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By R. W. Moore, A. B. Kinzel

Although the iron-carbon diagram has undergone many changes in the last 20 years, the region below the eutectoid line and up to approximately 1.7 per cent carbon has been little affected. This region is generally considered to consist of cenlentite and ferrite. Graphite has been noted occasionally in the hypereutectoid steel region, and the ready formation of graphite nodules in malleable cast iron is a phenomenon difficult to interpret in the light of cementite, supposedly stable at sub-eutectoid temperatures. In this case the graphite formation has been partly explained by the presence of silicon, and many have believed that silicon acts to change the stable state rather than to accelerate reactions so as to arrive at the stable state in a briefer period of time. Consideration of this phenomenon indicates that cementite is not the stable phase in the temperature composition zone referred to. In the course of examining a low-carbon steel tube taken from a petroleum cracking still, which had been in service for approximately three years at temperatures somewhat below the eutectoid temperature, observations were made that shed light on this entire subject. The tube in question analyzed:' C, 0.15 per cent; Mn, 0.49; Si, 0.02; S, 0.023; P, 0.015. The microstructure of the tube after service is shown In Figs. 1 and 2. From these it is evident that cementite as such is absent, and that in its place nodular graphite has been formed. In order to check this observation further, samples taken from the tube were heated at 850" C. for varying periods of time. The small samples were put into a large hot furnace, and the total time is recorded. The structure of the sample after 5 min. at 850" C. is shown in Figs. 3 and 4, and the nest of pearlite surrounding the graphite nodules is most satisfactory evidence of the character of the nodules. As the length of time of heating at this temperature increases, the pearlitic zone increases, with final restoration

Jan 1, 1935

By R. W. Moore, A. B. Kinzel

Although the iron-carbon diagram has undergone many changes in the last 20 years, the region below the eutectoid line and up to approximately 1.7 per cent carbon has been little affected. This region is generally considered to consist of cenlentite and ferrite. Graphite has been noted occasionally in the hypereutectoid steel region, and the ready formation of graphite nodules in malleable cast iron is a phenomenon difficult to interpret in the light of cementite, supposedly stable at sub-eutectoid temperatures. In this case the graphite formation has been partly explained by the presence of silicon, and many have believed that silicon acts to change the stable state rather than to accelerate reactions so as to arrive at the stable state in a briefer period of time. Consideration of this phenomenon indicates that cementite is not the stable phase in the temperature composition zone referred to. In the course of examining a low-carbon steel tube taken from a petroleum cracking still, which had been in service for approximately three years at temperatures somewhat below the eutectoid temperature, observations were made that shed light on this entire subject. The tube in question analyzed:' C, 0.15 per cent; Mn, 0.49; Si, 0.02; S, 0.023; P, 0.015. The microstructure of the tube after service is shown In Figs. 1 and 2. From these it is evident that cementite as such is absent, and that in its place nodular graphite has been formed. In order to check this observation further, samples taken from the tube were heated at 850" C. for varying periods of time. The small samples were put into a large hot furnace, and the total time is recorded. The structure of the sample after 5 min. at 850" C. is shown in Figs. 3 and 4, and the nest of pearlite surrounding the graphite nodules is most satisfactory evidence of the character of the nodules. As the length of time of heating at this temperature increases, the pearlitic zone increases, with final restoration

Jan 1, 1935

By M. A. Rigdon, R. E. Grace

The dissociation of cupric oxide to cuprous oxide and oxygen was studied with a microbalmce technique at 700" to 750°C. In this temperature range the dissociation pressure of the reaction 2CuO= Cu2O + 1/2 O2 was: The theory of near-equilibriwm reaction rates predicts a linear relationship between reaction rate and the Gibbs free-energy change for small values of AF/RT. This correlation is found to be valid for AF/RT = -0.1 or approximately 200 cal per mole away from equilibrium. THE theory of reaction rates near equilibrium as developed from classical thermodynamics suggests a small range of linear behavior between the overall reaction rate and the free-energy change accompanying the process. The extent of this linear correlation is generally unknown, even to the order of magnitude. The idea of linearity is also found in the formal mathematics of coupled transport phenomena, e.g., chemical diffusion, thermal diffusion, thermoelectricity, and so forth. The linear array of forces and fluxes which leads to various main and cross coefficients is predicated upon linearity between reaction rates and the bulk thermodynamics which govern the process. The general case in reaction kinetics is well-known: the magnitude of the free-energy change does not cor- relate with observed reaction kinetics, irrespective of whether the process occurs by diffusion or chemical reaction or both. The real need is to investigate specific reaction paths near equilibrium in order to learn of the limitations in attempting to correlate reaction rates and thermodynamics. It is the main purpose of this paper to examine the dissociation kinetics of cupric oxide under conditions of known driving force where the dissociation process is likely to occur by chemical reaction. A secondary objective is to obtain equilibrium data for the CuO-Cu20-O2 system. In a prior paper Edmiston and race' investigated reduction kinetics of wustite in H2-H2O gas mixtures. The present study was carried out in oxygen according to the following reaction:

