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By H. W. Schull

The Alligator Ridge gold deposits are located in northwest White Pine County at the southwest end of Alligator Ridge. Alligator Ridge is on the west side of Long Valley in the range of hills that separates Long and Newark valleys. The nearest population center is Ely, about 113 km (70 miles) to the southeast. Access to the Alligator Ridge gold mine from Ely is via US Highway 50 and the Long Valley Ruby Marsh Road. The latitude and longitude is approximately 39° 45' north and 116° 30' west. The Alligator Ridge gold deposits occur in the lower 61 m (200 ft) of the Mississippian-Devonian Pilot Shale formation, a laminated calcareous carbonaceous siltstone. The gold deposits contain carbonaceous, oxide, and jasperoid type gold ore. For more details on the geologic features of the deposits, see Schull, Sutherland, and Ilchik (in press). The discovery story of Alligator Ridge began in the spring of 1976 when the areas mapped as jasperoid on the 1:250,000 scale geologic map of White Pine County (Hose and Blake, 1976) were examined and sampled. Seventeen samples, about 23 kg (50 lb), were collected from an area about 0.65 km2 (0.25 sq mile). Of these 17 samples 10 reported atomic absorption values of less than 0. 1 ppm Au and 7 reported values in the 0.1 to 1.0 ppm Au range. In June of 1976 20 lode claims were staked to claim the area of the rock chip sampling. The claims' end and side center lines were used as a grid for soil sampling. Sample stations were 91 m (300 ft) apart and sample lines were 229 m (750 ft) apart. The samples were sieved to - 180 µm (- 80 mesh). Out of 99 soil samples, seven samples reported Au values in the 0.1 to 1.0 ppm range. Of the seven auriferous samples, five were located over the jasperoid outcrops previously sampled; one over unmineralized Pilot Shale a few hundred m (ft) downslope from some Au-bearing jasperoid; and one from a 15 x 15 m (50 x 50 ft) talus outcrop area of hitherto unnoticed mineralized Pilot Shale. Subsequent sampling, mapping and drilling would show that this 15 X 15 m (50 x 50 ft) outcrop area was the top of the Vantage 1 ore body, about 1.27 Mt (1,400,000 st) of over 3 g/0.9 t (0.11 oz/st) Au. Late in the summer of 1976 about 30 more 1.4 to 2.2 kg (3 to 5 lb) rock chip samples were collected in the course of preliminary geologic mapping. This mapping and sampling showed that the gold-bearing jasperoids occurred at the contact between the Pilot Shale and the underlying Devils Gate Limestone. Rock chip samples of 0.1 ppm Au or greater were restricted to the jasperoids and the mineralized outcrop area of Pilot Shale located by the soil sample survey. Rock chip samples from the area of mineralized Pilot Shale were in the 3 to 5 ppm Au range. Activity resumed in the summer of 1977 with a more detailed soil geochemical survey. The jasperoid areas were defined as large geochemical gold anomalies of values greater than 0.1 ppm and locally greater than 0.2 ppm Au. Soil samples from the area of mineralized Pilot Shale outlined a greater than 0.1 ppm gold anomaly 61 x 152 m (200 x 500 ft) in size. Further geologic mapping showed that elsewhere, even where bleached and silicified, the Pilot Shale areas were geochemically very low in gold (less than 0.1 ppm Au). In November, 1977 twelve rotary percussion drill holes were drilled to test the gold-bearing jasperoid areas and the mineralized Pilot Shale area. Drilling of the jasperoid areas showed that the jasperoids gave way at shallow depths [less than 24 m (80 ft)] to unmineralized unaltered Devils Gate Limestone. A five hole cross pattern was drilled to test the area of mineralized Pilot Shale. Four of the five holes re-

Jan 1, 1985

By Orville R. Lyons

This paper presents a method whereby the amount of misplaced material and the difficulty of the separation can be used to compare coal cleaning equipment of all types, from effectiveness and capacity standpoints. The correlations presented do not include all types of equipment currently available, but the method can be used to evaluate any make or type of coal cleaning equipment, both old and new. THE relative performance of coal washing equipment, or the effectiveness with which any type or make of equipment removes impurities from coal, has been most difficult to evaluate in the past. The most widely used yardstick is the Frazer and Yancey efficiency formula developed in 1922,' but Yancey in a later article states that "washers treating coals of different density composition or operating at different densities of separation cannot be compared directly on the basis of this criterion."' Prior to and since 1922, a variety of other methods has been used for comparison purposes, including the distribution curve, the error area, and the "ecart probable" or probable error. Yancey and Geer in discussing these methods conclude, "Performance can be evaluated in a number of different ways, with the choice of the proper method to use being dictated by the objectives of the investigation and the data available."' It is true that performance can be evaluated in a variety of ways, but if the equipment is to be evaluated on an effectiveness basis, there should be only one universal comparison method. Varying methods have been used because one universal comparison method has not been found or developed. In the article previously quoted, Yancey and Geer state in clear terms the primary concept for a universal comparison method: "One of the simplest, and certainly one of the most obvious evaluations of washery performance is the quantity of sink material in the washed coal and the float material in the refuse. If the washery products are tested at the density at which the washing unit is operated, the sink in the washed coal and the float in the refuse represent material that has been misplaced." The quantity of misplaced material was used as a criterion of washery performance by Lincoln in 1913," by the United States Bureau of Mines in 1938,' by Hancock in 1947," and by the national French research agency Cerchar in recent years.' In 1950 Andersone proposed the use of this criterion as an efficiency value to replace the Frazer and Yancey formula. However, none of the above-mentioned investigators used the misplaced material concept in a manner that would provide universal coal-cleaning equipment comparisons. The Correlation Theory The ideal coal cleaning process would treat all sizes and would make a perfect separation at any given specific gravity. All material lower in density than the desired value would report in the coal product and all material higher in density would report in the refuse product. Unfortunately, no known cleaning process achieves this goal and there seems little likelihood that any process yet to be invented will do more than approach it. When coal is treated in volume under operating conditions, it is impossible to avoid mechanical entrapment, fluctuations in throughput and effective gravity of separation, and the creation of turbulent currents, even when a true heavy-liquid bath is used and the feed is closely sized and contains little intermediate gravity material. This being so, it is possible to appreciate the difficulties inherent in trying to obtain a perfect separation when treating a wide range of sizes and a feed containing high percentages of intermediate material, using turbulent currents to help create the effective separation gravity, under operating conditions which normally tend to be on the overload side. When coal is separated from refuse in any coal cleaning equipment, some refuse always reports to the coal and some coal to the refuse; the writer therefore assumed that there should be a relationship between the total amount of misplaced material produced by any given piece of equipment and the difficulty of separation as represented by the percentage of near gravity material in the feed. With small amounts of near gravity or k0.1 material in the feed there should be less misplacement of material than would occur with large amounts of near

Jan 1, 1953

By Leslie W. Austen

ROTARY kiln operators will agree that some of the most severe conditions a refractory must stand occur in the hot zone of a kiln burning Portland cement, dead burn dolomite, magnesite, peri-clase, and similar materials. Frequently the operator is faced with factors beyond his control which drastically shorten the life of refractories. Shutdown due to mechanical failure can be serious if the period is of sufficiently long duration to cause the dropping of coating or the loosening of the lining. A change in slurry can affect the coating and cause ring buildup. A change in type of fuel and its effect upon the flame can cause a shift in location of the hottest zone. Weekend shutdowns or any other interruption can cause the operator trouble and may damage the refractories, since stopping and starting a rotary kiln is certainly more difficult than stopping and starting a motor. Some operators have tried to set an estimate of damage for each shutdown in equivalent days of running time. Conditions affecting the refractory may be roughly grouped in four classes: chemical attack, mechanical stress, thermal shock, and abrasion. Chemical Attack: The drive to obtain maximum production through a kiln demands maximum operating temperatures, temperatures which are limited more by the ringing up or melting of the clinker. This can cause interface temperatures at the junction of coating and refractory which require the use of a basic kiln block to withstand the chemical attack. Chemical changes take place within the refractory itself, especially in chemically bonded or unburned kiln blocks. These changes cause the formation of the ceramic or burned bond. Migrating liquids or fluxes from the kiln charge have an effect within the refractory and lead to mineral or glass formation. The alkalies, sodium and potassium, migrate into the refractory as silicates, chlorides, sulphates or other salts. They may move under capillary action or may be caused to move by volatilization with condensation in the cooler portion. Mechanical Stress: Concentrated stress may be caused by several factors or combinations thereof. I—The rings of refractories must be kept tight and rigid within the kiln, and this alone demands considerable force to hold the blocks in place. So that the force will not be concentrated, the blocks should fit the circle as perfectly as possible, with the faces in contact overall. 2—As the kiln is heated, thermal expansion takes place at the hot end of the kiln block. Since this disturbs the plane face it too can cause a concentrated stress at the two ends of the block, and shearing stress can be set up within the brick itself because of the difference in expansion between the two ends. 3—If a lining becomes loose and moves in the shell very severe stress can be set up, and as the kiln rotates this load changes and gives the effect of repeated loading. Permanent expansion of the refractory can also cause severe loading. 4—Not least important, flexing of the kiln is frequently the cause of concentrated stresses. Thermal Shock: Thermal shock, the result of heating and cooling too rapidly, occurs on starting and stopping or when a large patch of coating drops, exposing the bricks. Again, its destructive effect is often the result of phase change, liquid to solid or the reverse; dense refractories loaded with glass-forming impurities are particularly susceptible. Thermal shock is a. problem with refractories set in the wall or roof of a stationary furnace, and becomes even more serious in a rotary kiln, the tendency to spa11 being magnified with movement and concentration of stress. Uniform rate of feed and loading insures both better coating and a more uniform stress. Abrasion: If the refractories do not take a coating, abrasion can become a most destructive factor. Movement of the lining in shell or movement of loose blocks causes abrasion, which is also most destructive if the refractories do not take a coating. An analysis of the problem of basic lining for the hot zone reveals, therefore, a number of desirable characteristics: high refractoriness, basic chemical reaction, resistance to spalling, good strength at all stages, ability to take coating, true sizing, volume stability, and abrasion resistance. Increased demand

