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By Milton E. Wadsworth, Edward M. Eyring

BETTER understanding of solid surfaces and their associated adsorption products is of both academic and practical value. The study of detergents and their behavior in cleaning surfaces is fundamentally related to the nature of the products adsorbed and their ability to compete for certain surfaces. Similarly in flotation, the nature of the adsorbate before and after adsorption is basic to clear understanding of the process. The recently developed pellet technique1,2 employing infrared spectroscopy provides a powerful tool for the study of solid surfaces. Absorption bands, which are infrared-active, may be observed for adsorbed products. Also any changes in the surface substrate that occur as a result of adsorption may be detected by means of differential spectra. In applying the pellet technique to solids of large surface area, French and his coworkers3 have surveyed the adsorption of organic flocculants on clay minerals, oleic acid on fluorite, and ammonia on cracking catalysts. Recent work on application of differential infrared spectroscopy to the study of solid surfaces' has demonstrated that the difference between a sample and a reference can be obtained with double-beam instrumentation. In this way displacement of surface products, adsorption of new products, and differences in the substrate, if any, may be detected. Experimental Procedure: Potassium iodide pellets were used in this study, prepared from recrystallized analytical reagent grade KI. Grinding was carried out in a Fisher mechanical agate mortar. Two-gram plates containing the solid under study were pressed in a special evacuated die constructed in the laboratory at the University of Utah." Concentration depended on the solid in question. Zinc sulfide and willemite are sufficiently transpar- ent in the infrared region for concentrations as high as 20 mg of mineral in 2g of KI to be used. Zinc oxide is even more transparent, permitting concentrations as high as 60 mg in a 2-g plate. For non-differential operation, however, much lower concentrations (2 to 10mg/2g KI) had to be used. Spectra were obtained on a Per kin-Elmer 21 double-beam recording infrared spectrophotometer. A sodium chloride prism was used giving a spectral range of approximately 2 to 15 v wave length. For differential runs a resolution of 1000 was used and the scanning speed was controlled commensurate with instrument response. The response was checked continuously and each spectrum was repeated several times. For nondifferential runs a resolution of 927 was used. Zinc oxide used was analytical grade oxide fume. The zinc sulfide was precipitated from solution with analytical grade zinc sulfate and sodium sulfide. The precipitate was washed and centrifuged several times and dried. Before use the precipitate was washed in dilute HCl and then treated with saturated NH4Cl to remove any bulk oxides and sulfates. X-ray patterns of the precipitate were comparable to that of the natural mineral sphalerite. The precipitate was much more satisfactory than finely ground natural ZnS because of its very large surface

Jan 1, 1957

By D. L. Martin

THAT small amounts of impurities have a harm-J- ful effect on the malleability of metals and alloys is well-known. One common type of em-brittlement involves the formation of a small quantity of eutectic at the grain boundaries, and is typified by sulfur embrittlement of nickel. Another example of eutectic embrittlement—sulfur embrittlement of cobalt—is described in this report. In the preparation of specimens for a study of Co-Pt alloys, it was observed that the hot swagabil-ity of the alloys appeared to be influenced by the grade of cobalt used as melting stock. The cause of the hot-shortness was not traced to any particular impurity, although sulfur was suspected.' The damaging action of sulfur on the malleability of cobalt has not been generally recognized,'; in spite of the fact that the Co-S phase diagram8 eveals the same basic conditions—low solubility and eutectic formation—responsible for sulfur embrittlement of iron and nickel.7, 8 Apparently sulfur embrittlement has not been a serious problem in the fabrication of cobalt alloys. One related factor is likely the limited commercial experience with high cobalt alloys, since the predominant use of cobalt has been in alloys containing less than 75 pet Co. A series of Co-S alloys was prepared and studied to establish the effect of sulfur on the hot working characteristics of cobalt. Specimens, 5/8 in. diam by 4 in. long, were prepared by vacuum melting in magnesium oxide crucibles and casting in a copper mold. Two grades of low sulfur electrolytic cobalt were used as the basic material for the study, one from Johnson, Matthey and Co. and the other from the International Nickel Co. Each contained about 99.5 pet Co and had a nominal sulfur content under 0.005 pet. The sulfur was added initially as cobalt sulfide powder. Later, some low sulfur alloys were prepared by diluting the high sulfur alloys with cobalt. Trouble was experienced in controlling the sulfur content. Apparently much of the cobalt sulfide powder was lost during melting, as most of the samples contained a lower sulfur content than was added. The alloys were evaluated for hot brittleness by heating to 1000°C in a hydrogen furnace and swaging in air. The results of these tests are summarized in Table I. All the alloys containing less than 0.008 pet S were successfully hot swaged to 1/4 in. diam. The bars containing more than 0.015 pet S could not be swaged because of the formation of intercrystal-line cracks similar to those illustrated in Fig. 1. Examination of the microstructure of the cast bars revealed cobalt sulfide eutectic at the grain boundaries, Fig. 2. The sulfide was not always continuous at grain boundaries in bars that were hot embrittled but, in general, the particles did form a network that could account for the brittleness above the eutectic temperature, 880°C. There is no question about the brittle nature of a specimen exhibiting a continuous sulfide network such as is shown in Fig. 2b, though a sulfide distribution similar to that in Fig. 2a is marginal. This particular bar cracked when hot-swaged. However, other bars with lower sulfur content but with some sulfide phase at grain boundaries were successfully worked. The reduction of area of a hot tensile test specimen was also found to be a sensitive indicator of sulfur embrittlement. The variation of reduction of area with sulfur content is shown in Fig. 3 for specimens fractured at 900°C in an evacuated capsule. The ductility of cobalt is greatly reduced when the sulfur content exceeds 0.005 pet. Similar results were obtained for alloys tested at 800°C, below the eutectic temperature. The upper sulfur embrittlement limit of 0.015 pet, Table I, agrees with the observation of Kalmus8 hat

