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By F. M. d’Heurle

Films of molybdenum have been prepared by sputtering onto oxidized silicon substrates. The resistivity. lattice parameter, orientation, and grain size were studied as a function of substrate temperature and substrate bias. Under normal sputtering conditions, the resistivity of the films was found to be quite high (600 x 10 ohm-crn). However, with the use of the negative substrate bias of 100 v and a substrate temperature of 350°C, films weve produced with a resistivity of ahout twice that of bulk molybdenum. The lattice parameters measured in a direction nornzal to the surface of the films weve found to be gveatev than the bulk value. This was interpreted as being at least partly due to the presence of compressive stresses. The effects of annealing in an Ar-H atmosphere were studied in terms of diffraction line width, lattice parameter, and resistivity. BECAUSE of its relatively low bulk resistivity (5.6 x 106 ohm-cm)' molybdenum is potentially interesting as a thin-film conductor in integrated circuits. An additional feature which makes it attractive for this purpose is its low coefficient of expansion (5.6 x KT6 per "c),' which is fairly well matched to that of silicon (3.2 x 10 per c). It is possible to deposit molybdenum films by evaporation but generally films produced in this manner have a high resistivity. In order to achieve resistivities close to bulk value, Holmwood and Glang found it necessary to operate in a vacuum of about 107 Torr and to maintain the substrates at 600 C during film deposition. Sputtered molybdenum films have been examined by Belser et a1.7 and, recently, by Glang et al.' This paper describes the results of an attempt to extend some of that work and examine the effects of annealing and getter sputtering on the physical and structural properties of the films produced. SPUTTERING APPARATUS AND PROCEDURE The apparatus used for most of the film sputtering work described here consisted of two "fingers" serving as anode and cathode, respectively, which were mounted within an 18-in.-diam glass chamber. A liquid nitrogen-trapped 6-in. diffusion-pump system was used to achieve a vacuum of about 1 x 107 Torr within the chamber prior to sputtering. The essential features of the equipment are shown in Fig. 1. Cathode and anode fingers are stainless-steel tubes isolated from the top and bottom plates by Teflon collars. In order to limit the discharge to the space between anode and cathode, each finger is surrounded by an aluminum hield, at ground potential, having an internal diameter 18 in. larger than the outside diameter of the finger. The cathode and anode fingers are 6 and 4 in. in diam, respectively. A 116-in.-thick sheet of molybdenum is brazed with a 10 pct Pd, 58 pct Ag, 32 pct Cu alloy to a copper disc which is mounted by means of screws and a large 0 ring onto the lower end of the cathode finger. The disc is cooled during sputtering by water circulation inside the finger. The use of several feet of plastic tubing for the water input and outputg reduces leakage to ground to less than 1 ma when the cathode potential is raised to 5 kv. The upper end of the anode finger is terminated by a brazed-on copper block. A variety of specimen holders can be easily mounted on the upper face of this block. Substrate heating or cooling is achieved by use of an appropriate unit attached to the lower face of the same block. Heating is achieved by means of cartridge-type heaters and cooling by copper coils fed with forming gas under pressure. The inner chamber of the specimen finger constitutes a small vacuum chamber of its own which is evacuated by an auxiliary mechanical pump in order to limit heating element oxidation and heat transfer by convection currents. An advantage of the finger arrangement is the absence of cooling and heating coils and wires within the main chamber. The stain less-steel shutter is useful to establish a discharge for cleaning the cathode at the beginning of each sputtering run. Water cooling of the shutter reduces heating and the out-gassing of impurities which might condense on the nearby substrates. Unless otherwise specified, the substrates used in these experiments were 1-in.-diam oxidized silicon wafe:s, 0.007 in. thick, having an oxide thickness of 6000A. The substrate holders were large copper discs onto the surface of which a number of molybdenum discs, 116 in. thick and 78 in. in diam, were brazed. The wafers were clamped to the molybdenum discs

