Monitoring phase behavior of sub- and supercritical CO2 confined in porous fractal silica with 85% porosity

Phase behavior of CO2 confined in porous fractal silica with volume fraction of SiO2 φs = 0.15 was investigated using small-angle neutron scattering (SANS) and ultrasmall-angle neutron scattering (USANS) techniques. The range of fluid densities (0<(FCO2)bulk<0.977 g/cm3) and temperatures (T=22 °C, 35 and 60 °C) corresponded to gaseous, liquid, near critical and supercritical conditions of the bulk fluid. The results revealed formation of a dense adsorbed phase in small pores with sizes D<40 A° at all temperatures. At low pressure (P <55 bar, (FCO2)bulk <0.2 g/cm3) the average fluid density in pores may exceed the density of bulk fluid by a factor up to 6.5 at T=22 °C. This “enrichment factor” gradually decreases with temperature, however significant fluid densification in small pores still exists at temperature T=60°C, i.e., far above the liquid-gas critical temperature of bulk CO2 (TC=31.1 °C). Larger pores are only partially filled with liquid-like adsorbed layer which coexists with unadsorbed fluid in the pore core. With increasing pressure, all pores become uniformly filled with the fluid, showing no measurable enrichment or depletion of the porous matrix with CO2.

Accessibility of pores in coal to methane and carbon dioxide

Fluid–solid interactions in natural and engineered porous solids underlie a variety of technological processes, including geological storage of anthropogenic greenhouse gases, enhanced coal bed methane recovery, membrane separation, and heterogeneous catalysis. The size, distribution and interconnectivity of pores, the chemical and physical properties of the solid and fluid phases collectively dictate how fluid molecules migrate into and through the micro- and meso-porous media, adsorb and ultimately react with the solid surfaces. Due to the high penetration power and relatively short wavelength of neutrons, smallangle neutron scattering (SANS) as well as ultra small-angle scattering (USANS) techniques are ideally suited for assessing the phase behavior of confined fluids under pressure as well as for evaluating the total porosity in engineered and natural porous systems including coal. Here we demonstrate that SANS and USANS can be also used for determining the fraction of the pore volume that is actually accessible to fluids as a function of pore sizes and study the fraction of inaccessible pores as a function of pore size in three coals from the Illinois Basin (USA) and Bowen Basin (Australia). Experiments were performed at CO2 and methane pressures up to 780 bar, including pressures corresponding to zero average contrast condition (ZAC), which is the pressure where no scattering from the accessible pores occurs. Scattering curves at the ZAC were compared with the scattering from same coals under vacuum and analysed using a newly developed approach that shows that the volume fraction of accessible pores in these coals varies between �90% in the macropore region to �30% in the mesopore region and the variation is distinctive for each of the examined coals. The developed methodology may be also applied for assessing the volume of accessible pores in other natural underground formations of interest for CO2 sequestration, such as saline aquifers as well as for estimating closed porosity in engineered porous solids of technological importance.

Adaptive and phase transition behavior in performance of discrete multi-articular actions by degenerate neurobiological systems

The identification of attractors is one of the key tasks in studies of neurobiological coordination from a dynamical systems perspective, with a considerable body of literature resulting from this task. However, with regards to typical movement models investigated, the overwhelming majority of actions studied previously belong to the class of continuous, rhythmical movements. In contrast, very few studies have investigated coordination of discrete movements, particularly multi-articular discrete movements. In the present study, we investigated phase transition behavior in a basketball throwing task where participants were instructed to shoot at the basket from different distances. Adopting the ubiquitous scaling paradigm, throwing distance was manipulated as a candidate control parameter. Using a cluster analysis approach, clear phase transitions between different movement patterns were observed in performance of only two of eight participants. The remaining participants used a single movement pattern and varied it according to throwing distance, thereby exhibiting hysteresis effects. Results suggested that, in movement models involving many biomechanical degrees of freedom in degenerate systems, greater movement variation across individuals is available for exploitation. This observation stands in contrast to movement variation typically observed in studies using more constrained bi-manual movement models. This degenerate system behavior provides new insights and poses fresh challenges to the dynamical systems theoretical approach, requiring further research beyond conventional movement models.

