Synthesis and properties of branched polyethylene/high-density polyethylene blends using a homogeneous binary catalyst system composed of early and late transition metal complexes

Branched polyethylene/high-density polyethylene blends (BPE/HDPE) with a wide range of molecular weights, melt flow indexes (MFI), and intrinsic viscosity were prepared using the homogeneous binary catalyst system composed by Ni(alpha-diimine)Cl-2 (1) (alpha-diimine = 1,4-bis(2,6-diisopropylphenyl)-acenaphthenediimine) and {Tp(Ms*)} TiCl3 (2) (Tp(Ms*)=hydridobis(3-mesitylpyrazol-1-yl)(5-mesityl-pyrazol-1-yl)) activated with MAO and/or TIBA in hexane at two different polymerization temperatures (30 and 55 degreesC) and by varying the nickel loading molar fraction (x(Ni)). At all Temperatures, a non-linear correlation between the x(Ni) and the productivity was observed, suggesting the occurrence of a synergistic effect between the nickel and the titanium catalyst precursors, which is more pronounced at 55 degreesC. The molecular weight of the BPE/HDPE blends considerably decreases with increasing Al/M molar ratio. The melt flow indexes (MFI) and intrinsic viscosities (eta) are strongly affected by x(Ni), but the melting temperatures are nearly constant, 132 +/- 3 degreesC. Dynamic mechanical thermal analysis (DMTA) shows the formation of different polymeric materials where the stiffness vanes according, to the x(Ni) and temperature used in the polymerization reaction. The surface morphology of the BPE/HDPE blends studied by scanning electron microscopy (SEM) revealed a low miscibility between the PE phases resulting in the formation of a sandwich structure after etching with o-xylene.

Factors which affect the catalytic activity of iron(III) meso tetrakis(2,6-dichlorophenyl)porphyrin chloride in homogeneous system

An optimization study of the reaction conditions of Fe(TDCPP)Cl when it is used as catalyst in the hydroxylation of cyclohexane by iodosylbenzene (PhIO) has been carried out, It was found that Fe(TDCPP)Cl follows the classical PhIO mechanism described for Fe(TPP)Cl, which involves the monomeric active species Fe-IV(O)P-+. (I). In the optimized condition ([Fe(TDCPP) = 3.0 X 10(-4) mol l(-1) in 1,2-dichloroethane (DCE); ultrasound stirring at 0 degrees C; PhIO/FeP molar ratio = 100), this FeP led to a yield of cyclohexanol (C-ol) of 96% and a turnover number of 96, Therefore, Fe(TDCPP)Cl may be considered a good biomimetic model and a very stable, resistant and selective catalyst, which yields C-ol as the sole product. DCE showed to be a better solvent than dichloromethane (DCM), 1 DCE:1 MeOH mixture or acetonitrile (ACN). Since the Fe-IV(O)P-+. is capable of abstracting hydrogen atom from DCM, MeOH or ACN, the solvent competes with the substrate. Presence of O-2 lowers the yield of C-ol, as it can further oxidize this alcohol to carboxylic acid in the presence of radicals, Presence of H2O also causes a decrease in the yield, since it converts the active species I into Fe-IV(OH)P, which cannot oxidize cyclohexane. Addition of excess imidazole or OH- to the system results in a decrease in the yield of C-ol, due to the formation of the hexacoordinated complexes Fe(TDCPP)Im(2)(+) (low-spin, beta(2) = 2.5 X 10(8) mol(-2) l(2)) and Fe(TDCPP)(OH)(2)(-) (high-spin, beta(2) = 6.3 X 10(7) mol(-2) l(2)), the formation of both Fe(TDCPP)Im(2)(+) and Fe(TDCPP)(OH)(2)(-) complexes were confirmed by EPR studies. The catalytic activities of Fe(TDCPP)C and Fe(TFPP)Cl were compared, the unusually high yields of C-ol with Fe(TFPP)Cl obtained when ultrasound, DCM and O-2 atmosphere were used, suggest that a parallel mechanism involving the mu-oxo dimer form, O-2 and radicals may also be occurring with this FeP, besides the PhIO mechanism.

Effects of light-curing time on the cytotoxicity of a restorative resin composite applied to an immortalized odontoblast-cell line

This in vitro study evaluated the cytotoxic effects of a restorative resin composite applied to an immortalized odontoblast-cell line (MDPC-23). Seventy-two round resin discs (2-mm thick and 4 mm in diameter) were light-cured for 20 or 40 seconds and rinsed, or not, with PBS and culture medium. The resin discs were divided into four experimental groups: Group 1: Z-100/20 seconds; Group 2: Z-100/20 seconds/rinsed; Group 3: Z100/40 seconds; Group 4: Z-100/40 seconds/rinsed. Circular filter paper was used as a control material (Group 5). The round resin discs and filter papers were placed in the bottom of wells of four 24-well dishes (18 wells for each experimental and control group). MDPC-23 cells (30,000 cells/cm(2)) were plated in the wells and allowed to incubate for 72 hours. The zone of inhibition around the resin discs was measured under inverted light microscopy; the MTT assay was carried out for mitochondrial respiration and cell morphology was measured under SEM. The scores obtained from inhibition zone and MTT assay were analyzed with the Kruskal-Wallis followed by Dunnett tests. In Groups 1, 2, 3 and 4, the thickness of the inhibition zone was 1,593 +/- 12.82 mum, 403 +/- 15.49 mum, 1,516 +/- 9.81 mum and 313 +/- 13.56 mum, respectively. There was statistically significant difference among the experimental and control groups at the 0.05 level of significance. The MTT assay demonstrated that the resin discs of the experimental groups 1, 2, 3 and 4 reduced the cell metabolism by 83%, 40.1%, 75.5% and 24.5%. Only between the Groups 2 and 4 was there no statistically significant difference for mitochondrial respiration. Close to the resin discs, the MDPC-23 cells exhibited rounded shapes, with only a few cellular processes keeping the cells attached to the substrate or, even disruption of plasma membrane. Adjacent to the inhibition zone, the cultured cells exhibited multiple fine cellular processes on the cytoplasmic membrane organized in epithelioid nodules, similar to the morphology observed to the control group. Based on the results, the authors may conclude that the Z-100 resin composite light cured for 20 seconds was more cytopathic to MDPC-23 cells than Z-100 light cured for 40 seconds. The cytotoxic effects of the resin discs decreased after rinsing them with PBS and culture medium. This was confirmed by MTT assay and upon evaluation of the inhibition zone, which was narrower following rinsing of the resin discs.

