Physical-chemical and thermodynamic analyses of steam reforming of ethanol to hydrogen production

The steam reforming is one of most utilized process of hydrogen production because of its high production efficiencies and its technological maturity. The use of ethanol for this purpose is a interesting option because this is a renewable and less environmentally offensive fuel. The objective of this study is evaluate the physical-chemical, thermodynamic and environmental analyses of steam reforming of ethanol. whose objective is to produce 0.7 Nm3/h of hydrogen to be used by a PEMFC of l kW. In this physical-chemical analysis, a global reaction of ethanol was considered. That is, the superheated ethanol and steam, at high temperatures, react to produce hydrogen and carbon dioxide. Beyond it's the simplest form to study the steam reforming of ethanol to hydrogen production, it's the case where occurs the highest production of hydrogen (the product to be used by fuel cells) and carbon dioxide, to be eliminated. But this reaction isn't real and depends greatly on the thermodynamic conditions of reforming, technical features of reformer system and catalysts. Other products generally formed (but not investigated in this study) are methane, carbon monoxide, among others. It was observed that the products is commonly produced in the moment when the reaction attains temperatures about 206°C (below this temperature, the reaction trend to the reaetants, that is, from hydrogen and carbon dioxide to steam and ethanol) and the advance degree of this reaction increases when the temperature of reaction also increases and when its pressure decreases. It's suggested reactions at about 600°C or higher. However, when the temperature attains 700°C, the stability of this reaction is occurred, that is, the production of reaction productions attains to the limit, that is the highest possible production. In temperatures above 700°C, the use of energy is very high for produce more products, having higher costs of production that the suggested temperature. The indicated pressure is 1 atm., a value that allows a desirable economy of energy that would also be used for pressurization or depressurization of steam reformer. In exergetic analysis, it's seem that the lower irreversibililies occur when the pressure of reactions are lower. However, the temperature changes don't affect significantly the irreversibilites. Utilizing the obtained results from this analysis, it was concluded that the best thermodynamic conditions for steam reforming of ethanol is the same conditions suggested in the physical-chemical analysis. The exergetic and first law efficiencies are high on the thermodynamie conditions studied.

Influence of light curing source on microhardness of composite resins of different shades

Introduction: The evolution of light curing units can be noticed by the different systems recently introduced. The technology of LED units promises longer lifetime, without heating and with production of specific light for activation of camphorquinone. However, further studies are still required to check the real curing effectiveness of these units. Purpose: This study evaluated the microhardness of 4 shades (B-0.5, B-1, B-2 and B-3) of composite resin Filtek Z-250 (3M ESPE) after light curing with 4 light sources, being one halogen (Ultralux - Dabi Atlante) and three LED (Ultraled - Dabi Atlante, Ultrablue - DMC and Elipar Freelight - 3M ESPE). Methods: 192 specimens were distributed into 16 groups, and materials were inserted in a single increment in cylindrical templates measuring 4mm x 4mm and light cured as recommended by the manufacturer. Then, they were submitted to microhardness test on the top and bottom aspects of the cylinders. Results: The hardness values achieved were submitted to analysis of variance and to Tukey test at 5% confidence level. It was observed that microhardness of specimens varied according to the shade of the material and light sources employed. The LED appliance emitting greater light intensity provided the highest hardness values with shade B-0.5, allowing the best curing. On the other hand, appliances with low light intensity were the least effective. It was also observed that the bottom of specimens was more sensitive to changes in shade. Conclusion: Light intensity of LED light curing units is fundamental for their good functioning, especially when applied in resins with darker shades.

