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By G. W. Healy

G. W. Healy (union Carbide Metals 0.)-The author's paper is a useful contribution to the store of maps of chemical activities of oxides in multi-component slag systems. It is also a good example of the utility of the Gibbs-Schuhmann technique for calculating activities in a system where that of one of the components has been measured. This paper Koh and Caugherty. This plot is reproduced by alor in X-ray Metallography. Because of this nonlinearity, preparation cf suitable standards and/or correction for absorption and enhancement are essential in microanalysis. However, our objection is not the conclusion that Dr. Aaronson has arrived at nor the technique he has used; but only to the foot-note credited to V. Macres. The level of chromium that he was concerned with (less than 3 pet) is so low that the deviation of uncorrected Cr-curve will be negligible. Besides Dr. Aaronson has used chromium intensity from martensite and set it equal the bulk chromium content of the alloy. Using this chromium-intensity as a reference, he has calculated the amount of chromium in the ferrite. This amounts to the same as using an internal standard. Since the chromium content in austenite and ferrite are almost the same, enhancement due to iron in both will be the same and therefore does not need to be corrected. together with the author's recently published one1 on the CaO-FeO-Fe2O3 system will be most helpful to others learning to apply Schuhmann's method, which merits a far wider application than it has received to date and should greatly aid our understanding of equilibria between metal and oxide phases. As shown by okcen" its use may even be extended to sections of systems with any number of oxides. I have some questions as to the selection of equilibrium constants made by Dr. Turkdogan. He has chosen one for the formation of Fez03 from FeO and oxygen which gives Fea3 activities 50 pct higher

Jan 1, 1963

By John Chipman

HE lecture on 'Thermodynamic Properties of Blast Furnace Slagso prepared in 1959 and published two years later required revision in one particular before it appeared in print. The activity of SiO, was deter mined through studies of the equilibrium: SiO, (in slag) 2C (graphite) = (in Fe) 2C0 (1 atm) The ratio for each experimental temperature was found from the heat of formation of cris-tobalite, the entropies and heat capacities of the re-actants, by virtue of the third law of thermodynamics. Discrepancies between several kinds of data led to investigations regarding other equilibria involving SiO, on the suspicion that there might be an error in the third-law value of its free energy. In particular the equilibrium: was restudied by Kay and Taylor who Confirmed the earlier results of Baird and Tayloron which their SiO, activities depended. The free energy of Sic was also rechecked4 independently. These and other equilibrium measurements led to the conclusion6 that the free energy of SiO, at high temperatures is in error and requires a correction of about -5 kcal. The exact source of the error is uncertain; it could lie either in the entropy of SiO, or in its heat of formation, but it more probably lies in the latter. Adjustment of this free energy lowers the ratio by a factor of approximately 4. Accordingly it will be necessary to multiply by this factor all of the SiO, activities determined by this method.',B Referring to the lecture cited, this correction should be applied in Figs. 8, 9, 10, 19, and 20. It applies also to the experimental data of Fig. 13, bringing these as well as those on the ternary system into good agreement with the work of Taylor and associates. At the same time it eliminates the discrepancy shown in Fig. 11, lowering both lines until the upper

Jan 1, 1962

By G. S. Hume

During the war years the drilling activity in Canada has been steadily increasing and still further increase is expected in 1945. The production of oil, which in the past has come largely from the Turner Valley field in Alberta, shows a decline since 1942, the peak year. New discoveries made in 1944, however, give promise of replacing the decrease from Turner Valley where the crude-oil production in 1944 was nearly 1,800,000 bbl. less than in 1942, but with an increase of 145,000 bbl. in natural gasoline, a product of great value to the war effort. A very considerable part of the decline in Alberta has been offset by new production of more than a million barrels in 1944 from the Norman Wells field, in the Mackenzie River area of the Northwest Territories. It should not be forgotten, however, that this is largely due to the Canol development, a war project, the future of which is dependent on many factors not connected with an ordinary commercial operation. The year 1944 has been the best in new discoveries in Alberta for all time. The discovery of a new deep field at Jumping-pound, 20 miles west of Calgary, with the hopc of a type of product similar to that of Turner Valley is the culmination of many years of effort to interpret the subsurface structures in relation to the complicated surface foothills faulting and folding. In this case the subsurface structure on the Paleozoic limestone was inferred from geological investigations but precisely defined by seismograph. In addition to Jumpingpound the discovery of oil of 34.5 gravity at a depth of less than 5000 ft, in the Devonian of the Plains at Princess, 125 miles east of Calgary, is of great significance since this is the first substantial production from the Devonian in Alberta, although previously some oil had been obtained at two places from the Devonian in the foothills. The effect of this discovery is already apparent in the number of wells now drilling to the Devonian in the southern Plains. In southern Alberta a new producing area has been found in a Lower Cretaceous sand at Barnwell, a few miles west of Taber. Also, at Conrad, 20 miles southeast of Taber, an important new discovery has been made at a depth of about 3000 ft. in a sand in Jurassic shales, in a strali-graphic trap on the northeast flank of the Sweetgrass arch. In northeast Central Alberta an important extension has been found in the Lloydminster area, where only a few wells have so far been drilled. A new well 3 1/2 miles south of the previous producers found a coarser sand at the productive horizon and as a result will have an increased daily yield. At Blackfoot, 9 miles west of Lloydrninster, a new producing area in the Lower Cretaceous may have been discovered at a depth of 2004 ft. At the end of 1944 the well was being tested. Forty-four unsuccessful wildcat wells were drilled in Alberta in 1944. The decline of Turner Valley, the major producing field, was anticipated at the beginning of the war and in an effort to offset this and encourage new development the Dominion Government put into force tax concessions and other measures that,

