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By F. W. Willard

VIEWING with alarm is a preoccupation not exclusively the habit of the political spellbinder. In good faith many of our mineral technologists have been and are genuinely alarmed over the prodigal consumption of our mineral reserves. Most competent observers are cautiously pessimistic. There are sound technical reasons for such caution. It is the purpose of this paper to discuss some of those reasons without benefit of a gift of prophecy. Perhaps the outstanding reason for caution is ignorance of accessible but undiscovered mineral reserves. The petroleum technologists have an edge on their metallurgical brothers for they have better tools for exploration. This is not to say that the mining geologist has to depend on hunches or the divining rod. The outstanding work on orogenesis by Lindgren and others has provided the mining geologist with some sound scientific knowledge as to where accessible metallic minerals are most likely to be found, As Clinton H. Crane has recently observed, most of the accessible areas of the earth have been combed for easily identified outcrops, and those have been or are being actively exploited. To find ore bodies hidden below the surface is still a costly speculation.

Jan 1, 1946

By J. Handin, S. J. Bauer, M. Friedman

Deformation mechanisms in room-dry and water-saturated specimens of Charcoal Granodiorite, shortened at 10-4s-1, at effective pressures (Pe) to 100 MPa and temperatures to partial melting (?1050°C) are documented with a view toward providing criteria to recognize and characterize the deformation for geological and engineering applications. Above 800°C strength decreases dramatically at effective pressures ? 50 MPa and water-weakening reduces strength an additional 30 to 40% at Pe = 100 MPa. Strains at failure are only 0.1 to 2.2 percent with macroscopic ductility (within this range) increasing as the effective pressures are increased and in wet versus dry tests. Shattering (multiple faulting) gives way to faulting along a single zone to failure without macroscopic faulting as ductility increases. Microscopically, cataclasis (extension microfracturing and thermal cracking with rigid-body motions) predominates at all conditions. Dislocation gliding contributes little to the strain. Precursive extension microfractures coalesce to produce the throughgoing faults with gouge zones exhibiting possible Riedel shears. Incipient melting, particularly in wet tests, produces a distinctive texture along feldspar grain boundaries that suggests a grain-boundary-softening effect contributes to the weakening. In addition, it is demonstrated that the presence of water does not lead to more microfractures, but to a reduction in the stresses required to initiate and propagate them.

Jan 1, 1982

[A Aall, Christian H., M49 D Mgr, American Metal Climax, Inc., 61 Broadway, New York 6, N.Y. Aaroe, S. L., A54 B Sales Mgr, The W. S. Tyler Co. of Can. Ltd., St. Catharines, Ont., Canada Abalos, Teodulo Q., J57 A Foreman, Lepanto Cons. Ming. Co., Mt. Province, Philippines Abbass, G., M55 P. O. Box 680, Hong Kong, China . Abbitt, James M., A54 770 Sole Blvd., Bartow, Fla. Abdullah, M. Y., J53 Dept. of Mines Res. Div., P. O. Box 1016, Tiger Lane, Ipoh Perak, Malaya Able, John F., Jr., J53 A Ming Engr, USA SIPRE 1215 Washington Ave., Wilmette, Ill. Abell, Leo M., M31 B Conct Supt, Phelps Dodge Corp., Morenci, Ariz. Abenius, Hakan Wilhelm, M52 A Mng Dir, Stora Kopparbergs Bergslags AB, Falun, Sweden Abenoroth, Harry F., A57 Natl. Carbon India Ltd., 18A Brabourne Rd., Box 217, Calcutta, India Abercrombie, Harry W., J56 1645 Camphor Dr., Lakeland, Fla.]

