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By J. V. N. Dorr

DEADWOOD and the Black Hills were familiar names to me from childhood, for. I had an uncle who was among the earliest eastern investors there and I used to hear of the Uncle Sam mine and its rich ore back in the eighties. The spring of my junior year at college, in 1893, brought me an offer of summer work at the Deadwood & Delaware smelter, in Deadwood, and full of the thrill of the long journey from New Jersey, I went out as chemist and stayed four months. Within a week or two of my arrival, I went through the tragic experience of seeing an associate drink cyanide by mistake and die within a few moments. I shall never forget the horror of feeling that my lack of knowledge of an antidote might be responsible for his death, but I found later that the solution he drank was so strong that nothing could have been done. A year after graduation, when I had settled down to chemical research work in New York, an offer came to go back to the smelter in Deadwood, and within a few days I was again tramping down "the Gulch" with my lunch bucket and putting in the standard assay office shift of that day, from 7 a.m. to 6 p.m., with a half-day off on Sundays. During my absence East, the D. & D. smelter had been changed from a pyritic smelter, using native pyrite, and Homestake concentrate to matte the siliceous gold ores, into a copper-matting smelter using copper ores brought from Butte, over the newly-completed Burlington rail-road. The work was interesting, and the laboratory offered many opportunities for making improvements. I remember also undertaking experiments at home on a new method of gold precipitation for the chlorination process and leasing a mine in Strawberry Gulch that promised great things, but soon petered out.

Jan 8, 1927

By J. H. Frye, J. W. Caum

One of the most important methods of increasing the hardness of metals is alloying. In spite of the widespread use of alloys, the fundamental mechanism of alloy hardening is little understood. This is true even of the simplest form of alloy, the primary substitutional solid solution in which solute atoms substitute for solvent atoms at random in the crystal lattice of the latter. A fundamental understanding of the mechanism of solid-solution hardening would be important, both because of the widespread use of alloys of this type and because of the light that might be thrown on the mechanism of hardening in more complicated alloys. The present investigation covers the hardness of primary substitutional solid solutions of zinc, gallium, germanium, and arsenic in copper. All of these are B subgroup elements from the third period of the periodic table. Cu, Zn, Ga, Ge, and As are in groups I, 11, 111, IV, and V, respectively, and lie just to the right of the transition elements. Because of their cost, it is unlikely that Ga-Cu and Ge-Cu solutions will ever be of commercial importance, but the intent of this study has been to discover some of the fundamentals of solid-sdstion hardening and it has been demonstrated that such a study is far more likely to be fruitful if alloys are made up on the basis of position of the constituent elements in the periodic table than if commercially important alloys are used. Many investigations have been made of the hardness of substitutional solid solutions, but lack of attention to purity of the metals, infrequent grain-size control, and the use of varying testing techniques have virtually invalidated any comparisons. The purpose of most investigations has been to solve immediate problems and not to solve the primary problem: Why do solid solutions usually have a greater hardness than pure metals? Previous Work Theories have been advanced to account for the hardness of solid solutions, but relatively little experimental work has been done. Perhaps the first experimental work of merit was that of Norbury1 on copper alloys. He showed that for several alloys there was a correspondence between the hardness of one atomic per cent solutions and atomic volume of the solutions. More recently Brick, Martin, and Anger2 have investigated the effect of various solute elements on the hardness of copper. They concluded that the hardening effect of these solutes depended "primarily on the difference in atomic volume of solute and solvent or, relatedly, upon the parameter change of the solvent or the extent of solid solubility." They also observed the effect of these elements on hardness and texture developed by rolling and by annealing of rolled material. Austin3 examined the hardness and response to heat-treatment of various iron solid solutions. Frye and Hume-Rothery4 measured the hardness of a number of silver solid solutions containing approximately 1 References are at the end of the paper.

Jan 1, 1943

By J. H. Frye, J. W. Caum

One of the most important methods of increasing the hardness of metals is alloying. In spite of the widespread use of alloys, the fundamental mechanism of alloy hardening is little understood. This is true even of the simplest form of alloy, the primary substitutional solid solution in which solute atoms substitute for solvent atoms at random in the crystal lattice of the latter. A fundamental understanding of the mechanism of solid-solution hardening would be important, both because of the widespread use of alloys of this type and because of the light that might be thrown on the mechanism of hardening in more complicated alloys. The present investigation covers the hardness of primary substitutional solid solutions of zinc, gallium, germanium, and arsenic in copper. All of these are B subgroup elements from the third period of the periodic table. Cu, Zn, Ga, Ge, and As are in groups I, 11, 111, IV, and V, respectively, and lie just to the right of the transition elements. Because of their cost, it is unlikely that Ga-Cu and Ge-Cu solutions will ever be of commercial importance, but the intent of this study has been to discover some of the fundamentals of solid-sdstion hardening and it has been demonstrated that such a study is far more likely to be fruitful if alloys are made up on the basis of position of the constituent elements in the periodic table than if commercially important alloys are used. Many investigations have been made of the hardness of substitutional solid solutions, but lack of attention to purity of the metals, infrequent grain-size control, and the use of varying testing techniques have virtually invalidated any comparisons. The purpose of most investigations has been to solve immediate problems and not to solve the primary problem: Why do solid solutions usually have a greater hardness than pure metals? Previous Work Theories have been advanced to account for the hardness of solid solutions, but relatively little experimental work has been done. Perhaps the first experimental work of merit was that of Norbury1 on copper alloys. He showed that for several alloys there was a correspondence between the hardness of one atomic per cent solutions and atomic volume of the solutions. More recently Brick, Martin, and Anger2 have investigated the effect of various solute elements on the hardness of copper. They concluded that the hardening effect of these solutes depended "primarily on the difference in atomic volume of solute and solvent or, relatedly, upon the parameter change of the solvent or the extent of solid solubility." They also observed the effect of these elements on hardness and texture developed by rolling and by annealing of rolled material. Austin3 examined the hardness and response to heat-treatment of various iron solid solutions. Frye and Hume-Rothery4 measured the hardness of a number of silver solid solutions containing approximately 1 References are at the end of the paper.