Jan 1, 1953

By R. L. Bleifuss

The object of this study was to evaluate the oxidized taconites of the western Mesabi iron range and to establish a correlation between the various basic taconite types and their concentratability. The initial work included a study of the original mineralogical and stratigraphic facies of the fresh taconite and traced the oxidation and leaching patterns developed during the conversion of this material to oxidized taconite. Subsequent studies have extended this work to include the semitaconites and also the wash and heavy media ore types widely developed in the area. Each basic original mineralogical facies or taconite type produces during alteration an equivalent secondary oxidized facies which has a unique mineralogical composition and texture. These control the concentratability of the oxidized taconites. Actually the influence of the original mineralogical composition of the iron formation extends even further and determines whether the most likely product of oxidation and leaching will be a wash ore or a heavy media ore and even to the direct shipping ores where the ratio of hematite to goethite is largely determined by the original taconite type. The relationship between original taconite, oxidized taconite, semitaconites, and wash and heavy media ores is briefly summarized in Table I. The terms are not precise and in some instances tend to overlap. The table is intended to point out only the essential differences between the various materials. The original taconite was dominantly composed of mixtures of magnetite, iron carbonate, iron silicate, and quartz (chert). In a few thin stratigraphic units, hematite was present as an original constituent. The alteration of the original taconite to oxidized taconite has resulted from the circulation of ground waters through an initial fracture system related to minor structures in the iron formation. The chemical reactions have involved the oxidation and decomposition of original minerals such as magnetite, iron carbonate, and iron silicates to hematite or goethite. The alteration at this early stage is characterized by pseudomorphic replacement of the original minerals by oxidation products although retaining the major textural features of the original taconite. There was very little secondary migration of iron at this stage and the total iron content of the rock has been only slightly increased. Further alteration of this material to form a semi-taconite, a wash or a heavy media ore, involves extensive removal of silica in solution and significant redistribution of iron units. Wash and heavy media ores are developed by the growth of coarse secondary iron layers, dominantly goethite, coupled with the removal of silica in solution and decomposition of the cherty layers. This paper is concerned primarily with the materials classified as oxidized taconites which are characterized by oxidation of the original mineral constituents with little secondary enrichment. The area studied, shown on the index map, Fig. 1, extends some 30 miles along the strike of the Biwabik formation roughly from Hibbing to Coleraine. This study was greatly facilitated by the basic stratigraphic and mineralogical studies of Gruner1 and white2. The bulk of the material in this presentation represents a portion of the author's contribution to a study sponsored by the Great Northern Railway on the oxidized taconites of the western Mesabi.3 METHOD OF APPROACH A total of 106 drill holes, representing some 30,000 ft of drilling, were examined and sampled. The drill holes were logged and some 1500 composite samples were prepared for chemical analysis and bench scale metallurgical tests. These samples were analyzed for total iron and ferrous iron; and magnetite iron was determined by a standard Davis tube test at minus 200 mesh. Standard reduction roast tests using 150-gram samples of minus 10 mesh material were made on these 1500 composite samples with a mixture of H2, CO2, N2, and H2O at a temperature of 650°C. This roasted material was pulverized through 150 mesh and concentrated in the Davis tube. The iron recoveries and concentrate grades obtained on the roasted products were used to assess the concentratability of the oxidized taconites. Detailed mineralogical work was done on thin sec-

Jan 1, 1964

By D. J. Carney, E. C. Rudolphy

IT has been demonstrated that inclusion size, distribution, and composition affect the machin-ability of resulphurized steels. Merchant and Zlatinl concluded that large sulphide inclusions aided machining by forming a (lubricating) coating on the tool face. Boulger et al.² and Van Vlack³ noted that the size, distribution, and composition of the inclusions in the steel affected the machinability. Steel specimens containing large globular sulphide inclusions usually exhibited excellent cutting properties, while machinability was adversely affected by the presence of numbers of oxide-type inclusions. Consequently a thorough knowledge of all the factors which affect the inclusions in the final product is desirable. Since almost all the inclusions have their origin in liquid steel, it was necessary to begin a study of inclusions in free-machining steels by studying the inclusions and chemical segregation in the as-cast ingot. Very little information is available on the size, distribution, shape, and composition of inclusions in large, capped, free-machining steel ingots, particularly the B1113 grade. Gregory and Whiteley4 made a general study of the inclusions in a small, high sulphur, free-machining steel ingot. Also, numerous authors have described the solidification and segregation characteristics of the four basic types of steel ingots, namely, rimmed, capped,7 semikilled,7,8 and killed7,9,10 ingots. Most of these studies were made with plain carbon or low alloy, low sulphur steel. It was desirable to study not only the ingot but also the change in size, shape, and number of inclusions on rolling an ingot to a bloom and thence to a billet. This procedure was followed and it is hoped that this study may serve the dual purpose of adding to the general knowledge of ingot solidification as well as contributing to the knowledge of the size, shape, distribution, and composition of inclusions from the ingot to the billet in a high sulphur, free-machining steel. Procedure A 12.000-lb 23x35x75 in. slab ingot of the B1113 grade was cast, sectioned, and studied both macro-scopically and microscopically. An adjacent ingot from the same heat and of the same size was rolled to a 77/8x77/8 in. bloom and thence to a 21/2x21/2 in. billet. These various bloom and billet sections were also sectioned and studied macroscopically and microscopically. Sectioning the Ingot: The ingot herein described was obtained from the United States Steel Corp.'s South Works Bessemer Blow No. 0193, a B1113 mechanically capped heat. The 23x35 in. ingot (No. 2) was teemed according to normal procedures and after stripping and transportation to the rolling mill was not placed in the soaking pit but allowed to air cool in an upright position. When completely solidified, the ingot was cut into sections by means of a powder scarfing torch and further sectioned by saw cutting as indicated in Fig. 1. Cut No. 2 (1x10x12 in.) from sections A through H was cleaned thoroughly, macroetched in a solution of 50-50 water and hot muriatic acid and used to obtain a macrograph of a horizontal section from the surface to slightly beyond the center of the 23-in. ingot dimension. Cuts No. 5 and 3 (lx81/2xl0 in. each) from sections A through H were treated in a similar manner to obtain a macrograph of a horizontal section from the surface to slightly beyond the center of the 35-in. ingot dimension. The composite macrograph of these horizontal ingot sections, which shows a vertical section of the ingot from top to bottom, is shown in Fig. 2. It should be noted that sections No. 2 are normal to sections 5 and 3 in the composite. Drillings for chemical analyses were obtained from selected positions within the above-mentioned ingot sections as noted in Fig. 3. The oxygen content was determined by the vacuum-fusion method. Samples for microscopic examination were cut from

