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P. W. BRIDGMAN.-Owing to a misunderstanding, I did not see Dr. McAdam's and Dr. MacGregor's remarks on my paper on Flow and Fracture (Metals Technology, December 1944, Pp. 32-38), until after their publication. Both Dr. McAdam and Dr. MacGregor speak of my analysis for the stress distribution at the neck of a tension specimen as containing several assumptions; in particular, that the strain is uniform across the section of the neck, that there is no hoop tension at the periphery, and that the plasticity conditions of von Mises hold. As far as the mathematics goes, the situation is no different in this problem of plastic flow than in a conventional problem of elasticity. That solution is unique which satisfies the boundary conditions on the stresses, the stress equations of equilibrium, and in addition the constitutive equations connecting stress and strain in the elastic case, or a corresponding set of equations, of which the von Mises relations are a special form, in the plastic case. In the particular case of the necked tension specimen I have found that there is a solution satisfying the boundary conditions, the stress equations of equilibrium, and the von Mises plasticity conditions in which the strain is uniform across the section, and there is no hoop tension at the periphery. This is therefore the solution, and the uniformity of strain and vanishing of hoop tension at the periphery are to be described as discoveries, over which the operator has no control, rather than as assumptions. The only part of the solution that can properly be described as an assumption is the von Mises plasticity condition. With regard to this it is to be noted that the condition is needed only in a much weakened form, for the analysis uses the condition only at the neck, where the strain is approximately constant. Thus, in the extreme case referred to in a footnote of my paper (p. 37, Met. Tech. Dec. 1944) the actually measured strain across the section varies from 2.4 to 2.6. Obviously it is a much weaker assumption to postulate that the von Mises condition holds in the strain range 2.4 to 2.6 than to assume it to hold for the entire range of strain from o up to 2.6, which would be necessary if the solution applied to the entire tension specimen rather than to the immediate region of the neck only. Furthermore, it is to be commented that under the special conditions of this problem the von Mises condition becomes identical with the maximum shearing-stress criterion of plastic flow; this amounts also to a weakening of the restrictions imposed by the von Mises condition. Dr. MacGregor refers to actual experiments of his own in which the strain was found not to be uniform across the neck. It is to be emphasized, however, that these were experiments on bars of rectangular section, and that the nonuniformity established was a nonuniformity around the perimeter, not a nonuniformity from the surface toward the axis. My method of solution applies only to a circular cross section. It can be said that the solution that satisfies the boundary conditions, etc., would definitely not be expected to demand a uniform strain for noncircular sections. In discussing my results, Dr. McAdam uses a definition of "flow stress" different from mine, so that the immediate applica-

Jan 1, 1945

By Cheri Eby, William R. Eby

INTRODUCTION Pneumatic conveyance systems provide for material placement at high compaction rates in confined spaces. This method of conveyance provides proper roof support and ground stabilization important to underground mining activities. Today underground mining activities are conducted far differently than those of our ancestors, in that the reclamation process is the final step in any mining activity. Responsible mine owners are constantly seeking innovative methods to assist them in their reclamation procedures. During the last few years, particular attention has been paid to previously mined areas, as many of these abandoned areas lay open, imposing a constant threat to humans and animals. Considerable attention is being directed to applying proper methods for the filling and sealing of underground slopes, drifts, tunnels, and adits, because today we are experiencing the effects of past mining activities such as subsidence, acid mine water run-off, buring refuse piles, and underground mine fires. Furthermore humans and animals who have ventured into abandoned mine openings have died from exposure, suffocating gases, and mine collapse. This paper explains the method of pneumatically filling and sealing these openings and underground works by means of employing pneumatic equipment and proper backfill material together, thus achieving high material compaction and thereby providing the complete filling of the voids and alleviation of the mentioned dangers. NEUMATIC SYSTEMS The use of air to transport material is widely used; however, conveying abrasive material (e., rock, earth, and cement) requires certain pneumatic transport systems designed to handle the abrasiveness as well as the size of these materials. The Eby pneumatic transport sys tem, known as a Mobile Stower, in mounted on a 42-foot trailer pulled by a Kenwor th tractor. This arrangement allows for quick mobilization and project set-up. The pneumatic system, composed of several components assembled together, produces the volume and pressure of air required to transport the material. Knowledge of elevation, ambient temperature, and material composition at the locations to be backfilled play a big part in the design and useage of the pneumatic system. In this particular system design, material is placed by a front-end loader into an eight (8)-yard hopper which is located over a belt conveyor. The conveyor transports the material up to an air lock feeder, which is the metering devise used to feed the material into the Tee Injector located directly below. Air is supplied by a positive displacement blower which, in this instance, delivers up to 4400 CFM's of air at 8 to 12 PSI. Horse power requirements to drive the blower are met with the useage of either a diesel engine or an electric motor. A diesel engine enables the Mobile Stower to operate in remote areas. As the air flows through the upstream air piping, it passes through the Tee Injector and picks up the material and conveys it through the material conveyance pipe, (referred to as down-stream pipe), and out the placement nozzle. Depending upon material composition and the amount of tonnage to be moved, either mild carbon steel pipe or specially heat- treated hardened pipe is used for the material conveyance line. The entire pneumatic system is controlled from the operator's console. With the aid of instrumentation, only one person is required to operate the system. Tonnage rates vary in accordance with horse power and air supply, as well as

