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By Frank C. Schrader

Page Introduction.............................. 196 Geology of the District......................... 196 Ore Deposits of the District....................... 198 Gcncral Description........................ 198 The Cerbat Mountains Group................... 199 General Description...................... 199 Tennessee Mine....................... 203 Midnight Mine........................ 203 Mineral Park........................ 204- Golconda Mine........................ 204 Other Ore-bearing Districts.................. 205 Lost Basin District ...................... 205 The Black Mountains Group.................... 206 Tom Reed-Gold Road District...................... 208 General Dcscription........................ 208 Development........................... 209 Topograplly............................ 210 Geology.............................. 210 Ore Deposits........................... 213 General Dwcription...................... 213 Zones.......................:....215 Structure of Ore Shoots.................... 217 Gold Road Mine ......................... 218 General Description...................... 218 Geology........................... 218 Ore Deposits......................... 219 Tom Reed Minc......................... 222 General Description..................... 222 • Ore Deposits.......................... 222 Development......................... 223 Character of Ore....................... 224 Other Mines........................... 224 Fields Similar to the Ton1 Reed-Gold Road District......... 227

Jan 1, 1917

By L. D. Mullins, W. R. Bartlett, R. H. Barham, W. L. Wahl

This paper describes an electrical model and its applicution to the analysis of four reservoirs in Saudi Arabia. The model has 2,501 mesh points and represents 35,000 sq miles of the Arab-D member. Details of modeling such as mesh size, control problems and standards of performance in matching reservoir history are discussed. The particular performance match achieved for the Arab-D rnember is presented. Details such as permeability barriers, aquifer depletion and iwerference between oil fields are given. The performance match realized in the Abqaiq pool is presented in detail. INTRODUCTION The resistor-capacitor network and associated control equipment described in this paper comprise an electrical analog of a reservoir system. Similar equipment has been used to study the transient response of reservoirs for many years. The unique feature of the model and application to be described is the extremely large size of the model and reservoir system, and the detail observed in simulating the reservoir with the model. The Arabian American Oil Co. first became interested in analog computers for simulation of oil reservoirs in 1949. Since that time, several models have been developed, each more elaborate and refined so that the reservoir system might be more closely simulated. The current model is the latest in a series designed, built and operated by the Field Research Laboratory of Socony Mobil Oil Co. in collaboration with Aramco. It has been and continues to be used to study the regional performance of the Arab-D member limestone reservoir. The Arab-D member is one of the Middle East's most prolific producing horizons.. THE MODEL The theory of simulating a reservoir system with an electrical system has been presented in the literature.1-5 Therefore, this paper will not discuss the theoretical aspect of the problem except to point out the correspondence between the fluid system and electrical system, as shown in Table 1. In general, the complete model is made up of input devices, output devices, central control and a resistance-capacitance (RC) network. At times, the RC network alone is referred to as the "model". However, it should be evident from the text which meaning is attached to the word "model". A discussion of the equipment follows. THE RESISTANCE-CAPACITANCE NETWORK The RC network consists of 2,501 capacitance decades interconnected through 4,900 resistance decades. The components are arranged to form a rectangular network of 2,501 mesh points in a 41- X 61-mesh array. Imposing the mesh grid system on the continuous reservoir system divides the reservoir into discrete areal segments. These discrete segments may be of various sizes. More precisely, the mesh size need not be uniform throughout the model. The RC network is fabricated in two sections which are connected at the top. An inside view of the "tunnel" formed by the two sections is shown in Fig. 1. The height and width of the tunnel are shown in the figure. Numerals appear along the bottom and along the back opening of the tunnel. These numbers denote the x and y co-ordinate positions of mesh points. Fig. 2 presents a rear view of one-half the model. The length dimensions of the model, as well as a rear view of the capacitor decades, are shown in this figure. The control dials used in adjusting the resistance and capacitance values on the model can be seen in the enlarged portion of the model shown in Fig. 3. The electrical capacity at any mesh point can range from 0 to 1.0 microfarads set to the nearest tenth of a microfarad. The electric resistance connecting any two mesh points can range from 0 to 9,990,000 ohms set to the nearest 1,000 ohms. External capacitors may be added to any or all mesh points if the need arises. The values of electrical resistance and capacitance are adjusted manually by manipulating the two types of decade units. INPUT EQUIPMENT A considerable quantity of equipment is used to control the input to the RC network. These input devices are

By John C. Sawyer

A brief review is given to show that catastrophic oxidation of stainless steel in the presence of lead oxide is similar in many respects to catastrophic oxidation as caused by MoO3 and V2O5, Experimental data are presented to show that lead oxide accelerates the normal oxidation process of stainless steel by chemically altering the normally protective oxide film formed on the base metal. Data are given to show that similar reactions occur during oxidation of stainless steel in the presence of MOO3,and V2O5. THE mechanism by which pure metals oxidize at high temperatures has been the subject of intensive research for many years and much has been accomplished towards understanding the processes involved. The mechanisms by which alloys oxidize have also been investigated, but due partly to the fewer number of investigations and partly to the complexity of the oxide systems present, available knowledge is not as extensive as with pure metals. When oxidation processes are further complicated by atmospheres contaminated with sulfide, halide, or oxide vapors, the knowledge of fundamentals becomes meager or altogether lacking. Thus, it is not surprising to find that the catastrophic oxidation of stainless steels in metal oxide vapors of MOO, and V2O5 is not a well understood phenomenon despite the fact that a number of investigations have been undertaken. The literature in dealing with the subject of catastrophic oxidation is primarily concerned with the effects of MOO3 and V2O5, but does mention that other metal oxide vapors, one of which is lead oxide, appear to promote a similar type of accelerated oxidation. While this latter effect is virtually unknown, the deleterious effect of lead oxide is of considerable commercial importance, as it is believed to be one of the fundamental reasons for exhaust-valve failure in gasoline engines. For this reason studies have been in progress for many years attempting to better understand the mechanism involved. Modern exhaust-valve alloys"2containing 20 to 25 pct Cr plus nickel and/or manganese are in effect high-grade austenitic stainless steels exhibiting ex- cellent oxidation resistance in air at exhaust valve operating temperatures of 1100° to 1700°F; yet these same alloys are prone to corrode during engine service because of the conditions attending their operation. These conditions are such that the valves become coated with deposits of complex lead compounds mainly derived from gasoline additives of tetraethyllead, ethylene dibromide, and ethylene dichloride. Literature searches3-7 and discussions with various investigators show that considerable difference of opinion exists as to the nature of the lead-bearing deposits found on the surface of exhaust valves and the atmospheres to which they are subjected; yet, all seem to generally agree that corrosion, a gradual transformation of alloy to nonmetallic products of corrosion, is a consequence of the presence of lead compounds. This majority opinion seems to be substantiated by laboratory engine tests which show that corrosion does not occur to any appreciable extent when lead-free fuels are used. The first observations of catastrophic oxidation reported in the literature were probably made by pfeil,8 but it was Leslie and Fontana9 who undertook the first detailed study of the phenomenon. Their work was chiefly centered on the acceleration of oxidation which took place when stainless steels containing more than 3 pct Mo were heated in air with restricted circulation. These investigators reported that the presence of other oxides near the surface would further accelerate the rapid oxidation which occurred. While they recognized that the effect was attributable to the presence of molybdenum, it was Rathenau and Meijering" who emphasized the fact that the presence of molybdenum in the alloy was incidental to the presence of MOO3 vapor in the atmosphere surrounding the specimens. Evans,11 as well as Cunningham and Brasunas 12 studied similar

