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By Hobart M. Kraner

THE mineralogy of blast furnace sinter is of interest because its mineral content is one of the important factors contributing to its character. There are so many other factors affecting the properties of the sinter, however, that it is well to mention them here. The proportion and character of the raw materials, that is, raw ores, concentrates, returns, and fuel, as well as the mixing and the water content, all have a marked effect on the physical properties of the product and the degree to which sintering action can be carried on. The process of sintering is a relatively fast operation. In as much as appreciable time is required to carry on processes of fusion in such masses of low thermal conductivity, large lumps of hematite ore frequently remain unfused and partly unchanged in state of oxidation in the sintering process. The kind, the grain size, and the amount of fuel used affect both the completeness of the fluxing reaction and the prevailing atmosphere. The rate of reduction in laboratory tests is not only dependent upon the state of oxidation of the sinter but also upon the sizing and porosity. Atmosphere and temperature affect the state of oxidation of the iron oxide, and the atmosphere alone may determine the ferrous minerals that finally develop. The rate and extent of cooling, the type of coolant, the subsequent handling, and screening all have serious effects upon the type of sinter that eventually enters blast furnace bins. The degree to which actual fusion or fluxing takes place in the sintering operation has a marked effect upon density. A sinter which has been extensively fused by high content of fuel in the batch will no doubt have a higher weight on the bulk basis than one which had a lower fuel content. As high temperatures are required to do this job, the iron oxide under these conditions will be largely magnetite. Sintering at low temperatures to produce larger proportions of hematite means a decrease in the amount of liquid formed and a much more sensitive bonding process. In this case the liquid must be distributed more uniformly and thereby used more efficiently than would be the case where higher temperatures were permitted to prevail more or less indiscriminately. Where coarse ore particles are used in a sinter mix it is not expected that any particles coarser than 1/4-in. can be fused and incorporated in the system to such an extent that the gangue contained within these lumps will have been converted or fused by the sintering process. It is for this reason that coarse ore, returns, or both, in a sinter usually result in a sinter which breaks easily and at the same time may contain some of the original minerals of the lump, such as quartz and hematite. In examination of sinters at Bethlehem Steel Co. minerals such as quartz and corundum have been found, none of which are considered normal associ- ates of wustite or magnetite. Some degree of heterogeneity or lack of equilibrium is not unusual in the sintering process. The differences in specific gravity between hematite and magnetite might be ample reason for poor strength in a not very well sintered mass containing coarse particles of. ore or returns. The shrinkage taking place in a lump of hematite in its conversion to magnetite by temperature and/or atmosphere is appreciable. Sintering of ores as it is carried out is crude chemistry, for the grain size is relatively coarse, the application of heat is certainly not uniform, and the time factor is inadequate for other than partial completion of reactions. Coarse lumps of coke or coal cause local heating around these centers, and fuel which is too fine may result in such slow burning that sufficiently high temperatures are not always obtained. High temperatures are essential to the work required. The Swedish practice of sintering is established on the basis of producing an easily reducible product high in hematite. This is achieved through uniformity of grain size in the sinter mix and close control of the temperature through careful regulation of fuel and sintering rates. This produces a sinter which is very tough in character and which has a high degree of porosity. Although the hematite content is not produced upon cooling by drawing air through the mass, there would be greater possibility of accomplishing this reaction with this type of sinter than is the case in American practice. In the latter, the temperatures are so high that temperature alone converts most of the mass to magnetite. The grains are so coarse in the final product that together with the fluxed condition it would be difficult to reoxidize them to hematite upon cooling. An examination of the iron-oxygen diagram' shows that hematite does not exist above 2651°F. It also shows that there is no liquid in the pure magnetite-hematite system until 2881°F is reached. On the other hand, in the system magnetite-wustite liquids exist at considerably lower temperatures than this. It will be seen, therefore, considering only the iron oxides, that the bonding action obtained in America in sinters comes about through considerable temperature and/or reducing conditions that produce compositions containing even less oxygen than is contained in magnetite or than results from the fusion of silicates. The bonding obtained from the iron oxides is encouraged by the reducing conditions that prevail in the vicinity of the fuel particles in a mass of this sort, where temperatures are above 2600°F. As magnetite and wustite are opaque, they do not lend themselves to petrographic study by transmitted polarized light. The silicates found in sinter and the glass that has not crystallized transmit light and can be studied by these methods in which indices of refraction and other optical properties of anisotropic crystals lead to their definite identification. The index of refraction is the only property that can be measured in glass under the microscope, and this is a clue to its probable approximate composition.

Jan 1, 1954

By F. D. George, M. J. Salkind

Al3Ni whisker-reinforced aluminum was found to exhibit good Charpy impact toughness and little notch sensitivity even though its room-temperature tensile elongation parallel to the whiskers is only 2 pct. This impact behavior was maintained d liquid nitrogen temperature (-196"C). It is postulated that this behavior is due primarily to the presence of the continuous aluminum matrix which provides sufficient 10calized ductility in the vicinity of the crack tip to absorb considerable energy from the advancing crack. The impact behavior of Al-Alni was found to be quite anisotropic. Of six orientations studied, the transverse orientation having the notch normal to the whisker axis was found to exhibit the lowest impact energy, whereas the transverse orientation having the notch parallel to the whisker axis was found to exhibit the highest impact energy. A significant differnce was noted between the impact behavior of material containing needlelike whiskers and that containing bladelike whiskers. Only two of the six orientations studied exhibited complete fracture for the material containing needlelike whiskers. On the other had, most of the specimens containing bladelike whiskers exhibited complete fracture. It was postulated that the bladelike whiskers block transverse flow, thus reducing the amount of plastic deformation ahead of the crack tip. One of the more significant advantages of composite materials is the prospect of combining high strength with toughness. In general, toughness is associated with materials which exhibit considerable ductility and can deform plastically in the presence of a stress concentration. Very strong materials which resist plastic deformation generally exhibit low toughness. At first glance, then, it would appear as though strength and toughness are mutually incompatible so that useful engineering materials would have to be a compromise between the two. One approach to the problem of combining the high intrinsic strength of ceramics with the toughness of metals was to mix them together to form a cermet. Unfortunately, the toughness of cermets was found to be rather disappointing. Whisker reinforcement of metals, however, appears to be a more promising approach. It has been demonstrated that whisker-reinforced metals produced by unidirectional solidification exhibit enhanced strength due to the presence of high strength nonmetallic whiskers. The total strain capacity of these composites in the direction of fiber alignment is limited to that of the fibers, the matrix being unable to carry the load once the fibers have failed. A characteristic, then, of whisker composites is low ductility in the direction of whisker alignment, on the order of a few percent elongation. This low elongation, which is usually associated with brittle behavior, should not be taken as an indication of low toughness. Such a material can exhibit significant ductility in directions other than parallel to the fibers7 and can therefore possess significant intrinsic toughness. Toughness in a fiber-reinforced metal is derived from several mechanisms. The first is due to the toughness of the matrix itself. A continuous ductile metal matrix can act as an effective crack arrest medium by undergoing localized plastic deformation. Cracks initiated from the surface of the composite or from a brittle fiber failure must travel through the matrix before reaching another brittle phase particle. A second crack arrest mechanism peculiar to fiber composites is due to the fact that, as a crack travels through the matrix and approaches a fiber, the plastic deformation ahead of the crack tip will result in loading of the fiber. This causes the matrix shear strength in the plastic zone to be apparently higher, thus extracting more energy from the crack and diverting the crack at an angle to the original direction of propagation. A third crack arrest mechanism occurs in fiber composites which exhibit a weak bond between fiber and matrix. The idea was proposed by Cook and Gordons that if a crack propagating transversely in a fiber composite were made to turn and run along the fibers by decohesion of the fiber-matrix bond, then toughness would be imparted by the blunting of the crack tip and the creation of new surfaces. The last mechanism, interfacial decohesion, is commonly noted in naturally occurring fiber composites such as wood, bone, and bamboo, and has been observed in man-made composites such as glass fiber-reinforced resins,g silica fiber-reinforced aluminum," laminated steel," and tungsten and silica fiber-reinforced electroplated copper.'' The first mechanism, crack arrest by plastic deformation in the matrix, has been noted in tungsten wire reinforced cast copper." The purpose of this investigation was to quantitatively assess the toughness of a whisker-reinforced metal as a function of orientation. Previous investigation considered only cracks propagating nominally perpendicular to the reinforcement. In this investigation, crack propagation in three mutually perpendicular directions as well as three intermediate orientations was investigated. The system chosen for study was the unidirectionally solidified A1-A13Ni eu-tectic alloy which has a microstructure consisting of 10 pct by volume of A13Ni whiskers in a matrix of aluminum This material exhibits two different kinds of whisker morphology, depending upon the rate at which it is solidified.' At low rates of solidification (less than 2 cm per hr) the whiskers are bladelike, whereas at higher rates of solidification they are

