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By S. J. Hruska

Rate expressions for the formation of two-and three-dimensional nuclei on foreign substrates are developed, taking into account previously neglected contributions to the standard Gibbs free energy of formation of critical nuclei. The temperature dependence of critical super saturation data predicted using these expressions is in accord with data for cadmium on copper and sodium on CsCl. EXPERIMENTAL data on the heterogeneous nuclea-tion of metal crystals from the vapor phase1&apos;2 exhibit the temperature dependence predicted by a nucleation rate equation derived by Pound et al.3 In their treatment, the critical nuclei are visualized according to the Volmer4 model as cap-shaped (three-dimensional). Accordingly, it seems desirable to compare these data with a nucleation rate equation which is derived on the assumption of disk-shaped (two dimensional) nuclei. Further, Lothe and Pound5 have recently shown that the standard Gibbs free energy of formation of these critical nuclei contains a contribution which has heretofore been neglected. Thus it is necessary to re-examine these nucleation data using a rate equation which contains this contribution. The van&apos;t Hoff isotherm relates n(i), the concentration of nuclei of critical size i (i = number of atoms), to nil), the concentration of adsorbed single atoms: where standard Gibbs free energy of formation of critical nuclei given by is temperature insensitive and is the bulk free energy change/volume of transformed material], T = substrate temperature and k = Boltzmann&apos;s constant. Previously,3 was determined by considering only the contributions of bulk and surface free energies in transforming i atoms from the population nil) to a cluster of i atoms. It has been shown5 that this procedure does not take into account the free energy contribution arising from the multiplicity of sites, q, where the clusters can be situated. If this contribution, -kT In q/n(l),is added to iG3 [Note that this increases n(i) by a factor q/n(l).] Since the above does not affect the remaining terms in the rate expression of Pound et al., the details are referred to their paper. The resulting nucleation rate is If the experimental AGV and T values at some common value of are employed, a plot of vs T(ln C3/l + In p&apos;) should yield a straight line of slope k/B<p and intercept . The corresponding plots for / = 1 nucleus per sq cm sec and C3 = 1018 are shown in Figs. 1 and 2 for cadmium on copper1 and sodium on CsCl2 and the values of obtained therefrom are entered in Table I. It is apparent that the data yield reasonable straight lines with about the same scatter as found using the equation of Pound et al. When the configuration of minimum free energy for a nucleus is a circular monatomic layer, the standard free energy of formation is

Jan 1, 1963

By J. S. Kirkaldy, R. J. Brigham

AS part of a program to investigate the diffusive properties of dilute ternary austenites we have made a determination of the effect of chromium on the activity of carbon in ? iron. Samples of pure iron and Fe-Cr alloys were simultaneously equilibrated at 1000°C with atmospheres of controlled CO/CO2 ratio following the procedures of Darken and Gurry 1 and smith.&apos; The 0.020 in. thick samples were analysed for carbon by microcombustion analyses3 to yield a set of isoacti-vity curves. The latter were converted to activity coefficient (standard state at infinite dilution) plots by combination with Smith&apos;s data2 for the activity of carbon in pure iron. Table I shows the compositions of the base alloys used while Fig. 1 shows the experimental results superimposed on a set of curves generated by the relation In?C=6.9NC- 10.7 Ne In the notation of wagner4 the interaction parameter is the second coefficient on the right, Sgr = - 10.7 This can be compared with a rather inaccurate value deduced from the transient equilibrium diffusion data of Kirkaldy et al.&apos; as The authors are indebted to the American Iron and Steel Institute for financial support. This material is condensed from a B.Sc. Thesis submitted to Mc-Master University by R.J.B.

Jan 1, 1963

By J. L. Green

Virginia-Carolina Chemical Corp., in its Florida Operations, uses both roller mills and ball mills in dry grinding of phosphate rock. The roller mills have been in operation since 1954 in the Mining Department. The ball mills were installed and put in operation in 1960 in the Harding Concentrate Superphosphate Plant. The roller mills in the Mining Department are used to grind phosphate rock for outside customers. This involves short notice orders of varying grinds, grades and types of rock. The ball mills grind phosphate rock for use in V-C&apos;s own phosphoric acid and concentrated superphosphate plant. These mills grind generally two types of rock for one grind. In 1959, a 10% speed-up was made in the operating speed of the roller mills. This paper deals with the operational gains and resulting cost savings which evolved from this speed-up, and compares the present operations of the roller mills and of the ball mills in grinding phosphate rock. In January 1959 it was decided to determine the feasibility of reducing the grinding cost on the roller mills, per ton of rock ground, by speeding up the mill 10%. At this time, one mill was completely reconditioned so it would be in top condition. Extensive tests were then run both before and after the mill speed-up to determine the resultant cost savings. These tests showed that, due to this 10% speed-up, the mill capacity was increased approximately 20% and grinding power costs per ton were reduced approximately 10%. Table I shows the results of these tests. Each test run actually represents several of the same type rock and grind, averaged together. Each test run lasted approximately three hours. The validity of these runs has been confirmed by subsequent operation in grinding over 1,000,000 tons of phosphate rock. Accurate records have been kept on power consumption and repairs as well as tons produced. Two types of feed rock were used for the tests — pebble phosphate rock and flotation phosphate concentrate rock. The pebble phosphate rock size is approximately 80-90% plus 20 mesh. The flotation concentrate phosphate rock size is approximately 15% plus 20 mesh and 95% plus 100 mesh. The same two types of rock feed were used for all the test runs. Test Nos. 1, 2, and 3 were run at the original mill speed of 85.5 rpm on the vertical shaft. Test No. 1 was run with a feed of high grade flotation concentrates; the desired fineness attempted was 70% passing 200 mesh. Tests No. 2 and No. 3 were run with a feed of low grade pebble. Test No. 2 was run for a desired fineness of 70% passing 200 mesh. Test No. 3 was run for desired fineness of 50% passing 200 mesh.

