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By A. J. Boyer, T. R. Meadowcroft

An experimental determination has been made of the efject of surface diffusion on the vapor pressure obtained in a Kwudsen cell. The results show that a knife-edge orifice in a molybdenum lid may give erroneous results for the vapor pressure of silver. when a correction suggested by winterbottom and Hirth is made, the results become meaningful. Experimental work with cylindrical orifices in molyhdenz~m lids and knife-edge orifices in ceramic lids shows that good vapor-pressure results may he obtained when the orifice is designed so that ejfusion is the only significant source of weight loss. THE Knudsen effusion cell technique has been used by many investigators to study relative and absolute vapor pressures over metals and alloys at elevated temperatures. As a result of this interest, some theoretical studies have been made of geometric factors affecting effusion from the orifice of a Knudsen cell. A review of these studies has been made by Margrave.1 Recently, Winterbottom and Hirth2 have suggested that a physical effect, that of condensation, surface diffusion, and re-evaporation, may seriously affect Knudsen cell measurements, especially when a knife-edge orifice is used. Inasmuch as many of the present vapor-pressure data have been obtained using knife-edge orifices. it was felt that an experimental evaluation of the effect of surface diffusion on Knudsen cell measurements would be of value both in the design of the cell orifice and in establishing realistic estimates of the limits of error for existing data. The experimental program was in two sections. Firstly, measurements of the vapor pressure of silver were made in cells with cylindrical and conical orifices in which the surface-diffusion contribution to the weight loss should be negligible. These results were correlated with existing data to give a reliable measure of the real vapor pressure of silver. Secondly, measurements made using knife-edge orifices were corrected using the surface-diffusion theory of Winterbottom and Hirth2 and were then compared to the real values. The experimental arrangement is shown in Fig. 1. The balance was an Ainsworth RV-AU-1 automatic recording microbalance capable of measuring weight changes of ±0.02 mg on a total load of up to 100 g. The temperature was measured by an optical pyrometer signted on the bottom of the suspended crucible. The temperature readings were calibrated in a separate experiment in which pyrometer measurements were made while at the same time thermocouple readings were taken of the temperature at the inside top and bottom of the crucible. The range of reproducibility with this technique was ±4°C. A constant voltage source maintained a temperature of ±2°C at 1200°C over 10 hr. Silver of 99.99 pct purity was used in nonporous alumina crucibles. Lids of molybdenum, tantalum, or magnesia were cemented to the crucible using a sodium silicate cement. Table I shows the characteristics of the lids used. The vapor pressure is obtained using the basic Knudsen formula:

Jan 1, 1965

By Paul J. Sirkegian

The problem of properly controlling the movements of underground trains in the Emma Nevada and Morris Brooks workings of the Consolidated Coppermines Corporation of Kimberly, Nev., became more complex as the rate of production increased. Ore from these mines, which are connected through a 7000-ft. single-track haulageway (Fig. I), is hoisted through the Emma Nevada shalt. All production to date has been from one level. Because of heavy ground, even on the main haulage horizon, experience has shown that it is necessary to have a minimum cross section in the drifts, thus making it impractical to have a double track system. In 1937, production was 3000 tons per day; in 1938 it was increased to 6000 tons per day and in 1940 to 9000 tons per day. Each increase necessitated a revision in the method of controlling the underground traffic. In 1937 the tramming signal system consisted of a few signal lights in the main haulage drift. These lights were two 100-watt bulbs in a metal box that had one green and one red lens on each side. The box was mounted on the underside of a drift cap timber and could be seen For a considerable distance. The lights were so arranged that all boxes showed either red or green at the same time and all were controlled by a magnetic contactor at the entrance to each lateral drift. When the lights showed green, the main haulage was clear of traffic and a train could enter it. As the motor entered the main haulage drift, the motorman pulled the cord of the magnetic contactor switch, thus changing all the main haulage lights to red, which indicated that no other train could use the main haulage until the first train had turned into a lateral drift. When a train left the main line, its motorman pulled the cord connected with the magnetic contactors, causing the haulage lights to show green again. This arrangement permitted only one train at a time to use the main haulage and thus limited the number of train trips per shift, but it was satisfactory when the ore handled was only 3000 tons per day. Second SystEM Installed With a gradual increase in production it became necessary to place a train dispatcher in charge of all trains. He controlled their movements orally, giving his orders direct or by mine phone, instructing them where to load, when to leave for the station and when to return. His objective was to group several trains traveling in the same direction. Because of the human element involved, some mistakes were made. The danger of a serious collision was always possible. There was a 90° turn and curve in the underground haulageway, therefore travel in this section was always dangerous if mistakes were made in directing traffic. To protect the train crew, particularly the rear switchman who rode the last car or caboose, a two-way push button and flash-signal system was installed on the

