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By Forrest K. Pence

Bentonite deposits are known to occur in Texas within the Jackson group of formations. This group represents the uppermost Eocene age sediments found in the coastal plain area of Texas. It outcrops across this area of the state in a narrow band of some 4 to 20 miles width. The outcrop pattern roughly parallels the present Gulf of Mexico shore line and is some 100 miles inland from the Texas shore, Fig 1. The principal bentonite deposits are found in the areas where this outcrop pattern cuts across the south-central Texas counties of Karnes, Gonzales, and Fayette. In these deposits, the better quality bentonite is found in the lower or bottom layers of the volcanic ash deposits in which they occur. Some of these better quality benton-ite~ develop very light colors upon firing and therefore justify their being classified as "white firing." The deposits in Karnes and Gonzales Counties apparently occur in commercial quantity, whereas the white firing strata so far uncovered in Fayette County have been too thin to be classified as yet as "commercial." A study of the ceramic properties of the weathered ash in Gonzales and Karnes Counties was reported in 1941.' Commercial development of the deposit in Gonzales County, 7 miles east of Gonzales, Texas. was started earlier by the Max B. Miller Co. for the purpose of marketing the material as a bleaching clay, and this operation has developed to very sizable proportions. In recent years, this company has offered a specially selected grade of the Gonzales material as a suspending agent in glaze slips. The white firing property especially adapts the material to use in white cover coat enamels. The strata in the deposit are practically horizontal and consist from top to bottom of approximately 2 ft of soil overburden, 10 ft of brown bentonite, 2 ft of coarse white bentonite, and 4 ft of waxy white bentonite overlying a he grained sandstone. The & being made in the quarry is approximately one-half mile in length. Only the bottom 4 ft of waxy bentonite is being recovered, the upper layers being stripped and wasted, Fig 2. It may appear somewhat surprising that the very bottom strata appears to have been the one most completely altered. To confirm this, samples from top to bottom of the various strata were studied microscopically by R. F. Shurtz. Professor of Ceramic Engineering, University of Texas. His interpretation is to the effect that the lower part of the seam was deposited at a much earlier date than the top, and that the lower part was chemically altered to a considerable extent before the upper part of the seam was laid down. The conclusion to be derived from these examinations may be stated briefly to he that the alteration in these strata or parts of strata has proceeded independently of the alteration in other parts of the strata during a considerable geological period. The presence of gypsum and iron stain throughout all of the strata indicates that alteration is now proceeding more or less uniformly throughout. It is contended that the alteration of the original ash to montmorillonite is not a result of the presently operating processes. A deposit which occurs approximately 7 miles southeast of Falls City and just south of the village of Casta-howa, has been explored and leased by J. R. Martin, of San Antonio. Mr. Martin has conducted mining and marketing operations in bentonite for a period of many years and asserts that the white firing strata found in this deposit occurs in commercial quantities. His pit, which is shown in Fig 3, exposes 2 ft of soil overburden, approximately 5 ft of white bentonite having coarse texture, and approximately 5 ft of waxy white bentonite which in turn overlies a brown sandy clay. Here, as in the Gonzales deposit, the most completely altered portion is found at the bottom of the seam, as per following report of microscopic examination by Mr. Shurtz. Sample No. 1: This sample was taken from the top stratum which is one foot thick. It is grayish in color and it contains visible fossilized plants. The color is probably the result of fine carbonaceous material in the rock. Under the microscope the sample is seen to consist of glass and feldspar; the amount of glass predominating. Both these substances are slightly altered. No montmorillonite or other clay mineral can be identified definitely; however, the products of the slight alteration mentioned are probably montmorillonite or mineral gel. Sample No. 2: This sample was taken from the stratum second from the top. This stratum is fourteen inches thick. The sample is light gray. It shows numerous veinlets of greenish translucent material ranging from one-eighth inches wide down to the limit of visibility with the unaided eye. It has the smooth, sub-conchoidal fracture characteristic of some bentonites. Microscopically the sample consists mainly of aggregates of clay minerals. The birefringence of the aggregates is lower than would be expected if the

