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By A. N. Holden, J. H. Hollomon

Inhomogeneous yielding during the early stages of plastic flow has been observed in many metals and has long been a subject of controversy. Low carbon steel, when strained at room temperature, exhibits a distinct yield point at which the metal ceases to behave elastically and begins to flow plastically without further increase in stress,† often with an actual decrease in stress from that existing at the yield point. One manifestation of this behavior is the familiar Lüders lines. The extent of the yield point elongation (the plastic strain which results without raising the stress above that at the initial yield point) may be several percent. Several explanations of this type of yielding in steels have appeared in the literature:1-3}; 1. The segregation of carbides or other constituents at the grain boundaries of ferrite forms cell-like blocks which break down at a higher stress than that at which the ferrite alone will flow. 2. The precipitation of various constituents within the ferrite itself in some way blocks initial flow until a higher stress is reached, after which a great deal of flow occurs without further increase in stress. 3. The restraining influence of neighboring, less favorably oriented grains in a polycrystal results in a storing up of energy, which on yielding is sufficient to cause the continued propagation of slip bands on the multiplicity of slip systems available in adjacent iron crystals without increase in stress. 4. Local segregation of carbon atoms increases the stress required for the initial propagation of dislocations. The stress required for further deformation is lower.3 Such an explanation would require the presence of upper and lower yield points in single crystals. Low and Gensamer2 have shown that heterogeneous yielding can be eliminated by removal of carbon and nitrogen from polycrystalline steels by wet-hydrogen treatment. They also demonstrated that the re-introduction of minute amounts of carbon or nitrogen caused a return of the yield point. Observations of the initial flow of single crystals containing small amounts of carbon and nitrogen- should provide a clue to the explanation of inhomogeneous yielding. Previous tests of iron crystals4-6 can not be considered conclusive because it is uncertain whether the carbon and nitrogen were satisfactorily removed by the decarburization technique employed. The purpose of the experiments described herein was to determine whether single iron crystals containing either carbon or nitrogen would exhibit in-homogeneous yielding. Experimental Procedures THE PREPARATION OF SINGLE CRYSTALS All crvstals were formed in the following way. Aluminum killed sheet material 80 mils thick was machined into specimens of the outer contour shown in Fig 1. These mildly tapered specimens were decarburized at 730°C for 16 hr in hydrogen that had been bubbled rapidly through water maintained at 70°. The resultant grain size after decarburizing was approximately ASTM 5. Several stress-strain curves were made of the decarburized niate-

Jan 1, 1950

By J. Philip Neal, Carroll P. Rogers

Feldspars, the most abundant minerals of the igneous rocks, occur in numerous forms and mixtures. The feldspars of commercial significance are found in widely distributed pegmatites as large crystals usually free of iron- bearing impurities and thus suitable for hand-cobbing, and also in larger bodies where the ore contains various types of feldspar inter- mingled with quartz and relatively free of iron- bearing impurities, or at least readily unlocked from impurities present at relatively coarse mesh. The latter type of ore includes some pegmatites, and the ''alaskite" bodies so common in the Spruce Pine district of North Carolina. On the west coast of the U.S. and in Oklahoma there is-r has been--commercial recovery of natural feldspathic sand as a source of alumina in glass and ceramics. "Aplite" in commercial terminology is a light-colored igneous rock with a granitic composition and a fine sugary texture, often banded with readily removable iron impurities. Two areas in Virginia produce aplite for the glass industry: one located in the vicinity of Piney River, Amherst County, and the other near Montpelier in Hanover County. According to Deer et al. (1966) the word feldspar derives from the Swedish feldt or falt (field) and "spath:" chunks of rock appearing in tilled ground overlying granite. Castle and Gillson (1960) indicate a Germanic origin, citing "spat," which is said to refer to any transparent or translucent material which is readily cleavable. The term "spar" has in the past been applied to minerals other than feld- spar, such as barite, calcite, and fluorite. It is correct to call the latter "fluorspar." There is a true barium feldspar, but it is rare and of no present economic importance. What is recognized as feldspar or "spar" by present producers and consumers consists of three silicate minerals which, if pure, would have the formu- las KAISi,O, (microcline or orthoclase), NaAlSi,O, (albite), and CaAl,Si,O, (anorthite). These are almost never found in pure form in nature, but occur together in great abundance in a three-component system. A considerable number of different combined ratios of these three exists, with the exception that isomorphism between potassium spar and calcium spar is very limited. User specifications for feldspar products are largely built around the prevalent naturally occurring ratios. Pas- sages following will refer to "K-spar," "Na- spar," or "Ca-spar." Nomenclature and Descriptive Terms Relating to both the mineralogy and the economics of feldspar are certain terms whose coverage it is useful to specify. Commercially, aplite is a feldspathic rock mined and beneficiated in two locations in Virginia, in which both titanium and feldspar minerals are present-the latter now being the major, if not the only, economic product. Technically, the term aplite when applied to this rock is of questionable accuracy. But, in light of accepted commercial usage, the term will be here used to designate it. Regarding the Virginia rock, Ross (1941) is cited.

