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By Donald Cummings

CERTAIN dusts are dangerous when inhaled, but most hazardous of all dusts are quartz or other forms of pure crystalline silica. The inhalation of dusts containing silica in combination with other elements gives rise to changes in the lung which differ from those produced by pure silica. As a generality, silicates are less dangerous than pure crystalline silica and vary greatly among themselves in harmfulness. Repeated analyses have shown that approximately 70 per cent of the total number of particles involved in any dust-producing operation are below 1 to 2 microns in diameter. (A micron is. approximately 1/25,000 in.) Similar studies of dusts recovered from silicotic lungs post mortem have demonstrated essentially the same size frequency distribu-tion, except that the upper limit of size retained in the air sacs is approxi-mately 10 microns. Experiments carried on by Gardner and the author have further demonstrated that greater changes were produced by a fixed weight of very fine quartz particles (2 to 3 microns and smaller) than by the same weight of slightly larger particles (8 to 10 microns). Any attempt to control a dust hazard should therefore be directed toward the removal from the working atmosphere of particles less than 10 microns in size, and particularly those below 3 microns. All industrial hygienists agree on this matter, but there remains considerable dispute as to the lower limit of particle size capable of causing injury. It has been gen-erally conceded, however, that particles of harmful dusts smaller than ¼ to ½ micron are not essentially concerned in the development of pulmonary fibrosis. This opinion is partly substantiated by the existence of large numbers of these small particles in practically all atmospheres that are, not associated with any known hazard. Such particles are so small that they have very little mass, fail to settle even in quiet air, and probably are not easily retained in the lung. Until further research proves that they are involved in the dangers provoked by the inhalation of certain dusts, engineers will generally agree that it is better to dis-regard them.

Jan 1, 1935

By Donald E. Cummings

Certain dusts are dangerous when inhaled, but most hazardous of all dusts are quartz or other forms of pure crystalline silica. The inhalation of dusts containing silica in combination with other elements gives rise to changes in the lung which differ from those produced by pure silica. As a generality, silicates are less dangerous than pure crystalline silica and vary greatly among themselves in harmfulness. Repeated analyses have shown that approximately 70 per cent of the total number of particles involved in any dust-producing operation are below 1 to 2 microns in diameter. (A micron is approximately 1/25,000 in.) Similar studies of dusts recovered from silicotic lungs post mortem have demonstrated essentially the same size frequency distribution, except that the upper limit of size retained in the air sacs is approximately 10 microns. Experiments carried on by Gardner and the author have further demonstrated that greater changes were produced by a fixed weight of very fine quartz particles (2 to 3 microns and smaller) than by the same weight of slightly larger particles (8 to 10 microns). Any attempt to control a dust hazard should therefore be directed toward the removal from the working atmosphere of particles less than 10 microns in size, and particularly those below 3 microns. All industrial hygienists agree on this matter, but there remains considerable dispute as to the lower limit of particle size capable of causing injury. It has been generally conceded, however, that particles of harmful dusts smaller than 1/4 to 1/2, micron are not essentially concerned in the development of pulmonary fibrosis. This opinion is partly substantiated by the existence of large numbers of these small particles in practically all atmospheres that are not associated with any known hazard. Such particles are so small that they have very little mass, fail to settle even in quiet air, and probably are not easily retained in the lung. Until further research proves that they are involved in the dangers provoked by the inhalation of certain dusts, engineers will generally agree that it is better to disregard them.