On the Milnor fibre and L numbers of semi-weighted homogeneous arrangements

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

Unrestricted linear dimensional changes of two hard chairside reline resins and one heat-curing acrylic resin

The selection and use of hard chairside reline resins must be made with regard to dimensional stability, which will influence the accuracy of fit of the denture base. This study compared the dimensional change of two hard chairside reline resins (Duraliner II and Kooliner) and one heat-curing denture base resin (Lucitone 550). A stainless steel mold with reference dimensions (AB, CD) was used to obtain the samples. The materials were processed according to the manufacturer's recommendations. Measurements of the dimensions were made after processing and after the samples had been stored in distilled water at 37° C for eight different periods of time. The data were recorded and then analyzed with analysis of variance. All materials showed shrinkage immediately after processing (p < 0.05). The only resin that exhibited shrinkage after 60 days of storage in water was Duraliner II; these changes could be clinically significant in regard of tissue fit.

Pre-weighted homogeneous map germs finite determinacy and topological triviality

In this paper we introduce the notion of G-pre-weighted homogeneous map germ, (G is one of Mather's groups A or K.) and show that any G-pre-weighted homogeneous map germ is G-finitely determined. We also give an explicit order, based on the Newton polyhedron of a pre-weighted homogeneous germ of function, such that the topological structure is preserved after perturbations by terms of higher order.

The influence of chemical activation on hardness of dual-curing resin cements.

During the cementation of metallic restorations, the polymerization of dual-curing resin cements depends exclusively on chemical activation. This study evaluated the influence of chemical activation compared with dual-curing (chemical and light activation), on the hardness of four dual-curing resin cements. In a darkened environment, equal weight proportions of base and catalyst pastes of the cements Scotchbond Resin Cement, Variolink II, Enforce and Panavia F were mixed and inserted into moulds with cavities of 4 mm in diameter and 2 mm in height. Subsequently, the cements were: 1) not exposed to light (chemical activation = self-cured groups) or 2) photoactivated (dual-curing = dual-cured groups). The Vickers hardness number was measured at 1 hour, 24 hours and 7 days after the start time of cements' spatulation. For all the cements, the hardness values of self-cured groups were lower than those of the respective dual-cured groups at 1 hour and 24 hours. At 7 days, this behavior continued for Variolink II and Panavia F, whilst for Scotchbond Resin Cement and Enforce there was no statistical difference between the two activation modes. All cements showed a significant increase in their hardness values from 1 hour to 7 days for both activation modes. Of the self-cured groups, Scotchbond Resin Cement and Variolink II presented the highest and the lowest hardness values, respectively, for all three times tested. Within the limitations of this study, up to the time of 24 h, chemical activation alone was unable to promote similar hardness as to that obtained with dual-curing.

Influence of activation modes on diametral tensile strength of dual-curing resin cements.

In metallic restorations, the polymerization of dual-curing resin cements depends exclusively on chemical activation. The effect of the lack of photoactivation on the strength of these cements has been rarely studied. This study evaluated the influence of activation modes on the diametral tensile strength (DTS) of dual-curing resin cements. Base and catalyst pastes of Panavia F, Variolink II, Scotchbond Resin Cement, Rely X and Enforce were mixed and inserted into cylindrical metal moulds (4 x 2 mm). Cements were either: 1) not exposed to light (chemical activation = self-cured groups) or 2) photoactivated through mylar strips (chemical and photo-activation = dual-cured groups) (n = 10). After a 24 h storage in 37 masculineC distilled water, specimens were subjected to compressive load in a testing machine. A self-curing resin cement (Cement-It) and a zinc phosphate cement served as controls. Comparative analyses were performed: 1) between the activation modes for each dual-curing resin cement, using Students t test; 2) among the self-cured groups of the dual-curing resin cements and the control groups, using one-way ANOVA and Tukeys test (alpha = 0.05). The dual-cured groups of Scotchbond Resin Cement (53.3 MPa), Variolink II (48.4 MPa) and Rely X (51.6 MPa) showed higher DTS than that of self-cured groups (44.6, 40.4 and 44.5 MPa respectively) (p < 0.05). For Enforce (48.5 and 47.8 MPa) and Panavia F (44.0 and 43.3 MPa), no significant difference was found between the activation modes (p > 0.05). The self-cured groups of all the dual-curing resin cements presented statistically the same DTS as that of Cement-It (44.1 MPa) (p > 0.05), and higher DTS than that of zinc phosphate (4.2 MPa). Scotchbond Resin Cement, Variolink II and Rely X depended on photoactivation to achieve maximum DTS. In the absence of light, all the dual-curing resin cements presented higher DTS than that of zinc phosphate and statistically the same as that of Cement-It (p > 0.05).

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.