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By M. King Hubbert, David G. Willis

A theoretical examination of the fracturing of rocks by means of pressure applied in boreholes leads to the conclusion that, regardless of whether the fracturing fluid be of the penetrating or non-penetrating type, the fractures produced should be approximately perpendicular to the axis of least stress. The general state of stress underground is that in which the three principal stresses are unequal. For tectonically relaxed areas characterized by normal faulting, the least stress should be horizontal; the fractures produced should be vertical with the injection pressure less than that of the overburden. In areas of active tectonic compression, the least stress should be vertical and equal to the pressure of the overburden; the fractures should be horizontal with injection pressures equal to or greater than the pressure of the overburden. Horizontal fractures cannot be produced by hydraulic pressures less than the total pressure of the overburden. These conclusions are compatible with field experience in fracturing and with the results of laboratory experimentation. INTRODUCTION The hydraulic-fracturing technique of well stimulation is one of the major developments in petroleum engineering of the last decade. The technique was introduced to the petroleum industry in a paper by J. B. Clark,' of the Stanolind Oil and Gas Co. in 1948, and since then its use has progressively expanded so that by the end of 1955 more than 100,000 individual treatments had been performed. The technique itself is mechanically related to three other phenomena concerning which ah extensive literature had previously developed. These are: (1) pressure parting in water injection wells in secondary-recovery operations, (2) lost circulation during drilling, and (3) the breakdown of formations during squeeze-cementing operations, all of which appear to involve the formation of open fractures by pressure applied in a wellbore. The most popular interpretation of this mechanism has been that the pressure had parted the formation along a bedding plane and lifted the overburden, notwithstanding the fact that in the great majority of cases where pressures were known they were significantly less than those due to the total weight of the overburden as determined from its density. Prior to 1948, this prevalent opinion had already been queried by Dickey and Andresen,2 in a study of pressure parting; and by Walker,"' who, in studies of squeeze cementing, pointed out that the pressures required were mostly less than those of the overburden, and inferred that the fractures should be vertical. J. B. Clark,' in his paper introducing hydraulic fracturing, and later Howard and Fast," and Scott, Bearden, and Howard," also of Stanolind, postulated that the entire weight of the overburden need not be lifted in producing horizontal fractures, but that it was only necessary to- lift an "effective overburden," requiring a correspondingly lower pressure. Hubbert,7 in discussing the paper by Scott and associates, pointed out that the normal state of stress underground is one of unequal principal stresses; and in tectonically relaxed areas, characterized by normal faults, the least stress should be horizontal. Therefore, in most cases, fracturing should be possible with pressure less than that of the overburden and, moreover, such fractures should be vertical. Harrison, Kieschnick, and McGuire,8 also on the expectation that the least principal stress should be horizontal, argued strongly in favor of vertical fracturing. Scott, Bearden, and Howard6 observed that, when

Jan 1, 1958

By Robert J. White

Strong's equation for calculating bottom-hole pressure reduction due to gas cutting of drilling mud is corrected, resulting in a simpler equation which is easier to use. Use of the equation is illustrated by examples. It is shown that reduction of weight of a 10 lb/gal mud by 50 per cent at the surface due to gas cutting produces only n 3 per cent decrease in hydrostatic head at the bottom of a 5,000-ft well. It is also shown that at the surface 5 volumes of air per volume of mud are required to reduce the apparent mud weight from 8.5 to 6.5 lh/gal in a 3,000-ft well. Illustrative graphs are included to show the effect of various degrees of gas cutting on apparent mud weight at depths of 2,000, .5,000 and 10,000 ft and to show variation of apparent mud weight, with depth for a 100 lb/cu ft (13.37 lb/gal) mud gas cut to 90 lb/cu ft (12.03 lb/gal) at the surface. INTRODUCTION In 1938, Strong' published the following equation for calculating reduction in bottom-hole pressure due to gas cutting of drilling mud h = 1/D [p + pn/100 In p + p(1-n/100)/p(1- n-100)] where: h = depth in feet P = pressure in atmospheres at depth h due to mud column only D = hydrostatic pressure in atmospheres of a col-umn of uncut mud 1 ft high p = back pressure at well-head (in atmospheres) n/100 = fraction by volume of gas in mud at well-head at back pres-sure p This equation was recently found to contain an error due to an incor-rect expression for variation of vol-ume fraction of gas with pressure. Values calculated by the original equation are close to the correct values for small percentages of gas for which it was derived but become increasingly erroneous as the gas content increases and are completely unusable at the very high gas con-tents employed in aerated mud. DERIVATION The nomenclature used is the same as in Strong's paper. The pres-sure dP exerted by a lamina of thickness dh at a depth h ft is ex-pressed by Eq. 1 where x = volume fraction of gas at depth h dP = D (l - x)dh . . . (1) When we express x in terms of the wellhead per cent gas n, the well-head pressure p and the pressure P at depth h, the result is Eq. 2. x = (np/p+p)/(100-n) + (np/P + p) When this is substituted in Eq. 1 and rearranged to separate the var-iables the result is dh = 1/D [dp + np/100-n dp/(P + p]. Integration between appropriate lim-its results in or if the wellhead is open so that p = 1 atm and we rearrange Eq. 4, the result is loss in head = hD — P = n/100-n In (P + 1) ...(5) Eq. 5 can be solved easily by successive approximation using hD as a first approximation for P on the right-hand side and calculating a first value for loss in head. This can then be used to get a new value of P using the left-hand side of the equation. Values converge very rap-idly even for quite large values of per cent by volume gas n. EXAMPLES The effect on bottom-hole pressure of 50 per cent gas cutting of the mud in a 5,000-ft well using 10 Ib/ gal mud will be calculated, we have: h = 5,000 ft 10 X 7.48 144 X 14.7 = 0.0353 atm/ft hD = 176.5 atm n = 50 Substituting these values in Eq. 5 and using hD as a first approxima-tion of P on the right, we have, approximate loss in head = 50/50 In (176.5 + 1) = 2.30 log 177.5 = 5.17 atm. We calculate a new value of P as follows:

