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By Charles N. Becker

The practice of drying phosphate in Florida is as old as the industry, which began a little more than half a century ago. The methods, however, have changed considerably. At first, the natural process of exposure to the sun and air was used, later supplemented by wood fires beneath open-air stationary dry kilns and drying towers of various designs. It was not until the early nineties that rotary driers came into use, and at first they were of very small design and fired with wood. As the industry grew and tonnage increased, so likewise grew the number and size of rotary driers, until today the largest installations are 6 ft. up to 7 ft. 6 in. in diameter, and 55 to 60 ft. long, fired with crude oil. The reasons for drying phosphate rock are: (1) to eliminate freight on water in the shipment and (2) to facilitate the good grinding qualities required by the buyers in their acidulation. Phosphate pebbles vary materially in natural characteristics and each property has a direct bearing on the processing. In making comparisons of cost and operating conditions, the following are usually taken into consideration: 1. The hard dense pebbles, which contain very little interior moisture and 6 to 8 per cent total moisture, usually produced from the low-grade deposits. 2. The lighter, porous pebbles, which contain 4 to 5 per cent interior moisture and a total moisture ranging from 9 to 15 per cent. 3. The product of recovery operations using oily reagents, containing from 15 to 25 per cent moisture. 4. The size of the pebbles Usually the plus 5-mesh material is considered as "coarse rock"; the minus 5-mesh plus 24-mesh is "fine rock," and the minute particles below 24 mesh are called "concentrate." 5. The amount of moisture allowed in the dried product. The practice is generally to dry down to 1.5 to 2 per cent moisture. There is, however, an actual range in guarantee of from 1 per cent maximum to 3 per cent maximum.

Jan 1, 1938

By Charles N. Becker

The practice of drying phosphate in Florida is as old as the industry, which began a little more than half a century ago. The methods, however, have changed considerably. At first, the natural process of exposure to the sun and air was used, later supplemented by wood fires beneath open-air stationary dry kilns and drying towers of various designs. It was not until the early nineties that rotary driers came into use, and at first they were of very small design and fired with wood. As the industry grew and tonnage increased, so likewise grew the number and size of rotary driers, until today the largest installations are 6 ft. up to 7 ft. 6 in. in diameter, and 55 to 60 ft. long, fired with crude oil. The reasons for drying phosphate rock are: (1) to eliminate freight on water in the shipment and (2) to facilitate the good grinding qualities required by the buyers in their acidulation. Phosphate pebbles vary materially in natural characteristics and each property has a direct bearing on the processing. In making comparisons of cost and operating conditions, the following are usually taken into consideration: 1. The hard dense pebbles, which contain very little interior moisture and 6 to 8 per cent total moisture, usually produced from the low-grade deposits. 2. The lighter, porous pebbles, which contain 4 to 5 per cent interior moisture and a total moisture ranging from 9 to 15 per cent. 3. The product of recovery operations using oily reagents, containing from 15 to 25 per cent moisture. 4. The size of the pebbles Usually the plus 5-mesh material is considered as "coarse rock"; the minus 5-mesh plus 24-mesh is "fine rock," and the minute particles below 24 mesh are called "concentrate." 5. The amount of moisture allowed in the dried product. The practice is generally to dry down to 1.5 to 2 per cent moisture. There is, however, an actual range in guarantee of from 1 per cent maximum to 3 per cent maximum.

Jan 1, 1938

By S. Katz, M. E. Nicholson, J. J. Kelly, D. R. Curran

A series of wedges of 1020 steel (2 1/2 by 6 by 8 in.) were explosively loaded, as shown in Fig. 1. A slab of explosive on the surface of the steel wedge was initiated simultaneously along one edge, producing an essentially two-dimensional oblique shock in the metal. Pressure and density in the metal were measured as a function of distance from the explosive-metal interface by a method described elsewhere.' While for pressures below 130 .kbars the technique produces accurate results, for greater pressures the presence of two shock waves in the metalzy3 makes interpretation of the data uncertain. However, the location of the transition in pressure at 130 kbars can be readily identified from the data. The assumption of a single shock in the region above 130 kbars overestimates the pressure computed on a multiple-shock model. After firing, the wedges were sectioned, lapped, and etched with 2 pct Nital. A photograph of an etched specimen is shown in Fig. 2. The specimens were examined metallographically. The dark region, at the top of the specimen, was heavily banded, Fig. 3, while the lighter area was comparatively free from banding, Fig. 4, the boundary between the two regions being quite abrupt. The very light regions at an angle of about 45 deg to the explosive-metal interface show virtually no banding. The origin of these light regions, which are not Luder's bands, is not yet explained. The thickness of the heavily banded area was measured and compared with the pressure at the boundary between the heavily and lightly banded regions. The results of these measurements and calculations are given in Table I. For all shots, the pressure at the boundary is approximately the same

