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By C. S. Roberts

Microstructural studies of a Mg-10.3 pct Al alloy showed that discontinuous precipitation during aging multiplies the grain boundary area available for easy deformation in elevated temperature creep. An increase of strain rate for a 6.2 pct Al alloy at 400°F, where precipitation and creep are concurrent, caused an increase in the volume percentage discontinuously precipitated at the completion of the process. The relatively poor elevated temperature creep resistance of heat treated alloys of the Mg-AI-Zn type was explained in these structural terms. C resistance of the heat treatable Mg-A1 based alloys is poor compared to that of Mg-Ce based alloys. While the latter show a continuous precipitate, Mg-A1 alloys prefer a discontinuous precipitate at grain boundaries. '.:' It has been concluded that the excellent creep resistance of Mg-Ce alloys was primarily due to the continuous precipitation which especially localized at the grain boundaries.' The purpose of the present investigation was to obtain a parallel correlation, if such exists, between the poor creep resistance and the state of precipitation in Mg-A1 alloys. Discontinuous precipitation produces about three times as many true grain boundaries as originally existed. This microstructure would be expected to have a marked influence in creep, where quantity of grain boundary area is important. Experimental Procedure The two experimental alloys contained 6.2 and 10.3 pct Al. They were made from electrolytic magnesium by alloying under flux and casting in 3 in. diam permanent molds. The ingots were extruded into 1 1/4 x 1/8 in. flat stock under the following conditions: billet preheat 700°F (2 hr), container and die temperature 700°F, speed 3 fpm, and area reduction ratio 45:1. The creep specimens were machined from blanks which had been solution heat treated 24 hr at 770°F and aged 16 hr at 400°F. Attempts were made to control the grain size as closely as possible for extruded stock. The grain size after solution heat treatment was about two thousandths of an inch for the 6.2 and five thousandths for the 10.3 pct Al alloy.

Jan 1, 1957

By J. S. Fulton

Those who live in steel-mill towns are so accustomed to the sight of flames spouting from the mouth of a Bessemer vessel that they seldom pause to think of the amazing process behind it. Actually cold air is being blown through a hot liquid and, instead of cooling it, raises the temperature of the liquid. When coffee is too hot to drink, we know that blowing on it will cool it, so it was no wonder that when Henry Bessemer (or William Kelly, as your patriotism chooses) first proposed this cycle of steel production, he was considered mad. When Bessemer and Kelly started their investigations around 1852, there was not much practical knowledge of metallurgy and, in consequence, there was wide variation in the product made by their process. It was appreciated that the silicon, carbon and iron were all potential fuels, but not until Mushet discovered the beneficial effects of having manganese in the pig iron did the process really become commercial. Bessemer's patent of 1855 covered a crucibleful of liquid iron into which a refractory tuyere was lowered and the blow started. Since that time virtually every conceivable form of vessel, bottom arrangemerit, tuyere size and location have been suggested or tried. There have been stationary vessels with fixed bottoms, that were side, top or bottom blown; tilting vessels with two sets of side tuyeres at different elevations; vessels like a three-compartmerit septic tank; vessels of a cylindrical form supported on the long axis with tuyeres along the side submerged by a partial rotation of the vessel (this type continues in copper refineries); portable vessels to make the blow in a ladle over a mold in a foundry; a combination of a cupola and converter in one shell, and various other arrangements. But in all these experiments, compressed air for the blast was presupposed and there was little discussion of the quantity or quality of the air delivered to the tuyeres. At one time or another various practices that now are forgotten have been tried or suggested: for instance, the use of inert gas at the end of the blow; the addition of fuel to the blast; the use of hot-blast stoves; the drying of the air to a minimum moisture in the blast. Except in the last-named method little attention was paid to the quality or quantity of the air blown. Phases Of the many Papers published On various phases of the Bessemer process, nearly '7' according to one bibliography, Over go per 'ent were concerned with the metallurgical phase and less than '0 per cent discussed various sections of the pneumatic phase. Since the two phases are coincidental, apparently nine times as much thought has been given to the result as has been given to One of the causes of the Bessemer process. IS it not possible that if more attention had been paid to the pneumatics so many papers would not have had to be written on the troubles in the metallurgical phase? A study of published papers and conversation

Jan 1, 1941

By J. S. Fulton

Those who live in steel-mill towns are so accustomed to the sight of flames spouting from the mouth of a Bessemer vessel that they seldom pause to think of the amazing process behind it. Actually cold air is being blown through a hot liquid and, instead of cooling it, raises the temperature of the liquid. When coffee is too hot to drink, we know that blowing on it will cool it, so it was no wonder that when Henry Bessemer (or William Kelly, as your patriotism chooses) first proposed this cycle of steel production, he was considered mad. When Bessemer and Kelly started their investigations around 1852, there was not much practical knowledge of metallurgy and, in consequence, there was wide variation in the product made by their process. It was appreciated that the silicon, carbon and iron were all potential fuels, but not until Mushet discovered the beneficial effects of having manganese in the pig iron did the process really become commercial. Bessemer's patent of 1855 covered a crucibleful of liquid iron into which a refractory tuyere was lowered and the blow started. Since that time virtually every conceivable form of vessel, bottom arrangemerit, tuyere size and location have been suggested or tried. There have been stationary vessels with fixed bottoms, that were side, top or bottom blown; tilting vessels with two sets of side tuyeres at different elevations; vessels like a three-compartmerit septic tank; vessels of a cylindrical form supported on the long axis with tuyeres along the side submerged by a partial rotation of the vessel (this type continues in copper refineries); portable vessels to make the blow in a ladle over a mold in a foundry; a combination of a cupola and converter in one shell, and various other arrangements. But in all these experiments, compressed air for the blast was presupposed and there was little discussion of the quantity or quality of the air delivered to the tuyeres. At one time or another various practices that now are forgotten have been tried or suggested: for instance, the use of inert gas at the end of the blow; the addition of fuel to the blast; the use of hot-blast stoves; the drying of the air to a minimum moisture in the blast. Except in the last-named method little attention was paid to the quality or quantity of the air blown. Phases Of the many Papers published On various phases of the Bessemer process, nearly '7' according to one bibliography, Over go per 'ent were concerned with the metallurgical phase and less than '0 per cent discussed various sections of the pneumatic phase. Since the two phases are coincidental, apparently nine times as much thought has been given to the result as has been given to One of the causes of the Bessemer process. IS it not possible that if more attention had been paid to the pneumatics so many papers would not have had to be written on the troubles in the metallurgical phase? A study of published papers and conversation

