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By B. M. Larsen, T. E. Brower

IN an earlier paper1 we discussed a simple, rapid method of taking samples of liquid steel and analyzing them for oxygen, which, though possibly not absolutely accurate (as is likewise true of all other methods), certainly yields results that are satisfactorily consistent. Accordingly, samples from hundreds of heats in different shops were analyzed for oxygen, with results sufficient in number to be handled statistically and permit estimation of some general trends. Measurements were made in acid as well as in basic open hearths, throughout the refining period, to learn how stirring, blocking, adding ore or lime or sand, affects the oxygen content of the bath; we also followed the changes brought about by tapping, teeming, and deoxidizing. Some of these results, discussed in an earlier paper.2 bring out the dominant role of the carbon-oxygen reaction in regulating degree of oxidation both of metal and of slag, also the marked variability of concentration of dissolved oxygen [0] in excess of that which would be in equilibrium with carbon and with carbon monoxide at a partial pressure of one atmosphere. As a logical beginning on this complex problem, we take up in the present paper the variability of this excess oxygen, ?[O], when other factors are as constant as they ever are in open-hearth operation; namely, toward the end of the refining period, when the bath may be regarded as in the comparatively steady state it approaches in absence of disturbing factors. This condition was chosen because by that time the significant reactions, except carbon oxidation, between slag and metal have come to substantial equilibrium; this facilitates interpretation of the complex situation and thus permits more definite conclusions to be drawn. This excess concentration of oxygen, ?[0], in the metal is needed, of course, to make the steelmaking process go at a reasonable rate; alternatively it may be regarded as a measure of the virtual pressure increment above one atmosphere, or of the degree of supersaturation, of carbon monoxide in the metal. According to our measurements, the excess concentration ?[O] in liquid steel varies from about 0.009 to 0.035 per cent oxygen by weight. It is quite sensitive to change of conditions, being altered temporarily by operations such as stirring with green poles, additions of ore, lime, or sand; but as the disturbance works itself out, it resumes a level within the intermediate range characteristic of the steady state. The conditions most common in average furnace practice are covered by the following : [ ] as in a reasonably steady state-that is, when it is boiling normally, is at proper temperature with a well-shaped slag, and has been free from disturbing effects during the preceding half hour-?[O] returns from

Jan 1, 1946

By H. O. Hofman

In the blast-furnace smelting of lead, copper and other non-ferrous metals, the largest part of the product obtained is slag. Its formation consumes more of the heat-energy of the fuel charged than any other chemical reaction that takes place. It is therefore of importance to know at what temperatures the different slags will form, so as to be able to choose in a given case the slag that will form at the right point in the operation, will keep the products thoroughly fluid, so as to insure a satisfactory separation, and will permit the consumption of fuel to be reduced to the lowest practicable point. While practical experience has brought out in a general way the leading differences as to the formation-temperatures of Rome silica—iron —lime slags, accurate details are still wanting. The object of the investigation here described was to supply some of these.* Prominent among the men who have worked on the fusibility of silicates are Lampadius, † Sefström,‡ Berthier,§

Jan 1, 1900

By L. S. Castleman, R. K. Hotzler

We are currently studying the effects on recrys-tallization of impurities diffused into dispersion-hardened alloys. Our interest in this phenomenon was originally aroused by the observation that the recrystallization temperature range of tungsten "doped" with alumina and silica, or with thoria, is lowered drastically if nickel is plated onto the tungsten prior to heat treatment.' In this note, we report a similar effect that sulfur has on the recrystallization behavior of thoriated nickel. The experimental procedure for this exploratory phase of the investigation has consisted simply in heating commercially obtained stress-relieved samples of thoriated nickel for varying temperatures and times in sealed capsules containing air and small quantities of sulfur. The samples contain 2.4 vol pct thoria and initially less than 18 ppm S by weight; they are prepared either from 0.5-in.-ciiam rod stock or from 0.092-in. sheet and are in the "as-received" (stress-relieved) condition prior to exposure. In an atmosphere free of sulfur, such samples do not show evidence of recrystallization after being annealed for 1 hr at a temperature of 2500°F (1372C).2 The photomicrograph in Fig. 1 shows the microstructure of one of our samples annealed for 75 hr at 1000° C (1832°F) in a sulfur-free capsule. The grain structure is hardly evident (if at all) at 465 times magnification. In contrast, the photomicrograph of Fig. 2 shows the recrystallization that has taken place in a sample exposed to sulfur for 5 hr at 1000°C (1832°F). A nickel sulfide phase is visible at the grain boundaries of the light-appearing grains. We have also observed recrystallization to occur in a sample annealed at 600°C (1112°F) for 25 hr. This temperature is below the 637°C (1178°F) eutectic in the Ni-S system. In the latter case, no nickel sulfide phase is evident in the microstructure. Moreover, we have noticed the occur-