Jan 1, 1960

By N. S. Stoloff, R. C. Ku, R. G. Davies

The stress-strain behavior of Fe-Co and Fe- V alloys containing up to 25 pct solute have been studied in the temperature range 25° to - 196°C. The microyield stress is independent of temperature for all alloys studied, while the temperature dependence of the ordinary yield stress is large and comparable to that for unalloyed iron. An alloy-softening phenomenon is observed for many alloys relative to unalloyed iron, and appears to be a consequence of removal of inter-stitials from solution and their subsequent agglomeration. The ductile to brittle transition temperature is increased markedly by both cobalt and vanadium. Transmission electron microscopy observations reveal that cross slip and cell formation are restricted with increasing solute, which can account for many aspects of yielding and fracture behavior. IRON and other metals of bcc structure slip on many planes of the (111) zone at moderate and elevated temperatures, giving rise to wavy glide. At low temperatures, however, there is a tendency for slip to be restricted to planes of only one or two crystallographic types; in the case of Fe-Si alloys for example, (110) glide predominates, giving rise to planar slip bands."' Restriction of cross slip at low temperatures in iron has been linked by Brown and Ekvall3 to increased strain hardening in the preyield microstrain region, leading to an apparently large temperature dependence of the yield stress. Support for this view has been provided by Lawley and Gaigher4 from a transmission electron microscope study of molybdenum. They concluded that dislocations at lower temperatures, by virtue of their inability to change planes readily, are unable to interact and annihilate, leading to an increase in internal stress and work-hardening capacity. Restriction of cross slip at low temperatures has also been suggested to be an important factor in determining the ductile to brittle transition of single-phase solids, including metals of bcc structure.5 It is pertinent to note that most solute elements tend to raise the ductile to brittle transition temperature of poly crystalline ferrite,6,7 although in some cases, e.g., Fe-Cr7 and Fe-Al,8 the dilute alloys may actually yield at lower stresses than unalloyed iron. It appears, therefore, that solute elements may have an effect analogous to lowering the test temperature with regard to restricting cross glide. Such an effect has indeed been observed in the ionic alloy system KCl-KBr,9 in which bromine atoms, although causing little misfit and consequently little effect on the yield stress of KC1, have a pronounced effect in restricting wavy glide and inducing brittleness. The purpose of the present investigation was to determine the effects of selected solute atoms on the yield stress and fracture behavior of iron, and to elucidate in turn how the slip character was related to these properties. Since it is known that interstitial atoms exert a strong influence on the mechanical behavior of iron, the solute elements chosen for study were vanadium, which reacts strong with interstitials,10 and cobalt, which does not form highly stable interstitial compounds." EXPERIMENTAL PROCEDURE Four-pound ingots of each of the following alloys were vacuum-melted in zirconia crucibles: Fe-1, 5, 10, 25 at. pct Co, and Fe-1, 4, 10, 20 at. pct V. An ingot of unalloyed iron from the same original stock as that used for the alloy was remelted under similar conditions to eliminate variations in interstitial content arising from differing thermal histories. Chemical analyses of the iron, cobalt, and vanadium melt stock are listed in Table I. All ingots were rolled and swaged, commencing at 850°C, to 1/4-in.-diameter bar. The bars were then annealed at 850°C for 1 hr (except that the 10 and 20 pct V alloys were heated for 2 hr) to give a uniform equiaxed grain size of about 0.05 mm. Tensile samples of 0.125 in. diameter by 0.8 in. gage length were utilized for studies of the ductile to brittle transition. A second set of tensile samples were utilized for microstrain experiments in which strain sensitivity of 1 x 10"6 was achieved by a capacitance method.3 Cylindrical compression samples 0.250 in. diameter by 0.4 in. long also were prepared to study the influence of composition on the macroscopic yield stress, and for metallographic analyses of defor-

Jan 1, 1965

By J. B. Wagstaff, R. A. Buchanan, J. F. Elliott

High speed photography through blast-furnace tuyeres showed coke particles moving rapidly. Model studies showed a raceway was formed and gave quantitative results which were correlated with actual blast furnaces. Another study showed the similarity between hanging and the flooding of a packed column. This was explored by models. THE combustion zone before the tuyere in an iron blast furnace is a vital region because here are generated: 1—most of the gases on which the furnace depends to carry out its basic operation of reducing iron ore to the metallic state, and 2—the major fraction of the heat required in the nearby regions of the furnace for the various reduction reactions, the fusion of the slag, and the melting of the iron. Since the greater part of the coke is consumed in this region, the descent of the burden must be greatly affected by the characteristics of the tuyere zone. This region then would seem to be a profitable field for study. Fortunately, a view into this important zone is available to the operator through the tuyere peep sight. Here he sees relatively dark pieces of coke "dancing" in the blast. What he sees is of considerable help in interpreting the behavior of the furnace at a given time but the very rapidly moving particles and the intense radiation obscures what is happening very deep in the zone. This investigation was initiated in the hope that a better understanding of the combustion region could be obtained by using a high speed camera with a maximum speed of 3000 frames per sec. It seemed the best practical method of "slowing down" this characteristically violent action within the highly luminous field. Model studies and tuyere probing also have been used to aid in explaining the observed phenomena. Above the combustion zone, but below the fusion zone, there is probably a region in which the coke is comparatively stationary. Here are zones in which the gases must flow up through the granular bed counter to descending liquid slag and metal. There is no easy way to observe this zone in a blast furnace, but model studies have been of some help in explaining the nature of the zone and the laws governing the flow of the fluids involved. The whole problem is difficult and involved and any approach to a complete solution may require long investigation. This preliminary report has been written, therefore, because it is believed that appreciable progress has already been made that would be of interest to others. Tuyere Studies, Chemistry and Kinetics It is well known from the early work of Kinney and coworkers1,2 that combustion of carbon before the tuyeres appears to occur in two zones: Zone A: C + O, = CO2; AH77°F. = — 14,108 Btu per lb of carbon [I] Zone B: CO2 + C = 2CO; H77°F = + 6,183 Btu per lb of carbon [2] Zone A (Fig. 1) is close to the tip of the tuyere and zone B is somewhat farther back; there being a transition region in which both reactions occur. It is interesting to estimate the rate at which coke is burned before a tuyere with a wind rate of 90,000 cfm in a modern furnace having 18 tuyeres. Approximately 0.55 lb of carbon is consumed by eq 1 per tuyere per sec. A like amount disappears by eq 2 for a total consumption of 1.11 Ib per sec per tuyere. Assuming the coke is 85 pct C and has a bulk density of 30 lb per cu ft, this figure can be converted to a total of 1.30 lb of coke with a bulk volume of 0.043 cu ft disappearing per sec per tuyere. At the temperatures prevailing in the combustion zone (according to Kozlovich,³ he maximum is about 3400°F), the rate at which carbon is con-

