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By D. W. Frommer

The investigation reported in this paper is one of several included in a broad program of developing new or improved concentration processes for the oxidized and partly oxidized deposits of lead and zinc, A sample from the Playter lease, Newton County, Mo., containing pyromorphite was successfully concentrated by fatty acid flotation to a grade of over 62 percent lead. Owing to the presence of a high content of slime-size values, the overall recovery of lead at that grade was limited to 44 percent. DESCRIPTION AND HISTORY OF PROPERTY The mineral pyromorphite is a chlorophosphate of lead containing 76.4 percent lead, and, although it occurs frequently in association with other lead minerals, it is considered a minor ore mineral of lead. The manner of occurrence of oxidized lead minerals, including pyromorphite, which frequently are no larger in grain size than the clay with which they are found, militates both against development of a simple beneficiation process and high recovery. The profitable exploitation of such deposits depends not only on a successful treatment procedure but a highly favorable metal market as well. For these, and perhaps other reasons, very little research has been done on the recovery of pyromorphite from its deposits.

Jan 1, 1956

By C. E. Lesher

Two processes for agglomerating fine sized ores with low temperature coke are described. One process (Orcarb) agglomerates ores with limited amounts of carbon; the other (ore-carbon pellets) pelletizes fine sized ores, using low temperature cokes as the binder. Data are presented on the products obtained when taconite, magnetite, and hematite concentrates and several titanium oxide ores were used. REDUCTION of finely divided oxide ores has long been a major metallurgical problem. Various methods of agglomerating, notably briquetting, sintering, nodulizing, and pelletizing, have been developed and are in industrial use. Carbon is the usual reducing agent for oxide ores and attempts have been made to agglomerate fine ores with coking coal in order to get the metallurgical advantages of intimate contact and increased particle sizes suitable for subsequent smelting or reduction.1-3 For the past three years, research has been in progress on two processes for combining fine sized ores with reactive carbon in the form of low temperature coke. By one process, designated Orcarb, the ore is coated with coke carbon in amounts limited to that required for reduction and the result is an appreciable but limited increase in product particle size over that of the original ore. The second process, called ore-carbon pellets, produces pellets of fine ore bound by low temperature coke. The first objective was to develop a process for combining an oxide ore with only enough carbon for its reduction, the amount being that derived from the simple reduction equations. The carbon (that amount theoretically required for the reduction of the oxides in an agglomerate with ore), calculated to CO, ranges from 10 pct for zinc calcines Or phosphate Ores to 21 pct for rutile and 26 pct for silica. The carbon required for reducing iron oxides falls between the extremes—10 and 26 pet' When the carbon in the agglomerate is low temperature coke, reduction by hydrogen may be expected to take place, thus modifying the calculated carbon require- ment. On the other hand, in practice, an excess of reducing agent over that required in theory is normally used. Screen sizes of three iron ores on which the greater part of the experimental work was performed are given in Table I. Most of the testing was done with Freeport (Renton Mine) coal, but Pittsburgh and Elkhorn bed coals were also used. The first objective was to agglomerate the ore with sufficient low temperature coke to provide carbon for reduction, i.e., in the range from 10 to 25 pct. This was accomplished by preheating the ore, mixing with pulverized coking coal, and completing the coal carbonization in a plain steel rotating retort. The pilot retort, as it is now constituted, is shown by diagram in Fig. 1 and photograph, Fig. 2. Ore is fed into the upper kiln by a screw; it is heated to 900° to 1100°F by direct flame and it is then discharged into an insulating hopper from which it goes

Jan 1, 1956

By A. C. England, William F. Haney, Paul B. Crawford, Bobby L. Landrum

The creation of unsymmetrical vertical or horizontal fractures in a producing well will result in a unique distortion of the normal shut-in pressures existing at the four surrounding wells. An electrical model study has been made to show how the shut-in pressures at the wells surrounding the fractured producing well may he used to estimate the size and orientation of vertical or horizontal fractures. The pressure differences at the four surrounding wells are recorded during production from the fractured well. The resulting pressure dato are matched from a table of several hundred possible fracture combinations. The table refers to the figure showing the effective size and orientation of the commercially created fracture. INTRODUCTION The creation of commercial fractures about oil and gas wells has led to considerable speculation as to the size and shape of the fractures. It is important that the size and shape be known in certain instances, especially when pressure maintenance programs are to be initiated. It was shown that if knowledge of a vertical fracture could be found that such information may be utilized in planning a waterflooding or gas cycling program and that in some cases the fractures might be utilized very effectively.' Other work showed that it may be desirable to create "pancake" fractures in certain reservoirs but that they should exist in a desirable range.' If the fractures are too large, they should be plugged prior to initiating a pressure maintenance program. If an irregular shaped "pancake" fracture is created, it is desirable to know the orientation of this fracture because similar but unreported studies have shown that "pancake" fractures may or may not substantially affect the sweep efficiencies and performance of the flooding or cycling program. Consequently, it may be desirable in some instances to estimate the effective size and orientation of the fracture. ANALOG An electrical model was used in making this study. The electrical model consisted of a circular reservoir approximately 8 in. in diameter, 1 in. thick and was filled with a dilute salt solution. A copper band formed the periphery of the reservoir. A vertical fracture was simulated by a copper strip soldered to the wire well located in the center of the reservoir. Vertical copper strips of various lengths and orientation were soldered to the wire well to represent vertical fractures in the reservoir. In studies reported here on vertical fractures it was arbitrarily assumed that two fractures originated at the well and extended out into the reservoir. An electrical potential was imposed between the wire well and the periphery of the tank. Plots of the iso-potentials are shown in Figs. 1 through 9. This model provides the steady-state isopotentials existing in a uniform, homogeneous circular reservoir having a vertically fractured well at its center. The permeability of the fracture is much greater than the permeability of the matrix proper. The effects of gravity are neglected. In preparing Tables 1 and 2, four symmetrically located unfractured wells were assumed to exist around

Jan 1, 1956

By J. D. Zetterstrom

This report supplements an earlier publication on lightweight aggregates of North and South Dakota.3/ The purpose of the investigation was (1) to study the expansion characteristics of large samples of Dakota clays and shales in a 12-inch by 15-foot rotary kiln; and (2) to improve the laboratory bloating test as a tool for predicting the suitability of samples for the rotary-kiln process. This was done by comparing results of the laboratory and kiln tests.

