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By Joseph B. Darby, Paul A. Beck

IN isothermal sections of several ternary systems, the a-phase was found1 to extend in the form of a relatively narrow elongated field, connecting the U-phases that are present in the adjoining binary systems. This was interpreted in accordance with the conception that the U-phase is an electron compound and the ternary U-phase fields were shown in several systems' to extend approximately in the direction of constant average d-shell electron vacancy number per atom. ' However, in the various isothermal sections of the Fe-Cr-Mo system" the ternary a-phase field was

Jan 1, 1958

By R. D. Joseph

This report deals exclusively with roof-fall accidents that occurred during 1955 and 1956 in both anthracite and bituminous-coal mines throughout the United States. The report stems from a cooperative study conducted by the Bureau of Mines and the Roof-Control Committee of the Coal-Mining Section, National Safety Council. The study includes an analysis of individual accident reports, sets forth the measurable factors, and compares such factors with a representative sample of average data from 39 anthracite mines and 117 bituminous mines (appendixes A and B). Particular emphasis is placed on fatal roof-fall accidents with respect to their causes, locations, and the methods of support used at the point of occurrence. INTRODUCTION The purpose of the report is to classify all measurable details of the occurrences of roof-fall fatalities so that the material presented will assist those promoting safety and will serve as a manual for those whose principal duty is inspection of mines.

Jan 1, 1958

By M. P. Tixier, M. Gondouin, G. L. Simard

In the quantitative interpretation of the SP logs, the electrochemical component is generally taken equal to — K log Rm /Rw where K has the theoretical value corresponding to solutions of pure sodium chloride. This method may be misleading when relatively large quantities of salts other than NaCl are present in form-rrtion waters—as is generally the case for low salinities —or in gyp-base muds. In such cases recourse is made in the field to changing the K value or to adding a correction term to the equation on the basis of local experience. An investigation has been made in the laboratory of the influence of HCO3, SO4=, Ca++, and Mg++ on the amplitude of the SP deflection, which included in par-ricular determinations of the activity coefficients of Ca++ and Mg++. The theory, the experimental techniques and a tentative method for applying the results are described. So far, applications to actual field cases where chemical analyses of waters were available have provided an excellent confirmation of the proposed method. The case of the SP in very salty brines is also considered and it is shown that the use of activity data for sodium gives satisfactory results. HISTORICAL In early times of electrical logging, the SP curve was used exclusively as a tool for the location of permeable beds and the definition of their boundaries. Later, with the introduction of methods of quantitative analysis, attention was called to the possibility of deriving from the SP log some information on the formation water resistivity, which constitutes one essential element for the computation of water saturation from log data. The first laboratory experiments' in 1932 had shown that, as a result of electrochemical phenomena arising at the contact of the niud and the formation, the amplitude of the deflection of the SP curve was, at least partly, a function of the salt concentration of interstitial water and accordingly of its resistivity. It was indicated that the amplitude of the electrochemical component of the SP should be equal to K log R1/R2, R1 and R2 being the resistivities of the mud and of the formation water respectively. However, the exact value of the K coefficient was not determined at that time because the surface clay used for a laboratory model was far from an ideal shale membrane. Consequently, the way was not yet open towards quantitative interpretation. In the early forties, Tixier reported2, on the basis of field log observations, the following equation for the case of NaCl solutions, SP = -71 log f1c1/f2c2, c1 and c2 being the concentrations and f1, f2 the mean activity coefficients. The local variations observed in the empirical values of K, chiefly in the Rocky Mountains, led him to advance the opinion that, besides the relative amounts, the nature of the salts present in the solutions had a bearing on the magnitude of the SP. At about the same time Mounce and Rust- ad published laboratory results which emphasized the part played by the shale in the generation of the SP. On the basis of laboratory tests and theoretical considerations, Wyllie in 1948' published the following equation of the electrochemical SP for the case of NaCl solutions, SP= - 71 log (a1)m/(a2)m

