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By P. D. Gorsuch, D. L. Newhouse, Irvin R. Kramer

ALTHOUGH many methods have been suggested for the calculation of tensile strength and yield point from chemical composition, their usefulness has been limited to a particular cooling rate or section size. Further limitations have been imposed by failure to take into account many of the alloying elements that exert a considerable influence on the tensile strength or yield point. These systems, nevertheless, have filled an important need in many instances. The value of a system for the calculation of the tensile properties from the chemical composition and cooling rate is that it permits the prediction of the effect of alloying elements and heat-treatment on the mechanical, properties, so that more efficient use of alloying elements may be made. Furthermore, it aids in the choice of steel for a given application and tends to decrease the number of steels that otherwise would have to be tested. It is the purpose of this work to present a method of calculating tensile strength and yield point from the chemical composition and to suggest a method of correlating the tensile-strength and yield-point factors and cooling rate. Steelmakers have been interested for many years in the calculation of the tensile strength of hot-rolled steels. Quest and Washburn' summarize several of the attempts that have been made to devise formulas. They show the inadequacy of each of these formulas and present one of their own. It is apparent from their work that a simple additive equation of the type TS = A + BX + Cy + DZ + ? ? ? , where A, B, C, D, etc. are experimentally determined constants and x, y, z, etc., are the percentages of alloying elements present in the steel, is not adequate to analyze fully the situation encountered in the calculation of tensile strength. For example, it was found that the difference between the calculated and observed values became progressively greater as the carbon and manganese contents were increased. Therefore, the effect of manganese was given as a function of the carbon content. Grossmann,2 in his work on the hardenability of quenched steels, and Walters,3 in his method of calculation of tensile strength of normalized steels, present two cases in which multiplying factors were successfully used to express the combined effect of alloying elements. The factors in both cases were obtained from the fractional increase in hardenability or tensile strength with increase of alloy content. Yield point often is more important in design than tensile strength. For quenched and tempered steels a linear correlation exists between yield and tensile strength .4 This is not true, however, for normalized

Jan 1, 1946

By I. R. Kramer

A delay time for yielding in cold-worked face-centered-cubic metals was found. Slip on (123) planes was observed. Glide on these planes occurred during the delay-time period before slip starts on the (111) planes. AN important approach to the study of the anchoring and blocking of dislocations is available through the delayed-yield phenomenon which has been observed in body-centered and hexagonal close-packed metal by several investigators. Clark and his associate1-5 showed that a delay time for yielding is present in mild steels and fine-grain molybdenum. Type 302 stainless, SAE 4130 normalized, SAE 4130 quenched and tempered, and 24s-T aluminum aid not have a delay time. Kramer and Maddin6 studied the delay-yield effect. in metal single crystals. While they found a delay time in body-centered-cubic metals none could be found in the face-centered-cubic metals. Later7 a delay time was found in hexagonal close-packed metals. cottrell8 has proposed an explanation for the difference in the yield phenomena of b.c.c. and f.c.c. metals based upon the anchoring of edge dislocations by the proper types of impurity atoms (C and N). In the body-centered-cubic lattice the interstitial atoms are near a cube edge and can interact with an edge dislocation, while in a face-centered-cubic lattice the distortion around an interstitial atom is of spherical symmetry and cannot anchor a screw dislocation which has practically no hydrostatic component. Cottrell's theory seems to account rather well for the behavior of body-centered-cubic . metals. EXPERIMENTAL PROCEDURE The apparatus used in these experiments is essentially of the same design as described previously.' Single crystals 1 in. long and having a diameter of % in. were placed in a pendulum which consisted of a bar 8 ft long designed with a crystal holder to accommodate the specimen at low temperatures. This portion of the apparatus was supported on fine molybdenum wires. A bar of the same diameter and length comprised the other portion of the apparatus. This bar was supported on a set of roller bearings arranged around the periphery of the bar to allow accurate alignment. This bar was propelled by means of a spring-loaded gun and allowed to strike the lead bar in front of the single-crystal specimen. SR-4 type A-8 resistance strain gages were cemented to the specimen and the strain measurements were obtained by amplifying the strain-gage output by means of a high-gain preamplifier. A tektronix 545 oscilloscope was used together with a polaroid camera to record the strain and time sweep. An Ellis Associate Bridge was used to calibrate the strain gages and calibration readings were obtained before each test. The sweep of the time signal was initiated by means of a miniature thyraton which was fired when the two bars came into contact. The single-crystal specimens were cut from single-crystal bars about 12 in. long, grown by a modified Bridgman technique. The aluminum crystals were made with material of 99.99 pct purity while the purity of the copper was 99.999 pct. A cut-off wheel was used to prepare the specimens which were then machined to the desired length. The two opposite faces of the specimen were parallel to each other and perpendicular to the axis of the specimen. The specimens were compressed 1 pct. No machining followed thereafter. In some cases prestraining was carried out in liquid nitrogen by impacting the specimens directly in the apparatus so that subsequent observations could be made without allowing the specimen to warm up to room temperature. The single crystals were compressed 1 pct at room temperature in a hand press without much control of the rate of deformation. In some cases specimens were recompressed to obtain the desired length change. As far as could be determined in these experiments this factor did not seem to influence the results. The SR-4 strain gages were glued with a cellulose type cement onto the specimen surface and baked at 45°C for 12 hr. As a check on the baking treatment gages were allowed to dry at room temperature. All delay time tests in this paper were conducted in a liquid nitrogen bath at -195°C. A schematic delay time oscilloscope trace is shown in Fig. 1. At point B the elastic stress wave caused by the impact reaches the strain gage on the specimen. The portion BC is the elastic strain. In this investigation the strain at point C was used to calculate the critical resolved shear stress by multiplying by the proper modulus depending upon the orientation of the single-crystal specimen. The time between C and D is the delay time portion of the curve. This portion of the curve is fairly flat but does have a definite microstrain associated with it. After the point D is reached the specimen deforms rapidly and the strain reaches a maximum at E. Following this, depending upon the length of the bar behind the specimen, the strain remains constant for a period and then decreases when the reflected elastic wave returns from the end of the pendulum bar. A permanent plastic strain is recorded on the oscilloscope trace and also measured by a strain-measuring bridge. The strain, E p,