Jan 1, 1953

By J. L. W. Birkinbine

This paper is a discussion of a part of the mineral wealth of the States of Oaxaca and Paebla, Mexico. It does not refer to the precious metals, sonie mines of which, in these States, are said to have been worked before the advent of the Spanish conquistadores in the sixteenth century, as my purpose is to invite attention to the exploration of deposits of coal and iron-ores in the Mixteca region. The prominence given to coal is warranted by the great effect of the scarcity of fuel upon the industrial development of Mexico. Under the progressive administration of President Porfirio Diaz, the Republic has made wonderful advances in the past three decades; and this progress would have been greater but for the limitations imposed by expensive fuel. In the spring of 1906 I was detailed by the Birkinbine Engineering Offices, of Philadelphia, to accompany A. B. Adams, of New York, in a reconnoissance of reported deposits of iron-ores in the State of Oaxaca. The result of this expedition was the formation, in 1907, of the Oaxaca Iron & Coal Co., of which Mr. Adams became, and has remained, President and General Manager, and I have spent the past three years as Chief Engineer of this company in Mexico, principally in western Oaxaca, where field-headquarters were established. GEOGRAPHY AND POPULATION. Although the geographical and topographical features of the Republic of Mexico are well known, few realize that the majority of its population is domiciled in the States which immediately surround the capital city of Mexico, including the Federal District, Mexico, Tlaxcala, Morelos, Puebla,

Jan 1, 1911

By W. L. Korbee, P. Hazebroek, M. Prats, E. E. Allen, C. A. 225-000-000-017 Verbraak, H. C. van Elst

In a recent paper,' one of us has presented some experimental evidence on the relationship between twinning and brittle fracture in steel. From metallographic examinations of brittle fracture it could be derived that mechanical twins and microcracks are formed already in front of a running brittle fracture. A tentative explanation based on the evaluation of the statistical distribution of mechanical twins vs various angles to the fracture was given in the above mentioned paper. It was suggested that these twins are caused by stress waves emitted by a running brittle fracture. With the aid of high-speed photography and the use of photo-stress sheet we are now able to study in more detail the propagation of a brittle fracture and the emittance of stress waves connected with fracture. A typical example is given in Fig. 1. In this figure a running brittle fracture in an ordinary Thomas steel is shown. The experiment was performed on a Robertson apparatus and the stress waves caused by the fracture were made visible with photo-stress

Jan 1, 1962

By J. J. Kanter

The choice of a nonferrous metal or alloy for a given Application is frequently predicated upon a consideration of properties other than merely the capacity to withstand stress. When ability to withstand stress is the dominant engineering requisite of the material to be used, economic considerations seldom lead to the choice of nonferrous metals and alloys. In most instances where a nonferrous metal is used it is because of some special quality of either corrosion resistance, electrical properties, thermal properties, antifriction, or fabrication advantage that commends its application. The mechanical properties, as a rule, present an incidental engineering consideration entirely secondary to the special quality deciding its use. Indeed, great ingenuity has often been exhibited by engineers and metallurgists in overcoming the mechanical shortcomings of a nonferrous base material. in order to take advantage of some outstanding property. . With this thought in mind, we might better appreciate some of the problems in stress design. encountered with nonferrous metals and alloys pertinent to a symposium on their creep characteristics. Our considerations must necessarily be far from complete because of the broad range of materials in the nonferrous category for which creep properties assume a technical interest. Creep deformation of these metals can be subject for study at temperatures ranging from ambient to incandescent, depending upon which one is under consideration. Whereas the steel metallurgist thinks of creep as an essentially high-temperature engineering consideration, the same is not necessarily true in the field at hand. The diversity of the creep problems in the nonferrous field is perhaps accountable to some extent for its virginity as a symposium subject. Each research has necessarily been sponsored by some organization or group interested either in promoting the use of a certain nonferrous base or in obtaining data toward the solution of a mechanical difficulty encountered in applying a material indispensable for its special attributes. Perhaps as many techniques of creep testing have been used as there are base metals implied under "nonferrous." Some of the creep problems that have occasioned researches are associated with steam-pressure vessels such as tubes, drums, castings, and forgings of copper-base and nickel-base alloys, cable sheathings of lead and lead-base alloys, electrical transmission lines of copper and aluminum, engine parts die-cast from alloys based on zinc, aluminum, copper— soldered and brazed joints-—as well as numerous duties at extremely high temperatures met with alloys based on cobalt, nickel, tungsten, molybdenum, platinum, and other precious or semiprecious metals. Postwar technology will have the benefit of much creep research on nonferrous metals, which for reasons of security cannot be discussed on this occasion. Suitability OF Metals As already intimated, the bulk of the constructional metal that ordinarily is