Jan 1, 1957

By R. R. Hartman, W. B. Agocs

IN the course of a return flight from Olympia, Wash., to Laramie, Wyo., an airborne magnetometer profile was recorded continuously. The level of flight was controlled at barometric levels along segments of the flight. Barometric altitude was changed from 3000 ft to a maximum of 12,000 ft above mean sea level to take care of topographic variations. Terrain clearance varied from 800 to 7300 ft. Horizontal positions were obtained by recording and tying to cities, towns, airports, river crossings, and other landmarks in the course of the flight. Figs. 1-6 show the course of the flight and the general geologic and tectonic features traversed. The flight line begins south of Olympia, Wash., and proceeds south across the Puget-Willemette depression to the Columbia River. Thence it proceeds eastward along the Washington-Oregon border across the Cascade Mts. and lava flows and the Umatilla basin to Pendleton, Ore. From Pendleton it traverses the Blue Mts. uplift of Oregon in a southeasterly direction, and then to the Boise basin of southwestern Idaho. The flight line swings in an easterly direction as it passes over the Snake River downwarp to the south of the Idaho batholith. It then passes over the northern portion of the Great Basin and the heavily overthrust area at the intersection of the Utah, Idaho, and Wyoming borders. The flight then assumes an easterly course to cross the series of basins and uplifts of southern Wyoming and terminates near the western flank of the Laramie uplift. It should be clearly understood that all statements in this article pertaining to the magnetics were interpreted on the assumption of elongate anomalies transverse to a single profile. Hence any theories or ideas advanced here are in line with future paths of research rather than trying to prove or disprove existing data. Magnetic Interpretation: Depth determinations were made by the slope method of Peters: which is stated as follows: "Draw a line in the maximum slope (at the point of inflection); draw a line whose slope is one-half this maximum slope; draw two lines parallel to this line tangent to the anomaly curve. The horizontal distance between the points of tangency is approximately equal to 1.6 times the depth [or the distance times 0.6251." Certain assumptions must be made for determinations of the causes of the magnetic anomalies:' 1) The anomaly is caused by a susceptibility change rather than basement relief. 2) Polarization of the basement rocks is in the same direction as the earth's inducing field. 3) The disturbing magnetic mass has a great horizontal length in comparison to its width and its sides are vertical and of great vertical extent. 4) The anomaly is unique and not affected by the anomalies from nearby sources.

Jan 1, 1957

By A. D. K. Laird, C. A. Johnson

Drag coefficients for a cylinder being towed through water at constant velocity and also at constant linear acceleration were measured. Drag coefficients for constant velocity towing showed reasonable agreement with previous results. The drag coefficients found for constant acceleration showed little correlation with either the magnitude of the acceleration or the value of the modulus AD/V2 and tended to be slightly lower than those for constant velocity. INTRODUCTION For the design of offshore structures, wave forces acting on immersed cylinders are of importance. Several investigations have been made of these forces and of how they can be predicted from wave theories. A paper by Crooke' summarizes much of the work already done. More recent research by the Wave Research Laboratory at the University of California, Berkeley, has added much to the body of data collected under ocean wave conditions, but has not found a reliable method of force prediction from basic theories of wave motion. The present investigation is part of a long-range program to collect data with which to test current and future theories and correlations. The immediate objective was to measure drag forces on a circular cylinder subjected to linear accelerations over the range of Reynolds numbers between l04 and 105 where the drag coefficient was a constant for constant velocities. In particular, the effect of constant acceleration from rest and from uniform motion was to be investigated. The effect of acceleration may be evaluated in terms of drag coefficients. A useful resistance coefficient, C, is defined by the equation for total drag force, D, exerted by the fluid on the cylinder. DT =CSp V2/2.........(1) The coefficient C may be plotted as a function of the parameter AD/V2. Here D is the diameter and S is the projected area of the cylinder. The acceleration and velocity are A and V. The mass density of the fluid is p. An alternate drag coefficient, C, corresponds to the total force of the fluid opposing the motion minus the virtual mass force. This drag coefficient, arising from the velocity of the fluid, may be compared with that for the same cylinder in uniform motion. The similarities and differences between this coefficient as calculated for accelerated and for steady motion are of interest in the inverse process of predicting drag forces on cylinders under arbitrary conditions. One serious difficulty in this method is the specification of the virtual mass which depends also on the flow picture about the cylinder.1 EXPERIMENTAL EQUIPMENT The experiment was performed in the combination wave and towing tank at the Engineering Field Station of the University of California. The tank is 200 ft long, 8 ft wide, and 6 ft deep. The tow carriage is externally propelled by a cable, and the velocity of the carriage is maintained essentially constant by means of an am-plidyne. For the purpose of the present investigation, the speed control of the amplidyne was modified by inserting a linear speed control rheostat, which was rotated at a constant speed by a small d-c motor equipped with a slip-clutch. Accelerations which were constant over a reasonable length of time were thus produced. The magnitude of the acceleration depended upon the speed of the d-c motor and the limiting speed of the carriage. Data were obtained for a range of accelerations of 2 to 10 ft/sec,2 and a range of velocities of 2 to 15 ft/sec. An accelerometer (Statham Type C-2-350) with a range of ±2g was attached to the carriage and connected to a Brush analyzer and penmotor. A continuous coil of wire with 10 turns/ft wound around a fixed wooden form extending for a distance of 40 ft along the length of the tank was connected by an electrical contact mounted on the carriage to a Brush analyzer and penmotor, to give the time-position history for each run. The test cylinder was machined from solid aluminum alloy, 17-ST. to a diameter of 1.250 in., and could be

