Search Documents

By E. H. Kelton, R. D. Grissinger

E. E. Schumacher.*—DO YOU control the humidity in your test room? What effect does the environment have on your results? E. H. Kelton.—We do not attempt to control the humidity. As a matter of fact, the humidity in the beam tests that were conducted in a constant-temperature room varied widely and, as far as we know, there is no effect. The tension tests were conducted largely in an oil bath. I suppose there would be an effect in highly corrosive atmospheres, sufficiently corrosive to notch the specimen; otherwise, I would say none. E. A. Anderson.*—The effect of the humidity on the corrosion of zinc does not become important until the relative humidity is 70 per cent. At that point the corrosion products are capable of absorbing moisture and the corrosion rate increases. Below that point corrosion is almost imperceptible. This does not take into account any effect due to stress. That may be important. E. E. Schumacher.—Recently 1 have become very conscious of the enormous effect that surface films can exert on the physical properties of certain alloys. Shortly, we are publishing an article in which it will be shown that the fatigue endurance of some lead alloys can be changed markedly by merely changing the type of film placed on their surfaces. Changes as great as tenfold were observed. These findings make me wonder whether in your creep test you might not obtain quite variable results, depending upon the type of liquid medium used to immerse your specimens. Did you use more than one type of oil and, if you did, what were your results? E. H. Kelton.—I think we have used no more than three different oils, and we could not see any difference in effect.

Jan 1, 1945

By T. R. Graham, R. G. Feustel, J. R. Long, R. S. Dean

The comprehensive study of the copper-manganese-zinc alloy system in the Bureau of Mines Laboratories has so far been principally concerned with alloys that lie within the alpha solid solution field of the system. Two regions, one centering about 65 per cent copper, 10 manganese and 25 zinc, and the other centering about 70 per cent copper, 20 manganese, 10 zinc, have been carefully examined. These have indicated that when the alloys are made with electrolytic manganese considerable amounts may be readily introduced and that the strength and hardness are increased without excessive losses in ductility. In the course of the work of establishing the limits of the alpha solid solution range,3 enough of certain of the alloys was prepared to permit determination of their- physical properties at a future date. The 60 per cent copper alloys concerned here are part of that series. They cross through the alpha field and into the adjacent alpha plus beta and alpha plus X fields, and are of interest because they offer some information on the effects of manganese on alloys lying in these fields. Composition and Fabrication of Alloys The chemical composition of the alloys involved is given in Table I. They were intended to contain 60 per cent copper with manganese increasing from 5 to 25 per cent in 5 per cent steps and zinc decreasing from 35 to 15 per cent. The analyses are so close to the intended composition that the alloys mill be referred to hereafter by their norninal compositions. They were finished into sheet by cold-rolling and intermediate annealing procedurzs calculated to produce sheet $i6 in. thick, cold-reduced by 20, qo, 60, and 80 per cent in thickness. Physical properties were determined on standard flat tensile specimens with 4-in. gauge length, although the test gauge section used was 2 in. The properties were obtained on cold-worked material and on material annealed at temperatures ranging from 700' to r500°F. after 60 per cent cold reduction. Since an annealing temperature of 1200°F.

Jan 1, 1946

By J. R. Long, T. R. Graham, R. G. Feustel, R. S. Dean

The comprehensive study of the copper-manganese-zinc alloy system in the Bureau of Mines Laboratories has so far been principally concerned with alloys that lie within the alpha solid solution field of the system. Two regions, one centering about 65 per cent copper, 10 manganese and 25 zinc, and the other centering about 70 per cent copper, 20 manganese, 10 zinc, have been carefully examined. These have indicated that when the alloys are made with electrolytic manganese considerable amounts may be readily introduced and that the strength and hardness are increased without excessive losses in ductility. In the course of the work of establishing the limits of the alpha solid solution range,3 enough of certain of the alloys was prepared to permit determination of their- physical properties at a future date. The 60 per cent copper alloys concerned here are part of that series. They cross through the alpha field and into the adjacent alpha plus beta and alpha plus X fields, and are of interest because they offer some information on the effects of manganese on alloys lying in these fields. Composition and Fabrication of Alloys The chemical composition of the alloys involved is given in Table I. They were intended to contain 60 per cent copper with manganese increasing from 5 to 25 per cent in 5 per cent steps and zinc decreasing from 35 to 15 per cent. The analyses are so close to the intended composition that the alloys mill be referred to hereafter by their norninal compositions. They were finished into sheet by cold-rolling and intermediate annealing procedurzs calculated to produce sheet $i6 in. thick, cold-reduced by 20, qo, 60, and 80 per cent in thickness. Physical properties were determined on standard flat tensile specimens with 4-in. gauge length, although the test gauge section used was 2 in. The properties were obtained on cold-worked material and on material annealed at temperatures ranging from 700' to r500°F. after 60 per cent cold reduction. Since an annealing temperature of 1200°F.