Jan 1, 1963

By J. W. Spretnak, G. W. Cunningham

A study has been made of the growth and disappearance of voids in the interface of pressure bonded copper. The formation of visible voids is primarily due to spheroidization and coalesence of microvoids produced during the application of pressure. The microvoids could be prevented from forming by the application of high pressures or by increasing the ductility of the copper. Migrating grain boundaries were found to be more effective in void removal, than stationary grain boundaries. DURING the course of an investigation on the mechanism of pressure bonding, it was found that voids formed in the bonding interface which inhibited migration of the interfacial boundary and grain boundaries in the bond region. Therefore, an effort was made to determine the nature of the voids and how they form, grow, and disappear. This paper reports the results of such an investigation. The existence of interfacial voids is not solely a characteristic of massive components of metal which have been bonded by the application of heat and pressure, but is a phenomenon which has been observed in sintering as well. Simonsen attempted to study the sintering process by hot-stage microscopy and thereupon observed the formation of interparticle porosity as sintering proceeded. It was assumed that the porosity was due to grooves created at the location where grain boundaries joined the surface of the particle. Pranatis, Castelman, and seigle2 have also observed voids along the areas of contact in wound-wire specimens used for sintering studies. They did not discuss the point in detail since this behavior was not general, but they did suggest that the voids might develop as a result of stresses along the interparticle contact area. In previous investigations on pressure bonding, workers3 have suggested that voids may exist in the region where mating surfaces are placed in intimate contact, but the existence of the voids was not verified and no attempt was made to study the growth and disappearance of these voids. Durst noted the existence of pores in roll-clad structures prepared by cold reducing two sheets to force them in contact and then annealing to improve the bond. Since his unbonded regions contained a gas which he assumed to be insoluble, he proposed a mechanism which consisted of spheroidization of the unbonded regions and a growth of the contact area, but no speculations were made regarding disappearance of the gas filled pores. One interesting comment made by Durst was the suggestion that flattened voids with sharp corners which are produced during roll bonding will have a greater driving force for spheroidization than the more rounded pores created by pressing metal powders and thus spheroidization and neck growth will occur at lower temperatures. In this study it was necessary to demonstrate conclusively that voids can actually exist in the interfacial bond area. Experimental work was then directed toward a study of the mechanism whereby the voids grow and subsequently disappear.

Jan 1, 1963

By F. R. Morral

In 1964, mining education in the United States will celebrate a 100th anniversary-that of the founding of our first school of mines at Columbia University. Prior to that, curricula leading to degrees in mining and metallurgical engineering were offered in 1853 by the Polytechnic College of Pennsylvania in Philadelphia. But the New World&apos;s earliest achievements in mining and metallurgical education were those of the Spanish in what is now Mexico. American metallurgy probably goes back to Father Jose de Acosta, who in 1590 described the metallurgy of silver and mercury in the New World.&apos; The Spanish priest and metallurgist Don Alvaro Alonso Barba Toscano (1569-1662), in his hook The Art of Metals, published in 1640, stated a need for a school of mining and metallurgical education in the New World. (The latest translation of this book was made by R. E. Douglas and E. P. Mathewson and published by J. Wiley & Sons, New York, in 1923.)