Jan 1, 1943

By Forrest K. Pence

BENTONITE deposits are known to occur in Texas within the Jackson group of formations. This group represents the uppermost Eocene age sediments found in the coastal plain area of Texas. It outcrops across this area of the state in a narrow band of some 4 to 20 miles width. The outcrop pattern roughly parallels the present Gulf of Mexico shore line and is some 100 miles inland from the Texas shore, Fig 1. The principal bentonite deposits are found in the areas where this outcrop pattern cuts across the south-central Texas counties of Karnes, Gonzales, and Fayette. In these deposits, the better quality bentonite is found in the lower or bottom layers of the volcanic ash deposits in which they occur. Some of these better quality bentonites develop very light colors upon firing and therefore justify their being classified as "white firing." The deposits in Karnes and Gonzales Counties apparently occur in commercial quantity, whereas the white firing strata so far uncovered in Fayette County have been too thin to be classified as yet as "commercial." A study of the ceramic properties of the weathered ash in Gonzales and Karnes Counties was reported in 1941.1

Jan 1, 1949

By M. E. Wadswort, A. S. Peck

Infrared data disclose that phenacite reacts with oleic acid to form a chemisorbed oleate monolayer on the mineral surface. The absorption band characteristic of the antisymmetrical C = 0 oleate structure appears at a spectral wavelength of 1623 cm-'. Chemisorption also results in the displacement of OH- and silicate from the mineral surface. Infrared absorbance at 1623 cm-1 is correlated with float-ability at different pH for -60-mesh phenacite particles. Phenacite, Be2SiO4, is an ore mineral often associated with quartz, microcline, and chrysoberyl in pegmatites and mica schist. Experimental phenacite beneficiating processes have been confined principally to the flotation of low grade ores occur-ing in several mountain ranges of Utah and Nevada. The U.S. Bureau of Mines ' has recently reported on the separation of phenacite from ore deposits of Mount Wheeler, Nev. Infrared techniques were previously applied by the authors to characterize the role of sodium oleate and oleic acid in the flotation of several non-sulfide minerals.23 A parallel study was projected to the flotation of the orthosilicate mineral phenacite with oleic acid. Infrared spectra provided a 'molecular fingerprint' of the mineral surface and permitted identification of the reaction mechanisms. Infrared data were complemented with flotation and chemical tests. EXPERIMENTAL PROCEDURES The experimental procedures used in this investigation, for which data are presented in graphical or spectral form, are described in chronological test order. Phenacite crystals from Mt. Antero, Colo., were obtained from Ward's Co., Monterey, Calif. The crystals were fragmented in a porcelain mortar to -60 mesh and then pretreated with 0.5 molar HC1 for 15 min to remove iron. Then, the mineral particles were washed free of acid with distilled water and dried. Part of the dried material was ground to a fine powder with a Fisher Grinder using an agate mortar and pestle. Next, the powder was placed in a graduated cylinder and mixed with 500 ml of distilled water. The mineral in suspension was decanted from the settled fraction after 5 min, and the colloidal suspension was used for adsorption tests in which a high specific mineral surface area was required for adsorption and infrared analysis. Conditioning was performed in 50 ml glass centrifuge tubes for both infrared and flotation test determinations. Twenty ml of colloidal suspension was used for the infrared adsorption tests. One and a half g of deslimed -60-mesh HCl pretreated phenacite was added to 20 ml of distilled water for flotation conditioning tests. Six mg of oleic acid was used for each infrared adsorption test, and 0.2 mg of oleic acid was used for the flotation conditioning tests. HCl and NaOH were used for pH modification. The pulps were stirred at a speed of about 1500 rpm for 3 min. Then, the solids were separated out and either dried at 50°C or immediately transferred to a float cell. The pH of the residual liquid was determined with a Beckman Zeromatic pH meter. The flotation procedure is described as follows: 1) A 325-1111 glass micro-float cell was filled with distilled water. 2) Conditioned mineral was placed in the cell and the pulp was aerated through the glass fritted bottom at 7 psi pressure. 3) Floated mineral was skimmed from the cell with a glass slide until flotation ceased. (The end point was reached in all tests in less than 2 min.) 4) The flotation products were dried, weighed, and the recovery was calculated. Samples for infrared analysis were made into mulls using either oleic acid or series 13-21 Halocarbon oil obtained from Halocarbon Products Corp., Hacken-sack, N.J. The mulls were placed between two sodium chloride windows. A characteristic phenacite infrared band at 1868 cm-' was used as an internal standard for quantitative determinations in which absorbance at this position was quantified by the baseline-tangent method4 and related to absorbance at 1623 cm-'. The ratio obtained by dividing absorbance at 1623 cm-' by absorbance at 1868 cm-' was defined as an absorbance quotient for use in graphical presentation.

