Characterization of mineral surfaces using FIB and TEM: a case study of naturally weathered alkali feldspars

Using a focused ion beam (FIB) instrument, electron-transparent samples (termed foils) have been cut from the naturally weathered surfaces of perthitic alkali feldspars recovered from soils overlying the Shap granite, northwest England. Characterization of these foils by transmission electron microscopy (TEM) has enabled determination of the crystallinity and chemical composition of near-surface regions of the feldspar and an assessment of the influence of intragranular microtextures on the microtopography of grain surfaces and development of etch pits. Damage accompanying implantation of the 30 kV Ga+ ions used for imaging and deposition of protective platinum prior to ion milling creates amorphous layers beneath outer grain surfaces, but can be overcome by coating grains with > 85 nm of gold before FIB work. The sidewalls of the foil and feldspar surrounding original voids are also partially amorphized during later stages of ion milling. No evidence was found for the presence of amorphous or crystalline weathering products or amorphous "leached layers" immediately beneath outer grain surfaces. The absence of a leached layer indicates that chemical weathering of feldspar in the Shap soils is stoichiometric, or if non-stoichiometric, either the layer is too thin to resolve by the TEM techniques used (i.e., <=similar to 2.5 nm) or an insufficient proportion of ions have been leached from near-surface regions so that feldspar crystallinity is maintained. No evidence was found for any difference in the mechanisms of weathering where a microbial filament rests on the feldspar surface. Sub-micrometer-sized steps on the grain surface have formed where subgrains and exsolution lamellae have influenced the propagation of fractures during physical weathering, whereas finer scale corrugations form due to compositional or strain-related differences in dissolution rates of albite platelets and enclosing tweed orthoclase. With progressive weathering, etch pits that initiated at the grain surface extend into grain interiors as etch tubes by exploiting preexisting networks of nanopores that formed during the igneous history of the grain. The combination of FIB and TEM techniques is an especially powerful way of exploring mechanisms of weathering within the "internal zone" beneath outer grain surfaces, but results must be interpreted with caution owing to the ease with which artifacts can be created by the high-energy ion and electron beams used in the preparation and characterization of the foils.

Thermally responsive elastomeric supramolecular polymers featuring flexible aliphatic hydrogen-bonding end-groups

The present paper details the synthesis, characterization, and preliminary physical analyses of a series of polyisobutylene derivatives featuring urethane and urea end-groups that enable supramolecular network formation to occur via hydrogen bonding. These polymers are readily accessible from relatively inexpensive and commercially available starting materials using a simple two-step synthetic approach. In the bulk, these supramolecular networks were found to possess thermoreversible and elastomeric characteristics as determined by temperature-dependent rheological analysis. These thermoreversible and elastomeric properties make these supramolecular materials potentially very useful in applications such as adhesives and healable surface coatings.

Double-gyroid morphology of a polystyrene-block-poly(ferrocenylethylmethylsilane) diblock copolymer: a route to ordered bicontinuous nanoscale architectures

A polystyrene-block-poly(ferrocenylethylmethylsilane) diblock copolymer, displaying a double-gyroid morphology when self-assembled in the solid state, has been prepared with a PFEMS volume fraction phi(PFMS)=0.39 and a total molecular weight of 64 000 Da by sequential living anionic polymerisation. A block copolymer with a metal-containing block with iron and silicon in the main chain was selected due to its plasma etch resistance compared to the organic block. Self-assembly of the diblock copolymer in the bulk showed a stable, double-gyroid morphology as characterised by TEM. SAXS confirmed that the structure belonged to the Ia3d space group.

Child anxiety and parenting in England and Italy: the moderating role of maternal warmth