Jan 1, 1960

By T. A. Wright

The sampling of waste materials containing copper, lead and tin has taken on a new significance within recent years, and is of increasing importance, on account of the entry of some of the copper refineries into this field and the tendency towards consolidations among the smelters. In the past, such material was sold on the basis either of a rough or grat) sample or of casual inspection of the lot. The two principal sources of this waste are the processes of fabrication and the scrapping of automobile, electrical, plumbing, railroad and other equipment. In both cases rnuch material can bc sorted, salvaged and sold by classification and grade to be melted "as is" or with the addition of new or virgin metal. The increasing care in classifying exercised in the large manufacturing plants tends to incrcase the proportion of this usable scrap; on the contrary, the increasing use of more complex and special non-ferrous alloys tends to makc sorting and grading more difficnlt in turnings, borings, clippings, etc., and conseqllcntly is making sampling of more moment. In tin, lead, alumiinum, and zinc furnace by-products such as ashes, drosses, skimmings, etc., the trade practice of evaluation has not varied much. For instance, tin drosscs, battery lcad, and aluminunl skimmings are ordinarily sold on what is called "metallic button" or "metallic recovery" or "metallic yield." Coppcr and Icad wastcl, howcvcr, is being sold more and more on actual copper and lead contents bascd on sarrlple and chemical analysts. This paper will be dcvotctl chiefly to the sampling of niaterials suitablc only for refining and recovery of one or more of the metals present. The methods described are often bascd on thc fact that but one, metal, such as copper, is to be paid for. The loss of volatile constituents in melting does not appreciably affect thc final copper result, as the "after-melting" assay can be readily calculated to the "bcfore-nltltingl' basis, but if smelter efficiency continues to increase, so that in tiltie zinc, for instance, may be rccovrred on a paying basis, thc method of sampling dirty brass, for example, will have to bc changed also. As a matter of fact, we may cxpect that improved refining proresses will make possible the partial reeovrry of lcad and tin which are now lost

By T. A. Wright

THE SAMPLING of waste materials containing copper, lead and tin has taken on a new significance within recent years, and is of increasing importance, on account of the entry of some of the copper refineries into this field and the tendency towards consolidations among the smelters. In the past, such material was sold on the basis either of a rough or grab sample or of casual inspection of the lot. The two principal sources of this waste are the processes of fabrication and the scrapping of automobile, electrical, plumbing, railroad and other equipment. In both cases much material can be sorted, salvaged and sold by classification and grade to be melted "as is" or with the addition of new or virgin metal. The increasing care in classifying exercised in the large manufacturing plants tends to increase the proportion of this usable scrap; on the contrary, the increasing use of more complex and special non-ferrous alloys tends to make sorting and grading more difficult in turnings, borings, clippings, etc., and consequently is making sampling of more moment. In tin, lead, aluminum, and zinc furnace by-products such as ashes, drosses, skimmings, etc., the trade practice of evaluation has not varied much. For instance, tin drosses, battery lead, and aluminum skimmings are ordinarily sold on what is called "metallic button" or "metallic recovery" or "metallic yield." Copper and lead waste, however, is being sold more and more on actual copper and lead contents based on sample and chemical analyses. This paper will be devoted chiefly to the sampling of materials suitable only for refining and recovery of one or more of the metals present. The methods described are often based on the fact that but one metal, such as copper, is to be paid for. The loss of volatile constituents in melting does not appreciably affect the final copper result, as the "after-melting" assay can he readily calculated to the "before-melting" basis, but if smelter efficiency continues to increase, so that in time zinc, for instance, may be recovered on a paying basis, the method of sampling dirty brass, for example, will have to be changed also. As a matter of fact, we may expect that improved refining processes will make possible the partial recovery of lead and tin which are now lost.

