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By Ronald K. Linde

Metastable Ag-Cu solid solutions at two compositions beyond the maximum limits of solubility obtainable by quenching from the solid state were obtained by rapid quenching from the liquid state. The process of transformation of the metastable solid solutions into the equilibrium phases was studied by means of X-ray diffraction intensity measurements and electrical-resistance measurements; metallographic examination was also performed. Results are compared with those for an alloy quenched from the solid state at a composition which exists as a solid solution at elevated temperatures. Activation energies for the trans-formation were computed to be 33,600 * 2500 and 33,100 * 2000 cal per g mole for the 60.1 and 75.0 at. pct Ag;Cu compositions, respectively THE kinetics of precipitation in supersaturated solid solutions obtained by quenching from high temperature has been thoroughly studied in many alloys, and detailed investigations of the early stages of nucleation and subsequent growth of the equilibrium phases have been carried out. All of these studies have been made on alloys quenched from the solid state, however, and it is the purpose of this paper to present some of the results on the kinetics of transformation of metastable solid solutions in Ag-Cu binary alloys whose compositions lie outside of the solid-state limits of solubility. Limits of solubility in the solid state can be increased by rapid quenching from the liquid state. This was first demonstrated by Falkenhagen and Hofmann, who obtained appreciable increases in solubility limits of the elements of the first transition series in aluminum by rapid cooling of liquid alloys through contact with a copper mold maintained at liquid nitrogen temperature.' The same basic idea of cooling a liquid alloy by conduction onto a substrate rather than by convection of a gas or liquid (conventional quenching) has been recently revived and extended to very high rates of cooling by Duwez and his collaborators. The new technique was first applied to Ag-Cu alloys because the existence of a eutectic in this system is not predicted by the Hume-Rothery rules of alloy phase formation. Rapid quenching from the liquid state resulted in metastable solid solutions at all concentrations. The kinetics of decomposition of these metastable solid solutions containing 60.1 at. pct Ag;Cu (eutectic composition) and 75.0 at. pct Ag;Cu is the subject of the present paper. EXPERIMENTAL TECHNIQUES Alloys were made in 10- to 20-g heats using silver of purity 99.99 pet and copper of purity >99.999 pct. Components were weighed accurately to 0.1 mg and melted by induction heating in an alumina crucible under an atmosphere of hydrogen. Weight losses amounted to less than 0.02 ~ct in all cases. Rapid cooling from the liquid state was achieved in an apparatus of the type described by Pietrokowsky. 3 In this technique a freely falling drop of molten alloy is caught between a stationary anvil and a fast moving piston, both anvil and piston being lined with copper. The resulting foils were approximately circular (about 2 cm in diam) and from about 50 to 150 u in thickness, depending on the pressure driving the piston. Metallographic samples were prepared for polishing by edge-mounting foils in Quickmount. The mostef-fective etching procedure was found to be: 10 parts NH4OH (concentrated), 1 part H2O2 (30 pct), 5 parts H2O, swab for 5 to 10 sec. The transformation of the metastable alloys to equilibrium was followed by X-ray diffraction and electrical-resistivity measurements. The peak intensity and the integrated intensity of suitable Bragg reflections of the metastable and stable solid solutions were studied with a Norelco dif-fractometer, using nickel-filtered copper KO radiation. The peaks were step-scanned at intervals of 0.05 deg. Using either a Kelvin bridge or a null circuit with a Leeds and Northrup K-2 potentiometer, the changes in electrical resistance due to phase transformation were measured for specimens cut into strips about 20 mm long and 4 mm wide. All resistivity measurements were carried out at liquid-nitrogen temperature. The isothermal heat treatment was accomplished by sealing the samples in argon-filled aluminum containers with stainless-steel O-rings. Containers were then suspended in wax baths with temperatures in the

Jan 1, 1967

By Kenneth M. Bravinder, Jonathan E. Koogle, Dean H. Sheldon

THE solution of subsurface geological problems requires an analysis of vertical and horizontal dimensional relationships. For many, the ability to visualize structures in three dimensions is not easily acquired, and for areas where the structural conditions are complicated by faulting the need arises for illustrative models. This has led to the many forms of peg models, in which the usual course of construction includes a peg for the well bore, and the suspension of strings from peg to peg to illustrate the formation correlation between wells, thus developing the usual folds and flexures. Such models proved unsatisfactory for the analysis of fault problems. Consideration was then given to the use of transparent materials. A model of the Dominguez oil field was constructed in 1935, which consisted of a series of glass panels from well to well on which the formations were shown in color. This model, though serving its purpose at the time, proved to be impractical from the standpoints of cost, breakage hazard, and extreme difficulty in maintenance. The cost of materials was estimated to be approximately $300, and the construction required the services of one man for a period of from 10 to 12 months. Maintenance after actual construction was an additional expense. Consideration was then given to the use of celluloid, and after some experimental work it was found that the advantages in its use were: (I) a short construction time, (2) ease of handling the material, (3) sections are easily reworked, (4) low cost. CONSTRUCTION It would be of little value to recount here the difficulties encountered in the building of the first celluloid model. The conclusions drawn, however, suggest the following procedure for those who contemplate the construction of such a model: I. Determination of the Scale.-Accurate geological interpretation requires the use of the same scale horizontally and vertically. It should be emphasized that the limited size of the celluloid sheets (20 by 48 in. maximum dimensions), the area to be studied, the maximum depths to be plotted, and area of possible future development are the controlling factors in adopting a scale to be used. 2. Construction of the Base.-A satisfactory base may be constructed by using two pieces of three-ply wood separated by strips of i by 2-in. material. This type of construction prevents warping of the base. The size of the base is determined by the dimensions of the area to be studied plus 5 in. on all sides. A map of the same scale as that adopted for the model, indicating the lines of section to be used, should be fastened to the base. 3. Construction of the Frame (Fig. I).-In the construction of the frame the use of 1/2-in. o.d. pipe welded in a box shape is suggested, with two horizontal rods on each of the four sides, top and bottom. The top rod should be at least I in. higher than the