Jan 1, 1969

Nominating Committee.-On the recommendation of the President, the Board of Directors, at their meeting on Apr. 25,1913, appointed the following Nominating, Committee to nominate officers and directors for next year: John Hays Hammond (Ex-President), Chairman. Robert H. Richards Chairman of Boston Local Section. Richard S. McCaffery, . . . . Chairman of Spokane Local Section. Chester F. Lee Chairman of Puget Sound Local Section. Frederick G. Cottrell, . . . . San Francisco, Cal. Charles W. Goodale Butte, Mont. James W. Maleolmson, . . . . Kansas City, Mo.

Jan 5, 1913

By W. C. Lilliendahl, H. W. Highriter

The method developed and used in this laboratory for the production of metallic uranium of such purity that it is ductile and can be cold-worked to fine wire or thin sheet by rolling has already been described1. It consists, briefly, in the electrolysis of potassium uranous fluoride (KUF5) in a molten bath composed of equal parts of sodium and calcium chlorides. The bath is contained in a graphite crucible, electrically heated to about 775° C., the crucible serving as the anode for electrolysis. The uranium deposits in finely divided form mixed with salts upon a molybdenum cathode suspended axially in the crucible. Upon completion of the electrolysis the cathode is removed and cooled, the deposit broken and leached to remove salts. The metal powder is washed with water and dilute acetic acid and dried in vacuo to reduce oxidation. Suitable amounts are then prcssed into pellets and heated in vacuo by high-frequency induction, using a thoria crucible. The uranium melts and flows away from the pellet, leaving a shell, which is largely oxide. In general, this method produced a satisfactory metal, although at times tile uranium was not ductile. The investigations recorded here were made to find the cause of this embrittlement. It was known that the metal generally contained carbon, derived from disintegration of the graphitc crucible in which electrolysis is conducted, in amounts dependent upon the thoroughness of washing the metal powder. Accordingly, analyses of several samples, both ductile and brittle, were made by combustion and absorption of CO² in Ascarite, using air instead of oxygen to reduce the temperaturc and rate of oxidation. Several of these metals were made with special precautions to reduce carbon content. The results show no relationship between ductility and carbon content in the range investigated (Table 1). Microscopic examination of ductile and brittle metals disclosed the presence in the latter of an intergranular constituent, harder than the matrix and less easily oxidizable, which was absent from the ductile material. Rough estimates of the volume of the hard constituent

Jan 1, 1935

By W. C. Lilliendahl, H. W. Highriter

The method developed and used in this laboratory for the production of metallic uranium of such purity that it is ductile and can be cold-worked to fine wire or thin sheet by rolling has already been described1. It consists, briefly, in the electrolysis of potassium uranous fluoride (KUF5) in a molten bath composed of equal parts of sodium and calcium chlorides. The bath is contained in a graphite crucible, electrically heated to about 775° C., the crucible serving as the anode for electrolysis. The uranium deposits in finely divided form mixed with salts upon a molybdenum cathode suspended axially in the crucible. Upon completion of the electrolysis the cathode is removed and cooled, the deposit broken and leached to remove salts. The metal powder is washed with water and dilute acetic acid and dried in vacuo to reduce oxidation. Suitable amounts are then prcssed into pellets and heated in vacuo by high-frequency induction, using a thoria crucible. The uranium melts and flows away from the pellet, leaving a shell, which is largely oxide. In general, this method produced a satisfactory metal, although at times tile uranium was not ductile. The investigations recorded here were made to find the cause of this embrittlement. It was known that the metal generally contained carbon, derived from disintegration of the graphitc crucible in which electrolysis is conducted, in amounts dependent upon the thoroughness of washing the metal powder. Accordingly, analyses of several samples, both ductile and brittle, were made by combustion and absorption of CO² in Ascarite, using air instead of oxygen to reduce the temperaturc and rate of oxidation. Several of these metals were made with special precautions to reduce carbon content. The results show no relationship between ductility and carbon content in the range investigated (Table 1). Microscopic examination of ductile and brittle metals disclosed the presence in the latter of an intergranular constituent, harder than the matrix and less easily oxidizable, which was absent from the ductile material. Rough estimates of the volume of the hard constituent

