Polyethylene/(organo-montmorillonite) composites modified with ethylene/ methacrylic acid copolymer: Morphology and mechanical properties

Several composites based on high-density polyethylene (PE), organically modified montmorillonite (OMMT) and ethylene/methacrylic acid copolymer (EMAA) were prepared by melt compounding. Three Na(+)-montmorillonites (MMT) of different precedence were modified with hexadecyl trimethyl ammonium chloride in order to change their nature from hydrophilic to organophilic. The composites morphology was examined by XRD, SEM and TEM. Mechanical properties were evaluated under static conditions. A slight reinforcement was achieved only when OMMT was added to PE. When EMAA was added to the composites, it negatively interacted with OMMT, diminishing the interlayer distance of OMMT, changing the composite morphology, as if OMMT was not present in composites, and deteriorating their mechanical properties. (C) 2008 Elsevier Ltd. All rights reserved.

Toluene and naphthalene sorption by iron oxide/clay composites

Commercial bentonite (BFN) and organoclay (WS35), as well as iron oxide/clay composite (Mag_BFN) and iron/oxide organoclay composite (Mag_S35) were prepared for toluene and naphthalene sorption. Mag_BFN and Mag_S35 were obtained, respectively, by the precipitation of iron oxide hydrates onto sodium BFN and S35 clay particles. The materials were characterized by powder X-ray diffraction (XRD), X-ray Fluorescence (XRF), and TG and DTA. From XRF results and TG data on calcined mass basis, a quantitative method was developed to estimate the iron compound contents of the composites, as well as the organic matter content present in WS35 and Mag_S35.

Adsorbent new materials and composites produced in a single step

The aim of this work is the production and preliminary characterization of adsorbent new materials useful for sensor development. A new plasma chamber was simulated and designed in order to obtain multiple layers and/or composites in a single step. Plasma deposited organic fluorocompound and hexamethyldisilazane (HMDS) thin films were produced and tested as adsorbent layers. Chemical characterization used ellipsometry, Raman. infrared and X-ray photoelectron spectroscopy. Hydrophobic and oleophobic character were determined by contact angle measurements. Adsorption characteristics were evaluated using quartz crystal microbalance. Not only HMDS but also the fluorocompound can polymerize but intermixing and a double layer are only obtained in very narrow conditions. The films are adsorbent and mildly hydrophobic. Films deposited on a microchromatographic column can be used on sample pretreatment to remove and/or preconcentrate volatile organic Compounds. Therefore, with this approach it is possible to obtain films with different monomers on double layer or composites, with organic/inorganic materials or particles and use them on sample pretreatment for chemical analysis. (C) 2008 Elsevier B.V. All rights reserved.

Long-term quantification of the release of monomers from dental resin composites and a resin-modified glass ionomer cement

This study quantified the release of monomers from polymerized specimens of four commercially available resin composites and one glass ionomer cement immersed in water:ethanol solutions. Individual standard curves were prepared from five monomers: (1) triethylene glycol dimethacrylate (TEGDMA), (2) 2-hydroxy-ethyl methacrylate (HEMA), (3) urethane dimethacrylate (UDMA), (4) bisphenol A glycidyl dimethacrylate (BISGMA), and (5) bisphenol A. The concentration of the monomers was determined at Days 1, 7, 30, and 90 with the use of electrospray ionization/mass spectrometry. Data were expressed in mean mumol per mm(2) surface area of specimen and analyzed with Scheffe's test (P < 0.05). The following monomers were found in water: monomers (1) and (2) from Delton sealant, monomer (5) from ScotchBond Multipurpose Adhesive and Delton sealant, monomer (3) from Definite and monomer (4) from Fuji II LC, ScotchBond Multipurpose Adhesive, Synergy and Definite. All these monomers increased in concentration over time, with the exception of monomer (1) from Delton sealant. Monomers (3) and (5) were found in extracts of materials despite their absence from the manufacturer's published composition. All monomers were released in significantly higher concentrations in water:ethanol solutions than in water. The greatest release of monomers occurred in the first day. The effect of the measured concentrations of monomers (1-5) on human genes, cells, or tissues needs to be considered with the use of a biological model. (C) 2002 Wiley Periodicals, Inc.

