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By G. E. Archie

Data given in this paper indicate that certain relations exist between different characteristics of sandstone. These relations are not rigid, for all sandstones are more or less heterogeneous. Not every increment of a given horizon follows exactly the relationship; however, studying a reservoir as a whole from a large number of samples, definite trends are found to exist. Apparently nature's processes of sedimentation and diagenesis are such as to give some degree of uniformity. Average relationships are valuable because electrical measurements in a borehole comprise a considerable volume of rock near the hole. Also, it is desirable that a given producing reservoir be studied as a unit. In a permeable reservoir whose pores are filled with a saline solution, it was found that the total porosity and the type of sandstone influence the relationship between its electrical resistivity and the RO and the resistivity of the brine R,. The relation can be expressed by the following empirical equation, Ro = R10O— [i] where 0 is the porosity expressed as a fraction and the numerical value of the exponent lies between 1.8 to 2.0 for consolidated sandstones, and is about 1.3 for clean, unconsolidated packs. This equation indicates that an appropriate electrical log can be used to estimate the porosity of a saline water-bearing reservoir when Rw and the type of rock are known. The fraction R0rw, is called the "formation resistivity factor." It reflects the effect of the nonconducting rock structure on the resistivity of the salt water that fills the tortuous paths through which the electricity must pass. The formation resistivity factor F is found to be related to permeability k. In this case the type of rock plays an important role, as shown by the relation F = ak-b [2] where the values of a and b must be determined experimentally for each horizon. Therefore Eq. I rather than Eq. 2 is used when it is desired to determine the value of F, because small changes in rock structure particularly in the pore size are not critical. Another useful relation, R = R0S- [3] where R = resistivity of rock when partially saturated with brine and partly with oil or gas, S = fraction of the pore space filled with brine, and n equals approximately 2 for both unconsolidated and consolidated sandstone, shows that the connate water of an oil or gas reservoir can be estimated in situ from a resistivity log. Equation 3 shows that in order to estimate the water content of a reservoir a knowledge of R and Ro is essential. The first value can be obtained from the electrical log when all factors influencing the resistivity curve can be properly taken into account. The latter may be obtained when a log is available on the same horizon where it is entirely water-bearing and has

Jan 1, 1946

By S. C. Sircar, B. K. Dhindaw

KINETICS and mechanism of sulfation reactions have been studied extensively. Qualitative and quantitative data are reported for the kinetics and mechanism of sulfation reaction of copper oxide pellets;''2 yet it remains a controversial Subject. The mechanism and kinetics of the sulfation of zinc oxide powder (B.D.H. analar quality) were studied by gravimetric technique. A spring of high-carbon steel wire with accuracy well within 0.2 mg was used for measuring weight change. The sample was taken in a Pyrex glass bucket, hanging freely inside a Pyrex glass tube reactor, with a gold wire attached to the spring, the reactor being surrounded by a movable furnace (double wound type) with a temperature control within *5"C. Flow of oxygen, 60 cu cm per min, and sulfur dioxide, 45 cu cm per min, were measured through calibrated flowmeters and the mixture dried over PZ05 before entering the reactor. The experimental results are presented in Figs. 1 and 2. The plot of weight change of zinc oxide, giving the amount of zinc sulfate formed, was found to be linear over the temperature range of 500" to 700° C and up to a conversion of approximately 60 pct, as beyond it they divert from linearity.' The rate of sulfation was found to be affected by total flow rate of gases at a fixed ratio of SO2/O2, up to 60 cu cm per min, and was found to be linearly dependent on quantity of total powdered sample taken. The plot of rate of sulfation of zinc oxide, 70 mg, with varying amounts of vanadium pentoxide, at a constant ratio of gases as mentioned above, and at a constant temperature of 625"C, was also found to be linear as seen in Fig. 2. Extrapolation to zero V2O5 addition gives the same rate of sulfation, as in case of pure zinc oxide, 70 mg. Vz05 was prepared by heating ammonium vanadate at 600°C for 15 min in a muffle furnace. The available literature points out that the theory of sulfation that has received the maximum support postulates the following mechanism for sulfation of ZnS: 2ZnS + 30, = 2Zn0 + 2SOZ; the ZnO formed acts as a catalyst for the reaction, 2 S02 + O2 = 2S03. This SO3 reacts with ZnO to give zinc sulfate. It is suggested here that the above widely supported mechanism is operative in the sulfation reaction and that the rate-controlling step in the sulfation reaction of ZnO is the formation of SO3 from SO, and 0,. The authors are carrying on further work in this line, and the details will be published later. The authors wish to acknowledge the facilities provided and the help extended by Prof. P. R. Dhar, Head, Department of Metallurgical Engineering, and the permission granted to publish this note by the Director, I. I. T., Kharagpur.

Jan 1, 1969

By M. E. Wadsworth, I. B. Cutler

Coprecipitation of anionic and cationic polyelectrolytes has been applied to floccula-tion of several mineral systems. Results obtained in a study of the flocculation of kaolinite and hematite suspensions of polycationic and polyanionic electrolytes are presented. Greatly increased settling rates were observed following precipitation of positive and negative polyelectrolytes on the surface of finely divided minerals in aqueous suspension. The ratios of polycationic to polyanionic electrolytes required to produce maximum sedimentation have been shown to correspond closely with the equivalence points obtained by light scattering studies of systems containing the positive and negative polyelectrolytes by themselves. DISPERSION of colloids has been of interest to surface chemists for many years. Flocculation studies have been employed to evaluate the limits of colloid stability. In water suspensions, colloids become unstable and flocculate when the ( potential, the potential of the kinetic solvation sheath, falls to a value at which van der Waals forces may act to draw the particles together. This may happen through an adjustment of the pH of the suspension or by addition of a salt. Optimum conditions for rapid formation of large flocs are found in the region of minimum ( potential. In addition to these well known considerations, colloids in water suspensions are known to be flocculated by certain large organic macromolecules. These polyelectrolytes in some cases minimize the i potential and in other instances increase the attractive forces by supplying sites for hydrogen bonding.' Use of organic polyelectrolytes in flocculation of mineral colloids has increased rapidly in recent years. These materials are now recognized as indispensable aids to fluid-solid separations in many extractive metallurgical operations. They have been found to increase both the settling rate in thickeners and the filtration rate of filters. In the elucidation of the characteristics of these organic reagents as floc-culants in this laboratory, it was discovered that interaction of certain polyelectrolytes had a surprisingly good effect on flocculation of mineral colloids. Experimental Procedure: The anionic flocculants used in this study were Lytron 886 and 887, produced by Monsanto Chemical Co. Both reagents are copolymers of vinyl acetate and maleic anhydride. Lime is added to Lytron 886, whereas Lytron 887 is all organic. These reagents possess two carboxyl groups for each acetate group and are therefore anionic in character. The cationic reagents used were the Peter Cooper Co. 1-X and 2-X glues. The structures are not definitely known, but the re- agents are amines and are cationic in character. The glues were prepared in the chrome-alum form. Both types of reagents may be classified as polyelectrolytes in that they are high molecular weight polymers and ionize in water. All data presented are in terms of sedimentation rate, measured in 250-ml glass-stoppered graduated cylinders. With suitable precautions such measurements are fairly reproducible and provide a sensitive means for selecting important parameters such as pH, reagent concentration, and floc size and density.2 Agitation was standardized with five complete end over end cycles of the suspensions in the stoppered graduated cylinders.

