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By K. A. Jackson, J. D. Hunt

A general theory for the growth of lamellar and rod eutectics is presented. These modes of growth depend on the interplay between the diffusion required for phase separation and the formation of interphase boundaries. The present analysis of these factors provides a justification for earlier approximate theovies. The conditions for stability of rod and Lanlellar structures are consitleved in terms of the mechanisms by which the structure can change. The mechanisms considered include both small adjustments to the lnnzellar spacing due to the motion of lamellar faults, and catastrophic changes due to instabilities. It is concluded that stable growth occurs at or near the minimum interface undevcooling for a gizierz growth rate. The conseqrlences of the existence of a diffusion boundary layer at the interface are discussed. The experimental results for the variation of growth rate, undercooling, and Lanzellar spacing are cornpared with the theory. We believe that the theory presented in this paper provides an adequate basis for understanding the complex phenomena of lanzellar and rod eutectic growth. The growth of lamellar eutectics has been the subject of several theoretical and many experimental studies. The foundations for the theoretical work were laid by zenerl and Brandt2 in their analyses of the growth of pearlite. Zener estimated the effect cf diffusion, and took into account the surface energy of the lamellar structure. He found that the lamellar structure could grow in a range of growth rates at a given undercooling provided the lamellar spacing was appropriate for the growth rate. Since pearlite grows with only one growth rate and one lamellar spacing at a given undercooling, there is clearly an ambiguity in the theory. Zener removed this ambiguity by postulating that the growth rate was the maximum possible at the given undercooling. He predicted then that the product of the growth velocity v and the square of the lamellar spacing A should be constant, i.e., A2v = const. Brandt2 started out by assuming that the interface between the lamellae and austenite was sinusoidal. Because of this, the ambiguity encountered by Zener did not arise. Brandt was able to obtain an approximate solution to the diffusion equation, but, since he did not take into account the surface energy, his considerations are incomplete. Tiller3 applied some of these ideas to the growth of eutectics, and proposed a minimum undercooling condition to replace the maximum velocity condition used by Zener. These conditions are formally identical. Hillert4 extended the work of Zener. He found a solution to the diffusion equation assuming the interface to be plane. Taking surface energy into account, and applying Zener's maximum condition, he was able to calculate an approximate shape of the interface. Jackson et al.5 used an iterative method employing an electric analog to the diffusion problem to refine the calculation of interface shape. It was found that the interface shape calculated from a plane-interface solution to the diffusion equation was negligibly different from the exact solution. The method provided an analog only for eutectics for which the volumes of the two phases are equal, growing from a melt of exactly eu-tectic composition. There has also been considerable experimental work on eutectics, Several experimenters8-10 found that A2v is constant as predicted by Zener.1 Hunt and chilton10 demonstrated that ?T/v1/2 is also a constant for the Pb-Sn system as predicted. Lemkey et al.11have recently found A2v to be constant for a rod eutectic. In the present paper, we present the steady-state solution for the diffusion equation for a lamellar eutectic growing with a plane interface, for the general case, that is, with no restriction on the relative volumes of the two phases, and with the melt on or off eutectic composition. A similar solution is also found for a rod-type eutectic. Expressions are obtained for the average composition at the interface and the average curvature of the interface. These equations for the average composition and curvature are similar in form to those derived by Zener1 and Tiller,3 and provide a justification for some of the approximations made by these authors. The mechanisms by which the spacing in a lamellar structure can change are considered. The important mechanism for small changes in lamellar spacing involves a lamellar fault. Examination of the stability of lamellar faults leads to the conclusion that the growth occurs at or near the extremum.* The insta- bilities which can develop in a rodlike structure are also discussed, resulting in the conclusion that this structure also grows at or near the extremum. Comparison of the conditions for rod and lamellar growth permits a prediction of the surface-energy anisotropy required to produce rods or lamellae for various volume-fraction ratios. The diffusion equation predicts the existence of a diffusion boundary layer at the eutectic interface unless the eutectic has 0.5 volume fraction of each phase and is growing into a liquid of eutectic composition. This boundary layer is such as to make the composition in the liquid at the interface approximately equal to the eutectic composition. This boundary layer permits changes in composition during the zone refining of eutectics. Photographs of the eutectic interface of a growing transparent organic eutectic system have been made. Both the components of this eutectic are transparent organic compounds that freeze as metals do.12 The in-

