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This paper presents an analysis of the mechanical properties of different polymer optical fibers (POFs) at ultraviolet (UV) radiation conditions. Cyclic transparent optical polymer (CYTOP) and polymethyl methacrylate (PMMA) optical fibers are used in these analyses. In this case, the fiber samples are irradiated at the same wavelength, pulse time and energy conditions for different times, namely, 10 s, 1 min, 2 min and 3 min. The samples are tested in tensile tests and dynamic mechanical thermal analysis (DMTA) to infer the variation in the static and dynamic properties of such fibers as a function of the UV radiation condition. Furthermore, reference samples of each fiber (without UV radiation) are tested for comparison purposes. The results show a lower UV resistance of PMMA fibers, i.e., higher variation in the material features in static conditions (Young's modulus variation of 0.65 GPa). In addition, CYTOP fiber (material known for its high UV resistance related to its optical properties) also presented Young's modulus variation of around 0.38 GPa. The reason for this reduction in the moduli is related to possible localized annealing due to thermal effects when the fibers are subjected to UV radiation. The dynamic results also indicated a higher variation in the PMMA fibers storage modulus, which is around 30% higher than the variations in the CYTOP fibers when different radiation conditions are analyzed. However, CYTOP fibers show a smaller operational temperature range and higher variation in the storage modulus as a function of the temperature when compared with PMMA fibers. In contrast, PMMA fibers show higher variations in their material properties when subjected to oscillatory loads at different frequency conditions. Thus, the results obtained in this work can be used as guidelines for the influence of UV radiation in POFs not only for the material choice, but also on the limitations of UV radiation in the fabrication of the grating as well as in sensor applications at UV radiation conditions.

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Several industry sectors have sought to develop materials that combine lightness, strength and cost-effectiveness. Natural lignocellulosic natural fibers have demonstrated to be efficient in replacing synthetic fibers, owing to several advantages such as costs 50% lower than that of synthetic fibers and promising mechanical specific properties. Polymeric matrix composites that use kenaf fibers as reinforcement have shown strength increases of over 600%. This work aims to evaluate the performance of epoxy matrix composites reinforced with kenaf fibers, by means of dynamic-mechanical analysis (DMA) and ballistic test. Through DMA, it was possible to obtain the curves of storage modulus (E'), loss modulus (E″) and damping factor, Tan δ, of the composites. The variation of E' displayed an increase from 1540 MPa for the plain epoxy to 6550 MPa for the 30 vol.% kenaf fiber composites, which evidences the increase in viscoelastic stiffness of the composite. The increase in kenaf fiber content induced greater internal friction, resulting in superior E″. The Tan δ was considerably reduced with increasing reinforcement fraction, indicating better interfacial adhesion between the fiber and the matrix. Ballistic tests against 0.22 caliber ammunition revealed similar performance in terms of both residual and limit velocities for plain epoxy and 30 vol.% kenaf fiber composites. These results confirm the use of kenaf fiber as a promising reinforcement of polymer composites for automotive parts and encourage its possible application as a ballistic armor component.

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Fiber-reinforced composites are among the most investigated and industrially applied materials. Many studies on these composites using fibers, especially with natural fibers, were made in response to an urgent action for ambient preservation. A particularly relevant situation exists nowadays in the area of materials durability. In this respect, no studies on water-immersion-accelerated aging in fique fiber-epoxy composites are reported. This work aimed to fill this gap by investigating the epoxy matrix composites reinforced with 40 vol% fique fabric. The epoxy matrix and the composite, both unaged and aged, were characterized by weight variation, water absorption, morphology, colorimetry (CIELAB method), Fourier transform infrared spectroscopy (FTIR) and dynamic-mechanical analysis (DMA). The main results were that degradation by water presents appearance of complex microfibril structures, plasticization of epoxy resin, and debonding of the fique fiber/epoxy matrix. The most intense color change was obtained for the water-immersion-aged epoxy by 1440 h. Cole-Cole diagrams revealed the heterogeneity of the materials studied.

