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By C. W. Lawr

The ores mined by the Santa Gertrudis Co. at Pachuca, Mexico, arc mainly silver-bearing; they also yield some gold and carry a little copper. Strong cyanide solutions are used to dissolve the silver and gold, and the mechanical loss of cyanide at the tailings filter has been considerable. Prior to the year 1923, the pulp, after agitation, was given a 35 to 37-min. wash with barren solution in a Butters-type leaf filter; the discharged slime cake was repulped and pumped into eight Merrill self-sluicing slime presses in which the slime was given a further wash with barren solution for 25 to 35 min., followed by a 10-min. water wash. At that time the barren solution titrated around 0.350 per cent. free KCN and 0.500 per cent. total KCN. (Aero brand cyanide is used.) It can readily be seen that a 10-min. water wash would leave considerable cyanide in the filter cake, which of course was a total loss. This averaged 0.522 kg. (1.15 Ib.) KCN per ton of solution. As the daily discharge to the dam was 1600 tons' of slime of a 2:1 ratio of liquid to solid, the value of this mechanical loss of cyanide was an important item and it's recovery held alluring possibilities. Principle of Cyanide-recovery Process As it had acquired the patent rights to theLayng (H. R.) and Halvor-sen (A. L.) processes, also those of Mills (L. D.) and Crowe (T. B.) after considerable experimental work in its own laboratory and at Tonopah, Nev., The Merrill Company of San Francisco early in 1923 notified the Mexican Corporation and compania de Santa Gertrudis of its process for the recovery of cyanide from weak wash solutions, or for the transference of cyanide from a foul mill solution to a clean alkaline solution. This method is known as the Mills-Crowe process, the principle of which is as follows: The solution from which the cyanidc is to be removed is made acid by bringing it into contact with sulfur dioxide (SO2). The acidified solution is the; transferred to a closed tank in which air and solution are brought into intimate contact. The air leaving the tank charged with HCN is then passed to another tank in which it is mixed with an alkaline solution,

Jan 1, 1930

By F. Brons, V. E. Marting

In the past, other authors.1, 2 have studied the influence of a skin effect on the productivity of a well. This skin effect, expressed by the skin factor S, is considered to be caused by a thin layer of impaired permeability immediately around the wellbore and extending vertically over the whole productive interval penetrated by the well. The skin factor S is defined as follows. Based on this, the impairment in productivity caused by a skin can be expressed by the fractional loss in productivity I, which is the loss in productivity divided by the total unimpaired productivity. For compressible flow in a stabilized well which drains a circular area of radius re, 1 is given by The present paper deals with a different kind of productivity impairment. Consider a well in which part of the productive formation is blocked off completely, either by incomplete penetration or by exclusion of parts of the productive zone by blank casing. In Fig. 1 (A, B and C), three examples are shown. Fig. 1(A) shows the situation where a well only partially penetrates the formation. This often is done to combat the actual or imagined danger of bottom-water coning. Fig. 1(B) shows a well producing from only the central portion of a productive interval. This type of completion is sometimes used where both water and gas coning are a problem. Although the case of a well producing through perforated casing cannot be treated in a manner similar to the previous two cases (where radial flow in the horizontal plane is assumed), Fig. 1(C) shows several intervals open to production and qualitatively describes this case (as will be discussed later). To study the loss in productivity in all these cases, two parameters are introduced which fully determine the impairment. The first is the penetration ratio "b," i.e., the total interval open to fluid entry divided by the total thickness of the productive zone. The second is the ratio hlrw. In this ratio, rw is the wellbore radius. The definition of h is more cumbersome. In Fig. 1(A), h is the thickness of the total productive interval. The streamline configuration for this case of partial penetration is basic to the other two cases considered (Views B and C of Fig. 1). It will be obvious from Fig. i (A) that the flow lines in the uppermost portion of the formation will be essentially horizontal, while those in the lower portion will curve upward toward the well. In Fig. 1(B), with only the middle portion of the zone open to production, the streamline configuration. of the upper half will be an exact mirror image of that in the lower half of the zone. Hence, for the case illustrated in Fig. 1(B), h is defined as one-half the total sand thickness. It follows, then, that in Fig. 1(C) h is one-half the distance between corresponding points in adjacent intervals. (In gun-perforated casing, h would be one-half the distance between perforations.) In a paper by Nisle4 and a paper given by the present authors5, the mathematical theory was developed for the cases under consideration. In the present publication, the emphasis is put on the results of these studies; consequently, the equations derived in Refs. 4 and 5 will be omitted, for the most part. The pressure drop p in a well producing from only a portion of the total formation thickness can, in analogy with Eq. 1, be expressed by Numerical solution of Eq. 5 by use of the IBM 650 leads to the following important conclusions. First, during a short period after starting production (usually on the order of a few minutes), the function p(b) is given by