Jan 1, 1946

By C. H. Curtis

The valuable mineral content of the current feed to the Miami concentrator is as follows: copper, 0.7 pct total; molybdenum, 0.01. Flotation of this ore yields a sulphide concentrate containing: chalcocite, 44 pct; molybdenite, 0.5; pyrite, 50.0; insol, 5.5. A combination of potassium ethyl xanthate and pentasol amyl xanthate as collectors, and pine oil as frother, are used in this flotation. Rejection of pyrite is encouraged by holding the amount of collectors used to the minimum consistent with copper recovery and by operating at high alkalinity (equivalent to 0.35-0.40 lb CaO per ton solution of pH 11.0).

Jan 4, 1950

By R. G. Ward, A. E. El-Mehairy

A technique was developed to calculate the density of liquid metals from the profile of a weighed levitated drop obtained by emitted light photography and calibration. The density of liquid copper was determined over the temperature range 1370" to 2100°K and expressed with the equation: The molar volumes and thermal coefficients of expansion are calculated. Copper, upon melting, was found to expand 3.34 pct. A knowledge of the density of liquid metals is essential as it is a parameter appearing in most theories of the liquid state. The liquid density is also necessary for the calculation of the commercially important contraction occurring on solidification. Unfortunately good density values are rarely available and the present work was undertaken to establish a new method of density determination free from the limitations of the existing methods. For liquid metals with high melting points, the variation and the limited number of density values reported in the literature have been caused primarily by difficulties in technique, a matter which has been adequately discussed by Urbain.' In all the methods used for measuring the density of the high-melting liquid metals there are sources of error, and corrections have to be made. For example, in the method of balanced columns, the formation of gas bubbles in one or both arms was a great source of error. In the pyknometer3 and immersed-sinker methods, corrections of certain volumes for thermal expansion to the operating temperature exceed 4 pct. In the maximum-bubble method5 a correction for the thermal expansion of the bubble-tube is used (about 1.6 pct); a second correction takes into account the change in the volume of liquid displaced by the bubble-tube (about 3.5 pct). Another method used is based on the shape of a drop of liquid, at rest on an inert refractory plaque, obtained photographically or radiographi-cally. The volume is calculated from the shape, which is sensitive to the surface tension and supporting material, by some intricate empirical relation. The drop contour changes with 90 deg rotation of the support.7 The application of all methods is limited by reaction between liquid metal and the apparatus. The successful stabilization of a mass of liquid metal during levitation melting8 afforded a technique for measuring the density of liquid metals out of contact with solid materials. The technique was developed by using copper as the density of liquid copper has already been studied extensively, thus allowing comparison with the new method. It consists of calculating the volume from the dimensioned profile of the levitated drop obtained by emitted-light photography and careful calibration. The molten egg-shaped drop spins around the magnetic axis of the coil (lined vertically) at a speed which seems to increase with increasing temperature. The method does not involve corrections and the experimental setup allows the use of vacuum or special atmospheres. The maximum operating temperature is limited by excessive evaporation of metal from the droplet. EXPERIMENTAL Levitating System. A stabilizing ring was used in conjunction with a 3-turn levitating coil energized by a 450-kc per sec, 10-kw Toccotron with a high current-low voltage output stabilized to f 1 pet.' APyrex glass tube with a Pyrex Optical flat window inserted through the coil and ring allowed the use of special atmospheres during levitation melting, as shown in Fig. 1. Optical System. Fig. 1 shows the optical arrangement used to photograph the profiles of the drop, parallel and perpendicular to the vertical spinning axis, simultaneously on the same frame of a high-speed 35-mm film. The optical system was adjusted to avoid any distortion of the profiles and to ensure that both profiles are in focus. The length of path from object to objective was about 30 cm, and a magnification factor close to 1 was obtained with the single-lens reflex-camera system. Temperature Measurement and Control. In operation, the specimen temperature was constant to 5 C for a fixed power input to the levitating coil and fixed rate of gas flow through the tube. The temperature was measured by an automatic two-color pyrometer (Coloratio) checked at the melting