Jan 1, 1954

By V. T. Stringfield, H. H. Cooper

ONE of the earliest investigations of ground water in Florida was made in 1513 when Ponce de Leon arrived at St. Augustine in search of the Fountain of Youth. The history of the development of the water resources of the State shows that the large artesian reservoir that underlies Florida was discovered in the latter part of the last century. Part of that history is given by L. C. Johnson' who states that the first successful artesian well in Florida was drilled at St. Augustine between 1880 and 1882. After the City of Jacksonville failed to obtain a flow of artesian water at a depth of nearly 400 ft and abandoned the drilling, R. N. Ellis, City Engineer, and L. C. Johnson, using Johnson's knowledge of the geologic structure of the artesian reservoir, estimated correctly that artesian water could be obtained at a depth of about 500 ft. Thus began the development of the large artesian system in the northeastern part of the State. In 1908, the Florida Geological Survey issued its first report on the ground water of central Florida. More recent reports give the results of investigations that have been in progress in cooperation between the Florida Geological Survey and the U. S. Geological Survey since 1930. As a result, the ground-water geology and hydrology of Florida are now so well known that ground-water problems such as confronted early investigators no longer exist. However, new problems arise and new discoveries are made as the demand for more ground water increases with the development of the State. Water-Bearing Formations Descriptions of the geologic formations and a map showing their distribution at the surface are given in a recent report by Cooke.' The geologic formations that yield the ground-water supplies in Florida represent only a small part (about 1000 ft) of the total thickness of the sedimentary rocks (more than 15,000 ft) that underlie Florida. The water-bearing rocks that yield fresh water include more than two dozen formations that range in age from Eocene to recent. The Eocene formations, which consist chiefly of limestone, are the oldest and the deepest of the formations in Florida that yield fresh water to wells. In 1944, on the basis of a study of the foraminifera, the Applins -ivided the limestone of Eocene age into six formations, which are as follows, from top to bottom: Age or group Formation Jackson Ocala limestone icAvon Park limestone Claiborne -j Tallahassee limestone aLake City limestone Wilcox Salt Mountain limestone xOldsmar limestone The Ocala limestone and the underlying formations of Claiborne age, along with some of the overlying limestone of Oligocene and Miocene age, constitute the principal source of water in Florida and southeastern Georgia and generally may be regarded as forming one artesian aquifer or water-bearing unit. This aquifer is referred to in this paper as the Floridan aquifer, a name proposed by Parker.' In part of Seminole County alone more than 1000 flowing wells yield water from the Floridan aquifer. A yield of 6500 gpm, or about 9.5 million gal per day, by natural flow from a well penetrating the aquifer at Jacksonville, Florida, was observed in 1942. A yield of about 7000 gpm by natural flow was reported for a well 1390 ft deep at St. Augustine in 1887. The largest yield reported from a pumped well penetrating the aquifer is 7500 gpm, or about 10.5 million gal per day. The aquifer is also the source of some of the large springs, such as Silver Springs, whose discharge, according to measurements made by the U. S. Geological Survey, has ranged from 526 to 1350 sec-ft, or from 340 to 872 million gal per day. The top of the Ocala limestone, as represented by contours in Fig. 1, indicates in a general way the geologic structure of the formations that comprise the Floridan aquifer. The Ocala is at or near the surface in the areas represented by shading in the northwestern part of the peninsula and also in an area in western Florida adjacent to Alabama and

Jan 1, 1952

By D. B. Hunter, H. W. Rosenberg

The titanium-rich portion of the Ti-Pd system was investigated from 0 to 75 wt pct Pd by metallo-graphic and X-ray techniques. A 0 eutectoid occurs at 24 wt pct Pd and 1190°F. Two compoutzds are indicated in the region below 75 wt pct Pd, Ti,Pd and Ti2Pd3. The solubility of palladium its a titanium is low, probably less than 1 pct. In 1960 Rudnitskii and Birunl published a complete version of the Ti-Pd phase diagram. However, their work was in disagreement with the earlier literature in that they reported only one inter metallic compound, whereas three had been reported earlier. In view of these discrepancies, it was therefore necessary to redetermine those portions of the diagram of immediate interest. The following account describes our work on the system over the range of 0 to 75 wt pct Pd. MATERIALS AND METHODS Distilled titanium sponge and elemental palladium were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 10 to 50 g blended compacts that were melted into buttons by arc melting under gettered argon on a water-cooled copper hearth. Weighing of the ingredients before and after melting showed that negligible weight changes occurred. Therefore, no analyses were undertaken and the compositions of all alloys are nominal. All alloys were fabricated by hot rolling at 1700°F to 0.070-in.-thick sheet. Scale was removed by sandblasting and pickling in a 5 pct HF-35 pct HNO,, balance H20 solution. For metallographic examination, specimens were mounted after heat treatment transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and then electro-polished using a solution containing 600 ml me-thanol, 60 ml perchloric acid, 360 ml butyl cello-solve, and 2 ml "Solvent X". Unless otherwise specified, etching of alloys containing up to 42 pct Pd was carried out by swabbing with a 12 pct HN03-1 pct HF aqueous etch where a bright etch was required, or by a 1 pct hydrofluoric in saturated oxalic acid solution where contrast between phases was required. The Ti-52.8 Pd alloy was etched with a solution of 25 ml HF, 40 ml glycerine, 35 ml methanol, and 18 g benzalkonium chloride. For X-ray examination, 1/2-in.-square speci- mens of sheet were mounted flat in a standard 1-in. metallographic mount and ground and polished as above. X-ray diffraction was performed using a Norelco type 12045 Diffractometer, employing CuKa radiation with a nickel filter at 40 kv and 20 ma. Specimens were rotated about the sheet normal during exposure. Although this procedure did not remove the effects of sheet texture from the relative intensities, it had the advantage that oxidation or contaminants entering during preparation of powder samples could not confuse the patterns obtained. RESULTS AND DISCUSSION Fig. 1 illustrates the Ti-Pd phase diagram according to Rudnitskii and Birunl with the work of the present authors superimposed. Both interpretations agree that the system is of the 0 -eutectoid type with an extensive 0-phase field, and that the eutectoid temperature is just below 1200°F. There is also agreement that the solubility of palladium in a titanium is restricted. Our work would indicate that the a solubility of palladium is low, probably less than 1 pct. However, whereas Rudnitskii and Birunl place the eutectoid composition at 41 wt pct Pd, this investigation shows it to be at about 24 wt pct Pd. Moreover, this investigation confirms the existence of compounds at Ti2Pd and Ti2Pd3, whereas Rudnitskii and Birun report only a single Berthol-lide phase covering the TiPd to TiPd, range. Laves et a1.' and Wallbaum, whose work was summarized by Maykuth , reported the existence of Ti2Pd3 and TiPd, in addition to Ti2Pd. More recently, Nevitt and Downe~' have reported the structure of

Jan 1, 1965

By D. W. Fuerstenau, P. C. Kapur

The kinetics of green pelletization in a laboratory balling drum have been studied, using pulverized limestone as a model system. The growth characteristics of green pellets were found to be extremely sensitive to the moisture content of the material. Empirical kinetic equations, which incorporate a function of specific surface of the pellets as the criterion for growth potential, have been found to describe growth in a nucleation region and in a ball growth region. The rate constants in the kinetic equations are strongly dependent on the moisture content of the material being pelletized. Size distributions of the balls at different stages of pelletiz-ing are also discussed. In many industrial chemical processes, particulate matter can only be utilized if it is in an agglomerated form, such as pellets. Pelletizing is now widely used in iron ore technology1, and it has also been applied to a number of diverse fields such as the production of cement-kiln feed2, fertilizers3, and fluorspar4. Recently, it has been proposed to pelletize dispersion-type ceramic nuclear fuel elements5. In iron ore technology, for example, the production of agglomerates by pelletizing involves two major steps: 1) the preparation of green balls by rolling particles in a suitable balling device and 2) the firing of the green balls to form compact, strong bodies upon sintering. The critical step in a successful iron ore pelletizing operation is generally considered to be the balling operation1. In this paper, which is not concerned with the sintering of green pellets, the words green pelletizing and balling will be used interchangeably. Green pelletizing, or balling, will be defined as the process of forming larger bodies by rolling fine particles on a surface without the application of direct pressure. Two recent literature surveys6" indicate that in spite of the considerable amount of industrial pelletizing, very little is known about the fundamental principles of balling and its kinetics. The first reported research on the kinetics of pelletizing is the work of Newitt and Conway-Jones8. Using silica sands of different sizes in a batch laboratory balling drum, they found that the average green pellet diameter increased linearly with time at constant drum speed, and qualitatively the growth rate increased with moisture content. Generalized conclusions cannot be drawn from their research since the materials which they pelletized were sand and sand-silt mixtures rather than comminuted materials. Moreover, Newitt and Conway-Jones used testing sieves to estimate the size distribution of the green pellets, and this technique limited the range over which they could study the growth kinetics of the pellets. Bhrany and co-workers9 investigated the kinetics of balling iron ore fines on disk pelletizers ranging in diam from 1 to 18 ft. In their investigation, balling was carried out as a continuous operation, and growth kinetics were studied in terms of retention time of the material on the disk. Although the feed material in their study was quite coarse (the maximum size being about 1/2 in.), they also found qualitative relationships between pellet growth and water content, and feed size. In the present investigation, a number of innovations were introduced that refined the experimental measurements and established the reproducibility of balling experimentation. This enabled extension of the range of measurements to include study of agglomerate nucleation phenomena in the fractional mm size. This paper presents a detailed analysis of the nucleation and growth of green pellets in a laboratory balling drum. MATERIALS AND METHOD Pulverized limestone of specific gravity 2.72 was used as a model system in these studies. It has already been established that the balling characteristics of limestone and silica are similar to those of iron ore concentrates 2,8,10, depending on physical, rather than chemical, properties of the particles. The size distribution of the limestone was determined by a wet-dry sieving technique in the sieve range and by a sedimentation balance in the sub-sieve range. Fig. 1 presents the size distribution of the limestone used in this research. This figure shows that the material is finer than 200p (65 mesh) and that 25% of it is finer than 12. The specific surface area of this powder, as measured by BET gas adsorption methods,

