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By J. S. Kasper, R. M. Waterstrat, B. F. Decker

THE existence of v phase in the Mn-Mo system was discovered in this laboratory several years ago,' but neither the conditions of its formation nor its composition were known, and preliminary attempts to reproduce the phase were unsuccessful. We wish now to specify the information appropriate to phase formation on the basis of experiments performed since that time. The starting materials were in every case electrolytic manganese and high purity molybdenum. Two methods of preparation were employed: l—arc-melting varying combinations of the elements in an inert atmosphere and subsequent heat treating, and 2—sintering compressed mixtures of finely divided powders of the elements. In the latter method, the powders were first passed through 200 mesh screen and then compressed into cylinders of % in. diameter and % in. length, which were sintered at elevated temperatures in an atmosphere of dry hydrogen. For some samples, the sintering temperature was 1200°C (for 1 hr), and these were then heat- treated at lower temperatures for times up to 24 hr. Eventually it was found, for the proper composition, that essentially pure a phase could be produced by sintering at 1125°C for 3 hr. Quenching to room temperature was effected by means of a stream of cold, dry hydrogen in a water-cooled chamber. The arc-melting procedure was found to be unsatisfactory after an investigation of many samples at different compositions and temperatures. Large quantities of manganese were vaporized during melting and none of the products were homogeneous or contained extended regions of pure phase. Nonetheless, these experiments established that no formation occurs in the Mn-Mo system below 1115oC, and indicated, at least roughly, the composition range of interest for further exploration. The more definite results obtained from samples produced by the second method are given in Table I. A portion of sample 2 heated for 16 hr at 1000°C in a Vycor tube transformed to molybdenum plus unidentified phases of complex X-ray pattern. From these few results it appears that the region of phase is quite narrow in composition. It is of interest that the composition is such as to make for difficulties in correlating this structure on an electron atom basis with other a structures of iron, cobalt, and nickel. In that respect Mn-Mo shows the same anomaly as Mn-Cr and Mn-V systems.' A second feature is that in common with the two other known molybdenum (Fe-Mo and Co-Mo), Mn-Mo v exists only at elevated temperatures. The X-ray powder pattern of the pure a phase of Mn-Mo is given in Table 11. It agrees well with the patterns established for other structures, especially with that for Fe-Mo as given by Goldschmidt.An attempt is being made to establish whether an ordering of the respective atoms occurs and such information will be reported in a future publication. Acknowledgment The authors acknowledge gratefully the assistance of Mrs. J. R. Belanger in some portions of this work. References 'J. S. Kasper, B. F. Decker, and J. R. Belanger: Journal of Applied Physics (1951) 22, p. 361. 2 A. H. Sully: Journal Inst. Metals (1951) 80, p. 173. H. J. Goldschmidt: Research (1949) 2, p. 343.

Jan 1, 1954

INTRODUCTION Besides the European export credit agencies covered in Ted Rides' paper in this Chapter, other agencies are also active (see Appendix) but the most notable for mining projects are The Export-Import Bank of the United States ("US Exim") and the Export Development Corporation ("EDC") of Canada. Mexico's Fomex is basically a short-term trade-finance fund administered by the Central Bank. US Exim This independent agency can provide loans, guarantees, and insurance. Like all export-credit agencies, its mandate is to support the export of goods and services from the US as a means of competing against other countries' products. If a piece of mining equipment can only he made in the US, the US Exim may very well not provide any financial assistance. (It is important not to place the order for any item for which export credit is sought because, once ordered, the situation is no longer competitive in US Exim's eyes.) Direct Credits and financial guarantees ("buyer credits") are commonly in amounts greater than 85 million and for terms longer than six years. An example here is the $48.5 million provided to PT International Nickel Indonesia (see Robert de Gavre's paper in Chapter 12). US Exim usually requires a 15% downpayment and, therefore, finances up to 857 of the goods; less if the US content is lower. The dollar funding can he US prime, London Interbank Offered Rate (LIBOR), or other sources. Exim can fund in either or both of the following ways: 1. Under a US bank Letter of Credit ("L/C") 2. Reimbursement to the buyer/borrower via a US bank account. US Exim will, without charge, issue a preliminary commitment. It will, however, need to approve the various credit agreements and prefers to tie other parallel financings into one loan agreement. US Exim's total commitments are large, up to $5R billion in aggregate under various programs. US Exim has been the world's leader in medium-to long-term minerals project financings/ co-financings but suffers from (i) aggressive foreign export-credit competition whereby other nations mix in soft-loans or aid programs ("mixed credits") to increase the percentage financed and lower the interest margin and (ii) an imbalance in its own cost of funds. A common US Exim package would be as follows: 15% Banks under US Exim guarantee, floating rate over prime or LIBOR. 35% US Exim funding, fixed rate 35% Pefco funding, fixed rate 857 Drawn down pro-rata under US bank L/C 15% Cash down payment (may have been financed within a project/corporate credit) 100% Repayment usually begins six months after planned start-up in equal semi-annual instalments, with the banks usually paid out first, Pefco next, and US Exim last. Medium-term credits ("supplier credits") are issued for US equipment exports for terms up to five years, again for 85% of the equipment costs although the exporter is expected to bear at least 10% out of that 857 for its own risk. The buyer is required to be a first-class credit such as some governments or highly credit-worthy companies. Otherwise a bank L/C would be required. (This may be wrapped into an overall project-finance package for a minerals development. The project-finance banks provide an L/C to US Exim instead of funding that portion themselves.) US Exim guarantees 100% of the political risk and either 85% or 95% of the commercial risk for