Jan 1, 1937

By Arthur T. Allen

THE Kingsport formation, a part of the Knox dolomite of Ordovician age, is composed of 538 ft of dolomitc and limestone. Numerous bands, layers and nodules of chert, arenaceous and shale zones are present. The characteristics displayed by these features have been useful in mapping, prospecting and mining. Perhaps a better understanding of the origin of these zones will increase their usefulness. Introduction The presence of numerous bands, nodules, and irregular bodies of chert within the Kingsport formation in the Mascot locality has long been recognized. Oder and Miller1 mention the general characteristics, but do not deal with the chert occurrences in detail. When the occurrence of chert is studied in fresh exposures underground, a variety of characteristics is noted which has been useful in correlation and in detailing the sub-surface stratigraphy. Although the writer has no desire to enter into a controversy over the origin of chert, many observations have been made of its local characterigtics. A detailed stratigraphic section is included which shows the position of the individual horizons discussed in the following paragraphs. The term "chertification" has been adopted from Fowler and Lyden2 for use here. It refers to the replacement of lime- stone by introduced silicic acid. The writer uses it to refer to the occurrencc of introduced or original chert in limestone and dolomite. In this writing "syngenetic chert" refers to chert which has been deposited contemporaneously with the enclosing limestone or dolomite. Also, it is considered to include interstitial silica shown by chemical analysis and insoluble residues. The term "epigenetic" is applied to all chert which has been introduced after consolidation of the rocks in which it occurs, regardless of the nature of the depositing solutions. Syngenetic Chert It is the belief of the author that a large percentage of the chert found in the Kingsport formation is syngenetic. The widespread occurrence of similar nodules and bands of chert in the same horizon far from one another and far from areas of deformation or alteration of the enclosing rocks is difficult to explain by infiltration of the silica after compaction of the enclosing rocks. When chert of this type does occur near zones of movement it is likely to be involved in faulting and brecciation which indicates that it was deposited prior to deformation. Older Epigenetic Chert There are several occurrences of nodules in the Kingsport which seem to be epigenetic as pointed out in the following examples: A cherty zone occurs 26 ft above the o bed (Fig =). This is not always present but is found in the greater part of mine work-

Jan 1, 1949

By Arthur T. Allen

THE Kingsport formation, a part of the Knox dolomite of Ordovician age, is composed of 538 ft of dolomitc and limestone. Numerous bands, layers and nodules of chert, arenaceous and shale zones are present. The characteristics displayed by these features have been useful in mapping, prospecting and mining. Perhaps a better understanding of the origin of these zones will increase their usefulness. Introduction The presence of numerous bands, nodules, and irregular bodies of chert within the Kingsport formation in the Mascot locality has long been recognized. Oder and Miller1 mention the general characteristics, but do not deal with the chert occurrences in detail. When the occurrence of chert is studied in fresh exposures underground, a variety of characteristics is noted which has been useful in correlation and in detailing the sub-surface stratigraphy. Although the writer has no desire to enter into a controversy over the origin of chert, many observations have been made of its local characterigtics. A detailed stratigraphic section is included which shows the position of the individual horizons discussed in the following paragraphs. The term "chertification" has been adopted from Fowler and Lyden2 for use here. It refers to the replacement of lime- stone by introduced silicic acid. The writer uses it to refer to the occurrencc of introduced or original chert in limestone and dolomite. In this writing "syngenetic chert" refers to chert which has been deposited contemporaneously with the enclosing limestone or dolomite. Also, it is considered to include interstitial silica shown by chemical analysis and insoluble residues. The term "epigenetic" is applied to all chert which has been introduced after consolidation of the rocks in which it occurs, regardless of the nature of the depositing solutions. Syngenetic Chert It is the belief of the author that a large percentage of the chert found in the Kingsport formation is syngenetic. The widespread occurrence of similar nodules and bands of chert in the same horizon far from one another and far from areas of deformation or alteration of the enclosing rocks is difficult to explain by infiltration of the silica after compaction of the enclosing rocks. When chert of this type does occur near zones of movement it is likely to be involved in faulting and brecciation which indicates that it was deposited prior to deformation. Older Epigenetic Chert There are several occurrences of nodules in the Kingsport which seem to be epigenetic as pointed out in the following examples: A cherty zone occurs 26 ft above the o bed (Fig =). This is not always present but is found in the greater part of mine work-