Jan 1, 1964

By Leslie W. Austen

ROTARY kiln operators will agree that some of the most severe conditions a refractory must stand occur in the hot zone of a kiln burning Portland cement, dead burn dolomite, magnesite, peri-clase, and similar materials. Frequently the operator is faced with factors beyond his control which drastically shorten the life of refractories. Shutdown due to mechanical failure can be serious if the period is of sufficiently long duration to cause the dropping of coating or the loosening of the lining. A change in slurry can affect the coating and cause ring buildup. A change in type of fuel and its effect upon the flame can cause a shift in location of the hottest zone. Weekend shutdowns or any other interruption can cause the operator trouble and may damage the refractories, since stopping and starting a rotary kiln is certainly more difficult than stopping and starting a motor. Some operators have tried to set an estimate of damage for each shutdown in equivalent days of running time. Conditions affecting the refractory may be roughly grouped in four classes: chemical attack, mechanical stress, thermal shock, and abrasion. Chemical Attack: The drive to obtain maximum production through a kiln demands maximum operating temperatures, temperatures which are limited more by the ringing up or melting of the clinker. This can cause interface temperatures at the junction of coating and refractory which require the use of a basic kiln block to withstand the chemical attack. Chemical changes take place within the refractory itself, especially in chemically bonded or unburned kiln blocks. These changes cause the formation of the ceramic or burned bond. Migrating liquids or fluxes from the kiln charge have an effect within the refractory and lead to mineral or glass formation. The alkalies, sodium and potassium, migrate into the refractory as silicates, chlorides, sulphates or other salts. They may move under capillary action or may be caused to move by volatilization with condensation in the cooler portion. Mechanical Stress: Concentrated stress may be caused by several factors or combinations thereof. I—The rings of refractories must be kept tight and rigid within the kiln, and this alone demands considerable force to hold the blocks in place. So that the force will not be concentrated, the blocks should fit the circle as perfectly as possible, with the faces in contact overall. 2—As the kiln is heated, thermal expansion takes place at the hot end of the kiln block. Since this disturbs the plane face it too can cause a concentrated stress at the two ends of the block, and shearing stress can be set up within the brick itself because of the difference in expansion between the two ends. 3—If a lining becomes loose and moves in the shell very severe stress can be set up, and as the kiln rotates this load changes and gives the effect of repeated loading. Permanent expansion of the refractory can also cause severe loading. 4—Not least important, flexing of the kiln is frequently the cause of concentrated stresses. Thermal Shock: Thermal shock, the result of heating and cooling too rapidly, occurs on starting and stopping or when a large patch of coating drops, exposing the bricks. Again, its destructive effect is often the result of phase change, liquid to solid or the reverse; dense refractories loaded with glass-forming impurities are particularly susceptible. Thermal shock is a. problem with refractories set in the wall or roof of a stationary furnace, and becomes even more serious in a rotary kiln, the tendency to spa11 being magnified with movement and concentration of stress. Uniform rate of feed and loading insures both better coating and a more uniform stress. Abrasion: If the refractories do not take a coating, abrasion can become a most destructive factor. Movement of the lining in shell or movement of loose blocks causes abrasion, which is also most destructive if the refractories do not take a coating. An analysis of the problem of basic lining for the hot zone reveals, therefore, a number of desirable characteristics: high refractoriness, basic chemical reaction, resistance to spalling, good strength at all stages, ability to take coating, true sizing, volume stability, and abrasion resistance. Increased demand

Jan 1, 1953

By Leslie W. Austin

ROTARY kiln operators will agree that some of the most severe conditions a refractory must stand occur in the hot zone of a kiln burning Portland cement, dead burn dolomite, magnesite, periclase, and similar materials. Frequently the operator is faced with factors beyond his control which drastically shorten the life of refractories. Shutdown due to mechanical failure can be serious if the period is of sufficiently long duration to cause the dropping of coating or the loosening of the lining. A change in slurry can affect the coating and cause ring buildup. A change in type of fuel and its effect upon the flame can cause a shift in location of the hottest zone. Weekend shutdowns or any other interruption can cause the operator trouble and may damage the refractories, since stopping and starting a rotary kiln is certainly more difficult than stopping and starting a motor. Some operators have tried to set an estimate of damage for each shutdown in equivalent days of running time. Conditions affecting the refractory may be roughly grouped in four classes: chemical attack, mechanical stress, thermal shock, and abrasion. Chemical Attack: The drive to obtain maximum production through a kiln demands maximum operating temperatures, temperatures which are limited more by the ringing up or melting of the clinker. This can cause interface temperatures at the junction of coating and refractory which require the use of a basic kiln block to withstand the chemical attack. Chemical changes take place within the refractory itself, especially in chemically bonded or unburned kiln blocks: These changes cause the formation of the ceramic or burned bond. Migrating liquids or fluxes from the kiln charge have an effect within the refractory and lead to mineral or glass formation. The alkalies, sodium and potassium, migrate into the refractory as silicates, chlorides, sulphates or other salts. They may move under capillary action or may be caused to move by volatilization with condensation in the cooler portion. Mechanical Stress: Concentrated stress may be caused by several factors or combinations thereof. 1-The rings of refractories must be kept tight and rigid within the kiln, and this alone demands considerable force to hold the blocks in place. So that the force will not be concentrated, the blocks should fit the circle as perfectly as possible, with the faces in contact overall. 2-As the kiln is heated, thermal expansion takes place at the hot end of the kiln block. Since this disturbs the plane face it too can cause a concentrated stress at the two ends of the block, and shearing stress can be set up within the brick itself because of the difference in expansion between the two ends. 3-If a lining becomes loose and moves in the shell very severe stress can be set up, and as the kiln rotates this load changes and gives the effect of repeated loading. Permanent expansion of the refractory can also cause severe loading. 4-Not least important, flexing of the kiln is frequently the cause of concentrated stresses. Thermal Shock: Thermal shock, the result of heating and cooling too rapidly, occurs on starting and stopping or when a large patch of coating drops, exposing the bricks. Again, its destructive effect is often the result of phase change, liquid to solid or the reverse; dense refractories loaded with glass-forming impurities are particularly susceptible. Thermal shock is a problem with refractories set in the wall or roof of a stationary furnace, and becomes even more serious in a rotary kiln, the tendency to spall being magnified with movement and concentration of stress. Uniform rate of feed and loading insures both better coating and a more uniform stress. Abrasion: If the refractories do not take a coating, abrasion can become a most destructive factor. Movement of the lining in shell or movement of loose blocks causes abrasion, which is also most destructive if the refractories do not take a coating. An analysis of the problem of basic lining for the hot zone reveals, therefore, a number of desirable characteristics: high refractoriness, basic chemical reaction, resistance to spalling, good strength at all stages, ability to take coating, true sizing, volume stability, and abrasion resistance. Increased demand

