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By James K. Stanley

Preferred orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.' In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurnical -literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanicai properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important information, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational understanding of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required—it is only necessary to punch or machine a I-in. disk of the sheet material and insert it into the testing device.

Jan 1, 1944

By James K. Stanley

Preferred orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.' In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurnical -literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanicai properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important information, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational understanding of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required—it is only necessary to punch or machine a I-in. disk of the sheet material and insert it into the testing device.

Jan 1, 1944

By Pedro Bolsaitis, Paul M. Sullivan

The activities of zinc in liquid Zn-A1 alloys in the temperature range of 1000' to 1160°K were determined by means of the isopiestic technique. The results are in reasonable agreement with the previous values determined by the radioactive tracer dew point method. Slightly negative excess entropies of mixing were found. The measured activities suggest that the a function for these alloys is not a constant, as has frequently been assumed, but is better represented by two straight line segments of different slopes. THE thermodynamic data of Al-Z alloys have been the subject of investigation by many authors. However, in the recent compilation of such data by Hult-gren et al.,5 the conclusion is reached that none of the previous measurements are reliable or consistent with each other. Since then two new sets of measurements have been reported,2, 8 both laying claim to good accuracies, yet showing very significant disagreement in the measured activity coefficients of zinc in Zn-A1 alloys and in the magnitude and sign of the excess entropies of mixing. Information on the thermodynamics of the system is of particular interest for interpreting results of the Bureau of Mines research on refining of zinc by distillation of die cast scrap. The present study was undertaken as an independent check on the recent values obtained from dew point measurements 8 and electromotive force measurements.' The isopiestic method, first introduced by Herasy-menko,' was chosen because it is one of the few thermodynamic techniques which, in principle at least, is carried out under perfect equilibrium conditions. The disadvantage of the method is that data are obtained at various random compositions and temperatures, which makes the interpretation somewhat cumbersome. The random errors arising from temperature gradients and fluctuations appear to be comparable to those of other techniques, as evidenced by the magnitude of the estimated uncertainties in the calculated integral thermodynamic quantities. An advantage of the method is that each run provides a relatively large amount of data; thus, it is less time consuming than those methods where samples of each composition must be measured individually. EXPERIMENTAL PROCEDURE The activities of zinc in liquid Zn-A1 alloys were measured by the isopiestic method which uses the principle of the tendency toward equilibrium of a series of samples at various temperatures under an imposed vapor pressure of the more volatile component (i.e., zinc, in this case). The basic apparatus is shown in Fig. 1. The small graphite crucibles that contained the metal samples were 15 mm ID and 13 mm deep with approximately 3 mm wall thickness. Each crucible was notched at the top and bottom to allow easy passage of vapor from one to another. At the beginning of an experiment each crucible was weighed on an analytical balance. Zinc and aluminum of spectrographic purity (99.999 pct) were then weighed into the crucibles. The amounts of each metal added were such that initial compositions varied above and below equilibrium values. One crucible contained only pure zinc. After weighing, the crucibles were stacked with the pure zinc on the bottom (corresponding to the lowest temperature in the furnace) and richest aluminum alloys at the top. The entire stack of crucibles was then placed in the silica glass container "E" which was then sealed under vacuum. Sixteen to twenty calibrated Chromel-Alumel thermocouples were attached by wire along the length of the silica tube, one or more adjacent to each sample.

