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ALTHOUGH the refining period of the heat is generally defined as A starting after the charge has been completely melted, it may more properly be considered as beginning with the first efforts to facilitate the shaping up of the slag and the making of corrective additions for the control of slag or metal composition. Such actions may be initiated during the latter half of the lime boil. The early part of the refining period may, then, in essence overlap the latter part of the melting period. The primary aims of the refining period are to reduce phosphorus and sulphur from the steel bath to levels safely below the maximum contents specified, to eliminate carbon as rapidly as possible and still allow time for proper conditioning of the slag and attainment of the necessary bath temperature, and to deliver the heat ready for tapping or furnace deoxidation, with slag in the proper physical and chemical condition, and with carbon and oxygen contents and the temperature of the steer bath at the proper levels for the composition and grade of steel being produced. The particular conditions that fulfil these aims are distinctly different, depending upon whether the steel is to be finished according to fully-killed, semikilled, or rimming practice and also depending upon the carbon range specified. Regard- less of the type of charging practice employed, the object of the refining period is to produce repeatedly the desired finishing and tapping conditions for the grade of steel being produced. The variations and proportions of raw materials used in the charge may cause some variations in the degree of control required during refining, but not in the method of control. The refining period can therefore be discussed from a viewpoint largely independent of charging and melting practice. SHAPING UP THE SLAG In the first helper's vocabulary, refining practice consists in "shaping up" his heat. This includes elimination of sulphur, phosphorus, and carbon, putting the slag in proper condition, and adjusting bath temperature. Shaping up the slag is a major consideration because

Jan 1, 1944

By W. H. Blauvelt

The subject of fuel-briquetting has attracted much attention on the part of engineers. and investors for the past 15 or 20 years, and especially in recent years, during which a number of plants have been built, with more or less commercial and technical success. Our technical literature contains numerous descriptions of certain processes, and discussions of the industry in general. For a history of the development of the art in the United States, and for descriptions of many of the processes which have been tried, reference may be made to the files of our Transactions, and, for more recent information, to a paper by C. T. Malcolmson, read before the First Annual Convention of the International Railway Fuel Association in June, 1909. The purpose of the present paper is to describe the briquette-plant of the Solvay Process Co. and the Semet-Solvay Co. at Detroit, Mich., which, after a period of long and costly evolution, is now operating satisfactorily on a commercial basis. I believe that it will be of interest to some of our members to have the details of operation, power-consumption, labor, etc., as worked out on a practical and commercial scale in a going operation.

Jan 1, 1911

By W. Crafts, J. L. Lamont

Selection of an alloy steel for a heat-treated article has been facilitated by methods for the calculation of harden-ability,' as-quenched hardness and tempered tensile strength.2 Ductility and toughness may also be estimated if the steel is completely hardened on quenching, 5,6 and the present study was carried out in order to develop a basis for estimating the Izod impact strength of partially hardened steel. The investigation was directed toward the prediction of Izod impact strength in steels of normal commercial quality without consideration of special compositions or heat-treatments that might produce abnormal brittleness. It was found that Izod impact strength of alloy steel is controlled by hardness, degree of hardening on quenching, and grain size. In finegrained steels the impact strength for any given degree of hardening is inversely proportional to the tempered Rockwell C hardness, and the relation of impact strength to hardness is lowered by incomplete hardening. Calculation of the tensile strength and impact strength of heat-treating steels has shown that, except at very high strengths, tensile strength is raised by alloys without loss of impact strength whereas the tensile strength gained by higher carbon contents tends to be accom- panied by a disproportionate loss of toughness. Plain carbon steels give relatively low and unpredictable impact strength. The calculation is sufficiently accurate to be helpful in the selection of alloy steel, and common grades of alloy steel have been evaluated with respect to combinations of tensile strength and impact strength attainable after heat-treatment in sections from I to. 4 in. in diameter. Procedure The study of the relation of hardness to impact strength was based on test data derived from 24 heats from four producers. The steels included the following SAE and AISI compositions: 1020, 1030, 1040, 1340, 3310, 33167 4320, 43.30, 4340, 8620, 8630, 8640, 8720, 8730, 8740, 931°, 9317, 9440, 9917 and three high-alloy chromium-nickel-molybdenum steels. As far as is known, the steels tested were of normal commercial quality. They were supplied in 4-in. sections, which were forged to smaller sizes, prenormalized, and machined to final dimensions. Heat-treatment was carried out by heating to the usual austenitizing temperature for the grade of steel, holding for one hour per inch of thickness and quenching in still oil at room temperature. Previous work had indicated that this quenching treatment approximates a severity of H = 0.3; The bars were tempered as follows: 34 in., I in., and 1% in., 2 hr; 235 in., 3 hr; 4 in., ; hr. All bars were air-cooled from the tempering tem-

