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By Kenric C. Owen

INTRODUCTION Situated 23 miles east of Pretoria the Premier Mine started diamond production in 1903. Two years later it produced the largest diamond yet discovered, the 3 106 carat Cullinan stone. For the period to 1932 when the mine was closed down due to economic circumstances, open cast mining was practised using inclined rope haulage traction and by this time had produced 48.5 million carats of predominantly industrial quality diamonds from 148 million tons of ore. In 1945 it was decided to re-open the mine using underground mining methods. A system using long hole benching was devised (Hodgson and Sewel 1960). This system was later modified but still forms the basis for approximately fifty percent of production. Following the successful introduction of block caving on associated diamond mines in the Kimberley area (Gallagher and Loftus 1960) this mining method was introduced to the Premier Mine in the late 60's and now accounts for nearly 50% of production. This paper will discuss block caving at Premier Mine in the light of our experience and discussion will be directed to the main geological and structural features of the orebody and host rocks and the related constraints imposed on the mining methods. Reference is made to the long hole benching mining method for comparative purposes. GENERAL DESCRIPTION OF OPERATIONS The ore from the block caving and bench mining areas gravitates via ore passes to a twin haulage, 500m below surface. Electric 13 tonne locomotives, each hauling a train of 10 Granby type cars, deliver the ore to two 42" x 48" (1.06m x 1.22m) jaw crushers. The ore is reduced in size to minus 0.15m before being hoisted to the treatment plant on surface. Hoisting is done with 12.5 tonne bottom discharge skips in a five compartment rectangular shaft using two 3 240 H.P. semi automatic Ward Leonard winders. A small single drum service winder operates in the other compartment. Men and materials travel in a separate shaft in a 5,4m x 2,8m cage operated by a Koepi winder. These two shafts are also the main intake airways to the mine. The two main extraction fans capable of 250 m3/s at 3,2 kPa are situated on surface and are connected to the underground workings by an incline and a network of air passes and return airways. GEOLOGY Although there are numerous occurrences of kimberlite bodies in the district, the Premier Mine kimberlite pipe is the only economic orebody. It is roughly oval in shape with surface dimensions of 900m on the long axis and 450monthe short axis. The surface area is 320 000 m2. The kimberlite has intruded a massive body of felsite and norite which is intersected by a number of faults. The contact between the kimberlite and host rock is clear cut and dips inward at an average angle of 80°. Cutting across the pipe and the country rock is a 75 metre thick gabbro sill, the top of which intersects the pipe below the 347m level and dips at 15' to the north west. The kimberlite has been metamorphosed a distance of some 20m both above and below the sill contacts. Age measurements on biotite from the gabbro date the sill as 1 115 million years, thereby providing a minimum age of the pipe. (Pre Cambrian). All other pipes in South Africa are of Cretaceous age (60 million years). A simplified geological plan and section of the Premier Mine orebody is shown in Figure 1. It is thought that the kimberlite intruded in at least three distinct phases. The kimberlites of these different phases can be distinguished most easily by their characteristic colour. BROWN KIMBERLITE. This is the oldest kimberlite and forms a crescent shape in plan on the south eastern side of the pipe. In depth it increases in relative area. Although the brown kimberlite carries the highest diamond grade in terms of carats per ton all the various kimberlites in the Premier pipe are economic to mine.

Jan 1, 1981

By Leslie W. Austen

ROTARY kiln operators will agree that some of the most severe conditions a refractory must stand occur in the hot zone of a kiln burning Portland cement, dead burn dolomite, magnesite, peri-clase, and similar materials. Frequently the operator is faced with factors beyond his control which drastically shorten the life of refractories. Shutdown due to mechanical failure can be serious if the period is of sufficiently long duration to cause the dropping of coating or the loosening of the lining. A change in slurry can affect the coating and cause ring buildup. A change in type of fuel and its effect upon the flame can cause a shift in location of the hottest zone. Weekend shutdowns or any other interruption can cause the operator trouble and may damage the refractories, since stopping and starting a rotary kiln is certainly more difficult than stopping and starting a motor. Some operators have tried to set an estimate of damage for each shutdown in equivalent days of running time. Conditions affecting the refractory may be roughly grouped in four classes: chemical attack, mechanical stress, thermal shock, and abrasion. Chemical Attack: The drive to obtain maximum production through a kiln demands maximum operating temperatures, temperatures which are limited more by the ringing up or melting of the clinker. This can cause interface temperatures at the junction of coating and refractory which require the use of a basic kiln block to withstand the chemical attack. Chemical changes take place within the refractory itself, especially in chemically bonded or unburned kiln blocks. These changes cause the formation of the ceramic or burned bond. Migrating liquids or fluxes from the kiln charge have an effect within the refractory and lead to mineral or glass formation. The alkalies, sodium and potassium, migrate into the refractory as silicates, chlorides, sulphates or other salts. They may move under capillary action or may be caused to move by volatilization with condensation in the cooler portion. Mechanical Stress: Concentrated stress may be caused by several factors or combinations thereof. I—The rings of refractories must be kept tight and rigid within the kiln, and this alone demands considerable force to hold the blocks in place. So that the force will not be concentrated, the blocks should fit the circle as perfectly as possible, with the faces in contact overall. 2—As the kiln is heated, thermal expansion takes place at the hot end of the kiln block. Since this disturbs the plane face it too can cause a concentrated stress at the two ends of the block, and shearing stress can be set up within the brick itself because of the difference in expansion between the two ends. 3—If a lining becomes loose and moves in the shell very severe stress can be set up, and as the kiln rotates this load changes and gives the effect of repeated loading. Permanent expansion of the refractory can also cause severe loading. 4—Not least important, flexing of the kiln is frequently the cause of concentrated stresses. Thermal Shock: Thermal shock, the result of heating and cooling too rapidly, occurs on starting and stopping or when a large patch of coating drops, exposing the bricks. Again, its destructive effect is often the result of phase change, liquid to solid or the reverse; dense refractories loaded with glass-forming impurities are particularly susceptible. Thermal shock is a. problem with refractories set in the wall or roof of a stationary furnace, and becomes even more serious in a rotary kiln, the tendency to spa11 being magnified with movement and concentration of stress. Uniform rate of feed and loading insures both better coating and a more uniform stress. Abrasion: If the refractories do not take a coating, abrasion can become a most destructive factor. Movement of the lining in shell or movement of loose blocks causes abrasion, which is also most destructive if the refractories do not take a coating. An analysis of the problem of basic lining for the hot zone reveals, therefore, a number of desirable characteristics: high refractoriness, basic chemical reaction, resistance to spalling, good strength at all stages, ability to take coating, true sizing, volume stability, and abrasion resistance. Increased demand