Jan 1, 1958

By W. M. Reilly, Martin E. True, O&apos

A technique, equipment, and a compound have been developed and field tested for sealing tubing joint thread leaks without removing the tubing from the well. This eliminates the necessity of killing the well with possible damage to the producing formation, which could result if it were exposed to drilling mud. A thread sealing compound, developed and tested in the laboratory, is introduced into the tubing and squeezed into the joint to eliminate the leak. A high percentage of successful field applications have eflected an appreciable cost reduction in repairing leaking tubing strings in East Texas and in the Louisiana Gulf Coast area. INTRODUCTION In producing oil and gas wells the industry has been plagued with a never ending problem of tubing connection leakage. This situation is becoming increasingly more significant as more gas wells are placed on production and as higher pressures are encountered at greater depths of current drilling. Substantial progress has been made in minimizing thread leaks by careful handling and cleaning of joints and by the use of improved sealing compounds in combination with controlled makeup. But even with the use of the best known methods and sealing materials during initial makeup, occasional leaks through tubing joint threads appear inevitable. In some instances, tubing joints in high-pressure gas wells have been found to leak gas at relatively less pressure than that at which the tubing had been tested satisfactorily using liquid. Many expedients have been employed to prevent the physical replacement of tubing when leaks have developed. Perhaps the most commonly used is the sodium silicate treatment in which the solution is lubricated into the tubing to form a crystalline plug in the leak. Generally, any benefit realized is of a temporary nature. In addition to field studies on handling and makeup of tubing, extensive laboratory work has been undertaken on the development and testing of thread dopes.' Also, substantial effort has been devoted to testing tubing joints using high-pressure gas as a pressure medium.' The results of this work have emphasized that tubing joints are susceptible to occasional leaks, especially when subjected to relatively high differential pressures. To cope with the problem of leaking connections, an extensive investigation was undertaken to devise means of sealing leaks without removing the tubing from the well and without reducing the inside diameter of the tubing. The purpose of this paper is to present a technique, together with the associated equipment and compound, which have been developed for effecting a seal of leaking tubing in place. DISCUSSION Work was initiated simultaneously on two ventures: (1) to develop a satisfactory leak sealing compound and (2) to develop tools necessary to find the leak and place the compound. Leak Sealing Compound In the development of a sealing compound, tests were conducted on those compounds commercially available which include: (1) conventional thread lubricants, (2) thermo-setting resins and (3) other materials which held promise of effecting a seal. Although none proved completely satisfactory in their available form, two commercial compounds proved nearly equally effective in sealing leaks during laboratory tests after proportioned quantities of graded silica had been added. Field usage has indicated that the preferred compound is one prepared of an aluminum-stearate base thinned to the proper constituency and carrying a mixture of fine mesh graphite and graded silica. The compound developed by Humble Oil & Refining Co. is designated as Tubing Thread Leak Sealant 800. Placement Tools and Technique In developing tools to detect joint leaks and to place the sealing compound, work was done initially on wireline equipment. Preliminary designs were completed of a tool somewhat on the order of a pressure bomb to test individual joints with gas at high pressure to determine if the joint was leaking. An entirely different tool equipped with opposed packers was intended for placement of the sealing compound at high pressures in each leaking joint. The application of these tools

