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Discussion of the paper of J. C. Febles, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 79, July, 191.3, pp. 1267 to 1283. J. W. RICHARDS,. South Bethlehem, Pa. :-In looking at these precipitating launders the idea has come to me that the iron could probably be kept much cleaner if there were laid on the bottom of the . launders some sheet copper, with which the iron would be in contact, and as the solution passed over the tendency would he to precipitate the copper on the sheet copper and thus keep the iron cleaner than it is under present conditions. As soon as a piece of iron becomes coated with copper, its surface becomes inactive, and the presence of a sheet of copper in electrical contact with the iron would tend to precipitate the copper on the sheet copper and to keep the iron clean.

Jan 11, 1913

By J. S. Kennedy, G. L. Simard, A. A. Lefrew, C. M. Judson, R. B. Booth

DITHIOPHOSPHATE collectors are commonly used in the flotation of sulphide minerals. Studies of the interaction of a typical dithiophosphate collector with galena surfaces have been previously reported from these laboratories.'* These fundamental studies were carried out by employing phosphorus labeled radioactive dithiophosphate. Radioactivity determinations then could be used to measure readily and accurately the small concentrations of dithiophosphate that are present under conditions of flotation processes. Measurements were made on ground mineral, determining the amount sorbed indirectly from the concentrations in solution; and studies were also made with single crystals, determining the amount sorbed directly by counting the crystal surface. The rates, isotherms and reversibility characteristics of dithiophosphate sorption, the competition between phosphate and dithiophosphate for the mineral surface, and the exchange of sorbed dithiophosphate with dissolved dithiophosphate were studied. These studies have now been extended by sorption measurements in flotations with a Fagergren machine. For this work, the selective flotation of galena and sphalerite from quartz was chosen, using ammonium di-(sec-butyl) dithiophosphate as the collector, sodium cyanide as depressant for sphalerite, and copper sulphate as an activator for sphalerite. While the selective flotation of galena and sphalerite using a single dithiophosphate collector is not typical of flotation practice (two different collectors are generally used), it was found that a reasonably good separation could be obtained by using zinc sulphate with the sodium cyanide in the galena flotation and by cleaning the sphalerite concentrate or by carrying out the sphalerite flotation in an alkaline medium. Data of practical importance on the distribution of collector between the concentrates, tailings, and solutions were obtained, particularly with regard to the effect of copper sulphate and sodium cyanide. In addition to the selective flotation of galena and sphalerite from quartz, single flotations of galena-quartz and sphalerite-quartz mixtures were carried out, along with blank flotations on quartz alone. The present paper describes the results of these experiments. As in previous papers, the term sorption is used to designate uptake of collector by the mineral, without implication as to the nature of the processes involved. Experimental Materials: The mineral system was a ground synthetic mixture of galena, sphalerite, and quartz. The galena was from Galena, Kans., and contained 75 pct lead (theoretical 85.6 pct Pb for PbS); the sphalerite, from Ottowa County, Okla., contained 63 pct zinc (theoretical 67.2 pct Zn for ZnS); and the quartz from Klondike, Mo., analyzed as 99.97 pct SiO,. Sulphur labeled radioactive di-(sec-butyl) dithiophosphate was prepared from SS supplied by the Oak Ridge National Laboratory on allocation from the U. S. Atomic Energy Commission. The synthesis consisted of precipitating barium sulphate, reducing the barium sulphate to barium sulphide, acidifying to form hydrogen sulphide, and oxidizing the hydrogen sulphide with iodine to elemental sulphur.

Jan 1, 1953

By J. S. Kennedy, A. A. Lefrew, C. M. Judson, R. B. Booth, G. L. Simard

DITHIOPHOSPHATE collectors are commonly used in the flotation of sulphide minerals. Studies of the interaction of a typical dithiophosphate collector with galena surfaces have been previously reported from these laboratories.'* These fundamental studies were carried out by employing phosphorus labeled radioactive dithiophosphate. Radioactivity determinations then could be used to measure readily and accurately the small concentrations of dithiophosphate that are present under conditions of flotation processes. Measurements were made on ground mineral, determining the amount sorbed indirectly from the concentrations in solution; and studies were also made with single crystals, determining the amount sorbed directly by counting the crystal surface. The rates, isotherms and reversibility characteristics of dithiophosphate sorption, the competition between phosphate and dithiophosphate for the mineral surface, and the exchange of sorbed dithiophosphate with dissolved dithiophosphate were studied. These studies have now been extended by sorption measurements in flotations with a Fagergren machine. For this work, the selective flotation of galena and sphalerite from quartz was chosen, using ammonium di-(sec-butyl) dithiophosphate as the collector, sodium cyanide as depressant for sphalerite, and copper sulphate as an activator for sphalerite. While the selective flotation of galena and sphalerite using a single dithiophosphate collector is not typical of flotation practice (two different collectors are generally used), it was found that a reasonably good separation could be obtained by using zinc sulphate with the sodium cyanide in the galena flotation and by cleaning the sphalerite concentrate or by carrying out the sphalerite flotation in an alkaline medium. Data of practical importance on the distribution of collector between the concentrates, tailings, and solutions were obtained, particularly with regard to the effect of copper sulphate and sodium cyanide. In addition to the selective flotation of galena and sphalerite from quartz, single flotations of galena-quartz and sphalerite-quartz mixtures were carried out, along with blank flotations on quartz alone. The present paper describes the results of these experiments. As in previous papers, the term sorption is used to designate uptake of collector by the mineral, without implication as to the nature of the processes involved. Experimental Materials: The mineral system was a ground synthetic mixture of galena, sphalerite, and quartz. The galena was from Galena, Kans., and contained 75 pct lead (theoretical 85.6 pct Pb for PbS); the sphalerite, from Ottowa County, Okla., contained 63 pct zinc (theoretical 67.2 pct Zn for ZnS); and the quartz from Klondike, Mo., analyzed as 99.97 pct SiO,. Sulphur labeled radioactive di-(sec-butyl) dithiophosphate was prepared from SS supplied by the Oak Ridge National Laboratory on allocation from the U. S. Atomic Energy Commission. The synthesis consisted of precipitating barium sulphate, reducing the barium sulphate to barium sulphide, acidifying to form hydrogen sulphide, and oxidizing the hydrogen sulphide with iodine to elemental sulphur.