The Behavior of Hydroxyl Units of Synthetic Goethite and its Dehydroxylated Product Hematite

The behavior of the hydroxyl units of synthetic goethite and its dehydroxylated product hematite was characterized using a combination of Fourier transform infrared (FTIR) spectroscopy and X-ray diffraction (XRD) during the thermal transformation over a temperature range of 180-270 degrees C. Hematite was detected at temperatures above 200 degrees C by XRD while goethite was not observed above 230 degrees C. Five intense OH vibrations at 3212-3194, 1687-1674, 1643-1640, 888-884 and 800-798 cm(-1), and a H2O vibration at 3450-3445 cm(-1) were observed for goethite. The intensity of hydroxyl stretching and bending vibrations decreased with the extent of dehydroxylation of goethite. Infrared absorption bands clearly show the phase transformation between goethite and hematite: in particular. the migration of excess hydroxyl units from goethite to hematite. Two bands at 536-533 and 454-452 cm(-1) are the low wavenumber vibrations of Fe-O in the hematite structure. Band component analysis data of FTIR spectra support the fact that the hydroxyl units mainly affect the a plane in goethite and the equivalent c plane in hematite.

Interpersonal pattern dynamics and adaptive behavior in multiagent neurobiological systems : conceptual model and data

Ecological dynamics characterizes adaptive behavior as an emergent, self-organizing property of interpersonal interactions in complex social systems. The authors conceptualize and investigate constraints on dynamics of decisions and actions in the multiagent system of team sports. They studied coadaptive interpersonal dynamics in rugby union to model potential control parameter and collective variable relations in attacker–defender dyads. A videogrammetry analysis revealed how some agents generated fluctuations by adapting displacement velocity to create phase transitions and destabilize dyadic subsystems near the try line. Agent interpersonal dynamics exhibited characteristics of chaotic attractors and informational constraints of rugby union boxed dyadic systems into a low dimensional attractor. Data suggests that decisions and actions of agents in sports teams may be characterized as emergent, self-organizing properties, governed by laws of dynamical systems at the ecological scale. Further research needs to generalize this conceptual model of adaptive behavior in performance to other multiagent populations.

Thermal behavior and decomposition of kaolinite-potassium acetate intercalation composite

A series of kaolinite-potassium acetate intercalation composite was prepared. The thermal behavior and decomposition of these composites were investigated by simultaneous differential scanning calorimetry-thermogravimetric analysis (DSC-TGA), X-ray diffraction (XRD) and Fourier-transformation infrared (FT-IR). The XRD pattern at room temperature indicated that intercalation of potassium acetate into kaolinite causes an increase of the basal spacing from 0.718 to 1.428nm. The peak intensity of the expanded phase of the composite decreased with heating above 300°C, and the basal spacing reduced to 1.19nm at 350°C and 0.718nm at 400°C. These were supported by DSC-TGA and FT-IR measurements, where the endothermic reactions are observed between 300 and 600°C. These reactions can be divided into two stages: 1) Removal of the intercalated molecules between 300-400°C. 2) Dehydroxylation of kaolinite between 400-600°C. Significant changes were observed in the infrared bands assigned to outer surface hydroxyl, inner surface hydroxyl, inner hydroxyl and hydrogen bands.

Red mud from Brazil : thermal behavior and physical properties

The main constituents of red mud produced in Aluminio city (S.P. – Brazil) are iron, aluminium and silicon oxides. It has been determined that the average particle diameter for this red mud is between 0.05 and 0.002mm. It is observed that a decrease in the percentage of smaller particles occurs at temperatures greater than 400°C. This observation corresponds with the thermal analysis and X-ray diffraction (XRD) data, which illustrate the phase transition of goethite to hematite. A 10% mass loss is observed in the thermal analysis patterns due to the hydroxide – oxide phase transitions of iron (primary phase transition) and aluminium (to a lesser extent). The disappearance and appearance of the different phases of iron and aluminium confirms the decomposition reactions proposed by the thermal analysis data. This Brazilian red mud has been classified as mesoporous at all temperatures except between 400 and 500°C where the classification changes to micro/mesoporous.