BACKGROUND: Parenting factors have been implicated in the aetiology and maintenance of child anxiety. Most research has been correlational with little experimental or longitudinal work. Cross-cultural comparison could be illuminating. A comparison of Italian and British children and their mothers was conducted. METHODS: A sample of 8- to 10-year old children, 60 Italian and 49 English, completed the Spence Child Anxiety Scale. Mothers also completed two questionnaires of parenting: the Skills of Daily Living Checklist (assessing maternal autonomy granting) and the Parent-Child Interaction Questionnaire (assessing maternal intrusiveness). Parenting was assessed in two video-recorded blindly rated mother-child interaction tasks, the 'belt-buckling tasks and the 'etch-a-sketch', providing objective indices of overcontrol, warmth, lack of autonomy granting, and overprotection. RESULTS: There were no differences between the children in overall anxiety and specific forms of anxiety. Parenting, however, was markedly different for the two countries. Compared to English mothers, on the two questionnaires, Italian mothers were significantly less autonomy granting and more intrusive; and in terms of the observed indices, a significantly greater proportion of the Italian mothers displayed a high level of both overprotection and overcontrol, and a low level of autonomy granting. Notably, Italian mothers evidenced significantly more warmth than English mothers; and maternal warmth was found to moderate the impact of self-reported maternal intrusiveness on the level of both overall child anxiety and the level of child separation anxiety; and it also moderated the relationship between both observed maternal intrusiveness and overall child anxiety and observed maternal overprotectiveness and child separation anxiety. CONCLUSIONS: Although, compared to the British mothers, the Italian mothers were more likely to evidence high levels of parenting behaviours previously found to be anxiogenic, the high levels of warmth displayed by these mothers to their children appears to have neutralised the adverse impact of these behaviours.

Effect of temperature and strain rate on the compressive behaviour of supramolecular polyurethane

Supramolecular polyurethanes (SPUs) possess thermoresponsive and thermoreversible properties, and those characteristics are highly desirable in both bulk commodity and value-added applications such as adhesives, shape-memory materials, healable coatings and lightweight, impact-resistant structures (e.g. protection for mobile electronics). A better understanding of the mechanical properties, especially the rate and temperature sensitivity, of these materials are required to assess their suitability for different applications. In this paper, a newly developed SPU with tuneable thermal properties was studied, and the response of this SPU to compressive loading over strain rates from 10−3 to 104 s−1 was presented. Furthermore, the effect of temperature on the mechanical response was also demonstrated. The sample was tested using an Instron mechanical testing machine for quasi-static loading, a home-made hydraulic system for moderate rates and a traditional split Hopkinson pressure bars (SHPBs) for high strain rates. Results showed that the compression stress-strain behaviour was affected significantly by the thermoresponsive nature of SPU, but that, as expected for polymeric materials, the general trends of the temperature and the rate dependence mirror each other. However, this behaviour is more complicated than observed for many other polymeric materials, as a result of the richer range of transitions that influence the behaviour over the range of temperatures and strain rates tested.

Effect of blood contamination on the shear bond strength at resin/dentin interface in primary teeth

Purpose: To assess in vitro the shear bond strength at the resin/dentin interface in primary teeth after contamination with fresh human blood. Methods: 75 crowns of primary molars were embedded in acrylic resin and mechanically ground to expose a flat dentin surface. The specimens were randomly assigned to five groups (n=15), according to the surface treatment. Group I (control) had no blood contamination. The other groups were blood-contaminated and subjected to different post-contamination protocols: in Group 2, the surfaces were rinsed with water; in Group 3, the surfaces were air-dried; in Group 4, the surfaces were rinsed and air-dried; and in Group 5, no post-contamination treatment was done. In all groups, a 3-mm dentin bonding site was demarcated, Single Bond adhesive system was applied and resin composite cylinders were bonded. After 24 hours in distilled water, shear bond strength was tested at a crosshead speed of 0.5 mm/minute. Results: Means (in MPa) were: Group 1: 7.1 (+/- 4.2); Group 2: 4.0 (+/- 1.8); Group 3: 0.9 (+/- 0.7); Group 4: 3.9 (+/- 2.2) and Group 5: 1.3 (+/- 1.5). Data were analyzed statistically by the Kruskal-Wallis test at 5% significance level. Groups 2 and 4 were similar to each other (P > 0.05) and both ware similar to Group 1 (P > 0.05). These groups (2, 3 and 4) had statistically significantly higher bond strengths than Groups 3 and 5 (P < 0.05). Blood contamination negatively affected the shear bond strength to primary tooth dentin. Among the blood-contaminated groups, water-rinsed specimens had higher bond strengths than those that were exclusively air-dried or not submitted to any post-contamination protocol before adhesive application.

