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By S. Oglesby, A. L. Thomas

Until recently, probably the best means of sampling airborne dusts has been the impinger method. Dust-laden air is drawn into a sampling tube, and the particulate matters separated from the air and collected in the liquid in the impinger. A sample of the suspension is prepared on a slide and counted through a projection microscope. This method is simple and reliable, but it does suffer drawbacks. Since the collected particles must be counted visually, results of the dust count are not immediately available at the time the sample is taken. This seriously impedes studying the effectiveness of dust inhibitors, such as water sprays, or making adjustments in equipment. Greatest disadvantage of all, however, is the tedious task of counting particles in the sample. With the growing desirability of taking more samples, the effort involved in making these counts is a real factor in the cost of dust control. Finally, it is generally recognized that impinger dust counts can be related to health hazard only for specific kinds of dust and under similar conditions. This is because the rather complex mechanism of dust damage depends so much on size distribution of the dust. Counts determined by impinger samples cover a limited size range that does not necessarily corre-

Jan 1, 1960

By W. E. Hall

The Darwin mining district of California, 160 miles north of Los Angeles, has yielded an estimated $45 million in lead, silver, zinc, and copper since 1875. The deposits are in silicated limestone of Penn-sylvanian and Permian age close to a stock of horn-blende-biotite-quartz monzonite. Steep left-lateral strike-slip faults that strike N 50o 70o E served as feeder channels for the ore solutions, and minor folds, favorable beds, and faults close to the feeder channels localized the orebodies. The orebodies are irregular, steep, pipe-like replacements that cut across bedding, bedding replacements, and fissure fillings in a calc-silicate country rock consisting mainly of wollastonite, grossularite-andradite garnet, idocrase, and diop-side. Near surface the ore consists of a soft, crumbly mass of cerussite, hemimorphite, jarosite, limonite, and some secondary copper minerals. The primary ore consists of galena, sphalerite, pyrite, pyrrhotite, and chalcopyrite with smaller amounts of andorite, matildite, scheelite, tetrahedrite, and a high silver-lead-bismuth-selenium-bearing galena. Preliminary X-ray fluorescence study of the primary ore has indicated unusually high concentrations of bismuth, selenium, and silver in galena from certain parts of the mine. One phase of this study concerns the distribution of these elements. Twenty-two samples of galena and thirty of sphal- erite have been purified and analyzed or are being analyzed. The selenium in 21 samples of galena ranges from 0.0045 to 2.11 pct; four contain more than 1 pct. These four samples were collected from the Essex orebody, where most of the selenium is concentrated. Three are from high-grade, near-surface ore, and one is from the 700 level. Four of the seven analyzed galena samples from the Thompson workings immediately north of the Essex orebody contain 0.29 to 0.74 pct Se; the others show less than 0.05 pct. Galena from the Defiance workings about 2000 ft south of the Essex has less than 0.03 pct Se. The selenium-bearing galena also contains concentrations of bismuth and silver. Preliminary spectographic analyses indicate as much as 3 pct Bi and more than 1 pct Ag in galena with high selenium content. Antimony is the only other minor element present in galena in amounts greater than 0.02 pct; most galena contains between 0.1 and 0.2 pct and the maximum is 0.72 pct. A second phase of the study is an attempt to determine the temperature range of the formation of the ore. The iron content of sphalerite deposited in equilibrium with pyrrhotite is being used as a geologic thermometer as it is a function of the temperature of deposition of the ore.' Preliminary results indicate temperature range from 430°C in replacement orebodies in the Defiance workings to 180°C in shallow fissure fillings.

Jan 1, 1960

By A. G. Metcalfe, A. Siede

The hardening of annealed copper during fatigue testing appears to be independent of the applied stress and to occur largely within the first 4000 cycles. Copper hardened by fatigue is more resistant to annealing than copper hardened by static means, and softens by a multistage process. Creep studies at 300°C show that copper hardened by fatigue also has greater resistance to creep than statically hardened copper. Some theoretical explanations are discussed. RECENT interest in the behavior of metals subjected to fatigue stems from observations of phenomena which could not be explained by current theories of the structure of metals. In 1953 Bullen et al.l showed that the hardening caused by fatigue at low stresses did not cause severe bending of the lattice as did hardening by static methods. This was later confirmed by Wood, 'and Broom and Ham.3 Clarebrough et al4 showed that as the stress level used in fatigue hardening was increased, bending of the lattice was introduced, eventually approaching that of metals deformed by conventional cold-working methods. The type of hardening introduced by fatigue has other interesting characteristics. Kemsley5 showed that copper fractured by fatigue at low stresses resisted annealing as compared to copper hardened an equal amount by static means. The work of Clarebrough etal, shows that the manner of energy release during annealing differs for fatigue-hardened and statically hardened metal in both magnitude and temperature range of release. In addition to hardening of the lattice, fatigue has been shown to cause softening in materials previously hardened by static methods,5 and also in age-hardened alloys.7 The superposition of a small fatigue stress on the static loading of high-temperature alloys has been shown to increase their resistance to creep.' The present work was an attempt to determine the relationship between fatigue hardening, resistance to annealing, and the creep properties of pure copper. EXPERIMENTAL PROGRAM The program described here was designed to answer three questions: 1) Can stress-cycle combinations well below the failure values give significant increases in hardness? 2) Does hardening, under different stress-cycle combinations, give increase resistance to annealing? And if so— 3) Does superior resistance to annealing confer superior creep properties over statically hardened material? Three-quarter hard OFHC copper was annealed in vacuo at 550°C for 1 hr to produce a strain-free material having a fine grain size and uniform hardness. (The standard deviation of the mean hardness of the annealed samples was less than + 1.9 Dpn). Annealing was performed after machining the fatigue specimens so as to avoid work-hardened surfaces. Jigs were used to avoid distortion. The fatigue properties of the annealed copper were determined using an accurately aligned Baldwin-Sonntag SF1-U machine operating at 1800 cycles per min. This limited the minimum number of cycles which could be examined to about 4000 stress reversals. Since failure resulted in specimen damage, hardness increase with number of cycles was measured by testing specimens fatigued to different fractions of the failure values. The results are shown in Fig. 1, and are superimposed on the S-N curve of the copper in Fig. 2. The resistance to annealing of fatigue-hardened material was compared to that of material hardened by uniaxial tensile straining. Specimens hardened to equal values by both methods were progressively annealed for 1 hr at temperature in vacuo. After each annealing treatment the hardness was measured using a Leitz Durimet hardness tester with a 500-g load. At least five tests were made for each hardness determination. The standard deviation for individual specimens varied from 0.26 to 1.48 hardness points. The results are shown in Figs. 3 to 5. The discontinuous nature of the annealing process has been brought out by drawing idealized curves through the data points. This can be justified by the consistency of the results as well as by general agreement with results of Kemsley.5 The creep resistance of fatigue-hardened and