Jan 1, 1941

By Robin O. Williams

The increase in internal energy as the result of deformation has been measured for lead, aluminum, silver, nickel, iron, and zirconium by using rapid, adiabatic compression. The stored energy increase is roughly Proportional to the strain; the propor-tionality constant increases rapidly with increasing melting point. The fraction of the mechanical energy which is stored increases more slowly, since the strength of the metals also increases with melting point. The values of the stored energy are considered accurate to about 10 pet. The present values appear about 50 pet larger than the more reliable published results where comparisons are possible. It is possible that this difference is due to the high strain rate used in this investigation. Immediately after deformation all these metals release energy at a rate roughly proportional to (time)-'. This release is considered to be associated with dislocation motion but in aluminum (and copper) some additional process seems to be present. This release can represent 20 pet or more of the stored energy. WHEN pure metals are plastically deformed, most of the mechanical energy is converted into heat. The energy remaining within the metal is significant in that it is the energy of the disorder produced and thus detailed knowledge of this energy is a powerful tool in understanding the nature of deformational disorder. While much effort has been expended on this problem, the amount of information available is limited. The situation as of 1958 has been carefully reviewed by Titchener and ever.' The present results have been obtained by a new experimental approach to this problem. The method necessitates high-strain rates which make comparisons with published results less certain, but a high-strain rate is an advantage in that the energy release immediately after deformation can be followed. EXPERIMENTAL PROCEDURE In the experimental method used, the internal (stored) energy is given as the difference between the mechanical work used in deforming the sample and the heat which is released (the first law of thermodynamics). The work is supplied by two identical hammers swinging freely from a fixed height, the available energy being the product of the mass, the gravitational constant, and the distance through which the center of gravity moves. The initial temperature rise of the sample represents the heat produced by the deformation. The sample temperature is determined by a small thermocouple embedded in and supporting the sample. This process can be repeated over and over to produce increased strains. Most samples are run through about five cycles to a total strain of around 0.7. Further details are covered elsewhere. The determination of the heat is dependent upon the sample weight, its specific heat, the rise in temperature, and any gains or losses to the surroundings. One is dependent on published results for specific heals (the values were taken from a collection).3 The values must be accurate to about 0.1 pet in order that they not affect the results. The best values thus do not contribute to the uncertainty, but this is probably not always the case. The accuracy of the temperature rise is limited primarily by knowledge of the thermocouple characteristics over short temperature intervals, but careful calibration eliminates this as an important factor. One can calculate readily the heat flow between the sample and hammers if the time of contact and the sample temperature are known and if there were no oil at the interface. Assuming the maximum temperature difference, upper values for this interchange have been calculated (the time of contact is determined from the decrease in sample length) and it may or may not be significant. However, no correction is colnsidered necessary because of the presence of a thin oil film which has a thermal conductivity much less than the metals. Except for the possible uncertainty in specific heat, the heat is considered to be adequately known. The mechitnical losses which are recognized as important are: 1) friction between the sample and the hammer:;, 2) the kinetic energy in the hammer suspension system which may not be entirely usable, 3) the rebound energy of the hammers, and 4) the vibration of the hammer heads. All these have been covered in detail elsewhere2 and only the more significant points are made here. The friction turns out to be small except for soft materials (lead)

Jan 1, 1962

By John Langton

In determining what kind of pourer should be adopted for the works of the Moctezuma Copper Co. at Nacozari, Sonora, Mexico, certain considerations imposed by local conditions had to be taken into account. Water.—During most of the year the water-supply is abundant for all purposes, but it dwindles rapidly when the dry season sets in, reaching a minimum flow which is entirely undergrouad. It was evident, that with the greatest care in keeping down the unavoidable loss of water in milling and smelting, these operations and hence the capacity of the works mould ultimately be limited for about two months of the year by the small watersupply available at the period of minimum flow. Transportation.—The nearest railway terminus was in Arizona, at the international boundary-line; and the price of supplies at that point would be enhanced at Nacozari by the additional cost of a 90-mile wagon-haul. During the rainy season, transport to Nacozari was much impeded, and at times made impossible, by the condition of the roads. Hence, to insure continuous operation at the works, it would be necessary to provide for hauling the year's supplies, including fuel for power and coke for smelting, in less than eleven months. In other words, the average freight delivered daily at the works should be at least 10 per cent. more than the average daily consumption. For moderate quantities of freight, pack-carriage by burros is astonishingly cheap. But it has a capacity-limit which is generally very soon reached. A 200-lb. load, and 10 miles a day, 5 with and 5 without load, is the full capacity of a burro. This means one burro per ton-mile of the round trip; and,

