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By S. P. Chong, N. C. Shih, G. A. Turner

Fine powders, with the bulk of the particle diameters Jess than 10 microns, were aerated so that each particle was, on the average, separated from its neighbours by 1.3 to 2 mean diameters. In this state, measurements were made of the viscosity and settling rate of the powder, and the interfacial tension between it and a moist pellet. From the viscosity measurements, qualitative analogies are drawn between the behaviour of the aerated powder and that of a dense gas near its critical point.

Jan 1, 1970

By Keros Cartwright

Sanitary landfilling has become one of the most widely used methods of disposing of solid refuse. A principal concern of regulatory agencies and the public itself is that landfill operations do not degrade the physical environment, including water resources, and the ground-water reservoir in particular. Ground-water and engineering geology can guide landfill operations into suitable terranes or develop measures to compensate for any natural limitations at a particular site Experience and research in Illinois suggest four activities relating to landfill disposal that warrant attention by geologists and engineers: (1) Regional delineation of favorable and unfavorable hydrogeologic conditions to facilitate planning and preliminary screening of potential landfill sites. (2) Site evaluations, with considerations of geologic materials, topography, water levels, flow systems, and local occurrence and use of water resources. (3) Re- search on aspects of the hydrogeologic environment that control effects of, or are modified by, landfills. (4) Formulation of practices in the siting, construction, and operation of landfills that prevent, mitigate, or isolate deleterious effects. The first two activities are basically in the domain of earth science, requiring the application of fundamental concepts of geology and hydrology and conventional site-exploration methods. The third activity, research, requires contributions from geology as well as other disciplines, including soil physics, sanitary engineering, and chemistry. The fourth calls for policy decisions by regulatory agencies and elected officials, using the contributions of scientists and engineers.

Jan 1, 1970

By H. P. Dibbs

An account is given of the application of neutron activation analysis to the rapid, non-destructive determination of copper in minerals, using a 14-MeV neutron source. Elements that interfere in the determination of copper by this method are given, together with the errors in the estimation of copper that result from the presence of varying amounts of these elements. The possible use of a compact "sealed-tube" 14-MeV neutron generator for the field assay of copper in minerals is discussed.

Jan 1, 1970

By C. W. Kovach, A. Moskowitz

Studies were undertaken to investigate the effects of manganese content on the machinability and other Properties of a free machining martensitic stainless steel (AISI Type 416). Machinability was found to be significantly improved in steels of high manganese content, and a direct relationship was obtained between machinability and steel Mn:S ratio. As the manganese content of the steel increases, the sulfide Phase present changes from CrS to (FeMn)Cr2S4 to (MnFeCr)S, and finally to MnS. The average sulfide inclusion hardness decreases through the same range of increasing manganese content. The mechanism for machinability improvement is discussed in terms of a soft ductile sulfide affecting deformation in the secondary shear zone. Type 416 containing relatively high manganese for improved machinability shows good general properties. The effects of increasing manganese content on mechanical properties, cold formability, and corrosion resistance are described. THE addition of sulfur is commonly used to improve the machinability of stainless steels. However, little attention has been paid in the past to the composition and characteristics of the sulfur-containing phase or phases present in these resulfurized steels. Recent information on the properties of sulfide phases, and their role in metal cutting, suggests that variations in these phases could have critical effects on machin-ability, as well as important effects on formability and other properties such as corrosion resistance. Manganese, chromium, and iron are strong sulfide forming elements present in stainless steels! of these, manganese has the greatest sulfide forming tendency and iron the least.1"1 The manganese content of resul-furized 13 pct Cr steels, often about 0.5 pct, can be insufficient or only barely sufficient to combine with the sulfur that is present; thus, the precise level of manganese can strongly influence the nature of the sulfide phase. Sulfide phases which may be present in stainless steels have been reported to include CrS, a spinel-type sulfide, chromium-rich manganese sul-fide, and manganese Sulfide.5,6 Detailed phase relationships for the Fel3Cr-Mn-S system have been reported by the present investigators,7 and a portion of this work will be referred to subsequently in this paper. Recent work by Kiessling6 and Chao et a1.8 has shown that sulfide phases can display wide variations in hardness, and may undergo considerable plastic deformation under isostatic loading.9-12 Early theories of metal cutting attributed the influence of sulfur to a lubricating effect. It is now apparent that the influence of the nonmetallic inclusions and their properties on crack initiation, deformation in the shear zones, and boundary films must also be considered in relation to the machining process. This paper presents the results of studies conducted to relate machinability to the various sulfide phases which occur in stainless steels. This work has led to the development of alloys with improved machinability, and has generated information on the effects of inclusions on metal cutting processes. Effects of sulfide inclusions and steel composition on other important metallurgical properties are also discussed. MATERIALS For drill machinability and inclusion studies, 10 lb laboratory heats were melted in an air induction furnace. These heats were made with sulfur contents be tween 0.10 and 0.50 pct and manganese contents be tween 0.05 and 3.0 pct. Residual elements were added to the heats in amounts typical for commercial steels. The typical compositional range covered by the heats is shown below: C Mn P S Si Ni Cr Mo Cu N 0.10 0.05 0.007 (M0 0.40 0.40 13.0 0.20 0.10 0.03 3.0 0750 The laboratory ingots were forged in the temperature range of 1800" to 2100°F to 3/4-in. sq bars, and all bars tempered to a hardness aim of 200 Bhn prior to testing. Because of differences in composition and tempering response, the tempered bars showed some variation in hardness (175 to 275 Bhn) as well as variations in delta ferrite content (0 to 50 pct). Composition, hardness, and delta ferrite content were considered in the analysis of the machinability data. Additional tests involving tool-life evaluation and determination of other properties were conducted on materials from commercially melted and processed 15-ton electric furnace heats. TESTS AND PROCEDURES Machinability of the laboratory heats was evaluated in a drill test. In this test, 1/4-in. diam holes, 0.4 in. deep, were drilled alternately in a test bar and in a standard bar for a total of four holes in each. This sequence was repeated three times using a freshly sharpened drill each time. The average time required to drill a hole in the test bar was compared to that for the standard bar. A drill machinability rating was assigned to the test bar relative to a rating of 100