Jan 1, 1961

By H. H. Podgurski, J. C. M. Li, Y. T. Chou, F. N. Davis, R. A. Oriani

When an Fe-2 pct A1 alloy is nitrogemted at 500ºC with a gus tnixture (NH3-H2) in which the nitrogen activity has been kept Lou] enough to avoid the formation of iron nitride, a two-phase alloy is generuled which consists of AlN particles and a ferrite phase cotaining a heavy network of dislocations. The amount of nitrogen contained in such an alloy, when equilibrated with the nitrogenating atmosphere, far exceeds both that needed to satisfy the normal solution requirements of a Fe and that needed to convert all of the aluninuwi to AlN. This excess nitrogen is accounted for as being trapped on dislocations, adsorbed at the ferrite -AlN interface, and as an en-Iuznced lattice solubility in strained ferrite. This excessive uptake of nitrogen had previously been attribuled by other investigators to the formation of a nonstoichiornetric aluminum nitride. Isotope exchange experiments revealed various amomts of exchargeable N14 present in the originally nitrided samples that could not be removed by reduction with HS at 500ºC. This exchangeable nitrogen has been identified us that bound to the AlN -ferrite interface. Estimates of inter facial areas in alloys containing -3 pct by weight of A1N are as high as 10 sq m per g of alloy. ThE first1 of this series of papers described the experiments forming the basis for the elucidation of the mechanism of the formation of aluminum nitride particles within an Fe-A1 alloy. It was found that not only are dislocations necessary for the nucleation of the AlN particles but also the nitriding reaction in turn produces a dense network of dislocations in the ferrite matrix. It was also observed that nitrogen in excess of that needed for the formation of stoichiometric AIN is taken up by the alloy without the formation of an iron nitride. The present paper is an analysis of the excess nitrogen sorbed by the nitrided Fe-A1 alloy which considers the structure generated by the formation of the aluminum nitride particles. Because of the high density of dislocations, this system has proved to be quite useful in studying nitrogen-dislocation interactions. Wriedt and Darken2 have already reported such studies in a cold-worked ferritic steel. EXPERIMENTAL Nitrogen Sorption. The specimens of this alloy were cold worked (50 pct reduction) to 0.011 in. thickness and chemically cleaned in a 2:1 concentrated phosphoric acid-50 pct hydrogen peroxide solution before nitrogenation. The flowing nitrogenating atmosphere (11 pct NH3-89 pct H2) was established before the ni- trogenating temperature was reached. The same gravimetric and gas-flow equipment described in an earlier paper1 was also used in this investigation. Changes in nitrogen concentration were followed gravimetrically when establishing the isotherms. In the isotope exchange experiments, concentration changes were followed volumetrically. In some instances chemical analyses (Kjeldahl method) were used to check for material balances in both the gravimetric and volumetric procedures. Our objective was to obtain reversible nitrogen sorption isotherms for alloys equilibrated with NH3-H2 gas mixtures over a large range of nitrogen activity* and temperature. The *Defined as equal to PN H /P3/2 ,where P corresponds to partial pressure in atmospheres. Actually the nitrogen activity, aN, in the alloy equals K PNH3 /p3/2H2, where K is the equilibrium constant for the reaction NH3 = N + 3/2H2. upper limit for nitrogen activity was below that which would produce iron nitride; for reasons which will become apparent later, most of the sorption studies were made in the temperature range between 400" and 500'C. The alloy sample studied most extensively in this investigation was given a series of successive reductions (100 pct H2) and nitrogenating treatments at 500°C to attain a stabilized structure. Presumably some dislocations were lost during these treatments. Throughout most of the sorption studies, temperature was held at ± 1°C and the gas-phase composition was held to k0.2 pet NH3. Based upon the results of numerous diffusion experiments with this alloy* the 'Results to be published in a third paper of this series. times chosen for equilibration were considered more than adequate, Nitrogen Isotope Exchange. The first exchange experiments were carried out by circulating a measured quantity of H2 and NH3* (with a predetermined isotopic *The NH3 was synthesized over a synthetic ammonia iron catalyst using H2, and N2, enriched with N15. AS the NH3 was formed it was removed continuously from the gas phase by circulating the mixture through a refrigerated (78ºK) trap. When most of the nitrogen had been converted to NH3, it was distilled from the trap into a glass storage vessel. composition, N15/N14) over a nitrided specimen at 450°C in a closed glass system. Attempts to reach the exchange limit isothermally, i.e., an isotopic ratio (N15/N14) in the gas phase identical with the extractable nitrogen in the nitrided alloy, were futile. The exchange rate between the gas phase and the alloy was too slow, involving many days. To circumvent the slow exchange with the gas phase, measured amounts of N15 and N14 were introduced into the alloy by nitrogenating with an NH3-H2, mixture at 500°C containing an N15/N14 ratio of 7.76; the charged specimens were then sealed by allowing an oxide film to form over them in air, and in this final condition the specimens were subjected to 500°C in vacuum for various times during which isotope exchange was allowed to proceed within the specimen. It was estab-

Jan 1, 1970

By M. E. Wadsworth, K. C. Bowles, H. E. Flanders, R. M. Nadkarni, C. E. Jelden

The kinetics of precipitation of copper on iron of various purity were carried out under controlled conditions. The rate of reduction has been correlated with such parameters as copper and hydrogen ion concentration, geometric factors, flow rate, and temperature. The character of the precipitated copper as a function of flow conditions and rate of PreciPitation has been observed under a variety of conditions. ThE precipitation of copper in solution by cementation on a more electropositive metal has been known for many years. Basile valentine' who wrote Currus Triumphalis Antimonii about 1500, refers to this method for extraction of copper. Paracelsus the Great2 who was born about 1493 cites the use of iron to prepare Venus (copper) by the "rustics of Hungary" in the "Book Concerning the Tincture of the Philosophers". Agricola3 in his work on minerals (1546) tells of a peculiar water which is drawn from a shaft near Schmölnitz in Hungary, that erodes iron and turns it into copper. In 1670, a concession is recorded4 as having been granted for the recovery of copper from the mine waters at Rio Tinto in Spain, presumably by precipitation with iron. Much has been published in recent literature on the recovery of copper by cementation, the majority of the articles being on plant practice.5-24 The rest include articles on investigation of the variables involved25-28 and a review of hydrometallurgical copper extraction methods." This literature has established: a) The three principal reactions in the cementation of copper are Cu + Fe — Fe+4 +Cu [ 11 One pound of copper is precipitated by 0.88 lb of iron stoichiometrically. In actual practice about 1.5 to 2.5 lb of iron are consumed. 2Fe+3 + Fe — 3Fe+2 [21 Fe +2H'-Fe+2 + H2 [3] Reactions [2] and [3] are responsible for the consumption of excess iron. Wartman and Roberson'28 have established that Reactions [ I] and [2] are concurrent and much faster than Reaction [3]. b) Acidity control is important in the control of hydrolysis and the excessive consumption of iron. he commercial workable range is approximately from pH = 1.8 to 3." c) Iron consumption is closely related to the amount of ferric iron in solution. Jacobi" reports that, by leaving the pregnant mine waters in contact wi th lump pyrrhotite (Fe7S8) for 3 hr, all the iron was reduced to the bivalent condition and scrap iron consumption was cut to 1.25 lb scrap per pound of copper precipitated. He also reported that SO2 has been used successfully to reduce ferric iron to the ferrous state. d) The ideal precipitant is one that offers a large exposed area and is relatively free of rust. e) High velocities and agitation show a beneficial effect upon the rate of precipitation, as it tends to displace the layer of barren solution adjacent to the iron and also dislodges hydrogen bubbles and precipitated copper to expose new surfaces. Little work, however, has been published on the reaction kinetics of copper precipitation on iron. Cent-nerszwer and Heller20 investigated the precipitation of metallic cations in solutions on zinc plates. They found the cementation reaction to be a first-order reaction. The rate constant was independent of stirring for high stirring rates and they concluded that the rate is governed by a diffusional process at low stirring speeds and by a "chemical" process at higher stirring speeds where the rate reaches a constant value. This conclusion has been challenged by King and Burger30 who could not find any region where the rate was independent of the stirring speed, although the rate constant they had obtained for high stirring speed was greater than the maximum value of the rate constant reported by Centnerszwer and Heller (by a factor of six). King and Burger, therefore, concluded that the rate of displacement of copper was controlled only by diffusion. Cementation of various cations on zinc has been summarized by Engfelder.31 APPARATUS A three-necked distillation flask of 2 000-mm capacity was used as a reaction vessel. A pipet of 10-mm capacity was introduced through one of- the side necks, the sample of sheet iron, mounted in a rigid sample holder, through the other, the stirrer being in the middle as shown in Fig. 1. The whole assembly was immersed in a constant-temperature bath. The stirrer was always placed at the same depth in the solution. EXPERIMENTAL PROCEDURE Reagent-grade cupric sulfate (J. T. Baker Chemical Co., N.J.) was used to make up a stock solution containing 10 g of copper per liter which was then diluted to various concentrations as required. Experimental data were obtained by measuring the amount of copper and iron ions in solution at successive time intervals. The initial volume of the solution was always 2000 ml, 10-ml aliquots being removed each time for chemical analysis. Because the total volume change of the solution was less than 10 pct, no correction was used for solution volume change. Nitrogen was bubbled through the solution before and

