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By C. Ernest Birchenall

AS a basis for further progress in several branches of metallurgy, particularly the study of physical properties of solid solutions and the kinetics of solid-solid reactions, a more complete understanding of the structure of solid solutions and the nature of the metallic bond is- necessary. Any investigation contributing to this understanding should be of primary interest to the metallurgist. Since the metallic bond is characteristic of an assemblage of atoms, it can be studied only where this assemblage exists. One of the most promising approaches to this study of the interactions in metals is through the general problem of binary metallic solutions. Although crystal structures of many solid metallic solutions have been determined and solubility limits for many systems are given in phase diagram studies, progress beyond this is irregular. Electromotive force and vapor pressure determinations have provided thermodynamic activity data for small concentration and temperature ranges in the amalgams and a few other systems.' In two systems, however, copper-zinc and iron-carbon, data are available for the calculation of activities over wide ranges of temperature and concentration. This activity data for the brass system is summarized in the preceding paper.= A detailed study of the solubility and distribution of carbon in iron is given by Smith and Darken.3 Their treatment of interaction energies is applicable only to dilute interstitial solutions. The objectives here will be to derive from activity gats given in the previous paper for the brasses and structural considerations as much new and detailed information as possible about the interactions between copper and zinc in metallic solid solution and the effect of these interactions in determining the short range structure of the equilibrium phases; that is, we shall investigate the energy of interaction between pairs of atoms of the same and different kinds, the deviations of the distribution of nearest neighbors from complete randomness, and show that the conclusions found are consistent with the observed behavior of the brass system. The method of treatment is fairly general for substitutional metallic solid solutions and will be applied to other systems. The determination of vapor pressures of the components of alloy systems is being undertaken in this laboratory to supply more data for this purpose. The information obtained from solid solutions may be extended by careful analogy to liquids as long as the metallic type of bonding is preserved. Since it will be necessary to employ the language of thermodynamics, a brief summary defining the terms used extensively in solution theory is given below. Solution Theory4 An ideal solution is one in which the vapor pressure of the constituent molecules

Jan 1, 1947

By Sandip K. Mukherjee, Anthony W. Laurito, Madan M. Singh, Jon C. Volkwein

In the past, little attention has been paid to the costs of ventilation, since it seldom represented a significant portion of the total mining cost. However, in recent years adverse mining conditions and increases in power charges have caused ventilation costs to rise. The federal regulations have set minimum standards for volumetric airflow rates in underground coal mines. As a mine develops, the air volume and pressure requirements increase. There are several methods by which the quantity of airflow to the mine and working faces can be increased. Some of the methods include (1) increasing main fan output or replacing the main fan by a new higher capacity fan, (2) reducing leakage across stoppings and overcasts, (3) adding a new ventilation shaft or borehole, (4) reducing resistance to airflow by reducing the resistance factor of the individual airways, increasing the number of airways (especially the parallel airways), or re- arranging the air courses by using the available entries, and (5) using auxiliary ventilation systems. This paper addresses the cost-benefit analysis of several of these alternatives as applied to a large operating coal mine located in southern Illinois. Pressure and quantity surveys were conducted under-ground, and measurements were taken at the main exhaust fans on the surface. The existing ventilation network was modeled by using the Penn State ventilation simulator. The input data included the configuration of branches, resistance of each branch (including a component for shock losses), and changes in pressure and volume. The results of the simulation were compared with the survey data to check the merits and accuracy of the model network. The net- work was designed to take into account shafts, major entries, overcasts, regulators, gob areas, working faces, and major leakage paths. The model network served as the basis for the cost analyses of networks designed for increased airflow. The applicable alternatives for increasing airflow were simulated. Performance data obtained from these simulation runs were utilized to conduct the cost-effectiveness analysis. The costs for each f the alternatives included capital, operating and maintenance costs. These costs were expressed as annual costs in terms of dollars per cfm of circulating air, taking into account the economic life associated with each of the alternatives. The benefits were expressed as increased airflow quantity in the critical sections. The result of these analyses show that for the short-range plans evaluated, the most cost-effective way of increasing airflow at this mine would be to reduce leakage through stoppings and overcasts.