Jan 1, 1946

By M. L. Lissberger

entirely suitable for certain uses and even possess advantages over present solders at high temperatures, but they are certainly not suitable for all uses. However, it is conceivable that their use in many places will effect a material conservation of tin. It will probably be wiser to use cadmium in solders where good results have been obtained than in brass where this element will be a source of possible trouble. F. F. Colcord,* New York, N. Y.-—The cadmium-lead solder has a higher conductivity than the lead-tin alloy, which ought to make it advantageous in the manufacture of electrical machinery. In the case of solder for tin-can work, one of the high officials of the American Can Co. said that he fully intended to .give it a good trial, and I do not believe they are going to reach hasty conclusions and run the risk of poisoning the public. Solder, Its Use and Abuse Milton L. LissbeRgeR,† New York, N. Y.—Solder is a mechanical mixture of tin and lead, a fact which is susceptible of very simple demonstration. A bar of solder of a grade even as low as 30 per cent. tin and 70 per cent. lead, passed through a buffing machine, will show a surface practically identical with that of a bar of second-quality or reclaimed tin. The buffings, on chemical analysis, will prove to be almost pure lead. According to the best practice, solder is made in the following manner. Virgin pig lead is first melted, and when it is thoroughly liquefied, virgin pig tin is added, together with a small amount of flux; the latter is for the purpose of bringing to the surface the so-called "liver," consisting of impurities that may have remained in either the lead or the tin as a result of incomplete refining. The combined material, when completely liquid, is thoroughly stirred for some hours, and is then cast into small pigs. Just before casting, and continuously during this operation, the molten metal yields dross, consisting largely of the oxides of lead and tin; this should be carefully skimmed off. After the pigs have cooled, they are taken to a smaller kettle, re-melted, and cast into the desired shape for use; or if wires, ribbons, etc., are to be made, the solder is cast into slugs suitable for extrusion and rolling. During this second operation, the skimming of dross should be even more carefully done than at first. Hand mixing has proved to be the only reliable method for the production of the best quality of solder, irrespective of its percentages of lead and tin. The best quality of solder is not necessarily that which contains the highest percentage of tin, but rather is that composition which performs best on the required piece of work. In order to produce

Jan 1, 1919

By S. Fróes Abreu

The importation of liquid fuels in Brazil amounts to about 1,300,000 tons; 30 per cent of this total being gasoline for automobiles and airplanes. Statistics show an increasing consumption of gasoline notwithstanding the use, daily greater, of fuel alcohol, a domestic fuel of low cost in the producing areas. The Brazilian market for petroleum products has shown a tendency to grow as the country has steadily developed— expansion of the industries in the areas already developed, and also the recent occupation and population of new zones. The war has brought many difficulties to Brazil. It has limited the importation of petroleum products, which came mostly from the United States, Venezuela and Mexico. During the first days of the present crisis automobile and truck traffic was vastly curtailed; but the national activity in the production of more fuel alcohol, and principally in the development of producer gas, has done much to provide a solution for the transportation crisis threatened at the beginning of the gasoline shortage. Many thousands of cars and trucks in Brazil are now burning producer gas made from charcoal. Producer gas for automobiles has been improved by Brazilian engineers and many new types have appeared. - Production There is only one producing oil field in Brazil—the one in the State of Baia, near the Baia de Todos os Santos. The first producing oil well was drilled in Lobato in 1939 by the Federal Government following studies carried on in that area by Oscar Cordeiro, S. Froes Abreu, G. Paiva and J. Amarai. The field and laboratory work done by these men was published in 1936 in a paper entitled " ContribuicBes para a Geologiado Petroleo no Reconcavo (Baia)," which indicated the potentialities of the area as an oil producer. After the discovery of the first producing well, the Brazilian Government issued a decree establishing an area, 60 km. in radius, as a National Reservation. This first well was drilled in Lobato. In no other locality in Brazil is any petroleum produced. Although many wells have been drilled in the southern part of Brazil, on the northeastern coast and in the Amazon Basin, they yield nothing. Actual production is below 1000 bbl. daily. The producing area covers Itaparica Island, Candeias and Arath, Joanes Island and Lobato. Since very little geological information was available, especially about subsurface structure, it was necessary to drill several wildcats in order to collect the data essential in the choosing of good locations. The United Geophysical Co. was contracted to perform a geophysical survey to clear up the major problems concerning the oil deposits in the Reconcavo beds. The best wells in Reconcavo are on Itaparica Island, where the daily flow amounts to about zoo bbl.; in other sectors production is considerably lower and most of the wells are pumping. In the Aratfi sector, near an area of very light oil, there is an important gas field, with wells producing about I0,000,000 cu. ft. daily.

Jan 1, 1944

By S. Fróes Abreu

The importation of liquid fuels in Brazil amounts to about 1,300,000 tons; 30 per cent of this total being gasoline for automobiles and airplanes. Statistics show an increasing consumption of gasoline notwithstanding the use, daily greater, of fuel alcohol, a domestic fuel of low cost in the producing areas. The Brazilian market for petroleum products has shown a tendency to grow as the country has steadily developed— expansion of the industries in the areas already developed, and also the recent occupation and population of new zones. The war has brought many difficulties to Brazil. It has limited the importation of petroleum products, which came mostly from the United States, Venezuela and Mexico. During the first days of the present crisis automobile and truck traffic was vastly curtailed; but the national activity in the production of more fuel alcohol, and principally in the development of producer gas, has done much to provide a solution for the transportation crisis threatened at the beginning of the gasoline shortage. Many thousands of cars and trucks in Brazil are now burning producer gas made from charcoal. Producer gas for automobiles has been improved by Brazilian engineers and many new types have appeared. - Production There is only one producing oil field in Brazil—the one in the State of Baia, near the Baia de Todos os Santos. The first producing oil well was drilled in Lobato in 1939 by the Federal Government following studies carried on in that area by Oscar Cordeiro, S. Froes Abreu, G. Paiva and J. Amarai. The field and laboratory work done by these men was published in 1936 in a paper entitled " ContribuicBes para a Geologiado Petroleo no Reconcavo (Baia)," which indicated the potentialities of the area as an oil producer. After the discovery of the first producing well, the Brazilian Government issued a decree establishing an area, 60 km. in radius, as a National Reservation. This first well was drilled in Lobato. In no other locality in Brazil is any petroleum produced. Although many wells have been drilled in the southern part of Brazil, on the northeastern coast and in the Amazon Basin, they yield nothing. Actual production is below 1000 bbl. daily. The producing area covers Itaparica Island, Candeias and Arath, Joanes Island and Lobato. Since very little geological information was available, especially about subsurface structure, it was necessary to drill several wildcats in order to collect the data essential in the choosing of good locations. The United Geophysical Co. was contracted to perform a geophysical survey to clear up the major problems concerning the oil deposits in the Reconcavo beds. The best wells in Reconcavo are on Itaparica Island, where the daily flow amounts to about zoo bbl.; in other sectors production is considerably lower and most of the wells are pumping. In the Aratfi sector, near an area of very light oil, there is an important gas field, with wells producing about I0,000,000 cu. ft. daily.

