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By N. J. Themelis, A. W. Last

Autogenous grinding, broadly defined as the self-comminution of ore in a cylindrical tumbling mill without using auxiliary grinding media, was first applied in the early 1930s in the so-called Hadsel mills (Hardinge, 1955) as seen in [Fig. 1], mainly used in gold mines on the US West Coast. A number of these mills were built in sizes of 6.1 to 7.3 m (20 to 24 ft) in diameter and 1.5 to 1.8 m (5 to 6 ft) in length but were later abandoned because of operating and maintenance problems. Further development of autogenous grinding led to the Hardinge wet grinding mill, the Aerofall dry grinding mill, and others. A tabulation of all known autogenous and semiautogenous installations around the world was sent recently to the authors by G. J. Kushner of Koppers Metal Processing Division. In the size range of 7.3 to 9.8 m (24 to 32 ft) in diameter, it lists a total of thirty mills used in the processing of copper ores. An additional 120 units are listed in the same size range for the processing of iron ores and other minerals. The largest mills in existence are 11.1-m-diam X 4.6-m-long (36-ft-diam X 15-ft-long) mills in Minnesota, powered by 8950 kW (12,000 hp) motors and used in taconite beneficiation. It is indicative of the phenomenal growth of this technology that none of the above 150 mills was in operation prior to 1964. Grinding rates in autogenous mills are very sensitive to variations in ore breakage characteristics and even with fairly constant ore type can exhibit large fluctuations in throughput. Autogenous grinding also depends on availability of a fraction of the ore to be ground in the form of "competent" rock which can withstand to a certain degree the tumbling and impact action within the mill. If the ore is uniformly "soft", it will soon be crushed into small size particles and further grinding, which depends on the existence of large size rocks in the mill, becomes impossible. This apparently is the case with most copper ores, as discussed by Bachman, Last and Nabbs (1970) who described pilot testing of a large number of ore samples from Kennecott 's Chino Mines. Under circumstances where autogenous grinding is impractical, it is possible to realize most of its benefits by utilizing large grinding balls in place of the "competent" rock and practice what has become known in the mining industry as semiautogenous grinding. In semiautogenous grinding (SAG), a grate discharge tumbling mill is fed the product of a primary crusher or run-of-mine rock. Forged steel or alloy grinding balls, in proportions ranging from 3.10% of the total volume in the mill, are used to complement the self-grinding ability of the ore. Semiautogenous circuits can be either designed for single-stage closed-circuit grinding which produces a final product for recovery processes, or for two-stage operation in which the SAG mill product is fed to a second stage of grinding in a conventional ball mill.

Jan 1, 1981

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

Large macroscopic nonmetallic inclusions were related to altered fireclay refractories by chemical and microscopic means. Pouring refractories are discussed as a source of these large inclusions. Nozzles and wells are major contributors. Use of alkali and titania contents as tracers is described. Recommendations are offered to minimize the sources of inclusions from pouring refractories. IN any attempt to improve the cleanliness of plain carbon and alloy steels, consideration must be given not only to the proper deoxidation practice to minimize inclusions, but also to sources of inclusions from pouring refractories. In some cases, the inclusions resulting from deoxidation may be minor in amount, yet a relatively dirty steel may be produced as a result of improper care in the pouring practices for the steel. The number of studies of inclusions resulting from pouring refractories has increased recently and some excellent reports on this subject have already been published.'4 Some of these reports were reviewed briefly in a companion paper by M. P. Fedock.5 Mr. Fedock's contribution is a fine addition to the studies necessary to improve steel cleanliness for the ultimate benefit of all steel producers and consumers. In the interest of constantly improving cleanliness, the authors have been actively engaged for the past two years in experimentation to determine more closely the sources of inclusions in steel. One phase of this work was associated with efforts to define more closely the sources of macroscopic inclusions which have been experienced on occasional heats. The term "macroscopic inclusions" is defined in general as those inclusions which are visible to the naked eye or at low magnifications of the order of less than X25. These inclusions sometimes can be seen in the macro-etch tests of billets and slabs. This report summarizes a few of the field experiments and laboratory studies conducted at the South Works of the United States Steel Corp., which were made regarding nozzles, wells, and ingot scums, as well as inclusions occurring in steel products. The data in the present study, together with the data of Mr. Fedock concerning ladle erosion, should be of value in regard to future studies of inclusions arising from pouring refractories. The knowledge gained as a result of data collected thus far at South Works has been helpful in improving the cleanliness of the products and in pointing the way toward further improvements. Similarity of Large Inclusions to Refractories and Altered Refractories In the routine inspection of billet etch tests, occasional inclusions visible to the naked eye have been observed. These large inclusions most frequently occur near the top of the ingot and near the billet surface. When such material was encountered, careful examinations were made in an attempt to determine the origin of these inclusions. In a relatively few cases, examination revealed that the material was unaltered fireclay refractory of a type similar to that used for hot-top material, with only the surface of the inclusions having an altered appearance under the microscope. However, the great majority of these inclusions were completely altered-refractory material. The term "altered refractory" is defined

Jan 1, 1955

By A. A. Smith, J. S. Smart, A. J. Phillips

The preparation of a sufficient quantity of high-purity copper for extensive laboratory use in the study of impurity effects has been an integral part of a research program in progress at the Central Research Laboratory of the American Smelting and Refining Co. for the past several years. Initially the degree of purity desired was that necessary to meet two essential requirements for experimental accuracy: (I) no impurity was to be present in the copper in an amount capable of producing a detectable effect on the properties to be studied, (2) even the minor changes in propertties caused by the addition of extremely small amounts of individual elements were to be measured without significant interference from contaminants. In the course of the investigation, evidence has accumulated to justify the conclusion that this copper is of exceptional purity; in fact, no impurity can be detected by any chemical method or spectrographic technique known to the authors. The present paper describes the method of production of the copper and presents some of its properties. Preparation oF High-purity Copper The elimination of impurities from commercial electrolytic copper is accomplished by a three-step purification process. The first operation consists of an electrolysis through a purified CuSO4-H2SO4 electrolyte using bagged anodes, low current density (5 amp. per sq. ft.) and low tem- perature (25°C max.). The electrolyte is prepared from commercial Cu2SO4 and is purified by heating the solution and adding I gram Fe as Fe2(SO4)3 to each 100 grams dissolved copper; sufficient hydrated oxide of copper, prepared from Cu2SO4 and NaOH, is supplied to precipitate Fe(OH)3, which carries down arsenic, antimony, tin, selenium, tellurium and other minor constituents. Silver and remaining traces of lead are removed by addition of Na2S to the acidified filtrate, which is then reatered after standing hot overnight. The cold solution is made up to 30 grams per liter Cu and 150 grams per liter H2SO4 and introduced without addition agents into the electrolytic system, which consists of a double row of hard-rubber battery boxes with the inside webbing and partitions removed, arranged in seven steps of ascending height. Electrolyte is uniformly supplied to the two highest cells by glass siphons operating from a constant-level reservoir, and flows by gravity through the bank of seven cells, entering each at the bottom and leaving at the top. Glass air lifts continuously supply the returning liquid to the constant-level reservoir for recirculation. Each cell contains three 4 3/4 by 4 3/8 by 1-in anodes cast from high-quality electrolytic wirebar copper, various lots of which have been used with equal success. The anodes are pinned to sheet copper hangars shaped to prevent crawl of the electrolyte to the multiple-wired bus bars—which would result in fouling of the contacts—-and hang inside wool flannel bags stretched over open wood frames. The deposit

