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By H. C. Jennison

Two distinct types of defects occur at times in copper wire as a result of the use of dies of improper design or undesirable wire-drawing practice. The conditions under which these defects may be produced, as well as precautions to be taken in order to prevent them, have been known to The American Brass Co. for many years. The quality of the copper wire bars and rods has too often and unjustly been held responsible for these particular defects and it is to correct any such belief that this paper is presented. An extremely high quality of electrolytic copper has been supplied to the trade by all refineries for the last 20 years at least. The purity of the copper would average well above 99.900 per cent. The casting of the wire bars has been handled in a generally satisfactory manner. The bars have been cast sound, with a flat to slightly crowning set and have been free from sloppy edges, cold sets, etc. In other words, the wire bars have met A. S. T. M. specifications and have been generally satisfactory. For the most part, they have been everything that could be desired from a quality standpoint yet most of the wire mills in this country and in Europe have at times held the quality of the copper responsible for the two types of defects described in this paper. As a matter of fact, these defects are produced entirely in the wire mills. The author has visited many of the large wire mills in the United States and in Europe to investigate these defects. In some cases the trouble has been so serious that the wire mill has ceased operations. At times the wire mills are reluctant to believe that they are responsible for the defective product. The effect of die design, wire-drawing practice, etc., upon the quality of copper wire has received' little study on the part of wire mills, particularly those that have commenced operations in the last few years.

Jan 1, 1930

A regular general meeting of the Canadian Mining Institute will be held in Vancouver, B. C., on Nov. 26-28. The Council extends a cordial invitation to all members of the American Institute of Mining and Metallurgical Engineers to attend.

Jan 11, 1919

By Mary Barrett, Walter Rose

INTRODUCTION The conventional way to program reservoir problems* for solution on the electric analyzer1 is one which concentrates the block units towards the inner radius of the prototype system being represented by the analog model. This is achieved by the device of considering block units of equal value radial resistance, leading to the consequences: (1) the ratio of the external to the internal radius of each block unit is a constant (i.e. r1/ri-l = constant a); (2) the external radius of the nth block unit is equal to the innermost radius of the system times the constant a raised to the nth power: (3) the capacitance of the block units increase by a factor of a2 going out radially from the innermost to the outermost boundaries of the system; (4) given n block units in the radial direction, the capacitance ratio of the outermost to the innermost block unit is a (2n-2); and (5) the vertical resistance of the block units decrease by a factor of a going out radially from the innermost to the outermost boundaries of the system, such that the ratio of the maximum to minimum vertical resistance is also given by the factor a(2n-2) PRESENT PROGRAMMING METHOD While this conventional way of programming problems is quite adequate for routine uses of the electric analyzer, it leads to difficulties in those cases where the inner radius of the prototype system (e.g., the well-bore) is small compared to the external radius (e.g.. the external reservoir boundary). To handle such a case by the conventional method would require either that a large value be selected for the constant a or that a large number n, of radial block units be chosen. In consequence, the capacitance and vertical resistance ratios become impossibly large, as will be evident from the relations given above. In any event, the size of the smallest and largest capacitors will always be limited by the size of commercially available components, and the analyzer itself will determine how many mesh points are available for radial block units. For example, it can be shown that if the maximum capacitance ratio which can be electrically handled is a factor of l04, the maximum external radius of the system which can be considered (assuming an internal wellbore radius of 0.25 ft is: It is thus seen that in direct consequence of having the inner wellbore radius small compared to the external radius, models extending beyond 30 to 40 ft are not possible when the capacitance ratio is limited to l04. (NB. A value of 10-9 farads can perhaps be taken as the minimum electrical capacitance possible if corrections for the capacitance of the lead wires are to be avoided. Values greater than 10-5 farads would require the use of unstable and inaccurate electrolytic capacitors). On the other hand, models extending out to 500 to 5,000 ft may be desired in single-well problems, and hence the need for a revised method of problem programming. * REVISED PROGRAMMING METHOD The revised method of programming is one which attempts to retain the desirable features of the conventional method (viz. concentration of block units towards the inner boundary, simplicity in computation, etc.) without having as a consequence that impossible capacitance and vertical resistance ratios will be required. Other advantages will also be achieved by the revised

