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By M. G. Benz, J. F. Elliott

A new type of solution calorimeter has been constructed to measure heats of mixing, enthalpy increments, and heats of fusion, formation, and reaction at temperatures above 1000°C. With it, measurements hove been made of the partial molar heats of mixing joy tin in the Cu-Sn system from 0 to 13 at. pet Sn at 1127°C and fir nickel in the Cu-Ni system from 0 to 9 at, pet Ni at 1200°C. The integral molar heat of mixing for the Cu-Sn system is strongly negative with a calculated minimum value corresponding to the composition Cu3Sn. The integrnl molar heat of mixing for the Czi-Ni system is slightly positive at these temperatures. These integral molar values have been measured with a probable error less than 30 cal per g-atom at an atom fraction of nickel or tin equal to 0.1. The estimated probable error for the Cu-Sn system is approximately 450 cal for a measured heat of solution of approximately 9000 cal. For the Cu-Ni system it is approximately 700 cal for a measured heat of' solution of approximately 60 cal. A new type of heat of solution calorimeter was designed and constructed to provide a more accurate experimental method for determining heat effects at high temperatures, (T > 1000°C). With it, partial molar heats of mixing, enthalpy increments, heats of fusion, and heats of formation and reaction for metal systems can be measured directly. Previously it has been necessary to rely upon the use of the dropping calorimeter or the van't Hoff equation applied to equilibrium data for this information. For the most part equilibrium data are scarce and difficult to obtain in many cases, and it has been necessary to rely upon the "method of mixtures" for the desired enthalpy measurements. An earlier study1 provides a prototype for this work. The "method of mixtures" as outlined by K. K. kelley,2 "consists of dropping the substance under investigation from a furnace, with controlled and measured temperature, into a calorimeter operating at or near room temperature.'' In this manner the change in the total heat content (enthalpy) of the substance between the temperature of the furnace and that of the calorimeter is determined. In order to determine high-temperature heats of mixing, enthalpy increments, and heats of fusion, formation, and reaction, it is necessary to take the difference between two such measurements, one before and one after the occurrence of the enthalpy change being studied. The desired enthalpy change is then the small difference between two large numbers. Small errors in the large numbers are included as large errors in this small difference. It is this difficulty that must be avoided for accurate measurement of the desired functions. The procedure with the new solution calorimeter consists of dropping the substance under investigation from a furnace, with controlled and measured temperature, into a solution calorimeter operating in the temperature range of 1000o to 1200°C. Measurements in the range of 1200" to 1600°C are planned for the future. By selection of the composition and

Jan 1, 1964

By W. A. Backofen, G. Mayer

Single crystals of iron, copper, and a Cu-7 wt pct A1 alloy were pulled through conical dies to simulate the constraint in a polycrystalline aggregate undergoing axisymmetric reduction. With Taylor-type hardening, dependence of the drawing stress, od, on the Taylor orientation factor, M, is predictable from the polycrystal stress-strain curve; in particular, for a power-law relationship, it should follow that d log od/d log M = (1 + n). A first-order agreement with analysis was found in the data from iron. For copper, the implied n from the observed d log od/d l°g M was -0, while for Cu-7Al it was negative. The trend was in the direction of random polycrystal behavior. Thus the idea of hardening only in response to the amount of prior slip loses validity as stacking fault energy (SFE) is lowered. Two possible explanations have been suggested: as stacking fault ribbons are widened, barriers from dislocation reactions become increasingly effective in dispersing slip and reducing the orientation dependence of the total glide strain dm that appears in alternatively, or conjointly, the polyslip shear stress, 7, acquires an orientation dependence of a kind which has the same leveling effect on M. The problem of relating the strain hardening of polycrystalline material to that of an isolated single crystal is still largely unsolved. In a new experimental approach from recent work, single crystals of different orientations have been deformed under the constraints found in an aggregate while measuring their deformation resistance. Procedures have involved drawing cylindrical crystals through conical dies1 and compressing slab-shaped crystals in plane strain.2'3 Predictions for the outcome of such experiments were made first by Taylor~ and later, in more general form, by Bishop and Hill.5'6 Taylor's example was the axisymmetric extension of an fcc crystal slipping on the usual {111}(110) systems or, equivalently, a bcc crystal undergoing 'kestricted" slip on {110}(111). In his solution, the deformation work supplied was equated to that dissipated internally in slip on all active systems. With o the single applied tensile stress, dc the resulting axial strain, and dyT the total glide strain on systems operating at resolved shear stress, 7: The orientation dependence of M was found by minimizing dyT for each orientation while activating five independent systems, Fig. l(a).? The Bishop and Hill analysis, based on a principle of maximum work, leads to essentially the same conclusion; the need for at least five active systems is recognized in the finding that either six or eight are actually brought into operation. The mean value from the entire stereo-graphic triangle in either case is M - 3.06. More recently, Hutchinson8 made a Taylor-type analysis for pencil glide in a bcc structure, from which piehlerg prepared Fig. l(b) as the counterpart in Fig. l(a); here M = 2.75. The obvious weakness in such analyses is the indifference to slip-system interactions. A condition of what might be termed "independent"

Jan 1, 1969

By Frank Milliken

IN September 1937, the Ohio Copper Co. inaugurated the treatment of its copper-bearing mill tailings at Lark, Utah. These tailings had been accumulated during the regular operation of the Ohio Copper mine and mill over the period 1007 to 1019. Gravity concentration had been employed except for a comparatively short period in 1919, when flotation was used. The ore milled during that period assayed about I per cent Cu. The chief copper mineral, chalcocite, was dissemi-nated in a shattered quartzite, mainly along fracture or cleavage planes. The quartzite gangue was extremely hard and grinding to liberation resulted in excessive sliming of the "sooty" chalcocite, with consequent high tailings losses. Recovery on the seven million tons treated was prob-ably less than 6o per cent of the total copper content. As early as 1918, attempts had been made to sample the dump. In 1928, a com-plete sampling program was undertaken. The sampling consisted of seventy-four 5-in. post auger holes drilled to the full depth of the dump at regular intervals of 250 ft. Each 10-ft. portion thereof com-prised a sample for analysis. Each sample was screened, rolled, divided into three parts, dried and assayed. The reject was retained for testing purposes. From the depth of the auger holes a contour map of the dump was plotted, Fig. 1, which gives percentages of tonnage and copper content.