Jan 1, 1957

By Lawrence H. Van Vlack, Alfred S. Keh

The distribution of sulfur in iron was found to be dependent upon the time and temperature of the treatment as well as the chemical composition of the sulfide. With higher temperatures, the sulfide phase spreads more extensively between the iron grains. A complete network, however, does not form until approximately 1300°C (2372°F), ot which temperature the dihedral angle approaches zero. Silicon has little effect on this change. Aluminum, oxygen, and manganese all modify the temperature of sulfide network formation to a higher value. The microstructures which result and have significance in relation to hot-shortness are discussed. SULFIDE inclusions in steel were recognized by metallurgists before the turn of the century. Considerable attention has been paid to them, and numerous studies have been made on the working properties of steel as affected by them. It has been suggested that ho t-shortness of steel is due to the presence of an enveloping liquid sulfide film at the grain boundaries of the steel in the range of the hot-working temperatures. However, several facts have been observed in commercial steels which do not seem to be completely consistent with this explanation: 1) the frequent absence of continuous films of sulfide as observed under the microscope, 2) the absence of hot-shortness in some high sulfur and resulfurized steels, and 3) the limitation of hot-shortness to a definite temperature range. The role that manganese plays in steel to eliminate hot-shortness is well known, but the theory behind it is still under question. Moreover, the effect of de-oxidizers such as aluminum and silicon, and the effect of oxygen are still not clearly known. In this study, the effect of heat treatments and of additions of manganese, aluminum, silicon, and oxygen upon the distribution of sulfide inclusions in iron was investigated. Both the as-cast and the heat treated structures were studied, using microscopic and autoradiographic techniques. Part of the results were interpreted in terms of Smith's' concept of microstructure. Review of Literature Metallurgists used to consider sulfide inclusions as suspended particles. It was Wohrman' who first pointed out that sulfide inclusions are soluble in liquid iron. Many observed facts may be understood on the basis of this concept of solubility. Wohrman found that small castings contain small inclusions. and larger castings contain larger ones. Also, inclusion sizes are smaller near the chilled surface. For the same size ingot, the average inclusion size in a given heat of steel depends upon the rate of solidification. That is, with slow solidification, enough time for precipitation and agglomeration of these

Jan 1, 1957

By Herty, C. H.

Three distinct processes take place during the conversion of iron ore to steel. First: the raw ore is reduced to metallic iron in the blast furnace and during this reduction certain constituents are dissolved in the iron, either through the solution of a solid into a liquid phase, as in the case of carbon, or by reduction of an oxide existing in the slag to the metallic element of that oxide, with subsequent solution of the metallic element in the iron. Thus by the process of solution and reduction, a pig iron results which contains about 4 per cent carbon, 1 per cent silicon, 1 to 2 per cent manganese, 0.1 to 0.4 per cent phosphorus, and 0.03 to 0.10 per cent sulfur. To obtain a sufficient yield of iron from the ore it is necessary that the reducing process be carried as far as possible, with the result that the impurities mentioned accompany the reduced iron. Second: to convert this iron into steel it is necessary to oxidize a part of the iron in eliminating the impurities to the extent desired for the particular product being made. In eliminating these impurities by oxidation a certain amount of iron oxide (FeO) dissolves in the steel. This dissolved FeO reacts with the metalloids, except sulfur, and to eliminate them to the desired extent it is necessary to leave a considerable amount of FeO in the metal. The reaction of iron oxide with silicon, manganese, and phosphorus results in the formation of the oxides of these elements. The oxides enter the slag and the extent of elimination of the elements depends on certain equilibria between the slag and the metal. The reaction of FeO with carbon results in the formation of the gases CO and CO, which, after saturating the metal, pass into the furnace gases. Third: after the iron has been purified to the desired extent as far as the elements listed are concerned, it is necessary to deoxidize the bath to remove the FeO, which is the vital factor in gas formation as the steel solidifies.

Jan 1, 1957

By O. Mellgren, A. M. Gaudin, P. L. De Bruyn

In the January 1956 issue: TP 4137B. Adsorption of Ethyl Xanthate on Pyrite. By A. M. Gaudin, P. L. de Bruyn, and Olav Mellgren. P. 65. Since P. L. de Bruyn is now a member of the AIME, the word "associate" should be removed in describing his status. The address of the third author, Olav Mellgren, should read: 74-2 Chingola, N. Rhodesia. P. 68, second paragraph, last line: the word "300-fold" should be replaced by "3000-fold." Also in the January 1956 issue: TP 4158B. Energy Transfer by Impact. By R. J. Charles and P. L. de Bruyn. The authors wish to express their disapproval of the omission of the abstract from the article, since they believe that an abstract fulfills a very important function in every paper.