Jan 1, 1948

By J. Rogers. K. L. Sutherland, E. E. Wark, I. W. Wark

Soaps have hem used as collectors for many years, but only in the last eight years have other long-chain paraffin salts been used. It may be anticipated that these newer collectors will be used mainly with nonsulphide minerals, for which the xan-thates and similar compounds are of little value. On the other hand, the xanthates are both cheap and effective for sulphide ores and seem likely to retain their present cminence in this field. During 1938 and 1939 two of us (E. E. W. and I. W. W.) commenced a comprehensive investigation of the principles underlying the use of paraffin chain salts as flotation reagents. This research was sponsored jointly by the University of Melbourne and a group of Australian mining companies. † A broad, semiquantitative survey was then made of the field covered in the present paper. This was followed in 1940 by further work by one of us (K. L. S.). In 1941 the investigation was taken over by the Division of Industrial Chemistry of the Commonwealth Council for Scientific and Industrial Research, Australia. Discovery of some principles upon which are based the flotation of minerals by paraffin chain salts was followed by their application in the development of processes for the recovery of certain strategic minerals from their ores. Promising results in the flotation of cassiterite from various ores will be described in a subsequent paper. The Paraffin Chain Salts 'he basic requirements for a "collector " in flotation are that it should form a film over the surface of the mineral to be floated, and that this film should be orientated so that hydrocarbon (nonpolar) groups form the effective surface. When modified in this way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince23 that such a film can be produced only if the collector compound contains an active (polar) group to attract it to the mineral surface as well as the nonpolar group. One section of this large class of polar-nonpolar compounds is the paraffin chain salts: CH3(CH2)nX where .X signifies a polar group that ionizes in aqueous solution. Though the compound can ionize, it may be a weak or a strong electrolyte, and the hydrocarbon chain may be in the cation or the anion (Table I). Many compounds of similar constitution are available, but the usual polar groups are: -Co2Na, -So3Na, -So4Na, — PO4Na2, or an aminonitrogen group, the

Jan 1, 1947

By J. L. Lamont, W. Crafts

Selection of an alloy steel for a heat-treated article has been facilitated by methods for the calculation of harden-ability,' as-quenched hardness and tempered tensile strength.2 Ductility and toughness may also be estimated if the steel is completely hardened on quenching, 5,6 and the present study was carried out in order to develop a basis for estimating the Izod impact strength of partially hardened steel. The investigation was directed toward the prediction of Izod impact strength in steels of normal commercial quality without consideration of special compositions or heat-treatments that might produce abnormal brittleness. It was found that Izod impact strength of alloy steel is controlled by hardness, degree of hardening on quenching, and grain size. In finegrained steels the impact strength for any given degree of hardening is inversely proportional to the tempered Rockwell C hardness, and the relation of impact strength to hardness is lowered by incomplete hardening. Calculation of the tensile strength and impact strength of heat-treating steels has shown that, except at very high strengths, tensile strength is raised by alloys without loss of impact strength whereas the tensile strength gained by higher carbon contents tends to be accom- panied by a disproportionate loss of toughness. Plain carbon steels give relatively low and unpredictable impact strength. The calculation is sufficiently accurate to be helpful in the selection of alloy steel, and common grades of alloy steel have been evaluated with respect to combinations of tensile strength and impact strength attainable after heat-treatment in sections from I to. 4 in. in diameter. Procedure The study of the relation of hardness to impact strength was based on test data derived from 24 heats from four producers. The steels included the following SAE and AISI compositions: 1020, 1030, 1040, 1340, 3310, 33167 4320, 43.30, 4340, 8620, 8630, 8640, 8720, 8730, 8740, 931°, 9317, 9440, 9917 and three high-alloy chromium-nickel-molybdenum steels. As far as is known, the steels tested were of normal commercial quality. They were supplied in 4-in. sections, which were forged to smaller sizes, prenormalized, and machined to final dimensions. Heat-treatment was carried out by heating to the usual austenitizing temperature for the grade of steel, holding for one hour per inch of thickness and quenching in still oil at room temperature. Previous work had indicated that this quenching treatment approximates a severity of H = 0.3; The bars were tempered as follows: 34 in., I in., and 1% in., 2 hr; 235 in., 3 hr; 4 in., ; hr. All bars were air-cooled from the tempering tem-

Jan 1, 1948

By E. E. Wark, I. W. Wark, J. Rogers. K. L. Sutherland

Soaps have hem used as collectors for many years, but only in the last eight years have other long-chain paraffin salts been used. It may be anticipated that these newer collectors will be used mainly with nonsulphide minerals, for which the xan-thates and similar compounds are of little value. On the other hand, the xanthates are both cheap and effective for sulphide ores and seem likely to retain their present cminence in this field. During 1938 and 1939 two of us (E. E. W. and I. W. W.) commenced a comprehensive investigation of the principles underlying the use of paraffin chain salts as flotation reagents. This research was sponsored jointly by the University of Melbourne and a group of Australian mining companies. † A broad, semiquantitative survey was then made of the field covered in the present paper. This was followed in 1940 by further work by one of us (K. L. S.). In 1941 the investigation was taken over by the Division of Industrial Chemistry of the Commonwealth Council for Scientific and Industrial Research, Australia. Discovery of some principles upon which are based the flotation of minerals by paraffin chain salts was followed by their application in the development of processes for the recovery of certain strategic minerals from their ores. Promising results in the flotation of cassiterite from various ores will be described in a subsequent paper. The Paraffin Chain Salts 'he basic requirements for a "collector " in flotation are that it should form a film over the surface of the mineral to be floated, and that this film should be orientated so that hydrocarbon (nonpolar) groups form the effective surface. When modified in this way, the mineral surface possesses some degree of air avidity. All investigators would agree with Taggart, Taylor and Ince23 that such a film can be produced only if the collector compound contains an active (polar) group to attract it to the mineral surface as well as the nonpolar group. One section of this large class of polar-nonpolar compounds is the paraffin chain salts: CH3(CH2)nX where .X signifies a polar group that ionizes in aqueous solution. Though the compound can ionize, it may be a weak or a strong electrolyte, and the hydrocarbon chain may be in the cation or the anion (Table I). Many compounds of similar constitution are available, but the usual polar groups are: -Co2Na, -So3Na, -So4Na, — PO4Na2, or an aminonitrogen group, the