Jan 1, 1940

By Alfred Brooks

Introduction PETROLEUM seepages are known in Alaska at four localities, all on Pacific seaboard. These, named from east to west, are Yakataga, Katalla on Controller Bay, Iniskin Bay on Cook Inlet, and Cold Bay on the Alaska Peninsula. Besides these, a petroleum residue has been found near Smith Bay on the north Arctic coast of the Territory. At Katalla, Cold Bay, and Iniskin Bay there has been some drilling for oil, and in the first field several productive wells have been opened up. Alaskan petroleum so far as its composition is known, is a refining oil, with paraffin base and low sulphur content. Most of what is known of the geology of Alaska oil fields is based on the investigations of Dr. George C. Martin, of the United States Geological Survey. A. G. Maddren, of the same service, has recently made a reconnaissance of the Yakataga oil field. The data to be here presented are chiefly taken from the following publications: G. C. Martin: The Petroleum Fields of the. Pacific Coast of Alaska, with an account of the Bering River coal deposits, Bulletin No. 250, U. S. Geological Survey, pp. 9 to 27 (1905). G. C. Martin: Geology and Mineral Resources of the Controller Bay Region, Alaska, Bulletin No. 335, U. S. Geological Survey, pp. 112 to 130 (1908). G. C. Martin and F. J. Katz: A Geologic Reconnaissance of the Iliamna Region, Alaska, Bulletin No. 485, U. S. Geological. Survey, pp. 126 to 130 (1912). A. G. Maddren: Mineral Deposits of the Yakataga District, Bulletin No. 592,. U. S. Geological Survey, pp. 143 to 147 (1914).

Jan 2, 1915

By G. H. Tausch, T. A. Huber

Very encouraging progress has been made ill the develop-ment of the permanent-type well completion which decreases considerable the cost of completions and workovers and aid-in the acquisition of reliable reservoir information at low cost. Completion and remedial operations are performed with tool,; which pass through the well tubing. Perforating and plug-hack operations can be done with the tubing in place and do not require pipe-handling equipment. Because of the many advantages afforded by this method, development work is going forward in anticipation of ultimately being able 10 use it to perform all usual well completion and workover operations. Effort is also being directed to the development of a more permanent type of lift equipment suitable for use with the permanent-type well completion. INTRODUCTION The permanent-type well completion in one in which the tubing and well-head are set in place only once in the life of the well and the completion or remedial work is performed through the tubing with a tubing-type perforator. a retrievable tubing extension. and other wire-line tools. This new type completion has made possible the saving of one to two days' rig time in the completion of each of several hundred wells During the last two years, and use of equipment developed for this type of completion has resulted in a 75 per cent reduction in cost. of certain types of workovers. In addition. the more reliable indication of the commercial value of a reservoir and the more accurate general reservoir information made Possible promise to be of even greater value in oil recovery than the reduction of costs for completions and workovers Recently. several well.. were worked over by using the retrievable tubing extension suspended on a swab line to plug back with cement and then perforating a higher producing interval with the tubing-type perforator, thus opening the way for complete through-the-tubing workovers which may be performed without pipe-handling equipment or mud. Those items attendant to the use of pipe-handling equipment and mud. such as hoard matting rig substructure. and pits. were also eliminated. There are indications that the elimination of drilling mud during completion and workover operations will frequently give increased well productivity, as plugging of the perforation. will not occur. It ii now possible to perforate selectively small sections of the producing interval and to test a well through these sections prior to perforating more interval. The perforating of additional interval will not entail the costly operations of killing the well and pulling tubing, nor will the old or the new perforations be plugged. The productivity of .mall sections of a reservoir and the actual gas-oil or oil-water contacts may now be determined economically under flowing condition.. Selective completions can be made in this manner to delay gas and water problems and bring about maximum oil recovery. At the present time, gas lift appears to offer the greatest potentialities for artificial lift in the permanent-type well com"letion since it can provide full-open tubing to accommodate the through-the-tubing tools and it may be ultimately developed into a fairly permanent type of lift. With precent-day pas-lift equipment. valve or mandrel failure necessitates occacio11al removal of the tubing. thereby reducing to some extent the permanence of the completion. New gas-lift valves are now