Jan 1, 1953

By B. N. Bose, M. F. Hawk

SINCE Davenport and Bain' introduced the isothermal transformation technique for the study of austenite decomposition in steels, a new field of investigation has opened up. Extensive research has been carried out on many different steels, but relatively little work has been done on eutectoid transformations in analogous alloy systems. The researches of Smith and Lindlief,² Mack,³ and Klier and Grymko²0 on the beta-phase transformation in copper-aluminum alloys, of Hibbard, Eichelrnan, and Saunders4 and Smith5 on the kappa-phase transformation in copper-silicon alloys, of Chaudron and Forester6 on the decomposition of "FeO," and of Wasserman7 on similarities between the iron-carbon, copper-aluminum, copper-tin, and copper-beryllium systems essentially comprise the field. The iron-nitrogen system, in view of its remarkable similarity to the iron-carbon system, is particularly attractive for the study of eutectoid decomposition. The present investigation is concerned with the study of isothermal transformation, proceeding by the familiar nucleation and growth processes, and of martensitic transformation characteristics of pure iron-nitrogen alloys. The kinetics of transformation and the morphology of the transformation products have been investigated, for these must be the factors determining the properties and behavior of the final product. The Iron-Nitrogen System he binary iron-nitrogen phase diagram has been a matter of considerable disagreement among vari01.1s investigators. However, the phase diagram according to Eisenhut and Kaupp8 and Lehrer10 is now considered essentially correct as reproduced in fig. 1. The important values, 2.35 pct nitrogen and 591°C, for the co-ordinates of the eutectoid point (obtained from this diagram and used in the re- search to be described) were confirmed in a concurrent study of Paranjpe, Cohen, Bever and Floe." The eutectoid decomposition involves the transformation of the ? face-centered cubic interstitial solid solution of nitrogen in iron to the a body-centered cubic interstitial solid solution of nitrogen in iron and the ?' nitride of iron. This nitride is essentially the compound Fe,N; it also possesses a face-centered cubic lattice but a considerably larger one than the ?; the nitrogen atoms in ?' are arranged in an ordered way in the centers of the unit cubes.8,10,11 A martensitic structure has also been reported8,12 in iron-nitrogen alloys and was studied in the research to be described here. Materials and Methods The specimens used in this investigation were prepared by nitriding "pure" iron. This iron was supplied by the Westinghouse Research Laboratories and is the product bearing their trade name "Puron"; it contains about 0.04 wt pct total impurities, the major portion of which is oxygen. Specimens were ribbons several inches long, a tenth of an inch wide, and 0.125 mm thick; this was the

Jan 1, 1951

INTRODUCTION This chapter summarizes porphyry copper deposits within the State of Alaska. Prospecting for porphyry copper-type deposits in Alaska germinated during the 1940's, grew slowly during the '50's, boomed during the '60's, and matured in the '70's. Although large expenditures have been made in the search for porphyry-type deposits, most accrued data lies dormant in company files. However, an adequate base exists in the literature for a general synthesis of areas that contain porphyry prospects. To simplify the summary, porphyry molybdenum deposits as defined by Clark (1972) are omitted. Description of deposits in their geologic setting permits some correlations between deposit characteristics and crustal environment. These correlations allow speculation about the genesis of the deposits. The summary also attempts to group deposits on the basis of general mineralogic characteristics because diorite model deposits are separated from quartz phenocryst-bearing hosts. Data presented in this chapter summarize observations by the author, published descriptions of specific areas and deposits as noted in the bibliography, and comments by various government geologists. E. M. MacKevett, Jr., D. H. Richter, and H. C. Berg of the US Geological Survey have been particularly helpful. Because few comprehensive descriptions of individual porphyry copper deposits exist for this area, much of the data presented is new to the literature. Details of structure, isotopic geochemistry, and petro- genesis for individual deposits are largely lacking and even the general geology of some belts is not well understood. Details on petrography of Alaskan porphyry copper occurrences are inadequate for construction of ternary diagrams (e.g., Figs. 36a, b, pp. 103, 104, for the northern Cordilleran orogen). Petrographic descriptions summarized in the text are largely from published descriptions whose sources are cited. Porphyry copper-type deposits in Alaska include deposits with pervasive pyrite that contain disseminated copper (but not necessarily coproduct molybdenum). Available data preclude differentiating the deposits by size. No Alaskan porphyry copper deposit is now in production but this is believed to be, in part, a function of economics. In some cases available geologic information is in- adequate for classifying deposits. Some de- posits included with porphyry copper may, with further exploration, be demonstrated to be some other genetic type. Alaska has three distinct porphyry copper provinces: the Hogatza plutonic belt, the Continental Margin belt, and the Interior belt. Each belt contains deposits with characteristic geologic features distinct from those of other belts. Fig. 24 shows the continental margin belt to extend inland from