Jan 1, 1970

By T. H. Patching

This paper provides a review of the available information on the origin and mechanisms of the release of gas from coal seams. With the opening up of new mines in Western Canada and the increased mechanization of underground coal mines, the study of gas emissions is of increasing importance in providing safe working places underground.

Jan 1, 1970

By C. H. P. Lupis, Henri Gaye

There are m -I conditions for the stability of a solution of m components with respect to infinitesinzal flucturations. However, in most cases, only one of these conditions has to be considered to determine the domain of instability and the existence of this more restrictive condition greatly simplifies the calculations. It may be used advantageously for the prediction of miscibility gaps and the method is illustrated in details for the case of the Ag-Pb-Zn system. THE thermodynamic conditions for the formation of a miscibility gap may be viewed as a necessary consequence of the conditions for spinodal decomposition. A previous article1 has examined in detail the form of these conditions for multicomponent systems. There is only one condition for the stability of a binary system (with respect to infinitesimal fluctuations), but there are two conditions for a ternary system, and m — 1 conditions for an m-component system. The probability of violating a stability condition, and thus forming a miscibility gap, obviously increases with the number of components, a result which is rather intuitive since the atoms of the solution have now many more ways of redistributing themselves and introducing complexities in the form of the free energy hy-persurface. It is of interest to take advantage of this possibility of precipitating new phases and to examine which stability condition is the likeliest to be violated, that is, which stability condition is thermodynamically the most restrictive. The finding of such a condition would greatly simplify the application of the stability criteria since only one condition could then be considered, instead of m - 1. In Ref. 1, coherency strain energy terms were neglected, thus restricting the applications of the treatment to solutions where they are negligible, such as liquid alloys. In the following study the same assumption will be made. To generalize the treatment to systems where the strain energy terms are sizable, the reader is referred to Cahn's classical article on spinodal decomposition.2 Let us designate by Gij the second derivative of the Gibbs free energy with respect to the number of moles ni and n j. There are several equivalent sets of m — 1 stability conditions.' The one considered here expresses that the successive diagonal determinants of order 1, 2, ... m — 1, associated with the symmetric Gij matrix (for 2 5 i, j 5 m) are positive.' For a binary solution 1-2, the condition for stability is: O(u=G22^0 [1] For a ternary system 1-2-3, the condition [I.] is re- tained (the value of G22 will differ, of course, according to the concentration of 3) and another condition is introduced: £>(21 = G22G33 - Gl3 ^ 0 [2] In a composition diagram, these two conditions define two domains of instability. Starting at a point where the solution is stable (for instance at a point where the solution is very dilute) we gradually change the composition until the condition [I] or [2] is violated. As already noted in the literature, e.g., in the work of Prigogine and Defay,3 it is the boundary of the domain (2) which is first crossed. For if we assume that the boundary of the domain (1) is reached first, at this point G22 = 0 and the second condition is necessarily violated (D(2) = -& 5 0), in contradiction with our original assumption. An exhaustive study of the ternary regular solution case may be found in the work of Meijering.4 Moreover if the boundaries of the two domains have a common point, they also have a common tangent. For if the two lines were to cross each other as is illustrated in Fig. 1(a) any point M in the line QP would be such that £> = 0 and 0"' > 0 which, as shown above, are incompatible results. Thus, the two lines must be tangent at their common point Q as illustrated in the example of Fig. l(b). The reasoning of Fig. l(a) implies that the point Q is not a "singular" point for either boundary line. This singularity may be of two types. First, the lines meet without crossing each other and without being tangent. Second, the tangent at Q for D"' or 0"' is not single-valued. Other types of singularity are unlikely because of the usual analytical forms of D"' and 0"'. The exception to the common tangent requirement due to the first type of singularity was pointed out by John Morral;5 it occurs when the common point, Q' or (3" in Fig. l(b), is located at a boundary of the composition diagram, e.g., at the line X3 = 0. It may also be noted that at the common nonsingular point Q of D(1) and D(2), Fig. 1(b), G23 is necessarily equal to zero, whereas at a point such as Q' or Q", this conclusion is no longer valid because the product G22G33 is now indefinite (of the form 0. a). The exception to the common tangent requirement due to the second type of singularity occurs when two branches of the same boundary line intersect, for example when D(1)or D(2) decomposes into a product of functions, at a point which belongs to the boundary of the other condition. It is possible to show by a simple analytical calculation that, in this case, if Q is a singular point of D(1), then it is necessarily a singular point of D(2), and that the reciprocal is true except if G33 = 0 at Q. For the present article, however, more elaboration on these singularities appears to be unwarranted. To generalize the previous results to an m -component system, we use the mathematical theorem stating that if the diagonal determinant D(r) = 0, then