Jan 1, 1960

By A. T. Peters

DURING an investigation concerning the use of large nozzles for pouring of low-carbon rimming steels, the practical details of which were reported elsewhere, it was noticed that increases of nozzle sizes were generally followed by improvements of slab surface quality. It is the purpose of this note to present the data available and some tentative opinions about this phenomenon. The problem of correlating pouring rates with the metallurgical performance of steels is complicated by several factors. The two most important are; 1) Variations of the steel pouring rate throughout a pour, these being due to the nozzle erosion, which enlarges the bore area, and the dropping ferrostatic pressure in the ladle. The pouring rate is lowest towards the end of a heat when the ladle is nearly empty. 2) Variations in the ingot pouring time due to the different ingot weights poured. Consequently, the use of the average pouring rate of a heat may not be exact, but in large-scale production it is not practical to treat ingots separately according to their pouring rates. The variations of ingot weights and sizes may be overcome by considering the rate of rise of steel in the mold. Hence, the average rate of filling of molds throughout the pour of a heat, inches per second, will be used in this note. Every ingot rolled at Inland is rated at the blooming mills prior to hot machine scarfing as being good, fair, or poor for cracks, scabs, and checking. The latter term refers to the network of breaks or lines associated with overheating or burning in the soaking pits. It is also known that thin-skinned steel is prone to show this defect if the subsurface blowholes are exposed during reheating or rolling. The experiences with the surface quality of slabs rolled from ingots poured at different rates are presented in Fig. 1. The data represent nearly 11,000 ingots. It appears that all three types of defects are in-

Jan 1, 1960

By O. E. Palasvirta

Close examination of most so-called n.eu processes in mineral dressing reveals that they were conceived and developed a long time ago. High-intensity magnetic separation is no exception. Although its application in iron ore beneficiation seems new, in Germany the process has been commercially successful for almost two decades. High-intensity separators have long been standard equipment in the glass sand industry; they have also been used in concentrating some of the more unusual para-magnetic minerals. The basic features of an induced-rotor, high-intensity magnetic separator were described by Desire Korda in Paris in 1905,' and many patents have since been issued for improvements on the original design. Fig. 1 shows the basic design of an induced-rotor separator. Several U. S. manufacturers have been supplying induced-rotor separators for many years, but these are all devices of relatively low capacity, not suitable for treating such low-cost commodities as iron ore. On the other hand, two German manufacturers are offering induced-rotor separators of high capacity, both proven in the field. The present investigation was prompted by the apparent success of the German installations and by the discovery of iron ores on this continent which may be amenable to high-intensity separation. The objective was to gain better insight into the underlying principles of separation in a high-intensity field and to use this knowledge in selecting or designing an optimum separator. THEORETICAL CONSIDERATIONS he well known low-intensity magnetic separators are. without exception, of the the magnet type with more or less similar field shapes. It is therefore permissible to speak of their comparative strengths in terms of field intensity alone. However, proper understanding of the high-intensity magnetic separation process requires somewhat deeper analysis of the relationship between the magnetic field and the attractive force. Contrary to a widely held belief, a magnetic field of parallel lines of flux exerts no attractive force on a magnetically susceptible particle, but merely aligns its poles parallel to the lines of flux. On the other hand, a non-uniform field attracts a magnetically susceptible particle in the direction of the converging lines of flux. Thus the force of magnetic attraction varies as the product of the field intensity and the field gradient: dH ds As the induced-rotor magnetic separator is primarily intended for separating feebly magnetic materials, it is important that maximum attraction be attained. For the designer, then, the relationship between the magnetic field and the attractive force has the following implications: 1) Insofar as possible, the separation gap must be saturated with flux. 2) The rotor surface must be shaped to insure maximum convergence of lines of flux toward the rotor. 3) The primary pole face (opposite the rotor, on the other side of the separation gap) must be shaped so that the lines of flux do not diverge from it at any location in the effective separation zone. The actual attractive force of the rotor, and its critical speed, can be calculated as shown by Runo-linna, provided that the true flux density, the field gradient, and the magnetic susceptibility of the mineral can be measured with sufficient accuracy. The irregular shape of the rotor surface makes flux measurements difficult, but it can be done if a suitable gaussmeter is available (see Fig. 2). Calculations by the author, and comparisons with the centrifugal force exerted by the rotor, indicate that the force pinning a hematite particle to the rotor is of the same order of magnitude as the force holding a

