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By Donald B. Evans, Robert D. Pehlke

The solubility of nilrogen in liquid binary alloys of iron with Litanium. zivconium, columbium, vanndiurn, and tantalum was measured for alloy composiLions up to the solalbility limils of lhe alloy nitrides. All five alloying agents were found to decrease markedly the activity coefficient of nitrogen in liquid ivon. The metal/nitvogen mole ralios in the alloy nitrides formed were generally .found to be slighlly greater than 1.0, but in no case greater than 1.5. From the experimental data, the standard free energies of fortmation of titanium and zir-conium nitrides have been calculated for the Lemperaluve range 1550° to 1750 C. The solublily Products for columbium, tantalum, and vanadium nitrides are also reported. A number of research investigations have examined the effect of refractory metals on the solubility of nitrogen in liquid iron. Although data on zirconium are not available, investigators are in agreement that titanium, vanadium, columbium, and tantalum markedly increase the solubility of nitrogen in liquid iron. This fact alone makes desirable the acquisition of thermodynamic data for these elements in liquid iron. Since refractory metals are known to be stable nitride formers, they have been suggested as steel denitrifying agents, and some of their nitrides have recently been considered as containment materials for liquid iron and iron alloys. Most available thermodynamic data for these metals relate to their dilute concentrations, but effective thermodynamic treatment of these applications requires data at concentrations near the solubility limit of the alloy nitride. Although some work has been done at relatively high alloy concentrations in liquid iron (particularly for vanadium 2,3 and titanium 2,4), the results have been somewhat contradictory. Disagreement may be partly attributed to the fact that the compositions of most refractory metal nitrides have been shown to be nonstoichiometric, and to vary 2,5-8 depending on the temperature and nitrogen gas pressure with which the solid nitride phase is in equilibrium. One purpose of this study consequently has been to determine the compositions of the refractory metal nitrides precipitated from a liquid iron solution. EXPERIMENTAL PROCEDURE Rao and Parlee2 and Evans and Pehlke 9 have discussed the technique for measuring the solubility product of an alloy nitride phase in liquid iron by finding the point of departure of the nitrogen solubility from Sieverts' law. The method consists of measuring the solubility of nitrogen in a melt of iron containing a known concentration of a second metal as a function of the nitrogen gas pressure over the melt. In this study the second metal was one of the refractory metals titanium, zirconium, columbium, vanadium, or tantalum. When the nitrogen pressure at which the refractory nitride forms is reached, a deviation of the measured solubility of nitrogen in the melt from Sieverts' law is observed in the form of a "pressure halt." The concentration of nitrogen in the melt associated with this breakpoint in the nitrogen-absorption curve is then used to calculate the nitride solubility. The Sieverts method was used to measure nitrogen solubility as a function of nitrogen pressure and temperature. The experimental equipment for this technique has been previously described in detail. 1,9 Charge materials used were vacuum-melted high-purity iron (Ferrovac-E) and the best commercial grades of the refractory metals obtainable (in all cases at least 99.8+ pct pure). Recrystallized alumina crucibles were used to hold all melts except those containing zirconium, for which zirconia crucibles were necessary. Temperatures were measured by a disappearing-filament type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diameter sight hole in the crucible lid. By means of a technique previously described, 9 in which the refractory-metal nitride was precipitated at one temperature then redis-solved by raising the temperature 50°C and precipitated again at a higher temperature, it was possible to obtain data over a temperature range of up to 200°C on a single melt. It was found that this technique could not be used with melts containing zir-

Jan 1, 1965

The Sub-committee on Coal Mining, since its appointment, has been collecting data about subsidences in coal mines in this country, and thinks that almost all of the available data about occurrences of this sort in bituminous mines has been collected. Similar data is being compiled for the anthracite regions, which it is hoped will be ready for the 1927 meeting. As most of the bituminous seams are nearly level, the records obtained give the problem in its simplest form, without complications due to the pitch of the seam. Copies of the questionnaire, Appendix A, were mailed to all of the coal operators' associations, to most of the large operating companies and to many engineers, with the request that any data on the subject be returned to the committee, or that advice of any subsidences known be given: the replies to most of the questionnaires were general, although some specific cases were given. Many of the companies were unable to reply to all questions, as they lacked the necessary data, but in nearly every case where accuratc data was available, it was cheerfully furnished, and any additional information requested was secured. All specific cases of subsidence were followed up by correspondence, and in several cases by personal inspection. Figs. 1 to 31 were made from the information furnished. Table 1 gives measurements of elevations taken in one case at intervals from October, 1913, to May, 1918. With one exception, where the evidence cannot be released on account of a lawsuit, it is believed that the cases submitted with this report include practically all that have happened in bituminous coal mining in this country of which actual measurements were secured. Some of these have been published by Young and Stoek,l and some have been secured from other publications. In collecting these data, the subcommittee had the Engineering Societies Library extend its bibliography to date; this list is given in Appendix B. To assist in the study of the problem, all of the subsidence literature in English was examined for cases in which spccific measurements were given, and the essential data for each case are shown in Appendix C.