Jan 1, 1949

By M. F. McCarty, R. S. Olson

New organic flocculants of high-molecular weight are replacing lime, glue, and starch in liquid-solid separation. Of these synthetic materials, poly-acrylamides are outstanding. Polyacrylamides form a class of compounds varying widely in composition and activity. Separan 2610, one of the first of these flocculants' released to the mining industry in 1954, is described' as a high-molecular weight polymer of acrylamide with or without a copolymer material and with some replacement of amide by carboxylic groups. MECHANISM OF FLOCCULATION In practice, flocculation makes solids settle faster and filter better. But two opposing factors control it. The random motion that causes particles to collide favors Van der Waals' forces, which hold the particles together. The effect of zeta potential opposes this contact, and particles are mutually repelled. Flocculation can be achieved by reducing the magnitude of the zeta potential; this is the mechanism of flocculation by lime addition. The way in which polyacrylamides accomplish flocculation is not fully understood, but the action is undoubtedly comp1ex and probably varies considerably depending on the system. To begin with, the active groups of these compounds have an extremely high affinity for solid surfaces, probably by hydrogen bonding." Initially some active groups of the molecule attach themselves to the solids with a large portion of the molecule extending into the solution. Two particles can become tied together by long flocculant molecules in the following ways—by bonding between the active groups of two flocculant molecules on different particles, or by an extended molecule from one particle attaching itself directly to the surface of the other particles." These flocculant bridges prevent the particles from moving apart through random motion, but when such motion moves them together other active groups on the flocculant bridge bond to the solids, holding them in the closer position. This process is repeated until the particles are close together. Although bridging is probably a major flocculation mechanism, it is not the only phenomenon involved. Relatively neutral acrylamide flocculants reduce the magnitude of the zeta potential by increasing the viscosity of solution in the immediate vicinity of the solid surface which contains the mobile counter ions of the double layer. In other words, it moves the shear surface which bounds the zeta potential out into the solution containing counter ions which tend to neutralize the zeta potential. This effect is probably more pronounced during the initial adsorption period, before the flocculant molecules are pulled close to the solid. In some cases the slight charge of the polyacry-lamide molecule tends to neutralize a zeta potential. However, this is not a primary flocculation mechanism, as evidenced by the fact that the polyacrylamides will flocculate solids with either positive or negative zeta potential. Adsorption of polyacrylamide flocculants by a solid is substantially an irreversible reaction. Since the flocculant molecule is attached to the particle surface by many active groups of high bonding strength, desorption would require the simultaneous breaking of many bonds—an unlikely occurrence. UNIQUE PROPERTIES The irreversible adsorption of certain polyacrylamides, the flocculant's high affinity for solid surfaces and its rapid adsorption make it effective, but these unique properties require special techniques to achieve maximum flocculation. If flocculants of this type are added to a pulp as a relatively concentrated solution, the solids in the

Jan 1, 1960

By L. D. Tracy

On Aug. 5 and 6,1918, and Mar. 26, 1919, the writer made an investigation of the mine-water neutralizing plant at the Calumet mine of the H. C. Frick Coke Co. The object of this plant is to develop a process of treating the water pumped from the mines so that it may be rendered suitable for use at the power plants of the mines and also at the coke ovens; at the same time, eventually producing a byproduct which will have enough commercial value to provide a sufficient revenue to place the plant on a self-sustaining basis. The Calumet mine is situated in Mt. Pleasant Township, Westmoreland County, Pa., on a branch of the southwest branch of the Pittsburgh Division of the Pennsylvania Railroad. It is about 6 mi. (9 km.) southeast of Greensburg, the county seat of Westmoreland County. The coal, which is the Pittsburg or Connellsville seam, lies at a depth of about 200 ft. (60 m.) and is brought to the surface by means of a shaft. The output of the mine averages 200,000 tons of coal annually, all of which is made into coke, either at the ovens, at the mine, or at byproduct ovens. There are 260 coke ovens at the mine. The continued development of the coal fields of Pennsylvania and the increased use of electric power in the operation of the mines has brought the problem of an increased water supply for the plants to the attention of the coal operators. This is especially true in the Connellsville coking region, where large quantities of water are used in quenching the coke at the ovens. Many of the streams receive the drainage from the mines; and as this water is highly acid and contains sulfur in various forms, some method of treatment is necessary to render it suitable for use at the plants of the mines. With this end in view, the H. C. Prick Coke Co., about 4 years ago, installed at its Calumet mine a plant for experimental purposes, in an endeavor to develop a process that would provide a maximum amount of suitable water at a minimum cost. From a purely technical point of view, the result of these experiments has been encouraging. The company is now endeavoring to place the plant on a commercial basis.