Jan 1, 1935

By Leon W. Dupuy

INTRODUCTION A BRIEF elemental discussion of the fundamental factors involved in diamond drilling often fills a need, particularly when a mine operator is contemplating for the first time an exploratory drilling campaign. Mr. James A. Barr, of the Mining Methods Committee of the Institute, has suggested that many engineers must undertake a drilling program of one kind or another and, in the case of diamond drilling, sometimes even are at a loss as to how to start correspondence. The Bureau of Mines has acquired much experience in managing exploratory diamond-drilling activities. Its activities in diamond drilling included exploring for potash in Texas, Utah and New Mexico 1-4 during the 1920's. The Strategic Minerals Exploration program was started in 1939 and was materially expanded during the war to include critical and essential minerals. At the peak of its war-time activity more than 200 engineers were employed, a majority of whom supervised diamond drilling. Many of them had little experience with such work prior to their employment with the Bureau, and it was necessary to instruct them in their duties. The purpose of this paper, therefore, is to present the fundamentals of exploratory diamond drilling from the viewpoint of management in such a way that they will serve as a basis on which those beginning exploratory diamond drilling may build an experience and acquire ability to direct exploration as they gain that experience. SELECTION OF METHOD OF DRILLING Selection of the method of drilling is governed by the type of material to be penetrated and by the type of sample needed to determine the quality and importance of a deposit. Types of drills that might be used for a given job include diamond drills, churn drills, hand auger drills, power auger drills, bucket drills, and rotary drills (sometimes called "seismograph rigs"). Each type has a specific field in which it is most useful. While the Bureau of Mines utilized all the types of drilling mentioned, diamond drilling was used on a majority of its exploratory projects. FACTORS GOVERNING SELECTION OF DIAMOND DRILLING The prime consideration in selecting a method of drilling is first to determine what results are desired and then to choose a method that will furnish reliable data in the ground to be penetrated. Use of diamond drills permits recovery of a core as well as sludge at a comparatively low cost. The core provides an excellent means of studying the formation being drilled and furnishes much information that would be difficult to obtain otherwise. Diamond drills will recover a satis-

Jan 1, 1947

By John W. Cahn, David A. Karlyn, Morris Cohen

The massive B(bcc) — am (fcc) transformation in Cu-Zn alloys has been studied isothermally by pulse-heating the retained ß phase from room temperature to the reaction temperatures. The transformation is found to occur only in the single-phase a region of the equilibrium diagram. The massive growth rate is of the order of 1 cm per sec and is constant at each temperature, usually after a delay time of some milliseconds. The delay time depends on the reaction temperature in C-curve fashion, while the growth rate increases monotonically with temperature over the single-phase range. The absence of isothermal massive transformation in the two-phase region does not arise from slow growth rates at such temperatures, but because the reaction cannot get started there. It is proposed that the massive transjormation initiates at small preexisting a particles which have rejected zinc into the surrounding 0 matrix. Only within the single-phase region can these particles consume the excess zinc during diffusion-controlled growth and thereby accelerate to the steady-state massive growth rate. The onset of massive growth marks the end of the delay time, and the growth rate then becomes interface-controlled. These isothermal transformation characteristics explain why the usual composition range for massive-kinetic studies by quenching is so limited. The same principles can be extended to more complex alloy systems by recognizing that the single-phase region in which the massive transformation can occur may not be stable with respect to phases not participating in the reaction. MASSWE transformations are now recognized as a regular class of solid-state reactions involving no compositional change (like martensitic transformations) and no shear displacements (unlike martensitic transformations). The name was first coined by Greninger1 in 1939 to describe the coarse grains of fcc a solid solution generated via a fast reaction from the parent bcc 0 solid solution in Cu-A1 alloys. However, some 9 years earlier, phillips2 had already described a similar transformation in the Cu-Zn system. The fact that the massive a formed as a single phase during drastic quenching from the 0 region of the equilibrium diagram signified that compositional changes were precluded. and the reaction was presumed to take place as in a one-component polymorphic transition by nucleation and growth. Phillips also observed that the occurrence of the massive transformation in the Cu-Zn system was extremely sensitive to alloy composition. For example. in a Cu-37.3 at. pct Zn alloy. the ß — am (am = massive transformation product) reaction was found to predominate and was not suppressed by iced-brine quenching from the 0 region. whereas at compositions greater than 38.3 at. pct Zn the massive reaction did not appear at all. Knowledge concerning massive transformations has bee11 substantially enhanced over the years by Massalski and his coworkers; an excellent summary of his papers and the current understanding of this type of reaction has been published recently by Barrett and ~assalski." he massive transformation product grows in roughly nodular form. often with irregular boundaries but sometimes with almost planar interfaces. The latter may have simple crys-tallographic indices relative to the 0 matrix. or the indices may be complex just as in the case of mar-tensites.'1 Little is known about the existence of orientation relationships between the massive and parent phases. A striking feature of massive transformations is that the massive units start almost exclusively at grain boundaries of the parent phase and frequently propagate on a broad front across matrix grains and grain boundaries of various orientations. Because of the rapid growth rate, it is thought that the interface motion is controlled. not by long-range diffusion. but by thermally activated atom jumps across the transformation boundary.