Jan 1, 1927

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

Notched and unnotched tensile specimens of wrought and recrystallized, oxygmted and hydro-genated tantalum and columbium were tested over a range of temperatures selected to encompass the ductile-to-brittle transition. Increasing the oxygen content of tantalum and columbium increased their strength, and raised their ductility transition temperature, but did not cause a marked deterioration of notch properties below that of commercially pure material. The adverse effects of oxygen were more pronounced for recrystallized structures than for wrought material. The effects of hydrogen are complicated by strain aging or slow strain rate hydrogen embrittlement at -105°F. However, in general, hydrogen had only a minor effect an strength, but markedly increased the effective transition tem-terature and caused a deterioration of notch properties . BCC metals including the refractory metals in Groups Va and VIa (V, Cb, Ta and Cr, Mo, W) can be expected to undergo a ductile-to-brittle transition and exhibit brittle fractures at low temperatures.' Notch embrittlement is associated with this phenomenon, and can be a serious design problem. Table I compares the tensile transition behavior and notch sensitivity of commercially pure Group Va and VIa refractory metals. The Group VIa refractory metals have considerably higher transition temperatures, and become notch sensitive at higher temperatures, than do the Group Va refractory metals. In addition, the Group VIa refractory metals are sensitive to metallurgical structure. Recrystallized structures generally have higher transition temperatures than wrought material of the same composition. The relatively poor transition behavior of the recrystallized structures of these metals is generally attributed to the segregation of interstitial impurity atoms at grain boundaries. Pronounced sensitivity to structure is not evident with commercially pure Group Va refractory metals, however. Since these metals have higher solubilities for interstitial elements than do the Group VIa metals ,4 it can be expected that higher total interstitial concentrations are necessary to develop a comparable degree of grain boundary segregation and to produce a similar sensitivity of transition temperature to structure. Increasing only the concentration of interstitial atoms in solution would tend to increase the flow stress of a metal in relation to its cleavage fracture stress and thereby raise its transition temperature, but would not be expected to cause a marked sensitivity of transition temperature to structure. A research program has been conducted at the Battelle Memorial Institute to evaluate the effects of interstitial oxygen and hydrogen on the transition behavior and notch sensitivity of tantalum and columbium, and to evaluate the effects of structure on "contaminated" material. EXPERIMENTAL PROCEDURES Notched and unnotched tensile specimens of oxygenated and hydrogenated tantalum and columbium with both wrought and recrystallized structures were tested over a range of temperatures selected to encompass the ductile-to-brittle transition Oxygen levels selected for study in both tantalum and columbium were nominally 500 and 1000 ppm, whereas nominal hydrogen contents were 150 and 500 ppm in tantalum and 150 and 300 ppm in columbium. Oxygen and hydrogen additions were made directly to 6-in. lengths of 1/2-in.-diam electron beam melted wrought bar stock, in a Sieverts Apparatus. Subsequent high-temperature annealing was required for homogenization of the oxygenated material, but was not necessary in the case of hydrogenated stock. The oxygenated and hydrogenated bars were then swaged to 1/4-in.-diam rods. Tensile specimen blanks were cut from the 1/4-in.-diam rods and annealed to achieve stress-re-

Jan 1, 1963

By W. O. Philbrook

An engineering analysis indicates that the coke rate in present blast-furnace practice is set not by chemical or thermal needs but to give adequate charge permeability for economical driving rates. An equation showing interrelations among pressure drop, gas flow, and charge characteristics has been derived. Flooding conditions and the location of the fusion zone are discussed. Maximum ore size is probably limited by chemical re-ducibility rather than by heat transfer. THE intention of this paper is to show that the ].imitations on the production rate and coke requirement of the iron blast furnace are not primarily chemical or thermal in nature but are related to characteristics of the burden and operation that govern gas flow, heat transfer, and stock movement. A semiquantitative analysis will be developed in terms of standard engineering principles to give a useful picture of the relative importance of physical and mechanical factors in contrast with the chemical features of the process that are more commonly emphasized. Most of the details of calculation have been omitted in the interest of brevity and to avoid submerging the rnain points in a sea of arithmetic. Numerical values have been arrived at by objective methods from reported operating data or by reasonable estimates of material properties where exact data are lacking and then tested to see how well they fit practice, rather than by working backward to find what assumptions are needed to give the desired answers. The analysis is oversimplified in many ways because exact engineering relations have not yet been studied for bed distributions as complex as are known to exist in the blast-furnace stock column. One objective of this paper is to show that the blast furnace, in spite of its complexity, can be at- tacked by engineering methods in the hope that this viewpoint will stimulate the kind of research needed for a more exact treatment. The basic ideas and many of the conclusions presented are qualitatively well known. A careful literature survey to credit the source of all observations not original to the author would indeed be voluminous, and such has not been attempted. T. L. Joseph's Howe Memorial Lecture' gives an excellent background of what is known about the internal workings of a blast furnace. Other important reference works or sources of specific information will be noted. It is hoped that the present paper will contribute something new, in method of attack and interpretation, that will aid in a clearer understanding of how to operate the blast furnace to best advantage. Factors Limiting Production and Coke Rates The rate of combustion of coke in a blast furnace, as in any fuel bed, is exactly proportional to the rate at which air is supplied. It is axiomatic, then, that the production rate of a furnace is limited by the rate at which it will take wind, i.e., burn coke, and the amount of coke that must be burned at the tuyeres to make a ton of iron of suitable composition. These two possible limiting factors will be considered briefly in the order mentioned. One common restriction on wind rate is flue-dust production. Since the volume of top gas is nearly proportional to the blast volume (by a factor of about 1.35 on a dry basis), an increased wind rate causes a correspondingly increased linear velocity of top gas in the throat of the furnace. The higher