Effect of curing regime on the cytotoxicity of resin-modified glass-ionomer lining cements applied to an odontoblast-cell line

Objective: The aim of this in vitro study was to evaluate the cytotoxicity of resin-modified glass-ionomer lining cements submitted to different curing regimes and applied to an immortalized odontoblast-cell line (MDPC-23). Methods: Forty round-shaped specimens of each experimental material (Fuji Lining LC and Vitrebond) were prepared. They were light-cured for the manufacturers' recommended time (MRT = 30 s), under-cured (0.5 MRT = 15 s), over-cured (1.5 MRT = 45 s) or allowed to dark cure (0 MRT). Sterilized filter papers soaked with either 5 μL of PBS or HEMA were used as negative and positive control, respectively. After placing the specimens individually in wells of 24-well dishes, odontoblast-like cells MDPC-23 (30,000 cells/cm2) were plated in each well and incubated for 72 h in a humidified incubator at 37 °C with 5% CO2 and 95% air. The cytotoxicity was evaluated by the cell metabolism (MTT assay) and cell morphology (SEM). Results: Fuji Lining LC was less cytotoxic than Vitrebond (p < 0.05) in all the experimental conditions. However, the cytotoxicity of Fuji Lining LC was noticeably increased in the absence of light-curing while the same was not observed for Vitrebond. The length of light-curing (15, 30 or 45 s) did not influence the toxicity of both lining materials when they were applied on the odontoblast-cell line MDPC-23. Significance: The light-activation plays an important role in reducing the cytotoxicity of Fuji Lining LC. Following the manufacturer' recommendation regarding the light-curing regime may prevent toxic effect to the pulp cells. © 2005 Academy of Dental Materials.

Relationships between the curing conditions and some mechanical properties of hybrid thermosetting materials

The relationship between the heat of polymerization (ΔH) and activation energy (Ea) parameters, obtained by differential scanning calorimetry (DSC) and the ratio of epoxy resin to hardener of the thermosetting materials based on an organic-inorganic hybrid epoxy resin (OG) was investigated. Activation energy (Ea) and heat of polymerization (ΔH) increased with an increasing OG content, up to 70 wt%. Further increase in OG content to 80wt% reduced Ea and ΔH. Dynamic mechanical analysis indicates that the maximum cross-link density is obtained at 83 wt% OG, whereas fracture toughness and tensile modulus mechanical properties are maximized at 70 wt% OG. ©2006 Sociedade Brasileira de Química.

Influence of cavity preparation and curing method on the marginal seal of resin composite restorations: an in vitro evaluation.

OBJECTIVE: To evaluate the influence of cavity design and photocuring method on the marginal seal of resin composite restorations. METHOD AND MATERIALS: Seventy-two bovine teeth were divided into 2 groups: group 1 received box-type cavity preparations, and group 2 received plate-type preparations. Each group was divided into 3 subgroups. After etching and bonding, Z250 resin composite (3M Espe) was applied in 2 equal increments and cured with 1 of 3 techniques: (1) conventional curing for 30 seconds at 650 mW/cm2; (2) 2-step photocuring, in which the first step was performed 14 mm from the restoration for 10 seconds at 180 mW/cm2 and the second step was performed in direct contact for 20 seconds at 650 mW/cm2; or (3) progressive curing using Jetlite 4000 (J. Morita) for 8 seconds at 125 mW/cm2 and then 22 seconds at 125 mW/cm2 up to 500 mW/cm2. The specimens were thermocycled for 500 cycles and then submitted to dye penetration with a 50% silver nitrate solution. Microleakage was assessed using a stereomicroscope. Data were analyzed using analysis of variance and Tukey test (5% level of significance). RESULTS: A statistically significant difference was found between groups when a double interaction between photocuring and cavity preparation was considered (P = .029). CONCLUSIONS: No one type of cavity preparation or photocuring method prevented micro-leakage. The plate-type preparation showed the worst dye penetration when conventional and progressive photocuring methods were used. The best results were found using the 2-step photocuring with the plate-type preparation.

Diametral tensile strength of dual-curing resin cements submitted exclusively to autopolymerization.