Jan 1, 1904

By Pol Duwez

IN the course of an investigation of the V-CO system, two intermediate phases were found. One of these phases corresponds approximately to the stoichiometric composition VCo and is isomorphous with the sigma phase in the Fe-Cr system.' The second phase has the composition V3Co; its crystal structure is described in the present note. The alloys were prepared by mixing the two metals in the powder form, pressing a small disk weighing about 5 g at 80,000 psi, and arc melting this disk on a water-cooled copper plate in an atmosphere of pure helium. The details of this technique have been described.' The vanadium powder was obtained from Westinghouse Electric Corp., Bloomfield, N. J. This powder is probably of very high purity, since when it is properly sintered or melted in the above-mentioned arc furnace, ductile specimens are obtained. The cobalt powder, from Charles Hardy, Inc., New York, contained 0.5 pct Ni, 0.1 pct Cr, and traces of Si and Fe. After melting, the V,Co samples were sealed in evacuated quartz tubes and homogenized for ten days at 800°C. Powder diffraction patterns were obtained with a 14.32 cm diam camera, using Ka copper radiation. The patterns were readily indexed on the basis of a primitive cubic lattice with a parameter equal to 4.675A. The density, determined by the immersion method, was 6.71 g per cu cm; hence the number of molecules per unit cell is approximately 1.95; i.e., 2. At this point, the possibility that the structure might be that of beta tungstena became apparent. The beta tungsten structure is described as follows: Space group 03,, — Pm3n 2 Co in (a) : 000; ?4lhYZ (hhl) reflection present only if 1 = 2n. Assuming this structure to be the correct one, intensities were computed by means of the usual eauation: 1 + cos220 I oc p F sin 0 cos 6 where F is the structure factor, 0 the Bragg angle, and p the multiplicity factor. The observed and calculated values of sin 0 and the intensities are given in Table I. The agreement between the observed and the calculated sin 0 is good and there are no flagrant discrepancies between the calculated intensities and those estimated visually. The (hhl) reflections for which 1 is odd are not observed, as required by the space group. In addition, the (410), (430), and (531) reflections are missing as expected, because of the special (a) and (c) positions in0%. However, six reflections—(llo), (220), (310), (411), (422), and (510)—which have very weak computed intensities were not observed. For these reflections, the structure factor is proportional to the difference between the scattering factors of the two atoms in the structure. Since the scattering factors of vanadium and cobalt are not very different, these reflections are weak. However, by using Ka chromium radiation, whose wavelength is just above the absorption edge of vanadium, the effective scattering factor of vanadium may be decreased by one or two units; consequently the difference between the cobalt and vanadium scattering factors is increased. It was, indeed, found that in a powder pattern taken with chromium Ka radiation, the three reflections (110), (220), and (310) were actually present. The three other reflections (411), (422), and (510), with spacings smaller than half the wavelength of chromium Ka, were obviously not obtainable with chromium radiation. All the experimental results appear to confirm the beta tungsten structure for V,Co. In this structure, each cobalt atom is surrounded by twelve vanadium atoms at 2.61A; each vanadium atom is surrounded by two vanadium atoms at 2.34A, four cobalt atoms at 2.61 A, and eight vanadium atoms at 2.86A. Acknowledgment This work was done at the Jet Propulsion Laboratory, California Institute of Technology, under contract number W-04-200-ORD-455 with the Army Ordnance Department, Washington, D. C. The author wishes to thank this agency for the permission to publish the results of this investigation. References 'P. Duwez and S. R. Baen: X-Ray Study of the Sigma Phase in Various Alloy Systems. Symposium on the Nature, Occurrence, and Effect of Sigma Phase. ASTM Special Tech. Pub. No. 110, pp. 48-54. Philadelphia, 1951. 2 C. H. Schramm, P. Gordon, and A. R. Kaufmann: The Alloy Systems Uranium-Tungsten, Uranium-Tantalum, and Tungsten-Tantalum. Trans. AIME (1950) 188, pp. 195-204; Journal of Metals (January 1950). 3 M. C. Neuburger: The Crystal Structure and Lattice Constants of Alpha and Beta Tungsten. Ztsch. fiir Krist. (1933) 85, pp. 232-237.

Jan 1, 1952

Lawrence Addicks, Perth Amboy, N. J. (communication to the Secretary*): The excellent series of photo-micrographs given in this paper shows clearly the relation between micro-structure and cuprous oxide in refined copper. The authors suggest that this method of examillation might be substituted for the " button " method now used to control the refining of cop

Jan 1, 1904

By Benjamin F. Tillson

Although portable fire extinguishers are valuable for fires in an incipient stage, some medium that will dissipate a large amount of heat is needed to fight a fire in mine timbers, because of the size to which the fire will probably have grown before it is discovered. Scaling off, or otherwise smothering such a fire with gases that will not support combustion, is often ineffective for the residual heat will cause reignition when the area is opened and fresh air reaches the hot charred timber. The most effective ways of fighting mine fires, therefore, are to drown and cool the hot zone with water, and to "load out" the partly burned material. Either of these methods requires a direct attack of water ; upon the inflamed material; therefore, every mine containing a large ' quantity of timber or other combustible should be as completely equipped with a fire-hydrant system as it is with compressed-air mains. Mine managers may object to the expenditure, especially if they have not suffered from mine fires. The cost of such preventative measures, however, is only a small portion of the possible losses, and the water pipes can be used for other purposes, which will pay the carrying charges. They can supply water to the rock drills, which will encourage more wet drilling with hollow-drill steel, for the trouble and expense of packing water to individual tanks at the drills will be removed. The carbon-tetrachloride hand extinguishers seem to have no place in mining except for fires that start in electrical equipment. They give off noxious gas, which may prove poisonous in confined quarters; and as it is heavier than air it is of no value for smothering fires overhead or in side timbers and would be dissipated by a good ventilating draft. The old soda-acid extinguisher or the more modern "foam" types ' are preferable. The former probably does not rely for its efficacy on the carbon dioxide generated but on the smothering and cooling effect of the water and the trajectory of stream that may be obtained because of the gas pressure developed. The production of a foam having a tough film to smother a fire, even on overhead surfaces, with the added

Jan 1, 1923

By Benjamin F. Tillson

Although portable fire extinguishers are valuable for fires in an incipient stage, some medium that will dissipate a large amount of heat is needed to fight a fire in mine timbers, because of the size to which the fire will probably have grown before it is discovered. Scaling off, or otherwise smothering such a fire with gases that will not support combustion, is often ineffective for the residual heat will cause reignition when the area is opened and fresh air reaches the hot charred timber. The most effective ways of fighting mine fires, therefore, are to drown and cool the hot zone with water, and to "load out" the partly burned material. Either of these methods requires a direct attack of water ; upon the inflamed material; therefore, every mine containing a large ' quantity of timber or other combustible should be as completely equipped with a fire-hydrant system as it is with compressed-air mains. Mine managers may object to the expenditure, especially if they have not suffered from mine fires. The cost of such preventative measures, however, is only a small portion of the possible losses, and the water pipes can be used for other purposes, which will pay the carrying charges. They can supply water to the rock drills, which will encourage more wet drilling with hollow-drill steel, for the trouble and expense of packing water to individual tanks at the drills will be removed. The carbon-tetrachloride hand extinguishers seem to have no place in mining except for fires that start in electrical equipment. They give off noxious gas, which may prove poisonous in confined quarters; and as it is heavier than air it is of no value for smothering fires overhead or in side timbers and would be dissipated by a good ventilating draft. The old soda-acid extinguisher or the more modern "foam" types ' are preferable. The former probably does not rely for its efficacy on the carbon dioxide generated but on the smothering and cooling effect of the water and the trajectory of stream that may be obtained because of the gas pressure developed. The production of a foam having a tough film to smother a fire, even on overhead surfaces, with the added