Jan 1, 1968

By Marius S. Darrow, William B. White, Rustum Roy

The PbS-PbTe systen has been studied by quench-ing and D.T.A. techniques f?om 400' to 1150°C. Runs were made in evacuated silica tubes so that all equilibria are at the vapor pressure of the system. Lattice parameters of the quenched salnples , measured by X-ray diffraction, show a complete crystalline-solution series existing over a narrow temperature range between approximately 805" and 871°C. An exsolution dome extends from a maximum of about 805"C (approximately 30 mole pct PbTe) to 1 and 96.5 pet PbTe at 400°C. A narrow melting region, deternined by D.T.A., extends form 918c (mp PbTe), The shapes of the liquides and solidus curves imply the existence of a minimum at 871°C at approximately 65 pct PbTe. THe exact composition of the minimum could not be established due to the very narrow two-phase region. At compositions containing less than 50 pet PbTe, liquidus temperatures begin to increase, while the solidus remains almost flat to about 15 mole pet PbTe before beginning to vise toward the mp of PbS (1075 C). LEAD sulfide and lead telluride are isostructural (NaC1 type) semiconductors whose electrical and optical properties have been extensively studied and used in recent years. If appreciable crystalline solution exists between these compounds, the variation of physical properties with composition could be of interest. The purpose of this investigation was to determine the extent, if any. of crystalline solution, and to obtain the phase diagram for the system. To the knowledge of the authors, only three studies of the system PbS-PbTe have been reported, and, in chronological order, each investigation found an increasing amount of crystalline solution. In 1956, Yamamoto reported finding no evidence of crystalline solution between the compounds. Sindeyeva and Godov-ikov,' in 1959, found very limited crystalline solution. but only under conditions of excess tellurium concentration. Finally Melevski s3 investigation in 1963 indicated that one solid phase exists in the region from PbS to 7 pct PbTe and from 82 pct PbTe to PbTe at 886'C, with an eutectic at 55 pct PbTe at that temperature. Detailed data on the solvus boundary were not given. EXPERIMENTAL EQUIPMENT AND MATERIALS Commercially produced PbTe and PbS powders were used as starting materials. Batches of specific mole percent composition were accurately weighed and mixed in a plastic bottle, in a shaker mill. An analy- sis of impurity content is given in Table I for pure PbS and PbTe and for two randomly selected batches after the powders were mixed. Individual samples, ranging in weight from 0.2 to 0.5 g, were sealed in evacuated silica tubes which had been thoroughly washed and rinsed with acetone and distilled water. Thus all data taken were at the pressure of the system. Subsolidus relations were studied down to 400°C by heating the samples in a vertical tube furnace for 24 hr. The sealed tubes were quenched in water with quench time from the hot zone not exceeding 1 sec. Temperatures were measured by a chromel-alumel thermocouple and controlled to 53°C for most runs. The number and composition of phases present were determined from powder X-ray diffraction patterns taken at room temperature on a Norelco diffractome-ter, using silicon as an external standard. Above 850°C quenching techniques were, in general, found to be unsatisfactory, and differential thermal analysis (D.T.A.) was used to determine melting relations. The evacuated tubes were recessed about 1 cm at one end to accommodate the differential thermocouple. Al203 was used as the reference material in a similar tube containing the other side of the differential couple. For temperature measurements, a separate thermocouple was placed in the recess of the tube containing the sample to be measured, thus providing an opportunity to obtain thermal, as well as differential, analysis. All thermocouples for these measurements were Pt-Pt 10 pct Rh. Temperature and differential curves were recorded separately on synchronized strip-chart recorders. Thermocouples and recording equipment were calibrated using NaCl and gold standards, using the melting points 801" and 1063 C, respectively, which span most of the temperature range of interest. Heating and cooling rates generally were from 4 to 7°C per min. It was found, in fact. that rates ranging from 1.5 to 25°C per min did not significantly change the data obtained.

Jan 1, 1967

By VILLIAN BRADEN

THIS paper is presented in the hope that it will be instructive in view of the future large expansion of the mining industry in the west-coast countries of South America. There is a more or less general impression that the Spanish-American workman is inferior to the American, but after some years of experience and observation I doubt the correctness of this view. Taking into consideration all the elements which make for efficiency of labor, it has been found, particularly in Chile, that under proper organization native labor yields as much, man for man, and more, dollar for dollar, than in the Western United States. If a manager is willing to accept unreservedly the c costumbres del pais, without combating intelligently and patiently the ones tending to inefficiency, he should expect no better results than he deserves. He must conscientiously insist that a " square deal " be given and exacted; that liquor be excluded from camp as far as possible; that comfortable quarters and other uplifting elements of life be provided; and that the costumbres del pais shall not be over-ridden roughshod. He should also insist upon the gradual and reasonable adjustment of these conditions to the exigencies of the work; and (by no means the least difficult of his tasks) he should select the most competent men to patiently direct and teach the natives in the several departments, and by their own example encourage self-respect and decency. While the Braden mine is by no means as yet operated on a large scale, according to modern rating, it will nevertheless be interesting to note what has actually been accomplished there. An illustrative description of the mines and mill of the\