Jan 1, 1967

By E. Teghtsoonian, K. G. Davis

Cobalt crystals of commercial purity have been tested in tension. Their resolved shear stress-shear strain curves are very similar in form to those for zinc, magnesium, and cadmium. There is an initial linear region for shear strains up to around 150 pct, the ratio of work hardening slope to shear modulus at room temperature being about 2 X x This is followed by an upturn, which is, PLASTIC deformation in metal single crystals with close-packed structures has been found strongly dependent on stacking-fault energy. The high stacking-fault energy hexagonal metals magnesium, zinc, and cadmium have been quite extensively tested, but up to now no data have been available for a comparable hexagonal metal with low stacking-fau1t energy' An however, smaller in magnitude for cobalt than for the other metals. Values for the critical resolved shear stress rise from 97 kg per sq cm at room temperature to approximately 170 kg per sq cm at -196 °C. The Cottrell-Stokes ratio is not constant either for variations in the strain rate or for temperature changes, its value decreasing with strain. investigation into the plastic deformation of cobalt, which has a very low stacking-fault energy, has therefore been undertaken. EXPERIMENTAL PROCEDURES Cobalt crystals in the form of rods 0.3 cm in diam were grown in an electron-beam floating-zone refiner at a rate of zone travel of 25 cm per hr. Details of the growing procedure are given in Ref. 1. The zoned cobalt rods had the following analysis:

Jan 1, 1963

By Olof Löfgren

PART 1 INTRODUCTION All modern pelletizing plants are equipped with either the drum or the disc circuits. Choice of one or the other circuit is not simple and it is desirable to establish a firm basis for such a task. For a meaningful and a fair comparison it is necessary to have the two systems working in parallel in the same plant with the same concentrate under the same supervision. Furthermore, the comparison has to be based on a defined green ball quality and size distribution. BALLING CIRCUITS The LKAB straight grate plant at Malmberget, Sweden, was started up in Septenber 1973. It was designed for a 2.5 Mton annual capacity and was equipped with five balling drum circuits. During the first year of operation it was found that the induration plant had the potential for a higher capacity which required increased balling capacity. For this purpose it was decided to install a balling disc circuit complete with a roll screen. The reasons for selecting a disc were space limitations and LKAB's desire to gather experience on balling disc circuits. The disc circuit was started up in 1975 and was run in parallel with the balling drums in the same plant and with the same raw material and under the same operating personnel. The necessary conditions for a comparison were thereby fulfilled. The data for the size distribution and quality of the green balls were obtained on random sampling during one year of operation, so that all the variations which appear in a commercial plant are covered.

Jan 1, 1977

By J. W. Evans

ONE possible method for the separation of hafnium from zirconium is by the vapor phase oxidation of the purified mixed chlorides. An important factor for success depends on the difference in free energies of the following reactions: ZrCl(g) + O2 = ZrO2(s) + 2C12 [1] HfCl4(g) + O2 = HfO2(s) + 2C12. [2] Prakash and Sundaram1 have calculated these values from certain data and carried out experimental work with partial success. However, their free energy values for reaction 2 diverge rather widely from other data which are presented here. The possibility of successful separation is briefly considered in the light of these alternative values. Table I shows the free energy values (?F°) for reactions 1 and 2 derived from the recent compilation of data on oxides and chlorides by Glassner.2 The corresponding values of Prakash and Sundaram for the same temperatures are also shown. The alternative values to those of Prakash and Sundaram for reaction 2 are substantially confirmed by the data of Kubaschewski and Evans" and Cough-lin' on heats of formation, entropies, and heats of vaporization. In spite of the considerable uncertainty in the hafnium data it is reasonable to suppose that the oxide-chloride free energy difference for two such chemically similar elements would not be very far apart. These figures indicate clearly that the oxidation of hafnium chloride is appreciable at all temperatures. Nevertheless, there is a significant difference between the values for reactions 1 and 2

