pH-mediated interactions between poly(acrylic acid) and methylcellulose in the formation of ultrathin multilayered hydrogels and spherical nanoparticles

Poly(acrylic acid) forms insoluble hydrogen-bonded interpolymer complexes with methylcellulose in aqueous solutions under acidic conditions. In this work the reaction heats and binding constants were determined for the complexation between poly(acrylic acid) and methylcellulose by isothermal titration calorimetry at different pH and findings are correlated with the aggregation processes occurring in this system. The principal contribution to the complexation heat results from primary polycomplex particle aggregation. Transmission electron microscopy of nanoparticles produced at pH 1.4 and 2.4 demonstrated that they are spherical and dense structures. The nanoparticles ranged from 80 to 200 nm, whereas particles formed at pH 3.2 were 20-30 nm and were stabilized against aggregation by a network of uncomplexed macromolecules. For the first time, multilayered materials were developed on the basis of hydrogen-bonded complexes of poly(acrylic acid) and methylcellulose using layer-by-layer deposition on a glass surface. The thickness of these films was a linear function of the number of deposition cycles. The materials were subsequently cross-linked by thermal treatment, resulting in ultrathin hydrogels which detached from the glass substrate upon swelling. The swelling capacity of ultrathin hydrogels differed from the swelling of the thicker films of a similar chemical composition.

Design of mucoadhesive polymeric films based on blends of poly(acrylic acid) and (hydroxypropyl)cellulose

Mixing of aqueous solutions of poly(acrylic acid) and (hydroxypropyl) cellulose results in formation of hydrogen-bonded interpolymer complexes, which precipitate and do not allow preparation of homogeneous polymeric films by casting. In the present work the effect of pH on the complexation between poly(acrylic acid) and (hydroxypropyl)cellulose in solutions and miscibility of these polymers in solid state has been studied. The pH-induced complexation-miscibility-immiscibility transitions in the polymer mixtures have been observed. The optimal conditions for preparation of homogeneous polymeric films based on blends of these polymers have been found, and the possibility of radiation cross-linking of these materials has been demonstrated. Although the gamma-radiation treatment of solid polymeric blends was found to be inefficient, successful cross-linking was achieved by addition of N, N'- methylenebis(acrylamide). The mucoadhesive potential of both soluble and cross-linked films toward porcine buccal mucosa is evaluated. Soluble films adhered to mucosal tissues undergo dissolution within 30-110 min depending on the polymer ratio in the blend. Cross-linked films are retained on the mucosal surface for 10-40 min and then detach.

Characterization of safe nanostructured polymeric materials

The addition of small quantities of nanoparticles to conventional and sustainable thermoplastics leads to property enhancements with considerable potential in many areas of applications including food packaging 1, lightweight composites and high performance materials 2. In the case of sustainable polymers 3, the addition of nanoparticles may well sufficiently enhance properties such that the portfolio of possible applications is greatly increased. Most engineered nanoparticles are highly stable and these exist as nanoparticles prior to compounding with the polymer resin. They remain as nanoparticles during the active use of the packaging material as well as in the subsequent waste and recycling streams. It is also possible to construct the nanoparticles within the polymer films during processing from organic compounds selected to present minimal or no potential health hazards 4. In both cases the characterisation of the resultant nanostructured polymers presents a number of challenges. Foremost amongst these are the coupled challenges of the nanoscale of the particles and the low fraction present in the polymer matrix. Very low fractions of nanoparticles are only effective if the dispersion of the particles is good. This continues to be an issue in the process engineering but of course bad dispersion is much easier to see than good dispersion. In this presentation we show the merits of a combined scattering (neutron and x-ray) and microscopy (SEM, TEM, AFM) approach. We explore this methodology using rod like, plate like and spheroidal particles including metallic particles, plate-like and rod-like clay dispersions and nanoscale particles based on carbon such as nanotubes and graphene flakes. We will draw on a range of material systems, many explored in partnership with other members of Napolynet. The value of adding nanoscale particles is that the scale matches the scale of the structure in the polymer matrix. Although this can lead to difficulties in separating the effects in scattering experiments, the result in morphological studies means that both the nanoparticles and the polymer morphology are revealed.

