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By M. L. Fuller

OWING to the nature of the die-casting process, freshly cast alloys are undoubtedly not at equilibrium from the standpoint of alloy phase relationships. After casting, therefore, they tend to undergo phase changes, with the ultimate effect of reaching a state of equilibrium at the aging temperature, beyond which no further change takes place. This phase alteration undoubtedly is one of the primary causes of the changes in dimensions and physical properties that zinc-alloy die castings undergo during aging. It is planned to report on this problem in a series of papers of which this is the first. The writers have made a study of commercial zinc die-casting alloys over a period of several years, utilizing the X-ray diffraction technic of determining the phase composition changes in the alloys. Up to the present, two principal phase changes have been observed which are capable of causing dimensional changes: (1) the segregation of secondary constituents from the zinc-base solid solution and (2) the beta aluminum-zinc decomposition. The latter is the subject of the present paper and studies on the former will be reported upon at a future time.

Jan 1, 1934

By George B. Clark

THE " Munroe effect" of shaped explosive charges was discovered by Charles E. Munroe more than 50 years ago (in 1888), but it was not until World War II that it was put to any practical use. Both Allied and Axis armies used the principle effectively in bazooka projectiles, artillery projectiles and in fixed shaped charges. The first two were used primarily to combat tanks and other armor and the latter to assault pillboxes and other fixed concrete emplacements. Many engineers and others who saw the military application of the jet effect of shaped charges believed application would be possible in many industrial fields where blasting is used, such as mining and quarrying. Some work has already been done on the problem of making shaped charges applicable to mining operations. Experimentation conducted at the National Tunnel and Mines' was directed primarily along the lines of use of shaped charges for secondary blasting in connection with long-hole stoping methods. Experimentation initiated earlier and conducted by the author2 at the University of Utah on a more scientific basis was directed at revealing the basic principles of the functioning of shaped charges, as well as the feasibility of using them in mining operations after the principles of their operation had been clearly defined. It was found that: (I) a given design of charge required an optimum standoff to make it most effective, either in penetrating solid rock or steel (see Fig 3); (2) for a given design of charge there exists an optimum ratio of charge diameter to charge height above which the increase in effectiveness of the charge decreases rapidly (see Figs 4 and 5); (3) partial confinement has the effect of making charge performance much more consistent; (4) the higher power and higher velocity explosives tested are much more effective than relatively low-strength explosives; and (5) shaped charges may be adaptable to mining operations in secondary breakage and drilling blasting holes. Fig I is a diagrammatic sketch of the action of a shaped charge for two types of cavities, while Fig 2 shows the approximate manner in which the jets are believed to be formed when an explosive wave encounters the cavity, approaching it from the top. The experimentation already completed has laid the foundation for further research in the study of shaped charges. Standoff effects, effect of the strength of explosives and other features have been fairly well established. Such elements in the design of shaped charges as (I) geometry of cavity liners, (2) relative horizontal dimensions of explosive column, (3) effect of

Jan 1, 1947

By Leslie C. Richards

The competitive position of producers of industrial minerals depends upon the delivered price of their product. Freight charges are a major factor in the sales to consumers. A comparison of freight rates on movements of limestone and silica rock in the Pacific North-west shows a wide variance in mills per ton mile for like hauls, thereby favoring some localities over others.

Jan 2, 1950

By K. R. Y. Simha

Successful explosive gas well stimulation requires a thorough understanding of explosively driven cracks under confining in-situ stresses. In a previous paper (Simha, et a1 1983) the problem of explosively driven cracks was experimentally investigated to reveal the features of crack propagation. It was observed that the explosively driven crack propagation is the result of two different but overlapping phases. The first phase involving the initiation and early time crack propagation is entirely governed by the explosively generated stress transients. The rapidly decaying stress transients then lead to the second phase of crack propagation largely controlled by the in-situ stresses. The purpose of this paper is to more fully understand the characteristics of the first phase concerning the initiation and early time propagation of explosively driven cracks. Experiments are conducted with plastic models under biaxial compression and the dynamic event is observed with a high speed multiple spark gap camera of the Cranz-Schardin type. The experimental observations are utilized to propose analytical models of crack initiation under explosive loading to aid in the design of multiple fracturing necessary for successful application of modern well stimulation techniques.

