Search Documents

By Howland Bancroft

AMERICAN investment in foreign mining interests today faces its greatest task. U. S. dollars must make possible the. steady procurement of the minerals our defense effort consumes in huge quantities. The two most vital factors involved in foreign procurement are time and the continued good will of the nations from which minerals are purchased. The Point IV program was formulated to care for the second item, but it has failed to do the job. Its lack of success has not been from intent or from basic failure in formula. Foreign Investment, Four Eras Foreign mineral development, in so far as participation by private capital from the United States is concerned, may be divided into four main chronological categories: First: The period prior to the first World War when people, capital and products moved with relative freedom across international boundaries, and London was the recognized mining seat of the world. By the end of 1919 the United States direct investments abroad amounted to $3.9 billion of which some $900 million were in mining and smelting and $600 million in petroleum. Investment climate throughout most of the world was excellent. Second: The period between the end of World War I, when the international economy had been shaken from its foundations, and the beginning of the great depression of the 1930's, which still further disrupted the world economy. By that time the world mining center had moved across the sea and the United States direct investments abroad had increased to $7.7 billion of which mining and smelting accounted for $1.2 billion and petroleum for $1.1 billion. Investment climate was good in most parts of the world. Third: The period of the depression of the 1930's and the beginning of World War II during which foreign trade was still further disorganized and the international economy collapsed. Nazi barter agreements were initiated in many parts of the world, and Soviet propaganda commenced to make its, influence felt in many countries. During this period United States direct investments abroad decreased to $7.3 billion. Mining and smelting investments during the same period decreased some $200 million, though direct investments in foreign petroleum areas increased an equal amount. Investment climate became less and less hospitable in all parts of the world affected by economic nationalism. Fourth: The period since the beginning of World War II during which total direct investments abroad increased from $7.3 to $13.7 billion. Of this sum, at the beginning of 1950 investment in foreign mining and smelting is reported to have been $1.2 billion-back to where it was in 1929, and in petroleum to have reached $3.7 billion. Investment climate remained favorable in the countries respecting contractual obligations and fair in their treatment of invested capital. [ ] As noted above, the relative freedom of passage across international boundaries by people, capital and products ended with World War I and the situation remains unchanged in a greater part of the world. While this same war upset international economy, the depression of the 1930's caused the collapse of world trade, and exports from all countries fell to an alarmingly low figure. Some countries almost ceased to export. Chile, for example, reported a drop of 88 pct in exports. Countries with

Jan 1, 1952

GENERAL GEOLOGIC DESCRIPTION The mineral deposit of this case study can be described as a "typical" porphyry copper deposit of the southwestern USA and northern Mexico mineral province. The copper mineralization is related to Laramide age intrusives of intermediate composition which have been intruded into older, mostly crystalline, host rocks. Post Laramide deformation and faulting have subjected the deposit to erosion, leaching, and enrichment processes, which have created a secondarily enriched chalcocite zone. Later basin and range faulting down dropped the ore zone, resulting in deep burial beneath late Tertiary conglomerates and gravels, thus preserving the deposit from further erosion and oxidation. Lower grade chalcopyrite mineralization constitutes the primary zone underlying the enriched blanket. MANAGEMENT OF SAMPLE DATA Sample data were obtained from exploration diamond drill holes that were collared vertically and drilled with surface rigs. Most of the holes were surveyed downhole and found to deviate significantly from the vertical. The data were keypunched from original drill hole logs to formats as described in Chapter 6. Three types of cards were prepared: 1) A heading card containing the following information: [Project Name Coordi-in_ Hole Collarnates Bear-clina-Total ID Northing Easting Elevinglion Depth] 2) Individual record cards following each heading card with the following information: [SampleMin. Zone interval Assay Fields Leached (enriched ID From-ToTotal Cu Oxide Cu primary)] 3) Where downhole survey data were available, a card was punched for each downhole survey point. The card image looked very much like the heading card, followed immediately after the heading card, and contained the following information: [Hole Sur Point Sur Point Sur Point ID Bearing Inclination Depth] The keypunched data were then processed by the drill hole survey program producing a record file which contained information as follows: [Line 1. Project Name Date Assay Field Identifiers Line 2. Hole ID Northing Easting Elevation Bearing Inclination Number of Samples Line 3 through N+ 2 (where N equals the number of samples in the hole) Top Min. of Min. Zone Zone Sample Sample Coordinates Sample Assays Leach InterLength Northing Fasting Elev Total Cu Oxide Cu (etc) face] MINERAL BOUNDARY PROBLEM AND TREATMENT According to the geologic description, at least three mineral zones are present within the ore limits, as well as fault boundaries and a buried topographic surface, each of which have to be considered. The interfaces of the various mineralogical and geological boundaries were identified as accurately as possible in each drill hole by the project geologist, the location of the interface was surveyed in the computer program in association with the nearest sample intercept to the interface (note last field of line 3). Thus, the boundary is represented as a point in 3D space at each intersecting drill hole. The linear interpolation (LINTERP) program then searched the last field of the surveyed record to find the top of each mineral zone, or geologic boundary, and read the coordinates associated with that sample point. The program then used the coordinates to compute an interpolated surface between all existing data points as described in Chapter 11. A contour map was plotted for each of the computed surfaces and reviewed by the project geologist. Where the surfaces were poorly defined due to lack of real drill hole information, the geologist, at times, inserted a "pseudo" drill hole intercept according to his best judgment and feeling for the configuration of the surface, and such points were entered into the data stream for LINTERP. When the project geologists were satisfied that they had obtained

Jan 1, 1980

By J. R. Lewis, J. H. Hamilton, V. D. Hanson, K. W. Heinlein, J. M.194-000-000-006 Vonfeld, J. P. Denny

TWO overfeed drum-type separators using a suspension of magnetite in water as the separating medium have been installed in the Champion NO. 1 preparation plant of the Pittsburgh Coal Co., Division of the Pittsburgh Consolidation Coal Company. A simplified flow diagram of the Champion No. 1 coarse coal circuit is shown in Fig. 1. A railroad car rotary dump, capable of handling 20 cars per hr, discharges the coal into a hopper. Coal is fed from the hopper of the rotary dump to a 60-in. belt conveyor by two reciprocating pan-type feeders. The belt conveyor feeds the run of mine coal onto the main raw coal screen. The first deck is fitted with 3 in. round hole perforated plate which removes the 3x0-in. coal. The second deck of the screen is equipped with 6-in. lip screens which separate the remaining coal into +6 in. and 6x3 in. The +6 in. coal is transferred to a shaking picking table and then discharged onto the loading boom. The 6x3-in. coal is fed to the No. 2 dense medium vessel for cleaning. The clean coal from this unit flows to a vibrating screen where the medium is removed and the coal sized into 6x4 in. and 4x3 in. The 6x4-in. coal is transferred to the loading booms and the 4x3-in. is conveyed to the clean coal classifying screens to remove degradation. The 3x0-in. raw coal is blended in a system composed of three storage bins having a total capacity of 400 tons. From these bins the coal is fed onto a 48-in. flight conveyor by three reciprocating feeders. This flight conveyor delivers the coal to the Rheo plant. The 3x0-in. coal is then cleaned in two 48-in. Rheolaveur launders each equipped with two Rheo boxes. The first set of boxes removes a primary refuse and the second set produces a middling product which is recirculated in the launders. The cleaned coal and water overflows from the primary launders to two sizing and dewatering shaker screens where the water and — -in. coal are removed for further cleaning in the Rheo fine coal plant. The 3x3h-in. clean coal is combined with the 4x3-in. coal from the No. 2 vessel, sized into 4x2 in., 2x1 34 in., and 1'/4x in., then sent to the loading booms. The 3x0-in. refuse from the primary launders is normally fed to the No. 1 dense medium circuit, but any portion or all of this material can, as an alternate, be processed in the Rheo rewash launder. The primary refuse when fed to the dense medium circuit is screened into YSXO which is cleaned in the fine coal plant and 3x for cleaning in the No. 1 vessel. The clean coal from this vessel is passed over a vibrating drainage and rinse screen, then sluiced to the rewash sizing shaker where it is dewatered and sized for loading. The installation of a pilot plant separating vessel using a suspension of magnetite in water was pro-

