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By D. W. Levinson, L. F. Mondolfo, N. A. Gjostein

MANY investigations are reported in the literature on the age hardening of Al-Mg-Zn alloys but most of them are concerned mainly with mechanical property changes. The present investigation was started to determine the structural changes in an AlMgZn alloy. The alloy composition was chosen in the existing phase diagram" so as to lie on the quasi-binary section Al-(AlZn)Mg Actually, it was found that the diagram as published was inexact at the lower temperatures and that the phase in equilibrium with aluminum at the lower temperatures is not the ternary compound. Technique The alloy used for the investigation was prepared from high purity materials and the resulting composition as determined by chemical and spectro-graphic analysis was: Zn, 6.17 pct; Mg, 2.13 pct; CU, 0.03 pct; Si, 0.009 pct; Fe, 0.005 pct; and the remainder, aluminum. An ingot -in. thick was cast, homogenized, hot and cold-rolled to strip 0.064-in. thick for dilato-metric and powder work, and to foil 0.005-in. thick for single crystal work. Solution treatment temperature for all specimens was 475°±5°C for periods of at least 1 hr, either in air furnaces or lead baths. Aging was done in oil or Pb-Bi baths controlled to within ±3°C. The aging was investigated at the following temperatures: room (30°), 130°, ZOO0, 260°, and 300°C. For the dilatometric study, the length changes were measured continuously, at temperature, using strips of alloy 10 in. long, shaped as channels to eliminate undesirable deflection due to bending. To compensate for thermal expansion and contraction due to the variations in the temperature of the aging baths, the dilatometers were built of the same alloy as the one being tested, with the same shape and size, but with material fully annealed. Gages on which 0.0005 in. could be read and 0.0001 in. estimated were used to measure the dilation. Length changes were also measured at room temperature. Strips approximately 10 in. long were solution-treated, quenched, and measured in a supermicrome-ter in which 0.0001 in. could be read and 0.00001 in. estimated. The specimens were immediately aged for a given time, remeasured, and then the cycle was repeated, including the solution treatment. The error of measurement with this technique was somewhat larger, but the results confirmed those obtained by continuous measurements. The sheet used for the dilatometric work was checked to determine grain orientation. Both X-rays and etching methods revealed a rather coarse grain size but only a negligible amount of preferred orientation. Thus, volume changes calculated from length changes are not invalidated by preferential orientation effects. Pieces of the sheet used for the dilatometric work were also used for the metal -lographic work. Filings for the powder X-ray study were produced from a homogenized piece of sheet. These filings were magnetically purged of iron, screened to 200 mesh, sealed in a Pyrex tube containing an argon atmosphere, and solution-treated. When quenching, the glass tube was broken, so that the powder dropped directly into cold water. After drying with alcohol, the powder was sealed into capillary tubes containing an argon atmosphere and then aged for the required times. In spite of all these precautions the three strongest lines of a( Al2o) appeared in all patterns, and were used as internal standards. By the use of these standards, accurate corrections for film shrinkage were obtained. For the back reflection patterns, annealed nickel powder was mixed with the specimen to act as internal standard. A preliminary investigation was made in small (57.3 mm diam) powder cameras. From these patterns the changes which took place in the solid-

Jan 1, 1957

By Kenneth E. Gray

The turbulent flow drag coefficients, or friction factors, have been experimentally determined for the cut-tings normally encountered in drilling operations. The gas law and average drag coefficients for characteristically flat particles (limestones and Shales) and for angular to sub-rounded particles (sandstones) were used to extend Newton's equation to a more useful form. The resulting equations are expressions for the slip velocity of a particle as a function of the particle size and shape, the bottom-hole injection Pressure, and the Bottom-hole temperature. The velocities necessary to lift actual rock cuttings as observed in the laboratory were compared with velocities predicted from the derived equations. Results indicate that there is no single correct circulating velocity and that the commonly used 3,000 ft/min linear velocity may he sufficient to lift only very mall particles. The advantage, in terms of horsepower requirements, of cycling high pressure air to obtain lower compression ratios was shown. INTRODUCTION A promising departure from standard rotary hydraulic drilling is air or gas drilling. In many instances the rate of penetration and bit life increases resulting from this method have been very substantial. Further the application of air drilling in areas of lost circulation or water sensitive pay zones has been highly successful. Purpose For the drilling contractor, the practical question remains, "How much air pressure and volume should I have?' lt is necessary to have a reasonable knowledge of the air velocities and pressures required in air drilling operations for the proper design and most advantageous use of surface equipment and for adequate removal of cuttings from the borehole. Eased on experience, most operators agree that at least 3,000 ft/min linear velocity is necessary for satisfactory hole cleaning.' It was the purpose of this investigation to evaluate the drag coefficients, or friction factors, for the cuttings normally encountered in drilling operations, i.e., sandstones, limestones and shales, and to utilize the values obtained to develop an expression for the minimum velocities and pressures (hence the volumes) necessary to lift these cuttings. THEORY Several investigators have done extensive work on the ability of drilling mud to lift bit cuttings. They conclude that the ability of a drilling mud to lift cuttings is dependent on the density difference between the rock being drilled and the drilling mud, the cutting size and shape, the mud flow constants, and the flow state (laminar, transitional or turbulent) of the mud. However, drilling muds are not true fluids but have a variation of viscosity with velocity in laminar flow and a constant apparent viscosity in turbulent flow. A survey of the literature revealed that no experimental work had been done to determine the velocities necessary to lift actual rock cuttings using a compressible fluid such as air or gas. In 1953, Nicolson6 stated that in air drilling fluid mechanics the particles could be assumed spherical in shape and that ; constant drag coefficient of 0.5 could be used due to the highly turbulent flow of the circulating air. By equating the turbulent resistance on the particle to the gravitational force on the particle, he obtained the expression, ^ = 2.67^y ,.......(1) where V, is slip velocity of spherical particle, ft/sec; D is particle diameter, in.; p, is particle density, 1b/ft8; and p, is fluid density, lb/ft3. However, as stated earlier, most operators seem to agree that adequate hole cleaning can be obtained by circulating a sufficient volume of air to give a linear velocity of 3,000 ft/rnin in the annular space. Basic Equation The velocity with which a solid particle freely falls through a fluid will increase until the accelerating force, gravity, is equal to the resisting forces, buoyancy due to the fluid displaced by the particle and friction due to the relative motion of the particle through the fluid. When the accelerating and resisting forces become equal,

By N. Mungan

A study was made of the effects of wettability and interfacial tension on the immiscible displacement of a Iiquid by another Iiquid from porous media. The influence of viscosity ratio was also investigated. Porous media used were polytetrafluoroethylene (TFE) cores prepared by compressing TFE powder under different pressures. lt is shown that displacement of a wetting by a nonwetting Iiquid is always less efficient than the displacement of a nonwetting by a wetting fluid, all other things being equal. In the former case, the recovery efficiency can be increased substantially by either reducing the interfacial tension or increasing the viscosity of the displacing fluid. A qualitative discussion is given on the implications of this work to the recovery of crude oil by water flooding. INTRODUCTION The high cost of oil exploration and new recovery schemes makes it imperative that waterflooding be conducted under conditions favoring most efficient oil recovery. To improve oil recovery by waterflooding, it is essential that the role played by interfacial forces in the entrapment of residual oil be studied and understood. Interfacial phenomena in natural rock, connate water and crude oil systems are very complicated because of the complexity of the natural liquids found in petroleum reservoirs, because of our inability to adequately describe the geometrical structure of the porous media and because of a lack of understanding of physical and chemical interactions between the liquids and surface of the pores. The problem becomes further complicated when one tries to elucidate the role of interfacial phenomena in fluid flow. Numerous studies of the displacement of oil by water under different interfacial tension or wet-tability conditions have been made.lm3 These studies have been performed in silica, alundum or sandstone systems using water and paraffin oil and also some surface active material to control the interfacial tension s and the contact angle 0. Unfortunately, the high energies of various interfaces involved favor adsorption and orientation of the surface active material at the interfaces. Also the surface active material concentration at the interfaces exceeds that in the bulk of the liquid phases. Such surface excess may cause the surfactant distribution, the contact angle and the interfacial tension to differ from their measured static equilibrium values and makes interpretation of the displacement experiments difficult. Furthermore, as changes in s also lead to changes in cos 0, the role played individually by one of these parameters in the displacement becomes obscured by the effect of the other. To circumvent these difficulties, a low surface energy solid and true solutions or pure liquids should be used. Use of a low surface energy solid minimizes adsorption and orientation effects at the solid-liquid interfaces. By controlling s and cos 0 through use of selected pairs of pure liquids or true solutions rather than by surfactants, the adsorption effects at liquid-liquid interfaces are eliminated. In the present study TFE cores were used as the porous media. Liquids used were water, sucrose solutions, paraffin oils and benzyl, n-butyl and isobutyl alcohols. The interfacial tension was varied from 40 to 1.1 dynes/cm by suitably choosing the liquid pair. A surface active material was added to the water-oil system only in the case where interfacial tension of 0.5 dyne/ cm was desired. No precise changes of cos 0 were attempted. However, either the displaced or the displacing liquid could be made the one which preferentially wets the TFE surface. Using sucrose solutions and blends of paraffin oils proved to be a convenient way of changing the viscosity ratio between the displaced and displacing liquids. The present investigation examines the effect of interfacial tension, wettability and viscosity ratio on the immiscible liquid-liquid displacement from porous media. Observed data permit a