Jan 1, 1957

AT A MEETING of the Shareholders of the Russo-Asiatic Cons. Ltd., in London, Oct. 23, 1922, LESLIE URQUHART, chairman of the com- pany made the following statement:* I come now to our recent negotiations with the Soviet Government and to the agreement which has resulted from them. You will remember that the conference at The Hague broke up without having achieved anything very definite. It was not, however, a failure. It elicited from M. Litvinoff an offer which will, I think, come to be regarded as a milestone in the progress of Russia from a ruinous and unpracticable Communism towards a modified form of capitalism. The offer made by M. Litvinoff at The Hague amounted in effect to this: that in return for political recognition on our part the Soviet Government would first acknowl-edge its liability for Russia's national foreign debts, and, secondly, would give the original foreign owners of property in Russia effective compensation. A very great advance that. It showed-and there have been many other signs to confirm it-how real and persistent has been the internal evolution of Russia during the past year from Marxism to the economics of the Western world. I will not now detain you with the reasons why M. Litvinoff's highly promising and significant offer came to nothing. The fact that it had been made and the further fact that The Hague Conference had separated indefinitely were the important things. The first fact seemed to indicate that the Soviet rulers, after all, proved to be people with whom one could do business. The second fact rather emphatically showed that the way to do business with them was not by unwieldy poly-glot conferences of ministers, officials and experts representing a few dozen different governments and a few dozen different sets of national interests. That method had been tried at Genoa. It was tried again at The Hague. Each time it failed, and having failed it left the road clear for a simpler and more direct approach.

Jan 12, 1922

By C. W. Schultz, R. B. Tippin

Statistical screening is so named because a particulate feed is separated into "size" intervals on the basis of the probabalistic behavior of the individual particles (i.e., their probability of passing the screen) rather than by physical restraint. To illustrate this statement, consider a conventional screening operation. A particle which is larger than the openings in the screen cloth is physically restrained from passing through and is repeatedly reflected from the surface until it is discharged as oversize. Of those particles smaller than the screen openings, the very smallest tend to pass the screen near the feed end while those nearer in size to the screen opening tend to pass at a greater distance from the feed end. Alternatively, we could say that the particles with high probability of passing through the screen are concentrated near the feed end while particles of low probability of passing are dispersed from the feed end. This tendency to segregate is the basis for size separation by statistical screening. The purpose of this note is to: 1) Show that the distribution of material passing an array of screens can be described by a modified binomial distribution. 2) Demonstrate that an efficient size separation can be made by this technique. 3) Relate some of the more important screening parameters to the efficiency of the size separation. The Distribution Function The distribution of undersize products along the length of a screen can be derived with the help of a few simple definitions and assumptions. 1) First, we must assume that each particle has some probability of passing a screen on a single presentation. Further, we must assume that this probability is constant and is not affected by the position of the particle on the screen. It must also be acknowledged that several factors enter into this probability. Among them are the "action" of the screen, the slope of the deck, the shape of the openings, etc. The relationship between these factors, however. is not the subject of this paper. 2) To simplify calculations, all particles falling within a size range on the Tyler scale, e.g., —x + x/ mm, are assumed to have the same probability. 3) It is assumed that particles which do not pass the screen on a presentation are reflected a unit distance forward, i.e., the direction of material travel. A unit distance is defined as the distance between the centers of consecutive wires in the screen cloth.

Jan 1, 1971

By R. H. Atkinson

With the object of improving the melting, casting, and working of palladium and 95.5 pct Pd-4.5 pct Ru, the effects of different melting atmospheres (reducing, oxidizing, and neutral), crucible linings, and annealing atmospheres have been studied. Some interesting observations are included about the solubility and diffusion of gases in palladium. THE object of the present work was to ascertain the effect of oxidizing, inert, and reducing ambient atmospheres on the melting and casting of palladium and a Pd-Ru alloy commonly used for jewelry. The need for such a study was indicated during World War I1 when jewelers experienced difficulty in their attempts to make small castings of the torch-melted Pd-Ru alloy by the lost-wax process. When the metal was melted under oxidizing conditions similar to those used for platinum, the castings were gassy; on the other hand, if the melting atmosphere was reducing, the castings were hot-torn and brittle. General Experimental Procedure Pure palladium sponge (99.9 pct Pd) and pure ruthenium powder (99.8 pct Ru) were used for making small ingots (50 g) of palladium and 95.5 pct Pd-4.5 pct Ru by induction melting. The coil, 3 in. high by 2 in. ID with 16 turns, was energized by a 20 kva Ajax high frequency converter. The melting crucibles, so-called sand crucibles, which were made of a highly refractory fireclay, were lined with different materials, including proprietary magnesia, alundum, zircon, and zirconia