Jan 1, 1953

By J. H. Hamilton, J. R. Lewis, K. W. Heinlein, V. D. Hanson, J. M. 194-000-000-006 Vonfeld, J. P. Denny

TWO overfeed drum-type separators using a suspension of magnetite in water as the separating medium have been installed in the Champion NO. 1 preparation plant of the Pittsburgh Coal Co., Division of the Pittsburgh Consolidation Coal Company. A simplified flow diagram of the Champion No. 1 coarse coal circuit is shown in Fig. 1. A railroad car rotary dump, capable of handling 20 cars per hr, discharges the coal into a hopper. Coal is fed from the hopper of the rotary dump to a 60-in. belt conveyor by two reciprocating pan-type feeders. The belt conveyor feeds the run of mine coal onto the main raw coal screen. The first deck is fitted with 3 in. round hole perforated plate which removes the 3x0-in. coal. The second deck of the screen is equipped with 6-in. lip screens which separate the remaining coal into +6 in. and 6x3 in. The +6 in. coal is transferred to a shaking picking table and then discharged onto the loading boom. The 6x3-in. coal is fed to the No. 2 dense medium vessel for cleaning. The clean coal from this unit flows to a vibrating screen where the medium is removed and the coal sized into 6x4 in. and 4x3 in. The 6x4-in. coal is transferred to the loading booms and the 4x3-in. is conveyed to the clean coal classifying screens to remove degradation. The 3x0-in. raw coal is blended in a system composed of three storage bins having a total capacity of 400 tons. From these bins the coal is fed onto a 48-in. flight conveyor by three reciprocating feeders. This flight conveyor delivers the coal to the Rheo plant. The 3x0-in. coal is then cleaned in two 48-in. Rheolaveur launders each equipped with two Rheo boxes. The first set of boxes removes a primary refuse and the second set produces a middling product which is recirculated in the launders. The cleaned coal and water overflows from the primary launders to two sizing and dewatering shaker screens where the water and — -in. coal are removed for further cleaning in the Rheo fine coal plant. The 3x3h-in. clean coal is combined with the 4x3-in. coal from the No. 2 vessel, sized into 4x2 in., 2x1 34 in., and 1'/4x in., then sent to the loading booms. The 3x0-in. refuse from the primary launders is normally fed to the No. 1 dense medium circuit, but any portion or all of this material can, as an alternate, be processed in the Rheo rewash launder. The primary refuse when fed to the dense medium circuit is screened into YSXO which is cleaned in the fine coal plant and 3x for cleaning in the No. 1 vessel. The clean coal from this vessel is passed over a vibrating drainage and rinse screen, then sluiced to the rewash sizing shaker where it is dewatered and sized for loading. The installation of a pilot plant separating vessel using a suspension of magnetite in water was pro-

Jan 1, 1953

By N. A. D. Parlee, I. D. Shah

The solubilities of oxygen in liquid Ag-Au, Ag-Pt, and Ag-Pd alloys have been determined in the range of 940° to 1200°C at 1 atm pressure of oxygen using an improved Sieverts technique. The additions of gold (0 to 57 pct), platinum (0 to 27 pct), and palladium (0 to 22 pct) to liquid silver continuously decrease the solubility of oxygen in liquid silver. Activity coefficients and interaction coefficients of oxygen in these alloys and have been calculated. The interaction coefficientscan be described by the following equations: Approximate second-order interaction coefficients (pM have been calculated. The contribution of the product, pMxNM, to In yo only becomes significant at high alloy concentrations. RECENTLY several investigators1"3 have redeter-mined the solubility of oxygen in liquid silver. In general the recent findings1" for Po, = 1 atm are in good agreement with the equation:4 log %O = 695.4/T + 1.086 [1] It is established1, 2 that the solubility of oxygen follows Sieverts' law reasonably well, at least up to 1 atm partial pressure of oxygen. It should be noted that a very slight deviation from Sieverts' law has been reported by Lupis and Elliott.3 Only recently has the solubility of oxygen in Ag-X binary liquid systems received much attention, and only the Ag-Cu, Ag-Au, Ag-Pt, and Ag-Pd systems have been studied. Par lee, Sacris, and zoellners reported that the solubility of oxygen in liquid silver increases progressively with the small additions of copper (0 to 0.5 pct) up to the point where the copper oxide phase appears. Lupis and ~lliott~ have reported that the solubilities of oxygen in liquid silver decrease progressively with the additions of gold, platinum, and palladium. However, their investigation was limited to 0 to 5 pct of these alloying elements, a range too limited to satisfy the requirements of the research program of this laboratory, where the solubilities of oxygen in the range of 0 to 30 pct were required for the calculation of chemical diffusion coefficients of oxygen in these alloys. The present paper deals only with the solubilities of oxygen in these alloys while another paper will deal with the diffusion of oxygen in these alloys. EXPERIMENTAL METHOD A Sieverts technique was employed which involved an improved design of the reaction tube, Fig. 1, as described briefly in a previous communication.4 Liquid melts (70 to 100 g) were held in Norton Alun-dum crucibles. The induction furnace used had a maximum output of 2.5 kw with very fine control. This induction system had excellent stability and the final equilibrium temperatures measured by calibrated Pt-Pt, 10 pct Rh thermocouples are believed to be within ±2C. These thermocouples were checked against the melting point of pure gold wire, and the results agreed with standard tables (±l°C). Each run involved a careful sequence of operations. The sample was heated to and held at about 900°C in vacuum for 3 to 4 hr with the thermocouple in a retracted position. After melting, the melts were usually exposed to a small amount of oxygen (0.5 to 2.0 cu cm) and then degassed slowly for 1 to 2 min to remove any oxidizable volatile impurities such as carbon and sulfur as CO, CO2, SO2, and SO forth. Argon gas was then allowed to enter the system. The protection tube containing the thermocouple was then