Jan 1, 1944

By L. P. Davidson

The new electrolytic zinc plant of the American Zinc Company of Illinois commenced operation in April 1941. The simple flowsheet using the standard current density and the economic reasons that dictated it are given herewith. The Evans-Wallower Zinc Co. built an electrolytic zinc plant at Monsanto, 111., in 1929 and operated it for about two years. The plant stood idle from 1932 and was purchased by the American Zinc Co. in 1940. Because of the condition of the , equipment, excepting the motor generator set, a complete rebuilding was necessary. The Fairmont City plant of the American Zinc Co. could treat the leach residues, the purification cake and the skimmings from the melting furnace in its various plants. This possibility permitted a simple flowsheet with good economic results. The flowsheet is shown in Fig. I. The calcined concentrates are leached in mechanically agitated tanks with spent electrolyte and such ferric iron solution as necessary. When the acid has been neutralized and the iron coagulated, the fluid is discharged to settling tanks. The underflow from these thickeners is filtered on a Moore filter; the filter cake leaves the plant for retreatment and the filtrate joins the thickener overflow. Zinc dust is added to this solution until the copper and cadmium are precipitated. The pulp is filtered through shriver presses, which deliver the purified solution to stor- age tanks, and the copper-cadmium-zinc cake is shipped for retreatment snd recovery of these three metals. The purified solution is electrolyzed; the regenerated acid is returned for use in the leaching plant and the cathode zinc, after stripping, goes to the melting furnace, from which it is cast in slabs. The skimmings from the melting furnace are shipped to the Fairmont City plant for reduction to metal in the retort furnaces. The choice of this simple flowsheet was made possible only because of the facilities of the Fairmont City plant. The long leaching period, with high acid content and high temperature which characterize the high-density process, gives a higher zinc extraction but also dissolves more impurities, which must be removed. The same is true to a lesser degree of the multi-step leaching of the western low-density plants. By the sacrifice of some initial extraction, solutid'ns can be obtained that are relatively easy to purify and give good ampere efficiency. This loss in initial extraction is made up in the retreatment of the residues in the Waelz plant. The impurities that accompany the zinc thus extracted are inconsequential when the Waelz product is treated in a distillation plant. It was recognized that this flowsheet would require a somewhat greater amount of sulphuric acid—either as acid or as sulphate sulphur in the calcine—because of poorer washing. The sulphuric acid plant at Fairmont City could deliver 60" BC. acid to compensate for the sulphate loss and the cost would be less than the cost of more intensive washing.

Jan 1, 1944

By R. T. C. Rasmussen, L. H. Banning, W. E. Anable

In the rapidly growing industry of elemental-phosphorus production from western phosphates, most of the vanadium and chromium contained in the phosphate rock collect in the byproduct ferro-phosphorus. Results are presented of a completed laboratory project, which developed a tristage crystallization and hydrolysis process for recovering strategic vanadium and chromium, as well as a valuable phosphorus product, after extracting these elements from the ferro-phosphorus by roasting and leaching. THE Phosphoria formation in Idaho, Montana, Wyoming, and Utah contains the Nation's largest reserve of phosphate rock. A unique feature of the Phosphoria beds is their content of a fraction of a percentage each of vanadium, chromium, nickel, and molybdenum. Vanadium is the most important as to quantity and value. Small-scale tests by the Bureau of Mines at Albany, Oregon, in 1947, indicated that most of the vanadium in the phosphate rock collects in the ferrophosphorus product of smelting. Subsequent electric smelting operations to produce elemental phosphorus from western phosphate rock (experimentally by TVA and industrially at Pocatello, Idaho) have shown that the vanadium and other metals in the rock are to a large extent recovered in concentrated form in the ferrophosphorus byproduct. This paper reports the results of completed laboratory research on the recovery of vanadium from ferrophosphorus, which was undertaken by the Bureau of Mines at Albany in 1948 as the first phase of a project entitled, "Vanadium and Fluorine from Western Phosphates." The various vanadium-recovery methods investigated, including the roast-leach method that showed most promise and was studied in greatest detail, are discussed in an earlier publication.' Subsequent systematic study of the roast-leach method of extracting vanadium from western ferrophosphorus developed the more effi- cient tristage crystallization process, which is the subject of this paper. Process Development The investigations were made on ferrophosphorus produced in the electric smelting of elemental phosphorus from western phosphate rock. The TVA provided two sample lots of ferrophosphorus produced in pilot plant smelting of phosphatic shale from the Fort Hall Indian Reservation in Idaho. The Westvaco Chemical Div. of the Food Machinery & Chemical Corp. supplied two sample lots of ferrophosphorus produced by its phosphorus smelter at Pocatello, Idaho. The analyses of all four lots are shown in Table I. Westvaco lot B was the starting material for the more recent tests. The roast-leach process for recovering vanadium from western ferrophosphorus, as originally developed, employed the following principal steps: Roasting of a mixture of pulverized ferrophosphorus, soda ash, and salt; extraction of the water-soluble vanadium, phosphorus, and chromium compounds from the calcine by leaching, settling, and decanta-tion of the pregnant solution; primary crystallization of trisodium phosphate from the pregnant solution; purification of the trisodium phosphate crystals by dissolution in water and secondary crystallization; purification of the pregnant vanadium solution from the primary crystallization step by adding calcium chloride to precipitate calcium phosphate; and hydrolysis of vanadium red cake from the puri-