Jan 1, 1963

By E. T. Turkdogan, P. Grieveson, J. F. Beisler

Jan 1, 1963

By N. Schapiro, R. J. Gray, G. D. Coe

A petrographic and chemical investigation was conducted to determine the occurrence and distribution of the organic and inorganic forms of sulfur in various size and specific gravity fractions of a high volatile, A-rank, Pittsburgh seam coal. The investigation was conducted to aid in the resolution of the problem of how metallurgical coke of lower sulfur content can be produced from high sulfur coals. The Pittsburgh raw coal contains about 2.4% S in two dominant forms: pyritic and organic. Pyritic sulfur constitutes about 57% of the total sulfur in the raw coal and occurs in macroscopic and microscopic-size particles. A plant cleaning process mechanically separates between 50 and 60% of the pyritic sulfur, mainly the macroscopic particles. The organic sulfur constitutes 41% of the total sulfur in the raw coal and 55% of the sulfur in the washed coal. Thus, organic sulfur is not reduced by physical methods of separation. Organic sulfur occurs in all the coal entities, but in general, increases as the exinoid content of the coal increases. In this study, it was found that carbonizing certain selected low gravity coal fractions containing an average of 0.45% pyritic sulfur and 1.01% organic sulfur produced cokes containing an average of 0.22% pyritic sulfur and 0.91% organic sulfur. However, the organic sulfur in the coke is probably derived in part from the heating of pyrite in the presence of carbon. Thus, the total sulfur in the coal carbonized is the most important factor affecting the sulfur content of the coke produced. Concentration of microscopic pyritic and organic sulfur in the middling-type coal indicates the necessity for rejecting as much of this material as is economically feasible. Most of the sulfur introduced into the blast furnace originates from the coke. Although the sulfur content of the hot metal can be controlled by the addition of flux, the flux used restricts the productivity of the furnace by displacing ore and requires first to be smelted; therefore, low sulfur coke is highly desirable. Since the sulfur content of coke is dependent upon the sulfur content of the coals from which the coke is produced, low sulfur coals are required to produce low sulfur coke. In the western Pennsylvania area, large quantities of good coking coal are available from the Pittsburgh seam, but this coal unfortunately contains relatively large quantities of sulfur. To provide information that might be useful in reducing the sulfur content of this coal in the cleaning process, an investigation was conducted to determine the physical and chemical forms in which this sulfur occurs and with what petrographic components it might be associated. The Pittsburgh seam coal, like most other coals, contains two dominant forms of sulfur: one occurs as the minerals pyrite and/or marcasite and is referred to as pyritic sulfur; the other is combined with the coal substance and is called organic sulfur. Pyritic sulfur is amenable to physical methods of separation, whereas organic sulfur is not. Pyritic sulfur particles must be freed from the surrounding coal if they are to be removed in the washing process. Generally, this requires crushing; the required degree of crushing being a function of the size and distribution of the pyrite. The present investigation was conducted to 1) determine the size, distribution and association of sulfur-bearing minerals in the coal and 2) to determine whether the organic sulfur has a preferential association with specific coal entities. If a preferential association exists, this knowledge may be useful in devising a method for organic sulfur reduction. In addition, a study was made to determine the extent to which pyritic and organic forms of sulfur in the coal contribute to the sulfur in the coke produced from this coal. A representative 3%-ton sample of raw coal was crushed to —3 in. and screened into square-mesh sizes: 3 to 1 in., 1 to % in., % to % in., % in. to 10 mesh, 10 to 35 mesh, and 35 to 200 mesh. Separate samples of the -200-mesh fraction and the all-size composite were also collected. Each size fraction (except the -200 mesh) was fractionated on heavy liquids of the following specific gravities: 1.280, 1.300, 1.325, 1.350, 1.375, 1.400, 1.425, 1.450,

Jan 1, 1963

By R. A. L. Black, J. E. Jennings

The problems of slope stability in open cast mines are examined. A criterion, the instantaneous stripping ratio, is suggested for use in the design of pit slopes and as an index of control at all stages of the exploitation of the orebody. This criterion may also be related to safety and to the maximizing of profits. Two approaches to safe design of slopes, one from the point of view of soil mechanics and the other from the point of view of rock mechanics, are described and critically compared. The effect on slope stability of the regional tectonic stress field is discussed. Explanation is given of the application of the Terzaghi effective stress concept to problems in both soil and rock environments, including possible effects when borehole deformation techniques are used to measure stresses in rock in situ. A company embarking on open cast mining is faced with two basic questions: 1) will the venture be profitable and 2) can it be carried out with safety? The two questions are obviously interrelated because both depend upon the slope angles adopted for the pit. The cost of open cast mining depends largely upon the stripping ratio, defined as the volume of overburden that must be removed to the volume of ore recovered. The steeper the slope angles, the more favorable the stripping ratio, but the stability of the slopes, and therefore the safety of men and materials in the pit, require that the angles be made relatively flat. Consequently, the design depends upon a compromise: the slopes must be steep enough to result in economical mining and flat enough to ensure safety. Today there is a world trend towards deeper mining by open cast methods. This is mainly due to the higher cost of underground mining and the lower cost of open excavation resulting from the introduction of large modern earth and rock-moving machinery. Deeper open cast mining has led to a very great increase in the volumes of wasted overburden, and much thought is being given to the considerable economic benefits which would result if pit slopes could be made steeper by even one or two degrees. The result has been an increasing interest in research into slope stability problems in the expectation that the application of scientific principles will provide solutions leading both to economies and to more predictable operation of the mines. In at least four places, the U.S., Australia, Western Germany and Southern Africa, comprehensive investigations are at present in progress, and it is the object of this paper to review some of the more important aspects of these programs. RELATION BETWEEN ECONOMY OF OPERATION AND SLOPE ANGLES The main object of any industrial enterprise in a free economy is to make a profit. In mining, where profits must be made from a wasting capital asset, a further definition of the profit motive is imposed, namely that the economic aim should be to maximize the total possible profit. But since profits deferred for a number of years are not as valuable as profits that are immediately available, it is usual to discount deferred profits at some rate of interest which reflects their current or present value in the hands of the investor. Thus, in mining the logical aim can be defined more closely still: to maximize the present value of the total future profits. In commercial terms the present value represents the market value of the operation as a going concern. Many factors enter into the forecast of current and future profits. They include the volume of production, the price of the salable product and the cost of production. Current profits can be estimated with reasonable accuracy by the operating engineers; but it is the task of economists and management to assess future trends in the mineral markets and in the economy as a whole, and together with the engineers, they can then estimate the future cost and profitability of the mining operations. In open cast mining, the rate of ore production once decided on remains a virtually constant factor unless a major change in the capital structure of the mine is made. But one factor over which the operator has a considerable measure of control is the ratio of the volume of ore mined to the volume of waste over-