Jan 1, 1923

George L. Heath, South Lake Linden, Mich. (communication to the Secretary): In presenting some notes on the "Heine's Blue Test" Mr. Smith expresses a preference for fresh standards and a cheaper bottle; but this is rather a reversion to the old method, since I devised in 1897 the newer method of preparation and preservation of' permanent standards, which were not used with any success in the original method. Many busy western assayers no doubt value a method for preparing a permanent set of standards in air-tight glass-stoppered bottles, whose use brings the method as near perfection as one could desire as regards rapidity of color-reading and avoidance of unnecessary work. Mr. Smith notes that his color-readings were compared with an electrolytic assay of another ore-sample, and that my electrolytic assays were made on the " blue test" solution from colorimetric assay. He omits, however, reference to the fact, showing the advantage of my procedure, that the next column in table of

Jan 1, 1901

By P. E. Demmler

The apparatus in which the process of bright annealing of copper wire was carried out consisted of a section of iron pipe, 6 ft. long and 3 ft. in diameter. The pipe was provided with flanges to which were bolted the end plates for sealing, also with inlet and outlet tubes to allow for the displacement of the air in the pipe by natural gas. After charging with copper wire, sealing and displacing the air, the pipe was heated to 350' C. (662" F.). It was expected that the natural gas would furnish a neutral atmosphere which would prevent oxidation and give a satisfactory bright-annealed product. It was found, however, that the outer layers of wire were discolored and not suited for the use for which they were mtended. To obtain an idea of what was taking place in the annealing furnace, skeins of the hard-drawn wire were placed in a glass tube so that all changes in appearance could be observed as they were heated to different temperatures and under varying conditions. The temperature in each case was determined by means of a thermocouple placed in the tube close to the wire. Following is a summary of the results of these experiments: 1. When the wire was heated for 1 hr. in a current of natural gas at a temperature of 350") 400") or 500" C. (662", 752", or 932" F., respectively), there was a marked darkening of the wire throughout the skein. 2. When heated for 1 hr. in natural gas at a temperature of 600" C. (1112' F.), there was no coloration, the wire remaining clean and bright. 3. When heated in natural gas to 350" C. until darkened and the treatment continued with the temperature raised to 600' C., the coloration disappeared and the wire became clean and bright.

Jan 1, 1923

By P. E. Demmler

The apparatus in which the process of bright annealing of copper wire was carried out consisted of a section of iron pipe, 6 ft. long and 3 ft. in diameter. The pipe was provided with flanges to which were bolted the end plates for sealing, also with inlet and outlet tubes to allow for the displacement of the air in the pipe by natural gas. After charging with copper wire, sealing and displacing the air, the pipe was heated to 350' C. (662" F.). It was expected that the natural gas would furnish a neutral atmosphere which would prevent oxidation and give a satisfactory bright-annealed product. It was found, however, that the outer layers of wire were discolored and not suited for the use for which they were mtended. To obtain an idea of what was taking place in the annealing furnace, skeins of the hard-drawn wire were placed in a glass tube so that all changes in appearance could be observed as they were heated to different temperatures and under varying conditions. The temperature in each case was determined by means of a thermocouple placed in the tube close to the wire. Following is a summary of the results of these experiments: 1. When the wire was heated for 1 hr. in a current of natural gas at a temperature of 350") 400") or 500" C. (662", 752", or 932" F., respectively), there was a marked darkening of the wire throughout the skein. 2. When heated for 1 hr. in natural gas at a temperature of 600" C. (1112' F.), there was no coloration, the wire remaining clean and bright. 3. When heated in natural gas to 350" C. until darkened and the treatment continued with the temperature raised to 600' C., the coloration disappeared and the wire became clean and bright.