By R. B. Gordon, D. A. Koss

Ultrasonic-atlenuation changes due to the formation of free dislocations have been observed during tensile tests of magnesium and LiF single crystals and samples of polycrystalline Results on the LiF and samples are similar: A preyield attenzration increase is observed which, however, be-corlzes smaller as the magnitude of the drop in load al yielding increases. This indicates that the yield point observed in these materials is due to dislovation rather than dislocation unpinning and that the initial density ' free dislocations must be low if the yield point is to be sharp,. Tests on the magnesium ere conducted at both 27" and 200C. Magnesium has the unusual property that the yield drop is larger at the higher test temperature and is accomplished by a decrease in attenuation. The latter is due principally to the temprovary pinning of detained dislocations by highly solute atoms. After strain aging., a stress as low as 0.3 bur suffices to unpin dislocations; microstrain measuements of sufficient sensitivity should. reveal plastic flow at stress levels this low IN another paper,' we describe the technique of simultaneously observing ultrasonic-attenuation changes and plastic microstrain during deformation of spher-oidized carbon steels. Changes of ultrasonic attenuation indicate damping effects caused by the oscillation of long, freely moving dislocation segments. Simultaneous microstrain measurements are used to indicate total dislocation motion. The dislocation-damping observations are most useful in the study of the early stages of deformation where the dislocation density is low and the plastic strain is small and relatively difficult to measure. Particularly interesting results are found in materials which display sharp yield points. Observations of these phenomena are reported here for three materials: single-crystal LiF and magnesium, and poly crystalline molybdenum. EXPERIMENTS Dislocation-damping effects were observed by measuring changes in acoustic attenuation with the ultrasonic-pulse method. The end faces of each of the specimens were ground flat and parallel and a quartz 10 Mc per sec, x-cut transducer was attached to one face. The bonding agents used were: a) "Nonaq" stopcock grease with magnesium, b) beeswax with LiF, and c) salol with molybdenum. With the LiF, the best acoustic signals were obtained at 45 and 50 Mc per sec; all other measurements reported are at 10 MC per sec. The Sperry Ultrasonic Attenuation Comparator2 was used to measure attenuation changes. In the

Jan 1, 1967

By Ta M. Li

A change in priorities is perhaps the underlying motivation reflective of governments and people in the Far East nations of the Philippines, Indonesia, and Thailand. While in the past, local governments have focused on feeding their large populations, the transfer of modern technology to the agricultural sector has produced record crop years in many of these countries. As a result, agricultural objectives have become more manageable, prompting governments to shift priorities to the accelerated development of their industrial sectors. The basis of any sustained industrialization program, the governments concede, is the development of a vibrant minerals sector.

