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By James A. Beck

Phosphorus is essential to all life processes and therefore to the existence of man. In this role, there are no substitutes for phosphorus. In a commercial sense, phosphorus and its compounds are important to our entire economy, both in agricultural and in nonagricultural applications. The world's phosphate requirements are met by mining phosphate rock. Two general types of phosphate ore deposits are commercially important-igneous and sedimentary. Igneous deposits generally are more difficult and more expensive to mine than sedimentary deposits and are of importance mainly in the USSR, North Vietnam, and South Africa. Approximately 15% of current world production comes from these deposits. Over 80% of world production is from the pellet sedimentary deposits of Florida, North Africa, and elsewhere. Guano, the second type of sedimentary deposit, is produced in South America but is declining in world importance. Production Production of phosphate rock was reported in 31 countries during 1972. However, about 80% of world output is produced in three countries: the United States, the USSR, and Morocco (Table 15.2A.1). Throughout the past 20 years, between 75% and 80% of world output has been produced by these three leading countries. Between 1948 and 1972 world production increased at an average rate of 10% per year, from 21.5 to 103.9 million tons. Growth was quite steady at 6% per year through 1963, but in the 5 years from 1963 to 1968 production increased 11 1/2% per year. Since 1968 production has increased about 91/2 % annually. Since 1948 several new phosphate mining ventures have been developed in Senegal, Togo, Israel, and North Vietnam. In the same period, only one important phosphate deposit, on Makatea Island, has been mined out and closed. A number of other phosphate mining ventures are in various stages of planning and development. The most important new venture in phosphate mining is in the Spanish Sahara. New mining capacity is expected also in Syria, and serious investigation is in progress in Peru, India, Turkey, and Australia. Major expansion of existing operations is expected in Morocco, Russia, Tunisia, Israel, and Jordan. Consumption Historical data on world consumption of phosphate rock are not available in detail, but world consumption of phosphate has closely paralleled world production in the past two decades. The United States is the world's largest user of phosphate rock, accounting for 30%

Jan 1, 1976

By Roscoe C. Clark

In October 1945. R. F. Farris. in an AIME paper entitled Method For Drtermining Minimum Waiting OIL Cenzent Time, presented a method for caiculating the minimum WOC* time required in oil well cementing operations. Briefly. this method consisted of shutting in a well. after the cement had been placed and noting the time required fur the wellhead pressure to reach a. maximum. This time was then multiplied by a factor of 1.5 to determine when the cement had reached sufficient strength to support the weight of the casing. As a result of this work, a number of areas have reduced their WOC time ~Wuirements with the subsequent saving of considerable rig time. The tests conducted by Farris were, for the most part, conducted under cementing temperatures in excess of 70°F. This was done because in the overwhelming majority of cases. cementing temperatures are in excess of 70°F (only in tile northern part of the country. primarily in the Rocky Mountain ares. in cementing surface casing are temperatures below 70° F. encountered, and such temperatures occur only during the winter months). The Stano-lind Research Laboratory since that time has performed a number of tests both in the laboratory and in the field to evaluate this WOC factor when cemeriting temperatures are lower than 70°F. The results of these tests indicated the need for greater WOC time in areas affeaed by abnormally low cementing temperatures. These tests indi.cated that a woc factor of 2 (Time from start to mix cement to maximum wellhead pressure x 2 = Time to drill plug) will allow sufficient time for the cement to develop adequate strength. A field test under abnormally low cementing temperatures (surface temyerature 35°F., mud discharge temperature <70°F. and cementing depth 500 ft.) in the Rangely Field, "* using the WOC factor of 2, indicated the time to drill the plug as 45 hours. Well conditions preventing getting back into the well until a 48-hour WOC time had elapsed. At this time, the plug drilled firm to hard indicating that the cement had reached its final set. It is contemplated that during next winter additional field tests will be performed to further check the results of the laboratory and field tests conducted to date,

Jan 1, 1949

By Roscoe C. Clark

In October 1945. R. F. Farris. in an AIME paper entitled Method For Drtermining Minimum Waiting OIL Cenzent Time, presented a method for caiculating the minimum WOC* time required in oil well cementing operations. Briefly. this method consisted of shutting in a well. after the cement had been placed and noting the time required fur the wellhead pressure to reach a. maximum. This time was then multiplied by a factor of 1.5 to determine when the cement had reached sufficient strength to support the weight of the casing. As a result of this work, a number of areas have reduced their WOC time ~Wuirements with the subsequent saving of considerable rig time. The tests conducted by Farris were, for the most part, conducted under cementing temperatures in excess of 70°F. This was done because in the overwhelming majority of cases. cementing temperatures are in excess of 70°F (only in tile northern part of the country. primarily in the Rocky Mountain ares. in cementing surface casing are temperatures below 70° F. encountered, and such temperatures occur only during the winter months). The Stano-lind Research Laboratory since that time has performed a number of tests both in the laboratory and in the field to evaluate this WOC factor when cemeriting temperatures are lower than 70°F. The results of these tests indicated the need for greater WOC time in areas affeaed by abnormally low cementing temperatures. These tests indi.cated that a woc factor of 2 (Time from start to mix cement to maximum wellhead pressure x 2 = Time to drill plug) will allow sufficient time for the cement to develop adequate strength. A field test under abnormally low cementing temperatures (surface temyerature 35°F., mud discharge temperature <70°F. and cementing depth 500 ft.) in the Rangely Field, "* using the WOC factor of 2, indicated the time to drill the plug as 45 hours. Well conditions preventing getting back into the well until a 48-hour WOC time had elapsed. At this time, the plug drilled firm to hard indicating that the cement had reached its final set. It is contemplated that during next winter additional field tests will be performed to further check the results of the laboratory and field tests conducted to date,