Jan 1, 1945

By C. N. J. Wagner, E. N. Aqua

Dilute Fe-Si alloys (0 to 5 wt pet Si) were cold-worked by making filings at room temperatuve. The analysis of the broadening of the X-vay powdev pattern peaks yields anisotropic particle sizes normal to the (110), (100), and (112) planes which are a consequence of deformation faults (probability a) and twin faults (probability p). The combined fault probability (1.5a +ß) increases from 0.01 in pure iron to 0.02 in Fe-5 pct Si. The root mean square stvains vary with crystallographic ovientation due to elastic anisotropy of the alloys, and increase from about 0.0035 in pure iron to 0.005 in Fe-5 pct Si measured in the [100] direction. Assuming that deformation and twin faults occur with equal probability, the X-ray data would imply that the stacking-fault energy does not change upon alloying. THE crystallographic aspects of the plastic deformation of dilute Fe-Si alloys has been studied many times since the observation of glide band structures by Barrett et a1.l These glide bands were much straighter than the wavy bands observed by Gough2 in unalloyed iron nearly 40 years ago. This difference in the morphology of the slip band structure has been verified many times, most recently by replication electron microscopy3 and dislocation etch-pitting methods.4,5 These observed differences in deformation behavior have been considered to result from the degree of cross slip that occurs in pure iron and in the Si-Fe alloys. The lowered tendency for cross slip would result from a lowering of the stacking-fault energy of iron by the silicon alloying addition. Experimental evidence for this lowered stacking-fault energy in the Si-Fe alloys, obtained with transmission electron microscopy, is the observation of dissociated dislocations in Fe-6 pct si6 and Fe-3 pct Si alloys,7 and the observation of sharply defined cellular substructures in Fe-3 pct si6,7 compared to the more diffuse substructure in zone-refined iron.' The activation energy for recovery of cold work is greater in the Si-Fe alloys than it is in pure iron, indicating that cross slip has become a more difficult process.9 The purpose of this investigation is to determine the change in stacking-fault probability from the broadening of powder pattern peaks in dilute silicon-in-iron solid solutions, when cold-worked at room temperature. The knowledge of the stacking-fault probability and the dislocation density, both of which can be deduced from line-broadening analysis of two orders of reflections from (110), (200), and (112) planes, will permit us to calculate the change in stacking-fault energy upon alloying silicon into iron. Previous X-ray investigation of cold-rolled Fe-5 wt pct Si (100)[001 ] single crystals did not reveal any line broadening, whereas cold-rolled Fe-3.1 wt pct Si (001) [110] and (001)[100] single crystals10 showed line bro2dening as a consequence of small particle sizes (-200A) and root mean square strains (-0.25 pct), which are comparable to those found in cold-worked iron filings.11 EXPERIMENTAL PROCEDURE A series of five Fe-Si alloys containing nominally 1 to 5 wt pct Si and pure iron were cold-worked by making filings at room temperature. The actual silicon content deviated at the most by +0.1 pct which is of no significance in the present study. The carbon contents of these materials were less than 0.02 pct. The X-ray diffraction patterns were measured with molybdenum, cobalt, and iron radiation using a GE and a Philips diffractometer. The (110)-(220), (200)-(400), and (112)-(224) pairs of reflections were