Jan 1, 1947

C. W. GENNET, JR.,* Chicago, 111. (written discussion?).-Since the Lehigh Valley accident, transverse fissures have become a source of constant anxiety to railroad officials, because such defects, only infrequently detected by the trackmen, may appear under a moving train entirely without warning. The number of actual accidents resulting from rails containing fissures is no doubt a small proportion of the total, but the serious losses that have been directly attributable to fissures, coupled with the continual possibility of repetition, creates an alarming situation which demands a full investigation of the cause of fissures; apart from other types of rail failures. Mr. Howard's position gives him a field for action and an opportunity for laboratory examination and research that are unsurpassed, and the results. of his investigations must be received with the utmost attention and respect. His admirable paper, summarizing his previously published studies and analyses of the transverse fissure problem, constitutes a convincing treatment of the subject chiefly from the standpoint of stress and strain to which rails are subjected. The intricacies of the problem are so great that seemingly any theory advanced for the cause of fissures may be attacked from some angle; and although Mr. Howard's deductions are logical in the direction followed, it is apparently necessary for considerable work to be done along other lines before his theories can be fully accepted. It is generally conceded that fissures, whether fundamentally clue to fatigue or something else, are of a progressive character, their ultimate size' being the result of growth from an originating nucleus or point of rupture. Abundant proof of this lies in the variable sizes of the fissures found, and there can be no doubt that their development or growth is the result of the strains to which rails are subjected in the track. Obviously, therefore, the most important factor in investigating the cause for fissures lies in determining the conditions that exist at the point or

Jan 4, 1918

By H. Bloom, H. E. Hawkes

STREAMS and rivers are the principal channels into which the weathering products of rocks and their contained ores are funneled. The inorganic load of a stream system is a crude sample of all the earth materials in the drainage basin of the stream, and the heavy mineral assemblage of sediments is one of the oldest and most successful guides to certain kinds of bedrock ore in unexplored terrain. Early application of this method was made possible by the ease of separation and identification of heavy minerals in the field with the simplest equipment. Water analysis for traces of base metals became a practical possibility about eight years ago with the development of rapid chemical tests that could be carried out at the field site.' , Since that time the water method has been widely used in mineral reconnaissance, and a substantial number of discoveries have been reported. Here again, the techniques developed for this work were relatively simple and could be performed easily at the field site. Sediment analysis by chemical methods, as distinguished from mineralogical, has received less at- tention. Some experimental work was done by Lovering and others," but to the authors' knowledge, chemical analysis of sediment samples has not been used in routine exploration programs until very recently. In spite of the obvious promise of this method, it was not pursued vigorously because of the lack of a simple and portable chemical test that could be used conveniently at the field site or in a field camp. Procedures that had been developed for trace analysis of soils all called for a rigorous chemical attack with hot acids—tests more conveniently applied in processing large volumes of routine soil samples at an established field headquarters. Recently an extremely rapid and simple test was developed by Bloom.4,5 The extractant used in this procedure is a cold solution of ammonium citrate. Elements measured are the heavy metals, principally zinc, lead, and copper. This method differs from the established procedures for soil analysis in that it measures only a small fraction, about 5 pct, of the total metal content of the sample. It has been found, however, that the significant pattern of metals in the sediments of streams below a base-metal deposit can be brought out as well and sometimes better by this simple cold-extraction procedure than by the more tedious methods requiring hot acids. To understand fully the significance of the relation between the readily extractable and the total

Jan 1, 1957

By C. M. Loeb, T. E. Norman

THE use of ball, rod and tube mills for grinding ore, cement and other materials has grown so rapidly during the past forty years that the world's annual consumption of ferrous grinding media for these mills is now estimated to be between one half million and one million tons per year. Ferrous grinding balls constitute the major portion of this tonnage. Obviously they represent sufficient value to justify thorough studies' of the factor sgoverning their performance. The selection of grinding balls is governed principally by: I. Quality (wear resistance, impact resistance, soundness, and the like). 2. Sources of supply and delivered cost. 3. Grinding characteristics or efficiency in the ball mill. This paper deals principally with the quality of ferrous grinding balls. In the study of these factors certain data relative to the fundamental nature of ball wear in ball mills have been obtained. These data are also presented and discussed briefly. THE DEVELOPMENT OF A SUITABLE WEAR TEST A study of the fundamental factors governing the quality of grinding balls has been hampered seriously by the fact that a competent test has, in the past, involved the purchase of several hundred tons of balls of a specific type which were then run in one or more ball mills for a period ranging from several months to several years' duration. Often, during the period of test, it became necessary to change operating conditions or the character of the ore fed, to the test mill with the result that the rate of ball consumption changed and the test figures became of little value. Under such circumstances, progress in the development of better grinding balls, has been necessarily slow. Economic factors and variations in the quality of balls produced by different sources of supply generally make it necessary for each mill operator to determine for himself the most suitable type of balls for his mills. In our own ball mill grinding operations at Climax, Colo., we were faced with this problem. After we had run a few large scale wear tests at considerable expense we decided to investigate the possibilities of a small scale wear test which would be capable of testing numerous types of balls within a relatively short time. The most important requirement of any test is, of course, that it give results which can be used to predict accurately the wear in full scale operations. It was known that Ellis and his associates1,2 had developed a method of testing grinding balls by small scale tests run at the Ontario Research Foundation. Ellis' method of testing was used as a starting point in our investigations. In the course of our tests a number of modifications of the original method were found to be desirable so that, by an evolutionary procedure, a method of small scale