Jan 1, 1969

By H. Doi, Y. Fujiwara, K. Miyake

In order to throw light on the mechanism of plastic deformation of WC-Co alloys, compressive tests of WC-(7 to 43) vol pct Co alloys have been carried out at room temperature, and stress-micro strain relation has been investigated in detail. The analysis of the factors affecting the yield stresses reveals that the yield stresses can be predicted by modified Oro-wan's theory if one properly estimates the planar in-terfiarticle spacings. Conzpressive straining of some of the alloys by 0.066 to 0.17pct increases the decrements by a factor of as much as 3.4 to 14, whereas the corresponding increase in the electrical resistivities is less than 10 pct. The analysis of the decrement data in terms of -Gramto and Lücke theory shows that the marked increase is attributed to increased dislocation darnping itt the binder (cobalt) phase. By cornbilling the decrement data and the conzjwession duta, one obtains the relation between flow stress in shear (?t) and increase in dislocation density (p): At = const . v6 . This is interHeted to mean that the mechanism of strain hardening of CirC-Co alloys is essentially sarne as the one for dispersion strengthened alloys. The possible effect of bridge formations between the carbide particles has also been examined. OWING to the combination of hardness, strength, and other physical and chemical properties, WC-Co alloys have opened the way for unique fields of applications, the recent ones being, for instance, anvils for super-high-pressure generation apparatuses. In such applications, the alloys are frequently subjected to very high compressive stresses: these stresses may cause the alloys to deform plastically and eventually to fail. However, much remains obscure regarding the nature of the plasticity of the alloys. Evidently, the alloys owe their high strength to the hard carbide particles which frequently occupy as much as 80 to 90 pct in volume fraction, whereas the ductility required for practical applications is provided by the small amount of the binder phase between the carbide particles. When the volume fraction of the carbide phase is not very large, deformation behavior of the alloys may be described by some of the current dispersion strengthening theories. However, greatly increasing the carbide phase is thought to lead to some carbide skeleton structure or bridge formations owing to the increased chances for direct contacts between the carbide particles;1,2 this may appreciably affect the plasticity of the alloys. Regarding the effect of formation of the carbide skeleton structure, it is interesting to note the work by Ivensen et al.3 on compression tests of the alloys containing somewhat large carbide particles; they observe extensive generation of slip bands in the carbide particles after application of some preliminary compressive stresses. They interpret the results in terms of plastic deformatiot: of the carbide particles which are supposed to have formed a skeleton structure; the binder phase plays only a passive role, at least in the early stages of the deformation. That carbide crystals exhibit microplasticity at room temperature is apparent from the work of Takahashi and Freise4 and French and Thomas5 on indentation of WC single crystals. On the other hand, Dawihl and coworkers6-10 maintain that even when volume fraction of the carbide phase is very large (for instance, more than 90 pet), a very thin binder layer generally exists between the carbide particles. They interpret the results of the extensive mechanical tests in terms of the plasticity of such a layer. Gurland and Bardzil11 point out that decrease in ductility of the alloys with increase in the carbide phase is caused by the effect of plastic constraint exerted by the dispersed carbide particles. Drucker12 further develops this concept from a continuum-mechanics approach on an assumption that a continuous thin binder layer separates the carbide particles. A common feature of the studies reported so far on the plasticity of the alloys is that the information deduced is invariably qualitative in nature. Thus, very few systematic experiments for obtaining reliable and sufficiently detailed stress-strain curves of the alloys varying widely in the microstructural features have been carried out. In particular, it may be of special interest to investigate in detail the early stages of the plastic deformation of the alloys in order to shed light on the strengthening mechanism. However, such work appears to be extremely rare. Doi et al.13 recently reported a first brief account of the results of some quantitative analysis of the plasticity of the alloys in terms of dislocation theory. Their experiment was rather limited in the composition range covered (volume fraction occupied by the carbide phase: 79 to 83 pct), and thus they could not necessarily elucidate the controlling mechanism of plastic deformation of the alloys of a more general composition range. Consequently, in the present investigation, deformation behavior and some other physical properties of the alloys were investigated and discussed in more detail over a much wider composition range. SPECIMEN PREPARATION WC-Co alloys used in this experiment were prepared in cylindrical or rectangular form by sintering in vacuo compressed mixtures of tungsten carbide and cobalt

Jan 1, 1970

By J. Sibakin, R. D. Hindson

In order to devise a practicable soaking pit schedule for use at The Steel Co. of Canada Ltd.'s Hamilton Works, soaking pit heating temperatures, sooking times, pit capacity, and safe maximum mill drafts were correlated with fluctuations in the current or load of the bloom mill driving motor. Other variables such as total delays in the pit, rolling schedules, mill delays, and track times were also investigated. IN order to show an easily applied and accurate means of establishing soaking pit heating temperatures, soaking times, pit capacity, and safe maximum mill drafts, these various factors are correlated herein with fluctuations in the current or load of the bloom mill driving motor. Rolling practices have a considerable influence on the production capacity of a blooming mill. The maximum values of the torque, in particular, are of importance, since even instantaneous current peaks lead to the tripping of the motor by the overload relay and result in loss of mill time. The establishment of safe maximum drafts and accelerations for ingots of different sizes and of a soaking pit practice which would ensure a consistent and satisfactory plasticity of the metal is of considerable importance for increasing the efficiency of both the blooming mill and the soaking pits. The Bloom Mill Dept. of the Hamilton Works, The Steel Co. of Canada Ltd., is equipped with one 44 in. mill driven by a 7000 hp motor with the setting of the overload relay at 22.0 ka. The speed of rotation of the motor is regulated after the Ward-Leonard system. There are three basic speeds of 9.5, 28, and 47 rpm and a further possibility of increasing the speed by weakening the field. This last possibility is hardly ever used during practical operations. The rolling program of the blooming mill is varied, both in the size of the ingots to be handled and in the steel grades. The total tonnage handled by the mill is about 2,000,000 ingot tons per year. At the time of the investigation, the Bloom Mill Dept. was equipped with 22 soaking pits (6 regenerative, 14 bottom-fired, and 2 one-way top-fired pits) with a total bottom area of 2770 sq ft. The pits are fired with a blast furnace-coke oven gas mixture having a calorific value of 155 Btu per cu ft. The foregoing figures show that the production program was such as to impose the necessity of a most efficient usage of the available equipment. For this purpose, the operations of the 44 in. mill and of the soaking pits were investigated, and the results of the investigation were used as a basis for a revised soaking pit schedule and drafting practice. The plasticity of an ingot of a certain chemical composition when being rolled is determined mainly by the following factors: I—the ingot size, both thickness and width; 2—the length of the gas soak; and 3—the surface temperature. The first two factors determine the uniformity of the temperature distribution over the cross-section of an ingot. The third factor introduces the level of the heating of an ingot. The torque produced by an ingot being rolled is determined by the area of the metal displaced, its plasticity, and acceleration values. On the other hand, with shunt motors the torque is determined by the current. This can be assumed to be correct with only a small degree of error for compound motors with a relatively small effect of the series windings as long as the velocity is not regulated by weakening the field. Since the spread is relatively unimportant when compared to the width of an ingot and since it is also reduced several times during rolling by edging passes, the draft alone and not the area of the metal displaced may be taken into consideration with ingots of a similar size. It is therefore possible to determine the main features of the heating and drafting of an ingot by measuring the current and acceleration of the mill motor. After the acceleration has been taken into account, the amount of current will be an indication of how the motor responds to a heating and/or drafting practice and these practices can be adjusted in order to get the desired result. As peak currents are more likely when heavier ingots are rolled, the rolling of plate and slab ingots was investigated. Conditions prevailing when smaller ingots are rolled can be deduced from the results obtained on heavier ingots. All measurements were made when plain carbon grades under 0.15 pct C were rolled. The motor current, the voltage across the armature, and the rpm were recorded simultaneously on synchronized charts, Fig. 1, which moved with the speed of 6 in. per min. Each draft was recorded by a special observer. The rpm curve made it possible to establish the acceleration at any given moment. For purposes of correlation, the maximum current during a pass and the corresponding acceleration were used. The charts made it possible to establish the position of the roller's lever at any given moment as well as the total time of a pass. The slab ingots were divided into three groups (28x35, 28x45, and 27Mx53 in. ingots) and each group was investigated separately. Since they account for most of the current peaks, only flat passes were used for purposes of correlation, a total of 1373 having been investigated.