Jan 1, 1963

By C. H. Mathewson

ABOUT fifty pages of Henry M. Howe's profound treatise, "The Metallography of Steel and Cast Iron," are devoted to twinning with special reference to the origin, nature and general significance of the Neumann bands in ferrite. Howe believed with Osmond and Cartaud1 that the Neumanns are mechanical twins and his careful observations leave no doubt that these straight-sided narrow bands habitually occur parallel to trapezohedral planes of form {211}. Attempt's to develop the structure of the bands by various methods so that their identity could be established beyond question have not been conspicuously successful. Howe thought that they deflected slip bands. Some of the etching figures which have been developed within and adjacent to Neumann bands support the contention that they are twins. A good example of this effect in ferrite containing 0.6 per cent. of nickel and 1.3 per cent. of phosphorus, originally due to Harnecker and Rassow,2 was reproduced in. the 1928 lecture before the Institute of Metals Division on twinning in metals.3 In this case, the sides of the figures might represent the traces of cubic planes laid bare by etching a properly oriented grain of ferrite, twinned along a plane of form {211}. Our own observations in this direction may be represented by Fig. 1 which shows in a deeply etched cavity in the boundary region between a Neumann band and the original crystal two small crystal surfaces which resemble the faces meeting at a reentrant angle in the simple cube twinned along a bisecting plane of form {211} as sketched in Fig. 2.

Jan 1, 1928

By L. H. Dushak

DURING the war period of quicksilver activity there were a number of departures from what may be termed the classical quicksilver metallurgy. Attempts were made to beneficiate low-grade ores by gravity concentration and flotation; mechanical furnaces began to replace the Scott furnace and the vertical coarse-ore furnaces, and condensers of sewer tile and redwood tanks were used in place of the older brick and stone condensing chambers. Other developments that have occurred during the current period of quicksilver, activity are mainly in the nature of improvement and further refinement of those started during the war period. Each period of quicksilver activity has been accompanied by the proposal of various new processes, including wet methods for the treatment of quicksilver ores and innovations in furnaces, retorts and condenser equipment. As far as the author knows, nothing of economic significance in the way of "new processes" has been developed. There is in fact no real need for any essentially new process for the treatment of quicksilver ores; the direct furnace treatment is simple and inexpensive. Moreover, with fare exceptions, the quicksilver industry has no complex or refractory ore problems corresponding to those which are receiving more and more attention from metallurgists in other branches of the nonferrous field. Under these conditions improvements in quicksilver metallurgy must be looked for through the adaptation of current developments in engineering and metallurgy generally to the particular needs of quicksilver practice rather than through the invention of new processes.

Jan 1, 1930

By Warren B. Weeks

The development of the relatively deeper fields discovered during 1937 helped build the 1938 production to 18,456,760 bbl., an increase of 6,295,910 bbl., or 51.6 per cent over 1937, and the largest production for south Arkansas since 1930. Schuler and Rodessa accounted for the increased production as well as for over half of the wells drilled in the state. There were 243 holes drilled during 1938, of which 200 were completed as oil or gas wells. Of the 29 wildcat wells completed, 25 were dry, 3 found oil in the Smack-over limestone, while 1 made a small oil well in the Nacatoch sand. This was less than half the number of wildcats drilled the previous year, but nearly twice as many field wells were drilled. The old depth record of 7973 ft. was exceeded twice during the year, with the present record of 8332 feet. Trend of Prospecting The porous "Reynolds" oolite of the Smackover limestone1 has been the object of most of the wildcat prospecting during the past two years. Seismograph work, which brought 22 crews into this area during 1938, was largely pointed toward a study of the structure of this limestone formation. Thirteen dry wildcats have been drilled to this formation and five pools have been opened in it since it was first found to be productive at Snow Hill in the spring of 1936. With the failure of "updip" prospects to produce, activity moved southward and basinward. Success in five instances in Columbia and south Union Counties has spurred activity in this area. Much of the acreage is under lease and half a dozen deep limestone tests are assured for the current year. Fig. 1 shows the location of the principal oil fields in south Arkansas, as well as one or two minor producing areas. The fields are numbered in the order of their discovery. It is shown that most of the recent discoveries are from the deeper formations. Dry wildcats that penetrated