Jan 1, 1947

By S. Andrew Kulin, L. Kaufman

A general treatment of the broadening of X-ray double-crystal spectrometer rocking curves due to distributions of tilts and strains has been carried out. The results of this treatment have been applied to the case where dislocations in a crystal give rise to both tilts and strains. On this basis it is found that the rocking-curve halfwidth due to imperfections in the crystal, ßC , increases with increasing Bragg angle, 8. These considerations predict linear relationships between & and tan2 , and ßCand tan 8, for Gaussian and Cauchy distributions of dislocations, respectively. The zero intercept of the ßC us 8 curve, which is a measure of the degree of imperfection of the crystal, is found to depend directly on the distribution rather than the number of dislocations. In addition, the slope-intercept ratio for the ßc - ? curve has been calculated for both the Gaussian and Cauchy distributions. Experimental determination of the - 8 curves for a series of copper single crystals prepared by the Bridgeman and Czochralski methods yields results in agreement with the calculated slope-intercept ratio for a Cauchy distribution of dislocations. CERTAIN X-ray techniques have been used to study the perfection of single crystals. Gay, Hirsch, and Kelly have considered the spreading of spots into arcs on Debye-Sherrer rings due to imperfections. The Double-Crystal Spectrometer has also been applied to this problem.2 The characteristics of Double-Crystal Spectrometer Rocking Curves have been described in the literature by various workers.2-4 By assuming a random spacing of dislocations which give rise to a Gaussian distribution of misorientations relative to some mean orientation in a crystal Gay, et al.,1 arrive at the conclu- sion that the most probable misorientation is given by where h is the spacing between dislocations, and 8 and are the relative misorientations of neighboring regions. If ßC is the halfwidth of the rocking curve (the width at one-half the peak intensity) due to dislocations in the crystal then5

Jan 1, 1960

By W. M. Bertholf

IN 1945 tests were made in the coal washery of the Colorado Fuel and Iron Corporation, at Pueblo, Colo., to determine the value of the Humphreys spiral. So far we have demonstrated that it is of definite value to us in rewashing a portion of our table middlings; and we are fairly certain that this is not necessarily the only place in which it can be used to advantage. Because of manpower and material shortages, experimental work has been discontinued for the present. Three of the spirals are being installed for use in rewashing the middlings, and testing and experimental work will proceed when this installation is completed. All evidence secured so far points to the fact that the spiral can make an effective separation of heavy material below 8-mesh; but that it is ineffective in removing larger, heavy material. This, of course, will limit its use to fine coal or a classified feed containing no heavy material larger than 8-mesh. In considering the results of our tests, it should be noted that the feed was our table middling, and that any real separation of this material is a "moral victory," as there is little material that could be properly called coal and practically no heavy rock, the consequence being that previous attempts to clean the middlings have not been at all successful. Several articles dealing with the spiral and its use in treating heavy minerals have already been published,1 but for the benefit of those who have not seen these we include a brief description of the spiral and of the way it operates, taken from Bulletin 4 of The Humphreys Investment Co.: The Humphreys Spiral Concentrator consists of a spiral conduit of modified semicircular cross section. Ore pulp is fed to the top and, as it flows downward, the heavier particles concentrate in a band along the inner side of the pulp stream (Fig. I). Outlets for removal of products are located at the lowest points in the cross section of the conduit. Wash water, added at the inner edge of the stream, flows outwardly across the concentrate band. The width of concentrate band removed at the outlets is controlled by adjustable splitters. Concentrate is usually removed from the upper portion of the spiral and middling from the lower portion. Tailing is discharged from the lower end. Tests are usually made in closed circuit, since this provides a maximum of information with a minimum amount of sample. Fig. 2 shows the spiral set up for closed-circuit testing, and gives a good idea of the general arrangement of such an installation. The small cyclone separator is used to provide clean wash water without introducing additional water into the circuit.

Jan 1, 1946

By L. Albert, A. M. Cameron, J. W. Gullick

International Nickel has 15 operating mines in Canada, and. 3 mines which are being maintained on a standby basis. Annual production is about 20 million dry short tons of ore, most of which is from underground mines, the remainder from open pit mines. Although some of the underground mines are served by ramps for trackless vehicles, most men, materials and ore are hoisted in vertical shafts. In addition to shafts and raises for ventilation and service purposes which are not equipped with hoisting plants, there are now 28 vertical shafts at Inco mines served by 47 hoists. Of these, 22 shafts and 36 hoists are located in the Sudbury District of Ontario, one shaft and two hoists are at the Shebandowan mine in Western Ontario, and 5 shafts with 9 hoists are located near Thompson, Manitoba. This paper describes the components of Inco hoisting plants-which have been applied at different times and under different conditions, and indicates the rationale for the various designs. Some engineering and maintenance practices, considered advantageous, are also described. MINE SHAFTS Many of the shafts sunk in the early days of the Sudbury District, on what are now Inco properties, were inclined shafts. Of the identifiable shafts sunk between 1885 and 1920, thirteen were inclined and at least four were vertical. Since 1920, thirty vertical and two inclined shafts have been sunk. All of the inclined shafts have been abandoned for hoisting purposes but the majority are still in use as service or ventilation ways. Shafts at Thompson- and Shebandowan are all vertical. The vertical shafts range from 2 or 3 compartment exploration and development shafts to 6 compartment shafts for ore, man and material hoisting. They vary in depth from 1,050 to 7,137 feet and in addition to hoisting compartments all contain manway and service compartments. Prior to 1948, unlined rectangular shafts with timber sets and guides were used. The rectangular cross-section was favoured since the rock is competent, the shape compatible with timber set framing, and since available shaft space could be used efficiently. Resistance to air flow was not of prime importance. Concrete linings were introduced for the first time at the Creighton No. 7 Shaft which was collared in 1948. All major shafts since that date have been concrete lined. Vertical set intervals were increased in steps, with the introduction of structural steel sets secured to the concrete linings. Whereas 7 foot set intervals were used with timber framing, this increased to 10 feet 6 inches with steel sets and more recently to 15 feet with steel and steel backed wood guides. With the advent of deeper shafts, or shafts which are expected to be deepened, the trend is to circular concrete lined shafts. The majority of shaft guides in service are of select Douglas Fir. This practice commenced as a component of timbered shaft design but continued as a

