Pore structure characterization of North American shale gas reservoirs using USANS/SANS, gas adsorption, and mercury intrusion

Small-angle and ultra-small-angle neutron scattering (SANS and USANS), low-pressure adsorption (N2 and CO2), and high-pressure mercury intrusion measurements were performed on a suite of North American shale reservoir samples providing the first ever comparison of all these techniques for characterizing the complex pore structure of shales. The techniques were used to gain insight into the nature of the pore structure including pore geometry, pore size distribution and accessible versus inaccessible porosity. Reservoir samples for analysis were taken from currently-active shale gas plays including the Barnett, Marcellus, Haynesville, Eagle Ford, Woodford, Muskwa, and Duvernay shales. Low-pressure adsorption revealed strong differences in BET surface area and pore volumes for the sample suite, consistent with variability in composition of the samples. The combination of CO2 and N2 adsorption data allowed pore size distributions to be created for micro–meso–macroporosity up to a limit of �1000 Å. Pore size distributions are either uni- or multi-modal. The adsorption-derived pore size distributions for some samples are inconsistent with mercury intrusion data, likely owing to a combination of grain compression during high-pressure intrusion, and the fact that mercury intrusion yields information about pore throat rather than pore body distributions. SANS/USANS scattering data indicate a fractal geometry (power-law scattering) for a wide range of pore sizes and provide evidence that nanometer-scale spatial ordering occurs in lower mesopore–micropore range for some samples, which may be associated with inter-layer spacing in clay minerals. SANS/USANS pore radius distributions were converted to pore volume distributions for direct comparison with adsorption data. For the overlap region between the two methods, the agreement is quite good. Accessible porosity in the pore size (radius) range 5 nm–10 lm was determined for a Barnett shale sample using the contrast matching method with pressurized deuterated methane fluid. The results demonstrate that accessible porosity is pore-size dependent.

Astrophysics and the solar nebula

The following types of experiments for a proposed Space Station Microgravity Particle Research Facility are described: (1) nucleation of refractory vapors at low pressure/high temperature; (2) coagulation of refractory grains; (3) optical properties of refractory grains; (4) mantle growth on refractory cores; (5) coagulation of core-mantle grains; (6) optical properties of core-mantle grains; (7) lightning strokes in the primitive solar nebula; and (8) separation of dust from a grain/gas mixture that interacts with a meter-sized planetesimal to determine if accretion occurs. The required capabilities and desired hardware for the facility are detailed.

Characterization of tight gas reservoir pore structure using USANS/SANS and gas adsorption analysis

Small-angle and ultra-small-angle neutron scattering (SANS and USANS) measurements were performed on samples from the Triassic Montney tight gas reservoir in Western Canada in order to determine the applicability of these techniques for characterizing the full pore size spectrum and to gain insight into the nature of the pore structure and its control on permeability. The subject tight gas reservoir consists of a finely laminated siltstone sequence; extensive cementation and moderate clay content are the primary causes of low permeability. SANS/USANS experiments run at ambient pressure and temperature conditions on lithologically-diverse sub-samples of three core plugs demonstrated that a broad pore size distribution could be interpreted from the data. Two interpretation methods were used to evaluate total porosity, pore size distribution and surface area and the results were compared to independent estimates derived from helium porosimetry (connected porosity) and low-pressure N2 and CO2 adsorption (accessible surface area and pore size distribution). The pore structure of the three samples as interpreted from SANS/USANS is fairly uniform, with small differences in the small-pore range (<2000 Å), possibly related to differences in degree of cementation, and mineralogy, in particular clay content. Total porosity interpreted from USANS/SANS is similar to (but systematically higher than) helium porosities measured on the whole core plug. Both methods were used to estimate the percentage of open porosity expressed here as a ratio of connected porosity, as established from helium adsorption, to the total porosity, as estimated from SANS/USANS techniques. Open porosity appears to control permeability (determined using pressure and pulse-decay techniques), with the highest permeability sample also having the highest percentage of open porosity. Surface area, as calculated from low-pressure N2 and CO2 adsorption, is significantly less than surface area estimates from SANS/USANS, which is due in part to limited accessibility of the gases to all pores. The similarity between N2 and CO2-accessible surface area suggests an absence of microporosity in these samples, which is in agreement with SANS analysis. A core gamma ray profile run on the same core from which the core plug samples were taken correlates to profile permeability measurements run on the slabbed core. This correlation is related to clay content, which possibly controls the percentage of open porosity. Continued study of these effects will prove useful in log-core calibration efforts for tight gas.