Jan 1, 1985

By C. D. Stahl, E. E. Templeton, R. F. Nielsen

It has been customary, in predicting saturation changes, to use the Leverett fractional flow formula", obtained by eliminating the unknown pressure gradient from the generalized Darcy equations for the separate phases. The formula presents difficulties in the case of counterflow, since the "fractional" flow may be negative, greater than unity, or, in the case of a closed system, infinite. Recently, it has been shown by several authors that the corresponding equations (with capillary pressure and gravity terms) for actual flow of the phase may be used just as well. These equations are in agreement with Pirson's1 statement that, if the two mobilities differ considerably from each other in a closed system, the flow is largely governed by the lower value. The present study was undertaken because of an apparent lack of experimental data on gravity counter-/low with which to test the theory. A 4-ft sand-packed tube in a vertical position was employed. Electrodes for determining saturations by resistivity were spaced along the tube, one phase being always an aqueous salt solution. Air, heptane, naphtha, or Bradford crude oil was used for the other phase. A reasonably uniform initial saturation was set up by pumping the phases through the system, alter which the tube was shut in and saturation profiles obtained at definite intervals. Cumulative flows over certain horizontal levels were obtained by integration of the distributions; hence, differentiation of the cumulative flows with respect to time gave instantaneous flow rates. To compare experimental and theoretical flow values, capillary pressures were assumed given by the final saturation-distribution curve. The upper part corresponds to the "drainage" region and the lower part to the "imbibition" region, where trapping of the nonwetting phase occurred. While calculations indicated that the capillary pressure saturation function and, probably, the relative permeability saturation functions changed during the segregation, the relation of the measured rates to saturation distributions are in general accord with the frontal-advance equation. It appears that the Darcy equations, as modified for the separate phases, are generally valid for counterflow due to density differences. The usual method of predicting saturation changes, which involves a continuity equation and the elimination of the unknown pressure gradient from the flow equations, should therefore be applicable. However, the need for advance knowledge of drainage and and imbibition "capillary pressures" and relative permeabilities during various stages presents difficulties. INTRODUCTION The present study was undertaken because of a seeming lack of experimental data relating to vertical counterflow of fluids of different densities in porous media. In particular, it was desired to determine whether data obtained from these laboratory tests were in accordance with certain mathematical treatments of counterflow which have been proposed. The gravity "correction" has been incorporated into the flow equations (and, hence, into displacement theory) nearly as long as both have been used. field4 and laboratory5 data have generally borne out the validity of the theory as applied, for instance, to downward displacement by gas, with all fluids moving downward. However, the modifications for counterflow have only recently been pointed out. 2-3 It has been customary to use fractional flow rates instead of actual flow rates in displacement calcuIations. In the case of counterflow, this results in negative values, values greater than unity and, when rates are equal and opposite, in infinite values. As pointed out by Sheldon, et a1,3 and by Fayers and sheldon,2 actual flow rates may be used just as well. The fact that these may be of opposite signs for the two fluids does not present any difficulty.

By A. P. Young, F. C. Holden

IN many of the early investigations of the aging of titanium alloys, it was observed that the retained beta phase could be aged to a high hardness without an apparent change in microstructure; moreover, in some alloys it was found that even a very rapid quench produced beta having an anomalously high hardness. What appeared to be hard beta phase was designated as "beta prime," to distinguish it from the softer normal retained beta phase. Frost and co-workers'.' demonstrated that the increased hardness is caused by the formation of a metastable phase, omega, which can be identified from its X-ray diffraction pattern. This reaction also has been studied by Brotzen, et a1.,3 and the structure of the omega phase has been published by Silcock, et al.," and by Austin and Doig.3 The X-ray diffraction analysis by Austin and Doig indicated that omega is low in alloy content, approaching the composition of the stable alpha. The aging process proceeds by the path Thus, overaging results in the formation of alpha and the ultimate disappearance of omega. This is accompanied by a decrease in hardness and a recovery of ductility. The present work represents a study of the aging process in a high-purity Ti-6.4 Mn alloy, in which optical and electron microscopy, X-ray diffraction, and hardness data were correlated. The specimens, 1/8-in. sections cut from 1/4-in.-diam rod, were heated in argon to a temperature just into the beta field (810°C), held for 1 hr, and water-quenched. The aging samples were heated in air for 1 hr at 300 to 500°C. The specimens were ground and mechanically polished, finishing with alternate etching and polishing on a slow-speed wheel to remove disturbed metal from the surface. The surface finally was swab-etched, rinsed with tap water, and air-dried. The etchant used was an aqueous solution containing 1 1/2 pct HF and 3 1/2 pct HNO3. This procedure is identical with that used for preparing metallographic specimens, except that the optimum degree of final etching required for electron microscopy may vary from that used for light microscopy. Metal replicas, backed with silica, were prepared from plastic strip-pings for examination with the electron microscope. Complete details of the procedures used for preparing these replicas are available elsewhere." Fig. 1 shows a comparison between the structures revealed by the electron microscope and those obtained by conventional light microscopy. Hardness and X-ray diffraction data are listed in Table I. No evidence of a second phase is apparent in the optical micrographs for the as-quenched sample, or for the specimens aged at 300 or 400°C; fine alpha particles can be seen in the specimen aged at 500°C. In the electron micrographs, visible equiaxed pocks appear in the as-quenched specimen, and, with increasing density, in the samples aged at 300 and 400°C. After aging at 500°C, the structure becomes markedly coarser and develops an oriented appearance of a second phase, coincident with the appearance of visible alpha particles in the light micrographs. These observations are confirmed by X-ray diffraction and hardness data. In these specimens, aged for 1 hr, the intensity of the omega pattern increases to a maximum at the 400°C aging temperature, corresponding to maximum hardness and the maximum density of pocks in the electron micrographs. At this point the beta phase shows a definite enrichment in Mn. At 500°C, little or no omega re-

