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By T. S. West

Completion and production data presented for three wells in the Oakville area of Live Oak County, Texas, which were completed near the gas-oil or water-oil contact, indicate that coning may not be as prevalent a cause of failure in such cases as is commonly assumed. Failure in the cases discussed is indicated to be due instead to: (I) erosion of the formation, (2) flowing out of mud filter cake, or (3) failure of the cement. An open-hole gravel-pack type of completion procedure is proposed for preventing failures of this kind by preventing movement of all solid material in the space in which completion is made. Various combinations of layers of gravel, sand, and cement are utilized for this purpose. Experimental results and theoretical discussion as to the applicability of gravel pack completion are included. Introduction This paper is primarily a study of the reasons for failure of oil-well completions near the gas-oil or oil-water contact, and suggests a procedure for increasing the efficiency of this type of completion. The value of improvement in completion effectiveness near the gas or water zone is not confined, however, to wells of relatively thin oil columns. Thick oil columns become thin as depletion progresses. It would seem to follow that the minimum distance from the gas or water zone at which completion can be made in a new well indicates the limit to which depletion may be carried in a well having an oil column of any initial magnitude. Only four ways can be postulated in which high gas-oil or water-oil ratio can initially occur if the zone exposed for production is within the oil column: 1. Failure of the cementing material. 2. Vertical coning. 3. Failure along the boundary between the cement and the wall of the well. 4. Failure of the formation comprising the wall of the well. Cementing materials such as portland cement and plastics have reached a high stage of development. Failures of this type are probably due almost always to extraneous causes such as mud contamination rather than to faulty cementing material. Vertical coning can and obviously does occur. However, the usual occurrence of thin impermeable streaks in sand sections and the success with which open-hole drill-stem tests can be made near the gas-oil contact suggest that over-all effective vertical permeability, and in turn vertical coning, is less prevalent than frequently is assumed. Much has been written on failure by flowing out of the mud filter cake between cementing material and the formation. A filter cake is always present if, prior to cementing, mud has come in contact with a permeable formation at pressures exceeding the pressure head of the fluid it contains. Mechanical methods are in use for removing filter cake during the cementing operation? which undoubtedly are of

Jan 1, 1947

By T. S. West

Completion and production data presented for three wells in the Oakville area of Live Oak County, Texas, which were completed near the gas-oil or water-oil contact, indicate that coning may not be as prevalent a cause of failure in such cases as is commonly assumed. Failure in the cases discussed is indicated to be due instead to: (I) erosion of the formation, (2) flowing out of mud filter cake, or (3) failure of the cement. An open-hole gravel-pack type of completion procedure is proposed for preventing failures of this kind by preventing movement of all solid material in the space in which completion is made. Various combinations of layers of gravel, sand, and cement are utilized for this purpose. Experimental results and theoretical discussion as to the applicability of gravel pack completion are included. Introduction This paper is primarily a study of the reasons for failure of oil-well completions near the gas-oil or oil-water contact, and suggests a procedure for increasing the efficiency of this type of completion. The value of improvement in completion effectiveness near the gas or water zone is not confined, however, to wells of relatively thin oil columns. Thick oil columns become thin as depletion progresses. It would seem to follow that the minimum distance from the gas or water zone at which completion can be made in a new well indicates the limit to which depletion may be carried in a well having an oil column of any initial magnitude. Only four ways can be postulated in which high gas-oil or water-oil ratio can initially occur if the zone exposed for production is within the oil column: 1. Failure of the cementing material. 2. Vertical coning. 3. Failure along the boundary between the cement and the wall of the well. 4. Failure of the formation comprising the wall of the well. Cementing materials such as portland cement and plastics have reached a high stage of development. Failures of this type are probably due almost always to extraneous causes such as mud contamination rather than to faulty cementing material. Vertical coning can and obviously does occur. However, the usual occurrence of thin impermeable streaks in sand sections and the success with which open-hole drill-stem tests can be made near the gas-oil contact suggest that over-all effective vertical permeability, and in turn vertical coning, is less prevalent than frequently is assumed. Much has been written on failure by flowing out of the mud filter cake between cementing material and the formation. A filter cake is always present if, prior to cementing, mud has come in contact with a permeable formation at pressures exceeding the pressure head of the fluid it contains. Mechanical methods are in use for removing filter cake during the cementing operation? which undoubtedly are of

