Resin composites: Modulus of elasticity and marginal quality

OBJECTIVE To investigate how the modulus of elasticity of resin composites influences marginal quality in restorations submitted to thermocyclic and mechanical loading. METHODS Charisma, Filtek Supreme XTE and Grandio were selected as they were found to possess different moduli of elasticity but quite similar polymerization contraction. MOD cavities (n=30) were prepared in extracted premolars, restored and then subjected to thermocyclic and mechanical loading. Marginal quality of the restorations before and after loading was analyzed on epoxy replicas under a scanning electron microscope. The percentage of gap-free margins and occurrence of paramarginal fractures were registered. Modulus of elasticity and polymerization contraction were analyzed with parametric and margins with nonparametric ANOVA and post hoc Tukey HSD or Wilcoxon rank-sum tests, respectively. The number of paramarginal fractures was analyzed with exact Fisher tests (α=0.05). RESULTS Grandio demonstrated significantly more gap-free enamel margins than Charisma and Filtek Supreme XTE, before and after loading (p<0.01), whereas there was no difference between Charisma and Filtek Supreme XTE (p>0.05). No significant effect of resin composite (p=0.81) on the quality of dentine margins was observed, before or after loading. Deterioration of all margins was evident after loading (p<0.0001). More paramarginal enamel fractures were observed after loading in teeth restored with Grandio when compared to Charisma (p=0.008). CONCLUSIONS The resin composite with the highest modulus of elasticity resulted in the highest number of gap-free enamel margins but with an increased incidence of paramarginal enamel fractures. CLINICAL SIGNIFICANCE The results from this study suggest that the marginal quality of restorations can be improved by the selection of a resin composite with modulus of elasticity close to that of dentine, although an increase in paramarginal enamel fractures can result as a consequence.

Influence of increment thickness on microhardness and dentin bond strength of bulk fill resin composites

OBJECTIVES To investigate the influence of increment thickness on Vickers microhardness (HV) and shear bond strength (SBS) to dentin of a conventional and four bulk fill resin composites. METHODS HV and SBS were determined on specimens of the conventional resin composite Filtek Supreme XTE (XTE) and the bulk fill resin composites SDR (SDR), Filtek Bulk Fill (FBF), x-tra fil (XFIL), and Tetric EvoCeram Bulk Fill (TEBF) after 24h storage. HV was measured either as profiles at depths up to 6mm or at the bottom of 2mm/4mm/6mm thick resin composite specimens. SBS of 2mm/4mm/6mm thick resin composite increments was measured to dentin surfaces of extracted human molars treated with the adhesive system OptiBond FL, and the failure mode was stereomicroscopically determined at 40× magnification. HV profiles and failure modes were descriptively analysed whereas HV at the bottom of resin composite specimens and SBS were statistically analysed with nonparametric ANOVA followed by Wilcoxon rank sum tests (α=0.05). RESULTS HV profiles (medians at 2mm/4mm/6mm): XTE 105.6/88.8/38.3, SDR 34.0/35.5/36.9, FBF 36.4/38.7/37.1, XFIL 103.4/103.9/101.9, TEBF 63.5/59.7/51.9. HV at the bottom of resin composite specimens (medians at 2mm/4mm/6mm): XTE (p<0.0001) 105.5>85.5>31.1, SDR (p=0.10) 25.8=21.9=26.0, FBF (p=0.16) 26.6=25.3=28.9, XFIL (p=0.18) 110.5=107.2=101.9, TEBF (p<0.0001) 63.0>54.9>48.2. SBS (MPa, medians at 2mm/4mm/6mm): XTE (p<0.0001) 23.9>18.9=16.7, SDR (p=0.26) 24.6=22.7=23.4, FBF (p=0.11) 21.4=20.3=22.0, x-tra fil (p=0.55) 27.0=24.0=23.6, TEBF (p=0.11) 21.0=20.7=19.0. The predominant SBS failure mode was cohesive failure in dentin. SIGNIFICANCE At increasing increment thickness, HV and SBS decreased for the conventional resin composite but generally remained constant for the bulk fill resin composites.

Polar Nature of Biomimetic Fluorapatite/Gelatin Composites: A Comparison of Bipolar Objects and the Polar State of Natural Tissue

The correspondence of the state of alignment of macromolecules in biomimetic materials and natural tissues is demonstrated by investigating a mechanism of electrical polarity formation: An in vitro grown biomimetic FAp/gelatin composite is investigated for its polar properties by second harmonic (SHGM) and scanning pyroelectric microscopy (SPEM). Hexagonal prismatic seed crystals formed in gelatin gels represent a monodomain polar state, due to aligned mineralized gelatin molecules. Later growth stages, showing dumbbell morphologies, develop into a bipolar state because of surface recognition by gelatin functionality: A reversal of the polar alignment of macromolecules, thus, takes place close to that basal plane of the seed. In natural hard tissues (teeth and bone investigated by SPEM) and the biomimetic FAp/gelatin composite, we find a surprising analogy in view of growth-induced states of polarity: The development of polarity in vivo and in vitro can be explained by a Markov-type mechanism of molecular recognition during the attachment of macromolecules.