Jan 1, 1975

By R. M. Brick

THE Institute of Metals Division Lecture in 1936, given by R. F. Mehl, on diffusion in solid metals1, was introduced with the statement that "the phenomena of diffusion are intimately related to many basic prob-lems of the metallic state, but in addition to this the process of diffusion is of first importance practically." In view of the scope of that lecture, it does not seem necessary to review the importance, history or present status of diffusion problems. One aspect of the subject of diffusion that has received little attention became of some immediate importance in the course of a study on segrega-tion. When a solid solution alloy freezes, the familiar mechanism of solidification requires that the first nuclei formed be low in solute con-centration, with a resultant normal segregation or coring effect during freezing. Theoretically, diffusion of solute atoms during solidification should result in a homogeneous solid solution. Actually, of course, it is impossible in most binary alloys to obtain a cooling rate that will permit diffusion to eliminate coring in the freezing dendrites. For a given alloy, the extent of diffusion attained up to the point of final solidification will determine the degree of enrichment in solute atoms of the final liquid phase. The flow of this liquid into dendritic contraction channels and the solute concentration of the liquid seem to be the determining factors as to whether the final gross segregation is normal, inverse or absent. The purpose of the present study of diffusion was to determine to some extent the separate diffusion rates of copper and magnesium into pure aluminum with a view to clarifying previous results on segregation in these alloys; i.e., the fact that under similar freezing conditions alumimum-copper alloys segregate inversely and aluminum-magnesium alloys segre-gate normally. Of concomitant interest were the questions of the homogenization times required for segregated ingots or partially melted, i.e., "burnt," structures, and the solution heat-treatment times required for cast, hardenable aluminum-copper and aluminum-magnesium alloys, for worked and annealed structures, and so forth.

Jan 1, 1937

By Henry M. Howe

This paper may be regarded as a report of progress of an investigation into the influence of prior exposure to different high temperatures, under different conditions, on the properties of steel after it has been cooled completely. The following are the chief divisions: II.—Experiments on toughening manganese-steel by sudden cooling. III.—A study of the critical points of common or carbon-steel, chiefly by examining the spontaneous retardations which occur in heating and cooling it, and by examining the ductility of pieces of steel which have been cooled suddenly from different temperatures by quenching them in water or brine. IV.—A brief note on Osmond's theory. V.—A study of the critical points by examining the ductility of pieces of steel which have been cooled slowly from different temperatures at, above, and below them. VI.—A description of the furnace used, with notes on thermoelectric pyrometry. It remains to throw further light on the questions studied by ascertaining the condition of the carbon and the hardness proper, and by studying the microstructure and the fracture of the many pieces treated. I hope to present later the results of experiments in some of these directions. With few exceptions, the experiments have been performed in my private laboratory. I tender sincere thanks to my assistant, Mr. William Haskins, S.B., on whom most of the labor has fallen, for his zealous and intelligent co-operation; to the Sterling Steel Co. for their extra hard steel, Series 17; and to Mr. Joseph Hartshorne and the Pottstown Iron Co. for their soft basic steel. Series 8, 9,10, and 18 were supplied by Messrs. Spaulding, Jennings & Co., of the West Bergen Steel Works; to them also my thanks are due. The temperature of the pieces treated has been very carefully

Jan 1, 1894

By E. L. Dougherty, J. W. Sheldon

Using the numerical techniques shown in this paper it is possible to compute the simultaneous dynamical behavior of multiple fluid-fluid interfaces in two dimensions. Hence, fluid-fluid inter face models of several oil recovery processes can be constructed which allow prediction of the effect of fluid flow in two dimensions on the behavior of these processes while taking into account various physical effects, such as saturation gradients, phase changes and thermal stimulation. Techniques for constructing fluid-fluid interface approximations for several oil recovery processes are reuiewed. The validity of these techniques is established by comparison to experimental results. The availability of a computer program for computing the behavior of multiple fluid-fluid interface problems makes the use of potentiometric models uneconomic. The results indicate the areal sweep efficiencies obtained from potentiometric model studies at high mobility ratios may be somewhat optimistic. The results also indicate that the areal sweep efficiency curves obtained at high viscosity ratios 2—4 using miscible fluids in porous media are misleading and that considerable care must be taken in defining the mobility ratio for a displacement process, especially for miscible fluids. INTRODUCTION Many of the methods used to estimate areal sweep efficiency assume that the oil recovery process can be represented by one or more fluid-fluid interfaces. When the mobilities of the displaced and displacing phases are assumed equal, this quantity can be computed using analytical mathematical methods.l.2 For non-unit mobility ratio, experimental methods based upon the fluid-fluid interface concept include potentiometric and electrolytic blotter models. Scaled models of porous media have also been used to study this problem. Fay and Prats3 and Aronofsky4 used numerical techniques to compute breakthrough sweep efficiency, but neither of these studies were extended beyond breakthrough. Numerical techniques which have been developed for solving a general fluid-fluid interface problem are presented in a companion paper.5 These techniques have been incorporated into a program for a large-scale digital computer which can treat simultaneously the dynamical behavior of as many as six fluid-fluid interfaces. Thus it is possible to simulate the behavior of several oil recovery processes taking into account such effects as saturation gradients. Techniques for representing several oil recovery processes by fluid-fluid interfaces are presented. Processes considered are conventional water flooding with and without a mobile gas phase, hot water flooding, miscible flooding and enriched gas drive. Other processes, whose effects could be studied by this technique, but are not considered in detail here, are underground combustion and steam injection processes and various slug processes such as gas-water injection and alcohol-solvent processes. Theoretical results obtained with single interfaces for mobility ratios of 0.25, 1, 2, 4, 8, 16, 32 and 64 in a repeated five-spot are compared to experimental results for this geometrical configuration obtained using miscible fluids and conductive analogs. Predicted recovery curves for water flooding in a repeated five-spot are compared to experimental results reported in the literature. Example calculations are shown for a conventional water flood in the presence of a free gas phase and for a hot-water flood. MATHEMATICAL PRELIMINARIES We assume that the rock matrix is homogeneous with constant thickness, absolute permeability and porosity. The fluids are incompressible. We also neglect the effects of gravity.