Jan 1, 1958

By W. J. Romanow

RECENT papers by Williams, Sherwood, and Boothby,1 Seybolt et al.2 Heikes; and Roberts4 attest to the increasing importance of the hexagonal ferromagnetic compound MnBi. Since the magnetic properties of MnBi crystals are highly anisotropic, it is useful and necessary to have appropriate aids for determining their orientations—a (00.1) standard stereographic projection and a corresponding table of crystallographic angles for this structure. The tables of crystallographic angles for the hexagonal system available in the literature5 are computed for c/a ratios greater than that of MnBi and cannot satisfactorily be used to find the crystallographic angles of MnBi. A table of angles between the crystallographic planes (HK.L) and (hk.1) was calculated for MnBi from the formula0 F=are cos Hh+Kk+ 1/2(Hk+hK) + 3/4 (a/c)2Ll/v(H2 + K2 + HK + 3/4 (a/c)2L2) (h2+ k2+hk + 3/4 (a/c)2l2) on an IBM Type 650 Magnetic Drum Data Processing machine. The lattice constants used are listed in Table I and are those determined by Willis and Rooksby7 at 20°C. More recently published values obtained by both X-ray and neutron diffraction"' show no difference from these significant to the calculation. From the crystallographic angles between the basal plane (00.1) and the general plane (hk.1) in Table I, an (00.1) standard stereographic projection was made for MnBi which is shown in Fig. 1. Acknowledgments The author wishes to thank R. G. Treuting and J. N. Hobstetter for their technical assistance, and Miss D. P. Booth for programing the IBM machine for the calculations. He appreciates the opportunity to read the paper of B. W. Roberts of General Electric Co. prior to its publication. References 1H. J. Williams, R. C. Sherwood, and 0. L. Boothby: Bulletin Amer. Physical Soc., 1956 vol. 1, p. 132. 2 A. U. Seybolt, H. Hangen, B. W. Roberts, and P. Yurcisin: AIME Trans., 1956, vol. 206, p. 605: Journal oF Metals, May 1956. 3R. R. Heikes: Physical Review, 1955, vol. 99, p. 446. .B. W. Roberts: A Neutron Diffraction Study of the Structures of Manganese B.W.Roberts:ANeutronDiffractionBismuthide, Physical. Review, 1956, vol. 104, p. 607. 5 A. Taylor and S. Leber: AIME Trans., 1954, vol. 200, p. 190; JouRNal of Metals February 1954. « C. S. Barrett: Structure of Metals, 2nd Ed., p. 635. McGraw-Hill Book Co. New York and London, 1952. 7B. T. M. Willis and H. P. Rooksby: Proceedings Physical Soc., London, 1954, vol. 67B, p. 290.

Jan 1, 1958

By V. I. Purcell, S. C. Sun. R. E. Snow

A study including effects of 7) pH value, 2) fatty acid collector, 3) fuel oil, 4) interfering ion, 5) particle size, and 6) operational variables. Test results indicate feasibility of fatty acid flotation under certain restrictive conditions. FATTY acids have been used as standard collectors for floating the matrix1-8 but not the leached zone phosphate ores. After a series of investigations, Davenport9 and Tarbutton10 concluded that the Florida leached zone ores tested were unamenable to fatty acid flotation and must be upgraded by floating the siliceous gangue with Armac-T as collector. The cationic flotation was estimated11 to cost almost ten times as much as a fatty acid process that would ideally give the same flotation grades and recoveries of phosphates. Mineralization: Extensive deposits of leached zone aluminiferous phosphate occur in Florida."= The ore sample used for this work was obtained from the Virginia-Carolina Chemical Corp., Clear Springs area, Florida. The ore is a potential source of uranium and aluminum as well as phosphorus. Since the uranium and the recoverable aluminum are contained in some of the phosphate minerals, an upgrading of phosphate results in a corresponding enrichment of both uranium and aluminum. The phosphate minerals in the ore are primarily pseudo-wavellite, millisite, and carbonate fluorapatite, with a minor amount of wavellite. Quartz and clay are the common gangue minerals, quartz being predominant. Others present in small amounts are ilmenite, hydrated iron oxides, staurolite, monazite, and zircon. Experimental Procedures: After being dried to less than 1 pct surface moisture the material was dry-ground in a Hardinge conical ball mill to —6 mesh. The ground product was classified into 6/20, 20/200, and —200 mesh size fractions. On the basis of Table I, the coarse and fine size fractions were considered as phosphate concentrates, because of their high phosphorus contents. In contrast, the 20/200 mesh fraction, which was low in phosphorus, was used as the flotation feed. All the flotation tests, unless otherwise stated, were performed in a laboratory Fagergren machine under the following conditions: 1) 400 g of solid feed for each test, 2) 2000 rpm impeller speed, 3) 8.9 pH and 4-min conditioning, and 4) 3-min flotation. The procedure used for the quantitative bubble pick-up tests has been described previously.18

Jan 1, 1958

By L. M. Pidgeon, P. G. Thornhill

A LTHOUGH a considerable number of experi--ti mental investigations dealing with the roasting of sulfide minerals have been reported in the past,'"" the behavior of the single roasting particle does not appear to have received the attention it perhaps deserves. This is understandable in that the natural sulfide counterpart of the slab or sheet of metal normally used in high temperature oxidation studies is difficult to obtain and prepare, and is, in most cases, virtually impossible to maintain in one piece at roasting temperatures. The employment, on the other hand, of static aggregations of small particles in masses great enough to permit evaluation of the roasting reactions by means of thermobalances or gas analyses introduces other complications, such as localized overheating, sintering, and variable gas-solid contact. In this investigation a compromise between the above extremes was attempted. Closely sized (e.g., 30 to 40 mesh) particles of natural sulfide minerals were isothermally roasted, out of contact with one another, in an air-swept system. The progress of the roasting reactions was followed by examination in polished section of the treated particles and by X-ray and chemical analysis of their residual sulfide kernels. In this way some conclusions respecting the mechanism of roasting reactions were drawn. Roasting Furnace—The vertical tube furnace used for roasting the sulfide particles had a heated zone 10 1/2 in. long in which four retractable light gage stainless steel trays were suspended. Each tray, and an accompanying baffle, was mounted on a 2 in. lengtn of 3/8 in. stainless steel tubing. These assemblies were axially suspended on a 30 in. length of ¼ in. stainless tubing, by means of which they could be lifted from the hot zone to a water-cooled brass chamber at the top of the furnace. Since each tray unit could slide freely on the 30 in. tube, any desired number of the trays could be retained in the cooling chamber by the manipulation of a horizontal plunger during a momentary withdrawal of the four trays from the hot zone. Although three heating coils, each equipped with variable external resistance, were employed, it was found impossible to avoid a drop of 10o to 15oC between the temperature at the top tray and that of the lower three. Consequently, only the bottom three trays were used for roasting. Temperature readings inside the furnace were made by means of a thermocouple inserted down the tray support tube at tray levels, and a separate thermocouple, inserted adjacent to the middle heating coil, was connected to a Micromax temperature control unit. Experimental Method—The sulfide minerals were obtained in a form as free as possible from gangue and contaminating sulfides, and were crushed and screened to the required particle size range. The tray assembly was kept inside the furnace during the heating-up period and, when a steady temperature had been reached, the trays were withdrawn. Each tray was sprinkled with from 200 to 500 mg of the sulfide grains, and the assembly was lowered into the furnace without delay in order to minimize the time required to achieve the operating temperature. The furnace top was then clamped into position and the thermocouple inserted down the center tube to the required level. It was found that, when this procedure was used, the trays achieved their former temperature within 2 min, after which time the flow of dry air was begun at a rate of 1 liter per min, and timing of the run was started. At the required intervals of time the trays were successively withdrawn from the hot zone and stored in the cooling chamber by means of the retention plunger. On completion of the run the treated particles were removed from the trays to be set aside for examination. The roasted particles were mounted in Lucite on a Buehler press Operating at a temperature of 140°C