Jan 1, 1957

ON FEBRUARY 4, 1952, the Phelps Dodge Corporation signed Contract GS-00P(D)-12068 with the United States Government. This interesting document dealt with the "Bisbee East" project as part of the Government's program to increase the supply of needed copper by encouraging private enterprise to expand production. The ore deposit involved was a relatively small body of low-grade ore lying east of the remnants of the old Sacramento Hill deposit that was exploited with indifferent success from 1923 to 1931, as related in THE PORPHYRY COPPERS. Planning for the entire enterprise had been directed from the start by Harrison M. Lavender, who in 1945, succeeded Percy G. Beckett as vice-president and general manager for all of Phelps Dodge's Western mines and smelters. The untimely death of Mr. Lavender in 1952 prevented him from seeing his plans brought to fruition; but in his honor the mine was fit- tingly named "The Lavender Pit" and was so dedicated on August 7, 1954. The Copper Queen Branch operates under- ground mines at Bisbee (production in 1955 was 28,000 tons) ; but, as this volume is concerned only with Porphyry operations, this chapter deals only with the Lavender Pit project, or as the Government knows it, Bisbee East. My reason for going into some detail regarding the floor-price contract is that it is fairly typical of contracts made by the Government in connection with a half-dozen other copper-expansion projects; and, incidentally, with various projects involving other strategic metals. Phelps Dodge did not seek a loan or other financial aid. The only encouragement asked consisted of (a) the privilege of a five-year write-off (commonly called rapid tax amortization)

Jan 1, 1957

By D. Perry, G. W. Binkley, G. K. Dumbauld, F. A. Brooks

A new cementing technique has been developed which is particularly applicable to permanent-type well completion operations. The technique makes use of the accelerating effect of calcium chloride on setting time and strength development of cement cake deposited in squeeze cementing. An unique feature is that the accelerator is applied after the unaccelera-ted cement slurry has been squeezed and the excess has been reversed from the well. Laboratory data on the accelerating effect of calcium chloride applied to the fi1ter cakes of three low-water-loss cementing compositions demorzstrate that the procedure results in relatively rapid development of strength and impermeability of the cement cake. Simulated squeeze-ceinenting tests made in the laboratory likewise corroborated the practicality of the procedure. The laboratory tests showed that a newly developed oil-emulsion cemerzting composition is more susceptible to acceleration of set than are modified cements containing high percentages of bentonite. The acceleration procedure has been used successfully in field operations. INTRODUCTION Nature of Problem In squeeze-cementing operations, a substantial amount of time is consumed in waiting on the cement to develop strength after it has been squeezed into the well. Frequently, an interval of 18 to 24 hours or longer is required for the development of strength sufficient to prevent failure of the cement during subsequent operations in the well. Reduction of this waiting-on-cement time offers appreciable savings both in time and in money. A particular type of squeeze-cementing operation to which an increasing amount of attention has been given is encountered in permanent-type well completion operations wherein perforations are to be squeezed off1. In this procedure, it is customary to pump the cement slurry down the tubing and out into the perforated section through a retractable extension pipe. Squeeze pressure is then applied, which forces the cement slurry into the perforations and causes the build up of a compact filter cake of cement within the perforations. The excess slurry remaining in the hole is then removed by reverse circulation. The extension pipe is then retracted, and, if a new interval is to be perforated, a perforating gun is run through the tubing. The newly perforated interval may then be tested by swabbing. In such operations, it has been customary to allow approximately 20 hours or so for hardening of the cement squeezed into the perforations. This time interval is usually measured from the time that the cement is reversed out of the hole to the time that subsequent swabbing is started. If the cement has not developed strength at the commencement of swabbing, the pressure differential caused by swabbing results in failure of the squeeze job. At the time that the work described in this report was initiated, particular consideration was given to the reduction of waiting-on-cement time in squeeze cementing by the permanent-type completion technique. Consequently, much of the experimental work was directed to this specific objective, though the process which was developed for acceleration of strength development has possible application in other than permanent-type completion operations. Method of Attack Although quick-setting cements

Jan 1, 1957

By F. H. Ellinger

A BRIEF description of the thermal expansion characteristics and of the four known crystal structures among the six allotropes of plutonium has been covered in a summarizing report on plu- tonium by E. R. Jette.' A detailed description of the crystal structure and thermal expansion of y plutonium has been published.' The present paper deals with the crystal structure of d plutonium, and with the thermal expansion of 6, 6' and € plutonium, as determined by X-ray diffraction methods. The X-ray diffraction patterns were taken in Uni-cam high temperature powder cameras using fil-