Jan 1, 1950

By S. S. Shen, M. J. Pool, P. J. Spencer

Heats of solution of silver and copper in dilute Ag-Cu-Sn alloys at 720°K have been determined using a liquid metal-solution calorieter. Values of the se2f-interaction coefficient n AgAghave been calculated at constant copper concentrations and n Cu Cuhas been determined at constant silver contents. The reliability of the experimental data is shown by the very good agreement between nCujAg and ij &$; these interaction coefficients have experimental values of -9100 and - 9590 cal per g-atom, respectively. Certain solution models are shown to be inadequate for prediction of solute interaction coefficients in dilute Ag-Cu-Sn alloys. In a previous publication' the results of a thermody-namic study of dilute Ag-Au-Sn alloys were presented. The present work represents the continuation of a program to investigate dilute alloys of the noble metals with tin and in particular is concerned with solute interactions in the Ag-Cu-Sn system. By determination of the magnitude and sign of the various interaction coefficients in dilute alloys it is possible to gain some understanding of the different types of solute-solute and so lute-solvent bonding changes that occur as the solute concentrations are varied. Hence systematic studies of alloys with similar physical characteristics as regards size, structure, electronegativity, and so forth, of their components can contribute a great deal to present theoretical knowledge of solutions. The recent definition of an enthalpy interaction coefficient, 11, by Lupis and Elliott2 is of particular value in calorimetric studies such as the present one: where j and i are solutes and s is the solvent; Si is the relative partial molar enthalpy of component i and x represents the mole fraction of solute or solvent. Values of ?Hi can be obtained directly by solution calorimetry and data for n are thus easily determined, often with a high degree of accuracy. ?Hi is related to the relative partial molar enthalpy at infinite dilution, ?Hi and to the enthalpy interaction coefficients by the expression: ?Hi?Hi + X;nz+ ... [2] The aim of the present work was to determine the self-interaction coefficients n AgAgand 178: in alloys of different compositions and also to establish values for n Agcg| and ncuAg. Since it is a thermodynamic requirement (resulting from the Maxwell-type relationships which can be applied to partial molar properties) that nAgcu and ncuAg should be equal, a further aim of this study was to demonstrate the agreement between experiment and theory. EXPERIMENTAL A description of the liquid metal-solution calorimeter used in this research has already been published,3 and no further details of its construction and operation will therefore be given here. Copper supplied by the American Smelting and Refining Co. was indicated by them as being 99.999 pct pure, and the silver obtained from A. D. Mackay, Inc., was also quoted as being 99.999 pct pure. A solvent bath consisting of between 70 and 80 g of 99.99 pct pure Sn was used for each series of experimental drops. Its weight was accurately determined and the appropriate amounts of copper or silver were added to give alloys of the desired composition. Approximately 0.00125 g-atom additions were used for determinations of the heat of solution of silver in the bath, while, for copper, specimens consisting of approximately 0.0015 g-atom were used. The heat capacity of the bath was determined at regular intervals during a series of drops using tin or tungsten calibration samples. The heats of solution of silver and copper in pure tin were first determined as a function of their concentration in order to establish the self-interaction coefficients 7AgAg and ncucu Alloys containing a constant 0.01, 0.02, 0.03, and 0.04 mole fraction of copper were then used to study 17:: in alloys of different copper content, while alloys of the same mole fractions of silver were used to determine equivalent data for 178: at constant silver concentrations. The composition of the bath was held at the desired copper or silver concentration by making calculated additions of the appropriate solute throughout the experiment. From the limiting values of ?HAg in the constant copper content alloys it was possible to study ?HAg as a function of xCu and hence to determine 42:. A similar analysis of the re, values permitted calculation of nAgcu. Heat content and heat capacity data from Hultgren et al* were used to calculate heat of solution values from the measured heat effects at the experimental temperature of 720°K. RESULTS AND DISCUSSION Determinations of ?HAg. A preliminary investigation of the heat of solution of silver in pure tin at 720°K was first made in order to establish the value of nAgAg before additions of copper were made and also to compare the value of ?HOAg(l) with that obtained in the previous study of Ag-Au-Sn alloys.' Then the heat of solution of silver in Cu-Sn alloys was investigated as a func-

Jan 1, 1970

By J. R. O’Connor

Stimulated emission from Nd+3 in yttrium uanadate fYVOJ is reported. Single crystals of YVO4:Nd, obtained from Linde Col-p., have improved substantially in the last several months. Pulsed thresholds of YVO, laser rods are now approximately 2 to 3 5, cowparable to tliose for YAG:Nd. Yttrium uanadate crystalli~es irz a space group similar to zircon. All rare-earth vanadates have this structure. Rare-earth ions sucll as Nd+3 which substitutes for Y+3, aye situated irz a strong tetragonal crystal field which lacks inversion symmetry. This condition increases the p'robability of the parity-forbidden f — f transitions. Yttrium anadate has strong absorption bands beyond -1000A. These are clue to Y-O, V-O charge transfer and molecular transitions. Under 2537 and 3660A irradiation pure YVO, fluroresces u bright yel-LOLO. This fli&orescence is corrzpletely quenched in YV04:Ncl crystals. This and other evidence of energy trut~sjer from the lattice is repovted. Optzcul atz 1user pvope 1-ties o! YI'U4:E[t are brieJy described. THIS paper describes some of the optical and laser properties of Nd+3- and Eu+3-doped yttrium orthovana-date (YVO4). It reports laser action for the first time in this low-symmetry host. For some time we have pursued a research program concerning laser hosts' wherein the rare-earth (RE) ion is situated at a site of low crystal symmetry so as to increase the probability of radiative transitions. Single crystals of doped and undoped YV04 are grown from iridium crucibles in an oxyhydrogen gas-fired furnace by a modified Czochralski technique.' This material crystallizes in a D4li tetragonal space group of the zircon (ZrSiO,) type.3 All RE vanadates have the same structure and form solid solutions with YVO4. Therefore, it will be possible to investigate a variety of cross-pumped laser systems, as in the case of yttrium aluminum garnet (YAG).4 At present, ~d'~-doped YAG is one of the most efficient solid-state lasers.5 Accordingly, most of the material to follow will compare the properties of YV04 to those of YAG. Fig. 1 shows the relative transmission of YAG and two types of YVO4. "Pure" YVO4 has a normal absorption edge and is colorless. A second type has a broad absorption peaking near 4200A and is yellow. Rubin and Van uitert6 suggest the yellow material is slightly reduced. Samples of each type are being investigated by electron spin resonance,7 but these studies are so far inconclusive. The pulsed laser threshold is much lower in the yellow material than in the colorless. Therefore, the absorption at 3500 to 5000.4 transfers energy to the Ndi3 ions. Photons of wave length between 2000 and 4500A cause undoped YVO4 to fluoresce at 4800, 5250, 5460, 5540, and 5750A. This emission, previously reported by Brixner and Abramsom,8 is partially quenched by EU'~ and completely quenched by Ndt3 at room temperature due to energy transfer from the lattice to the RE ions. At low temperatures, some lattice fluorescence is present. This implies that the energy-transfer process is in part phonon-assisted. Although the YVO, single crystals used in this work were prepared from Y2O3 containing less than 0.01 pct rare-earth impurities, there is aopossibility that emission lines between 4800 and 5750A are due to dysprosium, terbium, and so forth. However, these lines are not observed in other compounds, prepared from Y2O3, such as YP04, Y2MoO6, and so forth. Furthermore, extensive absorption measurements on our "pure" YV04 single crystals between 0.4 and 5.0 failed to reveal any characteristic rare-earth lines. Fig. 2 compares the absorption spectra of Ndt3-doped YAG and YVO4from 0.6 to 1.0 . The Ndt3 absorptions are labeled according to free ion, R-S coupling. These term designationsQ are appropriate for YAG:Nd. They appear to be inappropriate for YV04:Nd. In YVO, neodymium must substitute for yttrium. The yttrium site is situated In a strong tetragonal field, where point symmetry is (42m) or possibly lower.1° However, the reduced splitting of the Stark components of the YV0,:Nd spectrum implies that the NdT3 ion is in a cubic site. The only plausible explanation for this discrepancy is that the Ndt3 ion is in a low-symmetry site, lacking inversion symmetry, so that a substantial admixture of 4f and 5d wave functions occurs. In this case, R-S coupling is not valid and J is no longer a good quantum number." Consistent with this view, the 4~ metastable level of YV04:Nd has an oscillator strength larger and a