Jan 1, 1956

By G. Bhat, J. F. Libsch

lsoembrittlement curves depicting the influence of time and temperature in the range 800' to 1260°F (425' to 680°C) on the development of embrittlement in a commercial chromium alloy steel and a commercial molybdenum alloy steel are presented. Two distinct regions of embrittlement occur in the chromium alloy steel: I—at 800' to 1000°F (425' to 540°C) and 2—in the region just below the lower critical temperature. Embrittlement is most pronounced at 800' to 1000°F, decreasing very rapidly with increasing temperature above this region, only to increase again as the lower critical temperature is approached. The data suggest two distinct modes of embrittlement with possible superposition of the two modes at extended embrittling times in the temperature range 1100° to 1150°F (590' to 620°C). While the molybdenum alloy steel shows little susceptibility to embrittlement at 800' to 1000°F (425' to 540°C), considerable embrittlement may occur just below the lower critical temperature. THE subject of temper embrittlement in alloy steels has received considerable attention in the last few years. Points of view on the mechanism of embrittlement differ, however, resulting in part from the incompleteness of the data developed and in part from the speculation regarding the susceptibility of plain carbon steel to temper embrittlement. Libsch, Powers, and Bhat1 carried out short-time embrittling treatments on an AISI 1050 steel and demonstrated that hardened plain carbon steels are quite susceptible to embrittlement when tempered in the range from 850°F (455°C) to the lower critical temperature. The isoembrittlement diagram,' representing the embrittling characteristics of this steel, is reproduced in Fig. 1. It is evident from the shape of the curves shown that embrittlement in plain carbon steel increases progressively with both temperature and time in the embrittling range. A comparison of the isoembrittlement diagram for AISI 1050 steel with that presented by Jaffe and Buffum' for an SAE 3140 steel shows that up to 930°F (500°C) the isoembrittlement characteristics of the plain carbon steel are similar to those of SAE 3140 steel, although the embrittlement is much more severe in the latter steel. Above 930°F (500°C), the rate of embrittlement in the plain carbon steel increases continuously with increasing temperature; whereas, in the SAE 3140 steel, the embrittlement rapidly decreases. The influence of alloying elements upon embrittlement during tempering thus appears to cause a decrease in embrittlement above the region of maximum embrittlement, i.e., 850" to 1000°F. The question naturally arises as to what effect individual alloying elements have upon the embrittling characteristics of the plain carbon steel. Current knowledge on the influence of alloying elements on temper brittleness may be found in the review papers of Hollomon" and Woodfine. Hollo-mon," from the results of other investigators, has shown that, in general, the amount of embrittlement increases with increasing alloy content (except for molybdenum and possibly tungsten and columbium). Jaffe and Buffum," by a comparison of the embrittlement in a plain carbon steel with that of a SAE 3140 steel postulated that the presence of alloying elements in moderate amounts tends to retard the development of temper brittleness. It is difficult to determine what effect chromium has upon temper brittleness, since most of the information available has been based on the combined effect of other elements with chromium, particularly nickel and manganese. However, Wilten, and recently Jolivet and Vidal,' Vida1, and Woodfine have reported that chromium steels are temper brittle, that the embrittlement is reversible with a maximum rate of embrittlement at approximately 975°F (525"C)," and that the susceptibility increases with increasing amounts of chromium. Taber, Thorlin, and Wallacel" have found a large embrittling effect with increasing chromium content in a medium C-Mn-Ni steel. But Hultgren and Chang," from their experiments conducted on synthetically prepared ternary Fe-C-Cr alloys, could not conclude that these alloys are susceptible to temper embrittlement. However, on addition of manganese or phosphorus, these Fe-C-Cr alloys became susceptible, from which fact they concluded that the embrittlement developed in chromium-bearing Fe-C alloys is due chiefly to the presence of these elements. Considerable data are available to show that molybdenum decreases the susceptibility of steel to temper embrittlement. However, its effectiveness in preventing or decreasing embrittlement appears limited to its presence in small amounts. Vidal" has shown that a plain 2 pct Mo steel was susceptible. Hultgren and Chang" also have shown that molybdenum additions in excess of 2 pct to synthetically prepared Ni-Cr steels did not prevent embrittlement. Jolivet and Vidal' and Lea and Arnold found that molybdenum reduced temper brittleness. Lea and Arnold further stated that molybdenum decreased the rate of embrittlement rather than the total amount of embrittlement, whereas Preece and Carter" have shown that the presence of molybdenum greatly reduces the equilibrium extent of the change at a given temperature but does not appear to influence the rate of embrittlement. There appears to be very little information as to how molybdenum by itself affects the temper brittleness susceptibility of a plain carbon steel.