Jan 1, 1970

By A. E. Dwight, Paul A. Beck

Known CsCl-type phases in transition metal alloys are shown to be formed preferentially at an electron concentration of approximately 6; a tetragonally distorted version of the CsCl structure is stable at -e/a = 6.5. The relationship of the distortion to electron concentration is verified by experimental data for the quasibinary systems Time ,Os) , Ti(Re,Ir), and Ti(Re,Pt) and the ternary system Ti-Ru-Rh. It was noted some years ago1j2 that the occurrence of CsC1-type ordered structures in equiatomic binary alloys, AB, of transition metals correlates with the location of the component elements in the periodic table. One of the components, A, must be to the left and the other component. B, must be to the right of the chromium group. It was pointed out2 that the CsCl structure does not occur in CrFe. is metastable in VFe,3 and is stable in TiFe up to high temperatures, and that this progressively increasing stability may correspond to an increase in electron transfer between the two components and to a correlated decrease of the magnetic moment associated with the iron atoms. Such a decrease was in fact later demonstrated by Nevitt. 4 The binary CsC1-type phases that are formed by a transition metal with either another transition metal or a lanthanide are listed in Table I. Thirty-three of these phases occur at an average electron concentration (average number of electrons outside of closed shells) of e/a = 6. The five phases that are formed at an electron concentration of e/a = 5.5 appear to be borderline cases. This is suggested for instance by the fact that TiRe is bcc. without any long-range order, while TiTc (at the same electron concentration) has a CsCl ordered structure. Six of the undistorted CsCl phases formed by transition metals with one another have an average electron concentration of e/a = 6. 5. Table I. With the exception of Zr4,Rhs4 and Hf48Rh52. the B component in these phases is a first long-period transition metal, i.e.. iron or cobalt. TiNi. with an electron concentration of e/n = 7, appears to undergo transformation at around room temperature to a more complex ordered struct~re.~ The five other CsCl structures known to occur at e/a = 6.5 have either scandium or a lanthanide metal as the A component; the difference in the elec-tronegativity and in the e/a ratio between the component elements is in these phases very large, A(e/a) - 7, and they may be expected to have a rather strong ionic bond component. Presumably the ionic bond stabilizes the CsCl-type structure at the equiatomic composition and it overrides the electron concentration requirement. When the B element is not from the first long period and the A component is not a rare earth metal. equiatomic (AB) alloys of transition metals with an average electron concentration of e/a = 6.5 in most cases have a crystal structure closely related to the CsC1-type, but slightly distorted tetragonally, Table I. This was first found6 for VRu, NbRu. and TaRu. It was noted6 that the undistorted CsCl structure is also stable in the three systems. but at a lower electron concentration, near e/a = 6. In these systems this requires a deviation from equiatomic stoichiometry. which is otherwise ideally suited for the CsC1-type structure. A similar situation was later found in the Ti-Rh7 and the Ti-Ir systems. 8 The Ti-Rh alloys undergo a second distortion and become orthorhombic when the rhodium content becomes somewhat larger than 50 pct. As mentioned previously. TiRe does not have the CsC1-type ordered structure. In order to investigate how close TiRe is to the borderline of stability of the

Jan 1, 1970

By James K. Stanley

PREFERRED orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.1 In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurgical literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanical properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important in- formation, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational under- standing of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing 'stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required-it is only necessary punch or machine a disk of the sheet material and insert it into the testing device.

Jan 1, 1943

By W. H. Eardley

IT IS increasingly evident that the excellence of blast-furnace operation to a great extent depends upon the preparation of the products fed into the furnace. The preparation of these products is carried on largely in the roasting and sintering departments. Prior to the building of flotation plants in Utah and other western states for the treatment of lead-zinc ores, the gravity concentrates received at the Midvale smelter amounted to about 4000 tons per month, containing 24 per cent. lead and 10 or 11 per cent. zinc. This product was about 20 mesh-that is, 45 per cent. of it would be plus 20 mesh and the balance minus 20 mesh. About 1000 tons of pyrite per month, containing 5 per cent. lead and 10 per cent. zinc, was also received. These products were sent to the multiple-hearth roasters for calcining, after which they were sent to the Dwight-Lloyd machines for sintering with other ores. The sintering charge passed over the machines but once. The first flotation products received consisted of a wet, sticky, muddy mass, containing a large amount of moisture, up to 19 or 20 per cent., and it was almost impossible to feed .them with any degree of regularity, if at all, through our standard feeders; but the amount of flotation product received during the first year or so was relatively small and it virtually lost its identity by being mixed with a large amount of jig and table concentrates. As the quantity of flotation products increased, more efficient filtering was accomplished and the moisture greatly reduced. FLOTATION PRODUCTS RECEIVED At the present time the Midvale plant receives about 4300 tons per month of flotation product running 60 per cent. lead and 4.5 per cent. zinc, 85 per cent. of which is minus 200 mesh and contains about 8 per cent. moisture; and 4000 tons per month of pyrite of similar fineness, running about 2 per cent. lead and 3.5 per cent. zinc, containing about 10 per cent. moisture. The lower moisture greatly reduces the difficulties of handling, making it possible to run a 100 per cent. flotation feed on a multiple-hearth furnace without serious mechanical troubles. The calcine, however, would contain-nodules and balls of unroasted concentrates, sulfur elimination