Jan 1, 1955

By Brison Robertson, W. P. Fishel

The carbide-forming tendencies of the various steel-alloying elements, or their affinities for carbon, is a subject that has received considerable attention, but little more than a probable arrangement of the elements as to their carbide-forming tendencies has been proposed. The physical properties of alloy steels depend upon the relative proportions of the elements present and their combinations. one important phase of this subject is the distribution of carbon between the various elements present. The distribution of car. bon between iron and other elements evidently sill depend upon: (I) the affinity of each for carbon; (2) the relative atomic masses of the elements present; and (3) the possible formation of compounds between the alloying and iron and between the elements themselves, In ternary steels the case is simplified, especially in systems in which the element and iron form no compounds, In such systems iron and the alloying element are competing for the carbon present. In this work the distribution of carbon between titanium and iron has been studied by measuring the relative amounts of iron carbide and titanium carbide present ill a series of annealed steels in which the ratio of titanium to carbon extended from 0.527 to 4.61. Ten Fe-Ti-C alloys, weighing about 250 grams each, were prepared by melting under a Vacuum, in an Induction furnace, Armco iron, carbon-free ferrotitanium (25 per cent Ti), and pure carbon. Vacuum melting prevented the formation of titanium oxides and nitrides, which would the the problem. The melts were made in graphite crucibles lined with sintered magnesium oxide. The ingots were the in the furnace under a vacuum and "'ere then completely annealed at 950°C. The determination of the amount of titanium carbide present was based upon the established insolubility of titanium carbide in boiling dilute (1:4) sulphuric acid, and the complete solubility Of free titanium and titanium-iron compounds in this acid. High-carbon ferrotitanium, which had been treated to remove free Ti and Fe. was found to be completely insoluble in the acid; and the carbon-free ferrotitanium used in making the alloys was found to be completely soluble. Others have reported the insolubility of titanium carbide in sulphuric and hydrochloric acids. Turnings from the ingots were digested with boiling sulphuric acid (1:4) until all action had ceased. The carbide residue was filtered off and analyzed for titanium, and in some cases for carbon. This represerifs the titanium that was united with carbon The filtrate from the carbide residue contains the portion Of the titanium that was in solid solution in the ferrite. Titanium

Jan 1, 1945

By S. R. Zimmerley, John Gross

The method of measurement of surface on quartz particles was given in a previous paper.' With such a method the relation of surface produced in crushing quartz can be compared to the work in crushing without recourse to sieve sizing or microscopic measurement. In crushing, the work input must be known with a fair degree of accuracy. With crushers, rolls, ball mills, and similar apparatus the measurement of the work in crushing is subject to possible errors, due to friction in the transmission as well as in the machine itself. Moreover, relatively large quantities of material must be crushed to get an average figure. In the selection of a method of crushing, simplicity in design and operation was desired and this was most readily obtained by the use of a free-falling body. A description of the apparatus embodying this principle is given herewith. The Crushing Device The apparatus used is shown in Fig. 1 and in cross-section in Fig. 2. The material to be crushed is placed in the crushing chamber C in the steel mortar M. The mortar is 3 in. dia. by 3 in. high. Two mortars are used, one having a crushing chamber 1 in. dia. by 36 in. deep, with a capacity of 4 g. of quartz, the other having a crushing chamber 1 1/2-in. dia. by % in. deep, with a capacity of 12 g. of quartz. The position of the mortar is adjusted by means of three centering screws A. The steel plunger P, which fits neatly into the chamber, is placed on top of the material to be crushed. Plungers of different lengths were tried and as they were found to give practically identical results the length adopted was equal to the depth of -the chamber. The mortar rests on a solid steel base B but is separated therefrom