Jan 1, 1963

By D. J. Rose, W. M. Armstrong, A. C. D. Chaklader

The wetiability of single crystals of MgO by specimens of vacuum-cast iron was studied using the sessile drop technique in vacuo at 1550ºC. Formation of FeO at the liquid-vapor interface caused the contact angle (6) to decrease from 117 to 65 deg during the first minute. After cooling, all specimens possessed a peculiar annular interfacial deposit of Fe,O,. Within the annulus the interface showed no sign of chemical attack. Chemical reaction occurred where the iron was alloyed with Ti, V, Cr, Nb(Cb), Ta, cmd Zr. Vnriation of 6 with alloy concentration was studied. Although vanadium md chromium improved the wettability of MgO by iron, the effect of Zr, Ti, Nb, and Ta was indeterminable because the 8 derived from sessile drop considerations was that of the metal against a restrictive peripheral volume of liquid oxide wetting the substrate. INTEREST in the nature of metal-ceramic interactions has been stimulated by progressive development of metal-ceramic combinations. One of the more valuable methods used for bond investigation is the sessile drop technique. Recent attempts to improve wettability through solute additions to the drop have revealed that the solute may a) react with the oxide creating new compounds at the solid-liquid interface, b) adsorb at the interface in a monolayer formation, or c) distribute throughout the drop uniformly causing no wettability variation. This work, part m in a series1,2 of investigations of interface reactions between metals and ceramics, embraces a study of the Fe-MgO system. MgO possesses a large negative free energy of formation (-173 kcal per g mole 0, at 1550ºC) compared to FeO at this temperature (-73 kcal per g mole 02). Hence the electronegativity difference between the drop and substrate allows selection from an extensive group of metal solutes with intermediate electronegativity differences that would, in the absence of chemical reactions, be expected to adsorb pre- ferentially at the solid-liquid interface. However, the high oxygen pressure of MgO in vacuo creates an oxidation environment which influences the solute behavior. Recent studies of the Fe-MgO systemJ74 have been restricted by chemical reactions that obscured observations. In view of the current interest in liquid-phase sintering of metal-ceramic combinations under partial oxidizing conditions,5 a more comprehensive study of the Fe-MgO system seemed beneficial. EXPERIMENTAL PROCEDURE 1) Specimen Preparation. Optical-grade MgO single crystals and Ferrovac vacuum-cast iron were used in all experiments. A spectrographic analysis of the iron indicated 0.008 C, 0.05 V, 0.005 Mo, 0.01 Ti, 0.002 S, 0.01 Cr, 0.001 Mg, 0.01 Si, 0.003 A1 (wt pct). The MgO crystals were cleaved along (100) planes into plates approximately 20 by 20 by 1 mm. Following annealing in vactto at 1100°C for 3 hr, surface irregularities were removed by a chemical etch in phosphoric acid at 100°C. The iron rod was machined into small cylinders approximately 0.250 in. in diam and length and these were carefully cleaned in organic and acidic solutions to remove surface impurities. All specimens were weighed to the nearest 0.1 mg. 2) Apparatus. The apparatus described in detail by previous authors1,2 was modified for this work. A Polaroid Land Camera was incorporated into the optical system so that drop measurements at ten-second intervals after melting were possible with ultra-high-speed self-develop ing film. 3) Procedure. The iron cylinders were placed upright on the MgO plates and positioned in the molybdenum susceptor. After furnace assembly the system was pumped down to a vacuum of 1 µ and flushed with H2 at 800°C. The system was again evacuated to 5 x 10-5 mm of mercury and the temperature raised to 1550°C within 2 min. The molten drops were photographed at appropriate time intervals. TWO min after melting the iron vapor pressure caused gas discharge, or corona, within the tube. The specimens were then slowly cooled to room temperature, sectioned and examined metallographi-cally. X-ray identification of interfacial reaction products was attempted by the powder diffraction technique. Alloying elements (Ti, V, Cr, Zr, Ta, Nb) were added to the iron in various concentrations up