Jan 1, 1958

By T. H. Janes

THE POSSIBILITY of producing pig iron from iron ores of British Columbia for a west coast primary iron and steel industry has been investigated by the provincial government and by commercial interests on sever.al -occasions. The latest study is that currently under way by The Consolidated Mining and Smelting Company of Canada, Limited. The Company is studying the possibility of making pig iron from the oxide calcine resulting from the roasting of pyrrhotite. tailings used in making sulphuric acid for fertilizer production at Kimberley. A comprehensive report on the subject .of establishing a primary iron and steel works in the Province, based on local iron ores, was prepared by Arthur G. Mc-Kee and Company of Cleveland, Ohio, in 1942 for the B.C. Minister of Mines and is available to interested parties. A detailed survey on the subject was also pre-pared in 1954 by Dr. G. P. Con-tractor, then .of the British Columbia Research Council. Considerable information is there-fore available on most aspects of an integrated primary iron and steel industry in British Columbia to supply the needs of the western provinces. To date, however, no basic iron industry has been established despite the .occurrence of high-grade iron ore deposits on the offshore islands and the high freight charges on iron and steel products brought into the area from Eastern Canada and overseas producers. The chief deterrent has always been the relatively small and highly diversified market available to a local steel producer. Other major fact-ors have been the lack of sufficient proven reserves of iron ore, and the difficulty of making pig iron, suit-able for steel manufacture, economically on a small scale. Technical and economic conditions have changed considerably since World War II and the establishment of a primary industry based on electric furnace production of pig iron or on one of the direct reduction processes, coupled with electric furnace steel production, may now be economically feasible.

Jan 1, 1958

By John C. Machisak

Employment and related injury experience of the coking industry in the United States for 1956 contained in this publication is summarized under three general sections: (A) General injury experience: Tables 1 to 9: Current and comparable statistics on operating data, number, frequency, and degree of severity of injuries and major accident agencies involved in the cause of injuries. Data are presented for the industry as a whole, for each type of oven, and for the States in which coke was produced. (B) Selected injury experience: Tables 10 to 15: Comparable injury data covering 5- and 10- year periods on the number and degree of severity of injuries and major accident causes.

Jan 1, 1958

By D. S. Dinsmoor

Boron, estimated to comprise about 0.001 percent of the earth's crust (Fleischer 10), as an element is never found free in nature, although its compounds are found in many localities. the borates are the most important. Sassolite (B(OH)3) and boracite (Mg6C12B1406), non-borates, are-of-minor importance. The crystal structures of most natural borates are still unknown. A classification based solely on the ratio of boron to the total number of cations has been devised (Palache 28). This classification divides the borates into four, sub-groups; anhydrous borates, hydrated borates, borates containing hydroxyl or halogen and compound borates. Only four or five minerals of the hydrated borates group have ever been used commercially. In more recent years, the sodium borates have comprised all but a 'small fraction of all borates used. Borax, the hydrated borate compound, is the most important of all boron compounds. It has been used so long and so often that the layman often confuses borax and boron and, applies the terms synonymously.

Jan 1, 1958

By A. D. Pittuck

Refractory minerals .containing uranium and columbium have been successfully treated at Queen's University, Kingston, to produce high-grade concentrates. Recoveries of over 90 per cent of the uranium and columbium have been obtained when treating concentrates containing euxenite, fergusonite, betafite, and pyrochlore. The processes ?consisted -of leaching the columbium with hydrofluoric acid, and the uranium with nitric acid, sulphuric acid, or sodium carbonate solutions. The leach liquors were extracted with organic solvents from which the values were stripped and precipitated, producing final products assaying 45 to 55 per cent Ob2O5 and 60 to 70 per cent U3Os.

Jan 1, 1958

By C. S. Roberts, S. L. Couling

PLASTIC strain in polycrystalline metal as a result of bulk movement of one grain with respect to another along grain boundaries is not new. Rosenhain and Humphrey observed such effects shortly after the turn of the century.' Since then, observations of grain boundary deformation have been made on several metals. In recent years, intensive studies of the deformation at grain boundaries have been performed on polycrystalline metal and bicrystals.14-20 Aluminum or its alloys have been used in these latter studies. The subjects of controversy at present appear to be not whether grain boundary deformation exists, but 1) how quantitatively important it can be in polycrystalline metal, and 2) what its detailed mechanism is. Some investigators have concluded that such de- formation is minor in importance while others have concluded that it is a major consideration. Some have concluded that it involves shear of one grain over another at the interface while others have concluded that it operates by crystallographic deformation within the grains near ,the boundary. A categorical statement for electrolytic magnesium cannot be made on either of -these points. When polycrystalline magnesium is deformed in creep under conditions of high strain rate and low temperature, grain boundary deformation is relatively slight." Under these conditions, much deformation occurs within the grains and boundary contours change to a higher-energy jagged form. The result is shown in Fig. 1, where boundary jaggedness is pronounced upon polishing and etching after a plastic strain of approximately 6 .pct at 300°F and 3000 psi. No migration of the boundaries has been detected in this process. When the same metal is deformed the same amount at 600°F and 300 psi, resulting in a much lower strain rate, the boundaries migrate toward a lower energy configuration, where

Jan 1, 1958

By John C. Machisak

INJURY DATA and experience at, coal mines in the United States for 1953 and 1954 are presented in this publication with a minimum of interpretation and comment because of the numerous tables required to afford detailed comparisons between the 2 years. Corresponding tables for 1953 and 1954 follow in consecutive order under the following general sections: (A) General injury experience: Tables 1 to 11: Contain current data on number of fatal and nonfatal injuries, frequency and severity rates, and average severity and time-loss rates. (B) Selected injury data: Tables 12 to 85: Contain current data on causes of injuries, distribution of injuries by part of body injured, days of disability, extent of hand and machine loading, experience by employment and production groups, and various other operating factors and physical conditions related to the occurrence of injuries at the Nation's coal mines.

