Network structures of Bis-GMA/TEGDMA resins differ in DC, shrinkage-strain, hardness and optical properties as a function of reducing agent

Objectives. To evaluate the influence of different tertiary amines on degree of conversion (DC), shrinkage-strain, shrinkage-strain rate, Knoop microhardness, and color and transmittance stabilities of experimental resins containing BisGMA/TEGDMA (3: 1 wt), 0.25wt% camphorquinone, 1wt% amine (DMAEMA, CEMA, DMPT, DEPT or DABE). Different light-curing protocols were also evaluated. Methods. DC was evaluated with FTIR-ATR and shrinkage-strain with the bonded-disk method. Shrinkage-strain-rate data were obtained from numerical differentiation of shrinkage-strain data with respect to time. Color stability and transmittance were evaluated after different periods of artificial aging, according to ISO 7491: 2000. Results were evaluated with ANOVA, Tukey, and Dunnett`s T3 tests (alpha = 0.05). Results. Studied properties were influenced by amines. DC and shrinkage-strain were maximum at the sequence: CQ < DEPT < DMPT <= CEMA approximate to DABE < DMAEMA. Both DC and shrinkage were also influenced by the curing protocol, with positive correlations between DC and shrinkage-strain and DC and shrinkage-strain rate. Materials generally decreased in L* and increased in b*. The strong exception was the resin containing DMAEMA that did not show dark and yellow shifts. Color varied in the sequence: DMAEMA < DEPT < DMPT < CEMA < DABE. Transmittance varied in the sequence: DEPT approximate to DABE < DABE approximate to DMPT approximate to CEMA < DMPT approximate to CEMA approximate to DMAEMA, being more evident at the wavelength of 400 nm. No correlations between DC and optical properties were observed. Significance. The resin containing DMAEMA showed higher DC, shrinkage-strain, shrinkage-strain rate, and microhardness, in addition to better optical properties. (C) 2011 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Effect of repeated cycles of chemical disinfection on the roughness and hardness of hard reline acrylic resins

Objective: The aim of this study was to assess the effect of repeated cycles of five chemical disinfectant solutions on the roughness and hardness of three hard chairside reliners. Methods: A total of 180 circular specimens (30 mm x 6 mm) were fabricated using three hard chairside reliners (Jet; n = 60, Kooliner; n = 60, Tokuyama Rebase II Fast; n = 60), which were immersed in deionised water (control), and five disinfectant solutions (1%, 2%, 5.25% sodium hypochlorite; 2% glutaraldehyde; 4% chlorhexidine gluconate). They were tested for Knoop hardness (KHN) and surface roughness (mu m), before and after 30 simulated disinfecting cycles. Data was analysed by the factorial scheme (6 x 2), two-way analysis of variance (anova), followed by Tukey`s test. Results: For Jet (from 18.74 to 13.86 KHN), Kooliner (from 14.09 to 8.72 KHN), Tokuyama (from 12.57 to 8.28 KHN) a significant decrease in hardness was observed irrespective of the solution used on all materials. For Jet (from 0.09 to 0.11 mu m) there was a statistically significant increase in roughness. Kooliner (from 0.36 to 0.26 mu m) presented a statistically significant decrease in roughness and Tokuyama (from 0.15 to 0.11 mu m) presented no statistically significant difference after 30 days. Conclusions: This study showed that all disinfectant solutions promoted a statistically significant decrease in hardness, whereas with roughness, the materials tested showed a statistically significant increase, except for Tokuyama. Although statistically significant values were registered, these results could not be considered clinically significant.

Influence of Artificial Accelerated Aging on Dimensional Stability of Acrylic Resins Submitted to Different Storage Protocols

Purpose: The aim of this study was to evaluate the influence of artificial accelerated aging on dimensional stability of two types of acrylic resins (thermally and chemically activated) submitted to different protocols of storage. Materials and Methods: One hundred specimens were made using a Teflon matrix (1.5cmx0.5mm) with four imprint marks, following the lost-wax casting method. The specimens were divided into ten groups, according to the type of acrylic resin, aging procedure, and storage protocol (30 days). GI: acrylic resins thermally activated, aging, storage in artificial saliva for 16 hours, distilled water for 8 hours; GII: thermal, aging, artificial saliva for 16 hours, dry for 8 hours; GIII: thermal, no aging, artificial saliva for 16 hours, distilled water for 8 hours, GIV: thermal, no aging, artificial saliva for 16 hours, dry for 8 hours; GV: acrylic resins chemically activated, aging, artificial saliva for 16 hours, distilled water for 8 hours; GVI: chemical, aging, artificial saliva for 16 hours, dry for 8 hours; GVII: chemical, no aging, artificial saliva for 16 hours, distilled water for 8 hours; GVIII: chemical, no aging, artificial saliva for 16 hours, dry for 8 hours GIX: thermal, dry for 24 hours; and GX: chemical, dry for 24 hours. All specimens were photographed before and after treatment, and the images were evaluated by software (UTHSCSA-Image Tool) that made distance measurements between the marks in the specimens (mm), calculating the dimensional stability. Data were submitted to statistical analysis (two-way ANOVA, Tukey test, p = 0.05). Results: Statistical analysis showed that the specimens submitted to storage in water presented the largest distance between both axes (major and minor), statistically different (p < 0.05) from control groups. Conclusions: All acrylic resins presented dimensional changes, and the artificial accelerated aging and storage period influenced these alterations.