Jan 1, 1956

By W. J. Slatosky

W. 0. Philbrook (Cairiegie Institute of Technologyogv—Mr. Slatosky has presented an interesting and constructive paper that represents another step along the way of converting steelmaking from an art to a science. I am confident that his computer will be practical and successful and that with a very few months of experience it will provide a significantly better degree of control than his record of 65 pct of heats within range obtained with the slide-rule calculator . A paper such as this, with a lot of symbols and condensed mathematics, is difficult to comprehend quickly. Since I have had an opportunity to study it carefully, perhaps my evaluation of its validity and accomplishments will save time for others. Mr. Slatosky has correctly used standard principles of stoichiometry and heat balances, which are available to anybody, but he has also brought to them two original contributions: 1) He has developed from operating data some empirical relations for predicting the final FeO content of the slag (at 0.5 pct C end-point) as a function of slag basicity, lance height, and scrap, ore, and scale in the charge. This improves the accuracy of prediction of temperature or scrap requirement compared with assuming an arbitrary, constant FeO content at the end of each heat. There is no assurance yet that exactly the same relations will hold for other furnaces or practices, but similar correlations can be expected. 2) He has combined calculations that are ordinarily carried out laboriously as a number of individual steps into a single, simple linear equation that can readily be fed into a machine. This involved a tremendous amount of painstaking detail work as well as the imagination to see the possibility and work out the steps. While his particular Eqs. [3] and [6] are valid only for the furnace design, charge weight, and blowing time used at Aliquippa Works, only a few numerical values have to be changed to adapt it for other conditions. In order to arrive at a useable solution, Mr. Slatosky had to make some basic assumptions about the process that are similar to those used by others. He neglected variation in some process variables and assumed an arbitrary average value for waste gas analysis and temperature for want of more exact information at the present time. All of these judgments are clearly stated. In addition, some thermody-namic data presently available are not adequate for the job, notably in relation to heats of formation and sensible heat in slag, and some expedient has to be adopted to get around the difficulty. Other people might prefer slightly different judgments about these details and hence obtain somewhat different numerical solutions. This is not of serious importance, however, because the errors accumulate in the "heat loss" term and are largely self-compensating for a constant heat time. Although the extended Eq. l(a) in Appendix I was set up as a rate equation originally, for convenience in using an analogue computer as stated in the paper, the time dependence was removed by later mathematical manipulations and assumptions about the process. The final result is an integration of element and energy balances from initial to final states; this procedure is as legitimate here as in any other form of heat-balance calculation. The formal handling of stoichiometry and thermochemistry appears to be correct, and it is assumed that any arithmetical errors would have come to light in applying the calculations to furnace practice. Mr. Slatosky's approach is not necessarily unique, in that other people might start with apparently different equations or prefer another form of final equation for another type of computer. However, he has presented an accomplished result that appears to be a theoretically sound and practically useful way of applying scientific principles and rapid computation for better control of steelmaking. His success will undoubtedly encourage himself and others to improve on the mathematical model and its use as better informatioq becomes available. John F. Elliott (Massachusetts Institute of Teck-t2ology)-The last comment by Mr. Richards that a calculator is quite unnecessary for an L-D operation ?-equi??es a rebuttal. The L-D furnace is a very high capacity process which places a premium on close control. When one is making steel at rates between 100 and 200 tons per hr, one cannot afford the luxury of an extra 5 or 10 min at the end of a heat correcting for an error that should never have been made in the first place. Mr. Slatosky's paper is a very sound application of the simple principles of stoichiometry and the energy balance. It is a satisfactory and valuable start, but only the start of the development of methods of control for this process. An analysis of the process shows that it should be very suitable to control by a computer. This is especially the case when various grades of steel are to be made. In fact, it would seem that the organizations who are planning new and bigger installations of L-D vessels should consider carefully the advantages that would stem from computer control of a vessel with the operator present to do little more