Jan 1, 1968

By J. Chipman, T. Fuwa

The effects of various elements on the activity coefficient of carbon in liquid iron have been studied by two experimental methods: 1) equilibration with controlled mixtures of CO and CO2; 2) the solubility of graphite in the melt. Activity coefficient of C is increased by Al, Co, Cu, Ni, P, Si, S, and Srz. It is decreased by Cr, Cb, Mn, Mo, W, and V. THE thermodynamic properties of the iron-carbon binary system have now been fairly well established, although some uncertainty remains with respect to the exact location of some of the phase boundaries. The activity of carbon in ferrite and in austenite has been measured in the classic researches of R. P. smith' while similar measurements by Richardson and ~ennis, and by Rist and chipman3 have established the values of the activity of carbon in liquid iron up to 1760°C. On the other hand, our knowledge of the effects of alloying elements on the activity of carbon in dilute solutions is restricted to Smith's experiments on systems Fe-C-Mn and Fe-C-Si in the austenitic range and to some more recent experiments of schwarzman4 in the a range. In addition there have been a number of determinations of the effects of various elements on the solubility of graphite in liquid iron, and from these the corresponding effect in saturated solution may be obtained. The purpose of the present study was to extend the investigation of the liquid system to include the effects of alloying elements upon the activity coefficient of carbon, principally in dilute solutions. Equilibrium measurements were made on the reaction C + co, = 2 CO (g) The prepared mixture of CO and CO,, diluted with argon, flowed over the surface of the liquid metal which, after several hours' exposure to the gas, was quenched and anqlyzed. As in the earlier experiments, the principal experimental difficulty was in the deposition of carbon on the parts of the furnace at temperatures slightly below that of the metal bath. In order to minimize this difficulty, the ratio (Pco)2 /PCo2 was restricted to values not much higher than 100 atm, and correspondingly the carbon concentration in the metal seldom exceeded 0.30 pct. EXPERIMENTAL METHODS The method and apparatus were essentially the same as used by Rist and Chipman.3 The gaseous mixture consisting of highly purified CO, CO,, and argon, each controlled by a flowmeter, was led into the furnace and passed over the surface of the liquid-iron melt which was heated and stirred by high-frequency induction. One slight modification was made in that a molybdenum susceptor was placed outside the crucible for the sake of uniformity of temperature and to combat the tendency of carbon to precipitate on the crucible wall. Pure alumina crucibles approximately 25 mm ID were used. The charge consisting of about 30 g was made up of electrolytic iron, the alloying element to be added, and enough graphite to supply slightly more or less than the anticipated equilibrium carbon concentration. All metals used were of high purity. Metallic chromium, columbium, and vanadium were from special lots supplied by the Electro Metallurgical Co. Tin, copper, molybdenum, tungsten, cobalt, and nickel were of purest commercial grades. The electrolytic iron, after being cut to the proper size for charging, was prereduced by hydrogen at 850° to 1000°C to remove surface oxidation. The oxygen content of the reduced material was 0.002 pct. This treatment made it easy to control the carbon content of the initial melt. The charge was melted under the gas mixture to be used for the entire run. In some earlier melts the charge was melted under a stream of argon, but in this case some alumina was reduced from the crucible, and the aluminum thus absorbed in the melt was subsequently oxidized with the formation of a solid film of alumina on the surface of the melt. AS another safeguard against film formation, overheating of the bath was carefully avoided. All runs were made at a temperature of 1560°C. Under experimental conditions a charge of pure iron picked up 0.17 pct C in 3 hr and 0.23 pct C in 6 hr under an atmosphere for which the equilibrium concentration of carbon is 0.27. It is clear that the time required to reach equilibrium from an initially carbon-free melt would be very great. For this reason each experiment was started with a melt of known carbon concentration not far above or below the expected equilibrium value, and each melt was held at temperature for a period of at least 5 hr. Under such circumstances it was possible to chart the approach to equilibrium from both high-carbon and low-carbon materials. Temperature was controlled by frequent optical observation and adjustment and the metls were timed in such a way that the final 2 hr occurred during a time when electric power was steady; for example, 2 to 4 pm or after 11 pm. In melts containine volatile metals such as copper, tin, and mangane\e the time of holding was decreased somewhat in