Bond durability in erbium:yttrium-aluminum-garnet laser-irradiated enamel

This study sought to evaluate the influence of thermocycling and water storage on the microtensile bond strength of composite resin bonded to erbium:yttrium-aluminum-garnet (Er:YAG)-irradiated and bur-prepared enamel. Eighty bovine incisors were selected and sectioned. Specimens were ground to produce a flat enamel surface. Samples were randomly assigned according to cavity preparation device: (I) Er:YAG laser and (II) high-speed turbine, and were subsequently restored with composite resin. They were subdivided according to the duration of water storage (WS)/number of thermocycles (TCs): 24 h WS/no TCs; 7 days WS/500 TCs; 1 month WS/2,000 TCs; 6 months WS/12,000 TCs. The teeth were sectioned into 1.0 mm(2)-thick slabs and subjected to tensile stress in a universal testing machine. Data were submitted to two-way analysis of variance (ANOVA) and Tukey`s test at a 0.05 significance level. The different periods of water storage and thermocycling did not influence the microtensile bond strength (A mu TBS) values in the Er:YAG laser-prepared groups. In bur-prepared enamel, the group submitted to 12,000 TCs/6 months` WS (IID) showed a significant decrease in bond strength values when compared to the group stored in water for 24 h and not submitted to thermocycling (IIA), but values were statistically similar to those obtained in all Er:YAG laser groups and in the bur- prepared groups degraded with 500 TCs/1 week WS (IIB) or 2,000 TCs/1 month WS (IIC). It may be concluded that adhesion of an etch-and-rinse adhesive to Er:YAG laser-irradiated enamel was not affected by the methods used to simulate degradation of the adhesive interface and was similar to adhesion in the bur-prepared groups in all periods of water storage and thermocycling.

Adhesion to Er : YAG laser-prepared dentin after long-term water storage and thermocycling

This in vitro study evaluated the microtensile bond strength of a resin composite to Er:YAG-prepared dentin after long-term storage and thermocycling. Eighty bovine incisors were selected and their roots removed. The crowns were ground to expose superficial dentin. The samples were randomly divided according to cavity preparation method (I-Er:YAG laser and II-carbide bur). Subsequently, an etch & rinse adhesive system was applied and the samples were restored with a resin composite. The samples were subdivided according to time of water storage (WS)/number of thermocycles (TC) performed: A) 24 hours WS/no TC; B) 7 days WS/500 TC; C) 1 month WS/2,000 TC; D) 6 months WS/12,000 TC. The teeth were sectioned in sticks with a cross-sectional area of 1.0-mm(2), which were loaded in tension in a universal testing machine. The data were subjected to two-way ANOVA, Scheffe and Fisher`s tests at a 5% level. In general, the bur-prepared group displayed higher microtensile bond strength values than the laser-treated group. Based on one-month water storage and 2,000 thermocycles, the performance of the tested adhesive system to Er:YAG-laser irradiated dentin was negatively affected (Group IC), while adhesion of the bur-prepared group decreased only within six months of water storage combined with 12,000 thermocycles (Group IID). It may be concluded that adhesion to the Er:YAG laser cavity preparation was more affected by the methods used for simulating degradation of the adhesive interface.

Occupational exposure to radon and natural gamma radiation in the La Carolina, a former gold mine in San Luis Province, Argentina

Radon and gamma radiation level measurements were carried out inside the La Carolina mine, one of the oldest gold mining camps of southern South America, which is open for touristic visits nowadays. CR-39 track-etch detectors and thermoluminescent dosimeters of natural CaF(2) and LiF TLD-100 were exposed at 14 points along the mine tunnels in order to estimate the mean (222)Rn concentration and the ambient dose equivalent during the summer season (November 2008 to February 2009). The values for the (222)Rn concentration at each monitoring site ranged from 1.8 +/- 0.1 kBq m(-3) to 6.0 +/- 0.5 kBq m(-3), with a mean value of 4.8 kBq m(-3), indicating that these measurements exceed in about three times the upper action level recommended by ICRP for workplaces. The correlations between radon and gamma radiation levels inside the mine were also investigated. Effective doses due to (222)Rn and gamma rays inside the mine were determined, resulting in negligible values to tourists. Considering the effective dose to the mine tourist guides, values exceeding 20 mSv of internal contribution to the effective doses can be reached, depending on the number of working hours inside the mine. (C) 2009 Elsevier Ltd. All rights reserved.