Jan 1, 1928

By T. A. Wright

The sampling of waste materials containing copper, lead and tin has taken on a new significance within recent years, and is of increasing importance, on account of the entry of some of the copper refineries into this field and the tendency towards consolidations among the smelters. In the past, such material was sold on the basis either of a rough or grab sample or of casual inspection of the lot. The two principal sources of this waste are the processes of fabrication and the scrapping of automobile, electrical, plumbing, railroad and other equipment. In both cases much material can be sorted, salvaged and sold by classification and grade to be melted "as is" or with the addition of new or virgin metal. The increasing care in classifying exercised in the large manufacturing plants tends to increase the proportion of this usable scrap; on the contrary, the increasing use of more complex and special non-ferrous alloys tends to make sorting and grading more difficult in turnings, borings, clippings, etc., and consequently is making sampling of more moment. In tin, lead, aluminum, and zinc furnace by-products such as ashes, drosses, skimmings, etc., the trade practice of evaluation has not varied much. For instance, tin drosses, battery lead, and aluminum skimmings are ordinarily sold on what is called "metallic button" or "metallic recovery" or ('metallic yield." Copper and lead waste, however, is being sold more and more on actual copper and lead contents based on sample and chemical analyses. This paper will be devoted chiefly to the sampling of materials suitable only for refining and recovery of one or more of the metals present. The methods described are often based on the fact that but one metal, such as copper, is to be paid for. The loss of volatile constituents in melting does not appreciably affect the final copper result, as the "after-melting" assay can be readily calculated to the "before-melting" basis, but if smelter efficiency continues to increase, so that in time zinc, for instance, may be recovered on a paying basis, the method of sampling dirty brass, for example, will have to be changed also. As a matter of fact, we may expect that improved refining processes will make possible the partial recovery of lead and tin which are now lost.

Jan 1, 1928

By Daniel R. Hull

In 1926 Gendersl reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan3 and by Phillips and Brick,2 so that no résumé is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. Vapor Segregation There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table 1, which represents a cylindrical billet 7 in. in diameter by 55 in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. the lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps UP a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By Daniel R. Hull

In 1926 Gendersl reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan3 and by Phillips and Brick,2 so that no résumé is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. Vapor Segregation There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table 1, which represents a cylindrical billet 7 in. in diameter by 55 in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. the lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps UP a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By G. G. Sarkar

SHARPNESS of separation and washing efficiency are often confused. The sharpness index indicates the precision of a washing unit; the washing efficiency takes into account not only the unit's precision but also the washability characteristics of raw coal and the near-gravity materials at the effective density of cut. A sound basis for evaluating the sharpness index is essential in comparing the sharpness of separation attained by different cleaning units. Sharpness Index and Related Criteria: Washing plant sharpness of separation has been well represented by Hancock's efficiency chart and Tromp's curve of migrated materials. Some useful coefficients derived from Tromp's curve—the error area, probable error, and imperfection value—have been widely used to measure sharpness of separation. These are defined in a number of papers presented at the first and second International Coal Preparation Colsference held in Paris (1950) and Essen (1954).1-5 In evaluating the performance of a dense medium separator at four different gravities, Yan-cey and Greer6 bserved that even with similar operating conditions and the same size grading of feed, the imperfection value of a washing plant varies through a greater range than the probable error. The present writer also observed the same type of anomalies in comparing the imperfection values of one plant which were determined under almost identical conditions. He therefore devised a graphical method to evaluate a washing unit's sharpness of separation and define it by a single coefficient, which is substantially independent of coal characteristics under normal operation of the unit. Unlike imperfection value, the new coefficient can be expressed on a percentage basis. Coal preparation engineers generally agree that the amount of misplaced material resulting from any separation in a washing plant is almost directly related to the amount of +0.10 sp gr (near-gravity) materials. In actual practice, however, misplacement is not restricted to the 20.10 sp gr range. It will be evident from a study of Tromp curves that this misplacement often extends over unequal specific gravity ranges on the two sides of the actual density of separation. The same condition exists for near-gravity ash distribution and the resultant misplacement of ash units during any separation. But so far as the same unit is concerned, the total misplacements bear a definite ratio to the amount of near-gravity zone materials that is affected by misplacements. This ratio should be constant not only for various densities of separation but also for different qualities of feed coal treated in the same plant. This ratio, multiplied by 100, directly represents the inefficiency of the plant. When the plant inefficiency value is subtracted from 100, the re- ' sult is designated as sharpness index. Evaluating the Sharpness Index: The method of evaluating the sharpness index is explained here with reference to Fig. 1. Fig. 1 is a reproduction of the familiar diagram used by Cerchar of France to represent the inefficiency of a separation in terms of "triangle of errors," which is a measure of organic loss. It will be observed that the characteristic (yield/fractional ash) curve of the raw coal represented by GHAPR

