Yoshio Kawano

Thermal Behavior of Nafion Membranes

The thermal behavior of Nafion-117 membranes was investigated by thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). TG measurements revealed that the mechanism of thermal degradation of a Nafion membrane in the acid form is different from that of Nafion in the sodium form. The DSC curves for the first heating, for both acid and salt forms, display two endothermic peaks, near 120 and 230°C. The high-temperature peak was assigned to the crystalline domains melting in Nafion, and the low-temperature peak was attributed to a transition into ionic clusters, since this transition exhibits significant changes depending on the nature of the counterion and the degree of hydration.

Influence of BisGMA, TEGDMA, and BisEMA contents on viscosity, conversion, and flexural strength of experimental resins and composites

Different monomer structures lead to different physical and mechanical properties for both the monomers and the polymers. The objective of this study was to determine the influence of the bisphenylglycidyl dimethacrylate (BisGMA) concentration (33, 50 or 66 mol%) and the co-monomer content [triethylene glycol dimethacrylate (TEGDMA), ethoxylated bisphenol-A dimethacrylate (BisEMA), or both in equal parts] on viscosity (eta), degree of conversion (DC), and flexural strength (FS). Eta was measured using a viscometer, DC was obtained by Fourier transfer Raman (FT-Raman) spectroscopy, and FS was determined by three-point bending. At 50 and 66% BisGMA, increases in eta were observed following the partial and total substitution of TEGDMA by BisEMA. For 33% BisGMA, eta increased significantly only when no TEGDMA was present. The DC was influenced by BisGMA content and co-monomer type. Mixtures containing 66% BisGMA showed a lower DC compared with mixtures containing other concentrations of BisGMA. The BisEMA mixtures had a lower DC compared with the TEGDMA mixtures. The FS was influenced by co-monomer content only. BisEMA mixtures presented a statistically lower FS, followed by TEGDMA + BisEMA mixtures, and then by TEGDMA mixtures. Partial or total replacement of TEGDMA by BisEMA increased eta, which was associated with the observed decreases in DC and FS. Although the BisGMA content influenced the DC, it did not affect the FS results.

Contraction stress related to composite inorganic content

OBJECTIVES The role of inorganic content on physical properties of resin composites is well known. However, its influence on polymerization stress development has not been established. The aim of this investigation was to evaluate the influence of inorganic fraction on polymerization stress and its determinants, namely, volumetric shrinkage, elastic modulus and degree of conversion. METHODS Eight experimental composites containing 1:1 BisGMA (bisphenylglycidyl dimethacrylate):TEGDMA (triethylene glycol dimethacrylate) (in mol) and barium glass at increasing concentrations from 25 to 60 vol.% (5% increments) were tested. Stress was determined in a universal test machine using acrylic as bonding substrate. Nominal polymerization stress was obtained diving the maximum load by the cross-surface area. Shrinkage was measured using a water picnometer. Elastic modulus was obtained by three-point flexural test. Degree of conversion was determined by FT-Raman spectroscopy. RESULTS Polymerization stress and shrinkage showed inverse relationships with filler content (R(2)=0.965 and R(2)=0.966, respectively). Elastic modulus presented a direct correlation with inorganic content (R(2)=0.984). Degree of conversion did not vary significantly. Polymerization stress showed a strong direct correlation with shrinkage (R(2)=0.982) and inverse with elastic modulus (R(2)=0.966). SIGNIFICANCE High inorganic contents were associated with low polymerization stress values, which can be explained by the reduced volumetric shrinkage presented by heavily filled composites.

Stress-Strain Curves of Nafion Membranes in Acid and Salt Forms

Nafion membranes have been studied using dynamic mechanical analysis in the controlled force mode and clamp of tension film measurements for as received commercial Nafion membranes with different solvent contents and with different cations (Li+, Na+, K+, Rb+ and Cs+). In comparison with as-received Nafion membranes, the initial slope of the stress-strain curves decreases with increasing water contents in the Nafion membrane and also with the addition of methanol, ethanol and ethanol/water (50/50%, v/v) mixture. The initial slope decreases also with increasing temperatures. On the other hand, the initial slope increases when the cation is replaced, in the following order: Li+, Na+, K+, Cs+ and Rb+. Nafion in salt form normally shows an increase in the initial slope from room temperature up to approximately 90oC, after which the slope decreases with increasing temperatures.