Jan 1, 1970

By AIME AIME

TWO weeks ago the writer was lunching in the Engineers` Club in New York with a man who has perhaps the widest acquaintance among engineers of anyone in the country a member of another of the Founder engineering societies. "By the way," lie asked. "who have they nominated for your next president."' "Doctor Becket," I told him- "Oh. that's line," he replied, in a heartfelt tone that rang with sincerity. "I have come in contact with him occasionally and he is just the right type.' And that is the way Dr. Frederick M. Becket impresses everybody. The right type. Most Institute members of the western group of hard-rock minors do not know him, but then they meet him in his swing around the circle next year they will not require a long acquaintance to sense his kindly and outstanding personality, to realize that he is a gentleman in the bet meaning o1 that word, a man of wide sympathies and interests.

Jan 1, 1932

By M. K. Foster

Ten horizontal retort zinc blocks of a modified Hegeler design are in operation at Nueva Rosita, Coahuila, Mexico, and produce approximately 170 t of spelter daily, or 62 000 t/year. A block consists of two furnaces of 448 retorts each, making 8960 retorts as the plant complement. Each furnace block is fired with natural gas and air maintaining the combustion mixture in the furnace always slightly reducing. No attempt to recover energy through waste heat boilers is made. The spelter moves to market by rail and truck either in palletized bundles weighing approximately 1060 kg, as loose slabs weighing 26.5 kg each, or as 1088 kg ingots. At present 46% of the metal is exported and 54% is consumed domestically in Mexico. The present day trend toward equalized or alloyed spelter, as well as special shaped castings results in sales of 35% of the entire plant's production. Sulfuric acid is also produced by the Contact Process using vanadium pentoxide as the catalyst. The plant is basically a Monsanto contact system, producing approximately 68 t of 100% sulfuric acid daily. Both 98.5% sulfuric acid and 20% oleum are available. All of the acid made is consumed in Mexico. Shipments are made in 26,900 dm3 tank cars.

Jan 1, 1970

By Thomas D. West

The fact that iron expands when heated, until fusion takes place, and that molten iron is consequently less dense than solid iron of the same grade, is now universally admitted. It was proved by the extensive experiments of Mr. Thomas Wrightson, reported in the Jownal of the Iron and Steel Institute (1890, No. 1, p. 72, and 1891, No. 1, pp. 75, log), and, in a manner, is illustrated in heavy founding by the shrinkage 'of the molten metal, which must be " fed " in order to obtain solid castings. This decrease in volume requiring " feeding" while the metal is still liquid I call " shrinkage," applying the term " contraction" to the decrease in volume which takes place after solidification, while the iron is cooling to atmospheric temperature. The light-work founder, not having the opportunity to make heavy castings, in which shrinkage can be observed, is apt to confound the two; but they are in fact distinct, and are separated by an act of expanion, which takes place at the moment of solidification. The fact of this expansion was first practically demonstrated by Mr. John R. Whitney, of Philadelphia, Pa., whose experiments are recorded in the National Car and Locomotive Builder of May, 1889. Experiments recently made by the writer indicate that there is a constant relation between this expansion and the preceding shrinkage and forcibly demonstrate the necessity of " feeding " a casting to make its interior solid. This is a matter with which all makers and users of castings have experienced difficulty. The founder being heretofore unable to define correctly the principles involving the urgent necessity of " feeding " has failed to impress the moulder with its importance in making sound castings.