Jan 1, 1960

By L. F. Mondolfo

An aluminum-copper 4 pct Cu alloy aged at room temperature for times increasing up to 78,000 hr was annealed at 170°C and the hardness and electrolytic potential determined during retrogression and subsequent aging. It was found that there is a change of behavior with increasing time of aging at room temperature which indicates that, given sufficient time, retrogression disappears and the room-temperature aging tends to progress directly into the high-temperature aging. WHEN an age-hardenable alloy is aged at low temperature after proper quench, changes of properties and structure take place. If this material is then heated to a temperature higher than the previous one, but still well below the solution-treatment temperature, the properties and structure changes produced by the low-temperature aging disappear and the material apparently reverts to the as-quenched condition, ready to undergo aging from the start. This phenomenon is termed reversion or retrogression. First discovered by Cayler3l it has been extensively investigated, as shown by the number of publications listed in the bibliography. From all the information available the following facts emerge: 1) All aeg hardenable alloys can be retrogressed.9 13, 19) 24, 33, 41, 42, 44, 47, 53, 54, 61, 63, 64, 66, 73, 78 2) All the properties changes that take place during aging at low temperature can be retrogressed to a smaller or larger extent.4,5,7,12,19,32,49,50,57,58,60,67,75,76 67, 75, 76 3) Retrogression requires that the temperature be well above the preliminary aging temperature. If the difference between the two temperatures is small, Little or no retrogression takes place.7,20,32,33,41,49 57. 65 4) The larger the difference between the preliminary aging and the retrogression temperature, the faster and more complete is the retrogression.20, 33, 41, 48, 65, 67 5) Retrogression can be produced several times in the same alloy.23, 35,41,57,59 6) The amount of retrogression that can be obtained depends on the aging temperature. Alloys aged at the lower temperatures can be retrogressed the most. The higher the preliminary aging temperature the less retrogression can be produced.20,25,33,37,44,49,54,58 7) Appreciable retrogression after aging at elevated temperatures is possible only if the preliminary aging has lasted a short time. After a certain time of aging at high temerature retrogression does not take place any more,:5,6,9,10,11,21,40,58 8) During retrogression the Guinier-Preston zones redissolve and disappear. The other precipitate

Jan 1, 1960

By B. Hyatt, E. Klokholm

The reesistivity of Cu-Pd alloys of 9.6 to 29 pct Pd alloys was measured after plastic deformzation in tension. For all compositions a continzting decrease in resistivity with increasing plastic strain was observed. By comparison with the results of Damask on a brass ad Cu3Au, it was deduced that these anonzalous decreases in resistivity are due to the decrease in short-vunge order caused by cold work. An anomalous decrease in the resistivity of cold-worked CU-Pd alloys was first reported by Jaumot and Sawatzky.' They observed decreases in the electrical resistivity when disordered Cu-Pd alloys drawing at room temperature. Recently, a similar anomaly was reported by Aarts and Houston-Mac-Mi1lan2 in Ag-Pd alloys containing 10 to 45 pct Pd. The plastic deformation in this case was produced by tensile strain at liquid-nitrogen temperatures. For AE-Pd alloys the relative resistivity change becomes positive for tensile strains of about 20 pct.

Jan 1, 1960

By S. Saito, P. A. Beck

The crystal structure of MoNi3 was determined by means of X-ray diffraction. This structure is isotype with that of ovgered TiCu3. The lattice parameters are: a. = 5.064A, bo = 4.224A, co = 4.448A, and zf 0.157. If the orthorhombic distortion (slight relative to the corresponding orthohexagonal unit cell) is disregarded, the structure may be described in terms of a close-packed ordered atomic layer, stacked in the sequence: abab. The structztres of ordered TiCu3 and TiAl3 are homotectic. The three types of ordered hexagonal phases, iso-structural with TiNi3, MgCd3, and VCo3, are known to occur in AB3 alloys of transition elements of the first, second, ad third long periods. It was noted1 that phases with the TiNi3 structure occur selectively in alloys of Ti-group elements with Ni-group elements. In AB3 alloys of Ti-group and V-group elements with Co-group elements the AuCu3-type structure predominates.' The vCO3 structure, which was determined very recently,' has hexagonal symmetry, but the actual atomic arrangement here, too, is rather closely related to the ordered cubic structure of AuCu3-type. However, an ordered hexagonal close-packed structure of the MgCd3-type occurs in MOCO33 and WCO3.4 Consequently, the question arises as to whether or not the crystal structure of MoNi3 is also of the MgCd3-type. Grube and winkler5 found that MoNi3 has a hexagonal close-packed structure with a = 2.54A and c/a = 1.65. They pointed out that some additional weak diffraction lines could be observed in the powder pattern, which may have been due to an ordered atomic arrangement in this phase. However, no detailed information was obtained by them and the structure was apparently not further investigated by others. The present work was, therefore, undertaken in an attempt to determine in detail the structure of MoNi3, and to investigate the possibility of ordering. EXPERIMENTAL METHODS Alloys used in the present work were arc-melted in a water-cooled copper crucible under helium atmosphere. Electrolytic nickel and molybdenum, both 99.9 pct pure, were used. Chemical analyses were not made, but the melting loss was not higher than 2 pct for any alloy. Ingots were first homogenized at 1200°C for 48hr, quenched, heavily cold worked, and then annealed at 820" or 860°C for 1 week, followed by quenching in cold water. Powder specimens for X-ray work were prepared by crushing the heat-treated solid specimens. In order to remove strains, the powders were reannealed in evacuated scaled fused silica capsules for 6 hr at the same temperature at which the corresponding solid specimens were annealed. X-ray photographs were taken with an asymmetric focussing camera, using unfiltered CrK or CuK radiation. EXPERIMENTAL RESULTS The X-ray diffraction patterns of alloys containing 20.8, 25, and 26.4 at. pct Mo, homogenized at 1200°C, showed the face-centered-cubic structure of the Ni-base a-solid solution. It was revealed, however, by micrographic examination that the 26.4 at. pct Mo alloy contained in addition very small amounts of a second phase, in accordance with the phase diagram.6 On the other hand, the 20.8 at. pct Mo alloy after annealing at 820°C gave the X-ray diffraction pattern of the ordered face-centered-tetragonal MONi4.7 In this pattern several additional weak diffraction lines were also observed, corresponding to the strongest diffraction lines of MoNi3. The alloys containing 25 and 26.4 at. pct Mo after annealing at 820" or 860°C gave X-ray diffraction patterns, as shown in Tables I and 11, corresponding to MoNi3. Each one of the reflections which could be tentatively indexed on the hexagonal close-packed cell of Grube and Winkler,5 with the exception of the basal plane reflections, was split into a doublet, as seen in Table I. Since microscopically the alloy consisted of a single phase, it seemed probable that the lattice of MoNi3 is actually slightly deformed, as compared with the tentative hexagonal unit cell. In addition to these diffraction lines, several weak lines were also present, as shown in Table 11, which could not be indexed at all on the hexagonal close-packed cell considered. Satisfactory indexing of all diffraction lines observed was found to be possible by using an orthorhombic unit cell with ao = 5.064A, ft = 4.224A, and c = 4.448A. These values, whose accuracy is estimated to approximately ± 0.008A, correspond to 95.14A3 for the volume of the unit cell, and to an X-ray density of 9.50 g per cm3. If no attention were paid to the weak reflections listed in Table II, a reduced -unit cell of half the volume (a = 2.532A, b = 4.448A, and c = 4.224A), closely related to the orthohexagonal cell, might be used. The dimensions of the orthohexagonal cell of the same volume as the reduced cell are: a = 2.562A, b = 4.437 A, and c = 4.183A. It may be seen that in the reduced cell the a axis is slightly shorter, while the b and c axes are slightly longer than those corresponding to the orthohexagonal cell of the same volume. This slight orthorhombic distortion is re-