Jan 1, 1962

By H. G. Doll

As a continuation of the earlier paper on the general subject of the SP log, a more complete analysis of certain features of the SP log in shaly sands is given. The pseudo-static SP in front of shaly sands is compared, on a theoretical basis, to the static SP in front of clean sands, as a function of the respective amount of shale and sand in the formation, and of the relative resistivities of the shale, of the uncontaminated part of the sand. and of the invaded zone of the sand. As a conclusion, the advantage of using reasonably conduc. tive mud in this case is shown. The discussion is illustrated by field examples. INTRODUCTION The discussion reported in the present paper is based on a theoretical analysis, and not on experiment. The field examples, joined to the text. are shown only as qualitative illustrations of the essential results of this analysis. Although the hypotheses made in the theoretical developments may perhaps be somewhat improved, it seems, nevertheless, that the results obtained account reasonably well for the actual phenomena, and give a fair approximation of their order of magnitude. The paper contains a mathematical analysis of a tri-dimen-sional distribution of potentials and current lines. due to spontaneous electromotive forces arising at the contact of shales and free electrolytes. as a function of the geometry and of the respective resistivities of the different media involved. It is assumed, although this hypothesis is not proven, that the emf's remain the same even if the shale occurs in very thin layers or in dispersed particles. It has already been pointed out 1,2,3 that, all other conditions being the same, the deflection of the SP log in front of a shaly sand is smaller than opposite a clean sand. When the thickness and the conductivity of a clean sand are large enough. the deflection of the SP log reaches a limiting value which is equal to the "static SP" of the clean sand. It is generally convenient to take the static SP of shale as the reference value or "base line." As a consequence, and for the sake of abbreviation, the expression. "static SP of a clean sand," is often used to designate the difference between the static SP of that sand and that of the shales, which difference is a measure of the total electromotive forces involved in the chain mud sand-shale. A similar limiting value is; also observed for the SP deflec-lion opposite a thick shaly sand, but it is smaller. just as if the total electromotive force involved were smaller in that case. This limiting value has been called the "Pseudo-Static SP" of the shaly sand. The static SP of a clean sand depends on the salinity of its connate water with respect to that of the mud, and, to a certain extent. on the differential pressure which controls the electro-filtration potentials, but it does not depend on the resistivity of the sand. On the contrary. the pseudo-static SP of a shaly sand depends not only on the salinity of its connate water and on the differential pressure, but also on the percentage of shale and on the resistivities of the shale, of the uncontaminated part of the sand, and of the zone invaded by the mud filtrate. If the three resistivities above were equal, the pseudo-static SP would be proportional to the percentage of sand in the shaly sand, and its departure from the static SP of a clean sand having the same connate water would simply be proportional to the percentage of shale. In that case, the pseudo-static SP of a shaly sand containing 10 per cent of shale would he 10 per cent less than the static SP of a clean sand. When. however. the sand is. on the average. substantially more resistive than the shale. the percentage of departure of the pseudo-static SP from the static SP of a clean sand is much larger than the percentage of shale. For that reason, the peaks of the SP log opposite shaly sands are systematically of smaller amplitude when the sands are oil-bearing than when they are water-bearing, all other conditions being the same. This feature is observed even when the sand beds are thick. and even when they do not contain a large percentage of shale. All this has already been described in all earlier publication", but mostly in a qualitative way. The present paper will analyze in more detail the action of the local SP currents which are generated inside of the shaly sands, and which are responsible for the abnormally low value of the pseudo-static SP. The quantitative computations have been extended to the general case of thin interbedded layers of sand and shale, where the resistivities of the shale and sand streaks do not have the same value: they are summarized in charts giving values of the pseudo-static SP of a shaly sand as a function of the different parameters involved. DEFINITIONS The static SP of a clean sand has been defined as the potential that would exist in the mud opposite that sand, were the SP current prevented from flowing. Such an ideal condition is represented on Fig. I-A. By analogy, the pseudo-static SP of a shaly sand can be defined as the potential that would exist in the hole, if the circuit shaly sand — surrounding shales — mud column were interrupted by the insulating plugs placed at the boundaries

Jan 1, 1950

By R. S. Busk

Niels Engel (University of Alabama, University, Ala.)— In this paper it was pointed out that the electron-gas and energy-band theory accounts for the fact that the lattice parameters exhibit a sudden change when the electron concentration (number of bonding electrons per atom) exceeds a certain number around two. This statement is said to support and prove the electron-gas theory. But this theory is not able to account for a series of experimental data. Also several expectations, deduced from this theory, are not found to exist. In Figs. 6 and 7 the energy bands of the second and third periods are given as they must be assumed in order to account for the electrical properties of the elements in these periods. In Figs. 6 and 7 the electron-gas and energy-band theory is compared with the electron-oscillator hypothesis in accounting for the properties of the elements in the second and third periods. Fig. 6 shows the second period, The energy-bands are overlapping and separated to be in agreement with the electrical conductivity of the elements. The oscillator hypothesis explains conductivity due to electron vacancies. In graphite there is a closed s-shell in every other atom and two vacancies in the others. Conductivity is therefore only maintained by migration of s-electrons in graphite. In boron there are no s-electrons. The diatomic molecules of nitrogen and oxygen and the paramagnetism of oxygen can be accounted for by a similar behavior as the s-electrons of the bonding electrons. But this explanation will deviate too much for the purpose of this discussion. Fig. 7 shows the third period. In the energy-band picture about two s-electrons are assumed in magnesium and aluminum, but only one s-electron is assumed in silicon. The diamond lattice is assumed to be controlled by a sp3 hybrid. However the electron distribution develops ideally according to the oscillator hypothesis. Only sodium, magnesium, and aluminum exhibit electron vacancies and conductivity. To account for the insulator properties in Si, P, and S in the third period it must be assumed that the four last added p-electrons must be taken up in bands containing only one electron per band.' (Compare the electron band picture in Hume-Rothery.' Hume-Rothery does not consider the insulator properties of the nonmetals.) In the second period already the first p-electron must have entered a single electron band. Based on the energy-band picture in Figs. 6 and 7, the following questions must be asked: 1—Is it consistent with the energy-band idea that electrons of the same kind (p-electrons) can be divided into separated bands? 2—Is it consistent with the energy band idea that single electron bands can exist? 3—Why are the first two p-electrons (in boron and diamond) separated into two single electron bands in the second period, but overlapping in the third period (aluminum)? 4—Why are s-electrons and d-electrons taken up in continuous overlapping bands, while p-electrons are divided into single electron bands? 5—Why do the peaks and valleys (y and w and further x and z) of the energy band below four electrons per atom not show up in the electrical conductivity of alloys? For example consider the Li-Mg system or the alloys between Mg and three electron metals where the mentioned discontinuity in the lattice parameter is found. 6—Why does the beginning of the p-electron band (x) not show up in the lattice constants similar to the filling up of the s-electron band (z) ? In magnesium alloys the electron-gas theory postulates the first Brillouin zone to be filled at about two electrons per atom. This is claimed to explain the sudden change in lattice spacing and c/a values of several magnesium alloys when the electron concentration exceeds a few percentage points over two electrans per atom. This was emphasized in the paper by Busk. If the electron-gas energy-band theory is correct a sudden change in electrical conductivity and possibly other properties .should be expected when the same electron-concentration or temperature is exceeded. A sudden change in lattice spacing or other properties should also be expected when the filling degree is such that p-electrons are introduced into the p-band, for example at x in Figs. 6 and 7. Such phenomena are at found by experiment. and If the number of electrons should vary with the energy level depending on the average number of bonding electrons per atom, the electrical conductivity should be expected to vary in accordance with the energy band layout (Figs. 6 and 7) caused by different numbers of conducting electrons at different filling up degrees. Nothing indicating such a behavior is observed. In addition to these discrepancies between the electron-gas and energy-band theory and measured data, the theory violates the principles developed along with the Bohr theory of atomic structure. According to these principles a filled shell is saturated and therefore unable to form bonds. Therefore two S-electrons per atom should form a closed or saturated shell, which has been pointed out as accounting for the inability of helium to form bonds. Beryllium, magnesium, or calcium atoms with two s-electrons should be expected to form inert atoms with properties almost like the helium atoms. Several other inconsistencies and disagreements with measured data of the energy-band theory can be mentioned. Some of these are discussed with reference to other papers. 8 Because the electron-gas and energy-band theory seems to fail on several points, I have developed another theory which can account for all the phenomena the electron-gas theory is able to account for. This new theory is further able to account for things which are impossible to explain by the electron-gas theory at the present state.