Jan 1, 1941

By R. C. Earlougher

Based on laboratory tests conducted with the use of fresh core samples as well as a considerable amount of field data obtained from numerous water floods in northeastern Oklahoma, it appears that for any given oil saturation there is a critical maximum velocity above which the oil-recovery efficiency falls off very rapidly. In effect, when a water flood is operated above this critical velocity, the injected water-oil ratio rises extremely fast, thus shortening the economic life of the flood and reducing the ultimate oil recovery. This critical velocity apparently varies considerably with the percentage of oil saturation of the sand, so that in effect the higher the oil saturation at the beginning of a flood the higher the velocity that can be used successfully. In reviewing several of the earlier floods in the Mid-Continent area, it is concluded that most of the failures were due to two things: (I) too low an oil saturation, such as 30 per cent, and (2) too high water-injection rates, Although considerably more field data are necessary to establish definite limits, it would seem that the proper field injection rate for a 330 by 330 or 440 by 440-ft. spacing varies from approximately I bbl. per foot of sand per day where the oil saturation is as low as 30 per cent up to 5 bbl per foot of sand per day when the oil saturation is as high as 45 to 50 per cent, Introduction With secondary recovery by water-flooding receiving more and more attention throughout the industry, a greater working knowledge of multiphase flow under field conditions becomes more and more necessary A great deal of research has been carried on in highly idealized laboratory conditions, from which certain trends have been indicated, but with few exceptions no direct application to field use has been reported. widely varying conclusions have been drawn from the mass of idealized laboratory experiments and often this divergence apparently was due to the neglect of connate or interstitial water. Since interstitial water is such an important factor in water-flooding operations, it then follows that any laboratory flooding experiment must necessarily take it into account; and since it is difficult to set up laboratory models to allow for interstitial water, the next best procedure is to use fresh core samples for such tests. Even this procedure has its difficulties, inasmuch as it is possible to run only one flooding test on each sample, as each sample differs somewhat in character from all other samples. However, this disadvantage can be overcome to a large degree by the use of an extremely large number of samples. The next question that arises is: "IS it possible to get uncontaminated core samples having a true oil and water saturation like that existing in the reservoir?" If the sand under consideration is still in the primary stage of production, with a normal or relatively high amount of gas still in solution in the oil, probably it is not possible to get a nonflushed core. On the other

Jan 1, 1943

By D. Havlena, A. S. Odeh

The use of the straight-line method of solving the material balance equation is illustrated by means of six field cases. Also, the application of statistical criteria to arrive at the most probable answer is shown. The theory underlying the straight-line method of solution and the applicability of the statistical criteria was presented in a previous paper.' The field cases include saturated and undersaturated oil reservoirs with and without water drive. The aquifers discussed are: limited radial, infinite radial, very small aquifer and infinite linear. The field cases also include a gas reservoir producing under water drive. INTRODUCTION In a previous paper,' the authors presented the theory underlying the solution of the material balance as an equation of a straight line. The appropriate equations for various material balance cases as well as the methods of analysis and interpretation with comments and discussion were also included. To illustrate the various theoretical cases treated previously, five field cases are analyzed in this paper by employing the straight-line method of solving the material balance equation (MBE) and one example previously published is referred to. The use of statistical criteria to arrive at the most probable answer is also shown. All the field examples presented, except Case 2, are excerpts from complete reservoir studies. To illustrate the method, only sections specifically dealing with the material balance principles are included. Additional geologic information and basic data are reported to better acquire an understanding of the cases and thus to better follow the reasoning that suggested the successful application of the straight-line method of solving the MBE. The six cases are: (1) saturated reservoir, small gas cap, limited aquifer; (2) saturated reservoir, very small gas cap, infinite aquifer; (3) undersaturated-saturated reservoir, very small aquifer; (4) highly undersaturated reservoir, no water drive; (5) high undersaturated one-well reservoir, limited aquifer; and (6) gas reservoir, infinite linear aquifer. THE D4 SAND, GUICO FIELD, VENEZUELA The D, sand, which was discovered in 1943, is presently in a depleted state. Since its discovery it has produced under water drive, gas-cap-gas expansion, and solution gas drive. In Nov., 1947, water injection was initiated to arrest further pressure decline. When discovered, the D, sand was a saturated reservoir with a gas cap /oil zone volume ratio m estimated volu-metrically at 0.0731, an average permeability of 500 md, a porosity value of 25 per cent, and an oil viscosity at reservoir conditions of 0.3 cp. The volumetrically determined stock-tank oil initially in place was 23.1 million bbl. The volumetrically weighted physical data and production data available until Nov., 1953 are reported in Table 1. In Ref. 1, the effects on the straight-line plot of various values of ro/r for a constant ?to, or of various dimen-sionless times for a constant r8/r10 were theorized and were illustrated in Fig. 3A of that reference. In this field case, the previously theoretically predicted effects are established. Thus, the MBE calculations using Eq. 3c of Ref. 1 were performed for various r6/r10 and dimension-less time values. Eq. 3c of Ref. 1 is:

Jan 1, 1965

By R. C. Earlougher

Based on laboratory tests conducted with the use of fresh core samples as well as a considerable amount of field data obtained from numerous water floods in northeastern Oklahoma, it appears that for any given oil saturation there is a critical maximum velocity above which the oil-recovery efficiency falls off very rapidly. In effect, when a water flood is operated above this critical velocity, the injected water-oil ratio rises extremely fast, thus shortening the economic life of the flood and reducing the ultimate oil recovery. This critical velocity apparently varies considerably with the percentage of oil saturation of the sand, so that in effect the higher the oil saturation at the beginning of a flood the higher the velocity that can be used successfully. In reviewing several of the earlier floods in the Mid-Continent area, it is concluded that most of the failures were due to two things: (I) too low an oil saturation, such as 30 per cent, and (2) too high water-injection rates, Although considerably more field data are necessary to establish definite limits, it would seem that the proper field injection rate for a 330 by 330 or 440 by 440-ft. spacing varies from approximately I bbl. per foot of sand per day where the oil saturation is as low as 30 per cent up to 5 bbl per foot of sand per day when the oil saturation is as high as 45 to 50 per cent, Introduction With secondary recovery by water-flooding receiving more and more attention throughout the industry, a greater working knowledge of multiphase flow under field conditions becomes more and more necessary A great deal of research has been carried on in highly idealized laboratory conditions, from which certain trends have been indicated, but with few exceptions no direct application to field use has been reported. widely varying conclusions have been drawn from the mass of idealized laboratory experiments and often this divergence apparently was due to the neglect of connate or interstitial water. Since interstitial water is such an important factor in water-flooding operations, it then follows that any laboratory flooding experiment must necessarily take it into account; and since it is difficult to set up laboratory models to allow for interstitial water, the next best procedure is to use fresh core samples for such tests. Even this procedure has its difficulties, inasmuch as it is possible to run only one flooding test on each sample, as each sample differs somewhat in character from all other samples. However, this disadvantage can be overcome to a large degree by the use of an extremely large number of samples. The next question that arises is: "IS it possible to get uncontaminated core samples having a true oil and water saturation like that existing in the reservoir?" If the sand under consideration is still in the primary stage of production, with a normal or relatively high amount of gas still in solution in the oil, probably it is not possible to get a nonflushed core. On the other

Jan 1, 1943

By L. Guttman

THE equilibrium diagram of the indium-thallium system was of interest to us in connection with a study of the superconducting properties of metallic solid solutions in progress at this Institute. For this purpose, a series of alloys was prepared covering the range from pure indium to 75 atomic pet TI, and X-ray diffraction patterns were obtained. Roughly speaking, the results indicated a region of continuous decrease in the axial ratio of the face-centered tetragonal structure from the value ca. 1.08 in pure indium to unity at about 23 atomic pct TI. From this concentration to the solubility limit, the structure was face-centered cubic, a form not reported by Hansen.1 At this point we became aware of the work of Valentiner,2 who had found the same structures at room temperature but had not investigated further the relationship between them. To study the transformation f.c.c.??f.c.t., and to clarify the phase diagram, we undertook the work reported in this paper and that which follows." Preparation of Alloys Pure indium and thallium* (both about 99.9 pct, as estimated from spectroscopic analyses) were weighed out in quantities sufficient to prepare 10 to 25 g of alloy of the desired concentration. (Occasionally indium was mixed with a previously pre- pared solution.) The metals were melted over a flame, in an open graphite crucible, stirred with a graphite rod, and poured into a graphite trough. The rough slug was hammered and swaged into a rod of 2 to 3 mm diam, and annealed in a drying oven at about 125°C for 1 to 2 days. Samples were taken from the rod for analysis, as well as for diffraction and other measurements. The thallium was determined by electrometric titration, using a modification of the method of Beale and co-workers.' The precision of analysis was generally about 2 0.2 pct of the thallium content. The rods were sometimes found to vary in thallium content as much as 1.5 pct from end to end, but since analyses were also made close to the segments used in the various studies, the composition was usually known as accurately as the analyses could be made. Where one less significant figure is given, the error is estimated to be ±0.4 pct of the thallium content. X-Ray Diffraction Measurements Three different cameras were used: (1) A 7 cm Debye camera, with oscillating specimen (manufactured by the Picker X-ray Corp., Cleveland, Ohio); (2) a 9 cm diam Debye camera of the type designed by Bradley;" (3) a 10 cm diam symmetrical focusing back-reflection camera (manufactured by Geo. C. Wyland, Ramsay, N. J.). Samples were prepared from the homogenized rods, either by filing under liquid nitrogen, or more often, in the form of wires or foils made by working at room temperature or liquid nitrogen temperature. Sharp patterns were obtained from specimens annealed at room temperature, although higher annealing temperatures were also used (cf. below). Generally, copper radiation was used; a few patterns were obtained with

Jan 1, 1951

By I. S. Servi, N. W. Marr

TIN markedly increases the softening temperature of pure copper with only a moderate effect on conductivity. Smart and smith' indicated a substantial increase in softening temperature upon addition of different levels of tin up to 0.05 pct in oxygen-free copper. However, after finding no effect of tin in copper containing about 0.025 pct O, they concluded that "the presence of oxygen completely nullifies these changes in properties by precipitation of SnO2.'' Since preliminary tests on Cu-Sn-0 alloys indicated that this conclusion is not valid outside the extremely limited tin range investigated by Smart and Smith, research was primarily directed toward the partition of tin between the copper-base matrix and the oxide phases. Experimental. Material was prepared by sealing an 80 to 100-g charge consisting of oxygen-free copper, tin, and copper oxide into a y-in.-ID quartz capsule which was evacuated and back-filled with tank-grade argon to 3 atm. The sealed vials were heated to 1125ºC, kept at temperature for 30 min, occasionally agitated, and then allowed to air-cool outside the furnace ("as-cast"). The castings were cold-swaged to 0.370 in., annealed 1 hr at 600°C ("as-annealed"), and cold-swaged 16.5 pct ("as-swaged"). Cross sectional wafers were annealed for 1 hr at various temperatures and Rockwell F hardness measured. The "softening temperature" was defined as the interpolated temperature at which the hardness was 50 Rockwell F. Electrical resistance was measured by an ac poten-tiometric method on 0.040-in.-diam wires after a 1 hr anneal at 600°C. Relative accuracy was of the order of 1 pct. Chemical analyses for tin were performed by two methods, identified as "Acid flux" and "HN03 dissolution". The first consisted of fusing the sample with potassium pyrosulfate and leaching the resulting melt with 10 pct sulfuric acid. The spectrophotometric procedure which followed is described in Ref. 2. Oxygen analyses were performed by the vacuum-fusion method with a bath temperature of 1650°C. Tin content of oxides and copper phases was measured with the X-ray microprobe, using a calibration curve based on a series of oxygen-free Cu-Sn alloys. Results. In Fig. 1, the nominal tin composition for alloys containing nominally 400 ppm O was plotted vs the analyzed or the computed tin content—the latter derived from one of the following: 1) "acid flux" chemical analysis; 2) "HN03 dissolution" chemical analysis; 3) X-ray microprobe analysis of the copper matrix; 4) equivalent tin content, based on the measured increase in electrical resistivity (an increase in resistivity of 1.6 microhm-cm is approximately equivalent to 1 wt pct of sn1,3). It is evident from Fig. 1 that the results of the acid flux analysis are consistent with the nominal composition while the HNO3 dissolution method generally yields lower values, consistent with those obtained from electrical resistivity measurements and somewhat higher than those obtained by microprobe analysis. Microprobe and resistivity values are affected only by the tin in solid solution; hence the HN03 method