Jan 1, 1982

By J. M. Callow

H. A. MEGRAW, New York, N.,Y.-One interesting thing that might be brought out in this connection is the cost of making sulphide gas. I had a communication the other day which suggested that, in view of the high cost of oil, sulphur and sodium sulphide, we might make use of a well-known chemical reaction to form this sulphide gas by the use of aluminum sulphide. It is difficult to see any advantage in this, however, since aluminum has been affected just as much as any other commodity by the rise in prices, due, to war conditions. RUDOLF GAHL, Miami, Ariz. (communication td the Secretary*) Mr. Callow refers to my paper, History of Flotation at Inspiration, which was presented at the Arizona meeting of the Institute. These notes of Mr. Callow's contain much valuable information on flotation practice, as is to be expected from an article written by an author of Mr. Callow's experience in this branch of metallurgy. Nevertheless, I cannot help contradicting a number of the statements made in the references to my paper. In passing, I will also say a word about the reference in Mr. Callow's paper to the article by Messrs. Laist and Wiggin entitled "Flotation Concentration at Anaconda, Mont." Mr. Callow calls attention to the fact that evidently Callow flotation machines are not very sensitive, inasmuch as one man per shift handles four 800-ton sections of Callow machines or 3,200 tons per day at the Inspiration plant. While-it has been the experience of the Inspiration company that the four sections of Callow machines in the Inspiration concentrator are easily handled by one American operator per shift, it is only fair to state that each man operating four sections is assisted by two Mexican helpers who constantly clean the bottoms of the machines. The tonnage per section, by the way, whether equipped with Callow,, Inspiration or Minerals Separation machines, is considerably in excess 4 800 tons.. Mr. Callow further says that local opinion at Inspiration is that, two 800-ton sections consisting of two 10-compartment and four 6-compartment Minerals Separation machines (these machines are of the Hebbard type) is the limit that one man can properly attend. I do not hesitate to say that I consider it perfectly feasible to have four such sections operated by one man, perhaps assisted by "one helper. The Minerals Separation machines of this type have undoubtedly an advantage as far as easiness of operation is concerned,

Jan 4, 1917

By Michael B. Bever, Carl F. Floe

he possibility that carbon may be soluble in copper to a limited extent has bten recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are freauerltlv used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. Review of Literature In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of 0.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.9258 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy's request, Dick,3 in 1856, carried out various working tests on copper that had been ill prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as 0.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick's experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1946

By John Chipman, Theodore B. Winkler

In order to understand more fully the complexities of the reactions occurring between the liquid steel and the slag in the basic open-hearth steelmaking furnace, investigations in this country and. abroad have turned to laboratory equilibrium studies. This paper is one of a series of reports on investigations being conducted at the Massachusetts Institute of Technology. The experimental work was completed early in 1942. The slag systems found in the basic open hearth are very complex, being made up of at least eight major components and as many others whose effect might be classified as minor. The first two papers of the series, by Fetters and Chipman,l,2 as well as the paper by Taylor and Chip-man,3 dealt with the simplest possible slag system that would resemble those found in the basic ope), hearth—the slag system consisting of CaO-MgO2-SiOz-FeO. (Taylor's rotating induction furnace eliminated the necessity of contamination of the slag by MgO.) Having arrived at some reasonable conclusions regarding the physical chemis- try of the reactions between molten iron and the simple slags at equilibrium, the next step was to investigate more complex slag systems. The major purpose of the present investigation was to determine what factors control the distribution of phosphorus between molten iron and the more complex basic slags at equilibrium, and to what extent these factors are influential. The slags used contained CaO, MgO, SiO2, FeO, Fe2O3, P2O6, MnO, Al2O3 and CaF2, but not all of the slag samples contained all of these components at one time. Review of Literature Although a number of interesting papers have been published on the subject of dephosphorization of an iron bath, there are as yet no results from laboratory studies that give thoroughly reliable information on the dephosphorization reaction. Even for the supposedly simple Fe-O-P system involving iron-phosphorus melts and iron oxide-iron phosphate slags, the experimental results are contradictory and no formulas have been established that adequately fit the equilibrium conditions. The Fe-O-P system has been studied by Schackmann and Krings,4 von Samson-Himmelstjerna,6 Oelsen and Maetz,6 Bischof and Maurer,7 Diepschlag and Schürmann,8 and Herty,9 and the results of their investigations appear in Table I. A number of different equilibrium constants and distribution . Ratios

Jan 1, 1947

By Theodore B. Winkler, John Chipman

In order to understand more fully the complexities of the reactions occurring between the liquid steel and the slag in the basic open-hearth steelmaking furnace, investigations in this country and. abroad have turned to laboratory equilibrium studies. This paper is one of a series of reports on investigations being conducted at the Massachusetts Institute of Technology. The experimental work was completed early in 1942. The slag systems found in the basic open hearth are very complex, being made up of at least eight major components and as many others whose effect might be classified as minor. The first two papers of the series, by Fetters and Chipman,l,2 as well as the paper by Taylor and Chip-man,3 dealt with the simplest possible slag system that would resemble those found in the basic ope), hearth—the slag system consisting of CaO-MgO2-SiOz-FeO. (Taylor's rotating induction furnace eliminated the necessity of contamination of the slag by MgO.) Having arrived at some reasonable conclusions regarding the physical chemis- try of the reactions between molten iron and the simple slags at equilibrium, the next step was to investigate more complex slag systems. The major purpose of the present investigation was to determine what factors control the distribution of phosphorus between molten iron and the more complex basic slags at equilibrium, and to what extent these factors are influential. The slags used contained CaO, MgO, SiO2, FeO, Fe2O3, P2O6, MnO, Al2O3 and CaF2, but not all of the slag samples contained all of these components at one time. Review of Literature Although a number of interesting papers have been published on the subject of dephosphorization of an iron bath, there are as yet no results from laboratory studies that give thoroughly reliable information on the dephosphorization reaction. Even for the supposedly simple Fe-O-P system involving iron-phosphorus melts and iron oxide-iron phosphate slags, the experimental results are contradictory and no formulas have been established that adequately fit the equilibrium conditions. The Fe-O-P system has been studied by Schackmann and Krings,4 von Samson-Himmelstjerna,6 Oelsen and Maetz,6 Bischof and Maurer,7 Diepschlag and Schürmann,8 and Herty,9 and the results of their investigations appear in Table I. A number of different equilibrium constants and distribution . Ratios