Jan 1, 1957

By L. H. Van Vlack, T. Y. Tien, R. J. Martin

The phase relationships of the MnTe-MnS system were studied by DTA procedures. There is an eutectic at 810°C with about 10 mole pct MnS-90 mole pct MnTe. An eutectoid occurs at about 710°C with approximately 7 mole pct MnS where the MnTe(NaCl) solid solution dissociates on cooling to MnTe(NiAs) and MnS. There is very little solid solubility of MnTe in MnS. ALTHOUGH MnS may exist in three different crystal forms,' only the NaC1-type phase is stable.2 Above 1040°C, MnTe also has the cubic NaC1-type structure. Below that temperature, MnTe changes to the NiAs-type structure.3 This phase transition is rapid for both heating and cooling. As a result the high-temperature crystal form of MnTe cannot be retained at room temperature. Because MnO, MnS, and MnSe are all stable with the NaC1-type structure, and MnTe has this structure at high temperatures,4 solid solution formation could be expected among these compounds. It is interesting to note, however, that a complete series of solid solutions exist only in the MnS-MnSe system,' and that the solid solution is quite limited in the MnO-MnS system.' The MnSe-MnTe system possesses a complete series of solid solutions at high temperatures with separation at lower temperatures.7 Although ion size may be critical in the miscibility of MnO-MnS, it is quite possible that the bond type plays a more important role with the miscibility of MnSe-MnTe. This would permit us to speculate that the miscibility gap would be extensive in the MnTe-MnS system. EXPERIMENTAL Preparation. The samples were prepared by mixing and compacting MnTe and MnS powders. The MnS was previously prepared through the sulfur reduction of Mnso4.8 The MnTe had been prepared by mixing and compacting double vacuum distilled metallic manganese and high-purity tellurium in stoichiometric ratio modified with 1 wt pct excess tellurium. The compacted powders were put in a graphite crucible which was sealed in an evacuated vycor tube. The free space in the vycor tube was made minimal to reduce the loss of tellurium. The sealed assembly was then heated slowly to about 500° C where the free manganese and tellurium reacted vigorously, melting the MnTe which formed. Only one phase, MnTe, was detected by X-ray powder patterns and metallographic techniques. Each compact of MnTe-MnS was placed in a graphite crucible and then sealed in an evacuated vycor tube. The samples were heated at 1250°C for 4 hr and furnace-cooled. Microscopic examination revealed no third phase beyond MnS and MnTe. A typical microstructure is presented in Fig. 1. Identification. X-ray powder patterns were obtained using 114.6 mm Debye-Scherrer camera and Fe-Ka radiation. Mixtures of cubic MnS and hexagonal MnTe were observed in all of the compositions prepared. No lattice parameter change was noticed among different compositions, indicating no solid solution could be retained at room temperatures between these two end-members. A lattice parameter of 5.244Å for MnS was obtained by the Nelson and Riley9 extrapolation method using the diffraction lines of (h2 + k2 + 12) equal 12, 16, 20, and 24. The values, a = 4.145Å and c = 6.708Å, for hexagonal MnTe were obtained from the (006) and (220) lines in the back-reflection region. These values agree well with the values reported by Taylor and Kag1e.10 Differential Thermal Analysis. A differential thermal analysis procedure was used to determine phase relationships since the high-temperature equilibrium conditions could not be retained for examination at room temperature, even when the sealed samples (~0.5 g) were quenched in water. The samples were sealed in an evacuated 4 mm vycor tube with a recess in the bottom to accept a thermocouple. An Al2O3 reference was similarly prepared and the two placed within a piece of insulating fire brick to dampen spurious temperature changes within the furnace. The furnace was controlled by a mechanically driven rheostat which increased the temperature at a rate of about 15°C per min. Known phase changes in the Pb-Sn system1' and the a-to-ß quartz inversion12 were used for calibration