Jan 1, 1962

By L. V. Pirela, S. M. Farouq Ali

Some interest has been expressed recently in the application of solvents in conjunction with a thermal drive, such as a steamflood. At least one field project of this type has been reported. This paper makes the first attempt to provide some of the basic information necessary for choosing a solvent for such an application. Results of displacements conducted at elevated temperatures are also discussed. This paper shows that, in the case of alcohol-hydrocarbon-water or brine ternary systems, the system miscibility may increase, decrease, or both increase and decrease within the same system when the temperature increases. The distribution coefficient was consistently found to increase in favor of the oleic phase with an increase in temperature, which is advantageous from the standpoint of oil recovery. Results of solvent displacements in a sandstone core showed that even a relatively small temperature effect in the favorable direction (increase in miscibility and distribution coefficient) can lead to a 50 percent increase in oil recovery. On the other hand, if the system miscibility decreases with the temperature, even though the distribution coefficient increases, the oil recovery at the higher temperature may not increase. INTRODUCTION Miscible displacement has been the subject of many investigations. Miscible-phase solvent flooding, employing solvents such as alcohols that are miscible with both oil and water, has received considerable attention. Investigations conducted by Gatlin and Slobod,l Taber, Kamath and Reed,2 Holm and Csaszar,3 and Farouq Ali and Stah14 have helped in understanding the mechanism of solvent flooding. While the use of alcohols and similar solvents as oil recovery agents is economically unattractive, these solvents nevertheless provide a means of understanding the mechanistic aspects of important miscible-phase oil recovery processes such as the Maraflood process (discussed by Gogarty5). As shown by Taber et a1.,2 the phase behavior of a solvent-oil-water system is of .utmost importance in determining the efficiency of the oil displacement. This paper makes the first attempt to obtain the ternary phase behavior data for nine alcohol-hydrocarbon-water/brine systems at elevated temperatures. Results of core tests at elevated temperatures are also presented which corroborate the effect of temperature on oil recovery, as judged on the basis of phase-behavior data. The use of solvents at elevated temperatures has been suggested earlier by Farouq Ali.6 At least one field test of this type has been reportedO7 With the widespread use of thermal recovery techniques, it is possible in some situations (especially in steamflooding) that the use of a suitable solvent in conjunction with the heat carrier may be economically feasible. This paper attempts to provide some of the basic information needed for judging such feasibility. LOCATION OF THE PLAIT POINT The phase behavior of a typical ternary system consisting of a solvent, hydrocarbon and brine (or water) can be represented by a triangular diagram such as the one shown in Fig. 1 (for temperature TI). Point Pon the binodal curve represents the plait point, being the limit of tie lines such as Y1 Y2 The compositions of the coexisting oleic and aqueous phases are given by points Y2 and Y1, respectively, for any mixture composition along Y1Y2. The characteristics of ternary diagrams have been discussed by Findlay8 and others. Taber et aL3 have shown that the position of the plait point in a particular ternary system plays the decisive role in determining whether or not theoleic phase would be displaced in a continuous manner during an alcohol displacement. The area above the binodal curve also is important, since it represents

Jan 1, 1969

By Frank Doxey

AT Dominion Steel & Coal Corp. it has long been recognized that continued mechanization of mine operations is necessary in the Pictou, Cumberland, and Sidney coal fields of Nova Scotia. The varied physical conditions in these fields call for special consideration of individual cases before planning is finalized. Because standard equipment cannot be procured which would operate successfully, many experiments have been necessary over the years to keep pace with the progress made in other countries. There are two mines, producing 2000 tpd, located in the Pictou coal field. The field is badly distorted and crossed by many faults. Seams are highly inclined and irregular and vary in thickness from 5 to 40 ft. Entries are difficult to maintain because of squeezing of the coal. ribs and movement of the roof and pavement. Output from the three operating mines in the Cumberland field is 3000 tpd. The field is highly inclined, inclination varying from 12° to 32°. Overlying beds consist of shales and massive sandstone lenses of extreme toughness and are responsible for bumps when the stresses are relieved by extraction. At greatest depth these are among the deepest coal workings in the world. Depth of cover ranges from 2300 to 4000 ft. This prohibits room-and-pillar working and necessitates longwall operation. Working of contiguous seams concurrently to maintain output increases the already difficult conditions. The Sydney field, with a frontage of about 30 miles, is the most important of the Nova Scotia coal fields. With the exception of one small area it is now wholly submarine. Output is approximately 21,000 tpd. Seams are 21/2 to 8 ft thick, and cover in the areas varies from 600 to 2300 ft, with an average of 1500 ft from sea bottom to the top of the seam. The seams dip in a seaward direction, pitches ranging from 6" to 4.0". The shoreline is the last place of entry to the seams and distance from the bank to the working faces is generally over 3½ miles, in some cases as much as 6½ miles. Ventilation is a problem and requires the construction of large permanent airways. Getting and Loading Coal: In 1925, in view of heavy pressures exerted by thickness of cover overlying the seams, roadways and pillars of the room-and-pillar system being worked began to break up and coal was lost. It was decided that a change in the method of extraction in areas with heavy cover was necessary, and experiments were made with many short walls and longwalls varying between 90 and 250 ft. Trial and error proved that the best operating length was between 400 and 500 ft, delivering all coal to the dip, with roadways to the face following a level course. The change-over was gradual, and the technique of roof control developed with the system, so that falls to the face are now very infrequent. An advantage of longwall mining is that it yields 95 pct extraction, especially important in coal seams of high quality or in seams where faults or disturbances restrict the workable areas. This percentage of extraction is based on the fact that the longwall advancing system takes development faces where pitch permits instead of driving headings and leaving roadway pillars. This system yields high tonnage during development and limits loss in extraction to duff left during operations. Accompanying disadvantages, on the other hand, are the heavy construction cost of main roadways and the necessity of driving all new flank face roadways through the gob. If the main roadways are driven through the solid, and large enough pillars are left on each side for protection against flank face weights, then the width of solid coal is approximately 1700 ft. This represents 10.6 pct of the coal available, or 89.4 pct extraction of the whole. These pillars, however, are of such size that they provide a useful pillar drawing area as a final operation of the mine. It may be that although the seam cannot be generally mined by the room-and-pillar method, it can be adapted to