Jan 1, 1957

By J. W. Downey, M. V. Nevitt

MUELLER and Knott' have reported that Ti2Cu has the Si2Mo-type (Cllb) structure. The lattice parameters of Ti2Cu and the positions of the titanium and copper atoms are given by them as follows: ao = 2.944A; co = 10.786A 6 atoms per unit cell: 2 Cu (a) 000; 1/2: 1/2, 1/2 4 Ti (e) 002; 1/2, 1/2, 1/2 + z 00 -2 ; 1/2. 1/2. 1/2- z where z = 0.341 We have found eight other binary compounds which appear to be isostructural with Ti2Cu. All of them involve the combination of a titanium group element with a copper group element or a titanium group element with palladium. The compounds and their lattice parameters are given in Table I. The alloy samples were prepared by arc melting metals having a purity of 99.9 pct or better. They were homogenized for 72 hr at 900°C in evacuated capsules and quenched in tap water. Filings were prepared, and these were reannealed for 4 hr at 700°C, also in evacuated tubes. The lattice parameters were determined by a least squares Bnalysis of the back reflection lines of patterns made with cobalt radiation. It was not possible to make a precise determination of the lattice parameters of Zr2Au because the filings underwent rapid oxidation at room temperature. The evidence supporting the large tetragonal cell containing 6 atoms involves the presence of the reflections 002, 101, 004, 112, 114, 202, and other reflections with higher indices for which I = 3n. Three or more reflections corresponding to these indices, which cannot be indexed on the basis of a small body-centered tetragonal cell containing 2 atoms, are observed in the patterns of all of the compounds listed in Table I. They are strongest and most numerous when the components have large differences in their atomic scattering factors, as is the case in Ti2Pd, Zr2Cu, and Hf2Cu. The values of the z parameter should be regarded as approximate They were selected on the basis of the best agreement between the observed intensities of two pairs of closely spaced powder pattern lines (004): (112) and (114): (202) and the corresponding intensities calculated for several values of z. An ordering scheme was assumed in which titanium, zirconium, or hafnium atoms occupy the titanium positions of Ti2Cu, and copper, silver, palladium, or gold atoms occupy the copper positions. Calculated and observed intensities of the aforementioned lines and the other lines of the patterns are in satisfactory agreement, but a refinement of the z parameters and a final confirmation of the ordering arrangement must await a more detailed study. It is interesting to note that in transition metal systems at A2B stoichiometry the Si2Mo-type structure competes for stability with two other fre-

Jan 1, 1962

By J. B. Clark

An exploratory study of the 60 wt pct Mg and 80 wt pct Mg sections of the solid constitution in the magnesium-rich region of the Mg-Al-Ca-Zn system was undertaken. The objective of the investigation was to determine the general configuration of the phase fields with respect to the magnesium solid solution in this complex system. The 335°C (635°F) tetrahedron was selected for study because the solid constitutions of the bounding ternary systems—Mg-Al-Zn,1 Mg-A1-Ca,2 Mg-Ca-zn3—were well known and, at least in these ternary systems, diffusion was rapid enough at 335°C for equilibrium to be reached fairly rapidly. Metallography and powder X-ray diffraction were selected as the best corroboratory methods for determining the solid phase equilibria. A total of forty-six quaternary alloys on the 60 wt Mg and 80 wt Mg sections were prepared, annealed to equilibrium at 335°C, and the phases present identified. Singly sublimed (99.99 pct) magnesium, electrolytic (99.99 pct) zinc, high-purity (99.99 pct) aluminum, and USP calcium were alloyed in graphite crucibles under a chloride flux and chill cast into a split graphite mold. Alloy samples were sealed under argon in Pyrex vials and annealed at 335°C ± 1/2° for a minimum of 500 hr. At the conclusion of the anneal, the alloy samples were quenched rapidly in ice water. Standard metallographic procedures for magnesium alloys were used. Powder X-ray diffraction patterns were taken on a G. E. Camera with a diameter of 14.32 cm using nickel filtered copper radiation. The phase equilibria in the 60 wt pct Mg section of the 335°C (635°F) tetrahedron is shown in Fig. 1. The complex equilibria in the zinc-rich region were not accurately determined and are shown only tentatively with dotted lines. The equilibria of the three bounding ternary 335°C sections from pure magnesium to 60 wt pct Mg are also shown as though folded away from the tetrahedron. The 80 wt pct Mg section has the same configuration of phase fields as that shown in Fig. 1. Thus it is reasonable to conclude that in higher magnesium sections, the same relative configuration of phase fields is maintained though the relative proportions of the individual phase fields may change slightly as the magnesium solid solution is approached. Note that all the ternary phases present in these ternary diagrams enter into the quaternary equilibria with the exception of the phase of the Mg-Al-Zn system which becomes unstable with the addition of as little as 1/2 pct Ca. No quaternary intermetallic phases were found. No liquid phase was detected in any of the quaternary alloys annealed at 335°C suggesting that if a quaternary eu-tectic exists, it must lie between 335°C and 339°C, the temperature of the ternary eutectic in the Mg-Al-Zn system.