Jan 1, 1959

By S. Wallden, R. Lindstrom

The electrolytic copper refining process is an excellent method for producing high-purity metal for electric conductors and other demanding applications. However, the process involves very high capital expenditure, especially the amounts of metals bound in the process. Efforts have therefore been made for many years to increase the production rate by increasing the current density, without impairing the quality of the copper. One of the approaches has been to diminish the polarization by mechanical means, while another was to "polish" the cathode surface by periodic brief reversals of the current. Reversed current electrolysis was first developed for electro- plating purposes and in 1952 Boliden AB and the Dept. of Electrochemistry at the Royal Inst. of Tech., Stockholm tested the method for copper refining with good results. However, no suitable electrical equipment for current reversal was then available. The thyristor-controlled silicon rectifier became available during the '60s and provided the scope for industrial application of the process and the first large-scale development was made by the Bulgarian copper refinery in Pirdop. Many copper refineries are now studying or adapting the reverse current process. Further lab and pilot investigations have been carried out at Boliden AB during the past 4 years and these were mainly aimed at studying the optimization of factors influencing the quality of copper. A production unit containing two tank sections with a total of 56 cells and equipped with a rectifier for cur- rent reversal has been installed and will be started during 1973.

Jan 1, 1973

By D. G. Westlake

Resistance was measured as a function of temperature, 77° to 350°K,for niobium with hydrogen concentrations up to 3.76 at. pct. Cooling curves exhibited a discontinuity in slope that was attributed to the initiation of hydride formation. A thermal hysteresis was explained in terms of diffusion and the effects of mechanical constraint on nucleation and growth. The heat of solution of hydrogen in saturated Nb-H solid solution was 2. 737 * 0.045 kcal per g-atom, including an unknown stress contribution. The critical ternperatures for hydride formation during cooling and for embrittlement are correlated but not coincident. This, too, has been explained in terms of mechanical constraint and stress-itlduced tratzsfomtation. Nb-H alloys undergo a ductile-brittle transition with decreasing temperature.'-3 Similar behavior has been noted for v-H.1,5 For the latter system, there is evi-dence6 suggesting coincidence of the temperature of minimum ductility and the critical temperature T, for initiation of metal hydride precipitation during cooling. A decrease in ductility due to the presence of brittle hydride particles is readily explainable. The fact that ductility begins to decrease at some temperature higher than T,4,5 has led us6 to suggest that precipitation may be strain-induced locally during tensile testing. Wood and Daniels' have reported that a plot of temperatures for 10 pct reduction in ductility vs hydrogen concentration in niobium is not coincident with, but parallels, the solvus.7,8 They believe this indicates a correlation of precipitation and embrittlement. Unfortunately, the two reported solvuses 7,8 to which Wood and Daniels refer are not in agreement with each other. Furthermore, neither solvus was determined experimentally: each was a plot of calculated solubilities. Thus. neither is highly dependable for determining whether embrittlement coincides with initiation of hydride precipitation. Longson 9 studied phase relations in the Nb-H system between 77° and 473°K by dilatometry. Comparison with metallographic observations convinced him that discontinuities in the slopes of his dilatometric plots were coincident with the initiation of hydride precipitation. Plotting the logarithm of the hydrogen concentration vs the reciprocal of the temperature at which precipitation was initiated during cooling, he obtained a straight line shown in Fig. 1. Walter and chandler,'' using X-ray techniques to detect the for mation of a second phase? have obtained three experimental points in the temperature range 295° to 338°K which fall within Longson's experimental error for this plot. A similar plotg of temperatures at which dissolution was completed during heating was a parallel line shifted toward higher temperatures. A straight-line plot was obtained, also, for the temperatures of the ductile-brittle transitions,9 but it was shifted toward still higher temperatures. Longson calculated an activation energy of 2.980 * 0.300 kcal per mole for the hydrogen embrittlement mechanism, compared with 3.180 * 0.400 kcal per mole for hydride formation. Despite this agreement, he concluded, "It seems unlikely that embrittlement results from hydride formation..." because hydrogen embrittlement was observed at temperatures above the solvus. It is our contention that embrittlement is correlated with precipitation of the hydride.6 Because only Longson has investigated Nb-H phase relations at sub-ambient temperatures, we deemed it advisable to re-determine the temperature dependence of the solubility using the resistometric technique already proven successful for the V-H system.6 Coincidence of our solvus with temperatures for embrittlement would