Jan 1, 1939

By Warren B. Weeks

The development of the relatively deeper fields discovered during 1937 helped build the 1938 production to 18,456,760 bbl., an increase of 6,295,910 bbl., or 51.6 per cent over 1937, and the largest production for south Arkansas since 1930. Schuler and Rodessa accounted for the increased production as well as for over half of the wells drilled in the state. There were 243 holes drilled during 1938, of which 200 were completed as oil or gas wells. Of the 29 wildcat wells completed, 25 were dry, 3 found oil in the Smack-over limestone, while 1 made a small oil well in the Nacatoch sand. This was less than half the number of wildcats drilled the previous year, but nearly twice as many field wells were drilled. The old depth record of 7973 ft. was exceeded twice during the year, with the present record of 8332 feet. Trend of Prospecting The porous "Reynolds" oolite of the Smackover limestone1 has been the object of most of the wildcat prospecting during the past two years. Seismograph work, which brought 22 crews into this area during 1938, was largely pointed toward a study of the structure of this limestone formation. Thirteen dry wildcats have been drilled to this formation and five pools have been opened in it since it was first found to be productive at Snow Hill in the spring of 1936. With the failure of "updip" prospects to produce, activity moved southward and basinward. Success in five instances in Columbia and south Union Counties has spurred activity in this area. Much of the acreage is under lease and half a dozen deep limestone tests are assured for the current year. Fig. 1 shows the location of the principal oil fields in south Arkansas, as well as one or two minor producing areas. The fields are numbered in the order of their discovery. It is shown that most of the recent discoveries are from the deeper formations. Dry wildcats that penetrated

Jan 1, 1939

By R. E. Collins, Paul B. Crawford

Mathematical equations have been derived to show the effect of the slippage phenomomenon (Klinkenberg effect) on unsteady-state gas flow through porous media. The assumption is made that the slippage may be represented by an equation of the type It is pointed out that most of the existing data on unsteady gas flow may be corrected for slippage by a simple change in definition of the dimen-sionless groups. INTRODUCTION Several solutions to the various problems associated with the unsteady-state flow of gas through porous media have been recently presented in the literature.','" The cited publications have resented solutions for flow under ideal conditjons. The principal assumptions involved include: (a) the density of the gas obeys the perfect gas law; (b) the viscosity of the gas is constant; and (c) the gas permeability is constant. Few, if any, actual gases under reservoir conditions are believed to conform with the above, but the ideal solutions do provide the basis for making improved estimates on the performance of gas reservoirs. The purpose of this paper is to show the performance characteristics when assumption (c) is corrected for the slippage phenomenon or the Klinkenberg effect. This is believed to be a step nearer to reality. MATHEMATICAL DEVELOPMENT Case 1. Gas Flow — Ideal Conditions The equations describing the flow of gas under ideal conditions have been clearly presented in the cited literature; however, for completeness of this work they are repeated here. The basic differential equation describing the flow of gas is Equation (6). It may be derived as follows: The continuity equation, the perfect gas law and Darcy's law are combined to give: Manuscript received in the Petroleum Branch office Aug. 3, 1963 or If — is constant, Equation (5) is rewritten to form the basic Equation (6). or for the linear case A dimensionless equation is obtained by dividing through by (pl)z and making the substitutions shown below: The resulting equation is A similar procedure for the radial case leads to the following equations: where and Equations (11), (12), and (13) are those used by Bruce, et al., and Jenkins and Aronofsky for their computational work.

Jan 1, 1953

By O. Lietard, J. Yvon, R. Mercier, J. F. Delon, J. M. Cases

INTRODUCTION Fineness is one of the main characteristics of powders and this parameter is the object of several definitions based on criteria connected with their uses as well as their determination methods. In trying to obtain the best reaction surface, fineness is characterized by the determination of the specific surface, but in other cases, particle size analysis is used. These two main methods are not, in fact, entirely independent and their complementary nature provides information concerning the morphology of the particles. In the case of a product formed by isodimensional spheres, the relationship between the specific surface and the diameter is well known: [S = 6 spd] where p is the specific weight of the material and d the diameter of the spheres. With no monodimensional spheres, but rather a granulometric distribution whose occurrences follow a mathematical law (1), the relationship is more complicated. The relationship between the specific surface measured by gas adsorption and the data of the particle size analysis is much more difficult to predict in the case of asymmetric porous particles, whose particle size distribution curves do not correspond to a known statistical law.