Jan 1, 1962

By J. S. Marsh

JOSEPH PRIESTLEY prepared oxygen on Aug. 1, 1774, and noted with great surprise "that a candle burned in this air with a remarkable brilliant flame." On Aug. 2, 1774, some ironmaker possibly began to wonder if this substance could be used to increase his rate of production; at any rate, there is no disputing the fact that the notion of using oxygen for steelmaking in concentrations greater than that available in great abundance-as air-has been in existence for years. Action was delayed by the lack of enough oxygen at a cost within reach of the steelmaker. Within the last several years enough has been available to permit large-scale tests of its use for both combustion, with which this paper is concerned, and for decarburization. The literature is now enormous and easily available; it is sufficient here to cite three items of historic- importance in that all are about 25 years old and in that all are remarkably consistent as far as they go, with what is known today.1,2,3 SIGNIFICANCE OF HIGH-TEMPERATURE HEAT The principal 'function of the open-hearth furnace is to supply sufficient, high-temperature heat to melt the charge and then to increase its temperature to a range suitable for tapping, ordinarily in the neighborhood of 2900°F. That heat is required to make steel everybody; however, there seems to be some confusion now and then about the significance of high-temperature heat. Transfer of energy-and heat is energy is always from a point of higher potential to a point of lower potential and, other things being equal, the greater the potential difference, the greater is the rate of transfer of energy. In the open hearth the flame, of course, is the high-potential source. Perhaps the most satisfactory approach is through the notion of theoretical flame temperature; which is the ratio of heat input to the heat content of the combustion products,* the former is composed mainly of heat of combustion of the fuel plus sensible heat of the fuel plus sensible heat of the combustion air. Thus, flame temperature can be increased by increasing the value of the numerator, by decreasing the value of the denominator, or both. The first method is as old as the open-hearth process and, of course, makes use of preheated air; its possibilities have been by no means exhausted. The second method can be put into effect only by changing the composition of the combustion air, since the combustion of a given quantity of fuel produces a definite quantity of product, and since the denominator includes the non-reactive fraction of the air, principally nitrogen. In other words, the denominator consists of the volume of exit gas multiplied by its heat capacity and that volume consists of carbon l is understood by dioxide and water vapor as reaction

Jan 1, 1948

By D. A. Dukelow, G. Derge

THE Fe0-Mn0-Si0, system has many properties of fundamental interest besides its occurrence in steel-making. The system is the simplest ternary complication of the FeO-SiO, binary whose electrochemical properties have been explored. Therefore, knowledge of the conformance of Fe0-MnO-SiO, melts to Faraday&apos;s laws, as investigated by current efficiency measurements, would be of particular value in interpreting the observed variations of electrical conductivity, while at the same time furthering understanding of this type of molten oxides. Pertinent to the present study are conductivity data of FeO-SiO, and Fe0-Mn0-SiO2, and current efficiency data of FeO-SiO,. Concerning conductivity measurements, Inouye, Tomlinson, and chipman&apos; studied the specific conductivity, a, of molten wüstite as a function of temperature and oxide addition. Liquid FeO in equilibrium with an iron crucible was found to have a o whose magnitude and positive temperature coefficient were undeniably semiconductor in nature (o1400°C = 269 ohm-1cm-&apos;). Additions at 1400°C of 5 mole pct MnO decreased o to 227 while a similar addition of SiO2, dropped o to 125. Additional SiO2 produced an exponential decline of o. It was reasoned that because wüstite is known to be oxygen excess and since there is no pronounced change in oFeO upon melting, that UFeO(L)is p-type semiconduction. Björling2 gives o data for the ternary FeO-MnO-SiO, using fayalite, 2 FeO-SiO,, as the base substance. Upon addition of tephroite, 2 MnO-SiO, he noted a small decrease in o. Taking his data for 1400°C with one-half of the fayalite replaced by tephroite, o shows a decrease of some 40 pct relative to o for fayalite, i.e., 5 ohm-&apos; cm-&apos; to 3. In line with this observation, Mori and Matsushita3 reported that substituting MnO for FeO in the silicate de- creased o slightly except at high SiO, contents where the decrease was somewhat larger. Investigating the ionic nature of FeO-SiO2 melts, Simnad, Derge, and George4, found the anode current efficiency, C,, as calculated from iron anode weight loss, was temperature invariant and in general increased with SiO2 concentration. The authors suggested the possible presence of electronic conduction to explain why C+ < 100 pct. Fig. 4 includes their results as curve (b). EXPERIMENTAL METHOD Apparatus—Fig. 1 is a schematic section of the electrolysis cell used in all the current efficiency runs. The melt was contained in an iron crucible that rested on an alundum ring. A centered silica tube came within 1 in. of the surface of the melt and initially served as a thermocouple well and then as the guide for the anode.

Jan 1, 1961

By J. S. Marsh

Joseph Priestley prepared oxygen on Aug. I, 1774, and noted with great surprise "that a candle burned in this air with a remarkable brilliant flame." On Aug. 2, 1774, some ironmaker possibly began to wonder if this substance could be used to increase his rate of production; at any rate, there is no disputing the fact that the notion of using oxygen for steelmaking in concentrations greater than that available in great abundance—as air—has been in existence for years. Action was delayed by the lack of enough oxygen at a cost within reach of the steelmaker. Within the last several years enough has been available to permit large-scale tests of its use for both combustion, with which this paper is concerned, and for decarburization. The literature is now enormous and easily available; it is sufficient here to cite three items of historic importance in that all are about 25 years old and in that all are remarkably consistent as far as they go, with what is known today.1,2,3 Significance of High-temperature Heat The principal function of the open-hearth furnace is to supply sufficient high-temperature heat to melt the charge and then to increase its temperature to a range suitable for tapping, ordinarily in the neighborhood of 2900°F. That heat is required to make steel is understood by everybody; however, there seems to be some confusion now and then about the significance of high-temperature heat. Transfer of energy—and heat is energy— is always from a point of higher potential to a point of lower potential and, other things being equal, the greater the potential difference, the greater is the rate of transfer of energy. In the open hearth the flame, of course, is the high-potential source. Perhaps the most satisfactory approach is through the notion of theoretical flame temperature, which is the ratio of heat input to the heat content of the combustion products,* the former is composed mainly of heat of combustion of the fuel plus sensible heat of the fuel plus sensible heat of the combustion air. Thus, flame temperature can be increased by increasing the value of the numerator, by decreasing the value of the denominator, or both. The first method is as old as the open-hearth process and, of course, makes use of preheated air; its possibilities have been by no means exhausted. The second method can be put into effect only by changing the composition of the combustion air, since the combustion of a given quantity of fuel produces a definite quantity of product, and since the denominator includes the non-reactive fraction of the air, principally nitrogen. In other words, the denominator consists of the volume of exit gas multiplied by its heat capacity and that volume consists of carbon dioxide and water vapor as reaction