Jan 1, 1956

By D. R. Mash

A strong yield point with attendant enhanced mechanical properties was found in commercially pure beryllium under certain conditions of heat treatment. Beryllium specimens also responded to both quench and strain aging treatments. Based on these results, a possible means of obtaining increased normal temperature mechanical properties is suggested. COMMERCIALLY pure beryllium has been found to exhibit the yield point phenomenon and several other aging manifestations under certain conditions of heat treatment. This behavior is not surprising in view of the present accumulation of experience regarding such effects in numerous metals; but in addition to extending this experience to include beryllium, the present study is of interest because aging effects are generally associated with the presence of small amounts of solute elements. The well known lack of tensile ductility in beryllium at normal temperatures is also considered to be due to impurities in some way. In the present investigation, the view was taken that beryllium of commercial purity (greater than 98 pct) should be considered as a dilute alloy and that precipitation phenomena may well exist which could lead to enhanced mechanical properties. In connection with this possibility, published data on the variation of mechanical properties with temperature are of interest. For example, Fig. 1 illustrates the variation of ductility (percentage of elongation) and ultimate strength as a function of temperature for beryllium of various histories.* Although these curves are somewhat schematic in nature, they clearly indicate the possibility that precipitation of an unstable phase and/or aging effects occur during tests in the region 400" to 700°C. The existence of such behavior should be recognized as affecting the properties of the commercial material and perhaps can be employed advantageously. Experimental Method All testing was done at room temperature using a Baldwin universal testing machine. A microformer extensometer was used in conjunction with a micro-former-type stress-strain recorder. All tests were conducted at constant loading rate, the slowest rates being used. This corresponded to 120 lb per min in the 1200 lb full scale range and 300 lb per min in the 6000 lb full scale range. After the rate of loading was set in the elastic range of the material during the early part of the test, no further adjustments were made, allowing the test to proceed at that setting. In the plastic region of the curve above the yield region, strain rates of from 0.002 to 0.006 in. per min were regularly obtained. All experimentation was carried out on specimens machined from the same lot of beryllium, lot No. Y5036BP. Table I shows the chemical analysis as furnished by the supplier, Brush Beryllium Co., as well as the standard specifications to which commercial beryllium is produced. Both 1/4 in. thick hot pressed plate and ½ in. round hot pressed and warm extruded rods were obtained. The history of the material is reported to be as follows: 1—Beryllium metal plates, produced from a standard hot pressed QMV beryllium metal block 4x15x40 in., were cut off and finished machined to 1/4x6x12 in. flat plates. The original hot pressed block was made by hot pressing —200 mesh vacuum cast attri-tioned powder at about 1050°C under vacuum. 2—Beryllium rod was hot pressed and warm extruded. Extrusion billets were machined from the regular hot pressed blocks followed by extrusion at 425°C. The extrusion was done without jacketing, and graphite was used as a lubricant. The rods were then straightened at 720 °C, after which they were annealed at 800°C for 15 min. Both flat tensile specimens and round tensile specimens were tested. The former were machined from the plate stock into standard specimens according to specifications shown in ASTM E8-52T. The nominal cross-section was 0.25x0.500 in. and the gage length was 2 in. The round specimens were

Jan 1, 1956

By B. H. Bergstrom, Will Mitchell, T. G. Kirkland, C. L. Sollenberger

IN a previous article' the authors outlined a study of the variables in rod milling and also reported data from a series of open circuit grinding tests on a massive limestone in a 30-in. x 4-ft end peripheral discharge rod mill. As a second part of the experimental program, an analysis is now presented for the 30-in. x 4-ft overflow rod mill grinding under identical conditions, except that discharge ports on the periphery of the mill shell have been sealed so that the products from the present series overflowed through a 9-in. diam .opening in the center of the end plate. A variance analysis has been made of the combined data for the two experiments, and performances of the two mills are compared here. Included in the first report' were descriptions of feed preparation, rod mill circuit, instrumentation and controls, and techniques used to evaluate data. Dependent and independent variables were defined, and variance analyses were made to test the relative significance of variables and to establish magnitude of error for the experiment. Significant data were plotted in various combinations, and conclusions were drawn from the graphs. The procedure and analysis in this series of tests follows the first tests and is not repeated. Data from the second series are recorded in Table I. Listed in the first three columns are the independent variables of feed rate (1000, 2000, 3000, 4000, and 5000 1b per hr), mill speed (50, 60, 70, 80, and 90 pct of critical), and pulp density (50, 60, 70, and 80 pct). The dependent variables, Pso, P100, reduction ratio, slope of the log-log sieve analysis curve, power demand, and Bond work index follow. Of these, only the reduction ratio and the Bond work index were analyzed for significance. Production of new surface as calculated from sieve analyses has not been included for this series because of the questionable assumptions that have to be made to satisfy the formulas involved. The large number of products obtained during the runs precluded the use of surface measurement techniques by the gas adsorption methods at this time; however, samples of all products have been stored for future reference. To test the consistency of the reporting of the sieved products, an averaged sieve analysis was calculated from the wet-dry plots obtained from the three product samples of each run. The resulting averaged analysis was plotted and the P80, selected. The relative deviations of the P80's from each of the three product samples with respect to the P80 of the averaged analysis were then calculated. In only two sets were the relative deviations (6.2 and 9.9 pct) considered excessive. In each of these two sets, one sieve analysis was obviously out of line; hence that analysis was ignored and new averages were computed. This reduced the relative deviations to 1.2 and 2.7 pct respectively. The relative deviations of the product analyses with respect to their averages ranged from 0.1 to 1.4 pct at 1000 lb per hr, 0.0 to 1.1 pct at 2000 lb per hr, 0.2 to 3.0 pct at 3000 lb per hr, 0.3 to 4.3 pct at 4000 lb per hr, and 0.5 to 5.2 pct at 5000 lb per hr. The relative deviation of the 80 pct passing point for 96 dry sieve analyses of the feed with respect to that of the averaged analysis was 7.6 pct. This slightly higher percentage can probably be attributed to a greater proportion of tramp oversize in a crusher product than is ordinarily found in a rod mill product. The last column on Table I lists the adjusted work index, which has been used as the measure of efficiency for the various combinations of operating conditions investigated. Efficiency increases as the index becomes lower. It was reported in the previous paper that the work indexes for the Waukesha limestone used in these experiments decreased as the product size decreased (as calculated from Bond grindabilities). That is, this limestone becomes easier to grind as the material becomes finer. This is unusual, because the work index for most materials as calculated from the Bond grindability has remained constant as the product size decreased or has increased slightly. Table II lists the results of Bond grindability tests at all mesh sizes from 3 to 200 and the work indexes calculated from them. To remove this variation of work index with product size from the data so that results would apply to any material of constant work index, the work index values shown in Table II were plotted against product size on log-log paper. From this curve (a straight line function in this case), the expected work index for the product size for each of the runs of the experiment was obtained. The work indexes as calculated from the reduction ratio and energy consumption were then divided by the corresponding expected work index. The results obtained are reported in percentages on Table I as adjusted work index and are actually percentages of the work index for the Waukesha limestone at the size in question. Multiplication of the work index value for a material of constant index by these percentages should allow the application of the adjusted work index curves to the material. Only the adjusted work index values, not the actual experimental values, were used for the variance analyses and for the graphs.