Jan 1, 1930

By R. S. Busk, E. G. Bobalek

The relation between gases and metals has been a subject of increasingly active investigation during the past years, principally devoted to the study of metal-hydrogen systems. It has been found that hydrogen is soluble in most molten metals to an appreciable extent and somewhat soluble in most solid metals.l,2 In every known case there is a sudden decrease in solubility at the melting point. Thus a freezing mass of metal containing hydrogen in excess of the solid solubility must in some way expel that excess during the freezing process. This leads to internal blowholes, and such effects as pinhole porosity. Gas trapped in metal that is to be fabricated by a working process such as extrusion or rolling may be the cause of blisters. For some cases, notably in copper and iron alloys, the presence of hydrogen can lead to extreme embrittle-ment of the metal. The aluminum-casting industry has long recognized the importance of hydrogen in its techniques. Excess gas in molten aluminum alloys often leads to the formation of "pinhole porosity" in the solid casting.= To prevent this hydrogen pickup it is necessary to avoid overheating the melt and to protect it from such sources of hydrogen as water. In spite of all precautions, it is sometimes necessary to extract hydrogen from the melt just before pouring by bubbling with a gas such as chlorine or nitrogen. Reccntly it has been found that somewhat similar effects are possible with magnesium alloys, in that the presence of hydrogen can induce or aggravate micro-p~rosity.4-6 This paper is primarily concerned with a presentation of some facts concerning the solubility of hydrogen in magnesium and its alloys, with some discussion of the significance of these facts in a practical sense. In any study of gas-metal systems it is important to bear in mind a clear distinction between adsorption on surfaces and absorption within the lattice.' Considerable attention has been directed toward determining whether hydrogen is truly soluble in any solid metal, or whether the gas extracted from a sample was present at surfaces (external and internal) only.7 Most present day evidence supports the idea of true solution in addition to adsorption. A second important factor when dealing with gas solubility is the dependence of such solubility on external pressure. For diatomic gases such as H², solubility in both liquid and solid metals apparently is proportional to the square root of the pressure, indicating a breakdown to a monatomic gas before diffusion into the lattice.= For true equilibrium values of solubility, therefore, the pressure at the the surface must be constant and, preferably, known. Very little has been published concerning the hydrogen-magnesium system. Winterhager has presented the most

Jan 1, 1947

By R. S. Busk, E. G. Bobalek

The relation between gases and metals has been a subject of increasingly active investigation during the past years, principally devoted to the study of metal-hydrogen systems. It has been found that hydrogen is soluble in most molten metals to an appreciable extent and somewhat soluble in most solid metals.l,2 In every known case there is a sudden decrease in solubility at the melting point. Thus a freezing mass of metal containing hydrogen in excess of the solid solubility must in some way expel that excess during the freezing process. This leads to internal blowholes, and such effects as pinhole porosity. Gas trapped in metal that is to be fabricated by a working process such as extrusion or rolling may be the cause of blisters. For some cases, notably in copper and iron alloys, the presence of hydrogen can lead to extreme embrittle-ment of the metal. The aluminum-casting industry has long recognized the importance of hydrogen in its techniques. Excess gas in molten aluminum alloys often leads to the formation of "pinhole porosity" in the solid casting.= To prevent this hydrogen pickup it is necessary to avoid overheating the melt and to protect it from such sources of hydrogen as water. In spite of all precautions, it is sometimes necessary to extract hydrogen from the melt just before pouring by bubbling with a gas such as chlorine or nitrogen. Reccntly it has been found that somewhat similar effects are possible with magnesium alloys, in that the presence of hydrogen can induce or aggravate micro-p~rosity.4-6 This paper is primarily concerned with a presentation of some facts concerning the solubility of hydrogen in magnesium and its alloys, with some discussion of the significance of these facts in a practical sense. In any study of gas-metal systems it is important to bear in mind a clear distinction between adsorption on surfaces and absorption within the lattice.' Considerable attention has been directed toward determining whether hydrogen is truly soluble in any solid metal, or whether the gas extracted from a sample was present at surfaces (external and internal) only.7 Most present day evidence supports the idea of true solution in addition to adsorption. A second important factor when dealing with gas solubility is the dependence of such solubility on external pressure. For diatomic gases such as H², solubility in both liquid and solid metals apparently is proportional to the square root of the pressure, indicating a breakdown to a monatomic gas before diffusion into the lattice.= For true equilibrium values of solubility, therefore, the pressure at the the surface must be constant and, preferably, known. Very little has been published concerning the hydrogen-magnesium system. Winterhager has presented the most

Jan 1, 1947

By W. H. Craigue

The scope of this article covers only the mathematical principles involved in discounting to present worth future expected profits and it is believed answers definitely two questions, which were raised at a recent meeting of the Committee on Methods of Valuing Coal Properties, as follows: 1. The accumulative effect of carrying charges on the value of coal mines showing definitely the number of years beyond which the coal may not be mined at a profit and subsequent to which the possession of any unmined coal will be a liability rather than an asset. 2. The effect on the valuation of coal mines, in the presence of the carrying charges described in question 1, of an increase in plant capacity and production. In general, in considering these questions, it may be stated that the consideration of an increase in plant capacity and production follows as a matter of course after a determination has been made of the year beyond which no profits are to be realized (giving the carrying charges accumulative effect, or in other words capitalizing the carrying charges, as shown hereinafter). For example, if it is determined that any coal that is unmined after 45 years will have no value or less than no value, the question immediately arises as to whether or not a plant should be constructed that would result in a yearly production great enough to extract the entire tonnage in a time less than 45 years, and if so the number of years less than 45 years that would, from a financial standpoint, be the most desirable, all under the assumption that the market for the product or the transportation facilities are such that the yearly production can be increased to the desired amount. Specifically, the carrying charge is considered herein as yearly expense, such as state or local taxes, which are assessed each year against the total tonnage remaining in the ground (or the total coal acreage remaining) at the beginning of the year, at a fixed rate per ton (or a fixed rate per acre) OF a fixed percentage of the assessed value, in the latter case it being necessary to convert such percentage into a rate per