Jan 1, 1958

By R. G. Powell, R. Schuhmann, E. J. Michal

Liquidus surfaces in the ternary system FeO-Fe2O3-SiO2, were determined from 1250' to 1450°C by the procedure of equilibrating small samples in platinum crucibles, quenching, and microscopic examination. The experimental results were combined with previously published information to construct a ternary diagram for the system showing the entire temperature-composition range of stability of iron silicate slags. Metallurgical applications of the diagram, especially in copper smelting, are discussed briefly. IRON oxides are almost unique among the common oxide constituents of metallurgical slags in that the iron occurs in two different states of oxidation, ferrous and ferric. Moreover, in liquid slags the degree of oxidation of the iron is readily changed by reactions of the slags with oxidizing agents or reducing agents. This behavior of iron oxides in slags accounts, for example, for the effective transfer of large quantities of oxygen through slag layers in open hearth steelmaking. In this process, oxygen supplied by reactions at the gas-slag interface is dissolved in the slag with the oxidation of ferrous iron to ferric. Ferric oxide is transported across the slag layer by convection, and at the slag-metal interface the oxygen reacts with liquid metal while the ferric iron is reduced back to the ferrous state. Another group of processes in which variation in degree of oxidation of iron has great practical importance is in copper smelting. In matte smelting and converting, such large proportions of the iron are oxidized to the ferric state that problems are encountered in preventing or controlling the formation of solid magnetite. The ferrous-ferric relationship also affects the attack of iron oxides on high-SiO2 refractories, which appears to be most severe under reducing conditions for which ferrous iron predominates. Darken and Gurry' determined the chemical properties and phase equilibria of pure iron oxide slags. Their data show that iron oxide melts can have compositions ranging almost all the way from FeO to Fe2O3. The melts of lowest oxygen contents, which exist in equilibrium with metallic iron, approach ferrous oxide in composition but still have a small percentage of ferric oxide. The melts of highest oxygen contents, which have oxygen dissociation pressures of 1 atm, are above magnetite in oxygen content, with over two-thirds of the iron in the ferric state. The previously established phase diagrams for silicate slag systems all show FeO as the iron oxide component. However, Bowen and Schairer? who determined the FeO-SiO2 diagram and many of the other diagrams used by slag chemists, have been careful to point out that their systems always contained both ferrous and ferric iron. Thus, their data are for limiting mixtures with minimum contents of ferric iron, obtained by melting and equilibration in iron crucibles. Under these conditions, the Fe2O3 percentages found by analysis were small enough to justify simplification of the published phase diagrams by calculating the Fe2O3 to equivalent FeO and ignoring Fe2O3 as an additional component. On the basis of experimental measurements of melting points of iron oxides on silica in the presence of various gas mixtures, Darken3 worked out phase diagrams for the Fe-Si-0 system which show the important phase equilibria in terms of temperature and gas composition. This study clarified many aspects of the application of the phase rule to the FeO-Fe2Oa-SiO2 system and was an important basing

Jan 1, 1954

By F. H. Ellinger

TI HE crystal structure of neodymium has been re-A ported by Quill1 and by Klemm and Bommer"s to be hexagonal-close-packed, Strukturbericht-type A3, with a, = 3.650.4, c, = 5.890.4, c/a = 1.614. Klemm and Bommer,% owever, pointed out that the observed intensities of the lines of the neodymium powder pattern agreed only in part with the intensities calculated for the type A3 structure, and that the neodymium powder pattern showed extra lines which could not be traced to impurities. They found that these extra lines could be accounted for by doubling the c-axis, but apparently they did not consider their evidence to be sufficiently conclusive to justify reporting the doubled c-axis. In the present work, the structure of neodymium was found to be double hexagonal-close-packed. The neodymium metal used in the present investigation was obtained through the courtesy of F. H. Spedding of the Ames Laboratory. Its major impurity was stated to be 0.03 pct Ca. The author's spectrographic analysis indicated high purity and carbon was determined to be less than 30 ppm. X-ray powder specimens were prepared from filings stress relieved in vacuum at 200°C for 50 hr. Powder photographs were taken in an 114.6 mm diam camera (Straumanis film mounting) at room temperature and in a 19 cm diam Unicam high temperature camera at elevated temperatures. Copper x-radia-tion was used for all the photographs. The powder pattern of neodymium was found to index to a hexagonal unit cell with dimensions, as determined from the high angle Ka doublets, of: a.= 3.655+0.001.4; c, = 11.796+0.004.4; and c/a = 3.227 at room temperature. The measured density of neodymium shows that this cell contains 4 atoms, the calculated density is accordingly D, = 7.02 g per cu cm. The diffraction data for the first 15 lines of the powder pattern are listed in Table I. In a double hexagonal-close-packed unit cell, the 4 atoms would be in the positions (0,0,0), (0,0,%), (1/3, 2/3, 1/4), and (2/3,1/3,%) of space group P 6,/mmc. On the basis of these positions, the relative intensities of the reflections were calculated using the expression: 1+cos2 20 I oc \Frp 1 ' sin2 0 cos 0 where F is the structure factor and p is the multi- plicity factor. Since absorption was not taken into consideration, comparison of observed and calculated intensities should be made only for neighboring reflections. Each atom has 12 neighbors, 6 in the basal plane at a distance of 3.655.4 and 3 above and 3 below at the closer distance of 3.626.4. These distances correspond to an average radius of the neodymium atom of 1.820.4. The description of this structure in terms of A, B, and C close-packed layers of atoms is ABAC ABAC. ...... The structure repeats every fourth layer and the stacking sequence of the second, third, and fourth layers corresponds to cubic-close-packing of atoms. A series of powder photographs taken at successively increasing temperatures up to 680a10"C revealed that the double hexagonal-close-packed structure is stable up to this temperature. Acknowledgments The authw wishes to thank W. H. Zachariasen and A. S. Coffinberry for their helpful comments on this work and also Marion Gibbs for measuring the diffraction films. This work was sponsored by the United States Atomic Energy Commission.