A MORTALITY STUDY OF BUTYL-CHLOROBUTYL RUBBER WORKERS

Worker populations are potentially exposed to multiple chemical substances simultaneously during the performance of routine tasks. The acute health effects from exposure to toxic concentrations of these substances are usually well-described. However, very little is known about the long-term health effects of chronic low dose exposure to all except a few chemical substances. A mortality study was performed on a population of workers employed at a butyl rubber manufacturing plant in Baton Rouge, Louisiana for the period 1943-1978, with special emphasis on potential exposure to methyl chloride.^ The study population was enumerated using company records. The mortality experience among the population was evaluated by comparing the number of observed deaths (total and cause-specific) to the expected number of deaths, based on the U.S. general age, race, sex specific rates. An internal comparison population was assembled to address the issue of lack of comparability when the U.S. rates are used to calculate expected deaths in an employed population.^ There were 18% fewer total observed deaths compared to the expected when the U.S. death rates were used to obtain the expected. Deaths from specific causes were also less than expected except when numbers of observed and expected deaths were small. Similar results were obtained when the population was characterized by intensity and duration of potential exposure to methyl chloride. When the internal comparison population was utilized to evaluate overall mortality of the study population, the relative risk was about 1.2.^ The study results were discussed and conclusions drawn in light of certain limitations of the methodology and study population size. ^

Daily MODIS composites of thin-ice thickness and ice-surface temperatures for the Southern Weddell Sea

Based upon high-resolution thermal-infrared Moderate-Resolution Imaging Spectroradiometer (MODIS) satellite imagery in combination with ERA-Interim atmospheric reanalysis data, we derived long-term polynya parameters such as polynya area, thin-ice thickness distribution and ice-production rates from daily cloud-cover corrected thin-ice thickness composites. Our study is based on a thirteen year investigation period (2002-2014) for the austral winter (1 April to 30 September) in the Antarctic Southern Weddell Sea. The focus lies on coastal polynyas which are important hot spots for new-ice formation, bottom-water formation and heat/moisture release into the atmosphere. MODIS has the capability to resolve even very narrow coastal polynyas. Its major disadvantage is the sensor limitation due to cloud cover. We make use of a newly developed and adapted spatial feature reconstruction scheme to account for cloud-covered areas. We find the sea-ice areas in front of Ronne and Brunt Ice Shelf to be the most active with an annual average polynya area of 3018 ± 1298 and 3516 ± 1420 km2 as well as an accumulated volume ice production of 31 ± 13 and 31 ± 12 km**3, respectively. For the remaining four regions, estimates amount to 421 ± 294 km**2 and 4 ± 3 km**3 (Antarctic Peninsula), 1148 ± 432 km**2 and 12 ± 5 km**3 (Iceberg A23A), 901 ± 703 km**2 and 10 ± 8 km**3 (Filchner Ice Shelf) as well as 499 ± 277 km**2 and 5 ± 2 km**3 (Coats Land). Our findings are discussed in comparison to recent studies based on coupled sea-ice/ocean models and passive-microwave satellite imagery, each investigating different parts of the Southern Weddell Sea.

