Search Documents

By O. W. Simmons, L. W. Eastwood, C. M. Craighead

H. Schwartzbart and W. F. Brown, Jr.—The authors have divided the effects of recovery on the true stress-true strain curve into two types; metarecovery, which effects only the first part of the curve or the yield strength, and orthorecovery, which effects the flow stress at any strain. Both of these are said to be true recovery effects, involve no recrystallization, and are explained by the removal of two different types of imperfections caused by work hardening. However, there seems to be some question as to whether the data are sufficiently conclusive to exclude, as an explanation of the authors' results, a mechanism based on the relief of residual stresses between the grains or slip bands and recrystallization. It appears that metarecovery could be interpreted in the same fashion as a customary interpretation of the Bausch-inger effect. The balanced system of internal stresses which exists between grains in a strained specimen due to varying orientation and, hence, yield strengths, of the different grains is responsible for a reduced yield strength in compression following pre-tension, and, similarly, for an elevated yield strength in tension following pre-tension. If the specimen is now heated so that the internal stresses are relieved by creep, then the yield strength in tension following tension will have been reduced and in compression following tension will have been raised. There seems to be a very strong case for the lack of recrystallization in the aluminum investigated by the authors, if one defines recrystallization as the presence of visually detectable new grains or accepts the X-ray evidence as conclusive. One must remember, however, that the appearance of spots on the back-reflection X-ray patterns cannot be taken as the time when recrystallization first started. The areas of recrystallized strain-free material must first have grown to a size large enough to give distinct spots on the patterns and this may take some time. Averbachl7 in an investigation of brass has shown that recrystallization can be detected by extinction measurements at temperatures lower than those based on hardness or X-ray line width determinations. It can be seen from fig. 10 that the rate of recrystallization is extremely low over a considerable time period at the onset of the process. Observations on the rate at which small amounts of recrystallization effect the flow stress would have given further insight as to whether undetectably small amounts of recrystallization might have been responsible for orthorecovery. Also, the question arises as to whether the effects observed in fig. 6 for various times and temperatures could not have been obtained if the time at 212°F were sufficiently long. In addition, the argument that the curve in fig. 10 is not sigmoidal seems weak in view of the scattering of the points. It is conceivable that an accurate determination of the curve for the first 100 hr would exhibit a relationship other than the one drawn. There is one point we would like to raise about the condition of the starting material. The authors annealed their material at 750°F for 15 min to remove the effects of any previous work hardening or machining strains. Reference to the work by Anderson and Mehl shows that this treatment may not have completely recrystallized the aluminum, so that the starting material may have had some strained areas. Higher temperatures or longer times may have been required to remove the effects of any small strains. We would like to mention some results of tests being conducted at the Lewis laboratory of the National Advisory Committee for Aeronautics in an investigation of the Bauschinger effect in relation to fatigue. Tests were performed on annealed electrolytic copper and several annealed brasses. Specimens were pre-strained 1 pct in tension and then tested in compression or tension with and without intermediate stress-relieving annealing treatments at 500°F for various times. Specimens heated at 500°F for 10 1/2 hr showed an elevation of the flow curve in compression and an approximately equal lowering of the flow curve in tension when compared with the curves for the un-heat treated specimens. After approximately 0.8 pct strain, all flow stresses coincided and were equal to the flow stress of the virgin material at this strain. This behavior is consistent with the metarecovery observed for aluminum by the authors and for which a residual stress model can be used. On the other hand, increas-

Jan 1, 1951

By H. M. Zoerb

Based on the belief that operating details are a definite contributing factor to major economies, this paper traces the development of crushing cavity design in Symons cone crushers to attain maximum liner utilization. Wear rates are analyzed and compared in this presentation and drawings illustrate succeeding design changes. IN these times of rising labor and material costs, it has become more and more necessary that attention be paid to some operating details which, in their obscurity, may he the key to major economies. Liner wear in crushing cavities of secondary and tertiary crushers can become an appreciable cost item when the material to be crushed is hard and abrasive. This item of cost not only includes the value of the crushing members, but also more intangible costs such as labor and lost production due to more frequent replacement. The variables which are encountered in ores and minerals to be reduced; the design of plant and machine application; the sizes, shape, and fineness, characteristics of the crushed product; the moisture; hardness; friability; and abrasiveness of the material to be crushed are all influencing factors which must be taken into consideration in the selection of a crusher, and particularly in the design of crushing cavity and liners to be used in a crusher. Through a research program undertaken in cooperation with many operators of Symons cone crushers a new approach to crusher cavity design was made, resulting in the development of liners for specific operations which showed: 1—maximum utilization, as high as 70 to 80 pct of original weight of metal, and 2— maximum capacity of unit during the greater portion of its life. It has been found that liners so designed for a given operation will show added economies in power consumption, maintenance, and general wear and tear on the crushing unit. Initial work in the so-called tailoring of crushing cavitles was begun on the tertiary or fine crushing units where as a rule reduction ratios were low, varying from 3 to 6. Parallel or sizing zones in the lower portion of the crushing cavity were too long, resulting in a tendency to pack. It was found that very little additional crushing was done in the parallel zone after the initial impact in that zone and that a relatively small amount of' additional crushing was done by attrition, which required very careful feed control. A small amount of over-feeding would result in packing which not only consumed power but caused unnecessary liner wear as well. The illustrations which follow in this discussion will show only contours of crushing cavities, and for purposes of simplification the cavities will be considered only in their closed position. The first step, therefore. was to reduce the sizing zone to a minimum. This was done by removing the lower portion of the liner as shown in Fig. 1. The result of the change was a saving of 15 to 20 pct in liner cost, less power consumption, with no change in capacity. This change in design, while an improvement, did not go far enough. As wear took place, the change in the liner was not uniform throughout its entire length, resulting in a restriction of the feed opening and thereby loss of capacity. Furthermore, progressive wear of the liner had the effect of lengthening the parallel zone until finally the entire crushing cavity was all parallel zone, see Fig. 2. It is obvious from the reduced feed opening of the worn liner that the ability of the machine to receive material is lessened considerably. Furthermore, the long parallel zone with its worn, irregular profile did not operate at its highest efficiency. The first attempt to overcome this difficulty was carried out on a 5 1/2-ft crusher installed in a plant producing roofing granules. The material being crushed was a very hard graywacke and the crusher was closed-circuited with a screen having .232-in. slotted openings. A radical change in contour was developed, as illustrated in Fig. 3. Equal wear lines on both concave and mantle are designated 1, 2, 3, etc. The method of development of this contour is as follows: Since adjustment for wear is vertical, corresponding intersections of wear lines and vertical lines developed concave and mantle contours which maintained equal but lengthening wear surfaces in the parallel zone. The ideal contour, of course, is one in which the length of the parallel zone remains constant, but because of present foundry practice and heat treating characteristics this is impossible.

Jan 1, 1954

R. Schuhmann, Jr. (Purdue University)— Fulton and Chipman's results on rate of silica reduction from slags are analogous in many was to the results of Parlee, Seagle, and Schuhmann10 on rate of alumina reduction from alumina crucibles. Both investigations have given comparably low rates of reduction and slow approaches to equilibrium. Accordingly, we may hypothesize that the rate-determining step is the same in both kinds of experiments; that is, oxygen diffusion across the stagnant boundary layer on the liquid-metal side of the interface between the liquid metal and the oxide phase (slag or solid oxide). I suggest that silica reduction involves the following consecutive steps: I) At the slag-metal interface: SiO2(slag) Si+ 20 II) Transport of oxygen from slag-metal to gas-metal interface: a) diffusion across liquid-metal boundary layer at slag-metal interface. b) convection within the body of liquid metal. c) diffusion across boundary layer at metal-gas interface. 111) At the metal-gas interface: C +O- CO (gas) Iv) At the graphite-metal interface: C (graphite) -C At steelmaking temperatures it is reasonable to assume that equilibrium is attained in all three chemical reactions (I, 111, and IV) right at the respective interfaces. Convection within the stirred liquid metal (step IIb) is also rapid. Transport of Si and C should be orders of magnitude easier than transport of 0, because of the relatively high concentrations of Si and C. Accordingly, we might expect the overall reaction rate to be determined by boundary-layer diffusion of oxygen, either IIa or IIc. Fulton and Chipman's demonstration that bubbling CO through the system had no major effect on reaction rate indicates that IIc is not the slowest step. Therefore, it becomes logical to estimate the maximum rate for step IIa and to compare this theoretical estimate with Fulton and Chipman's experimental data. If oxygen diffusion across the liquid metal boundary layer at the slag metal interface (step IIa) is rate-determining, In this equation, dn sio, /dt is the rate of silica reduction in moles per sec,A is the area of slag-metal interface in sq cm, Do is the diffusivity of oxygen in sq cm per sec, 6, is the boundary layer thickness in cm, c,* is the oxygen concentration right at the slag-metal interface in moles per cubic cm, and co is the oxygen concentration in the body of the liquid metal, also in moles per cubic cm. Equilibrium data" on the silicon deoxidation reaction in liquid iron and steel at 1600°C indicate that the oxygen contents of the liquid metal in Fulton and Chipman's experiments at 1600°C probably fell in the range of 0.5 x10-3 x10-3wt pct. That is, the maximum conceivable value of co*-co for the system under consideration was on the order of 10"5 mole oxygen per cubic cm. On the basis of previously published data,1O,11 it is estimated that Do/0 will fall somewhere in the range from 10-3 to 10-1 cm per sec. The surface area A in Fulton and Chipman's experiments was approximately 20 sq cm, and the weight of metal involved was about 500 grams. Combination of all these figures with the above rate equation leads to an estimate that the rate of silica reduction should fall within the range from 0.002 to 0.2 wt pct Si per hr. This estimate is consistent with the experimental data. For example, Fulton and Chipman's Fig. 2 shows a change of about 0.3 pct Si in 10 hr, corresponding to an average rate of 0.03 pct per hr. According to the proposed hypothesis, increasing the temperature will increase the reaction rate ill two ways: 1) by increasing oxygen diffusivity and 2) by increasing the oxygen concentration (oxygen solubility) in the liquid metal. The combination of these two effects accounts for the high value of the observed activation energy. Summarizing, I propose that the rate of silica reduction, like that of the carbon-oxygen reaction, is diffusion controlled and that low oxygen concentration in the liquid metal is the major factor accounting for the very low observed rates of silica reduction. John Chipman (author's reply)—The authors thank Professor Schuhmann for his interesting contribution. His proposed explanation may well prove to be the correct one. There is clearly a need for much further experimental work on this problem, and further research is in progress.