Jan 1, 1970

By R. N. Lambert

This chapter discusses the evolution of high-speed shaft sinking in the South African goldfields. Whether we are talking of an additional shaft at an existing mine or the opening of a new mine, the increasing depth of the ore-bearing reef and the unremitting inflation of costs have provided the compelling incentive to shorten the time taken to sink a shaft and start earning revenue. The high costs of sinking a modern shaft system in South Africa are indicated by the recent example of a deep-level mine in the Orange Free State where the cost was nearly $22!42 million. This was for a single large shaft of 33 ft 6 in. diam (in all cases, shaft diameters refer to the finished diameter of the shaft, e.g., inside the concrete) and 7600 ft deep with a prestressed concrete brattice wall dividing the shaft into upcast and downcast compartments. Higher costs and the consequent demand for increased tonnages, deeper shafts with higher rock temperatures, which necessitate highly sophisticaled ventilation and refrigeration requirements, have all accentuated the importance of time in a shaft-sinking operation. Rectangular shafts with their simple design and comparatively reasonable sinking speeds remained popular for many years until greater mining depths combined with a host of the other allied problems inevitably led to changes in shaft design. Circular shafts appeared to offer many advantages, particularly when considering ventilation, strength, mechanization, and sinking through bad ground and heavily watered zones. However, these advantages were largely offset by the slow rate of advance necessitated by the need to stop sinking in order to line the shaft. The development of the curb ring which enabled lining to take place above the bottom of the shaft and the use of multideck stages allowing sinking and lining to be carried out concurrently resulted in a major break- through. Rectangular shafts, which are still popular elsewhere, have been superseded in South Africa by circular shafts which are almost without exception the only shafts sunk in our goldfields today.

Jan 1, 1970

By David R. Maneval

In 1956 the Legislature of the Commonwealth of Pennsylvania created a "Coal Research Board" in the Department of Mines and Mineral Industries. Over the years through amendments to the original legislation, the scope of authority for research has been expanded from the narrow area of improving and increasing the utilization of coal to covering all aspects of coal technology and any other area of interest which would be of value to the coal industry. In January of 1964, the Board commenced a vigorous program using appropriated funds and funds donated by the coal industry to finance a research program devoted to seeking solutions to the mine drainage problem. A review of published literature on the treatment of mine drainage indicated that much work done up to that point in time concerned only the mechanism of mine drainage formation and theoretical chemistry. Very few applied, developmental, or engineering studies had been devoted to finding practical solutions to the problem of polluted waters being discharged from active or abandoned mines. Projects were therefore undertaken on a wide variety of more utilitarian approaches. This paper will discuss briefly some of the pollution abatement approaches which have been funded by the Coal Research Board of this State, and will describe in some detail a multistage flash evaporator treatment plant now under construction.

Jan 1, 1970

By Robert M. Dreyer

Although lateritic deposits have long been a principal source of bauxite and are becoming an increasingly important source of nickel, the problems in the evaluation of such deposits are not generally understood. In the evaluation of lateritic bauxite and nickel deposits, there are many similarities, but there also. are significant differences. It has long been recognized that laterites with commercial concentrations of trivalent metals represent the ultimate in the intense leaching of tropical soils. Any factors which effect-the rate of soil leaching will effect the form of local lateritic concentrations. Although the most intense leaching generally occurs on somewhat elevated areas of gentle relief where there is a free downward flow of rain water, the- effect of local rock structures in effecting varia¬tions in soil metal concentrations has-not been well understood - primarily because the laterite forms a masking blanket over the rocks from which the laterites were derived. All of the-factors which facilitate downward movement of water may effect greater surficial concentrations of trivalent metals. Such features as zones of fracturing, zones of greater rock permeability, and areas of karst topography may, therefore, be responsible for greater leaching. The variations in rock structures and the vagaries of ground water flow pat¬terns impart, to the laterites, rapid lateral and vertical variations in thickness and metal concentrations. Because of such rapid