Jan 1, 1980

By Michael R. Cartwright

The Gold Acres outcrop was located by Lee Lakin in 1922, according to Mr. H. W. Treweek. There was no activity, however, until 1935, when prospect drifts and pits penetrated the deposit. It was then drilled by the Willow Creek Mining Company. Beginning in the late 1930s and continuing to the late 1940s more than 150 churn drill holes were drilled in the Gold Acres area. From this drilling came what is now known as the London Extension pit. Only oxidized ore amenable to cyanide vat leaching was mined during this time. Our records indicated that this period of mining removed some 1.4 Mt (1.5 million st) of ore at an average grade of 0.006 kg/ t (0.2 oz per st). Union Pacific and Newmont Mining Company worked in the area prior to acquisition by the Cortez Joint Venture. Union Pacific drilled a number of core holes in the area. The unoxidized nature of the ore, small tonnage, and low grade undoubtedly prevented mining at this time. From these indications of mineralization shown by previous companies, the Cortez Joint Venture developed and mined 2 Mt (2.4 million st) at 0.005 kg/t (0.15 oz per st) in the Gold Acres pit. This pit is located immediately southwest of the older London Extension pit. Cortez Gold Mines has continued to drill to the west and south of these pits along the downdip continuation of the former ore bodies. The downdip extension is unoxidized and more metallurgically difficult than the normal Carlin type ores, but, more than 2.4 Mt (2.7 million st) have been outlined. It depends now upon the gold price and milling costs to turn this mineralized area into an ore body. A possible lesson to be learned from this deposit is that continued mining success depends upon an ongoing adequately funded exploration-development-metallurgical research program. These three disciplines must always be present to locate the mineralization and to turn this mineralization into ore. [ ]

Jan 1, 1985

PRESIDENT WILLIAM L. SAUNDERS,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES F. RAND,1 NEW YORK, N. Y. BENJAMIN B. THAYER,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT PHILIP N. MOORE,1 ST. Louis, Mo. TREASURER GEORGE C. STONE,' NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, : NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON, . . . NEW YORK, N. Y.

Jan 5, 1915

PRESIDENT WILLIAM L. SAUNDERS,1 NEW YORK, N. Y. PAST PRESIDENTS CHARLES F. RAND,1 NEW YORK, N. Y. BENJAMIN B. THAYER,2 NEW YORK, N. Y. FIRST VICE-PRESIDENT PHILIP N. MOORE,1 ..... ST. Louis, Mo. TREASURER GEORGE C. STONE,' NEW YORK, N. Y. SECRETARY EMERITUS , ROSSITER W. RAYMOND, NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 7, 1915

By Gail F. Moulton

In spite of an increase of 7 cents per barrel in the posted price of oil for the Panhandle field effective June 16, 1943, there was less drilling during 1943 than ir, any of the several previous years. The drilling statistics are compiled as Table 2 and show the material increase in the percentage of the total number of field wells completed as dry holes. This increase suggests that the productive area of the field is largely drilled up on the well-spacing pattern now followed and that new discoveries will be required to permit any important new activity in the area. The fact that only four wildcats were drilled in the area during the year indicates that some new prospecting technique or some ncw point of view is required to stimulate exploration. No new producing areas were discovered during 1943 and no additions to oil reserves were made through extensions or discovery 'of new pays. Accordingly, the proven reserves in the area declined by the amount of the production, or nearly 31 million barrels. These results of drilling are similar to those obtained during 1942, whcn no new oil areas were discovered as a result of wild-catting, a total of five wildcat wells in 1942 resulting in four failures and one gas-fieid discovery of undetermined merit. sion. The number of oil-producing wells reported by the Commission increased during the year by 163 to a total of 5576 as of December.

Jan 1, 1944

By Gail F. Moulton

In spite of an increase of 7 cents per barrel in the posted price of oil for the Panhandle field effective June 16, 1943, there was less drilling during 1943 than ir, any of the several previous years. The drilling statistics are compiled as Table 2 and show the material increase in the percentage of the total number of field wells completed as dry holes. This increase suggests that the productive area of the field is largely drilled up on the well-spacing pattern now followed and that new discoveries will be required to permit any important new activity in the area. The fact that only four wildcats were drilled in the area during the year indicates that some new prospecting technique or some ncw point of view is required to stimulate exploration. No new producing areas were discovered during 1943 and no additions to oil reserves were made through extensions or discovery 'of new pays. Accordingly, the proven reserves in the area declined by the amount of the production, or nearly 31 million barrels. These results of drilling are similar to those obtained during 1942, whcn no new oil areas were discovered as a result of wild-catting, a total of five wildcat wells in 1942 resulting in four failures and one gas-fieid discovery of undetermined merit. sion. The number of oil-producing wells reported by the Commission increased during the year by 163 to a total of 5576 as of December.

