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By E. Miller, R. Geffken, K. L. Komarek

The thermodynamzc properties oJ liquid Cd-Sb alloys were investigated using the cell arrangement measurments were obtained every 2°C at a heating and cooling rate of 12°C per hr and at equilibrium every 2O0C frorn 500°C down through the stable liquidus. The S-shaped asCd US composition curve was used in the cotnposition regzon near Cd,Sb, to calculate a tempeerture-dependent inleraction coefficient from quasichemical theory. Rapid changes in a scd were observed at a transition temperature varying from 400" to 465°C depending on con/kosition. It could not be determined if the changes in aScd were discontinuous, but tlze composition dependeke of the magnitude of the change is indicative of a second-order phase transformation in the liquid. The values of the experimental changes in ASCd are in agreement with calculations from the slope of the transition temperature, using the concept that a second-ovdev phase transition occurs in liquid Cd-Sb alloys. II is suggested that the transformalion is associated with the formation of Cd4Sb3 molecules in the liquid. ThE structure of liquid alloys is the subject of many investigations. X-ray, resistivity, and thermody-namic data have been interpreted as indicating varying degrees of short-range order in the liquid in alloy systems forming inter metallic compounds. In general, the melting process is not a transition from an ordered to a completely disordered state, but some degree of order is retained in the liquid. Maximum ordering in the liquid state occurs close to the melting temperature of the compound and the arrangement of atoms becomes more random at higher temperatures. Of special interest in this respect is the Cd-Sb system. It is one of the few metallic systems which form both stable and metastable compounds when liquid alloys are cooled at normal rates. The stable system exhibits an intermetallic compound, CdSb, melting at 459"c.l A second compound, CdrSbs, has also been reported,' melting close to this temperature. The metastable system has one compound, CdsSbz, melting at 420"c.I Resistivity measurements on liquid Cd-Sb alloys close to the liquidus temperatures have been interpreted in terms of a complex ordering behavior which changes rapidly with increasing temperature.3 The resistivity-composition curve is characterized by two maxima corresponding in composition to CdSb and CdsSbz. The resistivity-temperature plots show sharp breaks for alloys in the composition range of 45 to 70 at. pct Cd on cooling through a transition temperature close to the stable liquidus. Fisher and phillips4 investigated the influence of temperature and composition on the viscosity of liquid CdSb alloys. The viscosity of some alloys increases sharply on supercooling below the stable liquidus. A maximum in the viscosity-composition curve occurs at the composition CdSb. The thermodynamic properties of liquid Cd-Sb alloys have been investigated by Seltz and ~e~itt' and Elliott and chipmane by the electromotive-force method and their results are in good agreement. However, these investigations were carried out at temperatures well above the liquidus temperatures of the alloys, and the temperature coefficients of the electromotive force, dE/dT, were obtained from experimental points for each alloy at a few temperatures considerably above the liquidus temperature. Scheil and ~aach' investigated the thermodynamic properties of this system by the dew point method in the temperature range from about 100°C above the stable liquidus down into the supercooled liquid region. They reported several anomalies, i.e., the activity of a melt on heating differed from that on cooling, and the activity increased sharply in the limited temperature interval immediately above the liquidus temperature of the stable alloy, followed by a sudden decrease below the liquidus. Values obtained on heating and cooling were not in agreement. A reinvesti-gation of a few alloys by Scheil and Kalkuhl' by the electromotive-force method failed to confirm these observations. The authors concluded that the anomalies were due to inhomogeneities in the starting alloys and they discarded their previous results. The present investigation was undertaken in order to obtain thermodynamic data close to the liquidus temperature and in the supercooled region where the anomalies were originally reported, employing the electro motive-force method. This method is quite precise and will most easily permit observations of small changes in activity and partial molar entropy with temperature. Measurements were taken every few degrees so that the dE/dT values could be calculated over the entire temperature range and small changes in the thermodynamic properties close to the liquidus temperature could be observed. I) EXPERIMENTAL PROCEDURE Specimens were prepared from 99.999+ pct Cd and Sb (Cominco). Surface oxide was removed by scraping and then melting the metals under vacuum and filtering through Pyrex wool. Appropriate amounts of the metals were weighed on an analytical balance to k0.1 mg, sealed in double Pyrex capsules under vacuum,

Jan 1, 1968

By E. W. Davis

THE large iron-ore producers on the Mesabi Range are able to maintain the silica in their shipping products at from 8 to 10 per cent by mixing ores of various grades, some assaying 4 per cent silica and some as high as 18 per cent silica. For each ton of 4 per cent silica ore mined, a ton of 14 per cent silica ore can be mined and mixed with it and the average grade maintained at 9 per cent. This mixing operation has made possible the utilization of large cluantities of ore too lean to be used alone. and herein lies the advantage of the producers who operate a number of mines at the same time. As the grade of the ore from one of the properties falls off, a little high-grade ore from another property can be mixed with it and the average maintained, while if one property alone were being operated all of the ore below grade would be left behind.