Jan 1, 1953

By M. E. Wadsworth, A. S. Peck

Infrared spectra disclose that oleic acid will not adsorb on the surface of pure beryl unless the mineral is first activated with HF. The adsorption of oleic acid on HF activated beryl is attributed to the hydrogen bonding of oleic acid monomers to F-surface bridging sites. These sites are formed as a result of the reaction of HF with chemisorbed water or surface hydroxyl. Characteristic infrared spectra of physically adsorbed oleic acid are correlated with flotation at different pH at temperatures of 25°C and 75°C for colloidal and -60-mesh particles. The usual mode of occurrence of the beryllium mineral beryl, Be3A12Si6O18, is in granite pegmatites as pale green, white, or yellow crystals. A dark green gem variety, emerald, may be found in the wall rock of pegmatite veins or in mica schist. The most important beryl deposits in the United States are in the Black Hills District of South Dakota, and several mountain ranges of central and west-central Utah contain potential commercial sources of this mineral. Several papers have been published concerning the flotation of beryl with different conditioning reagents. Kennedy and O'Meara1 reported on the essential use of HF in the flotation of beryl from different ores. The use of calcium hypochlorite to separate HF activated beryl from feldspar after flotation with an amine collector was made by Runke.2 A report on the activation of beryl with different cations using sodium oleate collector was presented by Viswa-nathan and co-workers.3 Flotation of beryl with sulfonate collector and different activating salts was employed by Fuerstenau and Bhappu.4 The role of the surface charge or zeta potential in the flotation of beryl with different collectors and salts was also extensively investigated.5"7 Previous infrared investigations by the authors8 disclosed that the orthosilicate beryllium mineral, phenacite, reacts with oleic acid to form a chemisorbed oleate monolayer on the mineral surface. Thus, chemisorption is the effective mode of adsorption in the phenacite-oleate acid flotation system. In contrast, neither chemisorption or physical adsorption of oleic acid occur on the surface of pure beryl as evidenced in this study. Efforts were subsequently made to determine the mechanism of activation and collector adsorption for HF pretreated beryl. EXPERIMENTAL PROCEDURES Large, white, terminated crystals of beryl were obtained from Madagascar through Ward's Co., Monterey, Calif. The crystals were broken into -60-mesh fragments in a porcelain mortar. Part of this prepared material was ground to a powder with a Fisher Grinder using an agate mortar and pestle. The powder was transferred to a graduated cylinder and mixed with 500 ml of distilled water. After 5 min, the colloidal suspension was separated from the settled particles by decantation and used as a stock for infrared test determinations. Adsorption tests were performed by first transferring 20 ml of colloidal suspension to 50 ml glass centrifuge tubes. The solids were then centrifuged out and the liquid was discarded. Then, the solids were pretreated with one molar HC1 or one molar HF. After 15 min, the solids were again centrifuged out. The mineral solids were washed free of residual acid by repeated centrifuging and water washing operations. Then, 20 ml of distilled water was added to the solids, and the resultant suspension was used for test purposes. In the preparation of mineral for flotation tests, 1.5 g of -60-mesh beryl was deslimed by removing the colloidal fraction by three successive water washes and decantations. Then, the coarse particles were pretreated with either one molar HCl or one molar HF for 15 min. The mineral was next washed free of acid with distilled water, and 20 ml of distilled water was added to the beryl prior to collector conditioning. The conditioning of mineral with collector was performed in 50 ml centrifuge tubes to which either NaOH or HC1 was added for pH modification. One drop (6.0 mg) of U.S.P. reagent grade oleic acid or 2 ml of 0.01 molar sodium oleate was added to the pulp and stirred at about 1500 rpm for 3 min at a

Jan 1, 1968

The Lornex mine is located in the Highland Valley area of British Columbia, Canada, one of the most,promising districts of low-grade porphyry-type copper mineralization in the world; Lornex is operated by Rio Algom Mines, Limited, a member of the Rio Tinto Zinc Group of London. Exploration from 1965 to 1968 disclosed an ore body of 293 million tons with a grade of 0.43% copper and 0. 14% molybdenum; this led to the decision to construct a 38,000 tpd operation, and production commenced in the fall of 1972. The ore is open-pit mined with 15 cu yd (11 5 m3 shovels, which load 100- and 200 -ton trucks. These trucks dump directly into a 60 in. by 89 in. Allis -Chalmers gyratory from two sides of the 14 ft 6 in. (4.42 m) deep dump pocket and across splitters mounted on the pocket sides. The unlined pocket would hold 1,000 tons level full. The crushedore discharges into a 300-ton surge hopper equipped with an automatic sonic level indicator to prevent over -filling. A 96 in. by 23 ft (2.44 m by 7 m) apron feeder delivers the ore from the surge hopper to a 72 in. (1.83 m) transfer belt equipped with a tramp iron metal detector. The transfer belt discharges to a 60 in. (1. 52 m) conveyor which conveys the ore about 3,000 ft (914 m) to the 475,000 ton ore storage pile located near the concentrator. Four 48 in. (1.22 m) pan feeders transfer the ore to the mill feed conveyors, which in turn supply the two 32 ft by 15 ft (9. 75 m by 4. 57 m) semi-autogenous mills, which easily accept the 10 in. (254 mm) product of the crusher. Each semi- autogenous mill is followed by a secondary ball mill. The unusually large open side setting of the crusher accounts for its 6,300 tph maximum capacity. Concentrator capacity is now 48,000 tpd. Eccentric removal is eased by the design of the door to the crushed ore pocket, which has the cart rails mounted on its outer surface and is lowered to a horizontal position in the pocket by an electric winch. The top of the door rests on wear bar covered concrete piers in the pocket. Another feature is a chute through the floor at the crusher base that extends into the crushed ore pocket. Dust and spills of ore on that floor during crusher repairs are easily swept into the crushed ore pocket. This feature is also used at Bougainville and Palabora and has been added to others after operation has commenced. The design follows the concrete rectangular box concept with four main service and maintenance levels shown in the sectional drawings, although a third additional section has been added at the maintenance