Influence of pulse repetition rate of Er : YAG laser and dentin depth on tensile bond strength of dentin-resin interface

The study evaluated the in vitro influence of pulse-repetition rate of Er:YAG laser and dentin depth on tensile bond strength of dentin-resin interface. Dentin surfaces of buccal or lingual surfaces from human third molars were submitted to tensile test in different depths (superficial, 1.0 and 1.5 mm) of the same dental area, using the same sample. Surface treatments were acid conditioning solely (control) and Er:YAG laser irradiation (80 mJ) followed by acid conditioning, with different pulse-repetition rates (1, 2, 3, or 4 Hz). Single bond/Z-250 system was used. The samples were stored in distilled water at 37 degrees C for 24 h, and then the first test (superficial dentine) was performed. The bond failures were analyzed. Following, the specimens were identified, grounded until 1.0- and 1.5-mm depths, submitted again to the treatments and to the second and, after that, to third-bond tests on a similar procedure and failure analysis. ANOVA and Tukey test demonstrated a significant difference (p < 0.001) for treatment and treatment X depth interaction (p < 0.05). The tested depths did not show influence (p > 0.05) on the bond strength of dentin-resin interface. It may be concluded that Er:YAG laser with 1, 2, 3, or 4 Hz combined with acid conditioning did not increase the resin tensile bond strength to dentin, regardless of dentin depth. (C) 2007 Wiley Periodicals, Inc.

Chemical and Morphological Features of Dental Composite Resin: Influence of Light Curing Units and Immersion Media

Aims: The study evaluated the influence of light curing units and immersion media on superficial morphology and chemistry of the nanofilled composite resin Supreme XT (3M) through the EDX analysis and SEM evaluation. Light curing units with different power densities and mode of application used were XL 3000 (480 mW/cm(2)), Jet Lite 4000 Plus (1230mW/cm(2)), and Ultralume Led 5 (790 mW/cm(2)) and immersion media were artificial saliva, Coke(R), tea and coffee, totaling 12 experimental groups. Specimens (10 mm X 2 mm) were immersed in each respective Solution for 5 min, three times a day, during 60 days and stored in artificial saliva at 37 degrees C +/- 1 degrees C between immersion periods. Topography and chemical analysis was qualitative. Findings: Groups immersed in artificial saliva, showed homogeneous degradation of matrix and deposition of calcium at the material surface. Regarding coffee, there was a reasonable chemical degradation with loss of load particles and deposition of ions. For tea, superficial degradation occurred in specific areas with deposition of calcium, carbon. potassium and phosphorus. For Coke(R), excessive matrix degradation and loss of load particles with deposition of calcium, sodium, and potassium. Conclusion: Light curing units did not influence the superficial morphology of composite resin tested, but the immersion beverages did. Coke(R) affected material`s surface more than did the other tested drinks. Microsc. Res. Tech. 73:176-181, 2010. (c) 2009 Wiley-Liss Inc.

Influence of Post and Resin Cement on Stress Distribution of Maxillary Central Incisors Restored with Direct Resin Composite

The current study evaluated the influence of two endodontic post systems and the elastic modulus and film thickness of resin cement on stress distribution in a maxillary central incisor (MCI) restored with direct resin composite using finite element analysis (FEA). A three-dimensional model of an MCI with a coronary fracture and supporting structures was performed. A static chewing pressure of 2.16 N/mm(2) was applied to two areas on the palatal surface of the composite restoration. Zirconia ceramic (ZC) and glass fiber (GF) posts were considered. The stress distribution was analyzed in the post, dentin and cement layer when ZC and GF posts were fixed to the root canals using resin cements of different elastic moduli (7.0 and 18.6 GPa) and different layer thicknesses (70 and 200 mu m). The different post materials presented a significant influence on stress distribution with lesser stress concentration when using the GF post. The higher elastic modulus cement created higher stress levels within itself. The cement thicknesses did not present significant changes.

Influence of NaHCO(3) Powder on Translucency of Microfilled Composite Resin Immersed in Different Mouthrinses

The regular use of mouthrinses, particularly when combined with the use of air-powder polishing, could affect the appearance of tooth-colored restorations. The current study sought to evaluate the effect of NaHCO(3) powder on translucency of a microfilled composite resin immersed in different mouthrinses, at distinct evaluation periods. Eighty disk-shaped specimens of composite resin (Durafill VS, Heraeus Kulzer GmbH & Co. KG, Hanau, Germany) were prepared. The composite specimens were then randomly allocated into two groups according to the surface treatment: exposure to NaHCO(3) powder (10 seconds) or nonexposure, and they were randomly assigned into four subgroups, according to the mouthrinses employed (N = 10): Periogard (Colgate/Palmolive, Sao Bernardo do Campo, SP, Brazil), Cepacol (Aventis Pharma, Sao Paulo, SP, Brazil), Plax (Colgate/Palmolive), and distilled water (control group). The samples were immersed for 2 minutes daily, 5 days per week, over a 4-month test period. Translucency was measured with a transmission densitometer at seven evaluation periods. Statistical analyses (analysis of variance and Tukey`s test) revealed that: distilled water presented higher translucency values (86.72%); Periogard demonstrated the lowest translucency values (72.70%); and Plax (74.05%) and Cepacol (73.32%) showed intermediate translucency values, which were statistically similar between them (p > 0.01). NaHCO(3) air-powder polishing increased the changes in translucency associated with the mouthrinses. Air-powder polishing alone had no effect on material translucency. Translucency percent was gradually decreased from 1 week of immersion up to 4 months. It may be concluded that the NaHCO(3) powder and the tested mouthrinses have affected the translucency of microfilled composite resin, according to the tested time. CLINICAL SIGNIFICANCE During the last decade, the demand for composite resin restorations has grown considerably, however, controversy persists regarding the effect of surface roughness on color stability.