Jan 1, 1968

By John Chipman

The concentration of a solute in a dilute ),zetallic solution may be measured by any of several parame- ters including weight percent, atom fraction, atom ratio, and lattice ratio. The ratio of filled to unfilled interstitial sites is useful for interstitial solutes. A variable 2 proportional to this ratio is used as a measuve of concentration. For component 2 irz a bitzary solution z2 = n2/Ym - nz/b) where b is the numberber of interstitial sites per lattice atom. For a t~lul-ticortzporzent solution this becomes zz = n2/(nl + Cvjnj) in which Vj = - l/b for an interstial solute and +1 for a substitulional solute. In the infinitely dilute solution the activity of an interstitial solute 2 is proportional lo z2. At finile concentration the departure from this limiting law is expressed us an activity coefficient, his coefficient is a function of concentra1io)z expressed as tevactiolz coeffcient 8; is analogous to the jark~iliar e£ bul is found to be independent of concentvation in certain solutions for which data are available. It is found that the same equations may be used to express the activity of a nonmetallic solute, sulfur, in liquid solutions of iron containing other solutes, both metallic and nonmetallic. For a nonmetallic solute or for one which strongly increases the actiuity of sulfur, it is convenient to assign arbitvarily a value vj = — 1. When this is done the derivative is found to be constant in each of the ternary solutions studied. The activity coefficient of sulfur in a complex liquid iron solution may be expressed as where nk is a second-order cross product determined in the quaternary solution Fe-S-j-k. The equation is used to calculate tlze activity of sulfur i)z three sevetl- component solutions. IN thermodynamic calculations concerning dilute solutions it is unnecessary to invoke laws and relations which extend across the concentration range to include concentrated solutions. In most binary metallic systems, as arkeen&apos; has recently pointed out, there exist two terminal composition regions of relatively simple behavior, connected by a central region of much greater complexity. When the solute is a nonmetal there is only one such region and in many systems the concentration range is extremely limited. It is the purpose of this paper to suggest a method for the calculation of activities in such a terminal region in which one or more solutes are dissolved in a single solvent of predominantly high concentration. HENRY&apos;S LAW In the usual textbook statement of Henry&apos;s law, concentration is stated in mole fraction. This has the advantage that it makes Henry&apos;s law thermodynamically consistent with Raoult&apos;s law. Since all measures of concentration at infinite dilution are related by simple proportion it follows that mole fraction, molality, atom ratio, weight percent, or any other unit of concentration can be used with the appropriate constant. At finite concentrations, however, calculations based on the law depend upon the unit employed. Deviations from Henry&apos;s law at finite concentrations depend upon the composition variable employed. They are evaluated in terms of activity and interaction coefficients2 which have become familiar features of metallurgical thermodynamics. It is the purpose of this paper to propose a measure of concentration for metallic solutions containing interstitial or nonmetallic solutes by means of which the calculation of activities in complex solutions may be simplified. The discussion will be restricted to free-energy interaction coefficients3 typified by Wagner&apos;s c|a BINARY SOLUTIONS The several measures of concentration which are to be considered are shown in line a of Table I. The corresponding activity coefficients are in line b and the deviation coefficients, sometimes called self-interaction coefficients, are in line c. Henry&apos;s law simply states that the activity coefficient approaches a constant value at infinite dilution. By adoptihg the infinitely dilute solution as the reference state and defining the "Henrian" activity as equal to the concentration in this state, the activity coefficient is always unity at infinite dilution. This convention is far sim~ler and more useful in dilute solution than emploiment of the &apos;Raoultian" activities and it will be used in the following discussion. The several definitions and equations of Table I will be referred to by means of their coordinates in the table. Early observations of deviations from Henry&apos;s law in metallic solutions were shown graphically4 rather than analytically. For the case of sulfur in liquid iron5 the slope of a plot of logfs vs (%S) was constant in the range 0 to 4.8 pct S, indicating constancy of eh2&apos; in Ic. He was proposed by wagnerz and has been widely adopted. The a function of IIIc recently employed by ~arkenl was designed specifically for dilute solutions. Darken has shown that the value of a12 remains essentially constant for many binary solutions within a substantial range of compositions. The atom ratio is directly proportional to the molalitv.<, a conventional measure of concentration. IVb and C served as the basis for smith&apos;s6 classic studies of