Jan 1, 1978

By Leendert de Witte

A review is given of the principles on which recently proposed methods of electric log interpretation in shaly sands are based and of the evidence brought up in support of the theoretical derivations. It is. pointed out that the qualitative techniques suggested to date have a tendency to be too pessimistic in the prediction of the presence of commercial hydrocarbon accumulations. In the quantitative treatment, a new concept is introduced, namely that of strongly reduced activity of the double layer counter ions which are present near the negatively charged rock surfaces. This lemmu when applied to the calculation of the equilibrium concentratiotls of interstitial waters yields a set of very simple relations. The resulting expressions for electrochemical potentials across rock samples appear in satisfactory agreement with laboratory experiments. The formulae obtained for the electrical conductivity of shaly formatioris are of the same form as those arrived at empirirally by previous workers. Combination of the expres.riorls for potentia1s and conductivities gives a direct proof of the Tixier relation which states that for shaly water sands the product of apparent formation water resistivity and apparent formation factor equals the resistivity of the sand 100 per cent .saturated with formalion water and which was verified by the work of Wyllie and Perkins and their co-workers. The relations for the resistivities and spontaneous porer11inI.s have been extended to the case of hydrocarbon hearing shaly formations, thus laying a formal basis for the quantitative interpretation of electric logs in shaly oil sands. INTRODUCTION The presence of disseminated clays in porous rocks saturated with electrolytic solutions has a strong influence on the transference of ions taking place under electrical or chemical potential gradients. Both the electrochemical emf's in evidence on the SP curves of electric logs and the electrical conductivity measured on resistivity logs arc directly dependent on the ionic transference in the interstitial waters of the formations traversed by boreholes. A large number of researches have been carried out on the nature and magnitude of the effects of clays on ionic transference. The most recent of these have been described in papers by McCardell and Winsauer,1 2 Wyllie and Southwick,3 poupon, Loy, and Tixier,4 and by Perkins et al.5 Most of these authors consider the effects of the clays as due to the fixed negative charges on the clay lattice. These charges cause the formation of diffuse surface layers with a high concentration of positive ions. The internal solution of the shaly reservoir rock has therefore a different ionic composition and concentration than the electrolyte with which it is in equilibrium (connate water produced from the formation or mud filtrate by which the formation is invaded). To calculate the equilibrium concentration of the internal solution, use is made of the Donnan6 relation, which states that the mean ionic activities of the internal solution and of the external electrolyte must be equal. From this and the

Jan 1, 1956

Discussion of the paper of F. M. Simonds and E. Z. Burns, presented at the New York Meeting, February, 1913, and printed in Bulletin No. 75, March, 1913, pp. 369 to 402. W. L. SAUNDERS, New York,. N. Y.:-Mr. Burns in his native Colorado modesty has said that he apologizes for things left out of this paper. I am much impressed by what he has put into the paper, as of all the papers that I have read on the subject, describing, as it does, a specific piece of work that has been accomplished, I do not recall one that gives so much information in such a practical way. Mr. Burns has also said that it is very hard to get men to put things down while the work is being driven. My experience is that it is very much harder to get the men in charge of work of this kind to bring them in in the form of a report before a body of engineers after the work is done. We have a great many cases where records are kept in much detail, but they are usually kept under cover, with the mistaken idea that the information gained is private information for the benefit of those who have done the work. Messrs. Simonds and Burns have opened up this case so that we can get the benefit of that experience which they have had, and so that we can learn something for the future. The description contained in this paper, as I have said, is a very practical one. You will notice in going through it. that the authors have given in detail a record of their work from the beginning to the end, and they even go so far as to publish an exact copy of the Rawley Mining Co.'s daily report. That daily report is something which those of us who are engaged in similar work might copy to great advantage, and having it before us we can check up our men while doing work and exact from them equal conditions, if it is possible to do so.

Jan 5, 1913

By W. P. Lass

(San Francisco Meeting, October, 1911.) TEE purpose of this article is not only to describe the plant and method of cyaniding the Treadwell concentrates, but to present some of the results of the experimental work obtained in the past three years for the Alaska-Treadwell Gold Mining Co., at Douglas Island, Alaska., under the direction of F. W. Bradley, Consulting Engineer, and Robert A. Kinzie, General Superintendent, of the affiliated companies. At the time the experimental work was undertaken the concentrates were being shipped to the smeltery at Tacoma, Wash., and the cost for treatment of 3-oz. (gold) concentrates was $11.95 per ton, divided as follows: Smelting-charges, . $4.00 Loading, freight, insurance, etc., 2.89 Interest due to time lost in transit and in settlement, . 0.05 Loss due to settlement for 95 per cent. of the gold at $20 per ounce, 5.01 Total, . . $11.95 From the experimental work described later, it was estimated that 96 per cent. extraction could be made by treatment on the ground, and that the cost, when treating 80 tons per day, would be $3.25 per ton, divided as follows; Per Day. Per Ton. Labor, . $66.16 $0.827 Chemicals, . 76.60 0.960 Power and steam-heat, 67.60 0.845 Marketing-, refining- and other charges, 49.36 0.617 Totals, . . $259.72 $3.250 Adding to this total the 4 per cent treatment-loss, which on 3-oz. concentrates amounts to $2.48, gives a total cost of $5.73 per ton. Comparing this with $11.95, the cost when shipping to the smelter, leaves a net gain of $6.22 per ton by the local