Bond Strength of Fiber Posts in Different Root Thirds Using Resin Cement

Purpose: The aim of the study was to assess the in vitro bond strength (BS) of glass fiber posts (GF) and carbon fiber posts (CF) in the cervical, middle, and apical thirds of root canals cemented with RelyX-Unicem (RX) and Cement-Post (CP). Materials and Methods: Forty maxillary canines were divided into 4 groups (n = 10) according to the cement and post used: group 1: GF and RX; group 2: CF and RX; group 3: GF and CP; group 4: CF and CP. The push-out test was applied in the cervical, middle and apical thirds of each specimen to assess bond strength of the cement/post complex to the root canal wall. The data obtained were submitted to ANOVA (Bonferroni test, p < 0.05), and fracture analysis was done with SEM. Results: The GF posts presented the best results when cemented with RX and with CF (p < 0.05). RX presented the highest BS values for both GF and CF (p < 0.05). For all the groups, BS was higher in the cervical third, followed by the middle and apical thirds. Fracture analysis showed a predominance of cohesive fracture of posts for RX, and a predominance of adhesive fracture between dentin/cement, and mixed failure mode for CP. Conclusion: GF posts cemented with RX presented the highest BS values in all root thirds.

Measurement of shrinkage of composite resin by laser speckle contrast analysis

The aim of this study was to evaluate the shrinkage of a microhybrid dental composite resin photo-activated by one LED with different power densities by means of speckle technique. The dental composite resin Filtek (TM) Z-250 (3M/ESPE) at color A(2) was used for the samples preparation. Uncured composite was packed in a metallic mold and irradiated during 20 s from 100 to 1000 mW cm(-2). For the photo-activation of the samples, it was used a LED prototype (Light Emission Diode) with wavelength centered at 470 nm and adjustable power density until 1 W cm(-2). The speckle patterns obtained from the bottom composite surfaces were monitored using a CCD camera without lens. The speckle field is recorded in a digital picture and stored by CCD camera as the carrier of information on the displacement of the tested surface. The calculated values were obtained for each pair of adjacent patterns and the changes in speckle contrast as a function of time were obtained from six repeated measurements. The speckle contrasts obtained from the bottom surface with 100 mW cm(-1) were smaller than those than the other power densities. The higher power densities provided the higher shrinkage.

Influence of pre-heat treatment and different light-curing units on Vickers hardness of a microhybrid composite resin

The aim of this study was to evaluate the hardness of a dental composite resin submitted to temperature changes before photo-activation with two light-curing unite (LCUs). Five samples (4 mm in diameter and 2 mm in thickness) for each group were made with pre-cure temperatures of 37, 54, and 60A degrees C. The samples were photo-activated with a conventional quartz-tungsten-halogen (QTH) and blue LED LCUs during 40 s. The hardness Vickers test (VHN) was performed on the top and bottom surfaces of the samples. According to the interaction between light-curing unit and different pre-heating temperatures of composite resin, only the light-curing unit provided influences on the mean values of initial Vickers hardness. The light-curing unit based on blue LED showed hardness mean values more homogeneous between the top and bottom surfaces. The hardness mean values were not statistically significant difference for the pre-cure temperature used. According to these results, the pre-heating of the composite resin provide no influence on Vickers hardness mean values, however the blue LED showed a cure more homogeneous than QTH LCU.

Flexural properties, microleakage, and degree of conversion of a resin polymerized with conventional light and argon laser

Objective: To evaluate the flexural strength, microleakage, and degree of conversion of a microhybrid resin polymerized with argon laser and halogen lamp. Method and Materials: For both flexural test and degree of conversion analysis, 5 bar samples of composite resin were prepared and polymerized according to ISO 4049. The halogen light-curing unit was used with 500 MW/cm(2) for 20 seconds and the argon laser with 250 mW for 10 and 20 seconds. Samples were stored in distilled water in a dark environment at 37 degrees C for 24 hours. The flexural property was quantified by a 3-point loading test. For the microleakage evaluation, 60 bovine incisors were used to prepare standardized Class 5 cavities, which were restored and polished. Specimens were stored in distilled water for 24 hours at 37 degrees C and thermocycled 500 times (6 degrees C to 60 degrees C). Specimens were then immersed in art aqueous solution of basic fuchsin for 24 hours. Longitudinal sections of each restoration were obtained and examined with a stereomicroscope for qualitative evaluation of microleakage. Fourier transform (FT)-Raman RFS 100/S spectrometer (Bruker) was used to analyze the degree of conversion. Results: ANOVA showed no statistically significant differences of flexural strength between the photoactivation types evaluated in the flexural study. Microleakage data were statistically analyzed by Mann-Whitney and Kruskal-Wallis tests. Enamel margins resulted in a statistically lower degree of leakage than dentin margins. No statistically significant difference was found among the 3 types of photocuring studied. ANOVA also showed no statistically significant difference in the degree of conversion among the studied groups. Conclusion: According to the methodology used in this research, the argon laser is a possible alternative for photocuring, providing the same quality of polymerization as the halogen lamp. None of the photocured units tested in this study completely eliminated microleakage.

