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By John Chipman, Raymond L. Orr

Recently reported high -temperatlnre thermal data have been incorporated in a reuieu' of the therinody-r~ar,zic propesties of iron. The recent data permit mot corlsisterlt and reliuble choices to be made for many of the pvoperties, resnlling in bettev eslablished tabrtlations of the thermodynamic functions. Values of Cp, h°t- - H°298. s°t - S2sa, and (G°T -H298/T are tabulated for -the solid and liquid phases of iron in both stable and melastable regions. Consistency of the tabulations has been maintained to the precision necessr~vg to yield the Gibbs energy change belween the bcc (a, 8) and fcc (y) phases of iron at temperatures pertinenl to alloy studies. THE importance of the metal iron has stimulated many investigations of its thermodynamic properties at elevated temperatures. Reviews and summaries of the data have appeared from time to time. Among these the 1951 paper of Darken and smith' deserves highest recognition for the quality of its criticism and for the precision and thermodynamic consistency of its tabulations. These and the more recent table of Kaufman, Clougherty, and weiss2 reproduce the Gibbs energy of the (a, 6)--Y transformation with sufficient sensitivity for alloy studies. Other recent compilations of equal validity3-' make no attempt to do this. Since this Gibbs energy change is not greater than 22 cal per g-atom over the temperature range 1100° to 1800°K, it is obviously desirable to tabulate values of (G°t - H298)/T to four places of decimals even though the absolute accuracy would not warrant such precision. The necessity for reconsideration of the problem is emphasized by the recent publication of several important researches on the enthalpy and heat capacity of iron. The older work is well-covered in the reviews cited and will be mentioned here only when actually employed in the tabulations. GAMMA IRON Transition temperatures are taken from the selec -tions of Elliott and Gleiser,5 based on the work of Boulanger7 and earlier workers. For the a-y (A3) transition at 1184°K we retain the value 215 cal per g-atom adopted by Darken and smith.' It has received confirmation in the recent work of Dench and Kubaschewski,' and of Braun8 using adiabatic calori-metry, and of Wallace, Sidles, and Danielson10 using a pulse heating technique. The enthalpy data of Olette and ferrier" and of Anderson and Hultgren12 at higher and lower temperatures may be extended to 1184°K to give the following values which are adjusted to the required value of ? 1184 Ha,1184 Ha 298 = 8030 cal per g-atom [11 hr,1184-ha298 = 8245 cal per g-atom [2]

Jan 1, 1968

By G. H. Alani, H. T. Kennedy

One of the major difficulties in predicting the performance of oil reservoirs from their early pressure history lies in the uncertainty of estimating the volume of the liquid hydrocarbons contained in them. As a first step in filling this need, an equation was developed to determine the Inolal liquid volume of pure hydrocarbons over a wide range of temperature and pressure. The second step consisted of adapting the equation to apply to mixtures, with the heary hydrocarbons expressed as c The equatious are similar in form to van der Waals equation. hut the constants a and b tire considered as furnctions of temperature. In addition to the gas constant R, there are four constants characteristic of each hydro- When comptired with experimental values jound in the literal the. the average absolute deviation in the calculated molal volumes is found to be a Maximum of 0.33 per -cem for any of the pure liquid hydrocarbons studied. This maximum deviation was that found when comparing the calculated and observed values over a temperature range of 86° to 482°F and a pressure range from the bubbl-point ro 10,000 psis. The equations expressing the correlation for. mixrurrc were developed from 647 experimental measure-rilents of volume on 47 bouom-hole samples covering ; temperature range of 72" to 250°F and a pressure znge from bubble-point ro 5,000 psig. The average absotute deviation was found to he 1.6 per cent with the maximum for any measurement of 4.9 per cent. INTRODUCTION Accuratc information of the pressure-volume-temper-iiture behavior of hydrocarbon liquids is of considerable importance in the field of both applied and theoretical science and, especially, in the solution of petroleum reservoir engineering problems. These PVT relationships can be expressed graphically, in tabular form or as equations of state. Equations of state for gases have been developed based on the ratio of pressure, temperature and volume to the pressure, temperature and volume at the critical points of the hydrocarbons. These equations have been successful in yielding values fairly accurate for reservoir engineering purposes. For liquids, however, relations of this type are more complex and have not yielded useful results. The composition of reservoir liquids is normally expressed in terms of the moles of hydrocarbons C,? C,. C,. elc, per mole of mixture. The composition must include the fraction of a mixture such as C,,, which cannot be separated with reasonable time and effort into specific hydrocarbons. Although there are several equations of state having variable degrees of accuracy applicable to pure liquid hydrocarbons, none includes a means for estimating the volume of mixtures as a function of temperature. pressure and composition expressed in this manner.

