Changes in portlandite morphology with solvent composition: Atomistic simulations and experiment

There is a special reason for reviewing this book at this time: it is the 50th edition of a compendium that is known and used frequently in most chemical and physical laboratories in many parts of the world. Surely, a publication that has been published for 56 years, withstanding the vagaries of science in this century, must have had something to offer. There is another reason: while the book is a standard fixture in most chemical and physical laboratories, including those in medical centers, it is not as frequently seen in the laboratories of physician's offices (those either in solo or group practice). I believe that the Handbook can be useful in those laboratories. One of the reasons, among others, is that the various basic items of information it offers may be helpful in new tests, either physical or chemical, which are continuously being published. The basic information may relate

Handbook of Chemistry and Physics

The flow of homogeneous fluids through porous media: analogies with other physical problems

Porosity plays a clearly important role in geology. It controls fluid storage in aquifers, oil and gas fields and geothermal systems, and the extent and connectivity of the pore structure control fluid flow and transport through geological formations, as well as the relationship between the properties of individual minerals and the bulk properties of the rock. In order to quantify the relationships between porosity, storage, transport and rock properties, however, the pore structure must be measured and quantitatively described. The overall importance of porosity, at least with respect to the use of rocks as building stone was recognized by TS Hunt in his “Chemical and Geological Essays” (1875, reviewed by JD Dana 1875) who noted:

> “Other things being equal, it may properly be said that the value of a stone for building purposes is inversely as its porosity or absorbing power.”

In a Geological Survey report prepared for the U.S. Atomic Energy Commission, Manger (1963) summarized porosity and bulk density measurements for sedimentary rocks. He tabulated more than 900 items of porosity and bulk density data for sedimentary rocks with up to 2,109 porosity determinations per item. Amongst these he summarized several early studies, including those of Schwarz (1870–1871), Cook (1878), Wheeler (1896), Buckley (1898), Gary (1898), Moore (1904), Fuller (1906), Sorby (1908), Hirschwald (1912), Grubenmann et al. (1915), and Kessler (1919), many of which were concerned with rocks and clays of commercial utility. There have, of course, been many more such determinations since that time.

There are a large number of methods for quantifying porosity, and an increasingly complex idea of what it means to do so. Manger (1963) listed the techniques by which the porosity determinations he summarized were made. He separated these into seven methods for …

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Characterization and Analysis of Porosity and Pore Structures

The evolution of porosity in shales with increasing maturity was examined in a suite of five New Albany Shale samples spanning a maturity range from immature (vitrinite reflectance, Ro 0.35%) to postmature (Ro 1.41%). Devonian to lower Mississippian New Albany Shale samples from the Illinois Basin used in this study contain marine type II kerogen having total organic carbon contents from 1.2 to 13.0 wt. %. Organic petrology, CO2 and N2 low-pressure adsorption, and mercury intrusion capillary pressure techniques were used to quantify pore volumes, pore sizes, and pore-size distributions. Increasing maturity of the New Albany Shale is paralleled by many changes in the characteristics of porosity. The total porosity of 9.1 vol. % in immature New Albany Shale decreases to 1.5 vol. % in the late mature sample, whereas total pore volumes decrease from 0.0365 to 0.0059 cm3/g in the same sequence. Reversing the trend at even higher maturity, the postmature New Albany Shale exhibits higher porosity and larger total pore volumes compared to the late mature sample. With increasing maturity, changes in total porosity and total pore volumes are accompanied by changes in pore-size distributions and relative proportions of micropores, mesopores, and macropores. Porosity-related variances are directly related to differences in the amount and character of the organic matter and mineralogical composition, but maturity exerts the dominant control upon these characteristics. We conclude that organic matter transformation due to hydrocarbon generation and migration is a pivotal cause of the observed porosity differences.

Porosity of Devonian and Mississippian New Albany Shale across a maturation gradient: Insights from organic petrology, gas adsorption, and mercury intrusion

A review of salt scaling: II. Mechanisms

A review of salt scaling: I. Phenomenology

The uptick in hydrocarbon production from shale in the United States has generated interest in metrics of unconventional reservoir quality, like permeability. We use conventional gas sorption to characterize shale microstructure, which provides insight on the features that govern mass transport. The gas sorption data are analyzed to determine the surface area, A S (m2/g), and pore volume, V P (cm3/g) of 30 samples from basins across North America. With this information, we quantify the effect of composition and thermal maturity on shale microstructure. In particular, we find that the specific surface area of the organic component evolves from ∼50 m2/g total organic carbon (TOC) in immature shale to ∼500 m2/g TOC for regions that produce dry gas. The increase in A S is accompanied by an increase in V P and concomitant decline in average pore size (e.g., r H = 4 V P/ A S). We contend that the latter is due to the development of nanometer-sized pores in kerogen as it is converted to mobile hydrocarbon which is ultimately expelled. This hypothesis is supported by similar measurements on companion samples after bitumen extraction or combustion, which underscore the intimate spatial association of petroleum and kerogen. Coupled with information on accessibility to the porosity garnered by varying the particle size, these results establish a clear link between organic matter, thermal maturity, and reservoir quality in unconventional shale systems.

Geochemical controls on shale microstructure

Over the past 60 years, concrete infrastructure in cold climates has deteriorated by “salt scaling,” which is superficial damage that occurs during freezing in the presence of saline water. It reduces mechanical integrity and necessitates expensive repair or replacement. The phenomenon can be demonstrated by pooling a solution on a block of concrete and subjecting it to freeze/thaw cycles. The most remarkable feature of salt scaling is that the damage is absent if the pool contains pure water, it becomes serious at concentrations of a few weight percent, and then stops at concentrations above about 6 wt%. In spite of a wealth of research, the mechanism responsible for this damage has only recently been identified. In this article, we show that salt scaling is a consequence of the fracture behavior of ice. The stress arises from thermal expansion mismatch between ice and concrete, which puts the ice in tension as the temperature drops. Considering the mechanical and viscoelastic properties of ice, it is shown that this mismatch will not cause pure ice to crack, but moderately concentrated solutions are expected to crack. Cracks in the brine ice penetrate into the substrate, resulting in superficial damage. At high concentrations, the ice does not form a rigid enough structure to result in significant stress, so no damage occurs. The morphology of cracking is predicted by fracture mechanics.

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John J. Valenza

Papers

A review of salt scaling: II. Mechanisms

A review of salt scaling: I. Phenomenology

Geochemical controls on shale microstructure

Mechanism for Salt Scaling

New Methods to Measure Liquid Permeability in Porous Materials