Jan 1, 1958

By Jack L. Henry, R. D. Holliday

GASEOUS products of an aluminum reduction cell consist mainly of carbon dioxide and carbon monoxide. Sulfur dioxide, hydrogen fluoride, and hydrogen sulfide have also been conc~usively identified. Carbon tetrafluoride has been observed only during the period when the anode is polarized.' This period, known as anode effect, occurs when the alumina content of the molten bath approaches depletion.= Increased resistance at the polarized anode results in a voltage rise from a normal 5 volts to as

Jan 1, 1958

By D. E. Wolfson, D. A. Reynolds, F. W. Smith

IN 1948 the U. S. Bureau of Mines began a three-phase program to evaluate the extent and quality of U. S. coking coal: 1) a factual appraisal of known recoverable reserves in beds of mineable thickness, 2) a study of preparation characteristics, and 3) a study of carbonization properties. A previous paper presented the methods used in assessing reserves.' Although this investigation is only partly completed, data on coking properties of the Pittsburgh district coals are now available. The results are presented in this article. When coals are selected for manufacture of metallurgical coke more factors must be considered than for any other major use, as no basic industry requires coal of such high quality and uniformity. This is particularly true in the Pittsburgh district, where blast furnace practice is based on use of cokes from high quality coals. Although it is true that inferior coals are carbonized in other industrial areas, both here and abroad, the Pittsburgh coals are the best economically obtainable in the required tonnages, even though they are not the most desirable for metallurgical use. In the general evaluation of suitability of coals for coke making, particular attention is given to: 1) reserve, 2) ash and sulfur content, 3) inherent properties of forming strong, well fused coke, 4) expanding characteristics, and 5) blending properties. Items 1 and 2 are covered in detail in the first two phases of the survey, and coking behavior is considered in items 3 through 5. Problems is Coal Evaluation: Although not all coal beds of immediate or potential use to the coking industry in the Pittsburgh area have been tested for their coking properties, enough tests have been made to permit certain generalized statements. Virtually all the coals that will be used in this district are from the Appalachian region, and except for high oxygen coals from outcrops or stripping operations, they are coking coals. Hence the evaluation problem is not so much that of distinguishing between coking and noncoking coals as attempting to measure quantitatively differences in the coking and expanding properties of the better coking coals. Quantitative differentiation between good coking coals, is complex, since differences in their coking abilities are frequently of about the same magnitude as the precision of the test. Small-scale tests are generally unsuitable for measuring these slight differences, and there has been gradual acceptance of pilot-scale tests. Test Methods Employed: All the data reported here were obtained in two units known as the Bureau of Mines-American Gas Association (BM-AGA) carbonization apparatus and the sole-heated expansion oven. The BM-AGA unit, which consists essentially of a cylindrical steel retort about 18 in. diam and 26 in. high, carbonizes enough coal (180 lb) to allow evaluation of the coke by standard methods of the American Society for Testing Materials. The BM-AGA carbonization procedure and methods of testing the gas, liquid, and solid products have been described.' Expanding characteristics of the coals were determined in the sole-heated expansion oven," wherein the coal charge, heated from the bottom only, is carbonized under a constant applied force and the linear expansion or contraction is measured. Although results in this oven have never been quantitatively correlated with the expansion behavior of coals in conventional slot ovens, they are useful in assessing expansion behavior. In this report discussion will be confined to results obtained from these pilot-scale units, although the following data are available for most coals: proximate and ultimate analyses, free swelling index, agglutinating value, and plasticity. Sources of Coals Tested: In selection of coals for coke manufacture, economic considerations are as important as quality, and each coke plant balances these two factors to meet requirements of the most satisfactory coke at lowest price. Although these economic factors may in some instances outbalance small differences in coke quality, they are usually specific to each coke plant and cannot be given in any general statement. Recognizing that coal and plant operating costs are beyond the scope of the survey, the USBM evaluates the coking quality of various coals without regard to their competitive economic status. For the purpose of this article, coals of interest to the Pittsburgh district are arbitrarily defined as