Jan 1, 1949

By J. R. Campbell

In order to discuss the subject intelligently, it will be necessary to touch briefly on the forms in which sulphur is supposed to exist in coking coal to be carbonized in beehive or byproduct ovens. Sulphur is known to exist in coal as sulphides and sulphates, as can be determined experimentally. Then there is the so-called organic sulphur, i.e., sulphur in combination with the carbon, &apos;hydrogen, and oxygen of the coal, about which much has been written, but nothing definitely proven in an experimental way. In fact, so far. as we know, there never has been developed a satisfactory and conclusive method in the laboratory for the direct determination of organic sulphur. For most coking coals, it can be safely assumed that the preponderance of sulphur is in the form of pyrite (FeSz). When exposed to comparatively low temperatures during the coking process, it loses its sulphur according to the following chemical reaction: 7FeS2 = Fe7Ss + 6S. It will be seen, therefore, that six out of the 14 atoms of sulphur (or 42.8 per cent.) are expelled, or volatilized. FelSa remains in the coke as pyrrhotite, or magnetic sulphide of iron; this accounts for the highly magnetic properties of the powdered coke. A more commonly accepted reaction is FeS2 = FeS f S, in which the straight sulphide of iron is produced with 50 per cent. volatilization of sulphur. In the beehive methods of coke making, air is introduced in sufficient amounts to carry on the distilling and the coking processes, and the sulphur is oxidized along with the other volatile products: First, into sulphur dioxide (SO2), known by the pungent andsuffocating odoremitted from the trunnel head; second, into sulphuric anhydride (SOa); and, finally, into sulphuric acid, as it comes into contact with the air and moisture. In a properly regulated draft on a beehive oven, there is never complete combustion of the gases. In other words, the coking process should be carried on in a reducing atmosphere, and a low-grade producer gas kept issuing from the trunnel head. For coals of about 30 per cent. volatile matter, the ratio of air to gas is 3½ to 1. In complete combustion, the ratio is 6 to 1, producing an extremely high temperature

Jan 1, 1916

By I. S. Servi, N. F. Graves

THE etch-pit technique has long been used to reveal low-angle boundaries and, in general, the distribution of dislocations in high-purity metals. Often this technique is amenable to quantitative computations,&apos; but generally is affected by some degree of uncertainty because etch pits can be nucleated not only by dislocations, but also by inclusions and surface imperfections. In the case of high-purity zinc, Gilman&apos; reported that etch pits were produced only after adding 0.1 atomic per cent of cadmium to the crystals and aging at a proper temperature. In the course of a study of low-angle boundary behavior in zinc crystals, etch pits were produced in 99.999 pct zinc without resorting to intentional contamination, by etching in a 50:50 HNO3H2O solution. The technique consists of etching until the heat of reaction brings the solution to a boil, and in displacing the etchant rapidly with a stream of cold water, thus avoiding staining. The undesirable features of this technique are the heating effect and the removal of a considerable amount of material. A high polish is obtained if staining is controlled properly; therefore, the etch pits appear very clearly and with excellent contrast when observed under dark field illumination. This is especially helpful for cursory examinations at low magnifications. Several observations were made on zinc crystals of square cross section, having one face parallel to the basal plane and one edge parallel to a slip direction, Fig. l(a). When such a crystal was bent about 2" over a glass die and annealed at 390°C, a sharp boundary was formed only in the inner portion of the crystal. Near the two prismatic faces, perpendicular to the basal plane, the boundary was always branched into many lower-angle boundaries, Fig. 1(b). Attempts to move the main boundary by applying a shear stress to the specimen invariably resulted in curving the boundary, the branched ends remaining pinned in their original location, Fig. 1 (c). The prismatic face, when etched as indicated in the foregoing, revealed the existence of numerous (sometimes up to 30) fine boundaries, nearly parallel to each other. Pre-existing lineage boundaries, generally parallel to the direction of growth, were barriers to the formation of polygonization boundaries and interrupted the continuity of the substructure, Fig. 2. Twin

Jan 1, 1959

By W. F. Stowasser

Robert E. Hagen (Oliver Iron Mining Div., U. S. Steel Corp.)—Mr. Stowasser and his associates are to be congratulated on their achievements in developing the design of a pilot agglomerating plant, based on information obtained from experiments made in a laboratory sinter pot, and subsequently constructing and successfully operating this plant. In his Transactions article, May 1955 (vol. 201) Mr. Stowasser stated that the output of his heat treating strand was about 2 Lt per sq ft of grate area per day and that the fuel consumption was 0.7 to 0.8 million Btu per Lt of product. If it is assumed that the burning zone extends from the back of the ignition furnace to the beginning of the recuperation windbox, only about 1/3 of the grate area over the windboxes is utilized for burning pellets, and the actual rate at which partially dried pellets are burned is about 6 Lt per sq ft of grate area per day. It may be interesting to compare the above operating data with that obtained at the Extaca plant, where taconite concentrate is treated on a conventional sin- tering machine using limestone or hydrated lime additives with no recuperation of heat. The entire windbox area is used for burning, and a production rate of 2.5 Lt per sq ft of windbox area per day has been attained at a fuel consumption of 1.8 to 2.0 million Btu per Lt of product, the latter being considerably in excess of that reported by Mr. Stowasser, partly because a circulating load of returns amounting to 28 to 30 pct of the machine feed is used and because no attempt is made to recuperate heat from the waste gases. With the high capital and labor costs prevailing today, it seems that future development of the downdraft grate pelletizing process should be directed toward taking advantage of the high burning rate of predried pellets and increasing capacity, perhaps at the expense of fuel economy, by decreasing the proportion of grate area utilized by ancillary functions. For example, eliminating the cooling zone and using this area for burning would increase the proportion of grate area available for burning from 33 to 50 pct of the total windbox area, and a proportionate increase in capacity would result.