Jan 1, 1970

By Howard N. Evanenson

WASTE of coal, or perhaps more properly the percentage of its recovery in mining, has keenly interested me during an experience of over a half century in coal mining. In the early part of that time and until a few years after World War I the use of better mining plans and supervision resulted in an increased recovery. Since then, and particularly since controlled prices have been effective and mechanized mining has been extensively practiced, the tendency has all been toward lesser recovery in mining. The purpose of this paper is not to criticize the methods being used, which after all are the result of economic forces, nor to point to any particular mining method or to any locality where the best recovery is obtained, but to call attention to the tremendous waste of our national coal resources that is constantly continuing. A possible method of reducing this loss will be suggested, but without any illusions that it will be followed or that such attention will be paid to it. AVERAGE RECOVERY The actual average percentage of recovery of coal in the ground is not known. Many papers giving figures of recovery have been published but no definite base of measurement has been agreed upon by those presenting the data. As an example, the Pittsburgh bed can be considered-it has produced a greater output than any other and has been sold or leased at higher prices in place than any other coal bed. Over a large part of its area where high prices have prevailed it has been customary for many years to draw pillars. In these mines it has been usually assumed that the average recovery was higher than in other beds and percentages of recovery of 85 to 95 per cent are usually said to be realized. In all of these mines, however, it has been customary to leave from 4 to 8 in. in the bottom, and 10 to 16 in. in the roof; thus from 14 to 24 in. of coal has been left in the mines out of a total seam thickness of about 96 in., or 15 to 25 per cent of the total coal. No attempt is made to mine this coal for metallurgical purposes, owing to its impurities, although this unmined coal is of excellent quality and better than much of the coal used for steam purposes. If we add to this discard the coal usually lost in mining and those parts of the bed that must be left because of bad seam conditions, barrier pillars, reservations for buildings, gas and oil wells, one can easily see that the actual recovery from this bed cannot be more than 65 to 75 per cent. In addition, the rooster or rider or wild coal over the mining bed often 3 to 4 ft. of coal, high in ash and sulphur but still good steam coal-is hardly ever mined, nor is any attempt made to mine it. It is safe to say that from a broad economic viewpoint not more than 50 to 60 per cent of the fuel value of this great seam is actually being recovered.

Jan 1, 1946

By Leo F. Reinartz

Part III of a four-part series on the history of steelmaking in the US, describes furnace developments, improvements during the last few decades, and the contribution of the AIME. THE invention of the dolomite machine was a great boon to the open-hearth furnaceman. By speeding up bottom making, it helped to increase tons per hour and decrease cost. The first homemade unit was built and operated before 1925 at the South Side works of Jones & Laughlin Steel Corp., Pittsburgh The first commercial machine, similar to those known today, was built for the Donner Steel Co., Buffalo, N. Y., in 1925. Heavy slab buckstays, 6 in. by 15 in., supplanted lighter I-beam buckstays as furnace framework in the middle 1920's. They greatly improved the rigidity of the furnace binding. Although the first sloping back wall had been in- stalled prior to 1920 on a small basic open-hearth foundry furnace at Columbus, Ohio, the impetus to install such back walls universally in ingots shops came after S. Naismith installed the first one on an open-hearth furnace at Illinois Steel Company's South works in June 1924. Before that event, back- wall life had already been improved somewhat by the use of chrome rock or metal-encased basic brick. Here again, these changes heralded major for- ward steps in furnace design, decreased costs, in- creased production, and improved safety and working conditions on the back standing of the furnace. Fuels Up to 1930, a number of different kinds of fuel were used to melt and refine steel in American open hearth furnaces. During World War I, powdered coal was used in a few plants as an open-hearth fuel, but because of the high sulfur and ash content in the coals, many operational difficulties arose. There were also dust, explosion, and accident hazards, so that after the War its use was discontinued. In some steel-manufacturing centers, natural gas was available as a fuel and gave good performance. In most steel-manufacturing centers, operators had to rely on producer gas made from bituminous coals in producer gas houses. Low-sulfur low-ash, high-fusion coals required for the manufacture of such gas were not readily available. The quality of producer gas was uncertain. The gas had to be pre-heated. Maintenance problems connected with the use of this fuel were serious. Tons per hour per month was unsatisfactory. Although petroleum had been first discovered by Edwin L. Drake at Titusville, Pa., in 1859, it was not until the early 1930's that heavy fuel oil residues for open-hearth use began to appear on the market. They were cheap; the calorific value was high, and it was not necessary to pass this fuel through the checkers to preheat it. Various plants began to use such oil as an open-hearth fuel. Others used it in combinations with tar, coke-oven, and/or blast-furnace gases. Because of its low calorific value, blast-furnace gas had to be preheated in the checkers. These fuels were cleaner and more dependable than producer gas. The dirty gas house adjacent to the open-hearth shop was no longer needed, and