Jan 1, 1953

By B. W. Howlett, M. B. Bever, Somnath Misra

The heats oj- formation at 0°C of the compounds AuSn,, AuSn2, AuSn, and the £ phase were measured in a metal -solution calorimeter with liquid tin or a liquid Sn-Bi alloy as solvent. The melting point, heat of fusion, and heat capacities near the melting point of- the compound AuSn in the solid and liquid state were measured in a constant temperature gradient calorimeter. The free energy and entropy of formation of the compound AuSn at its melting point and at 298 °K were calculated from the experimental results and published data. The heats of formation are discussed in relation to the nature of the compounds. The heat capacity below the melting point, heat of fusion, and entropy of fusion of AuSn are interpreted in terms of processes oc-curring before melting. The atomic arrangement in liquid Au-Sn alloys and the bonding in the intermediate phases of. the Au-Sn system are discussed in the light of the measured thermodynamic properties. THE available thermodynamic information on the intermediate phases in the Au-Sn system consists of the heats of formation of the compounds AuSn4, AuSn2, and AuSnly2 and of one composition of the < phase2 besides values of the heat content of the compound AuSn from 0" to 635".&apos; However, the heats of formation refer to different temperatures ringing from 90" to 450°C. Also, the reported error limits of some of the values are large and several inconsistencies are apparent. In the investigation reported here the heats of formation of the compounds AuS-, AuSnz, and AuSn and of three compositions of the < phase were determined for a single reference temperature of 0°C by liquid metal-solution calorimetry. The compound AuSn, which is the only congruently melting intermediate phase in this system, was further investigated in a constant temperature gradient calorimeter by measuring its heat of fusion, melting point, and heat capacity in the solid and liquid states near the melting point. From these data and published free energies of the liquid of composition Au~n,&apos; the free energies of formation of the compound AuSn at the melting point and at 298°K were calculated. The results shed light on the solid-liquid transition of AuSn and on the atomic bonding and state of association of gold and tin in the solid and liquid phases. 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Samples. Stoichiometric amounts of gold and tin, each 99.99+ pct pure, were melted in evacuated Vycor capsules (12 mm ID). The melts were maintained approximately 150°C above the liquidus for about 12 hr and shaken repeatedly. Samples of the compound AuSn were cooled slowly to room temperature. Melts of the other phases, all of which solidify by peritectic reactions, were transferred to the narrow end (5 mm ID) of the capsule, which was then quenched into iced brine. The solidified samples were annealed in the unopened capsules for 10 days at 30" to 50° C below the respective solidus temperatures. The absence of microsegregation and second phases was confirmed by metallographic examination. At least two batches of each composition were prepared. 1.2) Solution Calorimetry. The heats of formation were determined by liquid metal-solution calorimetry. In this technique, the difference between the heat effects on dissolution in a liquid metal, or alloy bath, of the compound and a mechanical mixture of its annealed components, adjusted for changes in composition of the bath, is the heat of formation of the compound at the temperature from which the samples are added. Details of the equipment and technique have been described."&apos; A tin bath at 300" or 350°C was used with the compounds AuSn,, AuSnz, and AuSn. The high gold content of the £ phase would have caused it to dissolve with an appreciable exothermic heat effect. In order to achieve thermal compensation, the samples were added from 0°C to a bath at 350°C consisting of 66.2 wt pct Bi (99.999+ pct pure), balance Sn (99.99+ pct pure). This solvent gives thermal compensation because gold dissolves exothermically in tin and endothermically in bismuth. The calorimeter was calibrated by adding from 0°C approximately 0.015 g-atom of the solvent.

Jan 1, 1965

By J. F. Pierce, S. M. Enterline

Since January 1959 a zinc refiner of novel design has been in operation at Blackwell, Okla., producing 99.995+ zinc from the output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyro-metallurgical unit with principal dimensions horizonhl permitting one floor operation. It is very ruggedly constructed. Furthermore it is not subjected to deterioration from high concentrations of iron in the feed metal because the boiling units are separate from the rectification columns and constructed with silicon carbide brick arches through which the heat is transferred radiantly to the zinc. A zinc refiner of novel design has been in operation since January 1959 at the Blackwell, Okla. plant of the Blackwell Zinc Co., Inc., a wholly owned subsidiary of American Metal Climax, Inc. Developed by the company&apos;s technical and operating staffs, the new refiner produces special high-grade zinc (nominally 99.995+ pct Zn) from the prime western1 slab output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyromet-allurgical, high-capacity unit employing fractional distillation to separate zinc from its impurities, consisting principally of lead, cadmium, and iron. In prime western slab, these elements may vary in concentration from 0.005 to 1.6 pct. Table I shows the impurities usually encountered in the Blackwell prime western metal fed to the refiner together with their boiling points and vapor pressures at 907oC. The commercial pyrometallurgical smelting processes for extracting zinc from ore include distillation from retorts and a limited degree of refining can be accomplished by redistillation in similar retorts. To achieve special high-grade purity, an impractical number of batch redistillations would be required, however, with an accompanying loss of much metal. A continuously operated and integrated unit is required in which fractional vaporization and condensation can take place in a large number of stages. The first commercial continuously operated unit was developed by the New Jersey Zinc Co.4 In the separation of any two substances the degree of separation is limited if a mixture exists having a constant boiling point. The Zn-cd5 and Zn-pb6 systems contain no constant boiling points and hence these metals may be separated to any degree of purity. Basically, the pyrometallurgical refining of zinc involves three steps: a) iron, copper, and other metals having no appreciable vapor pressures at 907ºC concentrate in the bath when the impure zinc is boiled, b) lead, bismuth, antimony, and other metals having boiling points above but closer to that of zinc are selectively condensed from the vapor boiled from the bath, and c) cadmium and other metals having lower boiling points than zinc are fractionally distilled by reboiling and subsequent condensation of the zinc from the vapor. The boiling and condensation of zinc must be conducted in vessels constructed of materials which are refractory at the temperature involved (907 ºC) and it is highly desirable that they also be resistant to attack by the various metals. This requirement dictates construction from relatively small, simply shaped pieces which limits the pressures which may be employed to avoid leakage through the numerous joints. Stresses induced must be limited essentially to compressive ones and suitable provision must be made to permit thermal expansion of the components in order to minimize these stresses. Where heat is to be added for boiling or removed for condensation, refractory material through which the heat flows must have a high thermal conductivity. Silicon carbide is highly conductive but is subject to attack by iron and is expensive compared to other commonly employed refractories. A hard, dense aluminous fireclay is well suited to contain these metals where high thermal conductivity is not required. Zinc will penetrate the pores of fireclay brick but only to a limited depth in an exterior wall and has little effect other than an increase in weight and conductivity. The design objectives of the Amax refiner were: a) to achieve a long life by heavy, rugged construction and by employing silicon carbide refractories only where required for heat conductivity and not in contact with liquids of high iron concentrations, b) to simplify operation, manning and control by essentially horizontal construction, and c) to obtain high capacity in a single unit. DESCRIPTION Flow of metal through the Amax refiner is shown diagrammatically in Fig. 1 and schematically in Fig. 2.

Jan 1, 1963

By R. J. Charles

SEARCH for a consistent theory to explain the relationship between energy input and size reduction in a comminution process has accumulated, over the years, an enormous amount of plant and laboratory data. Although some correlation of these data has been possible for purposes of engineering design and for the advancement of research in fracture, there is still great need of a means of predicting behaviour of a solid when it is reduced in size by mechanical forces. The best known hypotheses proposed to describe the energy-size reduction relationships in crushing and grinding stem from a common origin. The present article analyzes problems of comminution in the light of the precepts of this origin. Its object is to reconcile points of difference between these well known hypotheses and to present relationships more widely applicable to comminution studies. Theoretical Considerations: Most existing relationships between energy and size reduction of a brittle solid stem from a single, simple, empirical proposition.&apos; Although this proposition can be demonstrated by observation and experiment, no theoretical derivation is yet possible. Mathematically, the proposition may be stated as follows: dE = -Cdx/xn [1] where dE = infinitesimal energy change, C = a constant, dx = infinitesimal size change, x = object size, and n = a constant. Eq. 1 states that the energy required to make a small change in the size of an object is proportional to the size change and inversely proportional to the object size to some power n. No stipulations are placed on the exponent n in either magnitude or sign. In 1867 Rittinger2 postulated that the energy required for size reduction of a solid would be proportional to the new surface area created during the size reduction. As far as can be determined there is as yet no physical basis for Rittinger&apos;s hypothesis. Rittinger&apos;s hypothesis can be stated mathematically as follows: E, = K(oa-a-0 . [2] Er = energy input per unit volume, K = a constant, <ti = initial specific surface, and o2 = final specific surface. In the size reduction of particles of size x, to particles of another smaller size, x2, Eq. 2 becomes the well known relation: ET = K&apos; {l/x2-l/xx) [3] where K&apos; is a constant. Eq. 3 may be arrived at from the proposition given in Eq. 1 by integrating and by assigning a value of 2 to the exponent n. J dE = J - C dx/x2 E = Kt (1x - 1x) where K&apos; = C. In 1885 Kick3 proposed the theory that equivalent amounts of energy should result in equivalent geometrical changes in the sizes of the pieces of a solid. For example, if one unit of energy reduced a number of equal-sized particles to particles of one half the size, then the same amount of energy applied to the particles resulting from the first test should result again in a size reduction of one half or a final size one quarter the original size. The Kick concept may be expressed as follows: Ek = K" log x1/x2 [41 K" = a constant and E, = energy per unit volume. The expression for Kick&apos;s law may be arrived at by again integrating Eq. 1 and in this case assigning a value of 1 to the exponent n. dE= J - C dx/x Eh = - C In {x/x2) = K" log (x,/x,) where K" = 2.3 C. Application of Kick&apos;s and Rittinger&apos;s laws to comminution has met with varied success. Gross and Zimmerley4 and Piret5 have shown that Rittinger&apos;s equation applies under certain conditions of experimentation. Walker and Shaw6 express the belief that in metal turning and shaping and in grinding of both metals and minerals the production of very fine particles (less than lP) follows Kick&apos;s hypothesis, whereas Rittinger&apos;s concept is valid for the size reduction of coarse particles. For the practical case of crushing and grinding, however, neither of the above hypotheses has received general acceptance. Bond&apos; has lately proposed that since neither Kick&apos;s nor Rittinger&apos;s hypotheses seem correct for plant design work, an energy-size reduction relationship somewhere between the two would be more applicable. The fundamental statement of Bond&apos;s work