Jan 8, 1979

By G. T. Pruitt, T. L. Irby, P. B. Crawford, H. Ferrell

In water flooding peripheral, center-to-edge, line-drive or water-encroachment patterns the question has arisen, "when should a producing well be converted to a water-injection well?". It is realized that, if the producing well is shut in when water breakthrough occurs, some oil could be left in an unswept area. Yet, operation to high water-oil ratios may require processing much additional water. If a well is shut in, "where should the allowable be transferred?". A review of the literature indicates that very few data are available to the engineer to assist him in answering these questions. It is the purpose of this paper to present information which may be of value in selecting the flooding technique and the injection and producing wells and in scheduling injection and production rates. Certain phases of these problems can be studied in the laboratory. The Potentiometric model is well suited for studying many waterflooding problems. This model assumes that steady-state flow exists, that the mobility ratio is equal to one and that gravitational effects are neglected.'-' The three-phase sand model also has been recognized as an effective means for studying certain reservoir problems. Both models were used in making the study reported here. This paper discusses seven cases utilizing various waterflooding techniques. Data for the first five cases were obtained on the potentiometric model. Data for Cases VI and VII were obtained by constructing and flooding an unconsolidated sand pack (a three-fluid-phase system) and by determining the swept area and cumulative oil recovery for various types of operations. APPARATUS AND PROCEDURE The potentiometric model reservoir was 30 in. long X 10 in. wide by about 1/2 in. deep. Four wells were equally spaced in a line array along the lateral center line. (See Fig. 1.) Well No. 1 initially was an injection well for each of the patterns reported. The cases studied with the potentiometric model and sand model are described herein. The laboratory sand model reservoir was a 30- 10-in. rectangular Lucite vessel packed with sand to a depth of about 0.65 in. Four wells were equally spaced in a line array along the lateral center line. The reservoir material was an unconsolidated sand into which the reservoir fluids were mixed to yield fluid saturations of 55 per cent oil, 25 per cent water and 20 per cent gas. The water was added to the sand and the material mixed, after which the oil was added. Kerosene and water, the fluids used, gave a viscosity ratio of 1.64:1. In packing the reservoir, care was taken to assure constant fluid saturations and constant porosities. A new mixture was prepared for each run. During water flooding, a colored water was injected by a constant rate pump. The injection rate was 1.1 B/D/ft of sand thickness. For this series of tests, each of the producing wells was open to the atmosphere and, as in the potentiometric model study, Well No. 1 initially was an injection well for each of the patterns. KESULTS OF POTENTIOMETKIC MODEL STUDlES Two cases (Cases I and 11) involving equal pressure injections were studied, with the following results. Case Water injection was initiated at Well No. 1; the producing wells (Nos. 2, 3 and 4) were operated at constant and equal bottom-hole pressures. When water broke through at Well No. 2 and achieved the selected water-oil ratio, Well 2 was converted to a water injection well, resulting in two injection and two producing wells. The injection pressures at Wells 1 and 2 were maintained equal and constant; pressures at the producing wells were held equal, but they were lower than those at the injecting wells. A similar process was repeated when water broke through at Well No. 3. The flood was terminated when

By C. F. de Mendonca, T. Kater, R. P. de Souza

Since 1976, Cia Vale do Rio Doce (CVRD) has carried out tests to develop a type of pellet made with an organic binder. Peridur is one binder that showed it could be used in industrial plants. Extensive tests were run in CVRD's pilot plant. The results are presented in this paper. The decision was made to carry out an industrial production of 50 ht (55,000 st) of pellets. The results are shown in this paper. No detrimental effects of the Peridur were observed in either the process or in product quality.

Jan 1, 1985

By Ross W. Smith, Salim Akhtar

INTRODUCTION Flotation of oxide minerals, particularly silicates, with cationic collectors differs substantially from classic flotation of sulfide minerals using sulfhydryl collectors. In the case of cationic flotation of these minerals, in general: 1. There is a greater importance of electrostatic interaction between mineral and collector. 2. Longer-chained collectors are required; as a rule at least 10 carbons must be present in the hydrocarbon chain. 3. Moderate concentration of collector is required. 4. Attachment between collector and mineral appears to be less strong even though the system may exhibit a large contact angle. 5. Required conditioning time before flotation is usually relatively short. 6. There is sensitivity to slimes. 7. The collectors usually possess frothing power. 8. Selectivity of cationic collectors for specific minerals is usually poor. Almost any of the oxide and silicate minerals may be floated using cationic collectors. However, specific response to these collectors varies with mineral type. The following classes and minerals are

Jan 1, 1976

By C. J. Bier, J. F. O?Keefe

THIS study was carried out with copper because it represents the simplest form of sintering, in that but one metal is involved and all reactions occur in the solid state. [ ] The present work will cover three variables affecting the sintering process; namely, briquetting pressure, sintering temperature and time in hot zone. Although strength and dimensional changes were observed, this is primarily a metallographic study of the sintering process in copper. The term "sintering" should be understood to mean the process by which the metal powder particles of the compact become united into one body. MATERIAL USED The copper powder used was made from reduced copper oxide, and is typical of a grade used for the mass production of parts formed of metal powders. The screen analysis of the powder was as follows: [ ] The minus 325-mesh analysis was made by using a Roller Air Analyzer.1,2 The apparent density is here defined as the weight per cubic centimeter of the [ ] loose, unpacked powder as measured with the Hall flowmeter. The value for the powder used was 2.57 grams per cubic centimeter.

Jan 1, 1944

By Fred D. DeVaney

MINNESOTA taconites are extremely hard, and fine grinding is required to produce an acceptable concentrate. To reduce grinding costs, waste material is rejected by magnetic separators as soon as it is liberated. Cyclones are now used in all Minnesota taconite plants to close the grinding circuits. Erie Mining Co. installed its first grinding section at Aurora, Minn., in 1948-a 9 ½ x12-ft. mill and a fine grinding section consisting of a 10 ½ x12-ft ball mill in closed circuit with a duplex 60-in. spiral classifier. Concentrates from the magnetic cobbers treating the rod mill discharge passed directly into the classifier; the ball mill discharge was also treated in magnetic separators and the concentrate from these machines also went to the spiral classifier. Both concentrates passed through ac demagnetizing coils. It is axiomatic that for proper classification the material in suspension must be well dispersed, and it follows that magnetic concentrate must be almost completely depolarized if classification is to be successful.

