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By Clarence Zener, Howard Clarke, Cyril Stanley Smith

The importance of cold-working in the fabrication of metals is in marked contrast with our ignorance as to the nature of the accompanying internal changes. The failure of the usual methods of testing to provide a consistent picture of these internal changes has given the incentive for the present program of investigating the effect of cold-working upon the internal friction of metals measured at small strain amplitudes. It has previously been shown1,2,3, that the internal friction introduced by cold-work is removed by annealing at comparatively low temperatures. In the present paper the following additional factors are investigated: (I) frequency of measurement, (2) amount of cold-work, (3) temperature of measurement. Special care was taken to minimize the internal friction due to causes other than cold-work. The present paper is purely experimental, the authors believing that any conclusions drawn from this work as to the nature of the internal changes accompanying cold-work would be premature.'l PrEpaRations oF Specimens In this study of cold-work it was desirable to eliminate as far as possible all other sources of internal friction. One disturbing source is the lack of temperature equilibrium between adjacent crystallites of a vibrating specimen.4 Temperature equilibrium is aided by small grain size and by the use of low-frequency vibrations. Unless unduly long specimens are used, low frequencies can be obtained only in transverse vibrations. But in transverse vibrations a second source of internal friction is present, that arising from transverse thermal currents.5 The effect of these may be reduced by increasing the transverse dimensions. The grain size and transverse dimensions of the specimens were thus so chosen as to render the vibrations simultaneously nearly isothermal with respect to intercrystalline thermal currents, and nearly adiabatic with respect to transverse thermal currents. The material for this investigation was a 70-30 brass, part of the same lot of material that was used for some earlier studies on the effect of strain on proportional limit.10 It had the following composition: copper, 70.59 per cent; zinc, 29.39; lead, 0.01; iron, 0.01. This material was received from the brass mill in the form of 3/4-in. rod, cold-drawn to final size by a 65 per cent reduction of area from material that had been annealed to give a grain size of 0.060 mm, Rods of appropriate length were annealed for 2 hr. at 400°C. and cooled in air. The annealed rods (grain size, 0.012 mm.) were then stretched in a tension-testing machine, using special grips1' to ensure axial application of the load. The rate

Jan 1, 1942

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By D. M. Davidson

The drill sampling and evaluation of the Piney River ilmenite property was carried out during the early part of 1944 by E. J. Longyear Co., using the company's standard core-drill outfits to complete 44 holes to an average depth of IIO ft., from which were collected 1100 samples. The Piney River ilmenite-apatite lode is 25 miles north of Lynchburg, in Nelson and Amherst Counties, Virginia (Fig. I). Its elevation is about 900 ft. above sea level and it lies in the old pre-Cambrian complex of crystalline rocks that make up the Piedmont physiographic province lying east of the Blue Ridge Mountains. The terrain is gently rolling and well watered and is drained by the Piney and Tye Rivers, which are tributary to the James. Geology The Piney River ore body comprises the upper, weathered part of a tabular basic rock, which occurs in a large area of granite-gneiss. The section containing profitable ore is about 3000 ft. long. It is separated naturally by thinning, into northeastern and southwestern segments with widths of 300 and 100 ft. respectively. The dip averages 4.5° southeast but steepens locally (Figs. 2 and 3). The unaltered rock is an even, granular mixture of feldspar, ilmenite, and apatite, to which Watson1 gave the name Nelson-ite. The decomposed ore body, which is now being exploited by open cut, is a yellowish clay material in which black ilmenite and glassy apatite are the only conspicuous minerals. An economically important structural feature of the deposit is a banding of minerals coinciding with the dip and strike of the dike. This is more pronounced in the footwall of the northeastern part of the intrusive, where there is also a higher than average concentration of ilmenite. According to Watson,' the TiO2 content of the Nelsonites of this region ranges from 10 to 42 per cent, while P205 varies from 4 to 15 per cent. It is inexpedient at present to disclose exact metal content of the Piney River ore body; suffice it to say that the average tenor lies well within the extremes noted by Watson. Sampling Methods and Procedure During a preliminary inspection of the ore body, Longyear engineers surmised that because of its soft, clayey character, drill sampling would yield little core, therefore they made all possible preparations to procure accurate samples of the drill cuttings, or sludge. The first requisite in obtaining representative drill cuttings is to secure their full recovery. Only under certain conditions, and by employing a most careful and rigid sampling technique, is this pos sible. There must be no loss of the water circulating in the hole, and the velocity