Jan 1, 1975

By P. L. Menaul, P. P. Spafford

This paper discusses the most dangerous form of corrosion encountered in condensate-well oil production, the discovery of the agent causing this corrosion and the remedial chemical treatment proved effective by field use. The injection of ammonium hydroxide, even as little as one quart per day, has proved effective in preventing gas-condensate well corrosion. The injection of "Bone oil" is applied to wells producing brines containing calcium and magnesium salts. Introduction The severe corrosion of equipment in high pressure gas condensate wells has been a problem for several years and numerous papers have been presented on the subject. The term "gas condensate" or "distillate well" is applied to a distinct variety of hydrocarbon producing well, the characteristics of these wells being high bottom-hole (formation) pressures and temperatures and high gas production. These wells usually produce about 40 gal of water per million cubic feet of gas and the gas contains from 0.1 pct to 2 pct carbon dioxide. In the operation of this type of well, the operators soon noted severe internal corrosion of the pipe carrying the production. In some instances the dl tubing has been found to be corroded to perforation in eight months. The high well head pressures of 2500 to 8000 psi makes any weakening of the well equipment by corrosion extremely hazardous. Bursting of the well equipment results in very expensive repair operations and may result in the loss of valuable production, loss of the costly well, or even loss of life. In November 1944, a gas-condensate well in a Gulf Coast field producing from 9500 ft showed a tubing leak. The well was "killed" by filling it with mud through the tubing, and then the tubing was pulled. Corrosion was found to have caused several perforations in the tubing, Fig I. While the mud was being circulated to kill the well, a high pressure jet from the corroded hole in the tubing perforated the casing and damaged the well to the extent that the cost of repairs amounted to $75,000. In November 1944, another gas-con-densate well in a Gulf Coast field producing from 11,400 ft showed tubing failure. This well had been producing an average of 2,500,000 cu ft of gas daily for two years. In the workover of this well, it was found that a hole one inch in diameter had corroded through the tubing and that corrosion had reduced the wall of the tubing to less than half the standard thickness over large areas of the interior of the tubing. It was found that corrosion had also caused two leaks in the casing. After four months spent in an attempted workover failed to make the well safe for further production, the well was plugged and abandoned at a total loss of $300,000,00.

Jan 1, 1948

By E. W. Dewing

The solubility of A14C3 in cryolite melts has been determined by holding the melt with aluminum in a graphite crucible for 4 hr at temperature, quenching the crucible in water, and analyzing the frozen salt by CH4 evolution. The solubility is given by log(wt % Al4C3) = 1.298 -1.l74 (wt ratio NaF/AlF3) independent of temperature in the range 985" to 1080°C. Additions ofA1203, .NaCl, CaF2, or LiF up to 10 wt pct do not affect the solubility, provided that LiF and CaF2 are replaced by equivalent NaFin calculating the ratio. The variation with ratio can be accounted for quantitatively on the hypothesis that the Mechanism of solution is Al4C3 + 2AIF3 = 3Al2CF2 since the solubility varies as (aAIF3) 2/3; Mechanisms involving C", C2- , AlC- , A12C2+, and Al2CF+are re-jected. At ratios above 1.5 truces of c;- are also present. It was noticed some years ago in this laboratory that carbon specimens made cathodic in a cryolite bath decrease in diameter over a period of time.' It was also found that cryolite which had been melted with aluminum in a graphite crucible was sometimes yellow, and that A14C3 could be seen intimately embedded in the cryolite crystals. CH, could be recovered by acid attack. There was thus reason to believe that A14C3 had a genuine solubility in molten cryolite, and the object of this work was to measure it. EXPERIMENTAL AND RESULTS A graphite crucible, 2 in. ID and 2.5 in. deep with a close-fitting lid, contained about 150 g of cryolite (plus additives) and about 20 g of 99.99 pct pure Al. It was placed in a vertical Inconel furnace tube, covered with refractory brick to provide thermal insulation, and the top of the tube was roughly sealed with disks of asbestos paper. An alumina tube led argon down to the level of the top of the crucible to expel air, and an alumina sheath with a Pt-10 pct Rh ther-mocouple inside was positioned between the crucible and the wall of the Inconel tube. The tube was heated in an electrical resistance furnace for the desired length of time; the refractory bricks were then removed, and the crucible was lifted out with tongs and quenched in water. After such a crucible was broken open it could be seen that its inner surface was yellow owing to the presence of A1,C3, and sometimes needle-like crystals could be observed (at X75 magnification) growing out into the nielt. It was concluded that Al,C, had been present as a separate phase when the crucible was at tenlperature and that the melt had been saturated: in

Jan 1, 1970

By H. R. Peiffer

Composite alloys of silver and alumina are shown to resist flow above the melting point of the continuous matrix. The ability to resist flow depends on the fineness of the dispersion and the oxygen content of the silver. It is believed that the oxygen influences very strongly the bond between the molten silver and the finely divided alumina. RECENT needs for materials with high strength and creep resistance at high temperatures initiated mechanical property studies on dispersed phase materials to near the melting point of the continuous matrix material. Results' of these investigations have shown that certain of these materials do have promise for high-temperature applications. Experiments performed on composite materials of silver and alumina by the author have resulted in the discovery of an interesting effect above the melting point of the silver. In these materials the silver was continuous and the alumina very finely divided (Linde B). It was observed that these materials exhibited strength and resistance to flow above the melting point of the silver matrix. The purpose of this paper will be to describe these properties. METHOD OF PREPARATION The materials were prepared by mixing the proper amount of Linde B alumina and high-purity silver oxide. The alumina content was varied from 5 to 20 wt pct alumina in silver in 5 pct steps. The materials were mixed by blending the constituents in an ordinary food blendor using ethyl alcohol as a vehicle. Enough alcohol was added to the powders to form a mixture with the consistency of a thin mud. After blending for about | hr the material was dried and the silver oxide reduced by heating to 450 OC. The material was then pressed at 25 tsi into a -in. billets 3 in. long. EXPERIMENTAL PROCEDURE The specimens were horizontally supported at either end by knife edge supports of cold-rolled steel. This holder was then placed in a "globar" furnace and a chromel-alumel thermocouple placed very close to the specimen recorded its temperature to within 10°C. Each specimen was heated rapidly to 900°C initially. The specimens were held at temperature approximately 30 min and then the temperature was raised 50 deg. The procedure was repeated until deformation was noted. Photographs were made of the specimens at various temperatures and increments of time using a Polaroid Land camera. RESULTS Fig. 1 shows the 5 pct by weight "Linde B" alumina and silver material after reaching 980 °C. Failure occurred after 15 min at this temperature. There were two points of failure and silver collected at them. No additional flow of the molten silver was noted at any other place. Fig. 2 shows a 20 pct by weight "Linde B" alumina in silver specimen. After 30 min at 1400°C, bowing of this material was observed. Other concentrations of alumina were added to