Jan 1, 1956

By R. B. Rosene, G. L. Foster, A. R. Hendrickson

he properties of some of the common fracturing oils, such as sand-falling rate, fluid loss and viscasity, are a function of the three major constituents of the oil. These are: asphaltic material, parafin waxes and a base oil. The base oil can be either high or low viscosity. Asphaltic material increases viscosity by thickening the oil, decreasing the rate of fall of sand through the oil. at temperatures up to 200" F. When large arnorrnts of parafin wax are present, much of the wax i.s not dissolved, but is present in the form of rnicroscopic crystals. 7'his, of course is limited to temperatures below the melting points of waxe.s. As a result, parafin waxes clo not function primarily as thickener.7, but rother as bullting materials. The functiori of wax, without asphaltic material, in a low viscosity base oil is uniquely unlike that of wax with asphalt coexistent in the oil. The resulting difierence in wax crystal size governs the sand-falling rate to a large extent. An ideal type of fracturing oil is one containing neither asphalt nor waxes. In such cases, the viscosity and resulting low sand-falling rate are apparently due to soluble resin- ous hydrocarbons, which are compatible with formation oils. INTRODUCTION Since the introduction of hydraulic fracturing as a method of stimulating production from oil and gas wells, a variety of fluids have been employed to open the fractures and carry the propping agent. Such fluids include gels, emulsions, and oils. In the latter category, the use of refined oils has increased tremendously, and it is probably safe to assume that such oils represent more than one-half of the total fluid used in fracturing. The general acceptance of refined oils for fracturing can be accounted for on the basis of their relatively low cost and general applicability. To minimize transportation costs, such refined oils are generally obtained within the local areas of operation. As a result there are several kinds of oil used in different areas, with a wide variation in the basic composition. These types may vary from a fair grade of lubricating stock to a highly viscous cut-back asphalt. or road oil. Originally, little attention was paid to the composition of the oils used for fracturing, and any oil which would carry sand was considered satisfactory. Recently, however, service companies and well operators have become more concerned with the type of oils used for fracturing. With this in mind, the present work was undertaken to evaluate and compare many widely used fracturing oils to determine which constituents were most desirable for fracturing purposes. Some of the important properties of fracturing fluids are sand-falling rate, viscosity, and fluid loss. Other properties, that are actually of no less importance, include flash point, pour point, emulsifying tendencies with formation brines, and compatability with the formation oils. This discussion has been limited, however, to the first mentioned properties in order to give some idea of the general composition of the refined oils, how they function, and why. PROPERTIES OF FRACTURING OILS The properties of fracturing oils are a function of the three major constituents of the oil. These may be designated as: (1) asphaltic material, (2) paraffin waxes and (3) a base oil, which may be of either high or low viscosity. The asphaltic material clas-

Jan 1, 1956

By J. E. Burke, Y. G. Shiau

SEVERAL attempts have been made to account for the fact that grains in a fully recrystallized metal will coarsen on annealing Two fundamentally different hypotheses have been advanced; with several variations of each. One school considers that the cause of grain growth is the surface energy of the grain boundary The theory of Jeffries1 that grain size and grain size contrast control growth is an example The second school considers the primary cause to be a difference in the lattice energy on either side of the grain boundary The more perfect grains are considered to grow at the expense of their less perfect neighbors, with a decrease in free energy, and a consequent increase in the stability of the system. Burgers2 presents the case for the strain or lattice imperfection theory of grain growth quite completely The latter theory is attractive, since there is no doubt that differences in lattice energy or lattice perfection can cause grain boundary migration A recrystallization nucleus grows for this reason as was beautifully demonstrated by van Arkel and Ploos van Amstel3 Although it is generally stated that grain growth does not precede recrystallization, several workers4,5 have shown that small strains may induce a single crystal in an aggregate to grow, or at least may cause some' grain boundary migration The origin and nature of the imperfections that are considered to be responsible for normal grain growth have never been clearly described, but it is generally agreed that they are a consequence of the difficulty of atomic reorientation in the solid state, and that they do not seriously differ from the type of imperfection that-can be introduced by mechanical deformation An object of the present work was to determine whether the introduction of mechanical deformation would cause grain growth in a specimen which would not otherwise show it under the conditions used It was also planned to determine the effect of such deformation the rate of growth in a specimen which would show - growth in the unstrained condition Recently Maddigan and Blank6 have indicated that slightly strained specimens of alpha brass can undergo considerable growth prior to recrystallization if annealed at low temperatures French7 has reported that at deformations less than 17 pct it is very difficult to detect the beginning of recrystallization in the same material. It was therefore planned to broaden this work to include a complete study of the microscopic behavior of alpha brass under conditions of temperature, time, grain size and deformation such that recrystallization would not occur or would occur to only a small extent EXPERIMENTAL PROCEDURE The brass was prepared by melting cathode copper and commercially pure zinc