Evaluation of the Bond Strength of Denture Base Resins to Acrylic Resin Teeth: Effect of Thermocycling

Purpose: The purpose of this study was to evaluate the thermocycling effects and shear bond strength of acrylic resin teeth to denture base resins. Materials and Methods: Three acrylic teeth (Biotone, Trilux, Ivoclar) were chosen for bonding to four denture base resins: microwave-polymerized (Acron MC), heat-polymerized (Lucitone 550 and QC-20), and light-polymerized (Versyo. bond). Twenty specimens were produced for each denture base/acrylic tooth combination and were divided into two groups (n = 10): without thermocycling (control groups) and thermocycled groups submitted to 5000 cycles between 4 and 60 degrees C. Shear strength tests (MPa) were performed with a universal testing machine at a crosshead speed of 1 mm/min. Statistical analysis of the results was carried out with three-way ANOVA and Bonferroni`s multiple comparisons post hoc analysis for test groups (alpha = 0.05). Results: The shear bond strengths of Lucitone/Biotone, Lucitone/Trilux, and Versyo/Ivoclar specimens were significantly decreased by thermocycling, compared with the corresponding control groups (p < 0.05). The means of Acron/Ivoclar and Lucitone/Ivoclar specimens increased after thermocycling (p < 0.05). The highest mean shear bond strength value was observed with Lucitone/Biotone in the control group (14.54 MPa) and the lowest with QC-20/Trilux in the thermocycled group (3.69 MPa). Conclusion: Some acrylic tooth/denture base resin combinations can be more affected by thermocycling; effects vary based upon the materials used.

Spectroscopic study of the penetration depth of grafted polystyrene onto poly (tetrafluoroethylene-co-perfluoropropylvinylether) substrates. 1. Effect of grafting conditions

This study concerns the radiation grafting of styrene onto poly(tetrafluoroethylene-co-perfluoropropylvinylether) (PFA) substrates and the penetration depth of the graft. Grafting was obtained by the simultaneous irradiation method, and the spectroscopic analysis was made with the micro-Raman technique. Effects of grafting conditions such as the type of solvent, dose rate, and irradiation dose on the grafting yield were investigated. Of the different solvents used, the most efficient in terms of increasing grafting yield were dichloromethane, benzene, and methanol, respectively. A mixture of methanol and dichloromethane used as a solvent for styrene achieved a higher degree of grafting and concentration of grafted polystyrene onto the surface of PFA substrates than solutions of the monomer in the separate solvents. The degree of grafting increased with increasing radiation dose up to 500 kGy, stabilizing above this dose. However, the grafting yield decreased with an increase in the dose rate. The increase in the overall grafting yield was accompanied by a proportional increase in the penetration depth of the grafts into the substrate. (C) 2002 Wiley Periodicals, Inc.

The effects of fillers on the chemorheology of highly filled epoxy resins: I. Effects on cure transitions and kinetics

This work examines the effects of level of silica filler (at 0, 10, 30, 50wt%) on the gelation and vitrification of a model silica-filled diglycidyl ether of bisphenol F (DGEBF)/methylenedianiline (MDA) system. An increased filler level is shown to decrease the gelation and vitrification times at low temperatures (below 80degreesC). FTIR cure kinetics show that the reaction rates are increased and the activation energies of gelation are reduced at these temperatures, indicating that network formation is made easier. Entropic and catalytic reasons for this phenomenon are discussed. (C) 2003 Society of Chemical Industry.

Modifying fish gelatin electrospun membranes for biomedical applications: cross- linking and swelling behavior

Development of suitable membranes is a fundamental requisite for tissue and biomedical engineering applications. This work presents fish gelatin random and aligned electrospun membranes cross-linked with glutaraldehyde (GA). It was observed that the fiber average diameter and the morphology is not influenced by the GA exposure time and presents fibers with an average diameter around 250 nm. Moreover, when the gelatin mats are immersed in a phosphate buffered saline solution (PBS), they can retain as much as 12 times its initial weight of solution almost instantaneously, but the material microstructure of the fiber mats changes from the characteristic fibrous to an almost spherical porous structure. Cross-linked gelatin electrospun fiber mats and films showed a water vapor permeability of 1.37 ± 0.02 and 0.13 ± 0.10 (g.mm)/(m2.h.kPa), respectively. Finally, the processing technique and cross-linking process does not inhibit MC-3T3-E1 cell adhesion. Preliminary cell culture results showed good cell adhesion and proliferation in the cross-linked random and aligned gelatin fiber mats.