Jan 1, 1956

By K. P. Anderko

INVESTIGATIONS of the constitution of the system Mg-Ba were first made by Grube and Dietrich1 between 0 and 47 atomic pct Ba and then by Klemm and Dincke1acker" ver the whole composition range. Klemm and Dinckelacker corroborated intermediate phases of the approximate formulas Mg9Ba and Mg4Ba, and showed a third compound to have the formula Mg2Ba, rather than Mg5Ba, as suggested by Grube and Dietrich. Mg2Ba had been previously recognized by Hellner and Laves3 s a MgZn2 (C14) type structure. The main discrepancies between the results of Grube and Dietrich and those of Klemm and Dinckelacker exist, however, in the liquidus temperatures and solidification equilibria of alloys containing more than about 10 atomic pct Ba. The liquidus temperatures measured by Grube and Dietrich, and the outline of the liquidus of Klemm and Dinckelacker are plotted in Fig. 1 on an enlarged scale. Although there are strong reasons to prefer the results of Klemm and Dinckelacker, it was considered worthwhile to remeasure liquidus temperatures of some alloys in the controversial composition range. The alloys, made up from sublimed magnesium and 99.5 wt pct pure barium, were melted in an Armco-iron crucible in a dynamic argon atmosphere. Thermal analyses were taken using a Speedomax auto- matic recorder. Careful stirring during the solidification process was required in order to avoid segregation. After thermal analysis some of the cast alloys were chemically analyzed. The intended and analyzed compositions of the ten alloys prepared are listed in Table I. Since standard barium determinations cannot differentiate between barium present as element and as oxide, both the barium and magnesium contents of the alloys were analyzed. The fact that the sum of barium and magnesium was close to 100 pct in each case was taken as evidence that no excessive oxidation had occurred. The liquidus temperatures measured are listed in Table I and plotted in Fig. 1. As can be seen, they are in good agreement with the liquidus found by Klemm and Dinckelacker. This leaves no doubt that the thermal results of Grube and Dietrich above 10 atomic pct Ba are incorrect. This work was performed under the sponsorship of the Pitman-Dunn Laboratories of Frankford Arsenal, Philadelphia, Contract No. DA-11-022-ORD-1975. Sponsorship and permission to publish by this organization are gratefully acknowledged.

Jan 1, 1958

By R. W. Smith, G. W. Delamore, J. A. Spittle

RECENT work by the authors1 has demonstrated that the crystals constituting the equiaxed zone in small ingots originate, on quenching, in the chilled liquid. Whether any partial remelting2 takes place of the den-drites nucleated in the chilled region was not examined. However, the claim3 that this normally occurs, leading to crystal multiplication, has been disputed.4 Thus, for an equiaxed zone to form in the central region of an otherwise columnar ingot, it is necessary to transport crystallites from the chill zone to this region. In view of the work of Uhlmann et al.,5 it was considered desirable to examine the transport process further. Experimental Technique and Results. In the earlier experiments by the authors.1 a stainless-steel crucible 17/8 in. diam, 41/2 in. high, ad containing an alloy of A1-4 wt pct Cu, was quenched from 660°C into a bath of Wood&apos;s metal maintained at 100°C. Under these conditions a central zone of equiaxed crystals was obtained. However, if a 2250-G unidirectional magnetic field was applied for 2 sec immediately following the instant of quenching, or subsequently, the equiaxed zone did not appear. Careful thermal analysis showed that the short application of the field had virtually no effect on the thermal conditions of the melt. It thus appeared that the crystallites which were ultimately to grow large enough to form the equiaxed zone existed in the liquid immediately ahead of the interface, occlusion being prevented by the convective fluid flow induced by freezing from the walls of the cylinder. When this relative movement was prevented by the Lorenz forces induced by the application of the magnetic field, the crystallites were caught up in the rapidly advancing dendrite solid-liquid interface. To test this assumption, a small ingot of super-purity aluminum was partially melted and poured into a heated stainless-steel mold which was then immediately quenched into molten Wood&apos;s alloy. The resulting structure is shown in Fig. 1, and consists of columnar grains with a central fine-grained zone. Thus the unmelted solid present at the beginning of solidification had been transported ahead of the columnar interface. Discussion. There appears to be little or no information available on the interaction of suspended particles with a metallic solid/liquid interface. However, some information is available for transparent organic sys-

Jan 1, 1969

By J. H. Hamilton, J. R. Lewis, J. C. Nixon, C. L. Graverson

Recently there has been much speculation concerning the advantages of using oxygen enriched air or pure oxygen in pyrometallurgical processes. The advantage of using oxygen in the iron blast furnace and elsewhere in ferrous production metallurgy has been given careful consideration and, as a result, several experiments have been tried and a number of papers have recently appeared on this subject.1,2 The use of oxygen in nonferrous smelting likewise poses interesting problems, therefore any experimental data obtained in this area should likewise be of general interest.3 Ashcroft4 in 1933 claimed to have obtained improved results when copper concentrates were roasted in pure oxygen. However, his paper gives neither data nor experimental details. A few years ago a research program was started in this laboratory which had for its objective the determination of the mechanism of oxidation of metallic sulphides under varying conditions. To date we have studied the oxidation of galena,5 sphalerite, and chalcocite. It is a well known fact that copper sul-phde minerals are oxidized slowly by weathering agents, so that the sulphides of copper which find their way into a tailing pond are gradually changed into water-soluble and acid-soluble compounds. Commercially, the oxidation of copper sulphide minerals is accomplished by roasting them at elevated temperatures in air using a suitable (usually multiple hearth) roaster. Most copper smelters are equipped with such roasters. In this phase of the study we were especially interested in determining the effect of temperature on: (I) the air oxidation of chalcocite and (2) the oxidation of chalcocite using commercial oxygen. The amount of sulphur removed as sulphur dioxide, the percentages of water-soluble copper, and of acid-soluble copper were determined for the air oxidation tests. In the tests using commercial oxygen, the percentages of sulphur dioxide, water-soluble copper, acid-soluble copper, water-soluble sulphur and acid-soluble sulphur were determined. For these experiments the temperature was varied from 250 to 700°C. Experimental Preparalion of Chalcocite (Cu2S) Natural chalcocite is not pure, Minerals such as bornite, covellite, and chalcopy-rite may be present. It was decided, therefore, to prepare some chalcocite in our own laboratory. An intimate mixture of sulphur and hool divided metallic copper in the ratio of 4 g of copper to I g of sulphur was prepared. TO this was added a slight excess of