Jan 1, 1961

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

ONE of the most important methods of increasing the hardness of metals is alloying. In spite of the widespread use of alloys, the fundamental mechanism of alloy hardening is little understood. This is true even of the simplest form of alloy, the primary substitutional solid solution in which solute atoms substitute for solvent atoms at random in the crystal lattice of the latter. A fundamental understanding of the mechanism of solid-solution hardening would be important, both because of the widespread use of alloys of this type and because of the light that might be thrown on the mechanism of hardening in more complicated alloys. The present investigation covers the hardness of primary substitutional solid solutions of zinc, gallium,, germanium; and arsenic in copper. All of these are B subgroup elements from the third period of the periodic table. Cu, Zn, Ga, Ge, and As are in groups I, II, III, IV, and V, respectively and lie just to the right of the transition elements. Because of their cost, it is unlikely that Ga-Cu and Ge-Cu solutions will ever be of commercial importance, but the intent of this study has been to discover some of the fundamentals of solid-solution hardening and it has been demonstrated that such a study is far more likely to be fruitful if alloys are made up on the basis of position of the constituent elements in the periodic table than if commercially important alloys are used. Many investigations have. been made of the hardness of substitutional solid solutions, but lack of attention to purity of the metals, infrequent grain-size control, and the use of varying testing techniques have virtually invalidated any comparisons. The purpose of most investigations has been to solve immediate problems and not to solve the primary problem: Why do solid solutions usually have a greater hardness than pure metals? PREVIOUS WORK Theories have been advanced to account for the hardness of solid solutions,, but relatively little experimental work has been done. Perhaps the first experimental work of merit was that of Norbury1 on copper alloys. He showed that for several alloys there was a correspondence between the hardness of one atomic per cent solutions and atomic volume of the solutions. More recently Brick, Martin, and Angier2 have investigated the effect of various solute elements on the hardness of copper. They concluded that the hardening effect of these solutes depended "primarily on the difference in atomic volume of solute and solvent or, relatedly, upon the parameter, change of the solvent or the extent of solid solubility." They also observed the effect of these elements on hardness and texture developed by rolling and by annealing of rolled material. Austin3 examined the hardness and response to heat-treatment of various iron solid solutions. Frye and Hume-Rothery4 measured the hardness of a number of silver solid solutions containing approximately

Jan 1, 1943

By G. A. Vissac

In the presentation which follows, wash-ability curves, such as are commonly used in making studies preliminary to the cleaning of any coal or to the concentration of any mineral, have been reduced in each instance to a single straight line; thus all the most important characteristics of the coal or mineral are represented in a form more advantageous than that in which such data usually are shown. To obtain consistent results, float-and-sink data must be based on a single definite narrow size range, which may be designated "a coal unit." It will be shown that such units, each embodying a different size range, can be grouped to form what may be termed "a composite coal." A three-dimensional presentation will emerge, which will closely identify the coal, illustrate its characteristics in a new manner and explain many obscure facts. Float-and-sink Tests For the preliminary study of any cleaning or concentration problem, or in the control of any operation, float-and-sink tests must be made. The results of these tests are grouped in tabular form and then illustrated in various systems of curves; but if such a graphic representation is to have the utmost practical value, it must offer at least the following advantages: (I) It must be easier to read than the tabular results, and (2) it must be easy to plot, check and interpolate. The first requirement will be attained by reducing the number of curves to a minimum, and the second by some system of representation that will use only straight lines. Of the many washing curves now in use, only the "recovery curve," often known as the "composite curve"—a somewhat misleading term—will be considered; Any point on the recovery curve will show what percentage of weight of clean coal can be recovered when the mineral is washed at a certain specific gravity. As an example, the tests listed below Fig. I are illustrated in the drawing by a curve obtained by plotting (I) as abscissas the ash content of the coal recovered and (2) as ordinates the corresponding percentage of refuse discarded; but, in general practice, instead of writing down that weight, it is customary to set down its complement, which is the corresponding weight of coal recovered. From this curve can be deduced the information necessary for the solution of most practical problems. New Form of Graphic Presentation The resemblance of the recovery curve ill Fig. 1, or, for that matter, the recovery curve obtained in common practice! to a Power curve is apparent. The general equation of such a curve is Y = axn, where n is negative. Taking logarithms: log y = a + n log x. Using a logarithmic scale, the equation of the recovery curve will be Y = A + bX. On this logarithmic basis! the recovery graph will be a straight line, using the same variables as in Fig. I; namely, the ash con-