Jan 1, 1965

By D. R. McCord

Data of a known statistical quality has been successfully used in a system of conventional fluid mechanics equations essentially free of empirical "conformance factors to prediet early detailed field 03 in a reservoir where gravity drainage is important and oil and rock properties vary con. siderably. The system is useful where comparative recovery predictions for one or more cases of natural depletion and gas cap pressure maintenance are needed and the reservoir is not too heterogeneous. INTRODUCTION Many authors, have examined various facet* of the gravity drainage-gas cap pressure maintenance problem over the last several years. Two of them. Burtchaell and Elkins, have published practical studies. In the case described in the present paper the best development and operating plan for one of the important reservoirs of the Bolivar Coastal Field in Western Venezuela was urgently needed. It was requested that sound comparative economics be presented along with an engineering evaluation of no additional drilling, maximum drilling. several cases of gas pressure maintenance, of water flooding and combination cases. A rapid analysis of the effect on recovery of the range of crude and rock properties indicated that none of the published methods using average properties would yield adequate comparative predictions. This paper covers the predictive system developed to deal with natural depletion and gas cap pressure maintenance. The large amount of data available for this field permitted statistically reliable correlations to be made of most rock and oil properties, and the evident smooth areal variations of these properties encouraged the construction of a lineal mathematical model of material balance and fluid flow equations, which could be manipulated by a modified iterative procedure. The manipulation is much more adaptable to computing machines than manually operated calculators and subsequent studies have been prepared for the IBM Card Program Calculator. A matrix as opposed to linear model has been tentatively worked out by other members of our group to deal with more heterogeneous reservoirs. It is more adaptable to computers such as IBM-701 or the Remington-Rand Univac. In 1950, when the system reported below was developed, no rapid computing machines were available to the author. Their existence and promise encouraged an initial approach by hand. Some details of oil and rock Property correlation are included because there are a surprisingly large number of medium-sized reservoirs in the world that show systematic property variations which are significant for a rigorous analycon. All large reservoirs (over half a billion barrels recovery) with which the author is familiar contain at minimum a significant temperature variation. Using the rock and oil property correlations, past pressure and production, the gas-oil ratio history of the reservoir was computed and found to be in close agreement with field measurements. The future performance under cases of natural depletion, gas injection of 100 MMcf/day, and of 130 MMcf/day, was then computed; a 70 MMcf/day case was also carried far enough to provide data for comparative economics. The 130 MMcf/day case proved to be the most attractive. A 50,000 horsepower gas turbine driven centrifugal compressor plant to take this quantity of adjacent field gas from 30 to 1,950 psia and inject it into the reservoir is under construction. The total cost of the project will exceed 20 million dollars.

Jan 1, 1953

By D. E. Thomas, C. E. Birchenall

ALTHOUGH Eoltzmann gave a mathematical solution for the diffusion equation (for planar diffusion in infinite 01. semi-infinite systems only) in 1894 allowing for variation of the diffusion coefficient with a change in concentration, it was not until 1933 that this solution was applied to an experimentally investigated metallic system. The calculation was carried out by Matano' on the data obtained by Grube and Jedele3 for the Cu-Ni system. Since that time concentration dependence of the diffusion coefficient has been demonstrated for many pairs of metals. However, the nature of this dependence has never been fully elucidated. Many investigators have suspected that these variations could be related to the thermodynamic properties of the solutions, one of the earliest explicit statements being contained in a discussion of irreversible transport processes by Onsager' in 1931. Development along these lines has been greatly retarded by the lack of reliable data on the variation of tliffusivity with concentration, the paucity of the thermodynamic data for the same systems at the same temperatures and compositions, and an incomplete understanding of the relation of the thermodynamic properties of the activated state for diffusion to the bulk thermodynamic properties. The last factor has been discussed by Fisher, Hollomon, and Turnbull.5 In many instances where data exist, it is difficult to know which are acceptable. This problem probably applies more strongly to diffusion data than to activity measurements. For instance, four sets of observers"-" have reported self-diffusion coefficients for copper. The average spread between extreme results is a factor of about four, though the individual sets of data are self-consistent to about 20 pct. Thus one or more factors are out of control, at least in these experiments, making estimates of internal error unreliable. The most reliable diffusion data in most systems have resulted from the use of welded couples with a plane interface from which layers for analysis are machined parallel to the interface after diffusion. The layers are analyzed, and the result is a graphical relation between distance and concentration, usually called the penetration curve. Given the same set of analytical data and distances and following the same procedure in computation, different observers will generally produce diffusion coefficients which vary appreciably, especially at the extremes of the concentration range. Experiments must be carefully designed so that the precision is good enough to answer a particular question unequivocally. In the first calculation of the dependence of the diffusion coefficient on concentration in the metallic solid solution Cu-Ni, Matano found that the coefficient was insensitive to concentration from 0 to 70 pct Cu, after which it rose more and more steeply to some undetermined value as pure copper was approached.' The same behavior was reported for Au-Ni, Au-Pd, and Au-Pt.* The data used were those of Grube and Jedele which were very good at the time, but are not considered particularly good by present standards. Furthermore, the method of calculation makes the ends of the diffusion coefficient-concentration curve unreliable. For better reliability, the high copper end of the curve has been checked by incremental couples, where the concentration spread is 67.7 to 100 atomic pct Cu. The implication of the curves calculated by Matano was that diffusion is very concentration sensitive in one dilute range of this completely isomorphous system and hardly at all in the other. Matano's result is confirmed. Later Wells and Mehll0 published data on diffusion in Fe-Ni at 1300°C, which represent a thorough test of the shape of the concentration dependence curve. They ran couples with the following ranges of nickel concentration: 0-25 pct, 1.9-20.1 pct, 0-20.1 pct, 20.1-41.8 pct, 0-99.4 pct, and 79.3-99.4 pct. Although the trend of the data indicates an S-shaped concentration dependence, their curve was drawn to the pattern set by Matano. Their original data have been recalculated for the 0-99.4 and 79.3-99.4 pct couples. Wells and Mehl's points and two independent recalculations from the raw data are plotted in Fig. 1. What appears to be the best curve is drawn through them. This curve shows little sensitivity to composition in both dilute ranges with a strong dependence at intermediate composi-tions.? Similar experiments on the Cu-Pd system are reported here at temperatures where solubility is unlimited. These lead to the same type of concentration dependence for the diffusion coefficients as was found upon recalculation of the data for the Fe-Ni system. Experimental Procedure Cu-Pd: The concentration dependence of the diffusion coefficient may be determined by the use of