Jan 1, 1949

By W. M. Bertholf

In 1945 tests were made in the coal washery of the Colorado Fuel and Iron Corporation, at Pueblo, Colo., to determine the value of the Humphreys spiral. So far we have demonstrated that it is of definite value to us in rewashing a portion of our table middlings; and we are fairly certain that this is not necessarily the only place in which it can be used to advantage. Because of manpower and material shortages, experimental work has been discontinued for the present. Three of the spirals are being installed for use in rewashing the middlings, and testing and experimental work will proceed when this installation is completed. All evidence secured so far points to the fact that the spiral call make an effective separation of heavy material below 8-mesh; but that it is ineffective in removing larger, heavy material. This, of course, will limit its use to fine coal or a classified feed containing no heavy material larger than 8-mesh. In considering the results of our tests, it should be noted that the feed was our table middling, and that any real separation of this material is a "moral victory)" as there is little material that could be properly called coal and practically no heavy rock, the consequence being that previous attempts to clean the middlings have not been at all successful. Several articles dealing with the spiral and its use in treating heavy minerals have already been published,' but for the benefit of those who have not seen these we include a brief description of the spiral and of the way it operates, taken from Bulletin 4 of The Humphreys Investment Co.: The Humphreys Spiral Concentrator consists of a spiral conduit of modified semicircular cross section. Ore pulp is fed to the top and, as it flows downward, the heavier particles concentrate in a band along the inner side of the pulp stream (Fig. I). Outlets for removal of products are located at the lowest points in the cross section of the conduit. Wash water, added at the inner edge of the stream, flows outwardly across the concentrate band. The width of concentrate band removed at the outlets is controlled by adjustable splitters. Concentrate is usually removed from the upper portion of the spiral and middling from the lower portion. Tailing is discharged from the lower end. Tests are usually made in closed circuit, since this provides a maximum of information with a minimum amount of sample. Fig. 2 shows the spiral set up for closed-circuit testing, and gives a good idea of the general arrangement of such an installation. The small cyclone separator is used to provide clean wash water without introducing additional water into the circuit.

Jan 1, 1947

By W. M. Bertholf

In 1945 tests were made in the coal washery of the Colorado Fuel and Iron Corporation, at Pueblo, Colo., to determine the value of the Humphreys spiral. So far we have demonstrated that it is of definite value to us in rewashing a portion of our table middlings; and we are fairly certain that this is not necessarily the only place in which it can be used to advantage. Because of manpower and material shortages, experimental work has been discontinued for the present. Three of the spirals are being installed for use in rewashing the middlings, and testing and experimental work will proceed when this installation is completed. All evidence secured so far points to the fact that the spiral call make an effective separation of heavy material below 8-mesh; but that it is ineffective in removing larger, heavy material. This, of course, will limit its use to fine coal or a classified feed containing no heavy material larger than 8-mesh. In considering the results of our tests, it should be noted that the feed was our table middling, and that any real separation of this material is a "moral victory)" as there is little material that could be properly called coal and practically no heavy rock, the consequence being that previous attempts to clean the middlings have not been at all successful. Several articles dealing with the spiral and its use in treating heavy minerals have already been published,' but for the benefit of those who have not seen these we include a brief description of the spiral and of the way it operates, taken from Bulletin 4 of The Humphreys Investment Co.: The Humphreys Spiral Concentrator consists of a spiral conduit of modified semicircular cross section. Ore pulp is fed to the top and, as it flows downward, the heavier particles concentrate in a band along the inner side of the pulp stream (Fig. I). Outlets for removal of products are located at the lowest points in the cross section of the conduit. Wash water, added at the inner edge of the stream, flows outwardly across the concentrate band. The width of concentrate band removed at the outlets is controlled by adjustable splitters. Concentrate is usually removed from the upper portion of the spiral and middling from the lower portion. Tailing is discharged from the lower end. Tests are usually made in closed circuit, since this provides a maximum of information with a minimum amount of sample. Fig. 2 shows the spiral set up for closed-circuit testing, and gives a good idea of the general arrangement of such an installation. The small cyclone separator is used to provide clean wash water without introducing additional water into the circuit.