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OBJECTIVES: To compare the biodegradability, mechanical behavior, and physicochemical features of the collagen-rich extracellular matrix (ECM) of artificial caries-affected dentin (ACAD), natural caries-affected dentin (NCAD) and sound dentin (SD). METHODS: Dentin specimens from human molars were prepared and assigned into groups according to the type of dentin: ACAD, NCAD, or SD. ACAD was produced by incubation of demineralized SD with Streptococcus mutans in a chemically defined medium (CDM) with 1% sucrose for 7 days at 37 °C under anaerobic conditions. Specimens were assessed to determine collagen birefringence, biodegradability, mechanical behavior, and chemical composition. Data were individually processed and analyzed by ANOVA and post-hoc tests (α = 0.05). RESULTS: CDM-based biofilm challenge reduced loss, storage, and complex moduli in ACAD (p < 0.001), while the damping capacity remained unaffected (p = 0.066). Higher red and lower green birefringence were found in ACAD and NCAD when compared with SD (p < 0.001). Differently to ACAD, SD and NCAD presented higher biodegradability to exogenous proteases (p = 0.02). Chemical analysis of the integrated areas of characteristic bands that assess mineral quality (carbonate/phosphate and crystallinity index), mineral to matrix (phosphate/amide I) and post-translational modifications (amide III/CH2, pentosidine/CH2, and pentosidine/amide III) (p<0.05) showed that NCAD was significantly different from SD while ACAD exhibited intermediate values. CONCLUSIONS: CDM-based biofilm challenge produced a dentin ECM with decreased mechanical properties and increased collagen maturity. The compositional and structural conformation of the ACAD suggested that CDM-based biofilm challenge showed potential to produce artificial lesions by revealing a transitional condition towards mimicking critical features of NCAD. CLINICAL SIGNIFICANCE: This study highlights the importance of developing a tissue that mimics the features of natural caries-affected dentin ECM for in vitro studies. Our findings suggested the potential of a modified biofilm challenge protocol to produce and simulate a relevant substrate, such as caries-affected dentin.

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One of the critical processing parameters-the speed of the extrusion process for plasticized poly (lactic acid) (PLA)-was investigated in the presence of acetyl tributyl citrate (ATBC) as plasticizer. The mixtures were obtained by varying the content of plasticizer (ATBC, 10-30% by weight), using a twin screw extruder as a processing medium for which a temperature profile with peak was established that ended at 160 °C, two mixing zones and different screw rotation speeds (60 and 150 rpm). To evaluate the thermo-mechanical properties of the blend and hydrophilicity, the miscibility of the plasticizing and PLA matrix, Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), oscillatory rheological analysis, Dynamic Mechanical Analysis (DMA), mechanical analysis, as well as the contact angle were tested. The results derived from the oscillatory rheological analysis had a viscous behavior in the PLA samples with the presence of ATBC; the lower process speed promotes the transitions from viscous to elastic as well as higher values of loss modulus, storage modulus and complex viscosity, which means less loss of molecular weight and lower residual energy in the transition from the viscous state to the elastic state. The mechanical and thermal performance was optimized considering a greater capacity in the energy absorption and integration of the components.

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Thiourethane (TU) additives and difunctional, polymerizable crosslinking agents have been demonstrated to increase toughness in methacrylate-based materials. The aim of this study was to evaluate the potential reinforcement of acrylic denture bases by combining thiourethane additives and 1,6 hexanediol dimethacrylate (HDDMA) as an additional crosslinking agent. One commercial acrylic resin (Nature-Cryl MC; GC America) was tested by adding 0 (control) or 10 wt% TU, each of them combined with 0 (control), 10, 20 and 30 wt% HDDMA, for a total of 8 experimental groups. Materials were processed using microwave energy (500 W for 3 min) using microwave-safe molds and flasks. Flexural strength, modulus and toughness were obtained in 3-point bending (ISO 4049) using bars measuring 2 × 2x25 mm (n = 6). Dynamic mechanical analysis was used to determine glass transition temperature (Tg), breadth of tan delta (as a measure of polymer heterogeneity) and crosslinking density in 1 × 3x15 mm bars (n = 6) tested in tension, using a 3 °C/min heating rate (-30 to 180 °C). Viscosity samples were evaluated in a parallel plate reometer. Data were analyzed by two-way ANOVA and Tukey's test (α = 0.05). Results showed that on the samples not containing TU, HDDMA up to 20 wt% increased the flexural strength and thoughness (and up to 30 wt% HDDMA increased the modulus). The addition of TU did not affect those properties (except for the increase in elastic modulus), but the combination TU + HDDMA led to decreased properties overall. The addition of HDDMA decreased the viscosity for all materials, and the presence of TU did not affect viscosity. The Tg increased linearly with the concentration of HDDMA, except in the groups containing TU - in general, the addition of TU reduced Tg. The crosslinking density increased with the addition of HDDMA for all materials, regardless of the presence of TU. The addition of TU significantly decreased crosslinking density. The breadth of tan delta was not affected by the addition of HDDMA, but significantly increased with the addition of TU. In conclusion, the chain-breaking effect of TU on polymerizing methacrylates was deleterious in the case of methyl methacrylate, since it forms a linear polymer. The addition of HDDMA up to 20 wt% and not combined with TU significantly improved the tested properties.