Jan 1, 1957

By P. L. Allsman

Butte mining district contains extensive manganese vein deposits forming a peripheral zone. Oxidation in the veins studied usually extends to a depth of about 75 ft. Secondary minerals formed by oxidation were found to be ramsdellite—always accompanied by intermixed pyrolusite—and cryptomelane. Enrichment of the gossan is accomplished by reduction of weight upon oxidation; theoretical enrichment is 32.2 pct. Additional enrichment is caused by leaching of soluble minerals, particularly calcium and magnesium carbonates. BUTTE mining district contains extensive manganese vein deposits in the outer zone, surrounding the copper and zinc deposits and corresponding to the well known silver zone. This article describes the mineralogy of the manganese veins, the oxidation and enrichment processes, and the use of this information in prospecting. Information was derived from a study of the Emma, Star West, Tzarena, and Norwich mines, selected as representative of the district. Vein exposures at these mines were mapped, studied, and sampled on the outcrops and throughout the oxidized zone. Specimens were cut and polished for minera-graphic examination, identification, and textural studies. Knowledge of the manganese oxide minerals is scanty, previous information having been rendered obsolete by publication of the first correctly identified list of manganese oxide minerals by Fleischer and Richmond in 1943. Positive identification of the manganese oxides is possible only by X-ray analysis. Identifications for this study were made by the author with a Phillip's Diffractometer at the Montana School of Mines and confirmed by Lester Zeihen of The Anaconda Co., using a Norelco X-ray camera. It was necessiary to re-evaluate some X-ray data, as published patterns of several manganese oxides proved to be of mixtures, mostly showing pyrolusite as a contaminant. Perhaps the most useful information on oxidation and enrichment of manganese is presented in recent books by Goldschmidt1 and Rankama and Sahama.2 While their hypotheses are not conclusively proved, all laboratory and field evidence has served to substantiate them. This information was very useful in this study. Mineralogy: The primary minerals of the manganese veins are chiefly rhodochrosite and quartz. Rhodonite is abundant in the northern part of the district and in places has been found to comprise over a third of the vein matter. A variable but generally small amount of sulfides may be present, principally pyrite and silver minerals. Sphalerite is progressively more abundant near the zinc zone. Rhodochrosite is believed to form complete iso-morphous series with siderite, ankerite, and calcite. Some variation into these compositions is common, and the intermediate forms are termed manganosid-erite, manganankerite, and rnanganocalcite. Much of the rhodochrosite is remarkably pure. Other manganese minerals in the district include huebner-ite, alabandite, and helvite. Ramsdellite (MnO2, orthorhnmbic) is the principal manganese oxide mineral, comprising perhaps two-thirds of the total oxides. It is dull to iron black, and generally massive or platy in structure. A prominent platy cleavage is the only distinguishing megascopic characteristic. Pyrolusite (MnO2, tetragonal) is next most abundant to ramsdellite, with which it is usually intimately mixed. The luster is often brighter or more metallic than in ramsdellite, and needle-like crystals are diagnostic. Pyrolusite is common in small cavities formed by oxidation of pyrite grains. It is relatively abundant in zones of high limonite content. Cryptomelane (KMnO16 tetragonal ?) is rare in the outcrop, but becomes more abundant with depth. At depths of several hundred feet it is the principal oxide. Although its appearance varies, a blue-black flinty luster and blocky to conchoidal fracture are most common. A potassium flame test will identify this mineral. Hardness of all three oxides varies from 2 to 6. The three are quite commonly intermixed, and their textures can vary greatly. The commonest textures are massive or colloform, representative of colloidal deposition, or vuggy and boxwork textures, formed by partial leaching and oxidation in place. A box-work of either ramsdellite or chalcedony is formed after rhodochrosite rhombs and is indicative of ore shoots in this district. Some replacement of both quartz and the granitic wallrock by ramsdellite has been noted, but most of the oxide was deposited as a fissure filling by fine particles. No trace of manganite, hausmannite, braunite, or manganosite was found. No minerals of the psilome-lane group were detected besides cryptomelane. Amorphous MnO, was found at several spots. A specimen of oxide coated with yellow barite crystals was amorphous and not psilomelane (BaMn9O18. 2H2O). Voids formed by the leaching of sphalerite were coated with cryptomelane, not hetaerolite (ZnMn2O4) as might be expected. No manganese sulfate minerals were found in the gossans; however manganese alum (apjohnite ?) has been re-

Jan 1, 1957

By F. A. Schaufelberger

METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on page 545. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.' The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited3 to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SO2,4 which may lead to contamination with sulfur, or C0,5 which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents,7 which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere.' It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution composition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farben10 claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic, antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373ºC), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred, probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

By Donald Ingvoldstad, Harold E. Lee

AT Bunker Hill the original charge storage and preparation system was installed in 1917 to accommodate lead-silver gravity mill products. Only minor tonnages of wet fines such as vanner and flotation concentrates were received. Charge flux and diluent requirements were .provided by an ample supply of siderite middlings and coarse lime-rock. While oversize material was crushed through ¼in., the use of roll crushers in series resulted in a more or less granular, free-running charge of adequate porosity. Under such conditions, receipts could be proportioned directly from receiving bins, and suitable blending was obtained by passing the resultant layered composite through a small Stedman disintegrator. This elementary system served well for production and smelting of an extremely lead-rich sinter, in the low column blast furnace. Here sinter physical quality is less critical, and appreciable quantities of raw flux and oxidized ore may be charged directly to the blast furnace without seriously impairing furnace capacity. Prior to 1938 the relative proportions of zinc receipts were low and extraneous flux requirements at a minimum. However, subsequent war-inflated zinc demands brought marked increase in fine concentrate and slimy zinc leach residue receipts and an abrupt introduction to smelting a more refractory zinciferous charge. The higher temperature demands of the more refractory zinciferous charge required a higher smelting column and the higher column, in turn, rendered the blast furnace less receptive to improperly prepared feed. Inadequate presinter processing facilities prevented the production of acceptable sinter, and blast furnace production declined to 50 pct of former capacity. In view of a prevailing contention among lead metallurgists as to the deleterious action of high zinc slag on blast furnace capacity, it was natural to overstress this factor and to concentrate on possible changes in furnace design. Another interpretation was that primary correction should be sought through expanded sintering facilities. This divergence of opinion, together with the extreme material shortages of the 1940's, delayed corrective