Jan 1, 1897

By H. L. Miaw, A. M. Gaudin, D. W. Fuerstenau

A quantitative method for evaluating density of slime coatings has been developed and applied to formation of iron oxide slime coatings on quartz and on corundum. Slime coating density is related to flotation recovery and to properties of the electrical double layer at mineral surfaces. IN spite of considerable study, the nature of slime coatings in flotation is still not completely understood. However, phenomena that control floc-culation and dispersion of colloidal systems are now interpreted in terms of electrical double layers.",' Colloids will flocculate even though the particles carry the same charge, but when two dispersed colloids of opposite charge are mixed. flocculation ensues even more rapidly. Analogous phenomena seem responsible for slime coating on minerals in flotation systems. To shed new light on the issue it was considered desirable to devise a tool that would measure slime coatings. The usual method has been to examine photographs of presumably representative surfaces, after. an intervening washing in running water. But such an examination is non-quantitative, and the changes in chemical environment represented by the washing may have removed the slime coatings that existed during flotation. To provide the possibility for a correlation with electrical double layer phenomena, the experiments were made with quartz, corundum, and iron oxide, for which elec-trokinetic data are available.'-" Since the properties of the electrical double layers of these oxides depend on the pH of the solution, pH will be the most important variable. Furthermore, because the zero point of charge for silica, iron oxide, and alumina occurs at pH 3.7, 8, and 9.5, respectively, the relative charge on the slime and mineral can be changed over wide ranges. Because of its practical importance in quartz flotation, iron oxide powder was chosen as the slime. Also, its uniform composition, contrasting color, and ease of analysis make experimentation simple. In this investigation, correlation was sought between the effect on flotation recovery of slime addition and slime coating density. Materials and Methods Details are available in a thesis by Miaw." The quartz was selected from pure Brazilian crystalline quartz, crushed, sized (65/150 mesh) acid-cleaned, washed, and stored in conductivity water. The corundum (synthetic alumina of high purity prepared by Linde Co., Chicago) was crushed, sized (65/100 mesh) deslimed, boiled in nitric acid, washed, and stored in conductivity water. The iron oxide slime, reagent-grade ferric oxide (—400 mesh) from Allied Chemical & Dye Corp., was heated to 160°C, cooled, and stored in a vacuum desiccator. In the electron microscope the slime particles appeared to be about 0.3µ in size, but their large specific surface (87,900 cm per g, by gas-adsorption method, using krypton) suggests that the actual particles are smaller than 0.3r. Had they been perfect nonporous spheres, they would have had a diameter of 0.13µ.

Jan 1, 1959

By Dale A. Vaughan, Oliver M. Stewart, Charles M. Schwartz

A. U. Seybolt (General Electric Research Laboratory)—The authors should be commended for adding some important information to our knowledge of the solubility of interstitial elements in metals. It is becoming increasingly evident that the effect of even traces of such elements have very far-reaching effects upon the mechanical properties of the body centered cubic metals. Those who have worked in this area know that the accurate determination of the small solid solubility limits in systems of the type reported by the authors is a quite difficult task, and it is therefore not surprising that frequently the results of different workers are not in agreement. It is instructive, and usually helpful, to plot the solubility results on log weight or atomic percent -1/T coordinates to find out if a straight line is obtained. A straight line is expected because in systems displaying solubilities of the order of 1 to 3 at. pet or less, Henry's law is usually obeyed—or at least well enough obeyed so that the deviation from linearity is not very appreciable. If Henry's law is obeyed, one canthen use the Van't Hoff Equation in the form In N = ?H/RT + C, where N is mole fraction, at. pet, or wt pet for small values, and AH is the partial molal heat of solution of the solute. R and T have the usual significance, and C is an integration constant. If one plots the reported nitrogen solubility values as indicated above, the three points fall reasonably well on a straight line. The oxygen values for the two upper temperatures fall very closely to the nitrogen values as shown in the authors' Fig. 15. However, the value at 500°C departs widely from the straight line established by the data at 1500" and 1000°C. It is, of course, true that one cannot place too much emphasis on the significance of a line established by only three points, but in the absence of reasons for anticipating deviations, data exhibiting wide departures from linearity should at least be examined closely. Fig. 16 shows the log at. pct -1/T plots for the authors Ta-O and Ta-Ndata including a solid circle point at 500°C and 1.8 at. pet for Ta-O, which is simply extrapolated from the two higher temperature points. In addition, the data of R. P. Elliott9 for Nb-O are shown. These points were picked off his curve and are not very exact, but as can be seen they line up well on a straight line. It is interesting, and probably significant, that the slope of Elliott's results is not far from those of Vaughn, et al. This is probably to be expected because one would anticipate that the partial molal heats of solution of oxyten in these two very similar metals should be not too far apart. AH for Ta-O is about -1900 cal per mol, while for Nb-O it is near -2300 cal per mol. Hence, this lends some support to the thesis that the point at 500°C for Ta-O is much too high. The data of Gebhardt and Preisedanz10 are also plotted, and it is seen that their data while lying on a linear plot, have an appreciably steeper slope. The possible reasons for this will not be discussed here except to point out that their pressure-composition data show anomalies which suggest that they may have been dealing with a different equilibrium from that being discussed. There is another consideration which would also suggest that the solubility at 500°C is lower than shown. The solubility values were obtained by the classic method of first establishing a lattice parameter-composition curve. This the authors did, and there is probably little doubt that it is quite accurate. Such a plot is generally almost error-free because it has a self-correcting feature in that any deviation from linearity makes a data point immediately suspect, and subject to confirmation. Unfortunately, this is not true with respect to the actual solubility values. These are obtained ordinarily by taking an alloy containing more solute than is soluble at some temperature and then thermally