Jan 1, 1944

By R. L. Klueh, W. W. Mullins

During the course of a study on the periodic precipitation (Liesegang phenomenon) of water vapor bubbles in solid silver, some interesting observations were made concerning the formation and growth of these bubbles. Under certain conditions it was found that the bubbles which formed in the single crystals led to the formation of large blisters ad cracks, and when poly crystalline specimens were used grain boundary cracking was observed. These two phenomena were examined in some detail, and it was found that an important step in the formation of the blisters and grain boundary cracks was the impingement of neighboring bubbles. DURING the study of Liesegang precipitation in solid silver,' some interesting observations were made concerning the formation and growth of water vapor bubbles. The bubbles were formed by annealing oxygen-saturated silver in hydrogen. Because of the similarity of this phenomenon to the hydrogen embrittlement of tough pitch copper,' it is known in the literature" as the hydrogen embrittlement of silver. In some respects it appears that the hydrogen embrittlement of silver is similar to the processes of hydrogen attack of steel5 and blister formation.' Hydrogen attack results from the high-temperature reaction of hydrogen with dissolved carbon or carbides in the steel to form methane (usually at grain boundaries). Blister formation occurs in steel and other materials as a result of hydrogen produced by corrosion, pickling, and so forth. Because of these similarities, some speculations were made concerning these other processes. EXPERIMENTAL PROCEDURE Water vapor bubbles were formed in 99.999+, 99.99+, and 99.9 pct Ag by annealing in a partial pressure of oxygen (pq) until saturated and then in a partial pressure of hydrogen (pH,). The hydrogen diffuses into the silver and reacts with the dissolved oxygen to form water vapor which precipitates in the form of bubbles. The specimens were then sectioned, silver-plated, mounted in cold-setting plastic, ground and polished through a preliminary polishing, and finally chemically polished.' The bubbles were visible without etching.

Jan 1, 1969

By A. W. Schlechten, Ernest J. Breton Jr.

Experiments on the separation of copper and zinc ions by selective action of ion exchange resins showed the carboxylic type to be more effective than the sulphonic resins. The latter demonstrated a greater capacity over a wider pH range. Data show the effectiveness of resins as a means of concentration. IN recent years the restrictions of stream pollution laws and the high price of metals have created an interest in ion exchange as a means for metal recovery. Some applications have proved successful. In Germany during World War 11, 17 tons of copper per day were recovered from rayon mill wastes by means of ion exchange resins;' and for some time in this country a large ion exchange unit has been in operation for the recovery of copper from rayon waste water. The possibilities of applying ion exchange to the recovery of metals occurring in plating rinse water is particularly promising. In most of these applications only the metal being recovered occurs in the waste. The ion exchange resins act merely as a means of concentrating the metals to a point where they can be recirculated. It would be highly desirable to use ion exchange as a means of not only concentrating but also of separating metals. With the exception of the impressive separations accomplished in connection with the atomic energy program, very little has been done on metal separations.' Therefore, an investigation was undertaken at the Missouri School of Mines and Metallurgy to determine if either of the two main types of ion exchange resins could be used to separate metal ions in solution. The selective removal of copper ions from a mixture of copper and zinc on carboxylic and sulphonic-type resins was investigated as a function of flow rate, pH, copper-zinc ratio, and concentration. It was shown that zinc can be separated from copper and that very large ratios of concentration can be obtained using ion exchange resins. Since ion exchange is relatively new to the field of metallurgy, a brief review of the subject will be included. Theory of Ion Exchange A comprehensive theory for ion exchange has not been developed as yet, but the mechanisms are analogous to metathetical reactions: R Na + Cu++ *=? K(SO3)2 Cu + 2Na+ R is the designation for the ion exchange resin. If a copper solution is passed over a resin bed in the sodium form, two ions of sodium will be released for every ion of copper removed. For the most part this reaction follows the laws of mass action and of electrical neutrality. Consequently, if an excess of sodium ions is passed over a bed containing copper, the reactions will be reversed, and the resin will be regenerated to its original form. A few empirical rules governing the exchange reaction have been set forth: 1—In general ions with a high valence will replace ions with a lower valence. 2—Ions having higher activity coefficients have a higher replacement potential. 3—In a series of mono-valent ions, those with the smallest radii of hydra-tion will tend to replace those having larger radii of hydration. 4—Where ions are similar in most respects, those with the higher atomic weight sometimes will take precedence. This last rule is not as definite as some of the others. These rules apply to rather dilute solutions at moderate temperatures and assume all ions to be present in about equal concentrations. Higher concentrations and temperatures may in some cases reverse the normal exchange reactions. Ion exchange materials are unique in that their efficiency increases as the concentration of the solution decreases. For many exchangers, most efficient operation is obtained at concentrations in the order of one thousandths of a percent. Most applications, though, are made in solutions containing considerably higher concentrations than this. Coste9 as shown that ion exchange resins will remove aluminum and iron effectively' from solutions of up to 10 pct chromic acid. Ion Exchange Resins Ion exchange resins are insoluble, porous, resinous structures to which active groups have been attached. Active groups such as (—SO,,)- and (COO)- pick up cations; hence structures saturated with groups such as these are called cation exchangers. Structures saturated with groups such as (—NH,)' which pick up anions, are referred to as anion exchangers. The resinous structure of necessity is resistant to strong acids, bases, oxidizing, and reducing agents, and most of the common organic solvents. An idea of the stability can be gaged from the fact that resins last for many years under constant use without detectable chemical or physical breakdown. The ion exchange reaction is not confined to the surface of these synthetic resins. Its porous structure permits active groups in the center of a particle as well as those on the surface to remove ions. A high capacity resin such as Amberlite IR-120 will remove up to 3.3 lb Cu per cu ft of resin. In this investigation several approaches to the problem of separating copper from zinc by ion exchange were considered. First, if a reagent could be found which would complex one of these metals and not the other, then by passing this reagent through a bed of exchanger containing copper and zinc, the