Jan 1, 1947

By M. Shelef, A. W. Fletcher

The effect of alkali sulfates in promoting the sul-fation of nickel and copper in a bulk sulfide flota -tion concentrate by fluidized bed roasting has been studied in the laboratory, and it was shown that the various alkali sulfates promote sulfation to approximately the same extent. The sulfation of a mixture of synthetically prepared iron and nickel oxide and of nickel ferrite has also been studied. Nickel sulfation was promoted by high ratios of Fe:Ni and by the presence of sodium sulfate. THE work described in this paper was a continuation of earlier studies into the role of alkali sulfates in promoting the sulfation roasting of nickel sulfides1,2 in an endeavor to determine how the system was affected by the presence of compounds of iron and copper. The earlier work1 showed that, in the sulfation of NiO at 680°C, the reaction was limited by the formation of an impermeable film of nickel sulfate on the oxide surface. The relative effect of the various alkali sulfates in promoting nickel sulfation varied in the order: Li > Na >Cs > Rb > K A study of alkali sulfate/ nickel sulfate interactions at high temperatures showed that the promoting action was due to the fact that the nickel sulfate product layer sintered and agglomerated only when the more active additives were present. This resulted in the formation of discontinuities in the nickel sulfate layer so that diffusion of the sulfating gases to the NiO surface was no longer impeded and the reaction could proceed to completion. A similar explanation was used for the observation that sodium and lithium sulfates promote the oxidation of NiS to NiO at temperatures below 750°C since small amounts of nickel sulfate were formed during oxidation.2 It was of interest to study the effect of alkali sulfates on the sulfate roasting of a sulfide flotation concentrate which is typical of material treated commercially. In order to control temperature it is essential to roast sulfides in a fluidized bed and this technique was therefore used, although the batchwise operation of a small-scale laboratory reactor does not reproduce all conditions which prevail in full-scale continuous plant. The results obtained are therefore only comparative, and cannot be used for predicting the optimum conditions for metal extraction. The sulfation of synthetically prepared mixed oxides of nickel + copper and nickel + iron and of nickel ferrite was also studied to evaluate the relative effects of alkali sulfates with more complex systems. SULFATION ROASTING OF A SULFIDE FLOTATION CONCENTRATE The bulk sulfide flotation concentrate used in this work contained 7.92 pct Ni, 1.74 pct Cu, 35.66 pct Fe, and 31.28 pct S. The sulfide minerals present in order of abundance were pyrrhotite FeS, pyrite FeS2, pentlandite (FeNi)S, and chalcopyrite CuFeS2. Two samples described as coarse and fine were used. The coarse sample, which was a flotation concentrate (58 pct plus 300 mesh), was ground to 100 pct minus 350 mesh to produce the fine sample. Before roasting, the sample of sulfide concentrate was agglomerated by wetting witli a solution of the alkali sulfate (or water), thoroughly mixing, and drying at 110°C. This gave a cake which was gently crushed and screened, the -18 +100 mesh fraction being used for fluidized bed roasting. A similar-size fraction had been used by the authors in pilot plant work with a 4-in.-diam fluidized bed reactor.' In this work it was found that the molar ratio of additive to the total iron + nickel + copper content of the sulfide sample should be adjusted to a value of approximately 0.06, as this was the optimum amount necessary for nickel sulfation. Experimental. The fluidized bed reactor consisted of a quartz tube approximately 60 cm long and 30 mm in diameter resting in a vertical tube furnace. The sulfide bed (30 g) was supported on a bed of -4 +12 mesh quartz particles 3 cm high, which rested on a sintered quartz disc welded to the tube. The temperature of the furnace was controlled with a variable transformer to give a final bed temperature of 680°C. The bed was fluidized with air or mixtures of air + 10 pct v/v SO2, at a total apparent gas velocity of 60 to 65 cm per sec at 680°C. The SO2 was introduced into the fluidizing air stream only when the oxidation of the sulfides was completed. At the end of the roasting period the calcine was leached with boiling water and the

Jan 1, 1964

By J. R. Hunter

Current trends in mining practices within the United Kingdom, with particular reference to longwall retreating systems in thick and steeply pitched coal seams at depth, are explained. Various successful mining layouts are considered with their associated machinery and operation, together with the future trends in mining practices to obtain higher outputs. Environmental difficulties are tabled and discussed, including strata control, methane emmision, and dust prevention, together with some modified systems and techniques to overcome them. The problems associated with developing and maintaining a continuance of longwall panels are outlined. The constraints on technical designs and output achievement imposed by noncommercial factors are also considered.