Jan 1, 1960

By B. C. Allen, W. D. Kingery

Surface tension and its temperature dependence have been determined for pure liquid Fe, Cu, Co, Ni, and Sn and for Fe-C, Co-C, and Ni-C alloys. The temperature coefficient of surface tension is negative for all these liquids. The surface tension and wetting behavior of tin and tin-titanium alloys on A120,, Si,N,, MoSi,, and Sic, as well as the behavior of titanium-containing nickel alloys on A1 20, have been determined over a wide temperature range. For all the solids investigated titanium additims markedly lower the contact angle. Some limits for the solid-surface energies have been calculated from liquid surface tension and wetting behavior. SURFACE tension and interface energy are important variables in a number of metallurgical and ceramic phenomena, and have been discussed at some length in connection with determining micro-structure of polyphase systems,' solid-state sintering,' thermal etching of grain boundaries, heats of solution and fine powders,'1 grain-growth phenomena,' the mechanical behavior of fine foils and fibers, nucleation, soldering and brazing,' and other phenomenz of academic or practical interest However, until recently few quantitative data have been available for high-temperature systems. Among available data are some indicating positive temperature coefficients for the surface tension of liquid copper,*,11,'2 cast iron,l3 and iron-carbon14 alloys. Although carbon was found to be not surface active in iron at 1570" some preliminary studies had indicated the possibility of a positive temperature coefficient for the eutectic composition at lower temperatures.16 One part of the present study has been largely concerned with determining the temperature coefficient of surface tension for several metals at elevated temperatures, In addition to surface-tension studies, the wetting behavior of alloys containing titanium has been investigated over a wide temperature range. Previous measurements indicated that titanium was selectively adsorbed from nickel at a liquid nickel-solid alumina interface,17 and the use of titanium hydride or titanium-alloy techniques for metal-ceramic soldering is well known. In the present study, previous data have been extended to new alloy systems, and measurements have been carried out with other oxidation-resistant ceramics. EXPERIMENTAL The sessile-drop method was employed to measure liquid surface tension and contact angle between liquid and solid, utilizing apparatus and techniques which have been described previously.'g The shape of a sessile drop depends on equilibrium between forces of surface tension tending to form a spherical surface of minimum area and forces of gravity tending to flatten the drop. Typical sessile drops are shown in Fig. 1. From precise measurements of maximum drop diameter and drop height the surface tension and drop volume were calculated. Four solid materials were employed as supporting plaques for the liquid-metal drops. Aluminum oxide (99.9 pct, J, T. Baker, reagent grade) was pressed and sintered at 1800°C. Molybdenum-disilicide powder (99.0 pct, Electro Metallurgical Co.) was pressed and sintered at 1650°C. Plaques were cut from silicon carbide (99.4 pct, hot-pressed at Alfred University) and silicon nitride (95.1 pct, with Al, Fe, 0 as major impurities, Norton Co.) rods. All plaques were polished, cleaned, and dried prior to use. A number of metals and alloys were employed. Chemical analyses of vacuum-melted ingots of iron, nickel, cobalt (National Research Corp.), commercial nickel-base alloys, electrolytic copper (International Smelting and Refining Co.), and tin (Mal-linckrodt Chemical Works) are given in Table I. Alloys were prepared in the laboratory by vacuum melting the base metal with either titanium hydride (Metal Hydrides, Xnc.) or spectroscopic-grade carbon (National Carbon Corp.). Nickel-titanium alloys contained between 0.001 and 0.005 pct oxygen and the ferromagnetic metal-carbon alloys contained 0.001 pct. Cylindrical metal specimens (1 to 2.5 g) were machined and bevelled at the bottom to insure a uniform advancing contact angle on melting. Before use the samples were acid-etched, cleaned with acetone, and rinsed in petrol ether.