Jan 1, 1961

By James K. Hallenburg

INTRODUCTION The delayed fission neutron, or DFN technique for uranium ore body analysis uses the first down-hole method for detecting uranium in place quantitatively. This technique detects the presence of and measures the amount of uranium in the formation. DFN TECHNIQUE DESCRIPTION The DFN technique depends upon inducing a fission reaction in the formation uranium with neutrons, resulting in an anomalous and quantitative return of neutrons from the uranium. Since there are no free, natural neutrons in formation, a good, low noise assessment may be made. There are several methods available for determining uranium quantity in situ. The method used by Century uses an electrical source of neutrons. This is a linear accelerator which bombards a tritium target with high velocity deuterium ions. The resulting reaction emits high energy neutrons which diffuse into the surrounding formation. They lose most of their energy until they come to thermal equilibrium with the formation. Upon encountering a fissile material, such as uranium, these thermal neutrons will react with the material. These reactions produce additional neutrons, the number of which is a function of the number of original neutrons and the amount of fissile material exposed. The particular source used, the linear accelerator, has several distinct advantages over other types of sources: 1. It can be turned off. Thus, it does not constitute a radioactive hazard when it is not in use. 2. It can be gated on in short bursts (6 to 8 microseconds). This results in measurements free of a high background of primary neutrons. 3. The output can be controlled. Thus, the neutron output can be made the same in a number of tools, easily and automatically. There are several interesting reactions which take place during the lifetime of the neutrons around the source. During the slowing down or moderating process the neutron can react with several elements. One of these is oxygen 17. This results in a background level of neutrons in any of the measurements which must be accounted for in any interpretation technique. These elements are usually uninteresting economically. The high energy neutrons will also react with uranium 238. However, the proportions of uranium 235 and 238 are nearly constant. Therefore, this reaction aids detection of uranium mineral and need not be seperated out. Upon reaching thermal energy the neutrons will react with any fissile material, uranium 235, uranium 234, and thorium 232. At present, we do not have good techniques for seperating out the reaction products of uranium 234 and thorium 232. However, uranium 234 is a small (.0055%) percentage of the uranium mineral and thorium 232 is usually not present in sedimentary deposits. When the uranium 235 reacts with thermal neutrons it breaks into two or more fragments and some neutrons. This occurs within a few microseconds after the primary neutrons have moderated and is the prompt reaction. One system uses this; the PFN or prompt fission neutron technique. We don't use this method because the neutron population is low and, therefore, the signal is small and difficult to work with, accurately. Within a few microseconds to several seconds the fission fragments also decay with the emmission of additional neutrons. Now, with a long time period available and a large neutron population we gate off the generator and measure the delayed fission neutrons after a waiting period. These neutrons can be a measure of the amount of uranium present around the probe. Thermal neutrons are detected with the DFN technique instead of capture gamma rays to avoid some of the returns from other elements than uranium. LOGGING TECHNIQUE The exact logging technique will depend, to some extent, upon the purpose of the measurement. However, the general technique is to first run the standard logs. These will include: 1. The gamma ray log for initial evaluation of the mineral body and for determining the position of the borehole within the mineral body, 2. The resistance or resistivity log for determining the formation quality, lithology, and porosity. 3. The S. P. curve for estimating the redox state and shale content, and measuring formation water salinity, 4. The hole deviation for locating the position, depth, and thickness of the mineral (and other formations), and 5. The neutron porosity curve. The neutron porosity curve is most important to the interpretation of the DFN readings. The neutrons from this tool are affected in the same way by bore hole and formation fluids as the DFN neutrons are. Therefore, we can use this curve to determine effect of the oxygen 17 in the water. Of course, this curve can be used to determine formation porosity. It can also be used to calculate formation density.

Jan 1, 1979

By A. Steiner, K. L. Komarek

Activities of aluminum in solid Ni-A1 alloys have been determined between 20 and 60 at. pet Al and 1200" and 1400°K by an isopiestic method in which nickel specimens, heated in a temperature gradient, are equilibrated with aluminum vabor in a closed all-alumina system. The activity of aluminum shows a strong negative deviation from Raoult's law at low concentrations but increases by three orders of magnitude within the ß(NiAl) phase. The partial molar enthalpy and entropy of mixing are negative. Using Wagner and Schottky's theory of ordered compounds, a degree of disorder of 4 x 10 -4 for NiAl and 1.25 X 10-2 for FeAl has been calculated THE Ni-A1 system has been studied by a great number of investigators, and the results, as far as the phase diagram is concerned, have been compiled by Hansen.1 The phase boundaries from 0 to 50 at. pet Ni are well-established. At higher nickel contents the boundaries are still in dispute and an additional phase, A12Ni3, has been reported.' The phase diagram is dominated by a very stable high-melting compound, NiA1, with a relatively wide range of homogeneity. Heats of formation of solid alloys have been determined calorimetrically by Oelsen and Middel3 from 20 to 95 at. pet Ni and by Kubaschewski4 from 25 to 80 at. pet Ni. According to the most recent compilation5 no other thermodynamic investigations have been reported for the Ni-A1 system. Due to the corrosive nature and the low vapor pressure of aluminum, a method has been employed for determining activities of aluminum which was previously developed for the Fe-A1 system.= Nickel specimens, heated in a closed evacuated alumina system in a temperature gradient, were equilibrated with aluminum vapor from a source within the system kept at constant temperature. After complete equilibration the specimens were analyzed and activities calculated from the known vapor pressure of aluminum. APPARATUS AND EXPERIMENTAL PROCEDURE Materials. The nickel specimens were made from wafers of electrolytic nickel (International Nickel Corp.) of 99.99 pet purity which were rolled to a 0.001-in.-thick foil by Driver-Harris Co. and to a 0.005-in.-thick sheet in our laboratory. The aluminum (Aluminum Corp. of America) had a purity of 99.99+ pct. The alumina tubes and crucibles were made of impervious recrystallized alumina with an alumina content of 99.7 pet (Triangle RR, Mor-ganite Inc.). Experimental Procedure. Annular specimens were punched from the sheet, the punching burrs removed, and the specimens degreased in carbon tetrachloride and acetone and weighed on a micro-balance to within an accuracy of ±0.01 mg. The specimens were positioned with alumina spacers along an alumina tube, and the positions measured. Aluminum metal was machined into cylindrical shape, and placed into an alumina crucible. The tube with the specimens was then inserted into a hole drilled into the aluminum metal. An alumina tube with its closed end at the top was slipped over the specimens so that its lower end fitted snugly into the alumina crucible. The assembled reaction tube was inserted into a mullite tube with a water-cooled brass head which had an opening for a quartz thermocouple protection tube and a metal-to-glass connection to a conventional vacuum system. A Pt-Pt 10 pet Rh thermocouple could be raised and lowered in the quartz tube which was placed along the outside of the alumina reaction tube. The mullite tube was heated by two separately controlled resistance-tube furnaces so that in the experimental temperature range an over-all temperature gradient of approximately 150o to 250°C could be imposed on the reaction tube. The position of the mullite tube was adjusted so that the surface of the aluminum metal was always at the temperature minimum. The reaction tube was thoroughly evacuated before and during slowly heating the assembly up to the melting point of aluminum. A pressure of less than 2 µ (Hg) was maintained during an experiment. Once the aluminum had melted, it isolated the contents of the alumina tube from the surroundings. Several times during an experiment the temperature gradient was carefully measured. An experiment lasted from 3 to 6 weeks and it was terminated by air cooling the evacuated mullite tube. For further details of the experimental procedure the paper on the Fe-A1 system6 should be consulted.