Jan 1, 1941

By Hans Neuberger

In our everyday life, visual perception plays perhaps a more important role than any of the other senses with which we are equipped by nature. It is, therefore, quite understandable that the average person associates with the term ''atmospheric pollution," clouds of dust, palls of smoke or deposits of soot, phenomena which are so familiar to the residents of industrial cities. On the other hand, "air" is usually considered the prototype of the invisible, of the intangible, and any suspensions in the air which do not conform to this concept, are regarded as foreign to the atmosphere and thus as "pollution." According to Webster, the term "pollution" implies uncleanness, impurity, in short, something undesirable. Although the scientist often accepts popular concepts, he is generally inclined to suspect that apparently "obvious" phenomena imply, literally, "more than meets the eye." To show that this suspicion is also justified with regard to atmospheric pollution, is the objective of this discussion. It will be shown that what seems foreign to the air at first sight, is by nature an integral part of it, and that the more important aspects of pollution generally escape attention. The Atmospheric Constituents We can distinguish two classes of atmos-pheric constituents: the Permanent gases, chiefly nitrogen, oxygen, traces of argon, neon, and others, and the variable constituents which include water in its different states, carbon dioxide, ozone, and various suspensions, either in gaseous, liquid or solid form. These suspensions, known by the collective term "Aerosol,"20 will be considered in detail. Dust There are two general types of aerosols: the first type is represented by the socalled "neutral" particles,3 commonly known as dust and experienced by everyone, as it is the more conspicuous type of suspensions. It often represents a special problem to the mining engineer, the mechanical engineer, the industrial engineer, and many other professional men. Dust consists of finely divided solids derived from weathering, drilling, handling and preparation of rocks and coal. Dust may also consist of organic or inorganic particles resulting from manufacture of a variety of products such as flour, rubber, lime and steel, from traffic on land be it on the highways, on rails or in city streets, from decomposed vegetation or from volcanic eruptions. Perhaps the most reviled member of this class of suspensions is the soot and fly ashes from coal fires and other combustion processes. The cosmic source of dust, namely the injection of meteoric matter into the atmos-,,here, is of minor significance because the concentration of particles is exceedingly small despite the relatively large mass of material which invades the earth's atmos-phere from space.

Jan 1, 1949

P. E. McKinney,* Washington, D. C.-Observation made after examination of a number of defective gun forgings, together with a history of their manufacture, has strongly suggested that so-called "flakes" and woody or fibrous fractures are not necessarily analogous and are often caused by entirely different conditions. While some flaked bars may show fibrous areas in the fracture, it does not necessarily follow that the conditions causing these areas are the same as cause the fibrous, or so-called laminated, structures so commonly met in gun forgings subject to transverse tensile test; the fibrous structure formed in some flaky bars are merely incidental to the conditions causing the flakes. It is believed that the so-called flakes, or bright silvery spots, are mainly due to inherent physical defects in the steel, which existed at the very origin of the steel, rather than metallographic defects caused by subsequent irregularities in mechanical or thermal treatment. While great care in forging and treatment may, in a measure, tend to overcome the evil effect of the defects, with many heats of ingots, no such precautionary measures are needed to produce perfect forgings- and with such heats of steel it would be impossible, no matter how carelessly handled, to produce intentionally a forging containing the defects commonly known as flakes. It has been found possible, on several occasions, to actually predict flaky forgings from an inspection f the ingot after it had solidified, and in such cases no amount of careful forging or heat treatment would prevent the occurrence of such defects in the forging. The inspection of the physical condition of the ingot, and especially the character of the shrinkage on. the top of the ingot, has been given too little thought and study in this connection.