A new approach to the synthesis of conjugated polymer-nanocrystal composites for heterojunction optoelectronics

We report a simple one pot process for the preparation of lead sulfide (PbS) nanocrystals in the conjugated polymer poly (2-methoxy-5-(2'-ethyl-hexyloxy)-p-phenylene vinylene) (MEH-PPV), and we demonstrate electronic coupling between the two components.

Do Low-shrink Composites Reduce Polymerization Shrinkage Effects?

Progress in polymer science has led to continuous reduction of polymerization shrinkage, exemplified by a new generation of ""low-shrink composites"". The common inference that shrinkage stress effects will be reduced in teeth restored with such restoratives with lower shrinkage was tested in extracted human premolars. Mesio-occluso-distal slot-shaped cavities were cut and restored with a conventional (SupremePlus) or low-shrink (RefleXions, Premise, Kalore, and LS) composite (N = 5). We digitized the coronal surfaces before and 10 min after restoration to determine cuspal deflection from the buccal and lingual volume change/area. We also determined the main properties involved (total shrinkage, post-gel shrinkage, degree of conversion, and elastic modulus), as well as microleakage, to verify adequate bonding. It was shown that, due to shrinkage stresses, buccal and lingual surfaces pulled inward after restoration (9-14 microns). Only Kalore and LS resulted in significantly lower tooth deformation (ANOVA/Student-Newman-Keuls post hoc, p = 0.05). The other two low-shrink composites, despite having the lowest and highest total shrinkage values, did not cause significant differences in cuspal deflection. Deflection seemed most related to the combination of post-gel shrinkage and elastic modulus. Therefore, even for significantly lower total shrinkage values, shrinkage stress is not necessarily reduced.

Characterization of dimethacrylate polymeric networks: A study of the crosslinked structure formed by monomers used in dental composites

The resin phase of dental composites is mainly composed of combinations of dimethacrylate comonomers, with final polymeric network structure defined by monomer type/reactivity and degree of conversion. This fundamental study evaluates how increasing concentrations of the flexible triethylene glycol dimethacrylate (TEGDMA) influences void formation in bisphenol A diglycidyl dimethacrylate (BisGMA) co-polymerizations and correlates this aspect of network structure with reaction kinetic parameters and macroscopic volumetric shrinkage. Photopolymerization kinetics was followed in real-time by a near-infrared (NIR) spectroscopic technique, viscosity was assessed with a viscometer, volumetric shrinkage was followed with a linometer, free volume formation was determined by positron annihilation lifetime spectroscopy (PALS) and the sol-gel composition was determined by extraction with dichloromethane followed by (1)H NMR analysis. Results show that, as expected, volumetric shrinkage increases with TEGDMA concentration and monomer conversion. Extraction/(1)H NMR studies show increasing participation of the more flexible TEGDMA towards the limiting stages of conversion/crosslinking development. As the conversion progresses, either based on longer irradiation times or greater TEGDMA concentrations, the network becomes more dense, which is evidenced by the decrease in free volume and weight loss after extraction in these situations. For the same composition (BisGMA/TEGDMA 60-40 mol%) light-cured for increasing periods of time (from 10 to 600 s), free volume decreased and volumetric shrinkage increased, in a linear relationship with conversion. However, the correlation between free volume and macroscopic volumetric shrinkage was shown to be rather complex for variable compositions exposed for the same time (600 s). The addition of TEGDMA decreases free-volume up to 40 mol% (due to increased conversion), but above that concentration, in spite of the increase in conversion/crosslinking, free volume pore size increases due to the high concentration of the more flexible monomer. In those cases, the increase in volumetric shrinkage was due to higher functional group concentration, in spite of the greater free volume. Therefore, through the application of the PALS model, this study elucidates the network formation in dimethacrylates commonly used in dental materials. (C) 2010 Elsevier Ltd. All rights reserved.