Jan 1, 1978

By Frederick C. Hull, Robert F. Mehl, Robert A. Colton

IT is known that pearlite forms from austenite by a process of nucleation and growth, and that the rate of formation of pearlite may be described by a rate of nucleation and a rate of growth 12 The manner in which these two quantities operate to produce the observed isothermal reaction curve has been analyzed in a paper published in 1939 3 Two types of process were described (I) that in which nucleation occurs at the grain boundaries of the parent phase, with the nodules growing toward the centers of the grains, initially as hemispheres and then after impingement as roughly radial-columnar structures, and (2) that in which nucleation occurs generally, with the nodules growing to full spheres until impingement with other growing nodules restricts growth Both cases are met in the formation of pearlite from austenite (Fig 1),2,3 the former, occurring near the knee of the S-curve has been named "grain-boundary transformation," and the latter, occurring at temperatures near AeI, has been named "group-nodule transformation " In developing our knowledge of the factors that determine the rate of formation of pearlite from austenite, it is important''' to obtain data on the rate of nucleation and the rate of growth of pearlite Such data, when obtained near the knee of the S-curve, will furnish information of use in understanding the actors that affect hardenability, when obtained at higher temperatures, such data will be useful in understanding the behavior of steels that during heat-treatment react to pearlite 2 It is the purpose of this paper to present data on the rate of nucleation and the rate of growth of pearlite in dependence upon composition, grain size, temperature,, and the degree of homogeneity of the parent austenite The studies are restricted chiefly to plain carbon commercial steels PREVIOUS DATA ON RAID OF NUCLEATION AND RATE OF GROWTH Data on the rate of nucleation and the rate of growth of pearlite have been published by Scheil and Lange-Weise,5 by Mirkin and Blanter,6,7 by Mehl,1 and by Dorn, De Garmo and Flanigan22 It is difficult to interpret the data, for in most cases too little information is given on austenitizing temperatures and times, the state of homogeneity of the austenite (presence or absence of carbide, etc ), austenite grain size, and mode of formation of pearlite at the temperatures given

Jan 1, 1942

By M. R. Pickus

THE study of the plastic deformation and recrystallization of metals has been the subject of many investigations. In regard to the simple deformational processes, such as tension and compression, the early knowledge gained from studies of polycrystalline material has been supplemented by many significant researches on the behavior of single crystals. Unfortunately, this has not been true for more complicated deformational processes. As far back as 1927, G. I. Taylor1 wrote: It is impossible in the present state of knowledge to do more than give a possible reason why (face-centered cubic) crystals set themselves with a (110) direction in the plane of rolling, and at right angles to the direction of rolling. The explanation of why the orientation of the crystal axes round the transverse direction is what it is, must be left till the distortion of metals, and particularly single crystals of metals in the process of rolling, has been studied in greater detail. That this gap in the systematic study of deformation and recrystalliza-tion has not yet been filled was indicated by C. H. Samans,2 who wrote in 1934 that "only four investigations upon cold-rolled single crystals of any of the face-centered cubic metals have been reported in the literature." Of these four studies, only those of S. Tanaka3 and T. Sakao,4 both of whom worked with aluminum crystals, had quantitative significance. The other two, carried out by F. Wever5 and W. G. Burgers,6 were of a. qualitative nature. It is our hope that the present investigation may contribute some-thing to the knowledge necessary for a rationalization of the origin of rolling textures in terms of the known behavior of single crystals, and may add pertinent information concerning the recrystallization characteristics of deformed single crystals.