Jan 1, 1967

By E. C. Barfield, D. G. McCarty

Two-dimensional analyses offer considerable promise in providing the basic information required to effect more precise control of petroleum reservoir performance. This paper describes a method for conducting some engineering analyses of this type using a high-qreed digital computer. The general approach is to (I) develop a representative numerical model of the reservoir and (2) employ a suitable numerical technique to solve the basic equation of flow and to develop the required engineering information for the particular case represented by the model. This technique has been used to calculate pattern performance in connection with several field projects involving water injection into oil reservoirs. This type of analysis involves sequentially (I) calculating the pres-' sure distribution in the reservoir and (2) tracking the progress of the interface between the displaced and displacing fluids in a step-wise manner to provide a depletion history of the operation. The particular analysis presented in this discussion is subject to the restriction that the mobility of the displaced and displacing fluids be equal and assumes that the fluids are incompressible and that gravity and capillary pressure do not affect the shape of the flood pattern. Complete two-dimensional .flexibility is maintained with regard to definition of reservoir rock and fluid characteristics, placement of physical restrains and boundary conditions, investigation of flow characteristics in the reservoir, and movement of the displaced and displacing fluid interface. The results of these studies indicate that the highspeed digital computer is well suited for conducting reservoir performance studies in two-space dimensions and that dependable numerical techniques are available for making such analyses. INTRODUCTION One of the problems facing petroleum engineers is that of providing more precise engineering control over reservoir operations at all stages during the depletion cycle. The most direct approach to this problem is to simulate the reservoir with some type of physical or mathematical model and use the information developed from the behavior of the prototype to predict the performance of the actual reservoir. This principle is, of course, not new, and a variety of simulation techniques have been developed to provide information on the behavior of oil and gas reservoirs. One straightforward refinement of present reservoir analysis techniques is the progress from one-dimensional reservoir models to those where the reservoir can be represented in two- and three-space dimensions. Multidimensional reservoir analyses are desired in order to show not only what is happening in the reservoir but in addition to show where in the reservoir the various phenomena of interest are occurring. Thus far, two-dimensional analyses have been confined predominantly to potentiometric and electrolytic model studies. However, when large numbers of wells are involved and where large-scale models are required, such problems become very tedious and instrumentation problems become acute." It is possible through use of numerical methods and general purpose digital computers to avoid many of the instrumentation difficulties and to relax some of the restrictions of previous techniques. The purpose of this paper is to discuss some recent experiences with the use of high-speed digital computers for predicting pattern performance in fluid injection operations and to describe the numerical procedures which have been used for making such analyses. THE NUMERICAL MODEL The problem of representing the reservoir with an appropriate numerical model is composed of at least two important considerations. The first requires that an adequate description of the reservoir mechanism be formulated in the form of the basic differential equation describing the process. The second consideration is definition of the physical characteristics of the reservoir. The latter requires that representative basic data be obtained, examined, and interpreted to provide sufficient detailed definition of the pertinent physical properties throughout the system. The Differential Equation One of the basic assumptions made for the purpose of performing the two-dimensional studies being dis-

By F. D. Rosi

The slip and twinning behavior in extended titanium crystals were studied in some detail. The formation and appearance of coarse kink bands are discussed. Their crystallographic geometry was determined by X-ray analysis. A phenomenological interpretation of the complexities in kink band development is also presented. The critical resolved shear stress, coefficient of shear hardening, and plane of fracture were determined for several crystals extended at room temperature. THE slip and twinning elements observed in the room-temperature deformation of titanium were enumerated in a previous paper1 in which considerations were advanced regarding the nature and selection of these elements and their effect on the known mechanical properties of this metal. The present study concerns the crystallographic, microscopic, and mechanical aspects of flow in relation to the slip and twinning elements, and includes a prediction of slip systems, nature of slip and twin markings, inhomogeneities of plastic flow, and stress-strain characteristics. Unless otherwise noted, arc-melted titanium sponge (99.77 pct) was used in these experiments. The method of production of crystals, their dimensions, and the surface preparation for micrographic examination have been reported.&apos; For obtaining stress-strain characteristics, only those crystals which traversed the entire width of the specimen and were at least 8 mm in length were used. Tensile deformation of the crystals was performed with conventional grips for sheet specimens and a constant-stress loading beam, designed after the method of Andrade and Chalmers.&apos; The specimens were loaded by allowing sand to flow from a reservoir into a bucket suspended from the longer end of a balanced 6:1 lever arm at a rate controlled to load the specimen approximately 2 kg per min. Strain measurements were made using the Baldwin SR-4, bonded, resistance-wire strain gage, Type A-8, which permitted a reading accuracy of 2 microinches per inch. The formulas used in the evaluation of shear stress and shear strain, as in deriving the coefficient of shear hardening, are given by Schmid and Boasv n terms of the original orientation and change in length of the crystal. For calculating the critical resolved shear stress, the standard equation was used. The crystallographic nature of the unpredictable slip observed in a number of specimens was determined by the single-surface X-ray method of analysis as described in ref. 1. Experimental Results Prediction of Slip System: It was reported&apos; that room temperature slip in titanium takes place predominantly on {10i0} and in a <1120> direction, giving three potential slip systems. Hence, it should be possible to predict the operative primary system in the manner used by Taylor and Elam&apos; for alu- minum (i.e., the one with the greatest component of shear stress in the direction of slip). The stereo-graphic construction in Fig. 1 shows that this is true. In all cases, slip was found to occur initially on the (0110) plane and, in a number of cases, in the [21f0] direction. (The direction of slip was not determined for all orientations.) It follows that duplex slip can be expected when two slip systems are geometrically equally favorable for slip, as demonstrated in Fig. 2. In both crystals slip took place simultaneously on the (1700) and (olio) prismatic planes, as indicated by Fig. 2a and b. In the case of crystal B the movement of the specimen axis with increasing extension was toward the (10i0) direction, which represents the stable end orientation resulting from alternate slip on the [2ii0] and [1120] directions. This is analogous to the duplex slip process in face-centered cubic metals." Unpredictable Slip: In a number of crystals whose orientations were well within the operation of a single slip system, secondary slip occurred on planes not predicted by the criterion of maximum shear stress. Examples are shown in Fig. 3. In addition to

Jan 1, 1955

By J. F. Smith, J. R. Ogren, N. J. Magnani

The uapor pressrcres of magnesium over binary alloys of magnesium with twelve of the yare-earth eletnetzts have been measured by the Knudsen effuion method in the temperature range 675° to 910°K. These vapor-pressure measurments were combined with data concerning the tevtrlitzul magnesium solubility and the vapor pressure of pure magnesinm to evaluale the standuvd free energies of pluase jormation. These free-etzergy values indicate that the CsCl structures of the heacy rave earths tend to be somewhat less stable than those of the light rare earths. This dif-]eying- behaviov covrelates with differences which have been obsevz~ed in other alloy systetns wherein a phuse appeurs, disappeavs, or changes crystal stvucture as the atomic number of the rare-earth com-ponent is changed. This behauior also appears to correlate with the struclurul rariations within the rare-earth elements themselves, and it is speculated that cariations in the spatial extent of the 4f orbitals are responsihle. STUDIES of the phase relationships and crystal structures in the binary systems between rare-earth metals (lanthanons) and magnesium are extensive but far from complete. However, the currently available information1-10 does produce a rather interesting pattern. This is illustrated in Table I. If one excludes europium and ytterbium from consideration because of their generally atypical behavior, it can be seen from the table that the phase relationships in the magnesium-rich regions show a distinctly different pattern for the lighter lanthanons as compared to the heavier lanthanons. For the lighter lanthanons, LnMg2 phases occur from lanthanum to gadolinium with the cubic MgCu2 structure, LnMg3 phases occur from lanthanum to terbium with the BiLi3 structure, and magnesium-rich phases occur from lanthanum to gadolinium with stoi-chiometries between Ln5Mg42 and LnMg12. In contrast, for the heavier lanthanons, those LnMg2 structures which have been examined have the hexagonal MgZn2 structure, LnMg3 phases have not been observed beyond terbium, and the magnesium-rich phases occur with the a manganese structure near a stoichiometry of Ln5MgZ4. The heavy lanthanon-magnesium systems thus appear to be analogous to the Y-Mg system""2 wherein YMg has the CsCl structure, YMg2 has the MgZn2 structure, and the region Y4Mgz5-Y5Mg24 has the a manganese structure, and no other intermediate phases are observed. Similarity in alloying behavior between yttrium and the heavy lanthanons occurs commonly, and on this basis it seems likely that LnMg2 phases will be found with the MgZn2 structure in the binary systems of dysprosium, thulium, and lutetium with magnesium when the appropriate investigations are made. In the case of the magnesium-rich phases of the lighter lanthanons, only the Ce-Mg phase relationships have been investigated thoroughly and in detail, and until similar investigations are made for the other systems there will remain questions as to which magnesium-rich stoichiometries represent equilibrium phases and what systematic variations occur in the sequence from lanthanum to gadolinium. Thus the data in Table I show that only the LnMg phases occur with the same crystallographic structure throughout the sequence from lanthanum to lutetium. It was speculated that the relative stability of these LnMg phases might vary from one lanthanon to the next in such a way as to presage the differences which occur among the more magnesium-rich lanthanon-magnesium phases. On this basis the present investigation of the thermodynamics of phase formation was Gndertaken for the LnMg phases. PROCEDURE AND RESULTS A generalized phase diagram for the lanthanon-rich portion of a lanthanon-magnesium alloy system is shown in Fig. 1 where ß represents a high-temperature bcc

