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By L. H. Sjodahl, J. B. Conway

of each particle on grain boundary movement is proportional to the area it occupies on the grain boundary and this increases with the square of the particle radius. In contrast to the impression gained by Tiwari the effectiveness of a particle, as a grain boundary obstacle, increases rapidly as the particle size increases. The counterbalancing factor in a dispersion of constant volume (e.g., those considered by Zener) is of course the rapidly diminishing number of particles, a situation which does not exist in thoria dispersed materials where the volume fraction of thoria remains constant. Although it has been assumed that the Zener approach is valid for the sake of the above argument, it is open to the following objections: 1) It assumes that the effect of many small particles along a grain boundary is cumulative and does not take into account the possibility of each small particle being overcome separately. In this case the boundary will not be able to move forward until the largest particle on the boundary has been overcome. This means that the rate controlling factor will be the rate at which a few relatively large particles are overcome with the remaining small particles playing a negligible role. 2) When the dispersion consists of very small particles the interparticle spacing is usually small compared to the grain size and most particles are located away from grain boundaries where they can play no part. The most efficient dispersion, from a purely geometrical viewpoint, is one where the particle spacing is equal to the grain size so that all the particles are on grain boundaries. Tiwari's second point that voids cannot prevent re-crystallization seems to be unfounded as several workes20-23 have shown that voids alone can retard grain boundary movement and recrystallization. To further convince Tiwari, Fig. 17 shows a void in deformed TD Nichrome holding back a recrystallization interface. Tiwari's explanation for the effect of voids on recrystallization, i.e., they reduce local strain energy and hence lower the driving force for recrystallization may be valid in itself but is irrelevant to the present case where even complete recrystallization after ONE of the more recently proposed expressions for describing stress-strain behavior is that due to Voce.1,2 This equation is usually written: s =s8 ?(s8?so)e??/?c [l] where s is the true stress, ? is true strain, cC is a constant called the characteristic strain, s8 is the asymptotic stress approached at high strain values, and so is the threshold stress at which the plastic deformation begins. While this expression has not been universally accepted as yet it does contain certain features which are consistent with experimental stress-strain behavior. In a more recent publication Hsu, Davies, and Royles3 employed the concept of generalized strain proposed by seth4 and identified a method for linearizing the stress-strain plot. In this approach the generalized strain was given by: where 7 is the generalized strain, 1 is the instantaneous length, 1, the datum length, and n is a constant called the "coefficient of strain measure". A value of n was said to exist which would yield the linearity: s —s+ S[.-(tf] [3] In recent studies of both these approaches, it has been found that while the Voce equation and the gen-

Jan 1, 1970

By P. E. Baker

The commercial neutron-gamma log measures the intensity of gamma-rays produced by the interaction of neutrons with nuclei in the formation and in the bore hole. This measurement gives information concerning the distribution of neutrons around the neutron source, and in particular gives information on porosity or fluid content. Another type of information is contained in the frequency or energy spectrum of the neutron capture gamma-rays. The capture gamma-rays of each element, in fact of each isotope, have only those energies characteristic of that isotope.'" The neutron capture gamma-ray spectrum, if obtainable, would permit the identification of the elements producing the spectrum. Such information would have considerable value in oilfield exploration work if it could be applied practically in well logging. Experiments have been carried out at the La Habra Laboratory of California Research Cop. to determine the feasibility of a method of well logging in which neutron capture gamma-ray spectra are measured down hole. In these experiments, spectra were obtained for artificial formations under simulated borehole conditions, using actual borehole geometry. This paper will describe the experimental apparatus and methods and will present the spectrum curves for several formations. THEORY Basic Formulas The neutron capture cross section of an element is a measure of its tendency to capture neutrons. The macroscopic cross section, or cross section per cubic centimeter, of a material composed of several elements is the sum of the cross sections of the nuclei making up 1 cc of the material. This is expressed in the equation SB = Sn1s2, ..........(1) where SB is the macroscopic cross section, s, is the cross section of a nucleus of type i, and ni is the number of nuclei of type i/cu cm. If N is the number of neutrons absorbed per second by the composite material, then the number captured by element j is Ni = N nisi/SB = N nisi/Si ni si ......(2) When the nucleus captures a neutron, a new nucleus is formed, which is usually in an excited state and falls to its ground or unexcited state by emitting one or more gamma-ray quanta.* The emission spectrum has been measured for many elements (see Table 1). The intensity of gamma-rays produced by an element is proportional to the number of neutrons captured per unit time by the element, which in turn depends on the capture cross section of that element and the capture cross sections of the other elements present which are competing with the first element for thermal neutrons. In a small sample of material the number of neutrons, N, captured per second is N = ?SB, ..........(3) where $ is the thermal neutron flux and SB is the macro-scopic cross section defined above. The number of neutrons captured by element j is N1 = ?ni si = N ni si/SB . ......(4) The number of gamma-ray quanta of energy, E, pro-duced per unit time by element, j, is I(E)=Nni si/SB P(E) .......(5) where P(E) is the emission probability of element, j, for this gamma-ray energy. Borehole Effects The capture gamma-ray spectra of many elements have been measured accurately in academic and government laboratories. These measurements are made on small samples, and from these measurements the emission spectra of the elements are obtained.