Jan 1, 1953

By E. A. Ernst, N. F. Carpenter

The benefits derived from an acidizing treatment are a function of the penetration achieved by the acid before complete spending. Additional penetration may be achieved by (1) controlling acid leak-08 into formation pores in the channel faces, and (2) retarding the reaction rate of the acid. A recently developed chemical additive consists of a synthetic polymeric material which absorbs hydrochloric-acid solutions, when suspended therein, swelling up to 40 times its original volume. These swollen particles have the ability to deform and seal-08 formation pores, providing fluid-loss control. In addition, they provide a diffusion barrier between the fracture face and the acid solution, prolonging the spending time of the acid. Field applications of this new technique have shown promising results. A method of conducting acid fluid-loss tests, using carbonate cores, is believed to provide fluid-loss data that are more representative of formation conditions than the conventional filter-paper determinations. INTRODUCTION The concept of oilwell acidizing has changed since its first commercial application, 30 years ago. Originally, it was visualized that the acid penetrated thousands of tiny pores and flow channels in the matrix rock, enlarging them by dissolving the carbonate walls. The resultant permeability increase was assumed to be the responsible factor in increasing production from the well. Recent laboratory studies,' however, have shown that this does not provide the complete picture. Although this type of individual pore penetration by the acid does take place during acid "soaks", designed to overcome "skin effect" due to mud invasion in the immediate vicinity of the wellbore, many years of experience have shown that considerable pressure is required to attain any appreciable injection rate into the fine capillary pores of the rock. During most acidizing treatments, the bottom-hole pressure build-up due to the restriction of flow into the formation exceeds the "breakdown" pressure of the rock so that a fracture is induced. In most cases, such fractures open up along natural, incipient fissures and zones of weakness in the rock and, therefore, tend to follow the natural stress pattern of the rock—whether it be horizontal, vertical or inclined. Because of the comparatively greater permeability of the channel in relation to that of the matrix, the bulk of the acid volume is diverted into the newly opened fracture. Here it quickly penetrates the formation, opening and ex- tending the fracture in much the same manner as a conventional fracturing fluid. Unlike the fracturing fluid, however, most acidizing solutions contain no propping agent; thus, the open fracture will again close when the injection pressure is relieved. Laboratory studies2 have shown that in many cases the etching of the fracture faces, resulting from the reaction between the acidizing solution and the carbonate rock, is nonuniform due to the heterogeneity of the rock structure. As a result, the two fracture faces no longer match when pressure is released, and support pillars and intermediate voids remain, forming a high-conductivity channel for well fluids. Unfortunately, this is not true over the entire area of the fracture, but only over that portion of the fracture where the rock has been partially dissolved by the acid. The acid solution spends as its travels away from the wellbore; once it has completely spent, even though it may provide additional mechanical fracture extension, no additional benefit due to etching of fracture faces can be expected. Studies of acid reaction rates under formation conditions,3 observing the effect of different variables upon spending time, have shown that the reaction was often so rapid that very little penetration of the formation occurred before the acid was spent. Study was undertaken to devise methods of increasing the penetration of the acid before spending, so as to provide greater benefit from the acidizing treatment by etching a greater portion of the fracture faces. Several techniques were devised to accomplish this purpose. First, chemical additives were developed which were designed to retard the reaction rate of the acid, causing it to penetrate a greater distance from the wellbore before finally becoming spent. Another method was to increase the injection rate of the acid. However, it was found that the resultant increased shear tended to accelerate the reaction rate of the acid, partially offsetting the benefits of the higher injection rate insofar as achieving increased penetration before spending was concerned.' Another approach to the problem of achieving increased penetration was the development of fluid-loss additives for acid solutions, which would minimize the volume of acid lost into formation pores in the fracture faces and provide maximum fracture extension for the volume of acid injected during the treatment. The use of fluid-loss additives is now considered the most effective method of providing maximum fracturing-fluid efficiency.~ Unfortunately, this latter technique does not solve the problem of rapid reaction rate, with consequent limitation of the fracture area benefited by reaction with unspent acid. A newly developed acid additive overcomes many of these limitations by providing the dual benefits of fluid-loss control and mechanical retardation of acid reaction

By H. L. Gilbert, C. Travis Anderson, W. J. Kroll

IN a previous paper,1 the use of a split graphite tube resistor as a heater element for high-temperature furnaces has been described. The principal advantages of this type of construction are: I. The quadruple resistance or voltage compared with the top-bottom clamp resistor furnace. 2. Free expansion of the resistor. 3. The ease of protection from oxidation by air. 4. The firmness by which it may be held in the compact split clamp. This construction appeared to be well adapted for the fusion of high melting metals which require fusion in a vacuum. Zirconium metal had previously been melted at the Albany Laboratory of the Bureau of Mines in a vacuum arc furnace on a water-cooled plate, using a movable tungsten top electrode.2 When larger furnace capacities were desired, this type of construction proved to have its limitations as the largest tungsten rods available were about 7/8in. in diameter. The supply of direct current of high amperage for producing the . desired arc characteristics was also not available. Considerable difficulty was also found in compensating the atmospheric pressure on the flexible tubing of the movable electrode, at the same time keeping its movement sufficiently free to enable the striking of an arc on any part of the metal briquet. Among the various materials used for the electrodes in conducting experiments in the vacuum arc furnace was graphite. It was found that zirconium fused in a graphite cup with a carbon arc was contaminated to only 0.2 pct carbon. It was therefore decided to melt zirconium directly in graphite crucibles. A high-frequency furnace was first used in the attempt to melt the zirconium in graphite crucibles. The high-frequency heating coil was placed outside a silica tube which was evacuated by means of an oil diffusion pump backed up by a mechanical pump. The graphite crucible was thoroughly degassed at 1900°C before use. Considerable difficulty was experienced in operating at such temperatures in vacuo because, as shown by Zintl,3 carbon vapor formed and reacted with silica according to the reaction: Si02 + C = SiO + CO. The silicon monoxide which is volatile at these high temperatures reacted with the zirconium, thereby contaminating it with silicon and oxygen. The presence of carbon monoxide was detected by means of a gas discharge tube placed in the vacuum system as indicated by the pale blue glow of the tube as soon as carbon vapor started to react with the hot silica. The reaction between the carbon vapor and hot silica was avoided by the use of split cylindrical molybdenum shields which were inserted between the graphite crucible

Jan 1, 1948

By Bruce F. Grant, Stefan F. Szasz

During 1947, a Sinclair research team was assigned to investigate thermal methods of oil recovery. The assignment was recommended by a survey of possible research approaches to increase the amount of oil that ultimately can be recovered from oil producing reservoirs. The use of heat to stimulate oil production rates by the melting of paraffin deposited in well bores can be traced back to within one or two decades of the drilling of the Drake well. The application of heat on a larger scale has been discussed by generations of oil producers. Shortly after the turn of the century, one intrepid operator is reported to have injected steam into a Pennsylvania property. After a few weeks, he apparently became discouraged and terminated his experiment. Subsequently, the literature contains references to several well-developed techniques for supplying heat to a producing well bore to melt paraffin or to reduce the viscosity of oil contained in the formation immediately around the well bore.1.?.3.4 Some early references discuss procedures to furnish heat to the reservoir,5,6 with the injection well as the heat source, thus obligating the process to maintain the entire rock mass at a temperature above that at which the desired improvement in oil recovery would occur. Another approach to reservoir heating was reported by a group of Russian technologists in 1935.7,8,9 They definitely demonstrated that combustion can occur within the porous structure of an oil-bearing sandstone. Their field experiments, however, relied less on combustion within the rock than on heat furnished by combustion of oil supplied to the injection well bore. Ignition of the air-oil mixtures in the well bore was found very difficult, and the field tests were carried on for only short periods of time. Publication of the Russian work spurred at least one independent operator in this country to try firing an air-gas injection well, on for only short periods of time. Publication of the Russian work spurred at least one independent operator in this country to try firing an air-gas injection well. The Brundred Oil Corp. reportedly obtained combustion in the sand immediately around the injection well bore, but the experiment was abandoned because of interference with normal production schedules. Injection capacity of the experimental well was greatly reduced by firing. The well was reshot and pieces of sand showing partial fusing of the quartz matrix were recovered. To the authors' knowledge no other field experiments utilizing combustion techniques for formation heating were undertaken prior to 1948, although the patent literature evidences continued interest in formation heating."'," CONCEPT OF COMBUSTION-SUPPORTED HEAT WAVE The references cited were in agreement that heat applied to a reservoir would increase recovery, but there