Jan 1, 1968

By E. P. Pfleider, Rolland L. Blake

IT is generally believed that the amount of diamond drilling will increase appreciably in the next decade, as the seaarch for minerals throughout the world becomes more difficult and intense. An attendant problem may be one of short diamond supply, resulting in higher bit and drilling cost. With this background, the U. S. Bureau of Mines' and the School of Mines at the University of Minnesota' have established comprehensive research programs in diamond drilling. One of the several aims is the design of a more efficient bit, which would lower diamond consumption and increase rate of advance, both essential in reducing drilling costs. The objective of the specific research problem" discussed in this paper was an investigation of the cutting action of the cliamonds set in a diamond drill bit, cutting action meaning the manner in which the diamonds cut or. loosen the minerals in the rocks being drilled. In the literature on cutting action such descriptive terms are used .as: grinding, wearing, cutting, breaking, shearing, scraping, melting, and chipping. These actions were seldom described or defined. Grodzinski describes the cutting action of a single diamond in the shaping of certain types of material as "breaking out chips of the material." Brittle mate-. rials break as small separate chips, and tough materials, because of heat generated, give a continuous chip. Deeby said about diamond drills: "When diamonds are forced into the formation and rotated, they either break the bond holding the rock particles together, or they cause conchoidal fracture of the rock itself. The former action occurs when drilling in sandstones, siltstones, shales, etc. and the latter action when drilling in chert, flint, or quartz." He said that diamonds cut on the "grinding principle" but he does not define or elaborate on this action. The cutting action of diamonds on glass was first investigated about 1816 by Dr. W. H. Wol-laston, an English physicist. The best glass-cutting diamonds have a natural or artificially rounded cutting edge. This edge first indents the glass and then slightly separates the particles, forming a shallow and nearly invisible fissure. Since none of the material is removed, this action is one of splitting rather than cutting. No other reports of research work on the cutting action of the diamond were found, and further work was considered justified and advisable. It is impractical, even if possible, to observe directly the cutting action of a diamond drill bit in rock; therefore it was necessary to devise an indirect method. It was believed that a study of the following three observations would lead to a better understanding of the cutting action: 1—the appearance of the minerals or rock surface in the bottom of the hole, 2—the size, shape, and other characteristics of the drill cuttings, and 3—the condition of the diamonds in the bit. The cutting action in a particular rock probably varies with bit pressure and speed. If the bit were slowly lifted off the rock, the effect of decreasing pressure might obliterate those bottom hole characteristics that are specific at the test pressure. Likewise, if the drill were stopped with the bit still in contact with the bottom of the hole, then decreasing speed effects would tend to obliterate the characteristics at the set test conditions. Therefore, in order to preserve those cutting effects impressed on the rock at test conditions, it seemed necessary to lift the bit off the bottom of the hole almost instantaneously once drilling conditions, i.e., revolutions per minute, pressure, and water flow became constant. In addition to observing the cuttings, the bit, and the bottom of hole, it seemed desirable to collect some quantitative data for purposes of correlation with the observations and for a record of bit performance. Consequently such data as revolutions per minute, force applied, and rate of advance of the bit were recorded. Six rock types, listed in Table I, were chosen for the tests. It was felt that these rocks had most of the variable characteristics of texture, bonding, and mineral hardness met in the common rocks generally being drilled. The sandstone was so poorly cemented as to be friable, even though most of the cement was silica. The limestone, though well cemented, was quite porous. Originally it was planned to conduct the tesk work with a full-scale drill unit, using EX bits, 7/8-in. core, 11/4-in. OD. The drill worked well, but was too cumbersome for rapid, accurate drilling of many short holes (1 ½-in.) in varied rock types. A new

Jan 1, 1954

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

A new mechanism of crystal growth involving oapor, liquid, crnd solid phases explains many observations of the effect of implurities in crystal growth from the vapor. The role of the impuuitq is to form a liquid Solution with the crystalline tnalerial to be grown from the vapor. Since the solution is n prefevred site for deposition firorti the uapor, the liquid becorrles supersaturated. Crystal growth occurs by precipitatzon from the supersaturated liquid crt tlie solid-liquid zntevfnce. A crystalline defect, such as a screw dislocation, is not essetztial for VLS (vapor -liquid-solid) growth. The concept of the VLS mechanism is discussed in detail with reference to tire controlled growth of silicon crystals using gold, platinum, palladium, nickel, silver, or copper as an implurity agent. RECENTLY a short communication' described a new concept of crystal growth from the vapor, the VLS mechanism. In this paper we present a detailed description of the process and its application to the growth of silicon crystals and we discuss its relevance to existing concepts of .'whisker" crystal growth. Crystal growth from the vapor is usually explained by a theory proposed by Frank2 and developed in detail by Burton, Cabrera, and Frank.3 In this theory a screw dislocation terminating at the growth surface provides a self-perpetuating step. Accommodation of atoms at the step is energetically favorable, and is possible of much lower supersatu-ration than required for two-dimensional nucleation. Crystals of a unique form resulting from aniso-tropic growth from the vapor are "whisker" or filamentary ones. Such crystals have a lengthwise dimension orders of magnitude larger than those of the cross section. For most filamentary crystals both the fast-growth direction and directions of lateral growth have small Miller indices. The special growth form for a whisker crystal implies that the tip surface of the crystal must be a preferred growth site. sears4 proposed that, according to the Frank theory. a whisker contains a screw dislocation emergent at the growing tip. Such an axial defect provides a preferred growth site and accounts for unidirectional growth. The hypothesis was extended by Price. Vermilyea. and Webb," still implying the presence of a dislocation at the whisker tip. They postulated that impurities arriving at the fast-growing tip face become buried while those arriving on the surface of slow-growing lateral faces accumulate and thereby hinder growth. These considerations led to a whisker morphology. There is increasing evidence that most whisker crystals grown from the vapor are dislocation-free. Webb and his coworkers6 searched for an Eshelby twist7 in zinc? cadmium, iron. copper, silver, and palladium whisker crystals. They found unequivocal evidence for an axial screw dislocation in only one element, palladium. However, not every palladium crystal examined contained a dislocation. Observations with the electron microscope have failed to show dislocations in whisker crystals of zinc, silicon.9 and one morphology of AlN.10 Since many whiskers are completely free of dislocations, an axial dislocation does not appear to be required for whisker growth of many substances. A significant advance in understanding whisker growth has been a recognition of the need for impurities. This requirement has been clearly demonstrated for copper,11 iron,13 and silicon9-1 whiskers. For silicon, detailed studies proved conclusively that certain impurities, for example, nickel or gold, are essential. Another pertinent phenomenon which has received little attention is the presence of a liquid layer or droplets on the surface of some crystals growing from the vapor. Crystals in which this has been observed include p-toluidine,14 MoO3,15 ferrites,16 and silicon carbide.'" The liquid layers or globules were considered to be metastable phases, molecular complexes, or intermediate polymers originating from condensation of the vapor phase. The possibility has been suggested that the halide being reduced is condensed at the tip18 or adsorbed on the surface11 of a growing metal whisker, for example copper. The literature on whiskers discloses illustrations of rounded terminations at the tips. These appear. for example, on crystals of A12O3,19,20 sic,21 and BeO.22 For BeO, Edwards and Happel suggested that during growth of the whisker the rounded termination consisted of molten beryllium enclosed in a solid shell of BeO. A recent paper9 on the growth of silicon whiskers contains many observations pertinent to an understanding of the mechanisnl of whisker growth. These observations are summarized as follows. 1) Silicon whiskers are dislocation-free. 2) Certain impurities are essential for whisker growth. Without such impurities the silicon deposit is in the form of a film or consists of discrete polyhedral crystals.