Jan 1, 1947

By A. W. Fahrenwald

Cell depth has been for many years a controversial question in a flotation-machine performance. In the impeller type of machine, we are really talking about impeller submergence—i.e., the depth in the pulp at which the impeller is required to produce aeration. The Flotation Machine a Compressor A flotation machine can be considered as an air compressor or blower in which the aeration mechanism takes in air under atmospheric pressure† (14.7 Ib. per sq. in.) and blows it into the pulp (the pulp being the receiver) against a head of 14.7 plus cell depth in feet times 0.4333 lb. per sq. inch. In commercial machines the impeller is submerged in the pulp to depths ranging from about 2 ft. in the smaller machines to as much as 5 ft. in some of the larger ones. In the 2-ft. cell, the hydrostatic head on the impeller is (2 X 1.25 =) 2.50 ft. (assuming a pulp density of 1.25), equal to (2.50 X 0.4333 =) 1.078 Ib. per sq. in. For the 5-ft. cell, the hydrostatic head against which the impeller must make air is (5 X 1.25 X 0.4333 =) 2.708 Ib. per sq. inch. In the small 2-ft. machine, the volume reduction is (1.078 ÷ 0.147 + 0.01078 =) 6.85 per cent and in the large, 5-ft. machine, the volume reduction is (2.708 0.147 + 0.02708 =) 15.5 per cent. It is obvious that for unit volume of free air intake the larger machine receives a lesser (8.65 per cent less) volume of aeration* than the smaller machine. The bubbles in escaping from the pulp expand and are greater in volume at the surface than at the moment of their formation in the pulp; 7.33 and 18.4 per cent larger, respectively, in the small and large machines. Just how this situation affects flotation is not known. It is interesting to note, however, that the bubbles are smaller in the zone of the coarsest particles and largest in the upper zones of the her, more easily suspended mineral particles. It would seem that the relationship might be reversed advantageously. The deep cell is at a greater disadvantage in this respect than the shallow cell. Nothing, however, presumably can be done about this situation. The shallow cell is a partial corrective. Not only does the compression ratio of aeration increase with impeller submergence but the hydrostatic head against which the impeller must operate also increases. The Flotation Machine as a Pump Since, in impeller machines that rely upon their own operation to produce aeration, pulp Passes through the im-

Jan 1, 1947

By A. H. Geisler, J. H. Keeler

Preferred orientations in unalloyed zirconium were determined by the Geiger-counter spectrometer X-ray diffraction technique. With increasing P-annealing temperature the following textures were obtained: l—a retained a-annealing texture, 2—additional orientations predictable from the a-p (Burgers) relationship, and 3—a texture derived from a cube texture in the p phase. Earlier work on cold-worked and a-annealed zirconium was reappraised to show a quantitative dependence of rotations on temperature and to identify spurious areas of some of the pole figures. IN a previous paper,' the preferred orientations of high purity zirconium sheet were described for cold-rolled and annealed samples. Annealing temperatures up to 900°C, which is slightly above the allotropic transformation temperature, were explored. Of interest was the observation that the orientation of the hexagonal-close-packed material after annealing in the temperature range of the stable body-centered-cubic phase was similar to that of the material which had been annealed in the a temperature region, although a change in texture would be expected because of the many new orientations based on an orientation relationship between the two forms of zirconium. The reversion to an original orientation after an allotropic transformation cycle is not unusual. It has been found for titanium,"* for thallium," and for cobaltB among the hexagonal metals. Burgers found in his original work7 that, when zirconium was cooled through the allotropic transformation and then reheated, the body-centered-cubic phase reverted to the original orientation. Additional experimental work has been carried out to further explore the textures of zirconium after annealing in the temperature range above the allotropic transformation. In addition, a reappraisal was made of the earlier results for zirconium' in light of recent work on titanium4 which has shown that the texture type depends quantitatively on the temperature of annealing and that spurious areas may be encountered in the pole figures of hexagonal metals determined by the X-ray spectrogoniometer technique of analysis. Experimental Procedure Crystal-bar zirconium prepared by the iodide process was the material used in this investigation. The major impurity was hafnium which was less than 0.3 pct. The composition obtained by spectro-graphic analysis is given in Table I. Cold-rolled specimens were prepared from crystal bar by a series of reductions of approximately 0.010 in. until the sheet reached a thickness of 0.010 in., after which it was cold rolled to 0.001 in. thickness between sheets of alloy steel. The total cold reduction amounted to about 99.8 pct. Specimens were annealed for % hr at 1000" to 1100" to 1200°C or 1 hr at 1400°C in an evacuated Vycor or quartz tube. The transmission pole figures were obtained by