Jan 1, 1962

By Che, C. W. Spencer, C. A. Steidel, Yu Li

Grain boundary grooving as it occurs in a 5.5-deg simple-tilt nickel bicrystal immersed in a saturated Ni-S liquid has been studied. A 1/3 (t= time) dependence for the depth of the groove indicates that the rate -controlling meckanism for groove developvnent is volume diffusion in the liquid. The activation energy for the diffusive process is estimated at 15 kcal per mole. Using an extended form of W. W. Mullins&apos; analysis for grooving reactions, a computer is employed to fit the appropriate diffusion equation by a numerical method. From the analysis a possible method of measuring L.S. the solid-liquid interfacial tension is demonstrated. WHEN a polycrystalline solid is heated in equilibrium with a saturated fluid phase, grooves will form at the intersections of the grain boundaries and surface. The equilibrium root angle of these grooves is determined by the balance between the grain boundary and solid-fluid interfacial tensions. The grooves deepen and widen with time due to a difference in chemical potential between the flat interface and the curved interface of the groove. In this investigation solid-liquid interaction at a grain boundary is studied, with the object to determine the mechanism of grain boundary grooving in the presence of a saturated liquid. Extension of Mullin analysis then permits the estimation of the solid-liquid interfacial tension. Herring has demonstrated by dimensional analysis that the quasi-steady state change of the dimensions of a small particle during sintering is proportional flow, evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, respectively, if geometric similarity of consecutive configurations of the particles holds. Mullins has extended this analysis to grain boundary grooving. In the case of shallow grooves he solves the diffusion equations for evaporation-condensation, volume-diffusion, and surface-diffusion mechanisms, and obtains the same time dependence for any linear dimension of a groove as Herring found for the change in dimension of small particles. In Mullins&apos; analysis2&apos;3 grain boundary grooving of a bicrystal by volume diffusion in the presence of a saturated fluid phase was considered. Several assumptions were made prior to the analysis: 1) the solid-fluid interfacial tension is independent of crystallographic orientation; 2) the Gibbs-Thompson equation relating curvature and chemical potential is applicable at the solid-fluid interface; 3) the relaxation time of the diffusion field is small compared with the time for appreciable changes in the curvature of the groove, so that the diffusion is divergence-less; and 4) the groove has a small slope relative to the initial flat interface. Usually this last condition is fulfilled only for solid-gas systems. The solution of the diffusion equation under the above conditions produces a t1/3 dependence for any linear dimension of the groove in the case where volume diffusion is rate-controlling. The t1/3 dependence is valid because geometric similarity of the grooves exists for all time. EXPERIMENT In the experiment a 5.5-deg nickel bicrystal of <100> simple-tilt orientation was used.4 Grooving was studied in the presence of a saturated Ni-S liquid alloy as a function of time at 750°, 800°, 850°, and 900°C. A low-angle bicrystal was chosen for study to insure that 2L.S. > .b., where l.s.

Jan 1, 1964

By F. Keller, R. H. Brown

BECAUSE of the extensive use of Alclad 24s alloy sheet in aircraft construction, there is much interest in the metallurgical changes caused by heat-treatment of this product.1,2 One of these changes is the result of the diffusion of soluble elements from the core into the coating during treatment. This paper deals with the thermal treatments that may influence diffusion and with the practical effects of diffusion on the serviceability of the product. As is well known, Alclad 24s-T sheet has a core of high-strength alloy combined with surface layers of relatively pure aluminum. The microstructure of a cross section of this product is shown by Fig. I. hot only does the relatively high-purity coating have a high resistance to corrosion, and hence serves as a mechanical barrier between the core metal and the corroding environment, but in addition this coating I exerts electrochemical protection over areas where the core may be exposed, such as cut edges. In addition, the coating affords electrochemical protection to projecting heads of *417S-T, 17S-T and 24S-T rivets, or attached members made from these alloys. Under some conditions of heat-treatment, however, diffusion of copper into the coating will alter the electrochemical relationship between the coating and the core to the extent that only partial protection will be obtained under some corrosive conditions. The reason for the electrochemical protection lies in the fact that the coating layers of pure aluminum are anodic to the alloy core. The addition of copper to aluminum produces alloys in which the potential is lower than that of the pure metal. Moreover, as the amount of copper in solid solution in z4S alloy is increased, the potential of the alloy becomes more cathodic. When heat-treated at 920°F. and quenched in cold water, 24s-T is about 0.16 volt cathodic to pure aluminum. However, copper will diffuse from the core into the coating, and if it reaches the surface the potential will be altered in a cathodic direction. Thus the potential dif-erence between the core and coating may be less than 0.16 volt, depending upon the thickness of the coating, and the time and temperature of heat-treatment. Of the methods available for determining the extent of diffusion of copper from the core into the coating of Alclad 24S-T, two are generally used; namely, the metallographic and the solution potential method.3 METALLOGRAPHIC METHODS Metallographic methods will reveal the progress of diffusion of copper into the coating. For instance, the diffusion zone in the coating intermediate between the coating surface and the core is shown in Fig. I. This photomicrograph is of a polished and etched cross section of 0.040-in. Alclad 24S-T sheet. Diffusion proceeds into the coating more rapidly along the grain boundaries than through the body of the grains. consequently, the diffusion zone is not of uniform width