Jan 1, 1969

By J. R. Mihalisin

Phase changes in as-cast alloys in the Ni2 CoCr-Ni, Ti-NSAl system containing 0.1 wt pct C were studied after heat treatment at 1650°F. It was found that a vegion of CrCo-type s was developed in this system after I1000 hr. The tendency for s formation was dePendent upon the aluminum and litanium content, the s -forming tendency generally becoming more pro-nounced as the latter two elements are increased. s lended to form in interdendritic regioues and was associated with solutioning- of- carbide phases. Electron- vacancy computations for prediction of s formation on these alloys mere in sufficient agreement with what was observed experimentally to indicate that the method should be of value in assessing a-forming potential in cast alloys. However, the correlation of electrotz- vacancy numbers may not be as favorable in cast as cormpared to wrought alloys. THE increasing use of high-temperature alloys for longer times at higher temperatures has resulted in a real need for obtaining information on the phase changes taking place in these alloys since these changes often have a direct effect on properties. This paper reports on a study of the phase changes in Ni-Cr-Co-Al-Ti alloys after prolonged heating at 1650°F. The alloys were selected from the pseudo-ternary system Ni2CoCr-Ni3Ti-Ni3Al and this system was chosen because it is the basis of many of the newer cast commercial superalloys. The attempt here was not to define accurately the boundaries of s formation in the NizCoCr-Ni3Ti-Ni3Al system but to delineate the phase transformations taking place upon heating alloys covering a wide range of chemistries in this system. An addition of carbon was made to all alloys to further simulate commercial alloys. It was hoped that the information generated in this manner would be of more direct use to superalloy designers than an equilibrium diagram approach since commercial alloys generally have outlived their usefulness when equilibrium is attained. EXPERIMENTAL PROCEDURE The alloys were vacuum-melted from carbonyl-nickel pellet, vacuum-grade chromium, electrolytic cobalt, high-purity aluminum and titanium, and spec-trographic-grade carbon.

Jan 1, 1968

By Leonard R. Weisberg

The general properties of diffusion in GaAs are reviewed. A total of .fourteen atoms have been studied to date, and activation energies for eleven reported are (in ev): Ga (5.6), As (lo), Zn (2.49), Cd (2.43), Sn (2.5). Mn (2.75). S (4.0). Se (4.2). Ag (0.33), Cu (0.52). and Li (1.0). The dijfusion of the first eight atoms, as measured by Goldstein using radiotracer techniques, established the principle of sub lattice diffusion for both host and impurity atoms, since atoms substituting for gallium have lower activation energies than those substituting for arsenic. The diffusion constant of interstitial copper has been determined for the first time by Hall and Racette using heavily doped p-type samples in which interstitial copper predominates. The anomalous behavior of zinc, which has an abrupt diffusion front and a strong dependence on zinc concentration, has recently been quantitatively explained in terms of an interstitial-substi-tutional equilibrium-diffusion mechanism. Lithium and silver diffuse mainly interstitially, while the diffusion of phosphorus is complicated by the continual formation ofGap. Junction-migration measurements indicate diiferent results than radiotracer techniques, and this is one problem that still remains, together with discrepancies in cadmium-diffusion results, and an unexplained dependence of impurity diffusion on arsenic pressure. BESIDES the usual insights into the behavior of atoms in solids, studies of diffusion in semiconductors have additional importance for device applications. In fact, the amount of diffusion studies performed on a semiconductor might serve as a simple barometer of its technological importance. Thus, the information accumulated for GaAs is not yet quite comparable to that for germanium or silicon, but considerable knowledge is available. The diffusion of at least fourteen atoms has been investigated for GaAs, and the diffusion constants have been determined for eleven of these. Interesting results were found for GaAs that elucidated problems not previously solved for germanium or silicon. For example, the interstitial-diffusion constant for the very fast diffusant, copper, was first measured in GaAs. Also, solutions for interstitial-substitu-tional equilibrium diffusion in extrinsic material were provided first for GaAs, although they are ap- plicable to germanium, silicon, and other semiconductors. Studies in GaAs firmly established the concept of sublattice diffusion, which should have application in many different compound systems. The purpose of this paper is to review briefly the general state of knowledge concerning diffusion in GaAs. First some general aspects of diffusion will be covered, and next attention will be given to the results mentioned above. Diffusion in GaAs has been measured both by radiotracer and junction-penetration techniques, and some discussion will be given of differences in the two sets of results. The comprehensive work of oldsteinl-' has served as the primary reference for the diffusion of well-behaved substitutional atoms in GaAs. Since a review has recently been presented of many of these reults, details of the diffusion data will not be repeated. Neither will any discussion be given of the experimental techniques of diffusion measurements, except to note here, in passing, the simplicity and effectiveness of the precision lapping device employed by Goldstein.' I) EXPERIMENTAL RESULTS AND DISCUSSION A) Summary of Experimental Results. Diffusion constants D = Do exp(E/kT) have been determined for eleven atoms in GaAs: a,' AS,' n,'" Cd,'" n,' n,8 s, e,' Ag,O CU," and i." These results are summarized in Table I. In addition, diffusion was investigated for phosphorus,4'12 germanium,I3 and ilicon,' but Do and E were not determined. Radiotracer techniques were used for most of the studies except for lithium, where a combination of chemical and electrical techniques was employed, and germanium and silicon, where junction-migration techniques were applied. The diffusion of zinc, manganese, sulfur, and tin was also measured using junction migration.13'14 Goldstein demon-

