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By George A. Guess

The increasing demand for greater speed and more accuracy, in making daily assays of ores and products from mills treating material containing but very small quantities of lead and copper, has caused the older analytical methods to be supplanted by new ones devised to meet the needs of modern work. For " control" work in copper-analyses, I had, previous to the present equipment, introduced in my laboratory the ordinary electrolytic method, using hollow cylindrical electrodes; and with these I began a series of experiments in determining the lead-content of daily mill-samples and controls. The results, proving accurate and satisfactory, I then devised, with Mr. H. E. T. Haultain, a cheaper electrode than the ordinary jaCket-electrode, which costs from $15 to $20,—the expense of the older form making the installation of many units very costly. The form of cathode finally adopted as the most satisfactory, shown in Fig. 1, is cut from 0.001-in. platinum foil. It is 12.5 cm. long, and is divided into a blade 4 cm. wide and 6.25 cm. long, and a tongue 0.7 cm. aide and 6.25 long, the immersion area being 50 sq. cm. and weight 1.5 grams. The blade is first sand-blasted and then corrugated lengthwise, in order to impart the necessary rigidity. Strips of platinum foil 0.001 in. thick, 12.5 cm. long and 0.5 cm. aide, having a median corrugation, form the anodes. Three electrodes are used in each cell; one anode in the middle and one cathode on each side of the anode. These electrodes are connected to slotted aluminum terminals, in which they are held by contact pressure. The terminals are 5/16in. rods, projecting 2 in. horizontally in front of the wall of the cabinet; at the back the middle electrode (anode) is connected with one pole of the current, and the two outer ones (cathodes) with the other pole.

Jan 1, 1906

By N. J. Grant, B. C. Giessen, Paul Predecki

ALLOYS of gold, silver, and aluminum with elements of the groups BII, BIII, BIV, and BV were prepared by a rapid quenching technique (splat) and were examined by X-ray diffraction. Five new intermediate phases were found and will be described briefly herein. For the gold and silver systems, the concentration ranges having an electron/atom ratio e/a of 1.4 to 1.5 ("3/2 Hume-Rothery phases") were studied primarily. Master alloys were prepared from high-purity metals (99.9+ pct or better) by melting either in evacuated fused silica capsules or by nonconsum-able-electrode arc melting in an argon atmosphere. Small pieces, 20 to 50 mg, of each alloy were blast-atomized to form a splat, by a technique similar to that described by Duwez and Willens.1 The technique used for this study is described in detail in Ref. 2; it utilizes a resistance-heated graphite crucible with a small hole at the bottom, directed toward a metal substrate or quenching plate. The prepared alloy rests over the fine hole, through which it is expelled by an explosion shock wave in the form of fine droplets (1 to 50 µ) of molten metal onto a copper or silver substrate, which is maintained at about -190°C. The resulting very high cooling rates (see Ref. 2 for quantitative measurements) can prevent the process of nuclea-tion and growth in many instances, resulting in the formation of metastable phases. The splat particles were transferred to a GE-XRD5 diffractometer and maintained at -190°C, where they were examined with CuKa radiation. The samples were then allowed to warm to room temperature or were heated to higher temperatures until the equilibrium structures formed. Of fifteen alloy systems considered, nonequi-librium structures were encountered in six; these are described below and summarized in Table I. In the system Au-Sb a metastable £ phase (A3 type, hcp, a = 2.898 + 0.002A; c = 4.731 * 0.004A; c/a = 1.633) was found in the concentration range Au + 13 to 15 at. pct Sb. This phase is isomorphous with the stable phases in the systems Au-Cd, Au-In, and Au-Sn, all at an average e/a ratio of 1.4 to 1.5. The concentration range of one-phase metastable was deduced from the small amounts of supersaturated gold solid-solution phase present in the splat product. It was found that ? could also be retained by splatting onto a substrate held at room temperature: however, decomposed into the equilibrium phases Au + AuSb2 after heating to 200°C for 1/2 hr, or on holding the powdered splatted alloy at 20°C for several months. Calorimetric measurements will be made in an attempt to decide the question whether ? is metastable at all temperatures or whether it is a stable phase at low temperatures. There is evidence that another phase, possibly also close-packed but with a different stacking sequence, can be obtained by rapid quenching of alloys with a different antimony content. Klement, Willens, and Duwez3 reported the existence of an amorphous phase on quenching Au-Si alloys (25 at. pct Si) to - 196°C. They found that on heating to room temperature another phase of unknown crystal structure was formed. This was confirmed (see Table I); however, the new crystalline phase, designated as ?, could also be formed simply by rapid quenching to room temperature, and even was found to exist already in the as-cast Au + 20 at. pct Si alloy. It was found that ? decomposed into Au + Si on the specimen surface at room temperature. This behavior, and the question whether or not there is an equilibrium-temperature region for ?, have not yet been resolved. It is probable that ? (Au + 20 to 21 at. pct Si) is cubic of the -brass type (D81-3) with a = 9.60, + 0.01A and N = 52 atoms per cell [compare 6 (CU-Sn)4]. Except for two very weak lines, the powder pattern of about thirty lines could be indexed on this basis; however, a determination of the atom positions has not yet been attempted. For Au-Ge the C phase was observed at about 21 at. pct Ge as reported by Luo et at.5 Lattice parameters a = 2.876A, c = 4.73,A, c/a = 1.64 were found. In the Au-Pb system, formation of a ? phase was not observed, but in the lead-rich region at 75 at. pct Pb, broad peaks belonging to an amorphous phase were found. The maximum diffracted intensity occurred at 28 = 32.4 deg which is about 1 deg larger than the position of the (111) line of lead (Cuka). For Ag-Pb, an amorphous phase analogous to the one found in the Au-Pb system was observed; this metastable phase exists probably at about 75 at. pct Pb. Since no lead-rich alloys were tested, all alloys consisted of silver + amorphous phase at -190°C. In A1-Ge alloys, line-rich and complex powder patterns were obtained at about 30 at. pct Ge; they bear similarities to those of aluminum and germanium, but are of lower symmetry; the existence of more than one intermediate phase is possible. The authors are grateful to the Kennecott Copper Corp. for Fellowship support, and ARPA (Contract