Jan 5, 1919

By D. W. Fuerstenau

Measurement of zeta potentials is a useful tool to study the surface chemistry of minerals under flotation conditions. Because there is continued interest in this approach, the apparatus for obtaining zeta potentials of nonconducting solids by the streaming potential method is outlined here. Fig. 1 illustrates the streaming potential apparatus. The streaming potential cell or plug consists of two 24/40 standard ground joints (4) joined with a piece of pyrex tubing 60 mm long and 12 mm in diam (5). The electrodes are made of bright platinum disks 19 mm in diam and 1 mm thick through which 0.5-mm holes have been drilled (6). To the surface of each is welded a piece of 80-mesh platinum gauze. Each electrode is permanently mounted on the ends of the inner parts of the two standard joints by means of a platinum wire (7) which connects it to the tungsten seal at the end of the cell (8). For ease in cleaning and handling the apparatus, the streaming cell is fastened to the 500-ml reservoir flasks (1) by means of two 18/9 ball and socket joints (2). This particular arrangement permits passage of the solution in either direction through the plug of particles. Flow of solution can be stopped by a stopcock (3). One of the reservoir flasks has a large opening to permit insertion of either a thermometer or a pair of electrodes for measuring pH of solutions within the system. In making the experiments, the plug is filled with 48 to 65-mesh particles, but a layer of 28 to 35-mesh particles is placed at each electrode to prevent any of the finer particles from passing through holes in the electrodes.

Aug 1, 1956

By J. B. Conway

RECENT studies of first-stage creep data have led to a special least-squares procedure for use in calculating the Andrade creep-equation constants. This procedure is easy to apply, uses only experimental data, and yields results which do not vary with the individual making the analysis. Taking logarithms of the Andrade equation I = lo(1 +ßl1/3)ekt leads to In l = In lo + In(1 + ßl1/3) + kt A residual can then be defined as the difference between the logarithm of an experimental length value and the logarithm of a calculated length value. Following the usual least-squares approach differentiation with respect to 10 and k of the expression for the sum of the squares of the residuals leads to two equations which cannot be solved directly for the three constants involved. However, values of ß can be assumed and corresponding values of lo and k can then be calculated. Then the sum of the squares of the residuals can be calculated. For a certain value of ß this sum will exhibit a minimum value to identify the least-squares values for ß, lo, and k. An illustration of the application of the above least-squares approach is obtained by employing the creep data for lead originally presented by Andrade' in the development of the one-third creep law. A plot of the sum of the squares of the residuals as a function of ß is shown in Fig. 1 along with the corresponding lo and k values. The minimum is seen to occur at ß = 0.0143 from which lo = 39.149 and k = 7.27 x 10-5. Based on these results the Andrade equation for these lead data is 1 = 39.149(1 + 0.0143 t1/3)e7.27 x 10-5t compared to the equation I = 39.13(1 + 0.01457/l/3)e6.95 X 10-5t developed by Andrade (calculation procedure not given but was probably a graphical solution). Calculating length values using the above equations and comparing with the experimental length values, residuals corresponding to the difference between experimental and calculated length values can be obtained. The sum of the squares of the residuals can then be calculated. For the case of the least-squares approach a value for this sum was found to be 2.37 x 10-3 compared to a value of 3.47 x 10" for the equation originally proposed by Andrade. In other words, while the constants proposed by Andrade provide an excellent fit for the lead data, a still better representation is afforded by applying the least-squares approach discussed above. A similar result was obtained for the lead data at 162oc.l The least-squares approach led to 1 = 9.866(1 + 0.0497 t1/3)el.011 x 10-2t compared to the equation I = 9.94(1 + 0.0433 l1/3)e1.06 X 10-2t given by Andrade. In this case, too, the sum of the squares of the residuals is slightly smaller for the equation based on the least-squares approach. It should be pointed out that a double trial and er-

Jan 1, 1965

By T. Suzuki

LABOR. conditions have finally caused rock-drilling machines to supplant hand drillers in the Japanese mining industry, and have encouraged this study. During a period of three years 25,000 tests were made on 67 different American, Japanese, and European rock drills, using, respectively, the Paynter testing machine, and drilling in granite and limestone. Recorded were: air consumption, speed of rotation, torque of rotation, foot-pounds of striking energy, air pressures, input horsepowers, and speed of rock penetration. The author expresses his views on the interrelation of these factors and offers theoretical support, as well, by formulas based upon the mechanics of impact. He discusses the different designs of the valves, cylinders, piston hammers and rotation devices involved in the different types of rock drills, with respect to their merits and defects and offers conclusions about the factors that should be considered in the new design of a superior rock drill. The author's mathematical demonstrations and arguments for a value of "best feed clearance" of the drill bit from the rock are based upon the hand-operated screw-fed type of hammer drill. Automatic feeds have not been considered in this paper except for the tests on one drifter with air feed, 10 air-feed stopers, and some hand-held blockholers. The following classes of drills, with one of each model, size, or type, were tested: 23 heavy drifters, 34 light drifters and hand-held drills, and 10 stopers. They represented the following makes and models: 40 from the United States—namely, Ingersoll-Rand 18, 148, L-74, 24-70, N-72, N-75, R-72, 26, BAR-33, BCR-430, DCRW-23, RA-12, CA-31, CC-11; Denver 7, 107, WT-21, WT-31, WT-331, WT-337 (models WT with motor rotation, screw feed), 11, Waugh 93, 95; Waugh 16; Sullivan DR-6, DW-64, T-3; DP-321, DP-331; DA-21, DT-44, DT-421; Gilman AX-321 (motor rotation and air feed); Cleveland D-5; AIBQ, 44-SWR,