Jan 1, 1945

By G. Sherburne Rogers

One of the features of oil-field work that puzzles operator, chemist, and geologist alike, is variation in the gravity of the petroleum produced on neighboring leases or even from adjoining wells. Few fields in the United States yield oil that is of uniform gravity throughout; in some fields the different grades are produced from different sands, in a few from different formations, and in many from different areas in the same sand. In a few cases, perhaps, a common assumption—that the heavier oil is derived from the lighter through the escape of the more volatile constituents—is valid, but many cases can not be explained in this way. Although in the California fields the specific gravity of the oil generally decreases with depth, there are numerous exceptions to this rule; and, as in many other regions the light oil is found nearest the surface, it is evident that evaporation underground is generally an unimportant factor. It is generally recognized that the great differences between petroleum from widely separated fields are due largely to differences in age and degree of metamorphism and to variation in the composition of the original organic matter; but in the writer's opinion some of these broader differences, as well as most of the minor variations in the character of the oil from any one field, are due to the local action of natural reagents such as sulphur or oxygen. This is particularly likely to be true if the oil has migrated from one formation to another, as in the California fields; and in some arcas it appears that variation in sulphur content may even afford a rough index of the extent or distance of the migration. It is the purpose of this paper to call attention to the chemical action of sulphur and oxygen on petroleum, to show that the gravity of the oil from any one field is intimately related to its sulphur content, and to discuss the possi-

Jan 1, 1918

By H. C. Fiedler

The development of cube-on-edge secondary re crystallization texture in Si-Fe strip depends upon the ability of inclusions, such as manganese sulfide, to restrain nomal grain gvowth. The ability of inclusions to perform this function is shown to depend upon their size and distribution. The desired uniform dispersion of many small inclusions is obtained by controlling the cooling rate from above the solution tempmature of the inclusions or, alternatively, by drastic 'quenching from above the solution temperature followed by heat treating at a lower temperature. The development of the cube-on-edge secondary recrystallization texture in Si-Fe strip depends upon both establishing the proper primary recrystallization texture and having inclusions to restrain normal grain growth. It has been suggested that the first requirement is met with a texture which, though weak, is near (110)[001]. A mechanism for secondary recrystallization originally proposed by ielsen' is consistent with the presence of this primary texture. It is visualized that a secondary grain appears where two adjacent grains happen to be sufficiently similar in orientation to be capable of behaving as a single large grain. This pair of grains will grow at the expense of its smaller neighbors as a consequence of its having lower grain boundary free energy. Other explanations of the origin of the secondary recrystallization texture have been offered,' and it can be concluded that the mechanism is not fully understood. Nevertheless, it is apparent that operationally the necessary primary recrystallization texture is obtained simply by interposing an anneal during the cold reduction to final gage. The role of inclusions in the development of the secondary recrystallization texture has been demonstrated by May and Turnbull4 in a comparison of a high-purity heat and a heat containing manganese sulfide. They showed that the driving force for secondary recrystallization is inversely proportional to the diameter of the matrix grains and that the function of the inclusions is to maintain a small matrix grain size. Other inclusions, such as various sul- fides,')' silicon nitride,8 and vanadium nitride,' titanium carbide,'' and vanadium carbide," have been shown to be effective in promoting secondary recrystallization to the cube-on-edge texture. There is also evidence that silica inclusions in Si-Fe strip made by powder-metallurgy techniques perform this function.' This report is concerned with the second of the two requirements for secondary recrystallization, namely the importance of the metallurgical control of the size and therefore number of inclusions. While the concepts involved are simple, they are fundamental to the making of this material. EXPERIMENTAL PROCEDURE A heat containing 3.27 pct Si, 0.026 pct S, 0.06 pct Mn, and 0.004 pct C was made in an air induction furnace from electrolytic iron, 98 pct ferro-silicon, electrolytic manganese, and iron sulfide. The heat was divided between graphite and baked-sand molds with a cavity 2-5/8 by 5 in. and with walls 2-3/4 in. thick. Slabs, 1 in. thick and 2-5/8 by 5 in., were cut from the ingots and hot-rolled either in the as-cast condition or after one of the heat treatments described later. After pickling, the 80- to 100-mil-thick hot-rolled band was, unless otherwise noted, heat-treated for 5 min at 900°C before being cold-rolled to 25 mils. After a heat treatment of 1 to 3 min at 860°C, the strip was cold-rolled to 12 mils, the final thickness. The percent cube-on-edge texture was determined by dividing the maximum torque as averaged from four samples by the maximum torque of a 3-1/4 pct Si-Fe single crystal having the (110) plane in the plane of the sample. The torque measurements were made in a field of 1000 oe on 1-in.-diam disks. RESULTS AND DISCUSSION The importance of the thermal history of the ingot is evident in Fig. 1 from the appearance of strips heat-treated in a temperature gradient. The sample