Jan 1, 1982

By C. L. T. Edwards

IN the preparation of this paper, the author has drawn upon experience with the operation of a blast furnace on 100 per cent scrap burden, which he believes was the first operation of its kind in the country. It is the writer's further belief that much of the controversy attending discussions of this subject may be obviated by the presentation of a group of facts that should be known by blast-furnace men and open-hearth men alike. The following question has been raised: "Is iron made with scrap in the blast-furnace charge as good iron as that made without scrap-made with straight ore?" This question may be answered in part by the fact that the open-hearth men of the Bethlehem Steel Co. who used pig iron from a blast furnace that operated on 100 per cent steel scrap found no difficulty in the processing of such iron other than that to be expected from the known analysis. OPERATION WITH 100 PER CENT STEEL SCRAP During World War I, there was accumulated at the Bethlehem plant of the Bethlehem Steel Co. some 22,000 tons of alloy-steel turnings and borings. This scrap material was highly corroded and, like alloy-steel turnings of that period, were as a drug on the market. There was also a small tonnage of scale, rich in valuable metal. If this scrap could be worked up into pig iron, it would become readily available for use in the open hearth. In order that the pig iron should contain the maximum percentage of nickel, permission was obtained from the Management to try a 100 per cent scrap operation. Accordingly, a blast furnace was swung over on July 25, 1919; the percentage of steel scrap increased more or less irregularly until July 29, when l00 per cent steel turnings were charged. Except for occasional charges of nickel scale as an "extra," the operation continued uninterruptedly until Aug. 27, when the furnace was swung back to the regular ore-ore and scrap-operation. During this period, the furnace production ranged from a low of 568.60 tons to a maximum of 766.07 tons. At the swing-over from i00 per cent scrap to the regular burden, the charge hung up rather severely. While the latter condition has nothing to do with the object of the paper, a brief discussion of the experience will appear later because of the interest it may have for blast-furnace operators. In Table I, results of the first and last days of the ore charge are shown, July 25 and July 29. The last column shows a summary for the period of maximum scrap charge. The furnace employed had a hearth 16 ft. 0 in., bosh 22 ft. 0 in., stock line 15 ft. 6 in., bell 11 ft. 6 in., batter ¾ in., bosh angle 73° 27' and a Baker-Neuman top, with gas-engine blowers. Analyses Range of Material Charged Gravel: Si02, 64.40 to .7o.54 per cent; A1203,3-52 to 4.58; CaO, 7.27 to 9.49; M90, 5.09 to 6.14; FeO, 1.67 to 3.34, ignition loss, 9.50 to 13.83.

Jan 1, 1941

By C. L. T. Edwards

In the preparation of this paper, the author has drawn upon experience with the operation of a blast furnace on Ioo per cent scrap burden, which he believes was the first operation of its kind in the country. It is the writer's further belief that much of the controversy attending discussions of this subject may be obviated by the presentation of a group of facts that should be known by blast-furnace men and open-hearth men alike. The following question has been raised: "Is iron made with scrap in the blastfurnace charge as good iron as that made without scrap—made with straight ore?" This question may he answered in part by the fact that the open-hearth men of the Bethlehem Steel Co. who used pig iron from a blast furnace that operated on Ioo per cent steel scrap found no difficulty in the processing of such iron other than that to be expected from the known analysis. Operation with ioo PeR Cent Steel Scrap During World War I, there was accumulated at the Bethlehem plant of the Bethlehem Steel Co. some 22,000 tons of alloy-steel turnings and borings. This scrap material was highly corroded and, like alloy-steel turnings of that period, were as a drug on the market. There was also a small tonnage of scale, rich in valuable metal. If this scrap could be worked up into pig iron, it would become readily available for use in the open hearth. In order that the pig iron should contain the maximum percentage of nickel, permission was obtained from the Management to try a Ioo per cent scrap operation. Accordingly, a blast furnace was swung over on July 25, 1919; the percentage of steel scrap increased more or less irregularly until July 29, when Ioo per cent steel turnings were charged. Except for occasional charges of nickel scale as an "cxtra," the operation continued uninterruptedly until Aug. 27, when the furnace was swung back to the regular ore—ore and scrap—operation. During this period, the furnace production ranged from a low of 568.60 tons to a maximum of 766.07 tons. At the swing-over from Ioo per cent scrap to the regular burden, the charge I hung up rather severely. While the latter condition has nothing to do with the object of the paper, a brief discussion of the experience will appear later because of the interest it may have for blast-furnace operators. In Table I, results of the first and last days of the ore charge are shown, July 25 and July 29. The last column shows a summary for the period of maximum scrap ' charge. The furnace employed had a hearth 16 ft. o in., bosh 22 ft. o in., stock line 15 ft. 6 in., bell 11 ft. 6 in., batter in., bosh angle 73' 27' and a Balrer-Neuman top, with gas-engine blowers. Analyses Range of material charged Gravel: SiO2, 64.40 to 70.54 per cent; A1203, 3.52 to 4.58; CaO, 7.27 to 9.49; MgO, 5.09 to 6.14; FeO, 1.67 to 3.34, ignition loss, 9.50 to 13.83. I

Jan 1, 1942

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

By E. S. Lenker, H. J. Van Hook

A complete swies of solid solutions has been found between the compounds InAs and GaAs Below the solidus. The melting relations determined by differential thermal and static quenching technzques, indicate that the liquidus and solidus are of the simple ascendant type. No evidence of unmixing of the homogeneous solid solutions was observed at sub-solidus temperatures. A quenching method for locnting the solidus, using X-ray diffraction techniques, is described in some detail. THE semi-conducting properties of compounds formed by various combinations of the less familiar intermetallic elements have created an increasing interest in the phase relations in systems involving these elements. The complete phase diagram of such a system, containing a compound of special interest, will often provide information as to the most favorable conditions for preparing large crystals from a melt, as well as specifying the temperature stability of the crystalline phase or phases produced. In view of the current importance of gallium arsenide in semiconductor research and of the structural similarities of indium arsenide, it was thought that the complete phase relations of the system InAs-GaAs should be investigated. Previous work on the system Ga-As by Koster and homa' and on In-As by Liu and peretti2 has shown that GaAs and InAs are the only compounds formed, having melting points of 1238° and 942°C, respectively. In a survey of various systems of elements from groups IIIb and Vb, spengler3 also re- Mines Ltd., for his continuing encouragement and for permission to publish the results of this work. ports complete miscibility of gallium, indium, and arsenic in the liquid state. In a partial investigation of the InAs-GaAs system, Woolley and smith4 found extensive solid solution throughout the alloy range. Their subsolidus work, however, was inconclusive at temperatures below 900" and they did not determine the liquidus relationships of the system. PRESENT INVESTIGATION The starting materials used were high-purity gallium, indium, and arsenic. The method of preparation of the compounds follows that devised by M. Shafer and is described in detail in a paper by Shafer and eiser.' The end-member compounds, GaAs and InAs, were first prepared by reaction of the elements in the desired proportions in evacuated silica glass vials. The vials were rotated in a furnace as the temperature was slowly raised to insure rapid and complete reaction at low temperatures. Thereafter the starting materials, GaAs and InAs, were melted by heating the sealed vials to 1300" and 1000°C, respectively; the vials in this case were filled as completely as possible to keep the vapor space small and thereby minimize the loss of arsenic to the vapor phase. Ten binary mixtures of these compounds were then prepared by reaction of the powdered material in the solid state just below solidus temperatures. At 900C preparations containing 3, 5, 8, 10, 25, 35, 50, and 75 mol pct GaAs were found to be single homogeneous phases, indicating a complete series of solid solutions between GaAs and InAs. Moreover, it was discovered that the homogeneity of any crystalline binary preparation could be very accurately checked by X-ray diffraction because of the large differences in unit cell dimensions of the end membe5s. The cubic lattice constant ofor GaAs is a = 5.652A and that of InAs is a = 6.061A

