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By W. E. Remmers

THE defect in wire known as "cuppiness" has appeared and disappeared from time to time but the exact cause of its appearance or disappearance has not heretofore been known definitely. This defect is not limited to one particular metal or alloy but seems to be found at various times in all of the materials that are drawn into wire. Fig. 1 represents cuppy wire made from an aluminum alloy and Fig. 2 illustrates copper wire that became cuppy in drawing without intermediate annealing. Differences of opinion are current among the manufacturers of wire and in the literature (see Bibliography at end of paper), some believing that the source of the trouble lies in segregation in the wire rod, oxides, sulfides, slag, etc. ; others that the trouble is created by an unevenness of stress distribution across the section of the wire, usually thought of as being a function of die shape. All of the published work is of a qualitative rather than a quantitative nature. With this in mind, it was deemed advisable to make a study of the shape of the wire-drawing dies, as well as the oxygen content of the copper to be drawn.

Jan 1, 1929

By Emil Gathmann

(San Francisco Meeting, September, 1915) THROUGH wide experience at numerous mills in the United States I have found that there is a decided difference of opinion among the producers of steel as to what constitutes commercially sound steel. Some metallurgists insist upon having, for certain grades of steel, a so-called "open steel," -i.e., one which contains numerous blowholes of varying sizes, and consequently but little volume of true pipe, although a central intermittent shrinkage cavity often extends well down into the ingot: Such blowholes and pipe are expected to weld up during rolling or forging, because their surfaces are not oxidized. Even if this be admitted, included slag particles and a high degree of segregation are bound to be present in the product of such ingots. Blowholes are the result of an oxidized heat, and all heats, unless made or finished in the electric furnace, are oxidized more or less. Subsequent deoxidation, or rather degasification, either in the ladle or in the mold, or in both, is necessary to reduce or prevent blowholes. As is well known, a greater yield of billets or sheets is secured from the ingot by allowing the formation of blowholes, but this is undoubtedly obtained at the expense of the quality of the product. Decided segregation of carbon, phosphorus, and sulphur, as well as small included slag particles, undoubtedly exists throughout the greater portion of all so-called open steel, and cannot be removed by cropping. The first requisite for sound, homogeneous steel ingots and blooms is therefore, in my opinion, so to treat the steel in the furnace, ladle, and mold that "piping" steel is produced. The line of demarcation between harmful and so-called "harmless" blowholes is practically impossible to define. Is it not, therefore, the better and safer practice to use means for the elimination of blowholes and correspondingly reduce the segregation and allow the formation of a well-defined shrinkage cavity or pipe .at the upper end of the ingot? With the relatively cheap deoxidizers available at the present time, e.g., ferro-silicon, aluminum and titanium,

Jan 8, 1915

By J. W. Bolton

THIS paper discusses some fundamental metallurgical principles involved in production of sound cast bronze. In a previous paper the writers advanced the theory that "oxidation" in bronze castings is due to incipient shrinkage, and showed the effect of reducing melting atmospheres. In the present paper the effects of certain impurities and of actual oxidizing conditions are shown. The appendix deals with the appearance of various inclusions. For many years the prevailing opinion has been that unsoundness, dark colored fractures and other phenomena accompanying porosity and weakness in bronzes are due to oxidation. The actual troubles are caused by fissures of intercrystalline type, which are often mistaken for intercrystalline films. These weaken the metal and make it porous. Grave doubt regarding the accuracy of the oxidation theory appears when several research papers presented within the last 10 years are reviewed critically. In 1919, Comstock conducted metallographic researches, attempting to identify "oxides" in synthetically prepared metals. He found that oxides of tin, aluminum, zinc, etc. are different from the intercrystalline films (or cavities) to which porosity is due. Apparently he believed that these "oxide films" may be caused by volatile oxides of zinc or of phosphorus or by dissolved gases thrown out of solution during solidi-fication of the metal. In 1923, Woyski and Boeck3 definitely questioned the accuracy of the oxidation theory and indicated the danger from reducing atmospheres. They say that "oxidation, gassing and shrinkage may produce effects very similar."