Jan 1, 1958

By R. J. P. Lyon, A. E. Prelat, H. Lawrence

Introduction In 1977, the US Bureau of Mines awarded a grant to the state of South Carolina to explore the possibility of using Landsat multispectral scanner (MSS) data as an aid in monitoring surface mining activities in selected counties of the state. Work had been done in Aiken County prior to the grant by USBM and state personnel at the EROS Data Center using both the GE Image 100 and ESL IDIMS systems. The initial work on the 1:100 consisted of locating and measuring the areas of various kaolin mines. The results were excellent on location, identification, and accurate area measurements of several mines as compared with aerial photos of each mine. The effort also included locating and measuring the size of all mines (including sand and gravel) within two US Geological Survey (USGS) 7 % - min quadrangle maps. Line printer overlays using the IDIMS equipment and software resulted in the location of all known mines within an estimated error less than zt 91.4 m. Mine acreage was calculated by counting each symbol (which represented one pixel) and multiplying by 1.1 (the number of acres per pixel). [Fig. 1] shows a portion of one quadrangle overlay. [Table 1] gives a comparison of acreage measured for several mines from the 1-100 and IDIMS system vs. aerial photo measurements. The success of the preliminary work resulted in the South Carolina Land Resources Conservation Commission submitting a proposal to USBM for funding to expand the scope of work to other mineral mining operations within the state and determine if Landsat Imagery could be used to accurately locate and measure mining and reclamation activity on a continuing basis. Three separate tasks were proposed for selected kaolin mines in Aiken County: Task 1, to measure changes in active mine developments over the period 1974-77; Task 2, to measure reclamation activity, and, if time permitted, seasonal changes in mine signatures over the same period of time; and Task 3, to classify one complete mining operation (i.e., differentiate between active, spoil, overburden, water, reclaimed portions and surrounding terrain. The major effort was centered around J.M. Hubeis Richardson mine. Mining operations were progressing in a northerly direction and included three areas of reclamation: one prior to 1974; one started during early 1974; and one reclaimed during 1976. A discussion of all work done under the grant is available in the March 1979 Final Report listed under References. Computer compatible tapes (CCTs) containing MSS data from Landsat Path 18, Row 37, were purchased from the National Aeronautics and Space Administration (NASA) covering the period February 1974 through January 1977. The MSS data were processed on the General Electric Image 100 using parallelepiped classification at the EROS Data Center&apos;s Data Analysis Laboratory, Sioux Falls, SD, and at the Stanford Remote Sensing Laboratory, Stanford University, Palo Alto, CA, utilizing both an unsupervised classification (ISOMIX) and a supervised classification (sequential discriminant analysis). Studies at Stanford University Remote Sensing Lab (SRSL). In Feburary 1977, initial work was begun at Stanford using the STANSORT computer program running on a DEC PDP-10 (Honey, Prelat, and Lyon, 1974). This software is fully interactive and designed to study Landsat CCT data at high resolution (small areas) on a pixel-by-pixel basis (Lyon, 1977). Unsupervised Classification. The initial step was to locate the Richardson mine on the positive print of the full Landsat scene from CCT 1644-15252, dated 6/17/74. This was relatively easy due to a large abandoned kaolin mine and a long narrow pond clearly visible in the scene. Two unsupervised classifications of the Richardson mine were run using ISOMIX clustering (Honey, Prelat and Lyon, 1974). (ISOMIX essentially follows the interactive clustering procedures of ISOCLS Kan, Holley, and Parker. 1973). Although the classifications were successfully accomplished, it was apparent from the TV display that the results did not clearly define the mine areas. A supervised classification would have to be made in order to clearly separate each portion of the mine. Supervised Classification. This classification was done using the Stepwise Discriminant Program (BMDO7M) which is part of the BIOMED package (Dixon, 1970) and involved the following steps: Training group populations were selected and the digital

Jan 1, 1982

By Alan Stanley

THE MacIntyre Development of National Lead Co. is located at Tahawus, N. Y., in the heart of the Adirondack Mountains. Operations involve the mining and concentrating of a titaniferous iron ore to produce ilmenite and magnetite concentrates. A general description of the operation and metallurgy has been given by Frank R. Milliken.&apos; Pigment plant production demands that the MacIntyre mill produce a 44.7 pct TiO, ilmenite concentrate. To achieve the required ilmenite grade and tonnage it is important that the table concentrate grade be closely controlled. Unfortunately, however, the titaniferous orebody which feeds the MacIntyre mill is not uniform. Ore dressing characteristics vary from one end of the orebody to the other, and from • one level to the next. The changeable nature of the mill feed precludes a single adjustment of the equipment for long periods of time. Thus the operators must constantly watch the equipment to insure a uniform concentrate from the fine and coarse tables and Wetherills, or dry magnetic separators. Chemical assaying of mill products requires about 4 hr from the time the sample is taken until assay results are obtained, and this is available only on a two-shift basis. The ore may change rapidly, even several times during a shift, so that assay results lose most of their control value by the time they are reported to the mill operating crew. Members of the crew have therefore tried to evaluate the table and Wetherill concentrate by visual inspection, since through long experience the shift operators, under most circumstances, can gage closely the grade of the mill products. However, there are times when the physical nature of the ore is radically different from normal. Under these conditions visual inspection is of no value, and at such times final ilmenite as low as 43 pct TiO, has been produced and shipped before the assay results have been received. The specific gravity method of assaying for TiO, has been attempted to eliminate the shipping of ilmenite below normal grade as well as to help control day to day and hour to hour mill production. Table I shows the minerals found in the MacIntyre ore along with their average weight proportions and specific gravities. The first two products considered for the specific gravity method were fine and coarse table concentrates. It was reasoned that these products were essentially ilmenite with the higher specific gravity gangue minerals. Since they were always produced the same way, and the desired grade of TiO, was always constant, the specific gravity of these materials would increase or decrease as the amount of ilmenite increased or decreased. Thus for table concentrates which assayed 40 pct TiOz a constant gravity would invariably be obtained, and as the TiO, value changed the specific gravity would change in direct proportion. The third product considered was Wetherill ilmenite. It was assumed that a desired grade of 44.7 pct Ti02 would also always contain the same amount and type of gangue minerals along with the ilmenite, and thus would always have the same specific gravity. As the TiO, value of the ilmenite concentrate changed so would its specific gravity. Dr. Kenneth Vincent, chief metallurgist of the Baroid Division of National Lead Co. at Magnet Grove, Ark., ran specific gravity tests on 17 samples of the desired products. The lowest specific gravity reading assayed the lowest in TiO, and as the specific gravity increased the trend was for the TiO, assay to increase, see Fig. 1. Since these results warranted further investigation, a 500-g capacity Torsion balance and 250 ml Le Chatelier specific gravity bottles were obtained. Shift samples of fine table concentrate, coarse table concentrate, and final ilmenite were tested. Each sample was split and 85 g weighed on the Torsion balance. The Le Chatelier bottle was filled with water to a zero mark. To avoid wetting the neck of the bottle it was found necessary to do this