Jan 1, 1963

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 A. E. Dwight, A. F. Berndt

ThE published U-Ru equilibrium diagram indicates the existence of six intermetallic compounds in this system.' The structure of only two of the compounds, u2Ru2,3 and URU3,4 have been identified. This communication reports on the crystal structure and density of Uau3, which is formed by a peritectoid transformation at 1025° ± 5°C: U3Ru4 + U3Ru5 = U2Ru3. An alloy with the stoichiometric formula U2Ru3 was prepared by arc melting electrolytic uranium and ruthenium of 99.9 pct purity on a water-cooled copper hearth under an argon atmosphere. After homo-genization at 1000°C for 3 days, a metallographic examination revealed that the peritectoid transformation was complete and less than 5 pct of a second phase was present. A powdered sample, obtained by crushing the brittle compound, was annealed for 1 hr at 1000°C and air-cooled. Debye-Scherrer patterns were obtained with filtered CrKa, FeKa, CoKa, or CuKa radiation. The X-ray patterns of U2Ru3 weFe indexed as an fcc structure with a. = 12.895 0.00lA. The unit-cell constant and its standard deviation were calculated by a computer program described by Mueller, Heaton, and Miller.5 The density, measured by an immersion method, was 14.45 g cm-3. A calculated density of 14.48 g cm-3 was obtained on the assumption that twenty-four formula units (120 atoms) comprise a unit cell. The space group is either oh7 Fd3m, or the less symmetric, T4h, Fd3, since reflections indexed as hk0 with h + k + 4n are absent. All values of h2 + k2 + 12 permitted by both space groups are listed in Table I together with dc, do, and I. values. The calculated d spacings were obtained by the computer program of Mueller, Meyer, and simonsen.6 The observed d spacings above 0.77A were obtained from X-ray" patterns prepared with CuKa radiation, above 0.90A with CoKa radiaaion, above 0.98A with FeKa radiation, and above 1.16A with CrKa radiation. An attempt was made to identify the crystal structure of U2Ru3 by comparison with published data on other A2B3 compounds. A recent compilation7 of intermetallic compounds lists thirty-two structure types with the A2B3 stoichiometry. Only two of the structure types are fcc and they are Sb2O3(r), senarmontite, with 16 Sb2O3 per unit cell, and In2Te3 for which several structures have been proposed.8 However, the two cases cited do not have twenty-four formula units in the unit cell. We therefore, cannot identify UPRU3 with any of the other known A2B3 compounds. Ternary alloys were made in which 5 at. pct Os, Rh, or A1 were substituted for 5 pct of the Ru in U2Ru3. The osmium substitution increased the unit cell constant to 12.899 * .001A, which is to be expected since the atomic volume of osmium is slightly larger than

Jan 1, 1969

By M. H. Pilkuhn, H. Rupprecht

The junction luminescence of GaAsxP1-x diodes containing up to 47 pct Gap was studied. Diodes were prepared by diffusing zinc into n-type material which was eithw boat- or vapor-gvown. Observations concerning the energy and the line shape of the spontaneous emission are presented and discussed; in particular the influence of inhomogeneous phosphorus distribution is considered. The role of reabsorption of the junction radiation is pointed out. With increasing current, the peak emission shifts to higher enwgy. This is alm true in cases where slow line narrowing occurs simultaneously. The length dependence of the threshold current density for lasing at 77 °K was examined for lasers made from the same material. It was found that longer lasers have lower threshold curvent densities, Estimates of the characteristic laser losses are given. Data concwning the range of Gap concentration in which stimulated emission was observed are presented. FORWARD-BIASED p-n junctions in mixed alloys of GaAsxPl-, emit light whose wave length depenfs on the composition of the alloy ranging from 8400A (x = 1) to 5350A (x = 0) at 77°K. Laser action in vapor-grown material was first reported by Holonyak and evacqua,' and in boat-grown material by Ainslie, Pilkuhn, and Rupprecht.' In both cases this was observed for low Gap concentration where GaAs,Pl-, is still a "direct" semiconductor with the lowest conductance-band minimum at k = 0 and a subsidiary minimum in the [loo] direction. As the Gap concentration is increased, the subsidiary [loo] minimum in the conduction band is lowered and finally becomes the lowest minimum for Gap concentrations above 50 pt,3 making the alloy an ''indirect" semiconductor. It is of interest to determine up to which Gap concentration stimulated emission can be observed. EXPERIMENTAL Boat-grown material was prepared by N. Ainslie of IBM by horizontal Bridgman technique. The material was n type and silicon-doped up to a concentration of 10'' cm-'. Vapor-grown material was made by E. Hull of IBM or received from Merck & Co. Diodes were fabricated in a similar manner as in the case of GaAs by zinc diffusion. Details about the diffusion can be found in a later paper.4 All diodes were of Fabry-Perot structure with two parallel sides cleaved and the other two sides sawed. Their width ranged from 50 to 150 p and their length from 50 to 700 p. RESULTS AND DISCUSSION Spectral Distributions. A typical display of the junction luminescence of a GaAsxPl-, diode is shown in Fig. 1. The liquid-nitrogen and room-temperature curves which were taken at a very low current (25 ma dc) show a relatively sharp high-energy emission which is band-edge radiation. They also show a broad low-energy emission which is due to transitions to deep impurity levels. This latter emission line may have different shapes and positions depending on the nature of the material. It can sometimes be quite near the band gap giving rise to "bumps" in the high-energy line. The results presented in this paper will be concerned only with the high-energy emission which becomes more intense relative to the low-energy emission when the current is increased and the temperature is lowered.