Jan 1, 1964

By Walter Stern

THE self-potential or spontaneous polarization method is one of the oldest in the field of electrical exploration. When applied in prospecting for ore bodies, it is one of the most rapid and inexpensive means of locating indications of ore bodies at shallow depth. Usually, the procedure is to survey the equipotential lines of the electrical field that is generated by the electrochemical activity of the ore near the ground-water level, and to localize the so-called negative centers or points of greatest negative anomaly. Another field procedure involves the measurement of potential differences along potential profiles, generally laid out at right angles to the assumed strike. Again, in such survey, the basis for establishing the presence of ore is the location of negative potential anomalies. The earlier writers on the subject, notably Schlumberger1 and R. G. Wells,2 did much to clarify the fundamental electrochemical phenomena involved. Interpretation of the field data, however, remained largely qualitative. In 1925, A. Petrovsky3 analyzed the relation between the shape of the potential anomaly curve and size and depth of an ore body by assuming the subsurface body to be a polarized sphere.4 Along similar lines of approach, Edge and Laby5 considered the ore body a dipping sheet with limited extent in the direction of strike, while Poldini6 based the theory on the assumption of a dipping bar. The following study endeavors to enlarge [ ] FIG. I.-ORE BODY CONSIDERED AS DIPOLE upon these earlier investigations and attempts, on the basis of the potential distribution of a polarized bar, to indicate certain characteristics of the anomaly curve that make possible the determination of depth, size and dip of a subsurface body. THE SPONTANEOUS POLARIZATION FIELD SET UP BY AN ORE BODY If a sulphide ore body is subjected to oxidation varying in degree in its upper and lower parts according to the difference in the concentration of oxygen within the surrounding medium, an electrical potential field is set up. The form and distribution of this field will be investigated herein with special reference to its components on the earth's surface. Under the simplifying assumption that the ore body may be considered as a dipole with the point sources QI and Q2 situated at its upper and lower ends (Fig. I), the potential of the spontaneous polarization at point P is given by the following equation:

Jan 1, 1944

By R. R. French

Investigations were conducted by the lndiana Geological Survey for some dry methods of bene-ficiating low-grade gypsum ore. Seventy-two batch and continuous flow tests were performed with a roller mill, rod mill, pebble mill, electronic color sorter, electrostatic separator, and an air separator. Approximately 650 size analyses and 550 chemical analyses were performed during the investigation. Batch samples were tested by the Survey, and most of the continuous flow tests were handled by com-mercial laboratories. INTRODUCTION Although many companies producing gypsum have been interested in dry beneficiation, very little information has been published in the past. One of the most comprehensive investigations was reported by the Canadian Department of Mines.5 Other reports of interest have been published by the Canadian Department of Mines,' the South Australian Department of Mines,2 and the U.S. Bureau of Mines.3 Some beneficiating practices, such as hand picking, selective mining, crushing and screening, milling, and air classifying, were already in use in the Canadian industry prior to MacPherson's investigations.5 MacPherson examined the effect of tabling, air separation, screening, flotation, electrostatic separation, calcining, washing, and various types of milling, in his efforts to eliminate dolomite, limestone, and small amounts of silica and clay from the gypsum ore. RAW MATERIAL Gypsum and anhydrite occur within the lower part of the St. Louis Limestone (Mississippian) in southwestern Indiana. Gypsum in single beds 10 or more ft thick occur at Shoals, Martin County; near Freedom, Owen County; near Bloomfield, Greene County; and in the Devonian strata of LaPorte County. Only the Shoals deposit has been exploited commercially. The western edge of the Shoals deposit is contaminated by a continuous bed of shale, about 1 1/2 to 2 ft thick, near the top of the evaporite and by thin continuous strata or irregular masses of carbonate rock. The low-grade material used in these investigations was obtained from the waste pile of the National Gypsum Co.'s plant at Shoals. The waste ore averaged about 67.4% gypsum and was contaminated by various amounts of shale, dolomite, and limestone. All the material had been previously crushed and screened to minus 1 1/4 to plus 3/8 in. X-ray analyses of powdered, sedimentated, gly-colated, and heat-treated samples of the shale showed that it was composed of slightly structurally disordered illite, Fe-rich chlorite, and very finegrained disseminated silt. The clays and silt were partly cemented with carbonate material. Light-gray argillaceous limestone and gray or brown porous dolomite made up most of the carbonate rock contamination. Crushing Characteristics: The rate unweathered gypsum, carbonate rock, and shale reduce in size was determined by crushing handpicked samples in a rod mill and screening at minus 100 mesh (.0059 in.). Fig. 1 graphically represents the data. These data indicate that carbonate rock should be relatively easy to separate from gypsum, but that shale should be difficult to separate from gypsum by differential crushing. Controlled Samples: Eight rod mill tests of hand-picked samples of mixed gypsum and shale and mixed gypsum and carbonate rock were made. Sample weight and crushing weight were standardized, but the scalping screen size was varied from 3 to 10 mesh (.265 to .0787 in.) in order to obtain the optimum purity and recovery. The data obtained from the tests (see Table I) illustrate that the relatively hard carbonate rock allows appreciable beneficiation (13.6 to 18%), but the low strength gypsum and shale allows only minimal separation (3.1 to 7.5%).* Semi control led Samples: During the investigation considerable slaking of the shale was noted when the ore was subjected to alternate wetting and drying. As demonstrated in laboratory tests, as much as 76% shale can be removed by two cycles of wetting and drying in a 48-hour period with subsequent screening at .265 in. Five ore samples, stockpiled and weathered, were screened, rod-mill crushed and rescreened at .157 or .187 in. with excellent results (Table 11).