Jan 1, 1960

By Herbert W. Huse

Nitrogen, and its compounds, unique among the materials described in this volume, is absolutely essential to the existence of the human race. Almost all minerals are important and the absence of any one of them would be sorely felt; but nitrogen is an integral part of the cycle of life itself. Man cannot live without nitrogen which, as an inert gas, composes the major part of the air he breathes; as compounds, nourishes the vegetation which he eats; and, as protein, forms a part of his very flesh and blood. Nature originally provided man with a vast reserve of usable nitrogen compounds in the form of fertile soil. She constantly replenishes the supply by "fixing" nitrogen in the air at the estimated rate of 400,000,000 tons per year (an insignificant 6 lb per acre) during electrical storms. She has also placed certain microorganisms in the soil which are able to "fix" nitrogen and convert it into forms which plants can use. Legumes like cow peas, soy beans, clover, and alfalfa have extraordinary roots which serve as stimulating hosts to these bacteria which, in turn, nourish the plant. By plowing in all or part of such crops, their above-average nitrogen content can be returned to the soil for other more useful crops. The mechanism for this recycle is supplied by "denitrifying" bacteria which attack the dead plant tissue and liberate nitrogen and ammonia. However, since one crop of grain, sugar beets, potatoes, tomatoes, etc., takes out a major portion of the nitrogen which a plowed-in legume crop can supply, this method of fertilization is obviously inadequate. Drastic intervention by man has become necessary to support the ever-growing population of the world.9,15,20 Old civilizations with a high population density, such as the Chinese, were able to exist for centuries by carefully tilling the soil, rotating crops, and returning to the soil all the nitrogen in vegetable wastes plus human and animal excreta. But the lack of a means for augmenting their supply of nitrogen placed a ceiling on further development and kept the mass of the population in a chronic state of undernourishment, frequently punctuated by famine. Nitrogen plays another important role in the life of mankind. In the form of explosives, nitrogen helps to wrest from the earth many materials needed for our material well-being. Also, in the form of explosives and propellants, nitrogen increased the destructiveness of wars to a point only exceeded by the fantastic power of atomic energy. Man's first really effective efforts to improve his position with respect to nitrogen began in the 18th Century with the mining of sodium nitrate. By the late 1880's this had become a big industry serving a large part of the world. In the late 1890's nitrogen, in the form of ammonia, was being recovered from coke-oven operations. In 1900 nitrogen, in the form of nitric oxide, was being obtained from the air by an electric-arc process. About 1904 another "fixation" process based on the reaction of nitrogen with calcium carbide to form cyanamide was commercialized. By 1913 the Haber-Bosch process of "fixing" atmospheric nitrogen by reacting it with hydrogen to produce synthetic ammonia was successfully applied on a large scale, first in Germany and then throughout the industrial areas of the world.9 All the above methods of obtaining nitrogen compounds are still in use and, between them, they assure mankind of adequate supplies for all time. While this fortunate situation is not unique amongst industrial raw materials, all too few of man's needs are so well in hand.

Jan 1, 1960

By R. W. Fountain, W. D. Forgeng

A new constitutional diagram is presented for the cobalt-rich end of the cobalt-titaniurn system. The modifications result from the presence of a new, intermediate, fcc phase, ?, the existence and homogeneity limits of which were established by metallo-graphic and X-ray studies of alloys containing from about 3 to 30 pct Ti. The precipitation of the ? phase from supersaturated solid solution was studied by hardness and electrical resistivity measzsrements, and two distinct stages in the process were observed. COBALT forms the base for a number of precipitation -hardenable alloy systems which may be divided into two distinct categories of practical interest, a) those hardened by intermetallic compounds and b) those hardened by carbide formation. The precipitation of intermetallic compounds from solid solution in cobalt-rich alloys has, however, received very little attention. Although the phase diagrams for some binary systems capable of precipitation have been determined,' there is an almost complete lack of data on the property changes associated with the precipitation, and even less information on the kinetics of the reactions or morphology of the products. More information is available on the precipitation of carbides because of the practical significance in superalloys. A survey of cobalt binary phase diagrams suggested that the cobalt-titanium alloys might provide interesting and useful precipitation-hardenable alloys. The equilibrium diagram as proposed by Wallbaum2 is shown in Fig. 1. Köster and wagner3 have indicated that the maximum solubility of titanium in cobalt is about 10 pct at the eutectic temperature (1135oC), and this decreases to about 7.2 pct at room temperature. The temperature of the allotropic transformation in cobalt is lowered by the addition of titanium, about 5 pct being sufficient to retain the high-temperature fcc modification to room temperature. Wallbaum and Witte 4,5 have indicated that the precipitating phase in alloys containing up to about 29 pct Ti is Co2Ti, a hexagonal Laves phase of the MgNi, type. With slightly higher titanium contents, they also report a cubic modification of Co2Ti of the MgCu2-type Laves phase. Duwez and Taylor6 confirmed the existence of the hexagonal (MgNi2) modification but not the cubic (MgCuz) modification of Co2Ti and suggested that existence of the cubic form may have resulted from impurities in Wallbaum's alloys. In their work on Laves-type phases, Elliott and Rostoker 7 reported the cubic modification of Co,Ti, but did not confirm the existence of the hexagonal modification. However, Dwight8 in a discussion of the work of Eliott and Rostoker again showed the existence of both modifications of Co2Ti, a result which was confirmed at that time by Elliott and Rostoker. As a result of a study on the iron-cobalt-titanium system, Köster and Gellers suggested the existence of a Co3Ti phase isomorphous with Fe3Ti. Witte and Wallbaum,' however, established the fact that no compound, Fe3Ti, exists in the iron-titanium system, and in a later publication, wallbaum2 stated that Kitster and Geller's reasoning was not valid, and no compound, Co3Ti, exists. This conclusion was later acknowledged by Köster.10 Preliminary experiments by the present authors to determine the precipitation-hardening characteristics of the cobalt-rich, cobalt-titanium alloys re-