Jan 1, 1970

By John V. Beall

The "free form life," The Wall Street Jourlzal called it. That is what the young people are practicing who have dropped out after successfully completing a college education. The ones described were first-rate students who did not embark on careers but instead selected such nonintellectual jobs as delivering mail, short- order cooking and the like. We couldn't help thinking that it wasn't so long ago, that we had the ideal setup in mining for folks of this persuasion when most college grads were started out as muckers. Actually there isn't much new in this business of doing your own thing. Being a type that takes westerns seriously, we jumped at the chance to catch the rerun of the wide-screen flick "How the West Was Won." There was Jimmie Stewart playing the part of the mountain man, with a canoe full of furs going east down river. Coming west up river, is a settler with his daughters. This mountain man had on his fringed buckskins, his two-year growth of long hair and a tremendous thirst. He had been doing his thing and planned to keep right on doing it. However, one of the pretty settler girls had other ideas. The same fate probably awaits today's individualistic youths.

Jan 1, 1970

By J. Szekely, G. P. Martins

A formulation is given for describing the rate of expansion of spherical bubbles rising in liquids the freeboard of which is evacuated. The computer solution of the resultant differential equations has shown that, for low freeboard pressures (less than about 5 mm Hg), on approaching the free surface the bubbles expand much less rapidly than predictable from equilibrium considerations. In other words, in this region the pressure inside the bubbles will be significantly larger than the static pressure in the liquid corresponding to the position of the bubble. These theoretical predictions were confirmed by experimental work, using two-dimensional air bubbles rising in mercury. The important consequence of these findings is that the expansion of gas bubbles in vacuum degassing operations will be a great deal less than expected from hydrostatic considerations. This would lead to a significant reduction in the available interfacial area and may explain the apparent poor efficiency of many vacuum degassing units. VACUUM degassing as a treatment for liquid steel has gained widespread popularity in recent years; the number of known installations exceeds several hundred at the present time.' Although much information is available on both the thermodynamics of the system and the overall performance of various industrial units, much less is known about the fundamental aspects of the process kinetics.2-4 The basic physical situation common to virtually all vacuum degassing operations is the interaction between gas bubbles (swarms of bubbles) and the surrounding molten metal, held in a container, the freeborad of which is at a low absolute pressure. Once formed (or introduced from an external source) the bubbles will ascend, due to the buoyancy forces, and, during this ascent, a significant increase in their volume will occur. This progressive increase in the bubble volume is due to two factors: a) the continuous reduction in the static pressure acting on the bubble during its rise; and b) mass transfer into the bubble from the surrounding molten steel. In a recent paper Richardson and Bradshaw developed equations5 for describing mass transfer into gas bubbles from molten metals at reduced pressures. However, in deriving these expressions it was assumed that the pressure inside the bubble was identical to the static pressure in the adjacent liquid. In other words, the volume of the bubble was considered to be in equilibrium with the pressure of the fluid adjacent to it. This assumption, thus their analysis presented, was thought to be reasonably accurate for most of the bubble's ascent; however, it was unlikely to be valid in the immediate vicinity of the free surface, held at a low pressure. It was pointed out in the discussion6 that the region close to the surface may be of considerable importance as both the driving force and the interfacial area available for mass transfer are at their highest value here. The ' 'anomalous" behavior of gas bubbles when approaching a free surface at low pressures was recently confirmed in a preliminary investigation by Szekely and Martins. ?1 Here high-speed motion photography was used to study air bubbles rising in a column of n-tetradecane with a freeboard pressure of 0.1 mm Hg. It was found that significant distortion of the bubbles occurred on approaching the free surface; furthermore, the expansion observed was much less than what one could expect from hydrostatic considerations, i.e., factor a previously discussed. It follows from the foregoing that a detailed study of these phenomena would be justified both from fundamental considerations and because of their potential relevance to technology. The purpose of the paper is to present a more realistic formulation for the expansion of a gas bubble approaching a low-pressure region, together with a comparison of the theoretical prediction with experimental measurement. An inert bubble will be considered in the first instance; it is thought that the understanding of the fluid mechanics is an essential first step toward the realistic formulation of the mass transfer process. This latter problem will be the subject of a subsequent publication. FORMULATION The Physical Model. Consider a spherical bubble, of initial radius Ro, rising in a fluid, having a density pL. Initially let the bubble be at a distance H from the free surface, and at a pressure Pgo, as illustrated in Fig. 1. Pgo, the initial pressure in the bubble, is given by the following equation: pgo = Po = Ptp +pLgH [ la] where Po is the pressure in the liquid corresponding to the initial position of the bubble and Ptp is the pressure at the free surface. The fluid pressure at

Jan 1, 1970

The Bureau of Mines performed cratering experiments in a homogeneous granite to test scaling laws for charge weights of 0.00476, 0.0220, 0.0900, 0.304, and 1.03 lb. Agreement among the data was best when empirical scaling exponents greater than one-third were assumed. Although the analysis showed that the best empirical scaling exponents were 0.37 for crater volume, 0.38 for crater radius, and 0.39 scaling for crater depth, all three crater dimensions could be scaled with a 0.38 scaling exponent.