Jan 1, 1967

By H. W. Meyer, H. N. Lander, F. D. Delve

A method of calculating the changes in blast-furnace performance brought about by burden and/or blast modifications is presented. Essentially the method consists of three simultaneous equutions derived from materials and heat balances. These equations can be used not only to evaluate quantitatively the effect of changes in process operating variables on furnace performance, but also to provide a useful means of evaluating changes in process variables which cannot be measured directly. It has been customary for a number of years to use simple heat and materials balances as a basis for assessing blast-furnace practice. A good example of the method used to set up these balances is that proposed by Joseph and Neustatter.1 This approach to process assessment has limited utility, however, in that it cannot be used to predict the furnace coke rate or production under new operating conditions. Using an approach based on multiple correlation of blast-furnace variables, R V. Flint2 has developed an equation which may be used to predict the change in coke rate that will result from some changes in operating conditions with a reasonable degree of accuracy. Although this equation has useful applications in production planning, it cannot be used to study the relationships between the operating variables and the fundamental thermochemi-cal characteristics of the process. In attempting to analyze the blast-furnace process quantitatively, the idea of dividing the furnace into zones3 may at first appear attractive. In our present state of knowledge, however, it is not possible to define with any accuracy the physical limits of such zones in relationship to their temperatures or to the reactions which may occur in them. Although its application is restricted, the zonal approach to blast-furnace analysis is useful in some instances. For example, the change in the calculated flame temperature in the "combustion zone" caused by injecting steam constitutes information which is helpful in understanding why the addition of steam to the blast is best accompanied by an increase in blast temperature. The zonal approach cannot, at the present time, be used to establish the relationships between process variables and process performance if the whole process rather than part of it is to be considered. One of the earliest approaches to the problem of relating blast-furnace operating variables to pro- duction and coke rate was that developed by Marshall.4 Essentially Marshall's work showed that it was possible to estimate the performance of a furnace by solving three simultaneous equations which consisted of rudimentary carbon and heat balances plus a further equation relating the production, wind rate, and the carbon burned at the tuyeres. Although these equations did not include all of the chemical and thermal variables of the process, their derivation and application seems to be the earliest attempt which achieved any success in relating prior furnace operating data to the calculation of furnace performance under different blast conditions. Work carried out in Germany has been directed mainly towards prediction of coke rates using material and thermal balances rather than statistical methods. wesemann5 used prior furnace operating data as part of the basis for predicting the change in coke rate accompanying a change in burden composition. This author employed a method of successive approximations to estimate the secondary changes in slag volume and stone rate brought about by the change in coke rate. The most recent analysis, which seems to have been developed concurrently with the thermochemical model presented in this paper, has been described by Georgen.6 This author has succeeded in improving on Wesemann's approach by expressing the total changes in the slag volume and stone rate in terms of the change in coke rate itself. This is accomplished in a manner similar to that used in the thermochemical model described in this paper. Although Georgen makes use of a calculated furnace heat loss, he does not relate the heat loss per unit of hot metal to the production rate as is done in the present work. Georgen's approach may be used to calculate the changes in materials requirements accompanying changes in furnace operation; it cannot be used to assess the resulting changes in production. The fact that blast-furnace behavior can be interpreted by consideration of the heat requirements of the process was demonstrated by Dancy, Sadler, and Lander.7 In the analysis of blast-furnace operation with oxygen and steam injection these authors showed that it was possible to account for the changes in production and coke rate

Jan 1, 1962

By Joe O. Ledbetter

INTRODUCTION Health physics as a profession really got a significant start during the Manhattan Project of World War 11. The Health Physics Society has recently published its 25th anniversary issue of the journal (June 1980). There was concern over radiation exposures during and after uranium production, especially about radium and its daughter products [Jackson 19401 and, as evidenced by the frequency of articles in the literature, there still is. The reason for this concern was expressed by Harley as "Workers engaged in the mining and pro- cessing of radium-bearing materials are exposed to dusts of the parent, to radon, and to the radon daughter products. In- haled radioactive particulates may be retained in the lung or redistributed to other organs of the body. Relatively minute de- posits of radioactive substances, particularly alpha emitters, have been clearly shown to be the etiological factor in a variety of injuries to industrial and re- search workers. " [Harley 1953] Emphasis in measurements has been placed on radium in water and radon in air, since these are the principal mobilized phases; however, it should be kept in mind that radium-containing particles do become suspended in air as aerosols and radon absorbs in liquids. Much of the uranium mining and production is being carried out aboveground. The principal difference between underground and surface (pit or leach) mining of uranium is the reversal in the relative importance of roles for the types of radiation dose. For aboveground the major radiation exposure is external gamma ray, whereas for underground it is internal alpha; for aboveground, the whole body penetrating is of greater importance than the lung alpha dose. AS a result of the politics involved and the law- suits for any and all diseases as being occupationally- caused, today , more than ever before, the successful performance of the activities connected with uranium production--before-, during-, and after-the-fact-- must include the provision of first class radiation protection. Such protection can be achieved by good measurements, thorough risk evaluations, and adequate controls. Meeting the ALARA (As Low As Reasonably Achievable) philosophy necessarily entails the determination of what is reasonable exposure. The necessary and sufficient elements of radiation safety under the ALARA dictum require a hard look at the dose versus effects data. There are times when the health physicist needs to make decisions of judgement rather than compliance with a well-defined regulation value. In order to facilitate such decisions, the real world must be separated from opinions that are merely artifacts of statistical variation and from the unprovable "what ifs" that are slanted to question the morality of any non-Luddite. UNITS VOCABULARY FOR DOSIMETRY There have been many radiation quantifying and dosimetric units introduced in the past. Fortunately, most of them did not catch on enough to become required knowledge for reading the health physics literature. The unit definitions necessary for our purposes here are the following: -curie (Ci)--unit of radioactivity equal to 3.7 x 10 10 disintegrations per second Webster&apos;s 19711 or the quantity of radionuclide that undergoes 3.7 x 10 nuclear transformations per second. Environmental levels of radioactivity are usually measured in picocuries (10-l2 Ci) per cubic meter for air and in picocuries per liter (pCi/~) for water and sometimes for air. .roentgen (R)--exposure dose of x or gamma rays that gives 1 esu of charge (either sign) to 1 cc of dry air @ STP. The roentgen is equivalent to an energy absorption of 86.7 ergs/g of air [Gloyna and Ledbetter 19691. .rad--radiation absorbed dose of 100 ergs per gram of absorber. The SI unit for absorbed radiation dose is the Gray; 1 Gy = 100 rads. orem--radiation absorbed dose of 1 rad times the quality factor (QF) for that radiation. The QF is 1 for x rays, gamma rays, beta rays, and posi- trons. For heavy ionizing particulate radiation, QF is a function of the amount of energy trans- ferred per unit length of travel, i.e. , the linear energy transfer (LET); the values of QF:LET in keV/um are as follows: 1:<3.5; 1-2:3.5-7; 2-5:7-23; 5-10:23-53; and 10-20:53-175 [Morgan and Turner 19 671 . For radiobiology, relative biological effectiveness (RBE) is recommended for use instead of the quality factor above that is for radiation protection: the RBE is the ratio of the dose of 200 kVp x rays to the dose of radia- tion in question (both in rads) to cause the same