Jan 8, 1957

By Lyall Zickrick

NUMEROUS brands of virgin pig lead are used in the manufacture of lead and lead-alloy cable sheath for commercial cables. In changing from one brand of pig lead to another a readjustment of press operating conditions is nearly always necessary. This is due largely to different flow characteristics, and some brands extrude at a much lower pressure than others; for example, copper-bearing lead requires much more pressure than a low-bismuth lead under the same operating conditions. With the modern type of lead press the extrusion practice in general differs very little. Molten lead at a temperature of 375° to 400° C. (710° to 750° F.) is cast in a water-cooled cylinder and allowed to cool or solidify into a slug for six to nine minutes. . This slug is forced into the die block and around the core tube through which the cable runs. The die block is held at an optimum temperature by means of gas flames, usually 175° to 225° C. (350° to 4.35° F.). Measurements of the tem¬perature of the cable sheath taken at the time of extrusion have covered a range of 190° to 225° C. (375° to 435° F.). According to Tammann, the rate of extrusion for a metal under constant pressure through a simple orifice is almost doubled for each 10° C. rise in temperature. Because of the irregularity of die-block construction, such a great increase is not obtained in lead-cable extrusion practice. To obtain more" definite information about the effect of small per¬centages of metals usually present as impurities in virgin pig lead, a series of compression tests were made covering several different brands of lead and various alloys. Since the usual temperature of the sheath is approxi¬mately 200.° C. as it emerges from the die block, these compression tests were all performed at 200° C. Five different brands of virgin pig lead were selected, as follows: Brand A: A desilverized western lead of very high purity. This lead contains neither copper nor bismuth. Brand B: A bismuth-free southeastern Missouri lead, usually con¬taining 0.05 to 0.08 per cent copper. Brand C: A copper-free mid-western desilverized lead of very good grade, usually containing around 0.06 to 0.10 per cent bismuth.

Jan 1, 1932

By Freeman Bishop

This year the metal mining industry is in for some difficult decisions as the nation struggles to control inflationary pressures resulting from higher production costs and a money-squeeze policy. Re- clouding these problems will be campaign oratory as Congress seeks reelection. Charges will be hurled back and forth between a Republican White House and a Democratic Congress. Inflation and Vietnam will be the big one. Hut pollution i. coming on strong. President Nixon has formed a new Council on Environmental Quality although he already had named a similar unit within his Cabinet six months ago. Both are charged with bringing 1.0 bear all of the Federal Government's talents on the focal points of antipollution measures The biggest task will be to find out how many different "units" are currently mixed up in these efforts.

Jan 1, 1970

By R.J. Anderson

Roughly, a crack in a casting may be considered, for the moment, to be due to fracture of the alloy resulting from the stress set up by the contraction in volume on passing from the liquid to the solid state. Cracks may be external or surface, internal or deep-seated, or incipient or so-called strain cracks. Draws may appear as depressions, unevenness, and "pinching in" of the surface of a casting. Roughly, draws are due to contraction in volume and are governed largely by the same factors as cracks. A casting may be cracked, however, without being drawn. Shrinkage is a foundry term and refers to the contractio~l in volume of a metal or alloy on passing from the liquid to the solid state. Patternmaker's shrinkage is the total contraction in volume (including liquid, solidification, and solid shrinkage) that occurs when an alloy is poured into a mold. The contraction in volume of aluminum is one of the principal factors affecting the occurrence of cracks, as will be shown later, and the question of shrinkage and its control requires careful study in any treatment of cracking in castings. In the case of sand and die castings, cracks have been attributed to a number of causes, but in the case of most light aluminum alloys, they are due to the large contraction in volume on freezing and the lack of its regulation or control. The most important factors are: (1) Contraction in volume; (2) composition of alloy; (3) quality of melting charge; (4) design of casting; (5) method of molding; (6) hardness of ramming; (7) method of gating; (8) hardness and characteristics of cores; (9) chills; (10) risers; (11) melting temperatures; (12) furnace used for melting; (13) pouring temperatures; (14) inclusions in alloys; (15) hot shortness of alloys; and (16) physical properties of alloys at high temperatures. Of these, the first, second, third, and eleventh to sixteenth involve ascertainable metallurgical facts; the remainder are largely matters of opinion, judgment, and technical knowledge of men experienced in the production of castings.