Jan 1, 1949

By J. S. Marsh

Joseph Priestley prepared oxygen on Aug. I, 1774, and noted with great surprise "that a candle burned in this air with a remarkable brilliant flame." On Aug. 2, 1774, some ironmaker possibly began to wonder if this substance could be used to increase his rate of production; at any rate, there is no disputing the fact that the notion of using oxygen for steelmaking in concentrations greater than that available in great abundance—as air—has been in existence for years. Action was delayed by the lack of enough oxygen at a cost within reach of the steelmaker. Within the last several years enough has been available to permit large-scale tests of its use for both combustion, with which this paper is concerned, and for decarburization. The literature is now enormous and easily available; it is sufficient here to cite three items of historic importance in that all are about 25 years old and in that all are remarkably consistent as far as they go, with what is known today.1,2,3 Significance of High-temperature Heat The principal function of the open-hearth furnace is to supply sufficient high-temperature heat to melt the charge and then to increase its temperature to a range suitable for tapping, ordinarily in the neighborhood of 2900°F. That heat is required to make steel is understood by everybody; however, there seems to be some confusion now and then about the significance of high-temperature heat. Transfer of energy—and heat is energy— is always from a point of higher potential to a point of lower potential and, other things being equal, the greater the potential difference, the greater is the rate of transfer of energy. In the open hearth the flame, of course, is the high-potential source. Perhaps the most satisfactory approach is through the notion of theoretical flame temperature, which is the ratio of heat input to the heat content of the combustion products,* the former is composed mainly of heat of combustion of the fuel plus sensible heat of the fuel plus sensible heat of the combustion air. Thus, flame temperature can be increased by increasing the value of the numerator, by decreasing the value of the denominator, or both. The first method is as old as the open-hearth process and, of course, makes use of preheated air; its possibilities have been by no means exhausted. The second method can be put into effect only by changing the composition of the combustion air, since the combustion of a given quantity of fuel produces a definite quantity of product, and since the denominator includes the non-reactive fraction of the air, principally nitrogen. In other words, the denominator consists of the volume of exit gas multiplied by its heat capacity and that volume consists of carbon dioxide and water vapor as reaction

Jan 1, 1949

By Reynold Q. Shotts

The small domestic underfeed stoker as now designed is unusually sensitive to the coking and plastic properties of coals, and when the attempt is made to burn the high rank coking and caking coals of the Appalachian fields, serious trouble may occur. Part of the trouble may be caused by the ash content and clinkering characteristics of the particular coal in use, but more often it is the result of an excessive ac-in of coke in the form of &apos;&apos;trees,, or masses in the fuel bed. Often the zone of burning becomes so restricted that the fire goes out, and in extreme cases the fire may be lifted completely out of the fuel bed and away from the air ports. Even if the fire is preserved, excessive coking may cause response to subsequent heat demand to be slow and irregular. Coke trees seem to grow most readily during periods of hold-fire operation, so that in order to preserve the fire in mild weather it is often necessary to set the timer for such a long operating period each hour that much unneeded and unwanted heat is developed, causing discomfort. During demand periods the fire may pick up so slowly that the intense burning which develops just before stoker cut-off causes a serious overshooting of the thermostat. Stoker coal performance tests which have been made in a number of labora- tories1,2,3,4,5 are one method of approach to the problem Of selecting stoker coals- As yet these tests have not been standardized and they are expensive and time-consuming. The value of the results probably increases with the length of the test. Sherman and co-workers at Battelle Memorial Institute believe that even a one-week test is not too reliable a trial2 and it is quite likely that Others will agree. A great advantage of such tests is that characteristics of coals, other than the tendency to form coke masses, may be evaluated from them. The selection of stoker coals would be greatly facilitated if there existed some simp1e measure Of the tendency Of a a to form coke in a fuel bed. Although possessing all Of the disadvantages Of any small-scale laboratory test, the test for the free-swelling index of coal has been found useful for evaluating the probable effects Of swelling properties upon combustion.7 Ostborg, Limbacherand Sherman, have shown that the test can Predict, roughly, the tendency Of coke to accumulate in the fuel bed Of a domestic stoker. They also gave instances of its value in predicting combustion behavior in some large installations. The use of the test for free-swelling index has become well established and has been adopted as a standard by the American Society for Testing Materials.8 When domestic stoker coal investigations began at the State Mine Experiment Station in the summer of 1944, it was decided

Jan 1, 1949

By L. D. Clark, S. S. Saluja

A physical law, governing the rupture of rock by confined explosive charge correspondent to current expressions for determining weight of charge to rupture rock burden, W, was developed in the form Q = cVw3 by two early investigators performing unique experiments with ice. The coefficient C, is found by trial blast. Recent physical tests conducted with rock, synthetic materials and ice to establish the validity of the theory on which it and other related formulae are based indicated: (a) that failure under hydrodynamic impact pressure is by tension rather than shear as was assumed; (b) that the fundamental law of mechanics, enabling the determination of Q = cvw3, modified to the form P = R x Sa x Wb is valid when low velocity explosives are used; (c) that rock breakage under the action of low velocity explosives is entirely due to explosion gas pressure, as was believed; (d) that under the action of high velocity explosive it is due to the joint effects of scabbing and gas pressure; and that further possible modification could make the above equation also applicable to these joint mechanisms. shape could be easily frozen and because large loads would not be required. They found: (a) that the not unfamiliar shearing equation for metals was applicable to ice where P = load in lb; S = periphery of pressure surface, in.; W = burden, in.; K = modulus of rupture by shear in lb per in.2; and (b) that "the form of cavity produced by the application of gradual pressure is similar to that obtained by blasting in rock under similar conditions of free face and pressure surface!" This similarity in crater shapes leads to the conclusion that rock would rupture by shear, as did ice, and its behavior under the force of a blast could be governed by such a relationship as P = S x W x K. Three important interrelated empirical expressions were derived and rock, charging and spacing coefficients C,, C, and e were established and substantiated by trial blasts. In checking the accuracy of the main assumptions, duplication of the ice tests, substituting rock, suggested that K is not constant and that P = K x W x S, though valid for ice, does not necessarily hold for homogeneous limestone.&apos; Conclusions from this later work raised questions making continued investigation desirable because such conclusions do not destroy the practical value of the empirical equations or theory. Further study for the establishment of the relationship between load, burden and periphery of the pressure surface and possible application of these to the mechanism of rock blasting was undertaken by the authors of this paper. MECHANICAL TESTING - EXPERIMENTAL PROCEDURE Certain inconsistencies in the results of the aforementioned tests repeated on three types of limestone suggested these inconsistencies be attributed to rock inhomogeneity. It was also suspected that the loading speed, which could not be held uniform, may have contributed. The earlier work with both rock and ice