Jan 1, 1980

President MRS. ROBERT HURSH River Road, Silvermine Norwalk, Conn. First Vice-President MRS. THORNE E. LLOYD 14 Green Hill Road Morristown, N. J. Second Vice-President AIRS. JOHN PAUL DYER Short Hills New Jersey Third Vice-President MRS. FELIX E. WORMSER Acorn Lane Larchmont, N. Y. Fourth Vice-President MRS. JOHN J. LINCOLN Elkhorn, McDowell Co. West Virginia

Jan 1, 1942

By Charles H. Jacoby

Solution-mined salt cavities are being used for storage of liquid petroleum gas, natural gas, and other hydrocarbons; waste disposal or storage; storage of radioactive wastes; and as a surge vessel for air compressed by an electric utility during off-peak hours. Examples of each use are given. Other contemplated uses of salt cavities are noted.

Jan 1, 1973

By W. S. Row

This mine is operated at 4000 to 4500 tons daily through a single shaft, with one rock hoist and one service hoist. Latest shaft construction is concrete with wooden dividers. Economics of drifters and air-leg drills are compared, as well as costs of shrinkage and sub-level stoping. Economy of large haulage equipment and underground crushing is shown.

Jan 3, 1953

By R. C. Wilmoth, R. D. Hill, R. B. Scott

A cost breakdown is given for reclamation and mine drainage abatement conducted by the Federal Water Quality Administration&apos;s demonstration project near Elkins, W. Va. Costs for construction of control measures have been developed and include backfilling strip mines, sealing subsidence areas, reconstructing stream channels, and installing mine seals to prevent the entrance of water and air.

Jan 1, 1973

By F. N. Ward, E. H. Bailey

Camp and sample-site methods useful for determining about 0.5 to 16 ppm of mercury in soils and rocks have been devised to complement the analytical methods already widely used in geochemical prospecting. In the camp-site procedure the sample solution is obtained by digesting the finely powdered sample with hot nine-molar sulfuric acid and bromine, the latter generated in place. The solution is buffered at a pH of 4 and the mercury is extracted into a relatively small volume of an organic solvent. Estimations are made by comparing the color of the mercuric dithizonate extracted from the sample with that extracted from a standard. In the sample-site method the mercury is volatilized as the iodide and the latter is dissolved in a buffer solution from which the mercury dithizonate is extracted as in the camp-site method. The estimation is made by a similar comparison with standards or by comparing the color of the mercuric dithizonate with artificial standards prepared from Orange II, an azo dye. Except for the establishment of standards, the time required by an experienced analyst seldom exceeds 10 min for a camp-site determination and 5 min for a sample-site determination. Camp-site determinations are useful for commodity studies and intensive exploration programs; sample-site determinations are applicable to extensive and reconnaissance-type geochemical prospecting programs. The results obtained on samples taken along traverses above known mercury ore deposits in the California Coast Range and western Nevada demonstrate the usefulness of both methods in geochemical prospecting. The increasing use of the mercury content of soils, rocks, plants, or water in geochemical prospecting emphasizes the need for analytical methods which are sensitive and at the same time require a minimum of readily available equipment. Sensitive methods based on the absorption of ultraviolet light by mercury vapor are common in the literature31 12. Although none of these methods have been used to analyze the large number of samples required in geochemical prospecting, they could be extremely useful except for the expensive instrumentation usually required to make the methods quantitative Also, such methods are perhaps too sensitive for field use, especially around areas of possible contamination. Other methods involve the distillation of mercury from a relatively large sample and subsequent collection of the vapors in nitric acid6. The mercury is then estimated by titration with a suitable reagent such as thiocyanate. These methods are not trace methods because the actual amount of mercury measured is often as great as 50 to 100 milligrams. Also, such methods are unsuitable for geochemical prospecting because of the amount of equipment necessary and the time required. Still other methods involve colorimetry, and the sensitive reaction between dithizone and mercury (11).. is the basis for a number of reports on the determination of mercury in biological materials 5,7. Moreover, by the judicious use of solvent extraction and suitable complexing agents, the dithiaone method can be made almost specific for mercury. However, none of the dithizone methods have yet been applied to the determination of mercury in soils and rocks. In most colorimetric methods he sample solution