Jan 1, 1964

By R. DiBella, H. Biloni, G. F. Bolling

A study of the detailed relationship between solidification substructure and microsegregation in dilute tin alloys has been continued. New observations reveal that depressions form at the solid-liquid interface not only as an initial form of segregation but throughout the range of increasing constitutional supercooling. In order to show the importance of this node formation it proves convenient to make two simplifications. Although substructure changes continuously as constitutional- supercooling increases,&apos; the following discrete stages may be used for discussion: 1) the planar solid-liquid interface; 2) ordered nodes, or depressions at the interface;&apos; 3) two-dimensional or elongated cells;3 4) regular or hexagonal cells;4 5) distorted cells, or hexagonal cells with branches;4 6) dendrites. It is also convenient to ignore observations made near grain boundaries which interact with the cellular substructure.2-4 And, it should be clearly pointed out that all singular depressions at the solid-liquid interface will be called nodes. Heretofore, the term "node" has been used without clear justification to describe both the truly isolated depression and the junction of cell walls appearing in a later stage of segregation. This usage is continued because it seems proved by the observations. Standard systematic growth of tin crystals was undertaken over a broad range of constitutional supercooling using various added solutes. Except for one or two chance observations, this research failed to reveal any appreciable range of growth conditions over which a disordered array of isolated nodes exists. Even though &apos;some finite range of random instability must exist, it is now concluded that stage one passes very rapidly to stage two. Next, after confirming that stage two passes to stage three by the elongation of isolated nodes: a reexamina-tion of stages three, four, and five followed. Standard metallography showed that pockets of higher solute concentration (for ko < 1) became more numerous in cell walls the more severe the growth conditions. These high-concentration regions must arise from depressions; however, in stage three their segregation is not distinguishable from the segregation of the nodes which join cell walls together. It seems, therefore, that the presence of nodes is causal in the formation of new cell walls, and that the mechanism by which stage three passes to stage four is initiated by nodes. If a similar reasoning is followed, the separation of stage four from stage five appears to be just a convenience that has arisen from the decanted interface observations made in the past. The present observations again show that more severe growth conditions relate directly to an increase in the number of nodes in the hexagonal cell walls. These nodes apparently serve as the origin for lines of segregation extending within the body of a cell, and can thus be assumed to represent the earliest form of branching,* as shown here in Fig. 1. The examination of stage six involved decanted-interface structures as in Fig. 2, which are similar to those considered by Rutter and Chalmers,5 Plaskett and winegard,6 and Hellawell and Herbert,7 and where distinct protrusions are each surrounded by a depressed boundary. The corresponding microsegregation behind the interface, but not far enough behind to allow a smearing of the segregation because of diffusion,4 is shown in Fig. 3. Both the shape of the decanted interface and the segregation pattern behind it

Jan 1, 1968

By Phillip E. La Moreaux

Fluoride, generally less than 0.5 ppm, is present in ground water from rocks of Paleozoic age and older, in northern and eastern Alabama. Some of the water-bearing formations in the Coastal Plain area of the State yield water with as much as 6.8 ppm fluoride. IN June 1940, the U. S. Geological Survey, in cooperation with the Geological Survey of Alabama, began a study of the ground-water resources of the part of Alabama where water is obtained from Cretaceous rocks. The purpose of the study was to determine the quality, quantity, occurrence, and availability of ground water in that area. These studies have been expanded to include ground-water investigations in the area of Tertiary rocks, or southern quarter of the State, and certain areas in northern Alabama. The first report issued on these studies was by C. W. Carlston,1 of the Alabama Geological Survey. In the present paper all references to ground-water data for the Cretaceous area are taken from this earlier publication. In 1945, the Dentistry Division of the Alabama Department of Public Health became interested in the correlation of tooth decay and mottled enamel with the chemical quality of ground water used for public supplies in the State. Through a cooperative arrangement between the State Department of Public Health and the Ground Water Division (now Branch) of the U. S. Geological Survey, a report by the author2 was published in 1948. These two reports give accurate information on the occurrence of fluoride in the Coastal Plain of Alabama. At present, only scattered information is available on fluoride in ground water of the crystalline-rock or Piedmont area and for the Paleozoic area of Alabama, but it is hoped that in the future more complete information on the presence of fluoride in ground water in these areas can be collected. Outline of Geology and Ground Water: As described by Adams,3 the State of Alabama includes parts of two major geologic divisions, the Appalachian region and the Coastal Plain. The boundary between these divisions is irregular and is known as the Fall Line of the Atlantic and Gulf Coast States. The Fall Line enters Alabama near Phoenix City, extends westward to Wetumpka, Clanton, and Tuscaloosa, and then swings northwestward to the northwest corner of the State. The Appalachian region in Alabama includes three major provinces, the Piedmont province, the Appalachian Ridge and Valley province, and the Appalachian Plateau province (fig. 1). The rock formations in the Piedmont province in east-central Alabama are mainly of pre-Cambrian age, chiefly crystalline schists and gneisses injected by younger igneous rocks (fig. 1, I). They are faulted and folded and have a complicated structure. These rocks are the oldest and among the most complex rocks in the State. Generally, only small yields of ground water are obtained from rocks in this area. Even though ground water is of great importance for the development of domestic and farm supplies in rural areas and a few small industrial and municipal wells, yields in the area from individual wells generally range from 5 to 25 gpm and rarely exceed 50 gpm. The geologic formations of the Appalachian Ridge and Valley province and the Appalachian Plateau province (see fig. 1, II, and III) are separated on the basis of their structure. These rocks are of Paleozoic age, ranging from Cambrian to Carboniferous, and comprise a succession of formations consisting chiefly of shale, sandstone, limestone, and dolomite, aggregating many thousands of feet in