Since production curtailment for other than engineering reasons is gradually disappearing, and more and more wells are now producing at capacity and showing declining production rates, it was considered timely to present a brief review of the development of decline-curve analysis during the past three or four decades. Several of the commoner types of decline curves were discussed in detail and the mathematical relationships between production rate, time, cumulative production and decline percentage for each case were studied. The well-known loss-ratio method was found to be an extremely valuable tool for statistical analysis and extrapolation of various types of curves. A tentative classification of decline curves, based on their loss ratios, was suggested. Some new graphical methods were introduced to facilitate estimation of the future life and the future production of producing properties where curves are plotted on semilogarithmic paper. To facilitate graphical extrapolation of hyperbolic-type decline curves, a series of decline charts was proposed, which will make straight-line extrapolation of both rate-time and rate-cumulative curves possible. Introduction During the period of severe production curtailment, which is now behind us, production-decline curves lost most of their usefulness and popularity in prorated areas because the production rates of all wells, except those in the stripper class, were constant or almost constant. While production-decline curves were thus losing in importance for estimating reserves, an increasing reservoir consciousness and a better understanding of reservoir performance developed among petroleum engineers. This fact, together with intelligent interpretation and use of electric logs, core-analysis data, bottom-hole pressure behavior and physical characteristics of reservoir fluids, eliminated a considerable part of the guesswork in previous volumetric methods and put reserve estimates, based on this method, on a sound scientific basis' At the same time, a number of ingenious substitutes were developed for the regular production-decline curve, which made it possible to obtain an independent check on volumetric estimates in appraisal work, even though the production rates were constant. with the now steadily increasing demand for oil to supply the huge requirements of this global war, proration for reasons of than prevention of underground waste is gradually disappearing. More and more wells are, or will be, producing at capacity or at their optimum rates, as determined by sound engineering practice. With this trend, the character of producing wells seems to regain, more or less, its "individuality," and the old and familiar decline curve appears to have had a comeback as a valuable tool in the hands of the petroleum engineer. It may be timely, therefore, to retrace the development of decline-curve analysis in the past by presenting a brief chronological review of bulletins and papers published during the past three or four decades, which have

Jan 1, 1945

By T. H. Alden, H. W. Schadler

The strain rate dependence of the flow stress of the eutectoid Zn-Al alloy has been determined as a function of mechanical processing, microstructure, and temperature. The best superplastic properties result from the ultrafine, equiaxed structure produced by solution treatment and isothermal transformation at 0°C. Lamellar structures produced by isothermal transformation and coarse equiaxed structures produced by annealing also exhibit strain rate sensitivity in excess of 0.5, but at higher stresses and lower strain rates than the finest structure. Solution treatment and isothermal transformation eliminate the effect of prior processing history. Small composition variations in the binary alloy do not influence the mechanical properties. Below the eutectoid transformation temperature (.275C) increasing temperature lowers the flow stress at all strain rates. The data do not favor any of the present proposals for the mechanism of superplastic flow. ALLOYS of zinc and aluminum, near the eutectoid composition, have been investigated for: 1) the flow stress-strain rate and elongation behavior,1, 2) the transformation kinetics,3 and 3) structure,3"5 but the structure sensitivity of the mechanical properties is poorly understood. Using a near eutectoid alloy water-quenched from 380°C, Backofen et aL2 estab- high and increases with increasing strain rate. They found a correlation between strain rate sensitivity and tensile elongation as expected from the increased resistance to necking that a high strain rate sensitivity provides.296 The large elongation at high strain rates is attractive for metal forming. Since most other superplastic alloys7-l3 do not show high strain rate sensitivity at such a high strain rate (for the exception see Ref. 12) there is the possibility of a unique deformation mechanism for this alloy. The sensitivity of the mechanical properties of the eutectoid alloy to thermal history1 suggests a structure sensitivity that has not been demonstrated. Gar-wood and Hopkins3 identified a lamellar product for material transformed between 200" and 260°C. The size of the lamellae decreased with decreasing temperature. They also demonstrated that an unresolved transformation product formed below 200°C. A granular two-phase material was resolved for specimens quenched to below 150°C by Mitbauer and sauerwald4 who observed coarsening of the structure after annealing. The role of grain boundaries in superplastic deformation is suggested by the strong effect of grain refinement in encouraging this phenomenon at high strain rateS7-11, 13 and is emphasized in several proposals about rnechanism7, 8, 12 and in a theory14 of high-temperature deformation. Alden8 showed metallographic evidence that grain boundary sliding is occurring extensively at strain rates where m is large but less at high strain rates where normal plasticity is observed. Holt and Backofen10 have shown that sliding also oc-