Composite pre-heating: Effects on marginal adaptation, degree of conversion and mechanical properties

OBJECTIVES This study evaluated the effect of composite pre-polymerization temperature and energy density on the marginal adaptation (MA), degree of conversion (DC), flexural strength (FS), and polymer cross-linking (PCL) of a resin composite (Filtek Z350, 3M/ESPE). METHODS For MA, class V cavities (4 mm x 2 mm x 2 mm) were prepared in 40 bovine incisors. The adhesive system Adper Single Bond 2 (3M/ESPE) was applied. Before being placed in the cavities, the resin composite was either kept at room-temperature (25 degrees C) or previously pre-heated to 68 degrees C in the Calset device (AdDent Inc., Danbury, CT, USA). The composite was then light polymerized for 20 or 40s at 600 mW/cm(2) (12 or 24 J/cm(2), respectively). The percentage of gaps was analyzed by scanning electron microscopy, after sectioning the restorations and preparing epoxy resin replicas. DC (n=3) was obtained by FT-Raman spectroscopy on irradiated and non-irradiated composite surfaces. FS (n=10) was measured by the three-point-bending test. KHN (n=6) was measured after 24 h dry storage and again after immersion in 100% ethanol solution for 24h, to calculate PCL density. Data were analyzed by appropriate statistical analyses. RESULTS The pre-heated composite showed better MA than the room-temperature groups. A higher number of gaps were observed in the room-temperature groups, irrespective of the energy density, mainly in the axial wall (p<0.05). Composite pre-heating and energy density did not affect the DC, FS and PCL (p>0.05). SIGNIFICANCE Pre-heating the composite prior to light polymerization similar in a clinical situation did not alter the mechanical properties and monomer conversion of the composite, but provided enhanced composite adaptation to cavity walls.

Thermal degradation of biomedical polyurethanes—A kinetic study using high-resolution thermogravimetry

The kinetics of thermal degradation of polyurethanes (PUR) has been studied by means of high-resolution and constant heating rate thermogravimetry (TG), under nitrogen and synthetic air atmospheres. The high-resolution TG provided a way to increase resolution with decreasing the time of data acquisition. In this mode, the heating rate is dynamically varied to maximize resolution. A method to calculate the kinetic parameters from this technique was used. The TG curves showed two or three decomposition steps, depending on the atmosphere employed. The parameters calculated for the PUR decomposition were the activation energy, reaction order, and preexponential factor. A method to estimate the polymer lifetime was also used.

Bis-GMA co-polymerizations: Influence on conversion, flexural properties, fracture toughness and susceptibility to ethanol degradation of experimental composites

OBJECTIVES The aim of this study was to evaluate the influence of monomer content on fracture toughness (K(Ic)) before and after ethanol solution storage, flexural properties and degree of conversion (DC) of bisphenol A glycidyl methacrylate (Bis-GMA) co-polymers. METHODS Five formulations were tested, containing Bis-GMA (B) combined with TEGDMA (T), UDMA (U) or Bis-EMA (E), as follows (in mol%): 30B:70T; 30B:35T:35U; 30B:70U; 30B:35T:35E; 30B:70E. Bimodal filler was introduced at 80 wt%. Single-edge notched beams for fracture toughness (FT, 25 mm x 5 mm x 2.5 mm, a/w=0.5, n=20) and 10 mm x 2 mm x 1 mm beams for flexural strength (FS) and modulus (FM) determination (10 mm x 2 mm x 1 mm, n=10) were built and then stored in distilled water for 24 h at 37 degrees C. All FS/FM beams and half of the FT specimens were immediately submitted to three-point bending test. The remaining FT specimens were stored in a 75%ethanol/25%water (v/v) solution for 3 months prior to testing. DC was determined with FT-Raman spectroscopy in fragments of both FT and FS/FM specimens at 24 h. Data were submitted to one-way ANOVA/Tukey test (alpha=5%). RESULTS The 30B:70T composite presented the highest K(Ic) value (in MPa m(1/2)) at 24 h (1.3+/-0.4), statistically similar to 30B:35T:35U and 30B:70U, while 30B:70E presented the lowest value (0.5+/-0.1). After ethanol storage, reductions in K(Ic) ranged from 33 to 72%. The 30B:70E material presented the lowest reduction in FT and 30B:70U, the highest. DC was similar among groups (69-73%), except for 30B:70U (52+/-4%, p<0.001). 30B:70U and 30B:35T:35U presented the highest FS (125+/-21 and 122+/-14 MPa, respectively), statistically different from 30B:70T or 30B:70E (92+/-20 and 94+/-16 MPa, respectively). Composites containing UDMA or Bis-EMA associated with Bis-GMA presented similar FM, statistically lower than 30B:35T:35U. SIGNIFICANCE Composites formulated with Bis-GMA:TEGDMA:UDMA presented the best compromise between conversion and mechanical properties.