Jan 1, 1965

By R. E. Shinkosk

This paper outlines the development of a program for increasing the life of woolen bags used for filtering Dwight-Lloyd gases by treating the bags and gases with hydrated lime. Methods and apparatus are described for determining alkalinity of dusts, acidity and breaking strength of bag cloth. Procedure and results, based on several years of operation, are presented. DURING 1939, additional facilities were constructed in the Dwight-Lloyd Blast Furnace and Baghouse departments at the Selby, California, Plant of the American Smelting and Refining Co. In order to handle adequately the increased volume of gases from the resultant increase in production, it was necessary to increase gradually the amount of water used for cooling gases ahead of the sinter machine baghouse. As a result of this increased water cooling, the average bag life dropped from 27 months in 1939 to 14 months in 1941. (Table I). This drop in life meant an increased. bag cost, as well as lower recovery of dust and some curtailment of operation. During 1941, it was found new bags showed as high as 0.3 pct acidity* after two weeks of opera- tion and as much as 2.0 pct acidity after some months of operation. This high acidity was present in spite of the fact that free oxide or relative alkalinity of the unburned dust ran from 5 to 6 pct. In view of these circumstances, a twofold program was started in Nov. 1941.t Part one of this program consisted of vigorously dipping all new bags in a weak lime solution, containing 50 lb of hydrated lime per 50 gal of water. Part two consisted of feeding fine, dry, hydrated lime into the gas stream intake of the sinter baghouse fan. Apparatus for feeding this lime is shown in fig. 1. All baghouse chambers are shaken in rotation about once each hour. On alternate hours, the baghouse operator places 50 lb of hydrated lime (one sack) into the lime feeder, starts feeder and immediately starts the bag shaking machinery. The rate at which lime is fed is set to coincide with the approximate time necessary to shake all sinter bag-house chambers, or about 15 min. It is felt this method of lime addition is most effective for getting lime into the woolen bag fabric. The amount of lime so fed averages about 600 lb per day. The amount of lime fed per day is varied to keep a minimum relative alkalinity of 9 pct in the unburned sinter dust. A daily dust sample is taken for alkalinity by allowing dust to accumulate in a sample pipe over a 24-hr period. This sample pipe, placed in any chamber cellar, is 2 in. in diam, 4 ft long, is sealed on the inner end, and capped on the outer end. It has a 1/2 in. slot cut for 18 in. along the tip end. This slot faces upward and allows the pipe to fill gradually with dust as bags are shaken. Breaking strength of bags has, in most cases, been the deciding factor in bag replacement. Bags that normally test 100 psi breaking strength when new are replaced when they test under 35 lb. The method for determining breaking strength is shown in the description accompanying fig. 2. Since the start of the liming program in 1941, bag life has increased from 14 months to an average of over 23 months, with a consequent material decrease in bag cost per year. Acidity, as per cent sulphuric acid, may be determined by means of a Beckman pH meter as follows: From a piece of bag cloth. which has been thoroughly cleaned of dust, a 5 g sample is weighed on a balance. Cut the sample into fine pieces and place in a 400 cc beaker. Add 100 cc (measured) of distilled water and stir vigorously. Filter on suction funnel, holding cloth pulp in beaker with a stirring rod. Wash cloth sample and filter wash water four additional times, each time with 20 cc distilled water, the last time squeezing cloth pulp over funnel. Discard pulp and rinse funnel and filter paper. Pour wash solution jnto measuring graduate and make up to exactly 300 cc with distilled water. Place into clean 600 cc beaker and measure the pH on meter. The per cent acid in bag cloth is read from the following table:—