Jan 1, 1965

The Lead-Line Update held in conjunction with the 1977 SME-AIME Fall Meeting in St. Louis provided sessions on mining, mineral processing, extractive metallurgy, and economies to brief the record on the industry's activities and developments since the 1970 World Symposium on Lead and Line convened, also in St. Louis. Changes in the industry since 1970 have not been profound, notes the program committee, consisting of D. O. Rausch, F. M. Stephens, and B.C. Mariacher, cochairmen; and H. L. Clifford, S. C. Fall), and M. Snedeker. However, various environmental and conservation factors have had a direct impact on process consideration and operating practice; the result has been new mines, improved technology, and changing market opportunities. The general consensus of the participants is that the future for the Lead-zinc industry looks promising as new applications are found and new products resulting from intensive research reach the marketplace. The highlights of the HS technical papers presented at the 1977 session follows.

Jan 11, 1977

By Zay Jeffries

IT is well known that many properties of a given metal vary with the size of grain or cell. For most industrial purposes, where high ultimate strength and high elastic limit are desired, the manufacturer tries to produce a. fine-grained structure. For some purposes, for example in transformer iron, a coarse-grained structure is desirable. The terms fine-grained and coarse-grained are used only in a relative sense. For example, a fine-grained cast copper might have grains 100 times larger than coarse-grained high-speed steel. Similarly, a fine-grained steel rail might have grains or cells 100 times larger than coarse-grained wire, which was made of steel from the same heat. In some metals, the change in grain size is more appreciable than the changes in any of the properties determined by the tensile test. Furthermore, in metals which have been annealed or subjected to high temperatures, grain size may prove to be a better indication of the life of the metal in use than the tensile test. One of the authors was able to supplant the tensile test with grain-size determinations in the control of. metal for a specific use, the latter determination being more indicative of. the life of the metal part than the tensile test. A grain-size determination with a tensile test is, of course, more valuable than either singly. At present there is a decided dearth of data on actual grain-size determinations in metals, and consequently a corresponding lack of ability to interpret the determinations after they are made. It would be desirable to have correlation made between grain size and properties of metals, comparing thousands of determinations. In this way, grain-size determinations might be interpreted in much the same manner that tensile tests are now.

Jan 12, 1915

By P. Wynblatt, J. E. Dorn

The effect of strain rate, temperature, and interstitial impurity concentration on the flow stress was investigated in a poly crystalline Fe-2 pct Mn alloy. The temperature dependence of the flow stress was found to be independent of the interstitial impurity concentration, removal of interstitials merely decreasing the atherma1 stress level. Below 160%, the large temperature dependence of the flow stress was interpreted in terms of the Dorn-Rajnak theory of the Peierls mechanism of plastic deformation. Above 160"K, some other thermally activated intrinsic meckanisln seems to be operating. The strong temperature dependence of the flow stress of bcc iron at low temperatures has been studied by numerous investigators and interpreted in terms of several different thermally activated dislocation mechanisms. The following mechanisms have been proposed: a) interaction of dislocations with interstitial impurity atoms1 or with solute atoms in general; b) interaction of dislocations with clusters of impurity atoms;3 c) resistance to the motion of dislocations due to jogs on screw dislocations;* d) resistance to the motion of dislocations due to the Snoeck effect;' and e) interaction of dislocations with the intrinsic resistance of the bcc lattice or Peierls "hills". In previous work: it was found that the plastic behavior of polycrystalline iron containing 2 wt pct Mn (and 100 ppm C + N) is in good agreement with predictions based on the Peierls mechanismlo from 77" to 160°K whereas from 160" to about 370°K another as yet unidentified thermally activated mechanism is operative. The purpose of the present investigation was to determine the effect of interstitial impurities on the temperature dependence of the flow stress, by purifying the previously investigated alloy with respect to interstitial impurities. The investigation revealed that removal of the interstitial impurities to a level that eliminated Cottrell locking and the Portevin-LeChatelier effect (i.e., serrations in the stress-strain curve due to dynamic strain aging) affects neither the strong temperature dependence of the flow stress at low temperatures nor the general characteristics of the higher-temperature behavior. Such purification, however, lowered the athermal yield stress. I) EXPERIMENTAL PROCEDURE AND RESULTS The material used in this investigation consisted of an Fe-2 wt pct Mn alloy having the following additional elements present: 0.004 pct C, 0.006 pct N, 0.05 pct 0, 0.004 pct S, 0.003 pct P, and 0.001 pct Si. This was the same material as that studied in the previous investigation and will henceforth be referred to as the "impure material". The as received -jr by 2 in. hot-rolled bars were cold-rolled to 0.08-in. thickness, recrys-tallized under argon for 30 min at 80O0C, and further cold-rolled to 0.053-in. thickness. Flat tensile specimens 3 in. wide having a 1.625-in.-long gage section were machined from the sheet and then purified. The first stage of purification consisted of holding the specimens at 850°C for 24 hr in a stream of hydrogen saturated with water vapor at room temperature. Material prepared in this fashion will subsequently be referred to as "wet hydrogen purified material". It has been estimated that this type of treatment reduces the carbon content of iron to less than 5 ppm.' The second stage of purification consisted of holding the specimens in a closed system through which hydrogen was circulated past the heated specimens as well as a zirconium hydride getter. The specimens were held at 850°C and the getter at 800°C. The process was continued for 212 hr. The starting material for this process was wet hydrogen purified material. Material prepared in this manner will be referred to as "ZrHz purified material". The technique used was substantially the same as that described by Stein et al.' who have shown that the carbon level at the end of the process is reduced to about 5 parts per billion. The mean grain size of the three materials was found to be -60 C( for the impure material and -160p for the wet hydrogen and ZrHz purified materials. All tensile testing was carried out on an Instron Testing Machine either in controlled-temperature baths or at fixed-point baths such as boiling liquid nitrogen, and so forth. When fixed points were used the temperature was kept constant to better than *1°C whereas in all other tests the temperature variation was less than *2°C. Test of Purity. It was not possible to determine the purity achieved at each stage of the purification because the resulting level of interstitial impurities was near or below the limit of sensitivity of standard analytical techniques. It was possible, however, to obtain a qualitative measure of the extent of purification from the appearance of the stress-strain curves for the three materials. Fig. 1 shows the stress-strain curves for the three different materials tested at 300°K. It can be seen that the effect of wet hydrogen