Jan 1, 1923

By R. J. Anderson

Roughly, a crack in a casting may be considered, for the moment, to be due to fracture of the alloy resulting from the stress set up by the contraction in volume on passing from the liquid to the solid state. Cracks may be external or surface, internal or deep-seated, or incipient or so-called strain cracks. Draws may appear as depressions, unevenness, and "pinching in" of the surface of a casting. Roughly, draws are due to contraction in volume and are governed largely by the same factors as cracks. A casting may be cracked, however, without being drawn. Shrinkage is a foundry term and refers to the contractio~l in volume of a metal or alloy on passing from the liquid to the solid state. Patternmaker's shrinkage is the total contraction in volume (including liquid, solidification, and solid shrinkage) that occurs when an alloy is poured into a mold. The contraction in volume of aluminum is one of the principal factors affecting the occurrence of cracks, as will be shown later, and the question of shrinkage and its control requires careful study in any treatment of cracking in castings. In the case of sand and die castings, cracks have been attributed to a number of causes, but in the case of most light aluminum alloys, they are due to the large contraction in volume on freezing and the lack of its regulation or control. The most important factors are: (1) Contraction in volume; (2) composition of alloy; (3) quality of melting charge; (4) design of casting; (5) method of molding; (6) hardness of ramming; (7) method of gating; (8) hardness and characteristics of cores; (9) chills; (10) risers; (11) melting temperatures; (12) furnace used for melting; (13) pouring temperatures; (14) inclusions in alloys; (15) hot shortness of alloys; and (16) physical properties of alloys at high temperatures. Of these, the first, second, third, and eleventh to sixteenth involve ascertainable metallurgical facts; the remainder are largely matters of opinion, judgment, and technical knowledge of men experienced in the production of castings.

Jan 1, 1923

By N. LILIENBERGS

DURING the past few years, the requirements for steel have been raised so high that soundness is more important than ever before. The old practice was to mike steel ingots of sufficiently large sections to permit a considerable reduction of area in rolling and hammering to a given size, relying on the fact that by such rolling and hammering all cavities will be squeezed together and practically eliminated. The finished sizes, if found by inspection of the surface to be faultless, were therefore pronounced to be sound. But when such steel is ?worked up,? the manufacturer is surprised and disappointed to find that it splits, or that streaks and seams make the product unmarketable. Large sections, such as rails, beams or heavy forgings, may, within certain limits, be sufficiently strong, even if the sides of the cavities are only squeezed, and not welded together. But it is well known that, in the interior of heavy articles, under certain conditions, forging may develop small streaks into large cavities. Small sections, steel for ordnance and tubes, and numberless articles in the tool-trade, always show up the defects. It may be doubted whether cavities in steel ingots can ever be completely welded. The old theory, is, that the silver-clear blow-holes, without the blue oxide, can be welded by sufficient working. They are, however, not empty, but are filled with carbonic oxide. It is admitted that the "blue" cavities, resulting from air mechanically drawn down into the mold during the casting, can never be welded, because the oxide does not melt, and there would be no escape for it if it did. The only way in which steel can be made satisfactory for the above-named particular purposes is by having it ?dead molten." But then the trouble of piping is encountered. As is well known, a pipe is the result of the contraction of

May 1, 1906

By William F. Boericke

CONSIDERABLE waste of oil and grease in lubricating motors and other machinery results from the use of bearings that are not totally enclosed. There is also the likelihood of damage to the bearing through the accidental introduction of grit or dust both in the oiling process and after, unless the cover is entirely dustproof. With the ordinary sleeve bearing that is only partly enclosed, it is generally easier for a careless attendant to cause trouble through neglect than with the ball bearing type, which from its design, must be totally enclosed to give effective service, and needs a minimum of attention. At one of the large mining companies which has taken a leading part in reducing unit costs and pioneering new developments in mining machinery, ball bearings have been gradually supplanting the conventional type of sleeve bearings on many of their motors, centrifugal pumps, and other machines in the mines. This innovation is not recent, as substitution of ball bearings on mine motors was first tried out by this company in 1909. Since then an increasing number of such bearings have been put in. They are now favored because of increased operating efficiency and reduction in lubrication costs.