Jan 1, 1959

By C. M. Wayman, G. R. Srinivasan

A metallographic study of the isothermal products formed between 750° and 285°C was made in an Fe-7.9 wt pct Cr-1.11 wt pct C alloy, and a time-temperature-transformation diagram was determined. The study shows that the austenite decomposes into three different products: pearlite above 540°C, ferrite and carbide between 540° and 300°C, and lenticular bainite below 300°C. No upper bainite forms in this alloy. The results are discussed in terms of carbon diffusion models for upper bainite formation. AUSTENITE transforms into several products depending on the temperature, composition, and rate of cooling, and the various transformation products have been a source of controversy for a long time. Since the classical study of Davenport and ~ain' extensive work has been carried out. The present study concerns the isothermal transformations in an alloy which was used for a detailed investigation of bainite crystallography and provides information supplementary to the work of Lyman and Troiano who studied austenite decomposition in steels containing 1 pct C and varying amounts of chromium. Their work showed that increasing the amount of chromium in high-carbon steels had the effect of depressing the B, temperature and of shifting the TTT curves to longer times and lower temperatures. They further found that if the chromium content is increased in a 1 pct steel to about 9 pct no bainite would form even after a period of 100 days. However, a preliminary investigation by the present authors showed that bainite plates do form in steels containing about 8 pct Cr and 1 pct C. In view of this and some results from a thin-foil electron microscope investigation of the bainite formed in the present alloy: it was considered desirable to investigate the other isothermal products as well. EXPERIMENTAL PROCEDURE The alloy used in the present investigation was obtained from a triply vacuum-melted ingot prepared from high-purity materials. Chemical analysis for the alloy verified the composition to be Fe-7.9 wt pct Cr-1.11 wt pct C. Metallographic observations were made on i by i by « in. specimens which were aus-tenitized at 12 50°C for 50 to 60 hr in evacuated quartz capsules and then water-quenched. Since the M, temperature for this alloy is below room temperature, the homogenizing treatment produced a completely austenitic structure consisting of very coarse austenite grains (ASTM #0-1). Several samples of the austenitized specimens were metallographically prepared and observed for any proeutectoid carbide separation. It was found that all the carbon was in solution. The water-quenched specimens were upquenched and given isothermal treatments at temperatures between 285" and 750°C for varying periods in molten salt or lead baths. The specimens were then water-quenched, and those showing less than 5 pct transformation were used for plotting the beginning of the austenite decomposition. To ensure the removal of the disturbed layer, the mechanically prepared specimens were electropolished in a 1:6 HzS04, CHSOH solution for 10 to 15 sec at 20 v. Final polishing was done with a vibratory polisher using 0.05-p alumina. Various etchants including nital, ferric chloride, and hot ferricyanide (Murakami's reagent) were used to bring out details in the different transformation products. The ferricyanide etch was used whenever the preferential etching of carbides was desired.

Jan 1, 1969

By J. R. Morison, M. P. O’Brein, J. W. Johnson, S. A. Schaaf

The force exerted by unbroken surface waves on a cylindrical object, such as a pile, which extends from the bottom upward above the wave crest, is made up of two components, namely: 1. A drag force proportional to the square of the velocity which may be represented by a drag coefficient having substantially the same value as for steady flow, and 2. A virtual mass force proportional to the horizontal component of the accelerative force exerted on the mass of water displaced by the pile. These relationships follow directly from wave theory and have been confirmed by measurements in the Fluid Mechanics Laboratory of the University of California, Berkeley. The maximum force exerted by breakers or incipient breakers is impulsive in nature, reaching a value much greater than that produced by unbroken waves but enduring for only a short time interval. This impulsive force represents the ultimate development of the accelerative force and is produced by the steep wave front and large horizontal acceleration at the front of a breaker. This impulsive force greatly exceed. the drag force computed from the particle velocities of the breaker. The reader is cautioned that these preliminary results are applicable only to single piles without bracing and are likely to be modified somewhat where multiple piles are driven, one within the influence of the other or where multiple piles are connected by submerged bracing. This paper is essentially a preliminary report submitted at this time because of the current importance of wave forces in the design of offshore structures. An extended series of additional experiments is planned for the near future. Theoretical Relationships For the sake of simplicity of treatment, the theory will be developed from the equations for waves of small amplitude. The horizontal displacement of a water particle is described by the equation 2p cosh — (d + z) H L 2pt X =----------------------sin ----- . , (1) 2 2pD T sinh------ L The horizontal component of the orbital velocity is obtained by differentiation with respect to time as 2p cosh — (d + z) pH L 2pt u = ------------------- cos— .... (2) sinh- L The acceleration of the water particles at any position is obtained by again differentiating with respect to time as 2p cosh — (d + z) 9 u -2vH L 2pt -----=----------------------------sin ----- . . (3) 3 t T2 2pd T sinh------ L where H = wave height — ft L = wave length — ft d = still water depth — ft z = depth below the still water measured negatively downward — ft. T = wave period — sec t = time — sec The force exerted on a differential section, dz, in length is pD2 s u pD 1 dF= [CM (p/4) st + Cn/2 u2] dz • • (4) where D = pile diameter — ft p = water mass density — slugs/ft3 C, = coefficient of mass C,, = coefficient of drag Substituting for a s u/s t arid u2 from Eqs. (3) and (2), the force per unit length at any position z is dF p2 pD H2 &apos; / = — [- fM sin ? ± fD cos2 ? ] . . . (5) dz 2T2 fM D fD 2pt Cm = pA/H:CD = A2;? = T [+ cos2 ? for 0 < ? < p/2 cosh— (d+z) 3p L — < o < 2p Sin L -cos2 ? for p/2 <? <3p/2 The sin 9 term (inertia) i- negative for 0 < 0 < p and positive for p < ? < 2p. Values of A and A&apos; appear in Fig. 1

Jan 1, 1950

By P. P. Reichert, L. S. Gournay, N. T. Burdine

An investigation of equivalent pore entry radii in typical samples of petroleum reservoir rock and the pore volume associated with each value of pore entry radius has been made. Theoretical discussions together with experimental procedures for obtaining pore entry radii and the distribution of pore volume with pore entry radii are presented. Experimental results on a number of core samples, along with typical distribution curves, are shown. Data on the per cent of the pore volume filled by mercury at a pressure of 1500 psi are included. The results of re-runs of samples, made possible by regenerative apparatus, show the repeatability of the data and indicate the amount of physical change in the samples by mercury penetration. Theoretical equations for calculating permeability from pore size distribution data were derived and the results of such calculations are compared with measured gas permeability data. The effect of the shape, surface area, and weight of the sample on the pore size distribution of reservoir rocks was investigated experimentally. Mercury capillary pressure curves are compared with those obtained by the porous diaphragm method using pas to displace water. Standard core analysis techniques, in general, lead to quantities which are statistical averages of the varying properties of the samples under examination. Although such statistical information has real value in predicting the gross performance of porous bodies. it fails to provide fundamental information concerning the properties of the porous medium itself or any processes which may be occurring in it. For example, a gas permeability measurement on a core sample is an indirect way of determining an average pore radius for that particular sample. Since there are many combinations of pore radii that will give the same radius. and, hence, the same permeability, no information is obtained on the pore size distribution. Furthermore, similar values in permeability do not imply similarity in other properties of a porous medium. For instance, it is possible to have two core samples with identical permeability which would have different residual oil contents at the end of an air-oil drive, or even different amounts of interstitial water. It has been recognized for some time by the petroleum industry that a determination of pore size distribution for porous reservoir rocks offered promise of increased understanding of fundamental flow processes in the porous matrix. and therefore of petroleum res- ervoir performance in general. There have recently been published several methods for determination of pore size distribution in porous materials. A report is given here of the modifications in equipment and technique required to adapt one of these methods to measurements on petroleum reservoir core samples. Although only a few correlations or applications of the method are available for presentation at this time, the technique is brought to the attention of the industry so that the opinions and experience of others with this or similar techniques may be exchanged. It seems possible that the method will have wide application in the future. METHOD There are three general methods which may be employed to measure the pore size distribution in naturally occurring rock formations. One method1 is based on experimentally determined adsorption isotherms for calculating the surface area of the porous medium. Knowing the surface area and the pore volume, a rough estimate of the pore radius can be made. Since this method depends on the thickness and uniformity of the adsorbed layer, the validity of the results would be highly questionable. A second method utilizes capillary pressure data obtained by static dis-