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Reduced graphene oxide (rGO) was incorporated into plasticized cornstarch (TPS), poly(lactic acid) (PLA) and their blends. Small-angle X-ray scattering (SAXS) was used to investigate rGO dispersion within the materials. For the TPS/PLA blend at 70:30 composition, the incorporation of rGO led to a larger fraction of small-sized rGO sheets, which at 5.0 mass% content developed stable fractal structures and domains of correlated sheets. The formation of fractal structures resulted in substantial enhancements in macroscopic properties. For these hybrids, the electrical conductivity, melt viscosity, storage moduli and biodegradation rates presented enhancements in relation to the neat blend. For the TPS/PLA blend at 30:70 composition, SAXS results indicated the formation of smaller fractions of well-dispersed rGO sheets and of segregated larger rGO sheets. With rGO at 5 mass% content, less expressive increases in electrical conductivity, melt viscosity, storage moduli and biodegradation rates were observed.

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This paper presents a polymer optical fiber (POF)-based temperature sensor. The operation principle of the sensor is the variation in the POF mechanical properties with the temperature variation. Such mechanical property variation leads to a variation in the POF output power when a constant stress is applied to the fiber due to the stress-optical effect. The fiber mechanical properties are characterized through a dynamic mechanical analysis, and the output power variation with different temperatures is measured. The stress is applied to the fiber by means of a 180° curvature, and supports are positioned on the fiber to inhibit the variation in its curvature with the temperature variation. Results show that the sensor proposed has a sensitivity of 1.04 × 10-3 °C-1, a linearity of 0.994, and a root mean squared error of 1.48 °C, which indicates a relative error of below 2%, which is lower than the ones obtained for intensity-variation-based temperature sensors. Furthermore, the sensor is able to operate at temperatures up to 110 °C, which is higher than the ones obtained for similar POF sensors in the literature.

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Thio-urethane oligomers (TUs) have been shown to favorably modify methacrylate networks to reduce stress and significantly increase fracture toughness. Since those are very desirable features in dental applications, the objective of this work was to characterize restorative composites formulated with the addition of TUs. TUs were synthesized by combining thiols - pentaerythritol tetra-3-mercaptopropionate (PETMP) or trimethylol-tris-3-mercaptopropionate (TMP) - with isocyanates - 1,6-Hexanediol-diissocyante (HDDI) (aliphatic) or 1,3-bis(1-isocyanato-1-methylethyl)benzene (BDI) (aromatic) or dicyclohexylmethane 4,4'-Diisocyanate (HMDI) (cyclic), at 1:2 isocyanate:thiol, leaving pendant thiols. 20wt% TU were added to BisGMA-TEGDMA (70-30%). To this organic matrix, 70wt% silanated inorganic fillers were added. Near-IR was used to follow methacrylate conversion and rate of polymerization (Rpmax). Mechanical properties were evaluated in three-point bending (ISO 4049) for flexural strength/modulus (FS/FM) and toughness (T), and notched specimens (ASTM Standard E399-90) for fracture toughness (KIC). Polymerization stress (PS) was measured on the Bioman. Volumetric shrinkage (VS) was measured with the bonded disk technique. Glass transition temperature (Tg) and heterogeneity of network were obtained with dynamic mechanical analysis. The addition of TUs led to an increase in mechanical properties (except for Tg and FS). Fracture toughness ranged from 1.6-1.94MPam1/2 for TU-modified groups, an increase of 33-61% in relation to the control (1.21 ± 0.1MPam1/2). Toughness showed a two-fold increase in relation to the control: from 0.91MPa to values ranging from 1.70-1.95MPa. Flexural modulus was statistically higher for the TU-modified groups. The Tg, as expected, decreased for all TU groups due to the greater flexibility imparted to the network (which also explains the increase in toughness and fracture toughness). Narrower tan-delta peaks suggest more homogeneous networks for the TU-modified materials, though differences were marked only for TMP_AL. Degree of conversion was not affected by the addition of TUs. VS was similar for all groups, with one exception where VS dropped (PETMP-cyclic). Finally, PS showed a reduction of 23-57% for TU-modified groups (6.7 ± 1.3 to 11.9 ± 1.0MPa) in relation to the control (15.56 ± 1.4MPa). The addition of thio-urethane oligomers was able to reduce polymerization stress by up to 57% while increasing fracture toughness by up to 61%.