Jan 1, 1928

By D. W. White

The kinetics of isothermal transformation of ß-to-u uranium have been studied over a broad temperature range in alloys containing from 0.3 to 4.0 atomic pct Cr. Two modes of transformation are indicated by the existence of two C-curves in the TTT diagram. The upper temperature mode is regarded as a nucleation and growth mechanism, whose rate is controlled by diffusion of chromium in the ß phase matrix. The lower temperature mode is martensitic in nature. The M, temperature increases with decreasing chromium content, suggesting that the two transformation processes become synonymous in unalloyed uranium. URANIUM metal undergoes two allotropic transformations in the solid state. The a phase, orthorhombic in crystal structure,' is stable from room temperature up to about 665°C. The ß phase, characterized by a complex tetragonal structure,' prevails from 665" to about 770°C. The y phase is body-centered-cubic3 and is the stable modification from 770°C up to the melting point (about 1130"). In uranium of reasonable purity, neither of the two high temperature phases can be retained by quenching. However, the addition of certain alloying elements to uranium makes it possible to retain either the y-uranium phase or the ß-uranium phase at room temperature. Chromium alloyed in small amounts with uranium will permit retention of the ß-uranium phase in a metastable state at room temperature upon quenching from a ß-phase temperature.' From available information' on the equilibrium phase diagram for the U-Cr alloy system (Fig. I), it is to be expected that, however sluggish in its rate, the ß phase in such alloys should decompose eutectoidally to a phase and elemental chromium. It was the aim of this investigation to measure the rate and study the nature of this decomposition as a function of temperature and of chromium content. The investigation was reported in classified literature about five years ago and has recently been declassified for publication. In the meantime, there have appeared the papers of Holden,5 Mott and Haines,".' and Butcher and Rowe8 ealing with the metallography and the crystallography of the ß-to-a transformation in U-Cr alloys. These investigators have confirmed several of the phenomenological observations that will be described in the present paper and have examined in considerable detail certain aspects of the transformation and its mechanism. Although all of these investigations have concerned themselves experimentally with U-Cr alloys for the most part, an important consequence has been a clearer understanding of the nature of the ß-to-a transformation in uranium metal itself. Experimental Procedure This investigation dealt with a series of uranium alloys varying in chromium content from 0.3 to 4.0 atomic pct (0.066 to 0.90 weight pct). On five of the alloys, rates of isothermal transformation from the ß to the a phase were measured over a wide temperature range, leading to the development of TTT (time-temperature-transformation) diagrams. Transformation rates were measured over certain narrow temperature ranges on additional alloys. The alloys were prepared by vacuum melting and casting, using zircon or magnesia crucibles and graphite molds. Electrolytic chromium was used as the alloying addition, and the uranium was Mallin-ckrodt biscuit metal that had been vacuum remelted and cropped to remove many of the nonmetallic impurities that had floated to the top of the ingot. The ingots, 3/4 or 1 in. diam, were reduced in size by swaging. Alloys containing less than about 2 atomic pct Cr were swaged at 250° to 275°C, with initial and intermediate anneals at 550°C after every 75 pct reduction in area. Alloys with higher amounts of chromium were swaged at 550" to 600°C, although at the smaller sizes some of them were reduced by the procedure used on the more dilute alloys. Before use as test specimens, the swaged rods were annealed at 700" to 720°C for several hours, followed by slow furnace-cooling. The purpose of the anneal was to achieve the maximum amount of solution of the available chromium into the ß phase, as well as to remove extensive preferred orientation. The isothermal transformation rates were measured dilatometrically, using a quenching dilatometer and an experimental technique similar to those employed by Davenport and Bain in their original work on the transformation kinetics of austenite in

Jan 1, 1956

By H. C. Brown

SINCE 1934 the steel industry has been utilizing the spectrograph for supplementing wet chemical analysis in the production control of electric and open hearth furnaces. This means of control made great strides during the war years because of the general acceptance of the spectrograph and the increased emphasis that was placed on rapid control methods. However, in the post war era, with the demand still on increased production, it became apparent that a still more rapid and economical means of production control was needed. Since the spectrograph had been used mostly in the analysis of low alloying and residual elements, it also became apparent that equipment was needed to extend the spectrographic technique to the analysis of the high alloying elements in stainless steel. For these reasons, companies manufacturing spectrographic equipment were prompted to start development work on direct reading instruments. In June 1949, the Applied Research Laboratories of Glendale, Calif., announced that a direct method of spectrochemical analysis for stainless type steels had been developed. This paper will describe the use of the Applied Research Laboratories Production Control Quantometer in the quantitative control of stainless, silicon, and plain carbon steels being made at the Butler Pennsylvania Div. of the Armco Steel Corp. The Armco Butler Div. has one 70-ton electric furnace and six 150-ton open hearth furnaces. The electric furnace is employed in the making of all types of stainless steel and the open hearth furnaces are used for the production of silicon, wheel, and plain carbon steels. The ARL quantometer was purchased primarily for the purpose of controlling the steelmaking in the electric furnace, but its use has been extended for the analysis of final tests (ladle tests) on a number of different types of stainless, silicon, and plain carbon steels. Because of this additional work by the quantometer, substantial savings in manpower and time have been realized by the laboratory. In the analysis of a set of preliminary tests from the stainless steel furnace, approximately 40 min in laboratory time are saved due to quantometric analyses. Despite the fact that more specialty grades of stainless steel are being made in the electric furnace, the average tons per hour have been increased since the quantometer was put into operation. Specialty grades require more furnace time than regular commodity grades of stainless steel. The installation of the ARL production control quantometer was completed on March 13, 1952. By May 1, 1952, the instrument was calibrated for nickel, chromium, manganese, silicon, and molybdenum, which are the elements necessary for the production control of the stainless steel furnace. Within the following month, training of personnel on the quantometer was achieved and a study of the accuracy of the instrument showed that the results obtained were sufficiently accurate for control purposes. Therefore, on June 11, 1952, the quantometer was placed on production control for all types of stainless steels. Starting September 11, 1952, the instrument was gradually placed on ladle analysis (final tests) as the analytical curves were refined and additional curves were drawn. The quantometer has been relatively free of breakdowns since placing it on production control. The samples from only one stainless steel heat have had to be analyzed by wet chemistry because of instrument trouble. The previously existing heat-time record was also bettered by 15 min on a commodity grade of 18-8 stainless steel. Scope of Control In general, the quantometer determines all elements necessary for the production control of all types of stainless steel heats and for the ladle analysis of various types of stainless steel heats. It is also used in reporting final results for silicon, manganese, chromium, nickel, molybdenum, tin, copper, and aluminum on all silicon steel grades and manganese, chromium, nickel, molybdenum, tin, and copper on several plain carbon steel grades. Table I shows the elements and the concentration ranges of these elements in the various types of stainless, silicon, and plain carbon steel that are determined on the quantometer. A study of the results obtained on ladle test samples of stainless steel types 410, 430, 430 Ti, 446, 301, 302, 304, 304L, 305, and 17-7 PH will be discussed. Also included in the study are the results obtained on ladle test samples of a number of silicon steels. Apparatus In order to take full advantage of the potentials of the production control quantometer, the unit has been placed in an air-conditioned room with relative humidity control. The temperature is maintained at 73'22°F and the humidity at 45&5 pct. The air conditioning serves as a precaution to minimize the amount of adjustment and calibration needed during operation. It also reduces contaminating fumes and dust and thereby lessens the necessity for maintenance on the equipment. The quantometer is composed of three units: the high precision multisource unit, the 1.5 meter vertical spectrometer, and the console. The source unit supplies excitation conditions varying from spark-like discharges to arc-like discharges. The voltage to the source unit is supplied by a motor-generator