Jan 1, 1957

By B. C. Mariacher

EXTRACTION of uranium from ores is being ac-complished by processes which. for the most part, subject the entire ore to acid or carbonate leaching. Ore deposits with a U 3 O 8 content below 0.10 pct U 3 O 8 are seldom considered suitable for treatment by leaching. A preliminary concentration that would enrich the uranium content of an ore by a simple, low cost process based on physical properties of the ore might result in some low grade deposits becoming commercial ores. In addition, the process might be employed in existing operations to reduce transportation and leaching costs and to increase capacity of existing leaching plants. A study to attempt the development of a preliminary concentration process for primary uranium ores was undertaken by the Colorado School of Mines Research Foundation under sponsorship of the U.S. Atomic Energy Commission. The objective of this work was to produce concentrates containing 0.25 pct U3O8 from the low grade ores tested. Ores Tested: The main effort was devoted to the low grade primary uranium ores from northwestern Saskatchewan. Samples were obtained from the Beaverlodge operation of the Eldorado Mining & Refining Ltd. Additional primary ores, obtained from deposits in Gilpin County, Colo., contained from 0.07 to 0.10 pct U3O8. Summary of Concentration Tests: The Beaverlodge ore was tested to determine amenability of the ore to concentration by magnetic, electrostatic, gravity, and scrubbing processes. None of these produced satisfactory results. Both gravity and magnetic processes produced fairly good concentrates when closely sized fractions of the ore were treated, but on the basis of treating the total ore, recovery was poor. Preparation of sized fractions and the low capacity of equipment for suitable concentration made these methods impractical. As flotation offered the advantage of treating the total ore without intermediate sizing, the main effort was in this direction. A flotation process was developed that fulfilled the concentration objectives as set by the AEC. Pilot plant testing was used to verify results obtained from laboratory batch testing. Mineralogy: A petrographic examination of the Beaverlodge ore included a study of polished sur- faces and identification of the radioactive mineral by autoradiograph and X-ray diffraction. Approximate quantitative mineral identification was as follows: quartz, 60 pct; orthoclase feldspar, 20 pct; chlorite, 10 pct; carbonates, 5 pct; and miscellaneous minerals, 5 pct. Included in this last group were plagioclase feldspar, pyrite, mica, chalcopyrite, pyroxene, sericite, magnetite, galena, and uraninite. The most general occurrence of uraninite was in the form of crusts and thin coatings on limonite-stained grains of pyrite, quartz, and pyrite-quartz intergrowth. At least 90 pct of the uraninite was still attached to other minerals in a 100 by 200-mesh size fraction. The uraninite crusts were as small as 10 to 20 µ diam, and 5 to 10 µ thick. The Flotation Process Petrographic examinations of the Beaverlodge ore had indicated the impracticability of attempting to concentrate the uranium by floating individual grains of uraninite. Liberation of the uraninite required grinding to sizes below those suitable for flotation. However, there was preferential association of the uraninite with some minerals while others were free of uraninite attachment. The approach to the development of a flotation process was, therefore, based upon an attempt to concentrate the uraninite by floating carrier minerals. The following paragraphs discuss the various stages of the process with regard to the factors tested and the conditions under which best results were obtained. Grinding: The most effective size range for flotation was —150 mesh + 13 µ. The —13 µ material in the final concentrate had a higher U3O8 content than the total ore, but not as high as the average concentrate; however, rejection of slimes before flotation was prohibitive because of the loss in uranium carried in the —13 µ fraction. Grinding techniques which contributed to a minimum production of fines, such as stage grinding, were then employed. Quartz and Silicate Depression: These minerals represented approximately 80 pct of the ore and were free to a large degree of uraninite attachment. Significant improvement in the grade of the concentrate was obtained by depression of these minerals with hydrofluoric acid or sodium fluoride. Promoter: Selective stage flotation of uraninite carrier minerals was simplified by development of a single promoter mixture. The mixture consisted of an emulsion of a fatty acid, fuel oil, and a petroleum sulfonate and was selected after a comprehensive series of tests. It contained three parts by weight of an oleic and linoleic acid such as Emersol 300,

Jan 1, 1957

By W. R. Opie

The object of this paper is to show the manner in which typical electrodeposits of hexagonal-close-packed metals—zinc, titanium, and zirconium—tend to form. The conditions of electrodeposi-tion markedly affect the nature of the deposits in regard to crystal size, orientation, and appearance. No attempt is made to correlate cell conditions with deposit quality but, rather, characteristic types of deposits were selected and a study made to show the relationship between outward appearance and crystal structure. The zinc deposits were made in aqueous electrolytes and the titanium and zirconium deposited from fused salt baths. ZINC deposits studied were made in the American Smelting and Refining Co.'s Central Research Laboratories. They were representative of bright, shiny, smooth deposits, which can be obtained by using proper current densities and electrolyte addition agents, and of deposits which are dull and tend to be nodular. Four deposits were selected which ranged from smooth and bright to very nodular and dull, and their classifications are shown in Table I. These were examined microscopically and were found to differ quite markedly in outward surface structure and in microstructure. The outward surface variation is illustrated in Figs. 1 to 4. At X50 the texture could be seen to progress from granular to platelike to smooth. The microstructures of the deposits' cross sections from starting sheet to outer surface are shown in Figs. 5 through 8. The dull nodular deposits (sample Nos. 1 and 2) show some tendency for acicular growth. The platelike sample (No. 3) shows tendency for columnar growth development and the smooth deposit (No. 4) has a well developed columnar structure. Back-reflection X-ray patterns of the deposit surfaces revealed some interesting information. The crystal orientation was random in all deposits except the smooth deposit. Fig. 9 is a typical back-reflection pattern of a nodular deposit. All planes are reflecting in the proper relative intensity. The pattern of the smooth deposit is shown in Fig. 10. The only planes which reflect are the (10.4). This series of planes is in the right position, with the FeKa radiation used, to satisfy the Bragg equation if the basal planes {00.1) are at right angles to the X-ray beam. The results were interpreted to mean that in the bright smooth deposit preferred orientation has occurred with the basal hexagonal planes oriented in the plane of the sheet but with all other planes randomly oriented around the c-axis.