Jan 1, 1951

By M. E. Learmont, R. J. Lipp, I. Iwasaki

In the selective flocculation of iron ores, the concentration of alkaline earth ions in pulp solutions plays a critical role. Sodium silicate, alone or with sodium tripolyphosphate, has been used as a dispersant. When Ca+ + concentration exceeds 15 to 20 ppm, however, only a strong complexing agent, such as ethylenediaminetetraacetate (EDTA) was found to be effective (Heerema, Lipp, and Iwasaki, 1979). Some iron ores release Ca+ + in excess of 20 ppm. With ores that contain gypsum, the Ca+ + concentration may reach several hundred ppm. The purpose of this investigation was to compare the effectiveness of EDTA with nitrilotriacetate (NTA) in countering the adverse effects of Ca+ +, particularly at high Ca+ + concentrations. Emphasis was placed on the use of NTA since it is more cost-effective than EDTA. It is also used in detergents in some countries (Malaiyandi, Williams, and O&apos;Grady, 1979). NTA, like EDTA, forms a soluble complex with Ca+ + with a 1:1 molar ratio. Its structure and the value of log Kca are given below together with EDTA (Shibata, 1963). [ ] For experimental materials, an equal weight mixture of Lac Jeannine hematite and a high-purity quartzite from Thompson, MN, both ground to - 30 µm (- 560 mesh) was used. Selective flocculation test conditions and procedures were identical to those used in previous investigations (Heerema, Lipp, and Iwasaki, 1979). The optimum level of starch addition for the above mixture was determined to be at 300 g/t (0.6 lb per st). Initially, a series of selective flocculation tests were performed on the mixture pulped with 10-3M CaC12 (40 ppm Ca + +) at pH 11. With no NTA present, flocculation of the entire suspension resulted. The selectivities achieved in tests with 90, 100, and 150% of the stoichiometric amount of NTA were virtually identical to each other and also to the selectivity of separation obtained in the absence of Ca+ + Such an observation could have been expected since Ca+ + concentrations up to a few ppm may be tolerated in selective flocculation (Krishnan and Iwasaki, 1982). A similar series of tests were performed at 10-2M CaC12 (400 ppm Ca+ +). The results are shown in Fig. 1 as grade¬recovery curves. For comparison, the results obtained in the absence of Ca++ are included. At 90% of the stoichiometric amount of NTA, a large enough concentration of uncomplexed Ca+ + was left in solution to cause indiscriminate flocculation. Note in this figure that NTA is capable of countering the adverse effect of Ca+ + even at this high concentration when it is used in excess of stoichiometric amounts. The free Ca+ + concentrations at 100 and 150% are calculated to be 2.5 and 0 ppm, respectively. [ ] The relative effectiveness of NTA and EDTA was then compared at 100% of the stoichiometric amount using 10-2M and 10-3M CaCI2 (Fig. 2). EDTA appears to be slightly more effective than NTA. The free Ca++ of 0.02 ppm in 10-2M CaC12 with EDTA compared to 2.5 ppm free Ca+ + with NTA might account for the difference. As evident, prohibitively high additions of EDTA and NTA were required to complex high concentrations of calcium ion. The use of both of these agents would result in the accumulation of complexed Ca+ + in recycle water.

Jan 1, 1985

By R. V. Higgins, A. J. Leighton

A fast method is needed for calculating thoroughly the performance of two-phase flobr~ in reservoir rock with complex geotrietry. The authors present such a method and .slzow its accuracy by romparison with laboratory performrrnce of a five-spot pattern. In making the performance c.alculations, the octant of the five-spot pattern was divided into four channels. The computer tinle required for the culculation was one rllinrcte. This is rorighly about minute per channel. INTRODUCTION By using an electronic computer it is now possible to make reservoir performance calculations in which fewer assumptions and more significant variables are included than was possible with a desk calculator. These performance calculations include such variables as the properties of the reservoir rock and its contained fluids, properties of the rock-fluid system and even different well-spacing patterns. Usually, the more variables that are included the higher the computer cost—and time on the computer is expensive. As a result, a short procedure is needed so the many variables will be included and accurate performance calculations will result. If a reservoir is composed of alternate layers of permeable and impervioi~s rock, and if each conducting layer has a different relative permeability, the combined computer cost for calculating each layer by the present long computer programs (which includes different well-spacing patterns and other variables) would be expensive. The performances of complex spacing patterns in a field often are studied by a potentiometric model, but in these model studies the analogy is to the flow of only a single phase. This paper presents a procedure to calculate the performance of a five-spot pattern with two phases flowing using a potentiometric model as a guide for the dimensions of channels and other related data. The time required to calculate the complete performance is about one minute on the IBM 7090 or four minutes on the IBM 704. The procedure can be extended to calculate the performance of more complex well spacings or an entire field with little modification. The procedure has been tested on the performance of the laboratory water floods of a five-spot pattern reported by Douglas, et alThe range of viscosity ratios in the laboratory experiments is from 0.083 to 754, which is extensive. The accuracy of the performance calculations is excellent as shown by the plotted points in Fig. I. The recovery as influenced by the geometry of the five-spot, taking into account the deviation from true radial character, has been predicted by Aronofsky and Ramey." The authors used a potentiometric model to determine the sweep efficiency to breakthrough of the flooding agent. Dyes, Caudle and Erickson,&apos; by means of a laboratory model, show the influence of mobility ratio on recovery after breakthrough of the injected material. Dyes, et ai, used the X-ray shadowgraph technique and miscible phases in their studies. Craig, Geffen and Morse from the analysis of the performance of their laboratory model correlate many variables, including average saturation of a flooding agent determined by permeability relationship. Craig, et al, used X-ray shadowgraphs to determine the sweep efficiencies in sandstone models. In this report the sweep efficiency is not needed, and the important effect of continuously changing saturation gradients before and after breakthrough