Jan 1, 1968

By P. Duwez, C. B. Jordan

The phenomenon of the change of volume of pressed powder compacts upon sintering is well known in the field of powder metallurgy. Depending upon the metal or metals involved and the pressure used in forming, a compact may, in the course of time of sintering at a given temperature, expand mono-tonically, contract monotonically, or first show a volume change of one sign followed by a change of the opposite sign. It is clearly desirable to have accurate knowledge of the magnitude and sign of the change in dimensions to be expected in any given case, both from the point of view of direct usefulness in the fabrication of parts by powder metallurgy, and from the longer range viewpoint of elucidating the fundamental mechanism of metallic sintering. The present study was therefore undertaken as a first step in acquiring systematic and reasonably quantitative knowledge of the change in density of metal powder compacts during sintering. For practical reasons, copper was selected as the material to be studied first, and its densification followed as a function of temperature and time of sintering in hydrogen and in vacuum. Experimental Procedure The copper powder used was that designated by the manufacturer (Metals Disintegrating Co., Elizabeth, N. J.) as MD-151. This powder was sifted through Tyler standard screens to separate the fraction having particle size range between 200 mesh and 325 mesh, and this fraction was used in all the subsequent work. Compacts weighing about 10 g were then pressed in a 1 in. diam round die, using a pressure of 20,000 psi throughout. Sintering was carried out in commercially built electric furnaces in which the resistance windings are so disposed as to produce a nearly uniform temperature along the axis of the furnace for a length of about 18 in. centrally located. In order to be able to sinter in a controlled atmosphere, a 2 in. stainless steel tubing was inserted in the furnace. Each end of the tube was cooled by a water jacket about 7 in. long, and closed with a rubber stopper. The hydrogen used for one series of specimens was purified as described in Ref. 1. For the other set, a pressure of about 0.5 mm Hg was maintained during sintering by a Welch Duo-Seal Pump. The specimens were heated on square trays made of stainless steel. In placing specimens in the trays, a thin even layer of powdered aluminum oxide was first sprinkled on the bottom of the tray. A copper guard disk about half the thickness of the specimen was then placed in the tray and covered with a second layer of alumina. The actual specimen was then set on the guard disk, and a final coat of alumina sprinkled over the specimen. This technique was evolved for sintering the specimens in such a way as to reduce the influence of unknown extraneous factors to a minimum. If the specimen is placed directly on the tray and sintered, it is found that the resulting shape is that of a frustum of a cone, rather than a section of a right circular cylinder, since friction with the tray prevents the bottom of the specimen from contracting at the same rate as the top. In the arrangement used in these experiments, the guard disk provided a support which shrank at the same rate as the specimen, and the alumina powder reduced to a minimum friction between guard disk and tray, and between specimen and guard disk. The procedure followed in sintering consisted of bringing the furnace to the required temperature, and then inserting the specimen into the central heated portion of the furnace tube in one of the two atmospheres used. At the end of the heating period, the specimen was cooled by bringing it into a portion of the furnace surrounded by a water jacket. These manipulations were carried out without opening the furnace, by means of rods which were attached to the trays and operated through a sliding seal in the rubber stopper. The progress of densification of the copper compacts was studied at 1300, 1400, 1500, 1600, 1700, and 1800°F. At each of these temperatures, a specimen was allowed to sinter for each of the following time intervals: M, 1, 2, 4, 8, 16, 32, and 64 hr. The thickness and diameter of each specimen were measured with micrometers before and after sintering, and each was weighed on an analytical balance after sintering. Results The techniques described in the preceding section were found to give satisfactory results. The specimens were not detectibly warped after sintering, and were usually of uniform diameter (that is, truly round) to within 0.001 in., a very few showing a variation in diameter of ±0.002 in. All specimens were found to have the same diameter

Jan 1, 1950

By D. J. Carney, R. L. Stephenson

A sampling technique has been developed for procuring a sample of sinter representative of the entire depth of the sintering bed. The sampling method involves the use of an open-bottom metal basket that rides on the grate of the sintering machine and when removed contains a sample of the sintered product. Additional data have been obtained to indicate that the tumbler test is a suitable means of measuring sinter strength. IN the last few years additional sintering facilities have been installed in both the Pittsburgh and the Chicago district of the United States Steel Co. Since the construction of these sintering plants made possible the use of higher percentages of flue-dust sinter in our blast-furnace burdens, it became important to study means of controlling the quality of sinter to obtain optimum results in the blast furnace. For controlling an operating process, it is necessary first to establish standards by which the quality of the product can be judged. For sinter, it appeared that an important property was its strength or its resistance to degradation during transportation and charging into the furnace. Consequently work was undertaken to establish a standard for sinter strength that could be used both for controlling sintering-plant operations and for correlating sinter quality with blast-furnace performance. The first problem in setting up a standard was that of procuring a sample that would be representative of the sinter made under any particular set of conditions at the sintering plant. Since the United States Steel Co. sintering plants discharge the finished sinter either into a large pit or onto a rotary cooler, the sinter becomes inseparably mixed with material sintered 2 hr before or 2 hr afterwards. For this reason the exact identity of the sinter is lost. A sample selected as the cooler is discharged, or as the sinter is removed from the pit, cannot be said to be truly representative of the sinter made at any specific time. Sampling The first attempt to procure a sample that would be representative of a specific sinter mix and of specific operating conditions was made by stopping the Dwight Lloyd sintering machine and removing an entire pallet full of sinter. This method, however, proved very difficult to perform and interfered considerably with the operation of the plant. To overcome this difficulty, a sampling method was devised by technologists at South Works enabling them to secure, without interrupting the sintering operation, a sample of about 1 cu ft of sinter, representative of sinter for the full depth of the sintering bed. The South Works method involves the use of a steel-frame-work basket. A typical basket is shown in Fig. 1. The basket has been used both with and without crossbars along the bottom. As long as the crossbars are in the same direction as the grate bars on the sintering machine they do not interfere with the sintering process. The basket is set on an empty grate of the Dwight Lloyd sintering machine before it passes under the swinging feed spout, see Fig. 2. When the basket is removed after it has travelled the length of the sintering machine, it contains the sample. Just before the basket is removed, the sinter is scored and chipped to facilitate removal of the sample from the sinter bed. A view of the basket after its removal is shown in Fig. 3. Although the sampling method was originally designed for use on a Dwight Lloyd sintering machine, it can also be used on the Greenawalt type of machine. When used on the Greenawalt-type machine, the basket is placed on the sintering grate before the charging car passes over it, and finally it is removed just before the pan is dumped. Testing After a method of obtaining a representative sample of sinter had been developed, the next step was to select a method of measuring its strength. The irregular shape and size of the sinter pieces precluded the use of a simple compression test for determining strength; consequently, the shatter test and tumbler test were investigated. To perform the shatter test, a sample of sinter, approximately 5 lb, is dropped from a hinged-bottom box at a height of 3 ft onto a steel plate. The broken sinter is sieve-analyzed after a specified number of drops. The tumbler test is performed with the use of a standard ASTM coke-tumbling drum. The drum is 3 ft in diam and is equipped with two lifter bars diametrically opposite one another on the inner periphery of the drum. The drum is rotated at a speed of 24 rpm for 200 revolutions, and after tumbling the sample is sieve-analyzed. To express as single numbers the results of sieve analyses after shattering or tumbling, the method suggested by R. E. Powers1 was employed. This method involved plotting the size of the sieve openings on a logarithmic scale and the cumulative per cent larger than each sieve on a probability scale as described by J. B. Austin.&apos; By interpolating from the plotted data, which in most cases approximated