Feb 1, 1912

By Eugene McAuliffe

SINCE 1917, the bituminous coal industry has surged, violently at times, across the nation's social, industrial and economic foreground. To-day a silent, yet more active, force is working within the industry, and the movement now taking place, if allowed to continue, will cause serious consequences when coal is again wanted at the rate of 550,000,000 tons annually instead of at the rate of 400,000,000 tons, the apparent requirement for 1921. I refer to the shift of tonnage from the highly unionized fields of Pennsylvania, Ohio, Indiana and Illinois to the non-union fields of Pennsylvania, West Virginia, Alabama and certain western states, and to the so-called union fields in Kentucky and Colorado, on which the union saddle rests lightly. This movement, in the absence of the usual winter transportation shortage, is taking place rapidly and will be accentuated if, as is probable, work is suspended in the union mines on March 31 next. This drift of tonnage has been made possible by the unit wage reductions in the non-union fields and by the modification of the so-called conditions that have been saddled on all mines wherever the United Mine Workers have gained a foothold; these changes permitted the first reduction in mine cost, which made possible the securance of contracts; better running time assisted in making further reductions, and the transfer of ton-nage served to increase the unit cost in the field from which it was transferred. This situation not only opposes the highly unionized operation but brings about a transfer of traffic from the roads serving such mines to those that serve in a primary or secondary manner the more favored localities. The net result is evidenced in (a) the migration of union labor to the non-union mines; (b) the deteriora-tion and decadence of union properties; (c) the neces-sary curtailment in the purchase of new equipment and in the maintenance of existing equipment and track facilities on the part of the carriers serving the union fields. This, in turn, when business is restored to normal or to the point above normal that invariably follows an adverse swing of-the business pendulum, will cause (d) a shortage of coal and coal transportation facilities; (e) an era of coal speculative debauchery with exorbitant prices and serious deflection in the matter of quality; (f) a period of labor unrest followed by de-mands for increased wage rates supplemented by a marked loss in individual efficiency, with, resultant strikes, business unrest, and the pressure of new eco-nomic theories. In 1918, the labor status with respect to relative tonnage produced was approximately as follows: pro-duced in highly organized fields, 62 per cent.; produced in partly organized fields, 21 per cent.; produced in unorganized fields, 17 per cent. During the strike of November and December, 1919, the mines that remained at work attained 35 per cento of the nominal production of soft coal, a situation made possible by the migration of union labor to non-union mines and the concentration of the nation's coal trans-portation facilities on the rails of the carriers serving the non-union fields. The history of the efforts made by the carriers to untangle the car scrambling which took place during this period and which sent the self clearing battleship type of car into western territory where it could not be readily unloaded, and the western gondola type of car to New England and the seaboard, is yet painfully recalled. -This confusion proved a serious factor in the coal car shortage that continued throughout the following year. We are drifting toward a similar situation now, propelled by economic forces rather than by a sudden strike.

Jan 1, 1922

By R. S. Rickard, M. C. Fuerstenau

Anodic polarization curves for iron dissolution and cathodic polarization curves for copper deposition and ferric and hydrogen ion reduction were studied. These results were used to predict the relative rates of the reactions: The rates of the first two reactions were found to be first order with respect to the reacting ion, and the rale-controlling step was diffusion of the ions to the callzode surface. The rate of hydrogen ion reduction in an oxygen-free solution is dependent on the reciprocal of the square root of the hydrogen ion activity. In solutions containing oxygen, the rate of hydrogen reduction becomes dependent on the square root of the partial pressure of oxygen. At equal concentrations copper precipitation occurs about twice as fast as ferric ion reduction. In an air-saturated solution containing 0.01 M cupric ion at pH 2, the rate of hydrogen ion reduction zs about 10 times slower than that of copper precipitation. At pH values below 3, the rate of hydrogen reduction in oxygen-free solutions is very slozu. COPPER cementation has been utilized industrially for many years as a means of recovering copper from aqueous solutions. There are many different types of cementation plants, but all simply provide a means of contacting iron with relatively dilute copper solutions. In the past little or no attention has been paid to rates or mechanisms of the reactions involved. As a result, this and other studies'-3 have been undertaken recently to establish the important parameters in this system. The reactions involved in copper cementation by iron are: Since transfer of charge is involved in every case, these reactions should be considered from an electrochemical point of view. In any electrochemical system involving electrolytic conduction, passage of electrons necessitates ion transfer to the respective electrodes according to Faraday's law. The current in the system will be proportional to the rate of ion transfer, and, therefore, when the current in the galvanic cell is known, the rates of the reactions involved can be determined. Galvanostatic electrode measurements5" are applicable for these electrochemical studies, in that with this technique polarization curves (current density vs electrode potential) are established by impressing a constant current through an electrode and measuring the electrode potential. Once the current density, electrode potential, and reacting area are known for each reaction in this cementation system, the rates of the iron-consuming reactions can be determined. EXPERIMENTAL MATERIALS Several metal electrodes were used in this investigation; they are shown in Table I. Solutions were made with reagent-grade salts and conductivity water. Air, nitrogen, and oxygen were employed. All of these gases were saturated with water and degreased prior to use. EXPERIMENTAL PROCEDURE The experimental work was divided into two general areas. The first area involved galvanostatic measurements, which were used to determine the rates of reactions as a function of various parameters. The second area comprised actual cementation experiments to check the rates predicted from the electrode measurements. Galvanostatic Electrode Experiments. Polarization curves were obtained using a standard galvanostatic technique5'= with the apparatus shown in Fig. 1. The various electrode polarization experiments were run the same way except for changes in solution composition, polarity, and type of measured electrode. The general procedure involved the following steps: 1) a solution was made 0.5 M in sulfate ion and to the desired cation concentrations; this solution was placed in a constant-temperature bath and saturated with the desired gas; 2) the electrodes were cleaned and placed in the electrode holder; 3) the previously cleaned apparatus was assembled and immersed in a constant-temperature water bath (temperature controlled to ± 0.05"C); 4) the electrode was then positioned; the solutions were introduced, and the polarization meas-