Jan 1, 1958

By R. O. Pynnonen

Tunnel-driving is recognized as a hazardous occupation; adequate support of roof and sides for preventing accidents from falling material is usually one of the most important safety problems. Where extraordinary conditions of sand and water are found, this problem becomes even more difficult. Tunneling at the Tioga No.2 mine was stopped when a 22-foot bed of water-saturated, fine gray sand was encountered. The tunnel, designed to house an ore-conveyor belt, was being driven from both ends. Driving was extremely difficult at both the upper and lower faces when the sand horizon was reached. A distance of 178 feet remained between the faces. Heavy pressures deformed the steel-supporting rings at the upper face, and there was an inrush of mud and sand at the lower face.

Jan 1, 1958

By Nicholas J. Grant, Henry Epstein, John Chipman

FOR many years steel producers have been concerned with the presence of hydrogen in steel. Hydrogen dissolved in excess of its solid solubility at the melting point may cause bleeding and gross unsoundness in ingots and castings. In fully-killed steels the hydrogen content which results in these difficulties varies with the alloy content1 and may range from 6 to 12 ppm.* It is also recognized that of heat treatment diminishes rapidly as the size of the part to be treated increases. The time required to remove a specified fraction of the hydrogen present increases as the square of the diameter of the section, making the treatment of large- sizes impractical. In order to prevent bleeding and gross unsound-ness due to hydrogen, and in view of the inadequacy of corrective heat treatment alone to provide optimum properties when hydrogen is present in large sections, efforts to limit the hydrogen content must be taken while the steel is still liquid. The main subject of this paper is a discussion of the factors affecting the hydrogen content of liquid steel in acid and basic open hearth, and basic electric two-slag furnace processing. Literature Survey Because many of the results and observations reported in the literature have a direct bearing on the results obtained in the present research and form part of the basis for conclusions reached, a brief summary of the findings is necessary. Methods for experimental investigation of hydrogen in liquid steel are comparatively new. The first attempts to estimate the hydrogen content of the open hearth bath were by Kalling and Rudberg,6 who devised a method for collecting gases evolved from the boiling bath of a basic open hearth furnace. They found that the gas during the boil generally contained 2 to 3 pct H2. From this and Sieverts'

Jan 1, 1958

By John E. Bailey

The advent of Nuclear Energy has caused a phenomenal growth in the uranium mining industry. To keep abreast of this surge the mining industry has located many ore bodies, determined the best types of mining adaptable to this particular type of ore and developed a highly specialized type of operation. But, has the mining industry gone far enough in the planning? Has ?built-in? safety been included in the efficient methods of operation? Preplanning safety in the mining industry, as in all industries, takes engineering and ingenuity combined with the experience and cooperation of all concerned. A system of mining can be planned on a map and it will look good. However, when the actual mining takes place, conditions may be such that deviations from the original plans may be required because of excessive water faults or other conditions encountered. With safety we may also be required to change, to conform to the characteristics of a particular operation. People in the mining industry are well aware that loose back has killed miners each year. This condition occurred in practically all types of mines. The condition is not new to us. It is also known that explosives, haulage, machinery and conditions common to all types of mining have taken a heavy toll of human life in mining. In addition to these hazards in the uranium mines, the hazard of radon is also present, Radon is a radioactive gas liberated from ores containing radium. This gas is released into the active workings by the blasting or breaking up of the ore. Sometimes it is caused by radium contaminated water seepage from abandoned workings or from the ore body itself. Until the action of this gas on the human was known, many miners were affected. Un- less adequate precuations are taken to protect the people in these mines,, they may be exposed to this hazard, Health researchers made a study of this substance to determine how it would affect the health of the men, They also studied men who had worked in previous years, in mines known to have contained radioactive materials. All of this research contributed to the present knowledge of radon and its daughter products. It is not flammable nor explosive, but, if allowed to enter the body through the respiratory organs it can cause serious damage. Mines have been operated in the past and are still being operated, which were known to contain explosive and noxious gases, indicating that this problem can be controlled. Several states have instituted laws that make it mandatory to provide adequate ventilation and use of monitoring devices to limit radon and its daughter products to a maximum of 300 micro-microcuries per liter of air. This is considered a safe limit for sustained periods of human exposure. While the findings of research do not prove conclusively that the inhalation of excessive radon or its daugher products cause lung cancer, indications point to this as a possibility, particularly radium A and radium C1 of the daughter products. The threshold limits set by law in most uranium producing states are believed to be safe. In a few years, when tests and data now in the process of collection by interested state officials and laboratories is complete, these limits may be found to be ready for revision. Studies such as these take time. At present, the limits that are used are based upon estimates. The permissible limits of exposure to radon and daughter products include a large safety factor. It is considered that a good supply of fresh air delivered to the working places, adequate dust control, the sealing of unused or abandoned workings, the removal of mine water which is generally contaminated and a safe waiting period after blasting, will hold to a minimum the dangers from this source. There are, of course, problems accompanying each of these procedures. For example, the ventilating of untimbered raises and bringing fresh, uncontaminated air to the working places may be a problem. However, a good mining man can solve these problems as they apply in each particular operation. From the information available at the present time, the daughter products containing polonium and emitting alpha radiation, may be a health hazard. Fortunately, the half life of most of the daughter products is short, however, radium D has a half life of 22 years and presents a problem of contamination in the storage of old tailings. So we can see that failure to comply with the accepted good mining practices may have harmful effects on the health of miners. It is gratifying to note the interest in this potential hazard by the officials in the uranium ore producing states, who are making extensive studies and keeping records of the men who work in this type of mining. This all provide information necessary for preplanning safety. By contrast, little has been accomplished to control the injuries and deaths from some other factors connected with most underground mining operations. I would like to discuss briefly one of the hazards which take an annual toll in our underground mines, this is falls of back and walls. This problem or hazard is present, and will be