Oct 1, 1909

By Frederick L. Knouse

The south border of Espirito Santo begins about 400 km. north of Rio de Janeiro and extends along the Atlantic Coast northward some 325 km. and inland 100 to 150 km. The area under consideration, where quartz crystal of strategic grades has been mined, extends from 19º to 21º and 30º south latitude; and from 40º to 41º and 30º west longitude. This includes the central part of Espirito santo, chiefly south of the Rio Doce from the Atlantic ocean, and west across the border into Minas Gerais near the town of Aimores, in the municipalities of Aimores, Minas Gerais; Baixo Guandu, Santa Teresa, Santa Leopoldina, Colatina, Joao Neiva, Fundao and Domingo Mar-tines, Espirito Santo (Fig. I). During 1943 and the first half of 1944, this region accounted for approximately 3 to 5 per cent of the quartz crystal produced in Brazil. Shipments of crystal have been made chiefly by rail to Rio de Janeiro. This region is serviced by the E. F. Minas-Vitoria and E. F. Leopoldina to Rio de Janeiro through vitoria; and by the E. F. Minas-Vitoria and E. F. Centra] do Brasil through Bello Horizonte, Minas Gerais to Rio de Janeiro. The major deposits are accessible from the railheads by dirt roads, some being 5 to 30 km. off the road, reached by trail. In 1943 and the first half of 1944, the bulk of the production was from inter- mountain marshes and adjoining hillside alluvial placer deposits in the zone surrounding the town of Santa Teresa. Most of these deposits were formed from the erosion of pegmatite~, quartz veins and pockets in the gneiss, with minor quantities produced from miarolitic cavity fillings in the granitic rock. Early Operations Mining of quartz crystal in this region began in 1928 and has been stimulated by the market demand for military uses. Before 1936 little attention was given to it, either in Espirito Santo or eastern Minas Gerais. From 1936 to 1941 the Japanese sent agents to various points of production or potential production to acquire quartz through purchase. They bought crysta1 as small as 10 grams. Since '94' only the United States and Great Britain have received quartz from Brazil. The United States purchases crystals of 100 grams and larger for strategic purposes. The first known discoveries were made either in the municipalities of Aimores, Minas Gerais, or in Baixo Guandu, 01 Domingos Martines, Espirito Santo. Marketable quartz crysta1 was first found either in the massive quartz replacement veins of the Victor Hugo mine in the municipality of Domingo Martines, or in the large 'ores of quartz in the pegmatites near Baixo Guandu, extending into Minas Gerais. Production The production of quartz in Espirito Santo from 1936 through 1941 as recorded

Jan 1, 1948

By Frederick L. Knouse

The south border of Espirito Santo begins about 400 km. north of Rio de Janeiro and extends along the Atlantic Coast northward some 325 km. and inland 100 to 150 km. The area under consideration, where quartz crystal of strategic grades has been mined, extends from 19º to 21º and 30º south latitude; and from 40º to 41º and 30º west longitude. This includes the central part of Espirito santo, chiefly south of the Rio Doce from the Atlantic ocean, and west across the border into Minas Gerais near the town of Aimores, in the municipalities of Aimores, Minas Gerais; Baixo Guandu, Santa Teresa, Santa Leopoldina, Colatina, Joao Neiva, Fundao and Domingo Mar-tines, Espirito Santo (Fig. I). During 1943 and the first half of 1944, this region accounted for approximately 3 to 5 per cent of the quartz crystal produced in Brazil. Shipments of crystal have been made chiefly by rail to Rio de Janeiro. This region is serviced by the E. F. Minas-Vitoria and E. F. Leopoldina to Rio de Janeiro through vitoria; and by the E. F. Minas-Vitoria and E. F. Centra] do Brasil through Bello Horizonte, Minas Gerais to Rio de Janeiro. The major deposits are accessible from the railheads by dirt roads, some being 5 to 30 km. off the road, reached by trail. In 1943 and the first half of 1944, the bulk of the production was from inter- mountain marshes and adjoining hillside alluvial placer deposits in the zone surrounding the town of Santa Teresa. Most of these deposits were formed from the erosion of pegmatite~, quartz veins and pockets in the gneiss, with minor quantities produced from miarolitic cavity fillings in the granitic rock. Early Operations Mining of quartz crystal in this region began in 1928 and has been stimulated by the market demand for military uses. Before 1936 little attention was given to it, either in Espirito Santo or eastern Minas Gerais. From 1936 to 1941 the Japanese sent agents to various points of production or potential production to acquire quartz through purchase. They bought crysta1 as small as 10 grams. Since '94' only the United States and Great Britain have received quartz from Brazil. The United States purchases crystals of 100 grams and larger for strategic purposes. The first known discoveries were made either in the municipalities of Aimores, Minas Gerais, or in Baixo Guandu, 01 Domingos Martines, Espirito Santo. Marketable quartz crysta1 was first found either in the massive quartz replacement veins of the Victor Hugo mine in the municipality of Domingo Martines, or in the large 'ores of quartz in the pegmatites near Baixo Guandu, extending into Minas Gerais. Production The production of quartz in Espirito Santo from 1936 through 1941 as recorded

Jan 1, 1948

Pursuant to notice duly given in accordance with law and the constitution, a special business meeting of the members of the Institute was held at the office of the Institute on June 27, 1919, at 8.30 P.M., 1573 members were present in person or by proxy. On resolution duly made and seconded, the change of name to American Institute of Mining and Metallurgical Engineers, Incorporated, was authorized and the officers of the corporation were instructed to take the necessary steps to accomplish this result. The votes were 1565 in favor of the resolution and 7 against. It was then moved and seconded that the certificate of incorporation be amended to define the purposes for which the corporation was formed as follows: "To promote the arts and sciences connected with the economic production of the useful minerals and metals, and the welfare of those employed in the industries by all lawful means, " etc., etc.-the remainder of the article reading the same. The purpose of this change was to allow the Institute to take any legal means it desires to accomplish the objects mentioned above instead of restricting it within narrow limits. The vote was 1573 in favor of the resolution and none against.