Jan 1, 1968

By R. P. Alger, M. P. Tixier, D. R. Tanguy

In the combination induction-electrical log used at present in the field, the induction logging tool is appropriate for the investigation of moderately invaded formations. A new induction sonde with a radius and investigation about twice as large has been developed recently for the case of deep invasion. It has very nearly the same vertical resolution as the present sonde so that thin beds are defined as accurately as before. The characteristics of the new tool are described, the corresponding interpretation charts are given and field examples are discussed. The design of the sonic logging tool has been modified to improve the calibration and the reliability. The fact that porosity can be accurately recorded by means of the sonic log has prompted new interpretation procedures for saturation estimation, wherein the data concerning the various permeable beds in a given well are correlated. One approach consists of plotting transit time vs true resistivity, with an appropriate scale. With this approach, saturations can be estimated conveniently even in cases where formation water resistivity is not well known. In another approach, a comparison is made of the values of the formation waters computed from the re- sistivity and sonic logs. Using the concept of continuity, this procedure makes possible a quick determination of zones of saturation in shaly sands and/or in case of appreciable variations of formation salinities with depth. It has been found that the comparison of porosity from the sonic log with the apparent porosity computed from a short-investigation resistivity log may reveal, in many cases, the presence of residual oil and thus detect potentially productive formations; this procedure is valuable when the true formation resistivity and the resistivity of the formation water are in doubt. INTRODUCTION During the past year, the efficiency of log interpretation has been vastly improved. The improvements have largely resulted from the introduction of a deep-investigation induction device and from the application of new interpretation techniques that utilize sonic vs resistivity readings. Since the new interpretation techniques depend, in part, upon good values of true formation resistivity, the new induction log will be discussed under Part I. The sonic interpretation techniques will be studied under Part 11. Early in 1959, the 6FF40 induction equipment was introduced in the field. This device was designed for a better approach to true formation resistivities in deeply invaded zones. The greatly improved radial investigation of the 6FF40 equipment has been achieved without sacrificing vertical resolution. The first combination induction-electrical log, the 5FF40, was introduced as a standard tool in 1956 for the logging of wells drilled with fresh muds. The tool has received wide industry acceptance in the United States. &apos;The 5FF40 induction log has a radial investigation sufficient to overcome average depths of mud filtrate invasion. At 5d invasion, for example, the 5FF40 induction log will read about 1.4 R. in a water sand where R., = 10R,. At 10d invasion, such induction log would read 2.45 R. in the same water sand. In either case, the effects of invasion would not be sufficiently great to cause a water sand to be mistaken for a shale-free oil- or gas-producing zone. Some formations, however, invade deeply — in excess of 10d. Such water zones could be mistaken for oil-or gas-saturated sands unless the porosity balance&apos; can clearly make the distinction. It is for these deeply invaded formations that the 6FF40 was developed. CHARACTERISTICS OF THE 6FF40 Radial Investigation Characteristics To describe the comparative responses of the 5FF40

By T. E. Davidson, A. P. Lee

It is known from the early work of Bridgman that the two lowest-pressure transitions (I-II and II-III) are accompanied by substantial and abrupt changes in resistivity and Volume. However, unlike the temperature -induced allotropic transformations observed in such elements as lithium, cobalt, tin, and so forth, there is little actually known about many of the characteristics of the pressure-in&ced transitions. This current work involves an examination of the structural and transformation characteristics of the bismuth I-II and II-III transitions under hydrostatic pressures. The relationship of initial structure to the transformation pressure, rate, resistivity change, and resultant structure is discussed. It is shown that the transition pressure and transformation rate are independent of the presence of grain boundaries and associated anisotropy-induced deformation. An observed hysteresis in both the I-II and II-III transitions is shown. BISMUTH is one of the most interesting of the elements exhibiting pressure-induced polymorphs since it undergoes several allotropic transformations at pressures below 90,000 atm. It is known from the early work of bridman1,2 that the two lowest-pressure transitions (1-11 and 11-111) are accompanied by substantial and abrupt changes in resistance and volume. However, unlike the temperature-induced allotropic transformations observed in such elements as lithium, cobalt, tin, and so forth, there is little actually known about many of the characteristics of these pressure-induced transitions. It is the purpose of this work to examine some of the structural and transformation characteristics of the bismuth 1-11 and 11-111 transitions under hydrostatic pressures. Another interesting characteristic of bismuth is that, in its polycrystalline form, hydrostatic pressures of sufficient magnitude will induce severe progressive plastic deformation in the region of the grain boundaries.3 This deformation, which has also been observed in several other metals, is attributed to the high degree of anisotropy in the linear compressibility of bismuth, resulting in shear stresses in the grain boundaries when it is exposed to hydrostatic pressure. Most thermally induced allotropic transformations in metals, whether of the diffusionless ather-ma1 (martensitic) or isothermal nucleation and growth types, are dependent upon structure and prior history,4 viz., grain boundaries, deformation, and so forth. One logically wonders then whether the transformation characteristics of the pressure-induced polymorphs in bismuth might also depend upon initial structure, particularly with respect to the presence of grain boundaries and associated plastic deformation. In this investigation, the role of grain boundaries and plastic deformation on the characteristics of the bismuth I-II and 11-111 transitions will be established. The rather unique residual microstruc-tural changes associated with these transitions will be presented and discussed. The occurrence of a measurable hysteresis in both the I-II and 11-111 transitions will be demonstrated. The type of transformation mechanism based on the observed transformation rate will be discussed. EXPERIMENTAL PROCEDURE A) Apparatus. The hydrostatic pressure system utilized in this investigation is similar to that previously reported by Bridgman&apos; and Birch and Robertson,5 and has been previously described.3 For the purpose of this work, the pressure medium utilized was a 1:l mixture of pentane and isopentane. Pressure measurement was by means of a manganin coil in conjunction with a Foxboro Recorder. The manganin coil was mounted in the bottom closure and inserted inside the pressure cavity. Based on calibration against a controlled clearance piston gage at approximately 10,000 atm, the estimated error in the pressure measurement was +2 pct. Assuming the nonlinearity in the pressure coefficient of resistivity between 10,000 and 28,000 atm to be not greater than 1 pct, then the estimated error in the range of the I-II and 11-111 transitions was +3 pct. B) specimen Material and Preparation. The bismuth utilized throughout this investigation was of