Jan 1, 1964

By C. C. Clark, J. S. Iwanski

The purpose of this investigation was to study mi-crostructural changes that take place in a commercial nickel-chromium-iron alloy, such as Incoloy "901," over long periods of time at temperatures up to 13 50°F and to correlate such changes with creep-rupture properties. of the alloy. In the course of the investigation, some microstructural changes were observed which correspond to microstructural alterations found in previous studies of Inconel "X." Microstructural phases have been identified in both alloys with the aid of electron and X-ray diffraction and an electron probe microanalyzer. The materials used in this investigation were from commercial heats of the following chemical composition: Pct Cr Pct Ni Pct Mo Pct Fe Pct Cb Incoloy "901" 12.51 43.67 5.72 Bal. -Inconel "X" 14.61 73.44 - 6.61 1.02 Pct A1 Pct Ti Pct Mn Pct Si Pct C Incoloy "901" 0.10 2.46 0.46 0.24 0.05 Inconel "X" 0.70 2.43 0.51 0.36 0.04 Long-term creep-rupture tests were conducted on Incoloy "901" at temperatures of 1000°, 1200°1 and 1350°F. A summary of these results is shown in Table I along with the results of a long-term creep-rupture test conducted on Inconel "X" at 1500°F. The heat treatments given the specimens are also shown in Table I. When the creep-rupture results on Incoloy "901" are compared with shorter-tertn data, there is no evidence of any undue deterioration of the creep-rupture strength with time, nor is the elongation decreased more than would be expected from the influence of time alone. INCOLOY "901" PHASE IDENTIFICATION Microscopic examination of the Incoloy "901" specimens reveals a dark etching grain boundary constituent in the specimen which was under test for about 11,500 hr at 1000°F. This grain boundary constituent was seen to increase in size as the test temperature was increased to 1200" and 1350°F, Figs. 1, 2, and 3. Simultaneously, an acicular structure of definite crystallographic orientation appears within the grains of the 1350°F specimen, Fig. 3. Under examination with the electron microscope, a fine precipitate is observed in the 1200 °F specimen. Fig. 4. It becomes considerably larger in the 2850-hr 1350°F specimen, Fig. 5. In a few areas the precipitated particles have been replaced by, or transformed to, small needles or platelets. After 7380 hr at 1350°F, Figs. 3 and 6, the needles are much larger and have replaced nearly all of the fine precipitate. X-ray diffraction studies detected the presence of hexagonal Laves phase and hexagonal n phase (Ni,Ti) in the 1350°F specimens, Table 11. Only the Laves phase was detected by X-ray diffraction in the 1200°F specimen and none was detected in the 1000°F specimen. In this latter specimen, however, the small quantity of precipitate in the grain boundaries (presumed to be Laves phase) precludes its detection by X-ray diffraction. Composition of the hexagonal Laves phase is not yet known, although its diffraction

Jan 1, 1960

By P. Ramachandrarao, T. R. Anantharaman

CONSIDERABLE interest has lately been evinced as regards the nature of chill zones in solidified metals and alloys. Biloni and Chalmersl were the first to show through their study of segregation substructures in some nonferrous alloys that the formation of the dendritic region may be preceded by a diffusionless solidification process, viz., predendritic solidification. Subsequently Bower and Flemings2 tried a special solidification technique wherein the liquid was drawn into a narrow copper mold with polished surfaces and concluded that convection might trigger some multiplication mechanism leading to grain refinement. Using uncoated and partially coated surfaces for molds in the Bower-Flemings technique as well as in conventional molds, Biloni and Morando3 have very recently brought out the importance of the rate of heat extraction on the mechanism of solidification. We report here on the surface structures and substructures observed in a Sn-1 wt pct Pb alloy solidified at even higher cooling rates (riz., l05 to l07 ºc per sec) than those employed by earlier workers. The alloy was made by melting tin (99.99+ pct) and lead (99.9+ pct) in a silica tube under vacuum. Small quantities of the homogenized alloy (0.5 to 1.0 g) were then quenched (or splat-cooled) from the melt by the "gun technique" developed by Duwez et al.4 The thickness of the resultant foils varied from specimen to

Jan 1, 1970

By M. J. Marcinkowski, D. Koskimaki, A. S. Sastri

THIS is the second in a trilogy of investigations carried out in order to understand the solid state transformations and their accompanying effects on the deformation behavior of near-equiatomic Ni-Ti alloys. The first stage of this effort has dealt with the strictly martensitic structures obtainable in these alloys, i.e., those in which diffusion processes were not involved.1,2 These martensites could be produced either by rapid quenching or by plastic deformation of the originally B2 type phase. The present investigation, on the other hand, will deal with those transformations in Ni-Ti which do involve diffusion. A majority of investigators3-10 have shown that the B2 modification of TiNi, which is stable at elevated temperatures, decomposes into one or both of the intermetallic compounds NiTi2 and Ni3Ti below about 650°C. On the other hand, this has been disputed by several Workers was undertaken in order to resolve this discrepancy, as well as to shed more light on the nonmar-tensitic decomposition of B2 NiTi. EXPERIMENTAL PROCEDURE Sample preparation, fabrication, and examination were the same as those described previously in Ref. 2. In addition to the 50 at. pct Ni (55.06 wt pct) hypoeu-tectoid alloy used previously, a second hypereutectoid alloy containing 54.4 at. pct Ni (60 wt pct) was also prepared for this study. RESULTS AND DISCUSSION The equilibrium diagram for the Ni-Ti alloy system in the vicinity of Ni-Ti is shown in Fig. 1. The solid lines have been established by the work of Poole and ~ume-Ftothery4 whereas the dotted lines are based on findings obtained in the present investigation as described below. Structure and Morphology. Fig. 2(a) shows a bright field transmission electron micrograph of a two-phase structure obtained in a polycrystalline Ni-Ti alloy that was furnace cooled (approx 200°C per hr) from 1050' to about 300°C. Large plate-shaped precipitates can be observed in a matrix which was found by electron diffraction to possess the high temperature B2 structure. A selected area diffraction pattern of the region covered by Fig. 2(a) is shown in Fig. 2(b), while Fig. 2(c) is a detailed schematic interpretation of Fig. 2(b). The B2 matrix reflections are illustrated by squares while those of the precipitate are shown as circles. The d values associated with the precipitate reflections could be determined quite accurately since the reflections from the B2 matrix, for which the lattice constant is known precisely, were simultaneously present in the diffraction patterns. All of the reflections