Jan 1, 1942

By C. Williams, D. V. Carter

During 1943 five oil fields and two gas-condensate fields were discovered in the East and East Central Texas district. The New Hope field, discovered by Tide Water-Seaboard in Franklin County, is the most important oil discovery since the Hawkins field in 1940. At the close of the year two oil sands were producing and two additional oil sands were being tested. The gas-condensate fields of Appleby in Nacog-doches County and the Stewards Mill field in Freestone County had only one producing well each. The Carthage field was extended 3 miles north and 4 miles west. Another well that was testing at the year end indicated a probable eastward extension of several miles. The Quitman field, in Wood County, was the most active from the standpoint of drilling operations. Approximately 48 wells were complcted during the year. The second and third most active fields were Hawkins field, Wood County, and Kildare field, Cass County, respectively. Wartime restrictions of material, together with manpower shortage and Federal spacing regulations, reduced the number of oil and gas-well completions from 265 in I942 to 171 in 1943. This represents a drop of 35 percent, or approximately 1/3, enough to replace the 531 producing wells abandoned in the district during the year. No changes were made in the price of crude oil in the district in 1943. The district produced 177,652,940 bbl. of condensate and oil during 1943. This represents an increase of approximately 11 per cent compared with the previous year. The East Texas field, which is the largest and most important field in the district, had an annual production of 128,568,647 bbl. of oil, which is approximately 6.5 per cent more than the previous year, and represents 72 per cent of the district's production of condensate and oil for the year. The district had an estimated basic daily allowable of approximately 509,000 bbl. of oil on Dec. 31, 1943. The entire district produced approximately 30 pcr cent of the state's production for the year 1943. The Hawkins field, Wood County, was operated 271 days during the year and with an average daily production of approximately 52,488 bbl. for the year. This field, which is the second largest in the district, produced 14,224,164 bbl, of oil during the year. Changes in annual production in certain fields in the district can be attributed to their ability to produce at higher rates, the demand, and transportation facilities in the war effort. The East Texas field showed an over-all decrease in reservoir pressure of 8.30 lb. during the year. Indications were that through the first quarter of 1944 the return of salt water to the reservoir was having a beneficial effect. It is hoped that, as more and more water is returned to the reser-

Jan 1, 1944

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

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

Jan 1, 1943

By R. G. Patterson

The usual procedure in determining the magnetic susceptibilities of rocks and formations has been to take samples in the field and measure their volume susceptibilities in the laboratory, using one of numerous methods available. In none of these methods is the measuring instrument suited for field use. Usually the sample is pulverized; sometimes it is machined to a desired sue and shape, and in one method1 a cast of the sample is made and the susceptibility of the rock compared with that of a material of known susceptibility of the same size and shape, made from the cast of the original sample. Some writers assert that the difference in susceptibility of a rock sample in powdered and solid forms is negligible, and while doubtless this is true in many cases there are others in which the difference becomes appreciable. Further, the susceptibility of a small specimen may differ from that of the rock from which it is taken, owing to the stresses produced by the hammering or other forces used to obtain the sample and shape it for testing. Wilson2 found that an individual specimen of granite had about the same susceptibility in the solid as in the powdered form, but that pieces from different parts of the rock varied as much as 750 per cent because of unequal distribution of magnetite. The most accurate value of susceptibility would, obviously, be obtained from averag- ing a number of tests on the undisturbed rock instead of from one or two samples. No such procedures have been published, to the writer's knowledge. It is the purpose of this paper to describe a method by which susceptibilities of rocks may be determined in place by means of a portable instrument. Method The principle involved in this new method is that there is a change in inductance of a coil due to the presence in its magnetic field of a paramagnetic or dia-magnetic medium. In this case, however, the windings of the coil do not enclose any part of the rock under test. Instead, the coil is circular, being small in cross section as compared to its radius, and consists of several hundred turns of fine wire. It is placed flat on the rock of which the susceptibility is to be measured. Thus only part of the magnetic field from the coil penetrates the rock under test. The relation between the change in field strength or inductance of the coil and the susceptibility of the medium will be developed later. To measure the change in the inductance of the coil due to the presence of a magnetic material an alternating-current inductance bridge was chosen. Description of Apparatus Of many alternating-current bridge methods applicable,3 the one shown in Fig. 1 (Owen's bridge') was adopted for its simplicity and sensitivity. In Fig. I, the test coil is indicated by PlL1. It is connected to the bridge by about

Jan 1, 1946

By William R. Patterson

ACCORDING to the phase diagram for the Mn-Ni system,' the high-temperature, fcc y-manganese solid solution is stabilized to below room temperature, in the range approximately 22 to 28 wt pct Ni. However, pearson2 cites evidence in the literature showing that for manganese contents greater than about 75 wt pct the quenched phase in Mn-Ni alloys is fct. This is in keeping with zener's3 suggestion that in manganese-rich alloys the fcc high-temperature phase undergoes a diffusionless or martensitic transformation to a fct structure upon quenching. Work by Basinski and christian4 on manganese-rich compositions in the similar alloy system Mn-Cu established that in alloys of greater than about 82 wt pct Mn the y-manganese phase underwent a fee fct martensitic transformation upon quenching to room temperature. Striking evidence for this martensitic transformation was the highly twinned or banded microstructure, an example of which is shown in Fig. 1. Similar microstructures have also been found in quenched Mn-Cr5 and Mn-Au6 alloys. In the present investigation, we attempted to obtain similar evidence of a fcc — fct martensitic transformation in manganese-rich Mn-Ni alloys. Manganese alloys in the range 10 to 30 wt pct Ni were prepared by arc-melting, under argon, at atmospheric pressure. The alloys all were 50 g in size, and negligible weight loss occurred during melting. The starting materials were electrolytic manganese and nickel, both of 99.9+ pct purity. The alloys were subsequently homogenized 48 hr at 1750°F, hot-rolled 50 pct at 1700°F, annealed 2 hr at 1700°F, and water-quenched to room temperature. All heat treatment was done in purified argon. Both X-ray and metallographic techniques were used to examine the structures of the quenched alloys. X-ray diffractometer studies were conducted on powder specimens obtained from filings rean-nealed 2 hr at 1700°F in argon and water-quenched. Identification of the intensity peaks from the diffractometer counter traces showed that below about 10 to 12 pct Ni the y phase decomposed partially upon quenching to give an a- + ?-manganese structure. In the range approximately 12 to 25 pct Ni, the structure was found to be fct ? manganese with a c/a ratio approaching 1.0 at 25 pct Ni. Beyond approximately 25 pct Ni, the structure remained fcc. These results, including lattice-parameter determinations, are given in Table I. Metallographic examination. was carried out on specimens polished and etched after quenching, and also on polished specimens reannealed and quenched. In the first case, the distinctive twinning or banding so prevalent in Mn-Cu alloys was sought, while in the second, the surface relief effect generally regarded as being truly characteristic of a martensitic transformation was sought. The microstructure of representative alloys in the range 12 to 25 pct Ni is shown in Fig. 2. The structure of the Mn-15 pct Ni