Jan 1, 1969

By R. D. Pehke, J. F. Elliott

The solubility of nitrogen in liquid pure iron has been measured as a function of pressure and temperature. Sieverts' Law is obeyed at all pressures up to 1 atm and the temperature coefficient of solubility is 8 x 106 %/°C. The solubility of nitrogen in liquid iron alloys has been studied by the Sieverts' method and by the sampling method. The solubility is decreased by Al, C, Co Cu, Ni, 0. Si atzd Sn, and it is increased by Cr, Cb, Mn, Mo, Ta, W, and V. Interaction coefficients eN, for the effect of these elements on nitrogen dissolved in liquid iron, are reported. 1 HE effect of nitrogen upon the properties of steel may be desirable or not, depending upon the composition, processing treatment, and the use of the product. To understand the behavior of nitrogen in the various steelmaking processes, it is necessary to have reliable fundamental data pertaining to the solubilities, rates of solution, and chemical reactions of nitrogen in steel, particularly in the liquid state. In an effort to extend our knowledge in these areas, an investigation of the thermodynamics and kinetics of the solubility of nitrogen in liquid iron alloys was undertaken. The thermodynamic aspects of the study are presented in this paper. The solubility of nitrogen in liquid pure iron has received the attention of several investigators whose results are summarized in Table I. Reasonable agreement among the more recent researches1-l8 is found for the solubility of approximately 0.044 wt pct at 1600°C and 1-atm pressure of N,, for the temperature coefficient of solubility being small but positive, and for adherence to Sieverts' law for pressures up to 1 atm. The solubility of nitrogen in a number of binary liquid iron alloys has been studied: Fe-A1,3 Fe-As,16 Fe-C,3, 71 18, 19, 20 Fe-Cr ,5,7, 10, 11, 15 21 Fe-Co,'4, '6 Fe-Cu,'6 Fe-Mn,10, 11, 18 Fe-Mo,13, 16 Fe-Ni,10, 11, 13, 15, 16 Fe-O,16, 17, l9 Fe-p,7 Fe-S,l6 Fe-Sb,16 Fe-Se,lg Fe-Si,4) 97 '77 187 19>2° Fe-Sn,16 and Fe-v.51 '3 A few ternary systems have been studied, most of which were reviewed by ~angenberg" who applied the methods suggested by WagnerPz3 Chipman,24 Darken and G~rry, and Morris and Buehl26 for predicting solubilities in multicomponent alloys. Langenberg22 and Humbert and Elliott15 compared the solubilities computed from simple binary alloy systems with experimental measurements of nitrogen solubilities in liquid iron containing two or more alloying elements. The interaction coefficients for nitrogen in

Jan 1, 1961

By H. H. Keller, E. J. Couch

Damage to production wells subjected to the high temperatures associated with in-situ combustion projects has been a problem since the advent of this thermal recovery technique. Injection of water down the annulus of hot wells has been successfully utilized for cooling and prolonging the life of such wells. A mathematical model that is suitable for predicting the effectiveness of cooling water in a particular application is developed. Typical results for practical ranges of the various parameters involved are presented. INTRODUCTION In the normal course of in-situ combustion operations, highly damaging conditions develop in the production wells as the combustion zone approaches, and these wells are subjected to high temperatures (up to 1500F). The resulting well damage is recognized as one of the more serious operating problems unique to the in-situ combustion process. Even in operations where well completions have been specifically designed to cope with this problem, the question arises as to how this destructively high temperature can be kept within tolerable limits. A simple and economical approach to this problem is to circulate cooling water down-hole. This method has been used with some success in shallow reservoirs. At greater depths, however, the heat exchange with the overburden surrounding the well and between the fluids in the tubing and the annulus tends to equalize the temperatures of the two fluid streams so that the cooling capacity delivered to the bottom of the hole decreases with well depth. This method would provide no appreciable control over the bottom-hole temperature at great depths. In order to delimit the condition under which cooling by water circulation is effective, the wellbore temperature must be related to the water inlet rate and temperature; to the reservoir depth, production rate, and initial temperature; and to the combustion at at bot tom-hole depth. A model that meets these requirements and that will offer an approach for developing engineering solutions to practical design and operating problems is described in this paper. MATHEMATICAL MODEL Previous studies of temperature distributions include those for flowing wells1p2 and those for hot fluid injection. Adams and Haddenhorst 6 presented solutions for the down-hole circulation of hot oil in the treatment of paraffin-deposition problems. In this paper the thermal model presented by Ramey 4 is adapted to the flow system shown schematically in Fig. 1. Water at temperature Ti is injected at a rate wi and flows down the annulus outside the tubing. It mixes at bottom-hole depth D with the fluids produced at race w from the hot reservoir at temperature T. This mlxtureJ. of injected water and reservoir fluids flows up the tubing and is produced at the surface at TI,. In order to describe the temperature response in this system, we make use of the usual conservation of