Jan 1, 1930

By E. J. Dulis, R. M. Fisher, K. G. Carroll

IT is well known that ferritic steels containing more than 15 pct Cr when subjected to temperatures in the range of 700" to 1000°F exhibit increasing hardness and decreasing ductility. The phenomenon has been widely termed the "885 °F embrittlement," after the temperature of most marked effect.'.' In view of the excellent review articles available in the literature3-6 only a brief account of experimentally established facts need be given here. The extent of changes in physical characteristics during embrittlement depends on chromium concentration and time at temperature, higher alloy content and longer time both promoting more rapid and extensive changes. In a 27 pct Cr steel, changes in impact strength and in angle of fracture in bending can be detected after only a 1 hr exposure at 885°F; after 50 hr this steel becomes quite brittle. Hardness increases slowly with time during thousands of hours exposure and may attain a maximum hardness number twice as large as that of the unexposed steel. Microstructural changes accompanying embrittlement have been described as an initial widening of grain boundaries followed by eventual darkening of ferrite grains. Embrittled steels etch more readily, e.g., the weight loss of a 27 pct Cr steel in acid solution may occur at a rate one hundred fold greater following exposure at 885 OF. Marked changes which accompany embrittlement have been observed in electrical resistivity, specific gravity, and magnetic coercive force. Changes in physical properties may be readily removed by heating at temperatures above the embrittling range, such as a treatment at 1100°F for 1 hr. It has frequently been noted that the 885 °F embrittlement suggests precipitation on a submicro-scopic scale of a chromium-rich constituent, the nature of which has not been revealed by X-ray diffraction. Progressive broadening of the body-centered cubic diffraction lines during embrittlement has been observed," and recent observations by Lena and Hawkes' upon single crystals have shown early asterism in X-ray photographs, disappearing within an hour at 900 °F. Many workers have ascribed8-13 the phenomenon to a precipitation of a phase (FeCr), which is known to cause embrittling effects at temperatures much higher than 885°F. Two general observations, however. suggest that a precipitation cannot be responsible for the 885°F phenomenon: 1—prior cold work greatly enhances a formation, whereas it scarcely affects the 885 °F embrittlement, and 2—the presence of an alloying element such as nickel or manganese may have an effect on the 885 °F embrittlement which is opposed to its effect upon a formation. The slight enhancement of a formation and 885°F embrittlement observed in the presence of elements with strong carbide and nitride forming tendencies' is probably a consequence of lessened chromium depletion of the matrix. The bar graph in Fig. 1 shows a typical example, taken from two 27 pct Cr steels used in this work, of the hardness after exposure for 10,000 hr at 900°, 1050°, and 1200°F. Steel A (0.03 pct C, 3.13 pct Mn) showed marked hardening at 900" and 1200°F, whereas steel B (0.12 pct C, 0.63 pct Mn) exhibited only the 900°F hardening. The cr phase was found in steel A at the higher temperatures but not in steel B. Presumably a formation is enhanced by the low-carbon and high-manganese concentrations in A," Thus there are two distinctly different hardening phenomena present which cannot both be ascribed to v precipitation without invoking a transition phase possessing remarkable properties. Materials A number of chromium steels exposed for long periods (5000 to 34,000 hr) at 900°F, as well as unexposed samples of one of the steels, were available for this investigation. Table I gives the chemical compositions and aging treatments of these steels. In addition to these steels exposed in the elevated temperature test furnaces of the National Tube Division, a number of high-chromium steels were heated for short periods in small laboratory air furnaces and lead baths. Supplementing these commercial steels, a sample of high-purity (0.018 pct C, 0.002 pct N) 28 pct Cr iron, exposed 1000 hr at 887°F. was furnished by the Union Carbide and Carbon Corp. In addition, an alloy of iron and chromium of high purity containing 46 pct Cr was used. This

Jan 1, 1954

By Irving M. Symonds

Compania Minera de Penoles, S. A., at its Avalos unit operates a lead-zinc concentrator having a capacity of about 600 short tons per day. Lead and zinc concentrates are made by flotation methods. The concentrator is at Terminal de Provi-dencia, in the state of Zacatecas, some 70 miles south of Saltillo, Coahuila. The Penoles-Avalos railroad operating between the plant and Estacion Avalos, a distance of 6 miles, makes connections with the Coahuila and Zacatecas railroad, which in turn connects with the Nacionales de Mexico at Saltillo. The three railroads are each of different gauge, requiring the transfer of all supplies and concentrates at each junction. The mill operates on company ores, on ores from leased mines, and as a custom mill. The custom business is very small. The lead concentrates are shipped to company smelters at Monterrey, Nuevo Leon and Torreon, Coahuila. Since the European war, all zinc concentrates have been shipped to the United States. Ore Treated The major source of ore supply is a group of four mines owned or leased by the company, some three miles south of the mill in the mountains, from which the ore is delivered to the mill by a gravity aerial tramway. Custom ore comes in by rail. The ores occur in chimneys. The upper levels contained oxidized siliceous ores of lead, copper, silver and gold, with varying amounts of zinc. These ores were direct-smelted. In the first two years of operation a good deal of the tailing loss was caused by the oxidized content of the ores milled. Much of the ore in the transition zones between the oxides and sulphides was not mined. The ores now being milled are clean, hard sulphides in a limestone gangue, with only occasional contamination of oxides. The lead and zinc sulphides are of coarse structure and are freed even above flotation sizes. The galena is usually "steel" colored, easily and quickly floated. When there is any oxidation, it is usually on the coarsest crystals. The zinc minerals vary a good deal in color; a resin sphalerite predominates but there are varying shades of brown marmatites. On an average, the zinc sulphides contain 64 per cent zinc. The only common copper mineral is chalcopy-rite. Little is known of the occurrence of gold and silver. Waste minerals are mainly limestone and pyrite, both of which are barren. The ores vary from 20 to 35 per cent pyrite. Mill heads for the year 1940 and the first eight months of 1941 are given in Table I.

