The Impact of Carbonate Texture on the Quantification of Total Porosity by Image Analysis

Date of Acceptance: 31/08/2015 The authors would like to thank Total E&P and BG Group for project funding and support and the Industry Technology Facilitator for enabling the collaborative development (grant number 3322PSD). The authors would also like to thank Aberdeen Formation Evaluation Society and the College of Physical Sciences at the University of Aberdeen for partial financial support. Dougal Jerram, Raymi Castilla, Claude Gout, Frances Abbots and an anonymous reviewer are thanked for their constructive comments and suggestions to improve the standard of this manuscript. The authors would also like to express their gratitude toJohn Still and Colin Taylor for technical assistance in the laboratory and Nick Timms (Curtin University) and Angela Halfpenny (CSIRO) for their assistance with the full thin section scanning equipment.

The Impact of Carbonate Texture on the Quantification of Total Porosity by Image Analysis

Date of Acceptance: 31/08/2015 The authors would like to thank Total E&P and BG Group for project funding and support and the Industry Technology Facilitator for enabling the collaborative development (grant number 3322PSD). The authors would also like to thank Aberdeen Formation Evaluation Society and the College of Physical Sciences at the University of Aberdeen for partial financial support. Dougal Jerram, Raymi Castilla, Claude Gout, Frances Abbots and an anonymous reviewer are thanked for their constructive comments and suggestions to improve the standard of this manuscript. The authors would also like to express their gratitude toJohn Still and Colin Taylor for technical assistance in the laboratory and Nick Timms (Curtin University) and Angela Halfpenny (CSIRO) for their assistance with the full thin section scanning equipment.

Porosity measurement of solid pharmaceutical dosage forms by gamma-ray transmission

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Incorporation of chlorhexidine gluconate or diacetate into a glass-ionomer cement: porosity, surface roughness, and anti-biofilm activity

To evaluate the porosity, surface roughness and anti-biofilm activity of a glass-ionomer cement (GIC) after incorporation of different concentrations of chlorhexidine (CHX) gluconate or diacetate. Methods: For the porosity and surface roughness tests, 10 test specimens were fabricated of the GIC Ketac Molar Easy Mix (KM) and divided into the following groups: Control, GIC and 0.5% CHX diacetate; GIC and 1.0% CHX diacetate; GIC and 2.0% CHX diacetate; GIC and 0.5% CHX gluconate; GIC and 1.0% CHX gluconate; GIC and 2.0% CHX gluconate. To evaluate porosity, the test specimens were fractured. The fragments were photographed by scanning electron microscopy (SEM), and the images analyzed with the aid of the software program Image J. The surface roughness (Ra) was obtained by the mean value of three readouts performed on the surface of each specimen, always through the center. To analyze the anti-biofilm activity, strains of S. mutans ATCC 35688 were used, and the groups control and GIC +CHX diacetate 1% were divided as follows: GIC (1 day); GIC (7 days), GIC (14 days), GIC (21 days); GIC+CHX (1 day), GIC+CHX (7 days), GIC+CHX (14 days), GIC+CHX (21 days); GIC+ CHX (1 day), GIC+ CHX (7 days), GIC+ CHX (14 days) and GIC+ CHX (21 days) using 10 test specimens per group. For biofilm growth, the specimens were placed in a vertical position in 24-well plates and incubated overnight 10 times. The culture medium was renewed every 24 hours. The suspension was diluted and seeded on BHI agar for quantification of the bacteria present. For evaluation of all the tests the two-way ANOVA was used, and if necessary, the Tukey test was applied, with a level of significance of 5%. Results: Regarding GIC porosity, the ANOVA showed that the presence of CHX increased the porosity (P< 0.001) proportionally to the increase in concentrations (P= 0.001), without however, presenting interaction between material and concentration (P= 0.705). Regarding the number of pores, a significant increase in pores was observed with the increase in CHX concentration (P= 0.003). The surface roughness test demonstrated no statistically significant effect as to increase or reduction in roughness at any of the CHX concentrations used (P> 0.05). Anti-biofilm activity analysis pointed out a significant effect of the factors material (P= 0.006) and time (P< 0.001), with CHX diacetate CHX presenting greater effectiveness in reducing microorganisms.