Jan 1, 1970

W. M. CURSE, Mansfield, Ohio.-Outside of the commercial valu-ation of the material, for what purpose does this alloy-90 per cent. of copper, 6 ½ per cent. tin, 2 per cent. zinc, and 1 ½ per cent. Lead-seem to be eminently fitted? C. P. KARR.-So far as our tests go, it would be eminently fitted for steam valves and pistons, and for the work for which 88-10-2 bronze is generally used, although for very large castings it would not be superior to 88-8-4 bronze. P. E. MCKINNEY, * Washington, D. C.-Some time hack, clue to a desire to avoid some of the objectionable features of 88-10-2 bronze, particu-larly on heavy castings, also to save tin where possible, we took up the question of a substitute for 88-10-2 bronze, where red bronze was ordinarily specified. After trying most of the mixtures, we found that when using as low a tin content as is given in this proposed composi-

Jan 12, 1919

By G. K. Burgess

J. W. RICHARDS, South Bethlehem, Pa.-I think my affections are still rather with the radiation pyrometer than the optical pyrometer, for practical use, and I wish that Prof. Burgess would use the two together, under the same conditions, using the optical as his standard, if he prefers. Then, assuming the optical emissivity which he feels is correct for the optical pyrometer, he could calculate the thermal emissivity for use with .the radiation pyrometer. If we could thus get reliable values for the thermal emissivity, we could then use the radiation pyrometer, and would avoid the use of the standard lamp, which has to be frequently calibrated for use in the optical pyrometer. It is very advisable to distinguish carefully between the terms optical emissivity and thermal emissivity. There -is considerable confusion caused by the bare statement that molten iron has an emissivity of so much, meaning by that its optical emissivity, for a light wave of a certain length; whereas what we want in the radiation pyrometer is its total ther-

Jan 4, 1917

Zinc is just now a very important metal. Its use in cartridges and shrapnel brass are in the public eye. But its uses after the war are no less important. Brass as an engineering material for electrical machin-ery, journal bearings, and plumbing fixtures takes fully 50 per cent. of the production, and its use in these lines would have been increased in the last few years but for the price. Its use for barbed wire is probably more in war time than in peace. In the composition of paints, it is becoming more and more necessary. One of the forms of pigment, litho- pone, is the base of nearly all interior wall paints; of all the sanitary enamels for bath-rooms and bath-tubs, and is now in great demand. Zinc oxide is also increasing in use for paint, and for manufacture of linoleum. When we realize that this district-Missouri, Oklahoma, Kansas and Arkansas-produces now over one-third of the zinc ore of the world, it is at once seen that a meeting where the geology, mining, concentration

Jan 6, 1917

By Charles D. Russell, L. H. Jenks, W. J. Leas

A detailed description is given of an experimental method for determining relative permeability of porous media to gas. Results are presented for natural and synthetic cores. The experimental data for two and three phase systems are compared. The reproduci-bility of the equilibrium gas saturation ii demonstrated and the effects due to a variation in rate of gas flow are discussed. An attempt is made to correlate total permeability and rock textural factors with relative permeability to gas. Capillary pressure curves obtained simultaneously with the relative permeability curves are shown to be equivalent to those obtained in conventional displacement cells. INTRODUCTION The advances in petroleum reservoir technology during the past decade have made increasingly apparent the desirability of a simple, rapid, reliable metliod for obtaining relative permeability data on small cores. Such data are needed in order to study fluid mechanics in porous media and for the more refined reservoir behavior prediction calculations now under development. The early experimental work in this field was done by Wyckoff and Botset1 who measured relative permeabilities for gas-liquid mixtures flowing through