Effect of light-curing units on push-out fiber post bond strength in root canal dentin

The purpose of this study was to evaluate the effectiveness of different light-curing units on the bond strength (push-out) of glass fiber posts in the different thirds of the root (cervical, middle and apical) with different adhesive luting resin systems (dual-cure total-etch; dual-cured and self-etch bonding system; and dual-cure self-adhesive cements), Disks of the samples (n = 144) were used, with approximately 1 mm of thickness of 48 bovine roots restored with glass fiber posts, that were luted with resin cements photo-activated by halogen LCU (QTH, Optilux 501) and blue LED (Ultraled), with power densities of 600 and 550 mW/cm(2), respectively. A universal testing machine (MTS 810 Material Test System) was used with a 1 mm diameter steel rod at cross-head speed of 0.5 mm/min until post extrusion, with load cell of 50 kg, for evaluation of the push-out strength in the different thirds of each sample. The push-out strength values in kgf were converted to MPa and analyzed through Analysis of Variance and Tukey`s test, at significance level of 5%. The results showed that there were no statistical differences between the QTH and LED LCUs. The self-adhesive resin cement had lower values of retention. The total-etch and self-adhesive system resin cements seem to be a possible alternative for glass fiber posts cementation into the radicular canal and the LED LCU can be applied as an alternative to halogen light on photo-activation of dual-cured resin cements.

Biobased composites from glyoxal-phenolic resins and sisal fibers

Lignocellulosic materials can significantly contribute to the development of biobased composites. In this work, glyoxal-phenolic resins for composites were prepared using glyoxal, which is a dialdehyde obtained from several natural resources. The resins were characterized by (1)H, (13)C, (2)D, and (31)P NMR spectroscopies. Resorcinol (10%) was used as an accelerator for curing the glyoxal-phenol resins in order to obtain the thermosets. The impact-strength measurement showed that regardless of the cure cycle used, the reinforcement of thermosets by 30% (w/w) sisal fibers improved the impact strength by one order of magnitude. Curing with cycle 1 (150 degrees C) induced a high diffusion coefficient for water absorption in composites, due to less interaction between the sisal fibers and water. The composites cured with cycle 2 (180 degrees C) had less glyoxal resin coverage of the cellulosic fibers, as observed by images of the fractured interface observed by SEM. This study shows that biobased composites with good properties can be prepared using a high proportion of materials obtained from natural resources. (C) 2009 Elsevier Ltd. All rights reserved.

Buried screen-printed contacts for silicon solar cells

A Simple way to improve solar cell efficiency is to enhance the absorption of light and reduce the shading losses. One of the main objectives for the photovoltaic roadmap is the reduction of metalized area on the front side of solar cell by fin lines. Industrial solar cell production uses screen-printing of metal pastes with a limit in line width of 70-80 μm. This paper will show a combination of the technique of laser grooved buried contact (LGBC) and Screen-printing is able to improve in fine lines and higher aspect ratio. Laser grooving is a technique to bury the contact into the surface of silicon wafer. Metallization is normally done with electroless or electrolytic plating method, which a high cost. To decrease the relative cost, more complex manufacturing process was needed, therefore in this project the standard process of buried contact solar cells has been optimized in order to gain a laser grooved buried contact solar cell concept with less processing steps. The laser scribing process is set at the first step on raw mono-crystalline silicon wafer. And then the texturing etch; phosphorus diffusion and SiNx passivation process was needed once. While simultaneously optimizing the laser scribing process did to get better results on screen-printing process with fewer difficulties to fill the laser groove. This project has been done to make the whole production of buried contact solar cell with fewer steps and could present a cost effective opportunity to solar cell industries.

Comportamento de adesão da madeira de um híbrido clonal de Eucalyptus urophylla x Eucalyptus grandis proveniente de três condições de manejo

This study aimed to evaluate the adhesion ability of eucalyptus lumber from three tillage systems, using adhesives: resorcinol formaldehyde and two adhesives in water emulsion based on vinyl poly-acetate. The management systems were characterized by three strata, the stratum one (E1) characterized by wood from coppice and 70 months of age, the stratum two (E2) characterized by wood and retirement age of 166 months and stratum three (E3), also characterized by retirement at 70 months of age. The wood was derived from a random mixture of the first two sawn logs, each three feet from the base, which comprised three treatments on the adhesive used. We evaluated the shear strength by compression tests and the percentage of wood failure in the glue line. Based on the results obtained, it can be said that the adhesion had satisfactory performance with all the resins used, and the average values of shear strength of the glue line were shown to be equivalent to the shear strength of solid wood only for the samples which adhered with 'Wonderbond' adhesive and also provide higher values for wood failure (97.64%). The highest density present in the wood of the second stratum (E2) influenced only sticking with the resorcinol formaldehyde resin. For polyvinyl acetate (Cascorez 2590), shear values decreased in the third management condition (E3).