Jan 1, 1970

By R. A., D. L. Sponseller, Flinn

Using specially del'eloped titanium nitride crucibles and a pressurized syslem, it has been possible to determine the solzibilitv of liquid calcium in liquid iron and iron-base alloys. At 2925°F the solubility is 0.032 wt pet Ca in pure iron. The solubility is increased by aluminum, carbon, nickel, and silicon additions, and lowered by additions of gold. An inflection in the calcium-solubility curve occurs as carbon is added to iron. At approximately 0.87 Wt pet Ca the CaC, phase replaces liquid calcium, and the calcium concentration de- creases as more carbon is added to the iron. The maximum solubility, 0.36 wt pet Ca, was obtained in iron containing 10.5 wt pet Si. The data have important implications regarding the use of calcium in process metallurgy, as well as providing an interesting test of theories of metallic solutions. Reasonably good agreement is found with theories of Alcock and Richardson and of Wagner, and criteria are suggested which permit these theories to be applied more readily to systems of this type. AT the present time relatively little is known about the factors influencing solubility in liquid metals. Information of this type is important for such matters as the control of impurity levels in liquid metals, the use of magnesium in ductile-iron production, and the use of liquid-metal alloys as fuels and coolants in nuclear power plants. One important example of restricted solubility concerns the extent to which liquid calcium will dissolve in liquid iron. This is a matter of considerable interest in view of the strong potential of calcium for removing certain impurities in steel,. as well as the ability of calcium to desulfurize, inoculate, and produce spheroidal graphite in cast irons.' Since ferrous materials normally contain other elements in addition to iron, the interactions of third elements with the Fe-Ca system are of interest. In view of the foregoing, this investigation was conducted to determine the solubility of liquid calcium in liquid iron and the effects of various third elements upon the solubility. For reasons of theoretical and engineering importance, the elements investigated were aluminum, carbon, gold, nickel, and silicon. Numerous attempts were made in the early part of the present century to determine the solubility of calcium in both liquid iron and steel, employing a variety of open-melt and closed bomb-type systems.2-4 From the results of these tests Wever concluded that calcium is insoluble in liquid and solid iron.5 These investigations were unsatisfactory in that they failed to insure the presence of a liquid layer

Jan 1, 1964

By Nicholas J. Grant, Robert F. Wilde

TAYLOR and Floyd's"" work in establishing phase diagrams based on the elements Ni-Cr-Ti-A1 has led to an understanding of the precipitation hardening mechanism in alloys based on these elements. Nordheim and Grant4 concluded that in simple alloys, and where the aluminum to titanium atomic ratio was such that less than three out of five aluminum atoms were replaced by titanium, the precipitate on aging is the face-centered-cubic Ni 3A 1 phase, called They further found that increasing amounts of hexagonal ? phase, Ni3Ti, precipitated from these alloys when the titanium content exceeded the solid solubility of both matrix and Ni3A1. For alloys of Ni-Cr-Ti-Al, in which the titanium and aluminum contents each ranged from 0 to 4 wt pct, the titanium-rich was superior for strengthening to either pure ?' or 7. It was also noted that the combined titanium plus aluminum content (atomic pct) was a direct measure of the high temperature strength and overaging temperatures for these alloys.4 The present investigation was undertaken to extend existing data on precipitation hardening in the more complex commercial alloys containing higher titanium plus aluminum, and with significant quantities of cobalt, molybdenum, and carbon. Experimental Procedure Reforging of As-Received Bar Stock—The alloys were received as ground, forged bar stock. Chemical analyses and the as-received bar diameters are shown in Table I along with the ASTM grain size after the various treatments. All stock except the Waspaloy was reforged to % in. diam to gain material and to facilitate machining of stress-rupture specimens. Forging was carried out at 2100°F, and discontinued when the bar temperature fell to 1800°F. Heat Treatments—For experixental simplicity it was desirable to heat treat all of the alloys at, the