Jan 1, 1922

By C. J. Osborn

In oral discussion at the Columbus midyear meeting, September 26, 1949, these pertinent questions were asked: Was a satisfactory separation of metal and matte obtained? The matte was quite fluid and in most cases the separation was satisfactory. Were the mattes chlorinated after aging? The mattes were stored in sealed glass mason jars, and chlorina-tion experiments made after standing for several weeks gave satisfactory results. Was ferric chloride volatilized? Most of the iron content of the matte was converted to ferric chloride. However, because of the low chlorination temperatures used (150" to 250°C) the major part of the ferric chloride remained with the residue. Undoubtedly, some ferrous chloride was also formed, because of the reducing conditions within the reaction vessel, but no effort was made to separate it from the ferric chloride. Could the reaction be stopped before making metallic iron? No attempt was ever made to stop the reaction before making metallic iron. Generally, 20 to 60 pct of the iron in the charge was obtained as metallic iron which could be readily separated from the matte. In certain cases, metallic iron was dispersed through the matte in the form of globules, which could be removed by magnetic separation. Could other sulphides, i.e., calcium sulphide or sodium sulphide be used in place of iron sulphide? No other sulphides were investigated. It was felt that titanates of calcium and sodium would be formed should these sulphides be used to replace the pyrite. What were the sulphur volatilization losses during matte smelting? In the course of this laboratory investigation, a rather wide variety of variables was introduced from highly oxidizing to reducing conditions and various ratios of pyrite, rutile, and coke. These and other factors all have a definite bearing on the sulphur losses. In general, the higher the sulphur in the charge the higher were the sulphur losses and the percentage of titanium in the matte decreased. With sulphur additions more nearly the theoretical amount, the sulphur losses averaged approximately 10 to 15 pct. With a higher percentage of sulphur on the charges, the losses were in the order of 15 to 30 pct.

Jan 1, 1951

By W. E. Wickerham

THE Magnetic Storm Monitor is an instrument that continuously records variations in the earth's total magnetic field at a fixed location. It is intended for use in conjunction with airborne magnetometer surveys. There are stormy periods when changes in the earth's magnetic field are so violent that data obtained with airborne equipment would be of little value. The Monitor provides this information so that flights may be cancelled or terminated, thus eliminating useless flying. Moreover, when some unpredictable change in the earth's field occurs during an airborne survey, the Monitor record, showing a similar event, may serve to salvage the data. The utility of a base instrument is determined largely by its physical dimensions, power requirements, stability, and reliability. This instrument is small enough to be transported in any powered vehicle. It will operate from either a 110 v, 60 cycle power line or from an inverter powered by an automobile battery. The development of an electronic feedback circuit that measures the magnetic field strength and a fabricated buckout magnet having essentially zero temperature has contributed to instrument stability and reliability. A tripod supporting the magnetometer head, a chassis housing all electronic components, and an Esterline Angus Recorder comprise the equipment, shown in Fig. 1. The vibrator-type inverter shown is used when a 110 v, 60 cycle power line is inaccessible. Approxi- mately 60 w are required to operate the instrument and the circuit is insensitive to reasonable power line voltage changes or transients. The head unit contains a fluxgate-type magnetometer element and a special magnet mounted on a ceramic structure. Since this magnet is used to buck out most of the earth's field, adjustments are provided for properly positioning the magnet with respect to the element. This assembly is mounted in such a way that the element can be oriented into the total field. Fluxgate Element: The heart of the Storm Monitor is a fluxgate-type magnetometer element. The ability of this unit to detect changes in magnetic fields has been covered at length in the literature.1, 2 For this discussion it will suffice to say that the Gulf

Jan 1, 1956

JUST as I have told you that it is impossible to give an exact rule for the bell scale, so I say the same concerning the clappers. Yet, if one wishes the bell to sound well, it is necessary that it have a proportioned blow; for if it is struck with a clapper that is lighter than it should be, it will not give out all the sound that it contains, and if it is struck with a heavier one than it can support, it is forced and the sound is made crude and harsh, in addition to the danger of breaking the bell. Therefore-the clappers must be made so that they bear a certain proportion to the bell, and in order not to proceed by chance, I have diligently tried to find the method as well as possible. I have found that experienced masters [99] have given to bells weighing ten pounds a clapper of one and a half pounds [and, to larger ones, clappers as tabulated on the next page].* Larger numbers than these I have not found because, in truth, few of the extraordinarily large ones are made in our regions. In my opinion, the masters should not be limited to these rules for the differences in clappers but should proceed according to the kind of bell, using a certain discretion for it is not possible to give a definite rule.