Jan 1, 1947

By Ward C. Smith

The industry of producing and processing boron compounds is called the borax industry because the chief product is borax, the decahydrate of disodium tetraborate. For the same reason, it is common to speak of borax mining. Reference to borate mining also is common, and while appropriate where it emphasizes the diversity of borate minerals that are mined in various countries, it is rather unsatisfactory where used in a general sense, because it seems to exclude the important production of borax from brine at Searles Lake, California, and of boric acid from steam vents in Tuscany, Italy. The terms "boron industry" and "boron mining" might seem more comprehensive, but are little used, and this is fortunate because they would be misleading-the element boron is manufactured only in small amounts for special uses, and it is not found free in nature. In most occurrences, boron is combined with oxygen and is in a borate or borosilicate material. The history of the modem borax industry starts with the introduction into Europe of borax from Tibet in the 13th century, about the time of Marco Polo, if not actually by him. The discovery that borax has unique value as a flux in metal soldering and ceramic glazing must have been made at some unknown time much earlier. As a rule, any mineral that has been used so long that its early history is lost must occur in deposits that are easily recognized and worked, and this is undoubtedly true of borax in Tibet. According to meager accounts,9 the borax occurs there in arid mountain basins as surficial crusts that coat the ground about thermal springs and seeps of mineralized water, and as coarser crystals in the bottom muds of shallow pools and lakes. Much the same essential features of surface exposures and minerals easy to recognize and recover characterize most of the deposits later found and worked elsewhere. The borax industry at the present time is faced with rising demands for its products, and consequently is increasing its productive capacity and appraising its borate resources.18 The areas that contain the known borate deposits are most likely to yield additional production, hence their distribution in the world is of interest, and is summarized later in this chapter. Mineralogy The mineral raw materials used by the borax industry include various borates mined in several countries, borax extracted from brines at Searles Lake in California, and boric acid extracted from the steam of vents in Tuscany in Italy. The hydrated borates[$] of chief commercial importance are listed in Table 1, which also shows their chemical composition. The properties of only the four most important borates are summarized here, but detailed descriptions of the borates and the minerals commonly found with them can be found in mineralogy textbooks.41 Ulexite generally forms clusters of silky fibers rather than large individual crystals. A

Jan 1, 1960

By H. F. Hebley

In recent years, especially in the last decade, great interest has been shown and many advances have been made in the preparation and cleaning of coal. In the major coal-producing countries, the percentage of tonnage cleaned has been increasing ever since 1924. As separating media, both liquids and gases are used, these generally being water and air respectively. Some systems, instead of obtaining separation by the velocity of the medium in which the coal is cleaned, depend on the density of water mixed with sand, or coal dust and shale, or with chemicals such as calcium chloride. In studying the results of coal-cleaning equipment, it will be observed that the efficiency of the cleaning apparatus lowers as the size of the coal decreases. This inability to obtain any marked improvement in the fines has been partly responsible for the installation of dedusting equipment, to remove the fine sizes from the raw coal prior to cleaning. When considering the possibility of installing dedusting equipment, many factors must be taken into account. Very often, but not always, both the ash and sulfur content of the coal increase as the coal size decreases. When bituminous coal, containing soft powdery fusain, is subjected to a wet washing process, the porous fines of the fusain remain in the small coal or in the wash water and delay the dewatering of the washed coal and increase the difficulty of clarification in settling tanks or thickeners. When a dedusted coal is cleaned by a wet process, the sludge recovered from the settling tank often runs so high in ash that the sludge can be discarded without further treatment and still the loss is small. Where treatment of the sludge is desired, however, froth flotation may be used to advantage if the size of the feed is below 1/10 in. Dust from the deduster can be treated in a similar manner. Fusain, which is usually found in the fine sizes, has often a much larger ash content than other coal. Illustrative of this condition is a table of ash contents for the various petrographic constituents of Illinois coal (No. 5 bed) as given by Mitchell' (Table 1).

Jan 1, 1934

By David Cole

THE appearance of the Wilfley table in 1897 marked an epoch in the art of concentration of ores. The table has merited and received an almost unprecedented measure of public approval, lasting through its whole patent life. It has been very little improved in itself, or improved upon by competitors. The new machines bidding for popular favor have been of the Wilfley family, but without ability to do markedly better work than the parent m:-chine, or to (to more work except by the use of superimposed decks, the latter having obvious disadvantages. FIG. 1.-The- Butchart RIFFLE System. During the past three years there has been developed at Morenci a new type or arrangement of riffles applicable to the Wilfley type of concentrating table which corrects many of the objectionable features or limitations of the older system and obviates most of the difficulties encountered with it, particularly when handling ores having a low ratio of concentration. The new type is known as the Butchart1 riffle system, and its general arrangement is shown in Figs. 1 and 2.