Jan 1, 1956

By A. W. Fahrenwald

Cell depth has been for many years a controversial question in a flotation-machine performance. In the impeller type of machine, we are really talking about impeller submergence—i.e., the depth in the pulp at which the impeller is required to produce aeration. The Flotation Machine a Compressor A flotation machine can be considered as an air compressor or blower in which the aeration mechanism takes in air under atmospheric pressure† (14.7 Ib. per sq. in.) and blows it into the pulp (the pulp being the receiver) against a head of 14.7 plus cell depth in feet times 0.4333 lb. per sq. inch. In commercial machines the impeller is submerged in the pulp to depths ranging from about 2 ft. in the smaller machines to as much as 5 ft. in some of the larger ones. In the 2-ft. cell, the hydrostatic head on the impeller is (2 X 1.25 =) 2.50 ft. (assuming a pulp density of 1.25), equal to (2.50 X 0.4333 =) 1.078 Ib. per sq. in. For the 5-ft. cell, the hydrostatic head against which the impeller must make air is (5 X 1.25 X 0.4333 =) 2.708 Ib. per sq. inch. In the small 2-ft. machine, the volume reduction is (1.078 ÷ 0.147 + 0.01078 =) 6.85 per cent and in the large, 5-ft. machine, the volume reduction is (2.708 0.147 + 0.02708 =) 15.5 per cent. It is obvious that for unit volume of free air intake the larger machine receives a lesser (8.65 per cent less) volume of aeration* than the smaller machine. The bubbles in escaping from the pulp expand and are greater in volume at the surface than at the moment of their formation in the pulp; 7.33 and 18.4 per cent larger, respectively, in the small and large machines. Just how this situation affects flotation is not known. It is interesting to note, however, that the bubbles are smaller in the zone of the coarsest particles and largest in the upper zones of the her, more easily suspended mineral particles. It would seem that the relationship might be reversed advantageously. The deep cell is at a greater disadvantage in this respect than the shallow cell. Nothing, however, presumably can be done about this situation. The shallow cell is a partial corrective. Not only does the compression ratio of aeration increase with impeller submergence but the hydrostatic head against which the impeller must operate also increases. The Flotation Machine as a Pump Since, in impeller machines that rely upon their own operation to produce aeration, pulp Passes through the im-

Jan 1, 1947

By W. G. Pfann

The problem of forming points on wires that were from 0.002 in. to 0.010 in. in diam arose in the recent appearance of silicon and germanium point contact rectifiers as elements in microwave radar.' In these devices a pointed tungsten wire makes a delicate contact with the surface of a semiconductor. Because the quality of such rectifiers is largely determined by the nature of this contact, considerable attention has been given to the formation of the metal point. Reproducibility of contour and freedom from burrs and even microscopic irregularities are considered essential. The operations involved must be simple and rapid enough for mass production. Previously tungsten wircs had been provided with conical points by a grinding method which involved rotating a wire about its axis and causing it to bear at an oblique angle against a spinning abrasive disc. This was later complemented with an electrolytic polishing treatment which removed irregularities from the ground point and also rounded it off at the tip—a desirable feature. Finally, these operations were supplanted by the electrolytic pointing method described here. Mechanism of Point Formation The wires to be pointed are partially immersed in an electrolyte in a vertical position whereupon they are provided with smooth rounded points entirely by electrochemical action. The process is independent of the depths to which the wires penetrate the electrolyte because the points are formed at the surface level. It may be used to point a single wire or many of them simultaneously and is applicable to wires of different diameters within a limited range. Solution of the immersed portion of a tungsten wire is accomplished by making it the positive electrode in an electrolytic cell, as shown in Fig I. While the wire is maintained at constant voltage the current through the cell falls continuously, principally because of the decrease in wetted area which results from solution of the tungsten. This increase in resistance occurs in a reproducible manner and is used as a control in the process. As thc immersed portion of the wire dissolves, it remains cylindrical in shape except for the short section which is wetted by the meniscus. Here the rate of solution is lower and decreases as the top of the meniscus is approached. The result is the formation of a tapered section inside the meniscus. As solution continues, the cylindrical section either dissolves entirely or drops off just before complete solution, leaving only the taper which is now sharply pointed. Further action causes this point to become rounded and then quite blunt, until finally the end of the wire is almost plane. Fig 2 shows the stages in this development. Contour PF is most representative of those used in point contact rectifiers. Thus a variety of point

Jan 1, 1949

By R. Schuhmann

The expression "unit process " comes up with increasing frequency in discussions among metallurgists and mineral engineers, especially among those concerned with training the next generation. The unit process approach characterizes a significant advance along the road from metallurgy as an empirical art to metallurgy as a branch of engineering. The purposes of this paper are to define and list the unit processes in specific terms, to indicate the scientific and engineering principles basic to all the unit processes, and finally to show how these ideas have been applied to a reorganization of instruction in chemical metallurgy. Unit Operations and Unit Processes Metals are extracted from ores and other raw materials by stepwise procedures. In general, each metallic element is extracted by a different procedure. For many of the metals there is a choice of several flowsheets. However, the procedures all have steps in common. In fact, the many different flowsheets are all made up of a relatively small number of steps which are combined in different groups and sequences. For example, crushing, screening, roasting, sintering, melting, and gaseous reduction are steps which each appear in the Bowsheets for extracting the majority of the metals. The individual steps or flowsheet units can be designated as unit operations or unit processes. These terms are well established in the field of chemical engineering, as the American Institute of Chemical Engineers' definition of chemical engineering shows: " Chemical engineering is that branch of engineering concerned with the development and application of manufacturing processes in which chemical or certain physical changes of materials are involved. These processes may usually be resolved into a coordinated series of unit physical operations and unit chemical processes. The work of the chemical engineer is concerned primarily with the design, construction, and operation of equipment and plants in which these unit operations and processes are applied. Chemistry, physics, and mathematics are the underlying sciences of chemical engineering, and economics its guide in practice."'1a In this definition, the distinction between unit operations and unit processes is that the unit operations are physical while the unit processes are chemical. Table I gives a list of the principal unit operations and unit processes of chemical engineering, taken from Shreve.1b Table 2 lists the principal unit operations and unit processes used for metal extraction. The division between unit operations and unit processes is similar to the chemical engineers' distinction and also correspollds approximately to the division of labor bctween mineral dressing and chemical metallurgy which has been customary in the past. Furthermore, it will be noted that in the proposed classification the unit processes primarily involve chemical reactions and/or changes in state of aggregation; the unit operations primarily do not involve either bulk