Jan 1, 1978

By L. D. Fetterolf, G. T. Mahler, W. M. Peirce, R. K. Waring

Until recently, the only commercial method of producing magnesium has been fused salt electrolysis, despite a considerable amount of experimental work on the direct reduction of magnesium oxide. In this early work, a number of investigators demonstrated that magnesium oxide would react with any one of several reducing agents to produce magnesium vapor, but that the mixture of magnesium oxide and reducing agent must be heated to a high temperature even in a vacuum. In particular, it was demonstrated that silicon and aluminum are effective reducing agents and that when either of these is used the magnesium vapor can be condensed to massive metal. In spite of this knowledge, no successful commercial reduction process was developed, at least in this country, because of the operational difficulties imposed by the requirement of high temperature and vacuum and because of the high cost of the reducing agent. The outstanding experimental work done by Pidgeon, who carefully reviewed all of the known methods of making magnesium and then selected ferrosilicon reduction, overcame some of the operational difficulties. The process developed by Pidgeon comprises briquetting a mixture of calcined dolomite and reducing agent, preheating the briquets to about 600°C. in an externally heated alloy retort, reducing the MgO with silicon in an evacuated horizontal alloy retort heated externally to about II50 C., and condensing the magnesium vapor to a solid in a cold extension of the retort projecting beyond the front of the furnace. A major advantage of Pidgeon's process is that the retort is not cooled down between charges. Earlier investigators had used apparatus that necessitated cooling and reheating of the retort between charges. Early in January 1942, when the War Production Board was considering the Pidgeon process for quickly increasing the production of magnesium, The New Jersey Zinc Co. offered to have a research investigation of the process carried on, with the hope of assisting in its further development. This offer was accepted, and a two-retort pilot plant was built at Palmerton and put in operation on Jan. 29,1942. An intensive investigation of certain phases of the process was carried out in the ensuing four months. This investigation was completed in the last part of May 1942) and the pilot plant was then shut down. Subsequently, The New Jersey Zinc Co. was requested to have further development work done on the process, and a more extensive investigation was undertaken in August 1942 under contract with the War Production Board and under the supervision of the War Metallurgy Committee. This paper describes the ,phases of the investigation that are thought to be of sufficient general interest to merit publication.

Jan 1, 1944

By Michel T. Halbouty

South Texas, one of the world's important oil and gas-producing areas, continued to hold interest during 1939 as another scries of new fields and new producing levels was developed within its boundaries at a fairly continuous rate throughout the year. There were 1801 wells drilled in this area in 1939, compared to 1678 in 1938; of these, 1515 were drilled in established fields, or as extensions to proven areas (semi-wildcat), and 286 were drilled as rank wildcats, in search of new production. Among these rank wildcats, 22 produced oil, 7 produced distillate and gas and 257 were abandoned as dry holes (see Table 5). Of the 1515 field and cxtension wells, 1213 produced oil, or distillate and gas, 50 produced only gas and 252 were dry; 38 found new productive sand levels in proven ficlds. Jim Wells County led this district in discoveries, having had 9 new fields arid 9 new productive sands found within its border during 1939. Most activc of the 1939 discoveries were Reynold?; and Ben Bolt fields in Jim Wells County and Minnie Bock field in Nueccs County; among producing fields the most activc were: East White Point and Aransas Pass (McCampbell). Production from South Texas in 1939 totaled 55,105,506 bbl. against a total of 56,152,122 bbl. produced in 1938. South Texas should continue its present rate of developrnent and exploration and this should result in the discovery of many fields in its numerous oil-bearing zones, and should also lead to more knowledge of the possibilities of its deeper horizons, such as the Mt. Selman and Wilcox formations; with the latter holding particular interest at the present time. Tide Water Associated Oil Company's A. M. Bruni No. I, Cole-Bruni field, Webb County, the deepest well drilled along the Mirando trend, was carried to 8959 ft., where it started to blow out from a Wilcox sand topped at 8954 ft., making gas, distillate and mud under heavy pressure. After the well was killed, drill stem beeame stuck and was cemented in place in order to test a Queen City (Mt. Selman) sand logged from 5620 to 5675 ft. This and other shows found in other wells along this trend, but out of this district, have served to increase the importance of this but little explored Sparta-Wilcox trend of South Texas during the year, and more activity along it is to be expected in the near future.

Jan 1, 1940

By Michel T. Halbouty

South Texas, one of the world's important oil and gas-producing areas, continued to hold interest during 1939 as another scries of new fields and new producing levels was developed within its boundaries at a fairly continuous rate throughout the year. There were 1801 wells drilled in this area in 1939, compared to 1678 in 1938; of these, 1515 were drilled in established fields, or as extensions to proven areas (semi-wildcat), and 286 were drilled as rank wildcats, in search of new production. Among these rank wildcats, 22 produced oil, 7 produced distillate and gas and 257 were abandoned as dry holes (see Table 5). Of the 1515 field and cxtension wells, 1213 produced oil, or distillate and gas, 50 produced only gas and 252 were dry; 38 found new productive sand levels in proven ficlds. Jim Wells County led this district in discoveries, having had 9 new fields arid 9 new productive sands found within its border during 1939. Most activc of the 1939 discoveries were Reynold?; and Ben Bolt fields in Jim Wells County and Minnie Bock field in Nueccs County; among producing fields the most activc were: East White Point and Aransas Pass (McCampbell). Production from South Texas in 1939 totaled 55,105,506 bbl. against a total of 56,152,122 bbl. produced in 1938. South Texas should continue its present rate of developrnent and exploration and this should result in the discovery of many fields in its numerous oil-bearing zones, and should also lead to more knowledge of the possibilities of its deeper horizons, such as the Mt. Selman and Wilcox formations; with the latter holding particular interest at the present time. Tide Water Associated Oil Company's A. M. Bruni No. I, Cole-Bruni field, Webb County, the deepest well drilled along the Mirando trend, was carried to 8959 ft., where it started to blow out from a Wilcox sand topped at 8954 ft., making gas, distillate and mud under heavy pressure. After the well was killed, drill stem beeame stuck and was cemented in place in order to test a Queen City (Mt. Selman) sand logged from 5620 to 5675 ft. This and other shows found in other wells along this trend, but out of this district, have served to increase the importance of this but little explored Sparta-Wilcox trend of South Texas during the year, and more activity along it is to be expected in the near future.