Jan 1, 1949

By B. B. Rath, Hsun Hu

Rates of migration of large-angle boundaries have been studied in zone-refined aluminum crystals, defonned 80 pct by rolling in the (110)[112] orientation at -78°C followed by a recovery anneal at 80°C. Artificially nucleated grains show a marked variation. by an order of magnitude, in their growth rates in different directions. The average activation energy for the migration of all boundaries was found to be about 16,000 cal per mole. The anisotropy of the boundary migration is rationalized on the basis of the boundary structure. It has been observed by Beck and HU,1 Kohara el al,2,3 and Czjzek and Haessner4 that recrystallized grains formed upon annealing Of deformed sing1e crystals of aluminum show anisotropic growth characteristics. Kohara et al. found that single crystals rolled in the (110)[112] orientation, when random nuclei were provided on one side of the crystal by rubbing with emery paper and annealing, developed a sharp recrys-tallization texture on the other side of the crystal upon further annealing. This sharp recrystallization texture consisted of four components, which were related to the deformation texture of the crystal, i.e. (110)[112], by rotations of ±40 deg around each of the two common [ 111] axes&apos; They also noted that recrystallized grains were elongated in directions perpendicular to either of these two common [1111 axes. They attributed this anisotropic growth to the difference in the rate of self-diffusion or diffusion of impurity atoms along the tilt and the twist boundaries. A somewhat similar investigation was conducted by Czjzek and Haessner4 On strained single-crystal sheets Of alum- inum. These authors claimed that the matrix structure of the deformed crystal had a greater effect on the growth anisotropy of the recrystallized grains than did the boundary orientation itself. In the present investigation quantitative measurements of the rate of grain boundary migration in anisotropic growth have been made in zone-refined aluminum (99.9999+pct pure) crystals deformed 80 pct by rolling in the (110) 112] orientation. Crystals of this particular orientation were chosen because of the following desirable features: 1) the crystal does not change its orientation during rolling; 2) the rolling plane contains all the significant crystallographic directions; and 3) when annealed, following deformation, the crystal does not re-crystallize spontaneously but polygonizes to a stable and homogeneous structure. Hence, the initial orientation of the crystal and a constant strain energy in the matrix can be maintained during subsequent grain boundary migration studies. It is essential to keep the driving force constant for the study of boundary mobility.5 EXPERIMENTAL PROCEDURE A cylindrical single crystal of 1 in. diam was grown by the Bridgman method in a high-purity graphite mold. The resistance ratio, R(4.2°K) /R(298°K) , of the grown crystal was approximately 2.0 x 10-4. A number of slices, 1/4 in. thick, were cut from the crystal along the (110) plane and were mechanically and electrolyti-cally polished to remove the strained surface layer. The crystals were then rolled along the [112] direction to 80 pct reduction in thickness at -78°C. To minimize surface friction, the crystals were rolled between two layers of 0.005-in. teflon sheet. Rolling was interrupted, prior to completion, to remove the surface layers and the edges by electropolishing. These and similar precautions in handling the rolled crystals

Jan 1, 1967

By Robert L. Dean, Michael Hoch, Samuel M. Wolosin, Chung K. Hwu

The general shape of the 1450°C isotherm of the Ti-TiO-ZrO2-Zr region was evaluated from the surrounding binary phase diagrams and from thermo-dynamic data on the metal-oxygen binaries. The phase boundaries were accurately determined using X-ray and metallographic techniques. At 1450°C the system shows a large bcc ß field, which extends from the two metal-oxygen binary systems as a Gaussian error function, and is stable up to 30 at. pct 0 when Ti and Zr are present in equal amounts. At higher O Concentrations, the ß field is in equilibrium with t-ZrO . The following four regions, with three solid phases, are present: two a ß t-ZrO,, a TW t-ZrO,, and TiO t-ZrO2 c-ZrO2. On cooling the ß phase transforms into the a phase, going through the w transition phase. The isotherm at 1500°C for the region TiO-TiO,-ZrO, was obtained by using X-ray diffraction. At 1500°C a large c-ZrOz region is present as well as a large two-phase field, Ti0 c-ZrO,. The following regions, with three solid phases in equilibrium, were found These regions are relatively small. The solidus and liquidus relationships were determined by observing samples suspended in a tungsten crucible by means of a fine tungsten wire and heated in vacuum. Eleven univariant points were found. C-ZrO, decomposes through a peritectic reaction into liquid t-ZrO2. The activities of Ti and TiO in the TiO t-ZrOz and in the two a ß t-ZrO regions were measured using the Knudsen effusion method. In the a TiO t-ZrO, region the activities of Ti and Ti are the same, as in the a — Ti TiO binary. In the two a t-ZrO, regions, the Ti activity is high and the Ti0 activity very low, although all phases present contain at least 30 at. pct 0. This indicates a short-range order in the solid phases, Zr atoms being preferentially surrounded by 0. 1 HE system Ti-Zr-0 is of interest because of the wide ranges of solid solubility exhibited by the boundary systems; as titanium and zirconium both belong to the same group of the periodic table, large single-phase regions should occur within the system, with a great variation of properties (as the composition changes within the single-phase region). Furthermore, the possibility of modifying ZrO, to make it a more usable refractory by the addition of other metals makes this system also of interest. Because of the high affinity of titanium and zirconium for oxygen, the oxygen partial pressure is very low at all compositions; thus, there exists a ternary metal-metal-oxygen system in which the oxygen pressure is not an important variable, so long as it is low enough. When a sample is heated in vacuum to a temperature high enough for vaporization to occur, the vapor phase will consist of metal and metal-oxide gas, the oxygen concentration being very low. The phase relationships in the surrounding binary systems have already been reported in the literature; therefore, the study of the ternary diagram