Jan 1, 1969

By L. D. Jaffe, D. C. Buffum

EARLIER the authors and coworkers had pre sented data on isothermal temper embrittlement of an SAE 3140 steel?' In that work, however, attention was concentrated on embrittlement at 575°C and below. Preliminary measurements showed that embrittlement at 675 °C was much mote rapid than would be expected from the data at the lower temperatures: and indicated the need for further work above 575°C. The possibility of an upper nose in the time-temperature embrittlement diagram above 575°C was pointed out. Procedure The same heat of SAE 3140 steel was used as in the previous work, and experimental methods were the same. All blanks were austenitized 1 hr at 900°C and water, quenched. Groups were then tempered 1 hr at 675"C, water quenched, and given embrittling treatments for times of 5 min to 240 hr at 675" to 600 °C, as shown in Table I. Other groups, after the temper and quench, were embrittled 48 to 1440 hr at 550°C. Another series was tempered 240 hr at 675"C, quenched, and held for various times at 650" to 375°C (Table 11). For comparison, a series was tempered for these same times at 700°, 675", and 650°C (Table 111). The Ae, temperature for this heat of steel had been determined as approximately 690°C;1*a the treatments at 700°C were introduced to determine the effects of tempering in a range where a little austenite would fonn. A large number of other treatments, involving holding at two temperatures in succession after the temper, and occasionally slow cooling or heating, were also studied. These treatments are listed in the tables. Austenitizing was done in air; all subsequent treatments were in salt. Blanks were always water quenched after the last treatment. The heat-treated blanks were machined to standard V-notch Charpy specimens. A transition curve for each group was obtained by breaking the specimens at various temperatures on a 217 ft-lb impact machine having a striking velocity of 16.8 fps, and plotting the observed percentage of fibrous fracture vs the test temperature. From this plot, the transition temperature was taken as the lowest temperature at which the fracture appeared 100 pct fibrous; its accuracy is estimated as +5"C. Generally, hardness was measured on every bar. Since a decrease in hardness itself seems to decrease the transition temperature somewhat, a correctiona of —0.28"C per Bhn was applied to permit comparison of the transition temperatures on a uniform basis of 24 Rc. The transition temperature and hardness results are given in Tables I through VI. Where overlap of earlier work1.' occurred, data were combined.

Jan 1, 1958

By J. A. Fellows, Earnshaw Cook, Howard S. Avery

HEAT-RESISTANT alloys of the higher nickel and chromium ranges have been empirically developed through the practical experience of the past two decades to a position of significant industrial importance. Few quantitative metallurgical data have been published, however, that could be related directly to engineering specifications and design. Inadequate information led to the inauguration, in 1934, of a research directed toward a better understanding of the properties and performance of these steels at temperatures between 1400° and 2000°F. Investigation was concentrated upon the 26 per cent Cr:12 per cent Ni type, which owes its extensive application to an excellent combination of economy, strength and surface stability at elevated temperatures. The requirements of the oil-refining industry have been prominent in influencing the scope and evolution of the program. Creep strength at the maximum allowable deformation ranges has been employed to evaluate the merits of these alloys. Permissible elongation rates vary from 1.0 per cent in one million hours for turbine blades to 1.o per cent in ten thousand hours for tube supports and heating-furnace equipment. Throughout this paper, the limiting creep stress (L.C.S.) for a given temperature has been defined as the stress that will produce a uniform elongation rate (stage II) of one per cent in ten thousand hours as extrapolated from rates per hour or tests of less than two thousand hours duration. Certain current specifications require a minimum L.C.S. of 1600 lb. per sq. in. at 1800°F., of 3600 lb. per sq. in. at 1400°F., and include a tensile acceptance test at room temperature, after aging for 24 hr. at 1400°F., as a measure of embrittlement in service. An elongation of 4 per cent is considered satisfactory for general use, while a minimum of 9 per cent is prescribed on occasion. Many differences of opinion concerning the properties and performance of these alloys appear to result from their sensitivity to unappreciated variations of chemical analyses which, for example, may change their L.C.S. from 3500 to 350 lb. per sq. in. at 1800°F. Within broad chemical limits, it is possible to balance the six or more important elements present to attain desirable properties with a number of different combinations. One method for adjusting the composition has been described under the sponsorship of the Alloy Casting Institute,1 in which, by maintaining a substantially austenitic* alloy, optimum creep strength and minimum tendency to embrittle after aging are expected. Unless, however, the limits are undesirably dose, it has not been possible to ensure a moderate range of strength and of ductility by any chemical specification alone. There is a definite need