Jan 1, 1940

By Frank C. Appleyard

Gypsum, the dihydrate form of calcium sulfate, has a history of usefulness to man dating back several thousand years, and a worldwide industry has been built on the mining and processing of this versatile industrial mineral. However, anhydrite, the other principal calcium sulfate mineral has very limited use, so much so that separate statistics for it are not always kept, but are usually included with those for gypsum. Although often found in close association, the two minerals have important chemical differences in that anhydrite is the anhydrous form of calcium sulfate (CaSO,) whereas gypsum is the dihydrate (CAS0;2H20). These two molecules of combined water result in significant differences in hardness, density, and solubility of the two minerals. However, of most importance is the difference in thermal properties wherein gypsum, upon the application of a modest amount of heat, can be converted to the hemihydrate of calcium sulfate (CaS0;Vi H,O) or plaster of paris, an intermediate product upon which is based over 90% of the value of all calcium sulfate end products. Anhydrite, on the other hand, is inert at these temperatures and its uses have been limited to only those few cases where calcium sulfate in the anhydrous form may have an advantage. The earliest known use of gypsum plaster dates back some 5000 years to the time of the Pharaohs of Egypt who had discovered that gypsum rock, when exposed to fire, broke down into a powder which when mixed with water would form a putty that could be "plastered" on a rough mud brick or stone wall to make a smooth finish. It was used down through the centuries in a limited way for ornamental purposes, but did not achieve wide acceptance because of its quick (25 to 30 min) setting or hardening time which made it difficult to use. The first real understanding of gypsum chemistry was developed in France about 1755, and the gradual growth of its present utilization dates from that time. In the United States, the first utilization of gypsum was to grind it to a fine material for use as a soil conditioner at about the time of the Revolutionary War, and the term "land plaster" for ground gypsum has remained in use. Another cementituous material-lime or calcium oxide-had become the usual plastering material, but by about 1870 a method for retarding the set of gypsum plaster was discovered and it has today almost completely replaced lime as a plastering material. In recent years, gypsum products sold in the United States have reached a total valuation of approximately $500 million per year as illustrated in [Table 1].

Jan 1, 1975

By Forrest F. Craig

Both early and more recent1 laboratory measurements of gas-oil relative permeabilities were made by subjecting oil-saturated cores to external gas drives. In these runs it was generally assumed that the flowing gas/oil ratio was constant at every point throughout the core. Using this assumption, the resulting equation for the gas-oil relative permeability ratio becomes A where Q is the flow rate at the producing end of the system. This relative permeability was then specified for the average saturation of the core. The assumption and resulting equation fail to recognize that in an external drive, the oil flow rate varies from zero at the injection end to a maximum at the producing end. The assumption also fails to consider the existence of a saturation gradient during an external drive. This saturation gradient is due solely to non-steady-state flow. Some authors2,3,4 have used this erroneous method of calculating relative permeability ratios from external drives. Other authors5,6,7 have used relative permeability ratios in calculating expected field performance by external drive, using Equation (1) and making the incorrect assumption that the saturation is uniform within the driven portion of the reservoir. To find the correct relation between the relative permeability. ratio at the average saturation and the produced gas/oil ratio, the insertion in Equation (1) of a factor, F, to adjust it for oil velocity gradient has been considered. The equation then takes the form Assuming that the oil velocity is directly proportional to the distance from the injection point leads to the conclusion that, for a linear system, the average oil velocity is one-half that at the producing end. Thus, the average gas/oil ratio is twice the produced gas/oil ratio, and Equation (2) is transformed into However, here again the existence of a saturation gradient is not recognized. The produced gas/oil ratio is related to the relative permeability ratio at the saturation of the outlet end of the system. It can be shown quite readily that, if the true log k,/k, saturation relationship is linear over small ranges of saturation, then d log kjko Where aaxv and u2 are the average and outlet saturations, respectively. Examination of Equation (3) shows that the factor F cannot have a single value over the whole saturation range. Another method of dealing with external drives is that of Buckley and Leverett.' Their method, which assumes no gas expansion and outlet end effects, considers fully the saturation gradient present due solely to the displacement mechanism during an external drive, and applies Equation (1) to each point along this gradient. The calculation of production history using relative permeability ratio is straightforward. However, the calculation of relative permeability ratios from production history by this method is impractical. In a recent paper, Welge,1 using an approach similar to that of Buckley and Leverett, presents a simplified method for determining the saturation at the producing end of the system. At thi; saturation, the relative permeability ratio calculated by Equation (1) applies exactly, after breakthrough of the stabilizej front. By this method, relative permeability ratios or production history may be calculated with equal ease. Use of this method as a laboratory tool in determination of relative permeability ratios by external drive requires the knowledge of the total injected fluid volume; in addition to the average saturation and producing ratio. As a preliminary test of this method of calculation, laborntory external gas drives were run on a 3% in. diameter, 11 in. long sample of Nellie Bly consolidated sandstone. This core sample had a permeability of 824 md and a porosity of 28.1 per cent. The driving fluid was air. Three different oils were used, having viscosities of 1.4, 9.8, and 125 cp, respectively. The runs were made under identical pressure differentials,