Jan 1, 1934

By Arthur F. Taggart, Herbert H. Kellogg, Nathaniel Arbiter

The experimental work herein described is presented in support of the following broad hypothesis: Conditioning of metals and metallic sulphides by amine collectors involves metathetic reaction at the solid surface between the collector and an oxidized metallic compound, to produce a coating comprising an amine-bearing compound of low solubility in the system. The type of reaction is different in acid and in basic solutions; both types may occur simultaneously in near-neutral pulps. Experimental The experiments comprise contact-angle tests with a variety of metals and metallic sulphides and extraction teats on ground chalcocite. Contact-angle tests were made principally on metals. Covellite paralleled metallic copper in amine solution at pH 8.8 (Table 3) and in alkaline water, but maintained an angle of about 70° in Io-3 HCl solution, where metallic copper lost its angle. The tests with anionic collectors (Table I) indicate that the behavior of metals in general is parallel to that of their minerals in anionic solutions. It is believed that this is generally true with cationic collectors also, but the covellite test is a warning against a broad assumption to this effect. All test specimens were mounted in Transoptic.* All tests in conditioning solution were preceded by a test in distilled water; cleaning and polishing were continued in every case until the angle in water was zero. Subsequent transfers into and out of solutions and test cells were made in such a way as to prevent exposure of the surface to air.1 The amine used was primary laurylamine, Armour and Co., AM-1120. It was used in the form of the hydrochloride, obtained by precipitation with gaseous hydrochloric acid from an ether solution of the amine, and purified by two recrystallizations from ether-alcoho1.2 Inorganic and other test reagents were standard laboratory grades. Temperatures were not controlled; the probable range of test-solution temperatures is 650 to 80°F.

Jan 1, 1943

By Herbert H. Kellogg, Nathaniel Arbiter, Arthur F. Taggart

The experimental work herein described is presented in support of the following broad hypothesis: Conditioning of metals and metallic sulphides by amine collectors involves metathetic reaction at the solid surface between the collector and an oxidized metallic compound, to produce a coating comprising an amine-bearing compound of low solubility in the system. The type of reaction is different in acid and in basic solutions; both types may occur simultaneously in near-neutral pulps. Experimental The experiments comprise contact-angle tests with a variety of metals and metallic sulphides and extraction teats on ground chalcocite. Contact-angle tests were made principally on metals. Covellite paralleled metallic copper in amine solution at pH 8.8 (Table 3) and in alkaline water, but maintained an angle of about 70° in Io-3 HCl solution, where metallic copper lost its angle. The tests with anionic collectors (Table I) indicate that the behavior of metals in general is parallel to that of their minerals in anionic solutions. It is believed that this is generally true with cationic collectors also, but the covellite test is a warning against a broad assumption to this effect. All test specimens were mounted in Transoptic.* All tests in conditioning solution were preceded by a test in distilled water; cleaning and polishing were continued in every case until the angle in water was zero. Subsequent transfers into and out of solutions and test cells were made in such a way as to prevent exposure of the surface to air.1 The amine used was primary laurylamine, Armour and Co., AM-1120. It was used in the form of the hydrochloride, obtained by precipitation with gaseous hydrochloric acid from an ether solution of the amine, and purified by two recrystallizations from ether-alcoho1.2 Inorganic and other test reagents were standard laboratory grades. Temperatures were not controlled; the probable range of test-solution temperatures is 650 to 80°F.

Jan 1, 1943

By R. H. Jacoby, V. J. Berry

Future depletion performance and ultimate oil recovery from reservoirs producing under volumetric control are often predicted with the aid of a material balance equation. When the reservoir fluid is very volatile, however, certain assumptions implicit in the use of the conventional methods are no longer valid. This is became laboratory differential vaporization test procedures do not adequately represent the reservoir depletion process and the performance of surface separation facilities. In such cases recovery of stock tank oil per unit of pressure decline can be predicted only from a detailed knowledge of the separator conditions and the over-all composition of the fluid entering the wellbore at each stage of depletion. Surface recovery is not simply related to the total quantity of liquid flowing into the well under reservoir conditions. In order to improve predictions for reservoirs which produce volatile oils, a step wise method of calculation has been developed. This method uses relative permeability data and multicomponent flash calculations to predict oil and gas production as a function of reservoir pressure. Calculations are presented for a reservoir containing a volatile crude oil, and predicted tank oil recovery by primary depletion is more than twice that predicted by conventional methods which are known to be adequate for ordinary black crude oils. Calculated maximum produced gas-oil ratio is less than one-fourth of the conventional prediction. Wellstream compositions have also been used to determine variation in stock tank oil composition and liquid content of the separator gas. This information is of particular importance for crude stabilization calculations and for design of gasoline plant facilities to recover LPG and natural gasoline. INTRODUCTION The estimation of oil reserves and the prediction of future recovery performance of petroleum reservoirs is a frequent task of the petroleum engineer. If the reservoir produces under volumetric control, performance calculations for primary depletion are made by combining oil and gas material balances with the gas-oil flow characteristics of the reservoir rock. For black oil reservoirs, the Schilthuis1 type material balance is commonly employed. For gas or gas-condensate reservoirs, where only one phase is flowing under bottom-hole conditions, a more simplified material balance is used. In the period in which these material balance methods were conceived and put into practice, it was common to classify reservoirs according to the type of fluid produced as (1) black oil reservoirs, or (2) gas or gas-condensate reservoirs. Recently, however, deeper drilling and more extensive studies of reservoir fluid properties have led to the recognition of reservoir fluids with phase characteristics between those of ordinary black oils, and gases or gas-condensate fluids. These intermediate fluids contain relatively large amounts of the hydrocarbons ethane through decane and are found in deep, high temperature (250°F) reservoirs. Such fluids are often referred to as high shrinkage crudes or "volatile oils." They are usually characterized by tank oil gravities above 45° API. high solution gas/oil ratios,