Jan 1, 1969

By T. W. Smoot

Bentonites are composed chiefly of montmorillonites which are clay minerals generally distinguished from other clay minerals by their surface activity and extremely fine particle sizes. The uses of bentonite are many and varied, depending principally on one or more of the following characteristics: 1) Thixotropy, 2) Dispersion, 3) Plasticity, 4) Swelling, 5) Surface area, activity, ab- and adsorbtive properties. Some of the major uses of bentonite are briefly reviewed as are the mineralogical and physical properties. The uses of X-ray diffraction, differential thermal analysis and other tests for physical properties are reviewed as to their uses in evaluation. In the past 40 years, the industrial uses of bentonite have grown to include many applications. The physical and chemical properties of bentonites are such that they can be used as catalysts, adsorbants, plasticizers, binders, drilling muds, and pelletizers. Not all bentonites, however, can be used for all of these purposes and some are probably of little or no value for any use. The purpose of this paper is to briefly review the mineralogical, physical, and chemical characteristics and variations of bentonites. The determination of these characteristics and their uses in industry are also reviewed so that these determinations can be used as guides for evaluation. DEFINITION OF BENTONITE The word bentonite, as used in this paper, refers to a clay material, usually (but not necessarily) the result of the in-place-weathering of volcanic ash. Its mineralogical composition is dominated by the clay mineral montmorillonite and generally carries other clay minerals and silica minerals as the major 'impurities'. For this discussion, such a definition is justified since most of the economic uses of bentonite~ depend upon the physical and chemical characteristics of the montmorillonite minerals involved. The terms montmorillonite and bentonite have been used almost interchangeably in industry although the latter is much more commonly used. Therefore, where montmorillonite is discussed, it should be understood that the major feature of a bentonite is the subject. STRUCTIJRE OF MONTMORILLONlTE The economic importance of bentonites is generally based on one or more of the following characteristics of montmorillonite: 1) high-thixotropy and easy dispersion in water, 2) high-plasticity, 3) swelling properties, 4) large surface area/unit mass, 5) high surface activity, and 6) adsorptive properties. To understand these properties, an appreciation of the structural scheme of montmorillonite is helpful. Montmorillonite IS one of the three-layer clay minerals composed essentially of hydrous aluminum silicates. The essential building blocks of these layered silicate:; are: 1) silica tetrahedron composed of a silicon atom surrounded by four oxygen atoms, and 2) aluminun (iron, magnesium, etc.) octahedral unit that, ideally, has one of these atoms surrounded by six hydroxal units. Fig. 1 is a diagrammatic sketch of the montmorillonite structure. In the montmorillonite structure, the tetrahedron are pointed inward and attached to the octahedral units so that the O= atoms replace the hydroxal units where they are bonded; hence two-thirds of the hydroxal units

Jan 1, 1962

By A. M. STROKG

Discussion of the paper of Charles R. Keyes, presented at the Spokane meeting. Bulletin o. 34, October, 1909, pp. 867 to 903. A. M. STRONG, Bishop, Cal: (communication to the Secretary*) The paper of Mr. Keyes gives us the most complete account of the geology of the borax-deposits in the Death Valley region that has yet been published, and is a valuable addition to the geological literature of a very interesting though little-known territory. During the past ten years I have been over much of the northern part of the country described by Mr. Keyes and the region immediately north of it. Mr. Keyes seems to give the impression that Furnace creek is the northern end of these borate-bearing deposits, but such is not the case. Of the seven principal marsh-deposits which for years furnished the greater part of the borax supply in the manner described by him, four are north of the boundary-line as given on his map. The entire territory immediately east of the Sierra Nevada is composed of a series of sinks, each with a well-defined drainage-area.. Of these, Death valley is the deepest, and its drainage-area one of the greatest. The section given in the paper is typical of any line drawn eastward from the Sierra Nevada. At the lowest point of each of these sinks is a marsh, which, in times of heavy rain-fall in the mountains, is converted into a lake. These marshes always contain borax, which is now considered to have been derived from the washing of the Tertiary lake-beds in the surrounding mountains, of which they form a considerable part. Additional territory which I have studied shows that the boundaries given on Mr. Keyes's map should be considerably extended to the north. Just how far these borate-beds extend I am not prepared to say. J. E. Spurr says of them : 1

Feb 1, 1910

The United States has never been a large coal exporting nation, and normally such shipments, aside from those to Canada, have been relatively small. Since the first railroad was built across the Allegheny Mountains, the imports have been quite small also, although fairly large tonnages of Canadian coal have moved into the extreme northeastern and northwestern states at times. In Table 21 are shown all data available about these shipments from 1790 to 1939, inclusive.

Jan 1, 1942

By Wendell S. Williams

Single crystals of TIC doped with boron at high temperat~ires develop second-phase inclusions. The inclusions are in the form of lamellae lying parallel to {l 11 } planes of the Tic matrix and can be vevealed by etching [100] cleavage faces of the boron-doped Tic crystals. measurements of the critical resolved shear stress. t, of TIC crystals containing such inclusions showed that the ropid drop in t wilh increasing temperatu.ve found for pure Tic was greatly reduced. At 1600°C, the inclusion containing crystals had a value of t five limes that of pure Tic. The hardening effect also was found to inhibit hot pressing of TiC powders containing boron impurity. Thermochemical and crys-tallographic arguments suggest that the inclusions are TiB2. The boron content of the hardened carbide is a few tenths of 1 pct. TITANIUM carbide is noted for its high room-temperature hardness. However, measurements of the critical resolved shear stress, T, of single crystals of Tic at high temperatures have shown that t decreases exponentially with increasing temperature.' This temperature dependence of t is attributed to thermally activated dislocation mobility limited by a large Peierls stress.' In turn, this large Peierls stress is believed to be a consequence of strong co-valent and ionic binding in Tic. The rapid drop in 7 with increasing temperature, characteristic of pure Tic, is lessened by the introduction of second-phase inclusions. Exposure of Tic to boron at high temperatures produces such inclusions. A report of the influence of boron on t in Tic is presented, followed by a discussion of the nature and formation of boron-containing inclusions in Tic which are believed to be responsible for the hardening effect. I) CRITICAL RESOLVED SHEAR STRESS OF BORON-DOPED Tic CRYSTALS Tic single crystal boules grown by Union Carbide Corp., Linde Division, were doped with boron by placing them in a carbon crucible packed with boron powder and heating in a vacuum furnace to 2000°C for 1 hr. Samples 1 by 1 by 3 mm were cleaved from these doped boules. High-temperature compression tests' were made on these samples to determine the critical resolved shear stress as a function of temperature . The rapid drop in critical resolved shear stress found for pure Tic crystals' did not occur: tests indicated that the boron-doped crystals at 1600°C had values of T equal to those of pure Tic crystals heated to only 1100°C, Fig. 1. No difference in the shape of the individual stress-strain curves was produced by the boron doping, but the stress scale was multiplied by a large factor. The hardening effect of boron in Tic probably extends to temperatures lower than those used in the present work (1100°C minimum). At room temperature, however, the influence of boron is difficult to determine because the stress required for gross plastic flow in pure Tic is SO high that in practice fracture cccurs first. Microhardness is the only test that can give an indication of the yield stress in Tic at room temperature. such measurements were made5 on boron-doped Tic; the matrix had a hardness value