Jan 1, 1942

Discussion of the paper of K. Huessener, (Trans., vol. 53, pp. 402 to 4333, and of the papers of Linn Bradley, H. D. EGbert and W. W. Strong, pp. 303, 319. R. J. WysoR, So. Bethlehem, Pa. (communication to the Secretary*). —At our plant (Bethlehem Steel Co.), we have had several Bradshaw burners under course of construction and erection for some time, but up to the present we have not had opportunity to put them in service. I regret that I can not take part in the discussion with some actual results from these burners. Mr. Huessener properly emphasizes the importance of obtaining the highest combustion temperature practicable in boiler practice, which demands a near approach to perfect combustion conditions. The ideal burner is the one which, while meeting the various mechanical requirements, fulfills the above condition under a wide range of gas pressure. The question as to the relative value of hot raw gas and cold washed gas for boiler use is a very interesting one. I think that in the past the importance of low temperature of washed gas sometimes has been overemphasized. Mr. Huessener has pointed out that so far as temperature is concerned, no advantage accrues in washing gas below 100" F. In many plants, there is a notable operating economy in using furnace cooling water, which is appreciably warmer than the supply water. However, in a given type of washer, other conditions being constant, the lower the exit gas temperature the lower will be the dust content; this is equivalent to saying that the more washing water is used, other conditions being constant, the lower will be the dust content of the exit gas. For each type of washer there is a certain desired average temperature difference between inlet water and exit gas, concomitant with known average dust and moisture contents, and with economical operation. With the present tendency toward smaller stove checkers, it is generally agreed that gas for stove use should be cleaned to a dust content of 0.20 grain or less. The method employed and extent of gas cleaning are clearly problems for individual furnace plants. As a general proposition, wet washing is decidedly more attractive for furnaces smelting soft, fine Lake ores than for those reducing chiefly hard, lumpy ores, such as the foreign and domestic magnetites. In the former case the average moisture content of the gas is probably 35 grains per cubic foot, the dust content is relatively high and the top temperature relatively low. In our plant, the ore mixtures consist almost exclusively of hard magnetites. The average dust content of the gas leaving the dust catcher will average only about 2 grains and the moisture about 12 grains per cubic foot, corresponding to saturation at about 83" F. The temperature is fully 100" F. higher

Jan 1, 1917

By John Van N. Dorr

Introduction.................... 212 The DoRR Classifier.........212 History................ 212 Description................... 215 Regulation of Products............. 216 Cost of Operation.............216 Power...........216 Capacity..............216 Uses.................217 The Dorr Thickener.............219 History...........292 Description.............. 221 Speed............ 222 Power......,....223 Repairs.............,... 223 Labor................. 224 Capacity................ 224 Density of Underflow............... 224 Uses.........,.......226 Continuous Counter-Current Decantation....... 227 Concentration..............227 Industrial Uses................228 Acid-Proof Thickeners.......... 228 The Dorr Tray Thickener........... 229 Description.................. 229 Capacity................. 231 The Dorr Agitator................. 232 History................... 232 Description................... 233 Speed.................... 234 Power.................... 234 Renewals................... 235 Efficiency................... 236 Selective Agitation................ 236 Conclusion................... 237

Jan 1, 1915

By Dr. Hermann Wedding

Albert Ludwig Serlo was born February 14, 1824, at Crossen-on-the-Oder. After completing his school-studies and his training as a mining official, he received in 1851 an appointment as Royal Manager of salt-works (Salinenfactor) and member of the Administratioll of Salines at Konigsborn, near Unna, Westphalia. The issue of new regulations for the training of higher State officials in the Department of Mining, Metallurgy and Salines, led him to pass in 1856 a special examination for the rank of Assessor, in consequence of which he was called to Berlin, to serve for a few months as an assistant in the Ministry of Commerce, which had charge of mining, etc. In the same year he became Bergmeister and member of the mining administration at Bochum, Westphalia, and in 1858 Oberbergrath and member of the provincial administration, called the Oberbergamt, having its headquarters located at Dortmund. In 1861 he was appointed Director and head of the newly-reorganized mining

Jan 1, 1900

By William P. Blake

Travelers in the desert regions of the southwestern portion of United States, especially along the valley of the Colorado of the West, can hardly fail to note that most of the rocky outcrope of the harder rocks have a uniform prevailing blackness of the surface, in strong contrast with the normal color of the interior of the rock when freshly broken. For example, the granitic or gneissic rocks of Pilot Knob, below Yuma, are blackened beyond easy recognition. So also rocks upon the lower Mojave in California are so thoroughly blackened, as if painted, that ordinary gneiss can scarcely be recognized without breaking it so as to show the interior color and structure. The discoloration is not confined to the rocky outcrops in place, but is found upon boulders and upon the loose rounded pebbles which strew the surface of the mesas along the Colorado river. These fragmentary rocks partake of the general blackening.