Jan 1, 1942

By M. Hozayen, E. S. Radwan, P. A. Nawrocki, A. Jebbouri

"A major geomechanical study was conducted for one of the UAE onshore oil fields with the purpose of studying reservoir rock properties and stress distribution, based on which a 3D coupled reservoir geomechanical model was built. This model was later used for wellbore stability analysis and for analyzing the effect of fractures on future reservoir production performance, including fracture deformation and permeability evolution occurring due to reservoir depletion and resulting changes in local stress field. The subject of this study was a complex fractured Upper Cretaceous carbonate reservoir characterized by high degree of heterogeneity, both vertically and laterally. Wellbore instability related drilling problems were encountered while drilling the wells in this field. The problems were mainly in drilling the horizontal wells, including breakouts and mud losses. Experimental results of laboratory tests are summarized in this paper whereas wellbore stability analysis and formulation of a 3D geomechanical model that was built for that purpose is summarized in a sister paper (Part II).A suite of tests reported includes tensile strength, uniaxial and triaxial compression and permeability under stress at simulated reservoir conditions. All tested rocks have been grouped into twelve test units and reservoir geology, rock types and challenges related to designing a viable sampling and testing program for a big reservoir are discussed first followed by sample selection criteria and details of the testing program. All test units showed brittle behavior at zero confinement and some samples showed similar behavior at low confining stresses. With confining stress increase, the behavior gradually turned to plastic but some samples showed features of ductile behavior even at low confinement.Obtained experimental data have been summarized in the form of strength criteria and correlations. The Mohr-Coulomb strength equations were obtained for each test unit and also for the averaged values. It was noticed that triaxial compressive strength (TCS) increases with decreasing porosity or increasing density but their influence on TCS is getting smaller with confining pressure increase. Good correlation of porosity and density with Young’s modulus, Poisson’s ratio, unconfined compressive strength (UCS), friction angle, cohesion and tensile strength has been noticed and there was an increasing trend between the confining pressure and TCS. Rock type (mud or grain supported) was not influencing the TCS as much as porosity and density and the two lithologies encountered affected TCS approximately in the same way. These results and correlations are summarized and explained in this paper. They were further used in the numerical modelling part (Part II) of this paper, Hozayen et al. (2015). It is also concluded that rock lithology is not a decisive factor and mechanical properties of tested rocks should be rather considered dependent on porosity and permeability. This helped greatly in reducing the number of tests that had to be performed."

Jan 1, 2015

By Leonard G. Austin

INTRODUCTION Run-of-mine (ROM) coal generally falls into two major groups: that from underground mining (continuous mining machines) and that from strip mining. Continuous miners produce a finer product and strip mining a coarser product that is crushed to produce the desired size. Further size reduction depends on the proposed use or uses for the coal. For example, for pulverized coal power plants as a rough general rule, the coal is ground or pulverized to 80% less than 200 mesh (0.075 mm) before it is blown into the boiler furnace as a coal-air suspension. For solvent-refined coal processes, the desired size is about <30 mesh (< 0.60 mm); in fluidized bed uses, the coal is typically < 8, in. (< 1.6 mm); for Lurgi pressure gasifiers, the desired size is 1 to 2% in. (25 to 63 mm). Coal preparation plants typically work with a coarse size fraction of 6X 1/14 in. (150X32 mm). The past decades has shown a steady increase in the tonnage of coal cleaned, 1 but it seems probable that the next decades will produce much wider applica- tion of deep coal cleaning before use and that the stages of crushing and pulverization from ROM coal to end use will be integrated with coal cleaning processes. Since different cleaning processes work better with different ranges of coal size and the degree of cleaning possible is intimately connected with the size of coal, a systems design engineer will need as much information as possible concerning the size distributions produced by different types of machines and how these can be modified by different ways of operating the machines. In general, the following questions will be of concern: 1.What type of crusher or grinder is best, or most satisfactory, for reducing a given feed size and type of coal to a desired product size? Frequently, the desired product is smaller than some nominal size, but with as few fines as possible, or the fraction in some size range has to be as high as possible. 2. How big does the machine have to be for a given throughput rate? 3. How much electrical energy (or its equivalent) is required per ton of product? 4. How does the size distribution vary with change in throughput rate, and is a control scheme necessary or desirable? 5. Can the size distribution be readily varied if desired? 6. What is the optimum way to operate a machine in a given system? This section will emphasize certain general principles which guide us in answering these questions. PARTICLE SIZING Since particle size and size distribution are the raw information with which we work, it is worthwhile to review the terminology used. In this regard, see

Jan 1, 1991

By F. R. Hensel

PuRe silver and silver-lead alloys have been studied as to their suitability for bearing~.&apos; A review of the properties of thallium and the silver-thallium constitutional diagram was made by the author to analyze the possibilities of silver-thallium compositions for antifriction materia1s. t The silver-rich end of the diagram as reported in the literatureg-" was found to be sketchy and it was necessary to carry out corisiderable experimental work to arrive at definite conclusions. Some of the results of this work are reported in this paper. Test Materials In the beginning of the work, only fused alloys were investigated. Later, research Table i.—Composition of Fused Silver-thallium Alloys Tested for Antifriction Properties Percentage Alloy No. of Thallium 1533...................... 0.48 1534.................... 1.06 a31 HT................... 2.04 231....................... 2.10 232 HT................... 3.83 Balance 232....................... 4.07 Silver 233 HT................... 5.86 a33....................... 6.38 a34....................... 9.84 a34 HT................... 10.07 was carried out on electroplating methods and diffusion processes. In preparing the fused alloyst care was taken to exhaust the toxic fumes caused by the thaillium content. The compositions of the series of fused alloys are listed in Table I. The silver-thallium alloys were melted in clay-graphite crucibles and cast into preheated steel molds of 3/4-in, diameter. In the cast condition, they showed a cored structure, as indicated by the micrographs of Figs. I to 3. The etching reagent used was a mixture of 2 grams K2Cr207, 8 C.C. H2S04, and IOO C.C. H20. The cored structure is unsatisfactory for the type of corrosion resistance required for bearing applications, and homogenizing experiments were carried out at various temperatures, the results of which are shown in Figs. 4 through 8. The alloys with a lower thallium concentration, which were heated for 2 hr. at 525°C show an almost completely homogenized solid solution type of structure. With higher thallium concentration, the homogenizing temperature was dropped to 475OC. to eliminate the formation of a liquid phase. It is evident that heating for 2 hr. at this temperature did not iesiilt iii complete elimination of the cored structure. As would be expected, cold-working of the cast structure is an expedient in establishing equilibrium conditions. The fine homogeneous grain structure shown in Fig. 7 corresponds to the cold-worked area under the Rockwell ball penetration when the hardness was taken before heat-treatment. A detailed structural study was made on a cast silver-thallium alloy containing 3.67 per cent thallium. Three micrographs (Figs. 9, 10 and 11) show the transition