Jan 1, 1954

By J. J. Tietien, R. O. Clough

A technique previously used to prepare alloys of InAs1-xPx and GaAsl-x Px, miry: the gaseous hydrides arsine and phosphine, has been extended to grow single -crystalline GaAs 1-x Sb x by replacing the phos-phine with stibine. Procedures were developed for handling and storing stibine which now make this chemical useful for vapor phase growth. This represents the first time that this series of alloys has been grown from the vapor phase. Layers of P -type GaSb and GaSb-rich alloys have been grown with the carrier concentrations comparable to the lowest ever reported. In addition, a p-type alloy containing 4 pct GaSb exhibited a mobility of 400 sq cm per v-sec which is equivalent to the highest reported for GaAs. RECENTLY, interest has been shown in the preparation and properties of GaAs1-xSbx alloys, since it was predicted1 that for compositions in the range of 0.1 < x < 0.5, they might provide improved Gunn devices. However, preparation of these alloys presents fundamental difficulties. In the case of liquid phase growth, the large concentration difference between the liquidus and solidus in the phase diagram, at any given temperature, introduces constitutional supercooling problems. It is likely that, for this reason, virtually no description of the preparation of GaAs1-xSbx by this technique has been reported. In the case of vapor phase growth, problems are presented by the low vapor pressure of antimony, and the low melting point of GaSb and many of these alloys. In previous attempts1 at the vapor phase growth of these materials, using antimony pentachloride as the source of antimony vapor, alloy compositions were limited to those containing less than about 2 pct GaSb. This was in part due to the difficulty of avoiding condensation of antimony on introducing it to the growth zone. A growth technique has recently been described2 for the preparation of III-V compounds in which the hydrides of arsenic and phosphorous (AsH3 and pH3) are used as the source of the group V element. With this method, GaAs1-xPx and InAs1-xPx have been prepared2&apos;3 across both alloy series with very good electrical properties. Since the use of stibine (SbH3) affords the potential for effective introduction of antimony to the growth apparatus, in analogy with the other group V hydrides, this growth method has been explored for the preparation of GaAs1-xSbx alloys. In addition to GaSb, these alloys have now been prepared with values of x as high as 0.8. In the case of GaSb, undoped p-type layers were grown with carrier concentrations equivalent to the lowest reported in the literature. Thus it has been demonstrated that, with this growth technique, all of the alloys in this series can be prepared. EXPERIMENTAL PROCEDURE A) Growth Technique. The growth apparatus, shown schematically in Fig. 1, and procedure are virtually identical to that described2 for the growth of GaAs1-xPx alloys, with the exception that phosphine is replaced by stibine.* HCl is introduced over the gallium boat to *Purchased from Matheson Co., E. Rutherford,N+J. transport the gallium predominantly via its subchlo-ride to the reaction zone, where it reacts with arsenic and antimony on the substrate surface to form an alloy layer. The fundamental limiting factors to the growth of GaAs1-xSbx alloys from the vapor phase, especially GaSb-rich alloys, are the low melting point of GaSb (712°C) and the low vapor pressure of antimony at this temperature (<l mm). Thus, relatively low antimony pressures must be employed, which, however, imply low growth rates. To provide low antimony pressures, very dilute concentrations of arsine and stibine in a hydrogen carrier gas were used. Typical flow rates (referred to stp) were about 4 cm3 per min of HC1 (0.06 mole pct)+ from 0.1 to 1 cm3 per min of ASH, (0.002 to 0.02 mole pct), and from 1 to 10 cn13 per min of SbH3 (0.02 to 0.2 mole pct), with a total hydrogen carrier gas flow rate of about 6000 cm3 per min. Although no precise data on decomposition. kinetics exist, it is known4 that stibine decomposes extremely rapidly at elevated temperatures. However, the high linear velocities attendent with the high total flow rate (about 2000 cm per sec) delays cracking of the stibine until it reaches the reaction zone and prevents condensation of antimony in the system. To improve the growth rates of the GaSb-rich alloys, growth temperatures just below the alloy solidus are main-