Jan 1, 1951

By K. F. G. Hosking

I read Professor Gaudin&apos;s paper with great interest and pleasure because for some time I have held that the chemical aspect of comminution is a subject of considerable importance to the mineral dresser and deserves to be thoroughly investigated. It does seem appropriate, however, to emphasize the fact that "fresh" edges and corners produced by the grinding of solids display enhanced reactivity has been recognized and utilized in the development of certain mineral identification techniques. Some of these techniques are worth noting, not only because they might facilitate research in the aspect of mineral dressing under discussion, but also because they emphasize the fact that many mineral species commonly regarded as being very inert can display a surprising reactivity when in the freshly ground state. In 1951 Isakov6 published a number of tests for the components of certain mineral species which depend essentially on grinding in a mortar a mixture of the material under investigation with a solid reagent. Thus when stibnite, 4(Sb2S3), is ground with sodium or potassium hydroxide. the antimony is revealed by a momentary development of a yellow color which changes in air to orange-red. Other antimony minerals need a preliminary treatment before the test can be carried out. This consists of grinding with aluminium sulfate, ferric sulfate or potassium bisulfate, and breathing upon the resultant mixture. I have employed a similar technique to determine the approximate magnesia content of certain limestones.&apos; The method depends essentially on the fact that when a sample of limestone is ground under controlled conditions with solutions of sodium hydroxide and Titan yellow the color of the final product is, within limits, a function of the amount of magnesia present. I have also shown that the components of a wide range of minerals can be identified by applying chemicals to their streaks on portions of vitrified, unglazed floor tiles, etc. Under such circumstances the diversity of the reactions which take place in the cold (because of the reactivity of fresh corners and edges) is surprising. Thus, for example, if a garnierite, (Ni,Mg)3Si2O5(OH)1, streak is treated first with a drop of 0.880 ammonia and then with a drop of a 1 pct alcoholic dimethyl-glyoxime it immediately becomes red, indicating the presence of nickel.&apos; Stevens and Carron9 have evolved a simple field test for distinguishing minerals by "abrasion pH." A soft nonabsorbent mineral is scratched in a drop of water on a streak plate until a milky suspension is formed. A piece of pH indicator paper is dipped into the suspension, after which it is removed and the maximum deviation from neutrality noted. When a hard mineral or one which absorbs water is being tested, fragments are first ground for 1 min with a few drops of water in a mortar to make a heavy suspension. The importance of the findings of such tests to mineral dressing may be judged by the abrasion pH values, Table 11, recorded by Stevens and Carron for certain species usually regarded as comparatively inert. The combined results Of the above researches clearly indicate that comminution is capable of altering the pH of a pulp and of causing the chemical nature of the surfaces of some of the components to be profoundly changed&apos; Depending On circumstances such surface alterations may have a beneficial or an adverse effect if these products are subsequently subjected to flotation. The tests also suggest that by grinding "inert" minerals with appropriate solid or liquid reagents "reactive" surfaces may be developed which might facilitate separations by flotation. It is an interesting and instructive problem to determine the reactions that are likely to take place when dry solid substances are subjected to comminution and to the unavoidable heat liberated during the process. To do this it is theoretically necessary to know the free energy values of the reactants and possible resultants, but unfortunately there is a dearth of such data! However, the heats of formation of many substances are known, and generally speaking, if in a reaction of the type AB + CD = AD + CB the sum of the heats of formation of AB and CD is less than that of AD and CB the reaction will probably proceed to the right. Thus, according to a note I have (the author of which I cannot name) if PbS (black) is warmed with CdSO, (white), PbSO., (white) and CdS (yellow) are formed, and that the reaction does, in fact, take place is indicated by the change in color of the mixture. The reaction is expected, as the sum of the heats of formation of PbS and CdSO, is less than that of PbSO, and CdS (as shown below). PbS + CdSO4 = PbSO4 + CdS 22.2 + 218.0 < 216.2 + 33.9 Finally, certain other aspects of the chemistry of comminution, which are neither mentioned by Professor Gaudin nor referred to by me are to be found in a paper by Welsh" and in the printed discussion thereof. A. M. Gaudin (author&apos;s reply)—The observations contributed by Dr. Hosking are indeed welcome, as they add to our experimental knowledge of a topic which is believed to be of the first importance. In connection with the experiments cited it should be kept in mind that oxidation, hydration, and carbonation at various rates should always be deemed to be possibilities when grinding is done in water or in air, even in "industrially dry" air. Special precautions might lead to sufficient minimizing of these reactions and to the assertion, instead, of deliberately-created reactions. The author wishes to thank Dr. Hosking for his contribution.