OBJECTIVES: To evaluate, at different times, the diametral tensile strength (DTS) of dual-curing resin cements that were not photopolymerized. METHOD AND MATERIALS: Equal amounts of base and catalyst pastes of Panavia F (Kuraray), Variolink II (Vivadent), Rely X (3M ESPE), and Enforce (Dentsply) were mixed and inserted into cylindrical molds (4 x 2 mm) (n = 10). Cements were not photopolymerized. DTS test was performed in a testing machine at 30 minutes, 1 hour, 24 hours, and 7 days. The specimens were stored in light-proof containers with distilled water at 37 degrees C until the time of assay. An autopolymerizing resin cement (Cement-It, Jeneric Pentron) and a zinc phosphate cement served as controls. One-way analysis of variance (ANOVA) and Tukey test were performed separately for each cement and for each time (P <.05). RESULTS: All cements showed an increase in DTS when tested at 1 and 24 hours. Tests at 24 hours and 7 days revealed no statistically significant differences. In all groups, the zinc phosphate cement had the lowest DTS mean values (2.1 MPa, 3.6 MPa, 6.5 MPa, and 6.9 MPa), while Cement-It (35.1 MPa, 33.6 MPa, 46.9 MPa, and 46.3 MPa) and Enforce (31.9 MPa, 31.7 MPa, 43.4 MPa, and 47.6 MPa) presented the highest DTS mean values. CONCLUSION: All cements presented maximal strength at 24 hours. The dual-curing resin cements, even when nonphotopolymerized, demonstrated higher DTS than the zinc phosphate cement and similar or lower values than the autopolymerizing resin cement.

The effect of different light-curing units on tensile strength and microhardness of a composite resin

The aim of this study was to evaluate the influence of different light-curing units on the tensile bond strength and microhardness of a composite resin (Filtek Z250 - 3M/ESPE). Conventional halogen (Curing Light 2500 - 3M/ESPE; CL) and two blue light emitting diode curing units (Ultraled - Dabi/Atlante; UL; Ultrablue IS - DMC; UB3 and UB6) were selected for this study. Different light intensities (670, 130, 300, and 600 mW/cm2, respectively) and different curing times (20s, 40s and 60s) were evaluated. Knoop microhardness test was performed in the area corresponding to the fractured region of the specimen. A total of 12 groups (n=10) were established and the specimens were prepared using a stainless steel mold composed by two similar parts that contained a cone-shaped hole with two diameters (8.0 mm and 5.0 mm) and thickness of 1.0 mm. Next, the specimens were loaded in tensile strength until fracture in a universal testing machine at a crosshead speed of 0.5 mm/min and a 50 kg load cell. For the microhardness test, the same matrix was used to fabricate the specimens (12 groups; n=5). Microhardness was determined on the surfaces that were not exposed to the light source, using a Shimadzu HMV-2 Microhardness Tester at a static load of 50 g for 30 seconds. Data were analyzed statistically by two-way ANOVA and Tukey's test (p<0.05). Regarding the individual performance of the light-curing units, there was similarity in tensile strength with 20-s and 40-s exposure times and higher tensile strength when a 60-s light-activation time was used. Regarding microhardness, the halogen lamp had higher results when compared to the LED units. For all light-curing units, the variation of light-exposure time did not affect composite microhardness. However, lower irradiances needed longer light-activation times to produce similar effect as that obtained with high-irradiance light-curing sources.

Economical analysis of ethanol steam reformer for hydrogen production associated with a sugarcane industry

An expressive amount of produced hydrogen is generated by customers in-situ such as petrochemical, fertilizer and sugarcane industries. However, the most utilized feedstock is natural gas, a non-renewable and fossil fuel. The introduction of biohydrogen production process associated in a sugarcane industry is an alternative to diminish emissions and contribute to create a CO2 cycle, where the plants capture this gas by photosynthesis process and produces sucrose for ethanol production. The cost of production of ethanol has dramatically decreased (from about US$ 700/m3 in 1970s to US$ 200/m3 today), becoming this a good option at near term, inclusively for its utilization by customers localized in main regions (localized especially in regions such as Southeastern Brazil) Also in near future, it will possible the utilization of fuel cells as form of distributed generation. Its utilization could occur specially in peak hours, diminishing the cost of investments in newer transmission systems. A technical and economic analysis of steam reformer of ethanol to hydrogen production associated with sugarcane industry was recently performed. This technique will also allow the use of ethanol when its price is relatively low. This study was based on a previous R&D study (sponsored by CEMIG - State of Minas Gerais Electricity Company) where thermodynamic and economic analyses were developed, based in the development of two ethanol steam reformers prototypes.x In this study an analysis was performed considering the use of bagasse as source of heat in the steam reforming process. Its use could to diminish the costs of hydrogen production, especially at large scale, obtaining cost-competitive production and permitting that sugarcane industry produces hydrogen in large scale beyond ethylic alcohol, anhydrous alcohol (or ethanol) and sugar.