Jan 1, 1955

By Paul Giesecke

Since most modern metallurgical plants are operated continuously and on a large scale, successful operation at maximum efficiency demands that an accurate knowledge of the performance at each stage of the process be available at all times. Quantitative analyses provide the most practical process guides, and it is essential to have analytical procedures that combine accuracy and speed. In continuous plant operations, large losses may occur if the time interval between the development of trouble at any stage and its recognition and correction is great. Many metallurgical plants are using rapid colorimetric and spectrochemical methods of analyses for control purposes. So-called "color coppers" may be cited as an example of the colorimetric methods, in contrast with- the routine use of the ultraviolet spectrograph for the analysis of steels.42 By means of this more refined spectrochemical procedure, a complete quantitative analysis of the molten metal is obtained every few minutes. During the past two years the Physics Division and the Ore Dressing Laboratory of the American Cyanamid Company's Stamford Research Laboratories have collaborated in a study of the use of spectrochemical methods for the analysis of various metallurgical products. New methods have been developed, which have proved of practical value in plant operation. The following pages give a general review of the principles of spectrochemical methods and also the details of several specific analyses. Principles of Spectrochemical Analysis In general, it can be said that a visible light spectrochemical analysis can be performed for any ion or molecule that is naturally colored, or that can be made to react with another to produce a colored salt or complex. Whereas transmission measurements in the ultraviolet and infrared portions of the spectrum are most useful for the analysis of organic molecules, * visible light measurements are of particular value for metal salts. Such elements as copper, manganese, cobalt, nickel, iron, molybdenum, vanadium, chromium, phosphorus, mercury, zinc, lead, and a great many others, can now be determined with a high degree of sensitivity, accuracy and dispatch. From the simplest of qualitative determinations, color analyses have been improved to such an extent that, at the present time, through the use of recording spectrophotometers, hundreds of accurate quantitative analyses can be performed by a single analyst during an 8-hr. day after the standardization curves have been established for the ions to be determined.

Jan 1, 1947

By Paul Giesecke

Since most modern metallurgical plants are operated continuously and on a large scale, successful operation at maximum efficiency demands that an accurate knowledge of the performance at each stage of the process be available at all times. Quantitative analyses provide the most practical process guides, and it is essential to have analytical procedures that combine accuracy and speed. In continuous plant operations, large losses may occur if the time interval between the development of trouble at any stage and its recognition and correction is great. Many metallurgical plants are using rapid colorimetric and spectrochemical methods of analyses for control purposes. So-called "color coppers" may be cited as an example of the colorimetric methods, in contrast with- the routine use of the ultraviolet spectrograph for the analysis of steels.42 By means of this more refined spectrochemical procedure, a complete quantitative analysis of the molten metal is obtained every few minutes. During the past two years the Physics Division and the Ore Dressing Laboratory of the American Cyanamid Company's Stamford Research Laboratories have collaborated in a study of the use of spectrochemical methods for the analysis of various metallurgical products. New methods have been developed, which have proved of practical value in plant operation. The following pages give a general review of the principles of spectrochemical methods and also the details of several specific analyses. Principles of Spectrochemical Analysis In general, it can be said that a visible light spectrochemical analysis can be performed for any ion or molecule that is naturally colored, or that can be made to react with another to produce a colored salt or complex. Whereas transmission measurements in the ultraviolet and infrared portions of the spectrum are most useful for the analysis of organic molecules, * visible light measurements are of particular value for metal salts. Such elements as copper, manganese, cobalt, nickel, iron, molybdenum, vanadium, chromium, phosphorus, mercury, zinc, lead, and a great many others, can now be determined with a high degree of sensitivity, accuracy and dispatch. From the simplest of qualitative determinations, color analyses have been improved to such an extent that, at the present time, through the use of recording spectrophotometers, hundreds of accurate quantitative analyses can be performed by a single analyst during an 8-hr. day after the standardization curves have been established for the ions to be determined.