Influence of Photoactivation Protocol and Light Guide Distance on Conversion and Microleakage of Composite Restorations

PURPOSE To evaluate the effect of light guide distance and the different photoactivation methods on the degree of conversion (DC) and microleakage of a composite. METHODS AND MATERIALS Three photoactivation protocols (600 mW/cm2 x 40 seconds; 400 mW/cm2 x 60 seconds or 200 mW/cm2 x 20 seconds, followed by 500 mW/cm2 x 40 seconds) and three distances from the light source (0, 3 or 7 mm) were tested. Cylindrical specimens (5 mm diameter; 2 mm tall; n=3) were prepared for the DC test (FT-Raman). Class V cavities were made in 90 bovine incisors to conduct the microleakage test. The specimens were conditioned for 15 seconds with phosphoric acid (37%), followed by application of the adhesive system Prime & Bond NT (Dentsply/Caulk). The preparations were restored in bulk. The specimens were stored for 24 hours in distilled water (37 degrees C) before being submitted to the silver-nitrate microleakage protocol. The restorations were sectioned and analyzed under 25x magnification. RESULTS Statistical analyses (two-way ANOVAs and Tukey test, alpha=0.05) found significance only for the factor distance (p=0.015) at the top of the composite for the DC test. Conversion was statistically lower for the 7 mm groups compared to the 0 and 3 mm groups, which were equivalent to each other. At the bottom of the specimens, none of the factors or interactions was significant (p<0.05). The Kruskal-Wallis test showed that, in general, the soft-start method led to lower microleakage scores when compared to the continuous modes, mainly when associated with a distancing of 7 mm (p<0.01). With the exception of specimens irradiated with 400 mW/cm2 that did not demonstrate variations on scores for the distances tested, higher microleakage was observed for shorter distances from the light source. CONCLUSIONS Soft-start methods may reduce microleakage when the light guide distancing provides a low level of irradiance, which also causes a discrete reduction in the DC.

Hybrid Materials from Intermolecular Associations between Cationic Lipid and Polymers

Intermolecular associations between a cationic lipid and two model polymers were evaluated from preparation and characterization of hybrid thin films cast on silicon wafers. The novel materials were prepared by spin-coating of a chloroformic solution of lipid and polymer on silicon wafer. Polymers tested for miscibility with the cationic lipid dioctadecyldimethylammonium bromide (DODAB) were polystyrene (PS) and poly(methyl methacrylate) (PMMA). The films thus obtained were characterized by ellipsometry, wettability, optical and atomic force microscopy, Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), and activity against Escherichia coli. Whereas intermolecular ion-dipole interactions were available for the PMMA-DODAB interacting pair producing smooth PMMA-DODAB films, the absence of such interactions for PS-DODAB films caused lipid segregation, poor film stability (detachment from the silicon wafer) and large rugosity. In addition, the well-established but still remarkable antimicrobial DODAB properties were transferred to the novel hybrid PMMA/DODAB coating, which is demonstrated to be highly effective against E. coli.

Degradation of polyacrylonitrile by X-ray radiation

Abstract The X-ray induced degradation of polyacrylonitrile (PAN) films was investigated using IR, UV/visible, X-ray diffraction and electron spin resonance (ESR) techniques. After irradiation, the polymer became yellow and insoluble in dimethylformamide, and changes in the UV/visible spectra indicated the formation of conjugated polyenes. In the IR spectra, new bands associated with conjugated CN, as well as NH, NH 2 and CC groups, showed up as a consequence of intramolecular cyclization and conjugated polyene formation; a decrease in the band intensities of CN stretching and CH 2 bending vibrations was also observed. Furthermore, from the X-ray diffractograms, an increase in the sample crystallinity was observed after 16 h of irradiation. The ESR spectrum indicated the presence of free radicals in the irradiated sample; such radicals are presumed to be responsible for the observed changes in the PAN properties such as brittleness, color and solubility.