Jan 1, 1960

By J. M. Snook, F. C. Langenberg

FOR a better understanding of the melting and refining processes, the oxygen content of the steel bath should be determined. The oxygen content influences many process and product variables such as the efficiency of alloy recoveries, the ingot structure (through reaction with carbon in the steel), certain reaction rates, cleanliness (formation of indigenous oxide inclusions), and mechanical properties. Many methods of sampling liquid steel for oxygen have been devised. These methods can be divided into two main groups: 1) taking samples directly in the furnace or ladle;'-'0 2) removing the metal from the furnace or ladle in a sampling spoon and pouring it into a mold, or drawing the metal from the spoon into a sample holder.11-l4 The advantages and disadvantages of the two general sampling methods are presented in Table I. The bomb-sampling technique described by Huff, Bailey, and Richards8 has been used by the Crucible Steel Co. in certain research projects where oxygen contents were needed. It was recognized that a localized boiling condition could result when the mold is introduced into the steel bath, although the work of Gilbert and Bailey9 seems to indicate that the carbon boil occurring in the bomb-sampler cavity has a negligible effect on the oxygen content. In order to confirm the reported negligible effect of a carbon boil, additional work was done with adaptations of the conventional bomb sampler. The methods used are shown in Fig. 1 and are as follows: 1) Type A: aluminum wire (0.125-in. diam) coil in cavity; steel cap over mouth 2) Type B: aluminum cup in cavity; aluminum cap over mouth, 3) Type C: aluminum cup in cavity; steel cap over mouth, 4) Type D: fine aluminum wire (0.013-in. diam) in cavity; steel cap over mouth. The amount of aluminum wire in the Type A and D samples varied from 0.8 to 1.2 pct of the sample weight. The aluminum cups averaged 2.0 pct of the sample weight; the latter were used to ensure that the steel contacting the walls of the bomb cavity was fully killed. Samples were taken from plain carbon heats made in open-hearth furnaces. This grade of steel before silicon additions is essentially an Fe-C alloy and the effects of other alloying elements on the oxygen activity can be neglected. The results of sampling with the bomb samplers is shown in Fig. 2 where the percent oxygen is plotted against the percent carbon on log-log paper. Spoon sample results on the same grade of steel where the sample was killed in the spoon are shown in Fig. 3. The oxygen contents were determined by the vacuum fusion method. A comparison of Figs. 2 and 3 shows that the oxygen concentrations obtained with the spoon-sampling method (metal killed in the spoon after slag removed

Jan 1, 1960

By T. P. Floridis

It was deemed desirable to obtain an understanding of the vacuum desulfurization process. McKechnie1 has reported that the sulfur content of nickel- and cobalt-base alloys is reduced in vacuo. Keverian and Taylor2 have observed that vacuum melting causes desulfurization of iron-carbon-silicon alloys. Garnyk and samarin3 have desulfurized transformer steel by vacuum treatment. Experiments were conducted in order to investigate the desulfurization of liquid iron under reduced pressures, and to establish the effect of some alloying elements, and various crucible materials. A vacuum-induction furnace of 50-lb capacity was used. The charge was Armco iron. Silicon was added as 90 pct ferrosilicon, carbon as electrode graphite, and aluminum as high-purity aluminum metal. Magnesia and silica crucibles were used, their inside diameters were 5 1/2 and 5 3/8 in., respectively. The temperature was measured with an optical pyrometer and it was held at 1600 1 15°C. Samples were withdrawn with quartz tubes of 6 mm ID, without disturbing the furnace atmosphere. Pressures were measured with an alphatron gage. The experimental results are shown in Fig. 1. They indicate that: 1) Sulfur can be removed from liquid iron alloys by vacuum treatment; 2) The desulfurization is enhanced by the presence of silicon, carbon, and aluminum, all these elements increase the activity of sulfur dissolved in liquid iron;4 3) The pronounced effect of silicon indicates that probably a volatile silicon sulfide is formed, Alcock and Richardson5 have observed a similar phenomenon; 4) The same rate of desulfurization was obtained when the metal was contained in either magnesia or silica crucibles. Dr. J. Keverian has contributed many discussions and recommendations. M. S. Sutliff has helped in conducting the heats. The permission of General Electric Co. for this publication is gratefully acknowledged.

Jan 1, 1960

By T. Cantwell, N. C. Rasmussen, H. E. Hawkes

Beryl is a mineral that may be difficult to distinguish from quartz by casual field inspection. The easily recognized green color and hexagonal crystal form of coarse-grained beryl are by no means universal, even in beryl from pegmatitic deposits. If it occurred as a fine-grained accessory mineral in an igneous rock, it would almost certainly escape detection unless samples were submitted for petrographic or chemical analysis. There may be substantial deposits of some beryllium mineral, other than beryl, that has been overlooked because that mineral also closely resembles the common rock-forming minerals. A reliable and simple method of identifying beryllium minerals and determining the beryllium content of a rock would be helpful in exploration. This article describes preliminary experiments in applying nuclear reaction to the qualitative identification of beryl and to the semiquantitative determination of the beryllium content of rock samples. Gaudin,1,2 the first to apply a nuclear reaction in detecting beryllium minerals, developed a method that irradiates the sample with gamma rays, which react with beryllium nuclei to produce neutrons. The neutrons are then measured with standard equipment. The cross section for this reaction is about 1 millibarn. The cross section is a measure of the probability that a reaction will take place, for example, between a beryllium nucleus and an incident gamma ray or alpha particles.3-5 At 1-millibarn cross section for the reaction, satisfactory performance required a source strength of the order of 1 curie (3.7 x 10"' disintegrations per sec, where each disintegration releases one or more gamma rays). The reactions will not take place if the gamma radiation is below a minimum energy, in this case 1.63 mev. The size of the source and the energy of the radiation made heavy shielding necessary for these experiments, both to reduce the background count of the neutron counter and to safeguard personnel. The original discovery of the neutron by Chad-wick in 1932 resulted from experiments with another nuclear reaction, induced by bombarding beryllium with alpha particles in which the products are carbon-12 and neutrons. The equation for this reaction is as follows:' " ,Be" + ,He'? 6C12 + 8,n' [1] re-particle neutron In the above nuclear equation (Eq. 1), the sub- script number indicates the number of protons in the nucleus (the atomic number) and the superscript the total number of neutrons and protons (approximately the atomic mass). For the alpha-neutron reaction the cross section is about 250 milli-barns, or 250 times that of the gamma-neutron reaction used by Gaudin. The positively charged alpha particle is repelled by the positive charge of the beryllium nucleus; it must, therefore, have a certain minimum energy in order to approach close enough to the beryllium nucleus to react. For reaction with the beryllium nucleus, the lower limit of the alpha-particle energy is 3.7 mev. The alpha-neutron reaction, with polonium-210 as an alpha source, was selected for the present experiments. Alpha particles are emitted by polonium-210 at 5.30 mev, which is adequate for the reaction with beryllium. Furthermore, this isotope of polonium emits alpha particles with negligible associated gamma radiation, thus eliminating the necessity of shielding. The half-life of polonium-210 is 138 days. Inasmuch as alpha particles carry a possible charge and are large compared with most nuclear particles, their energy is rapidly dissipated in passing through matter. Their range in standard air is 3.66 cm,3 and they penetrate only a few tens of microns into a mineral sample. The short range in air can be minimized by preparation of a flat sample surface that can be brought very close to the alpha source during analysis. On the other hand, short range of alpha particles in air lessens the radiological health hazard and makes it possible to use this method without shielding. It must be emphasized, however, that the alpha emitters are potentially very dangerous if they enter the human body. Polonium must be handled with extreme caution. The literature has reported experiments on the yield of neutrons from reaction of alpha particles with beryllium nuclei. Feld" reports that in intimate mixtures of polonium and beryllium, 3 x 106 eutrons per sec are produced per curie of polonium. Elsewhere in the same reference it is stated that a sandwich-type source yields about one third as many neutrons as an intimate mixture. A table of neutron yields for full energy polonium alpha-particles on thick targets as reported by Anderson7 is the basis of Table I. From Table I it can be deduced that the elements most likely to interfere, i.e., those that also produce neutrons when bombarded by alpha particles, are boron and fluorine. These data also show that it will probably not be possible to determine very small quantities of beryllium in rocks because of the masking effects of the major elements, sodium, magnesium, and aluminum. The neutrons emitted in the alpha reaction are detected by another nuclear reaction. Either of the