Jan 1, 1946

By F. R. Hensel

PuRe silver and silver-lead alloys have been studied as to their suitability for bearing~.&apos; A review of the properties of thallium and the silver-thallium constitutional diagram was made by the author to analyze the possibilities of silver-thallium compositions for antifriction materia1s. t The silver-rich end of the diagram as reported in the literatureg-" was found to be sketchy and it was necessary to carry out corisiderable experimental work to arrive at definite conclusions. Some of the results of this work are reported in this paper. Test Materials In the beginning of the work, only fused alloys were investigated. Later, research Table i.—Composition of Fused Silver-thallium Alloys Tested for Antifriction Properties Percentage Alloy No. of Thallium 1533...................... 0.48 1534.................... 1.06 a31 HT................... 2.04 231....................... 2.10 232 HT................... 3.83 Balance 232....................... 4.07 Silver 233 HT................... 5.86 a33....................... 6.38 a34....................... 9.84 a34 HT................... 10.07 was carried out on electroplating methods and diffusion processes. In preparing the fused alloyst care was taken to exhaust the toxic fumes caused by the thaillium content. The compositions of the series of fused alloys are listed in Table I. The silver-thallium alloys were melted in clay-graphite crucibles and cast into preheated steel molds of 3/4-in, diameter. In the cast condition, they showed a cored structure, as indicated by the micrographs of Figs. I to 3. The etching reagent used was a mixture of 2 grams K2Cr207, 8 C.C. H2S04, and IOO C.C. H20. The cored structure is unsatisfactory for the type of corrosion resistance required for bearing applications, and homogenizing experiments were carried out at various temperatures, the results of which are shown in Figs. 4 through 8. The alloys with a lower thallium concentration, which were heated for 2 hr. at 525°C show an almost completely homogenized solid solution type of structure. With higher thallium concentration, the homogenizing temperature was dropped to 475OC. to eliminate the formation of a liquid phase. It is evident that heating for 2 hr. at this temperature did not iesiilt iii complete elimination of the cored structure. As would be expected, cold-working of the cast structure is an expedient in establishing equilibrium conditions. The fine homogeneous grain structure shown in Fig. 7 corresponds to the cold-worked area under the Rockwell ball penetration when the hardness was taken before heat-treatment. A detailed structural study was made on a cast silver-thallium alloy containing 3.67 per cent thallium. Three micrographs (Figs. 9, 10 and 11) show the transition

Jan 1, 1946

By James F. Kelly

"Research and development on the production of liquid fuels from coal is rapidly expanding worldwide. AImost every industrialized country is engaged in coal liquefaction research and process development. In Canada, the federal government, through CANMET, is actively supporting coal liquefaction research and development in a number of areas.A review of the basic principles and some of the processes in the production of liquid fuels from coal is presented with reference to the characteristics of the Canadian coal resource base. An overview of the CANMET coal liquefaction contract program is presented and specific results from the batch autoclave studies carried out with Saskatchewan lignite and Nova Scotia high-volatile bituminous coals are discussed. The development of a laboratory-scale continuous-flow coal liquefaction unit at the Energy Research Laboratories of CANMET to investigate the co-processing of coal and bitumen/heavy oil is also described.IntroductionThe CANMET coal liquefaction program is made up of two interrelated parts. The first part consists of the research and development work being carried out at the Energy Research Laboratories near Ottawa, Ontario. The second focuses on contracted research and development as part of the Coal Conversion Program of Energy, Mines and Resources Canada. The long-term objective of the liquefaction program is to contribute to Canadian liquid fuels production through the definition, research, development and demonstration of different coal liquefaction technologies for the Canadian marketplace.In coal liquefaction, the main objective is to produce liquid hydrocarbons with a higher hydrogen-to-carbon (HIC) ratio than the coal feedstock while reducing heteroatom (S,O,N) content, removing mineral matter and minimizing gas production. Typical atomic HIC ratios for a variety of Canadian fossil fuels are shown in Figure I. Canadian coals have about 500/0 of the HIC ratio present in tar sand bitumens and heavy oils and only about 20% of the ratio available in methane. In general, the cost of synthetic fuels production is related to the cost of hydrogen and, therefore, to the increase of HIC ratio between feedstock and products. On this basis, the production of liquid fuels from coal would be expected to be more costly than liquid fuels produced from bitumens and heavy oils. However, for mined tar sands and some heavy oils this difference tends to be offset by the large sand content (>90 mass %) of tar sand bitumens and the increased production costs of viscous heavy oils. For example, it can easily be shown that for equal weights of distillate <525°C) yield, current coal liquefaction processes required between two and three times less mined coal by weight than the mined tar sand s required for the most technically advanced processes proposed for bitumen upgrading."