Jan 1, 1952

By Claude P. Heiner, Carl S. Westerberg

OBSERVATION of the clinkering action of coal from the Castle Gate D seam in underfeed stokers over a period of years has given rise to the present investigation of the effect of bony coal on clinkering. Some very costly examples of slagging clinkers in particular cases have been of especial interest to the authors. In such cases coal analyses and ash-softening and fluid temperatures have been found of little value. In general, it was noted that slagging was accompanied by a somewhat higher ash content of the stoker slack, and the suspicion naturally arose that foreign matter was the troublemaker. One would naturally suspect bony coal and rock impurities because of their occurrence and prevalence within the seam and the relative absence of sulphur or other impurities in the coal mined. The test results given herein indicate that the concentration of the bony coal and rock impurities in the coal determines the clinkering tendencies of the ash during combustion. CASTLE GATE D SEAM Extending from the Utah-Colorado line near Grand Junction, Colo., westward to Greenriver, Utah and thence in semi-circular form north and westward to Castle Gate, and from there southward to Mt. Hilgard in central Utah, is a line of nearly perpendicular cliffs, composed of interbedded massive sandstone and shales, making up the coal-bearing horizon of the Mesaverde formation of Upper Cretaceous age. The cliffs face roughly concentrically toward the south and southeast and the strata, with conformably enclosed coal beds, gently dip away from the face of the cliffs and at right angles to their front line. Back of these cliffs the mountain masses rise to an altitude of from 8000 to 10,000 ft. above sea level. Stretching away from their foot is a great shale plain, on which the towns are situated and over which the railroad lines and highways run. The Castle Gate mines enter the coal beds at their outcrop; the workings extending within a particular coal bed away from the outcrop and under the mountain mass back from the cliff line (Fig. 1). Throughout the Mesaverde formation in the Castle Gate general area, there are from two to five workable coal beds. Usually not all of these are coincidentally of workable size and merchantable quality throughout any given large tract. In the Castle Gate mine area, the base of the Mesaverde horizon and coal measures is marked by a massive, cliffmaking, gray sandstone bed 6o to 8o ft. thick. Locally this is referred to as the "Castle Gate sandstone floor." Frank R. Clark, in U. S. Geol. Survey Bull. 793, designates it as the "Aberdeen sandstone." At Castle Gate the various coal beds are designated by the letters A, B, C, etc., commencing with the lowest bed. Fig. 2 is a graphic generalized vertical section, compiled from physical exposures