Jan 1, 1952

By L. C. Brown, A. J. Stewart

Phase transformations have been studied in Ag-Zn alloys quenched from the high-temperature bcc 0 phase and lying in the composition range 37.4 to 50.0 at. pct Zn. On quenching, the alloy with the lowest zinc content transformed to massive a (fcc); all other alloys formed the ordered (3' phase. On deformation, a martensitic reaction took place forming a close-packed structure. At Lou' zinc contents transformation to this structure was complete. However, above 43 at. pct Zn a p.rogressively increasing amount of ß' was retained following deformation. The close-packed structure was fcc at lower zinc contents (under 47 at. pct Zn) and either hcp or a mixture of fcc and hcp at high zinc concentrations. The structures produced by cold working were unstable and on aging transformed to the ß' phase or the complex hexagonal to phase. For low zinc contents (under 43 at. pct) the fcc st-ructure transformed directly to the equilibrium To phase. With higher zinc contents, some 13' was retained following defownation, and on aging the amount of this phase relative to the close-packed structure increased. On further aging both structures transformed cornpletely to PO. Metallographic examination indicated that the nature of the deformation product depended very markedly on the mode of deformation. Tensile deformation gave a microstructure characteristic of thermal martensite. KING and Massalski1 have shown that an alloy of Ag-50 at. pct Zn quenched from the high-temperature bcc ß phase undergoes a low-temperature ordering reaction forming ß' which can be retained to room temperature. On deformation an hcp phase is produced, although this is unstable and the structure reverts completely to ß' on aging. In the present paper, the work of King and Massalski is extended to cover a wide composition range in the p phase, observations being made of the structure of the quenched 13 and of the effects of deformation and aging. The relevant portion of the Ag-Zn phase diagram is shown in Fig. 1. King and Massalski have shown that close to stoichiometry the ß' phase is the equilibrium structure at low temperatures. The approximate composition range of this phase, taken from a recent paper by Pops and Massalski,3 is shown on the phase diagram. The locations of atom sites are very similar in the ß' and to structures, and the 4, structure can be derived from the 0' structure by a small movement of atoms mainly in the direction of the cube diagonal.4'5 However, the probability of filling any particular atom site by a silver or a zinc atom is markedly different in the two structures. The structure can be considered partly ordered but the arrangement of the ordered atoms is completely different from that in the p' structure and transformation from ß' to requires a large fraction of the atoms to change position. It has been shown that the ß' transformation is thermally activated involving normal nucleation and growth processes.5,8 Massalski and Barrett7 have shown that in the Cu-Zn binary the (3 phase can be retained in the ordered state to room temperature over a wide composition range. On deformation a new close-packed phase is produced, the structure varying from fcc to a mixture of fcc + hcp to hcp alone with increasing zinc concentration. It appears that an ordering reaction is necessary to retain the bcc phase to room temperature. In CU-Ga,8 the bcc phase cannot be retained to low temperatures as it transforms by a massive reaction above the ordering temperature of the ß phase. The structure of the massive phase is very similar to that in Cu-Zn, varying from fcc to fcc + hcp to hcp with increasing zinc concentration. Similar structures have also been observed in CU-A1,9 Ag-Cd,10,11 and Ag-Al.12 EXPERIMENTAL The alloys were prepared by melting fine silver (99.99 pct purity) and electrolytic zinc (99.999 pct

Jan 1, 1969

By C. R. St. John, R. W. Lindsay, Charles R. Austin

Many of the factors influencing the creep behavior of ferrous alloys have been investigated and reported upon in the literature, including such variables as grain size, steelmaking practice, nature and stability of the microstructure, and the effect of alloying elements in steels. However, with respect to the latter, the microstructures involved are usually heterogeneous and as a result the effect of the addition is related to its effects on the various phases present in the microstructure. In the instances where this structure consists of ferrite and carbide, the behavior of the alloy addition will be related to its action in strengthening ferrite and in opposing temperature softening of ferrite as well as coalescence of carbide. The present paper is the third in a series comprising a comprehensive review of investigations on the properties of iron binary alloys.l,2 Its purpose is to describe the results of isolating one microstructural phase, namely ferrite, and studying its creep characteristics in both the unalloyed and alloyed conditions. This should aid in establishing to a large degree the importance of ferrite in the creep behavior of steels consisting of the previously mentioned ferrite-carbide aggregate. In view of the fact that the present investigation deals only with the effects of silicon, manganese, chromium, molybdenum, nickel, and cobalt, and to a certain extent with the effects of carbon, the review of previous literature will be confined to these elements. Practically no references were encountered dealing with the influence of these elements on the creep characteristics of the isolated phase. However, various contributions have dealt with the creep behavior of low-carbon steels alloyed with the elements under consideration. A particularly concise review in this respect is given by Bullens (Battelle)= and much of this material has been drawn upon. The definite improvement in creep resistance and high-temperature strength conferred by molybdenum is well known. Published suggestions by the A.S.M.E.4 permit of an increase of some 2000 to 5000 lb. per sq. in. in permissible design loads over a temperature range from 650" to IOOO °F. as a consequence of additions of 0.40 to 0.60 per cent of this element in carbon steels of the order of 0.25 to 0.35 per cent carbon content. Babcock and Wilcox Tube CO.5 has published data showing the pronounced increase in stress necessary to cause one per cent creep per 10,000 hr. when additions of 0.5 or I per cent molybdenum are made to a plain carbon steel. These data apply to temperatures over a range from 800° to1000°F. 4