Jan 1, 1960

By C. M. Sellars, F. Maak

Electvomotie -force measurements hazle been made on ten Au-Ni alloys at temperatures 7754 825O, 900O, and 935°C using galvanic cells with solid electrolyte. Partial and ivtegral thermodynamic functions are derived from the determined activities. which show la9,ge positive deviations jvom Raoult's law. The enthalpies of mixing- are in close accord with calorinletric data and are of comparable accuracy. The results are used to determine the miscibility gap and the spinoidal curL1e, and are qlalitaticely interpreted in terms of the large size difference and electvonic interactions between gold and nickel. Tabulated nalues of the actielities and partial and inteqal free energies, entropies , and enthalpies of mixing are given in the appendix. The Au-Ni binary alloys are of particular interest thermodynamically as despite the large size difference between gold and nickel atoms they have a simple phase diagram.' This shows complete solid solubility above a miscibility gap with a maximum at about 71 at. pct Ni and 810°C. Activity measurements (over a range of temperature) have been made previously on this system using an electrolytic-cell method with a liquid chloride eletrolyte. The accuracy of this data has, however, been queried3'4 as it leads to values for the enthalpy of mixing which are too high when compared with calorimetric measurements.46 Also, the entropy of mixing is too high when compared with the values derived from specific-heat measrements. It was therefore considered worthwhile redetermining the activity data using a galvanic cell with a solid electrolyte (0.85 ZrO, 0.15 CaO). This method is based on a technique introduced by Kiukkola and aner'' and has been used to determine the thermodynamic data for Cu-Ni alloys.' THE ELECTROLYTIC CELL The cell used to determine the activity of nickel in Au-Ni alloys was: The cell reaction, which is discussed for a similar cell by Rapp and Maak, gives a direct measurement of the activity of nickel in the alloys as where aNi(alloy) is the activity of nickel in the alloy, 3 is Faraday's constant, E is the measured electromotive force, R is the gas constant, and T is absolute temperature. For the valid application of this type of cell the arrangement must be ther modynamic ally stable, which means that: 1) The free energies of formation of the oxides fulfill the relation 2) The vapor pressures or dissociation pressures of each component must be so small that during the time of the experiment the amount of any material transported by the gas is negligible. 3) Side reactions which change the alloy composition must be negligible. These reactions are possible both with the surrounding gas atmosphere and with neighboring solid material. The first two conditions are fulfilled by the above cell.' The third condition is approached by care in the experimental technique. The factors which control the attainment of equilibrium in this type of cell have been considered by Rapp and aak, who conclude that metallic diffusion in the alloy is the rate-control ling step. A lower temperature limit for the practical application of this cell is therefore set by the condition that equilibrium must be attained in reasonable times. EXPERIMENTAL MATERIALS AND TECHNIQUE The starting materials were mint gold (99.99 pct Au) and Mond nickel (99.9 pct Ni). Alloys, nominally 5 at. pct Ni and then each 10 at. pct across the system, were produced by vacuum-levitation melting compacts of mixed drillings of the pure metals. The nickel used for the reference tablets in the cells was melted in a similar manner. The alloy ingots, cast in boron nitride molds, were cold-forged and

Jan 1, 1967

By J. A. Grimes, Paul Billingsley

A. Introduction. 1. Association of Ores and Igneous Rocks. 2. Identity of Granite Rocks. B. General Geology. 1. Geologic Events of the Igneous Cycle. 2. Association of Igneous Intrusions with Tectonic Forces. C. Igneous Rocks. 1. Andesite Period. 2. Granite Period. (a) Diorite. (b) Quartz-Monzonite. (c) Aplite. (d) Quartz-Porphyry. (c) Quartz-Veins. 3. Rhyolite Period. 4. Comparative Analyses. D. Classification of Deposits. 1. Genetic Classification. 2. Parallelism Between Igneous Stages and Stages of Ore Deposition. Part 2.—The Ore Deposits Andesite Period. A. Andesite Phase. 1. Disseminations—Baggs Creek. 2. Contact Deposits—Iron Mines of Ekhorn Mountains. 3. Fissure Veins—Emery District. (a) Fissure Veins in Andesite Walls. (b) Mineralization Along Bedding of Flows. (c) Mineralization of Amygdaloidal Lavas. (d) Mineralization of Breccia. 4. Summary.

Jan 1, 1918

By AIME AIME

ENGINEERS in the past have been largely associated with private enterprise and there has been a considerable tendency on the part of some members of our profession to depreciate government service for engineers. We engineers must change our mental attitude about employment in government service, particularly in view of the present most friendly attitude of the U. S. Civil Service Commission toward engineers for major posts in our Government. We must also take a much more active interest in public affairs. It must be realized that the national-defense program, which we are now organizing, will require for its effectiveness large numbers of engineers skilled in a wide range of technical and administrative services. In fact, the success of this undertaking will depend largely upon the extent to which our Government can command expert engineering talent to serve during the emergency. There is an acute shortage of technical and supervisory engineering personnel not only in the industries concerned with national defense but also in the Army, Navy, and other defense agencies of the Government. By an Act of Congress, approved on Oct. 9. 1940. $9,000.- 000 was turned over to the U. S. Office of Education, the regular defense agency of the Government which has co-operated with higher education for

Jan 1, 1941

By AIME AIME

UNTIL recently, practically all geophysical prospecting in Australia was conducted by government departments, either by the Aerial, Geological and Geophysical Survey of Northern Australia or the New South Wales Department of Mines. At present, in addition, the Shell company is carrying out an extensive geophysical campaign in South West Queensland. The Northern Australia Survey has now been in operation for over six years, its work being carried out principally in the northern and central parts of Australia over an area of about a million square miles. At present this Survey is being brought to a conclusion but it appears certain that the geophysical section will be transferred to a Commonwealth Government department on a permanent basis. At present the officers of the Geophysical Section are preparing or have issued some 150 reports on their field work and also a special technical report on the geophysical practice of the Survey.