Jan 1, 1940

By T. Suzuki

LABOR. conditions have finally caused rock-drilling machines to supplant hand drillers in the Japanese mining industry, and have encouraged this study. During a period of three years 25,000 tests were made on 67 different American, Japanese, and European rock drills, using, respectively, the Paynter testing machine, and drilling in granite and limestone. Recorded were: air consumption, speed of rotation, torque of rotation, foot-pounds of striking energy, air pressures, input horsepowers, and speed of rock penetration. The author expresses his views on the interrelation of these factors and offers theoretical support, as well, by formulas based upon the mechanics of impact. He discusses the different designs of the valves, cylinders, piston hammers and rotation devices involved in the different types of rock drills, with respect to their merits and defects and offers conclusions about the factors that should be considered in the new design of a superior rock drill. The author's mathematical demonstrations and arguments for a value of "best feed clearance" of the drill bit from the rock are based upon the hand-operated screw-fed type of hammer drill. Automatic feeds have not been considered in this paper except for the tests on one drifter with air feed, 10 air-feed stopers, and some hand-held blockholers. The following classes of drills, with one of each model, size, or type, were tested: 23 heavy drifters, 34 light drifters and hand-held drills, and 10 stopers. They represented the following makes and models: 40 from the United States—namely, Ingersoll-Rand 18, 148, L-74, 24-70, N-72, N-75, R-72, 26, BAR-33, BCR-430, DCRW-23, RA-12, CA-31, CC-11; Denver 7, 107, WT-21, WT-31, WT-331, WT-337 (models WT with motor rotation, screw feed), 11, Waugh 93, 95; Waugh 16; Sullivan DR-6, DW-64, T-3; DP-321, DP-331; DA-21, DT-44, DT-421; Gilman AX-321 (motor rotation and air feed); Cleveland D-5; AIBQ, 44-SWR,

Jan 1, 1940

Discussion of the paper of W. C. PHALEN, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 93, September, 1914, pp. 2249 to 2265. DAVID T. DAY, Washington, D. C.-Consider the United States broadly and the distribution of the salt industry. Think of the old solar-evaporation process up in New York State, then of the more recent processes in Michigan and Kansas and Louisiana, where the rock salt furnishes a large industry, then of the solar-evaporation process at Salt Lake, then turn to the crucial place in the United States, where there is an embarrassment of salt, and that is California. I am not forgetting' the immense body of salt east of that in the Virgin River country of Utah; but in California the situation is interesting. There are very large quantities of salt in the Searles Marsh region; again, in Southern California, at the southern end of Death Valley, there are two or three mountains of salt which have been explored recently, where the salt is sufficiently pure to be used at once. There is also a large deposit of gypsum, and it would be possible there, by extremely cheap means, to produce an amount of salt sufficient to furnish the United States' greatest needs. The principal reason that capital has been deterred from developing such a large mass is not the fact that solar evaporation produces a great deal of salt around San Francisco, but the fact that if potash salt is to be produced in connection with the salt in the borax region a, great deal of ordinary salt must be disposed of. It cannot be dumped, for it would get back into the brine again; the first rains would bring that salt back into solution again. It must be sold, given away, or hauled to a distance, which would mean a considerable freight charge. The salt will be going begging. E. G. SPILSBURY, New York, N. Y.-The remark of Dr. Day's regarding the likelihood of the production of a large amount of waste salt brings to my mind the condition that obtains in Germany in all of the potash fields. In Germany salt is a government monopoly. In the development of the potash deposits, it becomes a grave question as to how much salt they may be allowed to extract and bring to the surface.

Jan 4, 1915

By Jean Howard

ALTHOUGH zone melting has found favor in recent years because of its convenience and its faster rate of production of single crystals, the older technique of strain annealing still has a number of advantages. It has been reported1 that the lattice of a crystal prepared in this manner has fewer defects than one grown from the melt and, of course, the control of the external geometry is easier. Also, the diameter of the crystal which can be grown by zone melting has a theoretical limit determined by the surface tension, thermal conductivity, and specific gravity of the material, while the size of that which can be grown in the solid state is limited only by practical considerations. In a program for the study of the structure-sensitive properties of niobium and its alloys it was desirable, for ease of handling, to have available single crystals of large diameter. This requirement dictated the choice of the strain-anneal technique. Induction heating was chosen in the present work in preference to other methods because of its deep penetration of large-diameter sections. A five-turn coil, powered by a motor generator operating at 10,000 cps, is contained in a vacuum chamber. The work is lowered through the coil for both the recrystallization and the crystal-growth steps. Starting with electron-beam melted material, the bars are cold-swaged, recrystallized, strained in a tensile machine, and then subjected to the growth step. Single crystals have been grown under the following conditions: Reduction in area during swaging— 79 to 99 pct, recrystallization temperature—1500o to 1667°C at the rate of 1.25 in. per hr, strain—1.0 to 2.5 pct, growth temperature—1600o to 2400°C at rates from 0.15 to 1.25 in. per hr. Starting grain sizes achieved after the recrystallization step varied from 0.6 to 1.55 mm. The starting grain size was found to be critical; if it is too fine and has any residual cold work, as shown by the presence of a fiberlike texture, a single crystal cannot be grown. Using this technique niobium single crystals have been grown from 0.250 in. diameter and 12 in. long to 1.00 in. diameter and 5 in. long as shown in Fig. 1. The 1-in. crystal is the largest to be reported for a refractory metal as compared to 0.500 in. for molybdenum grown by zone melting.2 As with zone melting, control of orientation is possible by the use of special procedures. Other investigators, see for example Williamson and Smallman,3 have reported that orientation control may be achieved by a bending technique. In the present work the strained rod is partially lowered through the coil to start the growth of the crystal. Then it is removed and bent at a point ahead of the interface between the single and polycrystalline portions. Finally, it is returned to the chamber and growth is continued "around the corner". The amount of bending which can be imparted to the rod is limited by coil geometry which up to now has been 10 deg. However, by repeating the bending and growing operations it should be possible to attain any desired orientation. The perfection of these single-crystal specimens as a function of process variables is being measured by X-ray and metallographic techniques and the results will be reported in a forthcoming paper. This work was partially supported by the Advanced Research Projects Agency.