Jan 1, 1962

By A. E. Powers

YEARS of experience and research have shown that molybdenum, tungsten, and vanadium are among the most useful and effective elements in augmenting the high-temperature strength of heat-treatable, ferritic steels. Grün, for example, in conducting an early survey of the strengthening effects of various elements in annealed, low-carbon steel at 750° and 930°F (400° and 500°C), found molybdenum and vanadium to be the most effective.&apos; Holtmann comprehensively studied the strengthening effects of molybdenum and vanadium in quenched and tempered steels at 930°F as a function of microstructure and carbon content.&apos; He found creep strength to be related to the saturation of the austenite at the austenitizing temperature, such that strength is increased by alloying until the y loop is reached—the terminus of complete austenitization. Beyond this degree of alloying, the inability to heat treat will result in lower strength, at least for low and moderate creep temperatures. Tungsten, owing to higher cost than molybdenum, has been little used in ferritic high-temperature steels. As a result, very few investigations have been made of its high-temperature strengthening ability, and reliable data on its effectiveness are not available. Grün rated tungsten far less effective than molybdenum at 930°F (500°C) on a weight-percentage basis.&apos; However, Tammann has found that tungsten is as effective as molybdenum in raising the recrystallization temperature of iron. For this reason Smith, in a review of the subject, has advocated a re-examination of the influence of tungsten on the high-temperature strength of steel.&apos; In any study of the effects of alloying additions on high-temperature properties, recognition must be made of the many variables involved, some of which can be controlled but have been ignored in innumerable investigations of the past, and some of which are difficult or even impossible to control. One cannot, for example, assign a definite strengthening index to any one alloying element, for this will be dependent upon the microstructure (heat treatment and mechanical treatment), testing con- ditions (temperature, time, and stress), and the complete composition of the steel (accompanying alloying elements, impurities, etc.). One ever-appear ing variable, hardness or tensile strength at room temperature, may be eliminated by heat treating all of the alloys to a single hardness level. An attempt may be made to control the variable of primary quenched structure by oil or water quenching the test specimen. The control of such variables may not be possible in cases of widely varying compositions, but at least such deviations should be recognized. Material and Procedure The alloys, made as 30-lb ingots in an induction furnace, all had the same base composition of about 0.18 pct C, 0.85 pct Mn, and 0.48 pct Si. They were grouped as follows: Mo Group—Containing up to 5.2 pct Mo. W Group-Containing up to 6.0 pct W. V Group—Containing up to 3.3 pct V. Mo-V Group—Containing up to 2.7 pct Mo and up to 1.4 pct V. Mo-W Group—Containing up to 2.5 pct Mo and up to 2.5 pct W. The steels, listed in Table I, were forged to ¾ in. sq bars and the material for the high-temperature, rupture-test specimens was further swaged to %-in. round bars.

Jan 1, 1957

By H. M. Davis, T. S. Jones

A methodfor accelerating the reduction of a metal oxide by carbon monoxide is to incorporate in the reduction system a nonreducible oxide which has a strong affinity for carbon dioxide and will remove it from the product gases. The effectiveness of this method was investigated by veduction experiments on specially prepared powder mixtures of SrO-ZnO ("active&apos;.) and SrCO3-ZnO (reference). Measurements at 750o and 677°C showed that the rate of reduction of ZnO by CO was as much as an order of magnitude greater in the presence of SrO. Under the experimental conditions at least as much CO2 as generated by veduction was absorbed when SrO was present. Enlzancernent of the veduction rate by SvO resulted from modification of&apos; gaseous djfitsion processes. THE specific question posed in this investigation was whether the reduction reaction CO + ZnO - Zn(g) + COa [1] could be accelerated by incorporating strontium oxide into the oxide charge undergoing reduction. Provided the strontium oxide was active enough, it could remove carbon dioxide from the product gases of ( 11 and form strontium carbonate, thus modifying Reaction [ 1] to CO + ZnO + SrO = Zn(g) + SrCO3 [ 2] This study of the comparative rates of Reactions [ I] and [2] can be considered as a particular case of a general scheme for increasing the rates of reduction of metal oxides by carbon monoxide. The limits of applicability of this scheme are indicated in the simple thermodynamic analysis presented in the appendix. This analysis primarily dictated the choice of the system, CO-ZnO-SrO, employed in this investigation. In addition, it was thought that a study of this scheme by use of the CO-ZnO-SrO reaction system would be of special interest in view of indications in the literature1-3 that the gaseous reduction of zinc oxide is prone to rate control by diffusion in the gas phase. The distinction should be pointed out between this and other efforts to increase the rates of reduction reactions through the use of addition agents. Additions of a wide range of chemicals have been tried with de- grees of apparent success varying from slightly negative to highly positive. The reasons for making additions have included the use of salts to produce effects akin to catalysis,4, 5 the alteration of the microstruc-tural details of the reduction process (including solid-state diffusion),6-8 and the conversion of an en-dothermic reaction into one that is exothermic or autogenous.9-12 The means used to attempt alteration of the enthalpy change has commonly been to incorporate lime into the charge, so that heat is generated by reaction with either of the reaction products, carbon dioxide or water. The use of lime in this way makes endeavors such as that of Edstrom and Wiberg similar to the present one. Furthermore, the basic principle behind the present work has previously been set forth.13 However, a detailed investigation of the type of reaction described in this work does not appear to have been conducted. EXPERIMENTAL PROCEDURE From both conceptual and physical standpoints, Reaction [2] is to be considered as the sum of two reactions:

Jan 1, 1968

By J. B. Dorsey, T. W. Brinkley

Performance of a high-pressure, vaporizing gas-drive project in a volatile oil reservoir is discussed. The project has been in operation for over 8 years. Present recovery from the over-all displaced portion of the reservoir is 40 percent, and an ultimate recovery of 60 percent is indicated. Calculations reflect an over-all displacement volume of 50 percent for the entire reservoir; therefore, ultimate oil recovery will be 30 percent of the entire reservoir oil originally in place. Laboratory vaporization tests conducted prior to project initiation also are presented and discussed, along with an analytical method of determining stock-tank oil production and gar injection requirements related to over-all volumetric displacement efficiency from these data. Introduction The Shoats Creek field is located in Beauregard Parish, La., in the extreme western part of the state (Fig. 1). Discovered in 1956, the field is productive in three Cockfield sand zones, ranging in depth from 8,000 to 9.000 ft. The upper two zones, 1st and 2nd Cockfield, are condensate-bearing gas reservoirs. The lowest zone, the 5th Cockfield, is a volatile-oil reservoir. Laboratory work conducted on crude oil from the 5th Cockfield zone shortly after field discovery demonstrated that, when contacted with dry gas, signidcant volumes of the oil could be vaporized at reservoir temperature and at an appropriately high reservoir pressure. Further study led to the conclusion that early initiation of a crude vaporization project in the 5th Cockfield zone would be superior economically to other methods of reservoir depletion. Consequently, the zone was unitized and gas injection operations started late in 1958. This paper discusses laboratory work performed in conjunction with the project, and project performance to the present. History of Development The 5th Cockfield zone in Shoats Creek is composed of a thin, very shaly, low-permeability sandstone. Oil accumulation is controlled by a structural trap bounded by faults along the north and west and by a water contact on the southern boundary (Fig. 2). The zone covers a productive area of 1,550 acres at an average depth of 9,000 ft. The net sand section is thin, having a maximum thickness of 10 ft and an average thickness of 5.5 ft (Fig. 3). Average reservoir rock properties, as determined from core analysis are presented in Table 1. Shaliness of the zone is illustrated by the typical electric log of the 5th Cockfield section in Fig. 4. Because of the thinness and poor quality of the sand, the 5th Cockfield was developed on a wide spacing. Eleven completions were made in the zone between 1956 and 1961 for an average density of 140 productive acres per completion, with the majority of wells being dually completed in the 2nd and 5th Cockfield. Average initial potential for producers in the 5th Cockfield was 130 BOPD. Oil from the 5th Cockfield has a stock-tank gravity of 50.5" API; with a bubble-point pressure of 3,515 psia, the oil was highly undersaturated at the original reservoir pressure of 4,675 psia. Pertinent properties of the oil as determined in the laboratory are presented in Table 2. Because of the volatile nature of the crude, laboratory studies of its susceptibility to vaporization, as well as a vapor-liquid phase study, were conducted in addition to a standard PVT analysis. The vaporization study was conducted in a visual cell; a stepwise illustration of this work and laboratory measurements are presented in Fig. 5. Field