Jan 1, 1923

By J. A. Berger, G. W. Wiener

Several transition metal nitrides have been prepared and their saturation magnetization determined. On the basis of an atomic model of ferromagnetism involving a consideration of nearest neighbor interactions and the assumption that all atomic moments of the metal point in the same direction, it appears that the nitrogen interacts with d-shell of the transition metal in such a way as to reduce the magnetic moment. THERE is a large class of materials having metallic properties which are formed by a combination of hydrogen, boron, carbon, oxygen, or nitrogen with the transition metals. Several attempts have been made to establish the type of metal-nonmetal bonding in these interstitial alloys because it is believed that many of the physical properties of these materials are determined by the characteristics of this bond. Several of these alloys are ferromagnetic, and thus a powerful method is available for investigating the structures in a direct manner by measuring the saturation magnetization. The latter is a fundamental property of ferromagnetic metals and alloys which depends primarily on the electron distribution surrounding the atom. For the first row of transition metals, this refers specifically to the 3 d-shell. Since bonding involves the electronic configuration between atoms, there is reason to suppose that a relationship exists between ferromagnetism and bond type. In the case of the interstitial structures studied in this work, bonding will refer to the distribution of electrons between the transition metal and the nonmetal. Since these alloys have metallic properties, it is further proposed that any bonding interactions will involve the outer p-shell of the interstitial element and the incomplete d-shell of the transition metal. If this is the case, then the relationship between ferromagnetism and metal-non-metal bonding is established qualitatively. In order to investigate the subject quantitatively, certain transition metal nitrides were chosen because they have simple crystal structures, are ordered alloys, and are ferromagnetic. They also have sufficiently high saturation magnetization to be of technical interest. Currently there are two major theories of ferromagnetism, each of which has been applied to the interpretation of the saturation magnetization in terms of atomic structure. They are usually referred to as the band theory and the atomic theory. The former has found widespread application to the study of pure metals and certain solid-solution allays. However, it has not been applied to the interstitial structures or ordered alloys because it does not interpret the properties directly in terms of the crystal structure. The atomic theory on the other hand is especially suited to the study of interstitial structures because it permits an interpretation of ferromagnetic phenomena in terms of the crystal geometry. As has been pointed out previously, the nitrides have simple ordered crystal structures and, therefore, the choice of the atomic theory for the interpretation of the data is a natural one. One of the prime difficulties with the atomistic theory is that its mathematical justification is much more difficult, and for this reason its general acceptance will depend to a large extent on the value it has in explaining and predicting the results of experiment. Before the presentation of the theoretical basis for understanding the metal-nonmetal bond, it is useful to review the ideas existing prior to this work. Four different interpretations have been given to the metal-nonmetal bond. These are summarized as follows: 1—acceptance of electrons by the nonmetal from the incomplete d-shell of the transition metal, 2—transfer of electrons from the nonmetal to the incomplete shell of the transition metal, 3—no exchange of electrons between the two atoms, and 4— a resonating type of bond involving the p electrons of the interstitial atom giving rise to half bonds. Zener'-4 in a recent series of papers has proposed a new theory of ferromagnetism and has developed an explanation of the observed saturation magnetization of iron nitride (Fe,N) using the concept that nitrogen accepts electrons from the 3d-shell of iron. Jack," on the basis of atom size considerations in iron carbonitrides, has proposed that nitrogen transfers or donates electrons to the inner 3d-shell. He found that the effective size of the carbon atom was less than that of nitrogen and thus suggested that the interstitial atoms give up electrons. Kiessling" has studied the borides of several transition metal atoms and proposed that boron loses one p electron to the transition metal. He postulated that the additional electron added to the metal lattice compensates for the loss in metallic properties which results from the increased metal-metal atom separation. GuillaudT3" has proposed similar arguments from some recent magnetic studies he had made on manganese nitride. However, he did not base his conclusions on a quantitative argument. Pauling," in a recent paper, discussed electron transfer in in-termetallic compounds. He classified nitrogen as a hyperelectronic atom which can increase its valence by giving up electrons. He classified the transition metals as buffer atoms which are capable of either accepting or giving UP an electron. He pointed out that two factors are operating which promote electron transfer because they lead to increased stability. The first is an increase in the number of bonds, and the second is a decrease in the electric charges on the atoms. These ideas when applied to the interstitial nitrides would indicate a viewpoint favoring electron transfer by nitrogen to the transition metal. Hagg7s arguments in favor of no exchange are adequately summarized by Wells." Implicitly, Hagg

Jan 1, 1956

By R. F. Krueger

Results are presented from tests of dynamic fluid-loss rates to cores from clay-gel water-base drilling fluids containing different commercial fluid-loss control agents (CMC, polyacrylate or smt,ch), organic viscosity reducers (quebracho and complex metal lignosulfonate) and oil at several different levels of concentration. In the dynamic system the most effective individual additives to the clay-gel drilling fluid, based on cost-equalized concentrutiom, were found to be starch and the viscosity reducers. These results do not conform with the rankings determined by API fluid-loss rests, which indicate CMC, polyacrylate and starch to be the most effective and comparable. Generally, minimum dynamic fluid-losr rates were attained at cost-equalized concentrations of additive (including thinner) of about $1.00/ bbl, or less. For chernically treated clay-gel drilling fluids, both the standard and the high-pressure API filter-loss tests were found to he inaccurate indicators of trends in dynamic fluid-loss rates under the test conditions used, particulurly for drilling muds containing viscosity reducers. From a practical field viewpoint, restrictions on the applicability of the API fluid-loss test are such that it is open to question whether or not results of this test can be used routinely with confidence as an indicator of control of down-hole fluid loss under field treating conditions. INTRODUCTION The petroleum industry spends large sums of money during drilling operations to control the fluid-loss properties of drilling fluids based on the standard API filter-loss test,' which is a static filtration system. Laboratory studies' ' of dynamic filtration have shown that in a given time period filtrate loss from a circulating mud stream is greater than from a static system and that it is a function of linear mud velocity, pressure and the properties of the drilling fluid. Ferguson and Klotz' and Horner, et al," observed that (I) the dynamic fluid-loss rates for the drilling fluids used were not related to the extrapolated API filter loss and (2) the drilling fluids with the lowest API filter losses did not have the lowest dynamic fluid-loss rates. However, there has been no published information on the relative effects on dynamic fluid-loss rate as a given drilling fluid is treated with increasing amounts of chemical additive to reduce the API filter loss. Such information is economically important because drilling-fluid costs rise rapidly as chemical requirements increase. This paper presents the results of a study of dynamic filtratioi rates to cores from a clay-gel water-base drilling fluid treated with various commercial viscosity reducers and chemical fluid-loss control agents. The dynamic fluid-. loss rates to cores are compared with the standard API filter-loss values at several different levels of additive concentration. Dynamic filtration rates were obtained in each experiment under two different simulated wellbore conditions: (1) filtration just above the bit through a new mud cake laid down dynamically on a freshly drilled formation and (2) filtration up-hole through a mud cake formed by deposition of a static filter cake on top of the initial dynamically formed cake. The latter case corresponds to the bottom-hole conditions existing above the bit when mud circulation is restarted after a stand of pipe has been added or a round trip has been made to change the bit. Except for the short-duration, high-rate filtration beneath the bit where no mud cake can form, these two conditions probably represent the two extremes of dynamic filtration. Because thickness of a dynamic mud cake formed on freshly exposed formation is limited by the shearing action of the mud stream, the filtration rate for this condition is high. On the other hand, once circulation is stopped and a static mud cake forms on top of the dynamic cake, re-starting circulation has only a small effect on the cake properties and filtration rate is much lower thereafter. A discussion of the mechanics of mud-cake deposition and dynamic filtration is outside the scope of this paper but may be found in more detail in publications by prior investigators. APPARATUS AND EXPERIMENTAL CONDITIONS The test equipment used to simulate the dynamic flow conditions existing during drilling was a modification of that described previously by Krueger and Vogel: A schematic flow diagram is shown in Fig. 1. In general, a power-driven, high-pressure mud pump capable of delivering up to 60 gallmin was used to circulate drilling fluid parallel to the faces of 1-in. diameter sandstone cores mounted in a 2 3/4-in. ID high-pressure test cell. Pump rates were controlled by means of a magnetic clutch to maintain an average axial fluid velocity of 110 ft/min in the annular space between the cell wall and a 1 1/2-in. rod positioned on the center line of the cell. The core specimens were Berea sandstone plugs sealed with plastic inside 1 1/8-in. OD tubes and were fluid-saturated prior to use. Burettes were used to accumulate fluid discharged from the cores. The mud sump shown was used for treatment and storage of the drilling-fluid samples during a particular test. The valve arrangement permitted either (1) circulating drilling fluid through the by-pass line while treating with