By Theron Wasson

The discovery of two new fields—the Reed City area of Osceola County and the Headquarters field, of Roscommon County —and the important development in Winterfield township, Clare County, again demonstrate the fact that it is the unknown and unexpected that enter very definitely into the oil-producing history of Michigan. This is particularly true in the area of thick glacial drift in the north central part of the state, where the new prolific fields have been discovered this year. This shifts the interest from the southwestern part of the lower peninsula, where a number of pools were rapidly developed during 1939 and 1940, back into the Central Basin area. As a result of strict proration in the new areas, the production for the state of Michigan for the year has not been as great as in 1940 or 1939. In 1941 the total production was 16,300,000 bbl., in 1940 it was 19,551,000 bbl., and in 1939, which was the peak year, it was 23,300,000 bbl. However, the discovery of the new fields this year nearly doubles the estimated reserves for Michigan reported at the end of 1940 In 1941 about 12,000,000 bbl. of oil was produced from the older fields, in which the individual well productions were so small that proration was not an important factor. The total production for the state from the discovery of oil in 1925 through 1941 now stands at 161,205,000 barrels. ActIVe Oil Fields Reed City Field.—In the Reed City field, Lincoln township, Osceola County, only small oil wells were completed during 1939 and 1940. The discovery of much larger production in wells drilled somewhat deeper, by The Pure Oil Co. and the Weber Oil Co., in the early part of 1941, led to the rapid development in this area. Some wells have had initial productions as high as 10,000 bbl. By the end of the year III producing wells were completed, with an average depth of 3600 ft., from the Detroit River formation of Devonian age. The entire development of the field to the end of 1941 was on 20-acre spacing. Headquarters Field.—The Headquarters field, which lies along the line between Clare and Roscommon Counties, was one of the most important discoveries of 1941 and will be the scene of vigorous development during 1942. Production so far has been from the Traverse lime at about 3400 it., and development has indicated that this is probably one of the most productive Traverse pools yet discovered. One well had been given a potential of 10,000 bbl. per day. Dry holes well located in relation to big producers indicate that it is a typical Traverse development. Winterfield Field.-This field, in Winter-field township, Clare County, was discovered late in 1940. By December 1941, 14 Dundee and 5 Traverse producers had been completed. The Dundee lime is found at a depth of 3750 it. and the Traverse lime at 3070 it. Producing conditions in the Dundee seem to be erratic because of varying porosity in the dolomit-ized limestone. Kawkawlin Field.—The Kawkawlin field, which was discovered by the Gulf Refining Co. in 1938, is in Monitor and Kawkawlin townships, Bay County. Small production

Jan 1, 1942

LIBERIAN ore has been called the richest iron ore mined in the world, and thus far, the output from the Liberian Mining Co.&apos;s Bomi Hills mine has lived up to its reputation. Iron content has been variously given as 68.47 pct to 68.825 pct. A recent United Nations survey gave it first place, surplanting the previously top-rated Swedish product. The first shipment of Liberian ore to the United States reached Baltimore in June, 1952 and went into blast furnaces at Republic Steel&apos;s Cleveland plant, where excellent results were reported. The physical make-up of the ore was hard, dense lumps, free of fines and with ideal size distribution. The Bomi hills mines were scheduled to be in full operation by the end of 1952. At the close of 1951, 200,000 tons of ore had been delivered to Baltimore. Liberian Mining Co. states that production is about 90,000 tons of ore per month at present. Between 1200 and 1500 men are employed at the mine site, with about 25 pct of them Americans. The Bomi Hill project was financed with the aid of the Export Import bank, which loaned Liberia Mining part of the sum needed to initiate and put the development into production. No definite expansion plans are in the making but extensive diamond drilling is being pursued. Original estimates of annual production for Bomi Hills ran in the neighborhood of 1.5 million tons, but the figure is no longer applicable. Liberia&apos;s potential as an iron producing country has been known for a long time, but the physical obstacles in the way of large scale production were such as to prohibit even contemplation of the project. Until recent years, the only route from the mine site to Monrovia was a foot trail. Once to the coast, over swamps and unbridged rivers, the ore was still useless because of the lack of loading facilities. Transportation Solved One problem was solved with the completion of the artificial harbor at Monrovia. Harbor construction was well under way when the mine project began in 1948. The island location of Monrovia also made the building of a bridge across the St. Paul River necessary. The 980 ft reinforced concrete structure, accommodating railroad and vehicular traffic, was opened in 1949. Meanwhile, preliminary work on railroad construction started. Grading was completed quickly. In April, 1951, the first train made the trip from Monrovia to the Bomi Hills. About half of the cost of the entire project went into railroad construction. More than 2200 men, often forced to resort to primitive methods, were engaged in clearing a path through the heavy forests between the mine and port. Swamps were drained and filled, and bridges, including the William V. S. Tubman, named for the Liberian President, were constructed. At the port, a Robbins Conveyor Belt Co., orehandling plant was installed. Ships can be loaded from the stockpile at the rate of 3000 tons per hr and vessels need spend only one day in port. Liberian Mining is operating under an 80 year lease, giving the company exclusive mining rights to all minerals, except gold, platinum, and diamonds, within a 40 mile radius of Bomi Hills. The contract provides a fixed royalty to the Liberian Government of five cents per ton of ore extracted, and a premium -based on the New York market price for Bessemer-grade pig iron. The entire project started because an American,

Jan 1, 1952

By James B. Macelwane

THE Mineral Industry Education Division of AIME has long been interested in geophysical education. Organized in 1938, a Committee on Geophysical Education presented a number of reports in succeeding years. The AIME is an engineering society; hence it might be expected that the interest of the Mineral Industry Education Division would have centered about the relation of courses in geophysics to engineering education. However, this was not the case. The burden of the discussion held under the auspices of the Committee on Geophysical Education bore on geophysics in general and particularly on its relation to geology. In the decade that has passed since those meetings much water has flowed under the bridge. Not only have the geophysical sciences developed at an extraordinarily rapid rate but the practical importance and the range of their applications have spread in ever widening circles and have even assumed a very prominent place in research programs of the military, the Army, the Navy and, particularly, the Geophysical Research Directorate of the Air Force at Cambridge, Mass. So enormously have the geophysical sciences as such grown in scope and in degree of specialization that no one man in a lifetime of study can hope to master the theoretical and experimental complexities or even to follow intelligently in the published literature all the varied accomplishments of basic research in these &apos;fields. As in the other sciences, most of the results of geophysical research have potential economic value and are being applied to a wider and wider range of human needs. Here we see a parallel with the older sciences and their relation to engineering. Whenever the applications of scientific results required the special experimental background, the economic outlook, and the practical knowledge characteristic of the engineer, a curriculum in that type of engineering grew up in the colleges and universities. In the words of the "Report of the Committee on Adequacy and Standards of Engineering Education" in the. January 1952 number of the Journal of Engineering Education: "Engineering education in America was not developed after a preconceived plan. It evolved in parallel with the needs of a growing country, a country engaged in the development of a vast industrialization. From the first it filled a practical need, and its design emanated largely from an evaluation of the professional requirement." The advent of the railroad created a need for scientifically trained engineers and the response was the curriculum in civil engineering. The development of steam power created the demand for a curriculum in mechanical engineering. Neither of these types of engineers was trained to cope with the requirements of electrical power, and so there came to be a curriculum in electrical engineering. The advent of radio communication and of electronics during the first World War and in the years that followed resulted in the establishment of electronics engineering, sometimes within the curriculum in electrical engineering and sometimes independent of it. The complexities of industrial management have created an ever increasing demand for industrial engineers and the consequent building up of a curriculum in industrial engineering. The wide industrial application of chemical processes required a type of engineer whose background was training in chemistry but who was able to design processes and plants on an industrial scale; hence we have the curriculum in chemical engineering. The advent of the airplane created an entirely new set of problems which were solved by the training of aeronautical engineers. Many of these have called for more and more science and mathematics. Such was the history of the older engineer-