Jan 1, 1961

By M. B. Bever, J. E. Reynolds

IN several alloys of iron, copper, and lithium as well as in some pure metals, martensite formed on cooling reverts to the parent phase upon heating to a temperature below the equilibrium temperature at which the parent phase becomes stable.&apos; These martensitic transformations, therefore, are thermally reversible, although appreciable hysteresis may be involved. The martensitic reaction has long been

Jan 1, 1953

By Herbert A. Stein, John B. Murdock

Perlite is a natural volcanic glass which expands into an insulation material upon the application of heat. This paper discusses the operating characteristics of eight different types of furnaces for the expansion of perlite. It also includes a section on the theory of perlite expansion which serves as the basis for the authors&apos; analysis of the furnaces.

Jan 1, 1950

By Paul H. Lu

Methods and results of measuring three basic parameters for ground stability control, ground pressure, strata movement, and geomechanical properties of mine rock are presented in this paper. It is found that these parameters can be measured in situ by simple and practical techniques with nonsophisticated and inexpensive instruments. Specifically, a drillhole dilation technique employing a cylindrical hydraulic borehole pressure cell (CPC) was used to determine the modulus of rigidity. Premining ground pressures were determined by pressure convergence tests with a combination of one CPC and two pre-encapsulated flat hydraulic borehole pressure cells (BPC) installed in a single drillhole. Abutment pressures and pillar loading were monitored with BPC&apos;s. Differential strata movements and bed separations were measured with self-recording 10-anchor-point extensometers. Roof-to-floor convergence was measured with self-recording convergence meters. Some applications of these in-situ-determined parameters to mine design and ground stability control are also discussed.

Jan 1, 1984

By D. J. DeLazaro, W. Rostoker, R. E. Riley, M. Hansen

At very low concentrations, carbon dissolves interstitially in molybdenum resulting in a linear expansion of lattice parameter with increase of carbon in solid solution. Geometrical consideration of the relative size of carbon atom to size of interstice approximately predicts the observed volume expansion. THE element carbon, occurring in molybdenum, either as an unavoidable impurity, or purposely added, markedly affects the mechanical properties of molybdenum. Several investigators1-" have noted the occurrence of molybdenum carbide at the grain boundaries of cast molybdenum, and Fischer and Rengstorff&apos; have shown that this intergranular constituent can induce intergranular brittleness. The appreciable change, with temperature, of the solid solubility of carbon in molybdenum, found by Few and Manning," suggests other important effects upon mechanical properties. Finally the relative atom diameters of carbon and molybdenum (the ratio of atom diameters is 0.59) are indicative, by analogy with iron (ratio of carbon atom diameter to iron atom diameter is 0.65), of a possible interstitial solid solution. If carbon dissolves intersti-tially in molybdenum, anelastic effects and age-hardening effects, similar to those observed in other body-centered cubic metals, could be expected. However, from the work of Sykes, Van Horn, and Tucker," it might be inferred that carbon forms only a substitutional solid solution with molybdenum. These considerations made it desirable to study the effect of carbon on the lattice parameter of molybdenum in greater detail than heretofore. All heat treating was done in a high temperature furnace7 built specifically for heat treatment of molybdenum. The temperatures and times of heat treatment were determined from the a solubility limit for the Mo-C system." These heat treatments were carried out in argon which was purified with respect to N, and H.!0." Purification of the argon was accomplished by passing the argon over hot (750°C) titanium and then through a magnesium perchlorate drying tower. As many as six samples were run concurrently and quenched at different times without interrupting the furnace cycle. Both the purity of the furnace atmosphere and ability to quench samples from any temperature up to 4000 °F were of prime importance in the successful heat treatment of samples for the lattice parameter investigation. Carbon Analysis The Leco Combustion apparatus was used for carbon analysis. This apparatus is capable of an accuracy of & 0.003 pct for a 1 g sample in the range below 0.10 pct. However, it is felt the degree of accuracy is somewhat better than this limit in view of the consistency evident by cross checking a number of determinations. The Battelle Analytical Laboratory consistently reported check results to within k 0.001 pct C. X-ray Measurements The molybdenum wire specimens (20 mils) were carefully filed down to about 12 mils and then etched with nitric acid to 8 mils. Carbon analyses were made on specimens before reduction in size; however, since there was no evidence of surface carburization, it is probable that the carbon was uniformly distributed throughout the sample. The resultant specimens were strain free and small enough to minimize the error in the lattice parameter determinations due to X-ray absorption. Diffraction patterns were obtained with a Debye-Scherrer powder camera 114.59 mm in diam utilizing the Straumanis type asymmetrical film mounting. Nickel-filtered copper. Ka radiation and zirconium-filtered molybdenum Ka radiation were used. Line positions on the film were measured with a traveling microscope equipped with a vernier scale permitting measurement to 0.001 cm. The average of five readings was used to determine the position of each line. The lattice parameter for each specimen was determined from the data by the extrapolation method of Bradley and Jay, Y.e., the intercept at 90" of the straight line obtained by plotting the apparent lat-