Jan 1, 1942

By AIME AIME

A METALLURGICAL research building is to be erected for the Armour Research Foundation at the Illinois Institute of Technology. It will be located at the corner of Federal and 34th Sts., Chicago, and fully equipped will cost $250,000. It will provide the Middle West with the largest and most complete of facilities for the conduct of developmental and industrial research in this field. The new building will be constructed around an existing foundry and metallurgical research building which has become too small to carry on and service the many research projects contracted for by the Foundation, having to do with steel, alloys, and nonferrous metals. After two bays of the new unit have been completed, the old unit will be torn down and the new one completed.

Jan 1, 1942

By M. R. Pickus, C. H. Mathewson

THE study of the plastic deformation and recrystallization of metals has been the subject of many investigations. In regard to the simple deformational processes, such as tension and compression, the early knowledge gained from studies of polycrystalline material has been supplemented by many significant researches on the behavior of single crystals. Unfortunately, this has not been true for more complicated deformational processes. As far back as 1927, G. I. Taylor1 wrote: It is impossible in the present state of knowledge to do more than give a possible reason why (face-centcred cubic) crystals set themselves with a (110) direction in the plane of rolling, and at right angles to the direction of rolling. The explanation of why the orientation of the crystal axes round the transverse direction is what it is, must be left till the distortion of metals, and particularly single crystals of metals in the process of rolling, has been studied in greater detail. That this gap in the systematic study of deformation and recrystallization has not yet been filled was indicated by C. H. Samans,2 who wrote in 1934 that "only four investigations upon cold-rolled single crystals of any of the face-centered cubic metals have been reported in the literature." Of these four studies, only those of S. Tanaka3 and T. Sakao,4 both of whom worked with aluminum crystals, had quantitative significance. The other two, carried out by F. Wever5 and W. G. Burgers," were of a qualitative nature. It is our hope that the present investigation may contribute something to the knowledge necessary for a rationalization of the origin of rolling textures in terms of the known behavior of single crystals, and may add pertinent information concerning the recrystallization characteristics of deformed single crystals.

Jan 1, 1938

By C. H. Mathewson, M. R. Pickus

The study of the plastic deformation and recrystallization of metals has been the subject of many investigations. In regard to the simple deformational processes, such as tension and compression, the early knowledge gained from studies of polycrystalline material has been supplemented by many significant researches on the behavior of single crystals. Unfortunately, this has not been true for more complicated deformational processes. As far back as 1927, G. I. Taylor1 wrote: It is impossible in the present state of knowledge to do more than give a possible reason why (face-centered cubic) crystals set themselves with a (110) direction in the plane of rolling, and at right angles to the direction of rolling. The explanation of why the orientation of the crystal axes round the transverse direction is what it is, must be left till the distortion of metals, and particularly single crystals of metals in the process of rolling, has been studied in greater detail. That this gap in the systematic study of deformation and recrystallization has not yet been filled was indicated by C. H. Samans, who wrote in 1934 that "only four investigations upon cold-rolled single crystals of any of the face-centered cubic metals have been reported in the literature." Of these four studies, only those of S. Tanaka3 and T. Sakaoj4 both of whom worked with aluminum crystals, had quantitative significance. The other two, carried out by F. Wever5 and W. G. Burgers16 were of a qualitative nature. It is our hope that the present investigation may contribute something to the knowledge necessary for a rationalization of the origin of rolling textures in terms of the known behavior of single crystals, and may add pertinent information concerning the recrystallization characteristics of deformed single crystals.

Jan 1, 1939

By M. R. Pickus, C. H. Mathewson

The study of the plastic deformation and recrystallization of metals has been the subject of many investigations. In regard to the simple deformational processes, such as tension and compression, the early knowledge gained from studies of polycrystalline material has been supplemented by many significant researches on the behavior of single crystals. Unfortunately, this has not been true for more complicated deformational processes. As far back as 1927, G. I. Taylor1 wrote: It is impossible in the present state of knowledge to do more than give a possible reason why (face-centered cubic) crystals set themselves with a (110) direction in the plane of rolling, and at right angles to the direction of rolling. The explanation of why the orientation of the crystal axes round the transverse direction is what it is, must be left till the distortion of metals, and particularly single crystals of metals in the process of rolling, has been studied in greater detail. That this gap in the systematic study of deformation and recrystallization has not yet been filled was indicated by C. H. Samans, who wrote in 1934 that "only four investigations upon cold-rolled single crystals of any of the face-centered cubic metals have been reported in the literature." Of these four studies, only those of S. Tanaka3 and T. Sakaoj4 both of whom worked with aluminum crystals, had quantitative significance. The other two, carried out by F. Wever5 and W. G. Burgers16 were of a qualitative nature. It is our hope that the present investigation may contribute something to the knowledge necessary for a rationalization of the origin of rolling textures in terms of the known behavior of single crystals, and may add pertinent information concerning the recrystallization characteristics of deformed single crystals.