Jan 1, 1958

By B. D. Cullity

Gold and beryllium form an intermediate phase composed of the two metals in equal atomic proportions and having the formula AuBe. According to Winkler,' this phase probably exists in two modifications: beta, stable below about 600°C, and alpha, stable between 600°C and the melting point, about 740°C. Only the low-temperature beta form will be considered in this paper. Experimental Procedure The gold used had a fineness of 999.75 to 999.85, balance mainly silver, and the beryllium purity was better than 99.8 pct. AuBe was prepared by melting the constituents in a beryllia crucible in an evacuated induction furnace. After melting and thorough mixing, the alloy was allowed to solidify in the crucible. No difficulty was encountered in obtaining a homogeneous ingot. Both chemical analysis and microscopic examination of the ingot showed that the alloy was essentially one phase, containing 50 at. pct gold. The alloy was quite brittle and powder samples could easily be prepared by grinding in an agate mortar. The X-ray diffraction patterns were made with CuK-alpha radiation in a Debye-Scherrer powder camera 57.3 mm in diameter. The film was placed unsym-metrically in the camera in order to afford a basis for film-shrinkage corrections. A sample homogenized at 500°C gave the same diffraction pattern as a sample taken from the as-melted ingot. General Results The diffraction pattern of AuBe was readily indexed on the basis of a simple cubic lattice with ao = 4.659 + 0.001kX. If the unit cell is assumed to contain four AuBe "molecules," the calculated X-ray density is 13.46 grams per cc as compared with the measured density of 13.55 gm per cc. The only missing reflections in the diffraction pattern are (100) and (220) (see Table I). Since these missing reflections are not those characteristic of body or face centering, the lattice of AuBe must be simple cubic. To locate the positions of the atoms within the unit cell, two possibilities had to be considered: I. The structure was disordered and there were eight positions to be filled by an LCaverage" gold-beryllium atom. That the structure was disordered seemed unlikely since the lattice parameter did not vary with composition in alloys containing sornewhat more and somewhat less than so at' pet gold, indicating a fixed composition for AuBe.

Jan 1, 1947

By B. D. Cullity

Gold and beryllium form an intermediate phase composed of the two metals in equal atomic proportions and having the formula AuBe. According to Winkler,' this phase probably exists in two modifications: beta, stable below about 600°C, and alpha, stable between 600°C and the melting point, about 740°C. Only the low-temperature beta form will be considered in this paper. Experimental Procedure The gold used had a fineness of 999.75 to 999.85, balance mainly silver, and the beryllium purity was better than 99.8 pct. AuBe was prepared by melting the constituents in a beryllia crucible in an evacuated induction furnace. After melting and thorough mixing, the alloy was allowed to solidify in the crucible. No difficulty was encountered in obtaining a homogeneous ingot. Both chemical analysis and microscopic examination of the ingot showed that the alloy was essentially one phase, containing 50 at. pct gold. The alloy was quite brittle and powder samples could easily be prepared by grinding in an agate mortar. The X-ray diffraction patterns were made with CuK-alpha radiation in a Debye-Scherrer powder camera 57.3 mm in diameter. The film was placed unsym-metrically in the camera in order to afford a basis for film-shrinkage corrections. A sample homogenized at 500°C gave the same diffraction pattern as a sample taken from the as-melted ingot. General Results The diffraction pattern of AuBe was readily indexed on the basis of a simple cubic lattice with ao = 4.659 + 0.001kX. If the unit cell is assumed to contain four AuBe "molecules," the calculated X-ray density is 13.46 grams per cc as compared with the measured density of 13.55 gm per cc. The only missing reflections in the diffraction pattern are (100) and (220) (see Table I). Since these missing reflections are not those characteristic of body or face centering, the lattice of AuBe must be simple cubic. To locate the positions of the atoms within the unit cell, two possibilities had to be considered: I. The structure was disordered and there were eight positions to be filled by an LCaverage" gold-beryllium atom. That the structure was disordered seemed unlikely since the lattice parameter did not vary with composition in alloys containing sornewhat more and somewhat less than so at' pet gold, indicating a fixed composition for AuBe.

