Composite materials based on silk proteins

A number of animals have evolved to produce silk-based composite materials for a variety of task-specific applications. The review initially focuses on the composite structure of silk fibers produced naturally by silkworms and spiders, followed by the preparation and applications of man-made composite materials (including fibers, films, foams, gels and particulates) incorporating silk proteins in combination with other polymers (both natural and synthetic) and/or inorganic particles. 

Characterization of Short Nylon-6 Fiber/Acrylonitrile Butadiene Rubber Composite by Thermogravimetry

The thermal degradation of short nylon-6 fiber reinforced acrylonitrile butadiene rubber (NBR) composites with and without epoxy-based bonding agent has been studied by thermogravimetric analysis (TGA). It was found that the onset of degradation shifted from 330.5 to 336.1°C in the presence of short nylon fiber, the optimum fiber loading being 20 phr. The maximum rate of degradation of the composites was lower than that of the unfilled rubber compound, and it decreased with increase in fiber concentration. The presence of epoxy resin-based bonding agent in the virgin elastomer and the composites improved the thermal stability. Results of kinetic studies showed that the degradation of NBR and the short nylon fiber reinforced composites followed first-order kinetics.

Rheological Characteristics of Short Nylon -6 Fiber Reinforced Styrene Butadiene Rubber Containing Epoxy Resin as Bonding Agent

The rheological characteristics of short Nylon-6 fiber-reinforced Styrene Butadiene rubber (SBR) in the presence of epoxy resin-based bonding agent were studied with respect to the effect of shear rate, fiber concentration , and temperature on shear viscosity and die swell using a capillary rheonzeter. All the composites containing bonding agent showed a pseudoplastic nature, which decreased with increasing temperature. Shear viscosity was increased in the presence of fibers. The temperature sensitivity of the SBR matrices was reduced on introduction of fibers. The temperature sensitivity of the melts was found to be lower at higher shear rates. Die swell was reduced in the presence of fibers. Relative viscosity of the composites increased with shear rate. In the presence of epoxy resin bonding agent the temperature sensitivity of the mixes increased. Die swell was larger in the presence of bonding agent.

Studies on the curing of short polyester fiber-polyurethane elastomer composite with different interfacial bonding agents

The cure characteristics of short fiber-polyurethane elastomer were studied with respect to different fiber-matrix bonding agents. A hexamethylenetetramine- resorcinol -hydrated silica based bonding agent was found to affect the stability of the composite. A new bonding agent, TP resin, based on polymeric toluenediisocyanate and polypropylene glycol has been developed. Cure characteristics of the composite with and without TP resin at different fiber loadings were also compared. Minimum torque, scorch time and optimum cure time increased with fiber content. Maximum torque was consistently higher with TP resin at all fiber loadings.

“Studies on short polyester fiber - polyurethane elastomer composite with different interfacial bonding agents”

The work presented in this thesis is regarding the development and evaluation of new bonding agents for short polyester fiber - polyurethane elastomer composites. The conventional bonding system based on hexamethylenetetramine, resorcinol and hydrated silica was not effective as a bonding agent for the composite, as the water eliminated during the formation of the RF resin hydrolysed the urethane linkages. Four bonding agents based on MDI/'I‘DI and polypropyleneglycol, propyleneglycol and glycerol were prepared and the composite recipe was optimised with respect to the cure characteristics and mechanical properties. The flow properties, stress relaxation pattern and the thermal degradation characteristics of the composites containing different bonding agents were then studied in detail to evaluate the new bonding systems. The optimum loading of resin was 5 phr and the ratio of the -01 to isocyanate was 1:1. The cure characteristics showed that the optimum combination of cure rate and processability was given by the composite with the resin based on polypropyleneglycol/ glycerol/ 4,4’diphenylmethanediisocynate (PPG/GL/MDI). From the rheological studies of the composites with and without bonding agents it was observed that all the composites showed pseudoplastic nature and the activation energy of flow of the composite was not altered by the presence of bonding agents. Mechanical properties such as tensile strength, modulus, tear resistance and abrasion resistance were improved in the presence of bonding agents and the effect was more pronounced in the case of abrasion resistance. The composites based on MDI/GL showed better initial properties while composites with resins based on MDI/PPG showed better aging resistance. Stress relaxation showed a multistage relaxation behaviour for the composite. Within the-strain levels studied, the initial rate of relaxation was higher and the cross over time was lesser for the composite containing bonding agents. The bonding agent based on MDI/PPG/GL was found to be a better choice for improving stress relaxation characteristics with better interfacial bonding. Thennogravimetirc analysis showed that the presence of fiber and bonding agents improved the thennal stability of the polyurethane elastomer marginally and it was maximum in the case of MDI / GL based bonding agents. The kinetics of degradation was not altered by the presence of bonding agents