Jan 1, 1926

By George W. Orton

i\- number of investigations have established that tungsten monocarbide (WC) forms throughout a wide range of temperatures (800° to 2200°C), but the di-tungsten carbide (W2C) forms only at the high end of this temperature range.1"7 In addition the decomposition of WC into WzC and C at elevated temperatures has been observed.8"10

Jan 1, 1964

By C. F. Clausen

"Cement" means binding agent or glue. It is derived from the Latin word "Caementum," the name of a limestone, chips of which were used in mortar more than 2,000 years ago in Italy. During the middle ages "cement" or "cement" generally denoted mortar. Today it means any binding material. The Thomas Register lists nearly 200 classifications for "cement" including automobile cement, household cement, rubber cement, etc. The material most commonly associated with this word, however, is portland cement which, when mixed with water and allowed to hydrate, is a ceramic binding material used to cement aggregates (crushed stone, gravel and sand) together in "concrete," the most universally used building material of today. It is estimated that more tons of concrete are used annually than all other building materials put together including steel, lumber, gypsum, bricks, tiles, aluminum and glass. Its use in foundations, building construction, sanitary work, dams, railroads, and highways, makes it difficult to conceive of modem civilization without concrete. A survey made in October 1955 showed the following uses of portland cement: [Percent Highways20 Nonresidential buildings20 Residential buildings15 Military construction10 Sewer and water works8 Public utilities10 Other (conservation, farm, and maintenance and repair)17 100] As of today, the percentage for highways is probably even higher. Ceramic binding materials have unquestionably been used in construction work for thousands of years. The mortar between the blocks of the great pyramids was calcined gypsum (plaster of paris). The use of calcined and slaked limestone goes back earlier than the Roman Empire. Gypsum, however, is relatively soft, and common lime mortar is not "hydraulic," i.e., it does not harden under water. The Greeks and Romans discovered later that an addition of a finely divided active siliceous material (Santorin earth or Pozzolana) would react with slaked lime to form a stronger, and hydraulic, cement. The Appian Way in Italy, Colosseum, and the great Aqueducts built by the Romans were made with this type cement, and some of these structures are still in existence today. However, not until 1756 did some serious research result in the development of better cements. In that year the English engineer, John Smeaton produced a stronger cement by burning a limestone containing considerable proportions of clayey impurities. Other investigations and improvements were made by Bryan Higgins, Bergmann, Joseph Parker, L. J. Vicat, J. F. John, James Frost, and I. C. Johnson.2 Traditionally, but perhaps unfairly to others, the invention of the prototype of today's portland cement is credited to the English mason Joseph Aspdin who in 1824 obtained a patent and gave the product its name, because in color the mortar produced from it resembled a natural building stone obtained from the British Isle of Portland. The contributions of Johnson and Aspdin were primarily the important step of preparing a synthetic mixture of lime and clay without depending on raw materials found in nature which might contain such elements in desirable proportions. However, even these early