Jan 1, 1954

A general discussion on the subject of Crushing and Grinding was held on August 24, 1927, during the meeting of the Institute at Salt, Lake City. G. H. Clevenger, Chairman of the Milling Methods Committee of the Institute, made the following introductory remarks "Several years ago, a number of us felt that the time was ripe for a fundamental investigation of crushing and grinding. At the outset, it appeared that the first thing we needed was a yardstick whereby grinding efficiency could be measured. "The U. S. Bureau of Mines has been most generous in cooperating with the Milling Methods Committee in getting this work well undrr way. John Gross, who served the committee for a year as secretary, was placed in charge of the investigation and has been ably assisted by S. R. Zimmerley. "Messrs. Gross and Zimmerley will now present the Progrcss Report covering their work to date." Progress Report J. Gross, Salt Lake City, Utah.—-This has not been a simple problem, and when I tell you that me can give you a verbal report of what we have done during three years in five or ten minutes you will realize that we have necessarily done a great deal of work that dors riot appear in the final results. We have been in a virtually new field. Therefore, we have had to feel our way at each step so as to be fairly sure we were correet. The first thing that was realized in this problem ass that unless we had some method of measuring what happened when we crushed an ore, we might as well quit and not go further. we realized that if we tried to measure the results of crushing or grinding by the ordiuary sizing test we would not get anywhere. We could sieve down to say 200 mesh fairly accurately; we could even go one sieve size further with a little less accuracy, and then we were absolutely lost, unless we went into microscopic measurement. Even this latter method would not have been satisfactory. The question was: what were we going to measure? If we were going to measure size, we might measure one particular dimension of a particle and be off 200 per cent. or more. If we tried to measure surfaee, we would have something tangible; the surface of a particle, no matter how irregular, is something definite, far more definite than any linear dimension would be. Moreover, if we could measure surface, we would immediately have a method of checking the Rittinger law as to whether it was or was not correct. So the first thing that we sought. was a method whereby we could measure surface on crushed particles or, we will sag., on particles; it would not make any difference whether crushed or not. It then became a question of what kind of particles we were going to use in obtaining a method for surface measurement. We realizcd that it would be rather a corn-

Jan 1, 1928

By M. D. Hassialis, A. F. Taggart

ark' observed some years ago that collector-coating reactions with xanthates and with fatty acids clearly follow paths parallel to those prescribed by the familiar mass-action law for reactions in dilute solutions. He proposed, therefore, the logical hypothesis that they are governed by the solubility-product principle. However, he went astray in the application of his proposal to collector coating by overlooking the fact that coating involves a heterogeneous reaction. A mistaken concept of the meaning of the word adsorption also entered. Wark thought that the concentration of metallic ion that must be used in setting up the solubility-product equation for the coating reaction was that which could be obtained by solution of the mineral. Since this is very low for sulphide ores, and since the amount of the collector ion necessary for coating produces an extremely low concentration, the resulting ion-concentration product, under conditions when coating occurs, is much lower than that which would indicate a saturated solution of the collector-coating compound. Hence he was forced to the position that the solubility product governing the coating is much smaller than the standard solubility product. To justify this position it was necessary to postulate a coating mechanism that did not obey the ordinary laws of chemical reaction. This Wark did by adopting the concept that adsorption is a property of matter, rather than merely a more or less ephemeral local concentration thereof. Thus he says (p. 142 of ref. I): "Adsorption is not a purely physical property of the solid surface, for the specific nature of the adsorbed molecule or ion is important." The result was that he destroyed the great potential utility of his postulate by tying it to this erroneous concept in the words (pp. 142, 143): "It will be obvious that the adsorption solubility product is less than the normal solubility product." The writers have found quantitatively in the case of galena and potassium ethyl xanthate, and semiquantitatively in the case of covellite and the same collector, that the coating reaction does follow the mass-action law to the extent that coating occurs when the ordinary solubility product of the coating compound is exceeded, and that coating does not take place under the reverse conditions. In the course of the investigation leading to the establishment of this fact it was necessary to work with xanthate concentrations so low (down to 0.0004 mg. per liter), that very long conditioning times, and bubble-contact times of as much as 16 hr. were necessary sometimes to follow the reactions. The results have led to some illuminating conclusions as to necessary collector concentrations in normal flotation operations, and the action of the frothing agent in connection therewith' The experimental work comprised accurate determination of the standard solubility product of lead ethyl xanthate, development of a much less laborious

Jan 1, 1947

By M. D. Hassialis, A. F. Taggart

ark' observed some years ago that collector-coating reactions with xanthates and with fatty acids clearly follow paths parallel to those prescribed by the familiar mass-action law for reactions in dilute solutions. He proposed, therefore, the logical hypothesis that they are governed by the solubility-product principle. However, he went astray in the application of his proposal to collector coating by overlooking the fact that coating involves a heterogeneous reaction. A mistaken concept of the meaning of the word adsorption also entered. Wark thought that the concentration of metallic ion that must be used in setting up the solubility-product equation for the coating reaction was that which could be obtained by solution of the mineral. Since this is very low for sulphide ores, and since the amount of the collector ion necessary for coating produces an extremely low concentration, the resulting ion-concentration product, under conditions when coating occurs, is much lower than that which would indicate a saturated solution of the collector-coating compound. Hence he was forced to the position that the solubility product governing the coating is much smaller than the standard solubility product. To justify this position it was necessary to postulate a coating mechanism that did not obey the ordinary laws of chemical reaction. This Wark did by adopting the concept that adsorption is a property of matter, rather than merely a more or less ephemeral local concentration thereof. Thus he says (p. 142 of ref. I): "Adsorption is not a purely physical property of the solid surface, for the specific nature of the adsorbed molecule or ion is important." The result was that he destroyed the great potential utility of his postulate by tying it to this erroneous concept in the words (pp. 142, 143): "It will be obvious that the adsorption solubility product is less than the normal solubility product." The writers have found quantitatively in the case of galena and potassium ethyl xanthate, and semiquantitatively in the case of covellite and the same collector, that the coating reaction does follow the mass-action law to the extent that coating occurs when the ordinary solubility product of the coating compound is exceeded, and that coating does not take place under the reverse conditions. In the course of the investigation leading to the establishment of this fact it was necessary to work with xanthate concentrations so low (down to 0.0004 mg. per liter), that very long conditioning times, and bubble-contact times of as much as 16 hr. were necessary sometimes to follow the reactions. The results have led to some illuminating conclusions as to necessary collector concentrations in normal flotation operations, and the action of the frothing agent in connection therewith' The experimental work comprised accurate determination of the standard solubility product of lead ethyl xanthate, development of a much less laborious