Jan 1, 1945

By R. P. Smith

Iron-carbon alloys containing a single-phase austenite region and a two-phase azcstenite + cementite region at the desired temperature were prepared by partial carburization of iron or partial decarburization of carburized iron. Each sample was held at a fixed temperature until equilibrium was achieved. Analysis of the austenite for carbon then gave the solubility of cementite in austenite. Solubility measzcrements were made for the temperature range 734° to 1012°C. These values together with other data give 7560 cal for the mean heat of solution of cementite in austenite, and 0.765 pct C for the eutectoid composition of austenite. They also indicate that graphite is the stable phase at all temperatures between the eutectoid and eutectic temperature. Measurements of the solubility of cementite in austenite at 927oand 1011 "C, using a method based on the equilibration of iron with boro-cementites, are reported. The solubility of cementite in austenite (?-iron) has been computed by Darken and Gurry1 from the observed solubility of graphite in austenite, and the thermodynamic properties of pure iron and of iron-carbon alloys. They have shown that the solubility of cementite is greater than that of graphite in the temperature range between the eutectoid and eutectic, and thus that cementite is metastable with respect to graphite and austenite saturated therewith. Since their computation is not in accord with the earlier experimental work of Mehl and wells,' the present direct determination of the solubility of cementite in austenite was undertaken. EXPERIMENTAL PROCEDURE Each iron rod about 1/2 in. O.D. by 4 in. was first carburized at a temperature and with a H2-CH4 gas mixture such that the carbon content would be greater than that corresponding to the solubility of cementite in austenite at the desired (lower) temperature; sufficient carburizing time was allowed that the carbon content became substantially uniform, as illustrated by Curve A, Fig. 1. The sample was then partially decarburized with a hydrogen-water vapor mixture, giving a carbon distribution as schematically illustrated by Curve B. The sample was then held in a helium atmosphere at the temperature at which the solubility was to be determined until the decarburized portion of the sample came to equilibrium with that containing cementite. Curve C of Fig. 1 represents schematically the final carbon distribution; the horizontal portion corresponds to the carbon content of austenite saturated with cementite. To bring the sample to room temperature without change in the carbon distribution and in machinable condition, it was first quenched in a salt pot at 480°C, then in water at room temperature. Successive layers were machined from the center 2 in. of the sample and analyzed for carbon by the usual

Jan 1, 1960

By H. Le Chatelier

An evident connection exists between chemical and calorific phenomena: the most important, of our sources of heat, the combustion of coal, is nothing else than a chemical reaction. Not satisfied with this indefinite statement, investigators have attempted to establish a more precise correlation between these two orders of phenomena, and have questioned whether there be not a necessary connection between the possibility of a chemical reaction and the algebraic sign of the quantity of heat which it would call into play (i.e., liberate or absorb). This question possesses the highest interest for metallurgical chemists. But the study of it by experimental methods only could not completely elucidate it. To arrive at a definite solution, it was necessary to appeal to a science much more general than chemistry,—namely, that of energetics, which embraces all the physical sciences. We can place absolute confidence in its conclusions, because they rest upon a proposition which can scarcely be denied, namely, the impossibility of The main facts in the history of the development o‡ this field of Triassic coals have been already set before the Institute in the papers of Mr. Oswald J. Heinrich, a former member of the Institute and the superintendent of the mines at Midlothian. † From these and other references to the field, it appears that coal was known to exist here as early as 1701; for on the 10th of May that year Colonel Byrd reported to the Colonial Council of Virginia the discovery of coal. Coal was mined from 1770 to 1780; but the amount shipped is unknown. It was much used in Richmond at this early date for gratefires. In 1789 shipments were made to northern ports. During the first half of the century just passed, mining operations attained in this field their greatest development, the number and extent of the collieries and the tonnage of coal raised per annum being greater for that period than for any similar period since. The maximum annual output exceeded 100,000 tons, while in two years only since the Civil War has the amount of coal raised exceeded 50,000 tons. This field covers about 150 sq. in. Its outline and the position of the strata in which the coal-outcrops occur are shown on the accompanying map, reproduced from the latest survey by the U. S. Geological Survey. Mining has been carried on along the margins of the area, often in the primitive manner in vogue at the beginning of operations, by means of shafts and slopes, usually too small in cross-section to permit the proper working of the beds. Most of the output has been won from

Jan 1, 1902

By J. C. McCarthy, J. B. Stone

AT Fresnillo a series of veins that has yielded very large quantities of silver and other metals has been developed over a length of 6500 ft. and to a depth of over 3000 ft. In the course of this work striking changes in the mineralogy and metal content of the principal veins have been disclosed and are well illustrated by assay data and ore reserve calculations. This paper describes those changes and suggests their bearing on theories of ore deposition. LOCATION The Fresnillo mines and the adjacent city of Fresnillo are in the central part of the state of Zacatecas, 35 miles northwest of the capitol city of Zacatecas, once a great silver-mining center whose total production is said to place it fourth in the world. Another famous old silver district, Sombrerete, lies northwest of Fresnillo. Fresnillo is connected by a 5-mile branch with Fresnillo station on the Mexican National Railways line from Juarez to Mexico City. Lying near the southwestern edge of the central plateau of Mexico, Fresnillo is surrounded by a semi-arid rolling plain from which rise widely scattered low hills. One of these is Proano hill, an inconspicuous elevation rising barely 300 ft. above the plain, but in and around Proa[n]o hill are the Fresnillo mines, and it is marked now by a great gash cut by gloryhole mining. HISTORY According to an account written in 1834 by Francisco García, then Governor of the state of Zacatecas, Fresnillo was discovered in 1554, and a presidio was established there in 1568 to protect travelers on the road between Zacatecas and Sombrerete. Little is known of the earliest mining at Fresnillo. which seemingly began soon after its discovery, but by piecing together various accounts, it appears that mines there were working in 1717 and were notable active in 1751 under an administrator named Murguía, who left detailed notes describing them. In 1757, however, the mines became inactive because of difficulties with creditors and no doubt also because of increasing water troubles, and they remained abandoned until 1830. In 1830 the mines at Fresnillo became the property of the State of Zacatecas because the interest of Governor García had been aroused by the long disregarded notes of Murguía. Under Garcia's energetic leadership the mines were reopened, and silver production began in 1832 in spite of serious difficulties, including abnormal rains and an epidemic of cholera. In 1833 English capital was sought to allow installation of steam-driven Cornish pumps at the two principal shafts and to build the great hacienda de benefacio (the present Proano hacienda). The company formed in 1835 (Cia. Zacatecano-Mexicana) operated successfully until 1872, when its career was brought to an end by the political and economic disturbances