Jan 1, 1969

By Howard L. Hartman

6.1-1. Introduction. Of necessity, the first of the unit operations conducted during the exploitation phase in surface mining is production drilling. It precedes blasting, with which it is associated as the two unit operations employed to break or fragment consolidated material (usually rock) in place. The purpose of production drilling is to provide the cavity for placement of the explosives. So far, no alternative to blasting has been devised for fragmenting very resistant rock in situ, although some forms of excavation (ripping, bucket wheel) are suitable without prior blasting for softer rock, such as weathered shale or mudstone, decomposed sediments, etc. For the vast majority of surface mines, however, drilling and blasting are pre- requisite to excavation and essential to the production cycle. Drilling is also used in surface mining for purposes other than providing blastholes. It finds application during exploration for obtaining samples and during development for drainage, slope stability, foundation testing, etc. Only in the exploitation phase of surface mining, however, are unique or specialized drilling methods and equipment employed; and the discussion in this Section is directed primarily to that application of drilling. Drilling is the most common means of rock penetration, the operation of placing a directed hole in rock. Closely akin to drilling for exploitation purposes is the cutting or freeing of dimension stone in quarrying. This operation, usually termed channeling or sawing, also takes the form of directional penetration of rock; but instead of producing a cylindrical hole, it yields a kerf or cut. The material thus freed from the solid is both a shaped and sized product, an objective of vital importance in the dimension stone industry. In sawing, holes are sometimes drilled to insert tools, but this drilling is a minor part of the sawing operation and employs conventional methods. Cutting, as a unit operation for freeing stone in quarrying, may be considered equivalent in purpose to drilling and blasting in other forms of surface mining.

Jan 1, 1968

By Robert B. Fulton

Commercially, celestite (SrSO,) is the only significant strontium mineral. Among other strontium-bearing minerals, only strontianite (SrCO,) occurs commonly; however, it is not an item of commerce. The principal production of celestite is in England, Mexico, and Spain. New production is now coming on stream in Canada. Consumption is mainly in the United States. Lesser quantities are consumed in Japan and Europe. Main uses are for the manufacture of strontium carbonate and nitrate. The carbonate is used in glass for TV tube face plates and in ferrites for magnets. The nitrate is used in pyrotechnics to which it imparts a characteristic brilliant red color, mainly in safety flares. Minor amounts of strontium compounds are used in electrolytic zinc manufacturing and very small quantities in greases, ceramics, soaps, alloys, and pharmaceuticals. Specifications and Prices Typical celestite specifications for the carbonate and nitrate markets are as follows: [ ] Celestite currently shipped from Mexico for carbonate manufacture tends to be slightly better than these industry specifications, assaying about 92-93% SrSO, with less than 1% BaSO, but it is generally below the 95% minimum required for nitrate production. Contract prices for celestite are approximately $32-34 per st at U.S. Port of Entry in 50 to 60-ton carload lots for Mexican material. Spot prices are generally reported as low as $20 per st but are for minor volumes. A recent sale of surplus from the U.S. stockpiles, announced by the General Service Administration (GSA), was 4005 st sold to Du Pont for $140- 455 or $35.07 per st. British celestite, ground, washed, and graded, 95% SrSO, bulk, ex- works, 240 mesh, is quoted at £ 28.75 per mt in British trade journals, and a recent figure quoted for crushed lump material was $36.00 per st f.0.b. vessel Bristol Channel port (1973). Specifications of manufactured carbonate made from celestite and sold in two grades, one to the glass industry, the other to the electronic industry for ferrites, are given in [Table 1]

Jan 1, 1975

By H. Scott

IN a paper read before the Institute of Metals, Rosenhain 1 described a new type of furnace designed primarily for the thermal analysis of metals by the inverse-rate method and used by him in the metallurgical department of the National Physical Laboratory with considerable success. In his discussion of this furnace, Rosenhain pointed out some difficulties met with in its operation, such as uniformity of rate of heating or cooling being inadequate for the degree of accuracy aimed at. To overcome this difficulty, he suggested, in place of motor propulsion, a gravity drive controlled by a"hydraulic cylinder with a relief valve whose width of opening can he regulated to allow of any desired rate of motion." The authors, in constructing a thermal-analysis furnace of Rosenhain's type, have therefore followed this suggestion and also added certain features that increase somewhat the convenience and simplicity of its operation. Requests for information regarding this furnace and the highly satisfactory results obtained from its use, it is believed, justify describing its construction and operation in sufficient detail to make possible its duplication or improvement. Description of Furnace.-The details of the furnace construction are shown in Fig. 1, which is drawn to scale. The heating tube is of /4 in. (6.35 mm.) wall "alundum" heated at the upper end by seventeen turns of 0.52 mm. platinum wire, which is coated with "alundum" cement supplied for this purpose. The cement coating is essential when a high temperature (over 1000° C.) is required, as it prevents hot spots with the resulting burning out of the heater. This platinum-wire winding, unlike "nichrome," is entirely satisfactory for temperatures of at least 1000° C. It has been maintained at that temperature continuously for 2 months and shows no signs of deterioration. This temperature is maintained by a current of 5 amp. drawn from 30 volts potential, so its necessarily continuous operation is quite economical.