Jan 1, 1967

By V. B. Kurfman

Grain refinement of Mg-Al melts by carbonaceous additions has been attributed to nucleation by aluminum carbide. The effects of process and alloy variables are interpreted and predicted in terms of the dispersion and chemistry of this phase. The grain coarsening action of Be, Zr, Ti, R.E., chlorination, temperature extremes, and prolonged holding times is described. Measures necessary to insure an adequate dispersion of the catalyst are discussed. CARBON inoculation treatments have become fairly well known and used for grain refinement of magnesium alloys containing Al. Although there is general agreement that a nucleation process occurs, the process is not understood and the inoculants are used in a rather empirical fashion. The treatment is applied to the class of alloys containing 3 to 10 pct Al, i.e., AZ31A to AM100A. Typical methods involve melting, alloying, and adjusting the temperature to 1400° to 1450°F. Then 0.01 to 0.5 pct C as CaC2, C6C16, or lampblack is added by any convenient means, and the melt poured within 10 to 30 min. Investigators generally have been impressed by an assumed similarity of this refinement process to superheat grain refinement, which depends on heating approximately the same alloys to a temperature in the range of 1550" to 1650°F, then pouring promptly after the melt is cooled to the pouring temperature. Various predictions have been made that carbon refinement would replace superheating in commercial practice due to reduced process costs, but this replacement has not fully taken place because of production difficulties and conflicting observations. Davis, Eastwood, and DeHaven1 agree with Nelson2 and wood3 in suggesting that an excess of inoculant may be harmful. Wood however says that overtreat-ment is not a problem in production use of hexa-chlorobenzene inoculation, and Hultgren and Mitchell4 claim no evidence of harm from excess additions. Various grain coarsening reactions are known to occur, including the possibility of overtreatment mentioned above. Trace amounts of Be,2 Zr, and Ti may prevent refinement by either a carbon treatment or a superheat. Occasionally treatment with cl25 may cause coarsening, although the Battelle refinement process' uses a CC14-C12 blend. Grain coarsening also tends to occur on holding at temperatures below 1350°to 1400°F, especially after a superheat treatment, and for this reason Nelson2 stresses the desirability of a refinement method useful at lower temperatures for open pot melting practice. Since a carbon treatment can be made to work at temperatures below 1400°F, it seems desirable to investigate the mechanism of the refinement and the mechanisms of the coarsening reactions in order to establish control conditions for use in commercial production. The identity of the nucleating phase must first be established and then the factors affecting its chemistry and physical dispersion must be determined. THE IDENTITY OF THE NUCLEATING PHASE Davis, Eastwood, and DeHaven suggested that the nucleating phase in this system is Al4c3,1 but Mahoney, Tarr, and LeGrand8 disagree, largely because they found no evidence of the compound in alloys after carbon treatment and because there is no indication that aluminum carbide should be unstable over the temperature range used in the superheat treatment. This latter objection is based on the assumption that both the carbon treatment and the superheat treatment introduce the same nuclei. Electron diffraction studies have been made to identify the nucleating phase. Samples of grain refined A292 have been selectively etched SO that clean surfaces are obtained and so that secondary phases are in relief. Electron diffraction patterns from these surfaces have established that the carbon treatment of A292 introduces into the metal a large number of small, plate-like particles with a structure very similar to Al4C3. In most cases, the plate-like nature of the particles prevented positive identification but in the cases where the identification could be made the particles proved to be AIN A14C3. However, enough variation in lattice constants was observed so that all compositions from pure A14C3 to the 50:50 solid solution A1N.Al4C3 were probably present.14 In A14C3 and especially AlN.Al4C3 the A1 atoms occur in layers within which they have the same hexagonal symmetry and spacing as the Mg atoms in a single basal plane of a magnesium crystal. The solid solution spacing lies between the 3.16 of AIN and the 3.3? for Al4C3, in satisfactory agree-