Jan 1, 1952

By J. T. Norton, Pekka Rautala

The phases and equilibria in the W-Co-C system have been studied by X-ray diffraction methods, metallographic technique, and thermal analysis. In addition to the 7 phase, two double carbides, called 8 and have been revealed. The compositions correspond to CO3 W6C2 and Co3-W10C4. The reactions leading to these phases have been explained and tentative diagrams of stable and metastable equilibria proposed. The basic reactions in sintering cobalt cemented tungsten carbides are discussed. THE W-Co-C system is of fundamental importance in practical carbide manufacturing as well as for the understanding of the sintering mechanism. Surprisingly little is known about this system, for the probable reason that all the important alloys are of two-phase structure and that the diagram Co-WC has been treated as a quasi-binary. This obviously is incorrect, because WC decomposes before melting. One ternary phase, 7, of composition Co3W3C has long been known. It was first studied by Adelskold, Sundelin, and Westgren,1 although the isomorphous iron-tungsten carbide was known earlier. There have been in the literature several reports of two 7 phases.' " Also the 7 phase has been considered unstable by Takeda4 and Westgren.1 The Co-WC diagram has been studied by Wyman and Kelley5 and a quasi-binary diagram has been published by Sandford and Trent.2 Takeda has published a tentative Co-W-C diagram, considering both metastable and stable equilibria. However, the lines of two-fold saturation are shown only partially and it seems impossible to complete the diagram without violating the phase theory. Therefore it seemed desirable to examine the system in more detail. Experimental Procedure The alloys used in the present investigation were made of powders of tungsten, tungsten monocarbide, cobalt, and carbon and were of the grade used in manufacture of commercial cemented carbides. The powders were ground and mixed in small stainless steel ball mills, using balls of the same material. Benzene was used as a dispersing agent. The mixing period was 1 hr, since this was shown to give suffi- ciently good mixing of the powders without too great a contamination from the mill. After ball milling, the specimens were pressed in cylindrical or rectangular dies. No paraffin or other lubricant was used and the small compacts had sufficient green strength to be handled without difficulty. Several sintering furnaces were employed. The most satisfactory arrangement was a vacuum furnace based on the Arsem principle which employed a graphite helix as the resistance heating element. Specimens were placed on graphite stands and there was generally a slight carburization or decarburiza-tion of the specimen surface, depending on the carbon content of the alloy. The evaporation of the cobalt at a sintering temperature of 1400°C was not significant, but became severe at 1500°C and higher. The sintering time was 1 hr at 2000°C and 2 to 4 hr at lower temperatures. It was not possible to quench the specimens, but the cooling rates were rather fast, greater than 300°C in the first minute. In the system under investigation, the reactions are sluggish, and it is believed that the high temperature structures are satisfactorily retained. The principal method of investigating the sintered specimens was X-ray diffraction by the Norelco recording spectrometer. Approximate determinations of the phase boundaries were made by the disappearing phase method. Ternary Phases To study the phase formation in W-Co-C system, a series of specimens was sintered at 1400°C. In this experiment two ternary phases, called here ? and k were formed in addition to the well-known 7 phase. The 7 phase, which has been completely described by Westgren: showed a range of homogeneity from 7 to 20 pct C and from 38 to 48 pct Co. At 1400°C the 7 phase was found to be in equilibrium with monotungsten carbide, 8, tungsten, 8, #?, and liquid. The boundaries toward #? and liquid were difficult to determine and appeared to be very temperature sensitive. The other boundaries are believed to be well fixed. The homogeneity range of 7, as measured in this work, is considerably smaller than the one

Jan 1, 1953

By Orville R. Lyons

This paper presents a method whereby the amount of misplaced material and the difficulty of the separation can be used to compare coal cleaning equipment of all types, from effectiveness and capacity standpoints. The correlations presented do not include all types of equipment currently available, but the method can be used to evaluate any make or type of coal cleaning equipment, both old and new. THE relative performance of coal washing equipment, or the effectiveness with which any type or make of equipment removes impurities from coal, has been most difficult to evaluate in the past. The most widely used yardstick is the Frazer and Yancey efficiency formula developed in 1922,' but Yancey in a later article states that "washers treating coals of different density composition or operating at different densities of separation cannot be compared directly on the basis of this criterion."' Prior to and since 1922, a variety of other methods has been used for comparison purposes, including the distribution curve, the error area, and the "ecart probable" or probable error. Yancey and Geer in discussing these methods conclude, "Performance can be evaluated in a number of different ways, with the choice of the proper method to use being dictated by the objectives of the investigation and the data available."' It is true that performance can be evaluated in a variety of ways, but if the equipment is to be evaluated on an effectiveness basis, there should be only one universal comparison method. Varying methods have been used because one universal comparison method has not been found or developed. In the article previously quoted, Yancey and Geer state in clear terms the primary concept for a universal comparison method: "One of the simplest, and certainly one of the most obvious evaluations of washery performance is the quantity of sink material in the washed coal and the float material in the refuse. If the washery products are tested at the density at which the washing unit is operated, the sink in the washed coal and the float in the refuse represent material that has been misplaced." The quantity of misplaced material was used as a criterion of washery performance by Lincoln in 1913," by the United States Bureau of Mines in 1938,' by Hancock in 1947," and by the national French research agency Cerchar in recent years.' In 1950 Andersone proposed the use of this criterion as an efficiency value to replace the Frazer and Yancey formula. However, none of the above-mentioned investigators used the misplaced material concept in a manner that would provide universal coal-cleaning equipment comparisons. The Correlation Theory The ideal coal cleaning process would treat all sizes and would make a perfect separation at any given specific gravity. All material lower in density than the desired value would report in the coal product and all material higher in density would report in the refuse product. Unfortunately, no known cleaning process achieves this goal and there seems little likelihood that any process yet to be invented will do more than approach it. When coal is treated in volume under operating conditions, it is impossible to avoid mechanical entrapment, fluctuations in throughput and effective gravity of separation, and the creation of turbulent currents, even when a true heavy-liquid bath is used and the feed is closely sized and contains little intermediate gravity material. This being so, it is possible to appreciate the difficulties inherent in trying to obtain a perfect separation when treating a wide range of sizes and a feed containing high percentages of intermediate material, using turbulent currents to help create the effective separation gravity, under operating conditions which normally tend to be on the overload side. When coal is separated from refuse in any coal cleaning equipment, some refuse always reports to the coal and some coal to the refuse; the writer therefore assumed that there should be a relationship between the total amount of misplaced material produced by any given piece of equipment and the difficulty of separation as represented by the percentage of near gravity material in the feed. With small amounts of near gravity or k0.1 material in the feed there should be less misplacement of material than would occur with large amounts of near

Jan 1, 1953

By R. E. Reed-Hill, W. H. Hartt

High-purity magnesium single crystals, oriented with basal plane parallel to stress axis, were deformed in tension at room temperature so as to form second-order (1011)- (1012) twins. Investigation by optical and replica electron microscopy revealed that these twins can support very large internal strains approaching 1000 pct and that fracture follows as a direct consequence of these strains. At low strains the basal plane within (10i1)- (10i2) twins rotates with increasing deformation until it becomes approximately parallel to the twin boundaries. This rotation is not consistent with deformation by basal slip in the double twin, but may be rationalized in terms of nonbasal slip. Observations also indicate that basal slip in the primary (1011) twin, prior to second-order twinning, may contribute to this rotation. Deformation markings that are difficult to interpret in terms of slip on previously observed systems were noted in the twin bands. A possible means of rationalizing these markings is to relate them to grain boundary shear. The fracture associated with these twins is thought to initiate by formation of voids at the twin boundaries. These grow into microcracks, with ultimate fracture occurring by tearing of the interconnecting regions. THE significance of deformation and fracture along second-order (10i1)-(10i2) twins in polycrystalline magnesium1-' and many magnesium alloys4 was discussed in a previous paper.5 It was noted that this double twinning mode effectively controls the room-temperature deformation and fracture of magnesium single crystals, oriented with the basal plane parallel to the tensile axis. Reed-Hill and Robertson6 observed that, although these crystals may fracture at a macroscopic strain of less than 1 pct, shear strains up to 1000 pct could occur within (1011)- (10i2) twin bands. They concluded that the fracture was "ductile" and resulted from concentrating the deformation into a very small volume. The present research was undertaken to obtain a better understanding of the deformation and fracture associated with these twins. EXPERIMENTAL TECHNIQUES The experimental procedure involved straining high-purity magnesium single crystals in tension at room temperature. Specimens were oriented so that the applied stress direction was within 2 deg of the [1010] crystal axis. The specimen cross section was rectangular with faces closely parallel to (1210) and (0002). The specimen preparation and testing procedures have been described in detail elsewhere.5 Second-order (1011)- (1072) twins nucleated during straining were studied using optical and replica electron microscopy techniques. For the latter, cellulose acetate-carbon double replicas were employed. Observations were made on the (1210) crystal surface, which is the plane of shear for twins of this type. In addition to the single crystals, some investigations were carried out on longitudinal polycrystalline specimens. These were obtained from high-purity magnesium plate with a texture in which the basal planes of the grains tended to be nearly parallel to the specimen axis. All. polycrystalline specimens were annealed prior to testing in order to produce a coarse grain structure, permitting Laue back-reflection X-ray photographs to be obtained from grains of interest. EXPERIMENTAL RESULTS a) Deformation Within ( 101 l )-( 1072) Twins. Fig. 1 is an optical micrograph demonstrating the extent of the plastic deformation that can occur in (1011)-(10i2) twin bands. Notice at the lower left corner of the photograph the large displacement of the dark band (a polishing step) where it crosses the twins. The shear strain in the twin band at this position was computed to be 700 pct, using the ratio of step width to twin thickness. It was previously shown5 that (1011)- (1012) twin bands are often composed of small, separate twins aligned close to the macroscopic habit plane. Fig. 2 is an electron micrograph from near the upper end of the twin band in Fig. 1. This illustrates that the twin habit often does not coincide exactly with the macroscopic band habit, but may be inclined at a slightly smaller angle to the matrix basal plane. Figs. 3 through 6 are electron micrographs of the twin band in Fig. 2 illustrating successive steps in the development of deformation inside the band. A twin band such