Jan 1, 1947

By J. K. Stanley, R. F. Meel

The recrystallization of cold-worked metals is studied ordinarily by determining the temperatures required for complete recrystallization to occur within a given arbitrary time period, usually within 15 min. to 2 hr. The results obtained are conventionally assembled in a three-dimensional diagram relating this temperature to the amount of cold-work (percentage deformation) and the resultant grain size, though sometimes other modes of representation are emp1oyed.l Such three-dimensional diagrams are not complete, for the number of variables exceeds the number represented. The process of recrystallization is characterized by a time-rate, a fact that is not portrayed upon ordinary recrystallization diagrams. It is known that recrystallization consists in the formation of new nuclei and the growth of these nuclei, a process that continues until the matrix is completely consumed and the original set of grains entirely replaced by the new. This knowledge is old.2 Truly heterogeneous reactions invariably proceed by nucleation and growth; the decomposition of eutectoid solid solutions provides an example about which much is known,3 and freezing, originally studied by Tammann, provides the classic example. Although recrystal- lization is not a heterogeneous reaction within the orthodox meaning of the term, the mechanism of the process is the same. As in eutectoid inversion and freezing, it should be possible to study the rate of isothermal recrystallization as a function of time, and it should also be possible to analyze the isothermal reaction curve into the component rates of nucleation and growth that determine them.* Other methods, not employing the rates of nucleation and growth, have been used to represent the rates of such reactions, but these in general have been artificial and have not led to progress. 4,5 The theory of recrystallization is not in advanced state; if recrystallization data were obtained in terms of the rate of isothermal recrystallization, and in terms of the rate of nucleation and the rate of growth of recrystallized grains, and in particular if the temperature coefficients of these rates were measured accurately, an adequate theory should be more readily developed.27 Such an effort requires proper experimental technique, but especially requires suitable methods of mathematical analysis to convert mcasurements made upon a surface of polish into values for the rate of nucleation and the rate of growth and to combine these into a rate of isothermal recrystallization. These methods are now available for the case of three-dimensional recrystallization (recrystallization of

Jan 1, 1942

By R. F. Meel, J. K. Stanley

The recrystallization of cold-worked metals is studied ordinarily by determining the temperatures required for complete recrystallization to occur within a given arbitrary time period, usually within 15 min. to 2 hr. The results obtained are conventionally assembled in a three-dimensional diagram relating this temperature to the amount of cold-work (percentage deformation) and the resultant grain size, though sometimes other modes of representation are emp1oyed.l Such three-dimensional diagrams are not complete, for the number of variables exceeds the number represented. The process of recrystallization is characterized by a time-rate, a fact that is not portrayed upon ordinary recrystallization diagrams. It is known that recrystallization consists in the formation of new nuclei and the growth of these nuclei, a process that continues until the matrix is completely consumed and the original set of grains entirely replaced by the new. This knowledge is old.2 Truly heterogeneous reactions invariably proceed by nucleation and growth; the decomposition of eutectoid solid solutions provides an example about which much is known,3 and freezing, originally studied by Tammann, provides the classic example. Although recrystal- lization is not a heterogeneous reaction within the orthodox meaning of the term, the mechanism of the process is the same. As in eutectoid inversion and freezing, it should be possible to study the rate of isothermal recrystallization as a function of time, and it should also be possible to analyze the isothermal reaction curve into the component rates of nucleation and growth that determine them.* Other methods, not employing the rates of nucleation and growth, have been used to represent the rates of such reactions, but these in general have been artificial and have not led to progress. 4,5 The theory of recrystallization is not in advanced state; if recrystallization data were obtained in terms of the rate of isothermal recrystallization, and in terms of the rate of nucleation and the rate of growth of recrystallized grains, and in particular if the temperature coefficients of these rates were measured accurately, an adequate theory should be more readily developed.27 Such an effort requires proper experimental technique, but especially requires suitable methods of mathematical analysis to convert mcasurements made upon a surface of polish into values for the rate of nucleation and the rate of growth and to combine these into a rate of isothermal recrystallization. These methods are now available for the case of three-dimensional recrystallization (recrystallization of