Jan 1, 1905

By John A. Hansuld

Molybdenum presents a series of baffling geo- chemical puzzles. It can exist in six different valence states, possessing three different coordination numbers. As a result, it combines with other elements to form a wide variety of negatively and positively charged ions and complexes whose exact chemical nature are relatively unknown. Its rather complex chemistry might be described as "ambidextrous, bi-sexual and polygamous". It is little wonder then that the geochemistry of molybdenum is relatively unknown, and compared to most common metals its geochemical behavior is somewhat unique. The behavior of a particular element or metal, such as molybdenum, in a given dispersion media is largely controlled by the stability relations among its various oxidation products. Recognition of these products and an understanding of their stability relations is therefore a prerequisite to a proper understanding of its observed behavior. Because most secondary dispersion media represent aqueous chemical systems, stability relations are best expressed as functions of Eh and pH.

Jan 12, 1966

By F. R. Conley, D. A. Shock

Solution Mining or In Situ Mining has received increasing attention in the past few years because the method offers many attractive possibilities in improving the environmental impact of mining as well as making feasible the extraction of deeper, low value mineral reserves. This paper will present a brief discussion of the state-of- the-art in total solution, slurry removal and leach mining. As a specific example of utilizing the method, the uranium deposits of South Texas are a type of deposit which have been considered as being amenable to in situ leach mining. The parameters required to ascertain the amenability of such a deposit for in situ leaching will be presented. The hydrological factors which influence the production of the soluble uranium solutions and their displacement will be discussed. Mathematical models for various well configurations have been made and graphic representation will be presented to illustrate various production methods and the resultant hydrological consequences.

Jan 1, 1974

By J. E. Dinger, Ross Gunn

Faraday's Law of magnetic induction states that the e.m.f. acting around a closed circuit is equal to the time rate of change of flux through that circuit. If the closed circuit is a conducting medium, there will flow an electric current which is propor¬tional to the conductivity of the material and the time rate of change of the flux. Electrical currents so induced in a con¬ducting material are often referred to as eddy currents. Eddy currents are thus induced into a conducting material by (1) a time rate of change of the magnetic field through the material, by (2) a relative motion of the conducting material and a magnetic field, or by (3) a combination of (1) and (2). Because the magnitude of the induced eddy currents is dependent upon the resistance of the equivalent conducting path, these currents offer a method of detecting electrical discontinuities in a

Jan 1, 1945

By Frank F. Aplan

In looking into the crystal-ball scene of minerals beneficiation for 1970 and beyond, an impartial observer becomes con- fused as to what has been done and what is possible in the way of improvements. The mining official must balance the burden which is being shouldered by the mineral industry for maintaining our environment in its pristine state on one hand, with the solid advancements made in technology and cost savings on the other hand. Then the official wonders if this is really the criterion for judging overall performance today. As a prospective engineer, Dave Bolles sees it this way: "Specialization has caused many engineers to subordinate everything to doing their job the cheapest and fastest way. In the future this won't be enough. The engineer in the mineral industry will be responsible not only for mining, concentrating and smelting, but also for the resultant wastes- the mine dumps, the tailing dams and the slag piles." (See Drift on page 63).

Jan 1, 1971

By W. Rostoker

INTRODUCTION THE process of diffusion alloying of mixed powders offers attractive possibilities both commercially and experimentally. It avoids the fabrication difficulties arising from high alloy contents. Indeed, the process is facilitated by larger alloy additions. The direct formation of the part or test piece and the opportunity to perform machining operations under more favorable conditions are of no small importance. However, it is necessary to make only brief mention of the interesting features. As yet there have been few attempts to study this process in detail and to carry it to completion, if such is possible. It was intended not only to measure the intermediate and optimum magnetic properties of sintered alloys but to use magnetic testing itself as a means of following the progress of alloying under various conditions. Having established that alloys could be successfully synthesized by this technique, the opportunity was taken to study the magnetic properties of several alloys of iron and silicon which had hitherto been too difficult to prepare in suitable test piece form, While avoiding some of the difficulties inherent in the fabrication of alloys by orthodox methods, the diffusion alloying process introduces a few of its own. The first of these is the evaluation of the approach to homogenization. In recent years some notable contributions have been made to this question, but considerable uncertainty remains in its definition and evaluation. This work has concerned itself with further study of this problem and it is hoped that more light has been shed on it, The second of these difficulties arises from the presence of porosity. It is inevitable that in the consolidation of a loose bulk of powder, there should remain some voids unless extremely high pressures are repeatedly applied. It was therefore of importance to investigate their effect on magnetic properties. Recently this effect has been studied and certain predictions made of its behavior. It is believed that the experimental results presented here provide a sound substantiation of the theoretical treatment. The attempt has been made to synthesize five alloys of the iron-silicon system and three each of the iron-nickel and iron-cobalt systems. A series of experiments was also conducted on some of these alloys to test their susceptibility to heat treatment. Some unfortunate experiences have provided opportunity to report data on the deleterious effects of nitrogen on magnetic properties when present as a contaminant in protective atmospheres. MATERIALS, PREPARATION OF SAMPLES AND TESTING The purest materials available were employed for this work. A specially purified,