Jan 1, 1964

By P. R. Kalischer

In the production of alloys by powder metallurgical processes it is often necessary or desirable to include one or more cornponents that tend to form very stable oxides. Included in this group of metals are aluminum, manganese, magnesium, silicon, and a few others. In many cases it is not necessary for the sintered compact to have full density and the other physical characteristics of a cast alloy and in that event no undue precautions need be taken. If, however, it is required that the sintered part be entirely homogeneous, and have maximum density and physical properties, some method must be found to reduce the surface films of oxide, which are always present on the metals, and for the metals mentioned above this is always extremely difficult, if not impossible. since the production of high-density alloys is of particular interest to powder metallurgists, some experiments were undertaken to devise methods of reducing the refractory oxides. For this work, alloys of iron, nickel, and aluminum were chosen because aluminum oxide is one of the most stable oxides and because these alloys in the right compositions form excellent permanent magnets. All of the pertinent properties of the magnets could be accurately and delicately measured by density measuremerits and magnetic tests of sufficient scope to give a complete demagnetization curve. From such a curve the maximum coercive force, residual magnetism, and energy products could be obtained and compared with the same properties for a cast material. Any lack of homogeneity, density, or solid diffusion would be immediately apparent as a decrease in the magnetic properties. Nature and Removal of Surface Barriers The early work of the present investigation was based upon published processes.* In the published information it was claimed that by intimately mixing iron, nickel, and iron-aluminum alloy (50 Per cent Fe, So Per cent Al) powders, compressing such a mixture into the desired shape and size, and then sintering (heating to a temperature below the melting point of the component metals) in hydrogen at 1200°C. or higher, a sound, homogeneous article could be made having the desired physical size, shape, and strength, and good magnetic characteristics. However. this early work showed clearly that something in the powder compress was inhibiting diffusion and the process was almost entirely unworkable. In the initial phase of the investigation samples of iron powder, nickel powder, and iron-aluminum alloy powder were pressed into separate bars and sintered in hydrogen. Both the iron and nickel powders sintered

Jan 1, 1941

By P. R. Kalischer

In the production of alloys by powder metallurgical processes it is often necessary or desirable to include one or more cornponents that tend to form very stable oxides. Included in this group of metals are aluminum, manganese, magnesium, silicon, and a few others. In many cases it is not necessary for the sintered compact to have full density and the other physical characteristics of a cast alloy and in that event no undue precautions need be taken. If, however, it is required that the sintered part be entirely homogeneous, and have maximum density and physical properties, some method must be found to reduce the surface films of oxide, which are always present on the metals, and for the metals mentioned above this is always extremely difficult, if not impossible. since the production of high-density alloys is of particular interest to powder metallurgists, some experiments were undertaken to devise methods of reducing the refractory oxides. For this work, alloys of iron, nickel, and aluminum were chosen because aluminum oxide is one of the most stable oxides and because these alloys in the right compositions form excellent permanent magnets. All of the pertinent properties of the magnets could be accurately and delicately measured by density measuremerits and magnetic tests of sufficient scope to give a complete demagnetization curve. From such a curve the maximum coercive force, residual magnetism, and energy products could be obtained and compared with the same properties for a cast material. Any lack of homogeneity, density, or solid diffusion would be immediately apparent as a decrease in the magnetic properties. Nature and Removal of Surface Barriers The early work of the present investigation was based upon published processes.* In the published information it was claimed that by intimately mixing iron, nickel, and iron-aluminum alloy (50 Per cent Fe, So Per cent Al) powders, compressing such a mixture into the desired shape and size, and then sintering (heating to a temperature below the melting point of the component metals) in hydrogen at 1200°C. or higher, a sound, homogeneous article could be made having the desired physical size, shape, and strength, and good magnetic characteristics. However. this early work showed clearly that something in the powder compress was inhibiting diffusion and the process was almost entirely unworkable. In the initial phase of the investigation samples of iron powder, nickel powder, and iron-aluminum alloy powder were pressed into separate bars and sintered in hydrogen. Both the iron and nickel powders sintered

Jan 1, 1941

By A. F. Crawley

THIS communication reports measurements of the densities of dilute liquid alloys of 0.1 and 0.5 pct Ag in Sn over temperature ranges of 170" and 210°C, respectively, above the melting point of pure tin (232°C). The work was earried out to provide accurate density data for some liquid diffusion studies performed by Davis.1 Densities were measured using a pycnometric technique established in this laboratory. Earlier papers2, 4 attest to the accuracy of ±0.05 pct and the reliability of the method. Tin, 99.999 pct pure, and silver 99.99 pct pure, were melted in a graphite crucible in a vacuum furnace and held at temperature for 10 hr to ensure homogenization. Ingots suitable for machining