Jan 1, 1930

By E. Robert Ruhlman

The term potash refers to potassium oxide (K2O), a compound not found in nature or produced by man but used as a basis for comparison of all potassium compounds and now is applied generally to various compounds of potassium used by agriculture and industry. Potassium, the last of the three major plant foods to be used in appreciable quantities by agriculture, was originally produced only from organic materials for chemical uses. The first recorded identification of a mineral source of potassium was in 1797; but, until the discovery in 1839 of the large deposits of soluble potassium salts in Germany and their development in 1860-61, nearly all potassium compounds continued to come from organic sources. With the importance of potash to plant life discovered in 1840 by von Liebig and the production of potash in Germany after 1861, agriculture soon became the major consumer of potash. In 1958 agriculture accounted for about 95 pct of the total potash consumption; the chemical industry used the remaining 5 pct. Mineralogy and Geology Potassium, an important constituent of the earth's crust, occurs in many forms in numerous rocks and minerals, including water solutions, but is not found in its native state. Twenty-five of the more important potash minerals are listed in Table 1. The properties of the five potash minerals most common in Permian salt formations follow: Sylvite is isometric; has a hardness of 2, a specific gravity of 1.98, vitreous luster, and cubic cleavage; and ranges in color from clear to brick red. In taste it is similar to halite but has a sharper taste and a cooling effect on the tongue. It is very plastic under pressure. Langbeinite is isometric; has a hardness of 4, a specific gravity of 2.82, vitreous luster, conchoidal fracture, and no cleavage; and ranges in color from clear to gray. It is taste- [ ] less, somewhat granular, and slowly soluble in water. Polyhalite is triclinic; has a hardness of 3, a specific gravity of 2.77, and dull luster; and

Jan 1, 1960

By L. M. Howe, J. Gordon Parr, E. Saarema

THE decreasing solid solubility limit at the titanium-rich end of the Ti-Cu constitutional diagram,' Fig. 1, suggests the possibility that titanium-rich alloys may be age-hardenable. However, results obtained by Holden et al. reproduced in Fig. 2 show that after quenching from 790°C the age-hardening of an alloy containing 1.7 pet Cu is very slight, while a 0.8 pet alloy decreases in hardness, during heat treatment at 400°C. It was believed possible that powder samples of alloys might show different results from the lump samples used by Holden et al., since small particles are often more sensitive to diffusion processes than larger samples. Consequently, a 1.9 pet (by weight) Cu alloy was made by the technique of levitation melting," checked for homogeneity, and filings of 48-65 Tyler screen size were cut from it for aging experiments. The filings were helium-quenched (by a technique described previously)' from 790°C, sealed in vacuo in silica tubes and aged at temperatures of 400°, 450°, and 500°C. Microscopic and X-ray examinations failed to reveal any structural changes during the aging process. This is not too surprising since early stages of precipitation do not usually manifest themselves in ways that are readily detectable by metallographic methods, and the extent of precipitation on overaging a 1.9 pet alloy is very small. However, hardness readings (taken on a Bergs-man micro hardness tester, using a 25 g load applied to a diamond indenter) do show a hardness peak at each aging temperature, Fig. 3. About a dozen readings were taken on each heat treated sample; the highest reading and the lowest reading were ignored and an average taken of the remaining values. In