Jan 1, 1958

By W. J. Millard

IT is well known that the excellent mica from Brazil played a most vital role in World War II. Increased production from Brazil was necessary and with the assent of the Brazilian Government engineers from the United States went down to study the problem. One of the means advocated by a former Chief of Metals and Minerals Branch of the Board of Economic Warfare, Mr. Carl Schwegler, was the use of stripping machinery. On a pegmatite dike favorable for stripping, a small number of miners could produce as much mica per day as an underground mine employing many times the same number of men. TYPE OF DEPOSIT FAVORABLE The most favorable type of pegmatite for stripping is that which lies more or less parallel to the surface of the slope of a hill. Pegmatite dikes that cut directly into a hill are not suitable for stripping except where a long outcrop extends along the slope. Then just the outcrop could be stripped to some advantage. The ratio at no time should be greater than I:3; i.e., I cu. m. of pegmatite to 3 cu. m. of waste, unless the pegmatite was extremely rich throughout the dike. THE ECONOMICS OF STRIPPING When a mineral is badly needed to win a war, not too much heed can be paid to costs. The object is to produce rapidly and in quantity. Again, a deposit containing a superior grade of mica may be worked although the pegmatite is more costly to work than another deposit containing a considerably greater amount of poor-grade mica. For example: one deposit may have a little mica that will run II per cent good stain and better when trimmed and contain 2 kg. of crude mica per cubic meter of pegmatite, while another may run 0.2 per cent of good stain and better, and have a mica content of 10 kg. per cubic meter. A number of stripping projects were found in the vicinity of Raul Soares, Minas Gerais. These were sampled in the various old workings by cutting out a cubic meter of pegmatite and saving the usable mica. Because of the proximity to the surface of most stripping projects, about 34 per cent only of the mica is good for trimming. The other 66 per cent is too badly weathered to be of use. In Table I are given data collected on five properties near Raul Soares. In Table I, "value per cubic meter of pegmatite" means the value of the qualified mica obtainable. This does not include the half trimmed and splittings. By "value per cubic meter of matter" is meant the value of the qualified mica per cubic meter of material excavated; i.e. both waste and pegmatite. This is the figure that should he used to determine whether the operation will be profitable or not, as the cost of stripping is about $0.I4 per cubic meter. With new machinery not subject to breakdowns, the cost per cubic meter should be around $0.10 to $0.I5. To this should be

Jan 1, 1946

By John G. Tate, George W. Nicolson, James L. Bruce

FOR more than 25 years modern mining has been carried on in the Island of Cyprus, Mediterranean Sea, by the Cyprus Mines Corp. of Los Angeles, Calif. The general features of these operations have been described.1 From 1935 to June 30, 1940, top slicing in the Mavrovouni mine produced in excess of 2,000,000 long tons. The rate for the last part of this period was approximately 50,000 tons per month. DESCRIPTION OF ORE BODIES The shape of the ore body now being top sliced in the Mavrovouni mine is an inclined irregular pyritic pipe or chimney of large dimensions, extending from unknown depths below the bottom level at elevation 250 ft below sea level, to the highest level at elevation 400 ft above sea level. The present surface above the ore body lies between 550 and 650 ft elevation. Undoubtedly the ore body extended to surface and was mined by the ancients by opencast and underground methods. The old pits were gradually filled up by erosion until now they show as slight depressions in the topography. The largest area of the ore body is at elevation 170 ft below sea level, where the horizontal section is almost elliptical, with a width of 600 ft and a length of 1000 ft. Below this elevation the shape of the ore body continues to be elliptical but with reduced dimensions. Above this elevation it rises flatly towards the south with a substantial depression in the upperside of the chimney and irregular ridges or wings rising on each side. It gradually grows smaller as it rises. The ore body is a pyritic replacement of andesitic extrusives which occur as flows and pillow lavas. With the exception of the upper portions of one or two small offshoots rising from the main ore body, all ore is completely surrounded by andesite. Most of the andesite lying above the ore body is covered by marl and clay sedimentaries of Miocene and later age. The Miocene is presumed to be older than the ore mineralization. That portion of the andesites which lies between the sedimentaries and the ore body has been broken by slumpage, and weathered, and iron-stained by the descending meteoric waters. It is a mass of crushed material that caves and follows downward readily as the top-slice stopes retreat. The main ore body is a heavy cupreous pyrites mass assaying on the average about 4.0 pct Cu; 48.0, S; and 42.0, Fe. In places the copper drops below 1.0 pct. On the borders of this heavy sulphide ore body lie disseminated cupreous pyrites ore deposits of large dimensions. Some portions of these appear to be closely related to the heavy sulphide ore, as the ratio of copper to pyrite is about the same. The greater part of the disseminated ore, most of which lies immediately to the east of the main ore body, contains less than 0.10 pct Cu and about 25.0 to 30.0 pct S. This probably can

Jan 1, 1947

By H. M. St. John

THE melting department is the heart of the foundry. From it clean metal flows to the molding floor, in the right quantity, at the right time and at a sufficiently low cost-or, if not, the foundry fails to thrive. Since it is our purpose here to discuss present-day melting practice in the foundry, it may be well at the start to emphasize the wide differences in foundries and the conditions under which they must operate in order to reach the goal stated in the first paragraph. In every foundry, large or small, jobbing or captive, the same factors must be dealt with but they are of varying consequence and must be dealt with in varying ways in different foundries. Particularly in the nonferrous industry, there is so wide a variation in the composition of alloys used and in the character of castings made that no one type of furnace, nor any one method of operation, can be expected to produce the best results at all times. The present discussion will not attempt to include all nonferrous metals. It is intended to cover only the copper-base alloys in which copper is the dominant element, most of which are commonly known as brass or bronze. The discussion is further limited to the melting of these copper-base alloys for use in sand-casting foundries. Die-casting plants, the brass-rolling mills and certain other metal industries have melting problems peculiar to those industries, which will not be considered here. The following considerations are elemental in all foundries and are listed in what is believed to be the relative order of their present-day importance: I. The melting department must meet the foundry's requirement for dean, fluid metal, of specified composition and purity, at a temperature suitable for the work the foundry has in hand. This is the prime consideration in any foundry, at any time, anywhere. 2. Working conditions surrounding the melting furnaces and attending their use must be good. 3. The cost of molten metal at the mold must be as low as possible. 4. The operating characteristics of the furnaces must be sufficiently flexible, to meet normal variations in foundry requirements. 5. The operation and maintenance of the melting equipment must not require more skill and experience than is available in the particular foundry in question. METAL QUALITY It is not a function of the melting furnace to refine or improve the quality of the metal but simply to melt it without impairing its quality. Good practice requires, therefore, that care must be taken to supply the melting department with metal of inherently good quality, assured by specification or otherwise, having all the properties necessary to produce the castings desired. An alloy contains a number of primary elements, which must be present in definite proportions if the castings made from it are to have the desired properties. If the castings are made to a customer's specification, this will state the range within which these principal elements (for example, copper, tin, lead and zinc) are permitted to vary.