Jan 1, 1942

By I. Iwasaki

In the flotation of iron ores and nonmetallic ores desliming is the key to a successful operation; the technology of flotation of well-deslimed ores has become fairly well established. When finely disseminated ores are ground to liberation, however, conventional desliming of the fully dispersed pulp results in an excessive loss of valuable constituents. Selective flocculation of iron oxides followed by removal of dispersed siliceous slimes is a new development and is one of the most promising approaches to the treatment of finely disseminated, oxidized iron ores, available in vast quantities both here and abroad (1,2,3). To apply selective flocculation to the variety of refractory iron ores or to cope with the fluctuations in an individual ore and the make-up water, the factors governing this technique must be clearly formulated. For the removal of siliceous and clayey slimes from oxidized iron ores by selective flocculation, the optimum conditions are extremely sensitive to the mineralogical characteristics of the ore, the type and the amount of soluble salts in pulp solutions, and the mesh-of-grind. Certain starches appear to function better than others (4, 5). Selection of the proper reagents and their judicious use is important not only for their efficient utilization but also for minimizing the adverse effects they might exert on the flocculation and flotation steps, and the pollution the effluents might cause when discharged, either intentionally or accidentally, into lakes and streams. In the present article some of the major factors that influence the selective flocculation of iron ores are summarized.

Jan 1, 1979

Jan 1, 1917

By L. C. Armstrong

Twice in the past two years and in two widely separated localities—ane near Williamsville, Mo., and the other in the Allard Lake district of Quebec— the Contract Drilling Division of the Longyear Company has experienced perplexing difficulties in drilling granitoid igneous rocks. The rocks in both places are characterized by appreciable amounts of feldspar intimately inter-grown with quartz particles of microscopic dimensions. The disappointingly slow rate of advance and the exceptionally high bortz loss, obtaining during the life of these two projects, are ascribed largely to the resistance to abrasion of these two minerals when arranged in this intergrown pattern. Whether all intergrowth-bearing igneous rocks would offer extraordinary resistance to bit progress cannot be stated with assurance on the strength of these experiences alone. More data on diamond drilling this sort of material in a number of localities are needed before any generalizations can be made safely. It should be pointed out that the lack of time and funds made it impossible for the writer, or other persons interested in correlating the details of bit histories with the kinds of rocks drilled, to be present during the performance of the contracts. However, the records kept in the normal course of drilling are deemed complete enough to be reportworthy. This information is presented here together with the findings made in studies of the rocks involved, with the thought that it may attract the comments of others who may have encountered similar refractory drilling conditions. A pooling of knowledge on the problem would be of material aid in devising more efficient cutting tools and procedures for penetrating this kind of rock. Drilling Blastholes in the Williamsville Granite Due to the unsatisfactory perform- ance of pneumatic percussion drills in boring blastholes on a construction contract near Williamsville, Mo., tests were made with a diamond drill. The poor progress achieved and the excessive loss of diamonds, however, soon led to the abandonment of these trials. The diamonds, in all of the bits tried, lost their cutting edges and acquired a polish after being in service for distances ranging from a few inches to a few feet. Coring bits containing surface-set, whole-stone bortz in a tungsten powder matrix were employed. The cost assignable to bortz wear averaged $7.17 per foot. This item of expense is several times the amount normally expended in diamond drilling in firm, unfractured, granitic rocks. Diamond-impregnated, tungsten carbide bits also were used without success. The diamond wear was at the rate of $0.98 per foot, but the diamond chips became too polished for further duty in less than a foot of drilling. The Williamsville granite is pink and medium-grained. In the hand specimen, it has a fresh, sound appearance; it is seemingly composed almost entirely of interlocking grains of feldspar and quartz and has no discernible features suggesting a greater durability than is usually found in rocks with this composition and texture. Microscopic examination, however, reveals a predominance of feldspar grains with more or less regularly distributed and sharply angular masses of quartz (see Fig 1). The pattern assumed by the two minerals in this mode of occurrence is referred to as a "graphic intergrowth," as it bears some resemblance to the cuneiform characters of ancient Persian writing. The other principal constituents are quartz-free feldspars (microcline and orthoclase) and quartz. All of these constituents are in nearly equidimensional grains, ranging up to about 3 mm in length. There are also