Jan 1, 1957

By D. F. Atkins, B. A. Rogers

The constitutional diagram presented herein is relatively simple. Complete mutual solid solubility exists for an interval below the solidus line, a continuous curve with a flat minimum near 22 pct Cb and 1740°C. Upon cooling, the solid solution breaks up, except at the columbium-rich side, from two causes: zirconium-rich alloys transform under the influence of the ß-a transformation in zirconium; alloys of intermediate composition decompose into two solid solutions below 1000°C. The combined effect is the formation of a eutectoid at a temperature of 610°C and a composition of 17.5 pct Cb. The eutectoid horizontal extends from 6.5 to 87.0 pct Cb. Some age hardening effects have been observed in the zirconium-rich alloys but the positions of the solvus lines remain uncertain. IN recent years, zirconium has been produced in much larger quantities than were available previously. Correspondingly, the incentive for studying its alloy systems has increased, as the number of recent publications on alloy systems testifies. However, only a partial diagram of the Zr-Cb system has been published and relatively few references have been made to alloys of the two metals. Hodge' investigated the Zr-Cb system up to about 25 pct Cb. His data on melting points were not sufficiently numerous to distinguish with certainty between the alternatives of a narrow eutec-tic horizontal and a wide flat minimum in the solidus curve. Although Hodge considered his results on transformations in the solid state to be only tentative, he suggested that the eutectoid in the zirconium-rich alloys lay at about 625 °C and 10 pct Cb and estimated that the solubility of colum-bium in zirconium at 625 °C was near 6 pct. According to Simcoe and Mudge,2 less than 0.5 pct Cb is soluble in zirconium at 800°C. These authors observed an increased strength in both the 0.5 and I pct Cb alloys made with hafnium-containing zirconium. According to Keeler,3 the strength of zirconium is increased by addition of columbium to a content of at least 3 pct. Keeler' also observed a maximum in hardness at about 10 atomic pct Cb and commented on the brittleness of alloys of this composition. Anderson, Hayes, Rober-son, and Kroll5 investigated the tensile properties of Zr-Cb alloys containing 5.1 and 12.9 pct Cb at room temperature and at 343°C. The 12.9 pct alloy had a high tensile strength at room temperature but also a low percentage of elongation. All alloys had high elongation at 343 °C. Littona measured strength and elongation values of annealed alloys containing up to 27.5 pct Cb and found low elongation values for all of the alloys of high columbium content. Some observations on the resistance of Zr-Cb alloys to corrosion in water at high temperature have been published by Lustman, De Paul, Glatter, and Thomas' who found that additions of columbium up to 1 pct had only a minor effect on the corrosion resistance of zirconium. Preparation of the Alloys Raw Material: Zirconium of a relatively good grade was available for making the alloys. It was obtained as scrap pieces that had been left over from an operation that included production by the iodide process, melting under a protecting atmosphere, and fabrication to plates. The individual pieces had hardness values of 24 to 32 Ra and a typical analysis is shown in Table I. The columbium also was scrap trimmed from sheets. It was furnished by the Fansteel Metallurgical Corp. and had a high ductility but its analysis was known only approximately. The metal probably contained about 0.5 pct Ta, perhaps 0.25 pct C, and a few hundredths percent each of iron, silicon, and titanium. Melting: The alloys were melted in a tungsten-electrode copper-crucible arc furnace similar to units that have been described recently in the metallurgical journals.'.' The crucible of this furnace is provided with a cavity in which a getter charge can be melted before the melting of the alloy charges. Hardness measurements on the ingots indicate that the getter charge takes up a considerable fraction of the oxygen and nitrogen from the helium atmosphere of the furnace. The alloys used in the investigation are given with their intended compositions, hardness, and melting points in Table 11. Fabrication: All alloys of the Zr-Cb system appear to be amenable to fabrication. At least, all of the compositions listed in Table II could be reduced to wires in a rotary swaging machine. The starting material was either slabs cut from ingots and ground by hand to rough cylinders or narrow strips trimmed from sheets made by cold rolling slabs. However, not all of the alloys could be fabricated satisfactorily by the same method. From 0 to 4 pct Cb and from 20 to 30 pct Cb or more, the alloys could be swaged cold from ¼ in. cylinders to 0.80 mm wires with only one intermediate annealing, sometimes with none. From 40 to 90 pct Cb, the alloys were difficult to swage either hot or cold but could

Jan 1, 1956

By R. N. Upadhyay, M. Maleki, I. Fatt

Conventional laboratory core analysis tests on samples of two limestone reservoir rocks indicate that about 20 per cent of PV is in dead-end pores. These tests (electric logging formation factor, mercury injection capillary pressure and miscible displacement) were carried out on 1/4-in. diameter test plugs. Test results show a clear dilference between these samples and sandstone or homogeneous limestone reservoir rock. Although the amount of dead-end pore space can be only roughly estimated, the presence of such pore space seems clearly indicated. Pressure transient studies also show presence of deadend PV. Although they do not give quantitative results, pressure transient data yield a reasonable estimate of the size of the neck connecting dead-end pores to the main flow channels. INTRODUCTION Equations conventionally used to describe reservoir flow behavior contain the implicit assumption that all connected pore spaces contributed to both porosity and permeability. Several authors3-7 have pointed out the changes in pressure transient behavior and in electric log interpretation that may result if this assumption is incorrect and, instead, dead-end or cul-de-sac pores are present. There is a need for laboratory tests that can detect presence of dead-end pores in core samples. With such information on hand the petroleum engineer can make more rational use of the mathematical tools now available for analysis of reservoir flow behavior. This paper describes laboratory studies designed to detect and, if possible, give a quantitative measure of dead-end PV in laboratory-size core plugs. Three reservoir rocks were used, two of which were limestones suspected of having deadend pore spaces and a well-known sandstone, used as a comparison standard, in which there is believed to be little or no dead-end pore space. All the studies were designed to measure the natural dead-end PV; i.e., the pore space which is dead-ended because of rock structure. During multiphase flow in a rock without dead-end pores, some parts of one of the phases can become surrounded by the other, thereby giving (for certain flow behavior) an effective dead-end pV8,9. Such behavior will not be described here.

Jan 1, 1967

By Harry V. Welch

Early in the development of the art of metallurgy, it was noted that a distinct difference existed in the character, collection possibility and health hazard of the "smoke" from lead furnaces and those from copper plants. Zinc-plant fumes, although not so detrimental to health, were closely allied in nature to those of the lead works. In Cottrell plants, there are sufficiently distinct differences in operation and amount of construction between those for lead and copper to justify their consideration under separate headings; therefore, while the application of the process at copper-reduction works was covered by the writer some two years ago in the Transactions1,† this discussion will confine itself more distinctly to "fume" collection. General information on the process has been presented in numerous articles and by many authors: Cottre112, Schmidt3, Bradley4, Anderson6, Labbe6, Shiga7, Rathbun8. "Fume" may be defined as material, metal or nonmetal, elemental or compound, evolved as a vapor from a furnacing or chemical reaction and condensing, chilling or reacting within the gas stream to yield a solid form, and in this definition liquid particles are solids in a sense as distinguished from gases or vapors. Such condensed particles are of minute form, on the order of "smoke," and, for example, on the order of a few hundredths of 1 micron (1 micron = 1/25,000 in.) to perhaps 3 microns, with agglomerates, in relatively small proportions of many particles. Metallurgically typical fume products are lead compounds, oxides, carbonates and sulphates; elemental zinc, more commonly encountered as a fume particle of zinc metal with a surrounding "skin" of zinc oxide; arsenic, both metal and oxide and some of its more complex salts such as added sulphates as found in flue dusts; antimony, more particularly its oxide forms; and elemental sulphur, sometimes a troublesome product, in Dwight-Lloyd sintering-plant fumes. These products, particularly the elemental or lower oxide forms, have relatively appreciable vapor pressures at the existing operating temperatures as reported by Welch and Duschak9, Ingold10, Johnstonll, Millar12,13.