Jan 1, 1950

By J. W. Marx, R. H. Langenheim

The injection of heat-bearing fluids may offer a wider application to secondary and tertiary recovery from conventional oil reservoirs than inderground combustion since the process is more easily controlled and the reservoir requirements, in general, are less critical. In all cares, conduction heat losses to overburden and un-derburden will impose an economic limit upon the size of the area which can be swept out from any one injection point for any given set of conditions. The present report describes a method for c.rtin~ating thermal invasion rates, cumulative heated area, and theoretical economic limits for sustained hot-fluid injection at a constant rate into an idealized reservoir. Full allow-ance is made for non-productive reservoir heat losses. Required solutions can be obtained directly from the numerical tables given here, as soon as all operating conditions are specified, withou extensive mathematica1 ~nanipulation on the part of the user. The injection of a heat-bearing fluid into a reservoir is frequently proposed as a means of secondary or tertiary oil production. This form of thermal recovery may offer a wider application to conventional oil reservoirs than underground combustion since the process is more easily controlled and the reservoir requirements, in general, are less critical. Because of its large gross heat capacity, steam appears to be the most efficient heat injection medium, although mixtures of steam and other gases, hot water, hot oil and hot non-condensable gases also have been employed. Whatever the nature of the injection medium, economic evaluation of such thermal recovery processes will depend upon thermal invasion rates, or rates of productive reservoir heating, at any given time after the start of heat injection. In all cases, conduction heat losses to overburden and underburden will impose an economic limit upon the size of the area which can be swept out from any one injection point, for a given set of reservoir conditions, at any given heat injection rate. The present report describes a method for estimating thermal invasion rates, cumulative heated area and theoretical economic limits for sustained heat injection at a constant rate into an idealized reservoir, making full allowance for non-productive reservoir heat losses. Required solutions can be obtained directly from the nu- merical tables given here, as soon as all operating conditions are specified, without extensive mathematical manipulation. It should be noted that ordinary water flooding may be used to move an annular-heated zone outward, even though the economic areal limit for straight heat injection has been reached. Thus well spacing need not be confined to the areal limits as determined here. However, the present calculations do not cover such supplementary heat scavenging programs. The operating element consists of a radial flow system, concentric about the point of injection, with the idealized step function temperature profile illustrated by the dashed line in Fig. 1. The solid curve shown in Fig. 1 gives a qualitative picture of the true radial temperature distribution. It will be shown later that the expressions given below, which are derived from the simplifying step idealization (dashed line in Fig. I), also can be interpreted in terms of the more realistic temperature distribution shown in Fig. 2. For this case, the thermal invasion radius is simply redefined as the distance from injection well to the mid-point of the temperature distribution.

By J. F. Havard

Gypsum is a useful industrial mineral found abundantly on the earth&apos;s crust. It is inexpensive to mine and process, and its calcined products have a wide range of readily controllable properties such as strength, density and setting time. It has proven to be such a useful material indeed, that ten American companies, operating some 57 calcining plants in 25 states in 1958, produced or imported in that year a total of 13,649,000 tons of the crude mineral valued at $39,361,000, which they then converted into manufactured products with a value of $329,070,000. Gypsum (CaSO4.2H2O) is calcium sulfate with two molecules of combined water, which are responsible for most of its useful properties. It is closely associated in most deposits with anhydrite (CaSO4), which contains no combined water and has limited commercial value in the United States. Man has long recognized the useful qualities of gypsum. It was utilized by the Egyptians in the construction of the pyramids and, later, by the Romans for important structures. Many of the ancient peoples prized gypsum for artistic and ornamental purposes, carving statuary from alabaster and making casts with plaster. The tabular variety, selenite, was used for windows, and the light transmitted through these windows reminded people of light from the moon (selene), hence the name selenite. The use of gypsum continued through the Middle Ages and into modem times. Benjamin Franklin was a famed exponent of gypsum because he applied ground gypsum to clover fields in the form of large letters which later read, in the more luxuriant growth, "land plaster used here." Gypsum is still used as an effective conditioner for some soils, but in recent decades, particularly in North America and Europe, it has become much more important as a major material for the building industry. Description Gypsum and anhydrite are closely associated minerals. Gypsum is found in a number of forms: massive rock gypsum, alabaster, selenite, satin spar, and gypsite. Anhydrite is found as massive rock or as smaller bodies or isolated crystals included in gypsum. Massive Rock Gypsum comprises most of the commercial gypsum and occurs as a sedimentary rock, interbedded in most places with shale, limestone or dolomite. This rock is soft and crystalline. Its color is white or shades of gray, pink, yellow, brown or other colors. Alabaster is a pure, compact and fine-grained variety suitable for use in sculpture or turning into artistic forms; it may be white or selected for attractive coloration. Selenite is gypsum crystallized in flat, transparent, flexible foliated plates, found in clays or in surface vugs in gypsum. Satin Spar is a fine silky fibrous variety with the axes of the crystalline fibers perpendicular to the vein or joint in which it has formed. Gypsite is an earthy mixture of gypsum with clay and sand in secondary formations; it is sometimes useful as a soil conditioner and has been used in making base-coat plasters. Pure gypsum contains 20.9 pct combined water, 46.6 pct sulfur trioxide (SO3) and 32.5 pct lime (CaO). Standard specifications (American Society for Testing Materials Designation C 22-50) read that minimum purity for material to be called gypsum is 70 pct CaSO4.2H20. Most of the commercial gypsum is 85 to 95 pct pure as produced. Impurities in