Jan 1, 1958

By W. C. Lacy

A WIDE variety of metalliferous deposits in Peru shows a close and consistent relationship to intrusive and extrusive igneous rdcks. This relationship furnishes a clue to the comp(osition of ore-bearing fluids and to the timing in separation of these fluids from differentiation magma Conclusions presented here are based on ten years' study of a large number of metalliferous deposits in Peru. The most important of these areas are shown in Fig. 1. The structural relationship of meta1 mineralization to the intrusive series and of the members of the series to each other can be illustrated by three examples: I The well described Cerro de Pasco (Ref. 1, p. 160) sulfide mass shown in Fig. 2 is localized along the ' eastern contact of an agglomerate-filled crater. Quartz-monzonite porphyry and related intrusive breccias, which in places border the pyrite mass On west, are replaced by the pyrite and cut by later transverse vein structures. Late unmineralized but

Jan 1, 1958

By V. N. Mackiw

IN the process employed by Sherritt Gordon Mines Ltd. for the production of metallic nickel, a sul-fide concentrate is leached with ammonia and air under pressure. Following the removal of iron, copper, and other impurities, there remains a purified solution having the following analysis: 40 to 50 g per liter Ni, 200 to 400 g per liter (NH4)2 SO 4, and 20 to 30 g per liter NH3. Metallic nickel is reduced from this solution by hydrogen under pressure at 300' to 350°F in mechanically agitated autoclaves. A catalyst, ferrous sulfate, is required to initiate the first reduction. After the reduction, the depleted solution is discharged, leaving the metallic nickel in the autoclave. The nickel produced, being in a finely divided form, is used as a catalyst for the reduction of the next batch of solution. Upon repeated use the metallic nickel particles increase in size and become more compact, resulting in the production of a powder with higher apparent density. For this reason, each reduction is termed densification. Finally, when the burden of metal powder in the autoclave becomes too great to obtain effective agitation, both powder and depleted solution are discharged. The autoclave is then filled with fresh solution, ferrous sulfate catalyst added as before, and a new cycle started. The operation is described in earlier publications.1-6 A comprehensive historical review of the reduction of metals from solutions in general was given in a paper by Schaufelberger.7 The experimental data presented in this paper were taken from the work done in the Research Laboratory of Sherritt Gordon Mines Ltd. in Ottawa during the development of the process in 1951 and 1952. The results of the work were tested on a pilot plant scale in Ottawa in the period 1952 to 1953. Following laboratory and the pilot plant studies a commercial process has operated successfully since 1954 in the Nickel Refinery of Sherritt Gordon Mines Ltd. in Fort Saskatchewan, Alberta. General Experimental Technique The experiments were carried out in a stainless steel, 1-gallon, agitated autoclave designed and manufactured by Autoclave Engineers Inc. The inside dimensions of the vessel were 5 in. diam and 12 in. depth. The stirrer consisted of a 1/2 in. diam shaft 11 in. long fitted, with an axial flow type impeller (three blades bent to throw downwards) and a radial flow

Jan 1, 1958

By James Westfield

Uranium activity has introduced a comparatively new hazard to United States mining. In addition to the hazards common to all mines, uranium mines have a complex health problem of radiation damage. Like many new processes, radiation and nuclear energy can be made to serve man in many useful ways when properly understood and handled; but, like fire, gases, and electricity, their potential dangers must be known and respected, and appropriate precautions must be taken or death may result. Since 1950 the Public Health Service has been conducting basic investigations on exposure to radon and its daughter products and the effect of exposure upon the health of miners in uranium mines of the Western States. The Bureau of Mines assisted in several of these investigations, especially in mines on Indian lands. The studies have shown that a serious health hazard exists from radioactive exposure that might cause lung cancer if continued over a number of years. The Public Health Service report, Control of Radon and Daughters in Uranium Mines and Calculations on Biologic Effects,6/ shows that 55 percent of the uranium mines employing 64 percent of the miners had atmospheric concentrations more than five times the working level now accepted as reasonably safe for industrial exposures. Extensive control measures are necessary to reduce these concentrations to the suggested working level of less than 300 micromicrocuries of total radon daughter products per liter of air.