Jan 1, 1964

By Lewis E. Dr. Young

MINING engineers in the United States understand that mining conditions in the British coalfields are much more difficult than in most of the mines now being operated in the United States. We realize also that in the near future we must face some of these same difficult problems. Early Mechanization The progress made in mechanical loading in the United States is the result of a long struggle in many coalfields to mine with power tools safely and to increase output per man-shift. Attempts to use power to loosen coal and to transport broken coal in the U. S. may be said to date from the Stanly Header, or Entry-Driver brought from England in 1888. The principle of this boring machine was used in the McKinlay Entry-Driver, almost continuously used in the U. S. since 1920. Since 1888 experimental loaders, scrapers, and conveyors were installed with more or less success. Beginning in 1918, considerable progress was made with mobile loaders, and in 1920 the first wage agreement for the operation of mechanical loaders was made in Indiana. In 1923 the Pocahontas Fuel Co. loaded nearly 1 million tons of coal using 23 Coloders. Labor Policy The United Mine Workers of America have never officially opposed the Mechanization movement. On December 10, 1945, in a statement before the House of Representatives Labor Committee, John L. Lewis said, regarding the policy of the United Mine Workers of America: "We have welcomed progress; we have welcomed machines. We have told our people that they had to accept that condition; that it was the process of progress, and that they would have to take their chances." Recent Development In 1951 about 71 pct of the tonnage mined underground was mechanically loaded. Over 4000 shuttle cars are in service and it is estimated that much more than half of the tonnage loaded underground is produced by trackless mining. In 1947 roof-bolting was introduced extensively and it is estimated that more than 2 ½ million bolts are now being used per month in about 600 mines. The use of roof bolts has permitted the more effective and safer use of loaders and shuttle-cars. Continuous Mining The McKinlay Entry-Driver could have been used for continuous mining, but for many years it was used only .for entry driving. In 1946 the Silver machine was developed in Colorado, and in 1947 this was acquired by the Joy Mfg. Co. and called the Joy Continuous Miner. Other types of combination mining-loading machines which eliminate drilling and blasting operations are the Marietta Miner, the Colmol, the Lee-Norse Miner, the Junior Miner, the Goodman and the Konnerth machines. There are several other types in the process of development. Probably by January 1953 there will be about 250 continuous miners in operation in the U. S. Payment of Mine Labor One of the most important problems in mechanizing was the establishing of rates of pay that would be attractive to the best men. Prior to the installation of mobile loaders the hand loaders and cutters have been paid by the ton. It was felt that a system of a day's pay should be established and that piece and tonnage rates should be abolished completely. Without exception, all coal loaded in mines equipped with mobile loaders is prepared and loaded by men paid an hourly rate. Trends in Mining Research There are two diverse approaches in coal production research; to try to design a mining machine to fit current methods, or to adapt mining practice to take advantage of proven machines. A great deal of credit must go to the mine operators who have been enterprising and dynamic enough to use available equipment intensively and to discard it as soon as an improved or new machine is available. Effect of Changing Markets Formerly there was an important demand for lump and prepared coal in the larger sizes for domestic use. The use of bituminous coal for house heating has decreased so that not more than 19 pct of the annual tonnage goes to retail trade, only 12 pct is used by the railroads, and much of the retail and most of the railroad coal is in stoker size. As a result of this decline in the market for coarse coal most of the large mining operations have crushers installed in the tipples or preparation plants. Mass production at the face requires increased preparation facilities. Another important trend is in connection with complete seam mining with mechanical loading. In many mines where the immediate roof is apt to fall with the coal no effort is made to separate roof material from coal prior to

Jan 1, 1952

By A. J. Heckler, J. A. Peterson

A capsule technique was successfully employed to investigate the effect of nickel on the activity of nitrogen in Fe-Ni-N austenite in the temperature range 600" to 1200°C. This technique consisted of equilibrating nitrogen among various Fe-Ni alloys within a sealed silica capsule. Nitrogen transfer among the specimens occurred by N, gas at 900°, lOOO? and 1200?C. Nitrogen gas pressures within the capsules were estimated to be as high as 22 atm. The activity coefficient of nitrogen, fN , in Fe-Ni-N austenite is adequately described by the linear interaction equation: log . wt pct Ni where the standard state is chosen such that fN = I as wt pct Napproaches zero in binary Fe-N. This relationship was determined over the temperature range 873" to 1473°K and for nickel contents of 0 to 35 wt pct. ALTHOUGH chemical thermodynamics of liquid iron alloys have been extensively studied, experimental data for the solid state are needed. These thermody-namic data will provide a basis for understanding phase transformations, precipitation reactions, metal-gas equilibria, and so forth. The interaction of sub-stitutional alloying elements with the interstitial elements is of particular interest. In this investigation the thermodynamic behavior of Fe-Ni-N austenite has been studied. The solubility of nitrogen gas in iron austenite is known to obey Sieverts&apos; law up to about 65 atm.1-6 In addition, the solubility of nitrogen in Fe-Ni austenite has been investigated5"8 using the classical method of equilibrating Fe-Ni alloys with nitrogen gas at 1 atm. A capsule technique similar to that used to study the activity of carbon in alloyed austeniteg&apos;&apos;&apos; was employed in the present work to determine the effect of nickel on the activity of nitrogen in Fe-Ni austenite over the temperature range 600" to 1200°C. EXPERIMENTAL PROCEDURE A series of Fe-Ni alloys up to 35 wt pct Ni was vacuum melted and cast into 1 by 3 by 6 in. ingots. Chemical analyses at the top and bottom of each ingot demonstrated that the ingots were homogeneous with respect to nickel content. The nickel contents are given in Table I. Additional chemical analyses showed that wt pct Si < 0.05, s < 0.01, C < 0.01, Al < 0.006, 0 < 0.004, Mn < 0.002, and P < 0.002. A 2 in. section of each ingot was cold rolled to 0.015 in. The material was then decarburized to a carbon content of less than 0.004 wt pct. A portion of the material of each nickel content was nitrided to various levels in a H2-NH3 gas atmosphere to provide a source of nitrogen during subsequent equilibration. The experimental technique consisted of equilibrating the series of Fe-Ni-N alloys in a partially evacuated sealed silica capsule at the temperature of interest. Both Vycor and quartz capsules were used. In general, the final equilibrium nitrogen content for each Fe-Ni alloy was approached from both higher and lower nitrogen levels. The criterion for establishing that equilibrium was attained was that the final nitrogen content for each Fe-Ni alloy was the same irrespective of the initial level. A schematic drawing of the sample configuration in a capsule is shown in Fig. 1. The samples were arranged so that there was a minimum of physical contact. The samples were also dusted with a fine, high purity alumina powder to help prevent sticking. Several different types of furnaces were used in this study. In each case, a thermocouple was placed immediately adjacent to the capsule during equilibration and the temperature was controlled to within *4?C of that reported. At each equilibration temperature, the following times were found to be more than sufficient to attain equilibrium: 600°C-250 hr, 900°C-150 hr, 1000°C-150 hr, and 1200°C-50 hr. After equilibration the capsules were quenched in water and the nitrogen contents of the specimens determined by a Strohlein analyzer. Analyses of samples after equilibration at 1000" and 1200°C showed no silicon pickup from the silica capsules. RESULTS AND DISCUSSION Transfer Mechanism. The mechanism by which nitrogen was transferred among specimens in an initially hydrogen flushed and partially evacuated capsule equilibrated at 1000°C was investigated. After equilibration the gas in the capsule was collected over water and an estimate of the pressure at temperature