Jan 1, 1950

By Donald M. Hausen

Microscopic evaluation of trace quantities of metalliferous phases in flotation products requires counting large numbers of particles. Particle counts of many thousands may be required for precision, but cannot be obtained practically by conventional microscopic techniques. A less tedious microscopic method for evaluating trace sulfides in mill tailings was developed for the O'okiep Mining Co. in South Africa. Hundreds of thousands of particles were evaluated by this method called "gross-counting." Gross-counting consists of counting microscopic fields rather than point-counting individual particles. Total counts are calculated by multiplying the average number of particles per field by the total number of fields examined over the entire mount. Total gross-counts range from about 20,000 particles for +200 to 100,000 or more for -400 mesh size material in lucite mounts. Sulfides and metallic particles in each field are identified and tallied along with field counts. Totals for each type of metallic particle are divided by the total gross-count to give volume percent which is corrected to weight percent by specific gravity factors.

Jan 1, 1973

By J. V. Calara, J. D. Miller

The sign of the surface potential for complex non-reactive ionic solids cannot be predicted solely from consideration of the hydration energy of gaseous ions which constitute the ionic lattice. Accurate analysis of these systems must involve the hydration energy of surface ions, which requires knowledge of the crystal structure, the identification of cleavage planes, and the calculation of binding energies of surface ions. Surface binding energies for ionic solids can be determined if the Surface Madelung Constant is known. A computational technique was developed for the calculation of Madelung Constants for infinite lattices which gives excellent agreement with the values calculated by other more complicated methods reported in the literature. Extension of this technique permits the calculation of Surface Madelung Constants and binding energies of surface ions, [Aus], for semi-infinite solids. The hydration free energy of gaseous ions, [AFh], together with the calculated binding energy of surface ions, [Aus], allows calculation of the hydration energy of surface ions,[AGh], as for the case of the ionic solid, MX: [ ]

Jan 1, 1976

By W. A. Backofen, R. L. Fleischer

AN effect of orientation on the creep behavior of aluminum at 4.2 OK has been observed. Stress relaxation was measured in a hard-type tensile device after stopping the drive. From the spring constant of the device the load-time record could be converted to strain as a function of time. The strain sensitivity was 2-10-=, and the usual creep time of 1 min normally allowed a stress drop of about 25 g per sq mm. Further details of the apparatus and sample preparation appear elsewhere.' It should be noted that neither stress nor strain were constant, so that quantitative comparison with current creep theories will not be made. Shear strain (y) as a function of time (t) was consistent with logarithmic behavior: y = A In t, where A is a constant. In some cases t was made as large as lo3 sec. In the results the quantity A divided by t (the resolved shear stress, which is the driving force for creep) is plotted as a function of strain prior to creep. The quantity A/t is thought to indicate qualitatively the ease with which dislocations can move during creep. In Fig. 1 are drawn tensile stress-strain curves and A/T-strain measurements for single crystals of three orientations: l(a) and l(b) for the maximum resolved shear-stress orientation, l(c) for an orientation 2 deg from [211], and l(d) for a [111] stress axis. The following observations were made: 1) At low strains the A/t values are nearly the same for the three orientations. 2) As strains increase, A/t drops most rapidly for [Ill.] and less rapidly for [211], while for the maximum shear-stress orientation it is constant during easy glide and drops abruptly at the termination of easy glide. 3) In stage 11, A/t values are again approximately the same for the three orientations. These observations are regarded as evidence that 1) the initiation of slip produces obstacles of essentially the same effectiveness for all of these orientations, while 2) the rate at which slip obstacles are produced before stage I1 is fully developed is strongly controlled by the amount of slip on more than one system. This second statement is consis-