Jan 1, 1970

By Karl C. Dean

The current emphasis on environmental problems has focused attention on the massive nationwide accumulations of mine, mill, and smelter wastes that represent potential air and water pollution hazards. The pollution hazards can be reduced or eliminated by utilization or stabilization of these wastes. The U.S. Bureau of Mines, since the inception of the Solid Waste Disposal Act of 1965, has been conducting research to determine the practicality of various utilization and stabilization procedures. Investigations include partial extractions of desirable waste components and full utilization of the wastes as simulated soils or in ceramic or other structural products. Chemical, vegetative, and combined chemical-vegetative methods of stabilization have been actively studied. This report updates information previously developed by the Salt Lake City Metallurgy Research Center and presents the current status of antipollution solid waste work 1/,2/.

Jan 1, 1970

By Donald E. Meyer

High current-low voltage EB-gun evaporation in an oil-free ultra-high vacuum system was found to be necessary, though not sufficient, for stability (300°C, 106 v per on) of aluminium gate MOSFET's and MOS capacitors not stabilized by a phosphorous glaze. five characteristics of the equipment used: 1) Vacuum purification of the aluminum charge, 2) Ionization of the evaporant by the electron beam, 3) X-ray formation, 4) Residual gases during evaporation, and 5) Metal film structure were studied as Possibly significant in MOS fabrication. EVAPORATION of contact metals common to the semiconductor industry historically has been accomplished with oil diffusion pump systems and various resistance heated evaporant sources as dictated by the type of metal evaporated. To meet a need for greater reliability of semiconductor devices, other metallization methods were developed. A good example would be application of the moly-gold contact system to integrated circuits with deposition by RF or triode sputtering.' More recently, fabrication of stable metal-oxide-silicon devices and circuits has put new demands on metallization. The purity of the thin metal films composing MOS structures is critical, particularly at the metal-oxide interface, and ultra-high vacuum metallization using sputter-ion pumping and electron beam gun (EB-gun) evaporation are well suited for the task. At this laboratory aluminum has been the most common contact-gate metal for both MOS capacitors and MOSFET's. In the earliest work with MOS capacitors, aluminum was evaporated from wetted tungsten filaments using both diffusion pump and ion pump vacuum systems. In spite of clean oxide techniques these capacitors were unstable under bias-tempera-ture stressing. Only after a switch to EB evaporation of aluminum were stable capacitors produced. Using the same techniques it was possible to make MOSFET's with equivalent stability. Stability data for a discrete MOSFET is shown in Fig. 1. This is a "clean" oxide gate (no phosphorus stabilization or no etch back of a thicker gate) having a thickness of lOOO? thermally grown on the (111) plane. Gate length after diffusion was 0.24 mils, and the devices were hermetically sealed. Stressing conditions were 300°C and 106 v per cm applied alternately as a positive and negative field for 10 min, 50 min, and 4 hr for a total stress time of 10 hr. An initial shift in turn-on voltage of 0.1 v was detected for 10 min of positive bias. All evidence at this laboratory indicated that while EB-gun evaporation of ultra-high purity aluminum was not sufficient for 300°C stability, it did seem to be necessary. There may well then be something inherent in the EB-gun deposition used which enhanced stability, and probably no single factor existed but rather a series of factors. It is the purpose of this paper to report on some of the investigations carried out to learn more about EB-gun evaporation in ultra-high vacuum systems. EXPERIMENTAL DESCRIPTION The EB-gun was self accelerated, had a maximum power rating of 10 kw, and used a water-cooled copper crucible able to hold a 20-g aluminum charge. The electron beam was bent 180 deg and focused by an electromagnet which also provided movement of the beam across the crucible. Normal power conditions in this work were 9 kv and 300 to 600 mamp. The gun can be described as high-cur rent/low-voltage and was quite different in its mechanism of operation from EB-guns with much higher acceleration potentials. An oil-free vacuum system capable of 5 x 10- l0torr, a quartz crystal rate and thickness monitor and a quadruple mass spectrometer completed the evaporation system, Fig. 2. A typical evaporation cycle consisted of a 3 to 4 hr pumpdown to the upper l0-9 range and evaporation at l0? per sec with the pressure in the bell jar not rising above 1 x 10"7 torr. Thickness control was 5 pct or less and could be automatically monitored and controlled. Five phenomena associated with the EB evaporation and considered as possible contributors to Ma performance included a purification effect, ionization of evaporating aluminum, X-rays, constitution of vacuum ambient during evaporation, and film structure dependence upon evaporation rate. These phenomena are now discussed. Vacuum Purification. The design of the EB-gun permitted purification of the aluminum charge by vacuum outgassing. Particular features included an efficiently water-cooled copper hearth with a capacity of over 20 g of aluminum and the capability for sweeping the beam across the charge. Such capacity meant that aluminum had to be added only after about every fifth evaporation. A new charge was not required each evaporation as is necessary with filament evaporation. An oxide "scum" which appeared on the charge could be completely cleared from the top hemisphere of the charge by sweeping with the beam prior to opening the shutter. An indication of the purifying effect was obtained by a series of analytical measurements on incoming aluminum, after melting but with little vacuum out-gassing, after 30 min outgassing, and the evaporated film itself. Either a solids (spark source) mass spectrometer or an emission spectrometer were used for analyzing the aluminum charge. Analysis of the evapo-