Jan 1, 1950

By E. M. Cox, T. Rosenqvist

IN a recent investigation, carried out at the Institute for the Study of Metals, the affinity of sul-phur for iron, copper, and manganese was studied over the temperature range 700" to 1300°C.' It was found that copper exhibits a rather high affinity for sulphur, especially at higher temperatures; and attention was called to the possibility that copper when present together with sulphur in liquid steel would tend to lower the chemical activity of sulphur and thus interfere with the desulphurization process. It was clear, however, that the data for the equilibrium between pure copper and pure copper sulphide (Cu2S) could not give any quantitative information about the effect of copper when dissolved in liquid steel. The present work is concerned with the activity of sulphur in the diluted range of the binary iron-sulphur system, and with the influence of small amounts of copper on this sulphur activity. This investigation is in principle based on the same method previously described for the binary metal-sulphur studies;1,2 namely, reaction with hydrogen to form hydrogen sulphide. The equilibrium ratio PH2s/Ph2 in the equilibrium gas mixture is, for a given temperature, directly proportional to the sulphur activity. The activity of sulphur in liquid iron has previously been studied by Chipman and Ta Li,3 White and Skelly,4 and recently by Sherman, Elvander, and Chipman.5 Morris and Williams6 have studied the effect of added silicon, and Kitchener, Bockris and Liberman,7 and recently Morris and Buehl,8 the effect of added carbon on the sulphur activity. In present day steelmaking processes the steel bath contains between 0.01 and 0.1 pct sulphur, and the copper content may be as high as 0.5 pct. The equi-librium gas ratio (H2S/H2) would, for such a low-sulphur content, be too low to be measured with the experimental technique we use. It has been shown by previous investigators that the H2S/H2 ratio is closely proportional to the sulphur content up to about 1 pct sulphur. The sulphur activity at very low-sulphur content can therefore be calculated by linear interpolation between 0 and 1 pct sulphur. In order to show the general trend with increasing sulphur content, the present work has been carried out to about 3.5 pct sulphur. As the effect of copper was assumed to be more a function of the Cu/S ratio than of the absolute copper content, the runs with copper were made for certain constant values for this ratio.

Jan 1, 1951

By K. F. G. Hosking

I read Professor Gaudin&apos;s paper with great interest and pleasure because for some time I have held that the chemical aspect of comminution is a subject of considerable importance to the mineral dresser and deserves to be thoroughly investigated. It does seem appropriate, however, to emphasize the fact that "fresh" edges and corners produced by the grinding of solids display enhanced reactivity has been recognized and utilized in the development of certain mineral identification techniques. Some of these techniques are worth noting, not only because they might facilitate research in the aspect of mineral dressing under discussion, but also because they emphasize the fact that many mineral species commonly regarded as being very inert can display a surprising reactivity when in the freshly ground state. In 1951 Isakov6 published a number of tests for the components of certain mineral species which depend essentially on grinding in a mortar a mixture of the material under investigation with a solid reagent. Thus when stibnite, 4(Sb2S3), is ground with sodium or potassium hydroxide. the antimony is revealed by a momentary development of a yellow color which changes in air to orange-red. Other antimony minerals need a preliminary treatment before the test can be carried out. This consists of grinding with aluminium sulfate, ferric sulfate or potassium bisulfate, and breathing upon the resultant mixture. I have employed a similar technique to determine the approximate magnesia content of certain limestones.&apos; The method depends essentially on the fact that when a sample of limestone is ground under controlled conditions with solutions of sodium hydroxide and Titan yellow the color of the final product is, within limits, a function of the amount of magnesia present. I have also shown that the components of a wide range of minerals can be identified by applying chemicals to their streaks on portions of vitrified, unglazed floor tiles, etc. Under such circumstances the diversity of the reactions which take place in the cold (because of the reactivity of fresh corners and edges) is surprising. Thus, for example, if a garnierite, (Ni,Mg)3Si2O5(OH)1, streak is treated first with a drop of 0.880 ammonia and then with a drop of a 1 pct alcoholic dimethyl-glyoxime it immediately becomes red, indicating the presence of nickel.&apos; Stevens and Carron9 have evolved a simple field test for distinguishing minerals by "abrasion pH." A soft nonabsorbent mineral is scratched in a drop of water on a streak plate until a milky suspension is formed. A piece of pH indicator paper is dipped into the suspension, after which it is removed and the maximum deviation from neutrality noted. When a hard mineral or one which absorbs water is being tested, fragments are first ground for 1 min with a few drops of water in a mortar to make a heavy suspension. The importance of the findings of such tests to mineral dressing may be judged by the abrasion pH values, Table 11, recorded by Stevens and Carron for certain species usually regarded as comparatively inert. The combined results Of the above researches clearly indicate that comminution is capable of altering the pH of a pulp and of causing the chemical nature of the surfaces of some of the components to be profoundly changed&apos; Depending On circumstances such surface alterations may have a beneficial or an adverse effect if these products are subsequently subjected to flotation. The tests also suggest that by grinding "inert" minerals with appropriate solid or liquid reagents "reactive" surfaces may be developed which might facilitate separations by flotation. It is an interesting and instructive problem to determine the reactions that are likely to take place when dry solid substances are subjected to comminution and to the unavoidable heat liberated during the process. To do this it is theoretically necessary to know the free energy values of the reactants and possible resultants, but unfortunately there is a dearth of such data! However, the heats of formation of many substances are known, and generally speaking, if in a reaction of the type AB + CD = AD + CB the sum of the heats of formation of AB and CD is less than that of AD and CB the reaction will probably proceed to the right. Thus, according to a note I have (the author of which I cannot name) if PbS (black) is warmed with CdSO, (white), PbSO., (white) and CdS (yellow) are formed, and that the reaction does, in fact, take place is indicated by the change in color of the mixture. The reaction is expected, as the sum of the heats of formation of PbS and CdSO, is less than that of PbSO, and CdS (as shown below). PbS + CdSO4 = PbSO4 + CdS 22.2 + 218.0 < 216.2 + 33.9 Finally, certain other aspects of the chemistry of comminution, which are neither mentioned by Professor Gaudin nor referred to by me are to be found in a paper by Welsh" and in the printed discussion thereof. A. M. Gaudin (author&apos;s reply)—The observations contributed by Dr. Hosking are indeed welcome, as they add to our experimental knowledge of a topic which is believed to be of the first importance. In connection with the experiments cited it should be kept in mind that oxidation, hydration, and carbonation at various rates should always be deemed to be possibilities when grinding is done in water or in air, even in "industrially dry" air. Special precautions might lead to sufficient minimizing of these reactions and to the assertion, instead, of deliberately-created reactions. The author wishes to thank Dr. Hosking for his contribution.

