly affected SBS to dentin for S, F, and E. However, S and F still exhibited higher shear bond strength to dentin with the thicker smear layer compared to the other self-adhesive materials. Only the universal adhesive in self-etch mode was not affected by the thicker smear layer and maintained significantly higher SBS. Conclusion: None of the materials tested were affected by bonding to overdried dentin or enamel. All of the self-adhesive materials exhibited lower SBS to specimens with a thicker smear layer. The newly developed material ASAR-MP4 compared favorably to the other self-adhesive materials tested under all test conditions. Keywords: adhesion to dental hard tissues, shear bond testing, glass ionomers, self-adhesive restoratives

Purpose: The material structure and chemical elemental composition of a new self-adhesive composite hybrid were investigated. The bonding performance when applied on flat (FLAT) vs high C-factor class-I cavity-bottom (CAVITY) dentin and in light-cure (LC) vs self-cure (SC) mode was determined. Materials and Methods: The self-adhesive bulk-fill composite Surefil One (Su-O; Dentsply Sirona) was compared with the resin-modified glass-ionomer Fuji II LC Improved (Fuji2LC; GC) and the ion-releasing alkasite material Cention N (CentionN; Ivoclar Vivadent). The material structure was examined with SEM and TEM, while the chemical elemental composition was analyzed using EDS. The immediate and aged microtensile bond strength (μTBS) of Su-O_LC/SC was compared to that of Fuji2LC applied without any pre-treatment, and to that of CentionN applied following bonding with Adhese Universal (AU) (Ivoclar Vivadent) in self-etch mode (AU/CentionN). All restorative materials were bonded onto FLAT and CAVITY dentin. Statistical analysis was performed with the Kruskal-Wallis nonparametric test. Results: EDS analysis revealed that Su-O was richer in C and P than the reference restorative materials. Applied to FLAT dentin, the significantly highest immediate and aged μTBS were recorded for AU/CentionN, which were not significantly different only from Su-O_LC. Applied to CAVITY dentin, the significantly highest immediate μTBS was recorded for AU/CentionN, which did not differ significantly only from Su-O_SC. Su-O_LC bonded to CAVITY dentin suffered from a high incidence of pre-test failures. Conclusion: While Su-O_LC bonded effectively and durably to FLAT dentin, Su-O_SC bonded more favorably than Su-O_LC in class-I cavities, which was probably related to shrinkage stress variously challenging the respective bond. Keywords: adhesion, aging, composite, curing, EDS, TEM

Purpose: To use shear bond strength (SBS) and shear fatigue strength (SFS) testing to determine the durability of adhesion of self-adhesive restorative materials compared to composite resin bonded with a universal adhesive. Materials and Methods: A universal adhesive, Prime & Bond Active, was used in self-etch mode to bond Z-100 composite resin to enamel and dentin. Three commercially available restorative materials and one experimental material with self-adhesive properties, Activa (A), Fuji II LC(F), and Equia Forte (E) and ASAR-MP4 (S) were also bonded to enamel and dentin. The SBS and SFS were determined for all materials. A staircase method was used to determine the SFS with 10 Hz frequency for 50,000 cycles or until failure occurred. Results: On enamel, S generated similar values to the adhesive/composite materials and higher values than F, E, and A. On dentin, the composite/universal adhesive showed significantly higher SBS and SFS than the self-adhesive materials. S, F, and E generated higher values than A on dentin. Conclusion: SBS and SFS values to enamel were similar for all materials tested except Activa which generated lower enamel values. On dentin surfaces, the self-adhesive materials generated similar SBS and SFS, with the exception of Activa. Those values were lower than that generated with composite resin and a universal adhesive. Keywords: adhesion to dental hard tissues, fatigue testing, glass ionomers, bond durability, self-adhesive restoratives

Purpose: This in vitro study evaluated marginal integrity, 2-body wear, and fracture behavior of an array of bonded and nonbonded posterior restorative materials after thermomechanical loading (TML). Materials and Methods: Eighty-eight MOD cavities with one proximal box beneath the CEJ were prepared in extracted human third molars according to a well-established protocol. Direct restorations were made using the following materials: amalgam (Dispersalloy), Ketac Molar Quick, Surefil One (with or without light curing), Activa, AdheSE Universal/Heliomolar, Fuji II LC improved, Equia Forte, Scotchbond Universal/Filtek Supreme, Xeno V+/CeramX.mono+, Prime&Bond active/Spectra ST CeramX HV, Prime&Bond elect/Spectra ST CeramX HV. Before and after thermomechanical loading (2500/5000/12,500 thermocycles between 5°C and 55°C + 100,000/ 200,000/500,000 x 50 N), marginal gaps and 2-body wear depths were analyzed on epoxy resin replicas using SEM and CLSM. Fractures were observed under a light microscope (20X). Results were analyzed with Kruskal-Wallis and Mann-Whitney U-tests (p < 0.05). Results: For marginal quality, Surefil One showed promising in vitro behavior close to that of resin composite bonded with a self-etch adhesive (p > 0.05). For wear, amalgam and resin composites with recent filler technology were still superior (p < 0.05), but Surefil One LC outperformed Activa, Ketac Molar Quick, Equia Forte Fil, and Fuji II LC (p < 0.05). When Surefil One was occlusally light cured, no fractures occured, even after 500,000 cycles of TML. Conclusion: The novel self-adhesive posterior restorative Surefil One did not exhibit superior outcomes for all evaluated aspects. However, it showed stable fracture behavior, good marginal quality, and acceptable wear resistance in vitro. Keywords: amalgam alternatives, resin composites, resin-modified glass-ionomer cements, self-adhesive materials