Jan 2, 1915

By Reuben B. Ellestad, Fremont F. Clarke

Lithium chemical plant extraction methods are discussed with reference to 1) base exchange with alkali sulphates; 2) processing based on roasting with lime; 3) miscellaneous methods; and 4) application of the Lithium Corp. process to extraction of lithium from run-of-mine, low grade spodumene ore, or concentrates. IN the early days of the lithium industry most of the production was from lepidolite, zinnwaldite, and amblygonite. Nearly all the early extraction processes described in the literature involve heating the finely ground mineral with sulphuric or hydrochloric acid. On subsequent water leaching most of the bases present in the mineral (especially aluminum) are dissolved as sulphates. As a result, the leach solution required extensive chemical purification before the lithium could be precipitated as carbonate. Following the remarkable growth of the lithium industry to its present size, zinnwaldite and amblygonite ores must be considered of minor importance only. Attention is now focused on spodumene, abundant enough in North America to be a major source of supply, and there are important supplies of lepidolite and petalite in Africa. The extraction processes described below all apply to spodumene, although several will also operate on other lithium minerals, such as petalite. Base Exchange with Alkali Sulphates: A distinct advance was made with the disclosures of Wadman and von Girsewalt. In these methods the finely ground silicate ore (spodumene or lepidolite) is intimately mixed with an excess of alkali sulphate (usually K2SO4) in at least a 1 to 1 proportion, and the mixture was heated to a relatively high temperature. Base exchange results, with the formation of lithium sulphate. A water leach dissolves the lithium sulphate, together with the excess potassium sulphate. Successful operation of this type of process requires very thorough grinding and mixing, as well as careful temperature control. The use of K2SO4 is objectionable from cost considerations since purification of lithium carbonate requires the use of potassium carbonate, if the K2SO4 is to be recovered and recycled. The lower solubility of K2SO4 as compared with Na2S04 is also objectionable, since it limits the concentration of the Li2SO4 solution to be precipitated by K2SO4. Early laboratory-scale investigation of this process by Lithium Corp. was not encouraging. Other related base exchange processes are those of Lindblad, Wallden, and Sivander3 and Sivander, Gard, Villestad, and Wallen4. The former covers the reaction of lithium silicate minerals with a sodium sulphate solution, at 100" to 300°C (under pressure), while the latter involves the extraction of silicate minerals with molten sodium sulphate. Both these processes would seem to be difficult and expensive to operate.

Jan 1, 1956

By I. C. Edwards, W. J. Dengler, D. F. Lillie

By 1959 the milling plant of Bicr oft Uranium Mines Ltd. had been in operation for two years. During this time many changes, both physical and chemical, had been made in an effort to improve plant efficiency. Investigational work had been facilitated greatly by the fact that the Bicroft mill consists to a large extent of two parallel circuits; however, the number of interrelated variables is great, and it is difficult to measure, let alone control, all of them simultaneously. The Bicroft mill staff feels that much progress has been made, but there is much yet to be done and many questions still to be answered. The Addendum outlines noteworthy developments to the fall of 1960. The property of Bicroft Uranium Mines is located in Cardiff Township in the Highlands of Haliburton County, southeastern Ontario, some 140 miles northeast of the city of Toronto and 70 miles due north of Lake Ontario. The ore-bearing dikes are classed as mafic. nonsegregated, syenite and granite pegmatite. Microline, microline perthite, quartz, sodic plagioclase, and pyroxene or biotite are the main constituents with uraninite, uranothorite, fluorite, titanite, cryolite, calcite, pyrite, pyrrhotite, and molybdenite as important accessories. The mill was designed for a nominal capacity of 1000 tpd with all sections except grinding, leaching, and clarification capable of 1500 tons. Feed was entered to one mill unit on Oct. 29, 1956, and to the second parallel line on November 13. The total feed rate was at 1000 tpd on November 15. The first precipitate was produced on November 12. By August 1958 the average entry had been increased to 1410 tpd without the installation of any additional major equipment. The overall recovery has been greater than 93.0 pct on several months, but a recovery of 92.5 pct appears to be most economical. Operating time for eight months in 1958 has been 97.1 pct although all grinding mills were relined during this period. A generalized flowsheet is shown in Fig. 1 and the plant layout in Fig. 2. The ore is crushed in three stages to -3/8-in. and then is wet ground in two stages to approximately 50 pct -200 mesh. The pulp is thickened to 68 pct solids and agitated by air for 33 hr at a pH of 1.9 as maintained by the addition of 93 pct sulfuric acid. Separation of the uranium-bearing pregnant liquor from the residue is accomplished by five-stage countercurrent decantation (CCD), following which the liquor is clarified for removal of fine slimes. The clarified liquor is treated in the ion exchange equipment in which both the upgrading of the solution and the removal of some impurities is accomplished. Addition of magnesia to the high-grade eluate from ion exchange precipitates the uranium as sodium-magnesium diuranate. After being filtered and dried this precipitate is packaged in drums for shipment. The residue from CCD and the barren solution from ion exchange are neutralized by the addition of lime and pumped to the tailings disposal area. CRUSHING All crushing is done on surface in a conventional three-stage unit consisting of a 36x48-in. Birdsboro Buchanan jaw crusher, a 4 1/4-ft standard Symons cone crusher, and a 4-ft Symons shorthead. Both the two primary and the two secondary screens are 4X 8-ft Symons rod decks. Moisture content of the feed ranges from 3 to 4 pct. In the initial installation the primary screens were equipped with 5/16-in. rods at 1 1/4-in. spacing and the secondaries with 5/16-in. rods at 1/2-in. spacing. With this arrangement the average crushing rate was better than 180 tph. To reduce the work required of the grinding circuit as tonnage was increased, several changes were made in the crushing circuit. By September 1957, both secondary screens had been reduced to 3/8-in. spacing, and rod size had been reduced to 3/16-in. to provide increased open area. Average throughput was reduced to 160 tph. Later, 50 pct of one primary screen was decreased to 1/2-in. opening to better balance the load between the two cone crushers. In May 1958,