Jan 1, 1947

By Fred H. Poettmann, A. L. Benham

correlation of waters and identification of mixtures of two and three waters is important in secondary recovery evaluation studies and studies involving underground movement of waters. The importance of such studies suggests the need for a method to correlate a great number of water analyses to accurately identify and improve the understanding of mixtures of waters. Geochemical analyses of waters furnish a quantitative measure of each of the ions present in a water. Table L shows a portion of the data on many oilfield water analysis report forms in use today. Under "parts per million" are listed the quantitative amounts of each ion in milligrams per liter. Following the work of Stabler' and Palmer", some laboratories have reported additional data to indicate the reaction capacity, or reacting value of each ion. Table I lists data under two subheads for the "reacting value". Under the first subhead, the reacting value is reported in gram equivalents per million, hereinafter called equivalents per million. This value is determined by multiplying milligrams per liter of the ion by a factor equal to the reciprocal of the equivalent weight of the ion. Under the second subhead (per cent) is listed the percentage of each ion based on the total equivalents per million. Sodium is not usually an analyzed value in routine analyses, but is determined by the difference between total negative equivalent per million values and the sum of all of positive ion values for which analyses were made. This difference is reported as sodium, hereafter labelled "sodium". On this basis, the subtotals of the equivalent per million and per cent reacting values of the positive and negative ions are equal. CORRELATION OF WATER ANALYSES DATA Previously reported methods for correlating oilfield waters have used part of the data in Table 1, and can be classified into two categories. Correlation by Chemical Character Correlation methods using the chemical character of waters, as represented by the per cent reacting values of the ionic constituents, have been used by Palmer2 and Tickell. These methods have the limitation of neglecting the ionic concentration of the waters. This limitation can be serious in areas where waters have the same chemical character, but differ in concentration. Correlation by Concentration of the Ionic Constituents The Reistle' and the Stiff methods use the ionic concentration in parts per million and equivalents per million. These methods are effective in differentiating waters of similar chemical character and varying concentration, as in the highly saline waters of the Mid-Continent area. These methods have the disadvantage that they correlate waters by comparing many graphs of individual water analyses to determine the similarity to, or the variance from "type" waters. PROPOSED METHOD OF CORRELATING WATER ANALYSES DATA Correlation graphs presented in Fig. 1 represent water analyses data as points to facilitate the correlation of waters. The graph on the left of Fig. 1 is a plot of per cent reacting value of magnesium vs calcium. The right

By A. J. Miles, A. D. Topping

in this paper, the theory of elasticity has been applied to the rock about a deep well, It is assumed that the rock has a modulus of . elasticity and a Poisson's ratio and that the theory of elasticity applies. It is necessary to know or assume the state of stress existing in the rock before it is penetrated by the well drill. The application of this theory indicates that stress concentration of shear, tensions, and compressions about the bore hole are of a high order. This is particularly true when a horizontal compressive stress exists in one direction only in the formation before drilling. If such an initial state of stress exists before drilling, then the rock will have stress concentrations of both tension and compression at the same elevation and of such magnitude that failure of the rock is likely. Accompanying these is a shearing stress of large proportion which is likely to produce spalling of the well walls. Internal pressure applied to the well bore will relieve the extreme compression but not the tension and has little effect upon the shear. Plastic deformation of the rock through a geological time tends to mitigate the stress concentrations. IntroductioN It has long been known that the stresses about holes and re-entrant corners of elastic solids under the influence of loads are different and generally more intense than those imposed upon the body else- where. Stress concentration at a re-entrant corner can be reduced by increasing the radius of the fillet at the corner. Stress concentration at the end of a crack in a plate undergoing either tension or compression Can be relieved appreciably by drilling a hole at the very end of the crack. Also, stresses can be increased in an elastic body in tension or compression by making a hole in it. The stress concentration is greatest at the edge of the hole. Considerable knowledge of the stresses which exist about the bore hole of a deep well may be had by applying our knowledge of engineering mechanics; or more particularly the theory of elasticity. It is, of course, necessary to make the assumption that the rock is elastic and behaves as an elastic solid, that is, that it obeys Hooke's law, has a modulus of elasticity, and a Poisson's ratio. It is also necessary to know, Or assume, the state of stress which exists in the rock prior to the penetration of the drill. With this knowledge it is possible to compute the stresses about the bore hole. The problem can be simplified by considering several simple cases separately and then by applying the principle of superposition to solve the more complex cases which are made up of the simpler ones. Case i—Rock Strata in Compression Penetrated by a Hole This case was first worked out by G. Kirsch* for structural material, but applies equally well to a horizontal rock strata in a state of in in one direction