Jan 1, 1962

By J. W. Spretnak, G. Sachs

The: iron-rich iron-nickel alloys have attracted considerable academic interest in recent years. The carbon-free alloys are of minor practical importance, but they are the base of many alloys with various outstanding properties. The iron-nickel alloys, therefore, have been investigated extensively regarding both their structures and their properties. The researches on these alloys up to 1938 have been collected and critically reviewed by J. S. Marsh,l and will be discussed in some detail in the sections of this paper dealing with specific subjects. These numerous investigations have not succeeded in establishing the equilibrium conditions in this system. Alloys containing more than a certain amount of nickel (8 to 10 per cent Ni) undergo the allotropic transformation extremely sluggishly, both on heating and cooling, showing a large hysteresis," which is not dependent upon the rate of cooling and persists even with very slow rates of cooling.3 Honda4 and Merica4 have therefore resigned themselves to proposing a diagram (Fig. I) for practical use, illustrating the structural relations under commercial conditions instead of attempting to establish the true equilibrium diagram. Marsh is less pessimistic and suggests an equilibrium diagram (Fig. 2) which conforms approximately to the facts known about this system. Recent X-ray investigations by Owen-Sully5 and Bradley-Gold-schmidt6 on powdered alloys indicate that the previous work on the iron-nickel system yielded very incomplete results. These investigators agree (Figs. 3 and ,+) that alloys in the powdered form containing more than 8 per cent and up to about 35 per cent Ni decompose into a stable heterogeneous mix-

Jan 1, 1941

By G. Sachs, J. W. Spretnak

The: iron-rich iron-nickel alloys have attracted considerable academic interest in recent years. The carbon-free alloys are of minor practical importance, but they are the base of many alloys with various outstanding properties. The iron-nickel alloys, therefore, have been investigated extensively regarding both their structures and their properties. The researches on these alloys up to 1938 have been collected and critically reviewed by J. S. Marsh,l and will be discussed in some detail in the sections of this paper dealing with specific subjects. These numerous investigations have not succeeded in establishing the equilibrium conditions in this system. Alloys containing more than a certain amount of nickel (8 to 10 per cent Ni) undergo the allotropic transformation extremely sluggishly, both on heating and cooling, showing a large hysteresis," which is not dependent upon the rate of cooling and persists even with very slow rates of cooling.3 Honda4 and Merica4 have therefore resigned themselves to proposing a diagram (Fig. I) for practical use, illustrating the structural relations under commercial conditions instead of attempting to establish the true equilibrium diagram. Marsh is less pessimistic and suggests an equilibrium diagram (Fig. 2) which conforms approximately to the facts known about this system. Recent X-ray investigations by Owen-Sully5 and Bradley-Gold-schmidt6 on powdered alloys indicate that the previous work on the iron-nickel system yielded very incomplete results. These investigators agree (Figs. 3 and ,+) that alloys in the powdered form containing more than 8 per cent and up to about 35 per cent Ni decompose into a stable heterogeneous mix-

Jan 1, 1941

By L. E. Young

LOADING machines may be classified in several ways: (1) Machines which cut or break down and load .the coal; (2) machines which simply load the coal; (3) devices which load and transport the coal; (4) de-vices which elevate; (5) devices which transport the coal after it has been shoveled onto the device. There are many types of mechanical loading devices, Bull. 17, Coal Mining Investigations, under the auspices of Carnegie Institute' of Technology, U. S. Bureau of Mines, and the Advisory Board, listing 31 exclusive. of -the large shovels used in thick coal seams. Mechanical loading of coal is not in its infancy; I think some of the early patents go back to 1890. One large coal company, properly called the early leader in this field of mechani-zation, has about 26 large machines at work. This company spent about thirty years in developing a ma-chine, and at the present time is loading approximately two million tons of coal a year in its mines. The chair-man directed a question at the previous speaker; inquir-ing if real progress was being made in mechanical load-ing. The experience of the company just referred to is in itself an adequate answer. A review of a list of mines using mechanical loading devices shows that there are 28 mines which we may say are 100 per cent mechanical. There are four more mines which have been 100 per cent mechanical, but which are idle at this time on account of labor condi-tions. There are at least 25 more at which the tonnage is more than 50 per cent mechanical. In speaking of a 100 per cent mine I do not mean that every pit car of coal is loaded by machine, because when complete, re-covery of the coal is attempted it is not practical to load all the coal at, the break line. In order to load the last 5 to 10 per cent of coal with a minimum of gob material and in order to keep the. working places along the break line timbered in a safe manner it is generally desirable to use a few hand loaders. At a certain mine operat-ing on the block system 90 percent of the coal is being loaded by what is properly a mechanical loading: device, and about 10 per cent -is being loaded by hand. This 10 percent is right off the break line, out of what might be called, the screen pillar. The mines referred to are scattered over the country, . in seven different' States, and the equipment used is produced by ten different machinery companies. As to size, these mines vary from small mines of 500 tons mining capacity-up. In one instance a company with one loading machine is producing an, average of 450 tons per day. One of the large mines that is idle pro-duced at the. rate of 4300 tons per day, of which 97 per cent was actually loaded by machinery.