Jan 1, 1937

By David A. Summers, Clark R. Barker, Marian Mazurkiewicz

In May 1975 the U.S. Bureau of Mines contracted with the University of Missouri-Rolla, Rock Mechanics and Explosives Research Center to develop a Hydrominer modification to a longwall shearer unit, wherein the rotating pick-laced drums and connecting gear drives are replaced by a water jet cutting ahead. The concept of the water jet cutting head is based on using the high localized energy of the water jets to isolate a slice of coal by cutting a slot under, at the back of, and at the top of the web. The plow blade of the head then advances into the cut and wedges the coal cantilever over onto the conveyor [(Fig. 1)]. There were several potential advantages foreseen for the system; perhaps the most significant were the elimination of coal dust from the working area and the ability, with a variation in nozzle geometry, to cut webs of greater depth with a small increase in haulage horsepower. The University initially designed the head, based on experiments carried out in the laboratory, under an earlier Bureau of Mines contract. The experiments showed that it was more advantageous to work at a pressure of 68.9 mPa (10,000 psi) with an estimated flow rate of 3.15 X 10 - 8 m3/s (50 gpm) than go to the higher pressures and lower flow rates which have been advocated elsewhere.

Jan 1, 1979

By E. A. Anderson, P. W. Ramsey, E. J. Boyle

Only a few zinc-rich alloys are in commercial use today, and these depend largely upon solid solution effects for their desirable properties. Typical examples are rolled alloys containing about 1 Per cent of copper, with Or without additions of elements such as magnesium, and die-casting alloys containing about 4 Per cent of aluminum with small amounts of magnesium and sometimes copper." A number of elements are capable of forming alloys with zinc, Which do not enter into solid solution except in limited degree. The Present Paper considers One such system, zinc-titanium, in which alloys having potentially useful properties in the rolled form were found. Zinc-titanium System The zinc-rich portion of the zinc-titanium diagram, as determined by standard methods in this laboratory,3 is shown in Fig. I. The portion of the diagram of significance in the present work extends from 0 to about 0.5 per cent titanium. Gebhardt4 places the eutectic at 0.45 per cent, but the evidence in favor 01 the composition given in Fig. I is considerable. The solid solubility of titanium in zinc is very low indeed and possibly places these alloys in a somewhat different category from the commercial alloys previously mentioned. Alloy Preparation All of the alloys used in this work were prepared with titanium metal of 98.9 per cent purity. In most cases high-purity zinc (99.99 per cent) was used but sufficient work was done later to show that zinc of about high-grade composition would yield approximately equal results. Best practice in alloy manufacture seemed to be to prepare a zinc-titanium hardener by adding about 4 per cent of titanium metal to molten zinc and holding under a boric acid cover, with frequent stirrings, at 750°C, until the titanium had dissolved. The desired titanium content could readily be obtained in the final alloy by adding the calculated amount 01 this hardener. The alloys proved to be quite stable in composition, unless overheated, and, with reasonable temperature control, required no cover or flux to prevent loss of titanium content by oxidatioll, Hot-rollig Tests Three alloys containing, by analysis, 0.05, 0.12, and 0.23 per cent titanium were selected for preliminary study. Slab cross sections a a marked grain refinement* (Fig. 2) in the two alloys of highest titanium content. Cast unalloyed zinc has a columnar grain structure similar to that shown for the alloy of lowest titanium content but without the scatter of small equiaxed grains at the center.