Jan 1, 1946

By L. R. Duncan, O. M. Wicken

Magnesium, the eighth most abundant element in the earth's crust, is found widely distributed in a variety of minerals. Among the more commercially important ones are magnesite (MgCO,), brucite (Mg[OH],) , dolomite (CaMg[CO,],), and the salts magnesium sulfate and chloride often found in natural brines. Among other commercially important magnesium-containing minerals are olivine ([MgFe],- SiO,) , talc (H,Mg,[SiO,],) , and serpentine (H,Mg,Si,O,) . These are valuable because of desirable characteristics given them by the magnesium content and its placement in the particular crystal structure. These minerals are the raw materials for a host of products including magnesium metal and several grades of magnesia or magnesia- containing materials for refractories, fluxes, fillers, insulation, cements, decolorants, fertilizers, and chemicals. Considering only those minerals valued for their magnesia or magnesium content, over 85% of the material tonnages are processed to be used as refractories. Dolomite, which is used in enormous tonnages for its physical properties in construction, has an important use as a refractory raw material in its own right and, after calcination, as a precipitant for magnesium hydroxide, which is an intermediate for the production of magnesia or magnesium metal. Magnesia from the reaction of calcined dolomite (or limestone) with sea-water or magnesium-containing brines has supplanted much of the production of magnesia from mined magnesite, particularly in the United States. The best known of the minerals directly and widely exploited for magnesia content is magnesite, one of the calcite group of rhombo- hedral carbonates which includes calcite (Ca- CO,) , siderite (FeCO,) , and rhodocrosite (MnCO,) among others. The members of this group enter into a wide range of substitutional solid solutions when the positive ions have similar radii. The radii of magnesium and iron ions are within 6% of each other; hence, magnesite and siderite form a complete series of which breunnerite (ferroan magnesite) is a well-known end member. However, the radius of calcium ion is 36% larger than that of magnesium ion, and only limited substitution exists at each end of the MgC0,-Cam, series. Dolomite is not a member of the calcite group, but results when calcium and magnesium ions alternate in equal number in an ordered structure among carbonate ions. The result of these relationships is that calcite and dolomite, often found intermixed with magnesite, occur commonly as identifiable crystal entities which can often be separated to a varying degree from the magnesite by various beneficiation techniques. Magnesite, when pure, contains 47.8% MgO and 52.2% CO,. The pure mineral is sometimes, but rarely, found as transparent crystals resembling calcite, but, preponderantly, magnesite contains variable amounts of the carbonates, oxides, and silicates of iron, calcium, manganese, and aluminum. Magnesite may be either crystalline or "amorphous" (cryptocrystalline). The crystalline form has a hardness of 3.5 to 4.0. The color may range from white to black with shades of yellqw, blue, red, or gray. The color is not a fundamentally significant indicator of purity, but in a given deposit, an experienced person can often roughly grade magnesite by assessing color and crystallinity. The crystalline form of magnesite occurs in

Jan 1, 1975

By John B. Campbell, George G. Binder, Loren H. Jenks

Conventional methods of producing crude oil generally leave in the depleted reservoir 1 to 3 bbl of oil for every barrel brought to the surface. This paper describes a field test which explores the possibility of using gas-driven liquid propane to improve oil recovery efficiency. Laboratory theoretical and experimental studies leading to the field test indicated that low residual oil values could be obtained using limited amounts of propane driven by gas. The field test involved (I) repressuring the reservoir to the vapor pressure of liquid propane, (2) injecting the liquid propane, and (3) injecting dry natural gas to drive the propane and oil to the producing wells. Considerable preliminary work, including new drilling, work-overs, and a pressure survey was necessary. During the test, oil production rates have averaged about nine times the final primary rates. The field average GOR is still below the pre-test value. Oil recovery to date is 112,000 STB. About one-third of the 143,-000 bbl of propane injected has been produced to date. Results of the C-2 block test are encouraging and larger, more definitive field projects ore indicated. INTRODUCTION The cost of finding new crude oil reservoirs continues to increase. Today the oil industry is drilling more and deeper wells and making fewer big discoveries. Nevertheless, the demand for oil and oil products increases each year. It is natural that oil companies, faced with this situation, concentrate on recovering more of the oil existing in our known crude oil reservoirs. There is room for much improvement. For every barrel of oil brought to the surface by present day methods of producing crude oil, generally 1 to 3 bbl are left behind in the depleted reservoirs. The "unrecoverable" oil in petroleum reservoirs is largely "trapped" by capillarity. Since flushing with a solvent is exceedingly effective in combatting oil loss due to capillarity, much effort in this direction has been made in recent years1,2,3,4,5. Liquefied petroleum gas (LPG) has been suggested as a relatively inexpensive. abundant, easily recoverable solvent for crude. Some operators have observed striking responses in oil recovery at production wells offsetting input wells in LPG storage reservoirs6,7,8. In spite of the low unit cost of LPG, however, it is uneconomic in general to inject a volume of LPG into a reservoir to remove a like volume of oil. A modification of solvent flushing in which a limited quantity of liquid propane is gas driven through a reservoir appears capable of recovering much more than 1 bbl of oil per barrel of propane injected. Also, most of the propane injected should be recoverable for sale or re-use. Since such a process could well have widespread and profitable application, The Carter Oil Co. is making an extensive evaluation of the technique's possibilities. Laboratory development of the gas-driven propane recovery technique was sufficiently encouraging to justify testing in the field. Since 1952, the Production and Research Departments of The Carter Oil Co. have cooperated in a field test in the C-2 Block leases of the