Jan 1, 1955

By Ellis Clark

The mining town of Pribram is situated in Central Bohemia, on the western slope of the Heiliger Berg. 30 miles southwest from Prague. Birkenberg, the village ill which most of the shafts and ore-dressing establishments are situated, is built on a mountain of the same name. It is about a mile from Pribram, is 1700 feet above the sea, and is surrounded by graywacke rocks of Silurian origin, which arc intersectd by greenstone dikes, and in the southerly, southeasterly, arid southwesterly direction are bounded by granite. The graywacke formations consist on one side of graywacke sandstone and quartzite, and on the other of graywacke slate. These last are separated from the first in the immediate vicinity of the mines by a graywacke seam converted into clay. For many years this so-called clay seam (lettenkluft) was considered as a boundary of the ore deposits in both zones of graywacke. The graywacke formation L divided according to its harduess, structure, texture, and color, into fine, coarse, compact, slaty, whitish-gray, reddish-gray, and black graywacke. The miner divides the formation into four divisions. The first or lowest division, which is in contact with the granite, consists of a fine-grained dirty gray slate; the -second is a very fine to a very coarse schist, white to reddish-gray in color, and rich in quartz, but containing little mica; the third consists of a slate with a confused cleavage, which has a dirty gray, dark gray, and very often black color and is often graphitic in its composition; the fourth consists of a fine to coarse-grained graywacke schist, of a grayish-white or reddish-gray color, and rich in quartz. The cleavage in all four divisions strikes from northeast to southwest, and the dip is sometimes northwesterly, sometimes southerly, and often vertical. All four zones are cut through by a great number of diorite arid greenstone dikes and chimneys. The thickness of these dikes, which are of

Jan 1, 1881

By W. L. Phillips

Stress-train curves were obtained for single crystals of silver, Ag-5 pct Zn, Ag-10 pct Zn, and Ag-20 pct Zn tested in tension and shear at 78°, 195°, and 297°K. At room temperature the critical resolced shear stress gC increased, the length of' the easy-glide region increased, and the rate of' work hardening dwving easy glide decreased with increasixg zinc concentration. The change in the ratio of uc at room temperature to that at lower temperatures was significantly greater for the alloys than for pure silver. It was found that an increment in stress was necessary to continue slip when the slip direction was rotated 60 deg. The magnitude of this increment increased with strain for all alloys, increased with zinc concentration for a given strain, and for a given strain increased with decreasing -temperature. DESPITE its practical importance in improving the mechanical properties, alloying is not fully understood. Except for copper alloys few sets of systematic data are available. Von Goler and Sachs' studied the deformation of Cu-Zn alloys of increasing zinc content and found that, for dilute alloys, the critical resolved shear stress increases linearly with concentration. The range of easy glide was found to increase with increasing zinc content. Schmid and seliger,2 Sachs and Weerts,3 and Osswald4 have shown that with Mg-A1, Au-Ag, and Cu-Ni crystals, respectively, the critical resolved shear stress also varies linearly with concentration. More recently, Linde and his coworkers have investigated the variation of the critical shear stress of copper alloyed with tin , antimony, indium, germanium, silicon, nickel, and gold. They found that the slope of the critical resolved shear stress is related to the change of lattice parameter with composition, and also to the difference in Goldschmidt's atomic diameter between solvent and solute atoms. Garstone, Honey-combe, and creetham6 have shown that similar relationships can be found for small additions of silver, gold, and germanium to pure copper. They found that, with increasing silver or gold concentration, the critical shear stress for glide is increased by alloying, and so is the range of easy glide, which reaches as much as 60 pct for 0.50 pct Ag alloy and 0.62 pct Au alloy, as compared to 6 pct for pure copper of similar initial orientation. They also found that the alloying additions had little effect on the rate of hardening during easy glide, the slope scarcely changing with increasing alloy content. General secondary slip was detected only when the crystals began to harden rapidly. Although the slip appeared to be very fine in the early stages of deformation, coarser slip bands were formed towards the end of the extensive easy-glide range. The present investigation describes the deformation characteristics of single crystals of Ag-Zn containing different concentrations of zinc. Tension and shear testing were used for this study. EXPERIMENTAL PROCEDURE The method of growing the single crystals, sample preparation, and method of testing have been described in detail previously.' EXPERIMENTAL RESULTS A) Tension-Room Temperature. The initial orientations and stress-strain curves of single crystals of silver, Ag-10.0 pct Zn, and Ag-20.0 pct Zn are shown in Fig. 1. It is evident that there is considerable change in the stress-strain characteristics as a function of zinc concentration. The effects of zinc concentration on the critical resolved shear stress for both CU-zn8 and Ag-Zn alloys are summarized in Fig. 2. At all concentrations the resolved shear stress of the Cu-Zn alloys is higher than that of the Ag-Zn alloys. The resolved shear stress increases parabolically as a function of composition for both alloy systems. The length of easy-glide region increased with increasing zinc concentration, Fig. 3b). As the length increased the slope (do/de) decreased slightly, Fig. 3(b). Metallographic investigations demonstrated two significant effects of increasing zinc concentration. First, the amount of clustering increased, compare Figs. 4(a) and (b). The slip lines changed from uniform in pure silver to clustered in the Ag-20 pct Zn and Ag-30 pct Zn alloys. Second, the amount of cross slip decreased as the amount of clustering decreased.

Jan 1, 1968

By Oscar Marzke

STUDIES on the precipitation of a face-centered from a body-centered structure-a common occurrence in alloy systems-are essential to the development of a theory for the formation of segregate structures. The separation of the alpha phase from the beta of the copper-zinc system is an example of this type of precipitation. EARLIER STUDIES ON THE SUBJECT R. F. Mehl and 0. T. Marzke1 in 1931 presented a paper giving the results of some investigations carried out by them on the segregate structures produced when the alpha and gamma phases of the copper-zinc system and the alpha phase of the copper-aluminum system precipi-tate from the beta phases of these systems. They showed that the alpha phase precipitates as needles close to the [111] directions of the beta phase. In the discussion of that paper some doubt was expressed about the nature of the segregate. More investigations were undertaken to determine the character of the precipitate in the copper-zinc system and also the orientation relationship between the matrix and precipitate. The present paper gives the results of these investigations. Since the publication of the earlier paper, several other papers on this subject have been published in this country and abroad. Haneman and Schroder2 reported that the alpha phase precipitates as needles along the [111] directions of the beta phase and that these needles align themselves to form plates on the {111} planes of the matrix. Mathewson and Smith3 pointed out that the {111} plane does not contain the [111] direction and that it would be quite impossible, therefore, for needles in the [111] direction to form plates on the {111} plane. They suggested

Jan 1, 1933

By R. E. H. Pomeroy

EARLY in 1917, it became evident, owing to existing and pending market conditions, that a substitute for crude petroleum must be found for firing the smelter furnaces. After a review of the plants then existing, it was deemed advisable to depart from their practice and to adopt the following described system of distributing pulverized coal to the furnaces. The principal advantages of the proposed system, which influenced this decision, were: (1) Equal safety; no pulverized coal is stored at the furnaces; (2) greater ease of operation, furnace fires being controlled by regulating valves in burner branches, as in gas firing; (3) better organization; all machinery, including pulverized coal feed, is under one roof, and the organization is separate from the furnace department; (4) greater cleanliness; all machinery is under vacuum; (5) greater flexibility of application; the coal and air mixture can be piped where needed. The design of the plant is the result of the combined efforts of the local engineering staff and of the machinery manufacturers. Many new features were embodied in this design to insure greater safety, cleanliness, and efficiency of handling. After 14 months of continuous operation, the plant has proved entirely satisfactory. The building is of structural steel, covered with corrugated steel, with many windows and is painted light gray inside and out. The building floor is of concrete with ample drains to the sewer, and the building is equipped with fire and service water piping. Fig. 1 shows the east side of the building and the incline conveyor from the raw-coal bins.