Jan 1, 1956

By M. P. Tixier, K. S. Kunz

A method for the interpretation of temperature curves recorded in gas producing wells is described. One essen-tial feature of the method is a simple graphical construction which conveniently reflects the amount of gas flowing from a given producing formation. This method, applied in conjunction with the Induction Log and radioactivity logs, is valuable to determine the points of entry of gas and to estimate the over-all thickness of the producing zones and their respective contributions to the total production. The method in particular is helpful in evaluating the effect of fracturing operations. An outstanding result of the application of the method is to bring to the light the relative importance of sand-shale interfaces in the production of gas. The paper is illustrated with field examp1es. INTRODUCTION The electrical logging tools involving conventional systems are not applied in wells which do not contain water base mud (empty holes, or wells filled with oil base mud), because of the absence of electrical connection between the electrodes and the surrounding formations. It is, therefore, common practice in this case to use other methods which do not require the presence of a conductive fluid in the borehole: resistivity log with scratcher electrodes, Induction Log, radioactivity logs, temperature log. . . . Such conditions are encountered in some regions, as the San Juan Basin, N. Mex., where a technique of drilling gas wells, using gas as a drilling fluid, has been introduced in the last two years. By the middle of 1953, an appropriate method for the logging of these wells was devised on the basis of field tests and of theoretical studies. It is the purpose of the present paper to give a description of this method. In these wells the logging operations are performed during the process of gas production, so that the temperatures in the boreholes are strongly affected by the cooling due to the expansion of the gas. On the other hand, a special thermometer, with a high sensivity and a short time constant, has been recently made available, which has enabled much more detailed and accurate recordings of the borehole temperatures than with the conventional instruments. As a result of these two circumstances, the temperature log constitutes the essential element of the method, in making possible the detection of the gas producing zones, the definition of their boundaries, and the estimation of the respective contributions of each separate zone to the total production. The method also involves the radioactivity and Induction Logs, as auxiliary documents. These logs in the present instance are helpful in the determination of the reservoirs. However, the information they give in this respect is limited. This comes from the fact that, due to the absence of the MicroLog and/or MicroLaterolog and of the SP log, the estimation of formation factors and connate water salinities is somewhat conjectural. Furthermore, little help is obtained from the Neutron log for the evaluation of porosity and of formation factor because the variations of gas saturation affect the Neutron log in a way similar to the variations of porosity. It should be said also that even an exact knowledge of the gas saturation of the reservoir beds would not

Jan 1, 1956

By E. C. Burke

IN view of rather widespread use of calcium as an alloying addition to magnesium alloys, it is rather surprising to find that, although the general features of the Mg-Ca equilibrium diagram are known with a fair degree of certainty,' ," considerable ambiguity concerning the solid solubility of calcium in magnesium exists. By using the disappearing phase technique in a metallographic study, Haughton' found that 0.6 pct Ca was soluble at 300°C and 1.8 pct was soluble at 516°C, the eutectic temperature