Jan 1, 1960

By M. H. Gaskell, D. M. Kehn, G. T. Pyndus

A correlation of the bubble point pressure for black oil systems is developed using the standard physical-chemical equations of soiutions. The correlation is based on 158 experimentally measured bubble point pressures of 137 independent systems and is expressed in terins of the usually measured field pnrameters— flash separation gm-oil ratio, rank oil gravity, total gas gravity, and reservoir temperature. The data were obtained on systems produced in Canada, Western and Mid-Continent01 United States, and South America. The average error (algebraic) in the representation is 3.8 per cent, and the maximum error encountered is 14.7 per cent. INTRODUCTION In the absence of experimentally measured properties of reservoir fluids, it is often necessary for the field engineer to make estimates regarding the fluid properties based on the usually measured producing parameters. To aid in these estimations, various correlations have appeared in the literature in recent years. Among the pertinent properties of interest is the bubble point pressure. A correlation for this parameter has been reported by Standing&apos;. However, this correlation was based essentially on California produced crudes and this limitation was pointed out with its presentation. The correlation presented in this paper utilized data on crude oil systems from Canada, Wes- tern and Mid-Continental United States, and South America. CORRELATION DEVELOPMENT The basic assumption used in this development is the same as employed by Standing&apos;, There is a wide variety of ways to combine these parameters; however, in this instance the combination was made on the basis of Henry&apos;s law2. Accordingly, the relationship proposed is Although Eq. 2 defines an individual system, it is of limited value since H&apos; is a function of gas-phase composition and the system temperature. It was observed that for the systems where the bubble point was measured at several temperatures that the ratio of the bubble point pressures and the ratio of the corresponding absolute temperatures (R) were practically identical. Thus, for correlation purposes the bubble point pressure may be taken as a direct function of the absolute temperature. This relation is valid only for those systems that are not near the critical point. Accordingly, this correlation will be inadequate for systems in the region of the critical point. The solubility of the various hydrocarbons found in the gas phase increases with the molecular weight. Thus, the saturation pressure should be inversely related to the gas gravity. Applying these principles to Eq. 2 and rearranging terms gives: The variables 02 the left side of Eq. 3 were designated as the "hubble point pressure factor". The number of mols of tank oil per barrel is a function of the "mclecular weight" of the tank oil. Although the tank oil is a complex mixture, it was assumed for the purposes of this correlation that a unique molecular weight could be assigned to a given oil. This was designated as the "effective molecular weight", and was related to the oil gravity, This empirical relationship was developed simultaneously with the correlation by assuming values of M,. and working to obtain a smooth curve for both the correlation and the effective molecular weight. The relationship between the oil gravity and the effective molecular weight used in this correlation is shown in Fig. 1. The effective molecular weight is somewhat higher than the molecular weight of the C fraction. The difference between these values is largest for the low-gravity systems. It is noted that this effective molecular

By K. G. Davis

Dilute alloys of silzer in tilz haz been solidzjzed a1 controlled rules, in lzorizontal tubes 2 mrz and 0.5 rn in diam. Radioactive; tracer techniques we?-e used to study solute distvihutions along llze specimens and irmpurity substructures, as functions of the conditions growth. The results have heen mzalyzed using Burton, Prim, and Slichter&apos;s tnodel for the solute disty-ihution in the liquid ahead of an advancing solid-liquid interface. DECANTING techniques have been used to establish criteria for the formation of impurity substructure during solidification in several alloy systems An analysis equating the appearance of impurity substructure with the incidence of constitutional supercooling was developed,= in which diffusion was assumed to be the predominant mode of solute mixing in the liquid. Substitution of experimental data into the equations derived from the diffusion analysis gave reasonable values for solute diffusivity in the liquid. However, in these investigations solidification rates of 10 cm per hr and over were used, to minimize the effect of natural conection, whereas for crystals of high perfection lower solidification rates are needed, usually between 1 and 5 cm per hr. A knowledge of the conditions under which impurity substructures will be formed at low growth rates, and the degree of segregation to be expected, is therefore of interest. In the present investigation, radioactive-tracer techniques have been used to study the effect of growth rate, initial solute concentration, and size of specimen on the formation of substructure in uni- directionally solidified rods of dilute silver in tin alloys, over a range of growth rate between 0.5 and 10 cm per hr. Criteria for the formation of substructure were established by auto radiography. This was believed preferable to the decanting technique, for the relationship of the structure on a decanted interface with that of the freezing interface is not clear, since a layer of liquid is left on the surface following decanting.&apos; The effect of substructure on the distribution of solute along the rods was also investigated. EXPERIMENTAL The procedure for sample preparation has been described in detail by einber. Alloys were prepared from tin of 99.999 pct purity and silver of 99.99 pct purity. A"&apos;, an emitter of both y and 0 radiation, was used as tracer. Samples of the alloys were drawn up into silica tubes with inside diameters 0.5 or 2 mm, remelted in a horizontal furnace, and solidified at controlled rates. A few centimeters of the samples were left unmelted for a measure of the initial concentration. Total sample length was approximately 20 cm. The temperature gradient in the furnace was kept constant at 36°C per cm in the region corresponding to the melting point for tin. To find how well this corresponded to the actual temperature gradient in the melt, a thermocouple of 38-gage wire was electrically insulated with a thin layer of Sauereisen cement and placed within one of the 2-mm-diam tubes, which was then filled with tin. The maximum diameter of the coated wire was 0.5 mm, the bead of the thermocouple junction being no larger than the diameter of the wire. A plot of temperature vs distance traveled by the furnace is given in Fig. 1 for a rate of furnace travel of 1 cm per hr. The temperature gradient in the liquid