Does Addition of NO2 to Carbon-Centered Radicals Yield RONO or RNO2? An Investigation Using Distonic Radical Ions

Nitrogen dioxide is used as a "radical scavenger" to probe the position of carbon-centered radicals within complex radical ions in the gas phase. As with analogous neutral radical reactions, this addition results in formation of an \[M + NO2](+) adduct, but the structural identity of this species remains ambiguous. Specifically, the question remains: do such adducts have a nitro-(RNO2) or nitrosoxy-(RONO) moiety, or are both isomers present in the adduct population? In order to elucidate the products of such reactions, we have prepared and isolated three distonic phenyl radical cations and observed their reactions with nitrogen dioxide in the gas phase by ion-trap mass spectrometry. In each case, stabilized \[M + NO2](+) adduct ions are observed and isolated. The structure of these adducts is probed by collision-induced dissociation and ultraviolet photodissociation action spectroscopy and a comparison made to the analogous spectra of authentic nitro-and nitrosoxy-benzenes. We demonstrate unequivocally that for the phenyl radical cations studied here, all stabilized \[M + NO2](+) adducts are exclusively nitrobenzenes. Electronic structure calculations support these mass spectrometric observations and suggest that, under low-pressure conditions, the nitrosoxy-isomer is unlikely to be isolated from the reaction of an alkyl or aryl radical with NO2. The combined experimental and theoretical results lead to the prediction that stabilization of the nitrosoxy-isomer will only be possible for systems wherein the energy required for dissociation of the RO-NO bond (or other low energy fragmentation channels) rises close to, or above, the energy of the separated reactants.

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.

Exploring the boundary between the siphon and barometer in a hypobaric chamber

Siphons have been used since ancient times, but exactly how they work is still a matter of debate. In order to elucidate the modus operandi of a siphon, a 1.5 m high siphon was set up in a hypobaric chamber to explore siphon behaviour in a low-pressure environment. When the pressure in the chamber was reduced to about 0.18 atmospheres, a curious waterfall-like feature appeared downstream from the apex of the siphon. A hypothesis is presented to explain the waterfall phenomenon. When the pressure was reduced further the siphon broke into two columns - in effect becoming two back-to-back barometers. This experiment demonstrates the role of atmospheric pressure in explaining the hydrostatic characteristics of a siphon and the role of molecular cohesion in explaining the hydrodynamic aspects.

Plasma-produced phase-pure cuprous oxide nanowires for methane gas sensing

Phase-selective synthesis of copper oxide nanowires is warranted by several applications, yet it remains challenging because of the narrow windows of the suitable temperature and precursor gas composition in thermal processes. Here, we report on the room-temperature synthesis of small-diameter, large-area, uniform, and phase-pure Cu2O nanowires by exposing copper films to a custom-designed low-pressure, thermally non-equilibrium, high-density (typically, the electron number density is in the range of 10 11-1013cm-3) inductively coupled plasmas. The mechanism of the plasma-enabled phase selectivity is proposed. The gas sensors based on the synthesized Cu2O nanowires feature fast response and recovery for the low-temperature (∼140°C) detection of methane gas in comparison with polycrystalline Cu2O thin film-based gas sensors. Specifically, at a methane concentration of 4%, the response and the recovery times of the Cu2O nanowire-based gas sensors are 125 and 147s, respectively. The Cu2O nanowire-based gas sensors have a potential for applications in the environmental monitoring, chemical industry, mining industry, and several other emerging areas.

Surface chemical modification of carbon nanowalls for wide-range control of surface wettability

Carbon nanowalls (CNWs) are self-assembled, free-standing, few-layered graphenenano-structures with large surface area, and thin graphene edges. For their application to nanobiotechnology, the effects of chemisorbed species on surface wettability were investigated. The surfaces of as-grown CNWs obtained using CH4/H2 mixture were hydrophilic. After Ar atmospheric pressure plasma treatments for up to 30 s, the contact angles of water droplets on the CNWs decreased from 51° to 5°, owing to a result of oxidation only at edges and surface defects. They increased up to 147° by CF4 plasma treatment at low pressure. The wide-range control of surface wettability of CNWs was realized by post-growth plasma treatments. We also demonstrated detection of bovine serum albumin using surface-modified CNWs as electrodes.

Hydrogen in plasma-nanofabrication : selective control of nanostructure heating and passivation

The possibility of independent control of the surface fluxes of energy and hydrogen-containing radicals, thus enabling selective control of the nanostructure heating and passivation, is demonstrated. In situ energy flux measurements reveal that even a small addition of H2 to low-pressure Ar plasmas leads to a dramatic increase in the energy deposition through H recombination on the surface. The heat release is quenched by a sequential addition of a hydrocarbon precursor while the surface passivation remains effective. Such selective control offers an effective mechanism for deterministic control of the growth shape, crystallinity, and density of nanostructures in plasma-aided nanofabrication. © 2010 American Institute of Physics.

Synthesis of functional nanoassemblies in reactive plasmas

Synthesis of various functional nanoassemblies, by using a combination of low-pressure reactive plasma-enhanced chemical deposition and plasma-assisted rf magnetron sputtering deposition is reported. This paper details how selective generation and manipulation of the required building blocks and management of unwanted nanoparticle contaminants, can be used for plasma-aided nanofabrication of carbon nanotip microemitter structures, ultra-high aspect ratio semiconductor nanowires, ordered quantum dot arrays, and microporous hydroxyapatite bioceramics. Emerging challenges of the plasma-aided synthesis of functional nanofilms and nanoassemblies are also discussed.