Jan 1, 1970

By D. O. Hobson

Zirconium single crystals of various specific orientations were fabricated by rolling or drawing. The resulting textures were determined and are discussed with respect to the deformation modes that produced them. The crystals deformed in a predictable manner by combinations of up to third-order twinning with three twinning modes and by slip. Twinning was found to play a major role in initial texture formation. Texture changes produced by slip occurred only at the higher reductions. The twinning sequences that produced each intensity peak during the initial reductions could be identified. Schmid factor criteria were found useful in predicting which deformation modes to expect for each crystal orientation and fabrication procedure. The possible application of these data to poly-crystalline material is discussed. PREFERRED orientation or texture has a significant effect on the properties of most materials, causing anisotropy in fabricated cubic metals and enhancing the natural anisotropy of noncubic metals. This study evaluates the effects of several fabrication methods on the textures formed from specific starting orientations of zirconium single crystals and, it is hoped, gives an insight into the effects of the same operations on poly-crystalline material. BACKGROUND In fcc and bcc metals, texture changes take place by gradual lattice rotations caused by the operation of one or more slip systems. Deformation twinning plays an insignificant role in the deformation of such metals. In zirconium and its alloys, however, and in many other hep metals the ability to twin allows very rapid texture changes to be made with very small amounts of deformation. The deformation systems found in zirconium and its alloys are prism slip and three twinning modes.1 Slip occurs on the {1010}< 1120) system. There is little or no appreciable basal slip in zirconium. The twinning planes, illustrated in Fig. 1, are {1012}, {ll2l}, and {1122}. Two twinning modes, the {1012} and the {ll2l} operate for a tensile stress along the basal pole. A compressive stress parallel to the basal pole is required for {ll22} twinning. These twinning operations cause a 35- to 85-deg reorientation of the basal pole. The {1012} twin is the predominant tensile twin at room temperature. The twinning shears, S, are shown in the figure. A criterion for predicting which deformation system will operate when a grain is subjected to a known stress state is the Schmid (orientation) factor. This factor gives the fraction of the applied stress that computer program was written2 to calculate the Schmid factors for the four deformation modes in zirconium. It assumed three orthogonal stress axes and considered ninety-one different orientations of the basal pole in one octant of this stress space. At each basal pole position the Schmid factors were calculated for seven positions of rotation at 10-deg increments of the unit cell about the basal pole. Schmid factors were determined for a total of 637 orientations and for twenty-four deformation systems in each orientation. The program listed the Schmid factors for uniaxial stress parallel to each axis and, to approximate rolling, or-thonormal biaxial stress was also considered. Fig. 2 shows the range of orientations over which the various types of deformation would tend to predominate in biaxial plane strain with the stresses, equal magnitude. The exact boundary position between regions of different deformation modes depends, however, on the relative values of the critical shear stress for each deformation mode. Fig. 2 is drawn on the assumption that they are equal and it therefore may be only approximately correct. It is also recognized that the biaxial stress analysis may not be applicable in certain crystal orientations. EXPERIMENTAL PROCEDURE Single crystals of zone-refined zirconium, produced by Wilson of this Laboratory,3 were electrical-discharge-machined to form specimens for rolling, tube-drawing, and rod-drawing studies. Specimens were rolled at room temperature on 2-|--in.-diam hand-powered rolls from three different starting orientations: 1) the basal plane parallel to the rolling plane and the [1120] in the rolling direction, (0001)[ll20]; 2) the (1120) plane parallel to the rolling plane and the basal pole in the rolling direction, (1120)[0001]; and 3)_the (1120) plane parallel to the rolling plane and the [1100] in the rolling direction, (1120)[ll00]. Drawing specimens were cut with the [0001] direction as the drawing direction in the tube blank and [1120] as the drawing direction in the rod specimen. The drawing

Jan 1, 1969

By C. N. Garman

Homestake-New Mexico Partners operate a 750-tpd carbonate leach uranium concentrate mill near Grants, N.M. The highly mineralized water available as process water leaves much to be desired. The 628 ppm as CaCO 3 makes the use of raw water very troublesome in pipes and on filter cloths. However, the residual sodium carbonate in the final filter cake going to tails makes an ideal softening agent. To take advantage of this fact, all makeup water used in the mill is first used as tailing slurry dilution water and comes to the mill from the tailings pond. The 5-acre tailings pond serves as a thickener and 100 to 150 gpm of nearly clear solution is decanted to a pump to be returned to the mill. Since this tailings water has small quantities of uranium in the solution an ion exchange scavenger unit was installed to remove as much uranium as possible. The ion exchange raffinate is then used as final filter wash ahead of the tailings slurrying step. In spite of the large settling area this return water is not clean enough for ion exchange feed. The solids present are very fine and composed of approximately 15 pct (by weight) burnable carbonaceous material common to the sandstone uranium ores in the area, 40 pct SiOz plus 45 pct CaC03. Laboratory work showed that this material responds very well to flotation. Before deciding to use flotation, various clarifying systems such as pressure leaf filters, sand filters, and continuous vacuum pre-coat filters, were considered. Each of these could have solved the problem but with much more operating labor, more reagents and greater installation costs than the flotation step. About 100 to 150 gpm of fouled water is fed to two 66-in. Fagergren cells, in series. Reagents used at the beginning were Arquad 2HT75 and Arquad C50, at the rate of about 1% lb per 8-hr shift, or about 0.0053 lb each per ton of ore. This did not completely remove the solids but does an acceptable job. Approximately 75 pct of the slimes are a size that can be caught on a 41-Whatman Paper are removed. Removal of these slimes also allows much better settling of the coarse nonfloatable material. Advantage is also taken of this fact in a small settling tank ahead of precipitation. Removal of this amount of the slimes makes the ion t:xchange feasible. PREGNANT SOLUTION CIRCUIT The carbonate? leach-caustic precipitation method of uranium concertration does not provide for any process purification step ahead of precipitation. Therefore, any fine solids getting into the pregnant solution through the filter cloth show up in the final concentrate. This, of course, lowers the grade, and, at times, the slimy nature of these very fine solids rendered final filtration of the concentrate difficult if not impossible At Homestake-New Mexico Partners a 75-ft thickener was available for gravity clarification of 100 to 120 gpm of this pregnant solution. However this did not sufficiently remove the slimes. Laboratory investigation of the whole range of flocculants that were suggested by literature, salesmen, and friends failed to turn up anything of consequence. A continuous vacuum pre-coat filter would do the job and was investigated. The capital cost and the operating labor and materials made this a last chance choice. Following work done in the metallurgical laboratory on the tailings return water, it was found that some changes in the reagent strengths and combinations made a very definite decrease in the solids in the pregnant solution. Concentrate grade improved about 5 pct anti the final product after drying had an appreciably greater bulk density. Compared to a cost of about 2.2e per ton for pre-coat filter opelation for cleaning just one circuit, flotation costs less than 1.0 per ton of ore for cleaning two circuits. While a pre-coat filter would do a more thorough job, the flotation does all that is required for either circuit. Gravity causes the froth produced to run back into the leach circuit. This does not appear to result in a build-up of objectionable slime. No extra manpower is required; the operators in the separate areas can observe the operation of the cells and mix the small quantities of reagents as needed. Normally the 66-in. Fagergren cell requires 15 hp per cell, but this very dilute slurry needs only 10 hp for both cells. Originally, a combination of the two Arquads mentioned previously served as frothers and promoters. As further testing

Jan 1, 1962

By R. F. Shurtz

R. Duval (Mining Engineer, Ancien eleve de PEcole Polytechnique, Paris, France) I do not agree with the Eq. 3, reading: m =1/100- [(0.214x30.4) + (0.7B6 x0.00)] =6.5pct CaO If 0.214 and0.786 were proportions by weight, the equation would represent the well known mixtures law of the conventional arithmetics and 6. 5 pct CaO would be the correct average content. But it is not the case as the author states: "In samples consisting of single grains of mineral, those grains must, as already mentioned, be either of dolomite or magnesite. Since 78.6 pct of the deposit consists of magnesite and 21.4 pct of dolomite (excluding for present purpose the presence of other minerals), for any single grains picked at random the probability will be 0.214 that is it dolomite and0.786 that is it magnesite. In 1000 such samples the expected numbers of dolomite and mapesite grains will be 214 and 786 respectively." 0.214 and 0.786 would be proportions by weigbt under the necessary condition that all grains of dole mite and magnesite should have an identical weight. Obviously it is not the case, as the specific gravities are not the same for mapesite and dolomite and the volumes of the grains are different. Furthermore, because of these differences the conditions for a random sampling are not fulfilled and we are not authorized to state that the probabilities are, respectively, 0.214 and 0.786. The author however makes a simple application of Eq. 1: M = 1/n— ? fi x i . n Should we deduce that this relation is wrohg? Not at all, but when applying Eq. 1 you must not overlook what it actually. means. Eq. 1 gives a definition of the arithmetic mean of a total of n observed values Xi and nothing else. But the average conteht of a deposit has not the same significance. It is the ratio between the weight of concerned mineral in the deposit and the total weight of the deposit. As from 1000 particles the 214 of dolomite and the 786 of magnesite have not the same weight, the two definitions do not concur, and when applying Eq. 1 the result is an arithmetic mean of figures which has no connection with what is named average contentof a deposit. The situation is similar to the calculation of an average velocity. If a car travels a first mile over at 30 miles per hr and a second mile over at 60 miles per hr, when applying formula 1 you find as average velocity for the 2 miles: 30+60 ------- - 45 miles per hour. Many people calculate in this way and they do not realize that a mistake is involved. In fact the definition of he average velocity for the 2 miles is the quotient of the distance of 2 miles by the time (in hours) necessary for 2 miles travel, i.e.: 2 ---------- = 40 miles per hr. 1 + 1 30 60 In other words, the average volocity wanted is not the arithmetic but the harmonic average of the two velocities. The above mentioned bias in the calculation of the average contents of deposits is frequent, even in the assessments made by experienced engineers and is independant of what is named the sampling error. In order to supress the bias and to be able to use Eq. 1, you must apply a correction. An example on the subject can be found in an article by Duval et al. in the January 1955 issue of the &apos;&apos;Annales des Mines" (French), page 19. R. F. Schurtz (Author&apos;s Reply) Mr. Duval&apos;s position is quite correct. The proportions shown for dolomite and magnesite., respectively, of 0.214 and 0.786 are, in fact, proportions by weight uncorrected for specific gravity. In our day to day operation of producing magnesite from these mines at a very substantial rate, we do not normally make corrections for the difference between the specific gravity of dolomite and that of magnesite. If these corrections are made in Eq. 3 as shown in my article, then the numbers of grains turn out to be in proportions of 0.226 dolomite and 0.774 mapesite instead of the values actually shown in the equation. For the purposes of our work, and in view of the inherently low accuracy of the data, this correction was not deemed worthwhile making.