Jan 1, 1952

By T. M. Geffen, R. E. Gladfelter

Lipson1 has recently presented a technical note wherein theoretical considerations were used to demonstrate. that the adsorption us saturation relation for a linear absorption method is not necessarily a single valued function of saturation.1 It was concluded that the absorption us saturation relationship is subject to the same hysteretic effect as is the flow behavior between the drainage and imbibition systems. It is the purpose of this note to show, by experimental results, that for the manner in which fluids are distributed in porous materials during fluid flow, the relative X-ray absorption us saturation relationship is single-valued regardless of the saturation history. The design of the apparatus used to measure relative X-ray absorption of cores undergoing fluid flow tests is similar to that described by Morgan, McDowell and Doty. A few modifications have been incorporated in the design to increase sensitivity and simplicity of measurement. The sensitivity is such that for usual types of cores a recording pen movement of approximately 12 linear in. is occasioned between the recording of the core dry and when it is completely full of an absorbing liquid, a solution of approximately five per cent by volume of iodo-benzene in a close-cut hydrocarbon fraction, or a solution of 50,000 ppm sodium iodide in water. Two types of experiments were conducted, one in which the liquid was inside the core, and the other with the liquid outside the core. Tests with the liquid inside the core were run to cover the saturation range encountered in both the drainage (gas drive) and imbibition (liquid flood) flow systems. It is pointed out that the same core was used, but the tests were conducted at different times with the recording mechanism balanced at a different position. Therefore, the absolute values of relative X-ray intensity at any saturation are not the same in each test. In the second type of test the same core was used, but this time its pore space cmtained only gas, and various thicknesses of oil contained in plastic cells were placed in front of the dry core. As before. the relative X-ray ah- sorption was measured and compared to the quantity of oil in front of the core. The arrangement of the fluids with respect to the path of X-rays in these two types of tests represent fluid distributions of a wider difference than can be expected between that established in a core just due to imbibition and drainage saturation flow histories. Thus any deviation from a straight line relationship of the log of the relative X-ray intensity us saturation calibration should be readily apparent. Results of the laboratory tests are given in Fig. 1. A schematic diagram showing the position of the fluids with respect to the path of the X-ray beam is given for the two cases investigated. In the case where the oil existed outside the core (Case B), the log of the X-ray intensity (log, I/I,) is related directly to the cell thickness (amount of oil in X-ray beam path). This correlation is in full agreement with X-ray theory. In the case where the oil or water existed inside the core (Case A) which covers both drainage and imbibition types of flow processes, again the relationship between absorption and saturation (amount of oil in X-ray beam path

Jan 1, 1952

THE activity of the principal oil fields of Rumania followed the same course as in 1939. It was marked by (1) collaboration between the various companies, particularly in exploiting oil at great depths with a view to rationalizing the exploitation and decreasing the difficulties inherent in very deep drilling; and (2) economy in the exploitation of the older pools in reducing to a minimum the cost of the extraction and working over of wells by the concentration of productive wells in groups. The pooling arrangement continued at Tintea as a measure of conservation, and exploitation of the unitized region went forward on the basis of the norms established in 1939. The same methods were applied in the fields of Liesti, Ceptura and Boldesti. The petroleum industry had some difficulty in providing the necessary material and the hands for work. Importation of material and machines from the United States was virtually stopped. Substitutes were provided from Germany but particularly useful were certain dispositions made by the local metallurgical industry. Despite the higher cost of the production of local material and machines, they were superior to the German product, the difference in quality justifying the higher price charged as the materials were found to be particularly adapted for the purposes of the petroleum industry. The cost of production was still further raised by the work that was imposed for national defense. The rise in costs per meter drilled was 50 per cent over those of 1939. According to bimonthly tables furnished by the Moniteur du Petrole Roumain, the deepest well completed in 1940 was an exploratory well, No. 201 of the Concordia company, drilled at Tintea and suspended at 3338 meters. This depth was reached toward the close of 1939 and the well was not deepened in 1940 became of large deviation from the vertical. The record for productive wells had been held by No. 429 at Tintea, drilled by Unirea to a depth of 3200 m., and in 1938 well No. 317 Cocorasti-Mislea, of the Colombia company, but these records were passed in 1940 by well No. 613 Liliesti of the Con-cordia company, which reached a depth of 3294 m. and had an initial production of 10 tons per day. In 1940, the same number of wells, II, had been drilled to a depth of over 3000 m. as in 1939. Five of these wells are at Tintea and six at Liliesti. Table I lists these very deep holes in the order of their depth. Table i.—Deep Wells Drilled in Rumania in 1940 Initial No. Produc- of Company Field Meters tion, Well Meters Tons per Day 405 Colombia......... Liliesti 3,001 10 629 Unireu............ Tintea 3,005 73 426 Unirea............ Tintea 3,050 48 410 Colombia. ........ Liljesti 3,055 30 627 Concordja (Unirea). Liliesti 3,072 75 430 627ConcordjaConcordia (Unirea). (Unjrea 3,II9 30 618 Colombia......... Liliesti 3,168 70 24 Steaua Romana. . . Tintea 3,184 18 412 24Unirea............ Tintea 3,211 23 613 Concordia......... Liliesti 3,294 10 Production in Rumania in 1940 reached 5,813,000 tons, in contrast to 6,~40,0oo tons in 1939, a decline of 427,000 tons, or 6.8 per cent. Drilling reached 241,500 m., in