Jan 1, 1956

By T. E. Evans, C. T. Baroch

ZrB2 was produced in batches of 4 to 6 Ib by interaction of ZrO2, B4C, B203, and carbon at around 2000°C in a simple graphite resistance furnace. Techniques of production are discussed and the final design of a suitable furnace is described in detail. Several other borides were made by the same technique and the process appears to have possibilities for commercial production. N seeking out new hard and refractory com- pounds, many researchers have turned to the investigation of the borides and excellent papers have been published on the properties of these compounds. Few papers, however, have appeared on the techniques and problems concerned with the production of these high temperature substances. This report describes progress made in developing a method for preparing zirconium diboride, ZrB2, on a pilot plant scale. The literature of the borides and other refractory hard metals recently has been reviewed, annotated, and classified so completely' that it is needless to attempt such an outline here. It is enough to say that three borides of zirconium have been reported: ZrB, ZrB2, and ZrB12.2 ZrB2 is the most stable of these and is especially stable in the presence of carbon up to and including its melting point of around 3000°C. Like most borides, it can be prepared in several ways. It can be prepared by synthesis of the elements, but these are expensive and difficult to produce in a high state of purity. Obviously, production directly from the oxides would have decided economic advantages. In electrolytic production such as that of calcium boride,:' the product is recovered as a sludge mixed with electrolyte; and separation of product from adhering electrolyte and regeneration of the electrolyte is an involved and difficult process. The work on borides was started on a small scale in 1948. Late in 1949, Naval Ordnance expressed a specific interest in ZrB2 and the project then centered on this compound. After the usual experimental work necessary in a new field, ZrB2 of good quality was produced by heating mixtures of B4C, ZrO2, B2O3, and carbon to a temperature of about 2000 °C in a resistance-type electric furnace. Over 100 lb was made for experimental use tests, and the method of production probably could be expanded into a commercial operation. A similar process has been described by Kieffer and coworkers.' The main chemical problems were the development of proper charges to insure complete reduction of the elements, determination of the proper temperature range at which these reductions took place, and adoption of techniques necessary to pre- vent inclusion of such impurities as carbon and nitrides. The mechanical problems consisted of developing a simple practical furnace that would attain the high temperatures required and permit use of a controlled atmosphere when necessary and determining of suitable refractories. Both problems were solved by designing a crucible resistance furnace. Crucible Resistance Electric Furnace Attempts were first made to produce ZrB2 in an electric arc furnace, but such a furnace would not provide the degree of carbon control required for producing clean graphite-free borides, so it was decided to try working in a crucible. Obviously, the furnace would have to be constructed of graphite, as the temperatures required are too high for other refractories or heating elements. Crucibles were made by hollowing out segments of graphite electrodes, which were fitted with a cover and clamped between two electrodes so that the current passing through the thin wall of the crucible would generate heat, using the principle of the Helberger crucible furnace."? Preliminary tests with this type of furnace were encouraging and led to the furnace design shown in Fig. 1. The essential components were a thin-walled graphite crucible resting on a graphite block, which formed the lower electrode assembly, and a top electrode assembly swung from a pipe column making contact with the top of the crucible. The space around the crucible was filled with graphite prepared from waste electrodes crushed to about ¼ in. This packing had excellent insulating properties, both electrically and thermally, and could be removed easily and quickly from around the crucible by means of an industrial vacuum cleaner. The largest resistor crucibles were machined from 8 in. electrode stock and were 26 in. long, with a side wall Yi in. thick and a 1 in. bottom. Temperatures were determined optically by sighting down a 1 in. hole drilled longitudinally through the top electrode and the crucible cover. Sealing this hole at the top was a water-cooled brass sight-glass assembly, shown in Fig. 2. An opening was provided for a light flow of helium to keep the sight opening clear of smoke, and a glass prism above the sight glass changed the line of sight to the horizontal for easier reading. More recently, the prism and optical pyrometer were replaced by a photoelectric recording pyrometer. At first the charges were placed directly in the resistor crucible but this meant that everything had to be withdrawn from the furnace every time the charge was emptied. Later, smaller crucibles were made up that could be placed inside the resistor

Jan 1, 1956

By R. H. Nielsen

A new, cheaper precipitation scheme has been developed to produce purified zirconium oxide, Technical-grade sulfuric acid is used to precipitate a basic zirconium sulfate from a hot dilute hydrochloric acid solution. With close control of temperature, pH, and zirconium - sulfate ratio, excellent purification and complete zirconium recovery can be attained. The process has been successfully applied for 3 months and has proved to be a more satisfactory procedure than the ammonium phthalate process used previously. INTRODUCTION The Northwest Electrodevelopment Laboratory of the Federal Bureau of Mines has developed and improved the Kroll process for the production of pure ductile zirconium and hafnium. metal. Since 1946 over 1 million pounds of zirconium sponge metal has been produced, mostly high-purity material for the Atomic Energy Commission

Jan 1, 1956

By E. L. Garton

Bureau of Mines routine crude-oil analyses of 88 samples from 60 fields are presented in this report. Similar analyses from other fields in California have been published in previous reports listed in the appendix, page 52. Yearly production of crude oil in California and the percentage of United States production represented by California production for 1948-54 are given in table 1. [ ] Analyses in this report are of samples from the fields listed in table 2, with production data for 1953, cumulative production through 1953, and year of discovery of each field. Information regarding the source and general characteristics of the samples is included in table 3 with a summary of analytical and computed data.