Jan 1, 1961

By A. P. Svenningsen

IN the early stages of design it was not considered necessary that separate crushing plants be built for the new sulphide concentrator and smelter until sometime in the future. The plan was to use the existing crushing facilities for both oxide and sulphide ore. A few additions were contemplated for the existing plants, such as increased bin capacity, and possibly two new secondary crushing units. The more the problem was studied and discussed with the plant operators, the more it became evident that it was complex. It involved the classification of different kinds of ore from the open pit mine -sulphide, oxide and mixed-and how best to separate them so that each kind of ore was given the proper processing and treatment. It also involved the problem of keeping the different ores from being contaminated in bins, hoppers and chutes. Added to these, transportation became complicated and would involve additional handling and loading of ore from crushing plants to conveyors, to bins, and finally to railroad cars which were to be hauled to the concentrator and dumped into the fine ore bin. General In the early part of 1951 it was decided that the concentrator be constructed with ten grinding units instead of seven as originally authorized. The smelter was to be increased proportionally and naturally also the overall tonnages of ore to be handled by the new sulphide plant. Due to this increase in plant capacity and the larger tonnages involved, the difficulties which would arise by using the existing crushing plants were increased to a point where it became evident that the building of new crushing plants for sulphide ore exclusively was technically, as well as economically, advantageous. Authorization was, therefore, given by the company to construct new crushing plants to handle 30,000 tons of ore per day, and capable of reducing the run-of-open-pit ore to the proper size feed for the 10x14-ft rod mills in the concentrator. The ore, mined in the open pit, sometimes comes in pieces as large as 6 to 7 ft diam. The rod mills may call for ore crushed to 3/4 in. The large .size of ore delivered from the open pit determined that a 60-in. gyratory crusher be used as primary breaker. Such a crusher will have a capacity considerably in excess of 30,000 tons per day. The crusher will be a single discharge unit driven by a 500-hp electric motor through a tear coupling and a floating shaft. This type of drive has proven successful at a number of other crusher installations which our company has operating in the United States, Mexico and South America. The tear coupling will protect both the crusher and motor against damage in case of overload. No new features are incorporated in the design of the crusher itself, except that the, discharge chute is made the full width of the crusher with parallel sides instead of the usual converging sides. This change in detail should eliminate, a feature which has been a bottleneck in some of the operating plants and has caused loss of production due to ore hanging up and blocking the chute. The secondary crushing plants will have three 7-ft standard Symons cone crushers and six 7-ft short head Symons crushers. Between the primary and secondary crushing plants a coarse ore bin will be constructed with a nominal draw-off capacity of 30,000 tons of ore. The standard Symons and the short head Symons will be in separate buildings. All the crushing plants and the coarse ore bin are interconnected with conveyor belts for transporting the ore to the crushers at the tonnage rate desired. The final product of the new crushing plants is produced by the short head crushers. It will be delivered onto a conveyor belt leading to the top of the fines ore bin in the concentrator. A separate conveyor belt running the full length of the fines ore bin and provided with a movable tripper of rugged design will discharge the sulphide ore into the bin. The concentrator bin is planned and designed so that the installation of this additional conveyor will not interfere with the operation of the two railroad tracks on which crushed ore is brought from the existing oxide plant. Thus when completed the bin can be filled simultaneously by ore from the new crushing plant and by ore from the existing leaching plant.

Jan 1, 1952

By F. H. Buttner, H. Udin, J. Wulff

Using a modified Udin, Shaler, and Wulff technique, the surface tension of gold Udin, purified helium was found to be 1400 ± 65 dynes per cm for the temperature range 1017° to 1042°C. IN the original Udin, Shaler, and Wulff technique for measuring the surface tension of copper: variously weighted wires were allowed to extend or contract in a copper cell held at elevated temperatures in vacuum. By plotting stress vs. strain for a wire array in one test, the stress at zero strain is obtained. This is the point where the contractile forces resulting from surface tension are balanced by the applied load, according to the expression: y = e=o r [1] where y is the surface tension in dynes per cm; a,,,, the stress at zero strain in dynes per cm; and T, the radius of the wire in cm. The assumption that the wires deform viscously permits the drawing of a straight line through the points on the stress-strain plot. Justification of the assumption has received further experimental support recently.&apos;-&apos; The presence of grain boundaries in the wires requires a correction to the original expression used." Thus: y = d4=T [l- (dl) (ar)Y1 [2] where, n/l is the number of grain boundaries per unit length, and a, the ratio of grain boundary tension to free surface tension. Alexander, Kuczynski, and Dawson in studying the creep of gold wire in vacuum were unable to obtain reproducible values of the surface tension of gold. In plotting stress vs. strain for progressively longer times, they found that the stress at zero strain drifted with time from positive stress values to negative values. Similarly, for the surface tension of silver, reproducible values were obtained only when a purified helium atmosphere was substituted.&apos; Evidently the evaporation rate of silver in vacuum is too high at the temperatures employed to obtain solid-gas equilibrium even in a similar metal enclosure. Thus reproducibility of results is lost. Experimental Procedure The experimental procedure was much the same as that originally developed by Udin, Shaler, and Wulff with a few modifications and improvements. For greater accuracy in strain measurements, knots gave way to cut gage marks as shown in Fig. 1. These were made with a hand-driven lathe in which razor blades serv&apos;ed as cutting tools. Also a more precise cathetometer with a screw accurate to 0.00015 cm was used. The tests were conducted in an atmosphere of purified .helium rather than in vacuum in order to avoid possible evaporation difficulties. Five mil wire of high purity gold (99.98 pct) was used. After cutting in the gage marks, each wire of a series of about 12 was differently loaded by welding a gold ball to one end. This was done by dipping the end of the wire in a cooling gold droplet, previously melted on a charcoal block with a No. 2 acetylene torch. The other end of the wire was strung through a hole in a gold lid and twisted over the edge to hold the wires fixed and in suspension from the lid. The lid and mounted wires were then dipped in pure ethyl alcohol to dissolve any skin oils and dirt on the surface of the wires due to handling. Finally the lid was put in place on an alundum crucible lined with gold so that the wires hung freely within the gold-lined chamber. This whole assembly was next heated in a quartz nichrome wound tube furnace and heated for a few minutes at 600°C to soften the wires. After this anneal the wires were easily straightened with tweezers. The wire assembly was finally annealed 10" to 25°C above the subsequent test temperature for 2 hr. This treatment allowed the grains to grow to equilibrium size and shape. After the anneal, the lid was mounted in front of the cathetometer. The gage length was measured by sighting the 40 power microscope on the upper lip of the lower gage mark for the first reading, then traveling up to the lower lip of the upper gage mark for the final reading. This procedure was repeated four times to give an average gage length value. In this manner the annealed gage length and the final gage length could be measured to determine the strains. During all measurements, grain counts were made.

Jan 1, 1952

By A. F. Crawley

The density and viscosity of 1iquid thallium have been measured by absolute methods to temperatures of about 200° and 150°C, respectively, above the melting point. These new data reported, especially density data, do not closely confirm previous work. Density p, in g per cu Cm, is shown to vary linearly with temperaluve t, in °C, according to the equation p = 11.658 - 1.439 X l0-3t. The viscosity data obey the well-known Andrade equation nv1/3 = A exp C/vT , the constants A and C for thallium having values of 2.19 x A and 79.648, respectively. This paper reports some new data for the density and viscosity .of liquid thallium. Measurements of these fundamental physical properties were undertaken as part of a continuing research program at the Mines Branch, Department of Energy, Mines and Resources, Ottawa. Canada. A literature search has revealed that data are so scarce that there could not be a consensus on the true values of the density and viscosity of liquid thallium. To be more specific, there exists only one set of viscosity data&apos; and only two acceptable sets of density data,273 one of which is limited in scope.3 In Liquid Metals Handbook,3 another density study is reported but indications of impurities in the thallium render the results suspect. In this situation, further careful experimentation was required to realize the true density and viscosity of thallium. EXPERIMENTAL METHODS Density. Densities were determined using a graphite pycnometer. The technique and its accuracy have been discussed in earlier papers.4&apos;5 It is considered that experimental data can be obtained which are accurate within +0.05 pct, all sources of random and systematic errors having been evaluated. Density results for thallium were identical whether measured under an atmosphere of argon or a vacuum of 5 x 10-6 torr and, for the most part, the argon atmosphere was used. Viscosity. Viscosity measurements were made in an oscillational viscosimeter by an absolute method—the liquid metal being held in a closed graphite cylinder. Design and operation of the apparatus, constructed in this laboratory, have previously been discussed.6 For thallium, runs were made under a vacuum of about 2 x 10-6 torr. To evaluate viscosity coefficients from the various experimental parameters, the mathematical analysis of Roscoe7 was used. Measurements of the necessary parameters and the accuracy of these measurements have also been discussed.6 The cylinder dimensions were corrected for the anisotropic expansion of graphite, as discussed for density measurements.4,5 It is well-known that thallium oxidizes rapidly and hence a newly machined surface quickly tarnishes in air. The oxide film, however. is nonadherent and is easily removed by rubbing or by solution in water. Hence, immediately before use, both density and viscosity charges were immersed in water, wiped dry, and quickly transferred to the apparatus which was then rapidly evacuated. Specimens removed after determinations were only slightly tarnished and there was no other evidence that tarnishing affected the results. For example, the sharpness of the specimen edges from the containing vessels indicated complete filling by the liquid metal. Thallium of 99.999 pct purity was used in this investigation. Because of its high toxicity care was exercised in handling this material. For example, the melting procedure to prepare machinable ingots was carried out in an open, well-ventilated area, while protective gloves were always worn when handling the solid metal. RESULTS AND DISCUSSION Density. Measurements were made over a tempera-ture range of about 200°C above the melting point. The results are listed in Table I and plotted in Fig. 1. From the graph it is evident that the relation between density and temperature is linear. Such a relation has been observed before in this program for other metals and alloys475 and elsewhere by other workers. A least-squares analysis of experimental data gives the equation: pT1 = 11.658 - 1.439 x 10-3t where p = density in g per cu cm and t = temperature in "C. In Fig. 1, together with the present results, the data of Schneider and Heymer2 in the corresponding temperature range have also been plotted. Evidently, the two sets of data do not agree well, the results of Schneider and Heymer being about 0.6 pct higher. Viscosity. Viscosity data were obtained from the melting point, 303.5°C, up to 457.5"C. The data are listed in Table I and in Fig. 2 the plot of these results demonstrates a smooth curvilinear relation between