Jan 8, 1919

By Ira B. Joralemon

The sampling of disseminated copper deposits has been describeu often but the method of combining assays to give the true shape and value of the orebody as it will be mined has received less attention. As the ore mined during five or ten years at several of the great disseminated properties has averaged materially lower in grade than the published estimates, the question of the sampling and estimating of these orebodies seems timely. In this paper, attention is given particularly to factors that may cause errors in the final estimate. Sampling of diamond-drill holes, churn-drill holes, and underground workings is briefly described in the first part of the paper; then the method of combining assays to give the average grade and tonnage that will be mined is taken up in some detail. The necessity of study of the geology of the deposit and of probable costs is emphasized. Finally, the methods of calculating tonnages are outlined. DlAMOND-DRILL SAMPLING There are three main requisites for accurate diamond-drill sampling. First, the core should be removed and the hole cleaned out at the beginning of every sampling interval, usually 5 ft. (1.5 m.). After the rods are let down, water should be run through them until it becomes clear. The water must be clear before drilling starts. 'In this way the material knocked down from the sides of the hole by the descending rods is washed away, instead of being left to salt the sludge sample. The second requisite is to save all the sludge and all the core from every sampling interval. Where the material is uniformly heavy, the cuttings will settle suffciently in a box, through which the sludge flows s1owly.l Where part of the material is too light to settle readily, the sludge should be run into barrels, and allowed to settle until the water becomes clear. Then the clear water is siphoned off, and the sludge evaporated to dryness over a slow fire, sacked, and assayed.2 To obtain

Jan 1, 1925

By Arthur B. Cummins

POWDERED nonmetallic minerals and rocks of many different types are used extensively in industry for incorporation in compositions and manufactured products The term "mineral filler" is commonly employed to designate a material that is used for a specific purpose but not as an essential or reactive component Such a definition is not without objections, and it is indeed difficult to define fillers in any fully satisfactory manner, since the term has come to have so many different meanings and to cover such a wide range of uses. A filler is defined, for the purposes of this chapter, as a substantially inert material not specifically employed as a reactive or essential component, the primary function of which is to modify the properties or processing of a composition of matter or fabricated article Emery1 has emphasized that fillers change the properties of the product but are themselves unchanged in compounding or use The term "filler" appears to be rather general when referring to usages m bituminous compositions, rubber, composition floorings, fertilizers, plastics, textile finishes, and some others. In paper manufacture, in the paint industry and with insecticides, other terms are frequently employed, as is indicated, herinafter By placing emphasis on the function of the material used in modifying the properties of the composition or article, it is believed that a more useful classification of filler products and their applications may be derived. FUNCTIONS OF MINERAL FILLERS All of the manifold functions of mineral fillers cannot be listed in a summary review. A survey of the uses for these materials, however, shows that in nearly all cases the powders are employed to modify the properties of a composition of matter or those of a fabricated article, or to perform some useful function In the manufacture of either. A generalized list of these useful functions may be given is follows 1 To Modify Optical Properties Color Surface texture Opacity Brightness and gloss (as in paper and plastics) Flatness (as in lacquers and paints)

Jan 1, 1949

By Norman Maxwell

There was more activity in crude production in northwestern Pennsylvania in 1935 than for several years before, resulting in an increased oil production and also in the number of wells completed. Crude -production approximated 16 million barrels for the state, an increase of about one million barrels over 1934. Demand, indicated by refiners' runs to stills, increased proportionally, leaving stocks of available crude at the end of the year at the lowest point since the middle of 1934, when they reached an all-time low. The price of crude varied during the year from a low of $2.02 to a high of $2.27 at the end of the year for Middle district oil. The price of Bradford and southwest Pcnnsylvania oil changed accordingly. The average for the year would be a lower price than in 1934. A summary of the production data for the year 1935 is given in Table 1. In making up this table, 1935 figures were simply added to the table published by S. H. Cathcart last year1. A list of important wildcats is given in Table 2. Bradford Field Approximately 10,000 acres of the proven producing area of the Bradford field is in Cattaraugus County, New York, and it is possible, by differences, to distinguish the Pennsylvania production from the New York portion. The listed production for the Bradford field includes only that portion of the field situated in Pennsylvania, but also includes production from a small pool, locally known as the Mt. Jewett-Kanesholm pool, where the Bradford sand is being developed and flooded in precisply the same manner as that of the Bradford field itself. The Mt. Jewett-Kanesholm pool is not, strictly speaking, an extension of the Bradford field, but inasmuch as it is so closely allied with the Bradford field-—that is, the sand is the same and the production methods are the same—the production and drilling figures include this area.

Jan 1, 1936

By Norman Maxwell

There was more activity in crude production in northwestern Pennsylvania in 1935 than for several years before, resulting in an increased oil production and also in the number of wells completed. Crude -production approximated 16 million barrels for the state, an increase of about one million barrels over 1934. Demand, indicated by refiners' runs to stills, increased proportionally, leaving stocks of available crude at the end of the year at the lowest point since the middle of 1934, when they reached an all-time low. The price of crude varied during the year from a low of $2.02 to a high of $2.27 at the end of the year for Middle district oil. The price of Bradford and southwest Pcnnsylvania oil changed accordingly. The average for the year would be a lower price than in 1934. A summary of the production data for the year 1935 is given in Table 1. In making up this table, 1935 figures were simply added to the table published by S. H. Cathcart last year1. A list of important wildcats is given in Table 2. Bradford Field Approximately 10,000 acres of the proven producing area of the Bradford field is in Cattaraugus County, New York, and it is possible, by differences, to distinguish the Pennsylvania production from the New York portion. The listed production for the Bradford field includes only that portion of the field situated in Pennsylvania, but also includes production from a small pool, locally known as the Mt. Jewett-Kanesholm pool, where the Bradford sand is being developed and flooded in precisply the same manner as that of the Bradford field itself. The Mt. Jewett-Kanesholm pool is not, strictly speaking, an extension of the Bradford field, but inasmuch as it is so closely allied with the Bradford field-—that is, the sand is the same and the production methods are the same—the production and drilling figures include this area.