Jan 1, 1957

By J. N. Butler, R. J. Morris

A series of organic collectors has been developed which successfully float synthetic secondary uranium minerals, such as autunite, carnotite, and torbernite. Recoveries up to 97 pct have been obtained. With cleaning of rougher concentrates, ratios of concentration as high as 15:1 are possible on head assays of 0.10 to 0.50 pct U 3 O 8. Additions of certain base metal salts aid in recovery and materially increase the rate of flotation and selectivity of the collectors for the synthetic minerals. Flotation tests on natural uranium minerals have not yet equaled results obtained on the synthetics, although these collectors do give better results than conventional collectors for nonsulfide minerals. RAPID increase in mining and milling uranium ores during the past seven years and the discovery of large tonnages of uranium-bearing material too low in grade to stand the cost of leaching have developed considerable interest in possible methods for beneficiating these marginal ores. Such ores are generally classed as those containing less than 0.10 pct U3O8. Development of a beneficiation method that would give both high recovery and high ratio of concentration would also make possible the beneficiation of higher grade ores and would provide higher grades of feed to existing leaching plants. Although considerable research and testing on physical or physico-chemical beneficiation of domestic uranium ores has been done in the past, to the best knowledge of the authors only a single application of physical beneficiation is now in operation on a commercial scale. Flotation has been attempted on the basis of mineral association rather than by direct concentration of the contained uranium minerals. Flotation studies conducted on this project on certain ores gave recoveries of 60 to 70 pct of the uranium by the use of conventional flotation agents such as oleic acid, but ratios of concentration were in the order of 1.5:1 to 2.5:1. Subsequent cleaning to upgrade the concentrates rapidly increased losses in the cleaner tailings, which were not later refloated in the rougher flotation. Selection of Collector: In selecting desirable organic collectors for these oxide systems, a thorough study was made of the relationship between structural characteristics and collector activity by an examination of the behavior of a number of different functional arrangements present in a variety of organic molecules, (see Fig. 1). It is generally accepted that a collector must have a relatively long-chain hydrocarbon radical and a chemically reactive elec-trophilic center. Such a requirement could be met by a large number of compounds, but steric effects at the uranium mineral surface, solubility, compat-ability with aqueous systems, air avidity, bond strength at the mineral surface, interfacial concentration of the collector, and diffusion rate of the formed complex from the air-water interface eliminated many as unsuitable for this purpose. Preliminary investigations were completed of possible collector designs consisting of aliphatic and aromatic hydrocarbon radicals attached to stable combinations of nitrogen, oxygen, sulfur, and halogen electrophilic centers, Fig. 1.Tests were made to determine melting point spans, solubility of mineral-collector combinations in various solvents, reactions with soluble uranium salts, contact angles, and floatability by semi-quantitative beaker methods.&apos; Contact angle determinations were not too useful because of the fine particle sizes of available mineral samples. From the foregoing study it appeared that nitrogen-sulfur electrophilic centers coupled with straight-chain saturated alkyl hydrocarbon radicals would hold the most promise for floating secondary uranium minerals. As the dithiocarbamate compounds can be made to combine these attributes they were selected for further study. The dithiocarbamates form a parallel structure to the xanthates, with the fortuitous exchange of

Jan 1, 1957

By R. C. Mahon

During the early history of the Lake Superior district, tamarack timber was used almost exclusively in the wines. It had the strength and lasting qualities necessary for a satisfactory mining timber. But about fifteen years ago the tamarack trees were attacked by a blight which killed nearly all of them so today no tamarack timber is available. Hemlock, spruce, and poplar have neither the necessary strength nor the lasting qualities for mining timber, but a large supply of maple and birch is available. These have ample strength but, when placed underground, fail by decay in about three years. This means that, instead of replacing the timber sets once in fifteen years, it must be done five or more times in the same space of time which involves not only incraesed timber costs but more important, an increased labor cost.

Jan 1, 1949

The earliest record of production in this county is for drilling a salt well in 1809. Some scattered data are shown in the table; the total figures are estimated. Little coal could be shipped in this period on account of lack of transportation. [ ]

Jan 1, 1942