Jan 1, 1938

By Joseph W. Roe

MaNY questions arising in the work of the mining engineer may be solved quickly and with suffcient accuracy by the methods of descriptive geometry; but, unfortunately, this subject is more often considered from a mathematical view-point than as an effective tool for solving practical problems. Some of the principles involved are merged into the ordinary operations of mechanical drawing, and are used unconsciously by the engineer in his every-day work. The rest are stowed away on the book-shelf with his forgotten or rarely-used college text-books. One reason for this condition of " innocuous desuctude " may lie in the uifortunate and often cumbersome notation which it has been found necessary to introduce. If some of these principles can be recalled to the engineer's attenti011 in terms of' every-day use they may prove of practical hearing. Recently, in talking with several mining engineers, I used some of the drawing-room methods of a machine-designer, to the evident surprise of those around me. These men were perfectly familiar with the methods, but their application to mining-work had not occurred to them. At their suggestion the present paper is offered, not in ally way as a treatise, but merely to suggest a certain point of view, in hope that it may lead others far more familiar with mining-problems to pursue the subject further. I. To Find the Strike. As the simplest and most fundamental problem, let it be required to find the strike of a vein when the location and elevation of three points on the outcrop are known. It mill be assumed for the present that the rein is a plane.

Jan 1, 1911

Jan 1, 1896

By Nicholas J. Grant, John Chipman

A FULL understanding of the behavior of sulphur in the basic open-hearth process has been delayed by lack of dependable data covering a wide range of slag conditions in the absence of other complicating factors that are likely to be present under operating conditions. It has been generally accepted that strongly basic slags will dissolve more sulphur than will those in which the acidic and basic constituents are more nearly balanced. It has been known that both slag and metal would absorb sulphur from the flame when the sulphur content of the fuel is high. It has been generally believed that manganese assists in the transfer of sulphur from metal to slag. Almost nothing has been known of the effect of temperature upon desulphurization; the data have been conflicting and there has been a tendency to depend rather heavily upon analogy with the better understood desulphurizing reaction of the blast furnace. Many attempts have been made to build up from open-hearth data a satisfactory theory of the chemical reactions involved in the process. That this has been an extremely difficult task is owing to two reasons that have been very generally recognized. The first is the parallel and simultaneous reaction of sulphur transfer between flame and bath. The second is the difficulty of distinguishing between the factors that ultimately limit the transfer from metal to slag-i.e., equilibrium conditions-and those whose influence is only upon the rate of transfer. It has been the object of the work here recounted to study the equilibrium distribution of sulphur between slag and metal in the absence of these complicating factors, with the hope that a better understanding of the equilibria involved would lead to a better control of the over-all process in the open-hearth furnace. A review of the literature on steelmaking reveals almost complete agreement with respect to the paramount importance of lime in promoting desulphurization. In expressing this effect in quantitative terms, however, and in formulating the relationships between the concentrations of other slag components and the desulphurizing power, there is little agreement. For instance, the "basicity" or basic strength of the slag is commonly measured by some kind of ratio of concentration of basic to acidic oxides. Of these, the following have been reviewed by Schenck :20 [ ] Among others there appear the following:

Jan 1, 1946

By E. P. Pfleider

DIAMOND drill research work was initiated at the School of Mines, University of Minnesota, in late 1949. The Drilling Symposium held in Duluth that spring highlighted the problem of high cost and core recovery and the need for controlled testing. An advisory committee made up of informed representatives of both mining companies and drilling companies was formed to suggest and advise on a program of drill research. A Hy-Mac hydraulic drill unit, see Fig. 1, especially designed for experimental testing, was obtained for this work by the School of Mines through the courtesy of the Carboloy Co. It is an extremely flexible unit, capable of exerting a forward thrust of about 1750 lb and turning at speeds from 650 to 2200 rpm. The feed arrangement is so designed that the advance can be set either at a constant rate or permitted to vary at a fixed pressure, see Fig. 2. The