Jan 1, 1958

By W. R. Bendy

GRINDING is a large and costly part of Portland cement manufacture. Prior to clinkering in the rotary kiln, raw materials are ground to a fineness of 80 to 90 pct passing 200 mesh. Then, after burning and cooling, the resulting clinker is ground to about 92 pct passing 325 mesh. In the cement industry the most favored method of grinding has always been by impact and attrition of a ball charge in a rotating mill. Other types of mills, in which materials are ground between die rings and rollers, or between die rings and large balls, are sometimes used for single-stage grinding and often for preliminary grinding followed by grinding in ball-type mills. Their efficiency is usually high, but maintenance and repair costs are high also, and the ball-type mill continues to be the most widely used. Together with 4 pct gypsum to retard setting time, the kiln run clinker—consisting of hard, semi-fused lumps that may have been crushed to — 1/2 in.—is ground to a Blaine surface area of 3000 sq cm per gram and about 92 pct passing 325 mesh. Approximately 32 kw-hr per ton, or 6 kw-hr per 376-1b barrel, are consumed in the grinding mills alone, not counting auxiliaries. Open Circuit Clinker Grinding: Many early clinker grinding plants employed two-stage, open circuit grinding. Comparatively short mills of large diameter, loaded with balls 4 in. and smaller, first reduced the clinker to 95 pct passing 14 mesh. Tube mills of smaller diameter and greater length, loaded with balls 11/4 in. and smaller, carried out the fine grinding operation. An early development was to assemble two or more stages of grinding in a single mill having two, three, or four compartments separated by division heads. There were difficulties in balancing the compartments, but compartment mills were popular in the 1920's because the layout was simple and there were no elevators and conveyors. Oversize Particles: Open circuit mills, whether separate ball and tube mills or compartment mills, always encountered the problem of tramp oversize in the product. A small percentage of clinker survived passage through the first grinding stage as particles—perhaps 1/16 in. diam—that were too large for the smaller balls in the following stages to reduce to —200 mesh. When the feed rate was lowered to reduce tramp oversize, there were serious losses in grinding efficiency. Many ingenious designs were perfected to incorporate perforated screen plates or wire mesh screens in the ball mills or in the first compartments of compartment mills. Their purpose was to prevent mate: rial passing out of the first stage until it was small

Jan 1, 1958

By F. V. Lenel, M. V. Rose, A. B. Backensto

WHEN aluminum-flake powders are compacted and hot pressed and the resulting compacts are extruded or hot forged, a group of materials with unique properties is obtained. Not only do they exhibit high room-temperature strength of the order of some of the aluminum alloys, but they maintain this strength even after prolonged heat treatment at temperatures up to 900°F. Moreover, their strength decreases much less with increasing temperature than that of aluminum alloys of comparable room-temperature properties. Irmann,'" who discovered and first described this group of materials, which was called SAP, showed that the room-temperature mechanical properties of the extrusions are a function of the oxide content of the powders and therefore the oxide content of the extrusions. The higher the oxide content, the higher are their tensile strength, yield strength, and hardness, and the lower their ductility. Lyle" investigated the relationship between mechanical properties at elevated temperature and oxide content in the course of the development work of the Aluminum Co. of America on materials, called APMP, similar to those developed in Switzerland. He found that at 600 °F, just as at room temperatures, tensile strength and yield strength increase and elongation decreases with oxide content. A careful study of his data (Fig. 3, loc. cit.) shows, however, that the scatter is more pronounced than at room temperature. Gregory and Grant's data on the creep5 and stress-ruptureb roperties of the one commercial grade of the Swiss SAP and the various grades of APMP indicate that creep strength and stress to rupture also generally increase with increasing oxide .content. Ever since this new group of materials was discovered, attempts have been made to explain the mechanism by which they obtain their high room-temperature and particularly their elevated-temperature strength. In most of the attempts the new material was considered as a dispersion of aluminum oxide particles in a matrix of aluminum. Ir-mann, Von Zeerleder, and Rohner' applied a theory on dispersion strengthening developed by Rohners to the flake-powder extrusions. According to this theory the elastic limit S, of a dispersion would depend upon the average distance between the dispersed particles L according to the equation: 2 E ¦ a where E is the modulus of elasticity and a the distance between nearest neighbors in the lattice of the matrix material. Irmann and co-workers assumed