Phenol-furfural resins to elaborate composites, reinforced with sisal fibers - Molecular analysis of resin and properties of composites

Resol type resins were prepared in alkaline conditions (potassium hydroxide or potassium carbonate) using furfural obtained by acid hydrolysis of abundant renewable resources from agricultural and forestry waste residues. The structures of the resins were fully determined by H-1, C-13, and 2D NMR spectrometries with the help of four models compounds synthesized specially for this study. MALDI-Tof mass spectrometry experiments indicated that a majority of linear oligomers and a minority of cyclic ones constituted them. Composites were prepared with furfural-phenol resins and sisal fibers. These fibers were chosen mainly because they came from natural lignocellulosic material and they presented excellent mechanical microscopy images indicated that the composites displayed excellent adhesion between resin and fibers. Impact strength measurement showed that mild conditions were more suitable to prepare thermosets. Nevertheless, mild conditions induced a high-diffusion coefficient for water absorption by composites. Composites with good properties could be prepared using high proportion of materials obtained from biomass without formaldehyde. (c) 2008 Wiley Periodicals, Inc.

Determination of the photoinduced birefringence and of the refractive index by Brewster method of epoxy resin doped with CdS

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Effect of pH variations in a cycling model on the properties of restorative materials

This study evaluated the effect of cycling various pH demineralizing solutions on the surface hardness, fluoride release and surface properties of restorative materials (Ketac-Fil Plus, Vitremer, Fuji II LC, Freedom and Fluorofil). Thirty specimens of each material were made and the surface hardness measured. The specimens were randomized into five groups according to the pH (4.3; 4.6; 5.0; 5.5 and 6.2) of the demineralizing solution. The specimens were submitted to pH-cycling for 15 days. The specimens remained in the demineralizing solution for six hours and in the remineralizing solution for 18 hours. Then, the surface hardness (SH) was remeasured and the surface properties were assessed. Fluoride release was determined daily. Data from SH and the percentage of alteration in surface hardness were analyzed by analysis of variance (p < 0.05); the Kruskal-Wallis test was performed for the fluoride release results. When hardness was compared, the variation in pH led to a positive correlation for glass ionomer cements and a negative correlation for fluoride release. For polyacid-modified resin composites, a negative correlation was found with regards to fluoride release; no significant correlation was observed for hardness. Surface properties were influenced: an acidic pH led to a greater alteration, except for polyacid-modified resin composites. The pH of the demineralizing solution influenced fluoride release from the tested materials. The pH variation altered hardness and surface properties of glass ionomer cements but did not influence polyacid-modified resin composites.

Analysis in vitro of direct bonding system with cyanoacrylate ester and orthodontic wires

The aim of this study was to evaluate the tensile strength of orthodontic wires bonded onto the enamel with cyanoacrylate ester. To obtain the specimens, 120 human premolars (extracted for orthodontic or periodontal reasons) were included in acrylic blocks of rapid polymerization with three teeth each. Four groups were formed with ten specimens each. In the specimens, a dental splint model was made with cyanoacrylate ester and round stainless steel wire. In groups I, II and III, cyanoacrylate ester was used with round steel wires, with variation in diameter: 0.014 inches; 0.016 inches and 0.018 inches, respectively. In group IV, round steel wire 0.018 inches was used with photo polymerizing resin composite with previous acid etching. The adhesive force of the materials was measured in two points under the action of the tensiometer (ETM-USA). The number of loose wires was counted along with those that remained fixed according to the different levels of force applied because of the direction of the tensile force (vertical or horizontal) and the diameter of the wire used. The data obtained were first submitted to a descriptive analysis and then submitted to a statistical analysis (Friedman's Test and Dunn's Test of Multiple Comparison - Epi-info 3.2). Within the limitations of the experimental conditions presented, the cyanoacrylate ester or 'Super Bonder (R)' maintained bonded to enamel and steel wires (0.016 and 0.018 inches) during the tensile strength tests under different levels of applied forces.