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 60°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. © 2009 Pleiades Publishing, Ltd.

Effect of light-curing units on push-out fiber post bond strength in root canal dentin

The purpose of this study was to evaluate the effectiveness of different light-curing units on the bond strength (push-out) of glass fiber posts in the different thirds of the root (cervical, middle and apical) with different adhesive luting resin systems (dual-cure total-etch; dual-cured and self-etch bonding system; and dual-cure self-adhesive cements), Disks of the samples (n = 144) were used, with approximately 1 mm of thickness of 48 bovine roots restored with glass fiber posts, that were luted with resin cements photo-activated by halogen LCU (QTH, Optilux 501) and blue LED (Ultraled), with power densities of 600 and 550 mW/cm 2, respectively. A universal testing machine (MTS 810 Material Test System) was used with a 1 mm diameter steel rod at cross-head speed of 0.5 mm/min until post extrusion, with load cell of 50 kg, for evaluation of the push-out strength in the different thirds of each sample. The push-out strength values in kgf were converted to MPa and analyzed through Analysis of Variance and Tukey's test, at significance level of 5%. The results showed that there were no statistical differences between the QTH and LED LCUs. The self-adhesive resin cement had lower values of retention. The total-etch and self-adhesive system resin cements seem to be a possible alternative for glass fiber posts cementation into the radicular canal and the LED LCU can be applied as an alternative to halogen light on photo-activation of dual-cured resin cements. © 2009 Pleiades Publishing, Ltd.

Effect of light-curing method and indirect veneering materials on the Knoop hardness of a resin cement

This study evaluated the Knoop hardness of a dual-cured resin cement (Rely-X ARC) activated solely by chemical reaction (control group) or by chemical / physical mode, light-cured through a 1.5 mm thick ceramic (HeraCeram) or composite (Artglass) disc. Light curing was carried out using conventional halogen light (XL2500) for 40 s (QTH); light emitting diodes (Ultrablue Is) for 40 s (LED); and Xenon plasma arc (Apollo 95E) for 3 s (PAC). Bovine incisors had their buccal face flattened and hybridized. On this surface a rubber mold (5 mm in diameter and 1 mm in height) was bulk filled with the resin cement. A polyester strip was seated for direct light curing or through the discs of veneering materials. After dry storage in the dark (24 h 37°C), the samples (n = 5) were sectioned for hardness (KHN) measurements, taken in a microhardness tester (50 gF load 15 s). The data were statistically analyzed by ANOVA and Tukey's test (α = 0.05). The cement presented higher Knoop hardness values with Artglass for QTH and LED, compared to HeraCeram. The control group and the PAC/Artglass group showed lower hardness values compared to the groups light-cured with QTH and LED. PAC/HeraCeram resulted in the worst combination for cement hardness values. © 2009 Sociedade Brasileira de Pesquisa Odontológica.

Assessment of the flexural strength of two heat-curing acrylic resins for artificial eyes