Jan 1, 1949

By J. Suiter, H. F. Ryan

H. F. Ryan and J. Suiter (CSIRO)—In this paper the authors have presented "a physical model which has as its central hypothesis the solution strengthening of regions along grain boundaries in the order of tens of angstroms thick", and their calculations have used 40Å as the zhalf-width of this boundary region. Selection of this value by the authors suggests that they were unaware of a number of recent field-ion microscope observations of grain boundary structures (e.g., Refs. 29 and 30). The accompanying figure, Fig. 9, shows a portion of an ion micrograph of a tungsten specimen containing a grain boundary, and the regular arrangement of atoms in various crystal planes in each grain can be seen, except in the boundary zone which is not more than two atom diameters in width. Since it is expected that solute atoms will segregate only to the region where the lattice is disturbed, it would seem that a value of 4Å for the half-width of the boundary region would be more appropriate than the value of 40Å assumed by the authors. If the former value is used in Eq. [8] of their paper to obtain curves showing solute concentration in the grain boundary as a function of temperature, the resulting curves differ significantly from those obtained by the authors. Although there are only relatively slight changes in the regions corresponding to higher temperatures (i.e., grain boundary concentrations of approximately 1 at. pet), at lower temperatures the curves are no longer realistic. For example, the curve corresponding to u = 7000 cal per mole gives a solute grain boundary concentration in excess of 100 pet at a temperature of approximately 360°K, and "flattens out" at a grain boundary concentration of about 300 pet! Similar results are obtained with each of the other curves. Ion microscopy of dilute solid-solution alloys has shown that solute atoms give rise to image points which in most cases are of higher intensity than those of the solvent atoms.31 If the same behavior occurs when the solute atoms are present in much lower concentrations then ion microscopy should provide a sensitive tool for studying the segregation of impurities to the grain boundary regions. Although many grain boundaries in tungsten have been examined after different thermal and mechanical treatments, there has not been, as yet, any systematic study of such segregation. In general the micrographs show no clear indications of marked grain boundary segregation, but occasionally areas are found where the grain boundary contains an appreciable number of image points of high intensity in a very narrow zone, see Fig. 9. If it is assumed that these correspond to impurity atoms then it is possible to estimate the impurity concentration both in the grain boundary and within the body of the grains. Application of this method (to a larger area

Jan 1, 1965

By A. R. Denison

Several productive areas in the Mid-Con-tinent are broadly and briefly examined with respect to the present depth of drilling on productive structures, and the thickness of sediments remaining untested. Evidence is offered to show that a vertical mile to two miles of untested but prospective formation remain within reach of the drill. In no case would a well deeper than 15,000 ft. be required, and in most cases to no greater depth than 10,000 ft. Recent outstanding success of deeper prospecting in West Texas demonstrates the merits of deeper drilling on known structure. Introduction New fields discoverd during I942 equaled or exceeded the number in any preceding year. The total amount of oil found by these discoveries was less than in any previous year, for which accurate records are available. This means that the pools now being discovered are much smaller than in past years. This is to be expected, since the prospects available during 1942 were largely those overlooked in the earlier years and therefore represent a second or third order (in quality) of structural feature. This failure to find pools of good size and quality raises grave doubt as to the security of our future oil supply. With military needs rising almost daily, and the period of heaviest con- sumption in our war effort still in the future, there is even a growing doubt as to our ability to supply the amount needed for our ultimate victory. This does not mean that our reserves are inadequate, but rather that our "capacity to produce" may be inadequate. Lacking large fields with flush production, our capacity to produce is rapidly approaching our current needs. ,Since the industry is unable to find the large new fields necessary to keep a safe margin of "capacity to produce," other means are needed. It seems obvious that one of these should be deeper prospecting on the large, proven, productive structural features now known. The exploratory wildcat is drilled primarily in search of a trap and the reason for failure to find oil and gas in nine out of ten cases is due to the absence of a suitable trap under the drill site. Therefore, deeper drilling on a known structural feature that is productive largely eliminates the greatest hazard in wildcat drilling. While by no means all the oil known today is found in structural traps—in fact, some have estimated that less than half is so located— the fact remains that structural traps are far more commonly the oil fields that have multiple horizons of production superimposed one over the other. Outstanding examples are the Eldorado field in Kansas, the Tonkawa and Cushing fields in Oklahoma, the Louden and Salem pools of Illinois, and the richest and most prolific of all structural traps, the Long Beach, Ven-tura and other similar fields of California.

Jan 1, 1944

By A. R. Denison

Several productive areas in the Mid-Con-tinent are broadly and briefly examined with respect to the present depth of drilling on productive structures, and the thickness of sediments remaining untested. Evidence is offered to show that a vertical mile to two miles of untested but prospective formation remain within reach of the drill. In no case would a well deeper than 15,000 ft. be required, and in most cases to no greater depth than 10,000 ft. Recent outstanding success of deeper prospecting in West Texas demonstrates the merits of deeper drilling on known structure. Introduction New fields discoverd during I942 equaled or exceeded the number in any preceding year. The total amount of oil found by these discoveries was less than in any previous year, for which accurate records are available. This means that the pools now being discovered are much smaller than in past years. This is to be expected, since the prospects available during 1942 were largely those overlooked in the earlier years and therefore represent a second or third order (in quality) of structural feature. This failure to find pools of good size and quality raises grave doubt as to the security of our future oil supply. With military needs rising almost daily, and the period of heaviest con- sumption in our war effort still in the future, there is even a growing doubt as to our ability to supply the amount needed for our ultimate victory. This does not mean that our reserves are inadequate, but rather that our "capacity to produce" may be inadequate. Lacking large fields with flush production, our capacity to produce is rapidly approaching our current needs. ,Since the industry is unable to find the large new fields necessary to keep a safe margin of "capacity to produce," other means are needed. It seems obvious that one of these should be deeper prospecting on the large, proven, productive structural features now known. The exploratory wildcat is drilled primarily in search of a trap and the reason for failure to find oil and gas in nine out of ten cases is due to the absence of a suitable trap under the drill site. Therefore, deeper drilling on a known structural feature that is productive largely eliminates the greatest hazard in wildcat drilling. While by no means all the oil known today is found in structural traps—in fact, some have estimated that less than half is so located— the fact remains that structural traps are far more commonly the oil fields that have multiple horizons of production superimposed one over the other. Outstanding examples are the Eldorado field in Kansas, the Tonkawa and Cushing fields in Oklahoma, the Louden and Salem pools of Illinois, and the richest and most prolific of all structural traps, the Long Beach, Ven-tura and other similar fields of California.