Jan 1, 1969

By J. M. Vonfeld, V. D. Hanson, W. K. Heinlein

TWO overfeed drum-type separators using a suspension of magnetite in water as the separating medium have been installed in the Champion No. 1 preparation plant of the Pittsburgh Coal Co., Division of the Pittsburgh Consolidation Coal Company. A simplified flow diagram of the Champion No. 1 coarse coal circuit is shown in Fig. 1. A railroad car rotary dump, capable of handling 20 cars per hr, discharges the coal into a hopper. Coal is fed from the hopper of the rotary dump to a 60-in. belt conveyor by two reciprocating pan-type feeders. The belt conveyor feeds the run of mine coal onto the main raw coal screen. The first deck is fitted with 3 in. round hole perforated plate which removes the 3x0-in. coal. The second deck of the screen is equipped with 6-in. lip screens which separate the remaining coal into +6 in. and 6x3 in. The +6 in. coal is transferred to a shaking picking table and then discharged onto the loading boom. The 6x3-in. coal is fed to the No. 2 dense medium vessel for cleaning. The clean coal from this unit flows to a vibrating screen where the medium is removed and the coal sized into 6x4 in. and 4x3 in. The 6x4-in. coal is transferred to the loading booms and the 4x3-in. is conveyed to the clean coal classifying screens to remove degradation. The 3x0-in. raw coal is blended in a system composed of three storage bins having a total capacity of 400 tons. From these bins the coal is fed onto a 48-in. flight conveyor by three reciprocating feeders. This flight conveyor delivers the coal to the Rheo plant. The 3x0-in. coal is then cleaned in two 48-in. Rheolaveur launders each equipped with two Rheo boxes. The first set of boxes removes a primary refuse and the second set produces a middling product which is recirculated in the launders. The cleaned coal and water overflows from the primary launders to two sizing and dewatering shaker screens where the water and - 3/8-in. coal are removed for further cleaning in the Rheo fine coal plant. The 3x3/8-in. clean coal is combined with the 4x3-in. coal from the No. 2 vessel, sized into 4x2 in., 2x1 1/4 in., and 11/4x3/8 in., then sent to the loading booms. The 3x0-in. refuse from the primary launders is normally fed to the No. 1 dense medium circuit, but any portion or all of this material can, as an alternate, be processed in the Rheo rewash launder. The primary refuse when fed to the dense medium circuit is screened into 3/8x0 which is cleaned in the fine coal plant and 3x3/8 for cleaning in the No. 1 vessel. The clean coal from this vessel is passed over a vibrating drainage and rinse screen, then sluiced to the rewash sizing shaker where it is dewatered and sized for loading. The installation of a pilot plant separating vessel using a suspension of magnetite in water was pro-

Jan 1, 1952

By Elmars Ence, Harold Margolin

The titanium-aluminum system has been investigated in the composition region 0 to 34 pct Al in the temperature range 800" to 1450°C. The phases encountered in this region were: a,ß, TiAl3, The reactions observed are as follows: 13 ; L - 6T. A1, 0 (15 pct Al) + 6 (18 pct Al) - yTi Al (16.5 pct Al) at -1170°C andP (7 pctpct Al) + y (9.2 pet Al) - ah(9 pct Al) at - 1060°C. A eutectoid reaction: y — a +d belm 700°C is postulated. THE Ti-A1 system has been the sub.ect of a number of investigations. Several of these1-3 have indicated extensive solubility of A1 in both a and ß titanium. Ence and Margolin, as a result of work on the Ti-A1-0 system:'5 have shown that the a solubility ofalumi-num is considerably restricted, and found that a compound, Ti2A1 existed in the region formerly designated as Q a This structure was identified as hexagonal with c/a = 0.803. Pietrokowsky confirmed the existence of this phase7 and pointed out that the structure was isomorphous with Ti3Sn.8 Although the existence of Ti,A1 has been confirmed by others,9-12 there has been considerable disagreement regarding the composition and mode of formation. A detailed reinvestigation of the Ti-A1 system has been published by Sagel et al.13 The tentative diagram indicated two phases, a, and e, occurring in the former all a region. The a, phase has the same structure as Ti2A1 and was indicated as having a broad region of solubility. Epsilon, a tetragonal phase, was shown to form within the a, solubility region. AS a result of unpublished work,14 Ence and Mugy3 olin disagreed with the interpretation of Sage1 et al., although some common features existed. The present study was conducted in an attempt to clarify prevailing uncertainties. EXPERIMENTAL PROCEDURE Alloy Preparation—Alloys were prepared from iodide titanium (99.9 pct Ti with less than 0.01 pct Zr) or Bureau of Mines electrolytic titanium (BHN-73) and high purity aluminum (99.99 pct). Alloys were arc-melted in argon or helium atmosphere as 15-g buttons in the composition range up to 34 pct Al. Depending on need, alloys were made in increments varying from 0.25 to 2 pct Al. Up to five 15-g buttons of some compositions were made. Weight losses during melting did not exceed about 1 pct of the charge and chemical analysis revealed that both titanium and aluminum were evaporated. In general, nominal and analyzed compositions agreed within 0.5 pct and therefore nominal compositions were used in plotting the data. Unavoidably, some overlap of composition occurred, particularly where small increments of A1 were used. The small increments were primarily used to obtain alloys which would fall into the narrow a -, r region and this purpose was achieved. In general, the data obtained from Bureau of Mines base titanium and iodide titanium alloys were in agreement. Forging—Both as-cast and forged samples were employed. Samples were heated for hand forging by an oxygen-hydrogen torch to the region 1200" to 1300°C. A titanium anvil and cover plate were used to prevent any iron pick-up and consequent formation of a low melting point compound. Frequent reheating kept the temperature in the desired range. Under these conditions, alloys containing up to 15.5 pct could be successfully forged. To check on the depth of contamination, forged alloys were heated slightlybelow the ß transformation temperature. Metal was removed to a depth below the contaminated surface so revealed, and the subsequent results obtained from these samples agreed closely with those secured from as-cast material. Heat Treatment—Prior to heat treatment, all alloys were vacuum annealed to remove hydrogen. Samples

Jan 1, 1962

By H. H. Hasler

THE mining and removal of coal from two or more beds, either simultaneously or consecutively, in vertically adjacent areas have always been matters of concern to mine operators from both operating and recovery points of view. However, with the progressive introduction and use of electrical and mechanical facilities, such problems assume even greater proportions. In this paper typical cases occuring in Cambia County, Pa., are given and procedures whereby such problems may be .greatly reduced, if not entirely eliminated, are suggested. Throughout a considerable portion of the Central Pennsylvania bituminous coal region, particularly in Cambria County (Fig. I), the portion of the region to which references in this paper are made, large areas are encountered where two or more beds of coal occur and have been mined extensively since the earliest days of mining in the county. Generally, operations were commenced in one bed of coal on a property, following which, as conditions appeared to warrant, operations were commenced in another bed or beds on the same property, in some instances by the same operator. Operating results by no means have been uniformly successful, as the following review of some typical cases indicates, partly because of lack of experience in earlier cases and in certain later cases to disregard for the experiences of earlier operators. It is suggested that repetitions of such failures may be reduced largely, if not eliminated entirely, by adherence to a few basic principles founded upon past experiences. Geology and Stratigraphy The geology, stratigraphy, and relief of almost all of Cambria County have been studied and reported at length by the U. S. Geological Survey in its Johnstown, Ebensburg and Barnesboro-Patton Folios and other publications, by the Pennsylvania Geological Survey and by various individuals. All exposed rocks occurring within the boundaries of the county are of sedimentary origin, consisting of alternate beds of sandstone, slate, shale, fireclay, coal, limestone, etc., and all have been classified by the U. S. Geological Survey as extending from the upper strata of the Catskill formation, Devonian system, to and including, in a few hilltop areas, the lower strata of the Monongahela formation, Carboniferous system. Included within that range is the Allegheny formation, Pennsylvania series, which embraces all of the commercially important beds of coal that occur in the county, viz., the A, or Brookville, to the E, or Upper Freeport, both inclusive, shown in Fig. 2. The measures are traversed by a series of anticlines and synclines, extending in a northeasterly and southwesterly direction, which form broad, gently sloping basins (flat to 15 pct pitch, exceptionally to 25 pct). However, the topography of the surface is such that long lines of outcrops of all beds of coal overlying bed B, and to a limited extent bed B also, occur over large areas, a factor which contributed to the early and extensive development of mining activities in the county. Earliest mining developments of commercial importance were made in B, C', D, and E beds of coal, and it is in these beds that the principal mining operations are being conducted. To a limited extent, mining operations also have been conducted in local areas in the A, B rider and C beds. Coal beds being mined today range in thickness from approximately 28 to 60 in. Intervals between the respective beds of coal are variable but conform somewhat to the following general averages: A to B, 60 to 100 ft.; B to C, 50 ft.; C to C', 70 ft.; C' to D, 45 ft.; and D to E, 45 ft. The following are typical mining cases obserced over a period of years in various parts of the county.