Jan 1, 1967

By John Chipman

The concentration of a solute in a dilute ),zetallic solution may be measured by any of several parame- ters including weight percent, atom fraction, atom ratio, and lattice ratio. The ratio of filled to unfilled interstitial sites is useful for interstitial solutes. A variable 2 proportional to this ratio is used as a measuve of concentration. For component 2 irz a bitzary solution z2 = n2/Ym - nz/b) where b is the numberber of interstitial sites per lattice atom. For a t~lul-ticortzporzent solution this becomes zz = n2/(nl + Cvjnj) in which Vj = - l/b for an interstial solute and +1 for a substitulional solute. In the infinitely dilute solution the activity of an interstitial solute 2 is proportional lo z2. At finile concentration the departure from this limiting law is expressed us an activity coefficient, his coefficient is a function of concentra1io)z expressed as tevactiolz coeffcient 8; is analogous to the jark~iliar e£ bul is found to be independent of concentvation in certain solutions for which data are available. It is found that the same equations may be used to express the activity of a nonmetallic solute, sulfur, in liquid solutions of iron containing other solutes, both metallic and nonmetallic. For a nonmetallic solute or for one which strongly increases the actiuity of sulfur, it is convenient to assign arbitvarily a value vj = — 1. When this is done the derivative is found to be constant in each of the ternary solutions studied. The activity coefficient of sulfur in a complex liquid iron solution may be expressed as where nk is a second-order cross product determined in the quaternary solution Fe-S-j-k. The equation is used to calculate tlze activity of sulfur i)z three sevetl- component solutions. IN thermodynamic calculations concerning dilute solutions it is unnecessary to invoke laws and relations which extend across the concentration range to include concentrated solutions. In most binary metallic systems, as arkeen&apos; has recently pointed out, there exist two terminal composition regions of relatively simple behavior, connected by a central region of much greater complexity. When the solute is a nonmetal there is only one such region and in many systems the concentration range is extremely limited. It is the purpose of this paper to suggest a method for the calculation of activities in such a terminal region in which one or more solutes are dissolved in a single solvent of predominantly high concentration. HENRY&apos;S LAW In the usual textbook statement of Henry&apos;s law, concentration is stated in mole fraction. This has the advantage that it makes Henry&apos;s law thermodynamically consistent with Raoult&apos;s law. Since all measures of concentration at infinite dilution are related by simple proportion it follows that mole fraction, molality, atom ratio, weight percent, or any other unit of concentration can be used with the appropriate constant. At finite concentrations, however, calculations based on the law depend upon the unit employed. Deviations from Henry&apos;s law at finite concentrations depend upon the composition variable employed. They are evaluated in terms of activity and interaction coefficients2 which have become familiar features of metallurgical thermodynamics. It is the purpose of this paper to propose a measure of concentration for metallic solutions containing interstitial or nonmetallic solutes by means of which the calculation of activities in complex solutions may be simplified. The discussion will be restricted to free-energy interaction coefficients3 typified by Wagner&apos;s c|a BINARY SOLUTIONS The several measures of concentration which are to be considered are shown in line a of Table I. The corresponding activity coefficients are in line b and the deviation coefficients, sometimes called self-interaction coefficients, are in line c. Henry&apos;s law simply states that the activity coefficient approaches a constant value at infinite dilution. By adoptihg the infinitely dilute solution as the reference state and defining the "Henrian" activity as equal to the concentration in this state, the activity coefficient is always unity at infinite dilution. This convention is far sim~ler and more useful in dilute solution than emploiment of the &apos;Raoultian" activities and it will be used in the following discussion. The several definitions and equations of Table I will be referred to by means of their coordinates in the table. Early observations of deviations from Henry&apos;s law in metallic solutions were shown graphically4 rather than analytically. For the case of sulfur in liquid iron5 the slope of a plot of logfs vs (%S) was constant in the range 0 to 4.8 pct S, indicating constancy of eh2&apos; in Ic. He was proposed by wagnerz and has been widely adopted. The a function of IIIc recently employed by ~arkenl was designed specifically for dilute solutions. Darken has shown that the value of a12 remains essentially constant for many binary solutions within a substantial range of compositions. The atom ratio is directly proportional to the molalitv.<, a conventional measure of concentration. IVb and C served as the basis for smith&apos;s6 classic studies of