Jan 1, 1960

Established as a Division February 16, 1948 H Rush Spedden, Chairman Neil Plummer, Associate Chairman Stephen E Erickson, First Regional Vice-Chairman D A Dahlstrom, Second Regional Vice-Chairman Win T Marston, Secretary-Treasurer Dorr-Oliver, Inc 77 Havermeyer Lane Stamford, Connecticut

Jan 1, 1960

By R. S. Archibald

The subject of this paper is particularly appropriate, since Daniel C. Jackling was active in early exploitation of taconites on the Mesabi Range and contributed greatly to their later economic development. After his success in developing the low grade porphyries in the West he looked for more worlds to conquer, and so undertook the concentration of low grade taconites, from which he hoped to produce commercial ore. Mesabi Iron Co., organized in 1919, actually did produce merchantable sinter from taconites in 1922. The enterprise did not prove commercial at the time, as cost of production was high and the surplus of iron ore in the Lake Superior District already contributed to a low market price, but this same property has since been developed by Reserve Mining Co. The work done by Jackling had much to do with the success of this later venture. Iron ore was first discovered on the Marquette Range in Michigan in 1845. The first ore from this range came from the old Jackson mine in Negaunee in 1848. During these early years this property and others on the Marquette produced limited tonnages for transportation to Lower Lakes and for consumption by charcoal furnaces in the area, where a plentiful supply of hardwoods furnished the charcoal for iron smelting. The Marquette and other ranges tributary to Lake Superior did not produce much ore for transportation to Lower Lakes until the locks at Sault Ste. Marie were constructed, but from the time the first lock at the "Soo" was completed in 1855 these ores were transported through the locks to consumer centers in the East. The Marquette Range has a history of continuous production from 1848 to the present day. In 1877 the Menominee Range was discovered at the location of the old Penn Mines near Vulcan, Mich. There were further discoveries of ore on the old Menominee Range and at Florence, Wis., in 1880 and at Iron River and Crystal Falls, Mich., in 1882. Penn Mines continued in operation from the date of their discovery until they were finally exhausted by Pickands-Mather in 1945, but operations still continue on the Menominee in the Crystal Falls and Iron River districts. Ore is shipped to a lake port at Escanaba, Mich.