Jan 1, 1958

By Walter B. Hester

All persons and communities that have experienced strong-motion earthquakes are convinced of the importance and complexity of earthquake problems thatmust be solved in order to reduce the personal hazards and property losses to a reasonable minimum. It is also clear that absolute elimination of all risks is impossible. Reduction of existing hazards and precautionary measures which will minimize chances for disaster can be accomplished by realistic appraisal of the effects of recent earth- quakes on modern structures and installations. Localities that have reason to expect so-called strong- motion earthquakes can anticipate these effects by taking appropriate steps. Valid earthquake information can only be obtained from earthquakes. Each earthquake contributes to the body of knowledge by additional facts and by clarification of previous observations. Rational interpretation of the data followed by practical application of the conclusions can contribute greatly to the safety of persons and property. The general public expects the architectural and engineering profession to accept this obligation and render this service. Most earthquake hazards are man-made and arise from the imperfections of the works of man and his failure to anticipate the consequences when the natural characteristics of his environment are ignored. If it is not given to man to prevent such natural phenomena as earthquakes, it is sometimes within his power to control their destructive effects and to reduce to a minimum the toll of life and human suffering.

Jan 1, 1958

By Joseph L. Gillson

IT is a somewhat curious circumstance that the newest of the Institute's several awards should be conferred in the oldest of our several professional fields—for there is little question that geology and mining have antedated metallurgy and petroleum. Perhaps so did geophysics. After all, one geophysical instrument, the magnetic compass, has been successfully employed for many centuries. Young in years the Jackling Award may be, but in distinction—whether in terms of the title it bears or in terms of the first three medalists (Reno Sales, E. D. Gardner, and the late Father MaceIwane)—the Jackling Award is already one of the ranking awards of the Institute. The name of the 1957 medalist will bring added luster to an already illustrious roll. J. L. Gillson was born and brought up in Evan-ston, Ill., in an area characterized by singularly flat and uninspiring topography, and devoid of ore deposits and even of bedrock—a most unlikely environment from which to expect a future Jackling medalist to emerge! On graduating from high school he enrolled as a chemistry major at Northwestern University. At the end of his frkshman year his scholastic prowess had won him a prize of two chemistry books. But these went unread, for about this time he came under the spell of U. S. Grant, that distinguished and enthusiastic geologist who for many years was head of Northwestern's geology department. From thence forward Joe was a dedicated geologist. After a Navy interlude in World War I, he went to MIT for graduate work, substituted for the late Professor Palache for one year at Harvard in mineralogy, received his doctorate at MIT and stayed on as a meniber of the MIT faculty, where the geology department was headed by that great dean of all economic geologists, Waldemar Lindgren. In 1926 Joe spent a summer looking into barite deposits for the du Pont Co., and since 1928 he has been du Pont's chief geologist. Do men who lead such active lives in our exploration organizations generally have permission to publish their observations? Do they generally find time to publish, even if they have permission? Alas, no. But in Joe Gillson's case, yes. His bibliography runs to well over two score papers, including one of the very first papers in this country on the applications of petrography to problems of Portland cement. He has written on such topics as the origin of talc and the genesis of ilmenite, fluorspar, and alkaline rocks. Each year for a number of years his annual reviews of industrial minerals in the Mining Congress Journal have been eagerly awaited. - Do men who do so much to advance their science have anything left to give to the advancement of their profession? In Joe Gillson's case, yes. He has been a vice president of the Mineralogical Society of America and has been active in the councils of the Society of Economic Geology, particularly in their research programs. This year he is president of the American Geological Institute, currently perhaps the most challenging post to which a geologist may be elected. His contributions to AIME scarcely need documentation, so I shall mention only three—his chairmanship of the Committee on Democratization of the Institute, a committee whose work and recommendations brought a new and hopeful leaven to AIME at a time when this was sorely needed; his chairmanship, a few years ago, of the Industrial Minerals Division; and his current place on the Board of Directors as Vice President of the Institute. Such' a catalogue of contributions and achievement, even as condensed as I have had to make it, certainly merits the Jackling Award. Yet, implicit although not often expressed in the conferring of most awards is the hope that besides recognizing a distinguished career, it will provide stimulus for further effort. In the present instance, such an expectation is already well on the way to fulfillment. Only recently Joe Gillson has undertaken the editorship of a new and greatly revised edition of the Institute's Seeley Mudd volume, Industrial Minerals and Rocks. And so, Mr. Chairman, it is with pleasure and enthusiasm that I present Dr. J. L. Gillson for the 1957 Jackling Award.