Jan 1, 1969

By S. H. Moll, R. E. Ogilvie

The investigation of solid-state diffusion phenomena may lead to much information concerning binary alloys. In particular, a study of the concentration gradients present in multiphase diffusion couples can lead to the determination of the solubility limits of the single-phase fields in the phase diagram. The specific concentration gradient which results from the heat treatment of a diffusion couple depends not only upon the time and temperature of diffusion, but also upon the number of phases existing in equilibrium at the diffusion temperature. Such concentration gradients possess sharp discontinuities whose terminal points correspond to the solubilities existing at the limits of the two-phase field in the phase diagram at the diffusion temperature. In general, there will be a discontinuity in the concentration curve for each two-phase field which exists in the phase diagram between the concentration limits of the couple. A number of investigators have analyzed the gradients present in multiphase diffusion couples. 1-8 The iron-titanium phase diagram exhibits a y loop in the temperature range from 900" to 1400°C, and the limit of the a + y field lies at some composition which is less than 1 wt pct Ti for any temperature. It was felt that a diffusion study could yield values not only for the diffusion coefficients involved, but also for the chemical solubilities in the phase diagram. The concentration gradients were analyzed by an X-ray absorption technique developed by Ogilvie.6 The absorption of a monochromatic X-ray beam is measured in steps parallel to the diffusion direction and the resulting intensity gradients are transformed into concentration gradients by applying the laws of X-ray absorption in a binary system. This technique has been applied by ogilvie6 to the systems Ni-Au, Cu-Au, Fe-Cr, and Ni-Cr; by Gelles7 to the systems Be-Fe, and Be-Ni and by Hilliarde to the system Al-Zn. Linear X-Ray Absorption Analysis—The use of X-ray absorption analysis as a tool for determining concentration gradients arises from the fact that the beam is absorbed according to the quantity and species of elements present in the sample and not according to their state of aggregation. This method is more advantageous than the chemical analysis of machined layers since it is less time consuming and less expensive and can analyze a very small area. IF a homogeneous binary alloy (A + B) is analyzed with two different monochromatic X-ray beams I0(2) and lo(2) the following relation between the transmitted intensities, the intrinsic absorption coefficients of A and B for the two different radiations and the weight fraction of each element may be derived.&apos; In (I/Io) (a+b) xa(u/p)a(2) + xb(u/p)8(2) Eq. [1] is independent of specimen thickness and density, but requires that either element A or B possess an absorption edge between the wavelength limits of the two monochromatic beams. I, is evaluated for each radiation by measuring the transmitted intensity through a varying number of foils of a suitable absorber. A plot of the natural logarithm of the transmitted intensity as a function of the number of foils, when extrapolated to zero foils, yields the value of I,. If a plot of the ratio in Eq. [ I] is calculated as a function of xA, then a master curve results. From

Jan 1, 1960

By B. K. Larkin, H. R. Bailey

One of the most complicated and potentially one of the most promising secondary recovery methods is that of underground combustion. A number of field tests1,2,3 have been performed recently, apparently indicating that the underground combustion process is technically feasible. Relatively little has been published concerning laboratory or theoretical investigations of the underground combustion process. A few results of laboratory tube runs have been published4,5 and these data are valuable in understanding the process. The tube run data also emphasize the complexity of the thermal recovery process. Under various conditions, problems in heat transfer, multiphase fluid flow and combustion rates arise. For example, at low temperatures the combustion process proceeds so slowly that the front cannot be propagated. It is a problem in heat transfer to predict what injection rate of air is necessary to sustain combustion in a particular reservoir. Certain fluid flow aspects of underground combustion have been studied by Wilson, et a13. In the development of some of the flow equations, assumptions of adiabatic combustion were made. Vogel and Krueger1 have devised an analog model of the heat conduction process for a constant temperature cylindrical source moving radially outward in a homogeneous conducting medium. Jenkins and Ramey7, in a discussion of the Vogel and Krueger paper, present an analytical solution of a heat conduction problem related to problems considered by Vogel and Krueger. In the present paper an idealized model of the heat conduction problem is considered, which is more general than the model of Vogel and Krueger or Jenkins and Ramey. In particular, initial well heating, vertical heat losses and arbitrary frontal velocities are included. Equations for the temperature are obtained in terms of integrals. These integrals have been evaluated numerically for the case of frontal movement corresponding to a constant air injection rate and the case of constant frontal velocity. These results are presented graphically. From these graphs one may estimate conditions under which nearly adiabatic temperatures are obtained. The application of these results requires some knowledge of reservoir thermal properties, combustion rates and residual fuel content. Assuming no vertical losses it is possible to obtain explicit evaluations of these integrals in the linear con- stant velocity case and in the radial case corresponding to a constant air injection rate. PRESENTATION OF RESULTS The geometry of the radial system is illustrated in Fig. 1 where the reservoir is represented as a slab of thickness h. By making an energy balance for an infinitesimal volume, one obtains the following equation. T= x T+F(z.r).........(1) where F (z,r) =HWv1/pc (r-r1), if z h/2 = 0, if z >h/2 . In Eq. 1, V- represents the Laplacian operator and 8 is the Dirac delta function. Eq. 1 is the well-known diff-sion equation with a source term and may be applied to a linear system. For example, if the source is moving in the direction of the x axis, then the argument of the delta function is x - 1,. In deriving Eq. 1 the following approximations were made concerning the actual combustion process: (1) all heat transfer is by conduction in a homogeneous medium, (2) the formations bounding the reservoir have the same thermal properties as the reservoir, (3) the combustion fuel is consumed instantaneously as the front arrives, (4) there is a constant fuel concentration