Jan 1, 1967

By S. Ramachandran, R. G. Woolery

INTRODUCTION Union Carbide is currently operating an in-situ leach project on the Palangana Dome area in Duval county. This deposit meets all the requirements for in-situ leach in that the ore (1) is below the water table, (2) is in a permeable horizon, (3) is amenable to chemical leaching, and (4) is confined by impervious layers. This project has been under commercial production since 1976, and its capacity has been expanded on three occasions since going on-stream. Recently, additional uranium reserves were discovered on the Rogers-Cardenas (R-C) property about 32 km north of the Palangana operation. The ore is located within the Oakville sands and its characteristics are quite similar to those of the ore at Palangana. Both are an unconsolidated Arkosic sand high in clay and calcium carbonate. The R-C ore, however, is somewhat coarser with a mean particle size of 0.15 mm as compared to a mean particle size of 0.07 mm for the Palangana ore. In all respects it would appear that this ore would be a candidate for in-situ leach as a satellite operation to Palangana. Unfortunately, R-C ore is above the water table and, therefore, not amenable to the Palangana practice. Because of the limited known reserves in this deposit, it is readily apparent that conventional mining and milling are out of the question. However, because of its proximity to our Palangana operation, it seemed worthwhile to consider other options. The most viable route based on our past experience was to heap leach the ore. Our recent success at our Gas Hills facility and our Maybell operation, in employing a heap leach practice to our marginal reserves seemed to be a logical approach for processing this ore. Our experiences at both locations are described in "Heap Leaching - A Case History" by R. G. Woolery et al., Mining Engineering, March 1978. In both instances the process is an acid leach circuit and acid consumption averages 20 kg/t H2SO4. A preliminary feasibility study showed that because of the high strip ratio required for the R-C project to be successful, additional ore reserves must be located and that a method of heap leaching with an alkaline circuit would have to be developed. As a result of this paper study, the decision was made to proceed with a program of additional exploration drilling to determine the total ore reserves that could be mined economically. The Mining Department will evaluate each ore zone for cutoff grade, strip ratio, and expected mining cost. At the same time, a laboratory program to evaluate the available core samples for amenability to heap leaching with respect to an estimate of uranium recovery and processing costs was developed. This program is currently in progress, and at this time, we are just completing our process amenability study. BENCH-SCALE EVALUATION OF THE R-C ORE The initial bench-scale slurry leach tests on the R-C ore showed an acid consumption in excess of 200 kg/t H2SO4. These data, of course, discouraged us from considering this process route. Not only would the acid cost be prohibitive, but the gypsum generated by the reaction of the sulfuric acid with the calcium carbonate of the ore would severely effect the percolation of the lixivant. For this reason, the laboratory program was directed toward an alkaline circuit compatible with heap leaching. Because of the proximity of the R-C property to our Palangana operation, it seemed advisable to integrate the processing of this ore into the production at Palangana. Doing so would enable us to bring the R-C property into production by merely enlarging our present facilities at Palangana; otherwise, construction of a grass roots plant would be necessary. Ideally, the simplest method would be to construct the heaps at Palangana and employ an ammonium carbonate/bicarbonate leachant compatible with the in-situ production liquor. The product liquors could then be co-mingled or processed separately as desired. To determine if this goal was practical, samples of the R-C ore were obtained, and a laboratory program initiated. Heap leach amenability testing consisted of preliminary bench-scale evaluation to determine optimum solution strength and ultimate uranium recovery, followed by small column tests to confirm the bench-scale metallurgy and to determine percolation characteristics. These bench-scale tests are being followed by pilot-scale testing approximating field conditions. As expected, the bench-scale tests showed that the dissolution rate is considerably slower for alkaline leach than has been our experience in acid leaching. Because of the slower reaction rates, product liquor grades will be lower than for acid, as greater volumes of solution are required for satisfactory uranium extractions. The greatest influence on reaction times found in the laboratory was the carbonate/bicarbonate strength and oxidant addition. However, the higher salt concentration reduced the efficiency of the IX resin circuit and about 25g/L salt proved to an upper limit compatible with subsequent IX treatment. The oxidant contributed significantly to the early extraction rate but seemed to have only minimal effect on the total practical U308 extracted or the time required to achieve it. This variable will require larger scale testing to determine if the added cost of the oxidant is actually justifiable. Thus, the small-scale laboratory slurry tests, based on the 0.088% U308 sample available, indicate that leaching at 25g/L ammonium carbonate/bicarbonate, with or without oxidant, we might expect an 80-85% U308 extraction on this ore.