Jan 1, 1947

By R. B. Sosman, J. C. Hostetter

It is well known that ferric oxide, Fe2O3, is paramagnetic, while magnetite, Fe3o4, is classed among the highly ferromagnetic substances. But magnetic data on oxides intermediate in composition between Fe2o3 and Fe3O4 have been almost completely lacking. Fe2O3 and Fe3O4 form a solid-solution series, according to present evidence.' In this series the properties change continuously from Fe2O3 toward Fe3O4, as the percentage of FeO increases from zero toward 31.03, which is the percentage in magnetite. It is possible that there is a break in the series near Fe3O4, but it has not yet been possible to establish the existence of such a break experimentally. The occurrence of solid solution in this series is shown by the dissociation pressure, or oxygen pressure in equilibrium with the oxides, which falls continuously over the range from Fe2O3 to Fe3O4. The oxygen-pressure curves at 1100" and 1200" are shown in Fig. 1. The existence of solid solution is also demonstrated by the continuous change in optical properties from Fe2O3 over to a composition containing about 18 per cent. FeO, at which point the opacity of the oxide becomes so great that it is impossible to obtain measurements at higher percentages of ferrous iron. Natural oxides of iron intermediate in composition between Fe2O3 and Fe3O4 are much more common than is generally supposed. If a mineral oxide is not strongly attracted by a small hand magnet and if it gives a red streak, it is usually labeled "hematite." If it is strongly attracted by the hand magnet it is usually labeled "magnetite" without further tests. As we shall show later, oxides containing from 1 up to 31 per cent. FeO can be thus erroneously lumped together as "magnetite." It is a fact, nevertheless, that the great bulk of natural oxides of iron lie fairly near either Fe2O3 or Fe3O4 in composition. The reason will be

Jan 1, 1918

By D. W. Mitchell

While pure magnesium does not corrode rapidly the presence of even very small quantities of certain other metals accelerates corrosion remarkably. Because magnesium is such an electropositive metal (E° = +2.34 volts)' the presence of substances that permit galvanic activity is extremely undesirable. It is stated that as little as 0.017 pct of iron in magnesium causes a marked increase in the corrosion rate.2 Magnesium and its alloys are commonly melted in iron or steel pots; consequently the commercial metal has the opportunity to pick up iron if it has that tendency. Quantitative data on the solubility of iron in magnesium are of practical as well as of academic interest. Some magnesium alloy castings tend to have large grain size unless suitable treatment is given to the liquid metal just prior to casting. One method of grain refinement consists of "superheating" the metal just prior to casting. "Superhcating" is heating to a temperature 100 to 200°C above the casting temperature and holding for a short period of time. Superheated metal has a much finer grain than unsuperheated metal. A satisfactory explanation of this phenomenon has not been forthcoming. One hypothesis attributes the grain refinement in the superheated metal to precipitation of some phase that is mis-cible at the temperature of superheat but not miscible just below the casting temperature and which is thought to provide nucleating centers for crystallization. This phase, if the foregoing hypothesis is correct, would probably be a metal or an intermetal-lic compound. Of the metals likely to be found in magnesium alloys, iron is one of the most likely candidates for the role of grain refiner for iron occurs in small quantities in all commercial magnesium and magnesium alloys. A. Beck³ states that magnesium, in either the liquid or the solid state, cannot dissolve iron and that iron exists as a finely divided suspension which does not settle out because of its extreme fineness. Beck also presents a micrograph showing a large iron dendrite in magnesium but does not comment on the crystallization of iron from a solution supposed to contain none. It is doubtful that dendrite formation from suspended iron -would be possible. This suspension theory is the basis of patents4 covering the removal of iron from magnesium by allowing the iron particles to act as nuclei for the formation of primary magnesium crystals which can be separated by segregation. Also covered by patents is the removal of iron by the addition of another metal to form an intermetallic compound with the iron which, because of its increased particle size, is able to settle out of the molten metal. Here, too, quantitative information on the extent of iron solubility in liquid magnesium is of more than theoretical interest. M. Hansen,5 in his critical collection of the data on binary alloys, states that iron is not soluble in liquid magnesium. W. R. D. Jones% ho studied the physical properties of low iron magnesium alloys observed a 57°

Jan 1, 1949

By K. U. Snowden, J. N. Greenwood

EARLY studies by Gough and sopwith' have shown that the fatigue resistance of certain metals increased when the test was carried out in a partial vacuum; lead showed this effect to a marked degree. This communication describes surface deformation differences between high-purity lead fatigued in air and in a vacuum of approximately 5 X l0-3 mm Hg. Both air and vacuum tests were carried out by the same alternating flexure machine at a frequency of 500 cpm. Flat cantilever-bend specimens with tapered sides were cut from strip, annealed at 100°C, and chemically polished.