Polymerization stress, shrinkage and elastic modulus of current low-shrinkage restorative composites

Objective. To compare currently available low-shrinkage composites with others regarding polymerization stress, volumetric shrinkage (total and post-gel), shrinkage rate and elastic modulus. Methods. Seven BisGMA-based composites (Durafill/DU, Filtek Z250/FZ, Heliomolar/HM, Aelite LS Posterior/AP, Point 4/P4, Filtek Supreme/SU, ELS/EL), a silorane-based (Filtek LS, LS), a urethane-based (Venus Diamond, VD) and one based on a dimethacrylate-derivative of dimer acid (N`Durance, ND) were tested. Polymerization stress was determined in 1-mm high specimens inserted between two PMMA rods attached to a universal testing machine. Total volumetric shrinkage was measured using a mercury dilatometer. Maximum shrinkage rate was used as a parameter of the reaction speed. Post-gel shrinkage was measured using strain-gages. Elastic modulus was obtained by three-point bending. Data were submitted to one-way ANOVA/Tukey test (p = 0.05), except for elastic modulus (Kruskal-Wallis). Results. Composites ranked differently for total and post-gel shrinkage. Among the materials considered as ""low-shrinkage"" by the respective manufacturers, LS, EL and VD presented low post-gel shrinkage, while AP and ND presented relatively high values. Polymerization stress showed a strong correlation with post-gel shrinkage except for LS, which presented high stress. Elastic modulus and shrinkage rate showed weak relationships with polymerization stress. Significance. Not all low-shrinkage composites demonstrated reduced polymerization shrinkage. Also, in order to effectively reduce polymerization stress, a low post-gel shrinkage must be associated to a relatively low elastic modulus. (C) 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Influence of matrix composition on polymerization stress development of experimental composites

Objective. Stress development at the tooth/restoration interface is one of the most important reasons for failure of adhesive restorations. The aim of this study was to evaluate the influence of BisGMA/TEGDMA (B/T) and UDMA/TEGDMA (U/T) ratios on polymerization stress (PS) and on the variables related to its development: degree of conversion (DC), polymerization maximum rate (Rp(max)), volumetric shrinkage (VS), elastic modulus (E), stress relaxation (SR) and viscosity of experimental composites. Method. Composites were formulated containing B/T or U/T in mol% ratios of 2: 8, 3: 7, 4: 6, 5: 5, 6: 4, 7: 3 and 8: 2, and 15 wt% of fumed silica. PS was determined with a universal testing machine. VS was measured with a linometer. E and SR were obtained in three-point bending. DC and Rp(max) were determined by real time NIR spectroscopy and viscosity was measured in viscometer. Data were submitted to one-way ANOVA, Tukey test (alpha = 0.05%) and regression analyses. Results. PS, VS, E and DC decreased and viscosity and Rp(max) increased with base monomer content in both series. PS showed strong correlation with VS, DC and viscosity. PS, VS and DC were higher and viscosity was lower for UDMA-based materials. Significance. Reduced viscosity, kinetics parameters and molecular characteristics led UDMA-based composites to elevated conversion and relatively lower PS at lower TEGDMA contents, compared to B/T composites. (C) 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

A critical view on biaxial and short-beam uniaxial flexural strength tests applied to resin composites using Weibull, fractographic and finite element analyses