Jan 1, 1957

By A. M. Gaudin, Olav Mellgren, P. L. De Bruyn

In commonly used to prepare the surface of the mineral to be floated so that attachment to air takes place. The quantity of agent required to make the mineral hydrophobic is usually very small, of the order of 0.1 to 0.25 lb per ton of mineral. Details of the mechanism of pyrite collection are for the most part unsettled. Adsorption of collector has long been believed to involve an ion exchange mechanism as demonstrated for galena&apos; and for chalcocite. In the work on chalcocite it was also demonstrated that a film of xanthate radicals unleachable in solvents that dissolve alkali xanthates, copper xanthate, or dixanthogen was formed at the surface of the mineral. The unleachable product increased with increasing addition of xanthate up to a maximum corresponding to an oriented monolayer of xanthate radicals. Pyrite is extremely floatable with xanthate if its surface is fresh,,&apos; but the floatability decreases rapidly as oxide coatings increase in abundance. Pyrite shows zero contact angle when in contact with ethyl xanthate solution at pH higher than about 10.5; at neutrality. a contact angle of 60° is obtained at a reagent concentration of 25 mg per liter. Alkali sulfides and cyanides are pyrite depressants.

Jan 1, 1956

By C. Schlumberger

SINCE the, beginning of the year 1928 the senior authors and their associates have applied a series of procedures which makes possible the detailed study in situ of the formations traversed by a drill hole before the casing has been landed. They have given the name "electrical coring" to the ensemble of these processes, which now replace in a large measure the mechanical coring performed by the drillers, and permit the gathering of bottom-hole data hitherto unobtainable. Three years have elapsed since the technique and interpretation of these measurements emerged from the experimental stage and entered the field of industrial application on a large scale. The total length of drill holes so far surveyed by the authors and their associates, all over the world, amounts to several millions of feet. Practical and strongly built equipment has been evolved, which permits the examination in a short time of an open hole several thousand feet long. No comprehensive paper has yet been published discussing the essential principles of the processes applied and bringing into evidence their economic interest. This is the object of the present paper.1 Numerous examples of field work performed under varied geological conditions are given, constituting a concrete illustration of the services rendered by the new methods.

Jan 1, 1932

By A. J. Jacobs, J. W. Spretnak, R. Speiser

The activities of nickel in liquid iron-nickel solutions containing from 10 to 90 at. pct Ni were measured over the temperature range .1510° to 1600°C. A special function was devised whereby activities can be computed by a graphical integration using the results of chemical analyses on the vapor phase alone. The liquid solutions studied exhibit negative deviation from Raoult&apos;s law, but they approach ideality as the temperature is raised from 1510° to 1600°C. The maximum heat of solution is less than -8.0 kcal per mole. The entropy of solution is less than —2.5 kcal per mole deg at 1510°C, and changes negligibly as the temperature is raised. The liquid iron-nickel solutions do not follow regular solution behavior. THE activities of the components of a liquid alloy system can be determined in favorable cases from the partial pressure of the vapor in equilibrium with the liquid alloy.&apos; Assuming that the vapor over the alloy behaves as an ideal gas, the activity of component i is given by the expression, Where the superscripts 1, v, and o signify the liquid, the vapor, and the pure component, respectively; the f&apos;s are the fugacities, and the P&apos;s, the pressures. The quantities Pi and Pi can be determined by the

Jan 1, 1960

By W. H. Emmons

INTRODUCTION THE deposition of metalliferous lode systems takes place at considerable depths and no one may observe the process. We see only the end results of the process and from these we seek to construct a theory that will account for them. Because there is an obvious relation between many lode systems and intrusive igneous masses, it is a natural inference that they have formed by fluids that were expelled from such masses. The metalliferous lode systems have been deposited by ascending thermal fluids that have risen mainly from great irregular bodies of intruding magmas which are called batholiths. Probably 95 per cent of such lode systems have formed in connection with acidic or "granitic" batholiths and probably less than 5 per cent have formed in connection with basic intrusives. The study of lode ores, therefore, should include the study of the intrusion and differentiation of the batholith. It was noted long ago1 that certain tin-bearing deposits are commonly associated with small stocks. That small stocks are cupolas of larger intrusive masses has generally been recognized. Butler,2 in his studies of the ore deposits of Utah, showed that the chief deposits in Utah are in and near the stocks; that is near the "apically truncated

Jan 1, 1933

By H. D. Kessler, Joseph B. McAndrew

WHEN there is occasion to make structural use of metals at temperatures above 900°C (1652°F), the choice of alloys is severely limited, and those materials which meet special requirements as to density, strength, toughness, and resistance to creep, oxidation, or fatigue at such temperatures are at a premium. Any new type of high temperature alloy which is found to be outstanding with respect to several of these properties is therefore likely to find special applications for which it is uniquely advantageous as compared to other alloys. Such is the case with the 7 titanium-aluminum alloys. This y phase is an intermediate phase based on the composition TiAl, and extends from about 35.5 to 44.5 wt pct Al at temperatures up to 1000°C, above which the field broadens to include 60 pct A1 at 1340°C.&apos; The alloys of principal interest have a narrow melting range, with 7 forming by the peri-tectic reaction, melt + ß=y at about 1460°C. Unlike most intermediate phases, the binary alloys containing titanium and aluminum in approximately equiatomic proportion possess low room temperature hardness,&apos; in addition to which they have low density, good resistance to oxidation, and relatively high modulus of elasticity.&apos; Unpublished work done at Armour Research Foundation showed