Jan 1, 1958

By Norman Lamont

The evaluation of certain reser-voir properties, such as porosity and fluid saturation, from electrical well surveys has been widely accepted in petroleum engineering. Various investigators have established relationships between these properties and certain parameters which affect the response of the electrical log. Among these are the resistivities of the mud, its filtrate, and its filter cake. In 1949, Patnode1 established a relationship between the resistivities of the mud and filtrate. The well logging service companies have contributed relationships for the mud-mud cake resistivities2,3 These have been valuable since it was the practice to measure only resistivity of mud at the well site. During the mid-1940's the industry began drilling wells with oil-emulsion drilling fluids. These were conventional aqueous muds with a dispersed oil phase. Since 1950, oil-emulsion muds have been used on an increasing number of wells each year. However, the practice of measuring only the resistivity of the mud at the well site has continued, and the mud filtrate and mud cake resistivities have been determined by the above-mentioned relationships. Service companies are now equipped to measure all three resistivities at the well site. An investigation was conducted on the resistivities of oil-emulsion muds, mud filtrates, and mud cakes to determine if these values conformed to the relationships for aqueous muds. TYPES OF MUDS Fifty-one oil-emulsion mud samples were prepared in the laboratory following a standard manual' published by a leading mud company. The diesel oil in the samples varied from 5 to 50 per cent, the majority of the samples being in the 10 per cent region. The basic aqueous mud types which were converted to oil-emulsion muds were commercial clay and bentonite muds, low pH and high pH, caustic-quebracho treated muds, and lime treated muds. The emulsions were stabilized by dispersed solids, lignins, lignosulfo-nates, sodium carboxymethyl cellulose, or sulfonated petrolatum. It is worthy of note that after a quiescent period of two weeks at room temperature all samples, regardless of emulsifying agent, remained stable. The make-up water for the muds was from the laboratory tap. Resistivities were varied by the addition of table salt to the water. A range of mud resistivities from 0.44 to 3.9 ohm-m was obtained in this way. Twenty-three field muds were tested. These covered the same range of mud types as did laboratory muds. Oil provinces of the Gulf Coast, South Texas, West Texas, Oklahoma, Montana, and Canada were represented. MUD TEST PROCEDURE Each mud was tested for density, viscosity, pH, and filter loss by standard testing techniques. The resistivity measurements were obtained with a Schlumberger EMT meter. This meter required small volumes of sample, e.g., 2 mm. Filtrate was obtained from a Standard Baroid fil-ter press at the end of a 30-minute test. The filter cake from the same test was used for cake resistivity measurements. Mud, filtrate, and cake samples were heated to 100" F in a constant temperature water bath prior to measurement of resistivities. RESULTS The relation between mud resistivity (Rm) and mud filtrate resistivity (Rmf) is shown in Fig. 1. The solid line represents an average for the data. The equation of this line is Rmf =0.876 (Rm) 1.075 . . (1) Arbitrary limits, indicated by the dashed curves, have been set. The majority of the data falls within these limits, but some points do lie outside the limits. The approximate equation Rmt = 0.88 Rm , . . . . (2) will give satisfactory results within these limits. The data on mud cake resistivity Rmc is shown in Fig. 2. The solid line is an average for the data. The equation for the line is Rmc = 1.306 (Rm)0.88 The dashed lines are arbitrary limits on the data. Within these limits, Eq. 3 may be simplified to Rmc = 1.31 Rm . . . . (4) DISCUSSION The limiting curves in Figs. 1 and 2 represent maximum deviations of ±25 per cent. Thus the use of the average curves can introduce considerable error. There is no substitute for accurate measurements of mud, mud cake, and mud filtrate resistivities at the well site. The mud sample tested should be representative of the mud opposite the formation being logged. The average mud filtrate resistivity curve of Fig. 1 is reproduced in Fig. 3 with two curves which have been published for clay-base aqueous muds2,3. The latter curves were determined from average values of a large number of drilling fluids. The three curves have essentially the same slope and the differences between them are from 7 to 22 per cent. Comparison is made only to illustrate the possibility of error

Jan 1, 1958

By J. G. Richardson, F. M. Perkins

Results and procedures are pre-cented covering a laboratory investigation of the effect of rate of water advance on the displacement of oil from clean water-wet sands. The experiments included water floods at atmospheric pressure with and without gas present over a range of flow rates from reservoir rates to rates ten thousand-fold higher. Water floods were also conducted at various rates at elevated pressure with no gas present. Other tests were made at elevated pressures by forming a free gas saturation by evolution of gas from solution in the oil before water flooding. Recovery of oil was found to be independent of the rate of water advance with or without gas present and independent of the pressure level of the water flood. A dimensionally-scaled model of a reservoir composed of a thick uniform sand was used to study the effect of rate on the tendency of water to underrun the oil because of the greater density of the water. Another model was used to study the effect of rate on the tendency of water to channel down the more permeable sand in a stratified reservoir composed of sands of diffierent per-meability in intimate contact. The effect of the presence of gas on the flooding conformance was studied with both models. The results obtained using these simple models provide a basis for predicting behavior in more complicated systems. INTRODUCTION In spite of the great amount of research on the flow of fluids in porous rocks, there still exists some disagreement as to the influence of the rate of water advance on the displacement of oil by water flooding. Various investigators have found that increasing the rate of water injection would decrease, increase, or have no effect on recovery of oil. One reason for this disagreement has been a lack of understanding of the effects of the capillary forces which influence the results obtained in the laboratory at low rates with short columns. Other causes of the disagreement have undoubtedly been inconstancy and uncertainty of the wetting properties of the porous media studied, inaccurate saturation determinations, and in some instances conclusions based on insufficient data. Capillary forces are involved in the displacement of oil by water in two ways. On the microscopic scale, the capillary forces control the dis- tribution of oil and water in the pore spaces of the sand. The magnitude of these forces is governed by the preference of the sand to be wet by water, the pore sizes and geometrical shapes, and the interfacial tension between the water and oil. On the macroscopic scale, differences in saturation at the flooding "front" when water displaces oil result in capillary pressure gradients. These gradients cause water to flow preferentially ahead of the front. In short laboratory columns at low rates, the front can span the entire column length. Also, at the outflow boundary the preference of sand to be wetted by water results in retention of water and a high water saturation in the region of the outflow face. This effect is commonly called the boundary effect.' The capillary pressure gradients which complicate the interpretation of flooding performance of short laboratory columns at low rates of water advance become negligibly small under certain conditions. The conditions where capillary pressure gradients are negligible are in long, homogeneous reservoir sands,' at high rates of water advance in short laboratory columns,3 and at any rate in laboratory columns as the residual oil saturation is approached. Thus, laboratory water floods, conducted