Jan 1, 1981

INTRODUCTION From its beginnings in the first decade of this century, flotation has gradually moved to a predominant role in mineral separation. There are several reasons for this, the continuing trend toward treat¬ment of lower-grade and more finely disseminated ores being the major one. Not only has this been true for sulfide ores to which the process was first applied commercially, but also for most nonsulfide ores as well. A second factor has been the broad applicability of the process with respect to particle size; it is effective from 8 to 10 mesh to below 10m. Finally, more so than for any other separation process, flotation has almost no limitations in separating minerals. Gravity, magnetic, or electrostatic processes are either applicable to particular minerals, or to a restricted number of mineral combinations. Flotation, on the other hand, can utilize the wide range of surface chemical differences among minerals, and an equally wide range of reagents. The recent availability of selective flocculation capabilities on a commercial scale as an adjunct to flotation should remove one of the limitations to the process in the very fine particle range. History Although flotation was anticipated in a 19th century patent to Haynes, its first significant industrial uses were in the early 20th century in Australia. According to Hoover,&apos; the Pottter-Del-prat pro¬cess had a "measure of success" at Broken Hill&apos;s Block 14 mine in 1905-1906, and was definitely successful at the BHP Mine, where it produced 80,000 tpy of zinc concentrates. Both the Mineral Separa¬tion and the Elmore processes had early trials in Australia also, with both successes and failures. The first application in the United States was in 1911, when the Hyde process was used by the Butte and Superior Copper Co. on a zinc ore in Montana. By 1916 Hoover could list 46 applications to copper, lead, and zinc ores, mainly in the United States. Ten years later Taggart2 listed almost a thousand patents covering processes and reagents which with few exceptions laid the foundations for modern practice. Included were: sulfidizing of oxides; leach-precip¬itation-flotation; cyanides, sulfites, sulfides, and oxidants for selective depression of sulfides; starch, tannin, and glue as depressants; and xanthates, dithiophosphates, and oleic acid as collectors. Within an¬other 20 years, all of these were in commercial use along with amines for floating silica from phosphates, and synthetic frothers were com¬peting with pine oil and cresylic acid. Flotation machine development followed a different course. Of the 170 patents listed by Taggart in 1927,1 those incorporating film and oil flotation-about a third of the total-were no longer then

Jan 1, 1985

By F E. Grader

A linear motor properly wound can serve as a mechanism for separating paramagnetic sulphide minerals, like pyrrhotite, from other sulphides and associated gangue minerals. The effectiveness of separation depends on the energising current of the separator, the frequency of the ac cycle, and the particle size of the minerals. The speed of travel of the minerals over the surface of the separator is also a function of particle size, and appears to be constant. The movement of pyrrhotite, magnetite and iron filings of comparable size fraction (150 ¦m +74 ¦m) on the linear motor surface has been observed using a cine camera. An attempt, has been made to give a theoretical basis for the movement of the particles by calculating the minimum electrical energy required to move them. Further, the rate of decay of magnetic moment of the particles has been estimated for magnetite and it has been found that sufficient residual magnetism existed in the particles after they had been exposed to the first half of an ac cycle for them to have like polarity with the second half of the cycle. The particles are therefore repelled from the motor surface every second half of the cycle. This repulsion due to remanent magnetism is the probable cause of particle movement over the linear motor surface.

Jan 1, 1980

By C. J. Farrow, M. J. Smith

"Bechtel has managed a number of test programs to establish autogenous grinding circuits and size mills for a variety of ores.This paper outlines the procedures whereby bench scale and pilot plant tests are used to select the most efficient circuit to grind the range of ore types likely in the mill feed.Five examples are given. One example traces the development of a pilot plant program; it shows how bench scale Work Indices provide a target for the grinding power requirement of an ore and relates how pilot circuits are changed as a result of interpreting the results from preceding tests. The other four examples relate the interpretation of the test results to provide design data; they illustrate a number of phenomena which have been observed.INTRODUCTIONConventional crushing and grinding circuits can be specified from bench scale test data such as Bond Work Indices. Bond Indices have been correlated to a large number of rod and ball mills and by applying appropriate factors, mills can be sized from the Work Index.For autogenous or semi-autogenous grinding circuits, bench scale tests are not sufficient to be able to specify the circuit and size of the mills for a commercial plant. It is necessary to run a series of pilot plant tests to determine how the ore behaves."