Jan 1, 1957

By B. H. Bergstrom, Will Mitchell, T. G. Kirkland, C. L. Sollenberger

SEVERAL constructive and fundamental studies have been made in the analysis of data obtained from experiments carried on with batch ball and rod mills. The operating characteristics of ball milling in small continuous circuits have also been appraised. It is from these analyses that some of the theories of comminution have been developed. Relatively few studies of continuous rod milling have added significantly to the fundamental concepts, because seldom have they yielded sufficiently consistent results. Perhaps they have been too limited in their scope. Careful control of the variables in batch grinding is simple compared with that encountered in a continuous operation. This factor alone has discouraged many investigators. Occasionally results of systematic changes made in industrial rod mill circuits have been published, but usually the data are sketchy and are restricted because -of the unwieldiness of the equipment used. The work, in general, has not been comprehensive; nevertheless it has provided empirical relationships that have bridged the gap between postulate and practice so that by proper manipulation of formulae, a mill designer can anticipate mill size and power requirements.1-3 Although operating variables of a small continuous mill are not so easy to control as with the batch mill, with present day devices, and with careful experimental work, consistent results can be obtained.

Jan 10, 1954

By T. E. Scott, D. H. Sherman, C. V. Owen

It has been established&apos; that vanadium exhibits a ductile to brittle transition temperature which increases with increasing hydrogen content. Optical microscopic examination at room temperature revealed no evidence of hydride precipitate in fractured specimens containing 100 ppm H, but hydrides were present in samples with 800 ppm H. More recently2 the strain rate and temperature dependences of the ductility drop in vanadium containing 6 ppm H were reported. It was argued that the ductile-brittle transition, while dependent on the presence of hydrogen, probably could not be explained by the precipitation of hydride. The bases of the argument were that 6 ppm H would not produce sufficient hydride to alter the ductility to the extent observed and no visual evidence of hydride was obtained. However, the data were not sufficient in these investigations 1,2 to define accurately the ductile-brittle transition temperature. Also, no information was available concerning the terminal solubility of hydrogen in vanadium at the low concentrations employed. westlake 3 has studied the electrical resistivity of vanadium at several hydrogen concentrations. He was able to detect the precipitation of hydride and to extend the hydrogen solvus to the composition and temperature range pertinent to the observed ductile-brittle transition behavior, Westlake compared his

Jan 1, 1968

By Alden Greninger

ALTHOUGH the crystallography of lattice transformations has been studied extensively during the past few years, these studies have been limited, with few exceptions1,2, to specimens in which the transformed lattice appears as a, segregate phase. A realization of the technical importance of the segregation mechanism, especially in the formation of martensitic structures and in age-hardening phenomena, has undoubtedly stimulated research in this direction. In the crystallographic studies of segregation, the general problem has been to relate the orientation of the parent crystal to that of the segregate crystals. The technique has been complicated by the fact that it has been necessary to deal with the presence of as many as 24 ideal segregate orientations within one parent lattice; furthermore, the segregate lattices are invariably scattered (seldom less than ±2°, often as much as 15° or 20°) about these ideal positions. It is probable that a more complete picture of phase transformations may result from a study in which complete lattice relationships between individual grains are evaluated, thereby providing an additional param-eter which, when it is necessary to work with multiple segregate-orienta-tions, cannot be evaluated. The present paper presents the results of such a study, ? wherein a peritectic reaction is made use of to produce the transformed lattices.