Jan 1, 1960

By H. K. Birnbaum

The effect of 1ow-temperature stabilization anneals on the structure of the 0 phase Au-Cd alloys and on the diffusionless transformations observed in these alloys was examined by X-yay diffraction techniques. A phase separation in the ß-phase region was proposed to account for the experimenta1 results. The effects of quenching from elevated temperatures on the transformation behavior of these alloys were shown to be consistent with the proposed mechanism. IT has been shown that the high-temperature ß phase (CsCl structure) of the Au-Cd alloy system transforms to a phase having an orthorhombic (D2) ß&apos; structurel1-3 for compositions near 47.5 at. pct Cd and a tetragonal (4/m, m, m) ß" structure* in the vicinity of 50.0 at. pct Cd. Both transformations are diffusionless, crystallographically reversible, and occur on cooling at about 60° and 30°C respectively. The temperature interval from the beginning to the end of the transformation is of the order of 5°C in each case. Although the transformations are normally athermal, some of them have been reported to occur isothermally.= wechsler6,7 has shown that the effects of quenching a 49.0 at. pct Cd alloy from elevated temperatures are consistent with the retention of a nonequilibrium number of lattice vacancies. Annealing of these quench effects results in a broadening of the X-ray reflections.8 After a suitable quench, the 47.5 at. pct Cd alloy transforms to a phase having not the p&apos; orthorhombic structure but another structure which has properties similar to that of the ß" tetragonal structure.5.9 This change in the type of transformation has also been obtained after long anneals in the ß-phase region at about 70oC10 The present investigation was primarily concerned with the structural changes accompanying the above transformation phenomena. The change in transformation product and accompanying physical changes during an anneal in the ß phase have been termed stabilization effects. Experimental Procedure —The results reported in this investigation were obtained with the use of a Norelco diffractometer fitted with a temperature-controlled cryostat. The specimen temperature was controlled to better than ± 0.l°C during the measurements. CrKa radiation monochromated electronically with the use of a scintillation counter and pulse height analyzer was utilized. Specimens containing 47.5 and 50.0 at. pct Cd were prepared by sintering filings obtained from homogenized ingots of the proper alloy composition. (Gold of 99.999 pct purity and cadmium of 99.98 pct purity were used). All heat treatments were carried out with the specimens capsulated in vacuum ( < 10 % mm Hg) or in a He-H gas mixture. The quenching technique used in these experiments was to drop the pyrex capsule which contained the specimen from the annealing furnace into water, the temperature of which was controlled. The pyrex capsule shattered on contacting the water resulting in a relatively rapid quench. After the heat treatment, the specimens were mounted in the diffractometer and were left undisturbed in the diffractometer specimen holder during each sequence of measurements. EXPERIMENTAL RESULTS A) Low-Temperature Annealing—The transformations which were considered "normal" for these alloys were those obtained athermally during furnace cooling at approximately 50°C per hr after an elevated temperature anneal. Under these experimental conditions, the specimens were observed to transform to phases having structures whose diffraction patterns could be indexed as the ß&apos; orthorhombic structure for the 47.5 at. pct Cd and as the 0" tetragonal structure for the 50.0 at. pct Cd alloys. The transformation temperatures on cooling were approximately 60" and 30°C, respectively. Under the "normal" conditions both transformations were observed to go to completion, i.e., the entire volume of the ß phase was transformed to the product phase. In some specimens an extremely weak ß 110 reflection was observed at 20°C indicating that a small amount of retained ß was present. The effect of low-temperature annealing on the nature of the diffusionless transformations was examined for the 47.5 and 50.0 at, pct Cd alloy. The specimens were annealed in evacuated capsules at temperatures in the vicinity of 600°C (as specified in Table I) for 24 hr and were then cooled to 100°C at a rate of 50°C per hr. The specimens were then removed from the capsules and mounted in the diffractometer without allowing the specimen temperature to drop below 80°C. Annealing at the low temperatures was accomplished in the diffractometer by means of the cryostat which was mounted around the specimen. During the low-temperature anneals the lattice parameter, integral breadth of the reflections, and ratios of the integrated intensities of the fundamental and super lattice reflections for the 0 cubic phase were periodically determined. After annealing for the required time, the specimens were slowly cooled in the diffractometer and the diffraction patterns were recorded as a function of temperature. The specimens were cooled until the phase transformations were completed, following which the specimens were heated and diffraction

Jan 1, 1960

By M. Smutz, C. J. Baroch, E. H. Olson

IN 1949 an orebody containing some 10 billion lb of recoverable rare earth metals was discovered in the Mountain Pass district of San Bernardino County, California.&apos; The following year Molybdenum Corp. of America purchased a number of claims at the deposit and a mill on the property which had been constructed to process the district&apos;s gold ores. Average composition of ore from the San Bernardino deposit is less than 0.1 pct Tho2, 25 to 35 pct calcite, 10 pct rare earth oxides, 15 to 20 pct silica, and 30 to 40 pct barite.&apos; Rare earth content of the ore analyzes 50.7 pct CeO2, 4.2 pct Pr6O11, 11.7 pct Nd2O3;, 1.3 pct Sm2O3,, and 34.3 pct La2O3 and others.&apos; By floating the barite and depressing the bastna-site, Molybdenum Corp. of America produced a concentrate that contained 60 to 70 pct rare earth oxides. More than 25 pct of the rare earths, however, was lost in flotation. It seemed likely that a more economical method could be found. At the present time most of the rare earths in the concentrates are converted to rare earth chlorides, which are either fed to ion exchange columns for separation of the individual rare earths or reduced to misch metal. Current investigation shows that solvent extraction may achieve this separation more economically than ion exchange. The study reported here was undertaken to develop an economical method of preparing a pure rare earth nitrate mixture from California bastnasite ore. Results indicated that more than 98 pct of the rare earths could be recovered. Several possibilities were considered for processing bastnasite ore, but only the method outlined in Fig. 1 was investigated. This involved leaching the calcined ore with nitric acid. The nitric acid process is discussed under the following headings: 1) calcination of the ore, 2) leaching of calcine, 3) filtration studies, 4) solvent extraction, and 5) nitric acid recovery. Calcination: Since California bastnasite ore contains 25 to 35 pct calcite and about 10 pct bastnasite, calcination was needed to reduce the violence of reaction with nitric acid. Weight losses of 26 to 30 pct were obtained by calcining the ore at 900°C for I hr or at 800°C for 4 hr. Longer periods resulted in no further weight loss. Leaching the Calcine: When the bastnasite calcine was leached with 30 pct nitric acid for 8 to 10 days, rare earth recoveries of only 45 to 50 pct were

Jan 1, 1960

By R. Didchenko

THERE are many methods described in the older literature which claim to produce anhydrous rare-earth chlorides in general. and cerium chloiide in

Jan 1, 1960

By G. L. Coleman, D. S. Hutton, W. C. Leslie

The occurrence of twins in a iron, generated during cooling through the ?-a transformation, is well established,1-8 but this phenomenon has been nearly ignored during the past 20 years. It is the purpose of this note to call attention to the prevalence of such twins and to illustrate their appearance. The work of paxton7 and Kelly8 has demonstrated beyond reasonable doubt that for Neumann bands (mechanical twins) in a iron the twinning plane is (112) and the twinning direction <III>. The agreement with McKeehan&apos;s earlier work4 on transformation twins indicates that both types of twins in ferrite follow the same twinning law. There is little doubt of this conclusion, but it could be strengthened by a microbeam X-ray determination of the orientation relationship between a single ferrite grain and a transformation twin within that grain, as in the technique used by Kelly8 on Neumann bands. RESULTS AND DISCUSSION Transformation twins, identified by their appearance on a polished and etched section, were found in

Jan 1, 1960