Jan 1, 1944

By P. W. Ramsey, E. J. Boyle, E. A. Anderson

Only a few zinc-rich alloys are in commercial use today, and these depend largely upon solid solution effects for their desirable properties. Typical examples are rolled alloys containing about 1 Per cent of copper, with Or without additions of elements such as magnesium, and die-casting alloys containing about 4 Per cent of aluminum with small amounts of magnesium and sometimes copper." A number of elements are capable of forming alloys with zinc, Which do not enter into solid solution except in limited degree. The Present Paper considers One such system, zinc-titanium, in which alloys having potentially useful properties in the rolled form were found. Zinc-titanium System The zinc-rich portion of the zinc-titanium diagram, as determined by standard methods in this laboratory,3 is shown in Fig. I. The portion of the diagram of significance in the present work extends from 0 to about 0.5 per cent titanium. Gebhardt4 places the eutectic at 0.45 per cent, but the evidence in favor 01 the composition given in Fig. I is considerable. The solid solubility of titanium in zinc is very low indeed and possibly places these alloys in a somewhat different category from the commercial alloys previously mentioned. Alloy Preparation All of the alloys used in this work were prepared with titanium metal of 98.9 per cent purity. In most cases high-purity zinc (99.99 per cent) was used but sufficient work was done later to show that zinc of about high-grade composition would yield approximately equal results. Best practice in alloy manufacture seemed to be to prepare a zinc-titanium hardener by adding about 4 per cent of titanium metal to molten zinc and holding under a boric acid cover, with frequent stirrings, at 750°C, until the titanium had dissolved. The desired titanium content could readily be obtained in the final alloy by adding the calculated amount 01 this hardener. The alloys proved to be quite stable in composition, unless overheated, and, with reasonable temperature control, required no cover or flux to prevent loss of titanium content by oxidatioll, Hot-rollig Tests Three alloys containing, by analysis, 0.05, 0.12, and 0.23 per cent titanium were selected for preliminary study. Slab cross sections a a marked grain refinement* (Fig. 2) in the two alloys of highest titanium content. Cast unalloyed zinc has a columnar grain structure similar to that shown for the alloy of lowest titanium content but without the scatter of small equiaxed grains at the center.

Jan 1, 1944

By B. B. Betty

H. L. Burghoff.*—Have the authors any information on the effect of grain size in these materials? There is a material difference in the grain sizes shown for the Monel and the Inconel. Is a wide range of grain size normally found for each material, and, if so, what is its effect upon creep strength? 11. L. Eiselstein.—The grain size for Monel shown in the micrograph is the usual size found in that product. The grain size of Inconel is about the same as that, too. However, we have run tests on Inconel at higher temperatures than those reported in this paper, and have found that the coarser grain size has a better creep resistance; and that the grain size that gives the best creep resistance at 1600°F. is about 0.005 in. in diameter. We have no test on Monel with varying grain size. J. J. KANTER.†-It has been known for a long time that Monel metal exhibits ductility anomalies at elevated temperatures. Even in short-time test, it can be demonstrated in the range of 900°F. that there is a distinct falling off of the ability of Mone1 metal to elongate, and in rupture tests this shortcoming is still further accentuated. Knowledge of this rupture anomaly of Monel metal may be one of the reasons for which designer's approach certain high-temperature applications with reservations. The authors of this paper have merely demonstrated that for 900°F. the alloy has an ability to elongate 1.7 per cent over a period of some 2700 hr. Before any conviction can be expected from designers that Monel metal is applicable to stress design in such range of temperature, I think it is desirable to demonstrate the capacity for the material to elongate over a longer period of time than has been done in this presentation.

Jan 1, 1945

THE paper on "Cross-cuts in Coal Mining," by J. J. Rutledge (published in MINING AND METAL-LURGY, February, 1927, p. 64) was brought up for discussion at the annual meeting, where the follow-ing comments were made T. D. Thomas (Lehigh Coal & Navigation Co., Lansford, Pa.) : This question has caused me a lot of worry, not in the particular district in which I am, but throughout other districts. There are always several angles to consider. If you are in a hurry to push development work, you might increase the distance between cross-cuts from 60 to 350 ft., but if you have a 40-ft. chain pillar every 60 ft. it will cut down your entry driving a whole lot. Looking at it from the ventilation angle, I agree that too many cross-cuts in entries are bad things. You have a tremendous amount of leakage, and I have seen currents starting out with 45,000 cu. ft., and after passing about 30 or 40 cross-cuts the current has dwindled down to about 18,000 or 15;000 cu. ft. The result is that the question of putting in auxiliary fans is raised. That involves several points into which I do not want to go too far, but I am in favor of not getting in too many cross-cuts, putting them in only where they are necessary: I think the state mining laws are wrong in a number of places on that, and that when you finish with a cross-cut it should be in the room. It should be well sealed on an entry. There are several ways of tightening up the cross-cuts so as not to have the great amount of leakage and wastage of: air that we now have. 'I prefer tile stopping; other people prefer cement or brick, but there is a big fac-tor to all mines, saving the mine. I checked up on the number of fans in the anthracite region and found there are 651. That was derived from the state report of 1921, and it enabled me to compute from the power the weight of the air. In the anthracite region of Pennsylvania we put in 9 tons of air to every ton of coal we get out. Tracing that back again and taking the Government's figures which they made some time ago, I found but 20 per cent of the air got to the faces where it was actually needed. That is a tremendous big loss and shows a possibility for saving, money for the various coal companies. Chairman Rice: I think what Mr. Thomas refers to was an investigation by R. Y. Williams, of the Bureau of Mines in Illinois, where a study was made of 100 typical mines, and, speaking off-hand, my recollection is that we found as little as 15 per cent of air reached the faces in one of the mines and another was as much as 50. That seems to be a reflection on the type of stoppings and general ventilation scheme.