Experimental Characterization and Quantification of Cement-Bentonite Interaction using Core Infiltration Techniques Coupled with X-ray Tomography

Deep geological storage of radioactive waste foresees cementitious materials as reinforcement of tunnels and as backfill. Bentonite is proposed to enclose spent fuel canisters and as drift seals. Sand/bentonite (s/b) is foreseen as backfill material of access galleries or as drift seals. The emplacement of cementitious material next to clay material generates an enormous chemical gradient in pore-water composition that drives diffusive solute transport. Laboratory studies and reactive transport modeling predicted significant mineral alteration at and near interfaces, mainly resulting in a decrease of porosity in bentonite. The goal of this thesis was to characterize and quantify the cement/bentonite interactions both spatially and temporally in laboratory experiments. A newly developed mobile X-ray transparent core infiltration device was used to perform X-ray computed tomography (CT) scans without interruption of running experiments. CT scans allowed tracking the evolution of the reaction plume and changes in core volume/diameter/density during the experiments. In total 4 core infiltration experiments were carried out for this study with the compacted and saturated cores consisting of MX-80 bentonite and sand/MX-80 bentonite mixture (s/b; 65/35%). Two different high-pH cementitious pore-fluids were infiltrated: a young (early) ordinary Portland cement pore-fluid (APWOPC; K+–Na+–OH-; pH 13.4; ionic strength 0.28 mol/kg) and a young ‘low-pH’ ESDRED shotcrete pore-fluid (APWESDRED; Ca2+–Na+–K+–formate; pH 11.4; ionic strength 0.11 mol/kg). The experiments lasted between 1 and 2 years. In both bentonite experiments, the hydraulic conductivity was strongly reduced after switching to high-pH fluids, changing eventually from an advective to a diffusion-dominated transport regime. The reduction was mainly induced by mineral precipitation and possibly partly also by high ionic strength pore-fluids. Both bentonite cores showed a volume reduction and a resulting transient flow in which pore-water was squeezed out during high-pH infiltration. The outflow chemistry was characterized by a high ionic strength, while chloride in the initial pore water got replaced as main anionic charge carrier by sulfate, originating from gypsum dissolution. The chemistry of the high-pH fluids got strongly buffered by the bentonite, consuming hydroxide and in case of APWESDRED also formate. Hydroxide got consumed by mineral reactions (saponite and possibly talc and brucite precipitation), while formate being affected by bacterial degradation. Post-mortem analysis showed reaction zones near the inlet of the bentonite core, characterized by calcium and magnesium enrichment, consisting predominately of calcite and saponite, respectively. Silica got enriched in the outflow, indicating dissolution of silicate-minerals, identified as preferentially cristobalite. In s/b, infiltration of APWOPC reduced the hydraulic conductivity strongly, while APWESDRED infiltration had no effect. The reduction was mainly induced by mineral precipitation and probably partly also by high ionic strength pore-fluids. Not clear is why the observed mineral precipitates in the APWESDRED experiment had no effect on the fluid flow. Both s/b cores showed a volume expansion along with decreasing ionic strengths of the outflow, due to mineral reactions or in case of APWESDRED infiltration also mediated by microbiological activity, consuming hydroxide and formate, respectively. The chemistry of the high-pH fluids got strongly buffered by the s/b. In the case of APWESDRED infiltration, formate reached the outflow only for a short time, followed by enrichment in acetate, indicating most likely biological activity. This was in agreement to post-mortem analysis of the core, observing black spots on the inflow surface, while the sample had a rotten-egg smell indicative of some sulfate reduction. Post-mortem analysis showed further in both cores a Ca-enrichment in the first 10 mm of the core due to calcite precipitation. Mg-enrichment was only observed in the APWOPC experiment, originating from newly formed saponite. Silica got enriched in the outflow of both experiments, indicating dissolution of silicate-minerals, identified in the OPC experiment as cristobalite. The experiments attested an effective buffering capacity for bentonite and s/b, a progressing coupled hydraulic-chemical sealing process and also the preservation of the physical integrity of the interface region in this setup with a total pressure boundary condition on the core sample. No complete pore-clogging was observed but the hydraulic conductivity got rather strongly reduced in 3 experiments, explained by clogging of the intergranular porosity (macroporosity). Such a drop in hydraulic conductivity may impact the saturation time of the buffer in a nuclear waste repository, although the processes and geometry will be more complex in repository situation.

Quantification of water content across a cement-clay interface using high resolution neutron radiography

In many designs for radioactive waste repositories, cement and clay will come into direct contact. The geochemical contrast between cement and clay will lead to mass fluxes across the interface, which consequently results in alteration of structural and transport properties of both materials that may affect the performance of the multi-barrier system. We present an experimental approach to study cement-clay interactions with a cell to accommodate small samples of cement and clay. The cell design allows both in situ measurement of water content across the sample using neutron radiography and measurement of transport parameters using through-diffusion tracer experiments. The aim of the high- resolution neutron radiography experiments was to monitor changes in water content (porosity) and their spatial extent. Neutron radiographs of several evolving cement-clay interfaces delivered quantitative data which allow resolving local water contents within the sample domain. In the present work we explored the uncertainties of the derived water contents with regard to various input parameters and with regard to the applied image correction procedures. Temporal variation of measurement conditions created absolute uncertainty of the water content in the order of ±0.1 (m3/m3), which could not be fully accounted for by correction procedures. Smaller relative changes in water content between two images can be derived by specific calibrations to two sample regions with different, invariant water contents.