Jan 1, 1953

By Owen Thornton

Recently equations have been presented by Rose and Bruce&apos; and by Rose², showing how the relative permeability of a reservoir rock may be determined from the capillary character of the rock. In particular, equations were developed to show the relationship between capillary pressure and the effective permeability to the wetting phase in a poly-phase flow system. The equations are as follows (nomenclature the same as in the Rose and Bruce paper) Rose and Bruce assume that the average length of path (L,), which the wetting fluid follows in flowing through a porous media is independent of the saturation to the wetting phase, so that 1 is a constant dependent only on the k rock, and the permeability to the wetting phase is a function of the saturation and of the capillnry pressure: In measuring the flow of ekctric current through partially saturated core samples, it has been observed that the electrical resistance usually is not a simple linear function of saturation. This fact indicates that the average length of path in the flow of electric current is not independent of saturation, but rather that the tortuosity of the path depends upon the average saturation to the conducting fluid as well as upon the characteristics of the rock. itself. Inasmuch as the flow of fluid and the flow of electric current in many respects are analogous, it may be indicated further that the length of path for fluid also may not be independent of saturation. The following relationship can be derived to express the resistance to flow of electric current through a core sample partially saturated with conductive wetting phase, the non-wetting phase being non-conductive: where L is the average length of path followed by the current in flowing through a length L of partially saturated core, where L is the length of current path when the core is fully saturated, and where Rs and R, are the specific resistivities of the partially saturated and saturated core sample, respectively. It will be noted that R., the specific resistivity of the core sample when S, = 1.0, is equal to the "formation resistivity factor"&apos; multiplied by the specific resistivity of the saturating fluid. If it be assumed that the average lengths of path for fluid flow and for the flow of electric current are the same, then equation (5) may be combined with equations (l), (2) and (3) to give the following relationship: The above equation suggests including a correction for tortuosity when calculating the relative permeability of a reservoir rock to a wetting phase. The correction factor may be obtained from the resistivity-saturation relationship. For instance, the following calcu- lations are obtained for the unconsoli-dated sands described by Leverett Kw Kw Sw R°/Rs Pt/Pc¹ (Calc.) (Obs.) 0.30 0.08 0.88 0.02 0.0 0.40 0.16 0.94 0.06 0.04 0.50 0.27 0.97 0.14 0.11 0.60 0.40 0.98 0.26 0.21 0.70 0.53 0.98 0.39 0.35 0.80 0.68 0.99 0.57 0.54 0.90 0.84 0.99 0.77 0.76 1.00 1.00 1.00 1.00 1.00 It will be noted that the agreement between the calculated points and the observed data is rather good. Further investigation of the above method for obtaining relative permeabilities may be merited. For many sands within specified ranges of saturations the following relationship has been found to hold approximately&apos;: — =SW"......(7) Rs The exponent n in the above equation has been found to equal two for many sands so that equation (6) reduces to the following: The writer acknowledges the permission of The Texas Co. to submit this note for publication. 1. Walter Rose and W. A. Bruce—Jnl. of Pet. Tech., Vol. 1, No. 5, p. 127 (1949). 2. Walter Rose—Jnl. of Petr. Tech., Vol. 1, No. 5, p. 111 (1949). 3. G. E. Archie— -Trans. AIME, 146, 54 (1942). 4. M. C. Leverett— Trans. AIME, 142, 152 (1941). 5. M. C. Leverett—Trans. AIME, 132, 149 (1939).

Jan 1, 1949

By Alan Stanley

THE MacIntyre Development of National Lead Co. is located at Tahawus, N. Y., in the heart of the Adirondack Mountains. Operations involve the mining and concentrating of a titaniferous iron ore to produce ilmenite and magnetite concentrates. A general description of the operation and metallurgy has been given by Frank R. Milliken.&apos; Pigment plant production demands that the MacIntyre mill produce a 44.7 pct TiO, ilmenite concentrate. To achieve the required ilmenite grade and tonnage it is important that the table concentrate grade be closely controlled. Unfortunately, however, the titaniferous orebody which feeds the MacIntyre mill is not uniform. Ore dressing characteristics vary from one end of the orebody to the other, and from • one level to the next. The changeable nature of the mill feed precludes a single adjustment of the equipment for long periods of time. Thus the operators must constantly watch the equipment to insure a uniform concentrate from the fine and coarse tables and Wetherills, or dry magnetic separators. Chemical assaying of mill products requires about 4 hr from the time the sample is taken until assay results are obtained, and this is available only on a two-shift basis. The ore may change rapidly, even several times during a shift, so that assay results lose most of their control value by the time they are reported to the mill operating crew. Members of the crew have therefore tried to evaluate the table and Wetherill concentrate by visual inspection, since through long experience the shift operators, under most circumstances, can gage closely the grade of the mill products. However, there are times when the physical nature of the ore is radically different from normal. Under these conditions visual inspection is of no value, and at such times final ilmenite as low as 43 pct TiO, has been produced and shipped before the assay results have been received. The specific gravity method of assaying for TiO, has been attempted to eliminate the shipping of ilmenite below normal grade as well as to help control day to day and hour to hour mill production. Table I shows the minerals found in the MacIntyre ore along with their average weight proportions and specific gravities. The first two products considered for the specific gravity method were fine and coarse table concentrates. It was reasoned that these products were essentially ilmenite with the higher specific gravity gangue minerals. Since they were always produced the same way, and the desired grade of TiO, was always constant, the specific gravity of these materials would increase or decrease as the amount of ilmenite increased or decreased. Thus for table concentrates which assayed 40 pct TiOz a constant gravity would invariably be obtained, and as the TiO, value changed the specific gravity would change in direct proportion. The third product considered was Wetherill ilmenite. It was assumed that a desired grade of 44.7 pct Ti02 would also always contain the same amount and type of gangue minerals along with the ilmenite, and thus would always have the same specific gravity. As the TiO, value of the ilmenite concentrate changed so would its specific gravity. Dr. Kenneth Vincent, chief metallurgist of the Baroid Division of National Lead Co. at Magnet Grove, Ark., ran specific gravity tests on 17 samples of the desired products. The lowest specific gravity reading assayed the lowest in TiO, and as the specific gravity increased the trend was for the TiO, assay to increase, see Fig. 1. Since these results warranted further investigation, a 500-g capacity Torsion balance and 250 ml Le Chatelier specific gravity bottles were obtained. Shift samples of fine table concentrate, coarse table concentrate, and final ilmenite were tested. Each sample was split and 85 g weighed on the Torsion balance. The Le Chatelier bottle was filled with water to a zero mark. To avoid wetting the neck of the bottle it was found necessary to do this

Jan 1, 1953

By Owen Thornton

Recently equations have been presented by Rose and Bruce&apos; and by Rose², showing how the relative permeability of a reservoir rock may be determined from the capillary character of the rock. In particular, equations were developed to show the relationship between capillary pressure and the effective permeability to the wetting phase in a poly-phase flow system. The equations are as follows (nomenclature the same as in the Rose and Bruce paper) Rose and Bruce assume that the average length of path (L,), which the wetting fluid follows in flowing through a porous media is independent of the saturation to the wetting phase, so that 1 is a constant dependent only on the k rock, and the permeability to the wetting phase is a function of the saturation and of the capillnry pressure: In measuring the flow of ekctric current through partially saturated core samples, it has been observed that the electrical resistance usually is not a simple linear function of saturation. This fact indicates that the average length of path in the flow of electric current is not independent of saturation, but rather that the tortuosity of the path depends upon the average saturation to the conducting fluid as well as upon the characteristics of the rock. itself. Inasmuch as the flow of fluid and the flow of electric current in many respects are analogous, it may be indicated further that the length of path for fluid also may not be independent of saturation. The following relationship can be derived to express the resistance to flow of electric current through a core sample partially saturated with conductive wetting phase, the non-wetting phase being non-conductive: where L is the average length of path followed by the current in flowing through a length L of partially saturated core, where L is the length of current path when the core is fully saturated, and where Rs and R, are the specific resistivities of the partially saturated and saturated core sample, respectively. It will be noted that R., the specific resistivity of the core sample when S, = 1.0, is equal to the "formation resistivity factor"&apos; multiplied by the specific resistivity of the saturating fluid. If it be assumed that the average lengths of path for fluid flow and for the flow of electric current are the same, then equation (5) may be combined with equations (l), (2) and (3) to give the following relationship: The above equation suggests including a correction for tortuosity when calculating the relative permeability of a reservoir rock to a wetting phase. The correction factor may be obtained from the resistivity-saturation relationship. For instance, the following calcu- lations are obtained for the unconsoli-dated sands described by Leverett Kw Kw Sw R°/Rs Pt/Pc¹ (Calc.) (Obs.) 0.30 0.08 0.88 0.02 0.0 0.40 0.16 0.94 0.06 0.04 0.50 0.27 0.97 0.14 0.11 0.60 0.40 0.98 0.26 0.21 0.70 0.53 0.98 0.39 0.35 0.80 0.68 0.99 0.57 0.54 0.90 0.84 0.99 0.77 0.76 1.00 1.00 1.00 1.00 1.00 It will be noted that the agreement between the calculated points and the observed data is rather good. Further investigation of the above method for obtaining relative permeabilities may be merited. For many sands within specified ranges of saturations the following relationship has been found to hold approximately&apos;: — =SW"......(7) Rs The exponent n in the above equation has been found to equal two for many sands so that equation (6) reduces to the following: The writer acknowledges the permission of The Texas Co. to submit this note for publication. 1. Walter Rose and W. A. Bruce—Jnl. of Pet. Tech., Vol. 1, No. 5, p. 127 (1949). 2. Walter Rose—Jnl. of Petr. Tech., Vol. 1, No. 5, p. 111 (1949). 3. G. E. Archie— -Trans. AIME, 146, 54 (1942). 4. M. C. Leverett— Trans. AIME, 142, 152 (1941). 5. M. C. Leverett—Trans. AIME, 132, 149 (1939).