Jan 3, 1927

By M. H. Richman, L. M. Markowitz

MUCH of the available information on which the heat treatments of a particular steel are based is found in the isothermal-transformation diagram. Such is the case despite the fact that the usual thermal treatments involve continuous transformations, i.e., transformations which occur on cooling, rather than isothermal transformations. This rather unusual practice is continued because of the abundance of published isothermal-transformation diagrams1, 2 which are relatively easy to determine experimentally as compared to continuous-transformation diagrams.3, 4 However, this can easily lead to the production of improper micro-structures and may not allow full advantage to be taken of the inherent hardenability of a steel. A mathematical method of estimating the continuous-transformation diagram from the available isothermal data was developed by Grange and Kiefer;5 but, due to the mathematical approximations required in the calculations, the computation of continuous-transformation diagrams has been limited to individual cases and no large-scale compilation of these diagrams is available. With the present availability of high-speed digital computers, the problem of time-consuming approximations may be minimized and continuous-transformation diagrams may be constructed with the insertion of isothermal data into a basic program. It is the purpose of this report to announce the availability of such a program and compare the computed and experimental continuous-transformation diagrams for two different steels. Let us first review the method of Grange and Kiefer5 and then compare the results of the machine calculations with the experimentally determined diagrams. In order to apply this method, one requires the isothermal-transformation diagram and a set of curves representing cooling at constant rates. A section of an isothermal-transformation diagram is shown in Fig. 1 together with a cooling curve of M0F per sec. The cooling curve is constructed to start from the A1 (eutectoid) temperature if the transformation product is the eutectoid microconstituent (i.e., pearlite or bainite), from the A3 temperature if the product is primary ferrite, or from the 4, if it is proeutec-toid cementite. The cooling curve in Fig. 1 intersects the curve representing the start of isothermal transformation at a point A' corresponding to a temperature TX and a time fX. An arbitrary lower temperature To (on the

Jan 1, 1968

By Keith Leonard Sutherland

THIS paper is a study of the differential flotation of the sulphide minerals in the presence of salts of silver, lead and zinc. In practice, accidental activation due to these salts is more important than their use as reagents to replace copper sulphate. The general method of investigation has been based upon contact tests, the temperature of 35°C. being chosen in conformity with earlier work. Potassium ethyl xanthate and potassium amyl xanthate were selected as collectors and pure sulphide minerals were used. The experimental procedure has been outlined in earlier papers and all solutions were kept carbonate -free.1,4 Contact, or spreading of an air bubble, at a mineral surface indicates the presence of an adsorbed collector film. PURITY OF REAGENTS The xanthates were purified in the usual manner.1 Neither the cyanide nor the sodium hydroxide solutions contained sufficient carbonate to give a precipitate with barium chloride solution. The silver sulphate was prepared from pure silver nitrate by evaporation with concentrated sulphuric acid until there was no evidence of brown fumes. This solution was diluted and the difficultly soluble sulphate washed with water so that unchanged nitrate was dissolved. The resultant crystalline powder was pure white. The lead and zinc salts were prepared by dissolving especially pure lead and zinc in C.P. nitric and sulphuric acid solution and the crystals drained. The standard solutions were checked by titration. It was felt desirable to use the sulphate radical wherever possible, but since lead sulphate was insufficiently soluble for the purpose of the experiments, it was necessary to use some other lead salt. A.R. copper sulphate was used without further purification. RESULTS The results are presented in the accompanying figures; the areas of noncontact (nonflotation) are shaded in Figs. 8, 9, 10 and 11; in the remainder they lie to the right of the curve. Zinc Sulphate The curves in Fig. I are to be compared with those for Fig. 2, for which zinc sulphate is absent. This comparison shows that the influence of the zinc ion is usually small. Its influence is more marked, however, for chalcopyrite in the absence of cyanide. The influence of zinc sulphate is also marked for copper-activated sphalerite, for which tests were made only in the absence of cyanide. The results are of importance in the separation of pyrite from copper-activated sphalerite when, zinc sulphate is added in the lead flotation section (p. 204 of ref. I). Sphalerite does not adsorb the collector (i.e., become floatable) under the conditions chosen.