Jan 1, 1952

By A. U. Seybolt, D. H. Haman

The rate of oxidation of the lowest nitride of chromium, Cr2N, was measured to be equal to the rate of oxidation of chromium metal. It was found that, while the presence of Cr2N in chromium does not affect the oxidation mechanism, a long exposure at high temperature affects the morphology of Cr2N in chromium, causing a massive internal nitriding along chromium pain boundaries. Marker expen' -ments showed that the rate of oxidation of Cr2N layers on chromium is determined by the rate of chromium diffusion through Cr,03. The rate of formation of Cr2N is determined by diffusion rate of nitrogen through Cr2N. This rate at 1000°C is around thirty times faster than the rate of oxiahtion. Evidence is presented which suggests that nitrogen from the air reaches the chromium through the Cr2O9 by migration through pores or cracks rather than by a diffusive process. IT has long been recognized that, when chromium or alloys containing substantial amounts of chromium are oxidized in air, some chromium nitride (Cr2N) is formed under the oxide scale. Although the presence of this nitride layer has often been described, there appears to have been no systematic study of the role played by the nitride during the oxidation process. Indeed, there have been conflicting re-ports'92 on the kinetics of oxidation of chromium and chromium alloys in air and in oxygen. However, it is now well-established'-5 that the rate-controlling process during the parabolic oxidation of chromium to Cr2O3 is chromium-ion diffusion through Cr2O3. Because of the importance of chromium-containing alloys as oxidation-resistant materials, it seemed desirable to investigate the behavior of chromium during oxidation with and without the presence of chromium nitride. Since a semicontinuous Cr2N layer forms relatively early during the oxidation of chromium in the air, chromium atoms must either pass out of or through the Cr2N layer to become incorporated in the growing Cr2O3 scale. Therefore, it seemed desirable to examine the oxidation behavior of the pure nitride. MATERIALS AND EXPERIMENTAL PROCEDURE The chromium used in this investigation consisted of slices of an ingot made from "five-nine" iodide chromium which had been argon-atmosphere melted in a Y2O 3-stabilized ZrO2 crucible in an induction furnace. The only impurity of any significance was 625 ppm of 0, which was usually reduced to a microscopically invisible amount by hydrogen annealing at 1400°C. However, one sample of chromium was used with the as-cast oxygen level as explained below. The samples were used after abrading through 600 Sic paper and then washing in toluene and alcohol. Both nitriding and oxidation experiments were performed in a vertical tube furnace connected to a glass vacuum system. 'This system was equipped with pressure measuring instruments for the range of 10 p to 1 atm, and a cartesian-diver pressure-control device was used in conjunction with a needle valve to allow control of pressure in the range of about 10 to 760 mm. The nitrogen or hydrogen gas was purified by passing through hot copper chips at 600°C, anhydrous calcium sulfate (Drierite), and liquid nitrogen. Oxygen gas was dried through the Drierite column and a dry-ice trap (-78°C). Changes in specimen weight were followed by a Pyrex helix used in conjunction with a cathetometer which could reproducibly be read to +0.001 cm, yielding an accuracy of about +0.2 mg. The spring was maintained in the cool upper part of the furnace tube where the temperature did not rise above about 35°C. The nitride in equilibrium with metallic chro-

Jan 1, 1964

By F. Gordon Smith

ALTHOUGH several geological indicators of the critical type are known, including quartz inversions and decomposition of hydrous minerals such as serpentine, there are very few of the general type. Solid solutions are excepted, but the limitations of use are very restricted and interpretations are sometimes ambiguous. General methods for determining temperature and pressure conditions during the crystallization of minerals would have considerable scientific and economic value. It is not the purpose of this paper to discuss the various methods of geological thermometry and barometry, but to present one general method, applicable to all minerals, and to describe what progress has been made in the methods of measurement. The general method, in brief, is a study of the stress conditions in and around various types of foreign inclusions which are trapped in minerals during growth. The method depends upon the fact that any homogeneous gas, liquid, or solid will in general have coefficients of thermal expansion and volume compressibility different from those of any given mineral. Therefore stress must develop in and around all types of inclusions in minerals if the temperature or the pressure, or both, are changed from the conditions which prevailed during the growth of the mineral. The methods of measurement consist of determinations of the temperature-pressure conditions of fit of the inclusions in the host mineral. The types of inclusions in minerals are: I—gas, or liquid plus vapor, when observed at room temperature, due to crystallization under pneumatolytic conditions; 2—liquid, or liquid plus vapor when observed at room temperature, due to crystallization under hydrothermal conditions; 3—glassy solid, or devitrified glass, due to crystallization under magmatic or high temperature metamorphic conditions, in a siliceous liquid; and 4—crystals, due to overgrowth of other minerals crystallizing simultaneously or of other minerals which crystallized previously. A survey of the literature shows that much valuable earlier work on inclusions, especially that car- ried out in England in the last century, has dropped out of current knowledge. The following is a brief summary of the significant contributions to the problem up to the present day. Davy in 1822 asserted that fluid inclusions in minerals consist of an aqueous solution of salts and a gas bubble, the whole being either at lower or higher pressure than atmospheric.' At intervals from 1823 to 1862, Brewster contributed information concerning other types of inclusion consisting of 1—aqueous solution, a much more expansible liquid, and a gas; 2—aqueous solution, salt crystals, and a gas; and 3—the very expansible liquid and a gas. The very expansible liquid fills the gas space between 20" and 30°C. Compression strain effects were seen around inclusions in diamond, topaz, and other minerals.'-" Sorby in 1858 and 1869 further advanced the study begun by Davy, stating that fluid inclusions represent a sample of the mother liquor of crystallization and that the degree of filling of aqueous inclusions at room temperature defines the temperature-pressure relations during formation of the host. The degree of filling may be measured by determining the minimum temperature of filling of the inclusion by the liquid phase. The very expansible liquid in some fluid inclusions is liquid carbon dioxide. The temperature at which salt crystals in fluid inclusions completely dissolve in the fluid is the minimum temperature of formation. Inclusions of glass or devitrified glass indicate crystallization from a melt. Inclusions of crystals in minerals are often centers of strain, which may be seen by optical effects or by radial tension cracks. Sorby realized that an analysis of stress-strain relations about inclusions could be used to provide precise data on the temperature of crystallization, but the matter was never pursued.' , Hartley (1876, 1877),".'" Hawes (1881)," Wright (1881),'V ohnsen (1920),I3 and Holden (1925)"