Jan 1, 1961

By A. J. Phillips, A. A. Smith, J. S. Smart

The preparation of a sufficient quantity of high-purity copper for extensive laboratory use in the study of impurity effects has been an integral part of a research program in progress at the Central Research Laboratory of the American Smelting and Refining Co. for the past several years. Initially the degree of purity desired was that necessary to meet two essential requirements for experimental accuracy: (I) no impurity was to be present in the copper in an amount capable of producing a detectable effect on the properties to be studied, (2) even the minor changes in propertties caused by the addition of extremely small amounts of individual elements were to be measured without significant interference from contaminants. In the course of the investigation, evidence has accumulated to justify the conclusion that this copper is of exceptional purity; in fact, no impurity can be detected by any chemical method or spectrographic technique known to the authors. The present paper describes the method of production of the copper and presents some of its properties. Preparation oF High-purity Copper The elimination of impurities from commercial electrolytic copper is accomplished by a three-step purification process. The first operation consists of an electrolysis through a purified CuSO4-H2SO4 electrolyte using bagged anodes, low current density (5 amp. per sq. ft.) and low tem- perature (25°C max.). The electrolyte is prepared from commercial Cu2SO4 and is purified by heating the solution and adding I gram Fe as Fe2(SO4)3 to each 100 grams dissolved copper; sufficient hydrated oxide of copper, prepared from Cu2SO4 and NaOH, is supplied to precipitate Fe(OH)3, which carries down arsenic, antimony, tin, selenium, tellurium and other minor constituents. Silver and remaining traces of lead are removed by addition of Na2S to the acidified filtrate, which is then reatered after standing hot overnight. The cold solution is made up to 30 grams per liter Cu and 150 grams per liter H2SO4 and introduced without addition agents into the electrolytic system, which consists of a double row of hard-rubber battery boxes with the inside webbing and partitions removed, arranged in seven steps of ascending height. Electrolyte is uniformly supplied to the two highest cells by glass siphons operating from a constant-level reservoir, and flows by gravity through the bank of seven cells, entering each at the bottom and leaving at the top. Glass air lifts continuously supply the returning liquid to the constant-level reservoir for recirculation. Each cell contains three 4 3/4 by 4 3/8 by 1-in anodes cast from high-quality electrolytic wirebar copper, various lots of which have been used with equal success. The anodes are pinned to sheet copper hangars shaped to prevent crawl of the electrolyte to the multiple-wired bus bars—which would result in fouling of the contacts—-and hang inside wool flannel bags stretched over open wood frames. The deposit

Jan 1, 1941

By H. M. St. John

THE melting department is the heart of the foundry. From it clean metal flows to the molding floor, in the right quantity, at the right time and at a sufficiently low cost-or, if not, the foundry fails to thrive. Since it is our purpose here to discuss present-day melting practice in the foundry, it may be well at the start to emphasize the wide differences in foundries and the conditions under which they must operate in order to reach the goal stated in the first paragraph. In every foundry, large or small, jobbing or captive, the same factors must be dealt with but they are of varying consequence and must be dealt with in varying ways in different foundries. Particularly in the nonferrous industry, there is so wide a variation in the composition of alloys used and in the character of castings made that no one type of furnace, nor any one method of operation, can be expected to produce the best results at all times. The present discussion will not attempt to include all nonferrous metals. It is intended to cover only the copper-base alloys in which copper is the dominant element, most of which are commonly known as brass or bronze. The discussion is further limited to the melting of these copper-base alloys for use in sand-casting foundries. Die-casting plants, the brass-rolling mills and certain other metal industries have melting problems peculiar to those industries, which will not be considered here. The following considerations are elemental in all foundries and are listed in what is believed to be the relative order of their present-day importance: I. The melting department must meet the foundry's requirement for dean, fluid metal, of specified composition and purity, at a temperature suitable for the work the foundry has in hand. This is the prime consideration in any foundry, at any time, anywhere. 2. Working conditions surrounding the melting furnaces and attending their use must be good. 3. The cost of molten metal at the mold must be as low as possible. 4. The operating characteristics of the furnaces must be sufficiently flexible, to meet normal variations in foundry requirements. 5. The operation and maintenance of the melting equipment must not require more skill and experience than is available in the particular foundry in question. METAL QUALITY It is not a function of the melting furnace to refine or improve the quality of the metal but simply to melt it without impairing its quality. Good practice requires, therefore, that care must be taken to supply the melting department with metal of inherently good quality, assured by specification or otherwise, having all the properties necessary to produce the castings desired. An alloy contains a number of primary elements, which must be present in definite proportions if the castings made from it are to have the desired properties. If the castings are made to a customer's specification, this will state the range within which these principal elements (for example, copper, tin, lead and zinc) are permitted to vary.

Jan 1, 1946

By Carl J. Christensen

This paper presents the development of diamond coring of the Weber sand section in the Rangely Field, Colorado. The description and operation of the diamond-coring equipment is included as well as the economics and results obtained by its use. Diamond coring is compared with the other methods used for drilling the Weber sand. Two types of diamond coring are discussed. The first and the one used most extensively is the regular 6 ?x 3¾-in. diamond bit and bottom hole 50-ft barrel. The second type, which has also been used successfully by Stanolind, consists of a 4 13/16 x 2 11/32-in. cutting bit and reverse circulation coring equipment. The first type will be referred to as regular or conventional diamond coring while the latter type will be referred to as reverse circulation diamond coring. Introduction Diamond coring has been used for many years in mines, quarries, surface coring at dam sites, laboratory work, and so on, but, until recently, had never been used very extensively in coring oil sands and other oil-bearing strata. It was demonstrated early in its development that hard forma-tions could be cut rapidly and that core recoveries far exceeded those obtained with conventional hard rock bits and quite often 100 pet recovery was obtained. However, the poorly constructed diamond-coring equipment and resulting high costs of early diamond coring slowed down its progress. Early in the development Of the Rangely Weber field, Rio Blanco County, Colorado, the Rangely Engineering Committee selected key wells that were to core the Weber section in its entirety. These cores were to be analyzed and various sections tested to gather sufficient information so that accurate reservoir studies could be made. The number of wells selected were kept at a minimum inasmuch as the productive Weber section, which is found at an approximate depth of 6000 ft, is thick, being as much as 600 to 700 ft on top of the structure. The Weber section is also comparatively hard to drill. For instance, one well took 60 days to core 490 ft of Weber sand with conventional coring equipment. It was noticed, however, that Core Labora-verse diamond plug cutter could quickly cut a plug from. one of these hard cores. This fact led to the serious consideration of diamond coring the Weber sand. The first diamond coring at Randy was performed by Stanolind in August 1946 andl although we experienced some difficulties, the results definitely indicated that diamond coring would be successful at Rangely for .coring the Weber sand. As more wells were cored and the equipment improved somewhat, diamond coring became less expensive than drilling the Weber sand with the conventional rock bit. In less than one Year diamond coring has definitely Proved its usefulness in oil-field drilling operations in the Rocky Mountain area where formations quite often drill very hard. The practice of spot coring in hard oil-bearing formations with conventional coring equipment is giving way diaimond coring of the entire sections, thus givng an operator the complete picture.