Curing, defects and mechanical performance of fiber-reinforced composites

Tradicionalmente, la fabricación de materiales compuestos de altas prestaciones se lleva a cabo en autoclave mediante la consolidación de preimpregnados a través de la aplicación simultánea de altas presiones y temperatura. Las elevadas presiones empleadas en autoclave reducen la porosidad de los componentes garantizando unas buenas propiedades mecánicas. Sin embargo, este sistema de fabricación conlleva tiempos de producción largos y grandes inversiones en equipamiento lo que restringe su aplicación a otros sectores alejados del sector aeronáutico. Este hecho ha generado una creciente demanda de sistemas de fabricación alternativos al autoclave. Aunque estos sistemas son capaces de reducir los tiempos de producción y el gasto energético, por lo general, dan lugar a materiales con menores prestaciones mecánicas debido a que se reduce la compactación del material al aplicar presiones mas bajas y, por tanto, la fracción volumétrica de fibras, y disminuye el control de la porosidad durante el proceso. Los modelos numéricos existentes permiten conocer los fundamentos de los mecanismos de crecimiento de poros durante la fabricación de materiales compuestos de matriz polimérica mediante autoclave. Dichos modelos analizan el comportamiento de pequeños poros esféricos embebidos en una resina viscosa. Su validez no ha sido probada, sin embargo, para la morfología típica observada en materiales compuestos fabricados fuera de autoclave, consistente en poros cilíndricos y alargados embebidos en resina y rodeados de fibras continuas. Por otro lado, aunque existe una clara evidencia experimental del efecto pernicioso de la porosidad en las prestaciones mecánicas de los materiales compuestos, no existe información detallada sobre la influencia de las condiciones de procesado en la forma, fracción volumétrica y distribución espacial de los poros en los materiales compuestos. Las técnicas de análisis convencionales para la caracterización microestructural de los materiales compuestos proporcionan información en dos dimensiones (2D) (microscopía óptica y electrónica, radiografía de rayos X, ultrasonidos, emisión acústica) y sólo algunas son adecuadas para el análisis de la porosidad. En esta tesis, se ha analizado el efecto de ciclo de curado en el desarrollo de los poros durante la consolidación de preimpregnados Hexply AS4/8552 a bajas presiones mediante moldeo por compresión, en paneles unidireccionales y multiaxiales utilizando tres ciclos de curado diferentes. Dichos ciclos fueron cuidadosamente diseñados de acuerdo a la caracterización térmica y reológica de los preimpregnados. La fracción volumétrica de poros, su forma y distribución espacial se analizaron en detalle mediante tomografía de rayos X. Esta técnica no destructiva ha demostrado su capacidad para analizar la microestructura de materiales compuestos. Se observó, que la porosidad depende en gran medida de la evolución de la viscosidad dinámica a lo largo del ciclo y que la mayoría de la porosidad inicial procedía del aire atrapado durante el apilamiento de las láminas de preimpregnado. En el caso de los laminados multiaxiales, la porosidad también se vio afectada por la secuencia de apilamiento. En general, los poros tenían forma cilíndrica y se estaban orientados en la dirección de las fibras. Además, la proyección de la población de poros a lo largo de la dirección de la fibra reveló la existencia de una estructura celular de un diámetro aproximado de 1 mm. Las paredes de las celdas correspondían con regiones con mayor densidad de fibra mientras que los poros se concentraban en el interior de las celdas. Esta distribución de la porosidad es el resultado de una consolidación no homogenea. Toda esta información es crítica a la hora de optimizar las condiciones de procesado y proporcionar datos de partida para desarrollar herramientas de simulación de los procesos de fabricación de materiales compuestos fuera de autoclave. Adicionalmente, se determinaron ciertas propiedades mecánicas dependientes de la matriz termoestable con objeto de establecer la relación entre condiciones de procesado y las prestaciones mecánicas. En el caso de los laminados unidireccionales, la resistencia interlaminar depende de la porosidad para fracciones volumétricas de poros superiores 1%. Las mismas tendencias se observaron en el caso de GIIc mientras GIc no se vio afectada por la porosidad. En el caso de los laminados multiaxiales se evaluó la influencia de la porosidad en la resistencia a compresión, la resistencia a impacto a baja velocidad y la resistencia a copresión después de impacto. La resistencia a compresión se redujo con el contenido en poros, pero éste no influyó significativamente en la resistencia a compresión despues de impacto ya que quedó enmascarada por otros factores como la secuencia de apilamiento o la magnitud del daño generado tras el impacto. Finalmente, el efecto de las condiciones de fabricación en el proceso de compactación mediante moldeo por compresión en laminados unidireccionales fue simulado mediante el método de los elementos finitos en una primera aproximación para simular la fabricación de materiales compuestos fuera de autoclave. Los parámetros del modelo se obtuvieron mediante experimentos térmicos y reológicos del preimpregnado Hexply AS4/8552. Los resultados obtenidos en la predicción de la reducción de espesor durante el proceso de consolidación concordaron razonablemente con los resultados experimentales. Manufacturing of high performance polymer-matrix composites is normally carried out by means of autoclave using prepreg tapes stacked and consolidated under the simultaneous application of pressure and temperature. High autoclave pressures reduce the porosity in the laminate and ensure excellent mechanical properties. However, this manufacturing route is expensive in terms of capital investment and processing time, hindering its application in many industrial sectors. This fact has driven the demand of alternative out-of-autoclave processing routes. These techniques claim to produce composite parts faster and at lower cost but the mechanical performance is also reduced due to the lower fiber content and to the higher porosity. Corrient numerical models are able to simulate the mechanisms of void growth in polymer-matrix composites processed in autoclave. However these models are restricted to small spherical voids surrounded by a viscous resin. Their validity is not proved for long cylindrical voids in a viscous matrix surrounded by aligned fibers, the standard morphology observed in out-of-autoclave composites. In addition, there is an experimental evidence of the detrimental effect of voids on the mechanical performance of composites but, there is detailed information regarding the influence of curing conditions on the actual volume fraction, shape and spatial distribution of voids within the laminate. The standard techniques of microstructural characterization of composites (optical or electron microscopy, X-ray radiography, ultrasonics) provide information in two dimensions and are not always suitable to determine the porosity or void population. Moreover, they can not provide 3D information. The effect of curing cycle on the development of voids during consolidation of AS4/8552 prepregs at low pressure by compression molding was studied in unidirectional and multiaxial panels. They were manufactured using three different curing cycles carefully designed following the rheological and thermal analysis of the raw prepregs. The void volume fraction, shape and spatial distribution were analyzed in detail by means of X-ray computed microtomography, which has demonstrated its potential for analyzing the microstructural features of composites. It was demonstrated that the final void volume fraction depended on the evolution of the dynamic viscosity throughout the cycle. Most of the initial voids were the result of air entrapment and wrinkles created during lay-up. Differences in the final void volume fraction depended on the processing conditions for unidirectional and multiaxial panels. Voids were rod-like shaped and were oriented parallel to the fibers and concentrated in channels along the fiber orientation. X-ray computer tomography analysis of voids along the fiber direction showed a cellular structure with an approximate cell diameter of 1 mm. The cell walls were fiber-rich regions and porosity was localized at the center of the cells. This porosity distribution within the laminate was the result of inhomogeneous consolidation. This information is critical to optimize processing parameters and to provide inputs for virtual testing and virtual processing tools. In addition, the matrix-controlled mechanical properties of the panels were measured in order to establish the relationship between processing conditions and mechanical performance. The interlaminar shear strength (ILSS) and the interlaminar toughness (GIc and GIIc) were selected to evaluate the effect of porosity on the mechanical performance of unidirectional panels. The ILSS was strongly affected by the porosity when the void contents was higher than 1%. The same trends were observed in the case of GIIc while GIc was insensitive to the void volume fraction. Additionally, the mechanical performance of multiaxial panels in compression, low velocity impact and compression after impact (CAI) was measured to address the effect of processing conditions. The compressive strength decreased with porosity and ply-clustering. However, the porosity did not influence the impact resistance and the coompression after impact strength because the effect of porosity was masked by other factors as the damage due to impact or the laminate lay-up. Finally, the effect of the processing conditions on the compaction behavior of unidirectional AS4/8552 panels manufactured by compression moulding was simulated using the finite element method, as a first approximation to more complex and accurate models for out-of autoclave curing and consolidation of composite laminates. The model parameters were obtained from rheological and thermo-mechanical experiments carried out in raw prepreg samples. The predictions of the thickness change during consolidation were in reasonable agreement with the experimental results.