Jan 1, 1967

By Langtry E. Lynd

The predominant tonnage use of titanium is as a white pigment, in the form of rutile or anatase, which are allotropic modifications of titanium dioxide. Because of its whiteness, high refractive index and resulting light scattering ability, titanium dioxide is unequaled as a white pigment for paints, paper, rubber, and a wide variety of other materials. Consumption of titanium dioxide pigments for these uses has been rising steadily for many years, United States consumption in 1956 amounting to about 486,000 tons, worth $250,000,000. Production was off a little in 1957 and 1958. An outstanding development in the titanium field in recent years is the expansion of titanium metal production. Virtually nonexistent before 1948, United States production of pure titanium metal sponge reached a high in 1957 of about 17,200 tons, worth about $77,000,000. United States titanium sponge metal production in 1958 was cut back to about 4,600 tons because of reductions in military requirements. Another major use of titanium, in the form of the mineral, rutile, is for welding rod coatings. United States consumption of rutile for this purpose in 1958 amounted to about 11,000 tons, worth $1,100,000. Titanium-Bearing Minerals Although several minerals contain titanium as a major constituent, only a few of these occur in sufficient quantities and concentrations to be of commercial importance. These are ilmenite (FeTiO3), rutile (TiO2), and alteration products of ilmenite which have been referred to as weathered ilmenite, leucoxene, or arizonite. The other polymorphs of titanium dioxide, brookite and anatase, occur in a few deposits, of which only one has been of even minor importance. Considerable concentrations of titanite or sphene (CaTiSiO5) and perovskite (CaTiO3) are known, but do not compete with ilmenite and rutile deposits in grade or size. Rutile is very widely distributed as an accessory mineral in most rocks, but large deposits of commercial importance are rare. A few rock deposits have been worked for rutile but only one, in Virginia, is in operation (1959). Development of one in Mexico was discontinued recently. At present, the main sources of rutile are the beach and dune sands of Australia and Florida. A major use of rutile is for the manufacture of titanium tetrachloride, which is the intermediate compound universally used in titanium metal manufacture. Another main use of rutile is for welding rod coatings. Although the whiteness and brightness of titanium dioxide pigment is due to the high refractive index of rutile or anatase, natural rutile is too impure to be used directly as a white pigment, is too expensive to use for manufacturing pure oxide pigment, and is too scarce to provide the required tonnages. Instead, the cheaper, more abundant, mixed oxide of iron and titanium, ilmenite, which is readily decomposed by sulfuric acid, is used for manufacture of rutile and anatase pigments. Ilmenite is mined from both rock and sand deposits. Rock deposits contain ilmenite in massive or heavily disseminated form along with magnetite or hematite and are almost invariably associated with anorthositic and gabbroic rocks. Ilmenite also occurs as an accessory mineral in a great many igneous and metamorphic rock types. Concentrations of

Jan 1, 1960

By R. J. Tailleur, M. Rosenberg

Oil well drilling muds prepared with lubricating aids such as oil, graphite or mica will not produce a sufficiently strong protective lubricant film for the bit bearing surfaces under high load conditions encountered in drilling operations. Consequently, the damage to the bearing surfaces resulting from the absence of such a film frequently results in a shortening of the drill bit life. Several different types of extreme pressure lubricating additives for use in muds have been developed. These arlrlitives are capable of providing a protective lubricating film for bearing surfaces subjected to high load pressures. A modified version of the Timken lubricant tester, an instrument commonly used for testing the extreme pressure lubricating properties of oils, is used for measuring and controlling the lubricating qualities of the mud. Comparison tests made in the laboratory with 55/8-in. tricone bits drilling on steel plates immersed in extreme pressure lubricating muds and conventional muds showed that the bearing life of those bits tested in the lrrbricating mud was three to four times greater than obtained with conventional muds. Drilling tests made with extreme pressure lubricating muds in West Texas increased over-all bit life three to fourfold, reduced drilling torque and wear on drill pipe and drill collars. INTRODUCTION Roller bit cones contain roller, ball and journal-type bearings that are subjected to very heavy loading during drilling operations in which the only lubricant available for these bearings is either water or drilling mud. These bearings must be able to operate satisfac- torily in order for the cutting structures on the surface of the cones to be fully utilized. Frequently, the bearings wear to the point that the cones freeze and the bit must be pulled before the cutting structures on the cones become worn. In some instances the bearings continue to turn with severe wear but the cones, which are held on the bit by the bearings, drop off; and this causes an expensive fishing job. In other instances the bearings wear to the point that the cones pinch in causing an undergauge hole and delays to ream the hole. The advantage of increasing bit bearing life is self-evident. Because of inability to control the internal wear of bits while drilling, it was felt that improvement of the lubricating qualities of the circulating mud would be helpful. However, the often-discussed lubricating property attributed to muds has been a rather vague and intangible one. The literature has implied that the oil-emulsion muds are more effective lubricants than non-emulsion muds. Actually, there has been no direct method of measuring the lubricating property of muds which would indicate that one mud was better than another; there has been no way to determine whether the lubricating property of any mud was adequate. Furthermore, in comparing lubricating properties of muds, two qualities should be considered—the coefficient of friction and the extreme pressure lubricating qualities. For example, graphite can reduce the coefficient of friction, but does not provide a strong enough lubricating film to protect bit bearings subjected to high loads. The primary object of the investigation reported herein was to find a method for prolonging the bearing life of drill bits; and considering the heavy loads used in drilling, it was felt necessary to find both a method of measuring lubricating properties under high load conditions and methods of establishing effective lubrication under these conditions. Extreme pressure lubrication deals with that realm of lubrication where metal surfaces are in rubbing contact with each other under very high pressures. These pressures may be quite high, as for example,

Mellon Institute of Industrial Research, University of Pittsburgh, Pittsburgh, Pa. The Mellon Institute of Industrial Research has carried on for years research and investigations for all type and manner of indus¬try. One of the provisions of the foundation of the Institute is the

Jan 1, 1933

By C. K. Leith

The question as to what grades of ore it pays to conserve for the future, and the valuation of low-grade reserves, are becoming immediate and definite as applied to the individual ore deposits, and seems to call for some sort of quantitative answer.

Jan 1, 1915

By L. E. Schiffman

This paper describes the operation of two kerosine flotation plants in Alabama for cleaning -10 mesh bituminous coal. One plant treats washer sludge, the other raw coal. Data on capacity efficiency and capital and operating costs is given. Methods for increasing cell capacity are discussed.