Objective. To evaluate the biaxial and short-beam uniaxial strength tests applied to resin composites based upon their Weibull parameters, fractographic features and stress distribution. Methods. Disk- (15 mm x 1 mm) and beam-shaped specimens (10 mm x 2 mm x 1 mm) of three commercial composites (Concept/Vigodent, CA; Heliomolar/Ivoclar-Vivadent, HE; Z250/3M ESPE, FZ) were prepared. After 48h dry storage at 37 degrees C, disks and beams were submitted to piston-on-three-balls (BI) and three-point bending (UNI) tests, respectively. Data were analyzed by Weibull statistics. Fractured surfaces were observed under stereomicroscope and scanning electron microscope. Maximum principal stress (sigma(1)) distribution was determined by finite element analysis (FEA). Maximum sigma(1-BI) and sigma(1-UNI) were compared to FZ strengths calculated by applying the average failure loads to the analytical equations (sigma(a-BI) and sigma(a-UNI)). Results. For BI, characteristic strengths were: 169.9a (FZ), 122.4b (CA) and 104.8c (HE), and for UNI were: 160.3a (FZ), 98.2b (CA) and 91.6b (HE). Weibull moduli ( m) were similar within the same test. CA and HE presented statistically higher m for BI. Surface pores ( BI) and edge flaws ( UNI) were the most frequent fracture origins. sigma(1-BI) was 14% lower than sigma(a-BI.) sigma(1-UNI) was 43% higher than sigma(a-UNI). Significance. Compared to the short-beam uniaxial test, the biaxial test detected more differences among composites and displayed less data scattering for two of the tested materials. Also, biaxial strength was closer to the material`s strength estimated by FEA. (C) 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Al(2)O(3)/GdAlO(3)fiber for dental porcelain reinforcement

The aim of this study was to test the hypothesis that the addition of continuous or milled GdAlO(3)/Al(2)O(3) fibers to a dental porcelain increases its mechanical properties. Porcelain bars without reinforcement (control) were compared to those reinforced with long fibers (30 vol%). Also, disk specimens reinforced with milled fibers were produced by adding 0 (control), 5 or 10 vol% of particles. The reinforcement with continuous fibers resulted in significant increase in the uniaxial flexural strength from 91.5 to 217.4 MPa. The addition of varied amounts of milled fibers to the porcelain did not significantly affect its biaxial flexural strength compared to the control group. SEM analysis showed that the interface between the continuous fiber and the porcelain was free of defects. On the other hand, it was possible to note the presence of cracks surrounding the milled fiber/porcelain interface. In conclusion, the reinforcement of the porcelain with continuous fibers resulted in an efficient mechanism to increase its mechanical properties; however the addition of milled fibers had no significant effect on the material because the porcelain was not able to wet the ceramic particles during the firing cycle. (C) 2008 Elsevier Ltd. All rights reserved.

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. (C) 2009 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Photoinitiator content in restorative composites: Influence on degree of conversion, reaction kinetics, volumetric shrinkage and polymerization stress

Purpose: To determine the influence of rate of polymerization, degree of conversion and volumetric shrinkage on stress development by varying the amount of photoinitiators in a model composite. Methods: Volumetric shrinkage (with a mercury dilatometer), degree of conversion, maximum rate of reaction (RP(max)) (with differential scanning calorimetry) and polymerization stress (with a controlled compliance device) were evaluated. Bis-GMA/TEGDMA (equal mass ratios) were mixed with a tertiary amine (EDMAB) and camphorqpinone, respectively, in three concentrations (wt%): high= 0.8/1.6; intermediate= 0.4/0.8 and low= 0.2/0.4. 80 wt% filler was added. Composites were photoactivated (400 mW/cm(2) x 40 seconds; radiant exposure=16J/cm(2)). A fourth experimental group was included in which the low concentration formulation was exposed for 80 seconds (32 J/cm(2)). Results: For the same radiant exposure, conversion, RP(max) and stress increased with photoinitiator concentration (P< 0.001). When the low concentration group exposed to 32 J/cm(2) was compared with the high and intermediate groups (exposed to 16 J/cm(2)), RPmax Still increased with the photoinitiator concentration between all levels (P< 0.001) but conversion and stress did not vary (P> 0.05). Shrinkage did not vary regardless of the photoinitiator concentration or radiant exposure. For the photoinitiator concentrations used in this study. Polymerization stress was influenced by conversion but not by rate of reaction. (Am J Dent 2009;22:206-210).

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.