Jan 1, 1947

By J. W. Spretnak, G. W. Cunningham

Grain growth across the bond region in Pressure bonded copper was found to be mainly dependent upon the presence or absence of microvoids, but it was also found that prior history, bonding pressure, bonding time, and bonding temperature are important variables. An increase in pressure, time, or temperature tends to promote grain growth in the interfacial region. Polygonization is observed after pressure bonding except for specimens previously annealed at temperatures on the order of 1800°F or higher. The dislocation density in bonded specimens was found to be greater in the bond region. THE bonding of metals by the application of gas pressure at elevated temperatures is a relatively new process, having been developed over the past 10 years. The technique, as described by Paprocki, Hodge, and Boyer,l is unique in that assemblies of many parts and complex shapes can be bonded with a negligible amount of deformation. The process thus differs metallurgically from pressure welding, cold welding, and recrystallization welding in that deformation occurs only in a microscopic region whereas, in general, the welding requires severe deformation and may extend the contact surface by a factor of 3 to 10 during the welding. From a practical standpoint, pressure welding is not amenable for bonding large surfaces. During the time in which Paprocki and coworkers were deve1oping the process, West2 established aproc-ess,for bonding aluminum to uranium, and Barnes and Maze? developed a gas-pressure-bonding technique for nickel and copper. Recently, Fugardi and Zambro4 have used equipment similar to that developed by Paprocki and coworkers to establish parameters for bonding stainless steel, aluminum, and zirconium. Most of the investigations on pressure bonding have been empirical in nature and, although methods have been developed for bonding such metals as molybdenum, columbium, titanium, zirconium, and stainless steel, the information concerning the mechanism of bonding is limited. Several workers5"7 have studied the pressure bonding of dissimilar metals in order to gain information on diffusion and formation of inter-metallic phases under application of pressure. Clapson and Robbins8 have shown by a series of annealing studies that voids in the interfacial boundary of roll-bonded copper can prevent movement of the boundary until the voids are spaced far enough apart to prevent pinning. They also indicated that recrystallization and grain growth can eliminate the voids. In this paper it is shown that voids are the major detriment to grain growth across pressure-bonded interfaces, but it is also shown that prior history, bonding pressure, bonding time, and bonding temperature are

Jan 1, 1962

By Carl F. Floe, Michael B. Bever

he possibility that carbon may be soluble in copper to a limited extent has bten recognized for over a century. The quantitative investigation of this problem, however, requires more sensitive techniques than have formerly been available. Three recent developments have made possible more accurate determinations: the vacuum-fusion method of analysis, the production of copper of high purity and the availability of high-purity refractories, particularly graphite. In addition to its obvious theoretical interest, the problem of carbon solubility in copper is of practical importance. In the production of copper and of high-copper alloys, carbonaceous covers are freauerltlv used. If even minute amounts of carbon are dissolved, insoluble carbon oxide gases will be formed when such metals are poured under oxidizing conditions. A mechanism of this kind could well be one of the principal causes of gas porosity in casting copper-base products. Review of Literature In 1823 Vivian1 raised the question as to whether copper by overpoling becomes "combined with a minute portion of carbon." Karsten2 asserted, in 1832, that carbon reduces the high-temperature strength of pure copper, so that when the carbon content has reached 0.2 per cent the metal will be brittle at a dark red heat. According to Karsten, carbon contents of 0.05 per cent make it difficult to hot-work copper. He also reported that the specific gravity of copper is 8.8969 and that it increases to 8.9258 if the copper is cemented with carbon and then melted. He emphasized the difficulty of determining analytically the small amounts of carbon present in copper. The metal was removed by wet methods and the residue considered as carbon. At Percy's request, Dick,3 in 1856, carried out various working tests on copper that had been ill prolonged contact with carbon, and found that the working properties of the metal had not been affected. He also attempted to determine the presence of carbon analytically. In one experiment the copper was dissolved and the residue was fused with litharge, and in another essentially a combustion analysis was made on a copper sample. In a final experiment, a sample was dissolved and the residue subsequently subjected to a combustion analysis. Indications of as much as 0.005 per cent carbon were found, but Dick considered his work inconclusive largely because of the possible interference of sulphur. Percy4 concluded, from Dick's experiments and from some experimental work of his own, that the solubility of carbon in copper had not been established with