Jan 1, 1958

By E. M. Furness, A. S. Henderson

ORIGINALLY the Babbitt experimental plant grinding circuit consisted of one rod mill 101/2 ft diam by 12 ft long in open circuit followed by two ball mills 101/2 ft diam* 12 ft long in parallel cir- the slow-speed ball mills. The next step was to improve rod mill operation by changing the speed of this mill. Such an attack would affect only one mill and would allow slower speed on the ball mills. The rod mill, as originally purchased, operated at 15.45 rpm. Additional pinions were purchased to test this mill at 16.45, 17.45, and 18.45 rpm. When the mill speed was increased by the use of these pinions, rod breakage with this short mill increased out of all proportion to the improved grinding, until at 18.45 rpm breakage became as high as 7 lb per

Jan 1, 1958

By R. D. MacDonald, John Dasher, A. M. Gaudin

ION exchange is a widely used unit operation in water treatment and elsewhere in chemical industries. It has occasionally been used in hydro-metallurgy for treating plating, pickling, and rayon wastes Concerning ion exchange in extractive hydrometallurgy—for treating ore leach solutions— the literature prior to the Geneva Conference has given only hints."-" Yet most of the ore leach plants now being built or completed in the last three years use ion exchange for this purpose. Most of these plants are used for extracting uranium. The overall process for leaching low grade uranium ores and the history of its development have been given in the authors' previous papers.',' The object of this paper is to discuss certain engineering aspects of the new application of ion exchange to recover dissolved values from ore leach solutions. Necessarily the illustrations will be taken from the first application—to uranium metallurgy. Although ion exchange processes have been devised in which separation of spent residue from pregnant liquor is not required, as in the RIP process,"-'I only ion exchange operation, in which the resin is contacted with a clear solution, will be discussed in this paper. Uranium exists in acid leach liquors mainly as the cation UO," and can be adsorbed completely by cation exchange resins, but the adsorption is not selective as other cations such as Fe++, Fe+++, Al+++, Mg++, Mn", and Ca++ are also adsorbed. Uranium, however, forms complex anions with sulfate, phosphate," Carbonate"~"~ and even with chloride if the solution is strong enough.15 These anions can be adsorbed by anion exchange resins. The strong base anion exchangers have a very strong preference for these complexes and hence this adsorption is very selective. In this paper, the examples concern acid sulfate leach liquors from which uranium is adsorbed as UO,(SO,),-% and UO,(SO,),". Materials and Equipment Ion Exchange Material—Ion exchange materials include natural and synthetic; organic and inorganic; cationic and anionic; and weak, intermediate, and strong varieties. They consist of fragments or beads normally in the size range —16 to $50 mesh. The newer varieties have been developed to have greater stability, chemical strength, and/or capacity than earlier varieties. The resin used for uranium recovery is a strong base anion exchanger.* To make * Such as Rohm and Haas Amberlite IRA-400 series, British Permutit DeAcidite FF. Permutit lonac SE. and Dow Nalcite SAR. this resin, styrene plus a few percent divinyl benzene are polymerized into long chains with occasional cross links. This resin in bead form is then reacted to introduce quaternary amine groups onto most of the aromatic rings.' These resins are water-avid gels of specific gravity of about 1.1, which shrink and swell by osmosis when the ionic content of the surrounding solution is changed. The beads which are shown in Fig. 1 can be broken like an onion by rapidly replacing 15 pct H,SO, with water. This organic gel can also be broken by mechanical handling as by a centrifugal pump. Otherwise it is remarkably stable. It is unharmed by fairly strong acid or alkali, oxidizing or reducing agents, and heat up to 70°C. The strong base resin when completely in the chloride form (with a chloride anion on each quaternary amine group) holds over 107 g of C1- per dry kg. As all these chloride ions can be displaced by other anions, the resin has an exchange capacity of over 3 g equivalents per dry kg. However, the resin is sold and used by moist volume. The moist resin contains about 50 pct water, weighs about 43 lb per cu ft, has 40 pct voids, and an exchange capacity of over 1 g equivalent per liter of bed volume. Ion Exchange Equipment—Ion exchange equipment used for recovery of uranium from leach solutions is substantially identical to that developed for water treatment and other applications.'" The resin beds are held in closed tanks or columns which, in the uranium plants, have been standardized at 7 ft diam and 12 ft high. The resin bed