The thermal behavior of kaolinite intercalation complexes : a review

The kaolinite intercalation and its application in polymer-based functional composites have attracted great interest, both in industry and in academia fields, since they frequently exhibit remarkable improvements in materials properties compared with the virgin polymer or conventional micro and macro-composites. Also of significant interest regarding the kaolinite intercalation complex is its thermal behavior and decomposition. This is because heating treatment of intercalated kaolinite is necessary for its further application, especially in the field of plastic and rubber industry. Although intercalation of kaolinite is an old and ongoing research topic, there is a limited knowledge available on kaolinite intercalation with different reagents, the mechanism of intercalation complex formation as well as on thermal behavior and phase transition. This review attempts to summarize the most recent achievements in the thermal behavior study of kaolinite intercalation complexes obtained with the most common reagents including potassium acetate, formamide, dimethyl sulfoxide, hydrazine and urea. At the end of this paper, the further work on kaolinite intercalation complex was also proposed.

Generation and characterization of ionic and neutral dihydroxy boron B(OH)(2)(+/0) in the gas phase

The dicoordinated borinium ion, dihydroxyborinium, B(OH)(2)(+) is generated from methyl boronic acid CH3B(OH)(2) by dissociative electron ionization and its connectivity confirmed by collisional activation. Neutralization-reionization (NR) experiments on this ion indicate that the neutral B(OH)(2) radical is a viable species in the gas phase. Both vertical neutralization of B(OH)(2)(+) and reionization of B(OH)(2) in the NR experiment are, however, associated with particularly unfavorable Franck-Condon factors. The differences in adiabatic and vertical electron transfer behavior can be traced back to a particular pi stabilization of the cationic species compared to the sp(2)-type neutral radical. Thermochemical data on several neutral and cationic boron compounds are presented based on calculations performed at the G2 level of theory.

Base-induced decomposition of alkyl hydroperoxides in the gas phase. Part 3. Kinetics and dynamics in HO-+CH3OOH, C2H5OOH, and tert-C4H9OOH reactions

The E-CO(2) elimination reactions of alkyl hydroperoxides proceed via abstraction of an (x-hydrogen by a base: X- + (RRHCOOH)-R-1-H-2 -> HX + (RRC)-R-1-C-2=O + HO-. Efficiencies and product distributions for the reactions of the hydroxide anion with methyl, ethyl, and tert-butyl hydroperoxides are studied in the gas phase. On the basis of experiments using three isotopic analogues, HO- + CH3OOH, HO- + CD3OOH, and H18O- + CH3OOH. the overall intrinsic reaction efficiency is determined to be 80% or greater. The E(CO)2 decomposition is facile for these methylperoxide reactions, and predominates over competing proton transfer at the hydroperoxide moiety. The CH3CH2OOH reaction displays a similar E(CO)2 reactivity, whereas proton transfer and the formation of HOO- are the exclusive pathways observed for (CH3)(3)COOH, which has no (x-hydrogen. All results are consistent with the E-CO(2) mechanism, transition state structure, and reaction energy diagrams calculated using the hybrid density functional B3LYP approach. Isotope labeling for HO- + CH3OOH also reveals some interaction between H2O and HO- within the E(CO)2 product complex [H2O center dot center dot center dot CH2=O center dot center dot center dot HO-]. There is little evidence, however. for the formation of the most exothermic products H2O + CH2(OH)O-, which would arise from nuclephilic condensation of CH2=O and HO-. The results suggest that the product dynamics are not totally statistical but are rather direct after the E-CO(2) transition state. The larger HO- + CH3CH2OOH system displays more statistical behavior during complex dissociation.

Microscale consolidation analysis of relaxation behavior of single living chondrocytes subjected to varying strain-rates

Besides the elastic stiffness, the relaxation behavior of single living cells is also of interest of various researchers when studying cell mechanics. It is hypothesized that the relaxation response of the cells is governed by both intrinsic viscoelasticity of the solid phase and fluid-solid interactions mechanisms. There are a number of mechanical models have been developed to investigate the relaxation behavior of single cells. However, there is lack of model enable to accurately capture both of the mechanisms. Therefore, in this study, the porohyperelastic (PHE) model, which is an extension of the consolidation theory, combined with inverse Finite Element Analysis (FEA) technique was used at the first time to investigate the relaxation response of living chondrocytes. This model was also utilized to study the dependence of relaxation behavior of the cells on strain-rates. The stress-relaxation experiments under the various strain-rates were conducted with the Atomic Force Microscopy (AFM). The results have demonstrated that the PHE model could effectively capture the stress-relaxation behavior of the living chondrocytes, especially at intermediate to high strain-rates. Although this model gave some errors at lower strain-rates, its performance was acceptable. Therefore, the PHE model is properly a promising model for single cell mechanics studies. Moreover, it has been found that the hydraulic permeability of living chondrocytes reduced with decreasing of strain-rates. It might be due to the intracellular fluid volume fraction and the fluid pore pressure gradients of chondrocytes were higher when higher strain-rates applied.