Jan 1, 1968

[ PRESIDENTS DAVID THOMAS 1871 &apos;R. W. RAYMOND 1872-1874 &apos;A L. HOLLEY 1875 &apos;ABRAM S. HEWITT 1876 &apos;T. STERRY HUNT 1877 &apos;ECKLEY B. COXE 1878-1879 &apos;WILLIAM P. SHINNY 1880 &apos;WILLIAM METCALF 1881 &apos;RICHARD P. ROTHWELL 1882 &apos;ROBERT W. HUNT 1883 &apos;JAMES C. BAYLES 1884-1885 ROBERT H. RICHARDS 1886 &apos;THOMAS EGLESTON 1887 &apos;WILLIAM B. POTTER 1888 &apos;RICHARD PEARCE 1889 &apos;ABRAM S. HEWITT 1890 &apos;JOHN BIRKINBINE 1891-1892 &apos;H. M. Hows 1893 &apos;JOHN FRITZ 1894 &apos;J. D. WEEKS 1895 &apos;E. G. SPILSBURY 1896 &apos;THOMAS M. DROWN 1897 &apos;CHARLES KIRCHHOFF 1898 &apos;JAMES DOUGLAS 1899-1900 &apos;E. E. OLCOTT 1901-1902 &apos;ALBERT R. LEDOUX 1903 &apos;JAMES GAYLEY 1904-1905 &apos;ROBERT W. HUNT 1906 &apos;JOHN HAYS HAMMOND 1907-1908 &apos;D. W. BRUNTON 1909-1910 &apos;CHARLES KIRCHHOFF 1911]

Jan 1, 1940

By Howard J. Smith

At the meeting of this Institute in February 1933,I presented a paper on potash development in southeastern New Mexico1, which contained a brief review of the Geological Survey&apos;s 20-year search for commercial sources of soluble potash minerals and of the events that led to the discovery, exploration, and first development of the deposits in that state. AS a more comprehensive review of the subject was published in December2, the present paper is intended only to discuss recent developments in the domestic potash industry, particularly in New Mexico. A summary of the findings of potash in the Permian Basin, by G. R. Mansfield and W. B. Lang, geologists of the United States Geological Survey, is now in process of publication by the University of Texas and will be omitted from this paper. In New Mexico prospecting for potassium salts during the past two years has increased materially the known area of commercial deposits; development has resulted in an increase from one to three in the number of shafts and the starting of a fourth; an increase of annual productive capacity to 1,000,000 tons of crude salts, or 250,000 tons of K2O; and an increase in annual refining capacity to 140,000 tons of muriate of 62.5 per cent grade. Construction has been completed to increase still further the production of high-grade salts. In California the American Potash & Chemical Co., operating on Searles Lake brines, has increased its plant capacity from about 100,000 tons to 180,000 tons of muriate a year and is now producing soda ash and salt cake in addition to potash and borax. Potash production from cement-plant and industrial-alcohol wastes remains unimportant.