Jan 1, 1956

By D. F. Atkins, B. A. Rogers

The constitutional diagram presented herein is relatively simple. Complete mutual solid solubility exists for an interval below the solidus line, a continuous curve with a flat minimum near 22 pct Cb and 1740°C. Upon cooling, the solid solution breaks up, except at the columbium-rich side, from two causes: zirconium-rich alloys transform under the influence of the ß-a transformation in zirconium; alloys of intermediate composition decompose into two solid solutions below 1000°C. The combined effect is the formation of a eutectoid at a temperature of 610°C and a composition of 17.5 pct Cb. The eutectoid horizontal extends from 6.5 to 87.0 pct Cb. Some age hardening effects have been observed in the zirconium-rich alloys but the positions of the solvus lines remain uncertain. IN recent years, zirconium has been produced in much larger quantities than were available previously. Correspondingly, the incentive for studying its alloy systems has increased, as the number of recent publications on alloy systems testifies. However, only a partial diagram of the Zr-Cb system has been published and relatively few references have been made to alloys of the two metals. Hodge' investigated the Zr-Cb system up to about 25 pct Cb. His data on melting points were not sufficiently numerous to distinguish with certainty between the alternatives of a narrow eutec-tic horizontal and a wide flat minimum in the solidus curve. Although Hodge considered his results on transformations in the solid state to be only tentative, he suggested that the eutectoid in the zirconium-rich alloys lay at about 625 °C and 10 pct Cb and estimated that the solubility of colum-bium in zirconium at 625 °C was near 6 pct. According to Simcoe and Mudge,2 less than 0.5 pct Cb is soluble in zirconium at 800°C. These authors observed an increased strength in both the 0.5 and I pct Cb alloys made with hafnium-containing zirconium. According to Keeler,3 the strength of zirconium is increased by addition of columbium to a content of at least 3 pct. Keeler' also observed a maximum in hardness at about 10 atomic pct Cb and commented on the brittleness of alloys of this composition. Anderson, Hayes, Rober-son, and Kroll5 investigated the tensile properties of Zr-Cb alloys containing 5.1 and 12.9 pct Cb at room temperature and at 343°C. The 12.9 pct alloy had a high tensile strength at room temperature but also a low percentage of elongation. All alloys had high elongation at 343 °C. Littona measured strength and elongation values of annealed alloys containing up to 27.5 pct Cb and found low elongation values for all of the alloys of high columbium content. Some observations on the resistance of Zr-Cb alloys to corrosion in water at high temperature have been published by Lustman, De Paul, Glatter, and Thomas' who found that additions of columbium up to 1 pct had only a minor effect on the corrosion resistance of zirconium. Preparation of the Alloys Raw Material: Zirconium of a relatively good grade was available for making the alloys. It was obtained as scrap pieces that had been left over from an operation that included production by the iodide process, melting under a protecting atmosphere, and fabrication to plates. The individual pieces had hardness values of 24 to 32 Ra and a typical analysis is shown in Table I. The columbium also was scrap trimmed from sheets. It was furnished by the Fansteel Metallurgical Corp. and had a high ductility but its analysis was known only approximately. The metal probably contained about 0.5 pct Ta, perhaps 0.25 pct C, and a few hundredths percent each of iron, silicon, and titanium. Melting: The alloys were melted in a tungsten-electrode copper-crucible arc furnace similar to units that have been described recently in the metallurgical journals.'.' The crucible of this furnace is provided with a cavity in which a getter charge can be melted before the melting of the alloy charges. Hardness measurements on the ingots indicate that the getter charge takes up a considerable fraction of the oxygen and nitrogen from the helium atmosphere of the furnace. The alloys used in the investigation are given with their intended compositions, hardness, and melting points in Table 11. Fabrication: All alloys of the Zr-Cb system appear to be amenable to fabrication. At least, all of the compositions listed in Table II could be reduced to wires in a rotary swaging machine. The starting material was either slabs cut from ingots and ground by hand to rough cylinders or narrow strips trimmed from sheets made by cold rolling slabs. However, not all of the alloys could be fabricated satisfactorily by the same method. From 0 to 4 pct Cb and from 20 to 30 pct Cb or more, the alloys could be swaged cold from ¼ in. cylinders to 0.80 mm wires with only one intermediate annealing, sometimes with none. From 40 to 90 pct Cb, the alloys were difficult to swage either hot or cold but could

Jan 1, 1956

By Strathmore R. B. Cooke, Eugene L. Talbot

THE perfluoro acids and derivatives show unusual surface-active properties that qualify them as possible flotation reagents. They lower the surface tension of water from 15 to 20 dynes below that obtainable with the corresponding hydrocarbon compounds.1, 2 Fluorochemicals adsorb very strongly on solid surfaces to give films that exhibit larger contact angles than films of the corresponding hydrocarbons."' * The large contact angles probably result from the terminal —CF3 group. The perfluoro acids are made by electrolysis of the corresponding carboxylic acid in anhydrous hydrogen fluoride.5 From the perfluoro acids many derivatives may be obtained, such as amides, amines, alcohols, xanthates, ethers and esters and others. Since the fluorinated analogues of the conventional hydrocarbon flotation collectors possess enhanced surface properties, a few were selected for testing. Because a survey of all possible minerals and reagent combinations would be out of the question, hematite was chosen to represent a nonsulphide system and pyrite to represent a sulphide system. The fluorinated reagents used in these experiments were prepared in the research laboratories of Minnesota Mining & Mfg. Co. Some were synthesized especially for this research. They are not available cokmercially. Separation of Nonsulphide Ores: The separation of oxides from silica has always been a challenge to the flotation industry because differences in surface properties of the minerals are normally insufficient to produce clean concentrates. Oleic acid," rosin acids,' and amine salts% ave been used to considerable extent to effect separation of metal oxides and silica. The system hematite-silica was chosen to represent the nonsulphides both because of its difficulty of separation and because large tonnages of easily obtainable material are available, such as gravity concentration tailings and nonmagnetic taconites on the Mesabi Range. The wash-ore tailings used here contained approximately 35 pct iron after desliming. Samples of the material used in this work were part of the same lot used by Chang, Cooke, and Huch9 and were prepared in an identical manner. Reagents for Nonsulphide Ores: Since one of the purposes of this investigation was to compare hydrocarbons with fluorocarbons, reagents of known behavior such as oleic acid, and the alkali metal salts of certain resin acids (Dresinates), were established as standards. Hydrocarbons and fluorocarbons of comparable chain length and other experimental fluorocarbons were tried as collectors for hematite. A list of the materials used and the concentrations of their stock solutions are given in Table I. Since silica can be selectively floated from hematite by conventional reagents," a few fluorocarbon reagents were also tried for this purpose. Their composition and concentrations are given in Table 11. Most of these reagents served the dual function of collector and frother. In the case of F-11 flotation did not occur but it served as a frother when F-6 was employed as a collector. Reagent grade sulphuric acid and sodium hydroxide were used to regulate the pH. Deionized water containing less than 0.1 ppm of salts expressed as NaCl was used for all solutions and flotation tests. The pneumatic flotation cell consisted of a 350-ml fritted glass Buechner funnel with a source of filtered air which could be controlled by a needle valve." A 50-g sample of ore and 250 ml of deionized water were added to the flotation cell and stirred slowly. The reagents were added and the pulp was conditioned before air was admitted to the cell. Approximately 15 ml of the pulp were removed for pH determination before flotation was started and were then returned to the system. The pH was again measured after flotation. Air was admitted to the cell until no further flotation occurred or until the character of the float changed markedly. Both the float and the nonfloat products were filtered, dried, weighed. and assayed for iron. The cell was washed in hot water and rinsed with deionized water after each test. Occasionally the cell was cleaned with concentrated hydrochloric acid to remove iron oxide particles from the glass frit. Experimental Results: Above a pH of 8, sodium oleate was an effective collector for hematite. The emulsification of equal parts of heavy fuel oil (20"