Jan 2, 1920

By J. V. Emmons

IT has long been known that the outside skin of tool steel frequently exhibits properties widely different from the interior of the mass. Within the last few years it has been generally recognized that many of these properties were clue to surface decarbonization. The origin and effects of this altering of the composition have been but little studied. C. M. Johnson' arrives at the conclusion that, in annealing, "the most active agent in surface decarbonization is the rust or scale (present on the surface), which is actually reduced to metal at the expense of the carbon in the steel to which it adheres." W. H. Hatfield in his admirable paper, The Chemical Physics Involved in the Decarburization of Iron-Carbon Alloys,' has given us the most tenable theory of the removal of carbon from iron. While Mr. Hatfield's work has been principally clone in connection with the annealing of white cast iron to produce malleable castings, it is frequently applicable to the decarbonization of tool steel. The following equations which he proposed have been fully borne out by the author's experiments: 2Fe3C + 2CO2 = 3Fe2 + 4C0 2C0 + 02 = 2C02 Continuous 2C02 + 2Fe3C = 3Fe2 + 4C0 It is the purpose of the author to show, in a quantitative manner, the effect of various treatments in eliminating the carbon in tool steel. Some of the phenomena of the decarbonized surface will also be described, as well as the practical problems they present to. the manufacturer and user of tool-steel products.

Jan 9, 1914

By A. R. T. Denues

LIQUID-OXYGEN explosives commonly consist of a carbonaceous absorbent enclosed in a canvas wrapper and soaked with a liquid con-taining more than 90 mol per cent of oxygen. Investigation of these explosives in this country was initiated in 1917 by George S. Rice, then Chief Mining Engineer of the Bureau of Mines. The early development is summarized in two papers.1,2 Their characteristics, advantages and disadvantages were considered in a recent bulletin of the Bureau of Mines.3 Other publications of this Bureau4,5 treat the technology of these explosives and contain adequate references to pertinent literature. These investigations defined the properties of liquid-oxygen explosives and improved them greatly; however, an outstanding disadvantage is their high inflammability, a property of critical practical importance. These explosives as hitherto prepared are easily inflamed; the combustion resulting from an accidental ignition is particularly dangerous because of the ease with which it passes into detonation. For this reason the Bureau of Mines undertook a cooperative investigation, which has resulted in the development of fire-retardant treatment for the minimiza-tion or elimination of this hazard without materially impairing the explosive properties, including the ease of detonation. This presentation will offer a general description of the investigation and the outstanding results. Further phases will appear in subsequent short papers, and the entire investigation including the results of detailed experiments will be available in a forthcoming bulletin of the Bureau of Mines (Bull. 429). The effects produced by fire-retardant treatments of the carbonaceous absorbent and of the canvas wrappers were investigated separately, and the efficacy of combinations of these treatments with particular reference to the possibility of inflammation and to the development of detonation from inflammation was studied. The experimental explosive was pre-pared from a granular carbonaceous absorbent and the results described may be more or less unique for such a material. An extensive preliminary

Jan 1, 1940

By W. S. McCain, B. A. Wilcox, A. H. Clauer

The creep and creep-fracture behavior of a Ni-200-2Th0, alloy has been studied over the temperature range 816° to 1038°C and stress range 4000 to 19,000 psi Specimens having their axes either parallel or transverse to the final sheet-rolling direction were tested in air, and the apparent activation energy for creep was found to be 92 kcal per mole, regardless of specinien orientation. The stress dependence 01- the steady-state creep rate, was satisfied by where n depended on orientation; n = 9.7 for rrzaterial transverse to the rolling direction and n = 24.3 for material parallel to the rolling direction. In the latter case, the relation was also valid. The rupture strength of material parallel to the rolling direction was -1.5 times gveater than the transverse rupture strength. Several tests in vacuum revealed that here the creep rate was higher and rupture life lower than for comparable tests in air. THERE is an increased interest today in producing improved dispersion-hardened alloys for high-temperature structural applications. This had led various materials designers to modify existing alloys, such as thoriated nickel. One system that has received considerable attention is based on chromium additions to Ni-ThO2, with the obvious motive of improving the oxidation resistance. Another effect of chromium is that of lowering the stacking-fault energy, y, of nickel. For example, the addition of 30 wt pct Cr decreases y from -225 erg per sq cm for pure nickel1 to -70 erg per sq cm.' This decrease in y could have several effects on the deformation behavior. There is some evidence that cross slip of dislocations around Tho2 particles is a mechanism of tensile3 and creep4 deformation in TD Nickel (Ni + 2 vol pct ThO2) at temperatures below 0.5 the absolute melting point of nickel, T,. A decrease in ? by chromium additions should increase the difficulty of cross slip. Also it has been suggested that the high-temperature (T > 0.5Tm) rate-controlling creep process in "recrystallized" Ni-Tho2 alloys is the climb of edge dislocations over Tho2 particles.5 According to weertman6 a decrease in the stacking-fault energy should decrease the dislocation climb velocity resulting in a decreased steady-state creep rate. Thus, chromium additions to recrystallized Ni-Tho2 alloys would be expected to decrease the creep rate, all other conditions being constant. However, a difficulty arises when the stacking-fault concept is applied to high-temperature creep of dispersion-strengthened metals which are produced on a commercial or semicommercial scale. This occurs because the materials are processed so that they have a high-stored energy of cold work, and the other substructural effects could obscure any influence of stacking-fault energy per se. An example of an alloy with a high stored energy of cold work is TD Nickel bar. This material has a fibrous grain structure (1 I diam by 10 to 15 p long), and the structure is stabilized by the ThO2 particles. Annealing at high temperatures, e.g., 3 hr at 1300°C, causes no recrystallization or grain growth.4 Previous work by the authors4 showed that the high -temperature creep behavior of TD Nickel could not be related to any simple dislocation theory of creep, and this probably was associated with the complex initial structure of the material.