Jan 1, 1970

By A. E. Back, K. E. Tame, W. F. Wyman, S. F. Ravitz

IN 1940, when it appeared that the United States soon might be cut off from foreign sources of high-grade manganese ore, the Bureau of Mines began an extensive series of investigations on the production of ferrgrade products from low-grade domestic ores by ore-dressing, pyrometallurgical, and hydrometallurgical methods. Among the hydrometallurgical processes for oxide ores investigated was a sulphur dioxide process in which the manganese was recovered from solution by precipitation with lime;1 this process is essentially as follows: The ground ore is suspended in water and leached with SO2 gas to extract the manganese as manganese sulphate. Calcium chloride is then added to the slurry to precipitate calcium sulphate and form manganous chloride solution, and the resultant slurry is filtered to remove the calcium sulphate together with the in- soluble portion of the ore. Calcium hydroxide is added to the filtrate and the mixture is agitated with air to precipitate hydrated oxides of manganese and regenerate calcium chloride. The precipitate is calcined, and the calcium chloride is recycled. To determine manganese extraction, reagent consumption, grade of product, and similar data for this process, a laboratory investigation was started. Two minor modifications in the process were soon made: (I) the ore was suspended in calcium chloride solution instead of in water in order to extract the manganese and precipitate the calcium sulphate in one step, and (2) the agitation with air after the addition of slaked lime to the filtrate was omitted because manganese hydroxide is readily precipitated without air agitation and can be nodulized or sintered to a satisfactory product. When the process was carried through a series of cyclic tests, it was noted that the concentration of dithionate ion (which is one of the products of oxidation of SO2 by MnOz) in the cycled solution gradually increased; at the same time the chloride content of the solution gradually decreased, owing to soluble losses in the leach residue and in the precipitate. After a number of cycles, the calcium chloride became virtually completely replaced by calcium dithionate, the quantity of dithionate ion formed during the leach being more than enough to make up for the losses of dithionate in filtering. The calcium chloride process thus developed into a calcium dithionate process. Since the latter eliminated the need for make-up calcium chloride, and the dithionate solutions appeared much less corrosive than the chloride solutions, work on the calcium chloride process was dropped in favor of the calcium dithionate process. ACKNOWLEDGMENTS The dithionate process was developed by the Bureau of Mines as part of a

Jan 1, 1946

By P. Chiotti, G. R. Kilp

Thermal, metallographic, vapor pressure, and X-ray data were obtained to establish the phase diagram for the zinc-zzrconiz~m system. Five compounds corresponding to the stoi-chiometric formulas ZrZn, ZrZn,, ZrZn,, ZrZn,, and ZrZn14 were observed. All these compounds, with the exception of ZrZn2, which melts congruently at 1180°C under constrained zinc-vapor conditions, undergo pexitectic reactians. The temperature at which the zinc vapor pressure is I atm for a series of alloys was determined from vapor-pressure measurements. The data obtained are summarized in the construction of a I-atm-pressure phase diagram and a phase diagram corresponding to a pressure of less than 10 atm. THE purpose of this investigation was to establish the phase diagram for the zinc-zirconium system. Thermal, metallographic, vapor pressure, and X-ray data were employed in determining the phase regions. Partial investigations of this system have been conducted by Gebhardt1 and Carlson and Borders.' Carlson and Borders studied the high-zirconium region and established the existence of a eutectic at 69 wt pct Zr with a melting point of 1015°C. The terminal phases of the eutectic horizontal were shown to be an intermetallic compound ZrZn and a solid solution of ß zirconium containing 21 wt pct Zn. The ß solid solution decomposes into ZrZn and a zirconium at 750°C. The eutectoid composition is given as 15 wt pct Zn, and the solubility of zinc in a zirconium at temperatures below 750°C is indicated to be negligible. Gebhardt studied the zinc-rich region and observed a lowering of the melting point of zinc from 419.5" to 416°C and temperature horizontals at 545" and970°C. Some preliminary observations by Chiotti, Ratliff, and Kilp were reported by Hayes.2 pietrokowsky3 has reported the compound ZrZn2 to have a cubic MgCu2 structure with ao = 7.396A. MATERIALS AND EXPERIMENTAL PROCEDURES The metals employed in the preparation of alloys were Bunker Hill slab zinc or Baker analyzed reagent granulated zinc, both 99.99 pct pure and hafnium-free iodide-process crystal bar zirconium obtained from the Westinghouse Electric Corp. The zirconium contained 200 ppm Fe, 200 ppm Si, 100 ppm C, and minor amounts of other impurities. The zirconium was milled or machined into thin chips or shavings. These were cleaned with a nitric-hydrofluoric acid solution, rinsed with water, and acetone, and dried just prior to their use in alloy preparation. The granulated zinc was similarly cleaned using dilute nitric or hydrochloric acid. Weighed quantities of these materials, 20 to 30 g total, were mixed and pressed at 20,000 to 70,000 psi to give relatively dense compacts. During the early part of this investigation the pressed compacts were placed in MgO-15 wt pct MgF, crucibles which were then sealed inside of quartz ampules. The compacts were given various prolonged heat treatments prior to their use for thermal analyses, or vapor-pressure measurements. Because of expansion of the compacts and the relatively high zinc vapor pressure it was difficult to heat to the melting temperatures of the alloys without failure of the quartz ampules. Homogenization at temperatures below the melting temperature gave brittle, porous alloys unsuitable for metallographic examination. It was also difficult to prevent condensation and segregation of zinc on the colder parts of the quartz ampules during heating and cooling operations. These problems were eliminated to a great extent by the use of tantalum crucibles. Tantalum proved to be a satisfactory container with little or no reaction between the alloys and the tantalum. Small tantalum thermocouple wells were successfully welded in the bottom of these crucibles. Pressed compacts were sealed inside the tantalum crucibles by welding on preformed caps under an argon atmosphere. Heat treating and differential thermal analysis were combined into a single operation. The experimental sample assembly is shown in Fig. 1. This assembly was enclosed inside a stainless-steel tube heating chamber which could be evacuated and filled with an inert gas. The thermocouple leads were brought out of the heating chamber between two rubber gaskets used to provide a vacuum seal for the water-cooled head. Most of the compounds in this system undergo peritectic decomposition. After heating above the temperature of a particular peritectic horizontal the sample was cooled to just below the peritectic temperature and held at temperature for several hours. The sample was then reheated through the peritectic temperature and the size of the thermal arrest, if still present, compared with the one previously obtained. If the thermal arrest was not characteristic for the alloy composition being investigated its magnitude diminished and repeated cycling and annealing eventually eliminated it. The peritectic thermal arrests characteristic of a particular composition were established in this manner.