Jan 1, 1941

By B. Lustman

IT has been known for a number of years that the addition of certain alkaline-earth and rare-earth metals to nickel-chromium base electric resistance alloys causes marked increase in their oxidation resistance as measured in an intermittent oxidation test similar to the ASTM—B 76-39 test. However, the mechanism whereby such additions confer protection is still unknown. On the basis of the experimental observation that the increase in life in intermittent tests of nickel-base alloys is proportional to the atomic radius of the added element, Hessen-bruchl has proposed that the added metal ions occupy holes in the oxide lattice which prevent diffusion of nickel ions in the oxide. Horn2 has postulated that the effect of such additions is to accelerate the rate of diffusion of chromium atoms in the metal and thus to favor the formation of Cr2O3 scales. Hickman and Gulbransen3 concluded from electron diffraction observation that the addition of the elements in question results in the formation of a barrier to the diffusion of nickel ions to the surface. In connection with some experiments conducted to develop a test for the resistance to oxidation of alloys in massive form under conditions of intermittent heating and cooling, some features of the oxidation of nickel-chromium base alloys were revealed which may serve to elucidate the mechanism of protection conferred by rare-earth and alkaline-earth elements. Specimens of cylindrical shape 0.360 in. diam x 0.37 in. long were placed in alumina thimbles and inserted into and withdrawn from a Globar-heated furnace operating at 2150°F at 7.5-min intervals. The weight of oxygen absorbed as well as the weight of oxide spalled were measured at intervals. With the particular experimental conditions used, the specimens in a 7.5-min cycle were at temperature for 2 min which corresponds to the heating time of the ASTM test. The weight changes of similar specimens under conditions of continuous heating in air at 2150°F were also measured. The specimens after oxidation were examined metal- lographically and samples of the spalled oxide collected for X-ray diffraction identification of the phases. The specimens used were from the same lot of material used by Hickman and Gulbransen3 and had the compositions shown in table 1. Included in table I are results of ASTM life tests on the materials in the form of wires. These materials, their composition and the ASTM life test data thereon were all supplied by F. E. Bash of the Driver-Harris Co. It may be noted that alloy 13246 of 80 pct nickel, 20 pct chromium nominal composition showed the shortest life in the ASTM test; alloy 12246 with the addition of small amounts of the elements zirconium, calcium, and aluminum, intermediate life; and alloy 12046 with the further addition of silicon, the longest life. In fig. 1 are shown the results of intermittent oxidation tests made on bulk specimens at 2150°F as well as continuous tests conducted at the same temperature. Duplicate tests were made on each specimen. The ordinate scale, inches of metal oxidized, was derived from the experimentally observed weight gain of oxygen by assuming the scale to be entirely Cr2O3. It may be noted that the metal-loss curves during intermittent oxidation show a constant or continuously increasing rate of weight

Jan 1, 1951

By J. E. Gruzleski, O. Knacke, M. J. Meixner

The evolution of CO from small specimens of solidifying steel was investigated using a thermobalance technique. Gas evolution begins in the temperature range between 1400" to .1450°C. This behavior is independent of the initial carbon content and the cooling rate. At a constant temperature above 1220°C, the rate of gas evolution is temperature independent. Out-gassing of the specimen is thought to proceed through small channels formed by the coalescence of bubbles between dendrites. LIQUID metals have a higher solubility for gas than the solid. During freezing, these gases form bubbles which may either escape or remain trapped in the solid. Recent work1 on the evolution of oxygen from solidifying silver showed that the gas is not liberated until a large fraction of the melt has solidified, and that the gas is evolved in an almost explosive manner. Because of the commercial importance of CO evolution in solidifying steel, a similar investigation was undertaken to study the mechanism of gas liberation in steel. EXPERIMENTAL The thermogravimetric method of Knacke and eixner1 to follow gas evolution by weight changes was employed. Weight differences of 0.1 mg could be reproducibly measured on specimens weighing 2.5 g. These specimens were taken from alloys with varying carbon contents from <0.01 to 0.11 wt pct and <0.01 wt pct of each of silicon, manganese, and aluminum. Specimens contained in 8 mm ID magnesium alumi-nate crucibles were heated to 1550°C under 1 atm of very pure (99.995 pct) CO with a tungsten resistance furnace. The specimen temperature was measured with a Pt-Pt/Rh thermocouple located directly beside the crucible. It is felt that the temperature thus measured was within 5" to 10°C of the specimen temperature since on fusion the weight of the specimen increased due to uptake of CO, and this weight increase was always observed to begin within the temperature range of 1530" to 1540°C. Even after 3 hr there was a small weight increase with time indicating that the molten specimen was not completely saturated with CO. Therefore, complete saturation was not attempted, and all specimens were simply held for 3 hr at 1550°C before cooling. Two types of cooling experiments were performed. One consisted of continuous cooling at linear rates from 5°C to 20°C per min down to 1020°C. The second type of experiment involved continuous cooling at 10°C per min to a predetermined temperature, and then holding the specimen at this temperature for a certain time. During all of these experiments, the sample weight was recorded as a function of time and temperature. OBSERVATIONS Continuous Cooling Experiments. No gas evolution was detected above 1450°C. The initial weight decrease always occurred between 1400" and 1450°C with the average at 1430°C. With further cooling, gas evolution continued to about 1150°C. Between this temperature and 1020°C no further outgassing was observed. This behavior did not seem to depend on the initial carbon content nor on the cooling rate in the range investigated. Typical patterns of gas evolution are shown in Figs. 1 and 2 for different initial carbon levels and cooling rates. The total amount of gas liberated during solidification varied with the rate of cooling. The total weight change on continuous cooling at a rate of 10°C per min

Jan 1, 1970