Jan 1, 1961

By Hugh Douglas

ANTIMONY Antimony (Sb) has been used since the early Egyptian dynasties. Prior to World War I, total demand amounted to only 6000 to 7000 tons per year (tpy). Wartime uses and rapid rise of industrialization in the Northern Hemisphere nations have pushed world antimony use to the 78,000-tpy level. An overwhelming supply of low-cost antimonial resources in the Sino-Russian bloc countries has and will continue to have a major impact on availability and price to users outside the bloc. Table 14.4.1 shows trends in world production, United States production and consumption, and prices. Demand Antimony is used principally as an alloy in lead-based metals and other alloys. Pure metallic antimony usage is small and is confined to such areas as laboratory and electronic applications. Lead-antimony alloys are used in automobile storage batteries, chemical pumps, and pipes, tank linings, roofing material, and cable sheaths. The metal increases the hardness of lead, and, for such uses as foundry printing type, reduces shrinkage for casting and lowers the melting point. Antimonial oxides are used for ceramic purposes, white paint pigments, glass forming, textile finishing, fire retardants in military clothing, matches, and solder. Wartime applications include use as hardener for bullets, an element for tracer bullets, and ingredient for producing dense white smoke for visual markers. A small but rapidly growing use for antimony is for metallic compounds in semiconductors and thermoelectric devices. In the United States demand for antimony is about evenly divided between metallic end-use markets and nonmetallic markets. In metallic end uses, antimonial lead accounts for 27% of total metallic and nonmetallic use; in nonmetallic areas major uses are flame retardants (15%) which is the fastest growing market, plastics (13 % ), and ceramics and glass (11%). While antimony has advantages in most of its applications, there are uses in which other materials can be substituted, including: mercury, titanium, lead, zinc, chromium, tin, and zirconium in paints and pigments; tin in sheathings; calcium in battery plates; and bismuth in type metal. Supply Antimony is produced from both antimony ores and as a byproduct of smelting other ores. The principal ore mineral is stibnite (Sb2S3), along with its oxidized antimonial minerals and derivatives which occur in small discontinuous replacement veins or fissure vein implacements. Stibnite occurs in quartz-gold veins and copper-lead-zinc

Jan 1, 1976

By J. P. Batcha, J. Robert Denny

Since 1964. Newmont Mining Corp. has been engaged in a systematic research and development of computer techniques for a variety of mine planning applications. The general objective of this effort has been twofold: first, to arrive at a viable near-optimum plan for mining a particular orebody and, second, to decrease the financial investment by reducing the man-hours required for mine planning. Three major phases in the evolution of Newmont's computer techniques for mine planning are discernible. In phase one, the computer's ability to duplicate manual drafting and contour mapping was developed. Obviously, all recognized geologic characteristics had to be included, and consequently the development of computer techniques for the proper incorporation of structure, stratigraphic trends, and other geological features was a significant aspect of phase one.

Jan 1, 1970

By G. V. Cullen, N. G. Siviour

It has previously been reported that metal loadings of up to 6.8 m. eq/g. of dry coal can be obtained by contacting brown coal or lignite with ammoniacal solutions of ammine forming metals. Application of equilibrium expressions to further experimental results indicates that the extraction is by ion exchange, that the exchange is divalent-univalent for Zn, Cd and Ni, but is mainly univalent-univalent for Cu, and that to obtain reasonably uniform values for the equilibrium constants correction formulae must be applied to compensate for multiple functionality of the coal and its pH dependence in ion exchange. The results are shown to be consistent with the hypothesis that metal ammine complex cations are exchanged for protons derived from carboxyl and/or phenolic hydroxyl groups in the coal.

Jan 1, 1981

By E. S. Vargas, T. W. Chapman, Samuel W-S Tse

Models for interphase mass transfer rates in the solvent extraction of metals are developed for zinc and copper chlorides being extracted by trilsooctylamine and for copper extraction by LIX 64N from ammonia solution. The approach is to adopt a stagnant film model on which film thicknesses are known and to derive the interfacial metal fluxes for the case where all reversible reactions are fast and locally equilibrated. A growing drop mass transfer cell is used to measure extraction rates. It is found that for the cases studied the transfer rates are mass-transfer limited On the other hand, copper extraction by LIX from acidic solution exhibits slow reaction kinetics, and earlier kinetics models are confirmed. Interactions that cause varying selectivity in the simultaneous extraction of copper and zinc chlorides are demonstrated.