Jan 1, 1960

By W. S. Landis

WHEN dealing with a new reagent, one is concerned with three principal factors: available supply, cost, and results. The atmosphere contains an inexhaustible supply of oxygen mechanically mixed with nitrogen (omitting rare gases and minor impurities) in the proportions of one volume of oxygen to four volumes of nitrogen. (All figures are based on slide-rule precision and minor impurities are neglected.) Expressed in terms of weight, 1 ton of oxygen represents a volume of 22,500 cu. ft. and is contained in a volume of 112,000 cu. ft. of air. Water, also an inexhaustible supply, is a chemical compound containing 89 per cent. oxygen and, 11 per cent. hydrogen. Of the hundreds of schemes proposed for the enriching of air or separation of oxygen, nothing of value has yet appeared. From the standpoint of mechanical separation, liquefaction followed by rectification is the only process that has been developed to a really commercial stage. Theoretically, it should be a .simple matter to separate the mechanical mixture of nitrogen and oxygen; but fractionation can be performed only by converting to the liquid phase and this phase can be obtained only at lower than critical temperatures. The problem, therefore, is not so simple and the cost of the actual operation bears no relationship to the theoretical simplicity of the process. The largest single unit of the required apparatus so far placed in commercial use will handle only 60,000 cu. ft. of air per hour through a compressor which operates at a little over 250 lb. per sq. in. After this apparatus has operated continuously for 14 to 18 days it must be shut down for 6 to 8 hr. to be thawed out, have accumulated impurities removed and again cooled down for production. The cost of such a unit erected in batteries, with necessary spares for maintaining production, and including prime movers, hoisting and all auxiliary equipment, will be about $125,000. To produce one ton of oxygen per hour requires two operating machines of this size; and if the production is to be absolutely continuous a spare unit must be provided. To operate a plant of two units requires 10 or 11 men, excluding boiler attendants, if steam is generated in the plant.

Jan 11, 1924

By C. G. Dunn, W. W. Martin

Various X ray diffraction techniques have been developed for determining orientations of crystals. Transmission and back-reflection Laue methods1,2,3 in particular have been found to be very useful. In many applications, however, a need still exists for a simplification of the details of analysis so that orientations can be determined more rapidly, and operators with little or no training in crystallography can be easily instructed in the necessary procedures. Filling this need in part is a system of analysis that has been in use for several years in the Metals Section of the Laboratory, General Electric Co., Pittsfield, Mass. This method is an extension of the one of Majima and Togino,4 which uses fifty-five indexed standard transmission Lauemams to cover the entire range of crystal orientations. Greater rapidity in determining the orientation of a crystal is achieved by using a slightly larger set of standard Lauegrams and by systematizing the steps followed. This system of analysis in its present form constitutes the subject matter of the present paper. Although the method uses transmission X ray Laue patterns, many of the operations are applicable to the analysis of back-reflection Lauegrams. Very briefly the method is based on the fact that Bragg and azimuthal angles for two or more identified Laue diffraction spots completely determine the orientation of a crystal, and standard Laue photographs of the Majima and Togino type provide a ready means for identifying Laue spots. After a preliminary analysis, which consists of identifying the pattern in terms of one of the standard patterns, a correctly marked Lauegram is selected to carry out the final analysis. From measured Bragg and azimuthal angles, the normals (poles) of the reflecting planes for the selected Laue spots are located on a stereographic projection and the orient.at.ion of the crystal determined (in terms of the positions of cube poles for example) by a few additional operations on a \I1ulff net. The actual procedure followed will be illustrated in detail after a brief treatment or X ray problems connected with orientation determinations and a discussion of useful principles and techniques. X Ray and Plotting Problems RELATIVE ADVANTAGES OF BACK-REFLECTION AND TRANSMISSION LAUE DIFFRACTION METHODS In the back-reflection Laue method it is easy to make a direct measurement of the tilt of a zone of Laue spots. Specimen thickness also is generally no problem. In the case of thin specimens, however, the time of exposure is less for the transmission Laue method. For example, with silicon ferrite this advantage holds up to a thickness of 0.6 mm if tungsten radiation at 40 kv peak voltage is used. Furthermore, the transmission photograph represents the entire thickness of the crystal whereas the back-reflection picture represents only a surface layer (a thickness of less than 0.05 mm for silicon ferrite), the deeper layers supplying a negligible amount to the diffraction pattern. If a crystal is distorted, the transmission Laue pattern gives more information particularly with regard to the orientation of the crystal and the overall amount of spread in orientation. Finally a 3 1/4 X 4 in. film suffices for transmission photograms; a 4 X 5 in. or 5 X 7 in. film with a central hole is needed for back-reflection patterns Not only is the manipulation of film easier because of the size of film, but

