The influence of moisture on the deformability of cement-polymer adhesive mortar

Adhesive mortars are widely used to set porcelain stoneware tiles on buildings because their bond strength and flexibility properties increase the cladding serviceability. However, their long-term performance is not well understood, mainly the degradation of the polymeric matrix. The influence of moisture content on the flexibility of six adhesive mortars is investigated, based on standard EN 12002. Four of them have defined formulations and the other two are commercial and are widely used to set porcelain stoneware tiles on building facades in Brazil. The results show that moisture content above 6% is sufficient to reduce 50% of the mortar deformability, but that the drying process allows it to recover to a value similar to that prior to saturation; a logarithmic function best fits the correlation between moisture content and flexibility; water immersion increases matrix rigidity. It is suggested that standards should consider flexibility tests on both dried and wet samples as a requirement for polymer-modified mortars. (C) 2010 Elsevier Ltd. All rights reserved.

Polymer toughening using residue of recycled windshields: PVB film as impact modifier

In this work, poly(vinyl butyral) (PVB) film originated from the mechanical separation of windshields was tested as all impact modifier of Polyamide-6 (PA-6). The changes undergone by PVB film during the recycling process and the blend manufacturing were evaluated by thermal analyses, infrared spectroscopy and loss oil ignition. Blends of PA-6/original PVB film and PA-6/recovered PVB film were obtained in concentrations ranging from 90/10 to 60/40. The mechanical properties of the blends were investigated and explained in light of the blends morphologies, which in turns were correlated to the changes undergone by the PVB film during the recycling process. The original film presented a plasticizer content of 33 wt.%, which decreased to as low as 20 wt.%, after the recycling and blend preparation processes. The PA-6/PVB film blends presented lower values of tensile strength and Young`s modulus than Polyamide-6, but all blends presented a dramatic increase in their toughness, with a special feature for the 40 wt.%(, blend, which resulted in a super toughened material (impact strength exceeding 500 J/m). Similar results were obtained with recovered PVB film and super tough blends were also obtained. The use of recovered PVB resulted in a smaller improvement of the impact strength due to the loss of plasticizer undergone during the recycling process. The morphological observations showed that if the interparticle distance is smaller than around 0.2 mu m (critical value), the notched Izod impact strength values increase considerably and the fracture surface of blends exhibit characteristics of tough failure. (C) 2007 Elsevier Ltd. All rights reserved.

Application of the essential work of fracture method in ranking the performance in service of high-density polyethylene resins employed in pressure pipes

High-density polyethylene resins have increasingly been used in the production of pipes for water- and gas-pressurized distribution systems and are expected to remain in service for several years, but they eventually fail prematurely by creep fracture. Usual standard methods used to rank resins in terms of their resistance to fracture are expensive and non-practical for quality control purposes, justifying the search for alternative methods. Essential work of fracture (EWF) method provides a relatively simple procedure to characterize the fracture behavior of ductile polymers, such as polyethylene resins. In the present work, six resins were analyzed using the EWF methodology. The results show that the plastic work dissipation factor, beta w(p), is the most reliable parameter to evaluate the performance. Attention must be given to specimen preparation that might result in excessive dispersion in the results, especially for the essential work of fracture w(e).

Influence of Water Content, Time, and Temperature on the Rheological Behavior of Polyethylene Terephtalate

In this work, the main factors affecting the rheological behavior of polyethylene terephtalate (PET) in the linear viscoelastic regime (water content, time delay before test, duration of experiment, and temperature) were accessed. Small amplitude oscillatory shear tests were performed after different time delays ranging from 300 to 5000 s for samples with water contents ranging from 0.02 to 0.45 wt %. Time sweep tests were carried out for different durations to explain the changes undergone by PET before and during small amplitude oscillatory shear measurements. Immediately after the time sweep tests, the PET samples were removed from the rheometer, analyzed by differential scanning calorimetry and their molar mass was obtained by viscometry analysis. It was shown that for all the samples, the delay before test and residence time within the rheometer (i.e. duration of experiment) result in structural changes of the PET samples, such as increase or decrease of molar mass, broadening of molar mass distribution, and branching phenomena. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 116: 3525-3533, 2010

Stress relaxation behavior of PMMA/PS polymer blends

In this work, the stress relaxation behavior of PMMA/PS blends, with or without random copolymer addition, submitted to step shear strain experiments in the linear and nonlinear regime was studied. The effect of blend composition (ranging from 10 to 30 wt.% of dispersed phase), viscosity ratio (ranging from 0.1 to 7.5), and random copolymer addition (for concentrations up to 8 wt.% with respect to the dispersed phase) was evaluated and correlated to the evolution of the morphology of the blends. All blends presented three relaxation stages: a first fast relaxation which was attributed to the relaxation of the pure phases, a second one which was characterized by the presence of a plateau, and a third fast one. The relaxation was shown to be faster for less extended and smaller droplets and to be influenced by coalescence for blends with a dispersed phase concentration larger than 20 wt.%. The relaxation of the blend was strongly influenced by the matrix viscosity. The addition of random copolymer resulted in a slower relaxation of the droplets.