Jan 1, 1970

INTRODUCTION Mineral explorationists range throughout the world looking for mineral deposits which can subsequently be made into mines. Mines are not found! Mines are made, usually at great cost and not often without significant risk. The process of making a mineral deposit into a mine involves a great deal more than a complete appraisal of the deposit. The making of a mine demands detailed feasibility studies of many factors, any one of which, if shown to be negative, could prevent the deposit from becoming a successful mine. Total feasibility analysis involves at least three major fields of study: (1) economic analysis, (2) financial analysis, and (3) political and environmental analysis. Economic analysis is essential for proper decision making at many stages in the evaluation of a mineral deposit. It is the yardstick by which the proposed mining project and alter- native investment opportunities are measured. Economic analysis is concerned with costs and potential profits and can be applied at various stages in the evaluation of a mineral deposit to determine if the project merits the additional funds necessary to bring about each succeeding stage. The nearer any deposit approaches to becoming a mine, the more carefully the economic analysis should be made. Financial analysis has reference to how, where, and at what cost the investment funds can be obtained to finance the proposed mine project. Political and environmental analysis has reference to the many intangible factors that can affect the making of a successful mine. These factors loom larger today than ever before, due to the profusion of government regulations and various environmental constraints now imposed upon the mineral industry both by law and by the weight of public opinion. Ultimately, many of these intangible factors can be resolved back into the economic analysis as an added cost to mine development, but more and more often they have become insurmountable obstacles to any development of certain deposits. The role of financial analysis and the analysis of intangible factors must never be underestimated when making a feasibility study upon which to base investment decisions; however, the emphasis of this text will be upon economic factors. THE PARAMETERS OF MINERAL ECONOMIC ANALYSIS The two major elements of economic analysis are: 1) The potential earnings or annual generated cash flow of the project. 2) The investment costs necessary to realize such earnings. If the difference between the two elements is large enough, i.e., if the return on investment from the cash flow is high enough to attract investors, the project can be said to be financially feasible. The mineral economic analysis must take into consideration many parameters, some of which are known or knowable within certain limits, and others of which are unknown or unpredictable within certain limits and for which estimates must be made. Because both known and estimated parameters enter into the same analytical computations, it is important for the analyst to realize the nature of each when considering the results of an analysis. Some parameters such as the grade of mining block, although estimated, are said to be known within mathematically defined limits. Other parameters, such as the future price for minerals produced, etc., can only be estimated or "guestimated" within reasonable limits for which no precision can be assigned. Known or Knowable Mineral Economic Parameters Known or knowable parameters are: 1) Tonnage and grade of valuable minerals for the total mineral body and for individual mining blocks. 2) Metallurgical recovery of valuable mineral. 3) Minimum operating life of mineral de- posit at any specified production rate. 4) Royalty schedule, property payments, etc. 5) Sales-purchasing agreements, smelter schedules, marketing contracts, etc.

Jan 1, 1980

By M. van Swaay, C. E. Birchenall

A. S. lBrling (Johnson, Matthey & Co. Ltd., Laboratories)— Because of its initial emphasis upon the production of membranes by powder metallurgy and by normal casting and rolling techniques, this paper is of considerable interest to those concerned with the design and application of industrial diffusion units. As the subsequent performances of the three grades of palladium were not compared in detail, it can perhaps be concluded that specific permeabilities were very similar. A short table in which the absolute diffusion rates obtained by the Authors with their three grades of palladium were compared with those of other investigators18-25 would, however, have been of particular value in view of the very variable results obtained with this membrane material. The Authors state early in the paper that the permeability of the thoriated samples decreased in much the same way as that of the nonthoriated samples. Later, they emphasize that sintered palladium without thoria was very susceptible to poisoning and did not respond as well as the other materials to the decontamination treatment. These results, which suggest that sintered membranes are less effective than those produced by normal methods, have considerable industrial implications, and amplified experimental details would be very welcome. The results of the Authors differ in one important respect from those of other investigators. Thus, no "bleeding" was required to maintain a constant rate of diffusion, although Davis, Darling, and De Rosset found this to be necessary. Davisz3 found that "bleeding" was necessary even when the hydrogen had already been purified by diffusion through a palladium tube, and it would be of value to know the purity of the gas stream emerging from the purification train shown on Fig. 1 of the Authors&apos; paper. The Authors show that diffusion rates varied according to the square root of the pressure difference providing that the palladium membrane was not contaminated in any way. This finding is in agreement with the results of those workers2,18,19,23,24 who diffused their hydrogen through the membrane into a partly or completely evacuated system.Those workers who did not find this square-root law dependence did not have a partial vacuum on the downstream-side of the membrane.&apos;&apos; The difference between the two experimental con- ditions appears to be significant, as the absolute diffusion rates per sq cm of diffusion area are lower when the square-root law dependence is not observed. While the effect could be attributable to poisoning of the membrane it is conceivable that a positive pressure on the downstream side of the membrane might influence the mechanism of diffusion. In view of the capricious behavior of palladium, factors of this type, which are likely to influence its industrial significance, should be carefully considered. M. van Swaay and C. E. Birchenall (authors&apos; 9-eply) — Our Eq. 191 may be compared with several others for hydrogen diffusion in palladium: D = 5.95 x exp (-5770/1)&apos; D = 3.55 x 10"3 exp (-5550/)&apos; D = 4.3 x 10"3 exp (-5620/1&apos;)&apos; Other values are given in the literature, but in many cases surface poisoning may have affected the results. No analysis was performed on the hydrogen gas stream after purification. It should be noted that the presence of liquid nitrogen traps near the heated membranes may have set up convection currents and provided the equivalent of "bleeding." The question of whether a partial vacuum existed on the downstream side of the membrane is not clear. Does it imply that there is something unique about the permeability measured near one atmosphere pressure? We do not believe that there is. When square root pressure dependence is not observed, diffusion rates are not measured. Is "absolute diffusion rate per sq. cm. of diffusion area" equivalent to permeability? The terminology is new to us. In any case we doubt very much that pressures of the order of several atmospheres can affect the mechanism of diffusion.