Jan 1, 1946

By John G. Koert, Koert D. Burnham, John G. Broughton

Wollastonite in Essex County, New York, occurs as a typical contact mineral in a series of rocks metamorphosed by anorthosite. Sole current use is in various types of electric welding fluxes. Its uniform lathlike shape suggests its use as a specialized filler. Introduction Wollastonite (CaSiO3) was first noted in the vicinity of Willsboro, Essex County, New York, about 1810 by Dr. William Meade, and described from the same locality in 1821 by Lardner Vanuxem.' Recent exploration and development indicate that the deposit is of adequate size for continued exploitation on a larger scale than the present operations. The only other known occurrence of like magnitude in this country is in Kern County, California.* Wollastonite has been reported from Michigan, Pennsylvania, and Lewis County, New York, but these are little more than mineral localities. Geology The Essex County wollastonite has been found outcropping at numerous separate localities in a belt of contact metamorphosed sediments, 1/4 mile wide, which begins 2 miles southwest of the village of Willsboro and trends N. 70" W. for approximately 6 miles (Fig. I). In this belt, the pre-Cambrian Grenville has been injected and partially replaced by the more liquid portions of an anorthositic magma. Bud-dington and Whitcomb3 have described the rock in this contact metamorphosed belt as "Mixed gneisses: Grenville mafic, pyroxenic and garnetiferous gneisses and skarns* with local nearly uniform garnet or pyroxene layers and with gabbroic anorthosite sheets. A few limestone layers." These rocks are underlain, presumably at no great depth, by gabbroic anorthosite gneiss, the typical Whiteface border facies of the Adirondack anorthosite massif. The occurrence of wollastonite in large quantities was discovered during the quarrying of the garnet-rich layer that overlies the wollastonite at one opening. Further prospecting revealed its presence elsewhere in the belt, overlain in most places by the garnet. Accurate tracing of the wollastonite is difficult, owing to the glacial cover and to the fact that the weathered surface of the mineral has a dark, dirty brown color, and that the wollastonite itself has been dissolved more or less completely along the outcrops. It has, however, been noted at 10 localities within the skarn belt in the first 2 1/2 miles from its southeastern end. It has not been found in the northern half of the belt and therefore may be limited to the southern half. At the Fox Hill quarry, which is the main opening, 150 ft. have been exposed, showing an aggregate thickness of 30 to 35 it. Of

Jan 1, 1948

By Koert D. Burnham, John G. Broughton, John G. Koert

Wollastonite in Essex County, New York, occurs as a typical contact mineral in a series of rocks metamorphosed by anorthosite. Sole current use is in various types of electric welding fluxes. Its uniform lathlike shape suggests its use as a specialized filler. Introduction Wollastonite (CaSiO3) was first noted in the vicinity of Willsboro, Essex County, New York, about 1810 by Dr. William Meade, and described from the same locality in 1821 by Lardner Vanuxem.' Recent exploration and development indicate that the deposit is of adequate size for continued exploitation on a larger scale than the present operations. The only other known occurrence of like magnitude in this country is in Kern County, California.* Wollastonite has been reported from Michigan, Pennsylvania, and Lewis County, New York, but these are little more than mineral localities. Geology The Essex County wollastonite has been found outcropping at numerous separate localities in a belt of contact metamorphosed sediments, 1/4 mile wide, which begins 2 miles southwest of the village of Willsboro and trends N. 70" W. for approximately 6 miles (Fig. I). In this belt, the pre-Cambrian Grenville has been injected and partially replaced by the more liquid portions of an anorthositic magma. Bud-dington and Whitcomb3 have described the rock in this contact metamorphosed belt as "Mixed gneisses: Grenville mafic, pyroxenic and garnetiferous gneisses and skarns* with local nearly uniform garnet or pyroxene layers and with gabbroic anorthosite sheets. A few limestone layers." These rocks are underlain, presumably at no great depth, by gabbroic anorthosite gneiss, the typical Whiteface border facies of the Adirondack anorthosite massif. The occurrence of wollastonite in large quantities was discovered during the quarrying of the garnet-rich layer that overlies the wollastonite at one opening. Further prospecting revealed its presence elsewhere in the belt, overlain in most places by the garnet. Accurate tracing of the wollastonite is difficult, owing to the glacial cover and to the fact that the weathered surface of the mineral has a dark, dirty brown color, and that the wollastonite itself has been dissolved more or less completely along the outcrops. It has, however, been noted at 10 localities within the skarn belt in the first 2 1/2 miles from its southeastern end. It has not been found in the northern half of the belt and therefore may be limited to the southern half. At the Fox Hill quarry, which is the main opening, 150 ft. have been exposed, showing an aggregate thickness of 30 to 35 it. Of

Jan 1, 1948

By C. G. Dunn

WITH respect to theories of recrystallization in metals plastically deformed, it has been said that the present status of this subject is far from satisfactory.1 It may also be said that before any mechanism of recrystallization for metals and alloys can be set forth in a satisfactory manner, there must be made available considerable data on orientation changes that occur during the deformation and recrystallization processes. Although extensive data have been published on recrystallization in single crystals and in polycrystalline specimens, more results of a type that can be classified according to simple orientation changes would be desirable in this complex field. It might even be said that before classifications are made according to types of orientation changes, it may be possible to classify a considerable amount of data into certain kinds of orientation states if groups of common or nearly common orientation occur. Methods for computing the probability of occurrence for various types of groups have been published2 and it has been pointed out in particular that it should be possible to analyze orientation data for high-order twin relationships between old and new grains even when agreement is not at all exact. In this connection, work on recrystallization in silicon ferrite reported in a paper concerned with complex groups of annealing twins' indicated that some data were consistent with primary nucleation occurring according to a second-order or a third-order twin transformation. However, further work in this latter direction was definitely needed. It is, therefore, the purpose of the present paper to report data and analyses for primary nucleation in silicon ferrite following small deformations that have been carried out at the Pittsfield Works' Laboratory of the General Electric Co. Analyses have been made with the aid of standard groups of twins that are reported elsewhere .4 PREPARATION OF SPECIMENS AND EXPERIMENTAL PROCEDURE The material used in the present investigation was taken' from the same heat of steel as that used in a prior report.3 The finished strip in both cases was made by the Allegheny-Ludlum Steel Corporation according to methods that produce a high degree of preferred crystal orientation. Samples with large grains had the following composition: 3.45 per cent Si, 0.003 C, 0.008 P, 0.020 S, 0.075 Mn, 0.031 Al and 0.072 Cu. Thickness of specimens was 0.012 inches. Plastic deformation was produced by cold-rolling the samples on a mill with