Jan 1, 1969

By C. W. Sherman, N. J. Grant

The correlation of the high temperature chemical properties of slag-metal systems with some easily measured property of either slag or metal at room temperature has been the goal of both process metallurgists and melting operators for many years. There are several rapid methods for estimating various constituents in steel in addition to the conventional chemical methods which are quite fast, but these do not reveal the nature of the slag as a refining agent, which is of primary interest to the steelmaker. Furthermore, there are several methods for examining slag, the three principal ones being slag pancake, petrographic examination, and the previously mentioned chemical analysis. The main objection to the last two is the lime required to make a satisfactory estimate of the mineralogical or chemical components. The objection to the first is the inadequacy of the information obtained. A new technique has been developed by Philbrook, Jolly and Henry1 whereby the properties of slags are evaluated from an aqueous solution leached from a finely divided sample of slag. It is known that the pH or hydrogen ion concentration (of saturated solutions that have dissolved certain basic oxides, notably calcium oxide) will indicate a pronounced basicity. Philbrook, Jolly and Henry devised the pH measurement technique in order to supply open hearth operators with a fast, reasonably accurate method of estimating slag basicity. They offered the method as an empirical observation and made no claims as to its theoretical justification. The results were presented as an experi-metally observed relationship which applied over an important range of basic open hearth slags. They found that, in plotting the measured pH against the basicity, the best relationship existed between the pH and the log of the simple V ratio, CaO/SiO2. Extensive investigation also showed that there were several variables in the experimental technique that influenced the results and necessitated following a standard procedure to obtain reproducible pH readings. These variables were: 1. Particle size of the slag powder used. 2. Weight of sample used per given volume of water. 3. Time of shaking and standing allowed before the pH was measured. 4. Exclusion of free access of atmospheric carbon dioxide to the suspension. 5. Temperature of the extract at the time the pH was measured. In subsequent investigations of the pH method by Tenenbaum and Brown2 and by Smith, Monaghan and Hay3 the general conclusions of Philbrook&apos;s work were reaffirmed. It was the object of the present investigation to extend the technique to a point where it could be used to evaluate slags of all types. Experimental Results PARTICLE SIZK OF SLAG POWDER A large sample of commercial blast furnace slag of intermediate basicity (V-ratio 1.15) was selected for the study. The slag had been put through a jaw crusher until all of it passed through a 20 mesh screen. Five fractions of this crushed material were separated, -20 to +40, -40 to +60, -60 to +100, -100 to +200, and -200 mesh. A representative sample of 0.5 g was removed from each fraction and the pH determined using the method of Philbrook. Check pH analyses on the sample fractions varied due to the different amounts of shaking. To eliminate this variable, a mechanical shaker was employed. In order to know the exact time of contact between the slag and water, it was found necessary to filter the extract at the end of the shaking period. Using the mechanical shaker and a filtering apparatus, similar runs were made on the five fractions for contact times of 5, 10, 20, and 40 min. Random checks gave reproducible results within 0.02 pH. The data are plotted in Fig 1. It can be seen from the plot that each slag fraction is hydrolyzed to an extent that is roughly proportional to the surface area exposed to the water. The (—100 to +200) mesh material changed very little in pH after 10 min. shaking time. The curves are symmetrical and lie in proper relation to one another. The —200 mesh curve appears to be somewhat flatter than the others, but this can be attributed to the portion of very fine material that is not present in the other fractions. The closeness of the (-100 to +200) mesh curve to the —200 mesh curve and the fact that a —100 mesh sample would contain amounts of slag down to 1 or 2 microns in diam were considered sufficient reasons for selecting a —100 mesh sample as representative of the whole sample of slag for the purposes of this investigation.

Jan 1, 1950

By David A. Thomas, David N. French

The lrnrdness of WC crystals has been measured with the Knoop indenter at loads of 100 and 500 g on the (0001) and (1070) planes. The hardness as tneasitred on the basal plane is 2400 kg per sq mm and shows little anisotropy. The hardness on the prism plane, however, shows a marked orientation dependence, with a low value of 1000 kg -per sq mm when the long axis of the Knoop indenter is oriented parallel to the c axis and a high value of 2400 kg per sq mm when the indenter is perpendicular to the c axis. Slip lines (Ire observed surrounding the microhardness indentations and they show slip on (1010) planes, probably in [0001] and (1120) directions. This slip behavior can be explained by the crystal structure of TVC, which is simple hexagonal with a c/a ralio of 0.976. The hardness anisotropy call be explained by [0001]{1010} and (1130) {10l0] slii) and the resolved shear-stress analysis of Daniels and Dunn. HARDNESS anisotropy is a well-known phenomenon and has been reported for many metals, with both cubic and hexagonal structure.1-6 For hexagonal tungsten carbide, WC, a wide range of hardness values is reported in the literature. For example, Schwarzkopf and Kieffer7 give a hardness of 2400 kg per sq mm and report a value of 2500 kg per sq mm by Hinnüber. Foster and coworkerss give the average Knoop microhardness as 1307 kg per sq mm with a maximum value of 2105 kg per sq mm. Although these values and the structure of WC suggest the likelihood of hardness anisotropy, no such measurements have been made. We first detected a large apparent hardness anisotropy in WC crystals about 75 p large, in over-sintered cemented tungsten carbide. Prominent slip lines also occurred around many indentations. This report presents further observations and interpretations of hardness anisotropy and slip in WC crystals obtained from Kennametal, Inc. Both Knoop and diamond pyramid indenters were used on a Wilson microhardness tester with loads of 100 and 500 g. EXPERIMENTAL RESULTS The carbide crystals tended to be triangular plates parallel to the (0001) basal plane of the hexagonal structure. The side faces were parallel to the ( 1010) prism planes. Specimens were mounted approximately parallel to these two types of faces and metallographically polished. Laue back-reflection X-ray patterns were used to orient the specimens, which werethen ground to within ±1 deg of the (0001) and (1010) planes. The Knoop hardness values measured on the basal plane are plotted in Fig. 1. There is only a small anisotropy, with a hardness range of 2240 to 2510 kg per sq mm. The additional points at angles from 52.5 to 67.5 deg confirm the sharp minimum hardness at 60-deg intervals, consistent with the sixfold hexagonal symmetry. The average hardness of all values obtained on the basal plane is 2400 kg per sq mm. While the basal plane shows only slight anisotropy, the (1010) plane exhibits marked hardness anisotropy, from 1000 to 2400 kg per sq mm. Fig. 2 shows the hardness as a function of the angle between the long axis of the indenter and the hexagonal c axis, the [0001] direction. The minimum and maximum occur when the indenter is oriented parallel and perpendicular to the [0001] direction, respectively. The anisotropy of the prism plane is contrary to that reported for hexagonal zinc and hard- However, the basal-plane anisotropy is similar to these two metals.1&apos;2 To check the accuracy and reproducibility of the measurements, a series of fifteen impressions was made at 100-g load in the same orientation in the same area of the specimen surface. The average for all was 2040 kg per sq mm, with a range of 1950 to 2130 kg per sq mm, giving an accuracy of about ± 5 pct. Thus the slight anisotropy on the basal plane is almost within experimental error. Fig. 3 shows slip lines around the Knoop indentations on the basal plane. The slip traces are in directions of the type (1130). The presence of slip steps on the basal plane indicates that the slip direction lies out of the (0001) plane. Because WC has a c/a ratio of 0.976,&apos; the shortest slip vector is [0001], which suggests slip systems of the type [0001] (1010). Fig. 4 shows slip lines around the Knoop intentations on the (1010) plane. These slip lines are inconsistent with [0001] slip but can be