Jan 1, 1953

By F. W. Jessen, R. W. Durie

The development in the laboratory of mall salt cavities illustrated that the rate at which salt dissolved was affected by the rate at which fresh water was injected into the cavity. Experiments carried out with small salt cores indicated, however, that the rate of salt removal with forced convection was not significantly different from that with natural convection, provided the flow was in the laminar range. The rate of salt removal was apparently controlled by the water salinity, which was indirectly determined by the rate at which fresh water was injected. With turbulent flow at the salt surface, the rate of salt removal could be increased several-fold with the same salinity in the cavity. A quantitative evaluation of the rate of salt removal under natural convection was attempted by using techniques developed for the analogous heat convection system. The values of the rate of salt removal obtained experimentally were considerably greater than the calculated values due to surface irregularities. To determine the effect of these irregularities, the rate of salt removal was found for a smooth surface by experimentally determining the rate of salt removal as an irregular surface developed and then extrapolating this trend back to initial time. Excellent agreement between the experimental and calculated values then were obtained. INTRODUCTION Underground cavities leached from massive salt formations have been used extensively for many years for storing LPG products. The development techniques for storing methane gases in the liquid state at a low temperature leads to speculation that underground salt cavities of controlled geometry may be quite important in this field. In any case, the increasing number of salt cavities used for storage indicates an impending need for a better knowledge of the washing process to efficiently develop maximum storage volumes within specified regions. It is the purpose of this paper to discuss some aspects of -the mechanism of the dissolution of salt in the formation of cavities of controlled geometry. Although no attempt is made to resolve the problems that may be associated with the storage of methane in the liquid state in salt formations, the fact that salt cavities can be formed at reasonable cost would appear to justify investigation in this direction. Further, underground cavities have the advantage of allowing storage at higher pressures (and hence higher temperatures) than surface installations. Although the thermal conductivity of salt is somewhat higher than frozen earths, 0.017 cal/(sec) (cm)(c) for salt at 32F vs 0.005 cal/(sec) (cm) () for ice at this temperature, this disadvantage is offset by the higher storage temperature in underground cavities. For example, at atmospheric pressure, the temperature of liquid methane would be —258F. In a storage cavity at 2,000 ft, the pressure would be approximately 1,000 psia, which would allow a storage temperature of -9OF. The formation temperature would be roughly 110F at this depth, hence the total temperature differential would be 200F. Under surface storage conditions the corresponding temperature difference would be some 333 F (75 F + 258 F). The results of this difference can be compared more readily by substituting the appropriate values of thermal conductivity, temperature difference, heat capacity and density into the solution of the diffusion equation for the unsteady linear conduction of heat. For the underground salt storage, the heat flux is 15cal/(sec) (sq cm), where t is the time in seconds from the initiation of the cooling. For the surface system, and using the thermal properties of ice at the average temperature, the corresponding figure is 21cal/(sec) (sq cm). Hence, the heat losses through ice under surface conditions would be some 30 per cent higher than the underground salt storage. This ratio would vary, considerablv. Of course, for other conditions, but it indicates that an advantage over surface facilities may be obtained by storage in underground salt cavities.

Jan 1, 1965

By Donald A. Corrigan, John Chipman

It is shown that the heat of solution of nitrogen in liquid-iron alloys is Proportional to the interaction coefficient. This proportionality forms the basis for a method of predicting nilrogen solubility at any temperature when the interaction coefficient is knoun at 1600°C ov when the solubility is known at some one temperature. A method for predicting the solubility of nitrogen in liquid steels, including alloy steels, was proposed some years ago by Langenberg.&apos; Since the data available at that time were restricted to temperatures of about 1600°C, his predictions were similarly restricted. More recently, Nelssonz devised an approximate method for estimating nitrogen solubilities at higher temperatures. It is the purpose of the present paper to present a method by which the solubility of nitrogen at any temperature within the steelmaking range may be predicted from the known interaction coefficients at 1600°C. Nitrogen in iron and in all of the alloys to be considered here is known to obey Sieverts&apos; Law; hence the activity of nitrogen in an alloy of fixed composition is proportional to its concentration, here expressed in weight percent. The activity of nitrogen is defined as equal to its weight percent in the binary Fe-N solution at any temperature. Its activity coefficient in any alloy is the comparison being made at equal values of T and PN2. In all alloys the activity coefficient changes with composition, log fN being a linear function of the percent of alloying element at low concentrations. In the following calculations the alloy compositions are restricted to those in which this linear relation is exhibited. For most systems this is a fairly wide range, for example up to 5 pct V and to 10 pct Cr or Ni. For this composition range. complex alloy is the same as that in the Fe-N-j ternary solution. Langenberg&apos;s method of prediction was based on Eq. [3], the values of log fN for various additions being taken from a graph. Instead of using the simple addition indicated in Eq. [3], he used a more complex method suggested for Fe-S-j alloys by Morris and Buehl.3 For the composition ranges in which Eq. [2] is valid the two methods are equivalent. Nelson extended the prediction to other temperatures on the assumption that logfN is inversely proportional to absolute temperature. It may be shown that inverse proportionality would result if the partial molal entropy of nitrogen were unaffected by addition of the alloy element, an assumption which Nelson designated as a "regular" solution. It has been shown recently by the authors4 that this assumption is not a good approximation. The heat of solution of nitrogen (N2) in an alloy may be obtained if the solubility is known as a function of temperature. Measurements of this nature have been reported recently by Beer5 for Fe-Mn alloys, by Nelsson2 for Fe-C, by El Tayeb and parlee6 for Fe-V, and by Pehlke and Elliott7 for many alloys embracing a wide range of compositions. In connection with the work of the last named authors it is noted that their Fig. 22 gives the heat effect per half mole rather than per mole of N2. In using their data we have shifted some of their values slightly by using the best straight line in preference to their curve. Their data, supplemented by others from the literature, are summarized in Table I. In Fig. 1 the heat of solution of nitrogen is shown as a function of composition for the several alloy systems. The difference between the heat effect in the alloy. AH; and that in pure