Jan 1, 1965

By R. W. Gurry

WHEN a steel in the austenitic state, with all its carbon in solution, is maintained, at constant temperature, in contact with a gas that removes the carbon from the surface, yet without otherwise altering the composition of the steel, the change in weight of the specimen, after any period of exposure, is a direct measure of the amount of carbon it has then lost. The purpose of the present paper is to show how, by application of established mathematical reasoning based on the fundamental diffusion law and on certain postulates, this loss of weight yields a complete picture of the distribution of carbon throughout a specimen of regular shape after any period of exposure, with all the accuracy required in any practical occurrence of decarburization. Precisely the same is true for the gain in weight during the reverse process of carburization, or for the gradual gain or loss of any element, so long as the steel comprises only a single phase at temperature, provided always that the experimental conditions conform to the postulates. The change in carbon content from surface to center of the specimen is always continuous, when everything is in solution, even though under the microscope the decarburized zone (or carburized rim) may appear to be sharply defined. The experimental procedure is described and some typical results are presented, which are then interpreted by application of the diffusion law. EXPERIMENTAL PROCEDURE Initially an endeavor was made to follow the gain of weight during the process of carburization in a hydrogen-toluene atmosphere, but it was soon found that the specimen became coated with graphite, which could not be removed without some loss of metal; therefore it was decided to continue carburization until the steel was saturated throughout, to remove all graphite from the surface of the specimen, and then to follow the loss of weight during decarburization in a moist hydrogen atmosphere at the same temperature as that used for carburizing. The carburizing procedure has been described in an earlier paper;1 it suffices to state here that the carburization lasted about 140 hr. at 760°C. (1760°F.) and 44 hr. at 1110°C. (2030°F.), these periods being long enough-on the basis of the calculations presented later-to ensure that the specimen was about 99.9 per cent saturated at each temperature. The specimen was a cylinder about 3.8 cm. long and 0.475 cm. in diameter; the materials were carbonyl iron, a commercial low-metalloid iron, and a steel with 3.6 per cent nickel and the usual proportion of other elements. The fully carburized specimen, after cooling at the top of the furnace tube, was placed in a lathe and sandpapered to remove all graphite; then the diameter was measured with a micrometer caliper, and the initial weighing (corresponding to complete saturation) was made. By means of a

Jan 1, 1942

By Walter S. Weeks

In this paper the effect of natural ventilation pressures is considered a part of the mine resistance and it is shown that their effect on the mine resistance is not the same as the total natural ventilation pressure of the shafts if the mine has several levels. It is shown that increasing the fan pressure causes the division of the air to approach the condition that would obtain if there were no natural ventilation pressure present. It is shown that if an appreciable difference in pressure is maintained between the beginning and end of a group of splits, the value of the integrated effect of the natural ventilation pressures on the individual splits does not change substantially with moderate changes of this pressure. A method is outlined for determining the resistance factor of the mine and the value of the effect of natural ventilation with the fan operating; also a method for determining this factor when circulation is caused by natural ventilation alone. Natural Ventilation Pressure Natural ventilation pressure (N.V.P.) is caused by the difference in weight of the air in two similar columns between two horizontal planes, and the difference in weight is caused principally by the difference in temperature of the two columns. The fan pressure causes some variation in density, but, since it is usually small and affects both columns, its effect is relatively unimportant. It has been suggested that "N.V.P." be called "stack effect"; but, since the term N.V.P. was used in a previous Institute paper,' applied in exactly the same manner, the term will be used. Frictional Resistance The frictional resistance to flow in a mine without natural ventilation may be expressed as RQ2 where R is a constant for a given air density and Q is the rate of flow. This frictional resistance plus the effect of velocity changes will be called the F pressure (F.P.) and a curve of F.P. against Q, the F characteristic of the mine. If a pressure is applied to a mine by a fan, the air flow so adjusts itself that the drop in pressure through any path from entrance to exit of mine, due to frictional resistances and velocity changes, is the same as that in any other path. The mine resistance varies as the square of the quantity. The air distribution without N.V.P. will be called "normal." Natural Ventilation Present When N.V.P. is irregularly distributed in a mine, it is more convenient in analysis to consider the N.V.P. as a part of the duct resistance. If it is so considered the resistance no longer varies as the square of the quantity, and if N.V.P. exists between levels the distribution of the air is no longer normal. The total N.V.P. of the mine is the pressure caused by the full length of the shafts. If a mine has several levels, N.V.P. exists