Jan 1, 1941

By R. A. Garling

INTRODUCTION Since the infancy of in situ uranium mining, a growing number of hydrometallurgical processes have been incorporated into pilot and commercial scale flowsheets. Although initial design efforts were geared toward maximizing uranium recovery and minimizing plant and wellfield flow circuit maintenance, recent emphasis has shifted to improved means of water conservation and aquifer restoration. As mining units approached depletion, evaporation ponds reached minimum freeboard, and state and federal agencies demanded proof of groundwater restoration, processes including mixed bed and conventional ion exchange, reverse osmosis and electrodialysis were adopted by the industry. These units served the additional function of reducing process bleed flows during mining in states where the deep disposal well permitting ice remains unbroken. This report concerns the use of electrodialysis as an alternative to the more conventional processes used in in situ mining. In addition to a brief history and description of the process, a comparison to reverse osmosis and operational data derived from testing an Ionics, Inc. 1.31 x 10-3 m /s (30,000 gallon/day) unit at the Teton-Nedco Leuenberger Research and Development pilot will be presented. HISTORY Commercially practicable electrodialysis was contingent upon the development of synthetic ion exchange membranes in 1940's. In 1952, Ionics Inc. demonstrated that the process was amenable to the treatment of salt and brackish water and, in 1954, made their first commercial sale. The following decade saw several major electrodialysis unit sales which were generally targeted for use on private or municipal potable water treatment. Major increases in membrane desalting unit capacities, facilitated by technological advances in the reserve osmosis industry, were noted during the 1970's. The development of polarity reversing electrodialysis equipment which reduced feed pretreatment requirements, increased water recovery rates, and simplified unit operation, kept Ionics Inc. competetive in the water treatment industry. Engineering advances which incorporated automated equipment, non-corrosive construction materials, and improved ion exchange membranes allowed the electrodialysis process to compete in industrial waste treatment among other commercial markets. PROCESS AND APPARATUS DESCRIPTION The electrodialysis process utilizes direct electrical current passed across a stack of alternating cation and anion selective membranes in order to achieve an electrochemical separation of ionized materials in an aqueous solution. The membrane stack has the appearance of a plate and frame filter press and auxilliary equipment includes solution pumps, electrically actuated valves, filters, piping and a direct current power source. The ion separation membranes are thin sheets of synthetic cation or anion selective resins. Attaching sulfonate or quaternary ammonium groups to the cross linked copolymer structure determines the ion selectivity of the membrane. The membranes are separated from each other in the stack by non-conductive spacers that house flow channels which route the flow tortuously and parallel to the membranes. Direct electrical current passing perpendicularly to the membranes and solution passages attracts cations toward the cathode and anions toward the anode (Figure 1). As the ions from the feed stream pass through the ion selective membranes, they become concentrated in the adjacent brine channel and are retained there by the combined attractive force of the electrode and the repelling force of the next membrane toward the electrode. Limiting factors on the degree of demineralization possible include chemical solubilities in the brine flow and the current density that will produce an unacceptable degree of polarization (Figure 1). Feed or brine solution treatment with complexing agents or acids has been successfully applied to prevent membrane scaling. Polarization can occur when sufficient current density is applied to dissociate water in the ion depleted region of the diluting compartments near the membrane surfaces. Significant polarization is evidenced by large electrical resistances across cell pairs and notable pH differences between diluting and concentrating streams. Limiting current densities have been increased in U.S. manufactured equipment by utilizing tortuous flow paths of relatively high linear velocities thereby promoting continous solution mixing. Energy consumption is due to separating electrolytes and solutions, oxidation and reduction reactions occurring in electrode compartments, overcoming electrical resistance, conversion from AC to DC power, solution pumping and auxiliary equipment actuation. A major improvement to the basic electrodialysis process was applied in 1970 which resulted in frequent, automatic cleaning and descaling of membrane surfaces. The process, polarity reversal, incorporates alternating the cathode and anode on a periodic basis while exchanging product and brine flow channels via electrically actuated values. The reversal reduces the potential of stack plugging with CaCO3 (calcite), CaSO4 (gypsum), and colloidal materials and, in most waters, eliminates feed pre-treatment requirements. For approximately two minutes during and following the reversal, off spec. water is flushed to waste or reintroduced to the feed supply. The usual feed treatment on polarity reversing electro-

Jan 1, 1982