Jan 1, 1936

By Eugene E. Ayres

The centrifuge has come into general use in the oil fields and in the establishments where lubricating and fuel oils are used. Probably centrifugal machinery will be found more useful in the refinery when the operators are more familiar with'the principles of modern centrifuga-tion and when centrifugal engineers better understand the refinery emulsion problems. It is not generally realized that centrifugal force and gravity have two distinct functions: First, subsidence wherein the suspended globules are brought into contact; second, coalescence (when this is possible) by rupturing the films around the globules. In the case of a water-in-oil emulsion, an exercise of the former function alone would yield: (1) oil, free, or as free as desired, from water; and (2) a concentrated water-in-oil emulsion—concentrated in the sense that it contains a relatively large percentage of the internal phase. An exercise of both functions will yield: (1) water-free oil and (2) oil-free water. Centrifugal force is much better than gravity for subsidence because, in the case of industrial emulsions where the suspended globules are visible under a microscope, subsidence is directly proportional to the force applied. Centrifugal force is only slightly better than gravity for coalescence. A minute trace of a proper reagent will immediately do more to nullify the interfacial surface tension opposing coalescence than an indefinite application of the highest attainable centrifugal force. No mathematical analysis has been made to explain the failure of high centrifugal force to induce a decidedly more rapid and more complete coalescence than is obtained by gravity. The adjustment of the centrifuge rotor depends more on the extent of coalescence that is desired or is possible than on any other factor. One reason for this dependence is to be found in the curious relation between the specific gravity and the hydrostatic pressure of emulsions. The continuous centrifuge works on the U-tube or Florentine flask prin-

Jan 1, 1924

By Milton Williams

IT is generally recognized that fluid is lost from rotary drilling mud s to permeable strata during normal drilling operations;1,2,3 but that this fluid is the filtrate from the mud, rather than the mud itself, has been shown by various workers.1,4,5 . The presence of this filtrate in oil-bearing or gas-bearing strata is undesirable and harmful. The decreased permeability of the stratum to oil effected by the presence of water has been pointed out by several investigators,6,7 and since, in the production of the reservoir fluid, the greatest pressure drop occurs immediately adjacent to the borehole, it follows that infiltered water is particularly objectionable in this region. Again, this filtrate tends to make electrical logs less reliable, since oil in the proximity of the borehole is probably flushed out to an appreciable ent by the water.8 Observation of side wall cores may be misleading for the same reason. Drill-stem tests in low-pressure areas may be of doubtful value where no oil is recovered, unless sufficient time is allowed for production of water lost from the mud. The infiltered water may hinder drilling operations by softening shales and causing sloughing; the "tight hole" occasioned by excessive deposition of filter cake in the hole is a common occurrence. The filter cake remaining on the face of the producing formation may itself sometimes be detrimental to production.9 In view of these implications of the importance of filtration of mud, an investigation was undertaken to determine the factors involved in the infiltration process, and to correlate these in such a manner that the values obtained in routine filter tests employing a conventional filter of the "wall-building tester" type,10 together with data on size of hole, drill pipe, and rate of mud circulation, could be used to estimate water loss and distance of penetration of the filtrate into strata.

Jan 1, 1939

By F. Cadena

HIWASSEE Dam, now under construction by the Tennessee Valley Authority on the Hiwassee River, a tributary of the Tennessee River, will require aggregate for approximately 800,000 cu. yd. of concrete. Near the damsite deposits of natural sand or gravel are not available and graywacke, a rock that is found in abundance, suggested itself as a likely source of manufactured aggregate. Graywacke is a metamorphosed sandstone composed principally of a mixture of quartz (65 per cent), mica (25 per cent), and feldspar (10 per cent). Other minerals are present in negligible amounts. The rock varies in different parts of the quarry from very fine to a coarse grain containing particles of about 1/4 in. maximum size, although the bulk of the deposit is medium grain. Extensive tests showed that graywacke would be suitable as a source of both coarse and fine aggregates. The aggregate plant available for use at Hiwassee Dam consisted of the coarse-aggregate and sand plant used on the Norris project. The coarse-aggregate plant had also been used at Chickamauga Dam. Although most of this plant equipment is now in use at Hiwassee, the present flowsheet is not only different from that at Norris and Chickamauga but is also unique as compared to the flowsheet of the average crushed-stone aggregate plant. It is hoped that this paper will show the importance of proper arrangement of equipment if the optimum in flexibility and capacity is to be attained. FLOWSHEET Rock is loaded by 3-yd. electric shovels into 12-yd. dump trucks, which carry the rock to the primary crusher, a 42-in. Superior McCully gyratory unit set at 4 ¾ in. (Fig. 1). The primary crusher discharges directly onto a 42-in. inclined belt conveyor, which carries the product to a surge storage pile with a maximum live storage capacity of approximately 3000 tons. A concrete tunnel under this storage pile houses the feed end of a 36-in. belt conveyor (conveyor B) fed by a 36 by 66-in.