Jan 1, 1984

By A. Kavetsky, W. J. Whiten

Data from ball mills with a wide range of diameters are analyzed using detailed mathematical/ numerical models. Analysis shows the relative power inefficiency of large ball mills is due to their inefficient breakage of coarse particles. The models developed can be used to scale-up mill behavior. The behavior of large mills at Bougainville and Pinto Valley is compared. It is concluded that the mills are equally inefficient at grinding coarse particles. Differences in coarseness of total mill feed are shown to account for the fact that Pinto Valley mills achieved design throughput whereas Bougainville mills did not.

Jan 1, 1985

By Strathmore R. B. Cooke

That calcium will activate quartz for flotation with anionic collectors such as soaps has been known for a number of years,1 2 3 and the method has been applied to the concentration of various iron ore 4 5 6 as well as to other materials. Clemmer gives the permissible pH range for the activation of quartz by calcium as between 9.5 and 12.5 with an optimum value of 11.0, and Hertzog7 has determined the calcium abstraction of iron ores and of Ottawa sand, but otherwise little quantitative data are available. The purpose of the present investigation was to determine those conditions under which dilute solutions of calcium chloride will activate quartz for anionic flotation and to determine the amount of calcium ion adsorbed by quartz. Those variables, the influence of which was primary, such as calcium, sodium, and hydrogen ion concentrations, were studied. Other factors which influenced the results are discussed in the description of the experiments. Three different experimental methods were used to determine the activation of the quartz. The first method was to treat a sample of ground, deslimed quartz with solutions of calcium chloride and sodium hydroxide, and to determine the calcium adsorbed by chemical analysis of the solution. Ad- vantages are that a direct value for the

Jan 1, 1949

By W. M. Pierce

THE present work has been done in an endeavor to correlate and complete the data on the constitution of alloys of zinc with other common, metals, dealing exclusively, however, with the zinc-rich alloys in which the zinc content is between 90 and 100 per cent. This investigation has included the systems lead-zinc, cadmium-zinc, iron-zinc, copper-zinc, aluminum-zinc, nickel-zinc, manganese-zinc, cobalt-zinc, tin-zinc, and magnesium-zinc. The important ternary system zinc-lead-cadmium and the zinc corners of other ternary systems have been investigated in connection with this work but will not be dealt with here. Zinc does not form a single homogenous zinc-rich solid solution over any considerable range of concentration with any of the metals mentioned. A limited range of solid solubility is said,; by previous investigators, to occur in several cases and certain effects on the properties of zinc are attributed (with varying degrees of consistency among different writers) to the presence of certain other metals dissolved in zinc. The increasing use of rolled zinc and the possibilities offered by zinc as a casting alloy in certain fields have it made essential to determine precisely these equilibrium relationships. In carrying out this .investigation reliance was placed chiefly on two methods, conductivity measurements and microscopic analysis. The first method proved valuable in determining the existence and extent of solid solubility. The second method stands alone as a means of determining structural characteristics and supplements the first method in the measurement of solid solubility. The scleroscopic hardness of all conductivity specimens was measured partly for its value from the point of view of mechanical properties and partly; as a check on the conductivity curves in indicating the limits of solid solubility. No hardness curves are included in this paper, for in no case were they important in arriving at the constitution of any system.

Jan 2, 1922

By D. K. Bose, C. K. Gupta, K. U. Nair

A new approach to processing an indigenously available low made molysulfide concentrate by chlorination with elemental chlorine in presence of oxygen is reported. Recovery of nickel and copper values associated with the sulfide concentrate by suitably treating the residue obtained after chlorination is also reported.