Jan 1, 1965

By M. D. Banus, M. B. Bever, A. K. Jena

Measurements of the heat effects on addition of various solid phases of InSb to a solution calorimeter have confirmed the existence of a new high-pressure plzase InSbQII), which was jormed at 37 kbar and 623°K. The heats of formation of InSbQ), InSbfl), and InSb(111) have been measured and the heats of transjormation of InSb(1) to InSb(1l) and InSb(Iii) and of &apos;InSb(ll) to InSb(iiI) at atmospheric pressure and 78°K have been determined independently. Other thermodynamic properties of these phases, the phase boundary InSb(i)/InSb(ll), and the relative positions of the triple points are calculated. The pressure-Dolume term is shown to be more critical than the internal energy difference in making the phase InSbQ) less stable than InSb(II) at high pressures. Observations on partially transformed specimens suggest that the transformation of&apos; metastable InSb (III) takes place in the two steps InSb(lll) — InSbQI) and InSbQI) — InSb(l). The compound InSb can exist as several phases depending on the temperature and pressure. The phase InSb(I), which is a semiconductor having the zinc-blende structure, transforms into the phase InSb(11) at a pressure of about 23 kbar and room temperature.&apos;-3 The phase InSb(II) has the 6 tin structure,4-6 is metallic, and becomes a superconductor below 2.lok7 An orthorhombic phase of InSb has been reported to occur above a pressure of approximately 30 kbar at room temperature.&apos; This phase is also a superconductor below about 3.4k9 The phase InSb(I1) is retained at atmospheric pressure if it is quenched to 78°K under pressure,6,7 but tends to transform at higher temperatures and does so explosively above approximately 210ok,7 A value of the heat of transformation of InSb(1) to InSb(II) at 210°K and atmospheric pressure has been reported.&apos; A concurrent publication&apos;0 reports evidence for a new solid phase InSb(III), which was formed by annealing InSb above 58 1°K at 37 kbar, above 560°K at 52 kbar, and above 473°K at 65 kbar. Specimens of InSb(II1) had a superconducting transition temperature of 4.lo ± 0.1oK. X-ray diffraction patterns also indicated the presence of a new phase. In this communication, thermodynamic properties of the phases InSb(I), InSb(II), and InSb(II1) are reported and discussed. The phase boundary InSb(I)/InSb(II) and the relative positions of the triple points are calculated. 1) EXPERIMENTAL 1.1) Preparation of Specimens. Specimens of the high-pressure phases of InSb were prepared in a belt-type high-pressure chamber by a tichnique described in detail elsewhere.&apos;&apos; Charges of 0.6 to 0.8 g of Cominco semiconductor grade InSb were used. The temperatures were measured with a chromel-alumel thermocouple, the hot junction of which was within 0.5 mm of the specimen. The specimens were heated under a pressure of 37 kbar for 1 hr at 723°K (which is well above the liquidus) and quenched to room temperature. One set was annealed at 523°K and another set at 623°K for 20 to 24 hr. These annealing temperatures were chosen because 523°K was below and 623°K was above the temperature of the transformation of InSb(II) to InSb(1Tl) at 37 kbar.10 The specimens were then cooled to 125°K by passing liquid nitrogen through the jacket of the belt die before the