Jan 1, 1958

By C. A. Doh, R. Q. Fields, M. Lebourg

A formation tester run on logging cable is now available to the oil industry. It offers a method of safely and rapidly testing possible producing formations in uncased holes. These tests can be made up the hole after running the electric log. Reservoir pressure data is continuously recorded at the surface as the fluid sample is extracted. The tester may be assembled with a reservoir of 1-, 2.75-, or 5.5-gal capacity. A retaining pad on the body of the tool is expanded against the wall of the hole at the exact depth desired; this depth is determined by electrical log control. Two bullets are then fired through the center of the retaining pad which create a connection between the formation and a flow line to the sample chamber. When the chamber is filled, a valve is closed and the fluid sample sealed at maximum pressure. The tool is retracted to minimum diameter and brought out of the hole. Electrical circuits permit a complete recording at the surface of the mechanical operations of the tool as well as the formation pressure build-up and the hydrostatic mud pressure. The tool was introduced commercially during the latter part of 1955 in the Gulf Coasts of Louisiana and Texas. Over 1,000 operations have been made to date (Sept. 1, 1956); 50 per cent of which resulted in successful tests. Failures have been due mostly to ineffective sealing in unconsolidated sands. One major company had 41 successful tests out of 80 attempts with 23 ineffective pad seals. Results for this company were very gratifying as to pinpointing gas-oil ratios, indicating productive permeabilities and aiding in determination of fluid content where electrical log and side-wall coring information were inconclusive. Eight typical pressure curves are discussed (including misruns). Six types of fluid recoveries are interpreted. Eight actual field examples of electric logs, showing the problems solved by the formation tester, are illustrated. The present applications of the tool are discussed: 1. Determination of productive fluid—varticularlv differentiating between gas and oil. 2. Determination of reservoir pressure as an aid to: (a) safety in completion technique, (b) reduction in drilling costs, and (c) reservoir analysis. 3. Determination of minimum gas-oil ratios. 4. Location of gas-oil or oil-water contacts. 5. Recovery of samples for examination and analysis: oil (gravity); gas (hydrocarbon content); water (salinity). Additional applications envisioned for the future are also given: (I) subsurface exploration based on accurate pressure, (2) recovery of fluid samples from the undisturbed reservoir for PVT work, and (3) possible quantitative study of permeabilities or productivity index. Running the formation tester requires no special pre-cautionary measures. Because full hydrostatic mud pressure is maintained at all times, well depth is no problem. Thus, the method allows safe, economical testing in wells which heretofore could only be tested by setting casing. INTRODUCTION A new method of safely and rapidly testing possible producing formations in uncased holes is achieving considerable success. The method offers promise of further advances in reservoir study. Called the formation tester, the new instrument is unique in that it operates on logging cable. It thus offers all the advantages of wire-line operations and becomes an important adjunct to present logging and side-wall coring services. The tester is operated against the wall of the hole at any depth desired. Zones to be tested are usually determined by a study of the electrical and the micro-caliper surveys. Reservoir data, as well as the operating cycle of the tool in the hole, are continuously recorded at the surface during the operation. The tester, as it was originally designed, was capable of recovering a 1-gal sample of reservoir fluid per trip in the hole. Tools with reservoirs of 2.75- and 5.5-gal capacity are now available. The 5.5-gal reservoir is equipped with a segregating system, set before going in the hole, so that the last portion of the recovery (usually 1 gal) is automatically separated from the first portion. This makes it possible

Jan 1, 1958

By A. E. Austin, J. R. Doig

Ti-Cr alloys age harden after B-quenching by formation of an W-phase. The structure and orientation of this transition phase have been determined. The hardness ap-pears to be caused by strain in the B-matrix produced by concurrent enrichment of alloy content in the W-phase. EARLY studies of age hardening in B-stabilized titanium alloys revealed the formation of a transition phase named o' This phase was detected by X-ray diffraction in binary alloys of Ti-Fe, Ti-Cr,

Jan 1, 1958

By Roy F. Abernethy

All samples tested showed some loss of heating value for the 5-month period under all 4 storage conditions. The losses increased as the time of storage increased, with the pan-storage samples showing somewhat greater losses than those in cans. The individual daily analyses for the first 2 weeks and the analyses every other day for the third and fourth weeks of storage vary within the approximate tolerance of the test for heating value. During the first 2 months of storage the changes in heating values were not Significant for the samples from Pennsylvania, Indiana, and Colorado. The Ohio coal indicated some loss by the end of I month, which increased to a value measurable with certainty by the end of 2 months. These data show that (1) small changes may occur even to samples in closed cans and (2) the laboratory sample should be handled as expeditiously as is practical until the analysis is completed. The statement by the ASTM that "If the B.t.u. determination is an important consideration in the sale of coal, the time elapsed between sampling and analysis shall not exceed 30 days,"3/ is quite adequate for 3 of the 4 coals tested. The change in the Ohio coal stored for 30 days is merely indicated and could not be determined with certainty by the techniques normally employed. The data on free-swelling indexes determined on can samples, after 30° C. air drying, show that only the Indiana coal lost more than one unit in free-swelling index number in 120 days. No significant changes were observed with the samples from Pennsylvania, Ohio, and Colorado in the 5-month period.