Jan 3, 1978

By D. K. Bose, C. K. Gupta, K. U. Nair

A new approach to processing an indigenously available low grade molysulfide concentrate by chlorination with elemental chlorine in presence of oxygen is reported. Recovery of nickel and copper values associated with the sulfide concentrate by suitably treating the residue obtained after chlorination is also reported. In the chlorination process, a gaseous mixture of chlorine and oxygen in the volume ratio bf 2:5 has been passed at 1.66 x 10- 5 m3/s for 1800 s over a 0.01 kg batch of molysulfide concentrate at a temperature of 573°K. Most of the molybdenum has been volatilized as molybdenum oxychloride which has subsequently been extracted in water. The molybdenum value from the aqueous solution has been recovered in the form of calcium molybdate (CaO.MoO3) by treatment with calcium chloride (CaCI2). In an alternative processing scheme, the molybdenum rich solution has been treated with an oxidizing agent (K2S20f.J) and allowed to boil to recover a major portion of the molybdenum value in the form of molybdic oxide (MOOS). The spent charge obtained after molysulfide chlorination has been mixed with about 1 wt % sodium chloride and heated at 773K under an oxygen atmosphere. The reacted mass has been water-leached to yield a nickel-copper bearing solution with limited iron. The process liquor appears to be well suited for further processing by known hydrometallurgical recovery processes for nickel and copper. In the conventional process of molybdenum extraction, the molysulfide concentrate (-59% Mo) is first subjected to roasting to produce molybdic oxide. The oxide is then further processed in sequential steps involving vacuum distillation, ammonia leaching, and calcination to higher purity prior to hydrogen reduction to metal. In India there is at present some small tonnage production of molysulfide concentrate from a byproduct recovery plant of the M/s. Uranium Corp. of India Ltd. (M/s UCIL), Bihar. Efforts are being made at this laboratory to process the low grade fraction of the concentrate which contains sulfides of copper, nickel, and iron; quartz; and chlorites. Here, the conventional routes involving roasting and vacuum distillation appear unsuitable to produce an acceptable quality of molybdic oxide at high recoveries. Formation during roasting molybdates of some of the impurities present in the sulfide concentrate make subsequent vacuum distillation less efficient. In view of these problems, in earlier work reported from this laboratory the low grade concentrate has been processed hydrometallurgically to P. produce calcium molybdate. Starting from this molybdenum intermediate, processes have also been developed for the production of molybdenum and ferromolybdenum. Chlorination as an alternative to roasting for metal sulfides has been drawing considerable interest. The high reactivity of chlorine, the relatively low temperature of operation, the suitability of application to low grade resources, the convenience of recovering sulfur in non-polluting form, and the purity of chlorides which are separated by distillation all favor chlorination. In recent years, considerable work has been reported on the chlorination of common metal sulfides. In the field of molybdenum extraction from its sulfide resource, use of chlorination technology has been rather limited. Senderoff and Labrie3 were the first to chlorinate molysulfide concentrate with elemental chlorine at about 823°K to molybdenum pentachloride for use in the electrolytic preparation of molybdenum. The only other reported work, by Haver, Uchida and Wong, involved reaction between molysulfide and chlorine at 673°K to recover sulfur. The reaction products were, however, identified as molybdenum pentachloride and sulfur monochloride.

Jan 1, 1979

By K. Hanumantha Rao, T. C. Rao, M. Vanangamudi

The effects of important variables such as pulp density, feed size, furnace oil dosage, degree of agitation, and time of agglomeration on the yield and ash content of the agglomerates obtained from the oil agglomeration of coal fines have been studied in a laboratory batch agglomeration cell. Optimum conditions for maximum yield and throughput have been discussed. The furnace oil dosage and pulp density were found to have more influence on the yield and grade of the agglomerates than the degree of agitation and feed size in the ranges studied.