Jan 1, 1946

By G. A. Vissac

IN the presentation which follows, washability curves, such as are commonly used in making studies preliminary to the cleaning of any coal or to the concentration of any mineral, have been reduced in each instance to a single straight line; thus all the most important characteristics of the coal or mineral are represented in a form more advantageous than that in which such data usually are shown. To obtain consistent results, float-and-sink data must be based on a single definite narrow size range, which may be designated "a coal unit." It will be shown that such units, each embodying a different size range, can be grouped to form what may be termed "a composite coal." A three-dimensional presentation will emerge, which will closely identify the coal, illustrate its characteristics in a new manner and explain many obscure facts. FLOAT-AND-SINK TESTS For the preliminary study of any cleaning or concentration problem, or in the control of any operation, float-and-sink tests must be made. The results of these tests are grouped in tabular form and then illustrated in various systems of curves; but if such a graphic representation is to have the utmost practical value, it must offer at least the following advantages: (I) It must be easier to read than the tabular results, and (2) it must be easy to plot, check and interpolate. The first requirement will be attained by reducing the number of curves to a minimum, and the second by some system of representation that will use only straight lines. Of the many washing curves now in use, only the "recovery curve," often known as the "composite curve "-a somewhat misleading term-will be considered. Any point on the recovery curve will show what percentage of weight of clean coal can be recovered when the mineral is washed at a certain specific gravity. As an example, the tests listed below Fig. I are illustrated in the drawing by a curve obtained by plotting (I) as abscissas the ash content of the coal recovered and (2) as ordinates the corresponding percentage of refuse discarded; but, in general practice, instead of writing down that weight, it is customary to set down its complement, which is the corresponding weight of coal recovered. From this curve can be deduced the information necessary for the solution of most practical problems. NEW FORM OF GRAPHIC PRESENTATION The resemblance of the recovery curve in Fig. I, or, for that matter, the recovery curve obtained in common practice, to a power curve is apparent. The general equation of such a curve is y = axn where n is negative. Taking logarithms: log y = a + n log x. Using a logarithmic scale, the equation of the recovery curve will be Y = A + bX. On this logarithmic basis, the recovery graph will be a straight line, using the same variables as in Fig. I ; namely, the ash con-

Jan 1, 1942

By M. E. Wadsworth, R. C. Peterson, W. M. Fassell

The temperature and pressure dependence of the reaction of tantalum in oxygen were investigated from 500° to 1000°C at pressures from 10 mm Hg to 600 psi total oxygen pressure. Tantalum was found to oxidize linearly under the above conditions. Three distinct regions of temperature dependence were found with different energies of activation. From 500° to 600°C the rate of oxidation of tantalum was found to be essentially independent of the oxygen pressure at the pressure investigated. The oxidation rate increases rapidly with an increase in pressure from 600' to 800°C. The dependence of the oxidation rate on the bulk concentration may be expressed by V = k'?, where k' is the specific rate constant and ?=k1Co2/(l + K1Co2), where k, is the equilibrium constant for the adsorption of oxygen on tantalum. ONLY a limited amount of data has been presented in the literature on the oxidation behavior of tantalum metal. Some values of its oxidation rate were reported in the Corroston Handbook' and by McAdams and Geil.' The first extensive investigation of tantalum was the work of Gulbransen and Andrews." They determined the reaction rates of tantalum in O2 and N2. Their results indicate that this metal follows the parabolic law in the temperature range of 250" to 450°C in O2 at pressures of 7.6 cm Hg with an activation energy of 27,400 cal per mol. In nitrogen, the metal follows the parabolic law from 500" to 800°C at 7.6 cm pressure. All experimental determinations were of 2 hr or less duration and deviations from the parabolic rate conceivably could occur at longer times. A spectrophotometric study of the oxidation of tantalum by Waber, Sturdy, Wise, and Tipton' indicated good agreement between this method and the microbalance technique. The experiments were conducted in air from 220" to 350°C. The metal was found to follow the logarithmic law up to 320°C and the parabolic law at higher temperatures. The activation energies in the logarithmic region were reported as 12.57 kcal per mol and 12.0 kcal per mol, respectively, for the microgravimetric and spectrophotometric methods. In the parabolic region the activation energy was found to be 27.2 kcal per mol, in good agreement with the value of Gulbransen and Andrews." The present paper is concerned with the behavior of tantalum from 500" to 1000°C in oxygen at pressures ranging from 1/2 to 40.8 atm pressure. Earlier preliminary data by McKewan5,6 indicated the following facts concerning the behavior of tantalum: 1—At temperatures from 500" to 600°C, the metal followed the linear law. 2—At 575°C the rate of oxidation was found to increase with O2 pressure. 3—The Arrhenius plot in this temperature region was nonlinear. The nonlinearity of the Arrhenius plot was indicative of a more complex behavior than originally suspected for this metal.