Jan 1, 1939

[Contents AH-Metal Mining and Industrial Minerals Pipeline Transportation of Phosphate. (Paper by I. S. Tillotson, R. B. Burt, and J. A. Barr, Transactions AIME, 193, 273; Mining Engineering. March 1952. Discussion by Howard Howie.) 1066 B-Minerals Beneficiation The Effect of Zinc Deleading Operations on Lead-Zinc Selectivity at the Parral and Santa Barbara Mines. (Paper by C. L. Boeke an G. C. Gunther, Transactions AIME, 193, 495; Mining Engineering. May 1952. Discussion by I. M. Symonds, L. H. Lange, Norman Weiss, H. S. Wildman, C. F. Zeuch, E. H. Crabtree.) 1067 Jaw Crusher Capacities, Blake and Single-Toggle or Overhead Eccentric Types. (Paper by D. H. Gieskieng, Transactions AIME, 190, 971; Mining Engineering. November 1951. Author s supplement.) 1069 Screened Ore Use for Fine Grinding at Lake Shore Mines. (Paper by Bunting S. Crocker, Transactions AIME, 193, 499; Mining Engineering. May 1952. Discussion by Fred C. Bond, J. Myers, Norman Weiss, Harlowe Hardinge, Oscar Johnson, L. E. Djingheuzian.) 1069 The Third Theory of Comminution. (Paper by Fred C. Bond, Transactions AIME, 193, 484; Mining Engineering. May 1952. Discussion by Milton C. Shaw and Donald R. Walker; R. J. Russell.)1071 Flotation Rates and Flotation Efficiency.t (Paper by Nathaniel Arbiter, Transactions AIME, 190, 791; Mining Engineering. September 1951. Discussion by Gregoire Gutzeit and Porter Clements.) 1074]

Jan 1, 1952

By J. E. Andersen, J. Halpern, C. S. Samis

In the presence of oxygen, galena is oxidized in an aqueous medium containing sodium hydroxide, in accordance with the following reaction: PbS + 2O2 + 3OH ? HPbO2 + SO4 = + H2O A novel method was devised for following this reaction which takes place in an autoclave under oxygen pressure, by measuring the concentration of HPbO2- in the solution with a cathode ray polarograph employing stationary platinum electrodes. Using this procedure a study was made of the kinetics of the reaction, in which the effect of a number of variables, including temperature, oxygen pressure, NaOH concentration, and agitation, on the rate, were determined. The results of this study are described and discussed, in terms of possible mechanisms for the reaction. IT is known that sulphide minerals can be oxidized in aqueous media in the presence of oxygen under pressure. Reactions of this type can be classified in two categories depending upon whether the products of oxidation are insoluble or soluble in the aqueous medium. An example of the first type of reaction is the oxidation of pyrite in alkaline solutions, giving rise to an insoluble iron oxide. The kinetics of this reaction have been investigated and its mechanism established.' It has been applied in the oxidation of iron sulphides present in refractory gold ores to improve the subsequent recovery of gold by cyanida-tion.' The second type of reaction finds application where it is desired to recover the metal by leaching during oxidation. In this case a medium is selected in which the oxidized mineral is soluble. For example, nickel, copper, and cobalt sulphide ores can be treated by oxidation in the presence of a solution of ammonia dissolving the nickel, copper, and cobalt as the metal ammine sulphate salts.:' A similar treatment has also been reported to apply to zinc sulphide ores.' It is known that lead sulphate is soluble in solutions of sodium hydroxide or ammonium acetate. It should therefore be possible to dissolve the lead from galena ores by aqueous oxidation with oxygen under pressure using either of these solutions. The applicability of the ammonium acetate treatment has been investigated and confirmed in a recent study.' The present paper describes the results of a similar study in which the kinetics of the oxidation of galena in sodium hydroxide solutions have been investigated. The object of this investigation was pri- marily to obtain information of a fundamental nature relating to the kinetics and mechanism of this reaction. The use of pulps of comminuted ore in a study of this type is undesirable because of the difficulty in controlling and measuring the surface area. The measurements were therefore made using galena crystals of measured surface area and in this way absolute reaction rates were obtained. The reaction was found to proceed as follows: PbS + 2O2 + 3OH ? HPbO2 + SO4 + H2O [I] The products are sodium plumbite and sodium sulphate salts which dissolve in the aqueous solution. The reaction studies were carried out in an autoclave in which a desired pressure of oxygen was maintained. The reaction was followed by measuring the concentration of lead in the solution with a cathode ray polarograph. The results obtained in this investigation are presented and discussed in the present paper. Experimental Materials: The crystals of galena were obtained from Violamac Mines, Sandon, B. C. The following impurities were indicated by spectrographic analysis carried out by the Provincial Assay Office, Victoria, B. C.: Sn, 0.02 to 0.2 pct; Sb, 0.07 to 0.7; Zn, 0.01 to 0.1; Si, Fe, Mg, As, less than 0.05 pct; Ag, 126 oz per ton, the latter determined by standard fire-assaying procedure. After cutting a specimen measuring approximately 5x7x12 mm, the crystal surfaces were ground parallel to the 100 axes using No. 2 emery, washed with water, and the dimensions were measured with a micrometer. Oxygen gas was of commercial grade and supplied in cylinders by Canadian Liquid Air. Solutions were made up with chemicals of chemically pure grade and distilled water. Equipment: Autoclave: The autoclave used in these studies was constructed of stainless steel and

Jan 1, 1954

By G. W. Jones

THIS paper describes experiments in which eight test samples of gelatin dynamite were fired in three different types of apparatus and the quantity and composition of the gaseous products of detonation determined. The special dynamites were so prepared that the oxygen balance of the samples varied from -35.0 to +6.0 g. per 100 g. of explosive, including the wrapper. By means of this graded series of explosives, the relation between oxygen balance and gaseous products of detonation could be studied explicitly. The effect of varying oxygen balance on explosive strength has been discussed in another paper.1 The apparatus employed in the work described in the present paper included (1) the Bichel gage, a steel bomb of 15-1. volume; (2) the Crawshaw-Jones confined detonation apparatus, a steel cannon from which the explosive is fired into a pipe of 90-1. volume; and (3) the Hercules tank, an apparatus in which the explosive is confined in a quartz block which is placed in a steel tank of about 4500-1. volume. A full description of the apparatus is given later. VARIABLES AFFECTING COMPOSITION OF DETONATION PRODUCTS The character of the detonation products of commercial explosives is governed in part by the same factors that affect the combustion products from explosive mixtures of air with gases or vapors. In either case, combustible materials-namely, carbon, hydrogen, and sometimes sulfur-are present and combined variously. In an exploding gas mixture the combustibles are oxidized by oxygen in the admixed air, whereas with explosives the necessary oxygen is provided by oxygen-carrying materials in the explosive ingredients.