Jan 1, 1962

By V. B. Kurfman

The temperature, strain rate, and orientation deDendence of defbrnzation of single-crystal MgAg has been examined. The crystals exhibit a tendency to single glide and little or no hardening at 25°C for many orientations. A much higher hardening rate is observed when multiple glide occurs, such as can be initiated by surface defects. The tendency for easy glide becomes less dependent on surface preparation and orientation as T — 100°C and bars so tested often fail after one-dimensional necking-. At T > 200°C (transition temperature for single-crystal notch sensitivity and poly crystalline ductility) single glide diminishes and two-dirnensionul necking begins. The crystals do not strictly obey a critical resolved shear stress law, but show the influence of {loo) cracks in determining the slip mode. The results are correlated with the difficulty of sciperdzslocation intersection and semibrittle behavior of this compound in single-crystal and poly crystalline form. Comparisons are made with the slip selection mode observed in tungsten, with the reported observations of easy glide in bee metals. and with the mechanical behavior of poly crystalline MgAg. PREVIOUS work on tensile deformation of polycrys-talline MgAgl and bending deformation of single-crystal MgAg2 has shown that the compound is semi-brittle (i.e., notch and grain boundary brittle). If this semibrittleness is supposed to result from the difficulty of multiple glide (associated with the problems of superdislocation intersection) one might expect single crystals deformed in tension to show pronounced single glide and strong orientation dependence of hardening rate. These experiments were done to examine this supposition and to study the tensile deformation of a highly ordered system which may be considered bcc if the difference between the two kinds of atoms is ignored (actual structure: CsC1). EXPERIMENTAL Single-crystal ingots were grown by directional freezing as previously described.&apos; These ingots were sliced into a by a by 2 in, rectangular bars by electric discharge machining, then round tensile bars were conventionally machined to 1/8-in.-diam by 1-in.-long reduced section. The bars were typically tested without an anneal because of the problem of magnesium vapor loss and they were typically tested as mechanically polished. The analyses are within the same limits as those reported earlier; i.e., the average composition for each specimen is within 0.5 at. pct of stoichiometry, while the total range from end to end in a given specimen varies from 0.7 to 1.4 at, pct. There has been no indication in the results of any variation in slip or fracture mode attributable to the composition fluctuations. The slip systems were determined by two-surface analysis of the bars after testing to failure at room temperature. Single glide was so dominant that there was little difficulty in identification of the dominant slip system even though the tensile elongation to failure often approached 7 to 8 pct in room-tempera- ture tests. Elevated-temperature testing was done in a silicone oil bath and low-temperature testing was done in liquid Np or a dry-ice bath. All stress measurements are reported as engineering stress unless otherwise specified, and crosshead travel is used as the strain measurement. RESULTS The tendency toward single glide is best seen in the pictures, Figs. 1, 2, and 3, which depict deformation at fracture as a function of test temperature. While it is possible to find regions of secondary slip by careful microscopy, such regions are very small. The development of a ribbon-shaped configuration from an initially round section bar pulled at 100°C is typical, occurred by single glide, and illustrates the degree to which such glide continues. At temperatures =100°C the bars typically show elongation of 20 to 50 pct by predominently single glide. Despite the large elongation, fracture even at 150°C occurs in a brittle mode, Fig. 2, in the sense that it is an abrupt failure which shows no discernible necking in the second dimension of the bar&apos;s cross section (i.e., there is no appreciable action of any slip modes which would decrease the broad dimension of the cross section). Near 200°C the fracture mode changes slightly. Although most of the sample extension is by single glide, after the bar develops the characteristic ribbon shape it begins to neck in the second (i.e., broad) cross-sectional dimension. The bar becomes very thin in the "necked down" region, Fig. 3, and the reduction in area approaches 100 pct. Often there oc-

Jan 1, 1967

Jan 1, 1913

Jan 1, 1902

(There are 70 Student Chapters in the United States, 2 in Canada) University of Alabama-University, Alabama, Mining and Metallurgical Society, Win L Mason University of Alaska-College, Alaska, Mining Society of the University of Alaska, E H Beistline University of Arizona-Tucson, Arizona, Miners Society Birmingham-Southern College-Birmingham, Alabama, Pick and Hammer Club, Daniel D Arden University of British Columbia-Vancouver, British Columbia, G M Dawson Club, H C Gunning University of California-Berkeley, California, Mineral Technology Association, W H Somerton Carnegie Institute of Teehnology-Pittsburgh, Pennsylvania, The Metals Club, Gerhard Derge Case Institute of -Technology-Cleveland, Ohio, Case Metallurgical Engineering Society, Robert F Hehemann

Jan 1, 1956

ALL critical and strategic materials procurement functions have been transferred from the Defense Minerals Administration, General Service Administration, and the Economic Cooperation Administration and are now centered in a newly formed agency, the Defense Materials Procurement Agency. DWA will report directly to the Director of Defense Mobilization. Mr. Truman stated that he intended to appoint Jess Larson, administrator or General Services to head the new agency (see Trends P. 756). W. C. Schroeder has been named acting director of the Defense Minerals Administration replacing James Boyd. He has been named also to a newly created assistant director position of the Bureau of Mines serving under Mr. Boyd who is director. Schroeder was formerly head of&apos; the Synthetic Liquid Fuels Division of the Bureau of Mines.

Jan 9, 1951

By H. C. Fiedler

THE development of the cube-on-edge secondary re-crystallization texture in Si-Fe strip depends upon the ability of inclusions to restrain normal grain growth. This ability is determined by the number and size of inclusions, which, for a given composition, is controlled by the thermal history of the material during the prior processing.&apos; It has been shown2 that increasing the silicon content decreases the solubility of sulfur, and it is the purpose of this note to show the consequences of this decreased solubility for secondary recrystallization. Heats were made as previously described and cast into graphite molds.&apos; The compositions are shown in Table I. Slabs 1 in. thick were cut from the ingots and either hot-rolled from 1000°C in the as-cast condition or after one of the heat treatments described later. The processing to the final gage of 12 mils followed the previous procedure.&apos; To avoid cracking, the 5.2 pct Si alloy was cold-rolled at 150" to 200°C rather than at room temperature. The percent cube-on-edge texture developed by isothermal heat treatments was determined by dividing the maximum torque measured on disk sam-

Jan 1, 1968

By d&apos, C. McCoul, C. Antonio, R. Krohn

MOST of the commercial colored gold alloys for jewelry applications are based on the Au-Ag-Cu-Zn system. Although work has been done on the constitution of the Au-Ag-Cu system.&apos;-4 there are no reports in the literature on the effects of zinc additions in these alloys. We have metallographically determined the a =al + a2 transformation temperatures in 91/2- and 131/2-karat alloys in which varying amounts of zinc have been substituted for copper and silver. Samples were cast in the form of 1/2-in. round bars