Clinical assessment of postoperative sensitivity in posterior composite restorations

This incidence of postoperative sensitivity was evaluated in resin-based posterior restorations. Two hundred and ninety-two direct restorations were evaluated in premolars and molars. A total of 143 Class I and 149 Class 11 restorations (MO/OD and MOD) were placed in patients ranging in age from 30 to 50 years. After the cavity preparations were completed, a rubber dam was placed, and the preparations were restored using a total-etch system (Prime & Bond NT) and a resin-based restorative material (TPH Spectrum). The patients were contacted after 24 hours and 7, 30 and 90 days postoperatively and questioned regarding the presence of sensitivity and the stimuli that triggered that sensitivity. The Chi-square and Fisher's Exact Test were used for statistical analysis. Evaluation at 24 hours after restorative treatment revealed statistically significant differences among the types of cavity preparations restored and the occurrence of postoperative sensitivity (p=0.0003), with a higher frequency of sensitivity in Class H MOD restorations (26%), followed by Class II MO/DO (15%) and Class I restorations (5%). At 7, 30 and 90 days after restorative treatment, there was a decrease in the occurrence of sensitivity for all groups. The percentage of sensitivity among the groups was not significantly different. This study shows that the occurrence of sensitivity is correlated with the complexity of the restoration.

Composite surfaces after finishing and polishing techniques

Purpose: To evaluate the effect of finishing and polishing techniques on surface roughness of resin-based composites (RBCs). Materials and Methods: Forty specimens of each material were cured under Mylar strips and immersed in artificial saliva for 1 wk. Samples were tested with a profilometer to obtain baseline average surface roughness (Ra). Specimens of both RBCs were then finished and polished according to four techniques: (1) Sof-Lex disks; (2) Sof-Lex disks followed by Prisma Gloss; (3) Enhance points; (4) Enhance points followed by Prisma Gloss application. New readings of the roughness pattern were carried out and the difference of post-polishing and baseline values were analyzed. Results: ANOVA test (alpha= 0.05) did not show differences between materials (P= 0.9393) nor interaction effects (P= 0.3094), but significant difference among the finishing/polishing techniques were detected (P= 0.0157). Tukey's test showed that the smoothest surface was obtained when the specimens were treated by Sof-Lex followed by Prosma Gloss polishing paste; and the worst results were obtained after using Enhance points alone.

Influence of ceramic surface conditioning and resin cements on microtensile bond strength to a glass ceramic