Jan 1, 1969

By W. J. Moore, E. M. Swiggard, H. Shenker

Beryllium is the most soluble of the double-acceptor impurities in germanium; the solubility is at least 1 x 10 19 atoms cm3. Photoconductive, optical, and electrical measurements were made on a set of Ge:Be samples grown without other intentionally added imp~ivities. The excited-states spectrum of beryllium in germanium was determined both in zero field and in magnetic fields up to 30 kc. It was found that the absorption 0-f lines in the vicinity of the G line increased markedly with increasing magnetic field. The ioniza-tion energy of neutral beryllium in germanium was determined to be 24.3 * 0.1 mez: using the excited-states spectrum. An infrared detector using a Ge:Be element was found to have a normalized detectivity D* (50 p, 1000 cps, 1 cps) of 9 X ldO cm-~ps"~-w-'. The Ge:Be sambles exhibited low-field breakdown and inibzirity band conduction effects at low temperatures. WHILE the properties of most dopants in germanium have been thoroughly investigated, the properties of beryllium in germanium have had relatively little attention. Much of the work that has been done' has been concerned with the properties of singly ionized beryllium in germanium. The purpose of the present work was to determine the photoconductive and electrical properties of beryllium-doped germanium (Ge:~e) with a small concentration of other electrically active impurities. Ge:Be is of special interest since beryllium is the most soluble of the known double-acceptor impurities in germanium. MATERIALS PREPARATION A set of &:Be crystals with beryllium concentrations between 5 x 1013 and 1x 10'' cmm3 and without other intentionally added impurities was grown in a hydrogen atmosphere by the horizontal zone-refining techniques described by Swiggard and Shenker.2 The segregation coefficient of beryllium in germanium was found to be about 0.07 and its maximum solubility was found to be greater than 1 x 10'' atoms cm-3 which is in agreement with previous results.' Most of the crystals were found to have a small net concentration of shallow acceptors; for example, a crystal having a beryllium concentration of 1.1 X 1016 cm-3 was found to have a net concentration of shallow acceptors of less than 1.5 X 1013 cm-3. Ingots designed to have a beryllium concentration of 1 x 1017 cm-3 or less exhibited a loss of electrically active beryllium. That is, the beryllium concentration was lower than expected and the decrease of the beryllium concentration along the length of the ingot was much larger than expected. It is hypothesized that this effect is due to the oxidation of the beryllium by the residual oxygen in the system. This effect is similar to but not as severe as the effect observed with boron in germani~m.3, 4 OPTICAL ABSORPTION SPECTRUM The excited-states spectrum of neutral beryllium atoms in germanium was studied by measuring the infrared optical absorption spectrum. A typical spectrum is shown in Fig. 1; the labeling of the absorption lines follows that of Fisher and Fan.* The spacings between the observed lines and the D line are nearly equal to the corresponding spacings for the other ac -ceptors in germanium.5-7 By the use of the theoretical result67' that the neutral impurity ionization energy is 2.53 mev larger than the energy of the D line, the ionization energy of neutral beryllium in germanium was determined to be 24.3 * 0.1 mev at 4.2"K. This method yields a more precise value of the impurity ionization energy than the usual Hall effect method.' The absorption spectrum of Ge:Be was also measured as a function of magnetic field using a magnetic field parallel to the incident radiation and using unpolarized radiation. A typical spectrum taken at 30 kG is shown in Fig. 2. An unexpected observation is that the absorption of the lines in the vicinity of the G line (there is a strong possibility that some of these lines may be associated with lines other than the G line) increases with magnetic field. RESISTIVITY AND HALL DATA Measurements of Hall voltage vs temperature were made on several of the samples. The thermal activa-

Jan 1, 1968

By E. H. Snow, B. E. Deal

Instability effects in semicanductor devices have long been attributed to the motion of charges on or within oxide layers on the surface. These effects are of critical importance in metal-insulator-semiconductor MIS) field-effect devices. For this reason, the capacitance-voltage or the conductance-voltage characteristic of these devices can be used as a sensitive detector to study charge transport and polarization effects in the oxide or insulator. A review is given of the results of such studies of thermally grown SiO2 as well as of other insulating films of importance in silicon technology. Three types of effects are distinguished. The first of these is the drift of mobile cations within the dielectric, examples being thermally grown SiO, which is often contaminated with sodium ions, and a variety of other glasses in which the mobile ions are a part of the glass composition. The second effect is a dipole-type polarization which occurs in phosphosilicate glass films obtained by reacting P2O5 with thermally grown SiO2. The third effect involves the transfer of charges between the dielectric and the silicon electrode. This occurs in silicon nitride and other deposited dielectrics. It is concluded that MIS studies have provided a powerful technique joy the study of charge transport and polarization effects in insulating films. The knowledge gained from these studies has led to an understanding of surface effects on conventional transistors and diodes as well as making possible stable MIS transistors. THE metal-insulator-semiconductor field-effect transistor is conceptually the oldest type of active semiconductor device.' The earliest attempts at making this device were frustrated because of high surface state densities at the interface between the semiconductor and the gate insulation.' However, by using a silicon substrate with thermally produced silicon dioxide as the gate insulation, this problem was solved and metal-silicon dioxide-silicon devices with good characteristics were made as early as 1960. 3 Yet it was still over 5 years before these devices became a commercial reality. This delay was largly due, not to surface states, but to stability problems associated with polarization effects within the insulating layer which caused the threshold voltage of the device to drift under temperature and bias treatments. The solution to these problems has not only made possible stable MIS devices, but it has added immensely to our understanding of failure mechanisms in conventional bipolar transistors and has added to the reliability of ali types of planar devices. In this review, we shall first describe the effects of various types of polarization phenomena on MIS device characteristics. Then, since thermally grown SiO, is by far the most important insulator used in these devices, we shall review historically the type of instabilities which have been observed in thermal oxides, the attempts at understanding and eliminating them, and the present status of the problem. We shall then turn our attention to the various deposited insulators which have been used, including lead glasses, phosphosilicate glass, vapor-deposited silicon oxide, and silicon nitride. Interestingly enough, many of these materials show polarization effects which are quite different from those generally observed in thermally grown SiO2. THE EFFECTS OF POLARIZATION PHENOMENA ON MIS CHARACTERISTICS The simplest MIS device and the one which has been most frequently used in the study of polarization effects is the MIS capacitor. Two modifications of this structure with single- and double-layer dielectrics are illustrated in Figs. l(a) and (b), respectively. The capacitance of this structure as a function of voltage applied to the metal gate electrode is plotted in Fig. 2 for the case of an n-type silicon substrate. When the silicon surface is accumulated (positive bias) the measured capacitance is just that of the insulating layer C. When the surface is inverted (negative bias), the capacitance is that of the insulator and a silicon depletion layer in series CoCs/(Co + Cs). Indicated on the horizontal axis of Fig. 2 is the voltage VT at which the silicon surface becomes strongly inverted. This voltage corresponds to the threshold or turn-on