Jan 1, 1948

By Oren C. Baptist, Eliot J. White

Samples of four reservoir sands having different degrees of water sensitivity were subjected to several laboratory tests to determine differences in capillary behavior attributable to clay-mineral effects. The degree of water sensitivity was estimated by the difference between gas and water permeability. Unsaturated pore volumes determined with mercury injection were comparable to irreducible water saturations determined with the semipermeable bar-rier method only for the non-sensitive sands that contained small amounts of non-swelling clay minerals. Irreducible saturations were independent of salinity of the water, which suggests that most residual water is adsorbed 0.7 a film over solid surfaces and that internal retention by clay minerals is relatively insignificant. The water-sensitive sands imbibed water to higher saturations than did non-sensitive sands, and this result is believed to be a combination of the effects of clay minerals and preferential wettability; however, the relative importance of each of these effects is riot determinable. Thus it is concluded that the semipermeable barrier method is the best of the laborafory methods used for estimating formntion water .saturations in the sands studied. INTRODUCTION This investigation is a continuation of studies of the role of clay minerals in petroleum production in the Rocky Mountain area. Previous work has shown large differences in gas and water permeability in numerous reservoir sands; these water-sensitivity effects observed in the laboratory have been correlated with well behavior in the field, and the degree of water sensitivity imparted to reservoirs by the various clay minerals has been determined.'.' The effect of interstitial clay minerals on formation water3 saturations is not so well known. It has been reported that formation water saturations probably are higher in clayey than clean sands,' but this effect has not been evaluated in the laboratory, and the relative effect of the various types of clay minerals on formation water saturation has not been determined. The clay-mineral groups of most importance to this study and to petroleum production in general are kaolinite, illite, and montmorillonite. The minute layers of montmorillonite are loosely bound to one another so that water enters between them, causing great expansion of the particles. Kaolinite and illite do not exhibit interlayer hydration, but they do immobilize considerable amounts of water owing to their large surface areas, which are of the order of 15 to 97 m2/gm of clay.5 The four Wyoming sands used in this study were selected to represent a wide range of water sensitivities. These sands, with the number of wells and fields from which the samples were obtained, are: Second Frontier, five wells in two fields; Newcastle, six wells in one field; Tensleep, two wells in two fields; and Lower Muddy, five wells in one field. EXPERIMENTAL METHODS AND PROCEDURES Water-displacement data were obtained by the semipermeable barrier method," using both fresh water and brines having either 16,500 ppm sodium chloride or calcium chloride. A displacement pressure of 35 psi was found to be sufficient to obtain the practical irreducible water or brine saturation (IWS, IBS) in most samples. Mercury-injection data were ob-tained with equipment and pro-cedures similar to those described by Purcell.7 Exceedingly high pressures are required to attain complete mercury saturation by this method; however, since saturations in most samples change very little with large pressure increases above 1,000 psia, the maximum pressure used was 1,400 psia. To facilitate comparison of mercury-injection and water-displacement results, it is convenient to express mercury-injection data in terms of unsaturated pore volume. The abbreviation, (100 - SHg)min, is used to denote the pore volume unsaturated by mercury at 1,400 psia injection pressure. Gas permeabilities, ki, were deter-mined by the method proposed by Klinkenberg.8 Methods of determining types and amounts of clay minerals by X-ray diffraction analyses, as well as methods of determining water permeability, have been described previously.' The imbibition characteristics of