Jan 1, 1959

By William B. Senseman

For reasons well known to mining engineers, wet grinding is quite universal in plants having to do with the extraction of metallic values from crude ores. In the processing of the nonmetallic and industrial minerals, dry grinding is the more common method. The crude materials usually contain less moisture than is required for wet grinding and the products usually are marketed in dry form; most of them as powders. To grind wet, therefore, would entail the addition of water and an expense for drying the product, which is not justified. Furthermore, the material would be a dried cake that would still have to be pulverized or disintegrated before use. For producing fine products, air separators have largely replaced the earlier practice of sizing with screens and bolting reels. Mills in which the air-separating feature is an integral part of the design are now commonplace. Mill designs are many and air systems have developed along various lines, but for the purpose of this discussion, only the fundamental idea need be emphasized— the idea of using air for sizing and removing pulverized material from a grinding mill. About 20 years ago, when the use of mills equipped with air separation had become common practice, heated air or gas was introduced to such a system for the removal of moisture. The purpose of this discussion is to outline the developments and trends that have followed this experiment. It is an important development, for mills equipped with air separation are now universally used for pulverizing not only nonmetallic and industrial minerals, but a great variety of other materials. All such mills are essentially the same. Dried material is pulverized, removed by an air stream, trapped in a cyclone collector, and relatively clean air from the cyclone is returned through a fan to the mill. There is no theoretical need for a vent from the system. The practical need is to vent the air that leaks into the system, and, since the cyclone is not 100 per cent efficient as a dust collector, this vented air carries some dust with it. The initial attempt at drying was made on a system like that described, by the addition of a furnace. The minus pressure within the mill draws hot gas from the furnace. Infiltration air, along with the drying gases and evaporated moisture, is vented as before. The first application was made to a mill used for pulverizing coal. The coal contained very little moisture, so very little drying effect was needed for the success of this experiment. Actually, some calculated efficiencies of over 100 per cent were obtained before due allowance was made for the conversion of mill power into useful heat. When moisture is low, the heat obtained from the conversion of mill power is an appreciable part of that required. That drying can be effected in the short time interval available in a grinding mill of this type is better understood by visual-

Jan 1, 1947

By William B. Senseman

For reasons well known to mining engineers, wet grinding is quite universal in plants having to do with the extraction of metallic values from crude ores. In the processing of the nonmetallic and industrial minerals, dry grinding is the more common method. The crude materials usually contain less moisture than is required for wet grinding and the products usually are marketed in dry form; most of them as powders. To grind wet, therefore, would entail the addition of water and an expense for drying the product, which is not justified. Furthermore, the material would be a dried cake that would still have to be pulverized or disintegrated before use. For producing fine products, air separators have largely replaced the earlier practice of sizing with screens and bolting reels. Mills in which the air-separating feature is an integral part of the design are now commonplace. Mill designs are many and air systems have developed along various lines, but for the purpose of this discussion, only the fundamental idea need be emphasized— the idea of using air for sizing and removing pulverized material from a grinding mill. About 20 years ago, when the use of mills equipped with air separation had become common practice, heated air or gas was introduced to such a system for the removal of moisture. The purpose of this discussion is to outline the developments and trends that have followed this experiment. It is an important development, for mills equipped with air separation are now universally used for pulverizing not only nonmetallic and industrial minerals, but a great variety of other materials. All such mills are essentially the same. Dried material is pulverized, removed by an air stream, trapped in a cyclone collector, and relatively clean air from the cyclone is returned through a fan to the mill. There is no theoretical need for a vent from the system. The practical need is to vent the air that leaks into the system, and, since the cyclone is not 100 per cent efficient as a dust collector, this vented air carries some dust with it. The initial attempt at drying was made on a system like that described, by the addition of a furnace. The minus pressure within the mill draws hot gas from the furnace. Infiltration air, along with the drying gases and evaporated moisture, is vented as before. The first application was made to a mill used for pulverizing coal. The coal contained very little moisture, so very little drying effect was needed for the success of this experiment. Actually, some calculated efficiencies of over 100 per cent were obtained before due allowance was made for the conversion of mill power into useful heat. When moisture is low, the heat obtained from the conversion of mill power is an appreciable part of that required. That drying can be effected in the short time interval available in a grinding mill of this type is better understood by visual-

Jan 1, 1947

By S. R. Zimmerley, John Gross

The deductions drawn in crushing and grinding operations have heretofore been based on a separation of the products into various sizes. A crushed product may be sized by sieving, by elutriation and by aid of the microscope. To estimate the surface of each size the relation of the surface to the estimated average diameter must be assumed. Such a relation, owing to the irregularity of the particles, may involve two assumptions: First, a factor to convert average diameter to surface for one particular size; and second, a variation in the factor as the diameter of the particle changes. Obviously a surface measurement in which such assumptions and estimates are involved is questionable. In the first paper of this series1 a method has been given by which an accurate measure of surface of quartz can be obtained from its dissolution rate. By the use of this method, surface measurements have been made on a series of sieve sizes of crushed quartz, the results of which are given and discussed in this paper. Prepaeation of the Quartz Sizes The quartz, consisting of large uniform pieces with a density of 2.65 and a purity of 99.5 per cent. SiO2, was crushed to pass 20 mesh and was then sieved. Tyler standard sieves were used, the sieving being done by hand according to the proposed standard method submitted by the senior author to the Milling Committee of the A. I. M. E. A wet split of the sample was made on a 270-mesh sieve. This was followed by dry sieving until less than 0.05 per cent. of the weight of the sample passed through the sieve in 1-min. sieving. The +28-mesh material was discarded because that size did not contain the difficult grains from the 20-mesh sieve.

Jan 1, 1930