Jan 8, 1919

By F. G. Jones, R. D. Pehlke, H. E. Gardner

The solubility of nitrogen in liquid Fe-18 pct Cr-8 pct Ni-0. 7 to 2.3 pct A1 alloys has been measured up to the solubility limit for the formation of aluminum nitride in the temperature range 1600° to 1700°C uszng the Sieverts' method. The solubility of nitrogen in 18-8 stainless steel increases with increasing aluminum content. Based on a nitride composition, AlN, the standard free energy of formation of aluminum nitride from the elements dissolved in liquid 18-8 stainless-steel alloys has been determined to be: ?G° = -42,500 + 20. IT in the range from 1600° to 1700° C. EVANS and pehlke1 have measured the equilibrium conditions for the formation of aluminum nitride, AlN, in liquid Fe-A1 alloys. The present study extends that work to the more complex solvent, liquid 18 pct Cr-8 pct Ni (18-8) stainless steel. Recent work by Small and pehlke2 has dealt with the effect of fourth-element additions on the solubility of nitrogen in 18-8 base alloys. They found the effect of aluminum additions, up to 0.74 pct, on the solubility of nitrogen to be small. The present study covered the range from 0.74 to 2.28 pct aluminum, and by extending the composition range may be used to better define the effect of aluminum on the nitrogen solubility in these alloys. EXPERIMENTAL PROCEDURE The Sieverts' method was used to measure the equilibrium solubility of nitrogen gas in liquid 18-8 stainless steel alloys containing 0.74, 1.49, 1.93, and 2.28 pct Al. The solubility was measured as a function of the nitrogen gas pressure at temperatures of 1600°, 1650°, and 1700°C. The apparatus used is the same as described by Small and Pehlke.2 The 100-g melts were made from Ferrovac-E high-purity iron, Crucible Steel Co.; 99.95 pct Cr, Union Carbide Corp.; 99.9 pct Ni, International Nickel Co.; and 99.99+ pct Al, Aluminum Co. of America. The aluminum was charged at the bottom of the crucible, surrounded by nickel and iron. The chromium was packed into the interstices to minimize vapor transport of the aluminum during initial melting. The hot volume of the system, measured for each melt with argon, ranged from 45 to 55 standard cu cm with a temperature coefficient of —8 x 10-3 cu cm per °C. The melt temperature was measured with a Leeds and Northrup disappearing-filament type optical pyrometer sighted vertically downward on the center of the melt surface. The temperature calibration of the system by Small and pehlke2 was assumed. Two problems are involved in determining the solubility product of a solid, metal nitride phase in liquid iron alloys. These are: 1) establishing the point of departure from Henrian behavior at the solubility limit of the metal nitride phase; and 2) determining the composition of the solid nitride which is precipitated. Determination of the solubility product of AlN was made by admitting small amounts of nitrogen into the reaction bulb until the deviation from Sieverts' law was clearly evident in the form of a pressure halt. To obtain the solubility product at several temperatures during one run the following procedure was used: 1) add increments of nitrogen to determine the Sieverts' law line at the lowest desired temperature; 2) continue to add nitrogen to precipitate a small amount of the nitride phase; 3) increase the melt temperature 50°C to dissolve the precipitated nitride; 4) repeat step 2 until either a nitride formed or the system reached ambient pressure; if a nitride formed at 1650°C, the sequence was repeated at 1700°C. The composition of the precipitated phase was checked by an X-ray diffraction pattern obtained from powder scraped from the surface of the solidified 1.93 pct A1 melt. RESULTS AND DISCUSSlON Solubility Measurements. Fig. 1 is a typical nitrogen-absorption curve obtained from measurements on a 1.93 pct A1 alloy. Since the initial absorption of nitrogen follows Sieverts' law the nitrogen solubility is plotted as a function of the square root of the pressure of nitrogen gas in the reaction bulb. The results of the solubility measurements for all alloys studied are summarized in Table I. The slope of the Sieverts' law line for each alloy was determined. Since this is also the solubility of nitrogen at 1 atm pressure of nitrogen gas, the latter designation is used for the data. It should be noted. however, that in most cases the value lies above the solubility limit for AlN. Fig. 2 shows the effect of aluminum on the solubility of nitrogen at this reference pressure and as a function of melt temperature. The solid portions of the lines represent attainable solutions; the dashed regions lie above the limit for precipitation of AlN.

Jan 1, 1969

By R. G. Davies

Above 500°C, where dislocation climb is rate controlling, it is observed that the activation energy for creep is independent of the apblied stress, although it varies from 62 kcal per mol at 15 pct A1 to 73 kcals per mol at 20 pctA1 due to the change in short-range ovdw with composition. Below 500°C, when the nonconservative motion of jogs upon dislocations is thought to be rate controlling, the activation energy is stress dependent. A sudden increase in the creep rate, for which no explanation is availab2e, occurs at the highest stress at all temperatures. CREEP has been the subject of numerous research publications during the past decade with most of the attention focused upon high temperature steady state creep, i.e., above 0.5 TM, where TM is the absolute melting temperature, as it is the most amenable to theory. Many of the proposed theories involve the climb of dislocations out of their slip plane, which allows them to circumvent obstacles or to annihilate dislocations of opposite sign on other slip planes.' For pure metals it is observed that the activation energy for this creep is equal to the activation energy for self diffusion.' The position is much more complicated in alloys as there are many possible microcreep mehanisms, as well as dislocation climb, which could be rate controlling. There has been little systematic investi- gation of alloys, but Weertman (lead and indium base alloys)3 and Lawley, Coll, and Cahn (Fe-A1 alloys)4 suggest a microcreep process as the controlling factor. A Cottrell-Jaswon atmosphere mechanism is proposed for the lead and indium alloys, and a mechanism involving crystallographic order for the Fe-A1 alloys. Lawley et al. showed that the formation of a super-lattice, either of the FeAl or Fe3A1 type. decreased the rate and increased the activation energy for creep. From the measurements of lattice parameters,= resistivity,' magnetic properties,7'8 internal friction: and dilatometry10 the ordered region is thought to commence at -19 at. pct Al. However, a recent investigation by the author indicates a value