Jan 1, 1982

Recently published extensions to the mill-dump cutoff grade theory for joint open pit-concentrator operations lead to equations that must be simultaneously satisfied as a necessary condition for an optimal operating policy. These equations are parametrically dependent upon ore quality parameters, other than grade, relating to the ease of recovery of the disseminated mineral in the concentrator. Since it is not possible to treat quantities of ore corresponding to the size of selective mining units separately in the concentrator some mixing is inevitable and often deemed desirable in the interest of homogeneity of mill feed. This renders the calculation of cutoff grades for individual mining units futile; mining units must be grouped to form larger parcels that can be dealt with separately. In doing so an opportunity cost may be incurred; the loss of potential benefit that would result from such separate treatment. This matter is considered from a theoretical, qualitative, point of view. A numerical example then shows that a significant variability in the quality parameters can be tolerated without incurring such opportunity cost, provided sufficient knowledge is available concerning the distribution and effect of these variables to enable the use of effective mean values of these parameters in the cutoff grade calculation. Lack of such knowledge can have major consequences for the economics of the operation.

Jan 1, 1981

Detailed characteristics of gold from Pliocene auriferous quartz gravels from Waimumu (Southland) have been studied using a combination of optical microscopy, energy dispersive microprobe analysis and scanning electron microscopy techniques. The gold at Waimumu is classified as either: 1. detrital gold, or 2. irregular gold. A number of different morphologies a recognisable within each &apos;gold type&apos;. Evidence is given for an predominently authigenic origin for some of the gold at Waimumu.

Jan 1, 1987

By Woodcock J. T

A sulphide ion selective electrode (ISE) is suitable for control of sodium sulphide additions in flotation because it has a rapid response to changeS in S2- concentrations, can indicate -low concentrations at differentpH values, suffers from few interferences, and is robust enou&apos;gh to use in a pulp. Three sulphidization techniques were studied using the lSE electrode for measurement and/or control of S2- levels. Metallurgy was assessedfrom concentrate grades and copper recovery.With slug additions of sodium sulphide, sulphidizing conditions were poorly defined and reproducibility tended to be poor. Although acceptable metallurgy could be achieved by multiple additions, sodium sulphide consumption was high.Controlled potential sulphidization readily gave good metallurgy. The optimum potential of the lSE for sulphidizing was about -500 mV versus SCE, but depended on sulphidization and flotation times; suitable times were3 and 5 min respectively for three to five stages. Application of this technique to previously untested ores gave good metallurgy in a first test in spite of variation by a factor of three in the sodium sulphide requirements ofthe ores.Simultaneous sulphidization and flotation was satisfactory when conducted at an lSE potential of -450 mV versus SCE. Mixed cha!copyrite-oxide copper ores responded satisfactorily.Besides optimizing sulphidization conditions it is also necessary to optimize xanthate additions (e.g. by measuring xanthate residuals).

Jan 1, 1978

By A. W. Schlechten, W. J. Kroll

As this paper is written, the only method for the commercial production of lithium metal is by the fusion electrolysis of LiC1-KC1 mixtures, as first proposed by Gunkz.2 The details of the industrial process have not been made public hut Osborg8 stated that an efficiency of more than 90 pct is obtained with a lithium metal recovery above 95 pct and that the metal is 99.5 pct pure. Pletenev9 gave a power consumption of 66 kw-hr per kilogram of lithium metal produced with a salt consumption of 9 kg of LiCl and 0.4 kg of KCI. Pletenev&apos;s figures indicate a somewhat lower recovery than that given by Osborg. In a recent report on&apos; German lithium plants, Motock7 gives figures that are also less favorable than those reported by Osborg. At the German plants the lithium recovery in electrolysis was only 83.4 pct, with a power consumption of 140 kw-hr per kilogram of lithium. The metal averaged only 97 pct pure, with sodium and potassium as the chief impurities. The presence of SO2, SO3, SiO2, Ba, Ca, and appreciable amounts of Na and Fe2O3 were especially disturbing in the electrolysis, and it was necessary to run the cell for some time to eliminate most of these impurities and condition the bath. It may be noted here that most of these impurities do not interfere with a thermal reduction process. These facts show that the present method of producing lithium is fairly efficient and would suggest that other methods could not compete. However, fusion electrolysis has certain drawbacks, such as the necessity of supplying costly, low-voltage direct current and of collecting and processing the anodic chlorine if it is not to be wasted. An even greater disadvantage is that lithium chloride must be used for an electrolyte. It is one of the most expensive salts of lithium, since it cannot be produced in anhydrous form by precipitation from aqueous solution, as is done with LiF or Li2CO3. The reduction of lithium by a vacuum process similar to the ferrosilicon method for the production of magnesium would have certain advantages. Small units such as Pidgeon retorts, would give flexibility of production to meet demand, and a small plant would require moderate capital outlay. There is a possibility of using idle Government-owned magnesium plants for such purposes. The raw materials needed for vacuum thermal reduction would not have to be extremely pure, Director, with respect to the iron and calcium Content. This paper describes a series of experiments to determine the effectiveness of various agents for the reduction of lithium compounds. The investigation is part of a program of vacuum metallurgy con-

Jan 1, 1949