Jan 1, 1955

By Harold Vagtborg

Equilibrium vaporization ratios were obtained for light hydrocarbons, nitrogen, carbon dioxide, and hydrogen sulfide in a reservoir fluid containing 35 mole per cent hydrogen sulfide. The data cover the range from 700 to 2500 psia at 154°F. The results of this study are compared with results obtained by other investigators on systems containing less hydrogen sulfide. When large amounts of hydrogen sulfide are present, the equilibrium vaporization ratios for ethane and heavier hydrocarbons are greater than the ratios for systems containing little or no hydrogen sulfide. Large amounts of hydrogen sulfide have the reverse effect on the ratios for methane. Routine PVT studies were performed on the reservoir fluid including flash and differential liberations of the dissolved gas. The pressure-volume relationships of the saturated fluid were also determined. It is shown that the use of published correlations on physical properties of reservoir .fluids can lead to gross errors when applied to systems containing large amounts of hydrogen sulfide. INTRODUCTION Equilibrium vaporization ratios for various components in naturally occurring crude oil and condensate systems have been reported in the literature.1,2,3,4 Recently, several papers have been published with emphasis on non-hydrocarbon components such as nitro- gen, carbon dioxide and hydrogen sulfide.5,6,7,8,9 The increased discovery of reservoir fluids having high concentrations of these non-hydrocarbon components, particularly hydrogen sulfide, has created a need for a further study of their phase behavior. Equilibrium vaporization ratios are known to vary with pressure, temperature, and overall composition of the system.'" It was anticipated that ratios for systems containing large amounts of hydrogen sulfide would differ from the ratios for systems containing small amounts of hydrogen sulfide. Therefore, the present work was undertaken in order to obtain reliable equilibrium vaporization ratios for the reservoir-fluid in question. PROCEDURE The procedure followed was evolved after considerable experimentation on methods of handling the very sour crude. It was found that drying agents (e.g. CaCl2 and CaSO4) absorbed an appreciable amount of hydrogen sulfide from the gas used to prepare the recombined samples. The concentration of hydrogen sulfide dropped as much as 10 mole per cent in a single pass through a 3-ft drying tube. It was also found that when undried gas was agitated with mercury in the PVT cell, a black scum, believed to be mercuric sulfide, was formed and the hydrogen sulfide content of the gas dropped several mole per cent. Because composition changes during a run could not be tolerated, separation of the mercury and sour fluid was necessary. In order to effect this separation, a stainless steel piston, equipped with Teflon O-rings, was placed in the PVT cell between the mercury and the sour fluid. This piston had to be constructed in three parts because

Jan 1, 1955

By W. W. Schmittroth, A. Y. Bethune

THE commercial analysis of Special High-Grade zinc usually involves the determination of lead, iron, copper and cadmium as impurities in the base metal. Over the past 20 years, as the result of metallurgical improvements in the art of producing Special High-Grade zinc metal there has taken place a gradual exclusion of almost all extraneous elements, and the few that do remain in the final product have been virtually reduced to the vanishing point. Thousands of tons of zinc .are now commercially produced annually and made available to the trade, in which impurities are present only in the order of 0.0010 per cent or less and the sum total of all impurities does not exceed 0.0025 per cent. To such zinc the term "superpurity" might well be applied without undue exaggeration. The techniques used for production control and final analysis of Special High-Grade zinc by means of emission spectra in the laboratories of the electrolytic zinc plant of the Sullivan Mining Co. are based on the premise that self-electrodes are to be preferred over all other forms for the examination of the zinc in question. Furthermore, after a survey of the literature and considerable experimental work,1 it was decided that the spectrographic method of internal control, the principle of which was first announced by Gerlach,2 using a modification of the high-voltage alternating-current arc source introduced by Duffendack and Thompson,3 with the calibration of each photographic plate as recommended by Wolfe,4 would yield the most accurate and reproducible results. Self-electrodes were chosen in order to make use of one of the unique advantages inherent in spectrographic analysis; namely, the rapid and almost effortless detection of elements other than those being quantified by the analyst; or conversely, the proof that the zinc is free from such impurities if no spectral line of the suspected element appears. This fact was verified for certain elements, and will be discussed later. Carbon electrodes impregnated or packed with zinc salts chemically prepared from the zinc to be assayed were avoided for a number of reasons. First, the chemical manipulation was another time-consuming step, which increased the chances for contamination. Second, none of the common zinc salts, such as the chloride, nitrate or sulphate, yielded reproducible results under our conditions, nor did the spectral line of the impurity appear as readily in the low concentrations as when using zinc metal. Third, no commercial carbon, except the very expensive, was pure enough to use with this grade of zinc and the continued time, effort and expense incurred in the purification of carbon was not desirable. The use of Special High-Grade zinc self-electrodes introduces certain complications with regard to obtaining satisfactory excitation conditions, because it seems necessary to raise the temperature

Jan 1, 1946

By Walter Crafts, C. M. Offenhauer

In a previous study of the carbide phase of chromium steels, it was shown that chromium carbide (Cr7C3) is 2 more stable carbide than cementite (Fe3C) at tempering temperatures above about 500°C. in quenched steels containing from about I to 7.5 per cent chromium. Below this temperature the carbide phase was found to consist of cementite in all of the steels examined. In the present investigation it was found that a similar change in the carbide phase takes place in molybdenum and in chromium-molybdenum steels at approximately the same tempering temperatures. The approximate ranges of occurrence of the alloy carbides Cr7C3, Cr4C, and Mo2C have been determined in steels containing up to 5 per cent chromium, I per cent molybdenum and 0.60 per cent carbon. The experimental steels were made in small high-frequency furnaces from Armco ingot iron, low-carbon ferrochromium and calcium molybdate and were poured into 2-in. ingots, which were forged to I-in. round bars. Sections of the bars were heated to the carbide-solution temperature and cooled rapidly to induce austenite transformation at relatively low temperatures. The steels were subject to some segregation, therefore comparatively high temperatures were necessary to dissolve all of the carbides. The microstructure of the quenched specimens was examined to verify the belief that the carbides had been dissolved, and also to determine the nature of the nonmartensitic structure of incompletely hardened steels. Ferrite and pseudo-martensite were present in some of the specimens, but all specimens were quenched at such a rate that pearlite was not formed, in order to ensure the formation of the carbides at temperatures lower than about 500°C. It had been found previously1 that in chromium steels the chromium carbide could be produced by transformation of austenite in the pearlite range above 500°C., and, in order to start the tempering treatment with the carbide present as cementite, the absence of pearlite was considered to be essential. The specimens were tempered for 64 hr. to permit the formation of the stable carbide. After tempering, the specimens were submitted to microscopic and X-ray examination. The carbides were separated either electrolytically in a 5 per cent HCl electrolyte or with an acidified copper-potassium chloride solution. The crystal structure of the carbide phases was determined by the Debye-Scherrer type of X-ray patterns. The X-ray patterns obtained from specimens near the boundaries between two types of carbides were generally weak and diffuse as compared with the other patterns. For this reason, and because the more soluble components may be masked, the boundaries between the phases could not be determined precisely. However, the X-ray analysis of electrolytically separated carbides has given consistently reproducible results