Statement of problem. It is not clear how different glass ceramic surface pretreatments influence the bonding capacity of various luting agents to these surfaces.Purpose. The purpose of this study was to evaluate the microtensile bond strength (mu TBS) of 3 resin cements to a lithia disilicate-based ceramic submitted to 2 surface conditioning treatments.Material and methods. Eighteen 5 X 6 X 8-mm ceramic (IPS Empress 2) blocks were fabricated according to manufacturer's instructions and duplicated in composite resin (Tetric Ceram). Ceramic blocks were polished and divided into 2 groups (n=9/treatment): no conditioning (no-conditioning/control), or 5% hydrofluoric acid etching for 20 seconds and silanization for 1 minute (HF + SIL). Ceramic blocks were cemented to the composite resin blocks with I self-adhesive universal resin cement (RelyX Unicem) or 1 of 2 resin-based luting agents (Multilink or Panavia F), according to the manufacturer's instructions. The composite resin-ceramic blocks were stored in humidity at 37 degrees C for 7 days and serially sectioned to produce 25 beam specimens per group with a 1.0-mm(2) cross-sectional area. Specimens were thermal cycled (5000 cycles, 5 degrees C-55 degrees C) and tested in tension at 1 mm/min. Microtensile bond strength data (MPa) were analyzed by 2-way analysis of variance and Tukey multiple comparisons tests (alpha=.05). Fractured specimens were examined with a stereomicroscope (X40) and classified as adhesive, mixed, or cohesive.Results. The surface conditioning factor was significant (HF+SIL > no-conditioning) (P<.0001). Considering the unconditioned groups, the mu TBS of RelyX Unicem was significantly higher (9.6 +/- 1.9) than that of Multilink (6.2 +/- 1.2) and Panavia F (7.4 +/- 1.9). Previous etching and silanization yielded statistically higher mu TBS values for RelyX Unicem (18.8 +/- 3.5) and Multilink (17.4 +/- 3.0) when compared to Panavia F (15.7 +/- 3.8). Spontaneous debonding after thermal cycling was detected when luting agents were applied to untreated ceramic surfaces.Conclusion. Etching and silanization treatments appear to be crucial for resin bonding to a lithia disilicate-based ceramic, regardless of the resin cement used.

Surface conditioning of a composite used for inlay/onlay restorations: Effect on mu TBS to resin cement

Purpose: To assess the effect of the composite surface conditioning on the microtensile bond strength of a resin cement to a composite used for inlay/onlay restorations.Materials and Methods: Forty-two blocks (6 x 6 x 4 mm) of a microfilled composite (Vita VMLC) were produced and divided into 3 groups (N = 14) by composite surface conditioning methods: Gr1 - etching with 37% phosphoric acid, washing, drying, silanization; Gr2 - air abrasion with 50-Im Al203 particles, silanization; Gr3 - chairside tribochemiCal silica coating (CoJet System), silanization. Single-Bond (one-step adhesive) was applied on the conditioned surfaces and the two resin blocks treated with the same method were cemented using RelyX ARC (dual-curing resin cement). The specimens were stored for 7 days in water at 37 degrees C and then sectioned to produce nontrimmed beam samples, which were submitted to microtensile bond strength testing (mu TBS). For statistical analysis (one-way ANOVA and Tukey's test, = 0.05), the means of the beam samples from each luted specimen were calculated (n = 7).Results: mu TBS values (MPa) of Gr2 (62.0 +/- 3.9a) and Gr3 (60.5 +/- 7.9a) were statistically similar to each other and higher than Gr1 (38.2 +/- 8.9b). The analysis of the fractured surfaces revealed that all failures occurred at the adhesive zone.Conclusion: Conditioning methods with 50-Im Al203 or tribochemical silica coating allowed bonding between resin and composite that was statistically similar and stronger than conditioning with acid etching.

Effect of resin luting film thickness on fracture resistance of a ceramic cemented to dentin

Purpose: The aim of this study was to evaluate the fracture resistance of ceramic plates cemented to dentin as a function of the resin cement film thickness. Materials and Methods: Ceramic plates (1 and 2 mm thicknesses) were cemented to bovine dentin using resin composite cement. The film thicknesses used were approximately 100, 200, and 300 μm. Noncemented ceramic plates were used as control. Fracture loads (N) were obtained by compressing a steel indenter in the center of the ceramic plates. ANOVA and Tukey tests (α = 0.05) were used for each ceramic thickness to compare fracture loads among resin cement films used. Results: Mean fracture load (N) for 1-mm ceramic plates were: control - 26 (7); 100 μm - 743 (150); 200 μm - 865 (105); 300 μm - 982 (226). Test groups were significantly different from the control group; there was a statistical difference in fracture load between groups with 100 and 300 μm film thicknesses (p < 0.01). Mean fracture load for 2-mm ceramic plates were: control - 214 (111); 100 μm - 1096 (341); 200 μm - 1067 (226); 300 μm - 1351 (269). Tested groups were also significantly different from the control group (p < 0.01). No statistical difference was shown among different film thicknesses. Conclusions: Unluted specimens presented significantly lower fracture resistance than luted specimens. Higher cement film thickness resulted in increased fracture resistance for the 1-mm ceramic plates. Film thickness did not influence the fracture resistance of 2-mm porcelain plates. Copyright © 2007 by The American College of Prosthodontists.