Jan 1, 1968

By E. M. Elkin, J. H. Schloen

All known methods of treating and recovering the various components of copper refinery slimes are discussed. The slimes treatment processes presently used by five copper refineries are described and flowsheets are given. A bibliography is appended. THE recent increase in anode copper production at the Noranda smelter placed an additional load on the Montreal East plant of Canadian Copper Refiners Limited. The consequent increase in the amount of anode slimes led to a careful consideration of the various methods of slimes treatment. A critical review of these methods is presented here in the belief that it would be of interest to copper refiners. No such review has yet been published, although a number of individual flowsheets have been described. To make the information of greater value, a questionnaire was sent to all copper refineries. While the overall response to the questionnaire was not entirely satisfactory, the foreign refiners gave much detail in their answers and expressed willingness to cooperate further if needed. Although the data below do not cover all refineries, it is thought that examples of all flowsheets currently in use are included. A comparison of these flowsheets should prove of interest. The paper is divided into two parts. One part deals with a discussion of all known methods of treating and recovering the various components of the slimes. The second describes the processes now in use at various copper refineries for the treatment of raw slimes up to the production of Doré bullion. A brief description of the two main electrolytic methods of parting Doré bullion is appended. Since the first commercial application of electrolytic refining of copper by J. B. Elkington in 1865, the treatment of anode mud or slimes has undergone many changes. The object of treating slimes has always been the recovery and separation of precious metals. With the passage of time, increasing attention has been paid to improvement in recovery and quality of byproducts, mainly selenium and tellurium. The original methods of treatment were crude, although relatively direct. For example," the slimes were fused on a dolomitic clay bed in a reverbera-tory furnace; the slag was removed and the resulting metal cupelled to silver and gold. In another process, the dried slimes were oxidized and scorified on the lead bath of a cupelling furnace. Later, these pyrometallurgical methods were modified by sulphuric acid leaching, followed by fusion with niter in a reverb eratory furnace. A preliminary oxidizing roast improved the leaching step. Straight hydro-metallurgy has not found practical application. No matter what method is employed, the result is Dorb metal—a silver-gold alloy, with or without the metals of the platinum group. Characteristics of the Slimes Anode slimes are made up of those components of the anodes which are not soluble in the electrolyte. They contain varying quantities of copper, silver, gold, sulphur, selenium, tellurium, lead, arsenic, antimony, nickel, iron, silica, etc. The color of raw slimes is grayish black and the particle size is —200 mesh. However, Baraboshkin and Gaev (Ref. 1, p. 37), describe light gray colored slimes from the electrolysis of secondary copper which are composed predominantly of sulphates and of basic salts. In anode furnace practice primary and secondary metals are not usually segregated and such slimes do not commonly occur. Copper in the slimes originates to a large extent in the cuprous oxide of the anodes and is therefore dependent on the oxygen content of the latter: Cu2O + H2SO4 + CuSO4 + H2O + Cu [I] Opinions have been expressed that some of the copper is formed by decomposition of cuprous to cupric sulphate Cu2SO4 ? CuSO4 + Cu PI The product of either reaction is very finely divided. Depending on the slimes composition, much of the copper is combined with sulphur, selenium, tellurium, etc. The balance of the copper is in the free metallic state.

Jan 1, 1951

By L. V. Gregor, C. F. Aliotta, P. Balk

The structure of silicon surfaces, thermally oxi&zed in dry oxygen and in steam, was studied using the electron microscope. It was found that the structure on the original (etched) surface is retained at the outer surface of the oxide, whereas the oxide-silicon interface is smoothed out considerably. This supports the idea that, both in oxygen and in steam, the oxidation reaction occurs at the oxide-silicon interface. Mechanical damage of the original silicon surface affects the rate of oxidation. It also changes the chemical properties of the oxide, as shown by the enhanced rate of etching in buffered HF at the locations of damage. However, the oxide at the originally damaged surfaces still exhibits a high electrical breakdown strength. Exposure of thermal oxides to P205 or BzOs vapor, which will yieldphospho- or borosilicate layers, results in complete annihilation of all fine structure on the surface. Reaction of silicon with C02 gives a surface film which probably does not consist of pure SiO,. THERMAL oxidation of silicon yields uniform and strongly adhering oxide films which are normally amorphous and continuous. Contamination and surface imperfections have been reported to cause local crystallization and the formation of pinholes."' The parabolic-rate law of film growth observed by several workers for the oxidation both in steam and in dry oxygen at higher temperatures suggests that diffusion of one or more reactants through the oxide is the rate-deter mining step. One of the dif-fusants is an oxygen species and oxide is continuously formed at the oxide-silicon interface. This was concluded for high-pressure steam oxidation by Ligenza and spitzer5 from an infrared-absorption study of the isotopic exchange of oxygen. Jorgensen arrived at the same conclusion for the oxidation in dry oxygen by measuring during oxidation the resistance change between silicon and a porous platinum marker electrode in the oxide. Recently, Pliskin and Gnall' reported similar conclusions concerning the growth mechanism from controlled etch studies using a phosphosilicate marker. The work communicated in the present paper was aimed at studying oxide growth on locally damaged silicon substrates and relating it to the chemical behavior and electrical breakdown properties of the films. Since etched and oxidized silicon surfaces normally appear to be very smooth when examined by optical microscopy except for some occasional pits, it was decided to use the electron microscope as a tool. In this way, the detection of surface roughness and damage on a scale comparable to or smaller than the thickness of the film is possible. Also, the microstructure of the original substrate surface constitutes a built-in marker which represents a minimum of perturbation to the growing oxide layer, and no foreign material is introduced. Thus information on surface reactions and additional evidence on the location of oxide formation in steam and in oxygen could be obtained. EXPERIMENTAL Electron micrographs7 were obtained using a Philips EM100 electron microscope. Collodion surface replication was used since this is a nondestructive technique and thus permits replicating the same surface at different stages of processing. In order to establish the effect of different treatments it was found essential to make successive observations of the same area by using a reference point. Reference points were conveniently provided by scribing a small v mark on the original surface with a silicon carbide tip. This procedure yields damaged and damage-free areas near the reference point. Upon replication, the samples were thoroughly cleaned before subjecting them to the next process step. Mechanically lapped silicon wafers (Dow-Corning, 100 ohm-cm p-type, cut perpendicular to the (111) direction) were chemically polished in a rotating beaker with a mixture of 1 part HF (48 pct), 2 parts glacial acetic acid, and 3 parts HNO3 (70 pct) by volume. This procedure yields a smooth surface with a faint "orange peel'' structure due to a "ripple" less than 20002i deep. Oxidation in steam or oxygen was carried out in an Electroglas tube furnace. Steam oxidations were always preceded and followed by a brief exposure to oxygen at the same temperattre. The thicknesses of the oxide films under 3000A were determined with a Rudolph Model 436-2003 ellipsometer,' whereas those over 3000A were measured using the VAMFO technique. In the present study, a solution of 300 g of N&F in 25 ml HF (48 pct) and 450 ml water was used to detect areas of increased chemical reactivity in the