Jan 1, 1949

By A. T. Aldred

HIS note reports the existence of several new scandium intermetallic compounds of the A2B and AB stoichiometries where the A element is scandium and the B element is from group VIII or IB of the periodic table. Alloys were arc melted from high-purity materials using 2-g charges. Typical lot analyses for the materials used are given in Table I. Chemical analyses were not made on the alloys as there was little or no weight loss on melting. After annealing the specimens for 14 days at 600°C and water quenching, metallographic and X-ray techniques were used to determine the occurrence of the various phases. Table II lists the relevant data for the A2B phases. The Ti2Ni structure,2 has ninety-six atoms in a face-centered cubic cell, whilst the Al2Cu structure is body-centered tetragonal.3 The occurrence and stability of the various A2B type phases in transition metal alloy systems has recently been considered by Nevitt.4 The Ti2 Ni-type phases occur over a relatively narrow range of radius ratios from 1.14-1.26 with A partners mainly from the titanium group and B partners predominantly from the cobalt group. This suggests that both a favorable relative size of the atoms and a favorable electron concentration are necessary conditions for the existence of this structure type. A12Cu-type phases involving Ti group elements as A partners are formed with B partners from the cobalt and nickel groups, predominantly the latter, and have a higher radius ratio (1.27-1.29) than the Ti2Ni-type phases. The occurrence of both Sc2Pd and Sc2Co can be rationalized in terms of these considerations but SczNi is anomalous because of its high radius ratio. The radius ratios are calculated from the Goldschmidt CN12 radii and it might be postulated that the scandium atom is reduced in size in the compound. Unfortunately the apparent atomic size of scandium in the compound cannot be calculated from a knowledge of the structure and lattice dimensions. The crystal structure of the Sc2Au compound could not be identified from the powder diffraction pattern, but it is interesting to note that it is isostructural with a series of A2Au phases where A is a rare earth element.5 Pertinent information concerning the AB phases found in this investigation is given in Table 111. All the phases have the ordered bcc CsCl structure. The occurrence and stability of CsC1-type phases have recently been discussed by Dwight,7 who concludes that the relative sizes of the atoms do not appear to be a controlling factor (the radius ratios of all the known phases vary between 0.985 and 1.439) but that the occurrence of the phase is predominantly dependent on the relative positions of the A and B partners in the periodic table. As a measure of the stability of a given CsCl phase it has been customary to define a lattice contraction on alloying, DAB — dAB, where DAB is the AB interatomic spacing as calculated from the Goldschmidt CN8 radii and dAB is the AB interatomic distance in the compound (= v3/2 ao). Values of the parameter DscB -dScB for the compounds found in this investigation are given in column 5 of Table III and are plotted in Fig. 1. If the lattice contraction does in fact reflect the stability of a phase then Fig. 1 shows two very interesting trends when the position of the B partner in the periodic table is considered. Firstly, within any given group the stability increases in order on going from the first to third long period. Secondly, within any given period the stability increases in order as the B partner is taken from the copper, nickel, and cobalt groups. In the case of the second long period, the lattice contraction reaches a maximum at ScRh and then decreases to ScRu. The same trend could

Jan 1, 1962

By G. K. Manning, M. C. Udy, L. W. Eastwood

Those who have examined beryllium and beryllium-rich alloys under the microscope have noted the results of the difficulties encountered when preparing these materials for examination. Hard constituents are readily chipped and pulled out of the matrix, and the soft ones are easily gouged out or embedded with abrasive or other material. The matrix is easily deformed, which makes it very difficult to remove the effects of scratches. Furthermore, the matrix and some of the constituents are also readily pitted during etching, which makes the structure difficult to develop. The metallographic techniques designed to avoid these difficulties are neither radically new nor necessarily the best possible procedures. They were developed at Battelle to fill immediate requirements as part of a study of the preparation and pouring of beryllium melts as described in a separate paper. A part of the research program on the causes of gas unsoundness in beryllium castings entailed a study of the effects of such gases or gas formers as oxygen or oxides, nitrogen or nitrides, and carbon or carbides. These gases or gas formers, if dissolved in the melt, might be an important factor in the study of unsoundness caused by gas evolution in beryllium. Because it was necessary to be able to distinguish these gases or gas formers, if present as alloy constituents, from metallic phases also present as alloy constituents, a series of alloys was prepared with additions of the various possible metallic and non-metallic constituent formers. It should be emphasized that the constituents referred to as gases or gas formers are important in the study of gases in beryllium only if they form a part of the alloy, that is, if they dissolve in the liquid or solid metal. During the first part of the development of metallographic techniques, the Massachusetts Institute of Technology, unpublished report (TC 3315, Nov., 1945) by Paul Gordon, describing various microconstituents in beryllium, was quite useful. Of particular interest in this report is the confirmation of one of the conclusions drawn from the present investigation, that is, that a distinct oxide phase apparently does not occur in beryllium. The Preparation of Metallographic Specimens GRINDING PROCEDURE The original specimen is either sawed or cut on an abrasive wheel to a convenient size. For best results, the surface to be polished should not be more than about 1/4 in. square, and it is convenient to mount the specimens in bakelite to facilitate handling. Two alternative grinding procedures have been developed. As one alternative, specimens are ground successively on 120-, 240-, and 400-grit, wet-or-dry metallographic discs. The abrasive discs are revolved at 1750 rpm on a conventional pedestal grinder. The coarsest disc (120 grit) is used either wet or dry, and in most instances, it can be eliminated from the procedure. Grinding on the two finer discs (240 and 400 grit) is accompanied by the application of kerosene. The technique consists of holding an oil can, containing kerosene, in one hand and the mounted specimen in the other hand. While the grinding is being done, several drops of kerosene are applied every few seconds close to the center of the disc. Carbon tetrachloride serves at least as well as kerosene as a lubricant; perhaps it is slightly better, but it volatilizes so readily that an additional health hazard is involved. Light oils and water are not satisfactory for the finer grinding operations. The second procedure is perhaps slightly slower than the first and requires a more careful technique, but it eliminates the use of kerosene. The specimen is first ground wet on a 240-grit disc, followed by dry grinding on a 400-grit disc. Finer grinding does not appear to be necessary with either of the two alternative procedures. The pressures used throughout either grinding operation must be extremely light, that is, barely sufficient to hold the specimen in contact with the disc; otherwise, flow and chipping are almost certain to occur. In both procedures, it is essential that the discs be sharp and that they be discarded as they show evidence of becoming dull or loaded. In general, not more than four or five specimens can be ground on a disc before the disc becomes dull enough to warrant discarding it.