Jan 1, 1958

By James Terry Duce

In order to facilitate interpretation of the data in this chapter, we print the following excerpts from circulars to authors, compiled by Mr. Frank A. Herald when he was Vice Chairman for Production of the Petroleurn Division: Generally in Table 1 the unit for presentation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive, locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions-—several units of continuous productive reservoirs of distinctly different structure and of distinctly different stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and/or commercial value. As to each space in the tabulation, it is either (1) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert 2; in spaces where the proper entries are determinable but not determinable from data available to the author, the author will please insert y; in spaces where the proper entries are deter-minable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use 2. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report 1,8xx,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations may be involved, our figures should represent as nearly as possible the total quantity of gas removed from the reservoir.

Jan 1, 1936

By P. P. Scott, George C. Howard

A field remedial procedure utilizing a kerosene-cement slurry as a water plug-off agent in fractured formations was evaluated both in the laboratory and in the field. This procedure has proved to be capable of effectively shutting off water without causing permanent impairment of the oil production. Success was attributed to the fact that an immobile cement slurry, when placed in a water-producing strata, will set and form an impermeable barrier; whereas when placed in an oil-producing section the cement will retain a relatively high permeability and may be removed by acidizing. INTRODUCTION One of the most perplexing problems facing the oil industry is the selective exclusion of water production from oil or gas-producing wells. This problem has been studied by many investigators in an attempt to develop a material that is not only capable of reducing water production but is also capable of being selective in that it will not impair oil production in either fractured or intergranular type reservoirs. A study of these two types of formations indicated that two distinct types of materials for controlling water production might be required — a completely liquid plugging agent for intergranular formations and a semi-liquid or slurry type plugging agent for fractured formations. This paper is limited to the control of water production from fractured formations. A common source of water in the vicinity of oil bearing rock reservoirs is water which previously has entered and, because of its higher density, generally lies near the bottom of the formation. When the deepest point of penetration of a well into such an oil and water-bearing formation is above the level of the water, and the dynamical gradients due to the flow of oil overbalance the difference in densities between oil and water, water production becomes a problem. Then the water level rises in the shape of a cone and is produced from the lower depths. Other investigators1,2,3,4 have developed theories which define the pressure gradients and contours of this cone in a homogeneous formation and have shown that the placement of a plug in the bottom of a well is only slightly effective in temporarily reducing the flow of water. Assuming that the manner of flow of bottom water from fractured formations to a well is generally similar to the flow in homogeneous formations, then it would be expected that some form of coning, perhaps of less symmetry, would also occur. Then, because of the similarity of the manner of flow of water, placement of a vertical plug in a fractured formation would also probably be ineffectual for controlling water production. However, as has been shown by electric model flow study,' the placing of a plug in a well and an impermeable horizontal streak in the formation might prove to be a means for materially reducing or even eliminating water production in a fractured formation. An indication of the difference in effectiveness between horizontal and vertical plugs based on theory developed from study of the flow of water and oil in rock reservoirs is depicted in Fig. 1. These curves show the expected

Jan 1, 1955

By James Terry Duce

In order to facilitate interpretation of the data in this chapter, we print the following excerpts from circulars to authors, compiled by Mr. Frank A. Herald when he was Vice Chairman for Production of the Petroleurn Division: Generally in Table 1 the unit for presentation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive, locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions-—several units of continuous productive reservoirs of distinctly different structure and of distinctly different stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and/or commercial value. As to each space in the tabulation, it is either (1) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert 2; in spaces where the proper entries are determinable but not determinable from data available to the author, the author will please insert y; in spaces where the proper entries are deter-minable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use 2. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report 1,8xx,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations may be involved, our figures should represent as nearly as possible the total quantity of gas removed from the reservoir.