Jan 8, 1928

By Frank G. Miller

This report presents developments of fundamental equations for describing the flow and thermodynamic behavior of two-phase single-component fluids moving under steady conditions through porous media. Many of the theoretical considerations upon which these equations are premised have received little or no attention in oil-reservoir fluid-flow research. The significance of the underlying flow theory in oil-producing operations is indicated. In particular, the theoretical analysis pertains to the steady, adiabatic, macroscopically linear, two-phase flow of a single-component fluid through a horizontal column of porous medium. It is considered that the test fluid enters the upstream end of the column while entirely in the liquid state, moves downstream an appreciable distance, begins to vaporize, and then moves through the remainder of the column as a gas-liquid mixture. The problem posed is to find the total weight rate of flow and the pressure distribution along the column for a given inlet pressure and temperature, a given exit pres5ure or temperature and given characteristics of the test fluid and porous medium. In developing the theory, gas-liquid interfacial phenomena are treated. phase equilibrium is assumed and previous theoretical work of other investigators of the problem is modified. Laboratory experiments performed with specially designed apparatus. in which propane is used as the test fluid, substantiate the theory. The apparatus. materials and experimental procedure are described. Comparative experimental and theoretical results are presented and discussed. It is believed that the research findings contributed in this * paper should not only lead to a better understanding of oil-reservoir behavior, but also should be suggective in regard to future research in this field of study. INTRODUCTION In recent years much time and effort has been consumed in both theoretical and experimental studies of the static and . dvnamic behavior of oil-reservoir fluids in porous rocks. Although lack of sufficient basic oil-field data, principally concerning the properties and characteristics of reservoir rocks and fluids, largely precludes quantitative application of research results to oil-field problems, qualitative application has become common practice. In effect. oil-reservoir engineering research is serving as a firm foundation for oil-field development and production practices leading to increased economic recoveries of petroleum. This province of research. however, still poses many perplexing problems. The thermodynamic behavior of two-phase fluids moving through porous media constitutes one facet of reservoir-fluid-flow research that has not received the attention it deserves. This report embodies a theoretical discussion of this subject and a description of a series of related laboratory experiments. The significance of the problem to oil field operations is indicated but in articular the report centers around a theory and method for analyzing the steady. macroscopically linear, two-phase flow of a fluid (a single molecular species) through a horizontal column of porous medium. For simplicity in showing how the thermodynamic behavior of two-phase fluids moving through porous media affects oil-reservoir performance problems, attention is focused temporarily on a particular well producing petroleum from an idealized water-free solution-gas drive reservoir, the reservoir rock being a horizontal, thin, fairly homogeneous sandstone of large areal extent confined between two impermeable strata. The flowing hydrocarbon fluid is considered to exist entirely as a Iiquid at points in the reservoir remote from the well; however. the decline in fluid pressure in the direction of the well causes vaporization of the hydrocarbon to begin at a radial distance r from the well. Upstream from r the fluid moves entirely as a liquid and downstream from r it moves either entirely as a gas or as a gas-liquid mixture depending on the properties of the hydrocarbon and on the thermodynamic process it follows during flow. The distance r would be variable under transient flow conditions. but for purposes of analysis the flow is considered to l~e steady at the particular instant of observation during the flowing life of the well of interest. If the flow were isothermal and the hydrocarbon a pure substance, the fluid would be entirely gaseous downstream from r. Thus, this isothermal flow process for a pure substance would require that the heat of vaporization be supplied at r. over zero length of porous medium, at the precise rate necessary to maintain the constant temperature. This means that the solid matrix of the porous medium (reservoir rock) and the surroundings (impermeable strata confining the reservoir rock) would have to serve as infinite heat sources. Heat-transfer requirements would be somewhat less severe for the isothermal flow of a multicorn-ponent hydrocarbon as bubble and dew points at the same temperature correspond to different pressures. In this instance isothermal conditions would be sustained without complete vaporization of the fluid over zero length of porous medium. Nevertheless. as the flow is in the direction of decreasing

Jan 1, 1951

By Frank G. Miller

This report presents developments of fundamental equations for describing the flow and thermodynamic behavior of two-phase single-component fluids moving under steady conditions through porous media. Many of the theoretical considerations upon which these equations are premised have received little or no attention in oil-reservoir fluid-flow research. The significance of the underlying flow theory in oil-producing operations is indicated. In particular, the theoretical analysis pertains to the steady, adiabatic, macroscopically linear, two-phase flow of a single-component fluid through a horizontal column of porous medium. It is considered that the test fluid enters the upstream end of the column while entirely in the liquid state, moves downstream an appreciable distance, begins to vaporize, and then moves through the remainder of the column as a gas-liquid mixture. The problem posed is to find the total weight rate of flow and the pressure distribution along the column for a given inlet pressure and temperature, a given exit pres5ure or temperature and given characteristics of the test fluid and porous medium. In developing the theory, gas-liquid interfacial phenomena are treated. phase equilibrium is assumed and previous theoretical work of other investigators of the problem is modified. Laboratory experiments performed with specially designed apparatus. in which propane is used as the test fluid, substantiate the theory. The apparatus. materials and experimental procedure are described. Comparative experimental and theoretical results are presented and discussed. It is believed that the research findings contributed in this * paper should not only lead to a better understanding of oil-reservoir behavior, but also should be suggective in regard to future research in this field of study. INTRODUCTION In recent years much time and effort has been consumed in both theoretical and experimental studies of the static and . dvnamic behavior of oil-reservoir fluids in porous rocks. Although lack of sufficient basic oil-field data, principally concerning the properties and characteristics of reservoir rocks and fluids, largely precludes quantitative application of research results to oil-field problems, qualitative application has become common practice. In effect. oil-reservoir engineering research is serving as a firm foundation for oil-field development and production practices leading to increased economic recoveries of petroleum. This province of research. however, still poses many perplexing problems. The thermodynamic behavior of two-phase fluids moving through porous media constitutes one facet of reservoir-fluid-flow research that has not received the attention it deserves. This report embodies a theoretical discussion of this subject and a description of a series of related laboratory experiments. The significance of the problem to oil field operations is indicated but in articular the report centers around a theory and method for analyzing the steady. macroscopically linear, two-phase flow of a fluid (a single molecular species) through a horizontal column of porous medium. For simplicity in showing how the thermodynamic behavior of two-phase fluids moving through porous media affects oil-reservoir performance problems, attention is focused temporarily on a particular well producing petroleum from an idealized water-free solution-gas drive reservoir, the reservoir rock being a horizontal, thin, fairly homogeneous sandstone of large areal extent confined between two impermeable strata. The flowing hydrocarbon fluid is considered to exist entirely as a Iiquid at points in the reservoir remote from the well; however. the decline in fluid pressure in the direction of the well causes vaporization of the hydrocarbon to begin at a radial distance r from the well. Upstream from r the fluid moves entirely as a liquid and downstream from r it moves either entirely as a gas or as a gas-liquid mixture depending on the properties of the hydrocarbon and on the thermodynamic process it follows during flow. The distance r would be variable under transient flow conditions. but for purposes of analysis the flow is considered to l~e steady at the particular instant of observation during the flowing life of the well of interest. If the flow were isothermal and the hydrocarbon a pure substance, the fluid would be entirely gaseous downstream from r. Thus, this isothermal flow process for a pure substance would require that the heat of vaporization be supplied at r. over zero length of porous medium, at the precise rate necessary to maintain the constant temperature. This means that the solid matrix of the porous medium (reservoir rock) and the surroundings (impermeable strata confining the reservoir rock) would have to serve as infinite heat sources. Heat-transfer requirements would be somewhat less severe for the isothermal flow of a multicorn-ponent hydrocarbon as bubble and dew points at the same temperature correspond to different pressures. In this instance isothermal conditions would be sustained without complete vaporization of the fluid over zero length of porous medium. Nevertheless. as the flow is in the direction of decreasing