Jan 1, 1963

Jan 1, 1963

By W. B. Dancy, A. Adams

Laboratory test work on heavy liquid separation of sylvite from halite is reported. Numerous tests were run on sylvite ore sized in the ranges of 4x20 mesh, 10x65 mesh, 8x100 mesh, -8 mesh and -10 mesh with heavy liquids in the range of 2.05 to 2.15 sp gr. From the test results, it was concluded that, with the type of ore under study and a size in the range of -8 mesh, a recovery as high as 90% could be achieved with a product grade of 70% KCl. However, a final product at an acceptable recovery cannot be made with one pass, and the float must either be further processed with heavy liquids or dried and sent to a conventional froth flotation circuit. Potash ores occurring in this country consist essentially of sylvite and halite plus minor amounts of magnesium sulfate salts and montmoril-lonite-type clays. Recovery of potash minerals from evaporite ores in the North American potash fields is accomplished almost exclusively by use of amine flotation. European practice involves froth flotation as well as solution-crystallization processes. Laboratory and pilot plant test work has been reported in Europe and the U. S. on the application of heavy media separation to potash ore beneficiation. Work was probably discontinued because of lack of ore with the required very coarse liberation characteristics (1/8 to 1/2 in. liberation size). Sylvite, with a gravity of 1.99, and halite, with a gravity of 2.17, appear to be ideal for separation by heavy liquids, which are now available in gravities from 1.59 to 2.95. This paper reviews preliminary results obtained from laboratory test work on heavy liquid separation of sylvite from halite. TEST WORK The heavy liquids used in the tests under discussion were chlorobromethane, with a specific gravity of 1.923, and dibromethane, with a gravity of 2.490. These liquids, completely miscible, were combined in the proportions needed to give a mixture having the desired specific gravity. Feed for the laboratory tests was mine-run ore screened to the desired mesh sizes. In conducting the tests, the sample was fed at a constant rate into a stream of heavy liquid and the mixture directed into a small separatory vessel. The float overflowed into a collecting pan while the sink collected in the bottom of the separatory vessel and was removed at the end of the test. Approximately 500 g of feed constituted a charge. Pulp density of the feed was kept low to prevent particle to particle interference in separation. With feed in the range of 8x100 mesh, a pulp density of under 10% solids by weight was found advisable. With coarser feed the pulp density could be carried as high as 15% solids. Time of separation was very rapid. In the case of 4x20-mesh material, separation was effected in 15 to 30 sec; with -10-mesh feed, separation required about 1 to 2 min. SPECIAL EQUIPMENT Since heavy liquids are toxic to varying degrees, all separatory work was carried out in a standard laboratory fume hood. It was noted that complete removal of fumes was not being effected; therefore the hood construction was modified, resulting in a completely satisfactory arrangement for heavy liquid test work. In the interest of safety, details of this fume hood are reported here. Unlike most fumes, heavy liquid fumes tend to settle and flow like water, rather than to rise like a gas. Working on this assumption, a standard water drain was installed in the hood. Across the front of the hood a 1-in. barrier was constructed. In the rear of the hood a false back was installed, with an adjustable sliding door on both the bottom and top of this panel. As shown in Fig. 1, the exhaust fan pulled a vacuum behind the barrier, sucking the heavy fumes from the bottom of the hood. Another addition was the drying box, shown to the right of the hood. This is simply a box covered on top with hardware cloth and connected by a 6-in. inlet to the hood. Sample trays made of fine mesh wire filter screens were found ideal for drying samples. With this arrangement, air flowed completely through the sample and all fumes were drawn into the hood. In use, it was found effective to cover with a

Jan 1, 1963

By M. L. Pearce

A comparison of the isotope-dilution, vacuum-fusion, and chemical methods of analysis for nitrogen in Si-Fe is made with particular emphasis on the effect of sample history. The superiority of the isotope-dilution method from the point of view of 1 HE analytical techniques used to determine nitrogen in Si-Fe have been subjected to close scrutiny in recent years primarily because of the marked influence of the element on the properties of the alloy. These investigations have led to a diversity of opin- both precision and accuracy is demonstrated. The solubility of nitrogen in 3.06 pct Si-Fe is investigated and the effect of silicon content on the activity coefficient of nitrogen is derived. ion regarding the reliability of the vacuum-fusion and chemical methods of nitrogen analysis when applied to si- Fe.&apos;-&apos; A majority of workers appear to favor the vacuum-fusion method over chemical methods particularly in those cases where part of the nitrogen may exist as silicon nitride or the total nitrogen content is very low. Contrary views have been expressed, however,&apos; and it has been demonstrated that for some Si-Fe alloys both methods yield results which are significantly lower than those

Jan 1, 1963

By F. W. Bowdish

Analysis of data on the equilibrium exchange of sodium ions from salt solutions for calcium ions, from various fractions of an oxidized calcareous iron ore from Lorraine, France, strongly suggests that the calcium may be attached to the solid by only one of its bonds. Nearly equal values were found for the equilibrium expression from data covering concentration ranges of 1000 fold for the salt and 235 fold for the ion-exchangeable calcium. Differences indicated between the exchangeable calcium contents of the slime and the sandy portions of the ore, as well as the equilibrium relationship itself, are of importance in the flotation of the ore. During an experimental program on the flotation of oxidized calcareous iron ores from Lorraine, France, ion-exchangeable calcium was found in the ore. Because this source of calcium ions, if not controlled, could thwart all efforts at flotation, an extensive study was made of the phenomenon. The part of that study reported here was to obtain data on the equilibrium established between ore solids and solutions of sodium chloride, and to analyze the data to try to understand better the physical chemistry of the exchange. The ore contains oolites of goethite and quartz grains embedded in a matrix consisting of calcite and a brown cement believed to be the residue from oxidation of the silicate minerals found in fresh unoxidized ore. When ground, a substantial fraction of the ore becomes a fine slime in which is concentrated more than half of the alumina content of the ore. It is believed that the alumina occurs as unidentified clay minerals with which most of the ion-exchange capacity of the ore is associated. A preliminary experiment on the exchange of ions from the ore for sodium ions from solutions of NaCl showed that calcium was about ten times as abundant as magnesium in the exchange solutions. Thus calcium was the predominant ion in causing difficulties with flotation, and it was the only one for which data was obtained in this study. It is believed that the omission of magnesium ion exchange from consideration does not invalidate the results. It is possible, however, that inclusion of magnesium in the analyses and calculations or its prior elimination from the samples would have improved the consistency of the results. EXPERIMENTAL Data about the equilibrium exchange of sodium from solutions for calcium from the solids were obtained using two different samples of material. The solids