Jan 1, 1953

By W. B. Gogarty

With the use of polymer solutions in secondary recovery operations, the need has developed to understand the mobility control mechanism. This study investigated mobility control by considering both permeability and rheological effects. Experiments used a high molecular weight, partially hydrolyzed polyacrylamide polymer. Flow studies took place in reservoir and Berea cores having zero oil saturation. Effective size of the polymer flow unit was inferred from Nuclepore filter tests. Clay studies indicated the particle size capable of decreasing the core permeability. Flushed permeabilities measured the approximate core permeabilities with flowing polymer solutions. These permeabilities were considerably lower than original values. With mobility data and the flushed permeability, maximum effective viscosities were determined for polymer solution flow in a core. Effective viscosities showed that rheological properties play an important part in mobility control with polymer solutions. The study showed that permeabilities decrease and stabilize with polymer flow. At the lower permeabilities, high shear rates exist in the cores. Because of the pseudoplastic character of the polymer solution, the high shear rates caused low effective viscosities. This condition pointed to the inefficient use of the potentially high viscosity of the polymer solution at low shear rates. INTRODUCTION In the oil industry, a great deal of interest is being shown in the use of polymer solutions for secondary recovery and a number of polymer floods are being performed in the United States.1 Some of these floods have become commercial while others have been reported as failures. A number of floods are still in progress and remain to be evaluated. With the advent of polymer flooding, the need developed to understand the mobility control mechanism in porous media. Rheologically, the polymer solutions behave as pseudoplastic fluids. Investigators have studied the rheology for this type of non-Newtonian fluid in porous media?-6 Results have also been reported on the ability of polymer solutions to decrease mobility.7-10 Some investigators indicated that polymer solutions show a different rheological behavior in cores than on the viscometer.7,8 This study is representative of an initiatory investigation on mobility control with polymer solutions. Some effects are considered on a qualitative basis. Mobility control is considered from the standpoint of both permeability and rheology and, to the extent possible, permeability and rheological effects are considered separately. Results show that mobility control occurs from a reduced permeability caused by polymer retention and an effective viscosity determined by the average shear rate in the core. In this respect, rheological behavior is as important in mobility control as permeability. PROCEDURES A high molecular weight, partially hydrolyzed, polyacrylamide polymer was used in the investigation. Solutions of various concentrations were made with this polymer in different types of water. Some solutions used distilled water and others used tap water. The tap water contained approximately 500 ppm dissolved solids. As used in this paper, concentrations in ppm refer to parts by weight solute to one million parts by weight of solvent. In the tap water, calcium and magnesium accounted for from 60 to 80 ppm of the solids, the remainder being mostly sodium chloride. All solutions contained a bactericide, and anti-oxidants and antiprecipitants were added to the tap water. Capillary and concentric-cylinder* viscometers determined the rheological properties of solutions. The capillary viscometer is described elsewhere.6 Berea and reservoir sandstone were used as core materials for this investigation. Cores were 1 in. in diameter by approximately 2 to 3 in. long. Prior to mounting, the Berea cores were heat-treated for 3 hours at 850F. This treatment decreased the water-sensitivity of the clays in the cores. The reservoir cores were cleaned with solvent and