By Percival Roberts

It may seem necessary to offer an apology for presenting for consideration a process which is conspicuous by its absence in the literature of the Institute, and which may be thought by some to belong to the past in metallurgy, and to have been already superseded. But the large capital invested in puddling calls for a careful consideration of the question whether the time has certainly arrived when the puddling furnace must be replaced by the converter and open-hearth furnace. May there not still be a place for puddled iron alongside of molten iron and steel, and is not the improvement of the puddling process itself worthy the attention of engineers equally with the Bessemer and open-hearth processes? The changes involved in the conversion of pig iron into wrought iron are well understood and need only be briefly alluded to. The patent of Henry Cort bears the date of 1784. Since that time * the improvements in the process have mainly consisted in the replacement of sand by iron bottoms by Samuel Baldwyn Rogers in 1818, and the still more recent substitution of iron oxide for the refractory materials used for the rides and bridge of the hearth, which distinguishes the wet or boiling process from the dry or pnddling process. Chemically, the process consists in the removal of the metalloids from the pig iron, a result effected mainly by the iron oxide. Silicon is first oxidized, then the phosphorus, and finally the carbon. The silicic and phosphoric acids produced pass into the cinder and the carbonic oxide burns as it escapes from the bath of metal. It is interesting in this connection to note the effect of temperature on the removal of the phosphorus from the iron. As is well known, no phosphorus is eliminated under the oxidizing influences prevailing in the Bessemer converter, while from 70 to 80 per cent. is removed in puddling. But we find, if in working cold short irons

Jan 1, 1880

By Lewis M. Haupt

IT has given me great pleasure to read, in the papers recently pub lished by this Society, the discussions on the subject of Technical Education, which were developed at the joint meeting held at the Franklin Institute in June, 1876; and since it was impossible for me to be present, I desire to improve this my first opportunity of adding the weight of my testimony and experience to what has been so ably presented by others. It is a subject about which the people need to be kept agitated, that their views may expand with the demands made for a higher and more thorough education. It is the public at large, the capitalist, the manufacturer, and the laborer, who are to be benefited more or less by this elevation of the standard of our professional schools, and it is but just, therefore, that the schools should look to them for the means with which to accomplish so de sirable an object. It is no doubt to the interest of a metallurgist to employ a skilled laborer who will prevent waste by properly proportioning his ma terials ; by regulating the supplies of air and fuel; by arranging his plant in the most economical manner, arid by disposing of his products to the greatest advantage. The engineer is benefited by selecting for an assistant a person able to determine the values of his factors of safety for the same materials in different forms and positions, avoiding expensive suits for damages and cost of reconsiruction; he should be able to so locate a road as best to fulfil the requirements of a through traffic, arid yet develop local industries. But I need not multiply instances to show what all will readily concede, viz.: the advantages of a theoretical education ; that was fully demonstrated at the previous special meeting, but it is still an open question whether the practical instruction should precede, accompany, or follow the theory.

By R. D. Nelson, J. C. Shyne

The ß and a ß transformations in plutonium were studied with particular emphasis on the transformation kinetics and microstructure. Significant observations are: 1) The kinetic data show conclusively that the ß — a transformation in high-purity plutonium can proceed isothermally with no athermal component. 2) Plastic deformation of the stable (3 phase retards the subsequent (3 — a transformation. 3) Plastic deformation of the stable a phase accelerates the a — ß transformation; the acceleration is attributed only to residual stresses. 4) The a and a?a volume changes occur anisotroPically in textured plutonium. 5) An apparent crystallogvaphic relationship exists between the parent and the product phases of the and (3 — a transformations. 6) Both applied uniaxial compressive stresses and uniaxial tensile stresses raise the starting temperature for the ß — a transformation. 7) A given uniaxial tensile stress favors the a — ß transformation more than an equivalent applied uniaxial compressive stress opposes the transformation. These observations of the (ß —a and a — ß phase changes in plutonium are consistent with known mar-tensitic transformations. ThIS paper elucidates some of the characteristics of the a— ß and ß —a transformations in plutonium. Because considerable conjecture exists about the mechanisms by which the phase transformations occur in plutonium, experiments have been performed to provide indirect information concerning the mechanisms responsible for the a —ß and ß -a transformations. Indirect information is of particular value in the study of plutonium because of the experimental difficulties presented by the metal. Single crystals have not been produced in any of the allotropes. The large density results in high X-ray and electron-absorption factors and consequently complicating X-ray and electron diffraction. The kinetics of ß — a and a — ß transformations of plutonium and the behavior of the transformations under a variety of conditions have been investigated in detail. Information about the mechanisms of the allo-tropic transformations of plutonium was obtained indirectly from three sources: 1) the effect of plastic deformation of the stable parent phase upon the transformation kinetics; 2) the behavior of the metal transforming under applied stresses; and 3) the microstruc-tural and crystallographic features between parent and product phases. PHASE-TRANSFORMATION CHARACTERISTICS In characterizing solid-state phase transformations in metals and alloys, it is useful to define several types of transformations. An aim of the present work was to identify the low-temperature transformations in plutonium by type, i.e., as martensitic or nonmar-tensitic. Practical definitions for these terms follow. The terms commonly used to categorize phase transformations lack universally accepted definitions. This confusion arises doubtlessly because some terms specify crystallographic or morphological character while other words have a kinetic or a thermodynamic connotation. For example, martensitic specifies certain definite crystallographic restrictions. Unfortunately, martensitic is sometimes used in an ill-defined way to imply kinetic characteristics. Further confusion attends the use of such expressions as nucleation and growth, diffusional, and massive. From time to time new systems of phase-transformation nomenclature are suggested; unfortunately none of these has gained general acceptance.1,2 The authors of the present paper have no intention of entering the controversy. We recognize that some readers may object to the nomencliture used here. For exampie, the terms military and civilian have recently been used in much the same way as martensitic and non-martensitic are used in this paper. This paper is intended to describe several specific details of the low-temperature phase transformations in plutonium. The authors have found it useful to identify these transformations as martensitic; the term was chosen as the best available to describe the experimentally observed features of the transformations studied. A martensitic transformation is one that occurs by the cooperative movement of many atoms; the rearrangement of atoms from parent to product crystal structure occurs by the passage of a mobile semico-herent growth interface. The geometric features characteristic of a martensitic transformation are a specific orientation relationship between the product and parent phase lattices, a specific habit-plane orientation for the growth interface, and a shape change with a specifically oriented shear component. There is no alloy partition between the parent and product phases in a martensitic transformation. Martensitic transformations may display either athermal kinetic behavior or thermally activated isothermal kinetic behavior. Some martensitic transformations occur isothermally, although more commonly martensitic transformations are athermal. Isothermal martensitic transformations are suppressible by rapid cooling. In athermal martensitic transformations, nucleation and growth are not thermally activated and the transformations are essentially time-independent. Nucleation, growth, or both can be thermally activated in isothermal martensitic reactions. Transformation of the parent phase into a marten-