Jan 1, 1964

By W. Philippoff

ALTHOUGH Gaudin1 and more recently Sutherland2 have calculated the probability of collision of a falling mineral particle with a rising bubble, there is no published information concerning the details of the mechanism of attachment of a collector-coated particle to a bubble. During the past year the writer has developed a theory for the mechanism of attachment, which has been substantiated experimentally. Funds for the investigation and for some of the equipment used have been supplied by the Mines Experiment Station of the University of Minnesota. Motion picture studies of the phenomena involved in the collision between mineral particles and bubbles, such as those of Spedden and Hannan," show that the contact can be completed within 0.3 millisec. Formulas developed for rigid bodies have hitherto been used&apos; for the calculation of the motion of bubble and particle, but it is obvious that a bubble cannot be regarded as a rigid body. On the contrary, Spedden and Hannan&apos;s pictures show a great degree of deformation during the collision. The time of attachment was calculated as the time the particle drifted past the bubble. Time of Collision The theory presented in this paper enables calculation of the time of collision, using the concept that the bubble, or more generally, a liquid-air interface, acts as an elastic body. The elasticity, defined as the restoring force on a mechanical deformation, is caused by the surface tension and is the result of the principle of the minimum of free surface energy. It is well known that an elasticity together with a mass determines a frequency of vibration. The vibrations of jets and drops caused by the elasticity of the interface are known to comply exactly with the classical theory of capillarity.&apos; However, the vibrations of isolated bubbles, as distinct from foams, have not been investigated previously. The following equation, presented elsewhere,&apos; has been deduced for these frequencies: 3_____________________ fB = 9.20.vV.vn. (n-1).(n+2)/8 [I] in which fB is the frequency of a harmonic of the bubble in cycles per second, V the volume of the bubble in cc, n a number determining the order of the harmonic, and n = 2 the basic vibration. The first (basic) harmonic describes a change of the spherical bubble to an ellipsoidal bubble. The higher harmonics are more complicated, for the circumference of the bubble is divided approximately into as many parts as the order of the harmonic. As an example, Spedden and Hannan&apos;s published motion picture of a vibrating bubble corresponds to the sixth harmonic. Eq 1 shows that only the first and third harmonics are simple multiples (1 and 3), all the others being irrational fractions of the basic frequency. This means that the shape of the vibration can change with time and is in general unsym-metric in respect to the time axis. Such conditions prevail when there is a distributed elasticity or mass, as in the case of vibrating membranes or rods. The constant 9.20 is valid for water at room temperature, but a general solution involving the physical constants of the liquid has not been found. The case of the floating particle is much easier to treat than that of the bubble. It can be assumed that the elasticity is caused exclusively by the interface and that the mass is concentrated in the particle together with some adhering water. The following expression for the frequency of a system of one degree of freedom can be applied: fP = -1/2-vE/m [2] Here fp is the frequency of the particle vibration in cycles per second, E the elasticity in dynes per cm, and m the mass in grams. The classical theory of impact phenomena gives the time of collision during the striking of a spring (in this case the surface of the bubble) by a mass, as: t, = 2/f = nvm/E [3] It is now possible to develop an expression for the elasticity of a floating cylindrical particle. The force equilibrium of a cylinder floating end on at the air-liquid interface is given by the well-known equation (Poisson7 1831) P = /4 D2-pL-g-h + D.y sin a [4] which accounts for the buoyancy and the action of the surface tension where P is the force acting on the particle in dynes (weight-buoyancy), D the diameter of the cylinder in cm, PL the density of the liquid in grams per cc, g the acceleration of gravity = 981 cm per sec2, h the depression of the cylinder below the surface of the liquid in cm, y the surface tension in dynes per cm and a the supporting angles or the one required to insure equilibrium, a being smaller than the contact angle 0. Although demonstrated by Poisson, it has not

Jan 1, 1953

By G. M. Schwartz, D. M. Davidson

THE Duluth gabbro outcrops containing sulphides of copper, nickel, and iron are located on both sides of State Highway No. 1 an airline distance of 8.5 miles southeast of Ely in northeastern Minnesota. The region of known sulphide occurrences includes parts of sections 5, T. 61 N., R. 11 W., and parts of sections 25, 26, 32, 33, and 34, T. 62 N., R. 11 W. These sections, given in Fig. 1, are all in Lake County, Minnesota. Part of the area, which lies entirely within the Superior National Forest, is shown on the topographic map of the Ely quadrangle. The original discovery was made in 1948 when a small pit was opened in weathered gabbro rubble for use on a forest access road. A shear zone had caused unusual decomposition in this glaciated area, and the resulting copper stain was noted by Fred S. Childers, Sr., an Ely prospector, who began searching the outcrops along the base of the intrusive. He was joined in further exploration by Roger V. Whiteside of Duluth. In the summer of 1951 a small diamond drill was moved into the area and a hole 188 ft deep was drilled, passing through 11 ft of glacial drift into sulphide-bearing gabbro. This paper is a preliminary report on the geology of the newly discovered ore. The Duluth gabbro is one of the largest known basic intrusives and may be defined as a lopolith.&apos; It extends northeastward from the city of Duluth as a great crescent-shaped mass that intersects the shore of Lake Superior again near Hovland, 130 miles to the northeast, see Fig. 2. The distance around the outside of the crescent is nearly 170 miles. The form of the intrusive is simple at Duluth where it ends abruptly north of the St. Louis River; at the east end, however, the gabbro splits into two elongated, sill-like masses separated mainly by lava flows and characterized by minor irregularities. The outcrop reaches a maximum width in the central part where it is about 30 miles across, and a maximum thickness of about 50,000 ft. It may be significant that the sulphides occur at the base of the thickest part. The lopolith has segregated into rock types ranging from peridotite to granite. The most abundant types are olivine gabbro, gabbro, troctolite, anortho-site, and granite. Of lesser importance quantitatively are peridotite, norite, pyroxenite, magnetite gabbro, and titaniferous magnetite. Grout estimates that two-thirds of the gabbro at Duluth is olivine gabbro. Variations in the percentages of plagio-clase, augite, olivine, and magnetite-ilmenite constitute the only essential differences found among the basic rock types. The predominant mineral is plagioclase, mainly labradorite. Plagioclase and olivine seem to have crystallized early, and the olivine rich rocks, usually troctolite, are found in the lower part. Segregations of titaniferous magnetite are abundant near the base of the gabbro along the eastern part and also occur far above the base. These have recently been described in detail by Grout.&apos; Near the top, segregation has produced a gradation to granite, or "red rock," as it is known locally. This consists of quartz, red feldspar, and hornblende. The red rock forms a zone with a maximum width of nearly 5 miles but is quantitatively unimportant from Duluth northward for 35 miles. In Cook county, where the gabbro splits, each of the two sill-like masses has a red rock top somewhat thicker in proportion to the gabbro below than in the main central mass. The intrusive ranges from coarse to medium in grain size and from granitoid to diabasic in texture. Throughout much of the Duluth gabbro in Minnesota banding and foliation are well developed, as Grout has emphasized.V he bands are mainly a result of variation in the percentage of minerals, as in troctolite with alternating bands high in olivine and in plagioclase. A few bands may consist largely of one mineral, as is true of some segregations of magnetite. Many of the banded rocks show a clearly developed parallelism of platy plagioclase crystals, and both banding and foliation are believed to conform to the floor of the lopolith. Throughout its extent in Minnesota the Duluth gabbro dips east and south toward Lake Superior. It is generally believed to extend beneath Lake Superior and is found as a smaller mass exposed along the north side of the Gogebic district in Wisconsin and Michigan. The dip at and near the base ranges along most of its length from 20 to 40°, but at places the internal banding dips even more steeply. The dip of the upper part is much less, and if it is assumed that the flows along the north shore of Lake Superior are a dependable indication, it does not exceed 15". The formations shown in Table I which are intruded by the gabbro range from Keewatin to Middle Keweenawan in age. They present a significant picture. At the top, the gabbro and its accompanying

Jan 1, 1953

By E. J. Roberts

The theory is developed that the tons ground through a given mesh per day in a wet ball mill is proportional to the percent plus that mesh in contact with the balls and the net power applied to the balls at this point. A grindability test is described. DURING the course of a study of the fundamentals of classification in 1937, the need for a more basic understanding of the action of a ball mill became acute. Unless one knows how classification affects grinding, one cannot hope to effectively improve on classification. The methods of evaluating grinding efficiency that depend on surface developed were studied but soon discarded for two reasons: 1. There was no apparent method which could be generally used to give a reliable figure for the actual new surface developed as a result of grinding. Subsequent papers have not changed this conclusion. 2. The practical evaluation of grinding in the main ore dressing applications was in terms of the percentage retained on a screen which passes 90 to 99 pct of the material and not in terms of surface area. The Probability Theory With the background of our experience in the field of closed-circuit grinding, together with the papers of Lennox,1 Gow,2 Gaudin,8 Fahrenwald,4 Coghill, and others, the approach of the theoretical physicist was then tried. The thought was somewhat as follows: When one grinds in a ball mill, a given expenditure of power leads either to a certain number of point to point blows per hp-hr or to a certain distance of line contact per hp-hr, depending on whether the action of the balls is considered to be cascading or rolling. It is also assumed that the balls actually come together on each blow or during the roll. Then a volume of slurry will be covered per minute which is some function of the size of the particle being considered (see fig. 1). All particles coarser than this size will be reduced through this size. This volume of slurry contains a certain weight of ore, depending on the percent solids and the density of the solids. If we fix the percent solids and the density of the solids and let w be this certain weight of ore in the volume covered, then, in mathematical terms, what we have just postulated is, w —— 8 hp (a) dt If W is the total weight of ore present in the mill, then we can write. W w/8 hp (b) W dt and if C is the cumulative percent plus the size chosen at the start of the time interval dt, w w c/dt W 8 hp x c (c) wc But wc/100 is the weight plus the size chosen which at 100 wc the close of time dt is finer than that size, and W is the decrease in the percent plus of the whole mass of ore or —dC. Then, —W dC/dt 8 hp x C. (d) In other words, the mesh tons ground through a given size per unit of time is proportional to the hp and the percent plus the mesh. A crude analogy would be to picture a 1-ft-wide steam roller going down the road at 1 ft per sec. If we place one egg on the road per square foot, one egg will be smashed per second. If we place a dozen eggs per square foot, a dozen eggs will be crushed per second. Similarly, if all the particles in w are plus the mesh, i.e., C=100, we should have a maximum rate of reduction. If only 10 pct of them are plus the mesh (C=10), we would have only one tenth the maximum rate; if only 1 pct are plus the mesh, the balls have a hard time finding anything to work on. This is where the term "probability theory" comes from. The chances of the balls crushing a particle through a given mesh depends directly on the concentration of particles coarser than this mesh in the general pulp in the mill. Giving W the units of tons and dividing equation (d) through by W, we obtain -dC hp ----- = k---— C [1] dt ton where k is a constant for any one size of particle, density of solid and moisture content of pulp. Eq 1 is the rate equation for a first order reaction and says that the rate of decrease of the percent plus a given mesh with time is directly proportional to the hp per ton applied to the body of ore and to the percent plus the mesh in the ore mass as a whole. Since it is a differential equation, it only