Jan 1, 1963

By Hermann Schmalzried, Carl Wagner

UPON heating a metal oxide or sulfide in H2, first only oxygen or sulfur is removed from the surface. Thus the metal/nonmetal ratio in the oxide or sulfide increases and the thermodynamic activity of the metal increases accordingly. For the formation of metallic nuclei, a certain super saturation is necessary, i.e., the activity of the metal must become greater than unity. Once nuclei of the metal have been formed, the supersaturation is supposed to decrease. Even under steady-state conditions of a reduction process, however, the activity of the metal inside an oxide or sulfide phase must be greater than unity in order to have a driving force for the individual steps of the reduction process. As an example, consider the reduction of Ag2S with a high mobility of cations and electrons. As shown schematically in Fig. 1, the reduction process involves the following steps:&apos; 1) sulfur removal along the entire Ag2S surface in form of H2S, 2) migration of Ag&apos; ions and electrons from the Ag2S surface to nuclei of metallic silver, 3) transfer of Ag+ ions and electrons from the Ag2S phase to the metal. For a finite rate of step 3, the activity of silver in Ag2S next to the Ag2S-Ag interface must be greater than unity. Moreover, for a finite rate of step 2, the activity of silver at the gas-Ag2S interface must be still somewhat greater. Theoretical considerations lead to the tentative conclusion that at least under steady-state conditions the supersaturation will be rather low.&apos; To test this conclusion, the average activity aAg of silver in a Ag2S tablet about 2 mm thick with a diameter of 5 mm was followed as a function of time by measuring the electromotive force E of the cell Pt I Ag | Agl I Ag2S I Pt where AgI is used as a solid electrolyte in which only Ag+ ions are mobile. The activity aAg is calculated as aAg=exp(-EF/RT) Since the diffusion coefficient for transport of silver in Ag2S is very high (- 3 . l0-2 sq cm per sec),3 the average activity aAg is representative for both the bulk and the surface of the Ag2S tablet. Experiments were conducted at about 400°C. The cell was surrounded by an aluminum block in order to secure a uniform temperature and to eliminate thermoelectric effects. With the help of a potentiometer, first a potential of 0.16 v was applied to the above cell in argon in order to obtain a well defined initial state with a Ag/S ratio close to 2.000.~ Then the cell was disconnected from the potentiometer and a gentle stream of H2 was passed along the Ag2S surface. In view of the removal of sulfur in form of H2S, the electromotive force E decreased within 20 to 30 min to zero corresponding to a Ag/S ratio of 2.003 and became negative, indicating a value of aAg> 1. A representative plot electromotive force E vs time is shown in Fig. 2. The minimum of the electromotive force characteristic of the onset of

Jan 1, 1963

By J. Rourke, F. S. Minshall, E. G. Zukas, C. M. Fowler, O&apos

The Hugoniot curves were determined for Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si. The pressure of the transition increased as the silicon content of the alloy increased. Single crystals of 2.9 wt pct Si-Fe were also studied. The pressure of the transition was not dependent on crystallo-graphic orientation. All of the Neumann bands (mechanical twins) were attributable to (112) planes but not all of the {112} planes showed twin markings. A thorough study of the iron Hugoniot (the relationship between specific volume and pressure) under plane wave shock loading revealed a pressure transition at about 130 kbar shock pressure. The results of this investigation were reported by Bancroft, Peterson, and inshall1 in 1956. At the time of this discovery, it was felt that this was probably the a, to y transition normally found in iron and many of its alloys. Subsequently a number of iron alloy systems were surveyed in which the alloying element has a considerable effect on the normal a, to y transformation. The influence of carbon and nickel and/or chromium have already been reported.2,3 At the present time, there appears to be some doubt that this pressure transition is the usual a, to y transition In this study, Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si were chosen for several reasons. To the present, the transition has been found only in iron-base alloys which were originally in the a, phase (bcc). Secondly, the y loop at atmospheric pressure extends to only about 2.5 wt pct Si. If the transition were a, to y, then one might expect a rather drastic pressure effect for alloys containing more than 2.5 wt pct Si. Finally, single crystals of Fe-Si alloys large enough for shock loading studies are readily available thereby making it quite easy to determine the effect of crystal orientation on the transition pressure and on the twinning behavior of the alloy. EXPERIMENTAL PROCEDURE Fe-Si alloys containing up to 7 wt pct Si were produced by normal vacuum casting procedures. Single crystals of Fe-2.9 wt pct Si were purchased from Monocrystals Co., Cleveland, Ohio. The orientations of these crystals were determined and samples cut so that the shock wave would be parallel (to within 1.5 deg) to either the (loo), (Ill), or (112) principal orientations. Three distinct experimental testing techniques were used. First, the pin technique, described elsewhere,4 was used to determine the transition pressure for the polycrystalline alloys as well as for the (111) and (112) orientations of the 2.9 wt pct Si single crystals. Secondly, the recovery studies, described in detail in an earlier paper,2 were used for determining the effect of alloy composition and crystal orientation on the plastic II compression-plastic I rarefaction interaction zone for several specific shock pressures. Finally, measurements of pressures above the two-wave threshold were made on the polycrystalline alloys so that more complete Hugoniot curves could be constructed for this alloy system. The optical techniques described by Rice et al.5 were used to measure the shock and free surface velocities of the samples from which the Hugoniot data were obtained. This method is applicable only in the single wave region, since velocities are obtained from the measured total transit times of the disturbances through measured sample thicknesses.