By H. Majima, E. Peters

The oxidation rates of pyrite, pyrrhotite, chalcopy-rite, chalcocite, covellite, bortzite, galem, sphalerite, and stibnite have beet2 carefully compared at 120 oC, using aqueous phosphate solutions buffered at pH 2.7, 7.1, and 11.2 as zvell as in 1.0 M NaOH and in am~onia-containing solutions. Under conditions of these studies, variations in rates of more than a factor of two per unit of mineral surface area were not observed for different minerals in phosphate buffered solutions, except that pyrrhotite showed unusually rapid oxidation rates In acid solutions, and stibnite showed very rapid oxidation rates in basic solutions. In caustic solutions, oxidation vates varied considerably, the most rapid being for pyrite and the slowest for sphalerite. In the presence of ammonia, only copper minerals showed more vapid oxidation rates in neutral solutions. Oxidation rates were measured on the basis of oxygen-consunzption rates per unit surface area of exposed mineral, using equivalent surface areas, mineral mesh sizes, pulp densities, agitation, and oxygen pressure. OXIDIZING pressure leaching of sulfide minerals has been a commercial method of treating concentrates of nickel, cobalt, and copper for over a decade, and recently the treatment of lead and zinc concentrates,' and even the recovery of sulfur from pyrrhotite by such processes, have been shown to be technically feasible.' Furthermore, the leaching of uranium ores by solutions acidified through the oxidation of pyrite and other sulfides present in the ore is commercially practicable.3 5 The mechanisms by which sulfide minerals oxidize in aqueous environments are not yet understood. However, certain generalities can be made for systems containing no unusual reagents, in which oxygen is the oxidizing agent. In acid solutions the oxidation of many sulfide minerals leads to the formation of elemental sulfur.8'7 The attack of some sulfides, notably galena (PbS), sphalerite (ZnS), and pyrrhotite (FeS), at temperatures below about 110°C leads to an almost quantitative conversion of the sulfide mineral to elemental sulfur according to the equation: On the other hand pyrite (FeS2) and copper minerals do not yield elemental sulfur quantitatively. Not more than 50 pct of the sulfur in pyrite is converted to the elemental form in acid oxidation, and this percentage is lowered by higher temperatures and possibly higher oxygen pressures.8'9 Copper minerals sometimes yield elemental sulfurlo'" but, since sulfur can reduce cupric ions with the precipitation of CuS or Cu2S, it is not likely that elemental sulfur is obtained in good yield. In acid solutions sulfur that is not converted to the elemental form always appears as sulfate salts or sulfuric acid. Sulfide minerals that yield elemental sulfur nearly quantitatively on oxidation in acid solutions tend to generate H2S when the conditions are not oxidizing. However, although it has been suggested that H2S is an essential intermediate in the mechanism of oxidation," this is doubtful because it is oxidized very slowly by oxygen. In basic solutions elemental sulfur is never formed, as predicted by thermodynamical considerations, summarized in the form of a potential-pH diagram in Fig. 1. However in neutral and basic solutions, unstable forms of sulfur not shown in the diagram appear during oxidation, notably thiosulfate (SOT-) and polythi-onates (S,O;-, x = 2 to 6).l3,l4 On prolonged oxidation only hexavalent sulfur as sulfate (SOi-) or sulfamate (NHzSO;) is found to remain, the latter appearing only in the presence of ammonia. The oxidation kinetics for thiosulfate by oxygen are the subject of a separate paper,'5 and were studied on the presumption that thiosulfate may, in fact, be a primary oxidation product for sulfide minerals, at least in neutral and basic solutions. A survey of the literature indicated that comparative oxidation rates for different sulfide minerals were needed to establish the role of the mineral structure and its thermodynamic properties on the oxidation rates and mechanisms.

Jan 1, 1967

By Alton B. Cook, G. B. Spencer, F. P. Bobrowski

In estimating production gas/oil ratios and oil recoveries from reservoirs containing highly volatile oils it is highly important to include condensate that may be recovered from the gas produced from the reservoir. The volume of the hydrocarbon liquid condensed from the production of the solution gas that has been liberated. in some reservoirs may equal or even exceed the volume of recoverable stock-tank oil as estimated by present methods. The usual procedure1, 2, 3 in estimating future reservoir performance includes use of relative permeability data of the reservoir rock to gas and oil and includes material-balance calculations utilizing data on the volume of the reservoir fluids, oil and gas production and reservoir pressure decline, and data on the physical properties of the initial reservoir fluids. The inaccuracy in the procedure results from the false assumption that all of the free or liberated gas that enters the well bore of reservoirs containing highly volatile oils remains in the gaseous phase as it is produced. This paper presents a method for estimating future reservoir performance and oil recoveries based on special labora. tory analyses of reservoir-oil samples and recognition of the additional volume of hydrocarbon liquid that will be recovered at various stages of depletion from a solution.gas.drive reservoir. The method also includes calculations of the volume and composition of the hydrocarbon liquids that can be recovered by processing the produced gas in a natural-gasoline plant. The development of the method resulted from a study of laboratory analyses of reservoir samples and of field data obtained from two reservoirs containing oil of the highly velatile type. Relatively high pressures and temperatures prevail in oil reservoirs discovered at the greater depths of present-day drilling. The contained fluids may have high saturation -Dressures and large volumes of gas in solution. The oils and gases under these conditions may be almost identical in compositions and densities.4,5 Also, engineers have noted that, for a number of oil reservoirs and especially the deeper reservoirs, the API gravity of the stock-tank oil increaees as the production gas/oil ratios increase. They attributed this increase in API gravity of the stock-tank oil to the formation of condensate as the liberated gas in the reservoir is being produced. SOURCE OF DATA FOR CALCULATIONS Subsurface oil samples and well-test data were obtained from the E. Constantin-Lambert Well No. 1 in the Elk City Field, Okla., to demonstrate the need for and a method of calculating future reservoir performance when consideration is given to the recoverable hydrocarbon liquid from the production of solution gas that has been or will be liberated in a reservoir. The Lambert well is located in C, SW 1/4, SW 1/4, Set- 18, T-l0-N, R-20-W, Washita County, Okla. At the time of completion it was on the east edge of the development and Was producing from conglomerate through 30 perforations in the 5 1/2-in. casing at a depth of 9,859 to 9,864 ft. The well Was completed on July 9, 1949, and subsurface oil samples were obtained July 29 and August 1, 1949. Production gas/oil ratio data were obtained during the operation in series of two Separators at high and low-pressures of 314 and 44 psia, respectively, and at an average temperature of approximately 60°F. The flowing bottom-hole pressure at the time of sampling was 3,934 psis. The static bottom-hole pressure was not obtained at the time of sampling, as the well could not be shut in long enough for testing because gas produced from the well was used for fuel at an offset drilling well. However, the initial reservoir pressure was calculated to be 4,364 psia from knowledge of pressure gradients in other wells in the field and the depth of the casing perforations in the Lambert NO. 1 well.

Jan 1, 1951