Jan 1, 1942

By J. S. Kennedy, A. A. Lerew, C. M. Judson, G. L. Simard

DITHIOPHOSPHATE collectors are commonly used in the flotation of sulphide minerals. Studies of the interaction of a typical dithiophosphate collector with galena surfaces have been previously reported from. these laboratories." These fundamental studies were carried out by employing phosphorus labeled radioactive dithiophosphate. Radioactivity determinations then could be used to measure readily and accurately the small concentrations of dithiophosphate that, are present under conditions of flotation processes. Measurements were made on ground mineral, determining the amount sorbed indirectly from the concentrations in solution; and studies were also made with single crystals, determining the amount sorbed directly by counting the crystal surface. The rates, isotherms and reversibility characteristics of dithiophosphate sorption, the competition between phosphate and dithiophosphate for the mineral surface, and the exchange of sorbed dithiophosphate with dissolved dithiophosphate were studied. These studies have now been extended by sorption measurements in flotations with a Fagergren, machine. For this work, the selective flotation of galena and sphalerite from quartz was chosen, using ammonium di-(sec-butyl) dithiophosphate as. the collector, sodium cyanide as depressant for sphalerite, and copper sulphate as an activator for sphalerite. While the selective flotation of galena and sphalerite using a single dithiophosphate collector is not typical of flotation practice (two different collectors are generally used), it was found that a reasonably good separation could be obtained by using zinc sulphate with the sodium cyanide in the galena flotation and by cleaning the sphalerite concentrate or by carrying out the sphalerite. flotation in an alkaline medium. Data of practical importance on the distribution of collector between the concentrates, tailings, and solutions were obtained, particularly with regard to the effect of copper sulphate and sodium cyanide. In addition to the. selective flotation of galena and sphalerite from quartz, single flotations of galena-quartz and sphalerite-quartz mixtures were carried out, along with blank flotations on quartz alone. The present paper describes the results of these experiments. As in previous papers, the term sorption is used to designate uptake of collector by the mineral, without implication as to the nature of the processes involved. Experimental Materials: The mineral system was a ground synthetic mixture of galena, sphalerite, and quartz. The galena was from Galena, Kans., and contained 75 pct lead (theoretical 85.6 pct Pb for PbS); the sphalerite, from Ottowa County, Okla., contained 63 pct zinc (theoretical 67.2 pet Zn for ZnS) ; and the quartz from Klondike, Mo., analyzed as 99.97 pet SiO2. Sulphur labeled radioactive di-(sec-butyl) dithiophosphate was prepared from S82 supplied by the Oak Ridge National Laboratory on allocation from the U. S. Atomic Energy Commission. The synthesis consisted of precipitating barium sulphate, reducing the barium sulphate to barium sulphide, acidifying to form hydrogen sulphide, and oxidizing the hydrogen sulphide with iodine to elemental sulphur.

Jan 1, 1952

By Blake M. Loring, Robert A. Colton

MELTING procedures for most metals and alloys usually include some provision for the control of oxygen, since this element frequently has some undesirable effect on the properties of the metal or alloy concerned. In the melting of the various bronzes, this is especially true, since oxygen can be introduced into the melt in a number of ways, most of which are difficult to control. In making bronzes from virgin materials, oxygen is usually present in the commercial grades of copper used; electrolytic he refined copper ingots usually contain from 0.02 to 0.05 per cent oxygen. When ingot metal or scrap bronze is used in the charge, oxides are almost always present to some degree. Under certain melting conditions and in certain types of melting equipment the atmosphere over the metal may be highly oxidizing. This, of course, may be desirable in the melting practice used, but is certain to introduce appreciable amounts of oxygen into the melt, and that may not be entirely desirable. From the foundry viewpoint oxygen may have several harmful effects on bronzes. The formation of excessive amounts of oxides may produce drossy metal, which, in turn, means dirty castings and a potentially high rejection rate. It is claimed, too, that oxides in the metal may combine with hydrogen to form steam and thereby produce porosity in certain of the bronzes. The presence of certain refractory oxides, such as SnO2, may be undesirable from the viewpoint of making machining difficult, or as possible stress-raisers in the metal matrix. It is often said that excessive oxide present in the liquid metal makes the metal run sluggishly. Since it appears impractical to try to control the amount of oxygen introduced into the metal beyond taking the economical limit of precaution about charging dirty scrap, it would seem that control of the oxygen content of the liquid metal offers the most promising approach to this problem. This might be done by using slags, or covers, or by the use of some element or compound added to the melt to remove oxygen preferentially. Most aspects of this problem have been considered and considerable work has been done along these lines. A reconsideration of the problem is indicated, however, by the controversial nature of the evidence at hand, especially on the possibility of using a chemical deoxidizer to control the oxygen content of bronzes. CHOICE OF DEOXIDIZER The choice of the chemical agent selected as a deoxidizer would naturally depend first on the alloy in which it is to be used; in this particular case the alloy is Navy gun metal. In Table I are listed a group of elements that might be considered as