Jan 1, 1960

By G. D. Rieck, M. M. P. Janssen

Chemical diffusion coefficients and heats of activation for diffusion in the NizAh fy), NiAl (6), and Ni3A1 (E) intermetallic phases and the solid solution of aluminum in nickel (( phase) were calculated from layer growth experiments. No finite diffusion coefficient for the NiAl3 ((3) inter metallic phase could be calculated. The values of the diffusion coefficients are dependent both on the method of calculation and the type of diffusion couple. The heat of activation for diffusion in the y phase was found to be 47 kcal per mole in the temperature range oj 428" to 610°C. Heats of activation of 41, 12, and 48 kcal per mole were found for diffusion in the 6, E, and ( phases, respectively , in the temperature range of 655" to 1000°C. Experiments with markers in the diffusion zone demonstrate a very pronounced Kirkendall effect. It appears that only aluminum atoms take an active part in the diffusion process during the formation of the 0 and y phases at temperatures of about 600°C. During the formation of the 6, E, and < phases at higher temperatures only nickel atoms are moving. It is suggested that the great stability of the intermetallic compounds in the Ni-A1 system governs the Kirkendall effect. SOME factors controlling layer growth during inter-diffusion in the Ni-A1 system (phase diagram, see Fig. 1) were studied by Castleman and Seig1e.l&apos;~ They found the NiA1, ((3) and NiAl3 (y) intermetallic compounds to appear in the diffusion zone of Ni-A1 couples at annealing temperatures of 400" to 625°C; the NiAl (6) and Ni3A1 (E) intermetallic compounds appeared in y-Ni couples at annealing temperatures of 800" to 1050°C. These authors carefully examined metallographically Ni-A1 couples after 340 hr annealing at 600°C. Besides the (3 and y phases they found very thin layers of the 6 and E phases. ~n~erman~ and Castleman and Froot4 observed a much more rapid growth of the 5 and E phases at 600°C in Ni-A1 couples in case a crack was present at the /3-A1 interface. Numerous layer thickness measurements carried out by Castleman and Seigle on the y phase prove that the layer growth of this phase obeys the parabolic law after a certain transient period. From this they concluded that the layer growth of the y phase is controlled by volume diffusion. The growth of the 13, 6, and E phases appeared to be volume-diffusion-controlled also. The authors estimated that at 600°C and at atmospheric pressure Dp was 1.8 x lo-"ll sq cm per sec, D, 9.1 x 10" ™ sq cm per sec, Qp 27 kcal per mole, and Qy 31 kcal per mole. The present work was carried out to obtain more quantitative data about the kinetics of growth of the phases of the Ni-A1 system and the reactions that occur during the formation of these phases. Because in this system the diffusion process results in the formation of several distinct intermetallic compounds, the current term reaction diffusion is used in the title of this paper. In order to obtain layers of the fl phase compound of uniform thickness, a new technique for preparing diffusion couples was developed. The kinetics of growth of the y phase in 6-Al, E-Al, and Ni-A1 diffusion couples was studied at different temperatures. The kinetics of growth of the 6, c, and ( phases in Ni-y, Ni-6, and Ni-c diffusion couples was also studied at different temperatures. The calculation of the diffusion coefficients Dp and Dy by Castleman and Seigle are critically considered in this paper; by means of a revised method of calculation more reliable val-ues of , and Dg were found. These values are in good agreement with the values of the diffusion coefficients obtained by the method of Boltzmann-Matano. From the temperature dependence of the diffusion coefficients the heats of activation for diffusion were calculated by means of an Arrhenius-type equation. The investigation of the Kirkendall effect has been used to obtain information about the ratio of the intrinsic diffusion coefficients of the separate atoms5 and the mechanism of diffusion. Moreover porosity as a result of a distinct Kirkendall effect would be of practical importance in connection with the bonding of diffusion coatings. The analyses of the diffusion couples were carried out by metallographic methods. The values of the concentrations at the phase boundaries and the concentration profile in each of the phases, which are needed for the calculation of diffusion coefficients, were obtained by electron-pro be X-ray microanalysis. EXPERIMENTAL PROCEDURE A) Materials for Diffusion Couples. The intermetallic compounds 6 (50 at. pct Ni) and E (74 at. pct Ni) were prepared from the pure metals by high-frequency induction melting in argon atmosphere. Use was made of aluminum wire (99.99 wt pct Al) and nickel sheet (99.95 wt pct Ni). The 6 and E phase melts and the nickel shiet (thickness 0.1 and 0.5 mm) used for preparing diffusion couples were annealed for 64 hr at 1200°~ for homogenization and grain coarsening (final crystal size 1 to 3 mm). composition and homogeneity of the intermetallic compounds were checked by mi-crohardness measurements and X-ray diffraction. From the 6 and E phase melts discs of 0.5 mm thickness were prepared by means of a water-cooled rotat-

Jan 1, 1968

By F. F. Aplan, P. H. de Bruyn

The adsorption density of hexyl mercaptan was measured at the gold-solution and the gold-vapor interfaces. This collector is strongly adsorbed at low concentrations, a monomolecular layer being formed at the gold-solution interface at concentrations as low as 2 x 10&apos;6 moles per liter. A maximum contact angle of 83 ± 3° is observed. From a thermodynamic analysis of the experimental data the changes in surface tension at the gold-gas and gold-solution interface are calculated. The data also suggest that the adsorption density of mercaptan at the gold-gas interface exceeds that at the gold-solution interface. In the equilibrium state, a simple flotation system consists of three phases, the solid to be floated, air, and an aqueous solution in stable contact along a line. During the process leading to this final state, a solid-gas interface is created at the expense of a portion of the liquid-gas and solid-liquid interfaces. This change of state is achieved by addition of a collector and, if necessary, suitable modifying agents to the system. By a combined application of the Gibbs Adsorption and the Young Equations, de Bruyn, Overbeek and Schuhmannl were able to show theoretically that the equilibrium distribution of the collector at all three interfaces determines the magnitude of the contact angle. Their analysis led them to conclude that the equilibrium adsorption density of the collector at the solid-gas interface exceeds its density at the solid- liquid interface. This paper succeeded in focussing attention on the neglected role of the solid-gas interface in flotation. In recent years the application of radiotracer, infrared, electrochemical and electro-kinetic techniques to studies of the solid-liquid interface2-5 enhanced our understanding of adsorption processes at this interface. Except for the measurement of contact angles, the solid-gas interface received no attention in fundamental flotation studies. In an attempt to apply the analysis of de Bruyn, Overbeek and Schuhmann to a simple flotation system, an investigation of the adsorption of hexyl mercaptan onto gold was undertaken. Gold was chosen as the solid phase in order to keep the number of dissolved chemical species in the solution phase to a minimum. Hexyl mercaptan (1 - hexanethiol) was selected as collector because its relatively high vapor pressure at room temperature makes it possible to obtain adsorption measurements at the solid-gas interface. This flotation system consists, therefore, of a pure solid phase (gold), an aqueous solution of a weakly dissociated collector (1 -hexanethiol), and a gaseous phase, nitrogen saturated with respect to both water vapor and mercaptan vapor. EXPERIMENTAL MATERIALS AND METHODS Materials: Liquid 1-hexanethiol (C6H13SH) was obtained from Distillation Products Industries and was further purified by double distillation. The purity of the final product was established by boiling point and refractive index measurements. For the adsorption studies from aqueous solution, the radiotracer element, sulfur-35, (half life 87.1 days, 0.169 Mev beta ray) was synthesized into the mercaptan by Tracerlab Inc., Boston, Mass. A close boiling fraction of the synthesized compound was used in the adsorption studies. The specific activity of the radioactive compound was 10 millicuries per gram.