Jan 1, 1944

By F. J. Fayers, R. L. Perrine

For many years the problem of increasing ultimate recovery of oil from a reservoir has been a subject of interest to the oil industry. At present, a standard secondary recovery technique is to flood the reservoir with water once natural forces of the system are depleted. The permeability characteristics of the rock, together with interfacial forces which exist between the two fluids and the porous material. allow only part of the oil in the rock formation to be recovered by the water-flooding process. Laboratory experiments have shown that when detergents are added to the flooding water, the flow properties of oil in a porous rock arc improved. This improvement results in greater oil recovery. Even though higher recoveries are obtained using detergents, the extra cost associated with the method may make it economically unsatisfactory. To establish economic feasibility requires experimental laboratory measurement of fluid and rock properties together with a calculational procedure to predict field results. Pilot tests in the field may also be required. This paper presents a mathematical procedure for predicting detergent flood behavior. A number of reasonable simplifying assumptions are made to obtain a tractable system of equations. The resulting method may be regarded as a generalization of Buckley-Lev-crett&apos; theory to solve simultaneously for water saturation and detergent concentration profiles. Consequently this type of calculation can be used in much the same manner as Buckley-Leverett theory is used to evaluate a water flood. The mathematical method employed is the so-called method of characteristics for solving hyperbolic partial differential equations. This application of the method is instructive because several other problems in reservoir analysis may be analyzed in a similar manner. FLUID FLOW EQUATIONS The flow behavior of oil and water without detergent through porous reservoir rock is usually expressed by Darcy&apos;s law and a continuity equation for each phase. If gravitational forces are neglected, vrg = kr (s)µr v p rg.........(1) vrg = kr (s)µr v p rg.........(1) ? pa va = F ?/?t (sd) where v is the volumetric flux, k represents permeability, S is saturation, and P the pressure. Fluid viscosity is denoted by 11, p is the density, 4 is porosity, and I the time. The subscripts w and o refer to water and oil. The capillary forces in the system lead to a difference in pressure between phases. This may be expressed by the relation: Pm -P0 =Pc(S).........(5) The capillary pressure? P,, is determined experimentally as a function of saturation. DETERGENT BALANCE EQUATION Addition of detergent to the water phase affects the flow properties of the system. Capillary pressure and relative permeability become functions of detergent concentration, c, as well as fluid saturation. That is: P--P (S,c) and k,,,.- - -- k,,,. At low oil saturation values, the presence of detergent reduces capillary pressure and reduces the relative permeability ratio. Detergents are surface-active and adsorb on rock surfaces. The quantity adsorbed, a, will depend on the concentration c of detergent solution and may also depend on the saturation; thus, a = a(S,c). In this analysis we have assumed that the detergents used are water soluble but not oil soluble, and their movement is therefore restricted to the water phase. The dispersion of detergent in water is neglected by comparison with transfer by flow within the system. Detergent movement is determined by the water flux and adsorption: ? cv m = -F ?/?t (cs + a) We will assume that the quantity of detergent in solution is too small to significantly change water density or viscosity. When the permeability and capillary pres-

By A. T. Yu

On March 18, 1964, the 52,000 dwt ore carrier M/S Houn Maru called at the port of Coquimbo, Chile, on its maiden voyage to take iron ore to Japan. This marked the first time a vessel of this size ever arrived at Coquimbo, and the event promises to drastically accelerate henceforth iron ore exports from Coquimbo province. This was made possible by the use of a versatile shiploading system recently installed by Cia. Minera Santa Fe. Coquimbo has no mechanized loading facilities other than six conventional 5-ton cargo cranes. Limited space on shore further complicates the stocking problems. To make the best of what is available, a meticulously organized semi-hand-loading system has been developed through the years.