Jan 1, 1949

By D. M. Davidson

The drill sampling and evaluation of the Piney River ilmenite property was carried out during the early part of 1944 by E. J. Longyear Co., using the company's standard core-drill outfits to complete 44 holes to an average depth of IIO ft., from which were collected 1100 samples. The Piney River ilmenite-apatite lode is 25 miles north of Lynchburg, in Nelson and Amherst Counties, Virginia (Fig. I). Its elevation is about 900 ft. above sea level and it lies in the old pre-Cambrian complex of crystalline rocks that make up the Piedmont physiographic province lying east of the Blue Ridge Mountains. The terrain is gently rolling and well watered and is drained by the Piney and Tye Rivers, which are tributary to the James. Geology The Piney River ore body comprises the upper, weathered part of a tabular basic rock, which occurs in a large area of granite-gneiss. The section containing profitable ore is about 3000 ft. long. It is separated naturally by thinning, into northeastern and southwestern segments with widths of 300 and 100 ft. respectively. The dip averages 4.5° southeast but steepens locally (Figs. 2 and 3). The unaltered rock is an even, granular mixture of feldspar, ilmenite, and apatite, to which Watson1 gave the name Nelson-ite. The decomposed ore body, which is now being exploited by open cut, is a yellowish clay material in which black ilmenite and glassy apatite are the only conspicuous minerals. An economically important structural feature of the deposit is a banding of minerals coinciding with the dip and strike of the dike. This is more pronounced in the footwall of the northeastern part of the intrusive, where there is also a higher than average concentration of ilmenite. According to Watson,' the TiO2 content of the Nelsonites of this region ranges from 10 to 42 per cent, while P205 varies from 4 to 15 per cent. It is inexpedient at present to disclose exact metal content of the Piney River ore body; suffice it to say that the average tenor lies well within the extremes noted by Watson. Sampling Methods and Procedure During a preliminary inspection of the ore body, Longyear engineers surmised that because of its soft, clayey character, drill sampling would yield little core, therefore they made all possible preparations to procure accurate samples of the drill cuttings, or sludge. The first requisite in obtaining representative drill cuttings is to secure their full recovery. Only under certain conditions, and by employing a most careful and rigid sampling technique, is this pos sible. There must be no loss of the water circulating in the hole, and the velocity

Jan 1, 1949

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By Howard Clarke, Cyril Stanley Smith, Clarence Zener

The importance of cold-working in the fabrication of metals is in marked contrast with our ignorance as to the nature of the accompanying internal changes. The failure of the usual methods of testing to provide a consistent picture of these internal changes has given the incentive for the present program of investigating the effect of cold-working upon the internal friction of metals measured at small strain amplitudes. It has previously been shown1,2,3, that the internal friction introduced by cold-work is removed by annealing at comparatively low temperatures. In the present paper the following additional factors are investigated: (I) frequency of measurement, (2) amount of cold-work, (3) temperature of measurement. Special care was taken to minimize the internal friction due to causes other than cold-work. The present paper is purely experimental, the authors believing that any conclusions drawn from this work as to the nature of the internal changes accompanying cold-work would be premature.'l PrEpaRations oF Specimens In this study of cold-work it was desirable to eliminate as far as possible all other sources of internal friction. One disturbing source is the lack of temperature equilibrium between adjacent crystallites of a vibrating specimen.4 Temperature equilibrium is aided by small grain size and by the use of low-frequency vibrations. Unless unduly long specimens are used, low frequencies can be obtained only in transverse vibrations. But in transverse vibrations a second source of internal friction is present, that arising from transverse thermal currents.5 The effect of these may be reduced by increasing the transverse dimensions. The grain size and transverse dimensions of the specimens were thus so chosen as to render the vibrations simultaneously nearly isothermal with respect to intercrystalline thermal currents, and nearly adiabatic with respect to transverse thermal currents. The material for this investigation was a 70-30 brass, part of the same lot of material that was used for some earlier studies on the effect of strain on proportional limit.10 It had the following composition: copper, 70.59 per cent; zinc, 29.39; lead, 0.01; iron, 0.01. This material was received from the brass mill in the form of 3/4-in. rod, cold-drawn to final size by a 65 per cent reduction of area from material that had been annealed to give a grain size of 0.060 mm, Rods of appropriate length were annealed for 2 hr. at 400°C. and cooled in air. The annealed rods (grain size, 0.012 mm.) were then stretched in a tension-testing machine, using special grips1' to ensure axial application of the load. The rate