Risk assessment in occupational exposure to formaldehyde: differences between anatomy and pathology laboratories and formaldehyde-resins production

Formaldehyde (CH2O), the most simple and reactive of all aldehydes, is colorless, and readily polymerizing gas at normal temperature. The most extensive use is in production of resins and has an important application as a disinfectant and preservative, reason why relevant workplace exposure may also occur in pathology and anatomy laboratories and in mortuaries. A study was carried out in Portugal, in a formaldehyde production resins factory and in 10 pathology and anatomy laboratories. It was applied a risk assessment methodology based on Queensland University proposal that permitted to perform risk assessment for each activity developed in a work station. This methodology was applied in 83 different activities developed in the laboratories and in 18 activities of the factory. Also, Micronucleus Test was performed in lymphocytes from 30 factory workers and 50 laboratories workers.

Genotoxic effects in occupational exposure to formaldehyde: A study in anatomy and pathology laboratories and formaldehyde-resins production

Background - According to the Report on Carcinogens, formaldehyde ranks 25th in the overall U.S. chemical production, with more than 5 million tons produced each year. Given its economic importance and widespread use, many people are exposed to formaldehyde environmentally and/or occupationally. Presently, the International Agency for Research on Cancer classifies formaldehyde as carcinogenic to humans (Group 1), based on sufficient evidence in humans and in experimental animals. Manyfold in vitro studies clearly indicated that formaldehyde can induce genotoxic effects in proliferating cultured mammalian cells. Furthermore, some in vivo studies have found changes in epithelial cells and in peripheral blood lymphocytes related to formaldehyde exposure. Methods - A study was carried out in Portugal, using 80 workers occupationally exposed to formaldehyde vapours: 30 workers from formaldehyde and formaldehyde-based resins production factory and 50 from 10 pathology and anatomy laboratories. A control group of 85 non-exposed subjects was considered. Exposure assessment was performed by applying simultaneously two techniques of air monitoring: NIOSH Method 2541 and Photo Ionization Detection equipment with simultaneously video recording. Evaluation of genotoxic effects was performed by application of micronucleus test in exfoliated epithelial cells from buccal mucosa and peripheral blood lymphocytes. Results - Time-weighted average concentrations not exceeded the reference value (0.75 ppm) in the two occupational settings studied. Ceiling concentrations, on the other hand, were higher than reference value (0.3 ppm) in both. The frequency of micronucleus in peripheral blood lymphocytes and in epithelial cells was significantly higher in both exposed groups than in the control group (p < 0.001). Moreover, the frequency of micronucleus in peripheral blood lymphocytes was significantly higher in the laboratories group than in the factory workers (p < 0.05). A moderate positive correlation was found between duration of occupational exposure to formaldehyde (years of exposure) and micronucleus frequency in peripheral blood lymphocytes (r = 0.401; p < 0.001) and in epithelial cells (r = 0.209; p < 0.01). Conclusions - The population studied is exposed to high peak concentrations of formaldehyde with a long-term exposure. These two aspects, cumulatively, can be the cause of the observed genotoxic endpoint effects. The association of these cytogenetic effects with formaldehyde exposure gives important information to risk assessment process and may also be used to assess health risks for exposed workers.

Determination of free furfuryl alcohol in foundry resins by chromatographic techniques

Two chromatographic methods, gas chromatography with flow ionization detection (GC–FID) and liquid chromatography with ultraviolet detection (LC–UV), were used to determine furfuryl alcohol in several kinds of foundry resins, after application of an optimised extraction procedure. The GC method developed gave feasibility that did not depend on resin kind. Analysis by LC was suitable just for furanic resins. The presence of interference in the phenolic resins did not allow an appropriate quantification by LC. Both methods gave accurate and precise results. Recoveries were >94%; relative standard deviations were ≤7 and ≤0.3%, respectively for GC and LC methods. Good relative deviations between the two methods were found (≤3%).

Determination of free formaldehyde in foundry resins as its 2,4-dinitrophenylhydrazone by liquid chromatography

Formaldehyde is a toxic component that is present in foundry resins. Its quantification is important to the characterisation of the resin (kind and degradation) as well as for the evaluation of free contaminants present in wastes generated by the foundry industry. The complexity of the matrices considered suggests the need for separative techniques. The method developed for the identification and quantification of formaldehyde in foundry resins is based on the determination of free carbonyl compounds by derivatization with 2,4-dinitrophenylhydrazine (DNPH), being adapted to the considered matrices using liquid chromatography (LC) with UV detection. Formaldehyde determinations in several foundry resins gave precise results. Mean recovery and R.S.D. were, respectively, >95 and 5%. Analyses by the hydroxylamine reference method gave comparable results. Results showed that hydroxylamine reference method is applicable just for a specific kind of resin, while the developed method has good performance for all studied resins.