Jan 1, 1964

By Reynold Q. Shotts

INTRODUCTION THE small domestic underfeed stoker as now designed is unusually sensitive to the coking and plastic properties of coals, and when the attempt is made to burn the high rank coking and caking coals of the Appalachian fields, serious trouble may occur. Part of the trouble may be caused by the ash content and clinkering characteristics of the particular coal in use, but more often it is the result of an excessive accumulation of coke in the form of "trees" or masses in the fuel bed. Often the zone of burning becomes so restricted that the fire goes out, and in extreme cases the fire may be lifted completely out of the fuel bed and away from the air ports. Even if the fire is preserved, excessive coking may cause response to subsequent heat demand to be slow and irregular. Coke trees seem to grow. most readily during periods of hold-fire operation, so that in order to preserve the fire in mild weather it is often necessary to set the timer for such a long operating period each hour that much unneeded and unwanted heat is developed, causing discomfort. During demand periods the fire may pick up so slowly that the intense burning which develops just before stoker cut-off causes a serious overshooting of the thermostat. Stoker coal performance tests which have been made in a number of laboratories 1, 2, 3, 4, 5 are one method of approach to the problem of selecting stoker coals. As yet these tests have not been standardized and they are expensive and time-consuming. The value of the results probably increases with the length of the test. Sherman and co-workers at Battelle Memorial Institute believe that even a one-week test is not too reliable a trial2 and it is quite likely that others will agree. A great advantage of such tests is that characteristics of coals, other than the tendency to form coke masses, may be evaluated from them. The selection of stoker coals would be greatly facilitated if there existed some simple measure of the tendency of a coal to form coke in a fuel bed. Although possessing all of the disadvantages of any small-scale laboratory test, the test for the free-swelling index of coal has been found useful for evaluating the probable effects of swelling properties upon combustion. 7 Ostborg, Limbacher and Sherman, have shown that the test can predict, roughly, the tendency of coke to accumulate in the fuel bed of a domestic stoker. They also gave instances of its value in predicting combustion behavior in some large installations. The use of the test for free-swelling index has become well established and has been adopted as a standard by the American Society for Testing Materials.8 When domestic stoker coal investigations began at the State Mine Experiment Station in the summer of 1944, it was decided

Jan 1, 1948

By H. P. Rassbach, E. R. Saunders

MUCH progress has been made in recent years in the theory and practice of making stainless steel. By effective utilization of oxygen for decar-burization and more suitable alloying agents, it has been possible to attain consistent production of very low-carbon stainless steel. In order to facilitate economical production of stainless steels, the Electro Metallurgical Co. has carried out an extended experimental program that has clarified some of the complex interrelations of temperature and composition under decarburizing and reducing conditions. These results&apos;-:&apos; have been founded in large part on small experimental heats, and in order to confirm their validity and significance under commercial conditions, a survey of stainless steel melting practice has been made with the cooperation of stainless steel producers. Conditions required for decarburization and associated oxidation of chromium, manganese, and iron have been fairly well established in relation to the beneficial effect of the highest practicable temperature. The recovery of chromium and manganese from highly oxidized slags by reduction with silicon has been indicated with somewhat less precision and this study has shown significant deviation in large commercial heats from the small experimental heats. In spite of an unsatisfactory degree of accuracy in estimating the conditions affecting reduction of metallic values, it has been possible to calculate a slag weight in reasonably good agreement with the results observed in large heats. While there still is much to be learned about both the qualitative and quantitative aspects of stainless steel melting, this survey has indicated the manner by which the efficiency of the production process may be measured. Oxidation Period In order to establish practices for the recovery of chromium and manganese from the slag the amounts of these metals oxidized should be known. Moreover, since reduction of oxidized chromium and manganese must necessarily be accompanied by similar reduction of iron, knowledge of the total quantity of metallics oxidized is essential. The relations between carbon, chromium, and temperature under oxidizing conditions were developed by Hilty in 1948.&apos; While it had been realized previously that retention of chromium in the metal during carbon oxidation is favored by high temperatures, the Hilty relation provided quantitative information useful for evaluating melting procedures. For example, it was shown that decarburization to moderate carbon levels can be achieved while retaining substantial amounts of chromium. However, in decarburizing to the low-carbon level necessary for producing 0.03 pct maximum carbon stainless steel, very little chromium remains in the bath at the temperatures generally employed. For this reason, Hilty, Healy, and Crafts&apos; later projected an extension of the chromium-carbon relation to the low-chromium region. Although this chromium-carbon-temperature relation defined the composition of a chromium steel bath at the end of the oxidizing period, it did not provide a direct means for estimating the total amount of metallic oxidation occurring during decarburization of a stainless steel heat. This subject was investigated by Crafts and Rassbach³ and, later, by Hilty, Healy, and Crafts" who demonstrated that metallic oxidation is a function of the chromium content of the initial furnace charge, the minimum carbon content attained, and the temperature. It was further demonstrated from data on 1-ton heats that an empirical relationship exists between the ratio of chromium plus manganese to iron in the slag (S) to the corresponding ratio of these components present in the metal bath. The following expression was derived to permit the calculation of the amount of metallics oxidized during decarburization of a given charge: W-2000 (Cr1 + Mn1)-(Cr2 + Mn2) 1 100s/s+1-(Cr3 + Mn2) where W is the pounds of chromium, manganese, and iron oxidized per ton of charge; Cr1, the percentage of chromium in the charge; Mn1, the percentage of manganese in the charge; Cr2, the percentage of chromium in the bath after oxidation; Mn2, the percentage of manganese in the bath after % Cr + % Mn oxidation; and S =%cr+ % Mn/%Fe in the slag after %Fe oxidation. In order to establish whether the slag ratios of commercial heats are consistent with those found in the experimental heats, the slag and metal analyses shown in Table I were evaluated. These data represent samples taken after the oxidation of two 1-ton and seven 15 to 25-ton heats of types 303, 304, and 304L stainless steel made in chromite, acid, and basic hearths. Fig. 1 illustrates that the results for the commercial heats correlate reasonably well with the relationship originally established for experimental 1-ton heats. It will be noted that in the range of metal composition of these heats, the slag values generally lie above the line. As was suggested by