In vitro evaluation of surface roughness of 4 resin composites after the toothbrushing process and methods to recover superficial smoothness.

OBJECTIVE: This study evaluated the efficiency of repolishing, sealing with surface sealant, and the joining of both in decreasing the surface roughness of resin-based composites after a toothbrushing process. METHOD AND MATERIALS: Ten specimens of each composite (Alert, Z100, Definite, and Prodigy Condensable), measuring 2 mm in thickness and 4 mm in diameter, were made and submitted to finishing and polishing processes on both sides of the specimens using the Sof-Lex system. The specimens were then subjected to toothbrushing (30,000 cycles), and surface roughness (Ra) was analyzed with a Surfcorder SE 1700 profilometer. The upper surface of each composite was etched with 37% phosphoric acid, and the surface-penetrating sealant Protect-it was applied on 1 surface. The roughness of these surfaces was again measured. On the other side, the surface of the specimen was repolished, and the efficiency of this procedure was measured using the profilometer. The surface roughness resulting from the joining of the 2 methods was verified by applying, in the final stage, the surface-penetrating sealant on the repolished surface. Data were analyzed with analysis of variance and Tukey test (P <.05). RESULTS: Results showed that the lowest surface roughness values were obtained for Definite, Z100, and Prodigy Condensable after the repolishing process and after the repolishing plus sealing. For Alert, the joining of repolishing plus sealing promoted the lowest values of surface roughness. CONCLUSION: Of the resin-based composites, Alert demonstrated the highest values of surface roughness in all the techniques tested.

Surface conditioning of a composite used for inlay/onlay restorations: Effect on μTBS to resin cement

Purpose: To assess the effect of the composite surface conditioning on the microtensile bond strength of a resin cement to a composite used for inlay/onlay restorations. Materials and Methods: Forty-two blocks (6 × 6 × 4 mm) of a microfilled composite (Vita VMLC) were produced and divided into 3 groups (N = 14) by composite surface conditioning methods: Gr1 - etching with 37% phosphoric acid, washing, drying, silanization; Gr2 - air abrasion with 50-l̀m Al2O3 particles, silanization; Gr3 - chairside tribochemical silica coating (CoJet System), silanization. Single-Bond (one-step adhesive) was applied on the conditioned surfaces and the two resin blocks treated with the same method were cemented using RelyX ARC (dual-curing resin cement). The specimens were stored for 7 days in water at 37°C and then sectioned to produce nontrimmed beam samples, which were submitted to microtensile bond strength testing (μTBS). For statistical analysis (one-way ANOVA and Tukey's test, · = 0.05), the means of the beam samples from each luted specimen were calculated (n = 7). Results: μTBS values (MPa) of Gr2 (62.0 ± 3.9a) and Gr3 (60.5 ± 7.9a) were statistically similar to each other and higher than Gr1 (38.2 ± 8.9b). The analysis of the fractured surfaces revealed that all failures occurred at the adhesive zone. Conclusion: Conditioning methods with 50-l̀m Al2O3 or tribochemical silica coating allowed bonding between resin and composite that was statistically similar and stronger than conditioning with acid etching.