Jan 1, 1963

By E. N. Smith, J. C. Redmond

The increasing need for materials capable of withstanding higher operating temperatures for various applications such as gas turbine blading and other parts, rocket nozzles, and many industrial applications, has brought consideration of cemented carbide compositions. The well known usefulness of cemented carbides as tool materials is attributable to their ability to retain their strength and hardness at much higher temperatures than even complex alloys. However, it has been found that the temperatures encountered in cutting operations do not approach by several hundred degrees1 those involved in the applications mentioned above where the interest is in materials possessing strength and resistance to oxidation at temperatures of 1800°F and above. At these latter temperatures, the tool type compositions which are made up essentially of tungsten carbide are found to oxidize very rapidly and to produce oxidation products of a character which offer no protection to the remaining body. As a further consideration, the density of the tungsten carbide type compositions is high, from about 8.0 to 15.0. The refractory metal carbides as a class are the highest melting materials known as shown by Table 1 which summarizes the available data from the literature for the carbides of the elements which are sufficiently available for consideration for these uses. The density is also included in the table, since as mentioned above it is an important consideration in many of the applications for which the materials would be considered. It has been established that in the tool compositions the mechanism of sintering with cobalt is such as to result in a continuous carbide skeleton and that the properties of the sintered composition are thus essen- tially those of the carbide.2 On the hypothesis that this mechanism holds to a greater or less degree in cementing most of the refractory metal carbides with an auxiliary metal, it appears from Table 1 that titanium carbide compositions would offer possibilities for a high temperature material. Titanium carbide has extensive use for supplementing the properties of tungsten carbide in tool compositions. Although the literature contains several references to compositions containing only titanium carbide with an auxiliary metal,3,4,5,6 it may be inferred from the meager data that such compositions were deficient in strength and were considered to have poor oxidation resistance.7 Kieffer, for instance, reports the transverse rupture strength of a hot pressed TiC composition at 100,000 psi as compared to up to 350,000 psi for WC compositions. The work described herein was undertaken to determine the properties of compositions consisting of titanium carbide and an auxiliary metal and to improve the oxidation resistance of such compositions. It appeared possible that the inclusion of one or more other carbides with titanium carbide might improve the oxidation resistance and also that this might be more desirable than other means from the point of view of maintaining the highest possible softening point. Consideration of the available carbides in Table 1 suggests tantalum and columbium carbides because of their high melting points and general refractoriness. The work on improving oxidation resistance was concentrated on the addition of tantalum carbide or mixtures of tantalum and columbium carbide. The auxiliary metals used included cobalt, nickel and iron. It was also desired to learn the general physical properties of these compositions. Experimental Procedure The compositions used in this study were made by the usual powder metallurgy procedure applicable to cemented tungsten carbide compositions. The powdered carbide or carbides and auxiliary metal were milled together out of contact with air. In some cases cemented tungsten carbide balls and in other instances steel balls were used to eliminate any effect of tungsten carbide contamination. A temporary binder, paraffin, was then included in the mix and slugs or ingots were pressed with care to obtain as uniform pressing as possible. The ingots were presintered and the various shapes of test specimens were formed by machining, making the proper allowance for shrinkage during sintering. Thereafter the shapes were sintered in vacuum at temperatures of from 2800 to 3500°F. Final grinding to size was carried out by diamond wheels under coolant. The titanium carbide used contained a minimum of 19.50 pet total carbon and a total of 0.50 pet metallic impurities as indicated by chemical and spectrographic analysis. It was found by X ray diffraction examination with

Jan 1, 1950

By William A. Johnson

THE fundamental role of diffusion in many reactions occurring in solid metals has long been recognized, and there have been careful measurements of rates of diffusion in numerous alloy systems, but our understanding of the atomic mechanism by which diffusion occurs is scarcely in an advanced state 1-3 It is doubtful that this mechanism can ever he directly ascertained, rather, all imaginable mechanisms must be examined and the one that is in best accord with such data as can be obtained from suitably chosen experiments should be selected Because of its relative simplicity, diffusion in a system containing only one kind of atomic species-commonly called self-diffusion-is of considerable theoretical interest It may be expected that diffusion theory will not be advanced appreciably until a wide variety of diffusion experiments-of which diffusion in a chemical concentration gradient and self-diffusion are two important types-are carefully performed and inter-compared Aside from the purely theoretical interest in self-diffusion measurements, such studies will be of considerable engineering importance The rate of any process in a pure metal requiring the movement of atoms, of which recrystallization and creep are two familiar examples, will be understood more readily with the aid of self-diffusion data † Self-diffusion implies the diffusion of something into its exact counterpart, the detection of such a process is patently impossible, and it is-necessary to substitute for it the diffusion of one isotope (in this case radioactive) into another isotope (in this case stable) of the same chemical element There is, however, no reason to suppose that a radioactive atom will not diffuse at the same rate as its stable isotope, for all of the isotopes of the same element have exactly the same chemical properties, neither the difference in nuclear energy nor the difference in mass would be expected to exercise an important influence in this phenomenon In this sense, self-diffusion may be thought of as the diffusion of radioactive atoms down a radioactivity concentration gradient, just as usual diffusion is the diffusion of one kind of atone down its chemical concentration gradient The first measurements of self-diffusion ii ere made by von Hevesy4-6 using the radioactive lead isotope thorium B in ordinary lead The recent development of means for producing artificial radioactive elements has made possible similar measurements on gold,7,8 copper,2,9 and zinc 10 11 Many of the data that have been obtained are rather poor, and no adequate reason has been given for their poorness, it appears, however, that the unsatisfactory results are characteristic of the particular experimental procedure employed, and not of self-diffusion measurements in themselves The experimental technique that has yielded the poorer results is the deposition of a thin layer of radioactive atoms on the surface of a specimen and the determination of the rate of inward diffusion