Jan 1, 1942

By Henry J. Welge

Laboortory apparatus has been devised which permits study of the displacement of oil from cores by water and by gas. The cores used contained interstitial brine as well as oil. Experiments were run to determine the comparative effect of varying the properties of the fluids used. No great effect was noted on the maximum displacement achieved. This observation made it unnecessary in initial work to use fluids in their exact reservoir conditions. Consequently, the displacements were run at near-atmospheric pressure in Pyrex glass equipment, using stripped crude oils. Introduction and Theory The chief object of this work has been to determine the efficiency of gas and water as primary agents for displacing oil from reservoir rock under laboratory conditions in which capillary phenomena were predominant. To this end the maximum displacement of oil from cores has been ascertained. This maximum displacement may not be equal to the maximum displacement from a reservoir; but it will be a close approxirnation to it sometimes, and other times the laboratory information will be useful in reservoir engineering predictions. It is] believed that the laboratory experimental maximum represents the upper limit for the reservoir recovery. The experiments were carried out by obtaining cores of interest from the reservoir, and filling the pores with interstitial brine and oil with the restored state tech- nique.1 Then the oil was displaced from the core as described later, either by brine from below, or by gas from above. The former type of displacement suggests analogy to production by water drive, but not to water flooding, for reasons discussed below. The latter type of displacement is believed to simulate production by gas cap displacement. The displacements were performed by what may be termed the capillary-pressure method. The cores are placed in capillary contact with an oil-wetted membrane which has very small pores (about I micron in diameter). Pores of this size will transmit oil but Prevent the Passage of gas or water, unless the Pressures used are higher than the capillary Pressures employed in this work. Accordingly, use of the membrane makes it possible to apply a capillary pressure differential between the displacing phase and the oil in the core. AS in the displacement of brine toward that condition of oil and water distribution existing originally in the reservoir,' it may not always be desirable to reduce the oil saturation in this experiment to an absolute minimum. With reservoirs having small productive closure, it is preferable to evaluate and use a displacing pressure no higher than the capillary pressure, Ap, which will ultimately become available for displacement in the reservoir. This pressure may be calculated from a knowledge of the density of the oil-in-place, do, the density of the displacing phase, dl, and Ah, the vertical distance between the section of the

Jan 1, 1949

By John M. Hartman

TWO systems are used for heating air in blast-furnace operations: I. The double surface system, in which a cast-iron pipe is heated on the outer surface, and, at the same time, heats the blast from its inner surface. This is simple in operation and gives a continuous effect, but is limited by 1100" F. as a maximum temperature of the blast. 11. The single surface system, by which large surfaces of fire-brick are heated, and air passed over the heated surface, absorbing the heat and carrying it on to the furnace. This system is more comylex than the double surface, as it invoives the reversing of the air and gas every hour and a half. The single surface system has two advantages: 1. The blast can be heated to a temperature of 1800° F. 2. The stoves are indestructible. From recent experience it has been found that 1300" F. to 1400' F. is the best average temperature for economy of coal for safe working. This is equivalent to a saving of 11/2 to 2 cwt. of coal per ton of iron over the extreme limit of cast-iron stoves. Independently of this, it is a strong point in favor of this system that the blast can be raised to a temperature of 1800° F. within an hour when the hearth is getting cold. All furnacemen know the ralue of a hot hearth for quality and quantity of iron. Cooling of a hearth occurs from leaky tuyeres, scaffolds, or heavy burden. When there is not sufficient coal at the tuyeres to seize on the oxygen of the entering air and convert it at once to carbonic oxide, there will not be enough heat to liquefy the cinder. Black cinder and poor iron are the results. The remedy is additional heat from the blast. If the stoves will give 1800" in place of 1100°, it is obvions that the furnaces will get around sooner, and without waiting for a change of burden at the tunnel head to bring extra coal to the hearth. The heat absorption caused by a leaky tuyere will chill the hearth and drive the zone of fusion higher up in the furnace. This loss must be supplied, and the calorics lost to the hearth must be regained before good iron can be made. Take another case: A furnace carefully burdened on No. 1 iron, during a spell of damp weather, goes on to No. 2 or No. 3. Heat is lost to the furnace through absorption by the moisture, and less burden must be carried in order to get back on No. 1. When the