Jan 10, 1950

By J. M. Smith, G. P. Willhite, J. S. Dranoff

Heat transfer rates were measured in sandstones with flow of gases perpendicular to the direction of energy transfer. Effective thermal conductivities ker ranged from 0.7 to 1.7 Btu/(br)(ft)(°F). The contribution of the solid phase appeared to be the most important in these consolidated materials, although the thermal conductivity of the gas had some effect. The velocity of the gas through the pores of the sandstones had no influence upon ker up to values of 168 lb/(br) (sq ft) in agreement with data obtained for unconsolidated beds of glass beads. The present results indicated that gas mixing, and hence heat transfer by convection in the pores, is less for perpendicular transfer of energy than when fluid flow and energy transfer are in the same direction. HEAT TRANSFER PERPENDICULAR TO FLUID FLOW IN POROUS ROCKS Heat transfer in porous media with pore sizes in the micron range depends upon the fluid in the pores and the geometry of the solid phase. The best characterized system is a bed of solid spherical particles. Heat transfer in this system has been studied extensive1y (Ref. 8 summarizes the literature up to 1959) when the pores contain stagnant fluid. When the fluid is in motion the directions of flow and energy transfer have an effect on the heat transfer rates, as demonstrated by comparing the work of Willhite, et al l3 for perpendicular flow and that of Kunii and Smith9 for parallel flow of energy and fluid. For perpendicular flow, no increase in effective thermal conductivity ke was noted up to mass velocities G of 77 lb/(hr) (sq ft). In contrast, for parallel flow ke, increased with G in the same range of flow rates. These higher values of ke in the direction of flow also have been observed3,4,10 in beds of larger particles, 0.1- to 0.5-in. diameter. For beds of consolidated materials, such as porous rocks, data are not available for these compar- isons, although Adivarahan1 reported results for the parallel case. Hence the primary objective of this work was to measure ke values for perpendicular flow of fluid and energy in porous rocks. Of interest also was the variation in effective conductivity with fluid velocity. APPARATUS AND PROCEDURE In the experimental method, a constant heat flux was applied to the inner surface of an annular section of the porous rock. By cooling the outer wall, a temperature gradient through the annular sample was established and measured with thermocouples placed within the sample at various radial positions, and at three elevations (A,B.C). The location of the 2-in. O.D., 3.75-in. long sample in the apparatus is shown in Fig. 1. Fluid entered the bottom (1) of the 3-in. I.D. (approximate) steel shell, flowed upwards through the sample and out at the top (3). pressure taps (2,4) were used to check the permeability of the sample. The energy flowed radially from the centrally-located electric heater through the sample and was absorbed in the water-cooled jacket. The samples studied were naturally occurring sandstones from different locations with the properties given in Table 1. These materials are identical with those used by Adivarahan 1 for the parallel flow of energy and fluid. Prior to use they were refluxed with toluene to remove hydrocarbons and leached with distilled water to remove soluble salts. Each sample was visually examined and discarded if large nonhomogeneities, such as cracks or stone particles, were noted. Eight copper-constantan thermocouples were inserted in holes drilled radially into the sample with

By Avnulf Muan, P. V. Riboud

The effect of Cr2O3 on melting relations of iron oxide at oxygen pressures slightly above those prevailing in contact with metallic iron has been determined. Liquidus and solidus temperatures of wüstite are raised by the addition of Cr2O3, from 1385°C for pure iron oxide to 1420°C at the peri-ledie point where wüstite, iron chromite, liquid, and gas coexist in equilibrium under the atmospheric conditions used in the present investigation (CO2/H2 = 1). It has been shown in a previous investigation1 that the liquidus and solidus temperatures of iron oxide are drastically increased by the addition of Cr2O3 under the relatively oxidizing conditions prevailing in air. This is to be expected in view of the easy substitution of cr3+ for Fe3+ in crystalline oxide structures which are stable at high oxygen pressures, as demonstrated for instance by the completeness of the solid solution series Fe2O3-Cr2O3 at high temperatures (>1000°C). The stable phase of iron oxide at oxygen pressures approximating those prevailing when metallic iron is present is wüstite. This phase, although commonly represented by the simplified formula FeO for sake of convenience, in reality has a defect structure in which a part of the iron ions are present as Fe3+. It is to be expected that at least a limited amount of cr3 ions will substitute for Fe in this structure when Cr2O3 is added to wüstite. Depending on the ease of this substitution in comparison with that of cr3 substitution for Fe in iron oxide-Cr2O3 liquids under the same atmos- pheric conditions, the liquidus and solidus temperatures of wüstite may increase or decrease upon addition of Cr2O3. The methods of establishing these melting relations and the results obtained are presented in the following. I) EXPERIMENTAL METHOD 1) General Procedure. The quenching technique was used in this study. Oxide mixtures were heated at chosen constant temperatures in an atmosphere consisting of equal parts of CO2 and H2 until equilibrium was established among gas and condensed phases. The samples were then quenched in mercury to room temperature, and the phases present were determined by microscopic and X-ray investigation. 2) Preparation of the Mixtures. Starting mixtures were prepared by weighing and thoroughly mixing Fe2O3 and Cr2O3, or wüstite and Cr2O3. The Fe2O3 and Cr2O3 used were "Baker Analyzed" reagent grades, whereas wüstite of composition was synthesized by reducing Fe203 at 1325°C in an atmosphere consisting of equal parts of CG andHz. In order to avoid contact with crucibles, the equilibration runs were made with small pellets suspended from thin (-0.004-in.) platinum wires. Mixtures made from FOs and Cr203 were readily pelletized at a pressure of 500 atm in a 9.5-mm die, whereas mixtures made from wüstite and Cr203 when treated identically were too weak for handling. In order to obtain a stronger product, these pellets were sintered by heating for 2 min at -1200°C in the same atmosphere as was subsequently used for the equilibration runs (CG/H2 = 1:1). During the sintering, these pellets were wrapped in thin (0.0004-in.) platinum foil, which was stripped off before the equilibration runs. In order to reduce the time needed for equilibrium to be attained, preliminary equilibration of relatively large pellets of each mixture was carried out at -1200°C for 4 to 12 hr. Smaller pellets