Jan 1, 1983

By Harold Markus, Gerhard Derge

THE first paper1 of this series described a technique of careful surface preparation by means of which reproducible results may be obtained from potential measurements of the behavior of tin in carbonate solutions with a pH range from 8.4 to 11.2. It then went on to establish the behavior of pure tin electrodes under these conditions and showed that the metal remains active at all times, though the steady potential attained after several hours decreases from I.I2[t] volts at a pH of 12.6 to 0.6 volts at a pH of 8.4. This behavior may serve as a norm with which all other data can be compared. In the second paper,2 small amounts of other anions were added to the carbonate solutions and the conclusion was reached that the common impurities encountered in alkaline materials packaged in tin do not increase corrosion. In fact, in some cases these anions may actually promote the formation of protective films. The present paper rounds out this survey by presenting data on the influence of cations added to the carbonate solutions, as well as the effect of alloy additions to the tin. In many cases the potential data are supplemented with weight-loss measurements. Information is also presented on the effects of some additional anions, the influence of gases above the electrolyte, the behavior of high-purity tin, and the effect of atmospheric oxidation on the corrosion resistance of the above-named alloys. Analysis of the entire body of data discloses some general rules applicable to corrosion in carbonate solutions. The experimental methods used are the same as those previously described. EXPERIMENTAL DATA Cations.-The carbonates of the cations K+, Li+, NH4+, which are soluble, were studied in the same way as the anions, by adding 0.01 mol of the metal carbonate to one liter of 0.2 M sodium carbonate solution, pH 11.2, or to 0.1 M sodium bicarbonate, pH 8.4. The other metallic carbonates are only slightly soluble, of the order of 0 7-3 mols per liter or less, and the sodium carbonate solutions were saturated by adding excess reagent several days before the experiment, shaking frequently, and filtering just before use. The chemicals were c.p. grade in each case except the indium salt. This salt was prepared by solution of the metal in hydrochloric acid and precipitation by addition of Na2CO3. These cations may be divided into two classes, according to their effect on the potential behavior of the tin: (I) normal, (2) passive. To offer a basis of comparison, curves I of Figs. I and 2 are given to illustrate the behavior of tin in carbonate solutions saturated with CaCO3. These curves are the

Jan 1, 1941

By Gerhard Derge

A SERIES of studies of the corrosion of tin is under way in the Metals Research Laboratory at the Carnegie Institute of Technology. The complete program includes examination of the corrosion properties of high-purity tin and the changes produced in these properties by the addition of varying amounts of alloying elements. Other studies of this subject have been made recently under the sponsorship of the International Tin Research and Development Council, but these researches have been confined largely to the weakly acid environments commonly encountered in the canning industry.1 There is little information available regarding the corrosion of tin under alkaline conditions, but such data would be of value, for a large amount of the metal is used under such conditions. The potential measurements to be described were made because they seemed to offer the most rapid method for obtaining a general view of the conditions to be encountered in such service. These experiments will also serve to establish a technique that will be of value in further studies. It must be emphasized that the results reported are those of controlled laboratory experiments and that the conclusions drawn cannot yet be applied to service conditions; rather, they point to the directions in which more exhaustive experimental work may be done to best advantage. EXPERIMENTAL PROCEDURE The first work was devoted entirely to the problem of obtaining reproducible results from a series of potential measurements. Only the methods finally adopted as standard will be described here, except when the variations from these have furnished results of interest. The cell used is shown schematically in Fig. 1. The electrolyte is contained in the vessel A (an inverted bell jar), whose ground top is fitted to the transite-board lid B. The controlled atmosphere can be admitted

Jan 1, 1938

By Gerhard Derge

A SERIES of studies of the corrosion of tin is under way in the Metals Research Laboratory at the Carnegie Institute of Technology. The complete program includes examination of the corrosion properties of high-purity tin and the changes produced in these properties by the addition of varying amounts of alloying elements. Other studies of this subject have been made recently under the sponsorship of the Inter-national Tin Research and Development Council, but these researches have been confined largely to the weakly acid environments commonly encountered in the canning industry.1 There is little information avail-able regarding the corrosion of tin under alkaline conditions, but such data would be of value, for a large amount of the metal is used under such conditions. The potential measurements to be described were made because they seemed to offer the most rapid method for obtaining a general view of the conditions to be encountered in such service. These experiments will also serve to establish a technique that will be of value in further studies. It must be emphasized that the results reported are those of controlled laboratory experiments and that the conclusions drawn cannot yet be applied to service conditions; rather, they point to the directions in which, more exhaustive experimental work may be clone to best advantage.