Jan 1, 1955

By G. A. Vissac

In the presentation which follows, wash-ability curves, such as are commonly used in making studies preliminary to the cleaning of any coal or to the concentration of any mineral, have been reduced in each instance to a single straight line; thus all the most important characteristics of the coal or mineral are represented in a form more advantageous than that in which such data usually are shown. To obtain consistent results, float-and-sink data must be based on a single definite narrow size range, which may be designated "a coal unit." It will be shown that such units, each embodying a different size range, can be grouped to form what may be termed "a composite coal." A three-dimensional presentation will emerge, which will closely identify the coal, illustrate its characteristics in a new manner and explain many obscure facts. Float-and-sink Tests For the preliminary study of any cleaning or concentration problem, or in the control of any operation, float-and-sink tests must be made. The results of these tests are grouped in tabular form and then illustrated in various systems of curves; but if such a graphic representation is to have the utmost practical value, it must offer at least the following advantages: (I) It must be easier to read than the tabular results, and (2) it must be easy to plot, check and interpolate. The first requirement will be attained by reducing the number of curves to a minimum, and the second by some system of representation that will use only straight lines. Of the many washing curves now in use, only the "recovery curve," often known as the "composite curve"—a somewhat misleading term—will be considered; Any point on the recovery curve will show what percentage of weight of clean coal can be recovered when the mineral is washed at a certain specific gravity. As an example, the tests listed below Fig. I are illustrated in the drawing by a curve obtained by plotting (I) as abscissas the ash content of the coal recovered and (2) as ordinates the corresponding percentage of refuse discarded; but, in general practice, instead of writing down that weight, it is customary to set down its complement, which is the corresponding weight of coal recovered. From this curve can be deduced the information necessary for the solution of most practical problems. New Form of Graphic Presentation The resemblance of the recovery curve ill Fig. 1, or, for that matter, the recovery curve obtained in common practice! to a Power curve is apparent. The general equation of such a curve is Y = axn, where n is negative. Taking logarithms: log y = a + n log x. Using a logarithmic scale, the equation of the recovery curve will be Y = A + bX. On this logarithmic basis! the recovery graph will be a straight line, using the same variables as in Fig. I; namely, the ash con-

Jan 1, 1942

By G. W. Healy, J. C. Schottmiller

Molten silicates were found to exist in the Cr-Si-0 system at temperatures above 1450°C. one atom of oxygen is readily removed from CrzOs in the presence of Si02 at 1700°C, forming a silicate melt. Steam-hydrogen ratio measurements made at this temperature indicate that the free energy of the reaction: Cr20s(c) + Hz = 2CrO (in Si02 -saturated melt) + H20 is approximately 5600 * 1500 cal. A deep-blue chromous silicate, probably Cr2Si04, forms from these melts at about 1400" to 1500°C, and is characterized by.its distinctive X-ray diffraction pattern and optical properties—distinct pleochroism and high refractive indices. THE question of the state of oxidation of chromium in slags has vexed metallurgists for many years The experiments of Koerber and Oelsenl suggested the probable presence of divalent chromium in silica-saturated slags equilibrated with high-chromium melts. Hilty and coworkers2 had also found chromium at lower valency, as Cr304, in inclusions formed from oxygen-saturated Fe-Cr melts with as little as 10 pct Cr. In both cases, disproportiona-tion of the lower oxide to CraO3 and chromium was found to occur to a greater or lesser extent, depending upon the rate of cooling from the high temperature. The work on Cr304 was sufficiently detailed for chipmans to derive its thermodynamic properties, but Oelsen's experiments in the silicate system were not extensive enough since most of his runs were made with slags containing large amounts of manganese oxide in addition to iron and chrome oxide and silica. The present study describes experiments carried out to map out an approximate liquidus diagram in the CrzOs, "CrO", SiOa portion of the Cr-Si-0 system, and to measure the partial free energy of solution of oxygen in the system. EXPERIMENTAL 1) Approximate Melting-Point Determinations. Preliminary trials showed that when an equimolar mixture of Cr20s and SiOa was treated with hydrogen in the temperature range 1500" to 1600°C, copious amounts of steam were evolved, and a low-melting liquid formed which could be quenched to a blue, crystalline, material having a distinctive X-ray diffraction pattern. It was found that the identical material could be produced by heating intimately mixed, finely divided Cra03, Cr, and SiOa, held in a tungsten crucible, under purified argon. Thus, it was possible to prepare mixtures containing any desired proportions of chromium, silicon, and oxygen, pel-letize them, heat to temperature in the furnace shown in Fig. 1, and observe, after cooling, whether the pellet remained unchanged or showed signs of incipient, partial, or complete melting. 2) Free Energy of Solution of Oxygen. This was studied by measurement of steam-hydrogen ratios for the reaction: H20 (gas) + O (dissolved in charge) + Ha (gas) The experimental method chosen was to prepare a

Jan 1, 1964

By Norman Weiss

Most papers on xanthate have dealt with principles rather than practice. On the assumption that many millmen are interested in knowing where and in what manner the xanthates are being used in mills other than their own, this paper will summarize the results of a recent survey of North American plants. A brief background story and a description of the xanthates will be followed with the results of that survey; then a few observations will be made on storage, feeding, and ore testing. The first xanthate was made in 1822 by Zeise of the University of Copenhagen. With commendable scientific detachment (or perhaps a bad cold) Zeise ignored a more pervading quality of the substance and named it for its color, after the Greek word "xanthos," meaning yellow. During the first 80 years of its recorded existence xanthate found use only in small quantity as an insecticide; after the turn of the century there was some further demand for it in the vulcanization of rubber. It was not until 1922, by coincidence the centennial of Zeise's discovery, that C. H. Keller of San Francisco, seeking sul-phidizing agents, recalled xanthate in connection with his experience years earlier when he had seen this material used in Europe to combat grape phylloxera. His successful tests with the new flotation reagent culminated in the basic xanthate patent (U. S. 1,554,216) in 1925. In the minds of many metallurgists the introduction of xanthate as a flotation reagent is identified with the beginnings of alkaline circuits, the first use of chemical collectors, and the beginning of selective flotation. Actually, these preceded xanthate by a number of years. The alkaline circuit in lead-zinc flotation was introduced by Lyster as early as 1912. In 1922 Sheridan and Griswold made their momentous discovery (Timber Butte) that alkali cyanides and zinc sulphate effectively inhibited the flotation of pyrite and sphalerite in pulps made alkaline with sodium carbonate or bicarbonate. The use of lime to retard pyrite in copper flotation began within two years after Ralston directed attention to its possibilities in 1917. These were the beginnings of modern selective flotation, which was practiced successfully on copper-iron ores at Nacozari in 1922, and at Inspiration, Cananea, and others only shortly afterward. In the lead-zinc mills, selective flotation was of even greater economic importance at that time. The Sunnyside plant of U. S. Smelting, Refining, and Mining Co. used the process earlier than 1920, and Consolidated, Timber Butte, and others soon followed. As a chemical collector xanthate was relatively a latecomer, for the Corliss patent of 1917 covered the first of these, alpha-naphthylamine, and the Perkins patent of 1919 the second, thiocarbanilid. Both of these were in extensive use before Keller's xanthate made its commercial debut in 1923. There is general agreement, nonetheless, that the introduction of xanthate was