Jan 1, 1970

By Strathmore R. B. Cooke, Paul B. Queneau

The kinetics of the dissolution of scheelite in basic solutions of carbonate and fluoride were investigated. Work was also done with solutions of alkali metal chloride, hydroxide, phosphate, and mixtures of phosphate and fluoride. The study was conducted at 90 psig and at temperatures ranging from 100" to 155"C, and both natural and synthetic scheelite single crystals were used. The interaction of scheelite with carbonate solutions generally followed a parabolic rate law, and resulted in the formation of calcite crystals on the attached surface. The transport of the CO3 through the calcite to the scheelite surface was probably rate -controlling between 115" and 135°C. Positive deviations from Parabolic behavior were observed at 100" and 155?C, presumably due to the calcite grain growth, and to the formation of a noncoherent calcite layer, respectively. The leaching of scheelite with alkaline fluoride solution produced a calcium fluoride reaction-product which covered the surface as a sheet-like layer. Below 110°C the dissolution rate was parabolic; at 115" and 135°C it was linear. In the linear region, the periphery of the calcium fluoride layer lifted from the sample. Only the lower layers, braced by the scheelite substratum, remained unbroken. This bound layer, approximately constant in thickness, limited the rate at which the fluoride could attack the scheelite. The phosphate and phosphate-fluoride leaches dissolved scheelite at a linear rate; solid reaction products were respectively hydroxyapatite and fluorapatite. Sodium hydroxide and chloride were not effective leachants, and did not produce observable solid reaction products. THE feasibility of pressure leaching of scheelite pulps with basic solutions containing either carbonate or fluoride ions, as indicated by the following equations, has been established by previous investigators:1-3 200°C CaWO4s + CO37q - CaCO3s+WO4aq [1] 200°C CaWO4s + 2Faq ^ CaF2s+WO4aq [2] It is to be noted that a commercial process employing reaction [I] is in use at Union Carbide's operation near Bishop, Calif. In the earlier work referred to, it was apparent that the precipitation of the solid reaction-product on the scheelite particles sharply reduced contact of the leachant with the scheelite. We have extended this work by studying the kinetics of dissolution employing single crystals of scheelite of known exposed surface area. In addition, the effectiveness of solutions of phosphate, of phosphate with fluoride, and of chloride and hydroxide as leachants for scheelite have been investigated. EXPERIMENTAL Apparatus. The low-pressure autoclave used in this wo (100 psig maximum) is essentially that of J. Halpern4 as modified by F. A. Forward.5 Constructed entirely of 316 stainless steel, its maximum capacity is 4000 ml. The temperature in the autoclave was regulated to *0.5?C by a Wheelco thermocouple controller. A 4-in. diam, three-bladed impeller, circulated solution upward against the sample, and a strobo-scope permitted holding the stirring rate to *15 rpm. A check valve and a "pop" type safety valve were installed, a sample holder was fixed to an externally adjustable rod, and a water-cooled condenser was placed in series with the sampling valve. The stainless steel sample holder, Fig. 1, held the epoxy-mounted sample (f) five mm above the impeller. Tightening the tapered sleeve (d) positioned the epoxy-resin specimen-mount by forcing it back against the spacer (c). The mount (e) was 1 in. diam. Sample Description and Preparation. Both synthetic and natural scheelite crystals were leached. The former were single crystals of 99.95 pct purity which were leached approximately perpendicular to the "c" axis; they were supplied by the Gallard-Schlesinger Chemical Manufacturing Corp. The natural crystals, supplied by Minerals Unlimited, were transparent, analyzed 99.8 pct CaWO4, and in ultraviolet illumination exhibited the characteristic blue glow of substantially molybdenum-free scheelite. To permit exposure of an essentially constant surface area of scheelite to the leachant, the samples were mounted in Scotchcast Brand Resin No. 250 (Minnesota Mining and Manufacturing Co.). The mount-

Jan 1, 1970

By Peter N. Calder

The orientation of planes of inherent weakness (joints) with reference to an excavation in rock is the critical factor determining stability. The purely frictional 'residual' strength remaining following the breakdown of initial cohesion is the only strength which can be counted on to resist sliding for the long term. A simple method of resolving driving and resisting forces in three dimensions along joint intersections 'undercut' by the excavation is presented. Contrary to the case of slope failure in soils, it is shown how significant changes in the slope angle sometimes have no effect on the degree of stability pre-sent in rock slopes. Wall control by reorientation of the slope, the use of cable bolts and water diversion are briefly discussed.