Jan 1, 1951

By A. L. Pranatis, G. M. Pound

Changes in length of copper foils of varying thickness and grain size were measured under such conditions of low stress and high temperature that it is believed that creep was predominately the result of interboundary diffusion of the type recently discussed by Conyers Herring. The surface tension of copper was calculated and results confirmed previous work within the limits of experimental error. Under the assumption of viscous flow, viscosities were calculated as a function of temperature and grain size. Predictions of the Nabarro Herring theory of surface grain boundary flow were borne out fully and the Herring theory of diffusional viscosity is strongly supported. ONLY a relatively few techniques for obtaining the surface tension of solids are presently available. Of these, the simplest and most straight forward is the direct measurement of surface tension by the application of a balancing counterforce. Thin wires or foils are lightly loaded and strain rates (either positive due to the downward force of the applied load or negative if the contracting tendency of surface tension is sufficiently greater than the applied stress) are observed. By plotting strain rates against stress, the load which exactly balances the upward pull is found and a simple calculation yields a value for the surface tension. The technique is of comparative antiquity, and solid surface tension values were reported by Chapman and Porter,&apos; Schottky; and Berggren" in the early part of the century. Later, the filament technique became fairly well established as a method for determining the surface tension of viscous liquids, and Tammann and coworkers,&apos;. " Sawai and co-worker and Mackh howed good agreement between the values of surface tension for glasses and tars obtained by the filament technique and by more conventional methods. With the increased confidence in the technique gained in these experiments, the method was applied to solid metals and the first reliable values of surface tension of solid metals were reported by Sawai and coworkers10&apos; " and by Tammann and Boehme." More recently, Udin and coworkersu-&apos;" have reported the results of experiments with gold, silver, and copper wires. Similar experiments with gold wires were carried out by Alexander, Dawson, and Kling.&apos;" The excellent review articles of Fisher and Dunn" and of Udinl@ should be referred to for detailed criticism of the foregoing work and for discussion of underlying theory. In all the foregoing calculations, it is assumed implicitly that the material contracts or extends uni- formly along the length of the specimen and also that it flows in a viscous fashion, i.e., that strain rates are proportional to stress. For an amorphous material, such as glass, tar, or pitch, the assumptions are quite valid and good agreement is obtained with values of surface tension measured by other techniques. The values reported for metals, however, are occasionally regarded with misgiving, since it can be argued that, because of their crystalline nature, true solids can not deform in a viscous fashion. If this is true, then the results reported for solid metals over a long period of years are of only doubtful value. Thus it is clearly necessary that a mechanism be established that would explain both the viscous flow and the uniform deformation that has been assumed. Such a mechanism has been proposed by Herring."&apos; Briefly, he suggests that, under the conditions of the experiment, deformation takes place by means of a flow of vacancies between grain boundaries and surfaces. This is a direct but independent extension of the theory proposed by Nabarro" in an attempt to explain the microcreep observed by Chalmer~.In a condensed form the Herring viscosity equation is TRL there 7 is the viscosity, T the absolute temperature, R and L grain dimensions, and D the self-diffusion coefficient. In its complete form, all constants are calculable and it includes such factors as grain shape, specimen shape, and degree of grain boundary flow. When applied to existing data, good agreement was obtained between predicted and observed flow rates. The theory received provisional confirmation from the work of Buttner, Funk, and Udin" who observed viscosities in 5 mil Au wire much higher than those in the 1 mil wire used by Alexander, Dawson, and Kling.&apos;" More significant were the completely negligible strain rates found by Greenough" in silver single crystals. Opposed to these observations were those of Udin, Shaler, and Wulff&apos;" who found indications of viscosity decreasing as grain size increased. Thus, complete confirmation of the theory was lacking in that the data to which it could be applied contained only a limited number of grain sizes. Hence, it was proposed that a series of experiments be carried out with thin foils of varying grain size up to and including single crystals, where, according to the Herring theory, deformation would occur only at almost infinitely slow rates.

Jan 1, 1956

By W. C. Clarke

An empirical study of the nature of the embrittle-ment which occurs in martensitic and semiaustenitic precipitation hardening stainless steels upon exposure at temperatures of from about 550" to 875°F has been undertaken. This work was aimed at determining cazusation and means of controlling this phenomenon. A commercial copper bearing precipitation hardening alloy was used as a basic material for study. The effect of heat treatment variables was studied as was the effect of variations in analysis. It is concluded from the evidence that martensitic and semiaustenitic precipitation hardening stainless steels are subject to 885°F ernbrittlement similar to that observed in the straight chromium stainless steels. A characteristic of precipitation hardening stainless steels which has limited their use in certain applications is that they embrittle when held at temperatures in the range of from about 550" to 900°F. This is true to a more or less degree in all currently available alloys, either the basically martensitic type or the semiaustenitic type. The rate of embrittlement varies markedly with exposure temperature, being low at 550" to 600°F and in-creasing as the temperature increases. In spite of this embrittlement, these alloys with their unique combination of high mechanical strength, reasonable toughness, and good corrosion resistance are used in many hundreds of applications. Nevertheless, there are potential applications where the embrittle-ment described is a limiting factor. The purpose of this investigation was to study the embrittlement of these alloys and to find a way to control or eliminate it. GUIDELINES USED IN PRESENT WORK The work reported in this paper is based on a study of 17-4 PH*, a very widely used alloy. It has been used *Trademark of Armco Steel Corp., licensor. in pressurized water and boiling water atomic reactors operating at about 550°F for a number of years. As the life of such equipment is extended or operating temperatures are raised, the possibility of embrit-tlement becomes of increasing concern to materials engineers. Much investigation work was done with respect to the use of 17-4 PH at 550°F. K. C. Antony&apos; states "Such estimation" (of an activation energy for the diffusion of chromium in iron) "would indicate W. C. CLARKE, Jr. is Senior Research Engineer, Advanced Materials Division, Armco Steel Corp., Baltimore. Md. This manuscript is based on a talk presented at the symposium on New Developments in Stainless Steel, sponsored by the IMD Corrosion Resistant Metals Committee, Detroit, Mich., October 14-15, 1968. significant secondary aging is improbable at temperatures less than 700°F within normal component service life". This statement is modified however by the recognition of the accelerating tendencies of applied stress and internal stress as well as the possible effect of irradiation. In this investigation of 17-4 PH, the H 1100 (1900°F-1 hr oil quench or air cool + 1100°F-4 hr-air cool) condition was used, partly because this condition is normally used in atomic reactors. As shown later, the precipitation hardening temperature has no real bearing on the rate of embrittlement. An exposure temperature of 800°F was selected since embrittlement at 800°F is rapid, permitting development of relative data in time periods of 400 to 500 hr. For those not familiar, a nominal present day analysis of 17-4 PH is: C Mn P S SiCrNiCuCbN 0.04 0.30 0.015 0.015 0.60 16.00 4.30 3.25 0.23 0.030 TYPICAL BEHAVIOR OF 17-4 PH Figs. 1 and 2 show the behavior of a commercial heat of 17-4 PH under the conditions defined. Characteristically, 800°F exposure causes a rapid drop in Charpy V-notch impact strength. Tensile and yield strengths gradually increase and a gradual loss of elongation and reduction of area occur, accompanied by an increase in hardness. Notched tensile strength increases to 125 hr exposure and then sharply decreases after exposure for 500 hr. The notched vs un-notched tensile ratio remains virtually constant to exposure for 125 hr (1.67 to 1.56) but drops to 1.15 after 500 hr. Tensile ductility is not alarmingly affected even after much longer exposure times than these. For example, samples aged at 1100°F for 1 hr exposed at 800°F for 4000 hr showed a drop in elonga-tion of from 13 to 11 pct and in reduction of area of from 58 to 37 pct. Notched impact is the property SmIgth KSI 3JJ[/__________^UTS-Nrteh 260 ;/- 240 —^ 200 UTS-Smooth________._, o ioo mo Sob" m Too Hours Exposure Fig. 1—Effect of exposure at 800°F for various times on notched tensile strength and smooth tensile and 0.2 pct yield strength of 17-4 PH in the H 1100 condition.