Jan 1, 1936

By W. M. Fox, D. P. Detwiler

IN the course of research on semiconducting inter-metallic compounds, it became necessary to obtain gallium metal of greater purity that that available commercially. Several methods were considered for further purification, including acid leaching,' fractional crystallization,' and zone-refining.3-5 The method of fractional crystallization was discarded as being equivalent to zone-refining in purification but inefficient in material and time. Both acid leaching and zone-refining were tried, and the method finally adopted is a combination of the two. The acid leaching technique has been reported' to produce gallium in which no impurities are detectable spectroscopically. Although this method is very effective in removing oxides and surface contaminants, semiconducting material made of gallium subjected only to leaching indicated little reduction in the concentration of metallic impurities. Zone-refining, however, appears very effective in removing trace metallic impurities, but comparatively ineffective in removing the surface oxide film. Consequently, the method evolved consists of acid leaching to thoroughly clean the surface, followed by zone-refining to remove metallic impurities. The low melting point and relatively high thermal conductivity of gallium introduce some difficulty in maintaining frozen and molten zones in zone-refining. To accomplish this, it is found necessary to reduce the effective ambient temperature by circulating ice water in coils about the regions that are to be kept frozen, while heat is supplied to the molten regions by resistance coils. The power supplied to the heating coils is regulated by a constant-voltage transformer and a variable autotransformer. Both heating and cooling coils are mounted on a transite base. The gallium ingot is held in a closed pyrex tube sliding inside the heating and cooling coils, the reciprocating method of Tanenbaum et al. being employed to move the molten zones through the ingot at a rate of 2 in. per hr. This apparatus is shown in Fig. 1. The results of a spectroscopic analysis f a zone-refined ingot, as well as of the material as-received and after acid leaching, are shown in Table I. The ingot was 32 cm in length, and received 37 molten-zone passes, the molten zone being about 4 cm long. The only impurity found was lead, the following elements being reported also as checked but not found in the pure material: Al, Sb, As, Ba, Be, Bi, B, Cd, Ca, Cr, Co, Cb, Cu, Ge, Au, Fe, Mg, Mn, Mo, Ni, Pt, Si, Ag, Na, Sr, Sn, Te, Ti, W, V, Zn, and Zr. There thus appears no indication of pickup of Al, Mg, or Si from the pyrex boat as reported by Zimmerman' in his fractional crystallization. Thus it appears that definite removal of lead from gallium occurs during the zone-refining process. It also may be concluded that a more sensitive analytical procedure than spectroscopy is required to evaluate quantitatively the purity of zone-refined metals. One such procedure which is proposed for use in the near future is the measurement of very low temperature resistivity. Although this will not identify the impurities present, it offers a very sensitive check of total impurity. Acknowledgment This work was supported by the Air Research and Development Command, United States Air Force.

Jan 1, 1956

By J. E. Hanlon, S. R. Butler, R. J. Wasilewski

The temperature, orientation, and strain-rate dependence of tensile flow in single-crystal NiA1 of equiatomic composition have been investigated up to 800°C. Compression tests at room temperature have also been carried out. Optical and replica electron microscopy and X-ray diffraction methods were used to investigate the slip mechanisms. NiAl exhibits {110)(001) slip and cube slip {l00)(010) was also observed. This results in very high strength of single crystals in cube orientation. The implications of this slip mode, with the resultant small number of possible slip systems and three mutually perpendicular slip vectors, are discussed. ThE CsCl structure compounds represent a class related to the bcc elements, but their behavior is affected by three additional variables: composition (within the stability range of the compound), extent of long-range order perfection, and bonding energy. Very little data are available on the effects of these variables on mechanical properties. Rachinger and ~ottrell' suggested slip to occur along (111) in compounds of low ordering energy; in compounds of higher bond strength (>0.06 ev), they observed (110) (001) slip. As pointed out by copley,' only three in- dependent slip systems are available in the latter case; hence general deformation is impossible. Brown3 carried out a theoretical calculation of the yield-point variation with the degree of long-range order in the CsCl structure, based on the assumption of superdislocations. More general approaches, based on considerations of superlattice dislocations and antiphase domain boundaries in ordered structures, were carried out by Flinn~ and by Vidoz and Brown.' These, however, give no information on changes in the slip structure—if any—between the ordered and the disordered compounds. This aspect was investigated experimentally and theoretically by Stoloff and Davies' and by Marcinkowski and chessin7 in FeCo. The latter workers proposed the deformation behavior of the ordered FeCo to be essentially the same as that in many other bcc metals. Investigations of polycrystalline A~M~'-'O indicate considerable variation in mechanical properties with composition and test temperature. The existence of {123)(111) slip was reported in AgMg.'9'9'0 (The formation energy of this compound, presumed to be ordered at all temperatures below melting, is 4.38 cal per g-atom," i.e., 0.024 ev per bond.) The yield strength has been reported as relatively independent of temperature below 0.45 T, (where T, is the absolute melting temperature). Tensile deformation of single-crystal AgMg was also investigated by Kurf-man," who observed marked tendency to single glide on{112}(111) and {110)(111). From observations of slip lines in deformed poly-crystalline NiA1, Westbrook et a1.I3 suggested the

Jan 1, 1968

By K. A. Gschneidner, O. D. McMasters

DgIel-ential thermal, nretallographic, and X-ray paramzetric methods were used to establish the Yb-Pb phase dingram. The terminal solid solubilities in the system are less than 0.2 at. pct. Lead additions lower the 792°C transformation tewzperature of pure ytterbiun~ at 787°C by means of an inverted peritectic veaction. Ytterbium additions raise the 327oC melting point of lead to 329°C by means of a perilectic reaction. Three intermetallic compounds Yb2Pb, YbPb, and YbPb, melt congruerttly at 1246", 1116o, and 740°C. respectively. YbsPb3 forms by a peritectic reacliorz at 1250°C. YbzPb crystallizes in the PbCh (C23) type structure and the orthorhombic latliceo constants are a, = 7.478. bo = 5.225, aud C0 = 9.549A. YbsPbs crystallizes in the hfnsSi3 (D8a) type structure. The hexa~nal lattice constants for this phase are a, = 9.325 and co = 6.92d. YbPbl crystallizes in the cubic AuCU3 (Ll2) type structure with a: = 4.8628 + 0.0008A. YbPb is diwrorphic with the structure change occurring al 507°C upon healing. The crystal structures of the two forttzs were not determined. Eulectic reactions occur at 5.1 at. pct Pb and 769oC, 41.5 at. pct Pb and 1086oC, and G8.0 at. pct Ph and 717°C: RELIABLE information concerning the alloying behavior of most of the rare-earth metals is scarce. A systematic study of the rare earth-lead alloy systems now in progress is an effort to supply such information. Determination of the phase diagram of the Yb-Pb alloys is the first step of this study. Variations in the valence of normally divalent ytterbium may be studied by comparing the characteristics of the Yb-Pb alloys to those of the trivalent rare earth-lead and of the divalent alkaline-earth-lead systems. Of particular interest are the melting temperatures of the intermetal-lic compounds since these are known to be high relative to the melting points of the constituent metals. Crys-tallographic and magnetic susceptibility data for the rare earth-lead alloys are to be included in the comparative study. Results from this and subsequent investigations should provide a better understanding of alloy formation. EXPERIMENTAL PROCEDURE Materials. The major impurities in the ytterbium and lead used in this investigation are listed in Table I. The lead was obtained from Cominco Products, Inc., and was specified to be 99.99 pct pure. The ytterbium was prepared in this laboratory by the lanthanum reduction of the oxide followed by a distillation of the ytterbium. Alloy Preparation. The alloys were prepared by