Jan 1, 1948

By Nicholas J. Grant, Italo S. Servi

THE creep and stress rupture properties of three grades of aluminum have been reported in a previous paper.' It was found that the stress coefficient of the creep rate and of the rupture time changes at the transition from low temperature-type to high temperature-type deformation. The transition corresponds to the equicohesion for grains and grain boundaries. In order to support the conclusions obtained from the examination of creep and stress rupture data, the deformed specimens were observed metallographically and a few special tests were conducted. The results of these qualitative observations are given in the present paper. Experimental Procedure and Results Table I gives the types of aluminum specimens.' The creep and stress rupture tests were conducted in simple tension at constant stress. Further details on the experimental techniques have been given.' The test bars were electropolished in a perchloric-acetic mixture before testing and were observed after testing without any further preparation unless otherwise specified. Observations of specimen cross-sections were made after electrolytic polishing and etching. The samples were extended along a direction parallel to the longer side of the micrographs of Figs. 12 through 27. The log-log plots of stress vs. minimum creep rate for the three grades of aluminum appear in Figs. 1 and 2. The reference numbers on each curve help relate the photographs to the conditions of testing, indicating where high temperature-type deformation and failure prevailed and where low temperature behavior prevailed. Deformation of Single Crystals at Very High Temperature: An annealed, high purity aluminum specimen was slightly strained at one end and re-annealed. A large single crystal was formed at the strained end of the specimen during re-annealing; the other end remained polycrystalline (see Fig. 3). A stress of 50 psi was applied to the cold specimen to avoid loading at 1100°F. The temperature was then raised to 1100°F, kept at 1100°F for 3 hr, and lowered again to room temperature. Fig. 4 shows the appearance of the specimen after testing. The single crystal deformed by gliding along parallel planes, while the polycrystalline part deformed mainly by grain boundary flow. Some grain growth occurred in the polycrystalline part. Another high purity specimen, which had two large single crystals at the two ends and a polycrystalline zone in the middle portion, was tested at 1000 °F under a stress of 100 psi. The appearance of the sample after test is shown in Fig. 5. Even though considerable slip occurred in the single crystals, the fracture occurred in the weaker polycrystalline portion. Evidence of Grain Boundary Migration during Creep Testing: A high purity, coarse grained specimen, which had a large crystal in the middle portion (see Fig. 6) was tested at 700°F under a constant stress of 175 psi for 30 hr. The appearance of the specimen after testing (Fig. 7) indicates that the large crystal deformed by gliding along parallel planes, while the rest of the specimen deformed mainly by grain boundary flow. Microscopic examination showed clear evidence of grain boundary flow and grain boundary migration, an example of

Jan 1, 1952

By R. L. Stephenson

The effect of fabrication variables on the creep-rupture properties of TZM (Mo-0.5 pct Ti-0.08 pct Zr-0.03 pct C), Cb-TZM [columbium-modified TZM (7140-1.5 pct Nb-0.5 pct Ti-0.8 pct Zr-0.05 pct C)], and TZC (Mo-1.2 pct Ti-0.25 pct Zr-0.15 pct C) has been studied at 982º. 1093º, 1204º, and 1315°C for rupture times up to 1000 hr. The creep tests were performed in vacuum creep furnaces, employing cold-trapped oil-diffusion pumps, operating at pressures 2 X 10-7 tory. After-test chemical analyses showed no significant changes in interstitial content. The creep-rupture properties of TZM, fabricated according to current mill practice, were determined in the stress-relieved and in the re crystallized conditions to provide control data. Specimens of TZM, Cb-TZM, and TZC fabricated according to each of two experimental fabrication schedules were then tested. The schedules differed in terms of in-process annealing temperatures and warm -working temperatures. The data make several conclusions evident. Fabrication variables do indeed have a profound effect on the long-time creep-rupture properties of molybdenum alloys. Strengths of these alloys compare very favorably with those of other refractory metal alloys in the temperature range studied. FOR several years we have been engaged in the evaluation of the creep-rupture properties of promising refractory metal alloys. We consider the determination of these properties to 1000 hr at several temperatures necessary for a valid comparison. Such an evaluation indicated that the creep strengths of Mo-0.5 pct Ti and TZM (Mo-0.5 pct Ti-0.08 pct Zr-0.03 pct C) compare favorably with those of other refractory metal alloys. Tensile and recrystallization data of other investigators1,2 show an effect of fabrication variables. More specifically, those fabrication schedules which produce high strength through work hardening exhibit the least thermal stability. A similar conclusion was reported by perkins3 for Cb-TZM. This would lead one to expect that, in terms of creep, those materials showing higher strength at short times and low temperatures would exhibit lower strength at long times and high temperatures. If these expectations were fact, a substantial improvement could be made in these alloys by optimizing their fabrication schedule in terms of their anticipated service temperature. We therefore undertook a study of the effect of fabrication variables on the long-time creep properties of TZM, Cb-TZM (Mo-1.5 pct Cb-0.5 pct Ti-0.08 pct Zr-0.05pct C) and TZC (Mo-1.2 pct Ti-0.25 pct Zr-0.15 pct C). MATERIALS All materials used were supplied by the Climax Molybdenum Co. of Mich. Our original intention was to test the same heat of each alloy in different conditions. Fabrication difficulties prevented this; however, heats with nearly identical analysis were selected. The compositions of the materials used are listed in Table I. All materials were supplied in the