Jan 1, 1968

By R. O. Williams

Measurements have been made of the internal energy of deformation in a Cu-A1 alloy and a Cu-Zn alloy as the deference between the work and the released heat. The method required the rapid compression of samples to reduce thermal interactions. The rate of energy storage is low initially but then becomes almost linear with strain. Both alloys stored about 60 cal per mole at a strain of 0.4 in the recrystallized condition. The fractional rate of storage increases at low strains reaching about 0.25 at a strain of 0.15 and then decreases slowly with increasing strains. As do pure metals, these alloys release appreciable energy immediately following deformation; in contrast with pure metals, however, the release continued for extended periods of time. This energy release is somewhat sensitive to the amount of deformation, the deformation temperature, and prior thermal & eatment. It is believed that this release is a composite of that observed in pure metals which has been attributed to dislocations and that due to the motion of vacancies which produces increased short-range order. IT is expected that changes brought about by deformation of a pure metal can be understood in terms of the three defects—dislocations, vacancies, and interstitials—along with the interactions possible between these defects. Frequently stacking faults are created and must also be considered. 1t is not immediately clear whether or not the stress fields which are created should be regarded as independent of dislocations. For alloys there is the important additional effect of atomic configuration, for example short-range order, which must also be considered and will, in general, interact with each of the above defects. While it is true that a complete understanding of pure metals is not yet possible, it would seem very valuable to establish the similarities and differences between pure metals and alloys. Such knowledge could contribute to the understanding of both. A study of the changes in internal energy resulting from deformation of two alloys is reported here. Although some information has been available for alloys almost as long as for pure metals, the volume of work has been substantially less. Sato&apos; and Quinney and Taylor&apos; were responsible for the earlier work, both using brass and annealing calorimetry. tizhnova&apos; studied stored energy in Cu-Ni alloys by a method somewhat similar to the one reported here. Bever and his co-workers have made extensive studies of Au-Ag alloys4&apos;5 and more recently CU-AU&apos;U&apos; using solution calorimetry. Clarebrough et a1.&apos; have recently studied brass using annealing calorimetry. EXPERIMENTAL METHOD The present results were obtained by the rapid, adiabatic compression of a sample about 1/4 in, diam by 1/2 in. long between two tungsten carbide hammers. A vacuum provided thermal isolation and oil provided effective lubrication between the sample and hammers. The increase in internal energy is the difference between the mechanical energy and the heat liberated within the sample. The mechanical energy was determined from the velocity of the hammers (calculated from the height through which the hammers traveled) and was essentially constant for each deformation cycle. The heat was determined from the temperature increase of the sample which was measured by an embedded thermocouple. Specific heat data were calculated from Neumann&apos;s rule using tabulated data for pure metals.9 Since the fraction of the energy which is stored is large compared to that for pure metals, specific heat data of high accuracy are not required. Successive increments of deformation were carried out by repeating the procedure, the limit being determined mostly by the decreasing accuracy caused by the increasing corrections and the decreasing storage of energy. About five cycles were used to give a true strain of about 0.5 while the time interval between cycles was 1 to 2hr.

Jan 1, 1963

By William Paxton Hewitt

In the Santa Eulalia mining district, Chihuahua, Mexico, the main mineral zone occurs in a gently warped dome with simple associated structures and contains orebodies distributed through a vertical range of over 900 m. The stratigraphy of 1945 m of geologic column is described and an abrupt shrinkage is documented in the volume of limestones immediately associated with large orebodies. Termed collapse, this shrinkage occurred during the course of mineralization. Contacts of limestone with igneous sills, and 366 m of fossiliferous limestone beds, particularly the main fossil bed, have been important localizers of ore-bodies. Up-dip gravitational controls may have been important. Fractures have exerted only local controls and over short distances. Thrust zones have displaced diabase sills and in turn have been intruded by upper members of a group of rhyolite porphyry sills. Mineralizers were related to the rhyolite porphyry, and ore has been introduced to the limestone where certain sills lie between the displaced segments of diabase and have been cut by north-south fissures. Speculations are raised that fields of unreleased strain may have influenced orebody locations; the district&apos;s zoning pattern may be a reflection of the filtering effects of large volumes of limestone; and that metal-rich brines mobilized by or incorporated within the invading porphyry might be the source of the mineralizers. PRODUCTION AND LOCATION The Santa Eulalia district has a production record approaching or exceeding 35 million tons of silver-lead-zinc ore from replacement bodies in limestone. In operation since the first years of the 17001s, production has been confined to two intensely mineralized areas separated by 2 km of barren limestone, the West Camp and the East Camp. Probably 50% has been mined since 1908, with over 90% from the West Camp. The West Camp, exploited through a vertical depth of 1945 m and now approaching exhaustion, is the subject of this paper. The district lies in the northern part of the Santa Eulalia Mountains in central Chihuahua in northern Mexico, 400 km south of El Paso, Texas, and 22 km southeast of Chihuahua City. Dominating the northern part of the range is the Cerro de Santa Eulalia, a broad rolling upland which contains the district&apos;s West and East Camps. The West Camp, on the west side of the range, centers around the village of Santo Domingo, which is 2 km northeast of the Real de Santa Eulalia (Fig. 1). REGIONAL GEOLOGY Thick-bedded middle Cretaceous limestones, probably Aurora, form the great bulk of the Cerro de Santa Eulalia. These beds, warped into a gentle dome, are severed on the west by a faultline scarp and truncated on the north by the Dolores Pass, a wind gap that