Jan 1, 1954

By M. I. Sherman, J. D. H. Strickland

USE of a hydrometallurgical approach to the oxidation of sulfide ores and extraction of metals therefrom may have advantages over the more common smelting techniques when a low grade deposit is difficult to concentrate or the subsequent separation of metals, coexisting in the ore, is laborious by any known smelting operation. For economic reasons, the most promising oxidants are either atmospheric oxygen or electric power. The use of oxygen, or air under pressure, has recently been revised. Pyrrhotite has been converted to iron oxide and elementary sulfur&apos; and a variety of sulfides have been treated by Forward and co-workers.2-4 Generally sulfate is the end form of the sulfur but with galena in an acid medium, elementary sulfur can be formed." For economic reasons chlorine and ferric iron salts are about the only possible alternatives to the atmosphere as oxidizing agents for base metal sulfides. If aqueous solutions of chlorine or ferric iron are employed, the reduction products can be oxidized electrolytically in situ and used again, thus acting as catalysts for electric power as oxidant. The use of ferric salts for this purpose is established hydrometallurgical practicea but, although chlorine gas has been employed in the dry state at an elevated temperature, its use in aqueous solution at or near room temperature has not found favor. The reaction of chlorine water with the soluble sulfide ion has been studied by several workers,7-9 and both sulfate and elemental sulfur are found as end products, the latter being favored by the presence of a low concentration of oxidant relative to that of sulfide in solutions of about pH 9 to 10. Of direct bearing on the work in hand are an early American patent" and a recent Austrian patent." The former advocates stirring powdered ore with an aqueous solution of ferric chloride chlorine oxides and chlorine. In the latter it is claimed that both metal and sulfur can be obtained by electrolysis, in a diaphragm cell, of a metal ore slurry in brine. Details in these patents are scant and no data or explanation is given for the mechanism of the reaction which, in the Austrian work, is attributed to the (unlikely) action of nascent chlorine at the anode surface. No mention is made of possible differences in behaviour between various ores. Apparatus A complication encountered when working with chlorine water is that a serious loss of chlorine occurs by gas partitioning unless an enclosed system is used and any air space in the apparatus is kept very small and constant. Arrangements were made, therefore, to take out samples for analysis without letting air into the system to replace the liquid removed. For convenience in studying a heterogeneous reaction the apparatus was so designed that a reproducible controlled stirring rate could be maintained and the ratio of surface area of ore to volume of solution was approximately constant throughout any experiment. The apparatus used is shown in Fig. 1. The ground ore was placed in the horizontal cylindrical vessel, A, of about 1 liter capacity, heated by a constant temperature circulating bath pumping water through the concentric jacket, B. By adding chro-mate to this water, an ultraviolet radiation filter effectively surrounded the reaction vessel, greatly reducing any possible photochemical decomposition of chlorine solutions. Stirring was effected by glass paddles, C, attached by an axle to a magnet which was rotated by another powerful Alnico magnet, D, outside the glass end, this magnet being itself rotated by an electric motor electronically controlled to constant speed. Speed could be varied from about 150 to 900 rpm and was measured and held to within 1 pct of a given value. The end of the reaction vessel remote from the stirring magnet was closed by another one-ended glass cylinder, E, connected by thin polyethylene bellows, F, clamped by screw clamps and watertight rubber gaskets to the main vessel. Through E, a glass electrode and calomel electrode projected into the solution and a hypodermic syringe pierced a small bung and allowed acid or alkaline to be added to maintain a constant pH. By pushing the fully extended bellows until the two cylinders touched, from 50 to 100 ml of solution could be forced out through a sintered disk into the three-way tap system, G, either to waste (for flushing purposes) or up into a 10 ml burette where the solution could subsequently be measured out for analysis. The ore samples were introduced at H, the tube being stoppered by a thermometer of —1 to +52ºC range, graduated to 0.1°C intervals. To prevent ore from being ground in the end bearings of the stirrer these bearings were pro-