Jan 1, 1952

By Larry Kaufman, Joan B. Berkowitz-Mattuck, Edward V. Claugherty

The oxidation characteristics of hafnium and zirconiunr diboride were measured between 1200 and 2200'K by a thermal- conductivity method which continuously ttzeasures the rate of reaction of oxygen with the diboride and by a metallographic air oridation method zuhich provides a measure of the total arr7ount of bovide conuerted to oxide for a given time interval. The oxidized specimens obtained from the tl~eritaal-coi~ductitrity method were also examined by quantitatire metal-lographic procedares. The significant results obtained in this investigation reveal that metal-rich compositions of lzafi~iutil diboride proride the most oxidation-resistatzt material up to 2000°K; hafnium diboride is tmre oxidation- resistant titan zirconium diboride at all tempevatures examined; the morphology of the oxide formed on H/B2 and Llie temperature coefficient qi. the oxidation rate constants change at the temperature of ttze monoclinic to tetragonal phase transition] in HfO2; the oxidation of neither HfB2 nor ZrB2, results iN catastrophic Jazlure at lorc. oxygen pressures; and pvefevetztial gvaLti boundary oxidation was not obsevued for either HfBi or ZYB, A comprehensive study of the high-temperature characteristics of refractory transition-metal di-borides is currently in progress. This program has included investigation of the physical, thermal, and thermodynamic properties of TiB2, ZrB2, HfB2, NbB2, and TaB2. In addition, aspects of the synthesis and fabrication of such materials have been studied. In view of the diverse nature of this research, a number of other laboratories have actively participated and contributed specific capabilities for analysis and characterization of these materials. As a consequence, an extensive description of the relevant properties of these compounds has emerged which is central in evaluating their high-temperature (1200" to 2500°K) performance. To date, information on thermodynamic stability, specific heat, and vaporization characteristics,1 hot hardness and electrical resistivity,1, 3 therma1 expansion:'4 and thermal conductivity 1, 5 has been presented. This information has been generated on materials of the highest purity (98.5 to 99.9 wt pct Me + B) and density currently available. Samples fabricated by zone melting6 and high-pressure hot pressing"3'7 techniques have been used to generate suitable specimens for all of the aforementioned studies. dation characteristics of the most oxidation-resistant of these materials, hafnium and zirconium diboride, is presented and a description of the synthesis and the experimental procedures used to prepare and characterize specimens is given. The high-temperature range under consideration (1200" to 2200°K) and the known dependence of oxidation characteristics on sample chemistry, density, and oxidation conditions required a close coupling of the synthesis, fabrication, and evaluation procedures.8 This was accomplished by continual surveillance of chemical composition of starting materials before and after specimen fabrication and by evaluation of density, phase constitution, and microstructural features prior to and after oxidation exposure. I) PROCUREMENT AND CHARACTERIZATION OF STARTING MATERIALS In view of the current state of the art in fabricating refractory boride materials, the methods used in preparing samples for the present study are given in detail as follows: starting materials were purchased in high-purity powder form and fabricated by high-pressure hot pressing into 0.40 by 1.00 in. bars from which oxidation specimens were obtained. The hafnium diboride used in this study was purchased from Wah Chang Corp.; the zirconium diboride from U.S. Borax and Chemical Co. These powders were routinely characterized by quantitative chemical analyses for metal, boron, carbon, oxygen, nitrogen, and iron, by qualitative emission-spectrographic analysis for trace impurities, by X-ray procedures for extraneous phase identification, and by powder densitometry for comparison with X-ray (theoretical) density. Hafnium and zirconium metal and elemental boron were also purchased as high-purity powders and characterized for impurities by emission-spectrographic analyses. The hafnium diboride was procured in three shipments which were designated as HfBl.g7(1), HfB1.88(2A), and HfB2.12(2). The indicated stoichiometry is based on the atomic ratio of total boron to total hafnium; the number in parentheses identifies the shipment number. Shipment 1 was 5 1b, shipment 2A, 1 1b, and shipment 2, 8 1b. The zirconium diboride was procured as a 20-1b shipment and designated as ZrB1.89(1). A small quantity of purified zirconium diboride was also supplied and designated ZrB1, 9(P). The averaged results for chemical analyses which were generally performed according to the procedures set forth in the compilation by KrieGe9 are presented in Table I. Qualitative spectrographic analyses indicated that Ca, Cr, Ti, Si, Zr (in H~B~), and A1 were present at levels between 0.01 and 0.10 wt pct. Other metallic elements were found to be less than 0.01 wt pct. Since it is virtually impossible to purchase these materials in the desired quantities (5 to 20 lb) as single-phase compounds it is necessary to obtain