Jan 1, 1967

By Walter A. English, Ralph Arnold

Though production began in Canada only a short time after the discovery of oil in the United States, it has never attained large proportions, and if we were to judge entirely by the past the reserves of Canada would be put at a very low figure. There are only two areas from which oil is marketed at the present time; one, the old district around Petrolia in southern Ontario, and the other is the small Sheep Creek field near Calgary in Alberta. The former district has produced between 200,000 and 800,000 bbl. annually for the past 40 years, recent figures being near the minimum amount. Sheep Creek has produced about 12,000 bbl. annually for the past five years. The known reserves in proved territory in each of these fields are exceedingly small, when considered in terms of world reserves. The chief hope of Canada for reserves of considerable magnitude lies in the western provinces. Sedimentary rocks similar to those in the productive fields of the United States occupy thousands of square miles in the western provinces, so that it seems likely that somewhere within this great area the peculiar conditions necessary for the presence of oil pools will be found. Prospecting is being carried on energetically by several large companies, as well as by many independents. The Dominion Government, which controls most of the public lands, is pursuing a fairly liberal policy toward the prospector, which should stimulate wild-catting, although the province of British Columbia, which controls public lands within t.hat province, is at present unwilling to give adequate encouragement to make wildcatting attractive. As there is really no assurance that any productive pools will be found in western Canada, the estimates of reserves are subject to a wide possibility of error. In making estimates, the various areas within which geologic conditions are more or less uniform are discussed separately; the estimates given for each area are not given with the idea that there is a reasonable probability of their eventually proving to be correct. It is hoped that an average of these estimates, taken together with those made for other undeveloped countries, will give a correct total of reserves

Jan 1, 1923

By Walter A. English, Ralph Arnold

Though production began in Canada only a short time after the discovery of oil in the United States, it has never attained large proportions, and if we were to judge entirely by the past the reserves of Canada would be put at a very low figure. There are only two areas from which oil is marketed at the present time; one, the old district around Petrolia in southern Ontario, and the other is the small Sheep Creek field near Calgary in Alberta. The former district has produced between 200,000 and 800,000 bbl. annually for the past 40 years, recent figures being near the minimum amount. Sheep Creek has produced about 12,000 bbl. annually for the past five years. The known reserves in proved territory in each of these fields are exceedingly small, when considered in terms of world reserves. The chief hope of Canada for reserves of considerable magnitude lies in the western provinces. Sedimentary rocks similar to those in the productive fields of the United States occupy thousands of square miles in the western provinces, so that it seems likely that somewhere within this great area the peculiar conditions necessary for the presence of oil pools will be found. Prospecting is being carried on energetically by several large companies, as well as by many independents. The Dominion Government, which controls most of the public lands, is pursuing a fairly liberal policy toward the prospector, which should stimulate wild-catting, although the province of British Columbia, which controls public lands within t.hat province, is at present unwilling to give adequate encouragement to make wildcatting attractive. As there is really no assurance that any productive pools will be found in western Canada, the estimates of reserves are subject to a wide possibility of error. In making estimates, the various areas within which geologic conditions are more or less uniform are discussed separately; the estimates given for each area are not given with the idea that there is a reasonable probability of their eventually proving to be correct. It is hoped that an average of these estimates, taken together with those made for other undeveloped countries, will give a correct total of reserves