Jan 5, 1964

By Sadao Maruyama

INTRODUCTION Since the big discovery of Kuroko deposits in Kosaka mine, Akita Pref., northeastern Japan in 1959, major Japanese mining companies have been engaged in extensive exploration for the deposits expending large amounts of money. Above all their exploration activities have been particularly fruitful in discovering new deposits in northern Akita Pref. It is estimated that the total ore reserves newly found in the area are at least 50 million tons. Kuroko deposits are the most important ore source of copper, lead and zinc in Japan and have been mined since last century in the said area. Kuroko (black ore) is fine, compact aggregates with sphalerite , glena and barite as principal constituents and chalco- pyrite, pyrite and tetrahedrite as subsequent constituents. The name Kuroko comes from its appearance. It is not rare that total grade of copper, lead and zinc reaches 20 - 30% and the gold and silver content is also fairly good. Accordingly the unit value of the ore is much higher than the ore from other types of deposits. Besides the Kuroko ore, the Kuroko deposits consists of Ohko (yellow ore, massive cupriferous pyritic ore), Keikoh (silicious ore, cupriferous network ore) and gypsum ore. This type of deposit is considered to be not only an important source of base metal but also a source of gypsum and barite. Although the importance of this type of deposit had been commonly recognized, sub-surface nature of the occurrence hampered exploration work. In recent years the improved exploration techniques and increased knowledge of the Kuroko deposits have met with remarkable success in the location of new deposits. This outburst of exploration and dis-

Jan 1, 1970

By V. H. Wilhelm

During the first half of the year 1935, the oil industry in California was on a fairly profitable basis, owing mainly to the operation of the Petroleum Marketing Agency. Coincident with the discontinuance of enforced curtailment, California production surged upward from an average of about 500,000 bbl. per day (over the first five-month period) to approximately 625,000 bbl. per day (over the last seven-month period). On Dec. 9 the state production had reached a peak of over 700,000 bbl., a figure that had not been approximated since the early days of voluntary curtailment (Fig. 1). A price cut was instituted during the last half of August, but had no deterring effect on operators that were determined to take advantage of the breakdown of curtailment and produce to capacity. New reserve figures, compiled from actual potentials, available after cessation of curtailment, revealed the startling fact that California reserves were rapidly declining. This situation, coupled with the desire among operators to obtain a more equitable price for their dwindling reserves, caused a restoration in November of a portion of the August price slash. A further rise in price was effected in early December, and crude quotations at the end of the year closely approximated those in effect during the first right months. At the close of the year, the industry felt confident that the production situation was under control. In all fields where competition is keen because of close spacing, production is gradually declining. In the Los Angeles Basin especially there is no likelihood of a large amount of overproduction, unless a new pool is discovered or deeper drilling reveals a prolific source of crude. As long as the fields that are operated by a few companies, such as Kettleman Hills, North Belridge, Ventura Avenue, West Coyote, Dominguez, and some others, can be controlled, it is believed that the overproduction problem in California will be solved.

Jan 1, 1936

By V. H. Wilhelm

During the first half of the year 1935, the oil industry in California was on a fairly profitable basis, owing mainly to the operation of the Petroleum Marketing Agency. Coincident with the discontinuance of enforced curtailment, California production surged upward from an average of about 500,000 bbl. per day (over the first five-month period) to approximately 625,000 bbl. per day (over the last seven-month period). On Dec. 9 the state production had reached a peak of over 700,000 bbl., a figure that had not been approximated since the early days of voluntary curtailment (Fig. 1). A price cut was instituted during the last half of August, but had no deterring effect on operators that were determined to take advantage of the breakdown of curtailment and produce to capacity. New reserve figures, compiled from actual potentials, available after cessation of curtailment, revealed the startling fact that California reserves were rapidly declining. This situation, coupled with the desire among operators to obtain a more equitable price for their dwindling reserves, caused a restoration in November of a portion of the August price slash. A further rise in price was effected in early December, and crude quotations at the end of the year closely approximated those in effect during the first right months. At the close of the year, the industry felt confident that the production situation was under control. In all fields where competition is keen because of close spacing, production is gradually declining. In the Los Angeles Basin especially there is no likelihood of a large amount of overproduction, unless a new pool is discovered or deeper drilling reveals a prolific source of crude. As long as the fields that are operated by a few companies, such as Kettleman Hills, North Belridge, Ventura Avenue, West Coyote, Dominguez, and some others, can be controlled, it is believed that the overproduction problem in California will be solved.

Jan 1, 1936