Jan 1, 1968

By David P. Shoemaker, Clara Brink Shoemaker

The I phase was discovered by Bardos, Malik, Spiegel, and Beck1 in the V-Ni-Si system at 1100°C and in the Mn-Co-Si and Mn-Ni-Si systems at 1000°C. Kuzma and Hladyshevskii2 and Kuzma, Hladyshevskii, and cherkashin3 have reported a new phase, which they named the S phase, in the Mn-Co-Si and the Mn-Ni-Si systems at 800°C at approximately the I phase compositions. The powder diffraction diagrams of the I and S phases, compared by Bardos el al.,1 are related but show distinct differences in relative intensities. Professor Paul A. Beck kindly sent us a specimen of the (v-Ni-Si) I phase for single-crystal study. Precession and Weissenberg diagrams taken with a tiny single-crystal fragment showed that the structure is monoclinic with a large unit cell. The cell dimensions were refined from a powder diffraction diagram taken with CrKa radiation in a 57.3-mm camera with our computer program LSCELP4 using only the indices of those reflections that were observed on Weissenberg diagrams (hnl, with n = 0 through 9 and n = 12) and precession diagrams (Okl, lkl, Izk0, hkl, hk2). Table I shows the agreement obtained between the l/d values calculated with the final values for the cell dimensions and the l/d values observed by Bardos et al .1 for I(V42Ni33Si25), by US for I(V41Ni36Si23), and by Kuzma and Hladyshevskii2 for S(MnpCoSi). The powder patterns contain many broad and diffuse lines. In fact practically all powder lines observed are near-superpositions of several reflections. The refinement program is not set up to handle several reflections contributing to one observed line: the position of each line is refined with the aid of one set of indices only. The final values for the cell dimensions were obtained from the lines of strong or medium intensity with the indices indicated by asterisks in Table I: a0 = 13.403(6), bo = 23.336(15), co = 9.129(6)A ß = 99.11(6) deg The standard deviations (given in parentheses) are those calculated by the refinement program from least-squares theory and do not take into account that the lines included in the refinement may not have been correctly indexed in every case or that the position of a line may also be partly determined by the overlapping reflections. The agreement between the calculated and observed I phase patterns is fairly good, although some discrepancies occur. Not all observed lines could be indexed with the incomplete set of sin-

Jan 1, 1968

By L. G. Sprague

THE fact that this latest and most modern of the Universal Atlas Cement Company's plants at Northampton, Pa., is the fifth to be built on these same properties, and their development has been coincidental with the development of the portland cement industry in the United States, makes it appropriate to sketch briefly the history of the successive steps. In 1889 the original Atlas Portland Cement Co. started its first plant at Coplay, Pa., which is just across the Lehigh River from the present operation. Here the first successful rotary kiln was operated. These kilns were 6 ft. in diameter and 60 ft. long; they used oil for fuel until 1895, when the company developed the first burner for pulverized coal. Shortly thereafter the Atlas company acquired property on the Northampton side of the river and built its plants Nos. 2, 3 and 4 within the following 10 years. During the same period the production of portland cement in the country was increasing rapidly; owing largely to the development of the rotary kiln and improved grinding machinery, which lowered the cost and improved the quality of cement. The general tendency has been to increase the length of the kiln and grind both raw material and finished product finer. In 1930 the Atlas Portland Cement Co. and the Universal Portland Cement Co. united to form the Universal Atlas Cement Co., and the same policy of improving the product has been continued. Because of the large amount of research carried on by manufacturers and consumers, including government agencies, there is a demand for cement of different chemical and physical characteristics for different kinds of structures. Hence many engineers in recent years have been asking for cements of certain definite chemical analyses, which they think are best for their particular jobs. This has compelled the manufacturer to make several different types of cement by variations of chemical composition. These are generally made by adding silica, iron and lime to the standard mixture, which necessarily increases the cost of the product. Therefore the Universal Atlas Cement Co., in planning the modernization of its Northampton plant, gave this particular phase of the problem considerable study. Research and experimentation have developed the practicability of making a wide variety of differently proportioned raw materials for cement by a process of subtraction rather than by addition. With such process, it is possible to discard the undesirable aluminates and silicates from the ample supply of impure limestone available from the company's property rather than by adding high-grade limestone obtained from distant sources. This procedure requires mineral separation by centrifugal sedimentation and froth flotation. Since the chemical and mineral constituents of Lehigh Valley "cement rock," together with the methods of separating them, have been thoroughly described in published