Jan 1, 1953

By F. Gordon Smith

ALTHOUGH several geological indicators of the critical type are known, including quartz inversions and decomposition of hydrous minerals such as serpentine, there are very few of the general type. Solid solutions are excepted, but the limitations of use are very restricted and interpretations are sometimes ambiguous. General methods for determining temperature and pressure conditions during the crystallization of minerals would have considerable scientific and economic value. It is not the purpose of this paper to discuss the various methods of geological thermometry and barometry, but to present one general method, applicable to all minerals, and to describe what progress has been made in the methods of measurement. The general method, in brief, is a study of the stress conditions in and around various types of foreign inclusions which are trapped in minerals during growth. The method depends upon the fact that any homogeneous gas, liquid, or solid will in general have coefficients of thermal expansion and volume compressibility different from those of any given mineral. Therefore stress must develop in and around all types of inclusions in minerals if the temperature or the pressure, or both, are changed from the conditions which prevailed during the growth of the mineral. The methods of measurement consist of determinations of the temperature-pressure conditions of fit of the inclusions in the host mineral. The types of inclusions in minerals are: I—gas, or liquid plus vapor, when observed at room temperature, due to crystallization under pneumatolytic conditions; 2—liquid, or liquid plus vapor when observed at room temperature, due to crystallization under hydrothermal conditions; 3—glassy solid, or devitrified glass, due to crystallization under magmatic or high temperature metamorphic conditions, in a siliceous liquid; and 4—crystals, due to overgrowth of other minerals crystallizing simultaneously or of other minerals which crystallized previously. A survey of the literature shows that much valuable earlier work on inclusions, especially that car- ried out in England in the last century, has dropped out of current knowledge. The following is a brief summary of the significant contributions to the problem up to the present day. Davy in 1822 asserted that fluid inclusions in minerals consist of an aqueous solution of salts and a gas bubble, the whole being either at lower or higher pressure than atmospheric.' At intervals from 1823 to 1862, Brewster contributed information concerning other types of inclusion consisting of 1—aqueous solution, a much more expansible liquid, and a gas; 2—aqueous solution, salt crystals, and a gas; and 3—the very expansible liquid and a gas. The very expansible liquid fills the gas space between 20" and 30°C. Compression strain effects were seen around inclusions in diamond, topaz, and other minerals.'-" Sorby in 1858 and 1869 further advanced the study begun by Davy, stating that fluid inclusions represent a sample of the mother liquor of crystallization and that the degree of filling of aqueous inclusions at room temperature defines the temperature-pressure relations during formation of the host. The degree of filling may be measured by determining the minimum temperature of filling of the inclusion by the liquid phase. The very expansible liquid in some fluid inclusions is liquid carbon dioxide. The temperature at which salt crystals in fluid inclusions completely dissolve in the fluid is the minimum temperature of formation. Inclusions of glass or devitrified glass indicate crystallization from a melt. Inclusions of crystals in minerals are often centers of strain, which may be seen by optical effects or by radial tension cracks. Sorby realized that an analysis of stress-strain relations about inclusions could be used to provide precise data on the temperature of crystallization, but the matter was never pursued.' , Hartley (1876, 1877),".'" Hawes (1881)," Wright (1881),'V ohnsen (1920),I3 and Holden (1925)"

Jan 1, 1953

By Wallace W. Wilson

The Cook Ranch Field produces from a very permeable lens of Cook Sand of lower Permian or upper Pennsylvanian age, occurring at an average depth of 1.300 ft. The field was discovered in 1926, and has been operated with low pressure gas injection since July, 1927, one of the first such projects in Texas. Cumulative recovery to Dec. 31. 1950, was 14,701,131 bbl of crude oil, an average of 1,013 bbl per acre-ft of oil rection. and 72.5 per cent of the oil originally in place. Analysis of the reservoir performance indicates that grav-ity drainage has been an important factor in the producing mechanism. The high permeability and uniformity of the reservoir were extremely Favorable tor this type of operation. INTRODUCTION The Cook Ranch Field is the largest of a number of relatively small, shallow producing areas near .Albany, in Shackelford County, Texas. This field is one of the first to be operated by gas injection in Texas, and probably is the most successful low pressure gas injection project ever attempted. The field is owned entirely by Koeser and Pendleton, Inc., and Continental Oil Co., and has been operated by Roeser and Pendleton, Inc., since it was discovered. This study has been made possible through the cooperation of Roeser and Pendleton, Inc.. in making availahle a remarkably complete set of records covering all phases of their operations. The purpose of this paper is to present a summary of the history of the operations through Dec. 31, 1950, and to analyze some of the factors which appear to be responsible for the success of the project. Information concerning the physical plant and the early gas injection history has been presented in an earlier paper.' RESERVOIR CHARACTERISTICS production in the Cook Ranch Field is from a large lens of Cook Sand. of lower Permian or upper Pennsylvanian age, occurring at an average depth of 1.300 ft. The average dip of the sand body, as shown in Fig. 1. is only about 50 ft per mile to the northwest. The reservoir has an area of 930 acres and contains 15,512 acre-ft of Sand, consisting of about 14.512 acre-ft of produc-tive oil zone. and an estimated 1.000 acre-ft of primary gas-cap. The iso-pachous map (Fig. 2) was prepared from drillers' logs. Recent coring in the field has proven these logs to be quite accurate. The productive limits of the field are defined by shale on all sides but the southwest where a small zone of edgewater was encountered. This water does not appear to have encroached into the reservoir, and water production has been small. A smaller producing area to the south of the Cook Ranch Field also produces from the Cook Sand. but is separated from the reservoir under consideration by a band of shale. The sand consists of well sorted, coarse grained. rounded and subangu-lar quartz fragments. very poorly cemented. The analysis of 46 chip-core samples from two recently completed test wells indicates a range of porosity values between 12.5 and 28.2 per cent. wit11 an arithmetic average of 24.0 per cent. Air permeability values range between 50 and 2,300 md, with an arithmetic average of 1.200 md. The reservoir where cored is a Solid sand body. with no discernible major shale breaks or impermeable streaks. Vertical permeability appears to be of the same magnitude as the horizontal permeability. A core of the Cook Sand was cut ill the smaller field to the south, using lubricating oil as drilling fluid. The connate water content of the sand in this core was found to average about ten per cent, and the porosity and permeability were comparable with the values reported above. No analysis was made of subsurface or recombined hydrocarbon samples,