Jan 1, 1969

By R. J. Quigg, G. S. Doble

Commercial stress -relieved TD Nickel bar was shown to retain room- and elevated-temperature tensile strength after exposure up to 2501°F. Cold swaging increased both room -temperature and 2000°F tensile strength. After annealing at 2500°F the strengthening due to swaging was retained at 2000°F hilt eliminated at room temperature. Annealing produced changes in hardness and X-ray half peak width indicating the presence of recovery processes as 1071° as 1000°F but no recrystallization of swaged material was noted at any temperature. In contrast to swaging, rolling induced a recrystal-lized structure after annealing. The tensile strength of this recrystallized structure was comparable to the cold-worked condition. High-temperature tensile properties of as -received bar were highly anisotropic with the transverse tensile strength being one fifth the longitudinal value. The aniso-/ropy is affected by working direction and may he partially reversed by changing the direction of metal flow. The divergence in tensile strength, beginning above 550°F or- approximate one third the absolute melting point, is strain-rate dependent. T D Nickel is a commercial dispersion-hardened alloy containing 2 vol pct thoria. The dispersion, consisting of spherical particles 0.030 to 0.050 in diameter with an interparticle spacing of less than 1 is reported to maintain stable properties up to 2400°F.1 This stability of second phase results in maintenance of elevated-temperature strength at higher temperatures and longer times than normal nickel-base superalloys.2 The purpose of this paper is to describe the effect of various mechanical working operations on the strength and microstructural stability of TD Nickel bar. MATERIAL AND PROCEDURES All material used in this study was commercial TD Nickel bar. This material is produced by a chemical process which results in a nickel powder containing a dispersion of thoria particles. The powder is then pressed, sintered, extruded, and subsequently worked to bar stock. Three starting materials from three separate lots were used: as-extruded bar. 1-in.-diam stress-relieved bar, and 1/2-in.-diam stress-relieved bar. Since TD Nickel bar stock is cold-worked without a recrystalliza-tion anneal, the accumulated deformation or degree of cold work in these materials increases as the bar diameter decreases. Some of the 1/2-in.-diam bar was swaged to 1/4 in. diameter at room temperature in order to produce an as-worked condition for comparison with the stress-relieved stock. Tensile testing was performed on an Instron Tensile Tester at a constant crosshead speed of 0.020 in. per min. The 0.2 pct offset yield strength was measured from the load-crosshead movement plot. Specimen gage dimensions were 0.080 in. in diameter by 0.40 in. in length, producing a strain rate of approximately 0.050 min-1. Specimens were tested in air and heated within a resistance-wound furnace controlled to ±5°F. A 15-min soak at temperature was employed before testing. Samples were heat-treated in air and specimens machined after exposure with sufficient material removed to eliminate any surface contamination. X-ray line breadth was determined from a diffractometer scan of a transverse face of a bar using copper K, radiation. Metallographic preparation utilized standard mechanical polishing with Carapella's etch. Specimens for electron microscopy were electropolished in a 1:7 sulfuric/methaol solution and chromium-shadowed collodion replicas prepared. RESULTS AND DISCUSSION I) Effect of Elevated-Temperature Exposure on the properties of TD Nickel. The effect of various elevated-temperature exposures on the room-temperature tensile strength of TD Nickel is shown in Table I. In the unexposed condition the tensile strength, reduction in area, and hardness all increase with increasing accumulated deformation while the elongation decreases. After exposure at 2500°F the strength of all three materials decreases to about 65,000 psi and the elongations increase slightly. The apparent increase in strength of the 1-in. bar after a 2000°F treatment is probably experimental scatter. These results indicate that the room-temperature strengthening due to additional deformation is annealed out upon elevated-temperature exposure. In contrast to the room-temperature data, the 2000°F tensile strengths increase in order of increasing deformation even after exposure. Although some loss of strength occurs after exposure, much of the effect of working is still maintained at 2000°F. The room-temperature hardness after various

Jan 1, 1965

By T. E. Scott, D. H. Sherman, C. V. Owen

Mechanical properties and optical metallographic characteristics of vanadium containing 53 ppm (wt) H were investigated from, 77° to 298°K. A sharp ductile to brittle transition induced by the presence of hydrogen was observed between 238° and 223°K and a mar-tensitically formed hydride appeared at 200°K. While there appears to be a subtle relationship between the hydride formation and the ductile-brittle transition, it was concluded that the hydride per se was not sufficietzt to cause the severe em brittletnent. On the basis of the metallographic experiments and the results of a Petch analysis it is suggested that the mechanism of the embrittlement involves a reduction of the true surface energy, or cohesion, of the uanadiunz. THAT hydrogen can severely embrittle vanadium is well-documented;'-5 however, the mechanism by which hydrogen induces the observed embrittlement has not been established. It is not known whether the embrittlement of vanadium is caused by the formation of vanadium hydride or by a more subtle role of hydrogen. Until very recently6>' the solid solubility of hydrogen in vanadium at temperatures in the,range of the embrittlement was not known to a useful accuracy. In general, a severe embrittlement of the type produced by the presence of hydrogen in vanadium can be caused by changes in either of two properties of a metal. Either the yield stress of the metal is raised to the extent that plastic deformation at the tip of a crack cannot occur or the cohesive properties of the metal are reduced, at least locally, to the point at which cleavage is the natural response to applied loads. Of course a combination of these is possible. It is not known which of these properties of vanadium is influenced most by the addition of hydrogen. The purpose of this investigation was to determine the role of hydrogen in the embrittlement of vanadium. Accordingly, the solubility of hydrogen in vanadium in the temperature range where embrittlement is most severe was determined, the appearance of vanadium hydride was examined in relation to the initial ductile to brittle transition temperature, and an attempt was made to evaluate the effect of hydrogen on the yield stress and cohesive properties of vanadium. MATERIAL AND PROCEDURES Sample Preparation. The vanadium used in this investigation was prepared by the iodide refining process described by Carlson and owen.' Three ingots, 3 in. diam by 6 in. long, were cold-swaged to 0.096 in. diam, cut into short lengths, and then arc-melted under purified argon into one ingot. This process was repeated to insure a uniform composition in the final ingot. Chemical analysis of the metal is given in Table I. On the basis of work of Loria et a/ .' the following sequence of treatments was performed in order to obtain a uniform equiaxed ultimate grain structure: a) cold swage q-in.-diam ingot to 0.230 in. diam; b) anneal 6 hr at 1000°C in vacuum; c) by cold swaging reduce 81 pct in area in three steps: 0.230 to 0.187 in. diam, 0.187 to 0.150 in. diam, 0.150 to 0.096 in. diam. This sequence provided the desired grain structure after subsequent annealing treatments. Because annealing in evacuated quartz capsules resulted in contamination by oxygen, all anneals in this investigation were performed in a 304 stainless-steel chamber under a dynamic vacuum of 10- I Torr with the vanadium wrapped in tantalum foil. Prior to all annealing treatments the wires were electropolished for 1 min at 16°C in an 80 pct methanol-20 pct sul-furic acid electrolyte at 12.5 v. Following the final reduction the 0.096-in.-diam wire was cut into 2-in. lengths. A 1-in. gage section was reduced to 0.090 in. diam by electropolishing as above. Five different grain sizes were obtained by annealing the 2-in. samples at different temperatures for 8 hr to insure uniform grain size and residual hydrogen removal. The annealing temperatures used and the resulting grain sizes are given in Table 11. The final step in sample preparation was to charge half of the specimens of each grain size with hydro-