Jan 1, 1970

By Rollyn P. Jacobson

THE town of Pacific, in Jefferson County, Mo., is 127 miles west of St. Louis. Since the area lies entirely on the flood plain of a cutoff meander of the Meramac River, it was considered a likely environment for accumulation of commercial quantities of sand and gravel. Excellent transportation facilities are afforded by two major railways to St. Louis, and ample water supply for washing and separation is assured by the proximity of the river. As a large washing and separation plant was planned, the property was evaluated in detail to justify the high initial expenditure. An intensive testing program using both geophysical and drilling methods was designed and carried out. The prospect was surveyed topographically and a 200-ft grid staked on which electrical resistivity depth profiles were observed at 130 points. The Wenner 4-electrode configuration and earth resistivity apparatus" were used. In all but a few cases, the electrode spacing, A, was increased in increments of 11/2 ft to a spread of 30 ft and in increments of 3 ft thereafter. Initial drilling was done with a rig designated as the California Earth Boring Machine, which uses a bucket-shaped bit and produces a hole 3 ft in diam. Because of excessive water conditions and lack of consolidation in the gravel there was considerable loss of hole with this type of equipment. A standard churn drill was employed, therefore, to penetrate to bedrock. Eighteen bucket-drill holes and eight churn-drill holes were drilled at widely scattered locations on the grill. The depth to bedrock and the configuration will not be discussed, as this parameter is not the primary concern. Thickness of overburden overlying the gravel beds or lenses became the important economic criterion of the prospect.** The wide variety and gradational character of the geologic conditions prevailing in this area are illustrated by sample sections on Fig. 2. Depth profiles at stations E-3 and J-7 are very similar in shape and numerical range, but as shown by drilling, they are measures of very different geologic sequences. At 5-7 the gravel is overlain by 15 ft of overburden, but at E-3 bedrock is overlain by about 5 ft of soil and mantle. Stations L-8 and H-18 are representative of areas where gravel lies within 10 ft of surface. In most profiles of this type it was very difficult to locate the resistivity breaks denoting the overburden-gravel interface. In a number of cases, as shown by stations M-4 and H-18, the anomaly produced by the water table or the moisture line often obscured the anomaly due to gravel or was mistaken for it. In any case, the precise determination of depth to gravel was prevented by the gradual transition from sand to sandy gravel to gravel. In spite of these difficulties, errors involved in the interpretation were not greatly out of order. However, results indicated that the prospect was very nearly marginal from an economic point of view, and to justify expenditures for plant facilities a more precise evaluation was undertaken. The most favorable sections of the property were tested with hand augers. The original grid was followed. In all, 46 hand auger holes were drilled to gravel or refusal and the results made available to the writer for further analysis and interpretation. When data for this survey was studied, it immediately became apparent that a very definite correlation existed between the numerical value of the apparent resistivity at some constant depth and the thickness of the overburden. Such a correlation is seldom regarded in interpretation in more than a very qualitative way, except in the various theoretical methods developed by Hummel, Tagg (Ref. 1, pp. 136-139), Roman (Ref. 2, pp. 6-12), Rosenzweig (Ref. 3, pp. 408-417), and Wilcox (Ref. 4, pp. 36-46). Various statistical procedures were used to place this relationship on a quantitative basis. The large amount of drilling information available made such an approach feasible. The thickness of overburden was plotted against the apparent resistivity at a constant depth less than the depth of bedrock for the 65 stations where drilling information was available. A curve of best fit was drawn through these points and the equation of the curve determined. For this relationship the curve was found to be of the form p = b D where p is the apparent resistivity, D the thickness of overburden, and b a constant. The equation is of the power type and plots as a straight line on log-log paper. The statistical validity of this equation was analyzed by computation of a parameter called Pearson&apos;s correlation coefficient for several different depths of measurements, see Ref. 5, pp. 196-241. In all but those measurements taken at relatively shallow depths, the correlation as given by this general equation was found to have a high order of validity on the basis of statistical theory.

Jan 1, 1956

By E. A. Slover

THE usual reverberatory system of smelting cop--1- per concentrate or calcine has for its component parts a furnace and one or two waste heat boilers. These parts are operated on a basis of compromise, since the furnace can send gas to the boilers at too high a temperature and the boilers by plugging, due to dust or slag, can place a definite limit on the amount of fuel the furnace can burn. Over the years the copper concentrate smelting furnace has had few advances in design. The simple rules of design such as the flame should wipe the bath and the speed of the gases should be reasonably low for dust carrying purposes seem to cover the main features. In the construction of the individual furnaces some innovations are always being introduced. Among these are charging so that the work of smelting is a complete bath process, the use of suspended brick arches in place of sprung arches, the use of basic brick, not only in the crucible, but also in roof and sidewalls, the use of various means to feed the charge, the use of magnetite or other heavy material to construct the hearth, water cooling of bridgewall and slag skimming bay, the smelting of raw charge instead of calcine, the use of preheated air, and possibly the use of oxygen-enriched air for combustion. But the general outlines of the furnaces have not changed much except as to size. Furnaces at Hurley As shown on Fig. 1, the furnace at Hurley is 126 ft long between the longitudinal buckstays and 32 ft wide at the skewback plates. The foundation is a concrete retaining wall with piers at intervals that go deeper into the earth. Purposely the wall at the burner end of the furnace is not backed-up as tightly as the other parts of the foundation so that movement due to expansion may take place here rather than into the boiler foundations. Within these foundation retaining walls of concrete, the earth has been removed to allow the placement of the crucible brick base inside of which a silica hearth is laid 4 ft 6 in. in depth. No expansion is left in the brick base and crucible where they are in contact with the hearth. The hearth itself is of quartzite crushed to 1 in. size with fines left in the product. An 8 in. layer is laid and tamped with paving tampers to about 6 in. in thickness. Then a layer of silica flour is spread and vibrated into the hearth. This operation is repeated until a depth of 4 ft 6 in. is occupied by the silica mass onion-skinned in layers of approximately 6 in. Before firing the entire hearth is covered with broken slag to a depth of 4 in. so that a seal may be formed on the hearth. The crucible is completely faced with magnesite chemically bonded brick while the outside, against the foundation, is made of silica brick. The side-walls are carried up with silica brick in which expansion joints are left at intervals. Above the crucible the sidewall is corbelled to form a shelf on which the charge may build up along the side-walls, see Fig. 2. The arch of the furnace is sprung 20 in. silica brick, with the longitudinal centerline horizontal the length of the furnace, and some 9 ft in the center above the bath. Both straight and wedge brick are used in the construction and a thin silica mortar is troweled for joints. After the arch under heat has assumed its permanent shape, a silica slurry is spread over the arch to fill any cracks that have formed, thus giving bearing surface to the brick and preventing dust from entering the body of the arch to act as a future fluxing agent. The uptake of the furnace slopes up to the boiler entrance where a brick pilaster divides the gas stream for the two boilers. Over this flared uptake is a suspended flat arch of firebrick. The pilaster and sidewalls are constructed of firebrick but the bottom of the uptake is lined with silica brick and fettled through holes in the roof with siliceous fettling. Close to the entrance of each boiler is a brick covered slot through which water-cooled dampers may be lowered in event of boiler trouble. These water-cooled dampers are hung permanently in position ready to be lowered when needed. Flexible hoses to follow the dampers as they are lowered are connected at all times and individual chain blocks are used to lower the dampers. A pump supplying water is started before the dampers enter the heat. Charging of the furnace along the sidewalls for some 80 ft from the bridgewall is accomplished by electric vibrating conveyors fed by belt from charge storage bins above the furnace. These conveyors