Jan 1, 1957

By E. J. Roberts, E. B. Fitch

THE mechanism of classification by settling pools is most simply shown in the case of batch sedimentation such as was analyzed by Oden.1 The batch model will be considered, therefore, and it will be shown that the same mechanism applies to continuous operation. Classification in Batch Settling Pools: Consider a beaker or tank of slurry containing particles so dispersed that they can settle independently of one another under the influence of gravity. Originally all particle sizes are uniformly distributed throughout the suspension. All particles start immediately to settle towards the bottom at rates determined by their size, shape, and density—among other factors. Particles reaching the bottom settle out of suspension. After some given time the slurry above the deposited solids is siphoned off or otherwise removed, leaving the deposited solids behind. The deposited solids, together with entrained and any unremoved supernatant slurry, represent the underflow of a classifier. The slurry removed represents the overflow. There is a certain separation, size of particle which during the sedimentation has just time to settle from the top surface of the slurry to the level at which underflow and overflow are parted. All particles with a faster settling rate will have dropped to below this level, no matter where in the beaker they started from originally, and therefore will be absent from the overflow. Particles with a slower settling rate will not reach this level if they started from the top of the slurry, but a portion of them,

Jan 1, 1957

By A. J. Griest, J. C. Danko

IN the course of vacuum evaporation experiments, sublimation figures were observed on the surface of a pure nickel specimen. A cubic figure, typical of those observed on this specimen, is illustrated

Jan 1, 1957

By Gordon G. Bentle, W. P. Fishel

GREINER, Marsh, and Stoughton1 have reviewed the literature in a monograph on the iron-silicon system. The lack of agreement among the various studies may be due to the difference in the purity of materials in some cases. The results of the X-ray method indicate only a general rather than a specific limit of the y loop. The iron-titanium system was investigated by Roe and Fishel,' whose results are used in determining the iron-silicon-titanium y loop. The literature indicates that no study has been made thus far of the iron-silicon-titanium system in the y loop region. Experimental Procedure The alloys were made from Armco iron, 99.86 pct Si, and 98.5 pct Ti. The titanium contains 1.07 pct Fe. The Armco iron contains 0.01 pct C, 0.005 pct Si, 0.02 pct Mn, 0.006 pct P, 0.01 pct S, and 0.04 pct Cu. A dilatation sample of Armco iron was prepared in the same manner as were the other samples. Several dilatation runs indicated that Ac3 begins at 905°C and ends at 910°C, which compares favorably with the study of Wells, Ackley, and Mehl' employing specially purified iron. All alloys were melted in an induction furnace in Alundum crucibles and were top poured into baked core sand molds. The ingots weighed about 600 g as cast. Dilatation samples of 4 in. by % in. diam were taken from the bottom end of the ingot, from which turnings for analysis were taken. Turnings from each end of two of the samples indicated that the alloys possessed uniform silicon content. A hole was drilled halfway through each end of a 4 in, dilatation sample. A chromel-alumel thermocouple was inserted in each hole and the surrounding metal peened in to hold the thermocouple in place. Fig. 1 represents the dilatation apparatus. The heating unit is an Alundum tube wound with resistance wire; the dilatation tube is a McDanel combustion tube; the push rod is zircon; the dial gage is graduated in 0.0001 in. and was vibrated to prevent sticking. A blank run over the temperature range of interest gave no significant dilatation. The thermocouples were attached to a multiple recording micromax which indicated the temperature at each end of the sample at 35 sec intervals. A Lindberg control unit governed the rate of heating of the furnace, and lowering or raising the

Jan 1, 1957

By F. H. Deily, L. W. Ledgerwood, J. E. Eckel

A new method for drilling the earth's formations has undergone extensive laboratory and shallow earth drilling experimentation. This method, pellet impact drilling, uses the energy of a large mass of high velocity steel spheres to break and crush the rock. Pellets are confined to a region close to the hole bottom. Motive fluid for transporting and recycling the pellets is supplied by a modified jet pump. The pellet drilling method has inherent advantages over conventional rotary drilling. First, only a nominal amount of weight need be applied to the hole bottom. Second, only a very small amount of torque is required for bit rotation. Third, means are available for continual replacement of the cutter medium. The experimental laboratory work and analytical procedures necessary for the design of a pellet drill bit are described. In the laboratory program approximately half the effort was devoted to the development of a better understanding of the physical process, and half to the empirical testing of new bit configurations. Factors such as pellet size and velocity, jet pump characteristics and modifications, and power distribution are discussed. The design and construction of a pellet impact bit for drilling a 9 in. hole with 1 1/4 in. steel pellets are described. Drilling performance in representative rocks, hydraulic operating characteristics, and metallurgical problems are discussed. INTRODUCTION This paper discusses an attempt to reduce drilling costs through the development of a drilling method basically different from rotary drilling. Publications on drilling research indicate that the major effort on the part of manufacturers and operators has been confined to research in rotary, or rotary-percussion drilling. This applied drilling research has produced significant gains in drilling rates and bit life, but thus far it has failed to achieve any major decrease in general drilling costs. From recent statistics released by Drilling Contractors, it can be shown that the total cost of drilling an "average" well in 1953 was about 2 1/4 times the corresponding cost in 1935. Analysis of the costs will show that they are not due to inefficient field operations; they are due instead to both an inflated economy and greater "average" well depths. Diligent work by the industry has reduced the backlog of potential economic improvements in rotary drilling to a group of rather marginal prospects. Increasing depths and poorer quality reservoirs at these depths continue to make the drilling cost problem more acute. Hence, the aim of the work reported here was to develop a new drilling method not limited by the inherent characteristics of rotary drilling and thus capable of attaining further significant reductions in drilling costs. The effort devoted to research on this proposed new drilling method was of considerable magnitude and represented .in excess of 37 man-years of research. The affiliates of Standard Oil Co. (N. I.) sponsored this development program which was conducted by the Drilling Methods Section of the Carter Research Laboratory in Tulsa, Okla. The purpose of this paper is to