By W. A. Backofen, D. Lee

Titanium of commercial purity (RC-70) and two all-a (hcp) alloys (4Al-1/4O2 and 5Al-2.5Sn) were tested in sheet form under conditions of combined-stress loading. Plane-strain compression and plane -strain tension together with uniaxial compression and tension provided information for constructing the tension-tension and compression-compression quadvants of the plane-stress yield locus. Coordinate values were obtained from yield-strength measurements; the slope at each point was based on a plastic-strain ratio. The materials represented a wide range of plastic anisotropy, which was reflected in correspondingly varied departures of the yield locus from that for iso-tropy. The tension-tension and compression-compression quadrants were not identical. If the uniaxial yield strength is insensitive to direction and the sign of the applied stress, the Mises or perhaps the Tresca criterion is adequate for predicting the onset of yielding under combined-stress loading. The prediction is not so straightforward in plastically anisotropic material. Depending upon details of texture, combined-stress yielding resistance may be substantially different from that indicated by the usual criteria.&apos; However. a continuum theory of yielding under such conditions is available for reasonably direct application.2,3 Whether or not it can be used successfully must, of course, depend upon how closely the conditions of the theory are satisfied in the material in question. In its present form the theory contains no provision for Bauschinger-type effects, nor does it allow for the consequences that might grow out of deformation by more than one mechanism, e.g., by slip and twinning.4 With those limitations, more importance must be attached to experimental information about the yield surface for anisotropic materials. Studies of the yield surface have generally been confined to states of plane stress (tension-tension and tension-compression) established in thin-wall tubes by externally applied forces and internal pressure. That approach would be entirely suitable for anisotropic materials if they were available in tube form or in sufficient bulk to be machined into test specimens. 6-9 It would not serve for the textured and anisotropic sheets of much current engineering interest, unless sheet could be formed into high-pressure tubing without structural change. Since there would seem to be little chance of the latter, practical alternatives are needed. One such alternative is the subject of this paper. It involves the use of a few selected but relatively simple uniaxial loading tests on sheet specimens. The underlying idea is presented here with some details relating to application and a few results bearing on how well it has worked. THE BASIS OF TESTING Conventional Measurements. Yielding for a general case of anisotropy is described by the plane-stress locus in Fig. 1. Reference directions in the sheet specimen are related to the stress coordinates as shown with the insert: x is the rolling direction, y the transverse direction, and z the through-thickness direction. The four reference-direction yield strengths (t, tension; c, compression), Xt, Xc, Yt, and Yc, are all different. Nine paths that can be followed in uniaxial loading experiments are identified. Paths 1, 2, 3, and 4 represent conventional tension and compression testing to establish Xt, Yt,.Xc, and Yc. Useful information also comes from the ratio of the transverse plastic-strain components associated with yielding and flow in conventional tension or compression. A condition to be satisfied in locus construction is that the plastic-strain vector be everywhere normal to the locus.10 The projection of the vector which would

Jan 1, 1967

By R. B. Falk, F. E. Luborsky

Small iron particles in mercury pow by diffusion of iron atoms through the mercury. Iron particles, with diameters about 200Å, have been stopped from gvowing in size, even up to the boiling point of mercury, by the addition of a third metal. The metal additives were classified according to whether they produced 1) negligible inhibition, 2) some inhibition, or 3) marked inhibition of the growth rate. Metal additives which resulted in a marked inhibition of iron-particle growth form a stable monolayer on the iron particles. Only those metals which may form compounds with iron showed this pronounced effect. The one exception was manganese. Metal additives which resulted in no inhibition of growth, showed no evidence for adsorption and could not form compounds with iron. None of the added metals, even those which strongly inhibited particle gvowth and thus had adsorbed on the particle surface, actually formed any compounds with iron at room temperature at the concentrations required for complete inhibition of growth. ThE stabilization of the size and shape of metallic particles dispersed in liquid metals has important technological implications in "homogeneous" nuclear reactor systems and in elongated particle magnets and is directly related to the problem of corrosion by liquid metals. Growth in these par-ticulate systems may occur by diffusion of atoms from surfaces of high energy, corresponding to a small radius of curvature, to surfaces of low energy or large radius of curvature. Thus, small particles dissolve and large particles grow to increase the average diameter of the particles. reenwood&apos; has analyzed this diffusional growth of a system of particles containing a distribution of sizes and has obtained reasonable agreement with data on the growth of uranium particles in liquid sodium and UPb3 particles in liquid lead. Greenwood concluded from his analysis that the chief factors promoting stability of dispersed particles growing by a diffusion mechanism are large mean radius, high density, and low molecular weight with low values of the solute diffusion coefficient, the solubility, and the interfacial tension. In the case of elongated particle magnets the system of interest is that of iron particles dis- persed in mercury. Previous work,2 concerned with "spherical" particles in mercury, has indicated a diffusional growth mechanism similar to that discussed by Greenwood. It has also been shown3&apos;4 that the addition of certain metals to Fe-Hg dispersions results in the formation of a monatomic layer of adsorbed atoms on the iron particles. In this paper we will show that this adsorbed layer provides the decrease in the iron-atom flux through the mercury necessary for size stabilization. The general features of the stabilization of the iron particles in mercury through the formation of this "coating", with many different metals, will be described. EXPERIMENTAL RESULTS Iron particles in mercury were prepared by elec-trodeposition,2, 4 and measurements2, 4 of coercive force HCi) and saturation induction (Is) were used to follow changes in size and composition during thermal aging in the mercury in the presence of relatively small amounts of an added metal. In Fig. 1 is plotted the aging behavior of spherical particle samples in the presence of some of the added metals to be discussed. The iron particles have an initial average diameter of 180Å. Each sample was aged for 20 min at each temperature in succession in the presence of a twofold to threefold excess of added metal over that required to form a monolayer on the iron particles. These are the same samples used previously3 to study the adsorp-