Jan 1, 1952

By I. H. Silberberg, R. L. Reed, O. K. Kimbler

interfacial films have frequently been observed at interfaces between certain crude oils and water. Several investigators have postulated that the presence of these films should influence the efficiency of oil recovery in water drive or waterflood operations. They may also influence the stability of emulsions which are sometimes a problem in petroleum production, and may be a factor in the fonation of paraffin deposits in oil well tubing and flow lines. This paper presents a technique with which a modified Langmuir film balance may be used to study the compressibility and collapse pressure of these natural interfacial films. Experimental data are presented for several nude oil-water systems. Data developed are used to infer the phase state of the film as a function of such variables as rate of reduction of interfacial area, ionic composition of the subtrate and pH of the subtrate. A film of known physical characteristics is shown to have a sinnificant effect on oil recovery from an unconsolidated sand pack. Possible applications of these results to petroleum production are discussed. INTRODUCTION The use of water to displace petroleum from reservoir rocks is of major importance both as a primary and a secondary recovery process. As water invades the rock, oil is completely displaced from some pores and left as a discontinuous phase in other pores. The manner in which water moves from pore to pore is strongly influenced by capillary forces. In view of the complexity of reservoir fluid systems, there can be little doubt that complicated interactions take place at both the liquid-solid and oil-water interfaces. One of the more interesting, and least understood, of the phenomena which take place at the oil-water interface is the formation of interfacial films. These films are believed to result from the adsorption of high molecular weight polar molecules at the interface.l.2 Presence of such molecules may cause a striking alteration in interfacial tension. When the oil-water interfacial area of certain crudes is rapidly reduced, a thin region (film) about the interface assumes the appearance of a solid membrane, and striations, wrinkles and gross distortions may occur. If such a film is solid, it should greatly alter the interfacial tension normally assumed to exist between the oil and water phases. If the membrane is continuous, a solid phase would separate the oil and water. Interfacial films between crude oil and water were observed in 1949 by Bartell and Niederhausers who commented upon the apparent rigidity of the films and their possible importance in the petroleum industry. Morrell and Egloff4 had earlier attributed the extreme stability of emulsions of sea water in fuel oil to very stable asphaltic films. Numerous investigators have observed rigid films in the course of crude oil-water interfacial tension determinations by the pendent drop method. Several investigators5,6,2 have separated inter-facially active materials from crudes and attempted to characterize them chemically. Reisberg and Doscher,2 using Ventura crude, showed the interfacial tension against water (as measured by the pendent drop method) to be affected by aging, contraction and expansion of the interface, and the pH of the water. These investigators attributed the adhesion of oil to a water-wetted surface and the distortions of flow paths in glass capillaries to the presence of rigid films. Dodd7 has studied the interfacial viscosity of adsorbed films and found them to be non-Newtonian in behavior. Craighead and Harvey8 reported a series of displacements in tubes packed with 60 mesh glass beads. They interpreted the results as indicating an effect of stearic acid films on waterflood recovery and imply that natural films may produce similar results.

Jan 1, 1967

By D. D. Pollock

Many constitution diagrams do not indicate the limits oJ solid solubility of the silver-rich solid solutions below 200°C. Thermoelectric measurements were employed to determine this limit in the nieighborhood of room temperature. The appearance of a second phase causes a discontinuity to occur in the tkevtrroelectric power as a function of cornposition at constant temperature and pressure. This discontinuity was employed to determine the limits of the silver-rich terzinal solid solutions of the Ag-A l, Ag-As, Ag- Bi, Ag--Ge, Ag-In, Ag-Pb, Ag-Sb, and Ag-Sn systenls at 30°C. CONSIDERABLE work has been done on the constitution of binary alloys of silver. The available data have been compiled by Hansen1 and Elliott.2 However, many of the binary diagrams do not show the limits of solid solubility of the silver-rich solutions below about 200° C. This work was undertaken in an attempt to extend these limits to the neighborhood of room temperature . PREPARATION OF ALLOYS All of the alloys were made with silver containing less than 0.014 pct (by weight) of impurities. The materials were weighed out into 225-g heats and melted in a high-frequency induction furnace. The indium, tin, and antimony alloys were melted in A1203 crucibles, under a boric anhydride cover, and were poured into split graphite finger molds. The aluminum, germanium, arsenic, lead, and bismuth alloys were melted in machined graphite crucibles; they were also covered with boric anhydride and poured into split graphite finger molds. The $-in.-diam ingots were heated to 750°C and were forged and hot-rolled down to 0.1 by 0.1 in. The wires were pickled in a 25 pct HNO3-75 pct H2O solution to remove any oxygen-rich surfaces. The wires were then annealed at 550°C for 2 hr in a dissociated ammonia atmosphere. They were then furnace-cooled for 20 hr to room temperature in this atmosphere. The wires were cold-drawn to 0.0808 in. diam. The finished wires were again annealed at 550°C in the same manner as in the first anneal. Thermoelectric Power. The thermoelectric power of a single specimen of each alloy was determined against pure silver which contained a maximum impurity content of 0.014 pct by weight. The wire specimens were straightened and then cleaned with ethyl alcohol. They were then reannealed in the same way as the finished wires to assure that any residual stress would be at a minimum level. Previous work has shown that the presence of small amounts of stress has the effect of decreasing the thermoelectric power. The alloy specimen was soldered to the pure silver wire to form the measuring junction. A standard set of copper leads was then soldered to the reference junctions of the thermocouple. These junctions were maintained in separate dewar flasks which contained finely shaved melting ice during the test. The thermal electromotive forces of the thermocouples were measured at four temperatures between 15° and 45°C. A known source of electromotive force was balanced against the output of the thermocouple until a null balance was reached. The data were then expressed in terms of the thermoelectric power at 30°C. The results were then converted to absolute thermoelectric power, s303.3 These data have an average error of less than ±0.2 pct. RESULTS AND DISCUSSION All of the experimental data are given in Table 11. Since the electromotive forces of the binary alloys of silver were determined against the pure silver from which they were made, the resultant thermoelectric powers are only a function of the intentionally added binary elements at the constant test temperatures. This provides a direct measure of the effects of the alloying elements. The absolute thermoelectric power of an alloy of silver is given4 by:

Jan 1, 1968

By J. E. Strongman

This paper describes a system dynamics model of the international copper system. The development of the model is described regarding the questions it was designed to address, model boundary, major sectors and actors, the availability of data, the copper life cycle, and major supply and demand dynamics. A base forecast is presented describing future supply, demand, capacity, prices, trade flows, scrap flows and capital expenditures from 1976-1990 for the major producing and consuming market economy blocs.