Jan 1, 1968

By M. D. Everell

A study has been made of the relationships between grinding selection functions and physical properties of rocks, particularly the failure loads of irregular particles and the compressive and tensile strengths of large regular specimens. The rocks used were limestones of various structures and impurity contents, a carbonatite, and a high-purity crystallized calcite. The selection functions were obtained from carefully performed grinding experiments on selected narrow size ranges in various grinding machines-a laboratory batch ball mill, a Hard grove grindability machine, and a mill of the type suggested by Yang, Mempel, and Fuerstenau. The specific rates of breakage during milling and the failure loads of irregular specimens correlated well for the rocks studied. The testing of irregular particles is suggested as a means of predicting the behavior of commercial mills.

Jan 1, 1973

By Henry J. Miller, Marcella Linderman

During some experiments made by Henry J. Miller, partly in Germany and partly in the United States, in which it was found necessary to melt metals in quantities up to 60 kg. in a vacuum or under low pressures of hydrogen, molybdenum was tried as the resistor in the electric melting furnaces. Molybdenum ribbons 16 by 0.55 mm. and 18 by 0.45 mm. were used as resistors. The furnaces were of the type shown in Fig. 1. About the heating tube, Y, are wound parallel resistors of molybdenum ribbon from the water-cooled electrodes, El, Ez. The whole is within a copper container having outlets for the removal or introduction of gases and a window, W, for observation, the space about the heating tube and electrodes being filled with insulating material. The life of the molybdenum used as the resistor was found to depend very much on the manner of using it, its failure being due in some cases to thinning by evaporation or chemical reaction and in others to hardening, which prevented it from following the expansions and shrinking of the heating tubing without cracking. As such failures are often rather expensive in commercial work, it was thought worth while to determine the causes. The factors influencing the behavior of molybdenum resistors used in this manner may be briefly stated as follows:

The John Fritz Medal is awarded from time to time for notable scientific or industrial achievement by a board composed of representatives from the four engineering Societies. The members of the Board of Award for 1917 are: A. S. C. E. A. S. M. E. George F. Swain Ambrose Swasey, Charles Warren hunt, John, A. Brashear, Charles D. Marx, Frederick R. Hutton, Clemens Herschel. John R. Freeman. A. I. M. E. A. I. E. E. Gybbon Spilsbury, C. 0. Mailloux, Charles F. Rand , Paul M. Lincoln, Christopher R. Corning, John J. Carty, Benjamin B. Thayer. Harold W. Buck. The John Fritz Medal was awarded in January, 1917, to Dr. Henry Marion Howe, for his "investigations in metallurgy, especially in the metallography of Iron and Steel." The presentation ceremonies were held in the Auditorium of the United Engineering Societies' Building, New York, on Thursday evening, May 10. Mr. Ambrose Swasey, Chairman of the John Fritz Medal Board of Award, presided, and addresses were delivered by Dr. Rossiter W. Raymond, Secretary Emeritus of the American Institute of Mining Engineers, and Dr. Ira N. Hollis, President of the American Society of Mechanical Engineers. Professor Albert Sauveur, Chairman of the Board at the time the award was made, presented the medal, and the ceremonies concluded with the response of Dr. Howe.

Jan 7, 1917

By Arthur E. Bousu, C. T. Eddy, L. W. Eastwood

THE recrystallization and grain-growth phenomena of cold-worked metals have considerable industrial importance because of their role in the fabrication of metals. For this reason, and because of the general academic interest in the subject, these processes have received considerable attention since the time of J. E. Stead's paper1 on The Crystalline Structure of Iron and Steel. There are considerable differences of opinion regarding the theory of recrystallization and grain growth and also differences in the observation of the modus operandi of the processes themselves. The value of many of the existing quantitative data on grain growth is decreased by the failure to distinguish between the grain sizes just after complete recrystallization and those resulting from coalescence. For this reason also, the value of the diagrams of stable grain sizes, like those produced by . Bass and Glocker2 and Czochralski3, is lessened in so far as an interpretation of the facts of recrystallization is concerned. It is hoped that the data presented in this paper will help to clarify and to simplify the facts relating to recrystallization, and at the same time will show that some of the present-day conceptions are untenable. A paper on the theory of recrystallization with additional data will be completed in the near future by the writers.