Jan 1, 1970

By F. H. Wilson, E. W. Palmer

The solid solubility of iron in 2 to 10 pct cupro-nickels increases with temperature and nickel content. Property changes accompanying various heat treatments indicate typical precipitation hardening behavior. Iron content also affects softening temperature and sub-scale formation. These factors, as well as impingement corrosion resistance, influence the optimum iron content of commercial alloys. FOR many years Cu-Ni alloys have been used extensively in the form of tubes, pipes, and plates for the construction of salt-water lines and surface condensers on shipboard and in tidewater power stations. The 30 pct Ni alloy has been considered more resistant to rapidly flowing sea water than alloys of lower nickel content, and has been standard on ships of the U. S. Navy. Some ten years ago, the still better corrosion resistance obtained by modifying the 30 pct Ni alloy with approximately 0.5 pct Fe was recognized, and the iron-bearing alloy rapidly superseded the plain alloy as the standard material for severe service. In 1945, Tracy and Hungerford1 published a study of the effect of iron on the corrosion of various cupro-nickels in sea-salt solutions, and their data indicated that the 10 pct Ni alloy containing about 0.75 pct Fe was equivalent to the 30 pct Ni alloy containing 0.5 pct Fe. This was confirmed by LaQue in discussion of the above paper, and by results in an experimental condenser set up at the Kure Beach marine test station of The International Nickel Co., reported by Freeman and Tracy.' The 10 pct Ni iron-bearing alloy is now being very widely used in applications where the 30 pct Ni iron-bearing alloy was formerly considered standard. While this "substitution" has undoubtedly been stimulated by the present extreme shortage of nickel, it must be emphasized that it involves no loss of service performance, and would have occurred anyway in the course of time, for economic reasons. In view of the increasing use of the 10 pct alloy, it seems desirable to make generally available the results of several investigations of Cu-Ni-Fe alloys carried out in the Metallurgical Research Laboratory of The American Brass Co. in recent years. The present paper, deals with the constitution of these alloys in the copper-rich corner of the system, and with the variations in hardness and tensile properties resulting from the heat treatment of alloys containing various amounts of iron. Most of this work is concerned with alloys containing 10 pct Ni. With over about 0.75 pct fe, the 10 pct Ni alloy is suscep- Alloys Several series of cupro-nickel alloys containing iron were used in these investigations. Most of them were prepared in the laboratory, but two samples of commercially fabricated alloys were included. Series A—Nominally 2 and 5 pct Ni, each with 0 to 1.5 pct Fe. Series B—Nominally 10 pct Ni with 0.1 to 0.4 pct Fe. Series C—Nominally 1.0 pct Ni with 0 to 2 pct Fe. Series D—Nominally 10 pct Ni with 3 to 5 pct Fe. Series E—Nominally 10 pct Ni with 1 and 1.5 pct Fe.

Jan 1, 1953

By Carl J. Christensen

This paper presents the development of diamond coring of the Weber sand section in the Rangely Field, Colorado. The description and operation of the diamond-coring equipment is included as well as the economics and results obtained by its use. Diamond coring is compared with the other methods used for drilling the Weber sand. Two types of diamond coring are discussed. The first and the one used most extensively is the regular 6 ?x 3¾-in. diamond bit and bottom hole 50-ft barrel. The second type, which has also been used successfully by Stanolind, consists of a 4 13/16 x 2 11/32-in. cutting bit and reverse circulation coring equipment. The first type will be referred to as regular or conventional diamond coring while the latter type will be referred to as reverse circulation diamond coring. Introduction Diamond coring has been used for many years in mines, quarries, surface coring at dam sites, laboratory work, and so on, but, until recently, had never been used very extensively in coring oil sands and other oil-bearing strata. It was demonstrated early in its development that hard forma-tions could be cut rapidly and that core recoveries far exceeded those obtained with conventional hard rock bits and quite often 100 pet recovery was obtained. However, the poorly constructed diamond-coring equipment and resulting high costs of early diamond coring slowed down its progress. Early in the development Of the Rangely Weber field, Rio Blanco County, Colorado, the Rangely Engineering Committee selected key wells that were to core the Weber section in its entirety. These cores were to be analyzed and various sections tested to gather sufficient information so that accurate reservoir studies could be made. The number of wells selected were kept at a minimum inasmuch as the productive Weber section, which is found at an approximate depth of 6000 ft, is thick, being as much as 600 to 700 ft on top of the structure. The Weber section is also comparatively hard to drill. For instance, one well took 60 days to core 490 ft of Weber sand with conventional coring equipment. It was noticed, however, that Core Labora-verse diamond plug cutter could quickly cut a plug from. one of these hard cores. This fact led to the serious consideration of diamond coring the Weber sand. The first diamond coring at Randy was performed by Stanolind in August 1946 andl although we experienced some difficulties, the results definitely indicated that diamond coring would be successful at Rangely for .coring the Weber sand. As more wells were cored and the equipment improved somewhat, diamond coring became less expensive than drilling the Weber sand with the conventional rock bit. In less than one Year diamond coring has definitely Proved its usefulness in oil-field drilling operations in the Rocky Mountain area where formations quite often drill very hard. The practice of spot coring in hard oil-bearing formations with conventional coring equipment is giving way diaimond coring of the entire sections, thus givng an operator the complete picture.

Jan 1, 1948

By K. A. Johnson, F. H. Ellinger, C. C. Land

The Pu-In phase diagram has been determined by thevmal, filtvation, micrographic, and X-ray diffraction methods. This alloy system is characterized by 1) limited solubility of indium (-2 at. pet) in 6 and e plutonium, 2) one eutectic, and 3) fizte intermediate phases. Of the latter, PuIn and PuIn3 melt con-gruently, and Pu31n, Pu31n5, and the high-temperatuve 7 solid solution are formed peritectically. The n phase decomposes eutectoidally into Pu3In and PuIn at 865°C. Although the 6 phase can readily be retained to room temperature, it is not thermo-dynamically stable below 300°C. The Pu-In system has been investigated at Los Alamos as part of a study of the alloys of plutonium with the group 111-B elements. Constitutional studies of the Pu-A1 and Pu-Ga systems have been reported earlier.'9' To date, published information on the constitution of Pu-In alloys covers only the identification of the intermediate phases Pu3In and PuIn3.3,4 EXPERIMENTAL The alloys were prepared from five different lots of plutonium and three different lots of indium. The principal impurities in the plutonium differed from lot to lot within the following limits (in ppm): iron, 30 to 80; nickel, 30 to 60; aluminum, 15 to 30; silicon, 20 to 145: thorium, 50 to 300; carbon, 75 to 335; and oxygen, 20 to 135. Spectroanalysis of the indium showed that two of the lots were 99.9 wt pct pure, and the third was 99.98 wt pct pure. The alloys, in the form of about 5-g buttons, were prepared by arc melting in conventional equipment. The components for each alloy were weighed to the nearest 0.1 mg. In most instances the weight losses during melting were negligible; therefore confirmatory chemical analyses were usually not made. A few results are given in Table I. Density measurements of the arc-cast buttons were made by the liquid displacement of bromoben-zene. Heat treating was done in muffle furnaces controlled to +2°C. The alloy buttons were wrapped in tantalum foil before being enclosed in evacuated clear silica capsules. As a precaution against breakage, each capsule was in turn placed in a silica tube closed with a refractory wool plug prior to being charged into the furnace. For a moderately fast quench of the alloys, the outer protection tubes containing the capsules were plunged into cold water. Differential thermal analyses (DTA) in racuo were performed at heating and cooling rates of about 1.5°C per min. Tantalum crucibles having inverted thermocouple wells were used for most of the analyses. It was found micrographically, however, that the liquid alloys containing more than about 35 at. pct In reacted with the tantalum, resulting in contamination of the surface of the alloy. A search for a more satisfactory crucible material was not successful: tungsten and yttria behaved comparably to tantalum; thoria, vitrified magnesia, and vitrified alumina severely contaminated the alloys. So as to minimize the contamination by the crucible mater-