Jan 1, 1970

By R. O. Williams

Analytical representation of the thermodynamics of solutions is highly desirable from the standpoint of accuracy, compactness, and numerical manipulations. In particular, computer calculations are greatly implemented. Mathematical considerations show that previous expressions have one or more serious defects. This investigation shows a Fourier series to be satisfactory but that it is also possible to derive a new series which fits certain additional conditions. Included examples show the value of analytical expressions in giving a simple characterization of each system using some two to five parameters, the elimination of the Gibbs-Duhem integration, and the es timation of the error for the experimental function as well as derived functions. It is further shown that the present characterization provides easy comparison between systems. IN the past, thermodynamic calculations have depended to a considerable extent on tabular and graphical methods. As the volume and precision of such data increase such methods become less satisfactory. Specifically, the selection of the optimum representation and the estimation of errors require statistical methods which in turn require analytical representation. The utilization of such data require further manipulations which are best done analytically for maximum precision. For example, phase equilibria are determined by common tangents to free-energy curves: a graphical determination is normally of low accuracy. As computers are increasingly used analytical representations become almost mandatory. Insufficient mathematical consideration has been given previously to the selection of empirical expressions. Those expressions having some theoretical justification are generally too inflexible and mathematically unattractive. We consider the problem in some detail and show that a Fourier series can be effectively used. Also a new series is defined which has certain advantages. ANALYSIS We wish to consider the analytical representation of the heat of mixing, AH, the excess free energy, ?Gxs, and the excess entropy, ?sXS, as a function of composition, X, for binary solutions relative to the pure components in the same state. When a distinction is not required, we use W to denote any one of the above functions. One may use a Taylor expansion around X = 0 to generate a power series. As the derivatives are un- known we represent the series as W = A + BX + CX2 + DX3 + EX4 + ... [l] where the constants A , B, C , ..- are to be selected to provide some optimum fit. For the extremes of composition W is necessarily zero so it follows that A = 0 [2a] B +C + D + E +••• = 0 [2b] Nonelectrolytes, which we are considering, appear to satisfy the condition that d3W/dx3 = 0 [3] in the terminal regions. This is the basis of the a, ß, and Q functions used by Hultgren et al.' and others. While this condition does not have a strong theoretical basis it does appear desirable that any analytical relation should satisfy this condition. Darken2 and Turk-dogan and Darken3 have shown that many systems exhibit this behavior over an extended range from each terminal region, departure being restricted to a limited intermediate region. Since we have no a priori knowledge as to where this transition occurs we can require that this condition be satisfied only as a limit at the extreme compositions as a general condition. We will show later how more restricted conditions can be included in specific solutions. Darken2 has called this behavior the quadratic formalism; we call our application the limiting quadratic formalism, LQF. This condition applied to the above power series requires that D = 0 [4a] 4-3-2E +5-4-3_F + 6 • 5 . 4G + ••• =0 [4b] The form of the power series normally used, due to Margules,4 is W=X(1-X)(A + BX + CX2 + DX3 + EX4 + •••) [5] where A, B, C, --. are a new set of constants. (Guggenheim5 has given a variation of this expression in a more desirable form. Since, however, it is contained in the above expression it does not require separate consideration.) This form is precisely what results by incorporating the conditions in Eq. [2] into the power series and regrouping the constants. The LQF requires that B =C [6a] and 4.3.2(D-C) +5-4-3(E-D) + ••• =0 [6b] Thus, the correct form of the Margules expression with two adjustable parameters is w =X(1-X)[A + B +X2-2/3x3)] 171 and the EX4 term must be included before three adjustable parameters are permitted.

Jan 1, 1970

By Guillermo Krstulovich

Pillar strength is a fundamental variable in the design of room and pillar mining. A number of researchers have investigated the strength of mine pillars by loading cubical, cylindrical and rectangular model pillars to failure in a compression testing machine (1). Several of these researchers have observed an increase in the compressive strength of model pillar with an increase in friction at the platen-specimen interface (2, 3, 4, 5). It has been postulated that the friction prevents lateral expansion of the specimen, thereby exerting a confining pressure at the interface. Seldenrath and Gramberg in their work with cylindrical specimens of limestone and marble noted that the effect of clamping the ends of the specimens, i.e., to restrict lateral movement of the specimen face, was to increase the compressive strength about 10% for marble and from 50-75% for the limestone, as compared to the same type of specimens when tested with the end planes free (6). No attempt was made to determine the confining pressure exerted by the clamps. In recent years, Bureau of Mines has conducted an extensive study, similar to Seldenrath and Gramberg's, with dog bone specimens. The confining pressure exerted by the clamps was determined and an increase in the compressive strength with increasing confining pressure noted (7, 8).