Jan 1, 1942

By N. Mungan

Laboratory water floods were performed in oil-wet and waterwet alundum and Torpedo cores, displacing a refined oil with n-hexylamine or Triton X-100 solution. Also, some floods were performed in which a sucrose solution was displaced with n-butyl alcohol. The Purpose ot the tests was to see if the oil recotlery could be increased and to examine what role the inter-facial tension reduction and wettability change play in the recovery mechanism. it was found that the chromatographic transport of amine was influenced by core wettability. In oil-wet cores, the rate of advance of the amine band could be predicted from equilibrium chromato-graphy, while in water-wet cores the amine band moved faster than predicted, indicating a non-equilibrium process. By reducing the interfacial tension to 1.1 dyne/ cm, oil recovery was increased. More oil was recovered from Dri-filmed cores than from water-wet cores. Reversing the wettability of the porous media from oil-wet condition also resulted in some additional oil recovery. Neutral wettability floods did not increase oil recovery. INTRODUCTION Interfacial forces in petroleum reservoirs are responsible for retention of large quantities of residual oil. Increasing exploration costs have created an incentive to attempt recovery of this residual oil by new and novel processes. One novel process involves changing the interfacial forces by introducing a chemical into the reservoir during water flooding. Recently, several investigators have carried out laboratory displacement tests using amines. lt3.4 The amines adsorbed onto initially water-wet core surfaces, changing them to oil wet. Additional oil was recovered when the cores were flooded in a manner reversing the. wettability from oil-wet conditions. In all these studies, the wettability reversal was considered responsible for increased oil recoveries although it was noted that amines also reduced oil-water interfacial tension. In the present study, displacement experiments were performed in water-wet and Dri-filmed cores. The purpose was to separate the effects of lowering the interfacial tension from changing the wettability. LABORATORY STUDY All experimental data given in this paper have been obtained at a temperature of 70F + 1 and prevailing atmospheric pressure. FLUIDS AND MATERIALS The oil used in these experiments* was washed with H2S04 and passed through two 100-200 mesh silica-gel beds to remove unsaturates and surface active impurities. Normal hexylamine** of practical purity was used, and the alundum cores*** were composed of nearly pure A1203. Fused quartz (SiOi) and Lucalox (A12 )t plates were used in the contact angle measurements. DISPLACEMENT TESTS Displacement tests were performed in alundum and Torpedo cores. Before displacement runs, cores were acidized with 0.1 normal HCI, flushed with distilled water and fired at 1,200F to make them water wet. This procedure also reduced water sensitivity of the Torpedo cores. Oil-wet cores were prepared from water-wet cores by flowing several pore volumes of 1 per cent by weight Dri-film SC-87 solution in heptane through the cores, flushing the cores with nitrogen, evacuating, and finally heating the cores at 300F for 4 or 5 hours. Between floods, cores were cleaned by conventional procedures and treated again as above.

Jan 1, 1965

By C. C. McDermond, Others, B. N. Zavoico

Production of crude oil in Venezuela for the year 1937 was 186,653,-916 bbl., as compared with 155,228,982 bbl. produced in 1936, an increase of almost 31,500,000 bbl. The oil-field strike, which started on Dec. 14, 1936, lasted until Jan. 25, 1937, when a total of 10,000,000 bbl. of production was estimated to have been lost (5,750,000 bbl. in 1936 and the remainder in 1937). Of the total of 186,653,916 bbl. produced in 1937, the Lagunillas field contributed 45.6 per cent, a drop of approximately 10 per cent under 1936 figures; Tia Juana, 14.3 per cent; Quiriquire field, 14.0 per cent; La Rosa area, 13.3 per cent and the Mene Grande field, 7.6 per cent, these being the five leading contributors of the year's production. Detailed production figures by fields and by companies are shown on Table 1. Of the total production of Venezuela the following four major companies accounted for the greater proportion: Standard of Venezuela and Lago Petroleum Corporation together, 48.3 per cent; Shell, 37.4 per cent and Venezuela Gulf, 14.0 per cent. At the end of the year, 2491 wells were producing, of which number 1291 wells were pumpers, or about 52 per cent. Production The accompanying statistics of production record of Venezuela oil fields from its inception to Dec. 31, 1937, shown on Table 2, indicates that the cumulative production reached 1,503,283,228 bbl. In order of importance, Lagunillas leads all the fields, having accounted for about 50 per cent of Venezuelan production, followed by La Rosa area, which produced about 21 per cent; Mene Grande, which produced about 13 per cent, and Quiriquire, which produced 6.5 per cent. Table 3 shows the age of each field. Mene Grande is the oldest, having produced for 24 years; Tarra is next, 21 1/2 years old, and El Mene third, 171/2 years. The gravity of the crude from the various fields, also shown on Table 3, remained unchanged, the only addition being the new Tia Juana field, which averages 15.6' A.P.I. Table 4 shows the method of production by fields as of Jan. 1, 1938; at the end of the year 2491 wells were producing, compared with 2005 wells producing at the beginning of 1937, or an increase of 486 wells. The completions for the year reached 512. Of the 2491 wells producing crude oil, 1291 wells, or approximately 52 per cent, were pumping, 925 (approximately 37 per cent) were flowing naturally and 275 (11 per cent) were on

Jan 1, 1938

By Edwin H. Olson, Morton Smutz, Charles J. Baroch

IN 1949 an orebody containing some 10 billion lb of recoverable rare earth metals was discovered in the Mountain Pass district of San Bernardino County, California.1 The following year Molybdenum Corp. of America purchased a number of claims at the deposit and a mill on the property which had been constructed to process the district's gold ores. Average composition of ore from the San Bernardino deposit is less than 0.1 pct ThO2, 25 to 35 pet calcite, 10 pet rare earth oxides, 15 to 20 pet silica, and 30 to 40 pet barite.2 Rare earth content of the ore analyzes 50.7 pet CeO2, 4.2 pet Pr6O11, 11.7 pet Nd2O3, 1.3 pet Sm2O3, and 34.3 pet La2O3, and others.2