Jan 1, 1958

By G. H. Lair, B. J. Langford, S. H. Rockwood

Volumetric reservoir analysis is dependent upon a firm relationship between porosity, connate water, and net pay. Capillary presswe data on core samples interrelate these three factors. It is shown that other reservoir problems may be resolved: (I) whether water production is indigenous or extraneous to the oil producing interval, (2) an oil-water contact is being approached, and (3) whether the oil-water contact is remotely situated. INTRODUCTION Volumetric analysis of carbonate reservoirs challenges the ingenuity of the reservoir engineer due to an absence of data on the minimum oil-bearing and oil-producing pores of a given reservoir rock. Many studies with this as the ultimate objective are available on the physical characteristics and fluid-flow behaviors of the carbonate reservoir. Some of these publications are: Hassler, Brunner and Deahl's1 study of the role of capillarity in oil production; Jan Law's' and A. C. Bulnes3 statistical treatment of core analysis data; Chalkley's method4,5 or estimating specific surface areas and porosity; Walter Rose's9 report on porosity, reserves, and recovery; Archie's78 tex-tural classification of carbonate rocks; Stewart and Spurlock's9 large core analysis; Purcell'sl0 mercury injection method in studying capillary pressure phenomena; Stewart, Craig, and Morse's" model multiple-phase flow test in investigating the relative permeability effect; and Fatt's12 illumi-nating network model of porous me-dia. The present study shows that the static reservoir parameters of porosity, connate water, and net productive thickness may be interrelated by utilizing a statistical arrangement of mercury capillary pressure data in addition to routine core analysis. This report summarizes the techniques that are followed to obtain these relations which are applicable to carbonate and sandstone reservoirs that do not contain clays. Capillary pressure statistical studies may be extended to include clay-bearing rocks by utilizing water capillary pressure data. POROSITY It is necessary that the laboratory determine the porosity value that includes the pores that are filled with hydrocarbons and water in the reservoir. This is the reservoir's total porosity. When true total porosity values are not available, correlations between porosity and capillary pressure characteristics lose their significance since they cannot be related through oil-base mud core data to the porosity and connate water values found in reservoirs. Methods used to obtain reliable porosity data will not be discussed; however, care should be exercised in selecting samples for measurement. In homogeneously porous formations, small core plugs sampled frequently will furnish adequate information. Where heterogeneity, particularly vugginess, is present, large-core porosity data may be required; in such reservoirs a suite of capillary pressure samples may be selected from small plugs. CAPILLARY PRESSURE Capillary pressure data provide a method for relating two carbonate reservoir parameters, porosity and connate water saturation, which in turn permit delineation of productive rock types necessary for selecting the third parameter, productive thickness. Specific applications of capillary pressure data to petroleum reservoirs were suggested by Archie8 and Pur-cell."' Their work demonstrated that in preferentially water-wet rock, porc

Jan 1, 1958

By L. Wahl, M. Allard, B. Trentini

REMOVAL of sulfur in steelmaking is presently a problem of utmost importance as requirements on final sulfur contents in finished steels become increasingly strict. This is in spite of often increased sulfur contents in the fuels used during the different stages of steel processing. According to local conditions or current economic factors, sulfur can be removed during one or more of the processing operations; for instance, in a blast furnace operated under high temperatures and with a high slag basicity ratio and also by means of high inputs of manganese into the burden. These methods of proceeding are, however, expensive and in contradiction with the acid practice which is gradually being developed owing to the fact that it allows coke and lime savings and usually permits an increase of productivity. In the melting-shop, desulfurization can proceed in the open-hearth or electric furnace with one or several very basic slags, or with special prefused slags (Perrin process) mixed with steels poured from the open-hearth, electric furnace, or converter. Liquid pig iron has also been treated separately before being used in the melting shop, in order to reduce high sulfur contents. This external desul-furization has been developed in Europe for the basic Bessemer Thomas process, which is again in favor owing to the great flexibility of such installations and to the fact that the steel produced is not polluted by impurities coming from the scrap. Since the basic Bessemer process, as usually practiced, has a low desulfurizing power, external desulfurization is generally carried out in ladles by means of alkalies such as soda ash. This method, which has the advantage of being simple and costing little, has only a medium desulfurizing power, which implies the necessity for repeating the operation several times when a substantial amount of sulfur has to be removed or when very low sulfur contents are desired. Thermal losses are high and there is a considerable decrease in output. Moreover, the resulting fluid and corrosive slag, which is extremely difficult to eliminate, attacks the refractory linings of the mixers and steel furnaces. Therefore, it seems necessary to devise a simple method for external desulfurization which would not only remove substantial quantities of sulfur from the hot metal coming from an acid blast furnace, but which would also bring the sulfur contents down to the low level required in the making of high quality steel and iron. Principle of the Process In this paper a new method will be described for desulfurizing hot metal. It has been perfected by