Jan 1, 1928

By Victor A. Phillips

A series of strips of a Ni-12.7 at. pct A1 alloy were Prepared containing cubical y'(NisAl) precipitates with edge lengths from 60 to 500A. A particle-free solution-tveated strip was included for cornparison. They weve cold-rolled 95 pct and the effects of particle size on the isochronal (1/2 hr) annealing behavior between 300° and 950°C studied (by hardness and light and electron microscopy). It ulas inferred that the particles deformed with the lnatvix becoming lamellae which remained coherent. Comparison with published data fov pure nickel showed that aluminum greatly re-tavded softening and recrystallization, but it made little difference whether or not particles were present. The presence of pakticles led to a heterogeneous distribution of precipitates after annealing at 700" to 750°C. Recovery was not detected. Recrystallization occurred by the growth of new grains into unrecrys-tallized material. In a previous study by the author,' the growth of Ll2-type ordered yl(Ni3Al) precipitates was followed in Ni-12.7 at. pct A1 alloy as a function of aging at 600" and 700°C. The particles were showo to be cubical in shape in all sizes from 50 to 3000A and remained coherent. This work was used as a guide in preparing the starting structures for the present study of the effect of these particles on the annealing behavior of heavily cold-rolled strip. Another question of present interest was whether dislocation and particle hardening were additive, since the structures before rolling ranged from solution-treated to peak-aged to overaged. Also, precipitation might occur on annealing after cold-rolling. Reference may be made to other papers2"5 for previous work in this relatively unexplored field and only some recent work will be mentioned her:. phillips2 studied the effect of deformable 0 to 590A-diam cobalt particles on a Cu-3.23 pct Co alloy rolled 95 pct and found that the particles, which rolled out into thin lamellae, impeded softening and recrystallization. Tanner and servi3 likewise studied the annealing of cold-swaged Cu-2 pct Co alloy containing 150A-diam particles and found impeding effects. Haessner et a1.,4 on the other hand, found that incoherent 2-p-diam non-deformable particles of B4C (0.04 vol pct) tended to increase the rate of recrystallization of copper rolled up to 95 pct reduction. They attributed this to the formation of new grains at the particle interfaces. Humphreys and artin' found that nondeformable silica particles in copper rolled to 30 pct reduction accelerated recrystallization if the particle spacing was large and retarded it if the spacing was smaller. Haessner et a1 4 also studied a rolled Ni-Cr-A1 alloy; however, the particles of y'(Ni3Al)-type precipitate were not put in before rolling, but separated during the isothermal annealing at 750°C. No previous work appears to have been carried out on the effect of y' (Ni3A1) particles on the annealing of Ni-A1 alloy. Hornbogen and ICreye7 redetermined the solubility c of aluminum in nickel as a function of temperature T and showed that it was given by c = 32.6 exp(-1940/RT). This relation gives aluminum solubilities of 15.1, 14.2, 12.0, and 10.7 at. pct at 1000°, 900°, 700°, and 600°C, respectively. The phase precipitated from the nickel-rich solid solution is fcc y1 (Ni3A1) which has a Cu3Au -type ordered structure8 and remains ordered up to 1000°C.B EXPERIMENTAL PROCEDURE The alloy used was identical with that used before. Chemical analysis showed 6.27 wt pct (12.71 at. pct) Al, the principle impurities being 0.065 pct Fe, 0.022 pct Co, 0.020 pct Cu, and 0.004 pct C. Bar stock of 1 in. diam was cold-swaged to % in. diam, cold-rolled to 0.300-in.-thick strip, and annealed at 900°C in dry hydrogen. It was cold-rolled to 0.100-in. thickness and solution-treated for 1 hr at 1000°C while sealed in a quartz tube in argon, quenching in iced brine with the aid of a device to snap off the nose of the tube. Lineal analysis gave an average grain size of 0.055 mm. Pieces of strip were aged at 700°C in vacuo for 30 min, 51/4 hr, and 1 week to produce nominal average particle widths of 60, 150, and 500A, respectively, as known from the previous work.' The average diamond pyramid hardness was determined. The heat-treated strips were rolled from 0.100 to 0.005 in., a reduction of 95 pct, and the rolled strips stored at about -5°C. Small pieces were annealed within 1 week for 30 min at temperatures from 300° to 950° ±2°C in a horizontal vacuum furnace. Strips were withdrawn into a cooling zone, giving an estimated initial cooling rate from 950°C of about 50°C per sec. Average diamond pyramid hardnesses were determined on a lightly electropolished spot on the surface of each strip using 300-g load. Each point on the softening curves represents a separate annealed specimen. Sections containing the rolling direction were examined by optical metallography. Selected specimens were electrothinned to the center plane' and examined by transmission at 100 kv in a Siemens Elmiskop I electron microscope. It is well-known that changes in the structure tend to occur when a deformed strip is electrothinned below a thickness of a few hundred angstroms, although this is less serious with a material such as nickel which has a high melting point, and also is apt to be less serious when particles are present. Observations were nevertheless confined to thicker regions of the foils with estimated thicknesses over 1000A. No changes were observed due to beam exposure.