Jan 1, 1958

By B. B. L. Seth, H. U. Ross

A generalized rate equation for the reduction of iron oxide was derived from which two particular equations were obtained: one for rate controlled by the transportation of gas, the other for rate controlled by the phase-boundary reaction. Pellets of pure ferric oxide having diameters of 8.5 to 17.5 mm and a density of 4.8 g per cm3 were prepared and reduced by hydrogen at 750° to 900°C. From the analysis of data obtairzed, it was observed that neither the phase-houndarv reaction nor the transportation of gas controlled entirely the rate of redziction. Rather, the mechanism of reduction can he divided into three stages. In the beginning, the process seems to depend predominantly on the surJrce reaction, hut after a layer of iron is formed the diffusion of gas becomes the controlling factor. Towards the end, however, the rate falls sharply due to a decrease in porosity. The times predicted by the generalized equation for a certain degree of reduction showed an excellent agreement with those obtained experinmentally for pellets of varying sizes. WIDE interest in iron oxide reduction has resulted in many valuable studies pertaining to thermody-namical properties, equilibrium diagrams, and chemical kinetics. Although the thermodynamical properties and equilibrium diagrams are now known with a fair degree of accuracy, the mechanism and rate-controlling step in the reduction of iron oxides presents a problem to research workers which is still unsolved. This is because the field of chemical kinetics is so highly complex. Besides the chemical reaction between oxide and reducing gas, several other processes are occurring simultaneously such as solid-state diffusion of iron through intermediate oxides (FeO and Fe3O4), the diffusion of reducing gas inwards and of product gas outwards, and the sintering of iron if reduction is carried out above the sintering temperature of iron. Furthermore, there is a large number of variables, including the nature and flow rate of the reducing gas, the chemical composition and physical properties of the ore, the temperature of reaction, particle size, and so forth, all of which can affect both the mechanism and the kinetics of reduction. Despite the controversy and diversity of opinion about the mechanism of iron oxide reduction, three main schools of thought have emerged. According to the first, the rate is controlled by the diffusion of gas through the boundary layer of stagnant gas; the second claims that the rate is proportional to the area of the metal-oxide interface, while the third believes the transportation of reducing gas from the main stream to the metal-oxide interface and of product gas from the metal-oxide interface to the main stream to be the rate-controlling step. 1) The boundary-layer theory is true mainly for packed beds where the flow of gas through the bed is important. For a single particle, the boundary layer may be prevented from being the rate-controlling step if a gas flow rate of reducing gas above the critical flow rate is used. 2) Several workers have reported a linear advance of the Fe/FeO interface which provides excellent support for the belief that reduction is controlled by the surface area. McKewanl has given formal shape to this concept with mathematical derivation and has shown it to be valid for reduction of several iron ores, hematite, and magnetite, both by H2 and H2, H2O, N2 mixtures. Some other investigators, however, do not find this theory to be entirely valid. Deviations have been observed2 and further confirmedS3 Hansen4 also agrees that deviations do occur, at least in the latter stages of reduction, while from the data of several investigators summarized by Themelis and Gauvin,5 it is clear that the theory is not always applicable and further that, when it is applicable, it does not hold in the final stages of reduction. 3) Among those who claim the transportation of gas to be the rate-controlling step are Udy and Lorig,6 Bogdandy and Janke,7 and Kawasaki el a1.8 The validity of the theory has also been acknowledged indirectly by other research workers who show that the sintering and recrystallization of iron cause a decrease in reduction rate, for it is only if the transportation of gas is important that this sintering has any bearing. However, the theory has been rejected by some because they have failed to obtain

Jan 1, 1965

By M. J. Marcinkowski, D. B. Crittenden, A. S. Sastri

A study co.mbining stress-strain .measurements in conjunction with transmission electron microscoPy has been made with near equiatomic Fe-Cr alloys which were aged for various times at 500°C. Associated with this aging is a marked increase in deformation twinning. The outstanding feature of these twins is that they generate stress fields sufficiently great so as to give rise to spontaneous dislocation loop nucleation nearly normal to the propagating twin. This observation is in agreement with the theoretically predicted elongation of the stress field of a dislocation Perpendicular to its direction of motion as it moves near the speed of sound. Dislocation loop nucleation is more difficult in the longer aged alloys so that this energy absorption mechanism is not effective in hindering twin propagation. Since crack nucleation can readily occur near the tip of a twin, the aged alloys become extremely brittle when deformed in tension. Iron-chromium alloys in the vicinity of the equiatomic compositions become severely embrittled when aged at about 500°C. Fisher et 01.&apos; have shown that this embrittlement is related to the decomposition of the original random Fe-Cr solid solution into a chromium-rich and an iron-rich phase. In addition, Mar-cinkowski et a1.&apos; have shown that twinning becomes an increasingly more important mode of deformation as the aging time is increased. These results have been recently corroborated by the transmission electron microscopy study of Mima and amauchi . The Fe-Cr alloy thus seems ideal for verifying the predictions made in Parts I4 and 115 of this investigation where the behavior of large static or blocked twins and those of large dynamic or propagating twins, respectively, were investigated numerically. It was thus decided to measure the stress-strain curves generated by embrittled alloys that were aged for various times and to examine sections by transmission electron microscopy. EXPERIMENTAL PROCEDURE Electrolytic iron and electrolytic chromium were vacuum-melted and poured into ingot form. The composition of the resulting alloy was found to contain 46.0 wt pct Cr (47.8 at. pct), the remainder being iron. The resulting ingot was swaged above 850°C into 0.250-and 0.400-in.-diam rounds. Compression samples of 0.250 in. diam and 0.400 in. long were cut from the smaller-diameter rounds. These samples were then sealed in evacuated quartz tubes and annealed for 30 min at 1150°C to produce a uniform and equiaxed grain size of mean diameter equal to 1.73 mm. They in turn were rapidly quenched from 850°C so as to preserve the condition of random solid-solution characteristic of the elevated temperature. The samples were then aged for various times up to 300 hr at 500°C in a massive Pb-Bi alloy bath. The samples were next polished and tested in compression at room temperature as described in Ref. 6 using an Instron tensile testing machine. The strain rate used was 0.05 in. per in. per min. The remaining larger round was converted into compression specimens of 0.325 in. diam and 0.500 in. long. This larger diameter enabled wafers of sufficient size to be prepared for examination by trans-mission electron microscopy techniques after subjecting them to a suitable strain. Foil preparation is described in some detail in Ref. 6. All foils were examined in a type HU-11A Hitachi electron microscope operating at 100 kv. RESULTS AND DISCUSSION Fig. 1 shows the effect of aging at 500°C on the room-temperature stress-strain curves of the FeCr alloys. For greater clarity the origin of each curve has been displaced upward. The same origin has been used for both the 0 and the 0.1 curves. It is apparent that with increased aging times a sharp drop in load is observed at the yield stress which becomes more pronounced as aging proceeds. A loud sonic burst accompanies this drop and subsequent metallographic examination shows the sample to contain numerous twins. For intermediate aging times, a number of smaller twin bursts follow the initial large one. The total plastic strain associated with the twinning mode of deformation can be obtained by adding up the contributions AE~ from all i twin bursts, i.e., £,¦££,-, in the manner illustrated schematically in Fig. 2. The contraction of the specimen, as measured from the strip chart of the Instron, after suitably correcting for the elasticity of the machine, was converted into true strain using the assumption that there was no volume change and that the sample remained cylindrical. The dashed lines are all drawn parallel to the