Jan 1, 1956

By Howard L. Hartman, Eugene P. Pfleider

The paper relates to the laboratory and pilot plant studies that have been carried out by Sherritt Gordon Mines Ltd., Metallurgical Research Div., in developing the ammonia pressure leach process for extracting Cu, Ni, Co, and S from high grade Ni concentrate produced from Lynn Lake ores and describes in some detail the chemistry of the process. In the leaching stage air, ammonia, and sulphide minerals react in a sequence of inter-related steps to produce soluble amines of Ni, Cu, and Co in a solution containing sulphate, thiosulphate, polythionate, and sulphamate ions and a controlled amount of free ammonia, the iron and other components of the concentrate remaining as an insoluble residue which is separated from the leach solution by filtration. The pregnant solution produced in leaching is further treated by boiling to precipitate and remove Cu as cuprous sulphide, leaving a copper-free solution with a composition suitable fir subsequent precipitation of Ni and Cu by H,. The progress of individual reactions in leaching and copper removal is discussed. The effect of variables such as temperature, pressure, ammonia concentration, particle size, and agitation is outlined and the technique of thionate control in leach solutions is described. Data is given for the physical and chemical reactions involved in precipitating copper from leach solutions as Cu sulphide by boiling.

Jan 1, 1956

By Glenn C. Waterman

Richard Strong (Oliver Iron Mining Div., U. S. Steel Corp.)—Mr. Waterman states (p. 59, Trans., January 1954): "Core-sludge combining factors have been calculaied for any combination of core-sludge recovery on the basis of several logical assumptions: 1—The sludge sample loses reliability geometrically as sludge recovery drops. 2—The sludge sample should not be used if the percentage of sludge return is less than the percentage of core recovered. 3—A core sample should receive a weighting at least equal to the percentage of core recovery." Assumptions 1 and 2 seem justified at Chuquicamata and most geologists would agree to the validity of assumption 3. However, contrary to the statement quoted above, the core sample does not in general receive a weighting at least equal to the percentage of core recovery when the Chuquicamata methgd is used. Furthermore, the basic Chuquicamata method is identical to the Longyear or relative volume core-sludge assay combining method. Finally, the Chuquicamata method does not, in its present form, reflect true geometric loss in sludge sample reliability according to the relationship L = AR (N-1) The basic equations representing the two steps of the Chuquicamata method can be combined algebraically as follows (using the symbology of the original article except as noted): Vol A + B Assay 2 = ASA = Assay 1 Vol A VolB Core Assay [I] Vol A CA.F + ASA (100 —F) Combined grade =[21 100 Pct where F and (100 — F) are the core and adjusted sludge assay factors from Fig. 3. Substituting Eqs. 1 and 2 and collecting terms Combined grade = Vol B Vol A + B CAF (100—-F) + Assay 1 (100-F) Vol A Vol A 100 pct Eq. 3 is a unified and general statement of the Chuquicamata method. The true core factor includes not only the factor F from Fig. 3 but also the quantity VolB ------------- (100 — F), which is implicit in the value of Vol A the adjusted sludge assay. This quantity is real and positive for all values of F and core recovery less than 100. Therefore the true core factor is always less than F except when F is equal to 100. If sludge recovery is 100 pct, Eq. 3 can be further simplified as follows: Let F = percentage of core recovered. Let Vol A = Vdh (100 Pct — Pct CR) where Vdh is the total volume of the sampled interval and let Vol B = (Vdh — Vc.) Pct CR where V, is the core volume in the sampled interval at 100 pct core recovery. Then combined grade = Vo V. CA Pct CR- + Assay 1, 100 Pct — Pct CR Vdh Vdh [4] 100 Pct Eq. 4 shows that when sludge recovery is 100 pct the laboratory sludge assay receives significant weight in the Chuquicamata method, even at 100 pct core recovery. The maximum weight assigned to the laboratory sludge assay depends on drillhole size, as follows: Eq. 4, with suitable changes in symbology, is identical to Royce's formula 8,' which is a statement of the Longyear or relative volume method of combining core and sludge assays. If Mr. Waterman's assumption 3 is of paramount concern to the geologist, the Royce method (for core recoveries of 60 pct and above) or a method employing the percentage of core recovered as a core weighting factor are the only recognized methods known to the writer which achieve the desired result. A modification of the latter method embodying Mr. Waterman's assumptions 1 and 2 would result from applying the factors from Fig. 3 directly to the laboratory core and sludge assays.