Jan 1, 1938

By Gerhard Derge

THE introductory paper1 of this series described the potential behavior of tin in sodium carbonate and bicarbonate solutions whose pH ranged from 8.4 to 11.2 and demonstrated that significant and reproducible results could be obtained by proper attention to experimental technique. In examining the corrosion of tin under such conditions, it is desirable to know the effects of anions, aside from carbonate, that are likely to be present in commercial materials packaged in tin. Therefore, in this paper the potential behavior of tin in carbonate solutions to which sodium fluoride, chloride, bromide, iodide, sulphate, nitrate, monobasic phos-phate, dichromate, perborate and acetate have been added will be described. For most of the additions, solutions containing 0.001 and 0.01 .moles of the added material were studied. The experimental procedure was exactly the same as that described in the first paper; the pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicar-bonate as follows: pH 0.1 M NaHCO3 8.4 2 parts 0.1 M NaHCO3, 1 part 0.1 M Na2CO3 9.5 1 part 0.1 M NaHCO3, 2 parts 0.1 M Na2CO3 10.0 0.1 M Na2CO3 11.2 The reagents used were all of C.P. grade. The anions studied may be divided into three groups: (1) anions that had little or no effect upon the potential curves-sulphate, nitrate, and acetate; (2) those that helped to prevent corrosion at low pH only-fluoride, chloride, bromide, and iodide; (3) those that helped to prevent corrosion at high pH also-phosphate, perborate, and chromate.

Jan 1, 1939

By Robert Mehl

THE importance of the Widmanstätten structure to structure theory in metallography has been recognized by many writers.1 It is a structure produced by the precipitation of a new phase from a solid solution upon cooling as a result of changing solid solubility, and displays a characteristic appearance indicating a crystallographic relationship between the new phase and the original solid solution (Fig. 1). First discovered in 1808 by Alois de Widmanstätten2, the structure has been traced by analogy through many alloy systems. Particularly is this true of the steels. Sorby's classic work3 on the microstructure of iron and steel was in essence an attempt to explain the origin of this characteristic structure in meteoric iron. He observed in a Bessemer steel and in a cast-steel ingot structures which we now recognize as typical Widmanstätten figures.4 Osmond5 observed structures in a steel ingot analogous to those found in meteorites. Arnold and McWilliams6 obtained (and recognized) a

Jan 1, 1930

By Robert Mehl

A STUDY of the structures arising from the decomposition of the a solid solutions in the Cu-Zn and the Cu-Al systems is of peculiar interest in the study of the mechanism of precipitation from solid solutions. It is possible in these alloys, by varying the composition within the ß field, to precipitate from the same basic lattice phases having different lattice structures. It has been rather generally assumed heretofore that the type of structure originating from the decomposition of a solid solution-the Widmanstätten structure-is determined by the lattice structure of the parent solid solution alone. In the first paper of this series1 evidence was advanced which threw doubt upon this hypothesis; but definite proof of the correctness or incorrectness of the hypothesis should be forthcoming from a study of these alloys, for if the structures originating, for example, from the precipitation of the a phase from ß and of the -y phase from the ß in the Cu-Zn system should be shown to be crystallographically different, the hypothesis would necessarily be held as definitely disproved. Furthermore, the newer proposal enunciated in the first paper of this series-that the origin of the Widmanstätten structure lies in a cooperation between the lattice of the parent solid solution and that of the precipitate-which at present seems the only alternative hypothesis, would in such an event be given added weight. The work here reported shows that the Widmanstätten structures originating in the precipitation of the a phase from the a and in the precipitation of the -y phase from the ß in the Cu-Zn system are indeed crystallographically different; and incidentally presents some new descriptive information on the Widmanstätten structure from a more general point of view.