Jan 1, 1958

By G. G. Sarkar

SHARPNESS of separation and washing efficiency are often confused. The sharpness index indicates the precision of a washing unit; the washing efficiency takes into account not only the unit's precision but also the washability characteristics of raw coal and the near-gravity materials at the effective density of cut. A sound basis for evaluating the sharpness index is essential in comparing the sharpness of separation attained by different cleaning units. Sharpness Index and Related Criteria: Washing plant sharpness of separation has been well represented by Hancock's efficiency chart and Tromp's curve of migrated materials. Some useful coefficients derived from Tromp's curve—the error area, probable error, and imperfection value—have been widely used to measure sharpness of separation. These are defined in a number of papers presented at the first and second International Coal Preparation Colsference held in Paris (1950) and Essen (1954).1-5 In evaluating the performance of a dense medium separator at four different gravities, Yan-cey and Greer6 bserved that even with similar operating conditions and the same size grading of feed, the imperfection value of a washing plant varies through a greater range than the probable error. The present writer also observed the same type of anomalies in comparing the imperfection values of one plant which were determined under almost identical conditions. He therefore devised a graphical method to evaluate a washing unit's sharpness of separation and define it by a single coefficient, which is substantially independent of coal characteristics under normal operation of the unit. Unlike imperfection value, the new coefficient can be expressed on a percentage basis. Coal preparation engineers generally agree that the amount of misplaced material resulting from any separation in a washing plant is almost directly related to the amount of +0.10 sp gr (near-gravity) materials. In actual practice, however, misplacement is not restricted to the 20.10 sp gr range. It will be evident from a study of Tromp curves that this misplacement often extends over unequal specific gravity ranges on the two sides of the actual density of separation. The same condition exists for near-gravity ash distribution and the resultant misplacement of ash units during any separation. But so far as the same unit is concerned, the total misplacements bear a definite ratio to the amount of near-gravity zone materials that is affected by misplacements. This ratio should be constant not only for various densities of separation but also for different qualities of feed coal treated in the same plant. This ratio, multiplied by 100, directly represents the inefficiency of the plant. When the plant inefficiency value is subtracted from 100, the re- ' sult is designated as sharpness index. Evaluating the Sharpness Index: The method of evaluating the sharpness index is explained here with reference to Fig. 1. Fig. 1 is a reproduction of the familiar diagram used by Cerchar of France to represent the inefficiency of a separation in terms of "triangle of errors," which is a measure of organic loss. It will be observed that the characteristic (yield/fractional ash) curve of the raw coal represented by GHAPR

Jan 1, 1958

By Denton R. Wieland, Harvey T. Kennedy

The frequency of bubble formation is measured for oils from the East Texas field and the Slaughter field in cores from these fields. East Texas oil was also tested in a Slaughter core. The data checked previous results in that a definite supersatrtration may exist without the formation of bubb1es in periods of observation totaling 158 hours. Measured frequencies varied from zero at supersaturations below 14 psi to 3.1 bubbles/sec/ cu ft of rock at 40 psi supersaturation INTRODUCTION The formation of bubbles is essential in a solution gas-drive reservoir in the displacement of oil. In formations where the basic pore structure consists of fine pores or fractures connected to larger pores or crevices, bubble formation in the fine pores may be the most effective means by which the oil may be displaced, even if secondary methods are applied. The most efficient oil displacement would occur where at least one bubble would form in every pore. As the pressure decreased, the bubbles would expand, due to the gas diffusing into the bubbles, and displace the oil toward the lower pressure area around the wellbore. Kennedy and Olson' have shown that the total number of bubbles formed in a reservoir is primarily dependent upon the rate of pressure drop, the rate of diffusion of gas through oil, and surface area of the rock. The surface tension of the liquid and other characteristics of the rock may also exert an important effect, which would give a different frequency to different rocks and oils and various combinations of different rocks and oils. The purpose of this paper is to present frequency measurements on two rocks and two oils. A hydrocarbon liquid is at equilibrium with gas when it contains the maximum volume of gas in solution that it can have at the prevailing temperature and pressure. If the temperature is maintained constant and the pressure is reduced below the equilibrium pressure, the liquid is supersaturated to the extent of the difference in the two pressures until the gas comes out of solution as a free phase. As shown by previous work, and confirmed in the present investigation, the number of bubbles formed per second increases with an increase in supersaturation. Kennedy and Olson showed that a tenfold increase in the rate of pressure decline resulted in a tenfold increase in the number of bubbles formed per cubic foot of reservoir rock, e.g., for decline rates of 0.1, 1, and 10 psi/day, the number of bubbles formed per cubic foot would be 40, 400, and 4,000, respectively. For another hypothetical system, Stewart, Hunt, and Berry' estimated that for pressure declines of 0.1, 1, and 10 psi/day, the number of bubbles formed would be approximately 10, 100, and 1,000 cu ft of reservoir rock. Their value of bubbles formed is lower than given by Kennedy and Olson; however, the order of magnitude agreed satisfactorily. The rate of diffusion will also affect the number of bubbles formed. If the diffusion coefficient is high, the gas in solution in the oil surrounding a single bubble will tend to diffuse into the bubble rather than forming other bubbles. On the other hand, the formation of more bubbles will tend to occur if the diffusion coefficient is very low. In his thesis dated Aug., 1953, Wood" reports on the frequency of bubble formation in a system consisting of oil and rock from the Rangely field. In the present work, the apparatus of Wood was redesigned to allow greater precision, especially at low supersaturations, where bubble growth is slower, and detection is more difficult.

Jan 1, 1958