Jan 1, 1963

By M. H. Caron

BASIC U. S. Patent 1,487,145 on ammonia leaching of nickel ores was issued to the author on March 18, 1924. Equivalent patents in other countries were obtained later. The Dutch Syndicate Brikcarbo became interested in the process in 1935; and a couple of years later the late Dr. H. Foster Bain sent samples of Surigao laterite iron ore to Delft and witnessed tests made there on this material for the Philippines Commonwealth. As a result, the author was asked in April 1940 by Dr. Bain to go to the Philippines to erect and take charge of a pilot plant for the process. The World War prevented carrying out this proposal. The Dorr Co. also became interested in the process at about the same period. The investigations by the Freeport Sulphur Co. on the process as applied to the Cuban nickeliferous laterites, which resulted in the Nicaro enterprise, and the results of this operation have been well described elsewhere.1,²,³,4,5 This Nicaro plant was, in operation for almost two years, and during this period produced about 10 pct of the world nickel production from laterites containing 1.35 pct nickel. This plant and its operation were war measures and, in view of this, activities were suspended in April 1947. The results obtained fully demonstrated the technical feasibility of the process and its economical aspects on a commercial scale. In this respect, it should be understood that it is probable that improvements may be made by further development, and that there are possibilities for advantageous application of the process to garnierite and similar ores with higher values in nickel than the laterite iron ores at Nicaro. While the articles cited above have given a certain amount of information, no general article containing all the important process data has been pub- lished. Since the process is of more than local interest, a fuller knowledge of the fundamental and practical factors of the method may be welcome to those interested in this new field of metals technology. The author, accordingly, takes pleasure in submitting this article to the AIME as it represents in a condensed form the results of many years of research. The brief outlines of the fundamental and other factors and the explanation of observed phenomena are presented with as little discussion of details as possible, consistent with clarity. It is a special satisfaction to the author to make some contribution of his own in return for the benefits of the many valuable publications issued by the Institute during his thirty years of membership. Ores Adapted for Ammonia Leaching: All nickel and cobalt ores which originate from weathering of peridotites or similar basic rocks having sufficient values are suitable for treatment by the ammonia leaching process after a preliminary reduction under proper conditions. The formation of these deposits was probably as follows: In the course of time the basic rocks were attacked by atmospheric agencies; MgO and SiO2 were gradually leached out, and secondary nickel minerals formed, such as garnierite, a hydrated silicate of nickel and magnesia. These secondary products are, however, not stable. They decompose in a further stage of weathering and ultimately only a relatively small residue of insoluble oxides remains, known as laterite iron ore with a small nickel content and very little cobalt. Under these mantles of laterite, richer nickel values may be found, usually indicated by the occurrence of garnierite. The more the ore is disintegrated by nature, the higher the iron content and the better the nickel extractions that may be expected therefrom. Table I shows extractions that may be expected from different types of ores, assuming treatment of -200 mesh products and that all precautions have been taken for obtaining maximum extractions. As for the distribution of the various nickel minerals and compounds that may be present, great variations may occur from locality to locality as well as vertically in a deposit. From such "run of

Jan 1, 1951