Jan 1, 1965

By G. A. Chadwick, D. Jaffrey

The morpho1ogies and orientation relationships of the phases in the Sn-Zn and A1-A13Ni eutectic systems were examined by electron microscopy and X-ray diffraction techniques. In each alloy the "transition" from the lamellar to the fibrous morphology was found to be one of scale, not of type. The minor phase in both systems exhibited certain well developed facets which were not affected by changes in the ingot solidification rate. The crystallographic relationships displayed by the pairs of phases in both systems were also insensitive to the growth rate. In the Sn-Zn alloy, the unique relationship of: growth direction - II [1201 Sn - II [01101 Zn and ribbon interface plane 11 (101) Sn 11 (7012) Zn was determined. The Al-Al3Ni alloy phases did not possess any particular orientation relationship, though the Al3Ni phase invariably grew in the [010] direction and exhibited the same set of facet planes. These results are discussed in relation to current eutectic growth theories and explanations of the "lamellar to fibrous transition". THE lamellar to fibrous transition that occurs in many eutectic alloys has been the subject of considerable speculation and experimental study. In some alloys it can be induced solely by an increase in the solidification rate,'-3 whereas in others the transition supposedly occurs only if the lamellae are forced to grow out of the overall ingot growth direction.4-6 he cause of this latter type of transition has been attributed to deviations of the lamellae from their low energy habit planes;4'5'7 fibers are produced because the sustaining force for lamellar growth (a low energy boundary) is destroyed. Implicit in these explanations is the assumption that fibers are circular in cross-section and completely lacking in low energy inter-phase interfaces. The "natural" growth rate dependent transition has been studied less thoroughly although Tiller8 has attempted a theoretical explanation of it. Tiller's arguments are not completely satisfactory9 but his suggestion that the relative undercoolings of the solid/liquid interface for lamellar and fibrous morphologies are growth rate dependent cannot be totally discounted; it is possible, for instance, that the relative interfacial undercoolings could alter and produce the observed morphology change if the orientation relationships between the phases and the associated interphase bound- ary energies were sensitive to growth rate. Salkind et al." have reported finding a change in the orientation relationships in the A1-A13Ni system accompanying the lamellar to fibrous transition, but contradictory evidence has also been reported for this3'" and another system,12 so the position remains unclear. In an attempt to clarify matters a study was made of the "lamellar to fibrous" transition in the Sn-Zn and A1-A13Ni eutectic systems; the morphologies of these two selected systems are quite similar when viewed by optical microscopy. In the present research the morphologies and morphology changes were investigated by electron microscopy. The orientation relationships existing between the eutectic phases were also determined for both morphologies in both eutectic systems. EXPERIMENTAL PROCEDURE The materials and method of alloy preparation and ingot solidification for the Sn-Zn system have been reported previously.2 In this investigation nine horizontally grown ingots of the highest purity (99.9997 pct) were used. The temperature gradient in the melt was not intentionally varied and was approximately 10°C per cm. Seven growth rates between 1.3 cm per hr and 20 cm per hr were imposed. The A1-A13Ni alloys were prepared from "Spec. Pure" nickel and 99.995 pct aluminum by melting the components in an open alumina crucible and casting the melt into the cold graphite mold. Six ingots of the Al-Al3Ni alloy were unidirectionally solidified at growth rates from 1 cm per hr to 12 cm per hr under high purity argon. A typical ingot was 20 cm long, 1 cm wide, and 0.75 cm to 1.5 cm thick. Samples taken from the bars at positions 12 cm from the nucleation end were examined by conventional orthogonal-section metallo-graphic techniques. When required, samples were mounted for X-ray diffraction analysis using the Laue back-reflection technique with a finely focussed X-ray source. The surfaces of the A1-A13Ni specimens were prepared by mechanically polishing them down to the 1 µ diamond pad stage followed by an electropolish in 80/20 methanol/perchloric acid solution at 0°C and 20 to 30 v. The Sn-Zn specimens were repeatedly polished on an alumina pad and etched in hot dilute (2 pct) nitric acid until the diffraction spots were found to be sharp. Thin films of the alloys were prepared for observation in an electron microscope by spark machining thin discs (0.03 to 0.04 in. thick) from longitudinal and lateral sections of the bars and elec-trolytically thinning them via a jet polishing technique. For the A1-A13Ni eutectic alloy, an 80/20 mixture of ethanol/perchloric acid at 40 v and 20°C was found to be satisfactory. A solution of 70/20/10 methanol/perchloric acid/butylcellosolve at 25 v and 20°C was used on the Sn-Zn alloy. For the former alloy the jet nozzles (cathodes) and the disc clamps were of aluminum;

Jan 1, 1970

By A. Raman, P. P. Singh

The constitution of the La-Rh system was studied by powder X-ray diffraction, metallopaphic, and differential thermal analysis techniques and an equilibrium diagram is presented. Eleven intermediate phases occur in the system and the crystal structural data for nine of them were determined. La3Rh crystallizes in an orthorhombic structure of undetermined type, whose unit cell is obtained by doubling the 'a; and 'c,,' edges of an FesC type unit cell. The other intermediate phases of the system are LarRh-3( undetermined structures also occur in the system. LaRh, undergoes a polymorphic phase transformation at 1240°C. LaRh3 and La2Rh7 also exhibit polymorphisnz. The phases Laah and LazRh7 melt congruently. The latter undergoes a eutectoid transformation into LaRh, and Rh at 1205°C. Laah3 is formed by a peritectoid reaction between Laah and La,Rh,,. The other Phases result from peritectic reactions between the liquid and the adjacent rhodium-rich phases. The intermediate Phases of the La-Rh system are compared with those of the La-Co and La-Ni systems. DURING the course of a detailed investigation to study the occurrence of CrB, FeB, A1B2, and related structures in the rare earth alloys it was found that much information is lacking for the rare earth noble metal systems. Although the structures of several rare earth alloys containing the noble metals at the AB and AB2 stoichiometries have been reported, the occurrence of related structures at other stoichiometries has not been studied. We have initiated a project to study the crystal structural features of selected rare earth-rhodium alloys and to map the equilibrium diagrams of representative systems with conventional methods. The results of our investigation in the La-Rh system are presented in this paper. Two phases were known in the La-Rh system. LaRh has the CrB-type structure.' LaRhz is a MgCu2-type Laves phase.z EXPERIMENTAL PROCEDURE Alloys weighing less than 1 g were prepared from commercially pure lanthanum (99.9 pct +), supplied by Lunex Company, Pleasant Valley, Iowa, and rhodium (99.92 pct +), supplied by Engelhardt Industries, Newark, N.J., in a conventional arc melting furnace under argon atmosphere. The buttons were turned upside down and remelted three times to insure homogeneity in the samples. Since negligible loss of material was encountered during melting, a chemical analysis of the alloy buttons was not undertaken. Powder specimens for X-ray diffraction studies in the as cast state were then prepared. The buttons were wrapped in thin molybdenum foils and homogenized by heating in vacuum at suitable high temperatures for more than 1 week. They were then broken into three or four pieces for annealing experiments. The pieces were wrapped in molybdenum foils and annealed at various temperatures in evacuated quartz capsules. The annealing was carried out for 2 hr at or above 1200°C, 1 day at temperatures close to llOO°C, 2 days at 1000°C, and for 1 week at temperatures below 1000°C. After annealing the alloy pieces were again broken and powder specimens for X-ray diffraction were prepared. The powders of the lanthanum rich alloys with more than 80 at. pct La were prepared by filing. The filings were sealed in molybdenum tubings and stress-relieved at 600°C in vacuum. It was not deemed necessary to stress-relieve the powders of the other alloys, since the alloys were very brittle and were ground easily. POWDER X-RAY DIFFRACTION X-ray diffraction photographs of powders (-325 mesh size) of the alloys in the as cast and annealed states were prepared in a Guinier-de Wolff focussing camera with copper K, X radiations. These patterns were studied to identify the stoichiometries and the crystal structures of the intermediate phases. The lattice parameters of the phases were calculated after minimizing the differences between the observed sin2 6 values, calculated from the diffraction angles 8, and the sin2 8 values, calculated using approximate lattice constants obtained from a few lines. These differences were minimized manually to less than 0.0005. The latLice constants are judged to be accurate to *0.005A for values less thp about 10A and to k0.01~ for values greater than 10A. The relative intensities of the lines were calculated using a computer program written by Jeitschko and Parthk.~ No attempt was made to refine the atomic positional parameters in the phases. METALLOGRAPHY The phase equilibria in the investigated alloys in the as cast and annealed states were also studied by metallographic examination. The polished specimen surfaces were etched with 10 pct picric acid in alcohol (alloys up to 25 pct Rh), concentrated picric acid (from 25 to 37.5 pct Rh), 2 pct nital (40 to 50 pct Rh), 10 pct nital (from 50 to 66.7 pct Rh) and with concentrated 48 pct HF for the other rhodium-rich alloys. Selected microstruture~ were then photographed using a Po-laroid Land camera. THERMAL ANALYSIS Differential thermal analysis of the alloys was carried out in DTA-668 Stone differential thermal ana-