Chromatographic techniques for the determination of free phenol in foundry resins

Phenol is a toxic compound present in a wide variety of foundry resins. Its quantification is important for the characterization of the resins as well as for the evaluation of free contaminants present in foundry wastes. Two chromatographic methods, liquid chromatography with ultraviolet detection (LC-UV) and gas chromatography with flame ionization detection (GC-FID), for the analysis of free phenol in several foundry resins, after a simple extraction procedure (30 min), were developed. Both chromatographic methods were suitable for the determination of phenol in the studied furanic and phenolic resins, showing good selectivity, accuracy (recovery 99–100%; relative deviations <5%), and precision (coefficients of variation <6%). The used ASTM reference method was only found to be useful in the analysis of phenolic resins, while the LC and GC methods were applicable for all the studied resins. The developed methods reduce the time of analysis from 3.5 hours to about 30 min and can readily be used in routine quality control laboratories.

Genotoxic effects in occupational exposure to formaldehyde: A study in anatomy and pathology laboratories and formaldehyde-resins production

ABSTRACT – Background: According to the Report on Carcinogens, formaldehyde ranks 25th in the overall U.S. chemical production, with more than 5 million tons produced each year. Given its economic importance and widespread use, many people are exposed to formaldehyde environmentally and/or occupationally. Presently, the International Agency for Research on Cancer classifies formaldehyde as carcinogenic to humans (Group 1), based on sufficient evidence in humans and in experimental animals. Manyfold in vitro studies clearly indicated that formaldehyde can induce genotoxic effects in proliferating cultured mammalian cells. Furthermore, some in vivo studies have found changes in epithelial cells and in peripheral blood lymphocytes related to formaldehyde exposure. Methods: A study was carried out in Portugal, using 80 workers occupationally exposed to formaldehyde vapours: 30 workers from formaldehyde and formaldehyde-based resins production factory and 50 from 10 pathology and anatomy laboratories. A control group of 85 non-exposed subjects was considered. Exposure assessment was performed by applying simultaneously two techniques of air monitoring: NIOSH Method 2541 and Photo Ionization Detection equipment with simultaneously video recording. Evaluation of genotoxic effects was performed by application of micronucleus test in exfoliated epithelial cells from buccal mucosa and peripheral blood lymphocytes. Results: Time-weighted average concentrations not exceeded the reference value (0.75 ppm) in the two occupational settings studied. Ceiling concentrations, on the other hand, were higher than reference value (0.3 ppm) in both. The frequency of micronucleus in peripheral blood lymphocytes and in epithelial cells was significantly higher in both exposed groups than in the control group (p < 0.001). Moreover, the frequency of micronucleus in peripheral blood lymphocytes was significantly higher in the laboratories group than in the factory workers (p < 0.05). A moderate positive correlation was found between duration of occupational exposure to formaldehyde (years of exposure) and micronucleus frequency in peripheral blood lymphocytes (r = 0.401; p < 0.001) and in epithelial cells (r = 0.209; p < 0.01). Conclusions: The population studied is exposed to high peak concentrations of formaldehyde with a long-term exposure. These two aspects, cumulatively, can be the cause of the observed genotoxic endpoint effects. The association of these cytogenetic effects with formaldehyde exposure gives important information to risk assessment process and may also be used to assess health risks for exposed worker

Development of a new U 200 pultrusion die to produce GRP composite profiles using different thermosetting resins

In this work, a steel heated pultrusion die was designed, developed and manufactured to produce U200 glass fibre reinforced thermosetting matrix (GRP) profiles. The finite element analysis (FEA) was used to predict and optimise the developed die heating by using cylindrical electrical powered cartridges. To assess the new die performance it was mounted in the 120 kN pultrusion line of the Portuguese company Vidropol SA and used to produce continuously U200 profiles able to meet all requirements specified for the E23 grade accordingly to the European Standard EN 13706: 2002. After setting up the type, orientation and sequence of layers in laminate, orthophthalic, isophthalic and bisphenolic unsaturated polyester as well as vinylester resins were used to produce glass fibre reinforced U 200 composite profiles. An appropriated catalyst system was selected and the processing variables optimised for each case, namely, pultrusion pull-speed and die temperature. Finally, the produced U200 profiles were submitted to visual inspection, calcination and mechanical tests, namely, flexural, tensional and interlaminar shear strength (ILSS) tests, to assess their accomplishment with the EN 13706 requirements.