Jan 1, 1977

By J. E. Worthington, W. H. Spence, I. T. Kiff

Gold was discovered at the Haile mine in Lancaster County, South Carolina, in 1827 or 1828, and since that time the mine has been worked intermittently by both open-pit and underground methods until its forced closure in 1942 by World War II. Production figures are incomplete, especially for the early years, but the total gold produced is estimated to have been greater than 200,000 oz. Thus, the Haile mine has been the most productive gold mine in the eastern United States. The upper, residually enriched ores were relatively rich, but the bulk of the production has come from the mining of lower grade ores. General Geology The Haile mine is located in late Precambrian or early Paleozoic rocks of the Carolina slate belt at the edge of the Atlantic Coastal Plain [(Fig. 1)]. The metamorphic grade is lower greenschist facies and the rocks have been folded into a sequence of northeast-trending isoclinal folds. The gold is associated with siliceous, pyritic, and kaolinized felsic pyroclastic and tuffaceous rocks in an interbedded volcanic and volcanoclastic sequence of felsic to mafic tuffaceous rocks and argillaceous sediments [(Fig. 2)]. The ore bodies occur in two northeast trending zones approximately 500 m apart; each zone is 30-70 m wide and 600 m or more in length, with possible extensions to the east beneath the Coastal Plain sediments. Mineralogy. Gold in the Haile mine is always associated with siliceous and/or pyritic ores. The gold occurs in at least three states: As native gold as originally deposited; as residual gold derived from the breakdown of pyrite; and as gold included in pyrite. Major associated minerals in addition to quartz and pyrite are kaolinite, sericite, and iron oxides. Minor molybdenite, arsenopyrite, pyrrhotite, copper sulfides, sphalerite, rutile, and topaz are also present. Petrology. The gold-bearing ore zones vary from highly siliceous rocks to pyritic massive sulfide lenses. This variation is most easily seen today along strike from the Haile pit to the Red Hill pit. Ore grade material still exposed in the wall of the Haile pit consists of a highly siliceous and very thinly bedded rock containing minor pyrite. Along strike, the character of the mineralization changes to pyritic massive sulfide lenses occurring interbedded with siliceous horizons at the Red Hill pit. The siliceous rocks vary from the thinly-bedded material as just described from the Haile pit to silicified fragmental-appearing rocks to totally recrystallized cherty rocks lacking any recognizable primary features. Scattered, apparently at random, throughout the very thinly-bedded and very fine-grained ore face of the Haile pit are seemingly anomalous silica-rich clasts or concretions up to 5 cm in diameter which will be discussed later in this paper. Alteration. One of the most striking features of the Haile deposit is the alteration mineral assemblage which is intimately associated with the siliceous and pyritic ores. This altered material has been intersected in drill core at depths greatly exceeding the modern weathering profile and is, therefore, of hydrothermal origin rather than from supergene processes. This "sericite," actually a fine-grained mixture of sericite, kaolinite, and quartz, can be shown to stratigraphically underlie the gold- quartz-pyrite zone, and is well exposed in the open pit just southeast of the Haile and Bumalo pits. Relict textures indicate that this highly altered material was originally a felsic ash flow. Other similar alteration zones have been found in outcrop and drill core underlying the remaining ore bodies. Thus each of the mineralized zones consists of two parts: A siliceous and/or pyritic gold-bearing ore zone which is stratigraphically underlain by a zone of high alumina minerals, in this case sericite and kaolinite along with variable amounts of quartz. A green chrome mica, presumably fuchsite, is present in trace amounts in the high alumina zone. Genesis An adequate model to explain the origin and distribution of the gold deposits in the Carolina slate belt is presently lacking. Worthington and Kiff1 suggested a volcanogenic origin for certain gold deposits in the North Carolina slate belt from the waning exhalations of felsic volcanic piles. They also pointed out that such an origin has similarities to many epithermal precious metal deposits located in more recent volcanic piles in the western United States. A further key to the understanding of the genesis of the gold mineralization at the Haile mine is the close association of the mineralization in siliceous and sulfidic horizons to the genetically related and stratigraphically underlying high alumina alteration. Such high-alumina alteration is common around felsic volcanic centers in the Carolina slate belt and the mineralogy as seen today consists of some combination of kaolinite, sericite, pyrophyllite, kyanite, andalusite or sillimanite depending on the local prevailing grade of metamorphism. Accompanying the high-alumina alteration are large quantities of pyrite and iron-oxide minerals as well as characteristic minor accessory minerals often including base metal sulfides, fluorine-bearing minerals (topaz, fluorite, apatite), titanium-bearing minerals (ilmenite, rutile),

Jan 1, 1981

Henry C. Carlisle: This is a husband-and-wife act, in which Mary Carlisle is going to listen, and break in as often as she feels like it. I am going to describe my career as a mining engineer. We are at Nantucket, in the 75 Main St. house; The year is 1959. Q: This is something the boys and I have wanted you to do for a long time. Carlisle: After leaving Columbia in 1910, I arrived at Ray, Ariz., January 1, 1911, and rustled a job from Louis Cates, Ralph Nowland and Sprott Boyd, who were running the Ray mine. I went to work as a surveyor's helper, made $90 a month, and paid $35 a month board. I lived in a dormitory where about 25 other engineers, graduates from different colleges, were living. It was very social and you made a lot of young friends early in the game. I did not think much of the idea of being a surveyor, or even a surveyors, helper; the higher-up surveyors only got $125 a month, and had been there quite a long time. So, I asked to be changed to underground sampling, where I would see the mine faces every day and learn more about mining. In about three months, I became an underground sampler and remained at this for a year, but in three months I was promoted to head sampler, with six people under me.

Jan 10, 1963

By J. W. Bolton

THIS paper discusses some fundamental metallurgical principles involved in production of sound cast bronze. In a previous paper the writers advanced the theory that "oxidation" in bronze castings is due to incipient shrinkage, and showed the effect of reducing melting atmospheres. In the present paper the effects of certain impurities and of actual oxidizing conditions are shown. The appendix deals with the appearance of various inclusions. For many years the prevailing opinion has been that unsoundness, dark colored fractures and other phenomena accompanying porosity and weakness in bronzes are due to oxidation. The actual troubles are caused by fissures of intercrystalline type, which are often mistaken for intercrystalline films. These weaken the metal and make it porous. Grave doubt regarding the accuracy of the oxidation theory appears when several research papers presented within the last 10 years are reviewed critically. In 1919, Comstock conducted metallographic researches, attempting to identify "oxides" in synthetically prepared metals. He found that oxides of tin, aluminum, zinc, etc. are different from the intercrystalline films (or cavities) to which porosity is due. Apparently he believed that these "oxide films" may be caused by volatile oxides of zinc or of phosphorus or by dissolved gases thrown out of solution during solidi-fication of the metal. In 1923, Woyski and Boeck3 definitely questioned the accuracy of the oxidation theory and indicated the danger from reducing atmospheres. They say that "oxidation, gassing and shrinkage may produce effects very similar."