Jan 1, 1943

By David R. Mitchell

The mineral pyrite (or marcasite) occurs in coal beds as balls, lenses, veinlets and bands. Several million tons are wasted annually on the refuse dumps from coal mining and coal-preparation activities. Sporadic attempts have been made in the United States to recover this pyrite for manufacture of sulphuric acid but only a few plants have succeeded in recovering it on a commercial scale. Several chemical companies in the East became concerned about supplies of pyrite early in 1943, but by late summer of that year the situation had eased. If for no other reason than national security and self-sufficiency during wartime, methods of recovering pyrite from coal-mine refuse should be worked out and made available to coal-mine operators who are potential producers of pyrite. Eastern sulphuric-acid plants are particularly likely to have their sources of raw material blocked by war conditions, so that special studies to determine where supplies of pyrite can be obtained for these plants from inland sources are desirable. Davis's1 summarization of conditions during World War I gives the following facts: During those years, the shortage of pyrite became acute. Shipments of hand-picked pyrite were made from a number of coal mines in Illinois, Indiana, western Kentucky, Ohio and Pennsylvania. A mechanical concentrating plant for sepa- rating pyrite from picking-table refuse was built at Danville, Ill., and operated for several years, and a small pyrite-concen-trating plant treating washery refuse near Gillespie, Ill., operated for several months in 1918. The Consolidation Coal Co. of Fairmont, W. Va., constructed and operated a sulphuric-acid plant using pyrite recovered from coal-mine refuse. The U. S. Bureau of Mines during 1917-1919 made a comprehensive survey of pyrite-production possibilities from coal mines and estimated that there was a potential yearly production of 435.000 tons from Ohio and Pennsylvania and 928,000 tons from Kansas, Missouri, Iowa, Illinois, and Indiana mines. This estimate included only mines that could produce one per cent or more of their coal production as pyrite containing a minimum of 40 per cent sulphur. PyRite Production According to the Minerals Yearbook,2 approximately 660,000 long tons of pyrite was produced in the United States in 1941, with an average sulphur content of 42 per cent. The average value f.o.b. mines was $3.09 per long ton. Spanish pyrite, 48 per cent sulphur minimum, was quoted at 12 cents a unit c.i.f. U. S. ports, equal to $5.76 a ton for shipments of minimum sulphur content. Most of the pyrite produced in the United States is obtained as a by-product in the dressing of copper and zinc ores. Metal mines in the East making pyrite concentrate for the market or use in company-operated sulphuric-acid plants

Jan 1, 1944

By C. M. Romanowitz, H. A. Sawin

PLACER dredging as we know it today, especially gold dredging, is an industry about 40 years old, dating from the beginning of this century, when a few mining men in California saw the possibilities in adapting earlier dredging methods to California placer fields in and immediately adjacent to streams. At first it was thought that dredges must be operated in existing stream beds, but experience soon pointed the way to dredging alluvial deposits of old stream beds, operating on landlocked dredging ponds. Within the first five or six years of modern dredging, experience was gained so rapidly that dredges to dig 60 ft. below water level were designed and built. This depth was believed by many operators to be the maximum at which successful dredging could be carried on. Alluvial deposits of gold, suitable for dredging, were readily handled by equipment available and developed early in the industry's history. Much of the gravel was easily dug and if deposits were cemented, contained large boulders, or for some other reason could not be handled by a dredge, the ground was abandoned in favor of other deposits that could be handled easily. Many failures, adversely affecting the dredging industry, resulted from attempts at that time to extend the scope of placer dredging with equipment not suited to the formation being dredged. Dredging ground suited to early equipment was exhausted eventually, but many supposedly undredgeable alluvial fields containing gold in commercial quantities were found and became known to dredgemen. Improved equipment was needed to work deposits known to exist at great depths or associated with unusual obstructions. Operating companies looked to dredge manufacturers and metallurgists, particularly manganese-steel foundries, for improved designs and materials. Experience developed in California has spread throughout the world, and dredges of improved types have been adapted to the mining of platinum and tin as well as gold. Space will not permit a description of all the improvements in dredging since the early days, but a few of the recent developments are worthy of note, because they make possible the dredging of placer deposits of great depth, those having hard, irregular bedrock or containing large boulders in great quantities, and compacted or cemented gravel deposits. DEEP DREDGING At Hammonton, Calif., Yuba Consolidated Gold Fields has, within the past two years, built its dredge No. 20. The company has operated continuously in that field since 1904, digging successively at maximum depths of 60 ft., 80 ft., 112 ft., and now 124 ft. below water level. The first dredges were equipped with buckets of 6 and 7 1/2-cu. ft. capacity; six dredges operating in the field today have 18-cu. ft. buckets, digging now 65 to 124 ft. below water level. Some ground near Hammonton has been dug for the third time, owing to the devel-

Jan 1, 1941

By O. B. Hopkins

The reports for the years 1942 and 1943 were written in 1943 and 1944, respectively, and were summarized at the meetings of the Institute in February 1941 and February 1944, but were held in manuscript form until released for publication in 1945. 1942 During the year 1942, developments in the Peruvian oil industry continued to be subject to repercussions from the swelling war effort, which steadily diverted more of the normal supply of men and materials into war channels, and necessitated the rerouting of supply lines. The result in Peru was an increasing demand for crude oil and products. The production of petroleum in Peru in 1942 was 13,626,259 bbl., as compared with 11,935,584 bbl. in 1941—an increase of 1,690,675 bbl., or approximately 14 per cent. The largest increase, amounting to over 61 per cent, was from the Lobitos fields, but this increase was caused largely by the subnormal production in 1941. International Petroleum Company's production in the La Brea y Parinas field increased 727,111 bbl., or 7 per cent, whereas the Peruvian Government's production in the small Zorritos field declined 10,380 bbl., or approximately 20 per cent. The final production figures for the Ganso Azul field at Agua Caliente were not available for 1942 at the end of the year, but the production was believed to have increased approximately 80 per cent from 1941, or from 13,750 to approximately 25,000 barrels. Development and Exploration Exploration in Peru in 1942 was very limited and confined to areas adjacent to the older producing fields, and the efforts there were largely expended in the extension and development of the producing areas. This situation resulted partly from the shortage of transportation and drilling equipment, and also from the strong demand for increased production of oil. . International Petroleum Co. completed 69 wells during the year, including seven exploratory wells, three of which added moderate extensions to the proven areas. Sixty of the completions were oil wells and nine were dry holes. Lobitos Oilfields, at Lobitos and Restin, is understood to have concentrated its drilling effort on development rather than on exploration. The Peruvian Government operating at Zorritos confined its drilling to the development of the small producing areas previously found. During the year it announced plans to drill three exploratory wells in the Pirin area of southern Peru (see map on p. 638). It was reported that the Government had made a survey of the Sechura area (representing the southern part of the Northern National Reserve as shown on the map), but no work under this arrangement was announced. The Cia. Ganso Azul, at Agua Caliente, completed its No. 6 well as a producer on March 27, and during the year it completed the installation of a 400-bbl. topping plant.

Jan 1, 1945

By David R. Mitchell

The mineral pyrite (or marcasite) occurs in coal beds as balls, lenses, veinlets and bands. Several million tons are wasted annually on the refuse dumps from coal mining and coal-preparation activities. Sporadic attempts have been made in the United States to recover this pyrite for manufacture of sulphuric acid but only a few plants have succeeded in recovering it on a commercial scale. Several chemical companies in the East became concerned about supplies of pyrite early in 1943, but by late summer of that year the situation had eased. If for no other reason than national security and self-sufficiency during wartime, methods of recovering pyrite from coal-mine refuse should be worked out and made available to coal-mine operators who are potential producers of pyrite. Eastern sulphuric-acid plants are particularly likely to have their sources of raw material blocked by war conditions, so that special studies to determine where supplies of pyrite can be obtained for these plants from inland sources are desirable. Davis's1 summarization of conditions during World War I gives the following facts: During those years, the shortage of pyrite became acute. Shipments of hand-picked pyrite were made from a number of coal mines in Illinois, Indiana, western Kentucky, Ohio and Pennsylvania. A mechanical concentrating plant for sepa- rating pyrite from picking-table refuse was built at Danville, Ill., and operated for several years, and a small pyrite-concen-trating plant treating washery refuse near Gillespie, Ill., operated for several months in 1918. The Consolidation Coal Co. of Fairmont, W. Va., constructed and operated a sulphuric-acid plant using pyrite recovered from coal-mine refuse. The U. S. Bureau of Mines during 1917-1919 made a comprehensive survey of pyrite-production possibilities from coal mines and estimated that there was a potential yearly production of 435.000 tons from Ohio and Pennsylvania and 928,000 tons from Kansas, Missouri, Iowa, Illinois, and Indiana mines. This estimate included only mines that could produce one per cent or more of their coal production as pyrite containing a minimum of 40 per cent sulphur. PyRite Production According to the Minerals Yearbook,2 approximately 660,000 long tons of pyrite was produced in the United States in 1941, with an average sulphur content of 42 per cent. The average value f.o.b. mines was $3.09 per long ton. Spanish pyrite, 48 per cent sulphur minimum, was quoted at 12 cents a unit c.i.f. U. S. ports, equal to $5.76 a ton for shipments of minimum sulphur content. Most of the pyrite produced in the United States is obtained as a by-product in the dressing of copper and zinc ores. Metal mines in the East making pyrite concentrate for the market or use in company-operated sulphuric-acid plants