Jan 1, 1944

By J. H. East, E. R. Maize

Probably no other type of equipment is now being introduced into American underground mines about which less is known and about which there is more misinformation than the Diesel mine locomotive. Any equipment installed underground brings with it hazards that were not present before, and it is the purpose of this paper to show that Diesel-powered equipment can be used with safety in underground mining if certain feasible but very important precautions are taken. Diesel locomotives are not new in underground mining, since they have been used successfully in European mines for at least 19 years, but their use in American mines is exceedingly limited; so far as is known, only five Diesel mine locomotives are operating at present in United States mines. Diesel locomotives were permitted underground in Great Britain for the first time in 1939, and the rapid increase in the number in use in those mines testifies to their safety and efficiency. More than 1300 Diesel mine locomotives are in use in European mines, according to the latest statistics; these locomotives are employed in coal, iron, lead-zinc and mercury mines. SO far as is known, the Diesel mine locomotive has not yet caused an explosion or mine fire, and has not been the cause of any fatalities from toxic gases in the mines in which it has been used. Adjustments of Diesel Engines foR Underground Use A Diesel engine adjusted to work in an underground mine should not be confused with the same engine adjusted for use outside the mine. Adjustment of the air:fuel ratio for engines that are used on the surface is intended to give the maximum fuel economy, and little or no attention is given to the chemical composition of the exhaust gas produced. Many such engines are poorly adjusted and perhaps poorly maintained, with the result that the engine emits smoke in quantity as well as the disagreeable odor familiarly associated with Diesel engines. The air:fuel ratio in the case of Diesel engines operated on the surface is generally around 15:1; that is, 15 lb of air to burn I lb of fuel. Diesel engines adjusted to work underground usually have an air:fuel ratio of about 20:1, as at this ratio the minimum quantity of toxic gases is given off in the engine exhaust. Diesel engines operated underground must be maintained in better condition than similar engines used on the surface; otherwise, the smoke emitted in the exhaust becomes objectionable if not unendurable. Practically normal air is required for safe operation of Diesel engines underground or in confined places; failure to provide virtually normal air for Diesel engine operation is almost certain to result in trouble. Bureau of Mines engineers have determined that the air in which a Dicsel Operates hi confined places should contain less than % pct of carbon dioxide and at least 20 pct of

Jan 1, 1949

By F. W. Bloecher

S. Mortsell and J. Svenssofi (Royal Institute of Technology, Stockholm, Sweden)—Bloecher states that the apparatus described by him should be a suitable instrument in the mineral dressing laboratories for determining the specific surface of such granular products that are generally investigated. We want to express a somewhat different opinion, as we doubt that the gas adsorption method of surface measurement really is the most suitable method in mineral dressing laboratories. It is well known that the surface area, as measured by this method, does not coincide with the surface area calculated from the size, shape, and number of particles, i.e. the superficial surface of the particles. It can be seen easily from Mr. Bloecher's own determination on ilmenite-leucoxene concentrate that the surface area measured according to this method may be several hundred times larger than the superficial surface. It is supposed that the surface of cracks, fissures, and pores within the particles also is included in the measured surface. However, this is an assumption which scarcely can be proved and certainly has not been proved. We believe that the mineral engineer could better use a method giving the superficial surface of the particles, as in most cases this surface only is of importance to him. Such is certainly the case when calculating the resistance of the fluid flow through granu- lar materials and the capillary forces of such materials, problems which are of great importance in connection with dewatering, filtration, and pelletizing'" etc. The same may also be the case when studying flotation problems, partly since the quantities of the introduced reagents usually are so small that they can only cover the most accessible surface of the particles, and partly since the molecules of at least the collecting reagents are so large that they cannot enter the smallest cracks and pores. As to the surface, which is of consequence in the application of Rittinger's law of crushing, one is inclined to believe, from theoretical reasons and from the work by Gross and Zimmerley, that the total surface here is the most important one. However, it seems as if in that case the superficial surface was as important as the total surface. Other reasons making the gas adsorption method less suitable for use in the mineral dressing laboratories are that the granular materials there very often are too coarse to be measured by this method, that the experimental technique is rather difficult, and that it takes a long time to measure the specific surface of a sample. Besides, the validity of the method must still be considered questionable. It is thus well known that with different gases one usually gets different values of the specific surface of the same sample, which values, even with such an ideal material as metal foils, can differ as much as about 50 pct.'" Still more serious

Jan 1, 1952

By L. P. Davidson

THE new electrolytic zinc plant of the American Zinc Company of Illinois commenced operation in April 1941. The simple flowsheet using the standard current density and the economic reasons that dictated it are given herewith. The Evans-Wallower Zinc Co. built an electrolytic zinc plant at Monsanto, Ill., in 1929 and .operated it for about two years. The plant stood idle from 1932 and was purchased by the American Zinc Co. in 1940. Because of the condition of the equipment, excepting the motor generator set, a complete rebuilding was necessary. The Fairmont City plant of the American Zinc Co. could treat the leach residues, the purification cake and the skimmings from the melting furnace in its various plants. This possibility permitted a simple flowsheet with good economic results. The flowsheet is shown in Fig. I. The calcined concentrates are leached in mechanically agitated tanks with spent electrolyte and such ferric iron solution as necessary. When the acid has been neutralized and the iron coagulated, the fluid is discharged to settling tanks. The underflow from these thickeners is filtered on a Moore filter; the filter cake leaves the plant for retreatment and the filtrate joins the thickener overflow. Zinc dust is added to this solution until the copper and cadmium are precipitated. The pulp is filtered through Shriver presses, which deliver the purified solution to storage tanks, and the copper-cadmium-zinc cake is shipped for retreatment and recovery of these three metals. The purified solution is electrolyzed; the regenerated acid is returned for use in the leaching plant and the cathode zinc, after stripping, goes to the melting furnace, from which it is cast in slabs. The skimmings from the melting furnace are shipped to the Fairmont City plant for reduction to metal in. the retort furnaces. The choice of this simple flowsheet was made possible only because of the facilities of the Fairmont City plant. The long leaching period, with high acid content and high temperature which characterize the high-density process, gives a higher zinc extraction but also dissolves more impurities, which must be removed. The same is true to a lesser degree of the multi-step leaching of the western low-density plants. By the sacrifice of some initial extraction, solutions can be obtained that are relatively easy to purify and give good ampere efficiency. This loss in initial extraction is made up in the retreatment of the residues in the Waelz plant. The impurities that accompany the zinc thus extracted are inconsequential when the Waelz product is treated in a distillation plant. It was recognized that this flowsheet would require a somewhat greater amount of sulphuric acid-either as acid or as sulphate sulphur in the calcine-because of poorer washing. The sulphuric acid plant at Fairmont City could deliver 60° Be. acid to compensate for the sulphate loss and the cost would be less than the cost of more intensive washing.