Jan 1, 1879

By T. G. Richardson, F. M. Perkins

In the recent paper of Richardson and Perkins entitled "A Laboratory Investigation of the Effect of Rate on Recovery of Oil by Water Flooding,"' the authors found very little appzrent effect on oil recovery of having free gas saturation present prior to water flooding in unconsolidated sands. We agree that the effect in this particular system was small but do not feel that the data presented should be regarded as disproving work of others which has shown an appreciable effect. The authors do not make such a claim, but neither do they advance an explanation of the difference. In our experience the following factors must be carefully considered when studying the relation between residual oil saturation after water flooding and initial free gas saturation: (1) the magnitude of the inherent residual oil saturation, i.e., the residual oil saturation with no free gas; (2) the increase in oil-water viscosity ratio with pressure lowering if the gas saturation is obtained by solution gas drive; and (3) the oil shrinkage which occurs with pressure lowering and gas evolution. The system studied by Richardson and Perkins gave residual oil saturations as low as 20 per cent without free gas present, and one should perhaps not expect much further lowering. As an illustration of the magnitude of the effect when the residual oil saturation is inherently higher we submit the accompanying figure. These data were obtained on an unconsolidated sand under elevated pressure in a system similar to the one described by Richardson and Perkins. Gas saturation was established by gas drive before water flooding. The viscosity ratio was 600:1 under the conditions of the displacement. Here the gas was extremely effective in reducing residual oil saturation. This fact was also indicated by Kyte, et al.2 Their plots of residual oil saturation vs initial gas saturation show trends of greater free gas effect with higher oil viscosities. The pressure-dependent effects were not discussed by Richardson and Perkins. They should be separated from the free gas effect if the objective of the study is a correlation of residual oil saturation vs initial free gas saturation. The increase in oil viscosity when gas is released from solution tends to increase residual oil saturation. This effect is rather small in the viscosity range of kerosene. A Buckley-Leverett calculation, assuming an increase in viscosity ratio from 1.2 to 1.8, indicates an increase in residual oil saturation of about 1 per cent of pore volume. Thus, one would expect this system, if operated at constant viscosity ratio, to show a slightly greater free gas effect. As Dyes- as shown, oil shrinkage can offset the beneficial effect of free gas on waterflood oil recovery, if the gas saturation is established by depletion. Since

Jan 1, 1958

By E. S. Machlin

THE function of this paper is to present certain results based on the fact that the strain energy arising from the solution of out-of-size solute atoms into the solid matrix is free energy and not internal energy, and that this strain energy is almost wholly shear strain energy as Zener1 pointed out. One natural consequence of this fact is an expression for the excess entropy of mixing due to the strain energy. Also, a derivation of the integral molar free energy of mixing partitioned to strain energy will be made using the model of Lawson2 and thermodynamics. This derivation has the advantage of showing in a simple way the assumptions involved in Lawson's treatment. The excess entropy of mixing partitioned to strain energy can be derived in two ways. The first way makes use of the fact that the strain energy is almost wholly in the form of shear strain energy. In this case, as Zener1 pointed out, the change in entropy due to the addition of shear strain energy is to a first approximation given by ?S/?? p,T = - ?lnµ/?T p,? Hence, the excess entropy of mixing partitioned to strain energy will be given by Sx ? = ?S/?? p,T Gx ? = - ?lnµ/?T p,? Gx ? where, Gx ? is the relative integral molar free en- ergy partitioned to strain energy; S is the entropy; is the shear strain energy; µ is the shear modulus; T is the absolute temperature; p is the pressure; and ? is the shear strain. Zener,1 as well as others, has pointed out that the shear strain energy stored in a compressible isotropic solid due to the insertion of an off-size incompres-sible sphere into a spherical hole in the solid, is approximately given by 2/3 µ/O (O°I - O)2 where a is the volume of spherical hole and no , is the volume of sphere. If we now consider the introduction of one mol of such spheres into an infinite volume of solid, then the relative partial molar free energy excess due to strain energy alone is GM ? = 2/3 µ/v (v ° 1 - v)2 where v is the molar volume of solvent and v°1, is the molar volume of pure solute type 1. Let us consider that these spheres are the two types of atoms in a binary solution, then there will be a similar relation for solute 2. The total relative integral molar free energy excess due to strain is then, to the approximations stated above GM ? = GM ? x1 + GM2 ? x2 = 2/3 µ/v [(v ° 1 - v)2 x1 + (v ° 1 - v)2 x2]. Lawson's relation for the strain energy can be de-