Jan 1, 1970

By William E. Newman

The smelting of galena in the ore hearth has been practiced in many countries for several hundred years with varying success. In the United States, the water-jacketed American hearths and the Jumbb hearths have found some favor in the Missouri lead belt, where large quantities of non-argentiferous galena concentrates are produced. In form and method of operation the ore hearth has changed but little since its earliest conception. A detailed description of the furnace is lot needed here; it has been fully described in most works on the metallurgy of lead and in many technical papers. Since its field is restricted to non-argentiferous galena, containing over 68 per cent. of lead, its use is limited to a few districts; and, on account of certain disadvantages attending its operation, modern sintering and blast-furnace practice has nearly driven it out of the Missouri field. It is not generally known that the cost of producing pig lead is smaller by the hearth method than by sintering and blast-furnace smelting. Yet it is doubtful if any metallurgist knowing this to be true would recommend an American hearth installation—by reason of the disadvantages which will be briefly enumerated. The furnace has been limited to a length of from 4 to 5 ft., requiring for its operation two men working an 8-hr. shift as a maximum. The product per man is small; the work is hot and laborious; and the difficulty of completely removing the dust and fume has made it a notorious source of lead poisoning, Although suitable for operations on a small scale a large number of hearths would be required for a plant smelting 10,000 tons of 68 to 70 per cent. concentrates per month; and the number of semi-skilled laborers would be six times the number of hearths—a condition which is prohibitive. On account of the high percentage of dust and fume produced, a large flue and bag-house installation is required and, in the past, the handling and re-treatment of this dust and fume has -been a serious problem.

Jan 1, 1916

By Rudolph Gahl

RUDOLF GAIL, Miami, Ariz.-Since I wrote the paper on flotation which is in your hands, important developments have taken place, and, for this reason, I will try in a few words to bring it nearer up to date as far as the Inspiration plant is concerned. You, may have noticed that in the Inspiration concentrator, flotation is not solely relied upon for the recovery of the coarser material, but that flotation tailings are split into a sand and a slime product on drag classifiers. The sand product is treated on tables which thus supplement the work of the flotation machines. Extensive tests have shown, us that, if we wanted to, we could leave out these tables and substitute additional flotation machines, as they will make fully as good, if not a better recovery than tables on the deslimed feed, but the treatment would be more expensive, especially in view of the fact that oils are required which cost more than those which we are now using in our main flotation plant. We have, however, decided to apply flotation treatment to our table middlings. I would also like to add a few words regarding the treatment of oxidized copper ores. Although our experience shows that the addition of hydrogen sulphide and other soluble sulphides effects a very good recovery of copper carbonates with certain ores, we have not been able to prove that we could use it advantageously for the ore mixture which we are treating in our concentrator, and for this reason, have looked toward leaching for extracting the carbonate and silicate copper that we are losing now. Experiments in this direction are going on and are giving very encouraging results. It may interest you to hear that we intend to use limestone for the precipitation of the copper which goes into solution, as electrolytic precipitation seems to be out of the question on account of the diluteness of the resulting solutions, and precipitation by iron was rightly objected to on account of the unavoidable contamination of the water supply. We feel very hopeful about the success of our limestone precipitation which, if it holds what it seems to promise, will develop into a novel feature of copper metallurgy.

Jan 10, 1916

By F. B. Plummer

THE practice of introducing acid into oil wells to increase production of oil and gas has been in use since 1894, when it was first used in the Pennsylvania. oil fields30.? It is only since 1928 that it has been used to any extent in the Mid-Continent18. The process has proved successful in increasing production, at least temporarily, in depleted oil fields where the producing formation is highly calcareous and where water drive is not too pronounced. In the Zwolle field in Louisiana, where the producing horizon is a chalk, increases of 100 per cent have been recorded25. In north-central Texas, where the oil is produced from the Marble Falls limestone, equally pronounced increases have resulted3. The production also in some fields yielding oil from quartz sand cemented with calcite has been benefited. The evidence of actual increase in total recovery of oil, however, has been questioned by some engineers18. It has been pointed out that the results of the treatment of a well in a new district, where the process has never been tried out, can never be predicted with certainty, since other factors besides percentage of calcareous content: of the oil sand play a large part in determining the success of the method. Numerous articles have been published on acid treatment and on the effects of acid on limestone1-35, yet very little has been written con-cerning experimental work on the actual effect, of acid on capillary pores and larger oil-coated voids of oil sands. This is due partly to difficulties in duplicating field conditions in a laboratory and partly to the fact that the process has been carried out largely by contracting companies that have been unwilling to publish details of their results for fear of loss of business to competitors. The authors, using equipment developed to measure the radial permeability of oil-sand cores29, have developed a method of investigating the results of acid treatment which has enabled

Jan 1, 1935

By R. C. Mahon

Operators concerned with the destruction of their piping by acid mine waters will be interested in the method by which this problem was solved at the Cardiff mine of the Homer group. Rubber lined, or acid resisting metal pipes were found too expensive. Casting concrete lining in pipe would have required a minimum thickness of one inch, thus excessively reducing the pipe&apos;s diameter, as well as taking twenty four hours per length of pipe. The Naylor Pipe Co. of Chicago, having experimented with centrifugal lining of pipe with concrete, provided information which eventually solved the problem. An experimental plant was constructed as shown, and the following procedure developed : (1) Kerosene is used to remove the interior oil coating of new pipe. Closed with blank flanges, the pipe is revolved for eight minutes at varying speeds. Stopping and starting the motor achieves a good washing action. The kerosene is then drained off, and similar washing action with caustic soda removes any excess. Swabbing in done with burlap fastened to a 1/2-in. pipe. (2) The aggregate, made of one. part quick-setting cement and two

Jan 1, 1949