Jan 1, 1963

By S. J. Matas, R. F. Hehemann, R. H. Goodenow

The hot-stage metallographic method has been employed to determine radial growth rates of upper and lower bainite. Lower bainite appears to grow as individual plates that increase in both length and thickness while upper bainite grows as sheaves of closely spaced plates or needles. A discontinuity in the temperature dependence of the growth rate appears to be associated with the transition from upper to lower bainite and stepped quenching experiments suggest that lower bainite will not continue to grow when the temperature is raised to the upper range. Thus, a single process does not appear to control the growth of both upper and lower bainite. A tentative model based on the forces acting on a dislocation interface is proposed to account for the slow growth of bainite. It has been recognized since the early studies of Davenport and Bain that a close relationship exists between the martensite and bainite transformations in steels. However, diffusion of carbon during the transformation has lead to considerable controversy concerning the reaction mechanism.1-7 Many studies4,5,7-9 have emphasized the structura and kinetic aspects of the bainite reaction and, in particular, the difference observed between the two forms of bainite—frequently termed upper and lower bainite. A kinetic difference between the two types of bainite has been revealed in the activation energy determined from the overall reaction;4,5 however, many difficulties arise in an interpretation of these activation energies since a number of temperature dependent factors contribute to the kinetics of the overall reaction. The displacive surface relief10 accompanying the bainite reaction permits a separation of the nuclea-tion and growth contributions to the reaction and allows the kinetics of the growth process to be examined. Several investigations of this type have been conducted; however, they have been restricted to the low temperature range.3&apos;6&apos;11 Here, bainite plates are observed to grow slowly in both length and width. The present investigation extends such studies to include the upper bainite range. MATERIALS AND PROCEDURE Materials. The composition of the steels studied in this investigation are presented in Table I. The range of composition permitted a study of the effect of carbon content on the growth rate of upper bainite in the 9 pct Ni steels and consideration of both upper and lower bainite in the higher carbon steels. These steels were received as hot-rolled rounds and were forged to approximately 1/2 in. thick plates for preparation of metallographic specimens. In order to produce an essentially zero carbon steel, Steel A was decarburized in wet hydrogen at 1550°F for 15 days with the result tabulated as Steel AD. Experimental Procedure. In order to study the slow growth of the displacive transformation product, a commercially available Leitz hot stage was modified to permit heating of the specimen by its own resistance in a manner similar to that employed by other investigators.6 The furnace chamber was maintained at a pressure of 2 to 3 X 10-5 mm Hg prior to austenitizing at 2000° ± 12° F for 5 min. Samples could be cooled from the austenitizing to the transformation temperature in approximately 15 sec and the progress of transformation was recorded with a 9 cm by 12 cm single frame camera or a 16 mm movie camera. RESULTS AND DISCUSSION Growth Characteristics. The general growth characteristics observed in this investigation were analogous to those reported previously.3,6,11 Typical growth sequences for the high temperature and low temperature forms are illustrated in Figs. 1 to 5. In both temperature ranges, bainite plates increase in length at slow, temperature dependent rates until interrupted by a grain boundary, another plate, or

Jan 1, 1963

By F. W. Schaller

TETRAGONALITY is an important aspect of the models of transformation, strengthening, and tempering of ferrous martensite. When the c/a

Jan 1, 1963

By V. N. Cox, C. H. Grant

Both the underwater method and the rock cratering method contribute useful information in evaluating and comparing new explosive compositions. Results indicate that metallized explosive systems which contain no high explosives can be formulated to offer more energy and to do potentially more work than other slurry explosive systems. Commercial field trials are presently being conducted with a metallized explosive that does not contain any high explosive. Although there have been only a few commercial blasts to date, the results are encouraging. The Dow Chemical Co. has been engaged in explosives research since 1953. The incentive for this research was based on the desire to find additional markets and uses for magnesium metal of which DOW is a heavy producer. The thermodynamic calculations for explosives incorporating light metals indicate energies approximately twice that of nonmetallized explosives currently being used. Early in 1960, additional patent rights were acquired from independent inventors and a development station at Virginia, Minn., was set up to conduct a commercial testing and market evaluation program with this new product. The actual manufacturing of the explosive was to take place in the boreholes. Due to the complexities involved in controlling the manufacture of the explosive in the borehole, performance was sometimes in doubt. Furthermore, experience indicated that the metallized explosive systems could not be evaluated by the standard laboratory methods then being used, and it was necessary for us to look for more suitable research methods. Tests were conducted on several known methods for explosive evaluation. The most promising were the Navy underwater method for energy evaluation and a modified Livingston crater method intended to compare explosive performance in rock. After shooting over 2000 charges of 8 to 60 lb under water and in taconites and granites with many types of explosives, a metallized explosive was developed which is now being manufactured at a pilot plant in Virginia, Minn. and is being evaluated commercially. UNDERWATER METHOD An underwater method of evaluating explosives has a number of advantages. A permanent site can be established and operated indefinitely. A large number of charges may be fired in a short length of time. The medium in which the explosive is shot is exactly the same for successive shots. Data are recorded electronically minimizing human judgment. A disadvantage of the underwater method is the lack of confinement provided by the water medium. Many explosive compositions require a greater degree of confinement to develop good energy release. Although the relative significance of the two components of energy release that are usually measured, the shock energy and the bubble energy, and their relationship to breaking rock are not clearly understood, the underwater method is a valuable research tool for screening explosive compositions and gaining an insight into the manner in which explosives release their energy. Fig. 1 shows schematically the underwater apparatus. The piezoelectric gages are calibrated tourmaline crystals which convert the shock wave to an electrical impulse which is transmitted to an oscilloscope and recorded on Polaroid film. The shock traces are picked up by scopes 1 and 2. Scope 1 is timed to pick up the full trace whereas scope 2 is timed to cover the first increment of the shock trace expanded, and therefore allows full inspection of the propagation and peak pressures. Scope 3 records the bubble trace. When the explosion occurs, a bubble of gaseous detonation products is formed. The outward momentum of the water keeps expanding the bubble even after