Jan 1, 1943

By W. W. Smeltzer

The linear formation rates of wustite films have been determined over the temperature range 590° to 1030°C using a vacuum microbalance technique. These rates are dependent directly on the partial pressure of carbon dioxide, Activation energies for film and scale formation in carbon dioxide and oxygen atmospheres are equivalent to either the dissociation energies of carbon dioxide and oxygen, or the activation energy for the diffusion of cation vacancies in wustite. Of the metals, iron is the most widely used basic constituent of durable alloys despite its intrinsic property of converting at a relatively rapid rate to the oxides from which it is derived. This property has accounted partially for many investigations on the oxidation of iron at low and high temperatures. Interpretation of the results have been complicated by formation of multilayers containing the various oxide phases. To aid in elucidation of the oxidation kinetics, measurements have been carried out in this investigation on the growth of the wustite surface layer. There are several studies directly related to the objective of this investigation. The growth of multilayer scales has been demonstrated to be diffusion controlled in oxygen at atmospheric pressure over the temperature range 450" to 1200°C by Davies, Simnad, and Birchenall.' To gain an insight into the diffusion mechanism, Himmel, Mehl, and ~irchenall' determined the self-diffusion coefficients of iron in wustite, magnetite, and hematite. These results were used to evaluate the oxidation rates of iron and its oxides, taking as a basis the theoretical parabolic rate equation developed by Wagner., The evaluations were compared to experimental data and were shown to provide essential confirmation of this theory. Fischbeck, Neundeubel, and salzer4 have demonstrated that the oxidation of iron in carbon dioxide and other atmospheres at high temperature obeys a linear relationship. Because the Arrhenius temperature coefficients of the reaction rate constants changed at the A, point they concluded that the passage of iron into the oxide controlled the reaction. This viewpoint has been accepted by Benard and ~albot' to explain the occurrence of linear rates in oxygen before the onset of diffusion-controlled parabolic oxidation. This basic premise of a rate-controlling reaction at the iron/oxide interface has been questioned recently by Hauffe and Pfeiffer.' Since the formation of wustite may follow a linear or parabolic relationship depending on the pressure of the gaseous re-actant, they propose that linear oxidation is determined by a chemisorption reaction while parabolic oxidation is controlled by diffusion. As confirmation of this viewpoint, Hauffe and pfeiffer6 and Pfeiffer and ~aubmeyer' have established that the linear scaling constants of wustite formation at 1000°C in carbon-dioxide or low-pressure oxygen atmospheres

Jan 1, 1961

By L. G. Sprague

The fact that this latest and most modern of the Universal Atlas Cement Company's plants at Northampton, Pa., is the fifth to be built on these same properties, and their development has been coincidental with the development of the portland cement industry in the United States, makes it appropriate to sketch briefly the history of the successive steps. In 1889 the original Atlas Portland Cement Co. started its first plant at Coplay, Pa., which is just across the Lehigh River from the present operation. Here the first successful rotary kiln was operated. These kilns were 6 ft. in diameter and 60 ft. long; they used oil for fuel until 1895, when the company developed the first burner for pulverized coal. Shortly thereafter the Atlas company acquired property on the Northampton side of the river and built its plants Nos. 2, 3 and 4 within the following 10 years. During the same period the production of portland cement in the country was increasing rapidly; owing largely to the development of the rotary kiln and improved grinding machinery, which lowered the cost and improved the quality of cement. The general tendency has been to increase the length of the kiln and grind both raw material and finished product Liner. In 1930 the Atlas Portland Cement Co. and the Universal Portland Cement Co. united to form the Universal Atlas Cement Co., and the same policy of improving the product has been continued. Because of the large amount of research carried on by manufacturers and consumers, including government agencies, there is a demand for cement of different chemical and physical characteristics for different kinds of structures. Hence many engineers in recent years have been asking for cements of certain definite chemical analyses, which they think are best for their particular jobs. This has compelled the manufacturer to make several different types of cement by variations of chemical composition. These are generally made by adding silica, iron and lime to the standard mixture, which necessarily increases the cost of the product. Therefore the Universal Atlas Cement Co., in planning the modernization of its Northampton plant, gave this particular phase of the problem considerable study. Research and experimentation have developed the practicability of making a wide variety of differently proportioned raw materials for cement by a process of subtraction rather than by addition. With such process, it is possible to discard the undesirable aluminates and silicates from the ample supply of impure limestone available from the company's property rather than by adding high-grade limestone obtained from distant sources. This procedure requires mineral separation by centrifugal sedimentation and froth flotation. Since the chemical and mineral constituents of Lehigh Valley "cement rock," together with the methods of separating them, have been thoroughly described in published