Jan 1, 1970

By R. A. Graham, R. W. Rohde

The effect of hydrostatic pressure upon the austenite start temperature of a commercial Fe-28.4 at. pct Ni-0.5 at. pct C alloy has been determined. For pressures to 20 kbar, the austenite start temperature decreased from its atmospheric pressure value of 380°C at the rate of about 4°C per kbar. These data are analyzed by two different thermodynamic approaches; first, considering the transformation as an isothermal process, and second, considering the transformation as an isentropic process. It was found that both these approaches fit the experimental data equally well. The effect of hydrostatic pressure upon the austenite start temperature is best described by considering the mechanical work done during the transformation as that work obtained by multiplying the applied pressure with the gross volume change of the transformation. It is widely recognized1 that strain has an important effect on the initiation of martensitic transformations.* For example, the martensite start tempera- *In this paper, use of the term martensitic transformation implies the reversal of martensite to austenite as wen as the formation of martensite from austenite. ture, M,, may be increased by plastic deformation. Similarly, plastic deformation is observed to lower the austenite start temperature, A,. The effect of uniaxial stress on the M, of iron-nickel alloys has been studied by Kulin, Cohen, and Averbach.2 They found that the martensite start temperature was significantly changed by stresses well within the elastic region. Moreover, the effect of tensile and compres-sive stresses differed. These effects were explained in terms of the interaction of the applied stress with both the dilational and shear components of the transformation strain. The magnitudes of the influence of uniaxial tension, compression and hydrostatic pressure on Ms were measured in 30 pct Ni 70 pct Fe by Pate1 and Cohen.3 Their thermodynamic calculations and similar calculations by Fisher and Turnbull4 predicted the experimental results when the transformation was assumed to occur isothermally at some fixed driving force. This driving force was assumed to be supplied by a combination of the chemical free energy difference between the austenitic and martensitic phases and the work performed during transformation by the applied stress. More recently, Russell and winchel15 reported the effect of rapidly applied shear stress on the reversal of martensite to austenite in iron-nickel-carbon alloys. They performed a thermodynamic analysis of this transformation based upon the assumption that the re- versal occurred adiabatically. They concluded that the applied shear stress did not significantly interact with the transformation strain and thus did not assist in inducing the reversal. Rather they concluded that the reversal was effected by localized strain heating which resulted from the gross local shear deformation of the experiment. In either the adiabatic or isothermal analysis it is necessary to compute the work performed by the interaction of the applied stress and the transformation strains. In the case of hydrostatic pressure this interaction has been treated by two different methods. In either case the applied pressure is assumed to remain constant during the transformation. In one treatment the applied pressure is assumed to interact directly with the dilatational strain associated with the formation of an individual martensite plate.3'4 This local strain has been measured at atmospheric pressure in iron-nickel alloys by Machlin and Cohen.6 In the above treatment this local strain is assumed invariant with temperature and pressure changes. In the other treatment the applied pressure is assumed to interact with the gross volume change of the transformation.7,8 The usefulness of this latter treatment has been demonstrated by Kaufman, Leyenaar, and Harvey7 who calculated the effects of pressure upon the martensite and austenite start temperatures of Fe-10 at. pct Ni and Fe-25 at. pct Ni alloys. Excellent agreement was obtained between their calculations and their experimental data on an Fe-9.5 at. pct Ni alloy. However, this treatment suffers from the fact that the data required to calculate the volume change of the transformation (i.e., the initial specific volumes, the thermal expansion and compressibility data for both the austenitic and martensitic phases) is, in general, not available for any material except pure iron. Thus the calculations of Kaufman et al.7 were necessarily performed by assuming that the volume change of the martensitic transformation in the iron-nickel alloys was that same volume change occurring during the a-? transformation in pure iron. While this approximation may suffice for very dilute alloys it is likely to be inaccurate in high nickel alloys. We have performed measurements of the effect of hydrostatic pressure to 20 kbar on the A, temperature of an Fe-28.4 at. pct Ni-0.5 at. pct C alloy. The composition is similar to the alloy used by Pate1 and Cohen3 to determine the effect of pressure upon the M, temperature. The present measurements permit calculation of the interaction between the applied pressure and the transformation strain. Additionally, measurements have been made which allow precise determination of the gross volume change of the transformation. The data allow direct comparison between the alternate hypotheses of the interaction between the applied pressure and a dilatational transformation strain characterized by either the formation

Jan 1, 1970

By H. W. Rogers

The first steam shovels used in this country were built by the Otis Company, of Boston, about 50 years ago, but as they were of very crude construction and rather unsuccessful only a few were built. For possibly 10 years prior to 1884 successful steam shovels were made and used on certain classes of work, but it was not until that time that they were manufactured in quantities and began to play an important part in all classes of excavation. From that time up to the present day there have been gradual but continuous improvements on the original shovel, not only in the mechanical construction, but also in the design of boilers and engines which are best adapted to this class of service. In proposing a change from steam to electric operation we have to deal with a steam equipment which has not only proved its worth but has probably reached its highest stage of development and efficiency. That the electric shovel is a possibility cannot be denied, as at present from 12 to 18 shovels are in operation in this country. These shovels may be divided into three classes: the friction electric, which is operated by a single constant-speed motor with friction clutches; the three or four motor direct-current equipment, and the three or four motor alternating-current equipment. It is the second and third classes that I wish to deal with, as the first class does not compare favorably with the steam shovel so far as speed is concerned, although it may be operated as cheaply. There is probably no other class of machinery that presents a duty cycle as severe as that of the shovel, which is very short, varying from 7 to 12 sec. on the hoist, from 7 to 12 sec. on the thrust, and from 10 to 18 sec. on the swing, making a complete cycle in from 17 to 30 sec., and the motor to meet these requirements must have a sufficiently low armature inertia to permit of rapid acceleration and quick reversals under small power. It should also be a motor of rugged design, as it must be subjected to severe overloads and shocks and frequent reversals. This is especially true of the hoist motors and, to a lesser degree, of the swing motor; the thrust motor being practically stalled during the digging operation, although it may revolve or overhaul, according to conditions, and is operated at full speed only after the hoisting operation is completed.