Behavior of sprayed tricyclazole in rice paddy lysimeters

The behavior of sprayed tricyclazole in rice paddy lysimeters was studied. Tricyclazole residues were measured from rice leaves and paddy water after tricyclazole spraying in paddy lysimeters. The rate of photolysis and hydrolysis of tricyclazole on the surface of rice leaves was also determined in a laboratory experiment. Tricyclazole was extracted from leaf and water samples and determined by liquid chromatography with UV or mass spectrometry. The hydrolysis half-lives of tricyclazole on rice leaves were 11.9 and 5.1 d for the formulated product and standard, respectively. The photolysis half-lives were longer, 16.4 d for the formulated product and 20.9 d for the standard. In the paddy lysimeter, tricyclazole dissipation on leaves involved either biphasic first-order kinetics or single-phase first-order kinetics, depending on the rainfall pattern. Half-lives of tricyclazole on lysimeter rice leaves were from 3.0 to 5.7 d. The dissipation of tricyclazole in paddy water followed single-phase first-order kinetics with half-lives ranging from 2.1 to 5.0 d.

Crash risk perception of sleepy driving and its comparisons with drink driving and speeding: Which behavior is perceived as the riskiest?

- Objective Driver sleepiness is a major crash risk factor, but may be under-recognized as a risky driving behavior. Sleepy driving is usually rated as less of a road safety issue than more well-known risky driving behaviors, such as drink driving and speeding. The objective of this study was to compare perception of crash risk of sleepy driving, drink driving, and speeding. - Methods In total, 300 Australian drivers completed a questionnaire that assessed crash risk perceptions for sleepy driving, drink driving, and speeding. Additionally, the participants perception of crash risk was assessed for five different contextual scenarios that included different levels of sleepiness (low, high), driving duration (short, long), and time of day/circadian influences (afternoon, night-time) of driving. - Results The analysis confirmed that sleepy driving was considered a risky driving behavior, but not as risky as high levels of speeding (p < .05). Yet, the risk of crashing at 4 am was considered as equally risky as low levels of speeding (10 km over the limit). The comparisons of the contextual scenarios revealed driving scenarios that would arguably be perceived as quite risky due to time of day/circadian influences were not reported as high risk. - Conclusions The results suggest a lack of awareness or appreciation of circadian rhythm functioning, particularly the descending phase of circadian rhythm that promotes increased sleepiness in the afternoon and during the early hours of the morning. Yet, the results suggested an appreciation of the danger associated with long distance driving and driver sleepiness. Further efforts are required to improve the community’s awareness of the impairing effects from sleepiness and in particular, knowledge regarding the human circadian rhythm and the increased sleep propensity during the circadian nadir.

Surface chemistry, dispersion behavior, and slip casting of Ti 3AlC2 suspensions

The surface chemistry and dispersion properties of aqueous Ti 3AlC2 suspension were studied in terms of hydrolysis, adsorption, electrokinetic, and rheological measurements. The Ti 3AlC2 particle had complex surface hydroxyl groups, such as ≡Ti-OH,=Al-OH, and -OTi-(OH)2, etc. The surface charging of the Ti3AlC2 particle and the ion environment of suspensions were governed by these surface groups, which thus strongly influenced the stability of Ti3AlC2 suspensions. PAA dispersant was added into the Ti3AlC2 suspension to depress the hydrolysis of the surface groups by the adsorption protection mechanism and to increase the stability of the suspension by the steric effect. Ti3AlC2 suspensions with 2.0 dwb% PAA had an excellent stability at pH=∼5 and presented the characteristics of Newtonian fluid. Based on the well-dispersed suspension, dense Ti3AlC2 materials were obtained by slip casting and after pressureless sintering. This work provides a feasible forming method for the engineering applications of MAX-phase ceramics, wherein complex shapes, large dimensions, or controlled microstructures are needed.