Instrumented indentation testing of an epoxy adhesive used in automobile body assembling

Instrumented indentation has been used to investigate the mechanical properties of BETAMATE 1496 (R) Epoxy adhesive. The properties of the adhesive were analyzed by measuring its hardness and its Young`s modulus in samples extracted from six different positions of the front door of a commercial passenger vehicle in two phases of processing: after application of the adhesive in the door assembling (""pre-cured"" state) and after final cure in the painting oven (""cured"" state). Special attention was given to setting the optimal parameters (""creep"" time and unloading time step) for the instrumented indentation testing for the present application. Young`s modulus values around 1.1 +/- 0.2 GPa and hardness values around 0.15 +/- 0.05 GPa were obtained for all samples, irrespective of the variation of the indentation parameters in the testing procedure and of the relative position of the adhesive in the door frame in both states. (C) 2008 Elsevier Ltd. All rights reserved.

Stress cracking and photodegradation behavior of polycarbonate. The combination of two major causes of polymer failure

This work investigates the effects of photodegradation on the environmental stress cracking resistance of polycarbonate (PC). Injection molded samples were exposed to the ultraviolet (UV) light for various times in the laboratory prior to solvent contact. The bars were then stressed with two different loads in a tensile testing machine under the presence of ethanol. During this period, the stress relaxation was monitored and, after unloading, the ultimate properties were evaluated. Complementary tests were done by size exclusion chromatography, UV-visible spectroscopy, scanning electron microscopy, and light microscopy. The results indicated that ethanol causes significant modification in PC, with extensive surface crazing as well as reduction in mechanical properties. The previous degraded samples showed a higher level of stress relaxation and a greater loss in tensile strength in comparison with the undegraded ones. The synergist action of photodegradation and stress cracking in PC may be a consequence of the chemical changes caused by oxidation.

Measuring Hydraulic Conductivity to Wilting Point Using Polymer Tensiometers in an Evaporation Experiment

The polymer tensiometer is a novel instrument to measure soil water pressure heads from saturation to permanent wilting conditions. We used tensiometers of this type in an experiment to determine the hydraulic properties of evaporating soil samples in the laboratory. Relative errors in the hydraulic conductivity function in the wet part were high due to the relatively low accuracy of the pressure transducers, resulting in a large uncertainty in the hydraulic gradient and therefore in the calculated hydraulic conductivity. In the dry part, the error related to this accuracy was on the same order of magnitude as the error related to balance accuracy. Therefore, the method can be assumed adequate for measuring soil hydraulic properties except under very wet conditions. In our experiments, relative error and bias increased significantly at pressure heads less negative than -1 m.

Investigation of charged polymer influence on green fluorescent protein thermal stability

Methods of stabilization and formulation of proteins are important in both biopharmaceutical and biocatalysis industries. Polymers are often used as modifiers of characteristics of biological macromolecules to improve the biochemical activity and stability of proteins or drug bioavailability. Green fluorescent protein (GFP) shows remarkable structural stability and high fluorescence; its stability can be directly related to its fluorescence output, among other characteristics. GFP is stable under increasing temperatures, and its thermal denaturation is highly reproducible. Relative thermal stability was undertaken by incubation of GFP at varying temperatures and GFP fluorescence was used as a reporter for unfolding. At 80 degrees C, DEAE-dextran did not have any effect on GFP fluorescence, indicating that it does not confer stability.

Randomized Evaluation of Two Drug-Eluting Stents With Identical Metallic Platform and Biodegradable Polymer But Different Agents (Paclitaxel or Sirolimus) Compared Against Bare Stents: 1-Year Results of the PAINT Trial

Objectives: We tested two novel drug-eluting stents (DES), covered with a biodegradable-polymer carrier and releasing paclitaxel or sirolimus, which were compared against a bare metal stent (primary objective). The DES differed by the drug, but were identical otherwise, allowing to compare the anti-restenosis effects of sirolimus versus paclitaxel (secondary objective). Background: The efficacy of novel DES with biodegradable polymers should be tested in the context of randomized trials, even when using drugs known to be effective, such as sirolimus and paclitaxel. Methods: Overall, 274 patients with de novo coronary lesions in native vessels scheduled for stent implantation were randomly assigned (2:21 ratio) for the paclitaxel (n = 111), sirolimus (n = 106), or bare metal stent (n = 57) groups. Angiographic follow-up was obtained at 9 months and major cardiac adverse events up to 12 months. Results: Both paclitaxel and sirolimus stents reduced the 9-month in-stent late loss (0.54-0.44 mm, 0.32-0.43 mm, vs. 0.90-0.45 mm respectively), and 1-year risk of target vessel revascularization and combined major adverse cardiac events (P < 0.05 for both, in all comparisons), compared with controls. Sirolimus stents had lower late loss than paclitaxel stents (P < 0.01), but similar 1-year clinical outcomes. There were no differences in the risk of death, infarction, or stent thrombosis among the study groups. Conclusion: Both novel DES were effective in reducing neointimal hyperplasia and 1-year re-intervention, compared to bare metal stents. Our findings also suggest that sirolimus is more effective than paclitaxel in reducing angiographic neointima, although this effect was not associated with better clinical outcomes. (C) 2009 Wiley-Liss, Inc.