Jan 1, 1915

By W. Mitchell, B. H. Bergstorm, C. L. Sollenberger

A unique compression testing machine was constructed to load individual 1/8 to I-in. spheres of glass, etc., at rates from 100 to 100,000 lb per min. During loading the applied load was continuously plotted us the deformation of the sphere-platen system. The load-deformation curve conforms to the theory of elasticity. The spheres were surrounded by steel retaining rings or by gelatin (to prevent secondary fracture). The product size modulus was determined from screen analyses. The data shows: 1) Energy input per unit mass is inversely proportional to the product size modulus (or directly proportional to the surface area per unit mass). 2) Increased loading rates slightly increase the energy input per unit mass required for fracture without affecting the preceding relationship. Theory and experiments show that much of the input strain energy is transformed into kinetic energy of fragments at fracture, this being a reason efficiencies based on "surface energies" are exceedingly small. This large kinetic energy component is usually dissipated as heat but may be partially reclaimed because impact of fragments against the surface of steel retaining rings causes additional comminution. There are currently several theories of crushing, all of which can be derived from the general energy equation of Gillilandl as was pointed out by Mitchellet al in 1954'and more recently by Rose and Sullivan. If the exponent of the equation dE-x-"dx is assigned values of 2,1, or 3/2, one obtains by intergration between suitable limits, the equations of Rittinger, kick,' and Bond,' respectively. Other investigators prefer to let the exponent be a variable parameter. To help resolve the controversy, the Allis-Chal-mers Research Laboratories set up a series of carefully controlled experiments in which the level of energy input required to induce the comminution of a single particle by slow compression loading was very accurately measured. The energy input requirement, in conjunction with the size analysis of the fragments produced at fracture, yielded an accurate energy-product size relationship for the conditions studied. APPARATUS The experimental apparatus was designed to apply a compressive load on opposite sides of an "ideal particle." Spherical shapes were chosen, because point contact loading is typical of the mechanics of conventional crushers. The bulk of the experimental data was obtained with glass spheres because glass is a fairly homogeneous, brittle material for which the properties follow definite statistical distributions. The spheres ranged from 1/8 to 1-in. diam. The compressive load was applied to the specimen at a uniform rate by a loading mechanism (Fig. 1) which acted through a system of levers. The uniform rates, ranging from 100 to 100,000 lb per min, were obtained by metering water into a bucket suspended at the end of the secondary level. Point contact was made with the sphere through tungsten-carbide platens. This latter material is extremely hard and has a high modulus of elasticity, thereby having a minimum of distortion when loaded. The actual load on the sphere was measured independently of the lever system by a load cell, Fig. 2, which was designed so that the voltage output of the load cell would be proportional to load. The deformation of the specimen was indirectly measured by a pair of transformers which were attached to opposite edges of the upper platen. The cores of the transformers, which were attached to the lower platen, moved relative to the transformer so that the voltage output was proportional to the deformation of the sphere-platen system. The load was plotted against the deformation on an X-Y recorder. The area under the curve, as shown on Fig. 3, was proportional to the energy input of the

Jan 1, 1961

By K. W. Smith, E. A. Thomas

Various grades of synthetic mullite have been developed in recent years to replace or supplement natural sources of mullite deriued from the mullite group of minerals consisting of sillimanite, kyanite, and andalusite. Raw materials and heat treating processes used in making synthetic mullite are described. Chemical and physical data are given for typical grades and crystalline structure is illustrated with micrographs. Use of synthetic mullite as a refractory material in the glass and metallurgical industries is discussed. Mullite (3A12O3.2siO2), the only stable compound formed in the alumina-silica system, is usually present to some degree in all aluminum silicate ceramic products. The formation of mullite is considered beneficial to give rigidity to the structure and is dependent upon the ratio of Al2O3 to SiO2 in the original composition, particle size, degree of mixing, firing temperature, cooling rate, and the presence of auxiliary glass-forming fluxes. Mullite may also be formed at the reaction interface of fire clay or alumina-type refractories in contact with glass or slag melts. The term synthetic mullite is commonly used today to identify a class of sintered and fused aggregates or grains in the alumina-silica system having a highly developed mullite structure but derived mainly from raw materials other than the sillimanite group of minerals. Within the past 15 years extensive research has been done to develop economical processes to form sintered synthetic mullite aggregate to replace calcined Indian kyanite in super-refractories. Severa1 brands of such mullite are now being produced in commerical quantity and finding extensive use in refractories. Based on the service results of such refractories in many applications throughout the metallurgical, ceramic, and glass industry these developments have been considered successful and suitable substitutes for Indian kyanite now appear assured. EARLY DEVELOPMENT The conversion of kyanite, sillimanite and anda-lusite minerals of the sillimanite group to mullite and their use in refractories and porcelain have been discussed quite extensively in the literature by peck,' Grieg,' Riddle and Foster,3 Bowen and Grieg,4 and others and will only be mentioned here for reference to compare properties with synthetic mullite. In 1928, curtis5 reported on the development of a high temperature gas-converter process for forming synthetic mullite. The raw materials were derived mainly from lumps of high alumina clay of the correct natural composition or blends of clays and alumina that was interground and briquetted to form a suitable charge to maintain a surface combustion firing within the converter. Curtis was, no doubt, the first to illustrate by micrographs in natural color the crystalline structure of mullite derived from kyanite and mullite derived by sintering clay and alumina mixtures at temperatures above cone 32 (3123°F) and by electric fusion. In 1937, sei16 was issued a patent covering the use of a mixture of alumina-silica minerals and alumina in the proportion to form a mullite-yielding material at temperatures in excess of 3100' F. During the period from 1930 to 1940, economic conditions were not favorable for the production of synthetic mullite mainly due to an adequate supply of good grades of Indian kyanite ore suitable for conversion to mullite. Uncertain conditions on availability of the Indian kyanite during the early stages of World War II fostered further study on the development of synthetic substitutes. In 1943, McVay and wilson7 reported on an extensive investigation of domestic substitute materials. Their work covered essentially the use of mixtures of electric furnace mullite, calcined topaz, and calcined domestic kyanite. Compositions were found that gave equivalent or better hot load strength than Indian kyanite in mullite-type brick compositions; however, the calcining of the topaz presented certain physical and chemical problems on the disposition of silicofluoride and hydrofluoric acid while the high cost of electric furnace mullite was a limiting factor. In this work it was pointed out that water-quenched fused mullite was found to be unstable on reheat and gave poor hot load strength due to excessive glass present whereas the slow cooled or annealed mullite contained large crystals of mullite and corundum with little glass and gave superior results.

Jan 1, 1961