Jan 1, 1943

By T. I. Harkins, J. Brian Eby

This paper outlines the geophysical investigation of the area covering the D arrow salt dome, Louisiana. Surveys with the refraction seismograph and torsion balance failed to disclose the dome, but reflection dip shooting was successful and was confirmed by later drilling. Introduction The D arrow salt dome and oil field lies in western Ascension Parish, Louisiana, on the outside of a sharp bend and on the east bank of the Mississippi River. The dome occurs about 30 miles south of Baton Rouge and 80 miles northwest of New Orleans. Its geology, shape and structure have been ably described in detail by Carroll E. Cook' and, except for the general features, will not be repeated here. The purpose of this paper is to record some of the interesting and pertinent geophysical data contributing to the discovery of the dome and eventually the oil field. The salt dome is circular in outliie and comes to within about 4625 it. of the surface. At this depth the diameter of the salt plug is approximately 4800 it. The dome has only a thin cap rock of less than 75 ft. Some oil has been found and is being produced in Miocene sands above the cap rock, but most of the field's production comes from a narrow ring of wells around the east and south flanks of the dome. Producing horizons on the flank are found at 5670 to 5840 ft. in the Miocene and 6890 to 6985 ft., 7028 to 7060 ft. and 8260 to 8270 ft. in the Oligocene. The deepest well that has been drilled is the Humble Oil and Refining Company's Community B-5, on the south flank of the structure, which reached a depth of 10,013 feet. The size and shape of the field and the area of production are indicated on Fig. I. The lie showing the area of production encloses all wells now producing and all abandoned producers, both on the top and flank of the dome. This line of production is shown on all subsequent geophysical maps as a direct means of comparing the early geophysics to later drilling development. Darrow dome occurs on the low, flat flood plain of the Mississippi River; it is protected from flood overflow by high artificial levees. The rich loamy soil supports a high degree of cultivation, principally sugar cane. Drainage is secured by many small canals and the water table of the area is at or near the surface. These particular conditions of topography, drainage and top soil greatly influenced the early geophysical picture, and the influence was always unfavorable.

Jan 1, 1946

By J. Brian Eby, T. I. Harkins

This paper outlines the geophysical investigation of the area covering the D arrow salt dome, Louisiana. Surveys with the refraction seismograph and torsion balance failed to disclose the dome, but reflection dip shooting was successful and was confirmed by later drilling. Introduction The D arrow salt dome and oil field lies in western Ascension Parish, Louisiana, on the outside of a sharp bend and on the east bank of the Mississippi River. The dome occurs about 30 miles south of Baton Rouge and 80 miles northwest of New Orleans. Its geology, shape and structure have been ably described in detail by Carroll E. Cook' and, except for the general features, will not be repeated here. The purpose of this paper is to record some of the interesting and pertinent geophysical data contributing to the discovery of the dome and eventually the oil field. The salt dome is circular in outliie and comes to within about 4625 it. of the surface. At this depth the diameter of the salt plug is approximately 4800 it. The dome has only a thin cap rock of less than 75 ft. Some oil has been found and is being produced in Miocene sands above the cap rock, but most of the field's production comes from a narrow ring of wells around the east and south flanks of the dome. Producing horizons on the flank are found at 5670 to 5840 ft. in the Miocene and 6890 to 6985 ft., 7028 to 7060 ft. and 8260 to 8270 ft. in the Oligocene. The deepest well that has been drilled is the Humble Oil and Refining Company's Community B-5, on the south flank of the structure, which reached a depth of 10,013 feet. The size and shape of the field and the area of production are indicated on Fig. I. The lie showing the area of production encloses all wells now producing and all abandoned producers, both on the top and flank of the dome. This line of production is shown on all subsequent geophysical maps as a direct means of comparing the early geophysics to later drilling development. Darrow dome occurs on the low, flat flood plain of the Mississippi River; it is protected from flood overflow by high artificial levees. The rich loamy soil supports a high degree of cultivation, principally sugar cane. Drainage is secured by many small canals and the water table of the area is at or near the surface. These particular conditions of topography, drainage and top soil greatly influenced the early geophysical picture, and the influence was always unfavorable.

Jan 1, 1946

By Irving M. Symonds

Compania Minera de Penoles, S. A., at its Avalos unit operates a lead-zinc concentrator having a capacity of about 600 short tons per day. Lead and zinc concentrates are made by flotation methods. The concentrator is at Terminal de Provi-dencia, in the state of Zacatecas, some 70 miles south of Saltillo, Coahuila. The Penoles-Avalos railroad operating between the plant and Estacion Avalos, a distance of 6 miles, makes connections with the Coahuila and Zacatecas railroad, which in turn connects with the Nacionales de Mexico at Saltillo. The three railroads are each of different gauge, requiring the transfer of all supplies and concentrates at each junction. The mill operates on company ores, on ores from leased mines, and as a custom mill. The custom business is very small. The lead concentrates are shipped to company smelters at Monterrey, Nuevo Leon and Torreon, Coahuila. Since the European war, all zinc concentrates have been shipped to the United States. Ore Treated The major source of ore supply is a group of four mines owned or leased by the company, some three miles south of the mill in the mountains, from which the ore is delivered to the mill by a gravity aerial tramway. Custom ore comes in by rail. The ores occur in chimneys. The upper levels contained oxidized siliceous ores of lead, copper, silver and gold, with varying amounts of zinc. These ores were direct-smelted. In the first two years of operation a good deal of the tailing loss was caused by the oxidized content of the ores milled. Much of the ore in the transition zones between the oxides and sulphides was not mined. The ores now being milled are clean, hard sulphides in a limestone gangue, with only occasional contamination of oxides. The lead and zinc sulphides are of coarse structure and are freed even above flotation sizes. The galena is usually "steel" colored, easily and quickly floated. When there is any oxidation, it is usually on the coarsest crystals. The zinc minerals vary a good deal in color; a resin sphalerite predominates but there are varying shades of brown marmatites. On an average, the zinc sulphides contain 64 per cent zinc. The only common copper mineral is chalcopy-rite. Little is known of the occurrence of gold and silver. Waste minerals are mainly limestone and pyrite, both of which are barren. The ores vary from 20 to 35 per cent pyrite. Mill heads for the year 1940 and the first eight months of 1941 are given in Table I.