Jan 1, 1969

By Strathmore R. B. Cooke, Thomas E. Ban

MUCH experimental work has been performed on the mechanism of agglomeration and pelletizing of moist ore and concentrates and on the process of firing agglomerates, but except for the work of Tigerschiöld and Ilmoni1 much of the published information is empirical, and the literature contains no information concerning the structure of fired pellets. Results of a preliminary study of the microstructures occurring in pellets produced both in the laboratory and on a pilot-plant scale are presented in this paper. Most of the results were obtained from pellets prepared from Mesabi magnetic taconite, but through the courtesy of the staffs of the Minnesota Mines Experiment Station and the Bethlehem Steel Co., fired pellets produced from limonite and hematite ores and from Lebanon magnetite have also been examined. The work has been restricted almost entirely to pellets produced without additives, the exceptions being those in which coal was. added to the filter cake before rolling. Schwartz has described the microstructures occurring in ore sinters produced under reducing conditions.2 Many of the structures and constituents he describes are common to fired pellets, but the constituents normally occur in markedly different proportions. His statement that "in all satisfactory sinter the amount of hematite is small, perhaps not over 2 or 3 per cent" is inapplicable to pellets produced by pilot plant operation or by any process in which air is not deliberately excluded. Pilot plant pellets contain over 90 pct by weight of hematite, and those produced in the smaller furnaces of the Minnesota Mines Experiment Station contain more than 80 pct of that constituent. Preparation of Specimens It is difficult to examine unfired pellets microscopically because of their insufficient coherency to withstand sectioning and polishing. Fired pellets sometimes lack coherency and frequently contain holes which are troublesome during polishing. Impregnation of both air-dried and fired pellets is readily accomplished by the use of methyl methacrylate monomer.3 The dry pellets are covered in a test tube with excess monomer, to which a small amount of accelerator has been added. When the test tube is placed in a cooling bath and evacuated with an aspirator, most of the entrapped air is removed, and disruption of weak pellets by boiling of the monomer is reduced to a minimum. Polymerization is then effected by immersion of the test tube in a water-bath at about 45°C, this temperature being held for 4 or 5 days. The test tube may then be broken away from the solidified mass and the pellets sectioned by a carborundum wheel or a diamond saw. Where time is important, impregnation is carried out at a higher temperature by Meyer&apos;s method.4 Air-dried pellets must be impregnated with especial care; otherwise swelling occurs and the solids are displaced. It is more important to be certain that the monomer forms a reasonably complete network throughout the specimen than that all entrained air is removed, and for this reason the vacuum technique may be omitted. Impregnated agglomerated products and pellets are extremely coherent, section well, and may be polished either by hand or by machine. Hand polishing is not satisfactory for the examination of conditions existing at the boundaries of grains, and for this machine polishing must be used. The Graton-Vanderwilt machine gives excellent results, provided that pressure on the specimen is considerably in excess of that recommended by the manufacturer. Mineralogy of Fired Pellets Only two opaque iron minerals, magnetite and hematite, have been recognized in pellets. The complete identity of these artificial minerals with their corresponding natural counterparts is shown by their mineralographic characteristics and their X-ray structures. Wüstite has not been found. Slag is the most common transparent constituent of fired pellets. Occasionally conditions have been appropriate for the crystallization of fayalite from the slag, and at other times another crystalline sil-

Jan 1, 1952

By J. E. Lawver, B. J. Clingan, R. E. Snow

Response surface methodology is a well-known and powerful technique for determining optimum conditions in flotation systems. One disadvantage is the onerous task of the numerical calculations and curve plotting. This paper describes a system in which the investigator simply selects the range of several flotation variables after which the design of the experiment, data analysis, generation of response surface equations, and response surface plots are automatically carried out using a digital computer and a computer-driven curve plotter. Several typical response surfaces of important variables in phosphate flotation are presented as examples.

Jan 1, 1980

By Earl L. H. Sackett

Barite, although not a glamour mineral and probably little known to many of those in the mining business, is produced in the US. in very respectable quantities and is an important factor in the mineral economy of this country. The scope of the various uses of this mineral is perhaps one of the most misunderstood things about it, for it is surprising how many of those with a casual knowledge of the subject speak of its primary utilization in terms of paint pigments and barium chemicals. The life blood of barite utilization, however, is the petroleum industry by virtue of its dependence on this high specific gravity, inert mineral as the weighting material in its drilling fluids. From 80 to 85% of barite usage in the U. S. is accounted for in this manner-in fact, its role in oil well drilling is the only excuse for some of the large-scale barite production facilities which have been developed. Other uses are important and widely varied, but comparatively they are of small scale. They include fine crushed barite of low iron content as a component in glass manufacture, barite as a source material for manufacture of barium chemicals, finely divided barite as a component of some rubbers and ground, bleached barite in pigments. The formerly substantial use of barite in lithopone, however, has declined markedly because of replacement of lithopone by titanium pigments

Jan 5, 1962