Jan 1, 1958

By Takashi Katsura, Avnulf Muan

Equilibrium relations in the system FeO-Fe2O3 Cr2O3 have been determined at 1300°C at oxygen pressures ranging from that of air (0.21 atm) to 1.5 x 10-11 atm. The following oxide phases have stable equilibrium existence under these conditions : a sesquioxide solid solution with corundum-type structure (approximate composition Fe2O3-Cr2O3); a ternary solid solution with spinel-type structure (approximate composition FeO Fe2O3-FeO Cr2O3) and a ternary wüstite solid solution with periclase-type structure and compositions approaching FeO. The metal phase occurring in equilibrium with oxide phase(s) at the lowest oxygen pressures used in the present investigation is almost pure iron. The extent of solid-solution areas and the location of oxygen isobars have been determined. ThE system Fe-Cr-O has attracted a great deal of interest among metallurgists as well as ceramists and geochemists. Metallurgists have studied the system because of its importance in deoxidation equilibria, ceramists because of its importance in basic brick technology, and geochemists because of its importance for an understanding of natural chromite deposits. Chen and chipman1 investigated the Cr-O equilibrium in liquid iron at 1595°C in atmospheres of known oxygen pressures (controlled H2O/H2 ratios). The main purpose of their work was to determine the stability range of the iron-chromite phase. Hilty et al.2 studied oxide phases in equilibrium with liquid Fe-Cr alloys at 1550°, 1600°, and 1650°C. They reported the existence of two previously unknown oxide phases, one a distorted spinel with composition intermediate between FeO Cr203 and Cr3O4, the other Cr3O4 with tetragonal structure. They also sketched diagrams showing the inferred liqui-dus surface and the inferred 1600°C isothermal section for the system Fe-Cr-O. Koch et al3 studied oxide inclusions in Fe-Cr alloys and also observed the distorted spinel phase reported by Hilty et al. Richards and white4 as well as Woodhouse and White5 investigated spinel-sesquioxide equilibria in the system Fe-Cr-O in air in the temperature range of 1420" to 1650°C, and Muan and Somiya6 delineated approximate phase relations in the system in air from 1400" to 2050°C. The present study was carried out at a constant temperature of 1300° C and at oxygen pressures ranging from 0.21 atm (air) to 1.5 x 10-11 atm. The chosen temperature is high enough to permit equilibrium to be attained within a reasonable period of time within most composition areas of the system, and still low enough to permit use of experimental methods which give highly accurate and reliable results. These methods are described in detail in the following. I) EXPERIMENTAL METHODS 1) General Procedures. Two different experimental methods were used in the present investigation: quenching and thermogravimetry. In the quenching method, oxide samples were heated at chosen temperature and chosen oxygen pressure until equilibrium was attained among gas and condensed phases. The samples were then quenched rapidly to room temperature and the phases present determined by X-ray and microscopic examination. Total compositions were determined by chemical analysis after quenching. In the thermogravimetric method, pellets of oxide mixtures were suspended by a thin platinum wire from one beam of an analytical balance, and the weight changes were recorded as a function of oxygen pressure at constant temperature. The data thus obtained were used to locate oxygen isobars. The courses of the latter curves reflect changes in phase assemblages and serve to supplement the observations made by the quenching technique. 2) Materials. Analytical-grade Fe2O3 and Cr2O3 were used as starting materials. Each oxide was first heated separately in air at 1000°C for several hours. Mixtures of desired ratios of the two oxides were then prepared. Each mixture was finely ground and mixed, and heated at 1250" to 1300°C in air for 2 hr, ground and mixed again and heated at the same temperature for 5 to 24 hr, depending on the Cr2O3 content of the mixture. A homogeneous sesquioxide solid solution between the two end members resulted from this treatment. A Part of some of the sesquioxide samples thus prepared was heated for 2 to 3 hr at 1300°C and oxygen pressures of 10-7 or 1.5 x 10-11 atm. Reduced samples (either iron chromite

Jan 1, 1964

By E. O. Jones, E. Whitehead

During the heating of cold-worked nickel silver, the tendcncy of the material to crack is well known. The present research deals with this question, and may conveniently be divided into the following sections: Changes in these alloys during heating and cooling, determination of the temperature at which cracking occurs, effect of grain size, quenching cracks, methods of overcoming annealing cracking. The work is far from complete, in particular the influence of impurities on this tendency has not been investigated, but the results so far obtained lead to certain definite conclusions, which are of theoretical and practical importance. Changes in Alloys During Heating and Cooling During the annealing of many metals at a temperature just below that at which recrystallization sets in, there is evidence of some change, the effect of which is to harden and embrittle the material. This effect has been most clearly demonstrated in the cases of aluminum, copper, brass, and nickel silver, and appears to be a common property of cold-worked metals and alloys, or, at any rate, the non-ferrous ones. The effect would obviously offer an explanation for certain types of annealing cracking, but the trouble is so much more common in the nickel silvers than in the other alloys that some special cause should be looked for. There is, however, fairly good reason for believing that similar cracking may occur in some of the brasses; D. Bunting1 suggests that the a brasses toward the saturation limit are subject to a transformation closely allied in nature to that known to occur in the nickel silvers at around 320" C. Although the existence of this critical temperature range was known, it did not necessarily follow that this transformation was responsible for the trouble under investigation, so the first portion of this paper deals with the attempts made to determine whether other critical changes might not occur in these alloys. There were already reasons for the belief that such would prove to be the case, as the mechanical properties of the nickel