Jan 1, 1942

By P. A. Beck

ACCORDING to the traditional definition,1 re-x crystallization is a process taking place upon annealing of cold worked metals, characterized by the appearance of new strain-free grains, growing at the expense of the cold worked grains until ultimately the new crystals completely replace the cold worked structure. In metals like brass this process was observed long ago to take place simultaneously with the return of the mechanical properties to those characteristic of well annealed material. The above definition implicitly assumes that the matrix in which the new grains are growing is essentially still in the cold worked condition at the time it is absorbed by the new grains, i.e., that the energy stored in the metal during cold working is not greatly decreased by recovery, prior to recrystallization. Accordingly, the bulk of this energy is assumed to serve as the driving force for the process of recrystallization. Recently, a great deal of evidence accumulated, indicating that the traditional concept may be considerably in error. Suzuki' found that by far the largest portion of the stored energy of cold work in compressed polycrystalline copper is released in the early stages of annealing, well in advance of recrystallization. Thus, the new recrystallized grains are undoubtedly growing in a matrix which is, at least energetically, no longer in the cold worked condition, but has nearly returned to the annealed state. It is true that in Suzuki's experiments the major hardness changes due to annealing were observed to take place concurrently with the formation and growth of the new grains, but this process apparently involved the release of only a minor residual fraction of the stored energy of cold work. Confirming in this respect the views of Wood," several recent investigations by various techniques lead to the conclusion that the grains of many, if not all, metals in the cold worked condition consist of small, slightly disoriented "crystallites" or "sub-grains".* (After appreciable deformation at room temperature, the subgrain size in copper appears to be about 7.104 cm and in high purity aluminum about 2.10-4 cm.) Recent investigations which demonstrated this phenomenon most convincingly are those of Heidenreich8 with hammered high purity aluminum, of P. B. Hirsch and collaborators7,8 with cold worked polycrystalline aluminum, copper, nickel, iron, gold, etc., and of Warren and Averbach9 with a rolled copper plus 2 pct Si single crystal. In addition to the existence of slightly disoriented sub-grains, the cumulative evidence from these investigations also shows that in the cold worked condition the subgrains themselves are severely strained. With regard to the early stages of annealing, Heiden-reich's results indicate that within the subarains of hammered high purity aluminum the strain gradually disappears, without discernible migration of the subboundaries. This recovery process presumably accounts for the major portion of the energy release

Jan 1, 1953

By Fred C. Bond

The Standard method of determining the crushing resistance of rocks consists of crushing prepared shapes under slow compression, and expressing the ultimate crushing resistance at the load causing failure in pounds per square inch of cross-sectional area perpendicular to the crushing force, with the height approximately equal to the diameter. One-inch cubes or cylindrical drill cores are commonly used. Cubes and drill cores are cut by a highspeed steel disk with diamond dust embedded in the edges, and running under a water spray. such a saw will cut one square inch or more of hard stone per minute. An oiled, spherical, swivel compression block of small diameter should be used to equalize the pressure. Each sample is crushed between sheets of cardboard or blotting paper extending about one-half inch beyond the edges of the stone. A cloth is wrapped around it to prevent dangerous explosive shattering. It is probably preferable to place the swivel block below the specimen, with either a rigid head or another swivel block above. Whatever the arrangement, the conditions should be selected that will develop the maximum crushing strength of the specimen, even though its top and bottom planes may not be precisely parallel. The cardboard pads may be dispensed with if the ends of the specimens are polished smooth. The use of lead pads was discontinued because of the observed tendency to split the material. The samples are weighed and measured before breaking, and the density is calculated. Cubes that contain bedding lanes or veinlets are usually placed with these vertical and parallel to the crushing force, in order to develop the maximum resistance possible. A number of compression tests were made on Canadian ores, by Forrest Nagler, of the Allis-Chalmers Manufacturing CO., and are listed alphabetically in Table I. These tests were made on one-inch cubes or on diamond-drill cores approximately one inch in diameter and One inch long. The drill cores represent virgin rock, while the cubes may have been previously weakened by explosives. compression tests have been made in the Allis-Chalmers Milwaukee Laboratory on a number of ores and other materials. These are listed alphabetically in Table 2. In test NO. 1339, on limestone from the Hanna Coal Co., comparison was made between 2 by 2-in. diamond-drill core segments and one-inch cubes cut from the cores in the same strata. Results for the cylinders are tabulated directly below those for the cubes. The bedding planes were normal to the compressive force in breaking the cylinders and parallel in breaking the cubes, which accounts for the lower strength obtained from the cylinders. The percentage of net linear compression at the ultimate pressure was measured in test No. 1055 for Fontana TV A quartzite as 0.30 for cube A, and 0.37 for cube D.

Jan 1, 1947