Jan 1, 1951

By C. J. Sparks, J. C. Ogle, E. A. Starke

DEFORMATION of cold-rolled fcc metals and alloys produces one or the other of two types of rolling textures, usually referred to as the copper type or the brass type. The pure fcc metals, with the exception of silver, develop the copper-type texture when rolled at room temperature. Silver, brass, and many other alloys develop the brass-type texture. Transition from one texture type to another can also occur. Solute additions to pure copper cause a transition from the copper-type to the brass-type texture.' Varying the deformation temperature also produces texture transitions. Copper rolled at -196°C developed the brass-type texture2 and silver rolled at elevated temperatures, 200°C, developed the copper-type texture.374 The work of Haessner,' Smallman and Green,6 and Hu and coworkers3'4 seems to have established an apparent correlation between the type of rolling texture (and the texture transition) and the stacking-fault probability. Thus materials with low stacking-fault energies are thought to develop the brass-type texture while high stacking-fault energy materials develop the copper-type texture. Mikkola and cohen7 measured by X-ray diffraction techniques the stacking-fault probability, a, in the ordered and disordered fcc alloy Cu3Au. Unexpectedly, ordered specimens showed about twice the stacking-fault probability as the disordered ones. Marcinkowski and Zwe118 also found stacking faults in ordered Cu,Au, but not in the disordered CusAu. More recently, Camanzi and coworkers9 have shown that the intrinsic stacking-fault energy of Cu3Au undergoes a considerable decrease (approximately 100 ergs per sq cm) when passing from the disordered to the ordered phase. In general, deformation reduces order'' but some of our measurements showed that some long-range order still remains in Cu3Au after cold reduction by rolling 80 pct. From the above considerations Cu3Au offers the possibility of studying the texture transition in fcc alloys without varying either the temperature or the composition. If the stacking-fault energy correlation is correct, an initially ordered alloy should develop the brass-type texture during rolling while a disordered alloy should develop the copper-type texture. The present communication describes some initial results of experiments designed to investigate this possibility. The rolling textures of ordered and disordered Cu3Au samples were determined after various amounts of deformation. The ordered sample had an initial long-range-order parameter of S = 1, determined from X-ray diffraction. The grain size of both the ordered and disordered samples was the same, and the initial textures of both were also identical and approximately random. No obvious differences in the deformation textures of the ordered and disordered materials were detected up to 35 pct reduction and the (111) pole figures of Fig. 1 resemble that of pure copper. However, with reduction larger than 35 pct and less than 50 pct, a marked deviation from the copper texture was noted in the ordered material. The newly developed orientation was close to the (110)[i12] ideal orientations re-

Jan 1, 1970

By R. M. Brick

Segregation can occur only in cast alloys that solidify over a range of temperatures with a difference in composition of liquid and solid phases within this range (ignoring monotectic systems and chemical reactions as in rimming steels). Thus a pure binary eutectic alloy should show no segregation unless undercooling occurs for one of the solid constituents of the eutectic; e.g., chill-cast Al-I2 per cent Si alloys. The phasial condition implicitly described above—solidification over a range of temperatures with a compositional difference between solid and liquid—is found in nearly all solid solutions or combinations of solid solutions and eutec-tics, Metastable conditions of solidification of these types of alloys cause coring; i.e., a difference in composition between the center of a dendrite and its periphery. This composition gradient can be detected usually only by microscopic examination of etched structures; it is a "micro" effect. The gradient of more immediate industrial concern is that between the center of a cast section and the surface layers. This gross (macro) effect is usually deter-minable only by sampling of the casting at different points, with chemical analyses of each sample. If the compositional difference is of the same type as in coring, the first parts to freeze being enriched in higher-melting-point constituents, and vice versa, the effect is called normal segregation. When what is apparently the first part of the casting to solidify shows a higher concentration of low-melting-point constituents, the effect is called inverse segregation. These macro effects are quite separate from the micro effect, coring, yet the latter must be described first because it is an essential part of the picture. Coring Solid Solution, Ni-Cu The nickel-copper phase diagram is reproduced in Fig. Ia, in which the solid lines represent the equilibrium liquidus I, 3, 7 and solidus 2, 5, 8, and where the vertical I, 4: 8 represents a 55 per cent Cu alloy. Upon moderately rapid solidification, the first dendritic axes of composition 2 (see Fig. Ib) start to form at a temperature somewhat under I. Solidification continues by growth of the dendritic nuclei, but at temperature 4 the increment solidifying is of composition 5. The rapidity of this crystal growth prevents diffusion of nickel and copper atoms from adjusting the composition of the entire dendrite at 5, which it would be under equilibrium conditions. The average composition of a specific dendrite, or the entire solid phase, at temperature 4 might be that indicated