Integrated plasma-aided nanofabrication facility: Operation, parameters, and assembly of quantum structures and functional nanomaterials

The development, operation, and applications of two configurations of an integrated plasma-aided nanofabrication facility (IPANF) comprising low-frequency inductively coupled plasma-assisted, low-pressure, multiple-target RF magnetron sputtering plasma source, are reported. The two configurations of the plasma source have different arrangements of the RF inductive coil: a conventional external flat spiral "pancake" coil and an in-house developed internal antenna comprising two orthogonal RF current sheets. The internal antenna configuration generates a "unidirectional" RF current that deeply penetrates into the plasma bulk and results in an excellent uniformity of the plasma over large areas and volumes. The IPANF has been employed for various applications, including low-temperature plasma-enhanced chemical vapor deposition of vertically aligned single-crystalline carbon nanotips, growth of ultra-high aspect ratio semiconductor nanowires, assembly of optoelectronically important Si, SiC, and Al1-xInxN quantum dots, and plasma-based synthesis of bioactive hydroxyapatite for orthopedic implants.

Performance and gaseous and particle emissions from a liquefied petroleum gas (LPG) fumigated compression ignition engine

In this study, an LPG fumigation system was fitted to a Euro III compression ignition (CI) engine to explore its impact on performance, and gaseous and particulate emissions. LPG was introduced to the intake air stream (as a secondary fuel) by using a low pressure fuel injector situated upstream of the turbocharger. LPG substitutions were test mode dependent, but varied in the range of 14-29% by energy. The engine was tested over a 5 point test cycle using ultra low sulphur diesel (ULSD), and a low and high LPG substitution at each test mode. The results show that LPG fumigation coerces the combustion into pre-mixed mode, as increases in the peak combustion pressure (and the rate of pressure rise) were observed in most tests. The emissions results show decreases in nitric oxide (NO) and particulate matter (PM2.5) emissions; however, very significant increases in carbon monoxide (CO) and hydrocarbon (HC) emissions were observed. A more detailed investigation of the particulate emissions showed that the number of particles emitted was reduced with LPG fumigation at all test settings – apart from mode 6 of the ECE R49 test cycle. Furthermore, the particles emitted generally had a slightly larger median diameter with LPG fumigation, and had a smaller semi-volatile fraction relative to ULSD. Overall, the results show that with some modifications, LPG fumigation systems could be used to extend ULSD supplies without adversely impacting on engine performance and emissions.

Thermophoretic control of building units in the plasma-assisted deposition of nanostructured carbon films

The role of the plasma-grown nanoparticles in the plasma-enhanced chemical vapor deposition (PECVD) of the nanostructured carbon-based films was investigated. The samples were grown in the low-pressure rf plasmas of CH 4+H2+Ar gas mixtures. The enhanced deposition of the building units from the gas phase was found to support the formation of polymorphous nanostructured carbon films. The results reveal the crucial role played by the thermophoretic force in controlling the deposition of the plasma-grown fine particles.

Effective control of nanostructured phases in rapid, room-temperature synthesis of nanocrystalline Si in high-density plasmas

An innovative and effective approach based on low-pressure, low-frequency, thermally nonequilibrium, high-density inductively coupled plasmas is proposed to synthesize device-quality nanocrystalline silicon (nc-Si) thin films at room temperature and with very competitive growth rates. The crystallinity and microstructure properties (including crystal structure, crystal volume fraction, surface morphology, etc.) of this nanostructured phase of Si can be effectively tailored in broad ranges for different device applications by simply varying the inductive rf power density from 25.0 to 41.7 mW/cm3. In particular, at a moderate rf power density of 41.7 mW/cm3, the nc-Si films feature a very high growth rate of 2.37 nm/s, a high crystalline fraction of 86%, a vertically aligned columnar structure with the preferential (111) growth orientation and embedded Si quantum dots, as well as a clean, smooth and defect-free interface. We also propose the formation mechanism of nc-Si thin films which relates the high electron density and other unique properties of the inductively coupled plasmas and the formation of the nanocrystalline phase on the Si surface.

Reactive species in Ar+H2 plasma-aided nanofabrication : two-dimensional discharge modelling

Understanding the generation of reactive species in a plasma is an important step towards creating reliable and robust plasma-aided nanofabrication processes. A two-dimensional fluid simulation of the number densities of surface preparation species in a low-temperature, low-pressure, non-equilibrium Ar+H2 plasma is conducted. The operating pressure and H2 partial pressure have been varied between 70-200 mTorr and 0.1-50%, respectively. An emphasis is placed on the application of these results to nanofabrication. A reasonable balance between operating pressures and H 2 partial pressures that would optimize the number densities of the two working units largely responsible for activation and passivation of surface dangling bonds (Ar+ and H respectively) in order to achieve acceptable rates of surface activation and passivation is obtained. It is found that higher operating pressures (150-200 mTorr) and lower H2 partial pressures (∼5%) are required in order to ensure high number densities of Ar+ and H species. This paper contributes to the improvement of the controllability and predictability of plasma-based nanoassembly processes.