Jan 1, 1946

By W. T. Isbell, Carleton C. Long

Zinc recovery from lead blast-furnace slags has heretofore been an indirect process, involving, first, the fuming off and collecting of an impure zinc oxide, and second, the reduction of the zinc portion of this oxide to metal either by electrolytic or pyrolytic means. (In a variation of this process, blue powder is the intermediate product rather than zinc oxide fume.) In 1940, W. T. Isbell proposed that molten slag from the lead blast furnace or stock-pile slag melted down in a blast or cupola-type furnace be charged directly into an airtight container (i.e., furnace) provided with means to heat further the slag by passage of electric current and means to introduce the carbon (coke) necessary to reduce the ZnO constituent of the slag to zinc as a zinc vapor and CO. He also proposed that the zinc vapors so obtained be condensed in a Weaton-Najariant internal condenser directly connected to the proposed furnace. It was thought that the Weaton-Najarian condenser could liquefy zinc vapor from lean mixtures of vapor and noncondensable gases. Such condensers have been in commercial use! since 1936 at Josephtown smelter, where the source of zinc vapor is a column of coke and zinc-bearing sinter electrically heated (charge resistor). Condenser output when supplied with vapor-gas mixtures containing approximately 45 per cent zinc and 55 per cent noncondensable gases, varies from 18 to 30 tons of slab zinc per day per condenser, depending upon the heat-transfer area (length) of the condenser and the volume of vapor (furnace size) fed to it. Lead-smelting operations at the St. Joseph Lead Company's plant at Hercu-laneum, Mo., produce a slag containing 12 to 16 per cent zinc. For several years this slag has been stock-piled with the object of recovering the zinc values if and when a commercial method was invented. Evaluation of the possibilities of the proposed method was made by pilot-plant operation at Josephtown. The first plant, designed in 1940 and operated in early 1941, consisted of a single-phase, two-electrode furnace. The evolved vapors were burned. Electrical characteiistics of the molten slag, power requirements, coke requirements, and extent of zinc elimination indicated the feasibility of the proposed method. In the latter part of 1941 a second pilot furnace was constructed, to which "was attached a small (6 ft. long) Weaton-Najarian condenser in order to develop an over-all picture of zinc-in-slag to zinc-in-slabs. This furnace was operated in the early part of 1942 and yielded such promising results that a decision was made to design- and construct a commercial furnace. Feed for the pilot-plant furnaces was granulated slag. A suitable deduction (300 to 350 kw-hr. per ton slag) was calculated in estimating power require-

Jan 1, 1944

By Edward L. Fidler, Thomas E. Finch

Thin seam coal mining in the western US nominally equates to recovery of stray seams associated with thicker, major seams. The thin or stray seams encountered are generally recovered, but not in all cases. The alternative to extraction is, of course, spoiling. The majority of thin seams are encountered somewhere in the overburden above the major seam or in the parting between thick seams. Although some are true strays and appear anywhere in the geologic sequence, others might be classified as thin "rider" seams immediately above or below a thick seam and separated by some equally thin parting. For the purpose of this discussion, stray or thin seams are defined as those which are less than 1.2 m thick or represent less than 10% of the expected extractable coal. [Figure 1] is a graphic representation of typical thin, stray, or rider seams which actually appear in a western operation. Operationally, stray seams create irritating scheduling problems and require special handling techniques which do not always lead to efficient equipment utilization. Additionally, coal recovery from a thin seam is considerably less than the 95% usually recovered from thick seams. Higher recovery in thin seams leads to dilution problems, which depreciates Btu quality, and most western coals are not in a position to lose heating value. Thin western seams also undulate and pinch or swell more than thick seams, and this leads to more difficult recovery. Often they are associated with equally dark carbonaceous shales and visual selectivity is difficult at best during daylight hours. Resource Recovery Regulations Thin seam recovery in western mines is encouraged by both federal and state regulations and by the mining industry's concern for total resource recovery. [Table 1] lists the western coal states and their recovery regulations. The federal regulations are found in the Surface Mining Control and Reclamation Act of 1977. They state, "General performance standards shall . . . require the operation as a minimum to … conduct the surface coal mining operations so as to maximize the utilization and conservation of the solid fuel resource being recovered." Economic stimulation for thin seam recovery appears to be marginal or at the least controversial. Scheduling and operational problems often outweigh the nebulous profits created by engineering analysis. The only alternative to extracting thin seams occurring above major production seams is to strip directly through them and lose the resource to the spoil pile. Although this is not palatable to environmental emotions or resource promoters, it is the most simple expedient to operations people.

Jan 1, 1981

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

Numerous investigations of the effects of the various impurities common to commercial coppers have been published, and the data have found wide use in industry. Naturally, emphasis has been placed on the oxygen-bearing coppers of the tough-pitch variety, but need is now evident for data covering the oxygen-free condition as well. Furthermore, relatively few of the important reactions between oxygen and the various impurities are well understood, and often the data at hand are not applicable to the low concentrations encountered in commercial coppers. This paper presents the changes in conductivity and softening temperature derived from individual additions of the group VIII triad, iron, cobalt and nickel, to high-purity copper, and constitutes a portion of the copper-research program being conducted at the Central Research Laboratory of the American Smelting and Refining Co. The method of preparation of high-purity copper and its alloys in either the oxygen-free or oxygen-bearing form has been described previous1y.l The purity of this material, and the methods developed to produce it, provide the means for direct investigation of the very low concentration range in which the various impurities generally exist in commercial coppers. The usual necessity for extrapolation to this range using the results obtained from higher concentrations, and the interfering effects of extraneous impurities, are thus simultaneously circumvented. Since previously published data have adequately presented the effects of higher concentrations of iron, cobalt and nickel, the present investigation has been confined to the composition range o to 0.05 per cent. All alloys were initially prepared in the form of oxygen-free continuous cast rod, the weighed alloying additions in suitable form being charged with the pure copper to the continuous casting crucible. The best of the available high-purity alloying materials were used, and spectrographic analyses confirmed the absence of interfering elements from the alloys formed. Each series was compounded in the direction of increasing concentration, starting with pure copper in a new crucible and finishing with the 0.05 per cent alloy. Composition was closely controlled by adding the alloying element in the form of a carefully compounded and analyzed master alloy rendered uniform by continuous casting. The accuracy of this method of synihesis was proved by chemical analysis of the more concentrated alloys, and, accordingly, there is every reason to credit the stated composition of the very dilute alloys in the range where chemical analysis becomes highly uncertain. Oxygen-free samples for measurements of conductivity and softening temperature Were obtained by drawing the continuous cast rod to wire of 0.08I-in. diameter. employing a number of intermediate anneals to refine the grain structure. The

Jan 1, 1942