Jan 1, 1965

By Harry M. Mikami

Chromite is the only ore mineral of metallic chromium and chromium compounds and chemicals. Because of this fact, chromite and chrome ore are used synonymously in trade literature. In commercial market quotations, chrome ore is the term commonly used. Chromite per se, because of properties imparted by its chromium content, is used in refractories and in special purpose molding sands for metal casting. There are many other minerals containing some, generally minor, amounts of chromium, but none are commercial sources of the element (Thayer, 1956). Chromium and chromite have many diverse uses that, directly and indirectly, critically affect vast segments of our modern industrial system. Most important are probably the metallurgical applications wherein chromium is a component of heat-, abrasion-, corrosion-and oxidation-resistant and high-strength alloys of many types. Stainless steels are the largest volume category of chrome-bearing alloys. Chromium chemicals are used in leather tanning, in pigments, dyes and mordants, printing, chemical process industries, photography, pharmaceuticals, metal plating, pure chromium metal production, and for many other purposes. Chromite is a necessary constituent in basic refractories indispensable for the production of steel, copper, cement, and glass. Under present conditions, the US and North America, with the possible exception of Cuba, have no commercial ore reserves. There are chromite deposits, as will be described, but they would be used only under highly abnormal conditions if all outside sources were cut off for an extended period. All chromite used in the US is imported from the eastern hemisphere in which are contained the principal world reserves. The main suppliers in 1980 were the Republic of South Africa (43%), the USSR (21% ), the Philippines (12%), Albania (11 %), Turkey (8%), and others (5%). The strategic nature of chromite is obvious. End Uses-Grades and Specifications As noted before, the three principal uses for chromite are metallurgical, refractories, and chemical with a fourth minor use as foundry molding sand. For metallurgical applications chrome ore is first reduced in electric carbon arc furnaces to various types of ferrochromium alloys. There are high, medium, and low carbon ferrochromiums with carbon ranging from 0.01 up to 10%. Chromium itself ranges from 50 to 73 %. Ferrosilicon chromium and ferrochromium-silicon grades have chromium from 33 to 67% and silicon from 3 to about 48%. Since iron is reduced with chromium, the Cr:Fe ratio of the ore will determine the ultimate grade of the ferrochromium whereas carbon and silicon can be controlled during processing. MgO, A12O3, CaO, and excess SiO2, are removed in slag. A small amount of pure chromium metal is prepared by alumino-thermic and electrolytic processes from essentially iron-free chrome components that have been made via the chemical route. The higher grades of ferrochromium with chromium in the 66 to 73% range can only be made from ores with not only high chromium content, but low iron, i.e., high Cr:Fe ratio. These ores, conventionally termed metallurgical grade, have Cr2O3 contents of 45 to 56% with Cr: Fe ratios of 2.5 to 4.3. A standard composition is generally 48% Cr2O3 and 3:1 Cr:Fe ratio. Very high grade ores are often blended with lower grades even with the high iron chemical grade. For some ferrochromiums, additions of high alumina refractory grade are used as slag conditioners to facilitate smelting while still contributing chromium values. A lower grade ferrochromium, the high carbon charge chrome, has become the predominant grade in use today for making chromium-bearing steel alloys. This

Jan 1, 1983

By R. S. Wagner, R. G. Treuting, W. C. Ellis

Use of the Weisseizbevg goniometer for the study of the morphology of whisker crystals and transfer of the results to a stereograplzic projection are described. While in almost all instances a complete and rapid solution is obtained with a purely gaphical treatment, an absolute analytical treatment applicable to difficult cases is given. Examples are given for determination of growth direction and external features of a crystal, for detection of &apos;twintzittg, and for establislting the orientation relntionships in a kinked whisker crystal. We give here a method for the use of the Weissen-berg goniometerl" in the study of orientation relationships in "whisker" (micro) crystals3-8 and direct transference of the data to the stereographic projection. The operations are straightforward and require no involved calculations: in almost all cases solely graphical treatment is adequate. In a few complex instances, a more exact analytic method may be required. In the method, not only are equatorial reflections of an oscillation photograph used, but also those on higher layer lines, or those not occurring on a recognized layer line. Such reflections off the zero level are often essentialy to detect the presence of twinning. The method is particularly suitable for examination of whisker crystals since the axial or growth direction is almost always one of high symmetry, permitting a more restricted oscillation range to obtain the necessary reflections and an accordingly shorter exposure time. The method is also applicable when there is no lattice-related external symmetry, and is as well able to identify external crystal surfaces, when such exist, with the aid of an optical beam. Thus growth direction, identification of lateral faces, twinning, and orientation relationships in a kinked crystal can be established. A test for the Eshelby twist6-8 can readily be made. The method can be used for orientation, for structure analysis, and as an aid in the identification of an unknown crystal. Moving-film techniques have previously been employed variously for crystal-orientation studies.1,2,9-13 In particular, use of the Weissenberg method for orientation determination has been reported by Wooster and wooster.14 While their method derives the same data as here described, it differs in depending on the tracing of constant p streaks, a less than dependable phenomenon with small specimens, a few microns or less in cross section. The Laue method can and has been used for orientation studies of microcrystals,15 e.g., 2 p in cross section, but requires the extreme intensity and concentration from a microfocus tube to obtain reasonable exposure time. PRINCIPLES OF THE PRESENT METHOD Consider a crystal of random orientation with respect to the oscillation axis in a Weissenberg goniometer. Its diffraction pattern need not necessarily result in recognizable layer lines. In Fig. 1, a stereo-graphic projection of the reference sphere is given with the equatorial plane XZ normal to the oscillation axis Y, and the X-ray beam directed from X towards 2. The great circle ZZ is then normal to the beam, and the axes are right-handed. Thus the reflected X-ray beam lies at the intersection R of small circle ARB of radius 28 from 2, and of small circle RE of radius a from the rotation axis Y. a is the conventional semiapex angle of a cone of diffracted rays from the atoms aligned in the direction

Jan 1, 1967