Jan 1, 1950

By W. C. Ellis, E. S. Greiner

Metallic titanium has been prepared in small quantities since the beginning of the century. Hunter1 reported in 1910 that he obtained a malleable product of 99.9 pct purity by the reduction of the tetrachloride by sodium in a closed container. Later Van Arke12 and Fast prepared small quantities of malleable titanium by thermal decomposition of titanium iodide. Another method for producing malleable titanium from tetrachloride was reported by Kr0ll4 who used magnesium as the reducing agent. More recently Dean, Long, Wartman, and Anderson5 working at the U.S. Bureau of Mines have reported the preparation of the metal on a pilot plant scale by the reduction of titanium tetrachloride by magnesium in an atmosphere of helium. Their product, which is malleable, was used in the present investigation. Early in 1948 after the work of this paper was completed Campbell, Jaffee, Blocher, Gurland, and Gonser6 described the strength and working characteristics of pure titanium which was prepared by the iodide method on a scale producing 300 to 600 g per run, in the form of 0.3- to 0.4-in. diam rods. Their product is characterized by low hardness and large capacity for cold work which they attribute to a high degree of purity with respect to oxygen, nitrogen, and carbon. Titanium has a melting point of about 1725 C," it may be classed as a light metal since the specific gravity is 4.5 g per cc-I. The crystal structure is close-packed hexagonal from room temperature to 885°C. Above this temperature the structure is reported7 as body-centered cubic. The change in crystal structure has been associated with discontinuities in specific heat,8 electric resistanceg and theimoelec-tric force10 at temperatures near 890°C. It is reportedll that annealed titanium has a tensile strength of 78,700 psi which can be increased by cold-work to 123,000 psi. In the present investigation, the lattice constants at room temperature, the thermal expansivity between 30 and 800°C, as well as the electrical resistivity and thermoelectric force against platinum between — zoo and I000 C have been determined. Materials For the measurements, two series of specimens were prepared from titanium furnished by the U. S. Bureau of Mines. The first was made from an annealed sintered compact, 0.38 in. thick. Sections of the compact were cold-swaged with intermediate anneals in vacuum to the sizes used. Sizes over 0.25-in. diam were annealed at I000°C and smaller sizes at 800°C. Specimens originating from the sintered compact are designated in this paper as A. The second series of specimens was made from a rod of titanium, 0.19 in. in diam, which was cold-swaged with the necessary intermediate anneals to the required sizes. This series of specimens is designated B. The impurities in the specimens of titanium, determined by chemical analysis, are given in Table 1. Oxygen and nitrogen which Were not determined by analysis, are probably present although in small quantities in view of the ductility of the material.

Jan 1, 1949

By W. C. Ellis, E. S. Greiner

METALLIC titanium has been prepared in small quantities since the beginning of the century. Hunter1 reported in 1910 that he obtained a malleable product of 99.9 pct purity by the reduction of the tetrachloride by sodium in a closed container. Later Van Arkel2 and Fast3 prepared small quantities of malleable titanium by thermal decomposition of titanium iodide. Another method for producing malleable titanium from tetrachloride was reported by Kroll4 who used magnesium as the reducing agent. More recently Dean, Long, Wartman, and Anderson5 working at the U.S. Bureau of Mines have reported the preparation of the metal on a pilot plant scale by the reduction of titanium tetrachloride by magnesium in an atmosphere of helium. Their product, which is malleable, was used in the present investigation. Early in 1948 after the work of this paper: was completed Campbell, Jaffee, Blocher, Gurland, and Gonser6 described the strength and working characteristics of pure titanium which was prepared by the iodide method on a scale producing 300 to 600 g per run, in the form of 0.3- to 0.4-in. diam rods. Their product is characterized by low hardness and large capacity for cold work which they attribute to a high degree of purity with respect to oxygen, nitrogen, and carbon. Titanium has a melting point of about 1725°C5 it may be classed as a light metal since the specific gravity is 4.5 g per cc-1. The crystal structure is close-packed hexagonal from room temperature t0 885°C. Above this temperature the structure is reported7 as body-centered cubic. The change in crystal structure has been associated with discontinuities in specific heat8 electric resistance9 and thermoelectric force10 at temperatures near 890°C. It is reported11 that annealed titanium has a tensile strength 0f 78,700 psi which can be increased by cold-work to 123,000 psi. In the present investigation, the lattice constants at room temperature, the thermal expansivity between 30 and 800°C, as well as the electrical resistivity and thermoelectric force against platinum between - 200 and 1000°C have been determined. MATERIALS For the measurements, two series of specimens were prepared from titanium furnished by the U. S. Bureau of Mines. The first was lade from an annealed sintered compact, 0.38 in. thick. Sections of the compact were cold-swaged with intermediate anneals in vacuum to the sizes used. Sizes over 0.25-in. diam were annealed at 1000°C and smaller sizes at 800°C. Specimens originating from the sintered compact are designated in this paper as A. The second series of specimens was lade from a rod of titanium, 0.19 in. in dial, which was cold-swaged with the necessary intermediate anneals to the required sizes. This series of specimens is designated B. The impurities in the specimens of titanium, determined by chemical analysis, are given in Table I. Oxygen and nitrogen which were not determined by analysis, are probably present although in small quantities in view of the ductility of the material.

Jan 1, 1948