Jan 1, 1981

By G. Ferrara

In process and plant simulation, more reliable prediction of industrial results and evaluation of data for designing purposes may be attained by the combined use of (a) modeling and simulation of ore characteristics and (b) modeling and simulation of integrated plant operations. The systems for modeling and simulation of ore characteristics are discussed as well as the conditions in which their use may be necessary (complex structure of the ore-body and variability of the ore fed to the plant). Two examples, for coal and bauxite run-of-mine (ROM), are reported. The procedure of linking the process unit models and the approaches for the solution of integrated systems are indicated. A general-purpose program for the simulation of integrated plant operations is described, and some examples of its use are reported.

Jan 1, 1984

By P. G. Dunn

Geologic studies during development at Copper Flat were directed at acquiring the necessary information in evaluating a low-grade porphyry copper deposit. In addition to the geologic mapping and core-logging of a typical exploration project, these studies included: - careful checks on the sampling and assaying, - selection of representative samples used to establish the recoverable amounts of precious metals in the ore, - examination of underground workings driven to provide samples both for metallurgical testing and for assay comparison, - evaluation of plant site and waste dump areas as non-material, including a placer examination of the tailings disposal area, and location of an adequate water supply. All these investigation were carefully documented to provide the necessary data both for the engineering design and, more importantly, for the feasibility studies required for successfully financing the project.

Jan 1, 1985

By C. S. Brooks

Several of the commonly used methods for deter-mination of effective grain densities of minerals have been evaluated for accuracy and precision, and their applicability to various types of petroleum reservoir minerals tested. Consideration was given to the effect of consolidation, swelling clay, and wettability on these grain-density determinations. Procedures with helium displacement, a modified low-pressure Boyle's law porosimeter, and liquid displacement (water, n-decane, and n-octanol) were tested. The helium-displacement procedure was used primarily as an independent reference for which the effects of fluid-solid interaction, e.g., adsorption and wettability, were negligible. The procedures with the Boyle's law porosimeter and with liquid displacement are the methods in common use. Minerals investigated included calcite, West Texas limestone core samples, California sandstone core samples, and Wyoming bentonite. The number of samples tested, while not large, was adequate to permit application of statistical methods. Grain-density measurements on calcite (Iceland spar) provided a basis of comparison for the accuracy and precision of the procedures under investigation for a material with a high degree of chemical and physical homogeneity and for which fluid-solid interactions were at a minimum. Liquid-displacement procedures (water or n-decane) provided the greatest reliability and precision for measurement of the grain densities of the limestone tested. Gas-displacement procedures (helium or Boyle's law porosimeter) provided the greatest reliability and experimental convenience, if not the greatest precision, for the measurement of the grain densities of the swell- ing clay, Wyoming bentonite, and the shah sandstones which -contained appreciable amounts of swelling, in-terstitial clays. These experiments were designed to evaluate the applicability of the grain-density procedures in common we to some of the less tractable minerals—tight limestones, shaly sandstones, and swelling clays. The results should provide a useful basis for a selection of the method most suitable for application to the various petroleum reservoir minerals encountered and especially for use in the estimation of formation porosity. INTRODUCTION These experiments were undertaken to evaluate the accuracy and precision of several commonly used methods for determination of effective grain densities of minerals, and to test their applicability to various types of petroleum reservoir minerals. Consideration was also given to the effect of consolidation, clay, and wettability on these grain-density determinations. Procedures used included measurements with helium displacement, with a modified low-pressure Boyle's law porosimeter, and with liquid displacement (water, n-decane, and n-octanol). The minerals investigated included calcite, West Texas limestone core samples, California sandstone core samples, and Wyoming bentonite. The accurate determination of the porosity of petroleum reservoir formations, in particular those of low porosity, has received much attention. Both bulk-volume and grain-volume measurements necessary in the evaluation of porosity have been examined by many investigators with the objectives of improving both the accuracy and the precision of these determinations. In this investigation statistical criteria for selection of the most reliable and suitable procedure for use with a given type of mineral are demonstrated. The grain-volume measurement procedures appear to be the most susceptible to improvement.

Jan 1, 1958