Jan 1, 1939

By R. S. Shoemaker, F. W. McQuiston

MAGMA COPPER COMPANY San Manuel Division The San Manuel Division of Magma Copper Company is located about 40 miles north of Tucson. Tons of ore milled in 1973 .were approximately 19 million at a rate of 63,000 tons per day. From this, about 42,600 tons of copper concentrate was produced as saying approximately 1.070 MoS2 and 28.5% Cu. As with many copper ores, the San Manuel ore contains a small amount of gold, but in this particular case, much of the gold follows the molybdenite. Separation of the molybdenite from the bulk sulfide concentrate by flotation produces a moly concentrate containing 9170 MoS2, just under 1.070 Cu, and 0.44 oz Au per ton. Cyanidation of this material for gold recovery is the only practice of its kind known to the authors of this Monograph. After thickening, the final moly concentrate is filtered for subsequent repulping with cyanide and lime. Gold dissolution takes place in three agitators in series with the pulp from the agitators being filtered in two stages in disc filters. Between filtration stages, the cake is repulped with barren solution. Filtrate from both filters is the pregnant solution. The Merrill-Crowe recovery unit is comprised of two solution tanks and the usual clarifying filter, vacuum tower, zinc dust feeder and Merrill precipitate press. Because of the presence of finely divided sooty chalcocite in the molybdenum concentrate, the cyanide consumption of 55 pounds per ton is extremely high. A compensating factor, however, is the low copper, moly concentrate produced. Precipitation of the gold from the highly copper-contaminated solution requires 0.56 pounds of zinc dust and 0.28 pounds of lead acetate per ton, high figures when compared to normal cyanidation practice. The Merrill- Crowe precipitate assays approximately 28.5% Cu, 8% Zn, 156 oz Au and 197 oz Ag per ton. The San Manuel cyanidation plant is an outstanding and innovative development.

Jan 1, 1975

By W. H. Andrews

The constantly increasing consumption of Portland cement in the State makes the above subject of particular interest at this time. The increasing demand is due to the rapid settling of the country and the fact that new uses are being found frequently for the above named commercial article. The industry is one that is bound to grow as the population increases, and this being the case it may be well at this time to consider briefly the matter of the chemical and physical composition of proper raw materials. A cement mixture is one that contains approximately 75 per cent, carbonate of lime, 15 per cent. silica, and 5 to 7 per cent. alumina and iron oxides; the other elements being magnesium carbonate and mall quantities of the rarer elements generally associated with limestone deposits. It can be readily seen from the above composition that it is possible to build up this mixture from a number of different materials. First.—A rock high in carbonate of lime can be mixed with clay or shale in such proportions as to bring about the desired composition ; the chief difficulty in the building up of such a mixture is that it is hard to find a clay or shale in which the silica-alumina ratio lies between 4 to 1 and 3 to 1 and at the same time shows physical characteristics which will make certain its adaptability to the practical manufacture of Portland cement. Very often clays or shales are found which are right chemically but contain large quantities of grit or free silica. Such clays or shale must be ground to extreme fineness in the mixture in order to make the silica and alumina combine with the lime when the mixture is burned. On the other hand, clays or hales are often found that have the proper physical characteristics but in which the amount of alumina is too great. Second.—A mixture can be built up of different limestones some of which run above the 75 per cent. requirement and others below;

Jan 1, 1914

By F. X. Tartaron

This paper deals with basic physical phenomena, which when combined and interpreted, lead to the same mathematical equations that describe comminution phenomena. Thus, a physical model is described that corresponds to the mathematical model presented in the writer's previous papers. '12 In the mathematical model, the energy consumed in breakage is related to the volume or weight of material broken and the size of particles broken. The equation E=2.303 Ck-a log x1/x2 was derived by multiplying the volume or weight of each size in an ideal Gates-Gaudin-Schumann size distribution by an energy factor. The product of these two factors gives the energy distribution among the different sizes in a single size distribution. The energy of breakage of a specific constant weight of one size distribution to another size distribution is given by the equation E = constant/kn-1. In this case, where the volume or weight is constant, the energy is proportional to the size factor 1/kn-1. In what follows, a physical theory will be presented showing that the energy consumed in comminution is proportional to the volume or weight of the material broken and to the reciprocal of the size of this material raised to a constant exponent. THE VOLUME FACTOR The atomic theory of matter reveals that in solids, atoms or ions are arranged so as to be in equilibrium at specific distances from one another. Although the atoms or ions are oscillating, there is a definite determinable mean distance between them and this distance is a balance between repulsive and attractive electrical forces. It therefore requires force to separate the atoms or ions and when an outside force is applied, it first produces strain in increasing the distance between the atoms or ions. This strain increases to the breakage limit on application of sufficient force. In brittle materials, there is negligible plasticity and when an elastic limit is exceeded, breakage takes place. The work done is the force applied per unit area times the cross sectional area of the ideal particle multiplied by the maximum strain per unit length at right angles to the area times the length of the particle. Thus the work done is proportional to the area times the length, which is equivalent to the volume of the ideal particle. If more than one feed particle is considered broken, each particle must be subjected to sufficient strain so that the breakage limit of its contained atoms or ions is reached in order for the particle to be broken. Thus, the energy of breakage is proportional to the total volume of the particles broken. If the particles are of different sizes, the size factor must be included to get a correct determination of energy of breakage. In the preceding, it has been assumed that there is a constant binding force between the atoms throughout the volume being strained. This, of course, is not true. It is known that there are many irregularities in the structure of matter and the binding force differs markedly in different portions. But the differences are only discernible by examining extremely small subdivisions of matter. In one order of magnitude of volume, cracks can be discerned separately from non-cracked neighboring material. In a smaller subdivision of volume, lattice dislocations can be isolated. When these situations are brought into focus, mechanisms of their behavior can be learned, leading to a fuller understanding of phenomena that occur in larger scale subdivisions of matter. Very often, however, the mechanisms that operate in small scale subdivisions have negligible effect in those of large scale, and there still is a place for deriving a mechanism for large scale conditions. The quantum theory is extremely valuable for use with photons and electrons, but is of negligible use with ordinary atoms and molecules. This paper deals with relatively large scale subdivisions of volume present in comminution phenomena. Hence, the effects of cracks, lattice dislocations, misplaced atoms, etc., are smoothed out in an average, constant for each relatively large subdivision of volume. This attitude is supported by experience. If two 10 cc samples of the same ore were ground identically, the same product would be obtained. However, if two samples, each a cubic micron, were conceived to be broken, then one sample might contain a crack and the other not, hence a different product would be obtained. Experience shows that ordinary samples used in comminution, behave as though no irregularity existed