Jan 1, 1954

By R. H. Parker, B. A. Wills, D. G. Binns

Introduction With the increasing need to mine lower grade ores, high energy-related costs in comminution are of major concern. Very fine grinding is needed to liberate the fine mineral particles in these ores. Not only is this expensive, but it leads to greater losses in slimes. Gravity concentration techniques become unacceptably inefficient for particle treatment below 25 to 50 µm, and even flotation fails in the ultra-fine range. Ore from the South Crofty mine near Redruth, Cornwall, was subjected to thermal pretreatment in the hope that differential thermal expansion of the minerals would lead to intergranular cracking, and thus enhanced liberation. South Crofty ore contains about 1% tin as cassiterite associated with a complex assemblage of quartz, chlorite, tourmaline, and hema¬tite in granite and slate. Recovery of cassiterite can be as low as 70%, as overgrinding occurs during stage reduction of the material to 1 mm (primary grinding) and 180 µm (regrinding). Cassiterite is present in grain sizes ranging from submicroscopic to + 10 mm, the bulk being predominantly in the range of 50 µm to 3 mm. Experimental Flat polished sections of the ore were photographed in reflected light using a Vickers M17 microscope. The sections were then heated in a Carbolite LMF4 muffle furnace. The heating rate and temperature were monitored by a thermocouple immersed in the bed of particles. Previous work by Sherring (1981) on the same material showed that a 55% reduction in grinding resistance occurred when the material was rapidly heated and cooled through the quartz inversion tem¬perature (573°C), where a volumetric expansion of 0.86% occurs. The samples were therefore heated to 650°C at 26°/min, and were then water-quenched to room temperature. The effect of heat treatment on the mineralogy and fracture network was assessed by examining the same area after treatment. Results Most of the sections examined showed that extensive transgranular cracking occurred as a result of heat treatment. Such cracking, although weakening the rock and hence reducing the work index, would in no way enhance the liberation of the cassiterite from the host minerals. Intergranular cracking, which would lead to enhanced liberation, was difficult to discern under reflected light, but there was evidence of such cracking in some of the sections examined. Figures 1 and 2 are examples of typical sections before and after heat treatment. Figures la and lb - show cassiterite in hematite, Fig. lb, in normal incident illumination, illustrating clearly that after heat treatment, transgranular fracture is evident in the cassiterite. If any intergranular cracking has occurred, it is not evident in this photograph. Figures 2a and 2b show cassiterite in quartz before and after treatment. Fracturing in both minerals after treatment can clearly be seen, and there is evidence of intergranular fracturing. However, protruding "arms" of cassiterite are severed by transgranular fracture. Subgrains of quartz have also been isolated by trans¬granular fracture. There is major transgranular cracking across the wider sections of cassiterite. Discussion The effect of rapidly heating South Crofty tin ore to 650°C, followed by water-quenching to room temperature, has been studied by observing the fracture networks in mineral grains. The choice of 650°C as the heating temperature was influenced by the work of Sherring (1981), who found considerable reduction in grinding resistance after thermal pretreatment of the same ore. Scheding et al. (1981), however, have shown, by means of a crude calculation, that heat treatment cannot be justified solely on the basis of reduced grinding costs. The cost of heat treatment far out-weighs that of grinding, resulting in the combined costs for heat treatment being over six times that for grinding unheated material. The most economically attractive aspect of heat treatment is the possibility of enhanced liberation of the valuable mineral due to increased intergranular rather than transgranular fracture. Grinding costs would be greatly reduced by improved liberation at coarser sizes, and the costs of ancillary processes, such as dewatering and tailings disposal, would be reduced. The most significant economic effect, however, would be in improved metallurgical efficiency. Improved liberation would increase concentrate grades, and recoveries would be higher, particularly in the case of ores where high slime losses are produced due to the excessively fine grinding required to produce adequate liberation. Manser (1983) has shown that only a 1% increase in tin recovery, at the same concentrate grade, would be sufficient to offset heat treatment costs on South Crofty ore. Heavy liquid analysis and shaking table separation have been used to evaluate the effect of thermal treatment on processing (Binns, 1984; Scheding, 1981; Sherring, 1981). However, treatment of unheated and heated samples of South Crofty ore, ground to the same product size, by such methods have shown little evidence of improved metallurgical efficiency after thermal pretreatment. The large amount of transgranular fracturing revealed by reflected light studies helps to explain this lack of improvement. Nevertheless, from the evidence of some of the fracture work, it is surprising that no improvements in metallurgical

Jan 1, 1988

By S. Storchheim

MORE and more attention is being paid to the bonding of metals in their solid states. For a better understanding of this technique for joining metals and how it is affected by changes in temperature, pressure, and time at temperature and pressure, a detailed report concerning nickel to aluminum bonding has been published.&apos; In order to broaden the knowledge accrued, some additional work concerning solid state joining of aluminum to copper and aluminum to zirconium was performed. The investigation of the Al-Cu system was considerably more extensive than the investigation of the Al-Zr system. For the A1-Cu system, not only were tensile sudies made but intermetallic penetration rate investigations also were carried out. The effect of temperature on intermetallic penetration rate for the A1-Cu system was determined at 11 tsi pressure, held 2 min. Procedure Apparatus: The hot pressing technique was the means of solid state reaction used and required the equipment depicted in Fig. 1. The following procedure was involved: The two metals to be reacted were placed in an aquadag-lubricated 18-4-1 tool steel die, 16 in. high by 1.440 in. ID, between punches of 1.366 in. diam made of the same material. A thermocouple well was located in the die body 3½ in. down from the top of the die, while another well was located centrally in the bottom punch 8½ in. from the bottom of the die. This die assembly was located in three cylindrical ceramic heating furnaces placed in tandem. Each furnace was controlled individually by a Variac power transformer. In turn, the die and furnaces were placed in a water-cooled stainless steel pot which could be evacuated. A cover, which contained a centrally located Wilson seal with an 18-4-1 1 in. diam ram running through it, was bolted on the pot. After sealing, the pot was evacuated by a roughing pump to 200 microns pressure, after which a diffusion pump was used to bring the pressure down to 5 to 15 u. At this pressure, the furnaces were turned on. As soon as they started to heat, out-gassing of the entire unit raised the pressure to 30 to 400 p. By the time the specimens were at temperature ready to be pressed, approximately 4/2 hr, the vacuum pumps had re-established the 5 to 15 u pressure. Once the desired temperature was reached, the required pressure was applied for a predetermined length of time to the 1 in. ram, through to the top punch, and to the specimen. When the time for keeping the specimen under pressure had elapsed, the pressure was released, the energizing coil current turned off, and the assembly allowed to cool. After cooling, the die was removed from the pot and the specimen was ejected. Specimen Preparation: Two different types of specimens were made for this investigation. One was for subsequent tensile testing, while the other was for determination of intermetallic alloy zone penetration into the parent metals. Tensile Bars—Commercially rolled copper pieces in. thick or zirconium sheet pieces 1/32 in. thick and 1.366 in. diam were placed between commercial 2-S aluminum rod 1 in. thick and 1.366 in. diam. This sandwich in turn was slipped into a 2-S aluminum sleeve 1.438 in. OD and 1.370 in. ID. This sleeve lined the couple up and prevented the aquadag lubricant from getting in between either the A1-Cu or Al-Zr interfaces. Immediately prior to the specimen assembly, the copper or zirconium was abraded on the flat surfaces with 320 grit silicon carbide paper, producing clean smooth surfaces. The aluminum was chemically cleaned just before assembly by: l—degrease in acetone, 2—distilled water rinse, 3—immersion for 3 min in 5 pct NaOH at 70" to 80°C, 4—distilled water rinse, 5—immersion for 2 min in 50 pct HNO3 solution at room temperature, 6—distilled water rinse, and 7—drying in a blast of gas. After the A1-Cu sandwiches were hot pressed and ejected, the specimens were machined such that the aluminum sleeve was removed, and the remaining aluminum was then threaded; the bar so produced was tested later for tensile strength. In all the instances where Al-Cu couples were tested, the specimens broke during the test at the Cu-A1 interface and never within the aluminum or copper. The ultimate tensile strength values at times showed considerable scatter for a set of given reaction conditions. Because of this, as many as three to five specimens were made for a particular set of conditions. The trend of the average tensile strengths obtained was not as conclusive as was the trend of the maximum tensile strengths, the latter values being obtained under optimum reaction conditions. Therefore, the values of ultimate tensile strength given herein are maximums.

Jan 1, 1956

By Paul M. Jr. Musgrove, Donald C. Moore

Conventional Smelting Practice Conventional copper smelting practice varies from smelter to smel¬ter, but generally consists of some or all of the following unit processes: roasting, smelting, converting, and fire refining. Roasting. Copper sulfide concentrates can be smelted directly or after an initial roasting step. Roasting is used in some smelters because roasting prior to smelting increases smelting capacity, less energy is required to melt hot roaster calcines than wet sulfide concen¬trates, roaster off gases are high in Sot concentration, 5-15% SO2, and some volatile impurities are removed from the concentrate prior to smelting. However, many smelters do not use roasters, because the problems associated with handling hot dry calcines outweigh the advantages mentioned. Concentrate roasting is performed in multiple hearth or fluid bed roasters. If the moisture is low, roasting can be performed autogenously, usually at 500-600°C. High roasting temperatures are avoided because excess oxidation of the iron compounds may lead to magnetite formation. Magnetite is detrimental to reverb operation because mag¬netite can combine with refractory minerals to form a highly viscous slag. This slag prohibits efficient matte-slag separation and leads to excessive copper losses. Also, magnetite can settle through the matte layer, deposit on the furnace bottom, and consequently reduce furnace capacity. Roasting is carried out only on sulfide concentrates prior to smelt¬ing in reverb or electric furnaces. For smelting processes, such as the flash and continuous that rely on the exothermic heat of oxidation of the sulfur minerals, roasting is not practiced. Reverberatory Smelting. The predominate copper smelting fur¬nace for the past 50 years has been the reverb. These furnaces are typically 100-120 ft long, 30-35 ft wide, and 12-15 ft high. A typical furnace layout is shown in Fig. 2. Refractory brick linings cover all internal surfaces of the furnace. Originally the flame was directed to reverberate or reflect off the furnace ceiling and melt the feed material. Current practice is to direct the flame down the furnace length to melt the concentrate. A method of charging the concentrates or calcines, generally along the side walls to minimize refractory erosion, is incorporated in the furnace design. The copper concentrates, calcines, and fluxes charged into the reverb undergo a series of complicated reactions as the temperature of the mixture increases. The reaction of the iron and copper sulfides with the oxygen in the furnace produces a molten Cu25-FeS mixture called matte. Copper smelting metallurgy is based on the fact that sulfur has a greater affinity for copper than for iron and most other common metals. Therefore, in a system containing copper, the copper will preferentially remain as a sulfide compound until all of the other metals have been oxidized. The oxidized metals combine with silica to form a silicate slag that floats on the matte and is removed from the system. Reverberatory furnace smelting chemistry can be approximated by the following chemical equations: FeS2 + O2 - FeS+ SO2 (1) The formation of FeS ensures that any copper present other than as sulfides will be reduced by the relationship: CuO2 + 2FeS + O2 - CuS + 2FeO+SO2 (2) or 2Cu +FeS - Cu2S + Fe (3) As the molten charge travels down the furnace, continued oxida¬tion of the iron minerals and sulfurization of the copper minerals occurs. When all of the copper has been converted to sulfides, the iron sulfides can then be further oxidized as: FeS + (3)2 O2 FeO + SiO2 (4) The FeO reacts with the silica added as flux in the furnace charge. A simplified equation is: FeO + SiO2 -FeO SiO2 (5) The iron silicate slag formed is skimmed from the surface at the end opposite the burners. The copper content of reverb slag is usually less than 0.6% Cu and is discarded. Matte is removed along the side wall and is taken to the converter for oxidation of the remaining sulfur and iron. The main objectives in reverberatory smelting are to produce a molten Cu2S-FeS matte containing 30-60% Cu and a throwaway slag. Production of matte permits complete conversion of all copper minerals into copper sulfides, which can migrate because of specific gravity differences, through the lighter slag layer. Also, the molten matte droplets collect the noble metals, gold and silver, as the matte settles in the furnace. The large settling area of the furnace provides enough separation time to produce a low grade slag, which can be discarded without further processing. High heat losses are associated with reverberatory smelting be¬cause of the large volume of gases sweeping through the furnace. Therefore, an outside source of heat is required to keep the smelting reaction going. Natural gas, fuel oil, or pulverized coal are used as this heat source.