Jan 1, 1923

By J. R. Vilelia

IN accordance with the custom of this society, we are gathered here, as we have every year since 1924, to honor the memory of the eminent American metallurgist and teacher, Professor Henry Marion Howe. Unlike many of the distinguished metallurgists who have preceded me as a Howe lecturer, I cannot bring to you reminiscences of his personality, for it was not my privilege to be associated with Professor Howe, or to be directly one of his students. Yet, Professor Howe and Professor Albert Sauveur, through the medium of their books, were my first teachers of metallography, as they have been of almost all American metallurgists of my generation. As a teacher, and for many years the acknowledged leader of American metallurgists, he exercised a profound influence in the growth of our science and was held in honor by the men of science of his time. I can speak no words of technical appreciation that will add luster to his fame, for by his prophetic vision, his teachings, and his researches he stands among the immortals in the memory of all metallurgists. In 1926, the third Howe Memorial Lecture was presented by Professor William Campbell' of Columbia University, who entitled it "Twenty-Five Years of Metallography." He took as a starting date for his chronology the turn of the century, which coincided with his arrival from England to work in association with Howe at the Columbia School of Mines. In that informative lecture Professor Campbell enumerated the important advances in metallography achieved during the first quarter of the century, and, it now appears, may have established the custom of reviewing such progress every twenty-five years. The scope of Professor Campbell's lecture was as broad as his metallurgical knowledge, for it embraced a wide portion of the field of metallography, both ferrous and nonferrous. Twenty-five years later, the Howe Memorial Lecture Committee saw fit to assign to me the honor of writing a lecture that would commemorate the work of Henry Marion Howe and would at the same time constitute the 25th anniversary of the lecture by Professor Campbell. The Committee suggested that this lecture might properly be called "Twenty-Five More Years of Metallography," a suggestion that I have adopted. I must confess, however, that I have not followed the precedent established by Campbell and have narrowed the scope of this lecture to an appraisal of those achievements which in my opinion have contributed most to the progress of microscopical metallography during the past twenty-five years. Progress in Metallography The metallographic methods most widely used today, with the exception of the electron microscope, were firmly established more than twenty-five years ago. In general, our specimens were prepared for microscopic examination in those days in much the same manner as they are today. It is true that new details of technique have been introduced from time to time, and that superior equipment is available today, but on the whole, these improvements have been in the nature of refinements, often a matter of personal preference, and none can be considered essential to the attainment of the ultimate goal of the art and science of metallography, which is to reveal the structure of metallic specimens with unequivocal clarity so that they may be interpreted correctly. Mechanical metallographic polishing, which was the only method available in 1926, is still universally practiced and still consists of abrading the metallic specimen with a series of abrasives of increasing fineness until a specular surface is attained. We have now the alternative method of electropolishing, but it is not widely used because, except in a few special cases, its results are inferior to those of competent mechanical polishing. Likewise, most of the etching reagents preferred today were in common use more than twenty-five years ago and were applied in the same manner as they are today. Valuable improvements have been made in the optical and mechanical performance of metallurgical microscopes, but there was no dearth in those days of excellent instruments equipped with achromatic and apochromatic objectives capable of yielding micrographs comparable in quality with the best that we can make today. In fact, it would be a difficult task for any metallographer today to make optical micrographs at magnifications in excess of 3000 diameters that would surpass those made by Lucas more than twenty-five years ago. One of these is shown in Fig. 1. Yet, it is unquestionable that on the whole, the micrographs appearing in the metallurgical literature today are vastly superior to those

Jan 1, 1952

By Victor deWolfe

INTRODUCTION The Henderson Mine, located near Empire, Colorado, utilizes a continuous panel caving system to extract ore as one of the world's major producers of molybdenum. Any mine using a caving-by-gravity technique of mining must rely on closely controlled draw of the caved ore. This control is essential to insure proper caving action, to avoid damaging load concentrations of weight and to minimize the dilution of ore with waste material. Henderson is no exception. Draw control is a major factor in all production planning, from long- range plans to short-range and day-to-day ore scheduling. Draw control is reviewed constantly and administered daily in an effort to optimize production efficiency, ore recovery, and cave management. MINING METHOD The cave at Henderson is massive, moving slowly through large panels that are 244 m (800 ft.) wide by 610 m (2,000 ft.) long. Generally two cave areas are drawn at one time. The areas under active draw vary in size but can be as large as 244 m (800 ft.) by 244 m (800 ft. ) containing 400 draw points. Each draw point contains 45,360 mt (50,000 st) on the average and takes about two and one half years to exhaust. A complete panel is worked for seven to ten years. No pillar exists between panels, but rather a buffer zone of broken ore, or "static face," is left in each panel to be drawn with the adjacent, yet-to-be-caved panel in efforts of minimizing dilution of a working area from an exhausted one. (Figure 1) Production drifts are driven on 24.4 m (80 ft.) centers through the ore body. Between the production drifts are funnel-shaped draw bells on 12.2 m (40 ft.) x 24.4 m (80 ft.) centers to receive ore from the cave. Each bell is accessed by two draw points, one from the production drift on either side, thus forming a 12.2 m (40 ft.) x 12.2 m (40 ft.) draw pattern. Extraction of the ore is by rubber-tired, 3.8 m3 (5 yd3) load-haul-dump equipment. The LHDs then tram the ore a maximum of 49 m (160 ft.) to ore passes. Cave initiation and bell development are done from the undercut drifts which are parallel to and 17 m (55 ft.) directly above the production drifts. Longhole rings are drilled and blasted from the undercut drifts to define the bells and establish the undercut for caving. (Figure 2) DRAW CONTROL Since the cave line at Henderson is constantly advancing, it is necessary to be continually initiating new cave at one end while exhausting it at the opposite end. There must exist, therefore, an angle on the ore-waste contact in the broken rock from initiation to exhaustion. The basic concept of draw control is to keep this angle as smooth and even as possible, particularly at the time of exhaustion. If this is achieved, draw points are exhausted more or less in a line, avoiding pockets of remaining ore surrounded by exhausted areas. These pockets would cause spotty ore extraction at the time of exhaustion, increasing the amount of dilution occurring while introducing the potential for significant weight problems in the production area. To arrive at the desired angle on the ore- waste contact, maximum tonnage percentages are assigned to each row of draw points increasing at 10% or 15% increments (depending on cave size and velocity of draw) working away from the cave line. The available tonnage indicated by these percentages is the maximum allowable tonnage to be extracted from each draw point until the available tonnage percent- age is increased. As the cave moves, these percentages increase for each draw point regularly. However, in general the tonnage drawn from each draw point is kept at about 50% of this allowable maximum in order to maintain adequate available tonnage in the cave to sustain production for seven months if cave initiation were to cease. This available tonnage cushion is a safeguard built into the draw control program at Henderson to accommodate fluctuations in the rate of cave advance. When draw points move past the row of 100% tonnage availability, they are drawn past the desired 50% at the same increments per row until exhausted. (Figure 3) To achieve proper draw control, the number of LHD buckets to be taken from each draw point is assigned daily. The actual buckets taken, which may at times deviate from the

Jan 1, 1981