Porosity contributions of radiolarians in ODP Site 110-671 and Hole 110-672A sediments

This study quantitatively addresses the significance of porosity within radiolarian tests in the décollement zone at the toe of the northern Barbados accretionary prism. Quantification was accomplished using scanning electron microscope images of core samples taken from Ocean Drilling Program (ODP) Sites 671 and 672, representing the décollement and proto-décollement, respectively. The décollement is localized to a radiolarian claystone, and its depth correlates with a low-density anomaly that has been attributed to high porosity at all relevant ODP drilling sites in the area (Moore, Klaus, et al., 1998, doi:10.2973/odp.proc.ir.171A.1998; Shipley, Ogawa, Blum, et al., 1995, doi:10.2973/odp.proc.ir.153.1995; Mascle, Moore, et al., 1988, doi:10.2973/odp.proc.ir.110.1988). Porosity in the décollement zone is presumably lost between Sites 672 and 671 because of shear enhanced consolidation (Moore et al., 1998, doi:10.1130/0091-7613(1998)026<0811:CPDIAE>2.3.CO;2).

Plasma and cold sprayed aluminum carbon nanotube composites: Quantification of nanotube distribution and multi-scale mechanical properties

Carbon nanotubes (CNT) could serve as potential reinforcement for metal matrix composites for improved mechanical properties. However dispersion of carbon nanotubes (CNT) in the matrix has been a longstanding problem, since they tend to form clusters to minimize their surface area. The aim of this study was to use plasma and cold spraying techniques to synthesize CNT reinforced aluminum composite with improved dispersion and to quantify the degree of CNT dispersion as it influences the mechanical properties. Novel method of spray drying was used to disperse CNTs in Al-12 wt.% Si prealloyed powder, which was used as feedstock for plasma and cold spraying. A new method for quantification of CNT distribution was developed. Two parameters for CNT dispersion quantification, namely Dispersion parameter (DP) and Clustering Parameter (CP) have been proposed based on the image analysis and distance between the centers of CNTs. Nanomechanical properties were correlated with the dispersion of CNTs in the microstructure. Coating microstructure evolution has been discussed in terms of splat formation, deformation and damage of CNTs and CNT/matrix interface. Effect of Si and CNT content on the reaction at CNT/matrix interface was thermodynamically and kinetically studied. A pseudo phase diagram was computed which predicts the interfacial carbide for reaction between CNT and Al-Si alloy at processing temperature. Kinetic aspects showed that Al4C3 forms with Al-12 wt.% Si alloy while SiC forms with Al-23wt.% Si alloy. Mechanical properties at nano, micro and macro-scale were evaluated using nanoindentation and nanoscratch, microindentation and bulk tensile testing respectively. Nano and micro-scale mechanical properties (elastic modulus, hardness and yield strength) displayed improvement whereas macro-scale mechanical properties were poor. The inversion of the mechanical properties at different scale length was attributed to the porosity, CNT clustering, CNT-splat adhesion and Al 4C3 formation at the CNT/matrix interface. The Dispersion parameter (DP) was more sensitive than Clustering parameter (CP) in measuring degree of CNT distribution in the matrix.

Plasma And Cold Sprayed Aluminum Carbon Nanotube Composites: Quantification Of Nanotube Distribution And Multi-Scale Mechanical Properties

Carbon nanotubes (CNT) could serve as potential reinforcement for metal matrix composites for improved mechanical properties. However dispersion of carbon nanotubes (CNT) in the matrix has been a longstanding problem, since they tend to form clusters to minimize their surface area. The aim of this study was to use plasma and cold spraying techniques to synthesize CNT reinforced aluminum composite with improved dispersion and to quantify the degree of CNT dispersion as it influences the mechanical properties. Novel method of spray drying was used to disperse CNTs in Al-12 wt.% Si pre-alloyed powder, which was used as feedstock for plasma and cold spraying. A new method for quantification of CNT distribution was developed. Two parameters for CNT dispersion quantification, namely Dispersion parameter (DP) and Clustering Parameter (CP) have been proposed based on the image analysis and distance between the centers of CNTs. Nanomechanical properties were correlated with the dispersion of CNTs in the microstructure. Coating microstructure evolution has been discussed in terms of splat formation, deformation and damage of CNTs and CNT/matrix interface. Effect of Si and CNT content on the reaction at CNT/matrix interface was thermodynamically and kinetically studied. A pseudo phase diagram was computed which predicts the interfacial carbide for reaction between CNT and Al-Si alloy at processing temperature. Kinetic aspects showed that Al4C3 forms with Al-12 wt.% Si alloy while SiC forms with Al-23wt.% Si alloy. Mechanical properties at nano, micro and macro-scale were evaluated using nanoindentation and nanoscratch, microindentation and bulk tensile testing respectively. Nano and micro-scale mechanical properties (elastic modulus, hardness and yield strength) displayed improvement whereas macro-scale mechanical properties were poor. The inversion of the mechanical properties at different scale length was attributed to the porosity, CNT clustering, CNT-splat adhesion and Al4C3 formation at the CNT/matrix interface. The Dispersion parameter (DP) was more sensitive than Clustering parameter (CP) in measuring degree of CNT distribution in the matrix.