Jan 1, 1943

By A. L. Mular

The flotability of crushed zinc oxide pellets which were doped to produce more n-type or less n-type (more p-type) properties was studied with a Halli-mond tube. Flotation data are presented to show that the pH at which 50% recovery occurs and the collector concentration for 50% recovery depends upon the concentration of doping agent added substitu-tionally for zinc in zinc oxide. The time of sintering of pellets has a slight effect on flotation behavior. A speculative model is proposed to explain the observed behavior in light of the fact that zinc oxide is a semiconductor and has a space charge region at the surface. Experimental verification is necessary before the proposed model can be established as correct. In recent years, the attachment of flotation reagents to minerals has been shown to depend upon the behavior of an electrical double layer which exists in the liquid near the mineral-liquid interface.' Thus, a mineral placed in water will undergo a surface re-arrangement, most likely be preferential dissociation of lattice atoms or by surface adsorp-tion-desorption reactions, to form a dissociation electrical double layer with the solution. Among the many factors which influence adsorption processes, the past history of the mineral itself is one of the most important. Because of trace impurities, minerals from different localities may exhibit marked differences in flotation behavior. This is not unexpected, since investigators who have studied the detailed structure of the double layer's3 have known for some time that the impurity content of many minerals may exert strong influence on double layer variables. For this reason, their studies were usually made with minerals of high purity. The precise relationship between impurities in a mineral and double layer parameters such as capacity and electrostatic potential has been obscure. However, impurities in a semiconductor type mineral which is in contact with a solution have been recently shown to produce changes in the properties of a space charge layer which extends into the bulk of the semiconductor to a distance of one micron or more.4 The double layer is influenced by the space charge layer, whose origin is best discussed in terms of the band theory of solids. A qualitative description of the behavior of impurities in the bulk of a semiconductor, from a chemical point of view, is useful at this point. Briefly, impurities or defects (lattice vacancies, interstitials, etc.) in semiconductors such as PbS, ZnS, FeS2, Cu2S, NiS, NiO, Fe2O3, ZnO, CdS, MnO2 and many others, behave somewhat like acids or bases in water. For example, water dissociates into hydrogen and hydroxyl ions according to

Jan 1, 1965

Discussion of the paper of G. K. Burgess and J. J. Crowe, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 82, October, 1913, pp. 2537 to 2591. HENRY M. Howe, New York, N. Y. :-I think we can hardly rate the importance of the entry of the Bureau of Standards into our field. There is no body in the world that is better fitted to undertake this work than that Bureau, and it is work which really calls for the aid of some national organization. The skill and care with which this work has been done speaks for itself. It is very striking that within a very few months the distinguished English investigator, Professor Carpenter, of whom I spoke before, thought that he had disproved the existence of beta iron by proving that the A2 retardation which Professor Burgess has now demonstrated did not occur. Dr. Burgess's demonstration of the existence of. this retardation makes the existence of beta iron very probable, in my opinion. Osmond used to call beta iron " decipuum." You knew of its existence as you know of the existence of certain planets, only by the perturbation which it caused. Certain phenomena could not be explained, except by assuming the existence of a third allotropic form, beta iron. The evidence that you got was always evasive and susceptible of other explanations, except that which we have to-day, which it seems to me is not capable of other explanation. Professor Carpenter proceeded in the same way that Dr. Burgess has, by taking the heating and cooling curves of exceedingly pure iron, and thought that he had shown that there was no thermal change, no absorption or evolution of heat at the supposed A2 point, and hence that the A2 point did not exist. This he did by a piece of reasoning which I think seems to most of us rather surprising. That is to say, if of ten witnesses, three have seen a thing and seven have not, the evidence of the seven who have not is set aside, and that of the three who have seen stands. In Dr. Carpenter's own experiments under certain conditions he found the A2 change, the heat evolution., under certain others he did not. That is like the three witnesses who saw and the seven who did not see. You can arrange your test so that this change will not become visible or so that it is masked. But though an existent change can be masked a non-existent one cannot be shown. So that the reasoning seemed to me wholly fallacious.