Jan 1, 1945

By Frederick N. Rhines, William A. Anderson

The investigations of Wymanl have demonstrated that copper deoxidized with several of the commonly used agents that confer immunily to ordinary hydrogen em-brittlement can still be embrittled if it is annealed alternately under oxidizing and reducing conditions. During the oxidizing cycle, oxygen diffuses into the copper and frequently deposits a subscale composed of the oxide of the residual deoxidizing agent. Upon subsequent reduction with hot hydrogen, the copper becomes ruptured along the grain boundaries to a depth sharply limited by the previous penetration of oxygen as delineated by the inner boundary of the subscale. Obviously the sensitivity to this kind of hydrogen embrittlement is engendered by the introduction of oxygen during the oxidizing anneal, but beyond this the mechanism of the process, and hence the controlling factors, remain obscure. There are several possibilities: (I) oxygen dissolved in the copper matrix of the subscale may, upon cooling prior to the hydrogen anneal, precipitate as cuprous oxide which is subsequently reduced by hydrogen as in the familiar case of hydrogen embrittlement; (2) oxygen in solid solution in copper may itself confer susceptibility to embrittlement by hydrogen; (3) the normally refractory oxides such as those of aluminum, silicon and titanium may themselves be reduced by hydrogen when in contact with copper; or (4) the precipitated oxides of the subscale may be complex compounds such, perhaps, as SiO2.Cu2O, which are partially reduced by hydrogen. These possibilities have been examined, and it has been concluded that the first three and possibly the fourth are operative collectively or individually under more or less predictable conditions. Effect OF Precipitated Cuprous Oxide and Dissolved Oxygen The literature provides no definite proof that oxygen in solid solution in copper can confer susceptibility to hydrogen embrittlement; indeed, the research of Leiter2 seemed to indicate the opposite—that to produce the effect, cuprous oxide must be present in massive form and in a more or less continuous network along the grain boundaries. To test this point, pure copper has been annealed in hydrogen under conditions designed to ensure the presence in various samples of: (I) precipitated cuprous oxide, (2) dissolved oxygen only, and (3) no oxygen in any form. Very pure copper" said to contain no oxygen and no spectro-scopically detectable traces of any other element (that is, no individual detectable impurity in quantity greater than 0.0001 per cent) was used. Strips of this material cold.-rolled 75 per cent to 1/8 in. in thickness were subjected to the following treatments, the results of which are noted:

Jan 1, 1941

By Frederick N. Rhines, William A. Anderson

The investigations of Wymanl have demonstrated that copper deoxidized with several of the commonly used agents that confer immunily to ordinary hydrogen em-brittlement can still be embrittled if it is annealed alternately under oxidizing and reducing conditions. During the oxidizing cycle, oxygen diffuses into the copper and frequently deposits a subscale composed of the oxide of the residual deoxidizing agent. Upon subsequent reduction with hot hydrogen, the copper becomes ruptured along the grain boundaries to a depth sharply limited by the previous penetration of oxygen as delineated by the inner boundary of the subscale. Obviously the sensitivity to this kind of hydrogen embrittlement is engendered by the introduction of oxygen during the oxidizing anneal, but beyond this the mechanism of the process, and hence the controlling factors, remain obscure. There are several possibilities: (I) oxygen dissolved in the copper matrix of the subscale may, upon cooling prior to the hydrogen anneal, precipitate as cuprous oxide which is subsequently reduced by hydrogen as in the familiar case of hydrogen embrittlement; (2) oxygen in solid solution in copper may itself confer susceptibility to embrittlement by hydrogen; (3) the normally refractory oxides such as those of aluminum, silicon and titanium may themselves be reduced by hydrogen when in contact with copper; or (4) the precipitated oxides of the subscale may be complex compounds such, perhaps, as SiO2.Cu2O, which are partially reduced by hydrogen. These possibilities have been examined, and it has been concluded that the first three and possibly the fourth are operative collectively or individually under more or less predictable conditions. Effect OF Precipitated Cuprous Oxide and Dissolved Oxygen The literature provides no definite proof that oxygen in solid solution in copper can confer susceptibility to hydrogen embrittlement; indeed, the research of Leiter2 seemed to indicate the opposite—that to produce the effect, cuprous oxide must be present in massive form and in a more or less continuous network along the grain boundaries. To test this point, pure copper has been annealed in hydrogen under conditions designed to ensure the presence in various samples of: (I) precipitated cuprous oxide, (2) dissolved oxygen only, and (3) no oxygen in any form. Very pure copper" said to contain no oxygen and no spectro-scopically detectable traces of any other element (that is, no individual detectable impurity in quantity greater than 0.0001 per cent) was used. Strips of this material cold.-rolled 75 per cent to 1/8 in. in thickness were subjected to the following treatments, the results of which are noted:

Jan 1, 1941

By D. H. Newland

New York has a small but not insignificant place in the oil and natural gas industries of the United States. It has had a continuous record as an oil producer since 1872, with an aggregate yield of about 104,000,000 bbl. The reported output for 1935 was 4,237,000 bbl., a gain of more than 10 per cent for the year and a total that has been exceeded only in the early period of flush production half a century ago. The industry has been steadily building up since 1920 with the successful practice of the water drive, which has given a new lease of life to pools that had been practically drained of oil recoverable by pumping. An additional output of 2000 bbl. or more per acre is being procured by this method. Altogether the fields in New York State cover about 55,000 acres. Their limits are well defined and it is unlikely that they will be extended in the future, although there is some prospect of finding additional supplies by deeper drilling. The oil from New York is all classed as Pennsylvania grade, for which the recent price has been about $2.50 a barrel. It is refined at Olean, Wellsville and Bolivar, in the oil district, and partly in Pennsylvania refineries. Exploration for natural gas, outside of the established districts, was considerable during the year. Altogether 59 wells were drilled, distributed over 13 counties, of which 33 were listed as producers and 26 were dry. At the close of the year, 13 wells were in process of drilling. The 33 producing wells had a combined estimated flow of 278 million cubic feet per day. The best results were obtained from exploration in Allegany County, where out of eight wells drilled to the Oriskany sandstone five were successful and showed a combined open-flow capacity of 107 million cubic feet. The Oriskany sandstone was encountered at a depth of 4500 to 4900 ft. In Steuben County, next east of Allegany County, two out of seven wells to the Oriskany proved productive, and one of these, in the town of Greenwood, on the Watkins structure, was probably the largest that has so far been opened in the state, with a reported yield of 35 million a day. In the central part of New York interest was awakened by the activity shown in exploring for gas in the Trenton limestone, in Camden, Florence and Rome townships, Oneida

Jan 1, 1936

By A. Mitchell, T. Bagshaw

A recent paper by Thomas1 has presented new data on the solubility of hydrogen in solid silver at 1 atm pressure in the temperature range 600° to 963°C. However, no data is reported in the literature on hydrogen solubility in liquid silver. The Sieverts technique which has been described previously2,3 was used in the present work. Charges of approximately 160 g were melted in Morgan "purox" recrystallized alumina crucibles and purified helium was used for the determination of the "hot volume" during each experiment. A chemical analysis of the silver indicates that the impurity content (Cu + Al) is less than 0.02 wt pct. Hydrogen solubility in the temperature range 963° to 1200°C was investigated. The results of three experiments are shown in Table I. Fig. 1 shows an Arrhenius plot of the present work together with the solid-state data of Thomas, Steacie, and johnson,4 Eichenauer et al.,5 and Siegelin et al.6 The following expression has been derived from the Arrhenius plot of the present data: log (solubility of hydrogen, cm3 per 100 g) = 2.154-3512.0/ToK The heat of solution derived from Fig. 1 is 31,150 cal per g mole H2 compared with the value of 33,020 cal per g mole H2 obtained by Thomas and 12,000 cal per g mole H2 obtained from the data of Steacie. It was observed that hydrogen evolution took place when the silver melts were solidified under 1 atm of hydrogen, which would not be expected from an extrapolation of the results of Steacie. Schenck and Lange7 have observed that, for several transition metals at their melting points, the ratio of the hydrogen solubility in the liquid to that in the solid lies in the range 2.1 to 3.1. The present results and those of Thomas are in accord in this respect having a ratio of 2.8. 'C. L. Thomas: Trans. TMS-AIME, 1967 vol. 239, pp. 485-96. 2T. Bagshaw and A. Mitchell: I. Iron Steel Inst., 1966, vol. 204, p. 87. 'M. Weinstein and J. F. Elliott: Trans. TWS-AIME, 1963, vol. 227, p. 382. 'E. W. R. Steacie and F. M. G. Johnson: Proc. Roy. Soc. (London), Ser. A, 1928, vol. 117, pp. 662-79. 'W. Eichenauer et al.: Z. Metallk., 1958, vol. 49, pp. 220-25. 6W. Siegelin et al.: Z. Elektrochem., 1957, vol. 61, pp. 359-66. 'H. Schenck and K. W. Lange: Arch Eisenhuettenw., 1966, vol. 37, no. 9, pp. 739-48.