Jan 1, 1949

By Theron Wasson

The discovery of eight new oil fields, two of which may be of major importance, was the outstanding record in Michigan this year. These new fields have helped to support the declining production from old areas and place the total of 18,559,000 bbl. in line with the past six or seven years. Thus, it appears that Michigan is doing its part in maintaining the production of the country in the third year of the war. The new fields are in the central basin area where oil was first discovered in Michigan, thus tending to focus attention on the deeper part of the lower peninsula of the state. Through 1944 the state of Michigan has produced a total of 222,-641,580 bbl. of crude oil from 100 pools, many of which arc relatively small. Among the previous1y discovered fields Reed City is still the outstanding producer, with Fork, Headquarters, and Adams following in the order named. The Reed City pool produced a little over 5,000,00 bbl., which was more than one third of the state's total for the year. Almost two thirds of the year's total oil production came from fields discovered in the past five years. Maps A map of the oil and gas fields of Michigan in 1943, published in the A.I.M.E. report for 1944,* shows the main producing areas and should be referred to if information in regard to their location is desired. The producing zones are shown in the columnar section in the same publi- cation." The data in Tables I and 2 have been carefully ' checked and every effort has been made to show as complcte information as possible. New Discoveries and New Developments Eight new producing areas were discovered during 1944 which, in order of importance, are: Deep River Field.—The discovery well in the Deep River field was drilled by Don Rayburn and others, and should be listed as a chance discovery, as, from a geological standpoint, it was not considered favorable until oil was found at a depth of 2838 ft. in a dolomitic layer in the top of the Dundee limestone. The first well was completed in January 1944, with an initial production of 2500 bbl. By the end of the year 15 wells had been completed, proying an area 2 1/2 miles long and 1/2 mile wide. Coldttater Field.-The Coldwater field was discovered in August 1944, by the Sohio Oil Co. Production is from secondary dolomite at the top of the Dundee at a depth of 3703 ft. To the end of 1944 nine wells had been drilled on 40-acre spacing. Essexville Field.—Essexville field was discovered by United Drillers and Producers, Inc. Eight wells had been completed to the Dundee lime by the end of 1944, and prospects were good for further development during 1945. Hilliards Field.—Hilliards field was discovered by Cook and Fortney. Production is from the Traverse lime at an average depth of 1588 feet,

Jan 1, 1945

By W. S. Pellini, F. N. Rhines

IN many of the otherwise well established alloy phase diagrams the solidus curves (temperatures at which liquid first appears upon melting) have not been located accurately, chiefly because the experimental techniques that have been most popular for determining solidus temperatures have been both cumbersome and subject to large errors. C. E. Homer and H. Plummer1 have described a sensitive and at the same time a very simple technique for locating the solidus curves in a number of alloys of tin. Their method consists simply in noting the temperature at which a specimen of the alloy ruptures under the influence of a light bending force. Although this method is not new, it has been little used for this purpose in the past; nevertheless, it appears so attractive in its possibilities of speed, simplicity, and precision that the investigations presently to be described were undertaken to verify its merits. The redetermination of the solidus and eutectic temperatures of the lead-antimony system was employed as a medium 0f experimentation. New values obtained in this way are believed to be sufficiently precise to warrant a revision of the currently accepted lead-antimony phase diagram (Fig. I). Determinations of the solidus of the lead-rich lead-antimony alloy series have been published by R. S. Dean2 and by E. E. Schumacher and F. C. Nix.3 Their points are represented in Fig. I. In their work the solidus was not located at antimony concentrations greater than 2 per cent; the curve was presumed to meet the eutectic horizontal at an antimony concentration of about 2.5 per cent. In the present studies the solidus has been traced to 3.5 per cent, where the eutectic horizontal is intersected (Table I and Fig. I). Within the range investigated by Dean and by Schumacher and Nix the agreement with their values is good. H. Seltz and B. De Witt,4 on the basis of activity measurements, have calculated that the intersection of the solidus and the eutectic reaction horizontal should lie at 3.86 per cent of antimony. The following determinations of the eutectic temperature have been reported: Roland-Gosselin,5 228°C.; Ewen,6 228°C.; J. E. Stead,7 247°C.; Campbell,8 228°C.; W. Gontermann,9 245° to 252°C.; R. Loebe,10 245°C.; E. Heyn and 0. Bauer,11 245°C.; H. Endo,12 250°C.; R. S. Dean,2 249° to 258°C.; E. Abel, 0. Redlich, and J. Adler,13 245°C.; W. Broniewski and L. Sliwowski,14 250° to 252°C.; H. Seltz and B. De Witt,4 250°C. A temperature of 249°C- appears to have been generally accepted in recent years; it is the value most frequently obtained by the method of cooling curves. Values below 249°C. have usually been obtained by inferior cooling-curve techniques; those above 250°C., by the method of heating

Jan 1, 1942