Jan 1, 1945

By R. M. Brick

SEGREGATION can occur only in cast alloys that solidify over a range of temperatures with a difference in composition of liquid and solid phases within this range (ignoring monotectic systems and chemical reactions as in rimming. steels). Thus a pure binary eutectic alloy should show no segregation unless undercooling occurs for one of the solid constituents of the eutectic; e.g., chill-cast Al-12 per cent Si alloys. The phasial condition implicitly described above-solidification over a range of temperatures with a compositional difference between solid. and liquid-is found in nearly all solid solutions or combinations of solid solutions and eutectics. Metastable conditions of solidification of these types of alloys cause coring; i.e., a difference in composition between the center of a dendrite and its periphery. This composition gradient can be detected usually only by microscopic examination of etched structures; it is a "micro" effect. The gradient of more immediate industrial concern is that between the center of a cast section and the surface layers. This gross (macro) effect is usually determinable only by sampling of the casting at different points, with chemical analyses of each sample. If the compositional difference is of the same type as in coring, the first parts to freeze being enriched in higher-melting-point constituents, and vice versa, the effect is called normal segregation. When what is apparently the first part of the casting to solidify shows a higher concentration of low-melting-point constituents, the effect is called inverse segregation. These macro effects are quite separate from the micro effect, coring, yet the latter must be. described first because it is an essential part of the picture. CORING Solid Solution, Ni-Cu The nickel-copper phase diagram is reproduced in Fig. Ia, in which the solid lines represent the equilibrium liquidus 1, 3, 7 and solidus 2, 5, 8, and where the vertical 1, 4, 8 represents a 55 per cent Cu alloy. Upon moderately rapid solidification, the first dendritic axes of composition 2 (see Fig. 1b) start to form at a temperature somewhat under I. Solidification continues by growth of the dendritic nuclei, but at temperature 4 the increment solidifying is of composition 5. The rapidity of this crystal growth prevents diffusion of nickel and copper atoms from adjusting the composition of the entire dendrite at 5, which it would be under equilibrium conditions. The average composition of a specific dendrite, or the entire solid phase, at temperature 4 might be that indicated

Jan 1, 1944

By M. J. Pool, with Appendix by Larry Kaufman, R. W. Krenzer

Thermodynmic properties of the Cu-Mn system have been deterrrzined in the temperature range 973" to 1273°K by measuring the vapor pressure of manganese in equilibrium with alloys of compositions varying from 0.13 to 0.91 rnole fraction manganese using the Knudsen effusion technique. Activities of manganese calculated from the measured vapor pressures show large positive deviations. Calculated heats and entropies of mixing are positive with a maximum occurring at approximately 0. 7 mole fraction manganese. ThE investigation of thermodynamic properties of binary systems involving transition metals is of considerable interest at the present time. The incomplete subvalency electron levels of transition metals lead to unusual behavior in some alloys, and considerable information can be obtained by determining the thermodynamic characteristics of these systems and relating the thermodynamic behavior to observed physical properties. The Cu-Mn system, shown in Fig. 1,' provides an example of an alloy system in which the determination of the equilibrium phase diagram and various physical properties has received considerable attention, but very little work has been done on measurement of the thermodynamic properties. Elemental copper and manganese have comparable electronegatives, atomic sizes, and cohesive energies, but differ in crystal structure. They form a continuous series of solid solutions only at high temperatures and the structure varies in a continuous manner from fcc at the copper-rich end to fct at the manganese-rich end.' The purpose of this investigation was to measure the vapor pressure of manganese over a series of Cu-Mn alloys and from these values determine the thermodynamic properties of the binary system. Vapor pressure measurements were made in the temperature range 973" to 1273"K, remaining within the solid-solution region for each alloy studied. EXPERIMENTAL PROCEDURE The relative thermodynamic properties of solid Cu-Mn alloys were determined from vapor pressure measurements by means of the Knudsen effusion tech- nique. Several discussions of the theory can be found in the literature. In the case of copper and manganese, it is assumed that manganese is the only component subliming, so the vapor pressure of manganese over the various alloys can be determined directly by measuring the weight loss of the effusion cell. This is a valid assumption since the vapor pressure of manganese is about four orders of magnitude higher than the vapor pressure of copper in the temperature region of interest. The vapor pressure of manganese over the alloys at any given temperature is then related to the weight loss of the effusion cell per unit area per unit time. An upper limit of 1.5 x 10"s has been measured for the ratio of polyatomic to monoatomic molecules for manganese vapor in equilibrium with solid manganese at 1180°K, so it was assumed that manganese vapor is monoatomic. The effusion cells, fabricated from high-purity alumina, are 26 mm high, 18 mm OD, and have a wall thickness of 1 mm. Three different sized holes of 2.03, 2.54, and 3.18 mm diam were drilled in the lids from the inside face to minimize chipping, and the lids were then slip-cast onto the cells to provide a gas-tight seal. Alumina was selected for this particular application both because of its resistance to thermal shock and reaction with manganese vapor. In the ideal case, the orifice of the effusion cell should have a knife edge so that effusion through the orifice