A simulation method to estimate closing forces in car-sealing rubber elements

The door-closing process can reinforce the impression of a solid, rock-proof, car body or of a rather cheap, flimsy vehicle. As there are no real prototypes during rubber profile bidding-out stages, engineers need to carry out non-linear numerical simulations that involve complex phenomena as well as static and dynamic loads for several profile candidates. This paper presents a structured virtual design tool based on FEM, including constitutive laws and incompressibility constraints allowing to predict more realistically the final closing forces and even to estimate sealing overpressure as an additional guarantee of noise insulation. Comparisons with results of physical tests are performed.

AFBC of coal with tyre rubber. Influence of the co-combustion variables on the mineral matter of solid by-products and on Zn lixiviation

The study focuses on the generation and distribution of mineral species in fly and bottom ashes. These were formed during a fluidised co-combustion of a fossil fuel (coal) and a non-fossil fuel (tyre rubber) in a small fluidised bed combustor (7cm x 70cm). The pilot plant had continuous fuel feed using varying ratios of coal and rubber. The study also focuses on the lixiviation behaviour of metallic elements with the assessement of zinc recovering.

Intraply fracture of fiber-reinforced composites: microscopic mechanisms and modeling

The fracture behavior parallel to the fibers of an E-glass/epoxy unidirectional laminate was studied by means of three-point tests on notched beams. Selected tests were carried out within a scanning electron microscope to ascertain the damage and fracture micromechanisms upon loading. The mechanical behavior of the notched beam was simulated within the framework of the embedded cell model, in which the actual composite microstructure was resolved in front of the notch tip. In addition, matrix and interface properties were independently measured in situ using a nanoindentor. The numerical simulations very accurately predicted the macroscopic response of the composite as well as the damage development and crack growth in front of the notch tip, demonstrating the ability of the embedded cell approach to simulate the fracture behavior of heterogeneous materials. Finally, this methodology was exploited to ascertain the influence of matrix and interface properties on the intraply toughness.