Jan 1, 1958

By Shiro Ban-ya, John Chipman

Equilibrium in the reaction was investigated at temperatures of 1500°, 1550°, and 1600°C for sulfur concentrations up to 7.2 wt pct. Multisample crucibles contained the liquid alloys in a resistance-heated furnace using a technique especially designed for the study of more complex alloys to be reported separately. Modern free-energy data are used to correct the H2S:H2 ratio for dissociation of H2S and calculalion of the partial pressure of S2. Published data on the equilibrium are similarly corrected. Thermodynanzic treatment of the data employs the composition variable zs = nS/(nFe — nS) and the activity coefficient Gs = as/zs The data at 1500" and 1550°C are fitted by the equation log s = —2.30zs. Within the limits of experimental error the same coefficient is applicable to the data at higher temperatures. Equations are given for the free-energy change in Reaction [I] as well as for the solution of S, gas in the metal. The heat of solution of 1/2 s2 is -32.28 i2.5 kcal. Uncertainty in the free energy is very much smaller. For dilute solutions of interest in steelmaking, the activity coefficient of sulfur is unchanged from that listed in Basic Open Hearth Steel-making. DETERMINATIONS of the thermodynamic properties of sulfur in liquid iron by Morris and williams1 and by Sherman, Elvander, and chipman' provided a basis for control of sulfur in steelmaking processes. From the standpoint of understanding the chemistry of metal plus nonmetal in liquid solution they left several questions unanswered. The activity of sulfur in dilute solution at about 1600°C was well-established but temperature coefficients were uncertain, due at least in part to the use of the optical pyrometer and uncertainty regarding the effect of sulfur on emissivity. It appeared that deviation from Henry's law increased with increasing temperature, a most unusual behavior requiring either confirmation or disproof. These studies were based on experimental determination of equilibrium in the reaction: At high temperatures H2S is partially dissociated so that the gas mixture contains HS, S2, and S in addition to HS. At the time of the earlier studies the free energies of these constituents were unknown and it was therefore impossible to make adequate correction for dissociation. Observations on the effects of alloying elements by Morris and coworkers1, 3 and by Sherman and Chip-man4 enable us to assess the effects of alloying elements on the activity and to make corrections for incidental impurities in the binary liquid. These studies as well as a number of more recent investigations will be reviewed in detail after out own experimental results have been presented. It was our purpose in planning this study to avoid uncertainties regarding the emissivity of alloys and the errors of thermal diffusion which plagued some of the early attempts,5 by using a resistance furnace and thermocouple in preference to induction heating and optical pyrometer. Modern data on free energies of the gaseous species are to be applied to our data and to those of other investigators to obtain corrected values of K1 and of the activity coefficient and ultimately to relate the sulfur content of the bath to the equilibrium partial pressure of S,. Extension of the study to include ternary and complex solutions will be described in a later section. EXPERIMENTAL METHOD a) Preparation and Calibration of H2-H2s Gas Mixture. The source of hydrogen sulfide was a preparer mixture of 43 pct H2S, balance hydrogen, contained in a large aluminum cylinder. This was passed through anhydrone and through a microflowmeter. Hydrogen was passed through platinized asbestos, ascar-ite, and anhydrone, and through a capillary flowmeter. Argon was passed through copper wool at 500°C, then through ascarite, anhydrone, and a flowmeter. The flow rate of hydrogen was kept constant at 200 ml per min, to which an arbitrary amount of the hydrogen-hydrogen sulfide mixture was constantly added and then the prepared gas mixture was introduced into the reaction tube through a gas mixer. In certain experiments 200 ml per min of argon was added to the hydrogen-hydrogen sulfide gas mixture to increase the total flow rate of gas. The ratio of hydrogen-hydrogen sulfide in the inlet gas was checked for each run by chemical analysis. A sample of the gas taken from a bypass was bubbled through zinc and cadmium acetate solution (4 pct zinc acetate, 1 pct cadmium acetate, and 1 pct acetic acid) to remove hydrogen sulfide from the gas mixture, and the flow rate of the remaining hydrogen was measured by a soap bubble method to determine the volume of hydrogen. The amount of hydrogen sulfide absorbed in solution was determined by titration with iodine against sodium thiosulfate, with starch used as the indicator. The ratio of hydrogen sulfide to hydrogen in the inlet gas could be kept within ±2 pct in the range from 10-2 to 5 x 10"4 which corresponds to from 0.2 to 7.0 wt pct sulfur in liquid iron. b) Furnace Arrangement. Fig. 1 shows the furnace arrangement and the shape of the alumina crucible used in this experiment. A vertical-tube silicon carbide electric resistance furnace contained the reaction tube which consisted of two parts, the gas-tight

Jan 1, 1969