Jan 1, 1944

By Paul H. Price, John P. Nolting

The history of the salt industry in West Virginia dates back nearly two hundred years; howTever, the history of salt as an important raw material for the chemical industry is much more recent. The earliest record of West Virginia salt was in 1753, when a raiding party of Shawnee Indians attacked frontier settlements in Virginia taking captive a number of the pioneers. One of these, who later escaped and returned to her friends, described how the Indians camped at a salt spring on the banks of the Kanawha River and evaporated the water to obtain a supply of salt to take back to Ohio with them. Settlement of the Kanawha Valley began in 1774, that same year the Battle of Point Pleasant ended the Indian's power in the Ohio Valley; and settlement of the Kanawha Valley progressed rapidly with a consequent increase in the importance of the Kanawha Licks as a source of salt. In those days the evaporation of the brine was a family matter for which the family wash-kettle was commandeered. In 1797, Elisha Brooks erected the first salt furnace in the Kanawha Valley. It consisted of two dozen small kettles set in a double row, with a flue beneath, a chimney at one end, and a fire bed at the other. He obtained his brine at a depth of 20 to 30 ft by sinking hollow logs, called "gums" into the salt lick and dipping the brine with a bucket. His production was about 150 lb a day and sold for 8 to 10 cents a pound. In 1806, the Ruffner brothers, David and Joseph, prospected for and drilled the first well in America using a spring pole and steel chisel bit. After several failures they succeeded, in 1808, in drilling to a total depth of 59 ft where they secured a good flow of strong brine. Most standard drilling tools, jars, casing, and practically all the basic oil well drilling machinery now in use, were developed in the drilling of salt wells. To evaporate this brine, the brothers built a wood-burning furnace similar to that of Brooks but with a better arrangement and with more and larger kettles. When production was started they reduced the price of salt to 4 cents a pound. By 1817, there were some 30 salt furnaces in the Kanawha area. It was in this year that bituminous coal first was used as an industrial fuel. David Ruffner again pioneered the way by converting his furnace for the consumption of coal. This year also brought about the formation of the first trust which controlled production and set a price of 1 cent a pound for the salt.

Jan 1, 1950

By David R. Mitchell

THE mineral pyrite (or marcasite) occurs in coal beds as balls, lenses, veinlets and bands. Several million tons are wasted annually on the refuse dumps from coal mining and coal-preparation activities. Sporadic attempts have been made in the United States to recover this pyrite for manufacture of sulphuric acid but only a few plants have succeeded in recovering it on a commercial scale. Several chemical companies in the East became concerned about supplies of pyrite early in 1943, but by late summer of that year the situation had eased. If for no other reason than national security and self-sufficiency during war-time, methods of recovering pyrite from coal-mine refuse should be worked out and made available to coal-mine operators who are potential producers of pyrite. Eastern sulphuric-acid plants are particularly likely to have their sources of raw material blocked by war conditions, so that special studies to determine where supplies of pyrite can be obtained for these plants from inland sources are desirable. Davis's1 summarization of conditions during World War I gives the following facts: During those years, the shortage of pyrite became acute. Shipments of hand-picked pyrite were made from a number of coal mines in Illinois, Indiana, western Kentucky, Ohio and Pennsylvania. A mechanical concentrating plant for separating pyrite from picking-table refuse was built at Danville, Ill., and operated for several years, and a small pyrite-concentrating plant treating washery refuse near Gillespie, Ill., operated for several months in 1918. The Consolidation Coal Co. of Fairmont, W. Va., constructed and operated a sulphuric-acid plant using pyrite recovered from coal-mine refuse. The U. S. Bureau of Mines during 1917-1919 made a comprehensive survey of pyrite-production possibilities from coal mines and estimated that there was a potential yearly production of 435,000 tons from Ohio and Pennsylvania and 928,000 tons from Kansas, Missouri, Iowa, Illinois, and Indiana mines. This estimate included only mines that could produce one per cent or more of their coal production as pyrite containing a minimum of 40 per cent sulphur. PYRITE PRODUCTION According to the Minerals Yearbook,2 approximately 660,000 long tons of pyrite was produced in the United States in 1941, with an average sulphur content of 42 per cent. The average value f.o.b. mines was $3.09 per long ton. Spanish pyrite, 48 per cent sulphur minimum, was quoted at 12 cents a unit c.i.f. U. S. ports, equal to $5.76 a ton for shipments of minimum sulphur content. Most of the pyrite produced in the United States is obtained as a by-product in the dressing of copper and zinc ores. Metal mines in the East making pyrite concentrate for the market or use in company-operated sulphuric-acid plants

Jan 1, 1944

By Walter Crafts, C. M. Offenhauer

In a previous study of the carbide phase of chromium steels, it was shown that chromium carbide (Cr7C3) is 2 more stable carbide than cementite (Fe3C) at tempering temperatures above about 500°C. in quenched steels containing from about I to 7.5 per cent chromium. Below this temperature the carbide phase was found to consist of cementite in all of the steels examined. In the present investigation it was found that a similar change in the carbide phase takes place in molybdenum and in chromium-molybdenum steels at approximately the same tempering temperatures. The approximate ranges of occurrence of the alloy carbides Cr7C3, Cr4C, and Mo2C have been determined in steels containing up to 5 per cent chromium, I per cent molybdenum and 0.60 per cent carbon. The experimental steels were made in small high-frequency furnaces from Armco ingot iron, low-carbon ferrochromium and calcium molybdate and were poured into 2-in. ingots, which were forged to I-in. round bars. Sections of the bars were heated to the carbide-solution temperature and cooled rapidly to induce austenite transformation at relatively low temperatures. The steels were subject to some segregation, therefore comparatively high temperatures were necessary to dissolve all of the carbides. The microstructure of the quenched specimens was examined to verify the belief that the carbides had been dissolved, and also to determine the nature of the nonmartensitic structure of incompletely hardened steels. Ferrite and pseudo-martensite were present in some of the specimens, but all specimens were quenched at such a rate that pearlite was not formed, in order to ensure the formation of the carbides at temperatures lower than about 500°C. It had been found previously1 that in chromium steels the chromium carbide could be produced by transformation of austenite in the pearlite range above 500°C., and, in order to start the tempering treatment with the carbide present as cementite, the absence of pearlite was considered to be essential. The specimens were tempered for 64 hr. to permit the formation of the stable carbide. After tempering, the specimens were submitted to microscopic and X-ray examination. The carbides were separated either electrolytically in a 5 per cent HCl electrolyte or with an acidified copper-potassium chloride solution. The crystal structure of the carbide phases was determined by the Debye-Scherrer type of X-ray patterns. The X-ray patterns obtained from specimens near the boundaries between two types of carbides were generally weak and diffuse as compared with the other patterns. For this reason, and because the more soluble components may be masked, the boundaries between the phases could not be determined precisely. However, the X-ray analysis of electrolytically separated carbides has given consistently reproducible results

Jan 1, 1943