Jan 1, 1969

By D. H. Newland

New York has a small but not insignificant place in the oil and natural gas industries of the United States. It has had a continuous record as an oil producer since 1872, with an aggregate yield of about 104,000,000 bbl. The reported output for 1935 was 4,237,000 bbl., a gain of more than 10 per cent for the year and a total that has been exceeded only in the early period of flush production half a century ago. The industry has been steadily building up since 1920 with the successful practice of the water drive, which has given a new lease of life to pools that had been practically drained of oil recoverable by pumping. An additional output of 2000 bbl. or more per acre is being procured by this method. Altogether the fields in New York State cover about 55,000 acres. Their limits are well defined and it is unlikely that they will be extended in the future, although there is some prospect of finding additional supplies by deeper drilling. The oil from New York is all classed as Pennsylvania grade, for which the recent price has been about $2.50 a barrel. It is refined at Olean, Wellsville and Bolivar, in the oil district, and partly in Pennsylvania refineries. Exploration for natural gas, outside of the established districts, was considerable during the year. Altogether 59 wells were drilled, distributed over 13 counties, of which 33 were listed as producers and 26 were dry. At the close of the year, 13 wells were in process of drilling. The 33 producing wells had a combined estimated flow of 278 million cubic feet per day. The best results were obtained from exploration in Allegany County, where out of eight wells drilled to the Oriskany sandstone five were successful and showed a combined open-flow capacity of 107 million cubic feet. The Oriskany sandstone was encountered at a depth of 4500 to 4900 ft. In Steuben County, next east of Allegany County, two out of seven wells to the Oriskany proved productive, and one of these, in the town of Greenwood, on the Watkins structure, was probably the largest that has so far been opened in the state, with a reported yield of 35 million a day. In the central part of New York interest was awakened by the activity shown in exploring for gas in the Trenton limestone, in Camden, Florence and Rome townships, Oneida

Jan 1, 1936

Frontino operates three underground lode mines at Segovia in the area of northwest Antioquia, Colombia, which has been an important gold producing district since the late 1800s. Auriferous pyrite, the pre-dominent sulfide, carries very finely disseminated gold. Other minor sulfides are galena, pyrrhotite, and sphalerite in quartz gangue with the host rock being granodiorite. Silver is associated with the galena and also occurs as a sulfo-salt. In 1.973 and 1974, at an annual milling rate of 145,000 mt (160,000 st), average mill heads were 7.80 g per mt (0.23 oz per st) Au; 20.0 g per mt (0.58 oz per st) Ag; and 0.37% Pb; with a production of 1,150 kg (35,700 oz) Au and 4,500 kg (141,000 oz) Ag. Over 300 mt (330 st) of Pb concentrate were shipped. The ore is crushed to minus 16 mm (5 18 in. ) and fed to a rod mill with the discharge passing over a 1.07 m by 1.07 m (42 in. by 42 in. ) jig operating in closed circuit with the underflow from a cyclone in closed circuit with two ball mills. Cyclone overflow is bulk-floated for sulfide recovery from which the tailings are sent to the river as waste with the flotation concentrate joining the jig concentrate for cyanidation. The combined gold bearing concentrates, after cyclone classification, are reground to a very fine mesh in closed circuit with cyclone classification, with the overflow going to the primary thickener. Regrinding, classification, and thickening is done in cyanide solution, and the primary thickener produces a pregnant solution for Merrill -Crowe precipitation. The thickener underflow is the feed to the agitators, thickener, and filter from which the overflow and filtrate are sent to precipitation. The washed filter cake is repulped and floated for the recovery of a galena concentrate for shipment. About 40% of the recovered silver is in this concentrate. In the refinery the precipitate is melted into a dore bullion. This 600 mt (660 st) capacity mill employs several interesting techniques. Gold recovery of 85% to 90% from a complex sulfide denotes good practice. While total power at 42 kwh per mt (46 kwh per st) is high, it would be recognized that the grinding units are small in size and the flowsheet is complicated due to the gold occurring in the sulfide minerals. The extremely low-cost electric power is generated by

Jan 1, 1981

By Jean Howard, E. V. Walker

ManY papers have been published during the last few years on the formation of cube texture in 3 1/4 pct Si-Fe, e.g., those of Assmus, Detert, Dunn, and Walter.1,5 All are concerned with the formation of the texture by a process involving secondary re-crystallization and the relative surface energies of (100) and other planes under certain conditions of annealing. The authors have found that cube texture can also be produced by heavily cold rolling strip in which the cube-on-edge texture has first been formed. Cube texture develops on annealing, but in this case it is not accompanied by secondary recrystallization. The starting material is a sintered compact, the preparation of which has been described elsewhere. Using a conventional processing schedule employed for producing commercial silicon-iron with the cube-on-edge texture, the sintered compact is cold rolled to such a thickness that, after annealing in pure hydrogen for 24 hr at 1350'~ to produce the cube-on-edge texture, the final thickness required can be obtained by giving a further cold reduction of 85 pct. Cube texture is developed by annealing at -900~~ in pure hydrogen: it has been produced in strip up to 0.024 in. thick. The microstructure of the strip consists of a mass of small primary grains within the boundaries of the much larger secondary grains which ex- hibited cube-on-edge texture before the final cold roll. If the strip is annealed at -1000 after the 85pct reduction, secondary recrystallization begins to take place, provided a strong cube texture is present. On raising the temperature more secondaries grow, complete secondary recrystallization being obtained on annealing at -1150'. From this it is concluded that the secondary crystals are produced by the texture inhibition mechanism: they show (110) and (111) planes in the surface of the strip, the former being the more numerous. It has been observed that the more perfect is the (110) [001] texture prior to cold rolling by 85 pct, the further from the ideal is the (100) [oo].] texture. A similar treatment applied to high quality commercial grain-oriented silicon-iron strip failed to produce cube texture. The tilt and rotation of the [loo] from the rolling direction was less than 10deg, but (to within a few degrees) the planes (130), (450) and (210) lay in the surface of the strip. Acknowledgment is made to the Engineer-in-Chief of the British Post Office for permission to use the information contained in this note.