Histological analysis of cobalt-chromium stents with and without Camouflage (R) polymer coating: experimental porcine carotid artery model

This study evaluated the arterial response to cobalt-chromium stents with and without polymer coating (Camouflage (R), Hemoteq AG, Wuerselen, Germany) implanted in pigs. Cobalt-chromium balloon-expandable stents (4 x 16 mm) were implanted in the common carotid arteries of nine pigs. Histological analysis of endothelialization, inflammation and injury was performed one month later. All stents were successfully deployed, and all but one animal survived the 30 study days. All arteries were patent. Endothelialization was nearly complete in most sections of all carotid stents in both groups. There were mild inflammatory infiltrate and mild-to-moderate injury, which were associated with the stent shafts and not significantly different between groups. Our findings suggest that, in porcine carotid arteries, the histological response to balloon-expandable cobalt-chromium stents coated with polymer (Camouflage (R), Hemoteq AG) is similar to the response to non-coated cobalt-chromium stents.

Evaluation of the Possibility of Removing Staining by Repolishing Composite Resins Submitted to Artificial Aging

This in vitro research verified the possibility of eliminating staining caused by coffee and red wine in five composite resins, after being submitted to thermal cycling. Thirty-six specimens were prepared and immersed in water at 37 degrees C for 24 hours. After polishing, specimen color was measured in a spectrophotometer Cintra 10 UV (Visible Spectrometer, GBC, Braeside, VIC, Australia). All specimens were submitted to thermal cycling at temperatures of 5 and 55 degrees C with a dwell time of 1 minute, for 1,000 cycles in a 75% ethanol/water solution. After thermal cycling, the specimens were immersed in water at 37 degrees C until 7 days had elapsed from the time the specimens were prepared. All specimens were then taken to the spectrophotometer for color measurement. The specimens were divided into three groups (N = 12): distilled water (control), coffee, and red wine. For the staining process to occur on only one surface, all the sides, except one, of the surfaces were isolated with white wax. The specimens were immersed in one of the solutions at 37 degrees C for 14 days. The specimens were dried and taken to the spectrophotometer for color measurement. After this, the specimens were submitted to 20 mu m wear three times, and the color was measured after each one of the wear procedures. Calculation of the color difference was made using CIEDE2000 formula. According to the methodology used in this research, it was concluded that the staining caused by coffee and red wine was superficial and one wear of 20 mu m was sufficient to remove the discoloration.

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.

Composite pre-heating: Effects on marginal adaptation, degree of conversion and mechanical properties

Objectives. This study evaluated the effect of composite pre-polymerization temperature and energy density on the marginal adaptation (MA), degree of conversion (DC), flexural strength (FS), and polymer cross-linking (PCL) of a resin composite (Filtek Z350, 3M/ESPE). Methods. For MA, class V cavities (4mmx2mmx2mm) were prepared in 40 bovine incisors. The adhesive system Adper Single Bond 2 (3M/ESPE) was applied. Before being placed in the cavities, the resin composite was either kept at room-temperature (25 degrees C) or previously pre-heated to 68 degrees C in the Calset (TM) device (AdDent Inc., Danbury, CT, USA). The composite was then light polymerized for 20 or 40s at 600mW/cm(2) (12 or 24 J/cm(2), respectively). The percentage of gaps was analyzed by scanning electron microscopy, after sectioning the restorations and preparing epoxy resin replicas. DC (n = 3) was obtained by FT-Raman spectroscopy on irradiated and non-irradiated composite surfaces. FS (n = 10) was measured by the three-point-bending test. KHN (n = 6) was measured after 24h dry storage and again after immersion in 100% ethanol solution for 24 h, to calculate PCL density. Data were analyzed by appropriate statistical analyses. Results. The pre-heated composite showed better MA than the room-temperature groups. A higher number of gaps were observed in the room-temperature groups, irrespective of the energy density, mainly in the axial wall (p < 0.05). Composite pre-heating and energy density did not affect the DC, FS and PCL (p > 0.05). Significance. Pre-heating the composite prior to light polymerization similar in a clinical situation did not alter the mechanical properties and monomer conversion of the composite, but provided enhanced composite adaptation to cavity walls. (C) 2010 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.