Jan 1, 1931

By Robert F. Mehl

THE solid solutions which aluminum forms with copper, and with magnesium and silicon, are not extensive, and accordingly could not be expected to form Widmanstätten figures profusely nor with great ease. A study of the Widmanstätten figures in these systems seemed desirable, however, because of the interest which these alloys bear towards age-hardening theories resulting from the necessary relationship between the age-hardening phenomena and the atomic processes leading to the formation of Widmanstätten figures.1 ALLOYS OF ALUMINUM WITH COPPER The most accurate determination f the solid solubility, of copper in aluminum seems to be that by Dix and Richardson,2 whose results are represented in Fig. 1. According to this work, aluminum dissolves 5.6 weight per cent of copper at 548°, and less than one per cent at room temperature. Judging from the constitutional diagram, this solid solution on cooling tends to precipitate the compound CuAl2, and this conclusion has been confirmed experimentally by Schmid and Wassermann .3

Jan 1, 1932

By Robert Mehl

THE Widmanstätten figures found in the steels have been long recog-nized and in some aspects carefully studied,1 especially as they occur in cast hypoeutectoid alloys. Aside.from the practical importance of the structures obtained in the steels by various heat treatments, a study of the characteristics of these figures is interesting because of the rich opportunity the system affords, to, obtain new data on the mechanism of segregation from solid solutions. This opportunity is twofold: first, by changing composition within the austenite range the proeutectoid precipitate may be changed from that of ferrite to that of cementite, thus offering the same opportunity for changing the type of precipitate while maintaining the same basic lattice as that afforded by the Cu-Zn alloys;2 and second, the eutectoid inversion leads upon drastic quenching to the formation of martensite, a Widman-stätten figure of unique interest from ;the crystallographic viewpoint, particularly in comparison with those formed on-slow cooling.3 We have, therefore, two types of structure to study: that formed on slow cooling of hypoeutectoid and hypereutectoid alloys, and that formed on quenching hypoeutectoid, eutectoid, and hypereutectoid alloys. For each of these types of structure we require the crystallographic plane in the mother austenite along which the precipitate forms (we shall see that the precipitates in these alloys are invariably platelike in form), and also the orientation of the precipitate upon this plane. Some of these

Jan 1, 1933

By Gerhard Derge

THE orientation relationships resulting from allotropic transforma-tions and the formation of segregate structures in metals and alloys have been the subject of the eight earlier papers in this series1. A brief summary of orientation studies has also been given by Sachs2. A survey of these papers discloses that the factors that determine the orientation relationship of a precipitated phase to its parent solid solution, as Well as the outward form and appearance of the new phase, are not completely understood. It is now evident that crystallographically analogous systems, as a rule, exhibit the same type of Widmanstätten figure and orientation relations, so that useful information is not to be expected from examination of a new alloy involving lattice combinations of which the orientation relationships are already known. Therefore, the determina-tion of the relations existing between lattice types that have not already been studied seems to be the most promising mode of attack upon the problem; both of the systems reported in this paper represent new com-binations of lattice types.

Jan 1, 1937

By Robert Mehl

IT has been shown that quenched iron of high purity exhibits a Widmanstätten figure much resembling martensite in appearance.1 This figure exhibits a maximum of four directions of the surface traces that characterize it, suggesting that a Fe forms from y Fe in plates parallel to the {111}, octahedral, planes in the y lattice. Because of this, and also because of the general similarity to the structural appearance of martensite and to the Widmanstätten figure obtaining in slowly cooled hypoeutectoid steels it has been suggested2 that the orientation relation-ships obtaining between the y and a phases in pure iron are identical with those demonstrated in martensite3 and in slowly cooled hypoeutectoid steels,4 and indeed that the crystallographic mechanism of formation of a Fe from y Fe is the basic mechanism determining the orientation relation-ships found in both martensite and in slowly cooled hypoeutectoid steels. This paper will present experimental evidence in support of this view.

Jan 1, 1934