Jan 1, 1950

By J. H. Jackson, J. G. Kura, M. C. Udy, L. W. Eastwood

The melting and casting of any commercial metal depends upon the success with which the problems attendant to the handling of the specific metal are overcome. Common difficulties encountered in the handling of commercial metals are tendencies to burn or oxidize excessively, low fluidity, entrapment of dross, hot cracking, cold embrittlement, cold shuts, and un-soundness caused by gas evolution. Beryllium is not only subject to these same difficulties but is generally more sensitive to them than are the more common metals, thus necessitating more exact founding precautions. Characteristics of Beryllium Certain characteristics of beryllium which make it particularly difficult to handle in the plant or laboratory are as follows: 1. The melting point of beryllium is about 2400°F and pouring temperatures vary from 2600 to 2900°F, depending upon the degree of fluidity required. The extreme chemical activity, combined with the high temperatures, makes necessary the use of inert atmospheres, slags, or vacuum for protection during melting and pouring. Furthermore, beryllium tends to react with the melting crucibles, tools, and molds, thus requiring the selection of suitable materials and proper maintenance of these items. 2. The very marked absorption of gas by molten beryllium and the subsequent evolution of gas during solidification causes a great deal of difficulty with unsoundness. Beryllium castings may also be subject to unsoundness as a result of gas formation by chemical reaction with the mold surface during solidification. 3. The very marked chemical affinity between molten beryllium and the normal atmosphere causes the formation of dross. On relatively quiescent melts, this dross forms a very tenacious film which, if carried over to the mold, can cause defects such as the formation of skins or dross in the interior or on the surface of the casting; folds or defects similar to cold shuts may also be found. 4. During the pour and attendant turbulence, the dross may be mixed into the metal and then carried to the casting. There it may be entrapped during freezing and cause internal defects, or it may float to the surface and cause severe dross defects on the cope side of the castings. 5. Solid beryllium is very weak at a temperature near the solidus line; brittleness is also a problem at lower temperatures. Thus, hot and cold cracking must be guarded against. Scope of the Experimental Work All of these problems have been given consideration in the work at Battelle. Before the work was started at Battelle, it was customary to melt beryllium in a vacuum furnace or under flux in graphite-lined induction furnaces. Because of the difficulty of preventing gas unsoundness in beryllium castings, an investigation was undertaken primarily to study this particular problem and, secondarily, to devise methods of overcoming the other difficulties encountered in the founding of beryllium. The objectives of the laboratory work were multifold: 1. To devise a practical method of melting, other than vacuum melting, by means of which consistently sound beryllium castings could be produced. 2. To obtain fundamental data which would promote a better understanding of the causes of gas unsoundness in beryllium. 3. To develop a casting technique which would permit low melt temperatures, minimize dross defects and hot cracking, and eliminate reaction with the mold surface. Up to the present time, a considerable amount of progress has been made on the first and third objectives, with the result that it can now be safely stated that consistently sound castings can be made by the open-pot melting method, using argon as a protective atmosphere and a proper casting technique. There has been some progress on the second objective of the project, but it cannot yet be safely stated that the problem is completely understood. Most of the experimental work has been conducted in an enclosed melting and pouring apparatus in which very-close control of melting variables has been effected. Findings based on the results of the work conducted in this small experimental apparatus have been applied to large-scale melts which have been made by techniques suitable for duplication on a commercial scale.

Jan 1, 1950

By E. T. Hayes, A. H. Roberson, M. H. Davies

R. F. Dornagala and D. J. McPherson (Armour Research Foundation, Chicago)—I should like to compliment the authors for a workmanlike job in determining the partial phase diagram of a system comprised of two rnetals which are certainly not easy to work with. We are completing work at Armour Research Foundation on an Atomic Energy Commission-sponsored project for the determination of eight zirconium binary diagrams. Work on the Zr-Cr system has been completed and should be published within the next year. For our work, Westinghouse Grade 3 iodide crystal bar served as the zirconium melting stock. Johnson-Matthey, electrolytic chromium, specially treated for oxygen removal, was employed. The overall constitution of the system determined at Armour Research Foundation is in very good agreement with the present work. We found a eutectic at 18 pct Cr and 1280 °C, somewhat lower than the value reported. This temperature was confirmed by thermal analysis, incipient melting studies, and regular isothermal anneals. The eutectoid was located close to 1 pct Cr and 835°C by metallographic analysis of annealed specimens. Maximum solubility of chromium in /S zirconium was 4.5 pct at the eutectic temperature. Chromium solubility in a zirconium was less than 0.28 pct at all temperatures. We found the compound at 53 pct to melt around 1700°C, with an open maximum, but determined its crystal structure to be hexagonal close-packed (MgZn, type). The lattice parameters were in excellent agreement with those determined by Wallbaum in 1942. The diagrams are in substantial agreement, and .part of the differences are undoubtedly due to the use of different zirconium melting stock. M. K. McQuillan (Birmingham, England)—I read this paper with a great deal of interest, as it covered the same field as some work of my own.&apos; There are a number of points in the present paper on which I would like to comment. First, I should say that I, too, used zirconium prepared by magnesium reduction of the tetrachloride and electrolytically prepared chromium, and melted the alloys in a Kroll-type arc furnace. The purity of my alloys should, therefore, be comparable with the purity of those of the present authors, and any differences in our observations would not be expected to be attributable to this cause. The differences between my observations and theirs concern the presence of the eutectic, the temperature of the eutectoid, and the melting point of the compound. I would be very much interested in any further evidence the authors may have for the occurrence of the eutectic at 1380°C. During the course of my work I noted that a number of my alloys containing 60 to 90 pct Zr melted at about 1400 °C, and for a time assumed that a eutectic occurred at this temperature as described in the paper. On further investigation, however, I found that the structures of the as-melted alloys could not be made to fit in with this interpretation of the system. If a eutectic exists in this region of the system it would be expected that the as-melted alloys would show the usual type of cast structure, i.e., dendrites of the compound plus eutectic. This, however, does not occur, as may be seen from Fig. 9. The compound seen there is not dendritic in form, and the remaining material is by no means certainly eutectic. It may be argued that a compound such as ZrCrl would not form dendrites but would tend to crystallize in geometric shapes. In this case, however, I have evidence to the contrary, as on the chromium side of the compound, where a eutectic occurs at about 1545"C, the compound formed from the liquid takes on a conventional dendritic form, and the eutectic is observed in the interdendritic spaces in the usual way. There is no reason to suppose that the compound would behave differently in an alloy lying on the zirconium side of the compound composition if a eutectic existed there too.

Jan 1, 1953

By Robert J. White

Strong&apos;s equation for calculating bottom-hole pressure reduction due to gas cutting of drilling mud is corrected, resulting in a simpler equation which is easier to use. Use of the equation is illustrated by examples. It is shown that reduction of weight of a 10 lb/gal mud by 50 per cent at the surface due to gas cutting produces only n 3 per cent decrease in hydrostatic head at the bottom of a 5,000-ft well. It is also shown that at the surface 5 volumes of air per volume of mud are required to reduce the apparent mud weight from 8.5 to 6.5 lh/gal in a 3,000-ft well. Illustrative graphs are included to show the effect of various degrees of gas cutting on apparent mud weight at depths of 2,000, .5,000 and 10,000 ft and to show variation of apparent mud weight, with depth for a 100 lb/cu ft (13.37 lb/gal) mud gas cut to 90 lb/cu ft (12.03 lb/gal) at the surface. INTRODUCTION In 1938, Strong&apos; published the following equation for calculating reduction in bottom-hole pressure due to gas cutting of drilling mud h = 1/D [p + pn/100 In p + p(1-n/100)/p(1- n-100)] where: h = depth in feet P = pressure in atmospheres at depth h due to mud column only D = hydrostatic pressure in atmospheres of a col-umn of uncut mud 1 ft high p = back pressure at well-head (in atmospheres) n/100 = fraction by volume of gas in mud at well-head at back pres-sure p This equation was recently found to contain an error due to an incor-rect expression for variation of vol-ume fraction of gas with pressure. Values calculated by the original equation are close to the correct values for small percentages of gas for which it was derived but become increasingly erroneous as the gas content increases and are completely unusable at the very high gas con-tents employed in aerated mud. DERIVATION The nomenclature used is the same as in Strong&apos;s paper. The pres-sure dP exerted by a lamina of thickness dh at a depth h ft is ex-pressed by Eq. 1 where x = volume fraction of gas at depth h dP = D (l - x)dh . . . (1) When we express x in terms of the wellhead per cent gas n, the well-head pressure p and the pressure P at depth h, the result is Eq. 2. x = (np/p+p)/(100-n) + (np/P + p) When this is substituted in Eq. 1 and rearranged to separate the var-iables the result is dh = 1/D [dp + np/100-n dp/(P + p]. Integration between appropriate lim-its results in or if the wellhead is open so that p = 1 atm and we rearrange Eq. 4, the result is loss in head = hD — P = n/100-n In (P + 1) ...(5) Eq. 5 can be solved easily by successive approximation using hD as a first approximation for P on the right-hand side and calculating a first value for loss in head. This can then be used to get a new value of P using the left-hand side of the equation. Values converge very rap-idly even for quite large values of per cent by volume gas n. EXAMPLES The effect on bottom-hole pressure of 50 per cent gas cutting of the mud in a 5,000-ft well using 10 Ib/ gal mud will be calculated, we have: h = 5,000 ft 10 X 7.48 144 X 14.7 = 0.0353 atm/ft hD = 176.5 atm n = 50 Substituting these values in Eq. 5 and using hD as a first approxima-tion of P on the right, we have, approximate loss in head = 50/50 In (176.5 + 1) = 2.30 log 177.5 = 5.17 atm. We calculate a new value of P as follows:

Jan 1, 1958

By Fred H. Poettmann

The vaporization characteristics of carbon dioxide in a League City natural gas - Billings crude oil system were studied at three temperatures, 38°. 120°, and 202°F and for pressures ranging from 600 to 8,500 psi. Variation of carbon dioxide concentration up to 12 mole per cent in the composite showed no effect on the equilibrium vaporization ratios (K values) of the hydrocarbon constituents or on the K value of carbon dioxide itself. It was shown that carbon dioxide is more soluble in crudes than in distillates which is contrary to the behavior of methane. A working chart of carbon dioxide K values is presented. INTRODUCTION The study of the equilibrium vaporization ratios of mixtures of paraffin hydrocarbons has been rather thorough.2,6,7,8,9 In the past few years considerable attention has been paid to the vaporization characteristics of the so-called noncondensable gases such as nitrogen, carbon dioxide, and hydrogen sulfide in mixtures of hydrocarbons. since they usually occur to some extent in most crude oils and natural gases.1,3,4,5 Knowledge of this behavior is useful to both the production and refining phases of the petroleum industry. This paper reports the equilibrium vaporization ratios (K&apos;s) of carbon dioxide in a mixture of League City natural gas and Billings crude oil, and compares them to those obtained in a natural gas-distillate system. The equilibrium vaporization ratios for the hydrocarbon components in this system had previously been studied by Roland.&apos; In addition to the determination of the K values for carbon dioxide, the K values for methane and ethane were also determined in order to observe what effect, if any, the presence of carbon dioxide had on these K values. The concentration of carbon dioxide was also varied in order to observe the effect of this variable on the carbon dioxide K values. EXPERIMENTAL PROCEDURE The apparatus used in this study cotlsisted of a stainless steel equilibrium cell of about 2 liters capacity. The cell was mounted on trunions permitting rocking in a thermostatically controlled oil bath. Two high pressure valves fitted with steel tubing were mounted on the top of the cell. one was used for sampling the equilibrium gas phase and the other for sampling the equilibrium liquid phase by means of an induction tube within the cell. Stainless steel tubing from the bottom of the cell led to a mercury reservoir and manifold which was connected to a free-piston type pressure gauge manufac- lured by the American Instrunlent Ctr. and to a volumetric. putrip. The temperature of the oil bath was measured by means of a ralibrated mercury-in-glass thermometer. The recorded temperatures are believed to be accurate to ±0.5 °F. The pressures are correct to 22 psi. The crude oil used in this study was stock tank oil obtained from the Wilcox formation in the Billings Field, Noble County. Okla. The natural gas was obtained from the League City Field. Galveston County, Tex. The oil was treated with anhydrous calcium sulfate in order to remove the last traces of water. To insure a supply of constant composition gas at room temperature the cylinders of League City gas were cooled to about 30°F, inverted, and the condensed liquid was allowed to drain from the cylinders. The analysis of the gas and crude are tabulated in Table I. The carbon dioxide came from Pure Carbonic, Inc., and was .stated to have a purity of 99.5 per cent or better. The procedure used to obtain samples of the equilibrium liquid and vapor was similar to that employed by others making use of the rocking type equilibrium cell.6,7,8 The equilibrium cell was evacuated and calculated quantities of carbon dioxide, natural gas, and crude oil were charged to the cell to the desired pressure. In charging the equilibrium cell an attempt was made to maintain the ratio of the natural gas to crude oil as close as possible to that employed by Roland. After the cell was charged, samples of

Jan 1, 1951

By Walter Rose

In a recent technical note, Owen Thornton&apos; suggests that wetting liquid relative permeability may be derived from the relationship: where Pd/Pc is the ratio of displacement pressure to capillary pressure at the wetting liquid satdration Sw, and I is the resistivity index at this saturation. Thornton shows that this expression gives values for relative permeability in good agreement with those experimentally determined by Leverett. We have recently developed another expression for krw which seems preferable to Equation 1 since it requires fewer experimental data for its verification. This equation may be derived in the following manner. Making use of the analogy between mass transfer of fluid in a porous medium and electrical conductivity through the fluid in the same medium, we can postulate a hydraulic formation resistivity factor analogous to an electrical formation resistivity factor. From Poiseuille&apos;s Law the resistivity to flow in a tube of radius R is of the form 8u/R², where is the viscosity of the fluid. Similarly7 the resistivity to flow in a porous medium of the same dimensions as the tube is given by D&apos;Arcy&apos;s Law as where k is the permeability of the medium. The hydraulic formation resistivity factor, Ff, is thus the quotient of these two resistivities, or: But permeability is defined by the KO-zeny equation as: where: r is the average pore radius of the porous medium, L. is the average tortuous length of the average pore, + is the porosity, and L is the bed length. This gives Fr as a function of the (La/L) .-.-.tortuosity ratio and porosity, or in explicit form: where: T = (La/L)&apos;, and N is the number of pores of radius, r, which will be found in any cross sectional area, x R&apos;. That is, N = R²/r². It will be clear from the foregoing considerations that the hydraulic formation fat. tor should be dependent on the value of R which in every case must be arbitrarily selected. By analogy, the hydrauiic formation factor, Fcf, characterizing the porous medium at Sw<1,will be given by: R² NT. where ke is the effective wetting liquid permeability obtaining at Sw<l, and Te is the square of the (Las/L) ratio defined by Thornton. Therefore, the hydraulic resistivity index, If, is: However, Thrnton gives I as: and it follows that: Equation 2, when checked against the data of wyckoff and Botset² and some of the Morse et al data³, gives comparisons as shown at the bottom of this page. Computations based on Leverett&apos;s data, quoted by Thorntaon, gives computed krw values somewhat lower than the experimental values. Moreover, other instances can be cited where we find that neither Equation 1 nor Equa tion 2 is checked by experimental data. The work of Botset&apos; on the Nichols Buff sandstone and Morse et a1 on oil wetted Bradford sandstone are such instances. A reason for these discrepancies may lie in the fact that if both Equations 1 and 2 are presumed always to give accurate values for krw, it follows that PC = Pd/Sw". Such an expression, it is well known, is too simple to describe accurately the capillary pressure behavior of all porous media. However, it is believed that a particular advantage resides on the use of Equation 2, since it is not dependent for its utility on a knowledge of the capillary pressures obtaining in dynamic flow svsterns. No practical technique for measuring the capillary pressures characterizing the fluid distributions in dynamic flow systems has yet been proposed. Acknowledgment is given to Dr. Paul D. Foote, executive vice-president of the Gulf Research and Development Company, for permission to publish this note. 1. Owen F. Thornton, "A Note on the Valuation of Relative Permeability," J. Pet. Tech., 1:7, Section 1, July, 1949. 2. R. D. Wyckoff arid H. G. Botset, "The Flow of Gas-Liquid Mixtures through Porous Media," Physics, 7:325-345, 1936. 3. R. A. Morse, P: L. Terwilliger, .and S. T. Yuster, "Relative Permeability Measurements of Small Core Samples," Oil and Gas J., 46:109-125, Aug. 23, 1947. 4. H. G. Botset, "Flow of Gas-Liquid Mixtures Through Consolidated Sand," Trans. AIME, 136:91, 1940.