Jan 1, 1970

[This paper was presented for the author, who is now in the National service, by H. M. Chance, and was illustrated by a working model built to the plans shown in the Bulletin, for February, 1918, p. 268. For more convenient operation, a small motor-driven centrifugal pump was attached to the overflow outlet (5, Fig. 1, p. 267) delivering to the inlet, 4. The pressure of ingoing water was then adjusted by a valve at 4, and was indicated by the column of water in a vertical glass tube connecting with the pressure chamber; an average pressure of 15 in. of water column was maintained during the demonstration. The sand used in the test was beach sand, which had simply been passed through a 20-mesh screen; about 45 per cent. was finer than 80 mesh. The circulation of water was at the rate of about 5 gal. per square foot per minute, and the rising velocity of the water in the box as a whole (not the velocity of the jets) was 6 in. per minute. At this consistency, the specific gravity of the fluid mass was between 1.55 and 1.60. Mr. Chance estimated that it would be possible to maintain a fluid mass of this consistency, 3 ft. deep, and with an area of 50 by 60 ft. with an expenditure of 15-hp. Mr. Chance then showed how a lump of coal would float on the fluid mass, and also made a separation of slate from coal on a small scale in a wire cage submerged momentarily in the fluid. The following demonstration relates to a matter not contained in the original paper, and was presented as of interest to the operators of cyanide and other lixiviation processes dealing with fluid mixtures of varying specific gravity.-Ed.]

Jan 4, 1918

By John Conley

THE production of lime by the burning or calcination of limestone, including all varieties from true dolomites and magnesian limestones to high-calcium types, continues as one of the essential basic industries. In 1937, a total of 4,124,165 tons of lime valued at approximately $30,091,000 was produced in the United States.1 The importance of any contribution to our knowledge on the mechanism of the lime-burning process is, therefore, obvious. The burning of limestone has been practiced since the earliest days of our civilization, and the literature on the various phases of the industry is voluminous. Calcination of the various types of limestone has been studied by many previous investigators, but some points require addi-tional research. Each occurrence of limestone provides an opportunity for specific investigation, because the characteristics of stones in different localities vary. Knibbs13 has given an excellent discussion of available data on the theory of lime and magnesia burning. The thermal dissociation of calcium carbonate has been studied more recently by Johnston,2 Smyth and Adams,3 Ralston et al.,4 Furnas,5 Potapenko,6 and Southard and Royster.7 As a result of these investigations the dissociation temperature at atmospheric pressure has been established as 894° to 898° C. The dissociation of dolomite and magnesite, although studied by several investigators, 4,6,8 still requires clarification by additional data. The calcination of limestone was studied for a twofold purpose: (1) to extend our information on the mechanism of the lime-burning process and (2) to standardize the conditions for calcination of high-calcium and dolomitic limestones for subsequent hydration tests on the lime.

Jan 1, 1939

By H. Rumfelt

Strip mining in the domestic coal industry is contributing a greater proportion bf overall production than at any time in the past. U.S. Bureau of Mines statistics show that the percentage of total production mined in 1958 by stripping methods increased to more than 30 pct, up from 22 pct in 1951. The tendency to favor strip and open pit mining exists in other mining activities, but such trends are not as clearly outlined as in the coal industry. Significantly, the depth of overburden in coal properties considered suitable for stripping is also increasing. A depth of 50 to 60 ft of overburden was once considered to be about the maximum amount that could be handled economically. Today, a depth of 80 to 100 ft is frequently taken into consideration for simple overcasting operations (i.e., excavating overburden and dumping it in the spoil position where it remains indefinitely).

Jan 5, 1961

By John E. Conley

THE production of lime by the burning or calcination of limestone, including all varieties from true dolomites and magnesian limestones to high-calcium types, continues as one of the essential basic industries. In 1937, a total of 4,124,165 tons of lime valued at approximately $30,091,000 was produced in the United States.1 The importance of any contribution to our knowledge on the mechanism of the lime-burning process is, therefore, obvious. The burning of limestone has been practiced since the earliest days of our civilization, and the literature on the various phases of the industry is voluminous. Calcination of the various types of limestone has been studied by many previous investigators, but some points require additional research. Each occurrence of limestone provides an opportunity for specific investigation, because the characteristics of stones in different localities vary Knibbs13 has given an excellent discussion of available data on the theory of lime and magnesia burning. The thermal dissociation of calcium carbonate has been studied more recently by Johnston,2 Smyth and Adams,3 Ralston et al.,4 Furnas,5 Potapenko,6 and Southard and Royster.7 As a result of these investigations the dissociation temperature at atmospheric pressure has been established as 894º to 898º C. The dissociation of dolomite and magnesite, although studied by several investigator,4, 6, 8 still requires clarification by additional data. The calcination of limestone was studied for a twofold purpose: (1) to extend our information on the mechanism of the lime-burning process and (2) to standardize the conditions for calcination of high-calcium and dolomitic limestones for subsequent hydration tests on the lime.

Jan 1, 1939

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members.) Members and guests who registered at Institute headquarters during the period April 1 to 15. William B. McKinley, New York, N. Y Collier Cobb, Chapel Hill, N. C. C. W. Goodale, Butte, Mont. E. P. Fleming, Guayacan, Chile. D. C. Brown, San Luis Potosi, Mex. Albert Sauveur, Cambridge, Mass. W. H. Rettie, Yonkers, N. Y. H. M. La Follette, La Follette, Tenn. Mark B. Kerr, San Francisco, Cal. E. Fleming L'Engle, New York, N. Y. H. W. Turner, San Francisco, Cal. H. Garlichs, St. Louis, Mo. Frank M. Leland, Mackay, Idaho. Henry Hay, London, England. Sir Robert Hadfield, London, Eng. Edward J. Way announces that his agreement as consulting engineer in South Africa for the Anglo-French Exploration Co., Ltd., having terminated, he will engage in professional consulting work with headquarters at 135 Cullinan Buildings, Simmonds St., Johannesburg, South Africa.

Jan 5, 1914