Jan 1, 1970

By John Griffen

K. F. Tromp (Kerkrade, Holland)—Your assumption that the Dutch State Mines have lead in the development of heavy medium processes—the Barvoys, Loess, Driessen—is not correct. The credit should be given to a Dutch engineer Mr. deVooys, the inventor of the Barvoys process. deVooys started in 1932 in Hiickelhoven, a German but Dutch-owned mine, where he was a director. Several plants on the Continent as well as in Great Britain were erected. The State Mines started their first plant in 1937. They could not get that plant working satisfactorily and built another one. Their process made no headway, and up to 1946 there was only one plant installed, the one at their own pit. Since 1946 they started the cyclone process and only since that time have they been more active, though industrial cyclone washeries are still in their infancy. deVooys sold his patents to the Dutch State Mines in 1946 and this might have given you the impression that the pioneer work had been done by the Dutch State Mines. John Griffen (author&apos;s reply)—I wish to thank Mr. Tromp for giving the correct story on the development of heavy medium processes in Holland.

Jan 1, 1952

By J. L. Keats

IN THE literature on the elimination of metalloids in basic open-hearth practice, there are a great many heats recorded in which excellent data on changes in slag and metal composition during refining are given, but in almost all of these heats either temperature data or weights and analysis of charge are unrecorded and observations on the physical characteristics of the slag are almost always lacking. With these points in mind, a test heat was made in which as complete as data possible on all the factors that affect the elimination of metalloids were obtained. THE TEST HEAT The test heat was made in a standard 100 ton stationary furnace at the Lackawanna Steel Co., Lackawanna, N. Y. on January 17, 1922. The Charge-Scrap.-The scrap consisted entirely of rail-heat butts, selected from a number of heats made, the week before the test. The average analysis of the scrap was calculated from the analysis of these heats-and from the weight of scrap from each heat. Pig Iron.-Two ladles of pig iron were used in the charge and two samples were taken from each ladle as it was poured into the furnace. These four samples were composited for the average pig-iron sample.

Jan 2, 1926

By H. H. Kaveler

Education is for the purpose of developing citizenship, and, if it is pursued for the additional purpose of preparing for a professional career, such as engineering, it is also directed to developing a knowledge of essential science, aptitude for the application of science to practical situations, and a knowledge of the industrial art in which the engineer will be engaged. The process of education required for engineering must of necessity extend beyond the classroom into industry. For that reason, the education of engineers should be divided as between the university and industry. Specialization in engineering should logically come as a result of experience in an industry. The student cannot take the time in a university, and, the university cannot teach the skills required to develop a specialist without sacrifice to the more essential broad purposes of formal education. In addition to talent in science, aptitude in the application of scientific fact, and knowledge of the industrial art, the engineer should possess certain personal qualities which are helpful in the pursuit of a professional career. Those personal qualities are: the ability to work as a partner in an enterprise, the ability to do jobs in a way whereby job performance is a means of gaining experience and increased responsibility, the capacity to write and speak in an understandable manner, and, a Proper regard for the "significance of answers." These pcrsOnal qualities may be of almost equal importance to acabemic accomplishments in the field of science. Development of such personal qualities are an essential part of the student&apos;s training in the university and in industry. They can be developed effectively through the leadership of instructors. Compulsory Education Nature played a mean trick On the human race when the evolutionary Process failed to develop in the individual a capacity to inherit knowledge. Were knowledge transmissible in a cumulative manner from generation to generation, mankind would be by inheritance wise beyond measure within a few generations. Then there would be little if any need for a "system of education." As matters stand, however, all must suffer the burden of starting life at the "zero " level of learning from which station each rises depending upon individual capacity to assimilate knowledge left of record by our predecessors and the individual effort exerted to compensate for Nature&apos;s failure to endow the offspring with intelligence. In the United States some degree of education is generally regarded as essential and necessary. Therefore, all citizens are subjected by law to an educational process covering the primary school age from six to sixteen years. Beyond the schooling required by law, many attend secondary schools, and beyond that, schools of higher learning. Our standard of living is at a level that permits an increasingly large fraction of the population the opportunity to go through all of the formal educational process. As a result, education in the colleges and universities has almost reached a mass production level. In spite of the high

Jan 1, 1949

By Edward Saibel

THE object of this study is to investigate the effect of prior tensile strain on the fracture stress of a metal. This is done in a theoretical manner starting from the point of view developed by the author in his thermodynamic theory of the fracture of metals. The results are compared with experimental findings and a rational interpretation is given to work that shows the variation of fracture stress with prior tensile strain. THEORY OF FRACTURE In the thermodynamic theory of the fracture of metals developed earlier,1 it was shown that a critical strain energy per unit volume exists. This is characteristic of the material and may be calculated from basic thermodynamic data. When the area under the flow curve reaches this characteristic value, fracture occurs. The general criterion for fracture is expressed in the form u ± uo = JLm?AV/V [1] where Lm, is the latent heat of melting of the unit volume, ?V/V is the ratio of the change in volume of the unit volume to the original unit volume on passing from the solid to the liquid state, [uo] is an initial energy density, and J is a conversion factor, which changes energy from heat to mechanical units. As a first approximation, it will be assumed that the stress-strain curve is the straight line that extends from the point of maximum load onward, extrapolated back to the axis of zero strain, for example, line AC of Fig. 1. If the point of intersection of the straight line with the axis of zero strain is represented by so, and the slope of the straight line is p, the analytic form of the flow curve is [s = s + pd [2]] and the strain energy per unit volume evaluated from [JvdS] becomes (vsod + pd2/ 2). When this latter term reaches the critical value JLm?V/V (designated hereafter by M), it is assumed that fracture occurs. This leads to the following expression for the fracture stress: [s1 = \/C r.2 + 2Mp [31] The strain at fracture may be calculated from Eqs 2 and 3. It is assumed in this paper that the initial energy density is either zero or that it may be neglected. Furthermore, the complicated states of stress and of strain existing in the necked region of the tensile specimen after "necking" has occurred will also be neglected for the present, so that average conditions will be assumed to prevail. FLOW AND FRACTURE CURVES Ludwig2 attributed to materials two fundamental properties: (I) a resistance to flow and (2) a resistance to fracture. He reasoned that at each instant the

Jan 1, 1947