Jan 1, 1964

State of Indiana, Department of Conservation, Division of Geology, Indianapolis, Ind. W. N Logan, State Geologist A list of the publications will be sent upon request. A series of yearly reports have been issued, with a few early exceptions, since 1869, up to and including the 41st (1916) Five of these are issued free, 18 are out of print, and the rest may be obtained at a quoted price. Beginning in 1917, the administrative reports of the State Geologist have been published in the Indiana Year Book. In 1919, the Department of Geology and Natural Resources became the Division of Geology in the Department of Conservation and separates of later reports in the Year Book are available, as follows. 3rd Report (1921), Gold in Indiana, 4th (1922), The New Albany shale, peat deposits of Indiana; 5th (1923), Petroleum conserva¬tion, 6th (1924), Conservation of natural gas; 7th (1925), Coal losses of Indiana, 10th (1928), Geological conditions in the Siosi oil field, 11th (1929), The mineral fuel resources of Indiana, 12th (1930), Oil and gas developments in 1930. (Titles of lesser interest are omitted ) The following Special Reports have been printed as publications of the Department of Conservation: Special Report 6, Kaolin of Indiana (1919), free; 21, Handbook of Indiana geology (1922), $5 to nonresidents and $3 to residents, 42, Geologic conditions in the oil fields of southwestern Indiana (1924), 75 cents to non-residents and 50 cents to residents; 55, Geology of the deep wells of Indiana (1926), $1; 75, Geology of the Silurian rocks of northern Indiana (1928), $1, cloth bound, 8125, 78, Indiana oolitic limestone map of Monroe-Owens counties (1928), $1, 79, Indiana oohtic limestone map of Lawrence County (1928), $1; 90, The geologic history of the vertebrates of Indiana (1929), $1, cloth bound, $125, 91, The ceramic materials of Indiana (1929), free, 98, The Borden (Knobstone) rocks of southern Indiana (1931), $1 25, cloth bound, $150, 101, Insoluble residue studies of Mississippian limestones in Indiana (1931), 25 cents