Jan 12, 1913

By Marston G. Fleming

CRITICAL pH has been defined by Wark1 as that pH value below which a mineral will float and above which it will not float in solutions containing a given concentration of collector but free from other depressants or activators. - The relationship between mineral, collector concentration, and pH is expressed in the form of a critical pH curve determined by the captive bubble method and is generally regarded as being fundamental to the system involved. The mechanism of alkali depression is currently in dispute, two general theories having received authoritative support. The view expressed in Taggart's chemical theory of flotation2 is that in the presence of a critical concentration of hydroxyl ions, all the metal ions available at the surface of the mineral are present as anions of the form [M (OH)x]-y. The formation of the necessary metal xanthate is thus precluded and, furthermore, any metal xanthate coating previously formed, at a lower pH, will be dissolved. Gaudin3,4 and the Melbourne school under Ware hold that alkali depression is caused by the preferential adsorption of hydroxyl ions by the mineral surfaces. This paper describes an investigation of the mechanism of alkali depression in each of the three systems: cerussite-aqueous carbonate-xanthate, cerussite-xanthate, and galena-xanthate. Alkali Depression of Cerussite by Control of Carbonate Ion Concentration Wark and Cox6 have shown that in the presence of Na2CO3 a higher concentration of xanthate is required to effect bubble contact with a cerussite surface than in carbonate-free solutions. To examine this depression of cerussite by sodium carbonate, a series of captive bubble tests was carried out on cerussite specimens in solutions containing 100 mg per liter of potassium ethyl xanthate and varying concentrations of sodium carbonate. The pH was adjusted by the addition of dilute hydrochloric acid. For purposes of comparison a standard critical pH curve was determined for cerussite with potassium ethyl xanthate in solutions containing no added carbonate. In the latter case pH adjustment was made with sodium hydroxide. The experimental method employed in both series was broadly similar to that described by Wark and Cox;7-9 a number of refinements suggested by Sutherland10 were adopted, and the procedure was further developed and modified to suit the particular requirements of the investigation. The relationship between pH and the concentration of potassium ethyl xanthate necessary to induce bubble contact at cerussite surfaces is shown in Fig. 1. The relationship between pH and the concentra- [ ] tion of sodium carbonate necessary to prevent bubble contact at cerussite surfaces in the presence of 100 mg per liter of potassium ethyl xanthate is shown in Fig. 2. Comparison of the. two curves shows that at a collector concentration of 100 mg

Jan 1, 1952

By M. Muskat, H. H. Evinger

A METHOD has been developed whereby one may calculate the productivity factors of producing formations from a knowledge of the reservoir conditions. Account is taken not only of the heterogeneous character of the gas-oil flow system but also of the detailed variations with pressure of the shrinkage and viscosity of the oil, the solubility of the gas in the oil, and even the variability of the gas viscosity and the deviation of the gas from ideal behavior. Curves are shown giving the results of numerical calculations on the production rate as a function of the pressure differential for a high-pressure and a low-pressure system, three values of gas-oil ratio being treated in each case. Curves are also given showing the variation with distance from the well of the pressure, oil saturation, and permeability. The effect of connate water is briefly discussed in relation to the apparently large discrepancies between the calculated and observed productivity-factor values. INTRODUCTION The significance of the productivity factor as a measure of the capacity of an oil-bearing formation to produce is well recognized; for it is the composite and integrated resultant of the physical properties of both the porous medium and the fluid stream passing through it with respect to the ease with which the particular petroleum fluids present in the formation can flow through it and into producing wells. The most direct method of determining the productivity factor of a well consists, as is well known, in the simultaneous measurement of reservoir-pressure differentials and rates of production and the expression of the data in terms of rate of flow per unit pressure drop.1 Actual measurements carried out in this manner on producing wells have given factors that generally lie in the range of 0 to 100 bbl. per day per pound pressure drop. This wide range arises not only from variations in permeability but also from the varying sand thickness of producing formations. One of the aims of developing a theory of the mechanics of oil production obviously is that of predicting what the productivity factor should be from a knowledge of the individual characteristics of the producing formation and the fluids produced. For homogeneous fluid systems passing through a porous medium into a producing well, it has been known for some time that the steady-state rate of liquid flow Q is given by the formula:* [ ] where k is the sand permeability, h its thickness, µ the liquid viscosity, [Ap] the pressure drop between the well and the distant parts of the reservoir, in particular that at a radius [ro ]and [r ] is the well radius. This gives the productivity factor: [ ] which will have a numerical value for a liquid of I centipoise viscosity of 0.9316 or

Jan 1, 1941

By Tell Ertl

THE Piceance Creek Basin in northwestern Colorado is believed to contain the richest large deposit of oil shale in North America. The major portion, about 1650 sq miles, is bounded by the White River on the north, the Grand Hogback, which runs from Meeker to Rifle, on the east, the Colorado River to the south, and the drainage basin of Salt and Douglas Creeks on the west. The Basin is a plateau 7000 to 9000 ft high, composed of 3000 ft of the Green River series of Eocene age and surrounded by a steep escarpment of 1000 to 3000 ft. From the escarpment the beds dip gently toward the center. Although oil shale is found in all members of the Green River series, the rich thick beds are found chiefly in the Parachute Creek member. This is normally capped by 100 to 200 ft of the Evacuation Creek, the youngest member of the Green River series. Actually the Piceance Creek Basin oil shale is not a shale, nor does it contain oil. It is magnesium marlstone holding solid organic matter capable of being broken down by heat into gases, some of which can be condensed into oil. The marlstone is resilient nonporous rock, difficult to sample by pick or hammer and moil. Many companies and individuals prospected the Colorado oil shale shortly after the first World War,1 see Fig. 1, but because of the discovery of large quantities of petroleum in the late 1920's in California, Oklahoma, and East Texas, interest in oil shale development waned and did not revive until World War II. In 1944 the writer, employed by the Bureau of Mines, prospected the high grade oil shale in numerous places along the southern outcrop of the Piceance Creek Basin. Several channel samples about 100 ft in length were cut, see Fig. 2. An eightman crew needed a week to cut a satisfactory channel 80 ft long in the cliff face. The Phillips Petroleum Co., the Union Oil Co. of California and others also prospected the oil shale outcrop. In 1945 the Bureau of Mines initiated a core drilling program for the purpose of obtaining accurate samples from the Piceance Creek Basin. The U. S. Geological Survey set up a program for the geological study of the Basin that is still going on.2 Until the end of 1951 a total of 31 holes was drilled for core with diamond drills, and, in addition, cuttings through the oil shale have been obtained from 4 gas wells drilled by standard rotary oil well rigs. The Bureau of Mines drilled 12 of the holes, the Union Oil Company of California 8, the Standard Oil Company of California 6, the Sun Oil Company 3,