Jan 1, 1948

By L. G. Sprague

The fact that this latest and most modern of the Universal Atlas Cement Company's plants at Northampton, Pa., is the fifth to be built on these same properties, and their development has been coincidental with the development of the portland cement industry in the United States, makes it appropriate to sketch briefly the history of the successive steps. In 1889 the original Atlas Portland Cement Co. started its first plant at Coplay, Pa., which is just across the Lehigh River from the present operation. Here the first successful rotary kiln was operated. These kilns were 6 ft. in diameter and 60 ft. long; they used oil for fuel until 1895, when the company developed the first burner for pulverized coal. Shortly thereafter the Atlas company acquired property on the Northampton side of the river and built its plants Nos. 2, 3 and 4 within the following 10 years. During the same period the production of portland cement in the country was increasing rapidly; owing largely to the development of the rotary kiln and improved grinding machinery, which lowered the cost and improved the quality of cement. The general tendency has been to increase the length of the kiln and grind both raw material and finished product Liner. In 1930 the Atlas Portland Cement Co. and the Universal Portland Cement Co. united to form the Universal Atlas Cement Co., and the same policy of improving the product has been continued. Because of the large amount of research carried on by manufacturers and consumers, including government agencies, there is a demand for cement of different chemical and physical characteristics for different kinds of structures. Hence many engineers in recent years have been asking for cements of certain definite chemical analyses, which they think are best for their particular jobs. This has compelled the manufacturer to make several different types of cement by variations of chemical composition. These are generally made by adding silica, iron and lime to the standard mixture, which necessarily increases the cost of the product. Therefore the Universal Atlas Cement Co., in planning the modernization of its Northampton plant, gave this particular phase of the problem considerable study. Research and experimentation have developed the practicability of making a wide variety of differently proportioned raw materials for cement by a process of subtraction rather than by addition. With such process, it is possible to discard the undesirable aluminates and silicates from the ample supply of impure limestone available from the company's property rather than by adding high-grade limestone obtained from distant sources. This procedure requires mineral separation by centrifugal sedimentation and froth flotation. Since the chemical and mineral constituents of Lehigh Valley "cement rock," together with the methods of separating them, have been thoroughly described in published

Jan 1, 1948

By Bernard Kopelman

The particle size of tungsten metal powder used to make tungsten wire for use in radio tubes and incandescent lamps must be closely controlled if the highly desirable feature of nonsagging is to be achieved. Our knowledge of factors affecting the particle size of tungsten powder has been limited by lack of any extensive literature on the subject. There are no publications in the English language discussing this problem in any but the most general terms. In this paper the published experimental information on this subject is reviewed. Based on the published data and some experimental data obtained by the author, a general theory of factors affecting the particle size of tungsten metal powder obtained by reduction of the oxides in hydrogen is offered. The various forms of the tungsten oxides and tungsten metal used in the experiments described were those prepared by commercial processes, so that the experimental results obtained on a laboratory scale would be more directly applicable to actual commercial reduction conditions. The effects of time of reduction, temperature. and concentration of water vapor in the hydrogen were observed by counting microscopically the particle distribution obtained. Such a method is very time-consuming, but the data obtained by this method are more reliable and more fundamental than those obtained by any of the several instruments available for measurement of particle size. Review of the Literature Until the year 1912, tungsten powder was prepared commercially by reducing tungstic oxide in the presence of carbon or one of its compounds (such as glycerin or ethylene glycol), usually by firing the mixture in a closed fire-clay crucible. The resultant powder contained about 95 per cent tungsten.' When reduction of tungsten oxides by H² was introduced Commercially,²,³ several investigators became concerned with the equilibria between tungsten metal and its several oxides in an atmosphere of hydrogen and water vapor.4-l3 While these many investigations were in fair agreement on the equilibria WO³ + H2 = WO2 + H2O and WO2 + 2H2 = W + 2H2O there arose considerable controversy as to the chemical composition of the oxide between WO³ and WO², because of very poor agreement on the equilibrium constant of this intermediate oxide reduction reaction. The controversy on this intermediate oxide has been in progress for more than 100 years. Thus Malguti,14 in 1835, decided it was WO2.56 In 1857, Riche15 proposed the formula W³O8. Usler,16 in 1865, confirmed the existence of WsO8 and further proposed W1O1l. In 1897, Desil7 agreed upon W²O8 but also found W5O14.

Jan 1, 1947

By Bernard Kopelman

The particle size of tungsten metal powder used to make tungsten wire for use in radio tubes and incandescent lamps must be closely controlled if the highly desirable feature of nonsagging is to be achieved. Our knowledge of factors affecting the particle size of tungsten powder has been limited by lack of any extensive literature on the subject. There are no publications in the English language discussing this problem in any but the most general terms. In this paper the published experimental information on this subject is reviewed. Based on the published data and some experimental data obtained by the author, a general theory of factors affecting the particle size of tungsten metal powder obtained by reduction of the oxides in hydrogen is offered. The various forms of the tungsten oxides and tungsten metal used in the experiments described were those prepared by commercial processes, so that the experimental results obtained on a laboratory scale would be more directly applicable to actual commercial reduction conditions. The effects of time of reduction, temperature. and concentration of water vapor in the hydrogen were observed by counting microscopically the particle distribution obtained. Such a method is very time-consuming, but the data obtained by this method are more reliable and more fundamental than those obtained by any of the several instruments available for measurement of particle size. Review of the Literature Until the year 1912, tungsten powder was prepared commercially by reducing tungstic oxide in the presence of carbon or one of its compounds (such as glycerin or ethylene glycol), usually by firing the mixture in a closed fire-clay crucible. The resultant powder contained about 95 per cent tungsten.' When reduction of tungsten oxides by H² was introduced Commercially,²,³ several investigators became concerned with the equilibria between tungsten metal and its several oxides in an atmosphere of hydrogen and water vapor.4-l3 While these many investigations were in fair agreement on the equilibria WO³ + H2 = WO2 + H2O and WO2 + 2H2 = W + 2H2O there arose considerable controversy as to the chemical composition of the oxide between WO³ and WO², because of very poor agreement on the equilibrium constant of this intermediate oxide reduction reaction. The controversy on this intermediate oxide has been in progress for more than 100 years. Thus Malguti,14 in 1835, decided it was WO2.56 In 1857, Riche15 proposed the formula W³O8. Usler,16 in 1865, confirmed the existence of WsO8 and further proposed W1O1l. In 1897, Desil7 agreed upon W²O8 but also found W5O14.

Jan 1, 1947