Jan 1, 1933

By M. I. Jacobson, A. S. Yue, A. E. Vidoz, F. W. Crossman

An equation governing the concept of constitutional supercooling under the combined effect of concentration and temperature gradients was used to produce platelike Al-CuAl2 eutectic composites for mechanical properties studies. Compression specimens were prepared from a single-colony Al-CuA12 eutectic composite ingot, 2 in. in diam and 12 in. long. The specirrzens were cut such that the platelets were oriented parallel, 45 deg, and perpendicular to the compression direction. Since the ingot was of eutectic composition, The aluminum-rich matrix could dissolve 5. 7 wt pct Cu in solid solution, and therefore could be strengthened by precipitation hardening. Specimens were tested at room temperature and elevated temperatures in the unidirectionally solidified, solution-treated, and solution-treated plus aged conditions. The results were compared with those for the conventionally cast and extruded specimens. For the controlled material, the highest strengths were obtained with platelets oriented parallel to the compression axis. In the unidirectionally solidified condition, 0.2 pct offset yield strength was 32,000 psi; however, this was increased to 59,000 psi by solution treatment, and further increased to 90,500 psi by solution treatment and aging. The attainment of high compressive strengths in the Al-CuAl2 eutectic composites was interpreted in terms of the buckling of elastic CuAl2 platelets in the plastically deformed a aluminum matrix. SINCE the discovery of high-strength whiskers,' scientists and engineers have made significant progress toward incorporating these whiskers into metallic matrices, forming composites for basic studies and structural application. The general procedure is to produce the whiskers first and then to bind them together with a ductile matrix. The production of whisker-reinforced composites requires tedious handling techniques,, particularly when it is desired to align the whiskers unidirectionally. Furthermore, the interfacial bond between the whisker and the matrix is frequently poor3 so that the resulting composite has strengths lower than expected. These disadvantages are generally true for any metallic composite produced by physically mixing the components. It is possible to eliminate these shortcomings by growing whiskers directly in the matrix material by eutectic solidification.4-8 In eutectic solidification, the matrix phase and a whisker phase are grown approximately simultaneously from a liquid of the same overall composition at the eutectic temperature. If the solidification process is controlled by varying the freezing rate, the temperature gradient, and the impurity content, platelike or filamentlike whiskers are produced parallel to the growth direction. The morphology of the grown-in reinforcement, i.e.. plates or rods, generally depends on the volume fraction9 of the dispersed phase present in the eutectic mixture. Since the unidirectional eutectic solidification is a one-step process, i.e., the liquid-solid transformation process, an excellent interfacial bond between the matrix and whisker is obtained. An additional advantage is that no special handling technique for whiskers is needed. In recent years, many investigators10-13 have studied the effects of growth variables on the micromorpholo-gies of binary eutectic alloys produced by controlled solidification. The study of their mechanical properties was initiated by Kraft and coworkers14-16 who found that the strength of cast A1-CuA12 eutectic alloy can be increased threefold by unidirectional solidification. In the A1-AL3Ni system, a strength of 50,000 lb per sq in, was reported for the unidirectionally solidified eutectic alloy, a value five times higher than for conventionally cast material. Thus, the unidirectionally solidified eutectics can be used as fiber-reinforced composite materials. In this paper, we shall first use an equation17 as a guide for the production of eutectic composites in general and the Al-33 wt pct Cu eutectic in particular. Experimental data supporting the theoretical prediction are given. Second, the compressive properties of the grown A1-33 wt pct Cu eutectic were thoroughly investigated in terms of platelet orientations, thermo-mechanical treatment, and temperature. The experimental data are interpreted in terms of a buckling model of fibers in elastic fiber-plastic matrix metallic composites. EXPERIMENTAL PROCEDURE Crystal Growth. The following experimental procedure was adopted for the production of controlled microstructures in the A1-33 wt pct Cu eutectic alloy. The controlled solidification was accomplished with a movable resistance-wound radiation furnace. Fig. 1 is a schematic drawing of the solidification apparatus. A water-cooled chiller was placed into a degassed high-purity graphite crucible containing the charge. Rubber stoppers wrapped with aluminum foil were used to seal both ends of the quartz tube through which a dried argon atmosphere was passed under a slight positive pressure. At both ends of the quartz tube, radiation shields were used to minimize heat loss. The quartz tube was held in place by two steel clamps and the furnace was drawn vertically by means of a steel cable against the steel truss which permits the furnace to move without touching the tube. The drive mechanism consisted of two pulleys, a counter weight.

Jan 1, 1969

By James C. Word, R. M. McLouski

This paper will describe the development and application of large-scale integration techniques employed in the fabrication of a germanium multielement array. The array consists of 100 by 228 PNP bipolar transistors fabricated on 5 mi1 centers. Back-biased p-n junction techniques are used for electrical isolation of the individual elements. The end use of the array is a high resolution, large area IR sensor. The monolithic array is fabricated in 1 ohm-cm p-type germanium epitaxially deposited on 6 ohm-cm n-type substrate. Epitaxy was accomplished through the hydrogen reduction of germanium te trachloride. Di-borane was used as the dopant. Base regions are achieved by the diffusion of arsenic from doped oxide or arsine sources. Oxide-masking of the arsenic im-pzlvity was achieved by the chemical deposition of a boron doped glass. The emitter is formed by an aluminum alloy diffusion technique. Vacuum deposited aluminum is used for the emitter, interconnections, and for the contact and bonding pads. ALTHOUGH a great volume of literature pertaining to the development of large scale integration techniques (LSI) has been published for silicon and in particular silicon imaging applications,' to date only a small number of similar devices have been constructed using germanium technology.' Since the physical and chemical properties of germanium are vastly different from those of silicon, the fabrication technology for integrated structures in germanium is also different from that of silicon. In particular germanium does not possess a stable oxide as can be grown on silicon by heating in an oxidizing ambient for masking of dopants and passivation. This paper describes the application of germanium LSI techniques employed in the fabrication of a multielement infrared sensor array. The array is used in a high resolution, large area infrared sensor for operation in the 0.8- to 1.5-u spectral range. Back biased p-n junction techniques are used for electrical isolation of individual elements. Discrete germanium devices have been fabricated routinely for some time. However, mainly due to the lack of a suitable mask for selective doping and the high current leakages inherent in germanium p-n isolation, few monolithic germanium structures have been constructed. THE INFRARED MOSAIC A cross-sectional view of the array is shown in Fig. 1. The monolithic structure consists of 12,800 PNP transistor elements in a 100 by 128 matrix fab- ricated on 5 mil centers. The emitters of each line of transistors are connected together using aluminum interconnects while the strip collectors are connected together in series at right angles to the emitter lines. The selection of this structure is dictated by the readout technique involved. Access to each element transistor is obtained by applying a bias voltage to a particular collector strip and separately interrogating each emitter row. A charge storage, i.e., an integration mode is used for reading out this particular array Construction techniques available for use with germanium do not include a selective p-type diffusion capability for surface concentrations greater than 10" per cu cm and junction depths greater than about 10 u. This fact limits the type of structure that may be used. Therefore, an array of PNP transistors that did not employ p-type diffusions was chosen. The structure was fabricated by growing a 1 ohm-cm p-type epitaxial layer on a carefully prepared 6 ohm-cm n-type substrate. N-type dopants were used for the isolation and base diffusions and alloyed aluminum was used to form the emitter junctions. The array was then completed by evaporation of aluminum interconnections and contact pads. SUBSTRATE AND SUBSTRATE PREPARATION Germanium substrates of (111) orientation grown by both Czochralski and zone leveling techniques were utilized for mosaic fabrication. Czochralski substrates were preferred because of the lower dislocation densities available in this type of material. Dislocation densities for the Czochralski material were typically less than 3000 per sq cm, while those for the zone leveled material were typically less than 5000 per sq cm. All substrates were uncompensated to minimize thermal conversion problems in subsequent epitaxial and diffusion processing. Both in-house and vendor polished wafers were used. The in-house polishing technique employed consisted of an initial gross chemical etch in CP4 to remove saw damage from both surfaces. This was followed by a chemical-mechanical polishing operation of one side of the wafer. The chemical-mechanical polishing solution used was Lustrox 1000 (Tizon Chemical Co.), and consists of zirconium dioxide, sodium hypochlorite, water and a surfactant. The wafer thickness before and after polishing was typically 0.020 and 0.010 in, respectively. THERMAL CONVERSION The problem of thermal conversion of both the substrate and epitaxial layer was particularly acute because of the relatively low carrier concentrations employed in both regions. This problem has been encountered by other workers in the past.3 Without special treatment before epitaxial growth substrate conversion (n-type to p-type) and changes in the re-