Jan 1, 1952

By J. F. Myers, R. J. Tower

"There is nothing new under the sun." All over the world, mineral-dressing engineers are working at their problems, no two of which are alike. Each encounters equipment and process problems. Many devise simple ways and means of overcoming their difficulties. Many of these problems are quite common in the industry, yet, since no one human being seems capable of thinking of everything, these problems at some plants often are looked upon as necessary evils. The purpose of this symposium is to gather together, from competent engineers, devices and practices that have been useful to them. Most of the ideas contributed are not new, yet there is no plant operator, old timer or youngster, who will not find some idea herein that will give him a suggestion for improving his operation. Space does not permit a complete elaboration on all of the contributions offered. Each item is summarized, but this will be ample for those skilled in the art of mineral dressing. A list of contributors appears at the end of the paper, and the superior number at the end of each item identifies its source. General Equipment A signal light to show that a steel bin, containing relatively line, moist ore, is full, can be made by suspending a copper rod in the bin to a sufficient depth to ensure ample contact with the ore. One wire of a 32-volt circuit should be attached to the rod and one to the side of the bin. Sufficient current will flow to make the signal light burn. A 110-volt circuit could be used, but 32 volts ensures safety.10 Fig I shows a circular bin for crushed ore. It is a concrete structure footed on the ground, using no supporting columns. Tailing from the sink-float was used for aggregate. Cross conveyors for discharging ore are not required, nor is a tripper for filling. Segregation is minimized by drawing from different gates. An exhaust fan on top of the bin eliminates condensation due to temperature of the ore.21 A beam with an adjustable point of suspension near the center permits rigging rolls for removal in a very few minutes. This makes unnecessary the lacing of the cable through the hub bolts on one side, around the shaft on the other, and the trouble of balancing the load.8 The ratchet handle on a Symons crusher may be replaced by a drum with a cable wound on it. When the cable is pulled by a crane or hoist it causes the drum to revolve and thus screws or unscrews the bowl. This reduces handwork and materially shortens the time required for the job.' TO Spread ore feed from an apron feeder over a belt conveyor, place a heavy steel bar about midway between the top

Jan 1, 1949

By C. H. Mathewson, J. A. Collins

The process of plastic extension of face-centered cubic single crystalline rods is so well understood, since the notable studies of Taylor and Elam,1 that the change in orientation of any crystal by slip and rotation may be predicted from the measured elongation. It is customary to assume a very homogeneous deformation, wherein gliding lamellar arc free to rotate so that their slip direction continually approaches the axis of the rod, until a second slip system comes into operation; whereupon conjugate slip proceeds quantitatively to an end adjustment with the [121] direction in the axis of the rod. This process has been checked in malty face.-centered cubie materialsand and readily permits the preparation of specimens that have been subjtvted to various determinable amounts of shearing action. It is elearly of interest to study in such measurably strained speeimens the, development of a recrystallized structure on annealing and if possilble detect the source of nuclei from which the new crystals grow. Strain-:~nneali~ig experiments of this charactcr have been performed by others but not in detail sufficient to permit a study, for example, of the number of recrystallized grains vs. the amount of shear. In the experiments now reported, this was done with a wide variety of orientations covering nearly the entire range of slip on a single system and corresponding to amounts of shear (ratio of shearing distance to distance between lamellae at the conclusion of a test of from 0.08 to 0.57. A particular point wa-made of determining the crystallite rotation, or small angular range. assumed by the octahedral slip plane after these various amounts of shear. The, mechanism of reerystallization and the magnitude and effeet of recovery on the recrystallization process was investigated.

Jan 1, 1940

By J. A. Collins, C. H. Mathewson

The process of plastic extension of face-centered cubic single crystalline rods is so well understood, since the notable studies of Taylor and Elam,1 that the change in orientation of any crystal by slip and rotation may be predicted from the measured elongation. It is customary to assume a very homogeneous deformation, wherein gliding lamellar arc free to rotate so that their slip direction continually approaches the axis of the rod, until a second slip system comes into operation; whereupon conjugate slip proceeds quantitatively to an end adjustment with the [121] direction in the axis of the rod. This process has been checked in malty face.-centered cubie materialsand and readily permits the preparation of specimens that have been subjtvted to various determinable amounts of shearing action. It is elearly of interest to study in such measurably strained speeimens the, development of a recrystallized structure on annealing and if possilble detect the source of nuclei from which the new crystals grow. Strain-:~nneali~ig experiments of this charactcr have been performed by others but not in detail sufficient to permit a study, for example, of the number of recrystallized grains vs. the amount of shear. In the experiments now reported, this was done with a wide variety of orientations covering nearly the entire range of slip on a single system and corresponding to amounts of shear (ratio of shearing distance to distance between lamellae at the conclusion of a test of from 0.08 to 0.57. A particular point wa-made of determining the crystallite rotation, or small angular range. assumed by the octahedral slip plane after these various amounts of shear. The, mechanism of reerystallization and the magnitude and effeet of recovery on the recrystallization process was investigated.