Jan 1, 1962

By R. L. Sandefur

Professor Kim's excellent review article1 on ultimate pit planning contains a statement of the apparently widely held but incorrect belief that "kriging provides information on the confidence limits around the estimate which no other extension technique is capable of supplying." If a geostatistical approach is valid, there are several good reasons for using kriging but uniquely provided confidence limits is not among them. If kriging is possible, then confidence limits can be calculated for any other linear estimate. Kriging is the procedure which finds the weighing coefficients which minimize the estimation variance [ ] is the variance of blocks like the one being estimated. wi is the covariance of the estimated block and the i-th sample. oij is the covariance of the i-th sample and the j-th sample. Ai is the weighing coefficient for the i-th sample. N is the number of samples. The formula for estimation variance can also be used to calculate confidence limits on blocks estimated by any linear combination of sample grades including: 1) Polygons a. Hole nearest block centroid is assigned weight 1. All other holes are assigned weight 0. b. Polygonal area weighing. The samples are assigned weights directly proportional to their polygonal areas of influence within the block. The weights sum to 1. 2) Inverse distance weighing. The samples are assigned weights directly proportional to the reciprocal of their distance to some power from the block centriod. The weights sum to 1. Often only holes nearer than a certain distance and/or the nearest hole in each octant is considered. If there is an antisotropy to the ore body, an elliptical transformation often gives more accurate results. The most popular inverse distance weighing function is inverse squared distances (IDS). 3) Simple average. All samples within a certain distance are assigned the same weights which sum to 1. As an example of the applicability of the above formula to any linear estimate an internal verification on copper grade of 665 blast holes on the 1040 bench at Utah's Island Copper mine is presented. Internal verification is simple and applicable to non-linear estimates as well. Any sample (drill hole, bulk, trench, or chip) is dropped out, the value of the dropped sample estimated and compared with the actual value. If this is done for all samples, a measure of confidence limits is obtained. Internal verification is used in Cominco's MEPS system4 and in the BLUEPACK system.5 Comparison of block values against estimates697 is not dissimilar to internal verification. Results of the internal verification are presented below:

Jan 1, 1980

By J. A. Clum, R. W. Heins, T. D. Tiemann

The use of Na-montmorillonite clay hinders (Western Bentonite) in the pelletizing of iron ore concentrates is well established as is the idea that alternative binders must be found. 1-6 This note summarizes work done7 in evaluating a Wisconsin montmorillonite clay binder. The clay occurs in irregualr beds overlying the Prairie du Chien Dolomite and the St. Peters Sandstone near Hersey, St. Croix County. The raw Wisconsin clay contained 65% quartz and 35% clay minerals. The Na20to CaO ratio was 0.234. Suspension viscosity tests of the raw clay gave results only slightly better than water alone, even after treatment with activator materials. Sedimentation treatment reduced the quartz in the decantate to 5% after 240 min (four hours). Twenty minutes of sedimentation produced a decantate with 27.5% quartz which was found as effective as the 5% quartz decantate in pelletizing behavior. The 20 min decantate was used in subsequent tests. The decantate was filtered and dried at 110°(230°F). The minus 200 mesh portion of this was added directly to the magnetite concentrate. Pellets were made in a laboratory sized disc pelletizer from pastes consisting of ore concentrate, balling water (9%) and binder (clay, or clay + resins, or resins). The pastes were premixed in a Waring blender. The binders were: (1) 1% of a commercially used Western Bentonite; (2) 1 % or 3% of the Wisconsin clay (raw, or 20 min decantate); (3) 20 min decantate washed with activator solutions, (to exchange Na for Ca in the clay); (4) decantate with activator added in the balling water; (5) decantate with organic resins; (6) organic resins. Measurements of the 0.46 m (18 in.) Green Drop Number, the Dry Strength and the Fired Strength (fired at 1260°C (2300°F) for 30 min) were made. The dry and fired compressive strengths were determined on an Instron testing machine using a C-load cell and a F-load cell, respectively. The cross-head speed was 0.004 m/sec (0.1 in./min) for both. The results of each measurement were averaged for 15 pellets. A summary of those results is presented in [Table 1]. More detailed results and procedures are presented in another report.7 In addition to the effects on pellet strength due to various binders the effect of varying magnetite concentrate characteristics is noted in [Table l]. There, a few comparative data are shown for Cornwall, PA Magnetite, which has a generally liner particle size than the Black River Falls magnetite which was used for most of the tests.

Jan 1, 1979