Jan 3, 1959

By P. W. Bakarian, John C. McDonald

Three magnesium alloys were processed in various ways to exhibit a wide variation in the ratios of yield strength and tensile strength in the rolling direction compared to the cross-rolling direction. Basal-plane pole figures were prepared from several specimens. A fair correlation was observed between the property ratios and the ratio of percent of poles oriented in the cross-direction quadrants compared to the percent oriented in the rolling-direction quadrants of the pole figures. THE modes by which magnesium crystals deform are such as to lead to marked preferred orientations in all forms of wrought products. The effect of the active modes at room temperature, coupled with these orientations, is often to produce a lower compressive yield stress compared to the tensile yield stress. The phenomenon is due to easy twinning in compression, and has been well-related to the preferred orientations as described by basal-plane pole figures of the hcp magnesium single crystal. The literature contains some information on the variation with test direction of the tensile properties of sheet, but no quantitative relationship to the observed pole figures has been established. These effects have been reviewed in the few com- prehensive treatises in English which have been written on magnesium technology and metallurgy.1°3 Roberts presents several pole figures, but no tensile-property data in the plane of the sheet. Raynor has no pole figures, but quotes Frommer's4 results. The information in Beck's compendium more or less parallels the results of Jones and powell.5 In both a Mg + 1.5 Mn alloy and a Mg + 4.6 A1 alloy, cold rolling was found not to change the general situation of higher properties in the cross-rolling direction,* than in the rolling direction. Thomas'6 X-ray studies of Jones and Powell's specimens did not permit correlation of properties and preferred orientation. Ansel and Betterton7 report tensile and compressive properties on three other alloys as a function of degree of cold rolling, plus a recrystallizing anneal. As rolled, there was a change in anisotropy with degree of reduction, but all alloys were reasonably isotropic in tension when annealed. X-ray diffraction photograms illustrated the kinds of orientations present, but were not correlated with the properties. Bakarian8 has described a method of determining quantitatively a preferred orientation, and illustrated the method by applying it to pure magnesium and two of its alloys. This method was used in the present work as a basis for correlating the strength properties with the texture.

Jan 1, 1965

By V. G. Mooradian, John T. Norton

THE diffusion of metal atoms into the crystal lattice of another metal and the assumption of regular positions to form a homogeneous alloy are some of the most fundamental phenomena of structural. metallurgy. The mechanism of this process has been the subject of a great deal of study from many viewpoints, but the picture is still far from complete. It is generally believed that if one metal is to diffuse into another, the first must have some solubility in the second1. This means that the solvent must be able to accommodate the stranger atoms, either on points of its own lattice or in the interstices between, without losing its own crystallographic identity. It is also a general observation that cold-working is a distinct aid in the diffusion process, causing it to take place with greater rapidity at the same temperature or with the same speed at a lower temperature. There is considerable doubt, however, as to the real significance of the deformation in its effect on the diffusion mechanism. Several factors associated with the cold-working. may be responsible for the increased diffusion rate. The plastic deformation causes a distortion of the solvent lattice, which may be an aid in the assimulation of atoms of another kind. There are many references2 in the literature that suggest that some distortion or "loosening" of the lattice is necessary for atomic migration and that diffusion cannot take place in the undis-

Jan 1, 1935

By Morris Muskat

TEe method of R. W. Moore' for determining subsurface interfacial depths by means of integrated curves of apparent resistivity has been analyzed theoretically. It is found that the only unique tangents that can be drawn to such curves are the asymptotes at infinite electrode spacing and the tangents through the origin at vanishing electrode spacing. Explicit expressions have been derived for the relationship between the electrode spacing at the points of intersection of these tangents and the thickness of the surface strata as a function of the conductivity parameters for the two-layer and three-layer earths. It is found that in all cases the electrode spacing at the points of intersection will exceed % of the thickness of the surface layer, and may even become indefinitely large as the resistivity of the deepest layers increases as compared with that of the surface layer. These results do not agree with the empirical findings of Moore that the intersection of the tangent lines fall at an electrode spacing very approxirnately equal to the thickness of the surface layer. Introduction In a recent paper, R. W. Moore1 proposed a new method for the analysis and interpretation of earth-resistivity measurements. This consists essentially in plotting against the electrode separation of a Gish-Rooney system the integral of the apparent resistivity with respect to the electrode spacing, and observing the breaks in the integral curves. Specifically, tangents are drawn to the various segments of the integral curves, which show appreciably different slopes, and the intersections of these tangents are used as indications of the depths of the various underlying strata. By numerous examples Moore has shown that the electrode separation at the first intersection so found agrees very closely with the depth of the bottom of the surface layer. Moreover, in a number of instances the intersections for greater electrode spacings seemed to correspond to the depths of deeper beds. From a strictly empirical point of view, the procedure proposed and demonstrated by Moore appears to be particularly interesting because of its simplicity as well as its apparent accuracy, Moreover, such a simple method would be especially valuable in view of the well-known difliculties heretofore encountered in the quantitative interpretation of resistivity data. It therefore seems appropriate to attempt a mathematical analysis of the problem to see whether the integral method of Moore has a sound basis. Such an analysis is presented here. Even on cursory consideration, it is clear that the remarkable successes observed by Moore in the application of his method are indeed surprising. For it depends upon the determination and choice of the slopes of smooth and continuous curves, which by their nature must show even more gradual- variations than the original apparent-resistivity plots that are already so difficult to interpret quantitatively. It is well established, of course,

Jan 1, 1946