Jan 1, 1940

By W. D. Robertson, Raymond C. Boettner

A study was made of the change in density during the first (transient) and second (linear) stages of the creep curve of polycrystalline copper as a function of 1) stress, 2) temperature, 3) plastic strain, 4) impurity and atmosphere effects, and 5) structure, including single crystals. Voids were not observed in single crystals strained 15 pct at 500°C, or in a polycrystal-line aggregate produced by recrystallizing a single crystal, within the limit of sensitivity, Ae/e = 1 x 10-4. It appears that voids are heterogeneously nucleated at grain boundaries by an insoluble phase, or phases, which can be removed by directional solidification. The principal controlling mechanism of void growth appears to be condensation of vacancies at grain boundaries. Vacancies are transported to a boundary and condense as a consequence of the tensile stress component across the boundary, which depends on the orientation and configuration of the boundary plane and on boundary shear across ledges and other irregularities. The ultimate source of vacancies is the free surface and diffusional transport is by way of the boundary plane. PREVIOUS investigations have dealt with the nucle-ation of voids at grain boundaries under creep condition~'-~ and with the connection between grain boundary voids and subsequent brittle fracture.5-7 Growth of voids during the creep process, particularly in the transient and linear stages of creep, has not been studied with the same intensity. Therefore, it seems pertinent to investigate the process of void growth with respect to the related creep curve, and the morphology of growing voids with respect to the structure.

Jan 1, 1962

By L. C. Raymond

Valuations in the mineral industry differ from those of other enterprises because mines and oil wells have a definitive life so cannot be considered a perpetuity. This requires that in any mineral-property evaluation the recovery of invested capital is necessary during the life of the property. Capital writeoffs for nonextractive industries are assumed to be continuously plowed back to sustain the operation and produce yields on the capital invested. The extractive or mineral industry, however, generally attempts to return to the investor both interest and principal during the life of a property. Normally this is done currently and the dividend includes both items. Where the mineral properly possesses large reserves and the life factor approximates a perpetuity, the return on investment is generally comparable to that of industrial stocks. The valuation of a mineral property, at best, is based on educated estimates and judgment factors. This is particularly true as it relates to estimating selling prices over a long term or assessing the quality of management. Also, it is possible to make various assumptions as to rapidity of working out the deposit, varying time for start-up of operations, varying earning rates, so as to obtain different results with the same basic facts. Thus it is not surprising that two engineers, irrespective of their abilities, may not agree exactly even when given the same facts, but their results should be close enough to be used in establishing a fair value for trading purposes. The valuation is no better than the source of basic data and the soundness of judgment factors. Fundamentally the basic principles of mineral valuation are similar for base metals, sulphur, oil, or any other mineral. Each mineral, however, requires an engineer to have a knowledge of such factors as its occurrence, distribution, mining and processing methods, and marketing problems in order to gather and analyze all the facts and data that have a bearing on the earning potential of the property. PRESENTVALUEOFAMINERALPROPERTY In essence the present value of a mineral property is a sum of money in today's dollars that future earnings from the property are worth. It differs