Jan 1, 1949

By J. T. Norton, H. Blumenthal, S. J. Sindeband

The interstitial phases formed by the transition elements with carbon, nitrogen and boron constitute a unique class of substances which are of considerable technical interest because of their well developed metallic properties and their high hardness and melting points. They are also of interest from the point of view of structure. It was pointed out by Hagg1 some years ago that the principal factor determining these structures was the relative sizes of metal and metalloid atoms. He predicted that if the ratio of the radii of metalloid to metal atoms was less than 0.59, the metal atoms would be arranged in a close-packed fashion of relatively simple type. This prediction has been amply confirmed. It appears, however, that this specification applies most generally to those structures in which the metalloid atoms occupy isolated positions in the lattice and there is no tendency for strong binding between the metalloid atoms themselves. The series of borides of the type MeB2 formed from the transition elements of the fourth (Ti, Zr) and fifth (V, Cb, Ta) groups of the periodic table provide an opportunity to investigate this situation further. If one takes as a basis the radius of 0.87 A for the boron radius and the Goldschmidt values for the metal atoms in 12 coordination, then the radius ratio varies from 0.54 for zirconium to 0.64 for vanadium, which latter is considerably greater than Hagg&apos;s limit of 0.59. It was of interest, therefore, to see if these five elements would form borides of the MeB2 type and have simple isomorphous structures. When this investigation was initiated, relatively little information had been published on the structure of this group of borides. McKenna2 reported the preparation of ZrB2 by a carbon reduction process. Its structure was hexagonal and the approximate lattice constants were given as a = 3.15 A, c = 3.53 A. Ehrlich3 reported the structure of TiB2 as being of the C 32 type with a = 3.02, c = 3.21 and c/a = 1.06 A. Recently, Kiessling4 published the results on ZrB2, showing it to be one in which the metal atoms are arranged in a simple hexagonal lattice with the boron atoms in flat sheets, midway between the layers of metal atoms. The structure is C 32 type with a = 3.169, c = 3.530 and an axial ratio =1.11 A. He also states that CbB2 and TaB2 are isomorphous with ZrB2. Preparation of Borides The borides of titanium, zirconium, columbium and tantalum were made by the electrolysis of fused salt baths after the method described by Andrieux.5 The bath, totalling about 6500 g in each case had the following general composition: Metal Oxide + B2O3 + CaO + CaF2. The actual proportions of the ingredients were determined for each individual case. Although Andrieux reports the preparation of vanadium boride by the same electrolytic method, several attempts proved unsuccessful. However, it was possible to prepare VB2 by the carbon reduction method used by McKenna to produce ZrB2. The mixture consisted of V2O5 + 6B2O3 + 11C and the reduction was carried out in an induction heated graphite crucible. This method proved satisfactory for ZrB2 and TiB2 and undoubtedly the others could be made in the same way. The borides, which were all in the form of fine gray metallic crystals from the electrolytic bath or gray powders from the reduction process, were carefully separated from other constituents and analyzed chemically for metal and boron content. The densities of the boride powders were measured using a standard 10 cc pyenometer at 18°C and ethyl benzene proved to be the most satisfactory liquid for this purpose. X Ray Technique The boride crystals, as prepared, were too small for single crystal examination so that powder techniques were employed. Patterns of the finely ground borides were prepared, using the Norelco recording X ray spectrometer. The lines on these patterns were indexed with the aid of Hull-Davy charts and the approximate dimensions

Jan 1, 1950

By Alan Stanley

THE Maclntyre Development of National Lead Co. is located at Tahawus, N. Y., in the heart of the Adirondack Mountains. Operations involve the mining and concentrating of a titaniferous iron ore to produce ilmenite and magnetite concentrates. A general description of the operation and metallurgy has been given by Frank R. Milliken.1 Pigment plant production demands that the MacIntyre mill produce a 44.7 pct. TiO2 ilmenite concentrate. To achieve the required ilmenite grade and tonnage it is important that the table concentrate grade be closely controlled. Unfortunately, however, the titaniferous orebody which feeds the Maclntyre mill is not uniform. Ore dressing characteristics vary from one end of the orebody to the other, and from one level to the next.. The changeable nature of the mill feed precludes a single adjustment of the equipment for long periods of time. Thus the operators must constantly watch the equipment to insure a uniform concentrate from the fine and coarse tables and Wetherills, or dry magnetic separators. Chemical assaying of mill products requires about 4 hr from the time the sample is taken until assay results are obtained, and this is available only on a two-shift basis. The ore may change rapidly, even several times during a shift, so that assay results lose most of their control value by the time they are reported to the mill operating crew. Members of the crew have therefore tried to evaluate the table and Wetherill concentrate by visual inspection, since through long experience the shift operators, under most circumstances, can gage closely the grade of the mill products. However, there are times when the, physical nature of the ore is radically different from normal. Under these conditions visual inspection is of no value, and at such times final ilmenite as low as 43 pct TiO2 has been produced and shipped before the assay results have been received. The specific gravity method of assaying for TiO2 has been attempted to eliminate the shipping of ilmenite below normal grade as well as to help control day to day and hour to hour mill production. Table I shows the minerals found in the Maclntyre ore along with their average weight proportions and specific gravities. The first two products considered for the specific gravity method were fine and coarse table concentrates. It was reasoned that these products were essentially ilmenite with the higher specific gravity gangue minerals. Since they were always produced the same way, and the desired grade of TiO2 was always constant, the specific gravity of these materials would increase or decrease as the amount of ilmenite increased or decreased. Thus for table concentrates which assayed 40 pct TiO2 a constant gravity would invariably be obtained, and as the TiO2 value changed the specific gravity would change in direct proportion. The third product considered was Wetherill ilmenite. It was assumed that a desired grade of 44.7 pct TiO2 would also always contain the same amount and type of gangue minerals along with the ilmenite, and thus would always have the same specific gravity. As the TiO2 value of the ilmenite concentrate changed so would its specific gravity. Dr. Kenneth Vincent, chief metallurgist of the Baroid Division of National Lead Co. at Magnet Grove, Ark., ran specific gravity tests on 17 samples of the desired products. The lowest specific gravity reading assayed the lowest in TiO2 and as the specific gravity increased the trend was for the TiO2 assay to increase, see Fig. 1. Since these results warranted further investigation, a 500-g capacity Torsion balance and 250 ml Le Chatelier specific gravity bottles were obtained. [ ] Shift samples of fine table concentrate, coarse table concentrate, and final ilmenite were tested. Each sample was split and 85 g weighed on the Torsion balance. The Le Chatelier bottle was filled with water to a zero mark. To avoid wetting the neck of the bottle it was found necessary to do this

Jan 1, 1952

By I. R. Kramer

In his technical note entitled "Specimen Temperature During Electropolishing of Aluminum Crystals" Dr. Nakada 1 reported that the temperature of his aluminum specimen increased 65°C when it was polished electrolytically; he therefore concluded that the temperature of the specimens used in our work (Nakada&apos;s Refs. 4 and 5) similarly increased by this amount. From this he further concluded that the change in plastic-flow characteristics associated with the removal of the surface by electropolishing during deformation were due solely to a temperature effect. We believe that these conclusions are not justified. It is, of course, realized that the amount of the temperature increase is associated with the total heat transfer of the entire system, including the efficiency of the stirring action, heat flow through the grip on the specimen, and so forth. Of great importance is the type of electrolyte used for polishing. For example, in Dr. Nakada&apos;s experiment a methanol-perchloric acid solution was used. This solution has a relatively low conductivity and for the current densities of 0.3 amp per sq cm the electrical input appears to be 30 to 40 w. In our research a methanol-nitric acid solution was employed and for the size of specimen employed by Dr. Nakada the power never exceeded 7 w. There are major differences in his test apparatus which also appear to affect the temperature rise. In our case a steel specimen holder was used in order to provide a good heat sink and conduction path. The cathode was a coiled aluminum tube through which a coolant was passed to provide additional cooling capacity near the specimen. The stirrer was placed in a position to obtain maximum cooling efficiency. On the other hand Dr. Nakada used a teflon grip to support the specimen at one end only and a flat copper cathode, thus providing a much less efficient heat sink as compared with the metal grips used in our studies. The relationship between current density and the temperature increase for two sizes of aluminum crystals tested in our tensile apparatus is shown in Fig. 1. The temperature measurements were determined from a thermocouple spot-welded to the surface of the specimen. The thermocouple was protected from the acid by means of a thin film of stop-off lacquer which covered just the outer surface of the thermocouple junction. Whereas Dr. Nakada reported a time delay of 8 min to obtain thermal equilibrium, our temperature change occurred in less than 15 sec. This emphasizes the importance of the heat transfer in the entire system. However, readings were taken over a period in excess of 5 min to assure thermal equilibrium. The data given in Fig. 1 were also confirmed by determining the thermal expansion of the specimen in a sensitive creep apparatus. As may be seen, for the smaller specimen the increase in temperature is 8°C for a current density of 1.5 amp per sq in. The majority of our data on the effects of surface removal on the plastic behavior of aluminum were obtained at current-density values at or below this value. Above 1.5 amp per sq in. the temperature rise is uncertain; for under certain conditions, especially in the vicinity of 2 amp per sq in., the anode can become polarized and the current flow is erratic. This condition is easily recognized because wide fluctuations in the creep and stress-strain data make it virtually impossible to obtain reliable results, a condition which was always avoided in our work. The temperature increase for the larger specimen is less than that of the smaller specimens below a current density of 1.5 amp per sq in. At a current density of 2 amp per sq in. the temperature increased 13°C. The above temperature data are in accord with observations made during creep experiments. Using a transducer capable of detecting strain in the order of 10 -6, temperature changes in excess of 8°C were not detected when the current density was increased to as high a value as 1.5 amp per sq in. Finally we wish to point out that our experimental data cannot be explained solely in terms of a heat effect. For example in Fig. 1 of Ref. 2, the change in slope of Stage II as a function of the rate of re-

Jan 1, 1965