Jan 1, 1930

By E. S. Bumps, M. Baeyert, W. F. Craig

SOME time ago during a study of impact properties of tempered martensite,1 it was postulated that the consistently good ductility of tempered martensite might be caused by its relatively small and peculiarly shaped ferrite grains. The fer-rite grains of tempered martensite have approximately the same size and shape as the martensite "needles." Thus they form an interlocking mass of needle-shaped grains quite different from equiaxed or lamellar ferrite grain structures. When the common mechanical test methods are applied to steel, variations are often observed in the ductility of specimens that have closely similar hardness and tensile strength values. The ductility so measured appears to be structure dependent. When steel from the same heat has been heat treated to produce different structures with the same hardness, the elongation and reduction of area values from the tensile test and the transition temperature determined by the notched-bar impact test vary according to whether pearlite, tempered martensite, or other structural constituents were produced by the heat treatment. It has been widely recognized that tempered martensite gives a consistently good performance, when tempered to the same hardness as many other structures with which it has been compared. In recent years the isothermal transformation of austenite to specific structural products and the quantitative evaluation of the character of these products with respect to their nature and response to deformation has received considerable attention. The objective of the present study was to pursue somewhat further the dependence of ductility upon structure; specifically, it was desired to ascertain whether ferrite grain structure, including both shape and size of the grains, can account for the consistently good performance of tempered martensite in the notched-bar impact test. It was thought that a simple experiment would indicate whether the ferrite grain structure plays any part in the good ductility exhibited by tempered martensite in contrast to other steel structures with different types of ferrite grains. By determining the impact transition temperature, it was proposed to compare spheroidites having similar carbide particle size and spacing but obtained in such a manner that their ferrite grain structures would be very different. Spheroidite obtained by tempering martensite, with its small, needle-shaped grains, was to be compared with spheroidite from pearlite. If the latter is produced by sub-critical annealing, the ferrite grains correspond to the pearlite colonies. Thus, if the pearlite was not too coarse, the ferrite grains of spheroidite from pearlite are equiaxed in contrast to the needle-shaped grains of spheroidite from martensite. It was thought that the ferrite grain structure of spheroidite from martensite might depend to some extent upon the grain size of the prior austenite. The austenite grain boundaries limit the maximum attainable size of the martensite needles and thus of the ferrite grains in the derived spheroidite. In order to evaluate any possible influence of prior austehite grain size, spheroidites were to be prepared from martensites that had been formed from fine-grain austenite and also from coarsened austenite. As the carbide particle size and distribution were to be essentially alike in the various spheroidites, the difference would be in the ferrite grain size and shape. Thus any marked difference in transition temperature could be attributable to the character of the ferrite grain structure. There are certain considerations in assuming that these spheroidites would be equivalent in all respects except ferrite grain structure, and an attempt was made to take them into account. One of the considerations was the choice of the carbon content of the steel. An approximately eutectoid steel was selected for two reasons. First, the pearlitic structure would contain no proeutectoid ferrite which might complicate the picture by producing a non-uniform ferrite grain structure in the resulting spheroidite. Then, too, the high-carbon content would inhibit ferrite grain growth during the sub-critical treatment. Another factor to be taken into account was the choice of an alloying element to assure a martensitic structure throughout on quenching the impact specimens. Nickel was chosen, because it is a common alloying element and resides in the ferrite both upon its formation from austenite and throughout tempering. The formation of alloy carbides, or even a large solubility of the alloying element in cementite, would have complicated the interpretation by changing the composition of the ferrite .during spheroid-ization. The possibility of temper brittleness was minimized insofar as possible by using a tempering temperature as high as consistent with the 1 pct of nickel in the steel, namely, 1150°F. While it certainly is not claimed that no difference other than ferrite grain structure could exist between the spheroidites, nevertheless, reasonable precaution has been exercised within the limits of steel metallurgy. It is believed that any large difference in transition temperatures would reflect the difference in ferrite grain structure and that relatively good ductility in the spheroidites from mar-

Jan 1, 1951

By Klaus Schwerdtfeger

The equilibria in the Cr-N system have been investigated in the temperature range 1100° to 1310°C by reacting chromium powder with Nz-Hz gas mixtures. The solubility of nitrogen in chromium in equilibrium with chromium subsitvide ("Cr,N") is given by Chromium subnitride is nonstoichiotnetric; its nitrogen content is always less than that corresponding to the formula CrzN. The lattice paranzeters of quenched samples have been measured; c, and a. parameters are found to increase with increasing nitrogen content. The growth rate of the subnitride layer on chromium plates was measured by a thermogravimetric technique, using a silica spring balance. The self-diffu-sivity obtained from the theoretical analysis of the parabolic rate constant is found to decrease with increasing nitrogen content, i.e., with decreasing vacancy concentration in the nitrogen sublattice. The intrinsic nitrogen diffuivity is derived from another series of rate measurements using "CrzN" plates; the intrinsic diffusivity, DN = 3.2 X 10-a cmZ sec-' at 1200 C, is found to be essentially independent of- the subnitride composition. The concentration gradient was measured in a chromium subnitride layer by the X-ray method and found to be consistent with the derived diffusivity value. TWO chromium nitrides are known to exist:' the nonstoichiometric subnitride "CrzN" and the nitride CrN. In the present work the kinetics of the formation of chromium subnitride from chromium and nitrogen have been investigated at 1100" and 1200°C. In additional experiments the relevant equilibria have been measured. The data are used to evaluate the diffusivity of nitrogen in chromium subnitride. Since chromium nitrides are often found in chromium-containing steels, the results are expected to be helpful in the interpretation of the chemical reactions between chromium steels and nitrogen. Equilibria in the Cr-N system have been determined by several investigators.2"3 The rate of nitriding of chromium was measured by Arkharov et a1 .' in ammonia in the temperature range 800" to 1200°C. The parabolic rate law was observed. Due to the undefined nitrogen activity of the ammonia atmosphere, it is dif- ficult to interpret these rate data theoretically. An additional difficulty arises from the fact that the two-layer scale consisting of CrN and "Cr2N" was formed at the temperatures below 1030°C. The rate of nitriding of technical chromium (95 pct) was measured by Zaks in nitrogen at -1 atm in the temperature range 800" to 1300°C. EXPERIMENTAL METHODS The chromium samples were reacted with Nz-HZ gas mixtures in a vertical tube furnace, wound with Pt-10 pct Rh resistance wire. The gas-tight reaction tube was of high-purity recrystallized alumina. In nitrogen solubility measurements the nitrogen content of chromium was determined by the Kjeldahl method, on samples quenched in the cold part of the furnace. The nonstoichiometry of the subnitride and the nitriding rates were measured thermogravimetrically using a sensitive (+0.1 mg) silica spring balance. For the equilibrium measurements samples of 1 g of chromium powder contained in high-purity alumina crucibles were used. In order to remove most of the oxygen and nitrogen impurities from the chromium, the samples were initially annealed in purified hydrogen until a constant weight was obtained. The chromium plates (approximate dimensions 2 by 1 by 0.08 cm) used for the rate measurements were machined from ingots obtained by arc-melting of iodine-processed chromium. According to manufacturers' specifications the purity of the chromium powder was 99.9 pct Cr and that of the iodine-processed chromium 99.99 pct Cr. Our own spectroscopic analysis of the chromium powder yielded 0.02 pct Fe, 0.05 pct Mn, 0.05 pct Si, and 0.02 pct Ti as major impurities with all the other detectable elements below 0.005 pct. The nitrogen partial pressure of the gas phase was controlled by mixing prepurified hydrogen and nitrogen with constant pressure head capillary flowmeters. Oxygen and water vapor were removed from the mixed gas by passing it through columns of platinized asbestos (450°C) and anhydrone. The gas flowed upward in the furnace with flow rates of 300 to 500 cu cm per min (25"~). Gas tightness of the furnace system was ensured by pressure checks at regular intervals. The furnace temperature was controlled electronically in the usual manner. The reported temperatures were measured with a Pt/Pt-10 pct Rh thermocouple and are estimated to be accurate within ±$C The X-ray measurements were made with a Debye-Scherrer camera and a diffractometer using chromium radiation {\Ka = 2.29092A). EQUILIBRIUM MEASUREMENTS The experimental results of the equilibrium measurements are contained in Tables I to In. Fig. 1 shows the solubility of nitrogen in solid chromium in the temperature range 1100" to 1310°C. In Figs.

Jan 1, 1968