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OBJECTIVES: Thio-urethane oligomers have been shown to reduce stress and increase toughness in highly filled composite materials. This study evaluated the influence of thio-urethane backbone structure on rheological and mechanical properties of resin cements modified with a fixed concentration of the oligomers. METHODS: Thio-urethane oligomers (TU) were synthesized by combining thiols - pentaerythritol tetra-3-mercaptopropionate (PETMP) or trimethylol-tris-3-mercaptopropionate (TMP) - with isocyanates - 1,6-hexanediol-diissocyante (HDDI) (aliphatic) or 1,3-bis(1-isocyanato-1-methylethyl)benzene (BDI) (aromatic) or dicyclohexylmethane 4,4'-diisocyanate (HMDI) (cyclic), at 1:2 isocyanate:thiol, leaving pendant thiols. 20wt% TU were added to BisGMA-UDMA-TEGDMA (5:3:2). 60wt% silanated inorganic fillers were added. Near-IR was used to follow methacrylate conversion and rate of polymerization ( [Formula: see text] ). Mechanical properties were evaluated in three-point bending (ISO 4049) for flexural strength/modulus (FS/FM, and toughness), and notched specimens (ASTM Standard E399-90) for fracture toughness (KIC). PS was measured on the Bioman. Viscosity (V) and gel-points (defined as the crossover between storage and loss shear moduli (G'/G″)) were obtained with rheometry. Glass transition temperature (Tg), cross-link density and homogeneity of the network were obtained with dynamic mechanical analysis. Film-thickness was evaluated according to ISO 4049. RESULTS: DC and mechanical properties increased and [Formula: see text] and PS decreased with the addition of TUs. Gelation (G'/G″) was delayed and DC at G'/G″ increased in TU groups. Tg and cross-link density dropped in TU groups, while oligomers let to more homogenous networks. An increase in V was observed, with no effect on film-thickness. Significant reductions in PS were achieved at the same time conversion and mechanical properties increased. SIGNIFICANCE: The addition of thio-urethane oligomers proved successful in improving several key properties of resin cements, without disrupting the procedures dentists use to polymerize the material. This approach has potential to be translated to commercial materials very readily.

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OBJECTIVES: To evaluate "low-shrink" composites in terms of polymerization kinetics, stress development and mechanical properties. METHODS: "Low-shrink" materials (Kalore/KAL, N'Durance/NDUR, and Filtek P90/P90) and one control (Esthet X HD/EHD) were tested. Polymerization stress (PS) was measured using the Instron 5565 tensometer. Volumetric shrinkage (VS) was determined by the ACTA linometer. Elastic modulus (E) and flexural strength (FS) were obtained by a three-point bending test. Degree of conversion (DC) and polymerization rate (Rp) were determined by NIR spectroscopy (6165cm(-1) for dimethacrylates; 4156 and 4071cm(-1) for P90). Photopolymerization was performed at 740mW/cm(2)×27s. Glass transition temperature (Tg), degree of heterogeneity and crosslink density were obtained in a DMA for the fully cured specimens. Analysis of extracts was done by (1)H NMR. Data were analyzed with one-way ANOVA/Tukey's test (α=0.05). RESULTS: The control presented the highest shrinkage and Tg. P90 showed the highest modulus, and NDUR demonstrated the highest conversion. The polymerization rates were comparable for all materials. NDUR and KAL had the highest and the lowest network homogeneity, respectively. The multifunctional P90 had the highest crosslink density, with no difference between other composites. The control had the greatest stress development, similar to NDUR. Crosslinking density and polymer network homogeneity were influenced by degree of conversion and monomer structure. SIGNIFICANCE: Not all "low-shrink" composites reduced polymerization stress. P90 and NDUR had no leachable monomers, which was also a function of high crosslinking (P90) and high conversion (NDUR).

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