Jan 1, 1965

By R. W. Heckel

A method is described whereby the relationship of both the "at-pressure" powder compact density and the "zero-pressure" compact density to the applied pressure may be obtained from continuous measurements of punch movement during a single compaction operation. The rate of density increase with applied pressure for the metal powders is found to be proportional to the volume fraction of pores for pressures exceeding a lower limit which varies from 15,000 to 30,000 psi, depending on the powder. 1 HE compaction of powdered materials is carried out primarily to increase the density of the material. If the ultimate goal of the over-all process is the attainment of minimum porosity, compaction is responsible for most of the densification. For example, loose powdered metals have porosities of about 65 to 75 pct. Axial loading in a die or hydrostatic pressure may effectively reduce the porosity of most powders to 20 pct or lower with pressures of 50,000 psi and greater. The relationship between the density of a powder compact and the pressure needed to achieve that density is most commonly obtained by pressing several compacts, each at a different pressure. Measurement of the densities of the individual compacts when they are removed from the die then provides the density-pressure relationship. However, this method suffers from several disadvantages. Because a large number of compacts and pressing operations are required, it is inherently slow. Furthermore, since density measurements are made after the specimens are removed from the die, data obtained refer only to pressures greater than those necessary to form a coherent compact. The third disadvantage is the inability of this method to provide information about the compact density at the applied pressure in the die. Because the determination of density-pressure relationships has been a slow, tedious process, investigators have sought to express the compaction behavior of powders by other means. The general terms "comparability" and L'compressibility" have been used to rank powders qualitatively according to their compaction characteristics. To restore a quantitative nature to the subject and to prevent confusion, Schwarzkopf1 has proposed that compac-tibility be defined as the minimum pressure needed to produce a given green strength, while compressibility should be used to indicate the extent to which the density of a powder is increased by a given pressure. Probably the most widely used of the compaction parameters is the "compression ratio,'' which is generally defined as the ratio of the compact density obtained by pressing at a given pressure to the apparent density of the loose powder.2 However, the description of the compaction behavior of a powder by these parameters provides only limited information about the process because of their applicability to just one specific condition such as a given green strength or a given pressure. The method of obtaining density-pressure relationships which will be described in the present paper was designed to eliminate the shortcomings of the previous techniques while maintaining equivalent accuracy and precision. EXPERIMENTAL TECHNIQUES The general principle employed makes use of the fact that the linear movement of the punch during a

Jan 1, 1962

By F. E. Rizzo, L. R. Bidwell, D. F. Frank

THE poor high-temperature oxidation resistance of the refractory metals becomes an important problem as higher operating temperatures are sought. A meaningful analysis of their oxidation behavior requires a knowledge of the phases that can appear during oxidation as well as their relative stability. Although several extensive investigations have been carried out to obtain this information for the W-0 system,1-10 serious inconsistencies still remain. First, the standard free energies of formation (AG°) determined in recent studies which used the solid electrolyte galvanic cell technique6,7,9 differ significantly from those obtained primarily from gas equilibration measurements.1,3,4,10 The disagreement is especially large for the highest oxides. These data have been used to predict the decomposition temperatures of WO2. 72 and WO2.90.1 A considerable extrapolation is required, resulting in a large uncertainty in the decomposition temperatures. Second, Bousquet and perachon3 have presented convincing evidence, ob- tained by gas equilibration measurements, in support of the long-contested existence of W30. Phillips and chang,ll on the other hand, were not able to observe this phase under similar experimental conditions. The purposes of this work, which is part of a continuing investigation of the W-Mo system, were to resolve the discrepancies between the AGO measured by gas equilibration and solid electrolyte galvanic cell techniques, to extend the latter measurements to lower temperatures, to redetermine the WO2.72 and WO2.90 decomposition temperatures, and to apply the more sensitive electromotive-force method to the question of the existence of W3O. I) EXPERIMENTAL PROCEDURE The measurement of ?G° of reaction by the use of calcia-stabilized zirconia solid electrolyte galvanic cells has been described previously.12 The method is based on the measurement of the difference in chemical potential of oxygen between an electrode containing the two oxides of interest and a reference electrode of known oxygen activity. Two different types of cell holders were used in this study. The first type of apparatus has been described earlier." It consisted of two solid electrodes separated by a disc of electrolyte. Both electrodes were exposed to the same stream of purified helium. With this design a gaseous transport of oxygen between the two electrodes is possible. The second type of apparatus, which has also been described earlier,14 effectively separated the two electrode atmospheres. It utilized a closed-end impervious, calcia-stabilized zirconia tube that was open to the atmosphere. The tube served as an electrolyte for the cell and provided a means for separating the anode compartment, which was held under a static vacuum, from an air reference cathode. The cells and reactions of interest are described in Table I. High-purity tungsten metal was obtained from the Fansteel Metallurgical Corp. and the Allied Chemical Corp. Table II contains an analysis of each material. WO3 was prepared by oxidizing the metal in air at approximately 600°C in high-purity recrystallized alumina boats and by the dehydration of reagent-grade tungstic acid in alundum boats. The two methods of preparing WO3 resulted in slightly different purities.

Jan 1, 1968