Jan 1, 1970

By R. E. Cech, T. D. Tiemann

It has been shown that hydrogen may be made to serve as a rapid and eflicient reducing agent for Cu, Ni, Co, and Fe sulfides if a scavenging agent for hydrogen sulfide is intimately mixed with the sulfide particles being reduced. Accelerated reduction kinetics are demonstrated for nickel sulfide. Copper, nickel, and cobalt sulfides, when treated at certain temperatures in a combined reducing agent-scavenging agent system, are converted to voluminous masses of fibrous metal product. Studies have been carried out to determine the conditions which lead, on the one hand, to irregular poly crystalline fibers and, on the other, to long single crystal filaments a few microns in diameter. A mechanism is proposed to account for the formation of single crystal filuments. The sulfide minerals of Cu, Ni, Co, and Fe are an important source of these metals yet there has been comparatively little scientific effort devoted towards understanding reduction mechanisms of these minerals. This may be, in part, due to the fact that the most convenient reducing agents for carrying out such studies, viz., hydrogen and carbon, do not react appreciably with sulfides. We have found that the reaction of hydrogen with metal sulfides can be markedly accelerated by placing a scavenging agent for hydrogen sulfide in close proximity to the metal sulfide. A brief series of experiments demonstrating relative reduction rates is reported in this paper to illustrate the effect. With the reduction process thus accelerated we have observed an unusual type of reduction behavior on some of the sulfides investigated. Under certain conditions the metallic product of the reduction reaction takes the form of filaments growing outward from the sulfide particles. The present paper deals largely with efforts to classify the various types of growth forms observed. This study has shown that filamentary growths from sulfides take a much greater variety of forms than has heretofore been reported by Ercker,1 Hardy,2 and Nabarro and Jackson3 in their reviews of metallic growths from copper and silver sulfides. THERMODYNAMIC CONSIDERATIONS The thermodynamics for hydrogen reduction of metal sulfides is quite unfavorable. For the sulfides considered here equilibrium constants typically range from 10-3 to 10-5. These low equilibrium constants impose severe kinetic limitations on reduction since hydrogen sulfide must be transported out of the system at concentrations of only a few hundred ppm. Unless extremely high gas flow rates are employed the atmosphere surrounding any sulfide particle will always be essentially in equilibrium with the sulfide. If, however, one places an efficient scavenging agent for hydrogen sulfide in close proximity to the metal sulfide particles the concentration of H2S near the metal sulfide will be held to a very low value. This would permit the reduction reaction to proceed with little or no inhibition from a buildup of reaction product gas. It is well known that calcium oxide is capable of removing hydrogen sulfide from a hydrogen gas stream of low dew point.4 If a sufficient quantity of calcium oxide is mixed with the metal sulfide particles the reaction: CaO+H2S=CaS+ H2O [l] will substitute moisture in place of hydrogen sulfide in the gas stream and this will not affect, in a direct manner, the reaction: MeS +H2=Me + H2S [2] A convenient method of considering the thermodynamics of the combined reducing agent-scavenging agent system is to consider the atmosphere when the partial pressure of hydrogen sulfide is the same over both the metal sulfide and the scavenging agent, i.e., pH2S (1) =pH2S (2). As a consequence: pH2O (1) pH2(2) =K1K2 The chemical driving force for reduction will depend inversely upon the moisture content of the gas and will be 0 when, in the system, pH2O = pH2.K1K2. Table I lists values of the equilibrium constants for reduction and H2S scavenging reactions for a number of sulfides at several temperatures. Data are taken from Rosenqvist4,5 and Kelly.6 The equilibrium constant products calculated from this data show that the limiting level of gaseous reaction product has been increased by a factor of 10' to l04 as a result of substituting a reducing agent-scavenging agent system for a simple reducing agent system. One possible side effect which must be considered is the possibility that the moisture evolved in the scavenging reaction might cause the atmosphere in the system to be sufficiently oxidizing to favor the formation of oxide rather than metal. This possibility was examined by comparing the equilibrium constant products listed in Table I with equilibrium constants for hydrogen reduction of the respective metal oxides. It was found that for copper, nickel, and cobalt the combined reduction-scavenging reactions could not develop a sufficiently high oxidizing potential in the

Jan 1, 1970