Jan 1, 1956

By R. W. Mancantelli, J. R. Woodward

IN 1947 a large low grade deposit of uranium was located in the northwest corner of Saskatchewan, in the Beaverlodge property of Eldorado Mining & Refining Ltd. Most of the values occur as thin seams and as coatings on other minerals, and the ore, which is light and friable, is not amenable to the usual gravity methods of concentration. The acid leaching process developed to retreat the company's Port Radium tailings was also impractical, as the percentage of carbonates is high and the percentage of sulphides relatively low. Construction of the mill building and installation of equipment, both scheduled for 1952, awaited selection of a satisfactory ore dressing process on or before Oct. 1,1951. An extensive research program on dressing of ores from the Ace mine therefore was undertaken by the Mines Branch in Ottawa, a research team at the University of British Columbia, and an ore dressing group at the company's Port Hope refinery. Pilot plant operations were conducted at the Ottawa plant of Sherritt Gordon Mines Ltd. under the general direction of C. S. Parsons, consultant on metallurgy and ore dressing for Eldorado. In mid-September, having compared results of the several research programs, Dr. Parsons recommended a process employing a carbonate or basic leach. He reported that, while the chemistry of the process had been proved, engineering of the flowsheet was incomplete, and he suggested that under normal conditions further pilot plant work at the Ace mine might be profitable. However, since this would involve a delay of 12 to 18 months in bringing the property into operation, he recommended that design of the concentrator proceed immediately. Concentrator capacity was determined by two considerations: 1) the amount of ore then available and 2) the expectation that continued improvements would be made in the ore dressing process as a result of the intensive research being carried out by the Mines Branch of the Department of Mines and Technical Surveys. As these improvements could affect both the chemistry and the en-

Jan 1, 1956

By Kenyon E. Richard, James H. Courtright

Thomas W. Mitcham (Strategic Minerals, Inc., Grand Junction, Colo.)—The authors have presented a significant contribution to the field of mining geology. The article is graphic, remarkably concise, and crisply original. The presentation is made on only three pages with two maps, but their Silver Bell story is entirely adequate in background, development, and conclusion. Most of their colleagues would agree that this paper reflects the high quality of the work which these unusually capable men have done in the Silver Bell area over the past few years. The Silver Bell area is one of complex tectonic structure, and time and spatial relationships are by no means apparent. Actually, most of the observations and interpretations in this paper are new to published geologic literature on the Silver Bell area. I am in agreement with these interpretations with two possible exceptions, which are discussed below. One might well define the three roughly parallel west-northwest faults, shown on the insert of Fig. 2, as the major structural elements of the area. North to south, I propose that these be named the Ragged Mountain fault, the Silver Bell fault zone, and the Waterman thrust, after the mountain ranges which are the results of these major structures. While I would agree with the authors that the northern two of these major structures are high-angle faults of the Laramide revolution, my impression is that the southern structure is a low-angle thrust of approximately Miocene age. In support of this opinion, I submit the following observations: 1) irregularity of the fault in strike; 2) scarcity of Laramide intrusives and alteration of sediments along the fault; 3) present high re- lief of the Waterman Range which indicates youth or certainly rejuvenation; and 4) existence of a series of parallel structures farther to the south which results in an outcrop pattern suggesting imbricate thrusting. The authors have stated that Laramide igneous activity began with the intrusion of alaskite. Some dacite flows appear to be conformable with Cretaceous beds, and thus my impression was that alaskite followed the intrusion and extrusion of dacite. I would be interested to learn of evidence in support of the reverse relationship suggested by the authors. Kenyon Richard and J. H. Courtright (authors' reply)—The authors appreciate Mr. Mitcham's attention to this paper. The names he proposed for the major faults seem appropriate. His suggestion that the Waterman fault is a thrust may be correct because he did more work in that particular area than the authors. However, it is believed that no direct evidence of a low-angle thrust relationship has been recognized, and the authors consider that indirect evidence favors a high-angle fault interpretation. The pre-dacite flow age of the alaskite is definitely established, the authors believe, by the fact that the flows rest on an erosion surface which was carved in the dacite porphyry, an intrusive clearly younger than the alaskite, as evidenced by inclusions of alaskite occurring in dacite porphyry. No direct evidence of Cretaceous sediment-flow rock relationships was found at Silver Bell, but in the nearby Tucson mountains dacite agglomerates, megascopically similar to those at Silver Bell, overlie a basal conglomerate which in turn rests on the truncated edges of steep-dipping Cretaceous arkosic beds.

Jan 1, 1956

By H. W. Knott, M. H. Mueller, P. A. Beck

The rolling and recrystallization textures in 300°C rolled uranium sheet were investigated using a Geiger counter diffractometer with the modified Schulz reflection technique. Seven sections of sheet material were used in order to obtain sufficient data for quantitative pole figures by the reflection technique. A special integrating specimen table was used for obtaining and recording the data automatically. The rolling texture was described in terms of several "ideal orientations" in which the stronger orientations have either the (1103 or (010) poles in the vicinity of the rolling direction. The recrystallization texture of the sheet uranium was also described by several "ideal orientations" which are somewhat different, except in one case, than the as-rolled "ideal orientations." RESULTS of an X-ray study of the deformation texture in rolled uranium rods were reported by Harris' in which a concentration of (010) and (110) poles was found in the rolling direction. More recently Seymour," Mitchell 'and Rowland,3 and Adam and Stephenson4 reported results obtained on uranium sheet rolled under various conditions of tem- perature and amount of reduction. Since the results of Seymour as opposed to those of the two other groups of investigators are not in full agreement, it seemed justifiable to publish the present data, obtained concurrently with the previously mentioned investigations.'-' The results with rolled and re-crystallized uranium sheet were also included in the paper, since they appear to be more complete than the only previously published texture data on recrystallized sheeL3 In the present investigation great care was taken to maintain complete separation of the reflections from different crystal planes, even in cases where the 20 angles differed from each other by less than

Jan 1, 1956

By M. E. Tyrrell

This Bureau of Mines investigation was made to determine the possibilities of using Florida beach-sand concentrator wastes in ceramic products. Sands used in the investigation originated in the Trail Ridge area of Florida, where continued operation of processing plants for recovering titanium minerals promises a dependable source of raw materials. Three general classes of ceramic products were studied, namely: (1) Structural, (2) refractory, and (3) electric-furnace slags.

Jan 1, 1956