Prosthetic eyes are artificial substitutes for the eyeball, made of heat-curing acrylic resin, serving to improve the esthetic appearance of the mutilated patient and his/her inclusion in society. The aim of this study was to assess the flexural strength of two heat-curing acrylic resins used for manufacturing prosthetic eyes. Thirty-six specimens measuring 64 x 10 x 3.3 mm were obtained and divided into four groups: acrylic resin for artificial sclera N1 (Artigos Odontológicos Clássico, São Paulo, SP, Brazil), heat-cure water technique (GI) and microwave-cured (GII); colorless acrylic resin for prosthetic eyes (Artigos Odontológicos Clássico, São Paulo, SP, Brazil), heat-cure water technique (GIII) and microwave-cured (GIV). Mechanical tests using three point loads were performed in a test machine (EMIC, São José dos Pinhais, PR, Brazil). The analysis of variance and the Tukey test were used to identify significant differences (p < 0.01). Groups GII and GIV presented, respectively, the highest (98.70 ± 11.90 MPa) and lowest means (71.07 ± 8.93 MPa), with a statistically significant difference. The cure method used for the prosthetic eye resins did not interfere in their flexural strength. It was concluded that all the resins assessed presented sufficient flexural strength values to be recommended for the manufacture of prosthetic eyes.

Effect of pre-heating resin composite and light-curing units on monomer conversion

The purpose of this study was to evaluate the effect of pre-heating resin composite photo-cured with light-curing units (LCU) by FT-IR. Twenty specimens were made in a metallic mold (4 mm diameter × 2 mm thick) from composite resin-Tetric Ceram® (Ivoclar/Vivadent) at room temperature (25°C) and pre-heated to 37, 54, and 60°C. The specimens were cured with halogen curing light (QTH) and light emitted by diodes (LED) during 40 s. Then, the specimens were pulverized, pressed with KBr and analyzed with FT-IR. The data were submitted to statistical analysis of variance and Kruskal-Wallis test. Study data showed no statistically significant difference to the degree of conversion for the different light curing units (QTH and LED) (p > 0.05). With the increase of temperature there was significant increase in the degree of conversion (p < 0.05). In this study were not found evidence that the light curing unit and temperature influenced the degree of conversion. © 2010 Pleiades Publishing, Ltd.

Temperature rise during adhesive and composite polymerization with different light-curing sources

AIM: This study evaluated the temperature rise of the adhesive system Single Bond (SB) and the composite resins Filtek Z350 flow (Z) and Filtek Supreme (S), when polymerized by light-emitting diode (LED XL 3000) and quartz-tungsten halogen (QTH Biolux). METHODS: Class V cavities (3 yen2 mm) were prepared in 80 bovine incisors under standardized conditions. The patients were divided as follows: G1: Control; G2: SB; G3: SB + Z; G4: SB + S. The groups were subdivided into two groups for polymerization (A: QTH, B: LED). Light curing was performed for 40 s and measurement of temperature changes during polymerization was performed with a thermocouple positioned inside the pulp chamber. Data were statistically analyzed using ANOVA and Tukey tests. RESULTS: The factors material (P<0.00001) and curing unit (P<0.00001) had significant influence on temperature rise. The lowest temperature increase (0.15 degrees C) was recorded in G2 B and the highest was induced in G1 A (0.75 degrees C, P<0.05). In all groups, lower pulp chamber temperature measurements were obtained when using LED compared to QTH (P<0.05). CONCLUSION: QTH caused greater increases in tooth temperature than LED. However, both sources did not increase pulpal temperature above the critical value that may cause pulpal damage.

Effect of thickness of indirect restoration and distance from the light-curing unit tip on the hardness of a dual-cured resin cement

This study evaluated the Knoop hardness and polymerization depth of a dual-cured resin cement, light-activated at different distances through different thicknesses of composite resin. One bovine incisor was embedded in resin and its buccal surface was flattened. Dentin was covered with PVC film where a mold (0.8-mm-thick and 5 mm diameter) was filled with cement and covered with another PVC film. Light curing (40 s) was carried out through resin discs (2, 3, 4 or 5 mm) with a halogen light positioned 0, 1, 2 or 3 mm from the resin surface. After storage, specimens were sectioned for hardness measurements (top, center, and bottom). Data were subjected to split-plot ANOVA and Tukey's test (α=0.05). The increase in resin disc thickness decreased cement hardness. The increase in the distance of the light curing tip decreased hardness at the top region. Specimens showed the lowest hardness values at the bottom, and the highest at the center. Resin cement hardness was influenced by the thickness of the indirect restoration and by the distance between the light-curing unit tip and the resin cement surface.