Jan 1, 1941

By John V. Beall

STREAM pollution caused by waste waters from mineral industry operations is a problem that has grown up with the industry. Its importance to each operator is dependent on the amount and type of waste he dumps into the rivers and streams; on whether this waste pollutes the waters sufficiently to make them unfit for potable water, irrigation, and conservation of wild life; and on whether this waste makes a safety or health hazard. Through the years our growing population and industry have made increasing demands on the mineral industries, the suppliers of the raw materials on which our industries are based; and we have met these demands at some sacrifice to the natural beauty and cleanliness of our country. However, that is often the unavoidable nature of the business, and along with the increased use of our

Jan 1, 1948

By W. P. Barba

IN THE early summer of 1917, it became evident that the then existing sources of supply of guns and gun forgings were totally inadequate for the enormous and rapidly growing requirements of the Ordnance Department of the Army, so arrangements were made with sixteen makers of other products to take up the manufacture of guns and gun forgings. Nine of these makers were required to produce their own steel from the raw materials and convert it into rough machined gun forgings; the others finished and assembled these forgings into completed guns. In December, 1914, four of these makers of steel and rough gun forgings were instructed to manufacture the same amount of the 6-in. and 9.5-in. guns and howitzers. It, therefore, seemed practical .and profitable to assemble these makers into a small group, together with the officers of the Ordnance Department, and provide standard 'equipment in each of the four works for the production of these two types of guns. The advantages of this cooperation were immediately manifested, and there commenced an interchange of shop practice and a free discussion of facilities and methods that covered not only the equipment but the manufacturing processes.

Jan 1, 1920

By Secretary

The two papers by Mr. C. M. Rolker, " Notes on Certain IronOre Deposits in Colorado," and "Notes on the Leadville OreDeposits," printed at pages 266 and 273 of this volume, were put to press (owing to the author's absence from the country) without final revision by him. The following corrections are thus made necessary: On page 272, line 13 should read, "respectively 12 and 4 feet" (instead of 12 and 14). On the same page, line 6 from the bottom should read, " the remaining 360 feet" (instead of 320). On page 284, lines 23 and 21 should read, " 111 some places, the dolomite sand roof has remained thicker; and in isolated parts of the bed no replacement has occurred."

Jan 1, 1886

By Roscoe C. Clark, Henry F. Coffer, J. J. Reynolds

A cement slurry lightweight additive has been adapted in the Conoco laboratories for use in oil well cements. This additive makes possible the use of air to lighten oil well cement slurries. Specifically, the additive consists of small clay bubbles of air having sufficient strength to resist crushing by bottom hole pressures. Clay bubble cement slurry weights can be safely reduced to 10 Ibs/gal. In addition, the clay bubbles tend to act as lost circulation materials and to provide a cement texture which should produce good perforating characteristics. Clay bubble cement is relatively impermeable. INTRODUCTION In many areas in Oklahoma, Texas, Wyoming, and California, difficulties are experienced during casing cementing operations with lost returns caused by the high density of the cement slurries. Wells in these areas are ordinarily drilled with 9 to 11 lbs/gal. drilling mud while neat cement slurries may range in densities from 14.5 to 17 lbs/gal. In these areas, cement slurry weights are at present being successfully reduced to around 12 lbs/gal. (under bottom-hole conditions) by the use of additives in the cement. Since the use of additives will decrease the strength which the cement will develop, the amount of additives which can be used must be based on the minimum cement strength which is acceptable; and thus the maximum slurry weight can be reduced. At present, the minimum tensile strength generally acceptable is 50 lbs/sq in. cured for 24 hours under bottom-hole temperature. This figure is based on laboratory tests1 and on a large number of cement jobs which have been conducted using cement which will not develop more than 50 psi tensile strength in 24 hours under bottom-hole conditions. Two additives are now in use for decreasing cement slurry weights. These are expanded perlite and/or bentonite. The density of both of these materials is greater than that of the cement slurry; however, large quantities of water may be added with these materials without producing a slurry which will settle out of suspension. It is these large quantities of water which contribute to the reduction in the slurry weight. The minimum slurry weight at present obtainable with expanded perlite and/or bentonite is approximately 12 lbs/gal. using a standard Portland cement slurry. In many areas, this weight reduction is insufficient; and returns are still lost during casing cementing operations. In many cases, the pay formation itself is fractured; and a considerable quantity of this cement is lost to the pay zone. It is therefore believed that if cement slurry weights can be reduced to as low as 10 lbs/gal., two advantages will accrue: 1. The lighter densities (10 to 12 lbs/gal.) should mitigate or eliminate lost returns during casing cementing operations. 2. Cement slurries above 12 Ibs/gal. (the present minimum limit ) should develop considerably more strength than is now being obtained. A tensile strength of 100 psi is desirable.' It is the object of this paper to describe a cement slurry having a weight of 10 lbs/gal. and capable of