Jan 1, 1985

By E. J. Roberts

The theory is developed that the tons ground through a given mesh per day in a wet ball mill is proportional to the percent plus that mesh in contact with the balls and the net power applied to the balls at this point. A grindability test is described. DURING the course of a study of the fundamentals of classification in 1937, the need for a more basic understanding of the action of a ball mill became acute. Unless one knows how classification affects grinding, one cannot hope to effectively improve on classification. The methods of evaluating grinding efficiency that depend on surface developed were studied but soon discarded for two reasons: 1. There was no apparent method which could be generally used to give a reliable figure for the actual new surface developed as a result of grinding. Subsequent papers have not changed this conclusion. 2. The practical evaluation of grinding in the main ore dressing applications was in terms of the percentage retained on a screen which passes 90 to 99 pct of the material and not in terms of surface area. The Probability Theory With the background of our experience in the field of closed-circuit grinding, together with the papers of Lennox,1 Gow,2 Gaudin,8 Fahrenwald,4 Coghill, and others, the approach of the theoretical physicist was then tried. The thought was somewhat as follows: When one grinds in a ball mill, a given expenditure of power leads either to a certain number of point to point blows per hp-hr or to a certain distance of line contact per hp-hr, depending on whether the action of the balls is considered to be cascading or rolling. It is also assumed that the balls actually come together on each blow or during the roll. Then a volume of slurry will be covered per minute which is some function of the size of the particle being considered (see fig. 1). All particles coarser than this size will be reduced through this size. This volume of slurry contains a certain weight of ore, depending on the percent solids and the density of the solids. If we fix the percent solids and the density of the solids and let w be this certain weight of ore in the volume covered, then, in mathematical terms, what we have just postulated is, w —— 8 hp (a) dt If W is the total weight of ore present in the mill, then we can write. W w/8 hp (b) W dt and if C is the cumulative percent plus the size chosen at the start of the time interval dt, w w c/dt W 8 hp x c (c) wc But wc/100 is the weight plus the size chosen which at 100 wc the close of time dt is finer than that size, and W is the decrease in the percent plus of the whole mass of ore or —dC. Then, —W dC/dt 8 hp x C. (d) In other words, the mesh tons ground through a given size per unit of time is proportional to the hp and the percent plus the mesh. A crude analogy would be to picture a 1-ft-wide steam roller going down the road at 1 ft per sec. If we place one egg on the road per square foot, one egg will be smashed per second. If we place a dozen eggs per square foot, a dozen eggs will be crushed per second. Similarly, if all the particles in w are plus the mesh, i.e., C=100, we should have a maximum rate of reduction. If only 10 pct of them are plus the mesh (C=10), we would have only one tenth the maximum rate; if only 1 pct are plus the mesh, the balls have a hard time finding anything to work on. This is where the term "probability theory" comes from. The chances of the balls crushing a particle through a given mesh depends directly on the concentration of particles coarser than this mesh in the general pulp in the mill. Giving W the units of tons and dividing equation (d) through by W, we obtain -dC hp ----- = k---— C [1] dt ton where k is a constant for any one size of particle, density of solid and moisture content of pulp. Eq 1 is the rate equation for a first order reaction and says that the rate of decrease of the percent plus a given mesh with time is directly proportional to the hp per ton applied to the body of ore and to the percent plus the mesh in the ore mass as a whole. Since it is a differential equation, it only

Jan 1, 1951

By Yu. A. Polozov, V. A. Lagunov, O. Yu. Lushinkova, Yu. I. Svirskiy, Eh. Ya. Kipko, Roy A. Williams

1.1 GENERALIZED METHODS OF SUPPRESSING THE INFLOW OF GROUND WATER DURING THE CONSTRUCTION OF SHAFTS, DRIFTS AND TUNNELS Various methods are used to prevent or minimize the inflow of ground water into underground workings during their excavation. The two most common methods include freezing the saturated rock and grouting using cement, sodium silicate, polyurethane and/or other chemicals. Each of these technologies for combatting the inflow of ground water is effective only under specific hydrogeological conditions. For example, although the freezing of saturated ground is among the more universally adopted methods, it is designed to provide only temporary protection during construction. Before the saturated rock thaws it is necessary to emplace a waterproof liner which is labor intensive, time consuming, and expensive. Consequently, freezing is used only in exceptionally complex hydrogeological conditions, namely in those cases where the water-bearing strata consist of unstable rock or the ground water has an anomalous hydrochemistry. The classical grouting of saturated rock, carried out from the surface or from the face of the underground workings for the purpose of limiting the inflow of ground water during excavation, utilizes both cement and a variety of chemical grouts. Cement grouting has been regarded as the main method of combatting the inflow of ground water in fractured rock throughout the world. In such countries as the Federal Republic of Germany (FRG), Canada, the Republic of South Africa and Great Britain, cement grouting is the main method of reducing the inflow of ground water during the excavation of mine openings. In Great Britain and the FRG, cement grouting has been used in 80% of all shaft excavations. In the Republic of South Africa cement grouting has been used in almost 100% of all the shafts that have been constructed. The installation of grout curtains into permeable water- bearing strata significantly reduces their permeability and increases the rock strength. Grouting has the greatest effect in fractured sandstones, certain well indurated shales, fractured granites, fractured quartzites, and karstic limestones or dolomites. The following principal factors must be considered when assessing the expediency of grouting rock with cement: the geometry of the network of fracture openings, the saturated hydraulic conductivity of the fractured rock, the hydraulic head acting on the water in the rock, and the chemical composition of the ground water. On the basis of the geometry of the fractures and the thickness of each hydrostratigraphic unit, the characteristics of the cement grout are selected. As a rule, the cementing of large fractured zones with high ground water velocities is carried out using inert fillers (sand, mill slag, loam, loess, crushed limestone), special types of cement, setting accelerators, and high cement concentrations in water. Calcium chloride, soda ash, sodium silicate, sodium nitrate, amino alcohols, tin bichloride, trisulphate nitrate, and lumnite are used extensively as the setting accelerators for cement grouts. In the FRG and Poland, special cement injection compounds that embody a mixture of cement and active cement metal salts, water additives and binding substances are being used for the cementing of saturated zones with rapid ground water velocities. These reagents accelerate the rate of structure-forming reactions. In spite of the wide variety of additives used for cement grouts, the effectiveness of the method in large fractures below the water table is either poor or it leads to a very large consumption of cement due to the erosion of the grout through the cracks before it hardens. At the present time, a large number of cement types and brands are being produced by various countries. These variations permit cementing to be employed in a variety of geological conditions. However, both pure cement grout and grouts with fillers constitute unstable systems with a high water loss rate. Therefore during the grouting of finely fractured rock the cement grout&apos;s premature loss of a large amount of free water causes its consistency to increase, whereupon the grout solidifies. Consequently, it inadequately penetrates into the fine fractures of the stratum. In addition the high water loss rate in the cement grout causes unreacted cement particles to remain, which greatly reduces the grout hardness and the resulting rock strength characteristics are weakened. As a result, the binding properties of the cement are utilized perhaps up to 60%. The remaining portion is left in the grout as a filler. All these conditions significantly decrease the efficiency of the isolation effort both with respect to strength and cost. In order to expand the cement grouting method, re- search is being conducted to improve the quality of cement grout, to increase its range of application with respect to permeability control, to reduce its water loss rate and to increase its capacity to withstand the erosive and corrosive effects of poor quality ground water. For example, mixtures of bentonitic clay, carboxymethyl cellulose, aerated sodium sulfide, sulphated alcohol distillery waste, nitrolignin, gip-

Jan 1, 1993