Jan 1, 1958

By W. N. B. Armstrong

CORROSION of metals, for the purpose of this talk, may be divided into two general classes, namely, atmospheric and chemical. Atmospheric corrosion is caused by the natural agents -water, air, salt, and temperature -as well as by the agents arising from industrial operations which pollute the atmosphere. Chemical corrosion affects metals in refineries and chemical plants where severe conditions exist due to .acids, alkalies, salts, solvents, gases, ?steam, etc. A special condition is encountered on road equipment and motor vehicles due to the large amounts of corrosive salts which are used on our roads in the winter. Exposure to corrosive conditions such as those referred to above causes metal to be destroyed and, therefore, it has to be protected. The non-metallic or organic coatings used to protect the metal are themselves destroyed ultimately by these same conditions. Since all types of organic coatings do not have the same kind and degree of resistance to degradation, a particular kind of -coating must be used for a particular set of conditions in order to obtain the maximum benefit. In ?addition to the above mentioned agents, organic coatings are degraded ?by sun-light, which is probably the severest single factor in the breakdown of organic coatings exposed outdoors. We can divide organic coatings, in a general way, into the following classes: (1) Conventional coatings, and (2) Special coatings.

Jan 1, 1958

By R. D. Russell, R. M. Farquhar

SOTOPIC tracers have become an important aid in following the progress of chemical processes in the laboratory. It has recently been found possible to utilize a system of naturally existing iso-topic tracers to obtain information about the geological history of lead ores. Common lead, such as is found in lead deposits, is a mixture of four stable isotopes having atomic weights 204, 206, 207, and 208. Of these, the last three are identical with the lead isotopes produced as stable end products of the radioactive decays of uranium and thorium: the first, lead-204, is not known to be produced on the surface of the earth by any process. Since uranium and thorium Occur in the surface regions of the earth in amounts comparable with lead, and since the half-lives of uranium and thorium isotopes are of the same order as the age of the earth, they produce the radiogenic lead isotopes in amounts comparable to the amount of nonradiogenic lead present. Every significant exposure of a sample of lead to uranium and thorium will therefore lead to the permanent alteration of the lead isotope ratios in that sample. It is this unique property of lead that serves as a means of tracing the history of a lead sample in terms of its contacts with the radioactive elements. If lead from a lead mineral has been analyzed with a mass spectrometer, the measured isotope ratios are determined entirely by the isotope ratios of primeval lead, which are identical for all minerals, and by the particular history of the sample. It follows that for samples from any particular geological area, observed differences in the isotopic composition are enough to distinguish different geological histories. An illustration of the qualitative application of this statement is given in Table I by analyses of some galenas from the western Cordillera. Samples from deposits in Pre-Cambrian sediments have very different lead isotope ratios from those of the ores in the Paleozoic sediments. Although the two types are associated closely geographically, it is apparent that they have had quite different histories and have probably been emplaced at quite different times, as the ideas outlined in the following section suggest. Even when applied quantitatively, a lead isotope analysis can never indicate a unique history of any lead sample. However, it greatly restricts the choices available and combined with other geological and geochemical data can lead to a much better understanding of the genesis of lead ores. General Character of Lead Isotope Variations: Early isotopic analyses of common leads by Nierl showed that geologically younger leads were generally richer in isotopes of masses 206, 207, and 208, with respect to that of mass 204. This regularity of measured lead isotope ratios can be easily observed by plotting each of the ratios Pb207/Pbm and Pb205/ Pb204 against the ratio Pb206/Pb204. In both graphs the points lie scattered closely about a well defined mean curve. It was immediately supposed that this regularity resulted from the growth of all leads from a common primeval lead present at some time, To, early in the earth's history. Lead in the outer part of the earth would become continually enriched in the radiogenic isotopes as a result of the uranium and thorium intimately associated with it. The subsequent extraction of some of this lead and formation of a lead mineral free of the radioactive parents provide samples of lead existing in the earth at the time of mineralization, T. Younger leads in general will be richer in the radiogenic isotopes because they have been associated with uranium and thorium for a longer time. Then lead ratios would be given by the formulae: (Pb206/Pb204)YTPb^/Pb204) +f "(u201) kdt T (Pb207Pb204)r = (Pb208/Pb204)T0 + J (U295/Pb204) k' dt T (Pb208/Pb204) t = (Pb208Pb204 + J (Th204) A." dt [1] where A, A', and A" are the decay constants of U238, U285 and Th232. Summaries of measurements of radioactivity of surface rocks, such as given by Faul,2 are of limited

Jan 1, 1958