Jan 1, 1926

By H. Scott

Since Bohler discovered, in 1903, on cooling certain alloy steels, the phenomenon of a new and lower temperature transformation than the usual Ar 3-2-1 obtained by increasing the maximum temperature to which the material was heated, much has been published1 connecting this phenomenon with a large number of dissimilar steels of high alloy content. From the fact that the transformation divides itself, taking place at two widely separated temperatures, it has been called a "split transformation." The significant facts established by recent investigators2 are: that when the transformation occurs at the higher temperature Ar1, troostite or a decomposition product is formed, and that when the transformation occurs at the lower temperature Ar", the resulting structure is martensite. The terminology Ar' and Ar" adopted here is that of Portevin. Previous Investigations Reviewing the work on this subject published in a recent issue of Revue de Metallurgie and referring in particular to his statement that martensite is a solution of carbide in alpha iron, Le Chatelier says :4 "How then can a theory already 20 years old demand new investigations? The reason for it is that we have not succeeded in proving directly the real presence of the transformation of iron during the very short duration of the quenching. The fall of temperature takes place at the rate of several hundred degrees per second and the observation of

Jan 1, 1920

By L. G. Jones

An approximate method of calculation is developed in this paper which allows duplication of radial unsteady-state gas flow computer results where Darcy's law applies, such as those reported by Aronofsky and Jenkins and Bruce, Peaceman, Rachford, and Rice. Moreover, the new calculation method can be used to obtain results for radial unsteady-state gas flow obeying the quadratic flow law proposed by Duwez and Green. Means are discussed for predicting well behavior at single or superimposed flow rates in finite or infinite reservoirs, determining reservoir rock properties from well-test data, reproducing and interpreting back-pressure test data, and determining the radial extent and reserves of gas reservoirs from well-test data. Example calculations are presented for gas flow following both Darcy's law and the quadratic flow law. INTRODUCTION Since the publishing of U. S. Bureau of Mines Monograph 7,1 most gas-well testing methods have been based on the equation q = y (pl2 - pw2)a, where q = production rate, pl and pw, are formation pressure and sandface pressure, respectively, and y and a are constants to be obtained from test data. These methods, used for predicting both deliverability and "open-flow" capacity of gas wells, have been useful and accurate in many cases but unsatisfactory in others. Even at best, however, they do not supply information about the formation or lead to an understanding of nonsteady-state gas flow in porous media. Many theoretically based studies2-4 of gas flow obeying Darcy's law have been made.' Since the partial differential equations which result from combining Darcy's flow law with the continuity equation are nonlinear, most of the published research consists of either numerical solutions or analytical solutions for linear approximating equations. Such solutions have been of limited value in field work due to their unhandy form and their failure to correlate most field data. There is evidence5,6 which indicates that Darcy's law is inadequate to describe gas flow at some flow rates of practical interest. A quadratic flow law: which reduces to Darcy's law at low rates, is more successful in accounting for experimentally observed behavior. This flow law has been applied successfully to a few hypothetical reservoir cases in work which has recently been published.10 However, these numerical solutions of the equations involved have been successful only on a special analog computer. Routine applications to field cases would be awkward and have not been attempted. The present paper describes an approximate method for computing nonsteady-state gas flow solutions which has been completely successful in predicting the results for both Darcy flow and quadratic flow obtained by elaborate numerical methods. The new calculation method allows determination of the observable variables in gas-well testing at constant rates. It is similar to the scheme of using a succession of steady states suggested by Muskat7 in that it makes use of steady-state and material-balance equations. It also is similar to the work of Aronofsky and Jenkins2 in that the new method includes Aronofsky and Jenkins' stabilized flow equation as a special case. It improves upon both of these calculation schemes in that it accurately describes all portions of reservoir history and suggests means of determining reservoir rock properties from well-test data. This paper deals only with production from a reservoir, in which case the rate is defined as being negative. The reservoir studied here is a homogeneous, disk-shaped porous body of uniform thickness, with all boundaries sealed except the inner radial boundary of the well.

By C. W. Nicolson

THE Tri-State zinc and lead-mining district is in the northeast corner of Oklahoma, the southeast corner of Kansas and the southwest corner of Missouri. The area throughout which active mining has been conducted is about 45 miles long and about 5 miles wide, extending northeasterly from Commerce, Okla., to Alba, Missouri. Although the lead ores were mined on a very small scale in the vicinity of Joplin, Mo., as early as 1848, nothing of any importance was done in the district until 1870, since when both mining and smelting have been prosecuted with considerable vigor. In the beginning the lead ores only were exploited, but within a few years extensive deposits of zinc ores were found and since that time the production of zinc ore has far exceeded that of lead. Both the surface and mineral rights in Missouri and Kansas were under individual ownership by the time ore was discovered. Although some of these rights were purchased by mining companies, most of the mining has been done under leases covering small areas, usually 40 acres, although in the past many leases were given on much smaller tracts. In Oklahoma most of the mineral land had been alloted by the Government to various Indian tribes and although the title to some of these lands had been acquired by various white men before the discovery of the rich Picher field, the title to most of the land has remained with the Indian tribes and the leasing of the mineral rights has been done by the Federal Government for the benefit of the Indians. The Indian allotments were of 200 acres each and some of the mining leases covered entire allotments, although many leases were granted for only 40 acres or even less. Practically all of the leases granted in the past required the erection of a concentrating plant on each lease, a condition that has had a pronounced effect upon the mining and milling methods of the district, since the apparent ore reserves on each tract were too small to justify large

Jan 1, 1938