Jan 1, 1961

By Charles De Witt

The ore treated at the reduction plant (called Yangdei) of the Chiksan -Mining Co., Korea, is brought from four of the company mines, and from the small tribute mines. The largest shipments conic from Sajunkohl mule, situated about a mile and a half from the mill (Fig. 1). The ore is quartz of medium hardness. The overage assay value in gold is $6.95 per ton. At the mine the ore is put into bin,, and is Mien trammed over an 8 per cent. grade to the tipple bins above the mill, where the ore is drawn through the hull holes as desired. The capacity of the tipple bins is about 3,500 tons. On, from Moonsukohl, Chung Tarrie, Yang Chun, and the tribute mines is brought in by bulls and bull wagons. The bulls carry from 350 to 800 lb.; the average wagon load is about 1,200 lb. (Fig. 2). One shovelful of ore out of every ten is taken as a sample. Considerable ore

Jan 5, 1915

By Cyril Stanley Smith

Somewhat over ten years ago the author described studies1'2 on the constitution of the copper-silicon system. The copper-rich portion of this diagram is shown in Fig. 1. The experimental points freely dotted about the diagram seemed to justify an otherwise unconvincing diagram and for several years the curious reverse bend in the alpha-phase boundary was accepted as substantially correct, even by later investigators3 of the system who introduced changes in the high-silicon phases. The binary diagram has been used as a base for several ternary systems5-9 without any suggested changes. Voce10 suspected the existence of another phase from his study of the cast alloys in the copper-manganese-silicon system, but evidently hesitated to extrapolate this to the binary diagram, particularly in view of the too ingenious explanation that was advanced1' to account for the pools of constituent clearly visible in castings; namely, that they were secondary alpha of twinned orientation deposited from beta. Von Schwarz,12 in 1932, called attention to the fact that this micro-constituent in copper-silicon alloy castings was anisotropic under polarized light and asserted that a new phase, not cubic, should be placed in the diagram .adjacent to alpha. Sautner,l3 on the basis of investigations with the polarizing microscope and with X-rays, introduced this phase into the diagram at about 6 per cent Si. The relevant part of his diagram is shown in Fig. 2. Sautner called the new phase beta, renaming the old beta phase zeta. To avoid confusion, in redrawing Fig. 2 the phases have been renamed in accordance with the terminology adopted in the present paper, in which the new phase is called kappa and the other phases retain the designation given them by Arrhenius and Westgren.4 The thermodynamic impossibility of Sautner's diagram and the paucity of experimental data left the exact location of the new phase field most uncertain, although his work proved beyond doubt that an additional noncubic phase exists. Because of the industrial importance

Jan 1, 1940

By Cyril Stanley Smith

Somewhat over ten years ago the author described studies1'2 on the constitution of the copper-silicon system. The copper-rich portion of this diagram is shown in Fig. 1. The experimental points freely dotted about the diagram seemed to justify an otherwise unconvincing diagram and for several years the curious reverse bend in the alpha-phase boundary was accepted as substantially correct, even by later investigators3 of the system who introduced changes in the high-silicon phases. The binary diagram has been used as a base for several ternary systems5-9 without any suggested changes. Voce10 suspected the existence of another phase from his study of the cast alloys in the copper-manganese-silicon system, but evidently hesitated to extrapolate this to the binary diagram, particularly in view of the too ingenious explanation that was advanced1' to account for the pools of constituent clearly visible in castings; namely, that they were secondary alpha of twinned orientation deposited from beta. Von Schwarz,12 in 1932, called attention to the fact that this micro-constituent in copper-silicon alloy castings was anisotropic under polarized light and asserted that a new phase, not cubic, should be placed in the diagram .adjacent to alpha. Sautner,l3 on the basis of investigations with the polarizing microscope and with X-rays, introduced this phase into the diagram at about 6 per cent Si. The relevant part of his diagram is shown in Fig. 2. Sautner called the new phase beta, renaming the old beta phase zeta. To avoid confusion, in redrawing Fig. 2 the phases have been renamed in accordance with the terminology adopted in the present paper, in which the new phase is called kappa and the other phases retain the designation given them by Arrhenius and Westgren.4 The thermodynamic impossibility of Sautner's diagram and the paucity of experimental data left the exact location of the new phase field most uncertain, although his work proved beyond doubt that an additional noncubic phase exists. Because of the industrial importance

Jan 1, 1940