Jan 1, 1964

By J. J. Gilman

RECENT experiments have shown that the mar-tensite reaction in a standard tool steel is influenced by the history of the reacting austenite. The martensite reaction proceeds to a given extent at a higher temperature in austenite formed from an annealed spheroidal structure than it does in austenite formed from tempered martensite: that is to say, a prequench lowers the temperature range of the martensite reaction in this steel. Furthermore, a prequench alters the appearance of the martensite as compared to martensite formed from "virgin" austenite. The steel used for this work was a manganese nondeforming tool steel of the following composition: C, 0.85 pct; Mn, 1.43; Si, 0.23; Ni, 0.12; Cr, 0.59; and W, 0.59. A piece from a rolled bar was forged to Vz in. sq and annealed to a spheroidal structure. Disks 1/8 in. thick were used in the experiments. Several sets of the specimens were prepared and austenitized in lead at 1475°F. Three sets were held at 1475°F for 15 min, quenched in water, and immediately reheated to 1475°F. After this quench the three sets were held for 5 min, 30 min, and 3 hr, respectively, at 1475°F and then the individual specimens in each set were quenched in molten baths to 325", 300°, and 275ºF, respectively, and held for 15 sec. Immediately after the quenching treatments? the specimens were tempered at 600°F for 30 sec to darken the martensite and then were quenched in water. The holding times were short enough to avoid isothermal transformation. Three other sets of specimens were given the same final quenching treatments as the first three, but they were austenitized at 1475°F for 20 min, 35 min, and 3 hr and 15 min, respectively, without an intermediate water quench. The two individual specimens from each set were quenched together in order to eliminate quenching errors. Several experiments were run in this way but only the six sets referred to are described in detail because they all yielded essentially the same results. By means of the stated heat treatments the martensite reaction was investigated for: 1—austenite formed from an annealed structure, and 2— austenite formed from tempered martensite. The martensite reactions of the two types of austenite differed significantly. This is shown by Figs. 1 and 2. Comparison of the photographs on the left in Figs. 1 and 2 with those on the right shows that less martensite was formed by a quench to a given temperature from prequenched austenite than from austenite formed from an annealed structure, that is, the prequench suppressed the martensite reaction. The effect was observed for specimens austenitized 20 min, 35 min, and 3 hr and 15 min. A comparison of Figs. 1 and 2 shows that the martensite reactions in both sets of specimens occurred at lower temperatures with increased austenitization time. This was caused by the increased dissolution of residual carbides with time at 1475°F. However, the difference in amount of martensite formed in prequenched austenite as compared to virgin austenite was approximately the same for all three austenitization times. One further observation should be noted. The needles of the martensite formed from virgin austenite are somewhat longer on the average and show less of a tendency to cluster than those of martensite formed from prequenched austenite. This causes the martensite on the right in Figs. 1 and 2 to have a more acicular appearance than the martensite on the left. Since the sets of specimens used in this work were austenitized for identical total lengths of time and the effect of a prequench on the martensite reaction existed for specimens held at the austenitizing tem-

Jan 1, 1953

By John S. Brock

INTRODUCTION The Oxford Dictionary says that the word "promoter" has usually been used in an opprobrious sense since at least 1876. This popular image of mining promoters is of cigar-chomping shysters and Brooklyn-Bridge vendors, improving their standard of living with the aid of funds raised through the sale of stock to little old ladies. It is unfortunate that mining promoters are considered crooks until they can prove their integrity and honesty by finding a mine. A common rule of thumb states that for every 1,000 prospects, 100 come to be drilled, and one becomes a mine. However, it is also a statistic that there have been mining promotions, where money raised has gone elsewhere than into the ground; Junior exploration companies can be handy vehicles for unscrupulous financial activity. One must remember though that every stock exchange has had its share of sound mining promotions that, because of the one in 1,000 odds, have failed for legitimate reasons. The promoter must be able to rationalize the worth of a mineral discovery which, on an industry- average basis, probably cost more to find than the discounted value of its net return, which return is not an assured percentage of invested capital, and furthermore, is ultimately from a wasting asset. So, it is easy to understand why the promoter must constantly justify the credibility of his operation to his grubstakers during the course of the "five phases of exploration," those being (1) euphoria, (2) disillusionment, (3) search for the guilty, (4) punishment for the innocent, and (5) distinction for the uninvolved. The promoter with the exploration organization that does not have the benefit of positive cash flow, by definition for the sake of this article, works for a promotional outfit, a Junior Company, that must raise its exploration budget from a variety of sources. Promotion, as discussed here, will not entirely refer to the formation and operation of a joint- stock company but rather to the overall methods of raising risk capital for mineral exploration ventures from outside sources. THE NECESSITY OF PROMOTION In Canada, the publicly financed Junior Company has had an enviable record of mine-finding success. In the Province of British Columbia alone, the discovery of fifteen out of twenty-four mines has been as a result of the activity of the Junior Company (B. C. & Yukon Chamber of Mines, 1977). In the Province of Ontario, one research study indicated that between 1951 and 1974 the &apos;Juniors&apos; spent only 28 percent of the total exploration funds but were responsible for 62 percent of all economic discoveries (Freyman, 1978). The reasons for the success of the Juniors are tied to a variety of factors, the main one being personal initiative based on incentive. In other words, the principals, or their employees have &apos;a piece of the action.&apos; The smaller companies can operate faster and more efficiently than their larger counterparts. The Junior Company is also destined to take some bigger risks, the &apos;long shots,&apos; many of which efforts by virtue of the Junior&apos;s perseverance coupled with a touch of &apos;ore is where you find it&apos; philosophy, result in major discoveries. The individuals, syndicates, private and publicly financed Junior Companies, because of high costs of exploration and development, cannot hope to finance most mineral prospects all the way to production. Exceptions do exist, those being the lower capital cost, small, high-grade deposits. Private investors and publicly financed Junior companies, therefore, can usually afford to finance most exploration through the initial drill-testing stage. The major resource company will enter a mining deal with a Junior Company usually by way of option or joint venture agreement, and will finance to production to earn an equity in the prospect or the Junior Company or both. The conventional lending institutions, banks and government agencies, will usually only participate through loaning a portion of capital

Jan 1, 1985