Jan 1, 1963

By S. K. Tarby, W. O. Philbrook

Limited experimental data and a critical review of the literature are given to indicate that the true equilibrium distribution of manganese between carbon-saturated iron and blast-furnace type slags has not yet been satisfactorily established as a function of the composition, temperature, and pressure of the system. THE distribution of manganese between carbon-saturated iron and blast-furnace type slags has been studied by a number of investigators.1-7 Generalization of the results of these works indicates that the weight percent distribution ratio, (%Mno)/[%Mn], decreases with increasing temperature and slag basicity, in accord with thermodynamic data and practical observation. However, where comparisons among these studies can be made for similar slag compositions and temperatures, the reported values of the manganese distribution ratio are discordant. The variations are attributed to failure of the experimenters to bring their systems completely to equilibrium with graphite and CO at 1 atm, as judged by departures from silicon equilibrium. Even in the most recent work,5-7 this problem was recognized but the authors made the questionable assumption that equilibrium could prevail for manganese distribution even though other reactions were still in progress. Manganese equilibrium values for three particular slag compositions were required incidental to a kinetic study8 and were determined experimentally. Special pains were taken to approach concurrent equilibrium with respect to silicon. Although the results were not completely definitive, they indicate that the true manganese equilibrium distribution ratios are lower than have heretofore been reported. The data are presented together with a brief commentary on the literature to suggest the need for further work in this area. EXPERIMENTAL METHOD Equilibrium runs were carried out in a stationary, induction-heated graphite crucible closed by a graphite lid and flushed continuously by a slow flow of carbon monoxide at 1 atm pressure. Temperature was controlled manually within ±3 deg C with the aid of immersed thermocouples in mullite tubes protected against slag attack by graphite sleeves. The desired temperature was established by a calibrated Pt vs Pt-10 pct Rh thermocouple and control was then maintained using a more stable W-Mo couple. Runs were made at 1500º and 1575ºC for durations of 7.5 to 10.5 hr. The charges were calculated to yield 400 g of metal and 100 g of slag. The primary slag compositions and designation numbers were as follows:

Jan 1, 1963

By Donald Ofte, L. J. Wittenberg

The absolute viscosity coefficients and activation energies for viscous flow of bismuth, lead, and zinc are reported. The viscosities were measured in an oscillating cup viscosimeter from nearly 1000°C to within 1 deg of the melting point of zinc; 2 deg of the melting point of lead; and in the supercooled condition of bismuth, 9 deg below the melting point. Two methods of relating the change in the viscosity coeflicient with temperature were compared. From the plot of the logarithm of viscosity (77) as a function of reciprocal absolute temperature (1/T), the equations of the lines which fit the data are: AS a part of the Reactor Fuels and Materials Research program at Mound Laboratory, precise measurements of the physical properties of liquid metals are of interest because the desirability for a low vapor pressure liquid coolant in high-temperature nuclear power plants has focused attention on the properties of the liquid metals.&apos; Also, a clearer understanding of the liquid metal state can be achieved when better measurements are available. For these reasons, the viscosity values of certain liquid metals have been determined. The viscosities of the liquid metals, bismuth, lead, and zinc are measured in an oscillating cup viscosi-meter. In this apparatus the liquid is sealed in a right-circular cylindrical cup which is attached to a torsion fiber so that the system forms a torsion pendulum. The damping effect of the molten metal upon the normal oscillations of the torsion pendulum is a function of the viscosity of the liquid. This method is advantageous because of the small amount of sample required (8 to 10 cc), the ease of remote operation of the apparatus in a vacuum system, and the containment of the liquid metal in a hermetically sealed, nonreactive, tantalum crucible. With the liquid metal sealed in the crucible, loss of liquid by vaporization and chemical reactions with atmospheric gases are prevented. Additionally, an absolute viscosity determination is obtained which avoids the sources of possible error in a relative measurement. The difficulties in a relative method include the repetitious cup calibrations, and the uncertainty inherent in the practice of calibration of the apparatus at room temperature and extrapolation to the high temperatures necessary for the investigation of most liquid metals. The oscillating cup viscosimeter was first described by Meyer in 1891.2 The first complete mathematical treatment offering an absolute measurement of viscosity with this type of apparatus was proposed by Andrade and chiong3 in 1936 for an oscillating sphere filled with a liquid. This solution was modified to include a right circular cylinder by Hopkins and Toye4 in 1950, and R. Roscoe5 in 1958. Roscoe&apos;s treatment for the calculation of the viscosity of a liquid at a particular temperature from the logarithmic decrement and period of oscillation of the torsion pendulum was used in this investigation. A detailed description of the method of calculating the viscosity from these measurements has been reported earlier.&apos; This calculation has been programmed for the IBM 704 and IBM 1620 computers for expedition of the otherwise laborious calculations. APPARATUS The cutaway view of the apparatus in Fig. 1 shows the suspension system within the high vacuum enclosure. The low residual gas pressure. maintained between 1 x 10-4 and 5 X 10-6 mm Hg during a determination, avoided both air drag on the pendulum and

Jan 1, 1963