Jan 1, 1965

By E. J. Roberts

Prior to 1916, thickening was an art, and any accurate decision as to what size of machine to install to handle a given tonnage of a specific ore must have been one of those intuitive conclusions, based on both intimate and extensive acquaintance with thick-ners and ore pulps. Then in 1916 "knowledge of acquaintance," became "knowledge about" with the publication of the Coe and Clevenger paper.&apos; The unit operation of thickening had graduated to the status of an engineering science. The fundamental similitude relationships for the two major phases of the operation were defined so clearly that batch tests on models as small as liter cylinders could serve to specify protypes as large as 325 ft in diameter. It is quite apparent from reading the literature that Coe and Clevenger&apos;s contribution is not generally appreciated. In so far as the basic engineering relationships are concerned, the only real advance which has occurred in the 30 odd years which have elapsed since the Coe and Clevenger paper is the recognition of the effect of the rakes on the thickening process. Bull and Darby2 noted this in 1926, and the extensive use of the "gluten type" thickener, in which the effect is magni-fied, bears witness to its importance. Comings3 further verified this effect of the rakes. As a matter of fact, a number of papers show an apparent regression from the Coe paper in that the area determinations are made on the basis of a single test from One concentration of solids. Coe and Clevenger amply demonstrated that this is unsafe, since the controlling zone may be one other than that of the feed dilution. Comings3 neatly demonstrated this without apparently realizing it. Of course there have been significant advances in the application of the operation to industry. Open tray thickeners were introduced to save area; balanced tray thickeners, washing thickeners, and multifeed clarifiers were developed with all of their special hydraulic and mechanical problems. Combinations of all kinds have been introduced, such as combination agitators and thickeners, combination flocculators and clarifiers, combination thickeners and filters. With the establishment of the operation on a firm engineering foundation, installation was facilitated and expansion proceeded. There are still problems, of course, functional as well as mechanical. Sometimes the moisture in the underflow obtained in practice is not as low as is expected on the basis of the test data. Sometimes the underflow is so "thick " that its discharge and subsequent handling requires special attention. Island formation plagues some operators. The use of the thickener as a surge basin and blending tank in the cement industry poses unusual problems. Design of rakes and the drive mechanism must be continually im-proved. Corrosion problems must he overcome. Power requirements for raking the settled solids occasionally is the controlling factor as it was in the case of the all American Canal desilting installation. Other similitude relationships and design problems come into the picture when we enter the field of clarification or nonline settlement. We have an energy dissipation problem in introducing the feed and any models must satisfy the Froude model relationships. Autoflocculation requires detention which involves the same similitude laws that we encounter in the compression zone. Approach to an Exact Science The next step beyond having control of the similitude relationships is to understand the why of these relationships right back up the line to first principles. The ultimate might be that, if given the mineralogical composition of the solids and their size distribution together with an analysis of the suspending liquid, we could calculate the entire thickening behavior of the system. Then we could say we had reduced the operation to an exact science. True it might be more trouble getting this basic analytical data than to make our empirical determinations for area and volume, and we would need an ENIAC to calculate the results, but that does not detract from the desirability of such understanding. Considerable work has been done by the chemical engineers with this end in view. Comings,3 Egolf,4 Work,5 Kam-mermeyer,6 Steinour,7 and others have studied the problem. The writer has no final answer to the thickening story but would like to propose a picture of the mechanics of the two phases of thickening which has been found useful in understanding the subject and which leads to some convenient relationship in treating the compression step and arriving at the compression depth.

Jan 1, 1950

By O. G. Paasche, Yuan-Shou Shen

THERE is a disagreement among the various authors about the exact manner of transformation of ZrCr2. Rostokerl and others2 stated that ZrCr2 had a C-14 (MgZn2) type of structure below 1000°C and a C-15 (MgCu2) type of structure at temperatures above 1000°C. Alisova3 and others4 reached the opposite conclusion and stated that the transformation temperature is close to the melting point of ZrCr2. A literature survey shows that various investigators3&apos;= who homogenized the specimens at a temperature higher than 1000°C have concluded that ZrCr2 had the C-15 structure at room temperature. Meanwhile, Jordan et al.4 reached similar conclusions without annealing the specimen. Other investigators1,2,6,7 who X-rayed the specimens in the as-cast condition without annealing reached different conclusions. The investigation reported herein was conducted with the aim of exploring the exact manner of transformation of ZrCr2 by various heat treatment tests. The alloys for this examination were prepared from iodide-reduced zirconium crystal bars, 99.9 pct purity, and electrolytic chromium, 99.9 pct purity. They were melted in a nonconsumable electrode arc furnace with water-cooled copper crucible in a helium atmosphere. The melting loss of each alloy was less than 1.5 pct by weight. Chemical analysis of a randomly selected specimen indicated that there was a very close agreement between calculated and analyzed compositions. Before being heat-treated each specimen was encapsulated in a vycor or quartz tube inside which an argon atmosphere was maintained at a pressure of lower than 1 atm. In determining the crystal structure of each specimen with a Debye-Scherrer camera, the standard procedure8 for X-ray quality analysis (Hanawalt method) was followed. The different series of heat treatment tests in this investigation are tabulated in Tables I and 11. The tests in Series I, specimens from 1-1 to 1-9, which were similar to Rostoker&apos;s experiment1 indicated that the transformation temperature seemed to fall between 870° and 900°C and that the crystal structure of ZrCr2 at lower temperature seemed to be of the C-14 type. However, once the compound is transformed to C-15 type, it is impossible to reverse the transformation back to the C-14 type by first heating the specimen above 900°C and then annealing it slowly below 900°C as shown in Experiments II-1 to II-3. Thus, it appears that the specimen of ZrCr2 will transform from C-14 to C-15 structure when heated above 900°C but will not transform from C-15 to C-14 when annealed slowly passing 900° C even after the extremely slow cooling process such as indicated in the experiment of Specimen II-3. As a valid transformation temperature is a temperature at which the transformation is reversible, therefore the temperature 900°C (or other temperature close to 900°C) is not the transformation temperature for ZrCr2 and the C-14 structure is not the stable structure of ZrCr2 at lower temperatures. The C-14 structure is retained at room temperature because the transformation to C-15 structure is very sluggish and the fast cooling after melting does not allow enough time for the transformation to take place. Additional energy is required to alter the metastable condition of the C-14 structure. The sluggishness of this transformation was again demonstrated through another series of experiments. Four specimens with C-14 structure were taken. Then they were annealed at 900°C but each specimen was soaked for a different period of time, Table 11. X-ray diffraction patterns of this group indicated that the C-14 structure gradually disappeared as the soaking period was lengthened. The figures listed under the column "C-14 Structure, pct" were estimated from the intensity of the d = 2.330 line of the diffraction pattern corresponding to the structure. Notice that the intensity of this line became weaker for longer soaking periods. To determine the transformation temperature of ZrCr2, specimens with C-14 structure (as-cast condition) were annealed at 1300°, 1400°, 1500°, 1550°, and 1600°C, respectively. A final specimen was first heat-treated to 1500°C in order to transform it to C-15 structure, then heat-treated at 1600°C again. From the X-ray analyses of this series of tests, Specimen Nos. III-1 to III-6, it is evident that a transition from C-15 structure at lower temperatures to the C-14 structure occurs at some temperature between 1550° and 1600°C.

Jan 1, 1969

By George B. Clark

Many basic engineering principles of all four phases of mining operations, namely, prospecting, exploration, development, and exploitation, can be analyzed better in terms of quantitative geology. Geological data from both field and laboratory will also complement scientific methods now being developed. THE geological data emphasized so successfully in prospecting for new deposits, that is, structural controls, strength of solutions, and type of mineralization, are basically those required for successful exploitation. In the mining of newly discovered deposits the most economical methods should be employed as early as possible to keep the overall cost per unit produced at a minimum and to permit maximum extraction of valuable minerals. A crucial question is: How can geological data be translated into useful quantitative results which will aid in achieving this end? H. E. McKinistry&apos; has suggested that a solution may be reached in one of two ways: 1—the usual approach, use of judgment based on experience; or 2—mathematical calculations and tests on models, both subject to certain limitations. He also suggests that in addition to better use of geology more case data and theoretical data are needed on which to base sound judgment. Further research, therefore, is necessary. Perhaps in this field the emphasis should be on more specialization in mining methods and ground movement by men with thorough training in physics, engineering, geology, and underground mining. These specialists would be equipped to point out the most economical and scientific methods of exploitation. Selection of a stoping method is governed by the amount and type of support a deposit will require in the process of being mined, or by the possibility of employing the structure of the deposit to advantage in mining the ore by a caving method. In addition to these factors there are others which almost invariably influence the choice of an economical method of mining:&apos; 1—strength of ore and wall rocks; 2—shape, horizontal area, volume, and regularity of the boundaries of the orebody, and thickness, dip and/or pitch of the deposit and individual ore shoots; 3—grade, distribution of minerals, and continuity of the ore within the boundaries of the deposit; 4—depth below surface and nature of the capping or overburden: and 5—position of the de- posit relative to surface improvements, drainage, and other mine openings. In the final analysis it is usually necessary to disregard the less important of these factors to satisfy the requirements of the more important. Because of the variation of geological conditions throughout and surrounding the deposit, no mining method will be everywhere ideally applicable to the conditions encountered in one ore deposit. The immediate problem is to interpret the above physical characteristics of deposits in terms of geological characteristics. Very few quantitative geological data are available on the factors related to a choice of mining methods. However, there are many descriptive data in mining and geological literature which collectively show how important an effect details of geology have upon all phases of mining operations. The following categories of basic mining methods were investigated to establish the geological factors that have affected their successful application: 1— open stopes with pillars; 2—sublevel stoping; 3— shrinkage stoping; 4—cut-and-fill stoping; 5— square-set mining; 6—top slicing and sublevel caving; and 7—block caving. It should be noted that the first five of these methods are listed in the order of increasing support requirements. Mines were selected as examples only where geological descriptions were complete enough to warrant their use. A study of the geological factors involved in mining operations led to a choice of the following classifications, employed in Table I: 1—structural type of orebody; 2—dimensions (geometry); 3— country rock (type); 4—faulting, folding, and fracturing; 5—alteration of ore and rock; 6—type of mineralization; and 7—geological factors determining mining method (summary). Of these factors only one yielded results that can be defined from available data in a quantitative manner, i.e., dimensions of the deposit. These are the most reliable guides that can be used in selection of suitable mining methods. They are, in general, the properties of geologic structure most difficult to evaluate by studies of models, pho-toelastic studies, and other laboratory methods, all of which are at present more limited in their applications than the geologic method. Application of geology has proved a reliable guide in other phases