Jan 1, 1970

By G. L. F. Powell

g samples of Cu-20 wt pct Ag alloy have been mdercooled to a maximum of 197°C by melting under a slag of commercial soda-lime glass in a vitreous silica crucible. No grain refinement of the primary copper was observed in samples undercooled to the maximum of 197°C. When the samples contained a small amount of oxygen, the copper dendrites were partially recrystallized at undercoolings greater than 97°C. In previous papers'-3 reporting the grain structure of undercooled silver and copper, it was observed that grain refinement was dependent on both undercooling and oxygen content. Grain refinement occurred in undercooled silver when the degree of undercooling exceeded the range 153" to 175"C, while in Ag-0 alloys (0.12 wt pct) fine equiaxed grains were exhibited when undercooling was greater than 50°C. Similarly, copper samples undercooled as much as 208°C displayed fan-shaped growth from a single nucleation site, while the grain structure of Cu-O alloys (0.08 wt pct) was fine and equiaxed at undercoolings larger than 150°C. Thus the presence of oxygen greatly reduced the undercooling at which grain refinement occurred. It was also observed that the change in grain size resulted from recrystallization and was not due to an enhanced nucleation rate in the liquid-solid transformation. It is possible that the influence of oxygen on recrystallization is due primarily to its presence as a solute element. walker4,' reported that, although a grain size change did not occur in pure nickel until the undercooling exceeded 150°C, small grains were observed in samples of Ni-Cu alloy solidified at small and large degrees of undercooling. Jackson et al.6 suggested that the fine grained structure of the Ni-Cu alloy resulted from the melting off of dendrite arms during recalescence. This remelting process may occur in alloys as a result of segregation during freezing which causes a variation in liquidus temperature from point to point within a dendrite. It was therefore decided to undercool copper with a metallic alloying element to ascertain whether the presence of a metallic solute would have a similar effect to oxygen in inducing grain refinement. A Cu-Ag alloy was chosen, since both metals had been shown to behave similarly on undercooling. The alloy Cu-20 wt pct Ag was selected since the eutectic constituent outlines the initial growth form of the primary copper, so that the as-frozen grain structure is not obscured if subsequent recrystallization occurs. This paper describes the results of undercooling experiments carried out with Cu-20 pct Ag samples undercooled to a maximum of 197°C and the effect of oxygen content on the grain structure of the undercooled samples. EXPERIMENTAL Melting was carried out in a small cylindrical resistance furnace using "fine" silver granulate and oxygen-free high conductivity copper. The procedure adopted was to melt the required quantity of silver in air in a clean vitreous silica crucible for approximately 15 min, freeze, and add granulated commercial soda-lime glass to form a complete surface slag cover, after which the sample was melted and frozen several times to reduce the oxygen content. The glass slag cover was approximately 3 in. thick. Pieces of copper (=50 g) were added to the crucible until the required quantity to make 350-g samples of alloy had been charged. Each piece was added quickly to the crucible which was held at a temperature slightly above the melting point of silver. The piece was quickly pushed beneath the glass to minimize oxidation and any oxide coating usually decomposed before the piece had settled down into the silver. After the full quantity of copper had been added, the melt was stirred with a silica rod to hasten homogenization and a Pt/Pt 13 pct Rh thermocouple enclosed in a vitreous silica sheath inserted for temperature measurement. Heating and cooling curves were recorded on a potentiometric chart recorder fitted with a zero suppression unit. The milli-voltage range of the recorder was adjusted so that temperatures could be read to 1°C. Heating and cooling curves were taken every hour until three consecutive readings gave the same solidus-liquidus range, consistent with the solidus-liquidus range for this alloy composition by reference to Hansen and Anderko.7 Metallographic examination of samples frozen at this stage, failed to show any variation in composition from bottom to top of the ingot. Consequently, it was considered that the melt was homogeneous at this stage and undercooling experiments were then car-

Jan 1, 1970

By R. A. Wyman

What unusual features are there about finding, winning, and using the industrial minerals of Canada which may be of interest and yet not widely known. Have you, for example, ever wondered where the raw material for those distinctive greenish grey statuettes, so readily recognizable as Eskimo carvings, comes from? Although stone suitable for carving is obtained at several northern locations, in recent years the Federal government, the Quebec government, and one or two private companies have shipped supplies of various rock types from other sources to central distribution points in the Canadian north for the express purpose of providing Eskimo artists with raw materials for carving. Canada is well endowed with industrial minerals, the extent and variety of which may be observed by a perusal of Table 1. In this table, materials currently produced are shown in the left-hand column; materials which are bordering upon economic viability are listed in the middle column; and materials which have been found in Canada in possible exploitable quantity, but for which [ ]

Jan 1, 1970