Jan 1, 1968

By M. V. Nevitt

In the systems Ti-Mn-O, Ti-Fe-O, Ti-Co-O, and Ti-Ni-O the bounda.r-ies of the Ti2Ni-type phases were determined at one or more temperatures and the variation of the lattice parameter with oxygen content was determined. Densities were calculated from the lattice parameters and compared with measured density values. The: results indicate that the occurrence of the phase in these systesms can be correlated qualitatively with valency electron concentration, and that the role of oxygen is that of an electron acceptor. The lower limit of oxygen solubility appears to be determined by the valencies of Mn, Fe, Co, and Ni, while the maximum oxygen concentration coincides with the filling of the 16 (c) positions of the O 7h - Fd 3m space group. THE suggestion has been made by several investigators'" that the phases having the cubic E9,-type structure, and known as 17-carbide-type, double-carbide-type and Ti,Ni-type, are members of a family of electron compounds. This concept has been given additional support by recent work8 in which new isostructural phases involving second and third long period combinations were found, and which provided further evidence of the regularity of occurrence of the phase in terms of periodic table relationships. In this laboratory attention has been focused on the isomorphs containing titanium, zirconium, or hafnium, and the role that oxygen plays in their occurrence. In some binary systems Ti,Nitype* phases occur having the formula A,B where A is the titanium group element. Based on previous workq and the present investigation, oxygen is known to be soluble in two of these binary phases, Ti,Co and Ti2Ni. It is probable that oxygen is also soluble in the other phases of this kind. In other binary systems the Ti,Ni-type phase does not occur, but does occur in the corresponding ternary systems with oxygen .3-5 The experiments described here were performed to determine whether the occurrence and composition of certain of the Ti,Ni-type phases could be related to an electronic effect and whether oxygen's stabilizing role is exerted through an influence on the electron: atom ratio. The ternary systems Ti-Mn-O, Ti-Fe-O, n-Co-O, and Ti-Ni-O were selected for study for two reasons: First, several schemes have been proposed for first long period elements which, although not in quantitative agreement, show a generally consistent trend for the variation of valency with atomic number. Although for a transition metal the term valency is difficult to define and is generally not a constant number which can be applied to all alloys, it is usually assumed to be an index of the number of electrons per atom involved in metallic cohesion. Second, the determination of the Ti2Ni-type phase boundaries was facilitated by the fact that the phase relations in several of these ternary systems have been investigated by other workers."' EXPERIMENTAL PROCEDURE___________________ The alloys were prepared by arc melting crystal-bar titanium, reagent grade TiO, and electrolytic manganese, iron, cobalt, and nickel. Each button was remelted at least three times. The metals had a minimum purity of 99.9 pct except the nickel whose purity was 99.4 pct, the major impurity in this instance being cobalt. The preparation of the manganese alloys was attended by the customary difficulties associated with the vaporization of manganese. The technique used in this case was to add approximately 10 pct extra manganese to the original charge and to continue remelting the button until the final weight was in agreement with its intended weight. At least three alloys in each system were analyzed chemically and the results, even for the manganese alloys, were in good agreement with the intended compositions. A few additional alloys in the Ti-Mn-O system were prepared by the sintering of mixed powders in evacuated quartz tubes followed in some cases by arc melting. For annealing, the alloys were wrapped in molybdenum foil and placed in fused silica tubes containing zirconium chips. The fused silica tubes were evacuated at room temperature to a pressure of 1 x l0-6 mm of Hg and sealed. These capsules were then annealed for 72 hr at an external pressure of 5 x 10-5 mm of Hg in a vacuum furnace whose temperature could be controlled to + 1°C. The success of this procedure in avoiding significant oxygen or nitrogen pickup was indicated by the bright, ductile condition of the molybdenum foil and by the complete absence of a microscopic reaction layer on the specimens. This method did not permit rapid quenching of the specimens but in no case did metal-lographic examination indicate that a solid-state transformation had occurred on cooling. Metallo-

Jan 1, 1961

By N. H. Emmons

(Canal Zone Meeting, November, 1910.) AN interesting development of copper blast-furnace construction has been brought about in adapting the blast-furnace to be a "burner" for sulphuric acid making. When the Tennessee Copper Co. first decided to construct an acid-plant, the standard type of brick-top furnace, supported by structural steel, was the only one in use at this plant. All the tests for temperature and strength of gas had been made on these furnaces, and had been satisfactory. When, however, the acid-plant was put on the flue, and the flue had to have a damper put in it to force the gas into that plant, troubles began. The furnaces were fairly tight, and for a few months the work was quite satisfactory., Fig. 1 shows the old type of furnace-top used at the start. It was soon found that this top would not stand the temperatures, particularly when dampered back, as was necessary to force the gas into the Glover towers. The structural steel, of which the furnace skeleton was constructed, warped and twisted so badly that it was not safe to use the furnaces. This effect is shown by Fig. 2, which is a photograph of old No. 4 furnace, after the brick-work had been removed. It became apparent that a new type of top was necessary and the engineering force was started oil the design of a new furnace-top, with the result that a low top, with brick-lined flues at each end below the feed-floor, leading to the main concrete dust-chamber, was constructed. This furnace, No. 7, is shown in Fig. 3. The charging-doors are made of cast-iron sections, three sections to a door, and three doors to a side. A door to the furnace was made of cast copper, but the heat was so great that the copper bent readily, due to the jarring of its * General Manager, Tennessee Copper Co.

Feb 1, 1911