Jan 1, 1969

By A. U. Seybolt

Experiments on both suljidation and hot corrosion have been carried out using ternary Ni-Cr-X alloys and commercial nickel-base superalloys. It has been shown that lhere are certain micro structural similarities between sulfidation using H,S/H2 mixtures and hot corvosion using Na,S04 in "crucible" experiments or hot corrosion tests using a flame tunnel apparatus. It is proposed that two key processes in the hot cowosion process are: 1) formation of chromium sulfides which deplete the alloy matrix, and 2) oxidation which can be accelerated because of chromium depletion. Other processes play an important role in the hot corrosion process, such as accelerated oxidation attack due to the presence of a N& S04 or N&SO,- NaC2 film which inhibits the formation of a protective external oxide scale. However, this latter phenomenon was not studied in this work. THE term hot corrosion has come to mean a combination of sulfur and oxygen attack on nickel-base or cobalt-base superalloys used as gas turbine blades or partitions. This attack can be initiated by any combustion process in air involving fuel containing sulfur if the sulfur level is sufficiently high. Levels of 5 pet SO2l for example, in the combusting gas have been observed to produce hot corrosion attack on nickel-base alloys. The important immediate corroding medium in aircraft gas turbines, however, has been established to be Na2S04, formed from reaction between NaCl from sea air and sulfur in the fuel.' The Na2S04 concentrates the sulfur sufficiently so that superalloy parts heated in the range 1400" to 1900°F can become sulfided by reducing the Na2S04 film which forms on the parts, and this reaction allows sulfur to gain access to the alloy. The sulfur thus released diffuses into the superalloy and forms primarily chromium sulfides of various compositions, but frequently Cr2S, has been identified. Figs. 1 and 2 show the morphology typical of hot corrosion of a cobalt-base superalloy X-45 (25 Cr, 10 Ni, 7.5 W, 0.25 C) and a nickel-base alloy, Udimet 500 (19 Cr, 19 Co, 4 Mo, 3 Ti, 2.9 Al, 0.07 C). Both alloy samples were subjected to the same hot corrosion conditions: 616 hr at 1600°F in a combusted 2.9 pct S distillate oil containing 125 ppm Na as NaC1. It will be noted at once that the nickel-base alloy is much more severely attacked. The depth of corrosion is much greater and the number and size of the sulfides present are much greater. Both alloys show a duplex oxide scale, which is more noticeable in the X-45 alloy. The external scale is probably a spinel in both cases, with CrQ3 lying next to the alloy. Many investigators1 -"ve been concerned with hot corrosion phenomena, but there has been a lack of unanimity of opinion as to the details of the hot corrosion mechanism. More than one definition of hot corrosion is possible. Some investigators con- sider as a measure of hot corrosion only the weight gain due to an accelerated oxidation. However another point of view is that the total depth of affected alloy may be used as a measure. While it is recognized that surface oxidation attack is greatly accelerated by the presence of salts like Na2S04 or Na2S04-NaC1 mixtures, sulfur penetration into the alloy also undoubtedly produces very important effects. The region of sul-fide penetration which is so prominent in Fig. 2 is one of the outstanding characteristics of hot corrosion. For highly stressed parts, such as first-stage buckets, this sulfur-penetrated region can be more significant in mechanical property loss than the reduction of cross section produced by the formation of the massive external scale. In addition, evidence will be presented that this sulfided region can be less resistant to subsequent oxidation attack. Since it appears that the sulfided region below the surface oxide scale plays an important role in the overall corrosion process,

Jan 1, 1969

By G. L. Smit

The Buffelsfontein Gold Mining Company is situated in the Klerksdorp district of the Province of the Transvaal in the Republic of South Africa, approximately 100 miles west of Johannesburg. Gold production commenced in January 1957 and Uranium treatment of residue slimes as a by-product started in July 1957. The mining property is 5435 mining claims in extent, the equivalent of 7988 acres or 12.5 sq miles. The mine was initially exploited by the Pioneer Twin Shaft System, consisting of a 26-ft diam down-cast shaft and a 22 ft-diam up-cast shaft, sunk in the north-west area of the mine to cater for the hoisting and ventilation requirements for a milling rate of 150,000 tons per month. To exploit the Eastern zone of the property and assist in increasing production to 200,000 tons milled per month, it was decided to sink a further Twin Shaft System consisting of a 28-ft diam downcast shaft and a ventilation up-cast shaft -22-ft in diam, both monolithic concrete lined — 200 ft apart and 5300 ft deep. This paper deals with the sinking and commissioning of these Eastern Twin Shafts. This was achieved by one sinking crew within a period of 20 months. A) PLANNING 1) Siting: The Eastern Shaft System was sited in the north-east area of the property, 12,000 ft east on strike from the Pioneer System. (Fig. 1). Initially the system was sunk to the 5300 ft elevation to conform with the original Pioneer Shaft System. On completion a sub-vertical main shaft will be sunk to the 8000 ft elevation in the immediate vicinity, and subsequently the surface ventilation shaft will be deepened to this elevation by raising from level to level and sliping to full size. The exact positions of the shafts were chosen after: a) underground development had located certain known water bearing zones, and b) geophysical and topographical surveys had been carried out. The shafts passed through the following geological succession: Surface to 4430 ft - Dolomites of the Transvaal System 4430 to 4470 ft - Quartzites and conglomerates of the Black Reef Series of the Transvaal System. 4470 to 4470 ft - Diabasic Lava of the Venters-dorp System (Ventersdorp Contact Reef at base). 4470 to 5250 ft - Quartzites of the Elsburg Series of the Upper Witwaters-rand System. The shafts were sited to ensure that the least possible water would be encountered during sinking, and this contributed to the rapid rate of sinking. 2) Duties: a) The 22-ft diam ventilation shaft was designed to up-cast 1,400,000 cfm of air (0.060 density) against a resistance of 22 in. water gauge. b) The main shaft was designed to handle 160,000 tons hoisted per month as well as the men, material and down-cast ventilation to serve this tonnage. The 284 diam main shaft is equipped with streamlined buntons spaced at 15 ft centers set in pockets which were left during sinking. There are six compartments, four of which are sewed by two dual purpose hoists, hoisting either, twedeck man cages or 13-ton bottom discharge skips. The other two compartments are served by a single purpose winder hoisting double deck cages accommodating 60 men per deck. (Fig. 2). 3) Timing: Permanent equipment was ordered well in advance to insure continuity in the operation. Development underground reached the shaft positions before the start of sinking operations. From this development, boreholes were drilled into shaft positions to drain off water in the vicinity of the shafts. To ensure complete co-ordination of effort, all relevant data, as well as the allocation of responsibility, were made known to all persons and departments concerned. 4) Models: The extensive use of scale models during the preliminary planning stages proved most useful in deciding on design such as buntons, bunton pockets and guide cleats, and complex layouts concerning loading, spillage and pumping arrangements. (Fig. 3). These models also proved invaluable in determining the walling routine. Normal working conditions could

Jan 1, 1964

By R. J. Charles, G. Agar

Experiments on single particles show that the amount of material created during impact that is finer than any chosen size is proportional to the energy of the impact. As the underlying principle of comminution, it might be stated that each unit of energy input to a given comminution system tends to add to the system an identical assembly of new particles and subtract an equivalent volume of larger particles. Thus, two of the consequences of the fact that each unit of energy tends to add identical assemblies of new particles to the system are: 1) on continued application of energy the total charge in any batch comminution system tends to assume the characteristics of this assembly, and 2) the process of comminution may be described by a relationship such as E = Ak-a. Recently Schuhmannl presented a theory of comminution which puts rational perspective on the extensive controversy surrounding most of the existent theories of comminution. With hindsight the origin of controversy can be ascribed to a relatively simple circumstance. In general, a progressive shift of a size distribution curve towards finer sizes is observed as energy is added to a comminution system. It is also observed that, with continued grinding, the size distribution curves usually change and appear to approach some constant shape. Inves-tigators generally felt that an appropriate method of relating and generalizing such data would be to consider the hypothetical case where particles in the system were uniformly subjected to comminution such that each of these particles, receiving its proportion of input energy, was transformed into a number of smaller particles of uniform size. Since the changes in shape of the size distribution curves during size reduction were clearly associated with the coarse particles in the system, it was also assumed that these changes accounted for little of the input energy and one could deal solely with the equilibrium shape towards which the size distribution curves tended. Although the unrealistic nature of the foregoing points of view was realized some justification was felt for such treatments since, in most cases, the resulting mathematical formulae could, by the adjustment of at most two parameters, satisfactorily describe experimental observation. Difficulties arose, however, in that the formulae required a specific influence of the feed size on the comminution process. In actual fact, the application of a feed size term in fitting experimental data was often found to be unnecessary or contrary to the above formulae. Secondarily, much discussion arose concerning the appropriate energy number that would relate the size change of one particle to the amount of comminution energy it received. As has been previously shown3 all the above theories that treat comminution as a continuous process of size reduction may be related to a proposition of the following form: dE = -Cfn [1] where dE is the increment of energy, dx is the size change, x is the particle size, and C and n are constants. It is now clear, as pointed out by Schuhmann, that Eq. 1 is inapplicable to comminution processes, since comminution cannot be considered other than as a discontinuous mixing process in which the overall size distribution of the product results from mixing, in various proportions, finished material with unfinished, and sometimes untouched, material. A striking illustration of this mixing phenomena may be obtained by comparing the size distributions of grinds in a typical batch ball mill with size distributions calculated on the basis of mixing various proportions of feed material with a ground material which obeys a power law size distribution relationship. Figs. la and lb illustrate such a comparison and the similarity of these figures indicates that mixing plays an important role in determining the overall shape of the product size distributions. Figs. la and lb illustrate, additionally, the underlying basis of the comminution theory presented by Schuhmann.' In the preliminary grinding of relatively close sized feed particles in a batch ball mill, one may visualize that, when a successful encounter of a ball with a feed particle occurs, then the particle undergoes severe size reduction and the size range in which the resultant particles reside is far removed from the size of the feed particles. After a number of feed particles are reduced by independent but similar impacts and one examines the size dis-

Jan 1, 1961