Jan 1, 1955

By Ralph Hultgren, David W. Mitchell

Magnesium alloys usually are superheated before casting in order to ensure fineness of grain. Superheat temperatures in common use range from 1600" to r 7o0°F.; the casting temperature, which depends upon the mold shape, is usually 200° to 300°F. lower. The process of superhcating requires considerable time and seriously shortens the life of the iron pots used. Recently it has been reported1 that if acetylene, carbon dioxide or natural gas is bubbled through molten electrolytic A.S.T.M. No. 4 alloy at 1400°F. for 5 min., grain refinement equivalent to that of superheating will take place. Addition of certain solids such as graphite or aluminum carbide accomplishes the same results? As will be shown in this paper, it is possible to achieve grain refinement in magnesium casting alloys at low temperatures by mechanical stirring of the molten metal for a short time. This process was developed in the course of research work, supervised by the War Metallurgy Committee under the "Restricted' project NRC-550, for the Office of Production Research and Development of the War Production Board. This paper, based on that work, has been released for publication by the O.P.R.D. Materials and Methods The alloys studied were the most common American sand-casting alloys designated as No. 4 and No. 17 by the American Society for Testing Materials. The magnesiun used in these alloys was of both carbothermic3 and electrolytic' origin. Chemical analyses supplied by the producers are shown in Table I. Each heat consisted of approximately 5 lb. of alloy melted in a Tercod crucible. It was refined by fluxing with Permanente No. 7* refining flux at 1300° to 1350°F. After cooling to 1200° to 1250°F., portions of approximately one pound each, were ladled into iron crucibles contained in an electric furnace at about 1250°F. The molten metal was covered with Permanente No. 21 † covering flux and then heated to the temperature to be investigated. Normally each of the four portions was given a different treatment. In a typical case one portion was stirred vigorously for 5 min., acetylene gas was passed through a second portion for 5 min., a third portion was superheated to 1600°F. for 15 min., then . cooled to casting temperature, and the fourth was held for 5 min. at the temperature of stirring or gassing without other treatment. Each portion was then cast into one-inch diameter cylinders in three "nonturbulent" molds of identical shape. One mold was made of cast iron and the other two of baked sand. The cast-iron mold and one of the baked sand molds were heated to 360°F., the other baked sand mold was at room temperature. The freezing times in these molds were

Jan 1, 1945

By R. W. Gurry

THERMODYNAMIC calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a. better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganeie, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B203 in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1943

Discussion of the paper of LAWRENCE ADDICKS, presented at the Salt Lake meet-ing, August, 1914, and printed in Bulletin No. 91, July, 1914, pp. 1671 to 1674. JAMES H. PAYNE, Baltimore, Md. (communication to the Secretary*). -Mr. Addicks's account of the behavior of the nodulizer at Chrome on blast-furnace flue dust leads me to outline what has been done so far upon the application .of the same apparatus to fine sulphide concentrates. As Mr. Addicks states in his paper, the conditions prevailing in the test kiln at Yorktown in the demonstration I made for him upon Chrome material were strongly oxidizing; so much so that the sulphur was roasted down to less than 1 per cent. It is therefore to be expected that the first test made upon sulphide ore a short time after this, in which Ducktown green ore fines were used, did not show very promising results. Although the Ducktown ore contained only 13.52 per cent. of sulphur its gangue was quite fusible, and the intense heat generated by the oxidation of. the extremely fine sulphide particles slagged the mass, bringing about a condition approximating that of a Brückner roaster in distress. During the spring and summer of 1912, the writer kept working upon different schemes to cut clown this slagging. Two successful methods were finally worked 'out embodying opposite principles, one promoting oxidation of the finer particles and the other retarding. their oxidation. In the early part of the present year the writer succeeded in interesting the Braden Copper Co. in nodulizing, with the result that an extensive series of tests were made at Yorktown upon oil-floated concentrates covering quite a wide range in analysis. These tests led to trials in the Chrome rotary on the part of the U. S. Metals Refining Co. of Minerals Separation concentrates which they had in stock, and later to test runs to check up the Yorktown runs on Braden concentrates. The large-scale tests checked up with the Yorktown tests in every way (except fuel consumption, which was, however, correctly predicted), and led to the Braden company's decision to adopt the process at Braden. The fuel consumption upon oil-floated concentrates is not over 6 gal. per ton and in many cases is less. The action in the furnace is independent of the sulphur content, and there is actually less tendency to form nose rings in the Chrome rotary than upon flue dust. It is believed that the improvements entering into the design of the Braden kilns will cut down the nose-ring trouble to where it will no longer be a drawback to the process.

Jan 11, 1914