Persistence of epoxy-based sealer residues in dentin treated with different chemical removal protocols

The presence of residual endodontic sealer in the pulp chamber may cause discoloration of the dental crown and interfere with the adhesion of restorative materials. The aim of this study was to compare the efficacy of different solvents in removing residues of an epoxy resin-based sealer (AH Plus) from the dentin walls of the pulp chamber, by scanning electron microscopy (SEM). Forty-four bovine incisor dental crown fragments were treated with 17% EDTA and 2.5% NaOCl. Specimens received a coating of AH Plus and were left undisturbed for 5 min. Then, specimens were divided in four groups (n = 10) and cleaned with one of the following solutions: isopropyl alcohol, 95% ethanol, acetone solution, or amyl acetate solution. Negative controls (n = 2) did not receive AH Plus, while in positive controls (n = 2) the sealer was not removed. AH Plus removal was evaluated by SEM, and a score system was applied. Data were analyzed by Kruskal-Wallis and Dunn tests. None of the solutions tested was able to completely remove AH Plus from the dentin of the pulp chamber. Amyl acetate performed better than 95% ethanol and isopropyl alcohol (p < 0.05), but not better than acetone (p > 0.05) in removing the sealer from dentin. No significant differences were observed between acetone, 95% ethanol, and isopropyl alcohol (p > 0.05). It was concluded that amyl acetate and acetone may be good options for cleaning the pulp chamber after obturation with AH Plus. SCANNING 35:17-21, 2013. © 2012 Wiley Periodicals, Inc. © Wiley Periodicals, Inc.

Repair bond strength of microhybrid, nanohybrid and nanofilled resin composites: Effect of substrate resin type, surface conditioning and ageing

Objectives: This study evaluated the microtensile bond strength (MTBS) of non-aged and aged resin-based composites (RBC) (nanohybrid and nanofilled) after two surface conditioning methods, repaired using the composite of the same kind or a microhybrid composite. Materials and methods: Nanohybrid (Tetric EvoCeram-TE) and nanofilled (Filtek Supreme-FS) RBC blocks (5 × 5 × 6 mm) (N = 128) were fabricated and randomly divided into two groups: (a) no ageing (control group) and (b) ageing (5.000 thermocycling, 5-55 °C). RBC surfaces were polished by up to 1,200-grit silicone carbide papers and conditioned with either (a) air abrasion with 30-μm SiO2 particles (CoJet Sand) for 4 s + silane coupling agent (ESPE-Sil) + adhesive resin (VisioBond) (n = 16) or (b) adhesive application only (Multilink A+B for TE; Adper ScotchBond 1XT for FS) (n = 16). In half of the groups, repair resin of the same kind with the RBC and, in the other half, a different kind of composite (microhybrid, Quadrant Anterior Shine-AS) with its corresponding adhesive (Quadrant UniBond) was used. The specimens were submitted to MTBS test (0.5 mm/min). Data were analysed using three-way ANOVA and Tukey's tests. Degree of conversion (DC) of non-aged and aged resin composites (TE, FS) (n = 3 per group) was measured by micro-Raman analyses. Results: RBC type (p = 0.001) and ageing affected the MTBS results significantly (p = 0.001). Surface conditioning type did not show significant difference (p = 0.726), but less number of pre-test failures was experienced with the CoJet system compared to adhesive resin application only. Repair strength on aged TE showed significantly less (p < 0.05) MTBS than for FS. FS repaired with the same kind of RBC and adhesive resin presented the highest cohesive failures (43 %). DC was higher for TE (71 %) than for FS (58 %) before ageing. Conclusion: On the aged RBCs, less favourable repair strength could be expected especially for nanohybrid composite. For repair actions, RBC surface conditioning could be accomplished with either adhesive resin application only or with CoJet system, providing that the latter resulted in less pre-test failures. Clinical relevance: Clinicians could condition the resin surface prior to repair or relayering with either CoJet system or adhesive resin application only, depending on the availability of the system. © 2012 Springer-Verlag Berlin Heidelberg.

Light-curing Time and Aging Effects on the Nanomechanical Properties of Methacrylate- and Silorane-based Restorations

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)