Propylthiouracil Quantification In Human Plasma By High-performance Liquid Chromatography Coupled With Electrospray Tandem Mass Spectrometry: Application In A Bioequivalence Study.

A rapid, sensitive and specific method for quantifying propylthiouracil in human plasma using methylthiouracil as the internal standard (IS) is described. The analyte and the IS were extracted from plasma by liquid-liquid extraction using an organic solvent (ethyl acetate). The extracts were analyzed by high performance liquid chromatography coupled with electrospray tandem mass spectrometry (HPLC-MS/MS) in negative mode (ES-). Chromatography was performed using a Phenomenex Gemini C18 5μm analytical column (4.6mm×150mm i.d.) and a mobile phase consisting of methanol/water/acetonitrile (40/40/20, v/v/v)+0.1% of formic acid. For propylthiouracil and I.S., the optimized parameters of the declustering potential, collision energy and collision exit potential were -60 (V), -26 (eV) and -5 (V), respectively. The method had a chromatographic run time of 2.5min and a linear calibration curve over the range 20-5000ng/mL. The limit of quantification was 20ng/mL. The stability tests indicated no significant degradation. This HPLC-MS/MS procedure was used to assess the bioequivalence of two propylthiouracil 100mg tablet formulations in healthy volunteers of both sexes in fasted and fed state. The geometric mean and 90% confidence interval CI of Test/Reference percent ratios were, without and with food, respectively: 109.28% (103.63-115.25%) and 115.60% (109.03-122.58%) for Cmax, 103.31% (100.74-105.96%) and 103.40% (101.03-105.84) for AUClast. This method offers advantages over those previously reported, in terms of both a simple liquid-liquid extraction without clean-up procedures, as well as a faster run time (2.5min). The LOQ of 20ng/mL is well suited for pharmacokinetic studies. The assay performance results indicate that the method is precise and accurate enough for the routine determination of the propylthiouracil in human plasma. The test formulation with and without food was bioequivalent to reference formulation. Food administration increased the Tmax and decreased the bioavailability (Cmax and AUC).

Mechanical properties and porosity of dental glass-ceramics hot-pressed at different temperatures

The objective of this work was to evaluate biaxial-flexural-strength (σf), Vickers hardness (HV), fracture toughness (K Ic), Young's modulus (E), Poisson's ratio (ν) and porosity (P) of two commercial glass-ceramics, Empress (E1) and Empress 2 (E2), as a function of the hot-pressing temperature. Ten disks were hot-pressed at 1065, 1070, 1075 and 1080 °C for E1; and at 910, 915, 920 and 925 °C for E2. The porosity was measured by an image analyzer software and s f was determined using the piston-on-three-balls method. K Ic and HV were determined by an indentation method. Elastic constants were determined by the pulse-echo method. For E1 samples treated at different temperatures, there were no statistical differences among the values of all evaluated properties. For E2 samples treated at different temperatures, there were no statistical differences among the values of σf, E, and ν, however HV and K Ic were significantly higher for 910 and 915 °C, respectively. Regarding P, the mean value obtained for E2 for 925 °C was significantly higher compared to other temperatures.

Reliability and discriminatory power of methods for dental plaque quantification

OBJECTIVE: This in situ study evaluated the discriminatory power and reliability of methods of dental plaque quantification and the relationship between visual indices (VI) and fluorescence camera (FC) to detect plaque. MATERIAL AND METHODS: Six volunteers used palatal appliances with six bovine enamel blocks presenting different stages of plaque accumulation. The presence of plaque with and without disclosing was assessed using VI. Images were obtained with FC and digital camera in both conditions. The area covered by plaque was assessed. Examinations were done by two independent examiners. Data were analyzed by Kruskal-Wallis and Kappa tests to compare different conditions of samples and to assess the inter-examiner reproducibility. RESULTS: Some methods presented adequate reproducibility. The Turesky index and the assessment of area covered by disclosed plaque in the FC images presented the highest discriminatory powers. CONCLUSION: The Turesky index and images with FC with disclosing present good reliability and discriminatory power in quantifying dental plaque.