Jan 1, 1935

By G. L. F. Powell, L. M. Hogan

Samples of silver and Ag-O alloy, 0.12 wl pet, have been undercooled to a maximum of 250°C by melting in a slag of commercial soda-lime glass. Grain refinement occurred in undercooled silver samples whet the degree of undercooling exceeded a critical value which varied from 153° to 175°C, depending on the melting conditions. In under cooled Ag-0 samples, the grain structure was fine and equiaxed at degrees of undercooling larger than 50oC. The grain refinement in both silver and Ag-0 alloy samples was the result of recrystallization during or immediately following freezing. When the oxygen content was increased, the degree of undercooling at which recrys-tallization occurred decreased. INVESTIGATIONS of the grain structure of strongly undercooled melts of nickel and cobalt1-4 have revealed a change in room-temperature grain size as a function of undercooling. At large degrees of undercooling the grain size was fine, but samples undercooled by smaller amounts exhibited a much coarser grain structure. The reported undercooling at which this grain size transition occurred in nickel varied between 140° and 175'C undercooling. Walker1 attributed this grain size change to an enhanced nuclea-tion rate. Cavitation at a melt-solid interface was con sidered to generate a high-pressure wave. This, in turn, produced nucleation in the liquid as a result of an elevated freezing point increasing the undercooling in the melt. A similar grain size transition was observed in undercooled silver between 133° and 153°C undercooling.5 The grain size transition in undercooled silver was found to be dependent on oxygen con tent. More recently, the authors5 showed that a simila transition occurred in an undercooled Cu-O alloy, =0.08 pet, but not in oxygen-free copper undercooled more than 200°C. The transition was attributed to recrystallization of the solidified grains after freezing; the greater the degree of undercooling, the more complete the recrystallization. In view of this effect of oxygen content on grain size transition, additional undercooling experiments were carried out with silver. This paper reports the results of these studies on silver and Ag-O alloys undercooled more than 50°C EXPERIMENTAL 1) Materials. The silver was supplied by Matthey Garrett Pty., Ltd., as fine granulate, silver mini' mum 99.9 pet, and contained the trace impurities shown in Table I. The silver originated from two different refineries resulting in the difference in impurity content shown in Table I. However, the variation in composition had no discernible effect on the undercooling behavior. Samples of the silver were melted in an open-ended, vertical, cylindrical resistance furnace, wound with Kantha] wire, the temperature of which was adjusted by means of a variable transformer, 2) Melting and Undercooling. Bulk samples of silver were undercooled by preoxidation and removal of oxidized impurities in a glass slag, as previously described,5 but special precautions were necessary to allow comparison between oxygen-free silver and a Ag-O alloy. Samples free of oxygen were prepared by first melting weights of granulate varying from 200 to 400 g in clean vitreous silica crucibles in air for approximately 15 min. A sample was frozen and a complete glass cover formed over the top surface by adding granulated glass rod. The sample was then melted and frozen several times until no oxygen bubbles appeared in the glass slag. Subsequent thermal analysis indicated that the oxygen content was negligible. The glass acted as an efficient barrier to absorption of oxygen from the air. Ag-O alloys were prepared by melting silver in silica crucibles with only a partial cover of glass, so that the top surface of the melt was in contact with air. The silver was held molten in air for several hours at 1000° to 1050°C, in the expectation that the oxygen in solution would reach equilibrium with atmospheric oxygen. At T - 1000°C the equilibrium oxygen content was calculated as 0.12 wt pet O, using Sieverts law and Eq, [l], derived by Mizikar et a!.7 from the data of Sieverts and Hagenacker8 for 1 atm of oxygen:

Jan 1, 1970

By R. S. Archer

THE name molybdena was employed by Pliny to denote various substances resembling lead. Later this name was applied to galena-the naturally occurring sulfide of lead-or substances of similar appearance. By the middle of the eighteenth century, it was applied to graphite and to the mineral sulfide of molybdenum (MoS2) now called molybdenite. This confusion is quite understand- able inasmuch as these substances look and feel very much alike. In 1778, the Swedish chemist Scheele published a treatise in which he pointed out essential differences between graphite and molybdenite. On treatment with nitric acid, molybdenite, unlike graphite, produced a peculiar white earth with acidic properties which he called molybdic acid. Since the same mineral gave off sulfurous fumes on heating, he concluded that it was a sulfide of molybdenum. In 1790, there appeared an account of the isolation by P. J. Hjelm of the new element molybdenum, as a metallic powder, by heating the oxide with carbon. It was not until Bertelius conducted the necessary experiments, about 1818 to 1825, that the foundation of the chemistry of molybdenum was laid. The only recorded use of molybdenum during the first century after its isolation was as a chemical reagent, primarily for the determination of phosphorus. It was not until the last decade of the nineteenth century that the use of molybdenum in steel appears to have been investigated. A

Jan 1, 1953

By W. P. Blake

Forty-five years have passed since I discovered the extensive and remarkable diatom-earth beds at Monterey, California., and now I have the satisfaction of bringing to notice still another wonderful deposit in the heart of Arizona. The Monterey beds mere described at the Philadelphia Academy,* and specimens were sent to Prof. J. W. Bailey, West Point, N. Y., at that time the leading American authority upon such microscopic relics of organic life. The earth from both localities is snow-white and pulverulent. It rubs off' like soft chalk upon the fingers when handled, and has the general appearance of chalk. But, unlike the Monterey beds, these newly-discovered deposits consist largely of volcanic ash, through which the siliceous shells of the diatoms are distributed. These deposits are in the central portion of the San Pedro valley,† in the southeastern corner of Pinal county. The region of their greatest development is a few miles south of the mining town of Mammoth, on the east bank of the stream, and near Redington, some 40 m. N. of Benson, on the Southern Pacific railway. The altitude is about 2600 ft. above tide. This portion of the San Pedro valley lies between the high Catalina and Rincon ranges on the west and the Galiuro mts. on the east. The Catalinas are composed chiefly of crystalline DIRECTOR OF THE ARIZONA SCHOOL OF WINES,

Jan 1, 1903

By Bruce E. Grant, Thomas Jancic, Lawrence G. Dykers, Frank Buchella

Principal factors influencing equipment selection can be grouped into five basic categories: tonnage requirements, ore and waste; topography and property line considerations; ore control requirements; physical characteristics of ore and waste; and climatic considerations. Loading, transporting and ground preparation equipment are largely determined by tonnage requirements. Large size equipment is appropriate for a production of about six million tpm, medium size for three million tons and small size for one million tons or less.

Jan 12, 1973

By E. A. Anderson, M. L. Fuller

The copper-zinc phase equilibrium diagram has been the subject of many investigations. Until recently, however, the boundary of the terminal solid solution of copper in zinc (eta) has not been thoroughly investigated. This paper reports determinations of the solid solubility of copper in zinc at temperatures from 100' to 400' C., the course of the liquidus and solidus for the eta solid solution and determinations of the peritectic temperature and peritectic point for the reaction between epsilon and the melt to form eta. The liquidus of the eta phase was determined by thermal analysis and the solidus by the microscopical examination of specimens quenched from temperatures above and below the solidus. The temperature of the peritectic horizontal was obtained by thermal analysis and the composition at the peritectic point was determined by extrapolation of the solid solubility boundary of the eta phase to the peritectic horizontal. The solid solubility boundary of the eta solid solution was investigated very carefully. Particular care was used to achieve equilibrium in the alloys at each temperature selected. The X-ray, electrical conductivity and microscopical methods mere used in determining the solid solubility limits. The X-ray method measures the changes in the solvent lattice with increasing solute content and in this manner locates the composition of the alloy at which no further change in the solvent lattice takes place, the limit of solid solubility. The method of electrical conductivity measures the conductivity of the alloys of a graded series of compositions, whereby the solubility limit is indicated by a discontinuity in the conductivity-composition relationship. The microscopical method distinguishes, by direct inspection, between the homogeneous solid solution alloys and those having a secondary constituent in addition to the solid solution phase, and thus indicates from the examination of a series of alloys the solid solubility limit.

Jan 1, 1934