Jan 1, 1979

By K. A. Semlak, F. N. Rhines

NFILTRATION is a term used to designate that i- process by which the pores of a metal powder are filled with a relatively low-melting liquid metal through the action of capillary forces. This is accomplished in practice either by heating the porous body in contact with the solid infiltrant metal above the melting point of the latter, or by preheating the porous body separately and then dipping it into the liquid metal. The liquid, as it sweeps through the porous body, replaces the gases progressively, thus yielding a relatively dense product in a short time.' Liquid-phase sintering, which is related to infiltration, is a process by which a mixture of two or more metal powders is sintered at a temperature between the liquidus and solidus of the ultimate alloy.' According to Cannon" liquid-phase sintering can be divided into three stages which he calls liquid flow, accommodation, and solid sintering. The largest density increase occurs during the first stage, where the lower melting component melts and, driven by capillary forces, flows among the particles of the higher melting component, where, after dissolution of the bonds between the solid particles, it moves them into close packing. This happens so quickly that little has yet been learned of its mechanism. A study of the rate of capillary rise of a liquid metal in a higher melting metal-powder compact may be expected, therefore, to contribute not only to a firmer understanding of the process of infiltration as such but also to a more extensive knowledge of what occurs during the initial stage of liquid-phase sintering. Theoretical Basis In order to derive a mathematical expression of the rate of infiltration, it has been assumed that a powder compact consists of a great many parallel capillary tubes and that the rate of rise of a liquid in an average capillary channel represents the rise in the entire compact. For a straight capillary, assuming that Poiseuille's law obtains for the non-stationary state and that wetting is very rapid, Ligenza and Bernstein' have derived the following differential eauation of motion where h is the height of rise of the column of liquid at time t, R, is the radius and 1 the length of the capillary, t) and 7, the viscosities of liquid and air, respectively, p and p, the density of the liquid and air, respectively, y the liquid-gas surface tension, 0 the liquid-solid contact angle, and g the acceleration due to gravity. The term on the left of Equation [I] represents the rate of change of momentum of the contents of the capillary tube. On the right the terms represent, respectively, the forces due to a) surface tension, b) viscous resistance, c) gravity, and d) end-drag effect. Equation [I] is not amenable to explicit solution, but for a tube of sufficiently small radius, the rate of rise may be slow enough so that the rate of change of momentum and end-drag terms may be neglected. The validity of this simplification was established by Ligenza and Bernstein' by graphical differentiation of observed data obtained from organic liquids rising in glass tubes. The solution of this simplified case is:

Jan 1, 1959

By AIME AIME

CADWALLADER EVANS JR. has long been a leading figure in the anthracite mining industry and one of Pennsylvania's prominent citizens. He is, in fact, a native son, having been horn in Pittsburgh on Sept. 17, 1880. At Lehigh, from which he graduated in 1901 with the degree of Mechanical Engineer, Tom Girdler was a classmate, and both were active in football affairs. Going hack to Pittsburgh, he got his first job as trouble shooter for the Oliver Iron & Steel Co. A year later he entered the coal industry, getting a job with the Blaine Coal Co. as inspector of construction and later was superintendent of the Blaine mine at Elizabeth. Pa.

Jan 1, 1943

By C. E. Birchenall, W. Batz, H. W. Mean

AT temperatures between 1095' and 1347ºC, 13 runs have been made on the diffusion of silicon in iron. In two of the runs the couple compositions were entirely within the loop of the Fe-Si system; the base alloys contained 0.0 and 1.0 wt pct Si. The other runs in which the couples consisted of a 2.3 wt pct Si alloy welded to a 3.7 pct Si alloy were a phase throughout. The alloys were made by melting electrolytic iron and commercially pure silicon. Trace impurities were not determined. The butt welded couples were diffused in an inert atmosphere of argon or hydrogen. After cooling, cuts of two mils or greater thickness were machined parallel to the weld interface. The chips were analyzed for silicon. When the concentration and distance data were examined on the conventional probability plot,' no marked variation of the diffusion coefficient with concentration was indicated over the narrow composition ranges employed. Therefore, a single diffusion coefficient is recorded for each run in Table I. The temperatures and atmospheres of the diffusion anneal are listed along with the compositions of the base alloys. For a iron the silicon diffusion coefficient is given by the equation: D = 0.44 e-48,000/RT where R is the gas Constant and T, the absolute temperature. However, since the scatter in the data is fairly large, the activation energy may be in error by as much as 6000 cal per g-atom. The two ? iron points do not permit estimation of the activation energy with any reasonable certainty. They do indicate that the coefficients reported by Smithells2 and Jost,3 based on the work of Fry,4 are much too high. Although very dilute solutions in iron of manganese,5 nickel,8 cobalt,7 and molybdenum8 give dif- fusion coefficients quite close to those obtained for self-diffusion in iron, the silicon values are considerably higher, though of the same order of magnitude. This seems to be consistent with the fact that the silicon atom is the only one of those listed here which is appreciably smaller than iron. The authors are grateful to the Office of Naval Research for their support of this work under Contract N6ori-47, Task order IV, Project NR 031-184, to J. K. Stanley and the Westinghouse Research Laboratories for the silicon alloys used, to several steel companies for the silicon analyses, and to C. Wells, of the Metals Research Laboratory, Carnegie Institute of Technology, for numerous suggestions during the course of the work. References 'C. Wells: Atom Movements (1951) Chapter 2. A.S.M. 2C. J. Smithells: Metals Reference Book (1949) p. 405. Interscience. Pub. Co. 3W. Jost: Diffusion (1952) p. 223. Academic Press. 4 A. Fry: Stahl und Eisen (1923) 43, p. 1039. T. Wells and R. F. Mehl: Trans. AIME (1941) 145, p. 315. "C. Wells and R. F. Mehl: Trans. AIME (1941) 145, p. 329. 7M. F. Hawkes and R. F. Mehl: Trans. AIME (1947) 172, p. 467; Metals Technology (August 1947). .J. L. Ham: Trans. A.S.M. (1945) 35, p. 331.

Jan 1, 1953