Jan 1, 1955

By Norman Lamont

The evaluation of certain reser-voir properties, such as porosity and fluid saturation, from electrical well surveys has been widely accepted in petroleum engineering. Various investigators have established relationships between these properties and certain parameters which affect the response of the electrical log. Among these are the resistivities of the mud, its filtrate, and its filter cake. In 1949, Patnode1 established a relationship between the resistivities of the mud and filtrate. The well logging service companies have contributed relationships for the mud-mud cake resistivities2,3 These have been valuable since it was the practice to measure only resistivity of mud at the well site. During the mid-1940&apos;s the industry began drilling wells with oil-emulsion drilling fluids. These were conventional aqueous muds with a dispersed oil phase. Since 1950, oil-emulsion muds have been used on an increasing number of wells each year. However, the practice of measuring only the resistivity of the mud at the well site has continued, and the mud filtrate and mud cake resistivities have been determined by the above-mentioned relationships. Service companies are now equipped to measure all three resistivities at the well site. An investigation was conducted on the resistivities of oil-emulsion muds, mud filtrates, and mud cakes to determine if these values conformed to the relationships for aqueous muds. TYPES OF MUDS Fifty-one oil-emulsion mud samples were prepared in the laboratory following a standard manual&apos; published by a leading mud company. The diesel oil in the samples varied from 5 to 50 per cent, the majority of the samples being in the 10 per cent region. The basic aqueous mud types which were converted to oil-emulsion muds were commercial clay and bentonite muds, low pH and high pH, caustic-quebracho treated muds, and lime treated muds. The emulsions were stabilized by dispersed solids, lignins, lignosulfo-nates, sodium carboxymethyl cellulose, or sulfonated petrolatum. It is worthy of note that after a quiescent period of two weeks at room temperature all samples, regardless of emulsifying agent, remained stable. The make-up water for the muds was from the laboratory tap. Resistivities were varied by the addition of table salt to the water. A range of mud resistivities from 0.44 to 3.9 ohm-m was obtained in this way. Twenty-three field muds were tested. These covered the same range of mud types as did laboratory muds. Oil provinces of the Gulf Coast, South Texas, West Texas, Oklahoma, Montana, and Canada were represented. MUD TEST PROCEDURE Each mud was tested for density, viscosity, pH, and filter loss by standard testing techniques. The resistivity measurements were obtained with a Schlumberger EMT meter. This meter required small volumes of sample, e.g., 2 mm. Filtrate was obtained from a Standard Baroid fil-ter press at the end of a 30-minute test. The filter cake from the same test was used for cake resistivity measurements. Mud, filtrate, and cake samples were heated to 100" F in a constant temperature water bath prior to measurement of resistivities. RESULTS The relation between mud resistivity (Rm) and mud filtrate resistivity (Rmf) is shown in Fig. 1. The solid line represents an average for the data. The equation of this line is Rmf =0.876 (Rm) 1.075 . . (1) Arbitrary limits, indicated by the dashed curves, have been set. The majority of the data falls within these limits, but some points do lie outside the limits. The approximate equation Rmt = 0.88 Rm , . . . . (2) will give satisfactory results within these limits. The data on mud cake resistivity Rmc is shown in Fig. 2. The solid line is an average for the data. The equation for the line is Rmc = 1.306 (Rm)0.88 The dashed lines are arbitrary limits on the data. Within these limits, Eq. 3 may be simplified to Rmc = 1.31 Rm . . . . (4) DISCUSSION The limiting curves in Figs. 1 and 2 represent maximum deviations of ±25 per cent. Thus the use of the average curves can introduce considerable error. There is no substitute for accurate measurements of mud, mud cake, and mud filtrate resistivities at the well site. The mud sample tested should be representative of the mud opposite the formation being logged. The average mud filtrate resistivity curve of Fig. 1 is reproduced in Fig. 3 with two curves which have been published for clay-base aqueous muds2,3. The latter curves were determined from average values of a large number of drilling fluids. The three curves have essentially the same slope and the differences between them are from 7 to 22 per cent. Comparison is made only to illustrate the possibility of error

Jan 1, 1958

The pressure of the gas in equilibrium with sphalerite has been determined in the temperature range of 680&apos; to 825°C, using the Knudsen orifice method. A comparison of these experimental pressures with those calculated from thermal data and from other equilibrium measurements shows that the vapor above sphalerite is predominantly dissociated ZnS. Equations have been given for correctly calculating dissociation pressures using the Knudsen orifice method. It has been shown that the experimentally determined pressure is the same, whether the zinc sulphide is sphalerite or not, or a mixture of wurtzite and sphalerite. CONFLICTING points of view appear in the literature on the constitution of the vapor in equilibrium with solid zinc sulphide in the vicinity of 800°C. By comparing the dissociation pressure calculated from thermodynamic data and the vapor-pressure determination of ZnS by Veselovski,1 Lumsden2 has concluded that the vapor consists largely of dissociated ZnS. Sen Gupta,&apos; however, concludes from his spectroscopic determinations that the vapor is largely ZnS molecules. In view of the fact that the thermodynamically calculated&apos; dissociation pressure is higher than that experimentally measured by Veselovski, it seemed in order to repeat Veselovski&apos;s measurements. Experimental Procedure The method used for the determination of the pressures in this papel- is the Knudsen effusion cell. The apparatus and procedure were described in a previous paper- from this laboratory on the determination of the vapor pressure of silver. The only difference is that the Knudsen cell in this work is made from platinum and there is no external cover around the cell. The cell is an ordinary platinum crucible of 2.2 cm top diameter with a capsule cover. It was thought that platinum might stand up at these temperatures to the solid and gaseous ZnS, since it was found that the weight of the platinum cell itself did not change appreciably on heating ZnS in it at the working temperatures. To insure that reaction of the zinc sulphide with the cell was not giving&apos; a false value, a stabilized zirconia cell was employed for check runs. Fig. 1 shows the comparison, which is satisfactory. Veselovski previously had measured the vapor pressure of ZnS using a silica Knudsen effusion cell. On repeating his experiment in this laboratory, it was found that ZnS at-tacked the silica cell, giving it a marked frosty appearance. This led to the belief that Veselovski&apos;s result:; may be in error. Also, he was operating at pressures above the range ordinarily considered safe for the Knudsen method. The effusion rate was measured by weighing the cell before and after each run. The weight loss during heating to temperature and cooling down was measured and subtracted from the weight loss during the actual run. The zinc sulphide used in this investigation was from two sources: Fisher cp grade, and a sample of pure sphalerite supplied by Mr. E. A. Anderson of the New Jersey Zinc Co. Before and after the series of runs with Fisher ZnS, X-ray analysis showed that both wurtzite and sphalerite were present. However, the ratio of sphalerite to wurtzite increased. All measurements were made below the transition temperature which has been reported" to be 1020°C. The data obtained in this investigation are tabulated in Table I. The pressure was calculated by the usual Knudsen formula" on the assumption that ZnS molecules were effusing. From these data, using pure sphalerite in the platinum Knudsen cell, the vapor pressure of ZnS, in mm of Hg, as a function of temperature is given by the solid line in Fig. 1. The best straight line, as determined by the method of least squares, is given by 14405 logpzns =-14405/T +11.032. A comparison of these results with Veselovski&apos;s shows that his results are about 50 pct lower. Discussion The vapor in equilibrium with solid zinc sulphide in the temperature range of this study will consist of Zn, S2, and ZnS mol, since other species of zinc and sulphur&apos; are relatively unstable. The question to be settled is whether or not ZnS is largely dissociated. The derivation8 which follows gives the method of calculating the pressure of zinc and sulphur over solid ZnS, assuming complete dissociation, from Knudsen cell data. The free energy of the reaction 2 ZnS(solid) ? 2 Zn(gas) + S2(gas) is given by ?F?° = -RT In K = —RT In p12p2 where p1 is the zinc pressure and p is the sulphur pressure. If dissociation occurs in a closed system,

Jan 1, 1955