Jan 1, 1938

By Howard J. Smith

At the meeting of this Institute in February 1933,I presented a paper on potash development in southeastern New Mexico1, which contained a brief review of the Geological Survey&apos;s 20-year search for commercial sources of soluble potash minerals and of the events that led to the discovery, exploration, and first development of the deposits in that state. AS a more comprehensive review of the subject was published in December2, the present paper is intended only to discuss recent developments in the domestic potash industry, particularly in New Mexico. A summary of the findings of potash in the Permian Basin, by G. R. Mansfield and W. B. Lang, geologists of the United States Geological Survey, is now in process of publication by the University of Texas and will be omitted from this paper. In New Mexico prospecting for potassium salts during the past two years has increased materially the known area of commercial deposits; development has resulted in an increase from one to three in the number of shafts and the starting of a fourth; an increase of annual productive capacity to 1,000,000 tons of crude salts, or 250,000 tons of K2O; and an increase in annual refining capacity to 140,000 tons of muriate of 62.5 per cent grade. Construction has been completed to increase still further the production of high-grade salts. In California the American Potash & Chemical Co., operating on Searles Lake brines, has increased its plant capacity from about 100,000 tons to 180,000 tons of muriate a year and is now producing soda ash and salt cake in addition to potash and borax. Potash production from cement-plant and industrial-alcohol wastes remains unimportant.

Jan 1, 1938

By M. A. Grossman

The harden ability of most steels can be predicted within 10 to I5 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In the method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a "pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain size may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter", namely, the diameter of bar, in inches, that will just harden all the way through (absence of un-hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test The data bring out certain features rather clearly. For example: i. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals,,) are known; thus an "incidental,, chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybdenum when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful, as would appear to be common experience; observe that an increase from no manaanese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added "20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the fist small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using I.o per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost 10 per cent in hardenability (in these units); this, however, does not apply to certain It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome-molybdenum and chrome-vanadium steels, un-dissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum Passible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the

Jan 1, 1942

By M. A. Grossman

The harden ability of most steels can be predicted within 10 to I5 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In the method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a "pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain size may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter", namely, the diameter of bar, in inches, that will just harden all the way through (absence of un-hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test The data bring out certain features rather clearly. For example: i. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals,,) are known; thus an "incidental,, chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybdenum when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful, as would appear to be common experience; observe that an increase from no manaanese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added "20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the fist small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using I.o per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost 10 per cent in hardenability (in these units); this, however, does not apply to certain It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome-molybdenum and chrome-vanadium steels, un-dissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum Passible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the

Jan 1, 1942

All the TECHNICAL PUBLICATIONS and CONTRIBUTIONS published in 1933 are available at Institute headquarters, unless otherwise noted. They are also on file in many public, university and technical libraries and, when so indicated in the list, may be found in the TRANSACTIONS. Copies of the TECHNICAL PUBLICATIONS have been mailed to those members of the Institute who are registered in the different classes: A-Metal Mining; B-Milling and Concentration; C-Iron and Steel Division; D-Nonferrous Metallurgy;. E-Insti¬ tute of Metals Division; F-Coal Division; G-Petroleum Division; H-Nonmetallic Minerals; I-Mining Geology; J-Mineral Industry Education Division; K-Mining Administration; L-Geophysical Prospecting. Other members may obtain copies by writing to the Secretary. Copies of CONTRIBUTIONS may also be obtained from the Secretary&apos;s office. Additional copies are sold at the rate of 1 cent per page; minimum charge, 25 cents. Nonmembers may purchase the papers at the prices mentioned. METAL MINING TECH- NICAL PUBLI- TITLE AUTHOR MEETING TRANS. CATION VOLUME No. AND PAGE* 499-A.47 Red Ore Mines of the Woodward T. C. DeSollar New York, Iron Company at Bessemer, Feb., 1933 Alabama (11) CONTRI¬ BUTION No. 1-A The Owyhee Tunnels (16) P. R. Hines New York, Feb., 1933 2-A Sinking and Equipment of the No. D. D. Homer New York, 2 Shaft at Minas de Mata- R. H. Cromwell Feb., 1933 hambre (25) 3-A Subsidence Resulting from the Charles W. Allen New York, Athens System of Mining at Feb., 1933 Negaunee, Michigan (8) 4-A Effect of Approximately Vertical P. B. Bucky New York, Cracks on the Behavior of Hori- Feb., 1933 zontally. Lying Roof Strata (16) 21-A Selection of a Mining System (11) R. K. Warner New York, Feb., 1933

Jan 1, 1933

[PRESIDENT AND DIRECTOR H. G. MOULTON3 NEW YORK, N. Y. PAST PRESIDENTS AND DIRECTORS - D. C. JACKLING1 SAN FRANCISCO, CALIF. DONALD B. GILLIES2 CLEVELAND, OHIO TREASURER AND DIRECTOR KARL EILERS3 SEA. CLIFF, N. Y.]

Jan 1, 1940

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9&apos;22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970