Jan 1, 1959

By Brahm Prakash, R. Schuhmann

Chemical conditions for flotation and nonflotation of quartz with oleic acid as collector and barium, calcium, aluminum, iron, and tin as activators were studied using a simple vacuum-flotation technique in glass-stoppered graduates. The detailed study of barium activation led to an interpretation based on ideal Langmuirian chemi-sorption. FLOTATION of quartz is of practical importance as something to be avoided in soap-floating many types of ores. Clean, unactivated quartz is not floated with fatty acids and soaps, such as oleic acid and sodium oleate, in the quantities normally used for flotation. However, data in the literature indicate that almost any multivalent cation will activate quartz if given an opportunity. Thus, a common problem is to prevent activation of quartz by the various inorganic cations inevitably present in flotation pulps. Wark and his coworkers1 have demonstrated the reversibility of the chemical reactions and adsorptions involved in the activation, depression, and collection of the common sulphide minerals. The procedure in much of their work was to bring a mineral surface to equilibrium with solutions of known pH, collector concentration, and activator concentration, and then to test the floatability of the mineral by contact-angle measurement. From the data, graphs were constructed with pH and reagent concentrations as coordinates. These graphs show fields of flotation and fields of nonflotation, separated by narrow transition regions whose locations are shown by so-called contact curves. From the shapes and locations of the contact curves, which roughly separate fields of flotation from fields of nonflotation, a quantitative understanding of the interaction of the reagents with each other and with the minerals often can be deduced. The study of quartz flotation to be described in this paper follows in broad lines the approach of Wark and coworkers. That is, pH, activator concentration, and collector concentration were varied to find equilibrium conditions of flotation and non- flotation, and the results are presented graphically by means of contact curves. However, instead of testing for floatability by measuring the contact angle on a polished surface, a simple vacuum flotation technique was developed and used. Purified oleic acid was the collector and terpineol the frother. Barium activation was studied in some detail, and exploratory studies were made of activation with calcium, aluminum, ferric iron, and stannic tin. Preparation of Materials Quartz: Large lumps of high-grade vein quartz were crushed dry in a cone crusher and rolls. The —20, +28-mesh portion was screened out and used in the subsequent steps. This material was passed through a high-intensity magnetic separator to discard iron, then leached twice with hot concentrated HCl and washed repeatedly with distilled water. The cleaned sand was then wet ground with porcelain balls in a porcelain pebble mill, deslimed repeatedly by settling and decantation to discard —800-mesh material, and again washed with hot HCl followed by distilled water. The resulting stock of quartz was stored under water. Chemical analysis gave 99.8 pct SiO2. Table I gives the size analysis of the quartz used for flotation tests. Calculations from these data, using shape factors given by Gaudin and Hukki9 indicate a specific surface of about 500 cm2 per g. Blank flotation tests in distilled water, and in water with added frother, showed the prepared quartz to be completely nonfloatable and thus indicated the absence of organic contamination. Oleic Acid: The preparation of oleic acid was based on fractional vacuum distillation of methyl oleate2,3 followed by regeneration of oleic acid, and finally fractional crystallization of oleic acid from acetone solutions at low temperatures." The pure oleic acid was stored in a refrigerator. The iodine number of the oleic acid was found to be 90.0 (theoretical 89.93). Oleic acid was used in the form of a dilute water solution of sodium oleate, after preliminary flotation tests showed no effects of form of addition and order of addition of reagents when an adequate conditioning time (that is, 30 min) was provided. Other Reagents: Sodium hydroxide solutions low in carbonate were prepared by first making 1:1

Jan 1, 1951

By J. N. Breston, R. V. Hughes

Conclusions drawn by previous research workers with reSPect to the relation between Pressure gradients and/or velocity and oil recovery obtained by laboratory water flood tests have been in disagreement probably due to variable procedures and unnatural conditions and materials. The Bradford Laboratory of the Pennsylvania Grade Crude Oil Association as part of its secondary recovery research program has conducted nineteen water floods on two long cores of widely differing characteristics in an attempt to clarify this relationship and make it an aid in predicting flooding pressures in the field. Unlike previous research procedures the present experiments were conducted with the aim of duplicating field conditions as closely as possible by using long unextracted consolidated cores, a live crude, and natural brines for both flooding and, connate water content. Also, the pressure gradients and flooding velocities were representative of field conditions where similar sands were being flooded. Eleven floods on one core and eight floods on the other core showed increased recoveries and lower residual oil saturation with increased flood pressure gradients and flood velocities. A marked decrease in recovery was obtained from both cores at very low flood velocities. This pressure versus recovery relationship is shown to hold up to the point of water breakthrough and also up to the 100 and 1 produced water to oil ratio point. INTRODUCTION The possibility of water flooding oil sands was suggested by Carl1 of the Pennsylvania Geological Survey in 1880. It is not known when the practice was tried intentionally for the first time, but its beneficial effects were noted in the annual production rate of the Bradford field as early as 1907. The practice was illegal in Pennsylvania until 1921. Early water floods in the Bradford field usually consisted of shooting or splitting the casing secretly to permit subsurface waters to enter the producing sands under hydrostatic head. As it was noted that the benefits of water flooding seemed to be proportional to the quantity of water dumped into the well many also began to utilize surface sources after the practice became legal. It was probably during the middle 20's before many producers realized that the pressurehead of the water upon the producing sand determined the rate and quantity of water that would enter the sand. Hence, rate and quantity of production appeared to be a direct function of input pressures. By 1927 a few producers had ventured the installation of pressure pumps in order to increase water-input rates and production through the combination of hydrostatic and hydraulic pressures. The adoption of pressure flooding and the "five-spot" drilling pattern in the Bradford field were essentially simultaneous. Water-input pressures in 1930 seldom exceeded 300 p.s.i. at the well head or 1100 p.s.i. at the sand face. Since that time, water-flood producers in the Bradford-Allegany fields have gone to higher and higher pressure until today 600 p.s.i. at the well heads is called a low pressure flood. Many high pressure floods now operate at 1300-1400 p.s.i. at the well head. The limiting and advisable pressure at the sand face has been pronounced as that pressure just under what is required to lift the overburden or to cause formation parting: According to this rule any water flood operation utilizing well-head pressures nearly equal in pounds per sq. in. to 1.1 times the average depth in feet to the top of the producing sand would be considered as a high-pressure flood. Despite the higher pressure trends in the Bradford-Allegany field operations and the results of early laboratory water flooding research, the desirability and benefits of high input pressures are still questioned by many operators, particularly in midwestern water flood operations. The present paper recounts a series of 19 laboratory water floods using two long, consolidated cores of widely differing characteristics saturated with live crude and flooded with oil field brines in an effort to simulate field conditions under • various pressure gradients and flooding velocities. For both cores, higher recoveries and lower residual oil saturations were obtained at higher pressure gradients and flood velocities. This relationship is shown to hold up to the water breakthrough point and also up to the 100 to 1 produced water to oil ratio point.

Jan 1, 1949