Jan 1, 1955

By H. O. Jahns, R. A. Greenkorn, R. E. Haring, L. K. Shallenbarger

This paper is a study of the effects of heterogeneity on flow in an analog of porous media, the Hele-Shaw model. l-3 A set of experiments in heterogeneous Hele-Shaw models showed streamlines through and around heterogeneities of various sizes, shapes and levels. (A level, we define as the ratio between the transmissibility of the heterogeneity and that of the rest of the model.) The heterogeneities were restrictions or expansions of the flow stream analogous to variations in the transmissibility of porous media. The experimental data agreed well with numerical results and with an analytical solution, which we derived for a circular heterogeneity in an infinite field. This study considers the flow-stream distortion due to the shape, size and level of heterogeneities. Size and level are much more important than shape provided the heterogeneity is not long and narrow. Our analytical solution shows that a circular heterogeneity in a large field can be replaced by an equivalent circle of either zero or infinite permeability. The radius of the. equivalent circle is a simple function of size and level of the actual circle. INTRODUCTION With the availability of high-speed computers and numerical procedures to predict reservoir behavior, we are faced with an important question. How much information about the reservoir do we need to justify the cost of the computer in any given case? To answer this question, we have to know how various reservoir parameters affect flow behavior. Reservoir heterogeneity is one of these parameters. In this study, we used a simple, two-dimensional model of porous media, the hele-shaw model, to investigate the effect of heterogeneity on flow behavior. We restricted ourselves to linear, single-phase, steady-state flow in a rectangular field with a single heterogeneity at its center. The analogy between flow in Hele-Shaw models and in porous media is easily verified. Let us first consider a homogeneous Hele-Shaw model with constant plate separation h. (The Hele-Shaw model is constructed by placing two plates, usually glass, very close together and allowing liquid to flow between them. Streamlines are made visible by introducing colored fluid into the space between the plates at a number of points across the model.) We assume a cartesian coordinate system with its origin in the middle between the plates and the z axis directed perpendicular to the glass plates (Fig. 1). The fluid flow is always in a direction parallel to the glass plates and varies from a maximum value to zero in the very small distance from the middle (z = 0) to either plate (z = h/2). For slow motion of an incompressible fluid, neglecting inertia and body forces, we have the viscous flow equation: where p is the fluid pressure, p the viscosity, and v the velocity vector with components u, v and w in the x, y and z directions, respectively. In our rase. and the derivatives of 3 with respect to x and y are small as compared with the derivative in the z direction. Therefore, approximately, with Vp and v being two-dimensional vectors in the x-y plane. Two integrations with respect to z give

Jan 1, 1965

By J. S. Kasper, R. M. Waterstrat, B. F. Decker

THE existence of v phase in the Mn-Mo system was discovered in this laboratory several years ago,' but neither the conditions of its formation nor its composition were known, and preliminary attempts to reproduce the phase were unsuccessful. We wish now to specify the information appropriate to phase formation on the basis of experiments performed since that time. The starting materials were in every case electrolytic manganese and high purity molybdenum. Two methods of preparation were employed: l—arc-melting varying combinations of the elements in an inert atmosphere and subsequent heat treating, and 2—sintering compressed mixtures of finely divided powders of the elements. In the latter method, the powders were first passed through 200 mesh screen and then compressed into cylinders of % in. diameter and % in. length, which were sintered at elevated temperatures in an atmosphere of dry hydrogen. For some samples, the sintering temperature was 1200°C (for 1 hr), and these were then heat- treated at lower temperatures for times up to 24 hr. Eventually it was found, for the proper composition, that essentially pure a phase could be produced by sintering at 1125°C for 3 hr. Quenching to room temperature was effected by means of a stream of cold, dry hydrogen in a water-cooled chamber. The arc-melting procedure was found to be unsatisfactory after an investigation of many samples at different compositions and temperatures. Large quantities of manganese were vaporized during melting and none of the products were homogeneous or contained extended regions of pure phase. Nonetheless, these experiments established that no formation occurs in the Mn-Mo system below 1115oC, and indicated, at least roughly, the composition range of interest for further exploration. The more definite results obtained from samples produced by the second method are given in Table I. A portion of sample 2 heated for 16 hr at 1000°C in a Vycor tube transformed to molybdenum plus unidentified phases of complex X-ray pattern. From these few results it appears that the region of phase is quite narrow in composition. It is of interest that the composition is such as to make for difficulties in correlating this structure on an electron atom basis with other a structures of iron, cobalt, and nickel. In that respect Mn-Mo shows the same anomaly as Mn-Cr and Mn-V systems.' A second feature is that in common with the two other known molybdenum (Fe-Mo and Co-Mo), Mn-Mo v exists only at elevated temperatures. The X-ray powder pattern of the pure a phase of Mn-Mo is given in Table 11. It agrees well with the patterns established for other structures, especially with that for Fe-Mo as given by Goldschmidt.An attempt is being made to establish whether an ordering of the respective atoms occurs and such information will be reported in a future publication. Acknowledgment The authors acknowledge gratefully the assistance of Mrs. J. R. Belanger in some portions of this work. References 'J. S. Kasper, B. F. Decker, and J. R. Belanger: Journal of Applied Physics (1951) 22, p. 361. 2 A. H. Sully: Journal Inst. Metals (1951) 80, p. 173. H. J. Goldschmidt: Research (1949) 2, p. 343.

Jan 1, 1954