Jan 1, 1957

By R. F. Domagala, M. Hansen, D. J. McPherson

Iodide zirconium was combined with calculated amounts of nitrided zirconium sponge and arc melted to prepare alloys in the 0 to 6 wt pct N region. Annealing treatments were carried out at 21 temperature levels. Metallographic examination of the heat-treated specimens permitted construction of the binary phase diagram from 0 to 6 pct N. Features of the diagram include the peritectic formation of both a and ß solid solutions. The maximum solubility of nitrogen is 0.8 pct in 8 zirconium and 4.8 pct in a zirconium. An X-ray study of nitrided materials was made in the range 6 to 13 wt pct N region because serious nitrogen losses were experienced when attempts were made to arc melt these high nitrogen alloys. PHASE relationships in the Zr-N system have been determined. Due to the inability to retain nitrogen in nitrogen-rich alloys subjected to arc melting, definitive work was possible only in the range 0 to 6 wt pct (0 to 30 atomic pct) N. Sufficient complementary X-ray work was done to permit construction of the binary phase diagram up to 13.3 wt pct (50 atomic pct) N (ZrN). Small ingots were prepared by arc melting master alloys with enough zirconium to produce an alloy of the desired composition. Following pretreatment, alloys were annealed at temperature levels between 600" and 2020°C. Determination of the phase boundaries was then accomplished by metallographic evaluation of specimens quenched from the various temperatures. Incipient melting techniques were used to corroborate solidus curves, and X-ray diffraction was employed to study the nitrogen-rich region of the a + ZrN phase field. Materials Westinghouse Grade 1 iodide zirconium crystal bar served as the base material for this investigation. The as-received bars were lightly sandblasted, pickled in a 20 pct HN0-5 pct HF aqueous solution, rinsed in water and acetone, and dried. They were rolled to about 1/32 in. strip and acid-pickled, followed by water and then acetone rinses. The material was sheared to approximately 1/4 in. squares, cleaned with acetone, and stored for use. Pure zirconium nitride is not commercially available, according to correspondence with possible suppliers. A literature survey indicated that nitrogen may be introduced into zirconium metal by passing nitrogen or ammonia gas over zirconium at an elevated temperature. After considerable experimentation, a train was devised whereby high quality nitrogen was passed through a series of bubblers to remove the last traces of oxygen, through an H,SO, bubbler and a cold trap to remove moisture, and finally over zirconium within a resistance furnace. Hand-picked Bureau of Mines magnesium-reduced zirconium sponge proved more amenable to nitriding than the crystal bar. The nitrogen used was extra pure gas purchased from Linde Air Products Co. The first two bubblers through which the gas was passed contained a solution suggested by L. F. Fieser" as being ideal for removing the last traces of oxygen from nitrogen. The solution contains 20 g KOH, 2 g sodium-anthraquinone ,9-sulphonate, and 15 g NaHSO, dissolved in 100 ml water. It is blood-red and turns brown when contaminated with oxygen. A saturated lead acetate solution, next in the series of bubblers, removed any H2S which might have formed in the 0, removal stage. An H,SO, bubbler and cold trap removed moisture before the nitrogen was passed over the zirconium. The zirconium was contained in a stainless steel screen within a Vycor or quartz tube in a resistance furnace. Unreacted nitrogen passed out of the system through a mercury bubbler. A nitriding run was performed in the following manner: Zirconium was placed in the screen within the furnace tube. The unit was assembled, suitably clamped off, and evacuated to remove the air and moisture within the tube and that trapped by the zirconium sponge. The unit was flushed with nitrogen and evacuated twice. After nitrogen was allowed to pass over the zirconium for about 30 min, the furnace was turned on; several hours were required to reach temperature. The reaction was allowed to continue at temperature for about 4 hr and the screen was then withdrawn from the hot zone of the furnace by means of a Nichrome or Kanthal rod. The screen and its contents were allowed to cool at the end of the tube and were then removed. At 800°C no more than about 5 pct N could be introduced into the sponge zirconium. This material was designated M-1 (master alloy No. 1) and reserved for the preparation of alloys in the dilute nitrogen region. A second set of experiments was conducted at 1000°C; no more than 7.2 pct N could be introduced into the zirconium at this temperature. Enough material (M-2) of this nitrogen content was prepared to produce a second set of alloys to complement the first and to provide alloys in the 0 to 6 wt pct N range. It was hoped that a diffusion anneal plus a re-nitriding might yield a material of higher nitrogen content. The material containing about 7 pct N was therefore given a homogenization treatment at 1000°C for 6 hr under an argon atmosphere. It was

Jan 1, 1957