Jan 1, 1937

By G. R. Speich

The interlarnmelm spacing, growth rate, and degree of segregation that accompany cellular precipitation in four Fe-Zn alloys containing 9.7, 15.2, 23.5, and 30.5 at. pct Zn have been determined in the temperature range 400" to 600°C. The chemical free-energy change for the reaction was calculated from the available thermodynamic data and the known compositions of the phases. The fraction of the chemical free-energy change for equilibrium segregation that is converted into interfacial free energy decreases from 0.43 to 0.08 as the magnitude of this free-energy change increases from 35 to 270 cal per mole. At constant temperature the cellular growth rate is proportional to the cube of the dissipated free energy. At 600°C newly 100 pct of the equilibrium segregation is achieved during cellulm precipitation whereas at 400°C only 85 pct of the equilibrium segregation is attained. During cellular growth, mass transport of zinc occurs by grain boundary diffusion; excess zinc remaining in the a! phase after the completion of growth is removed slowly by volume diffusion. A modified Cahn theory of cellular precipitation predicts the observed interlamellar spacing within a factor of two. In cellular precipitation reactions such as pearlite formation or discontinuous precipitation, the basic problem is to predict the variation of growth rate G, interlamellar spacing S, and degree of segregation P with composition and temperature. To accomplish this we need three independent equations relating these quantities. One of these equations comes from the diffusion solution. To obtain two additional independent equations, some assumptions must be made. cahnl has suggested recently that two plausible assumptions are 1) that growth rate is proportional to the dissipated free energy and 2) that the spacing which occurs is that which maximizes the dissipated free energy. According to the first assumption, this spacing also maximizes the growth rate and the rate of decrease of free energy per unit area of cell boundary. The present work was undertaken to test these assumptions. To test the first assumption it is necessary to study a cellular reaction over a wide range of supersatura-tions to establish a relationship between G and the dissipated free energy at constant temperature. This is possible only in discontinuous precipitation reactions since in pearlite reactions constituents other than pearlite form if the composition of the parent phase deviates even slightly from the eutectoid composition. The Fe-Zn system was chosen for study because 1) discontinuous precipitation proceeds to completion over a wide temperature and concentration range, 2) the degree of segregation within the cell can be measured by lattice parameter measurements,2 and 3) the thermodynamics of this system have recently been determined by Wriedt.3 In this system the cells consisting d alternate lamellae of a and r phases form from supercooled iron-rich a phase. The a phase within the cells is bcc as is the original a phase, cia, but has a different orientation and a slightly lower zinc content than the original a phase. The r phase has a zinc content of about 70 at. pct and a crystal structure isomor-phous with T brass. EXPERIMENTAL PROCEDURE Four Fe-Zn alloys with 9.7, 15.2, 23.5, and 30.5 at. pct Zn were prepared from carbonyl-iron powder (400 mesh, 99.8 wt pct Fe) and zinc powder (200 mesh, 99.99 wt pct Zn). The powders were ball-milled together and cold-pressed under 60,000 psi to discs $ in. thick by $ in. diam. The cold-pressed discs of the alloys with 9.7 and 15.2 at. pct Zn were sealed in evacuated silica capsules and heated slowly to 1100°C over a period of 1 week (3 days at 600°C, then 3 days at 80O°C, then 1 day at 1100°C). The alloys with 23.5 and 30.5 at. pct Zn were treated similarly except that the final homogenization temperatures were 1000" and 85O°C, respectively, to prevent melting. The alloys were quenched in iced brine from the final homogenization temperature. Specimens of each alloy were subsequently aged in salt pots at temperatures of 400°, 450°, 500°, 550°, 600°, and 650°C for times that varied from a few minutes to several hundred hours. At a late stage of this work, an alloy containing 11.2 at. pct Zn was prepared by vapor-impregnation of iron foil with zinc vapor at 890°C. This alloy proved useful for electron microscope studies because it was free of porosity. The homogenization and aging conditions were based on the recent Fe-Zn phase diagram of Stadelmaier and Bridgers4 rather than the earlier diagram of ansen.5 They consist of a homogenization heat treatment in the homogeneous a field followed by an aging treatment in the two-phase a + r field. The aged specimens were metallographically polished and etched in 2 pct nital and the radius of the largest cell in the microstructure determined. This radius plotted vs time gave a straight line whose slope is the boundary migration rate or growth rate G of the cell. To determine the interlamellar spacing, specimens were examined by surface-replica and thin-section electron microscope techniques. Because of the irregular nature of the lamellae within the cell, the average interlamellar spacing S .of the cell was measured by the method of Cahn and Hagel,6 where S is defined by:

Jan 1, 1969

By Herbert H. Uhlig

A STUDY of passivity in chromium-iron alloys holds considerable interest, both because of the present-day practical importance of the stainless steels, and because of the scientific importance attached to the mechanism of their corrosion resistance. Upon the discovery of the passive chromium-iron alloys in 1912, it seemed logical to attribute the observed phenomenal corrosion resistance to a thin, continuous, protective reaction product on the surface. The product was thought to be Cr2O3 or a similar oxide containing both chromium and iron. This mechanism seemed likely in view of Michael Faraday&apos;s conjecture that passive iron is not reactive in concentrated nitric acid because of an oxide on the metal surface.† Since 1912, data have accumulated that permit a further exploration into the nature of passivity and provide a new approach to the problem. A summary of the facts lends considerable weight to a mechanism based not on physical protection of an oxide or similar compound, although such compounds may be present on the surface, but to a change in tendency of surface metal atoms to react chemically. This change in reaction tendency is ascribed to chemisorbed films that effectively satisfy residual valence forces of the metal surface, but do not appreciably disturb the positions of metal atoms in the lattice. In other words, formation of a new lattice such as that of an oxide is not a necessary condition for this type of passivity. The decreased reaction tendency of the metal by reason of chemisorbed films can thereby account for low reaction rates of the stainless steels in many media, as well as a noble galvanic potential as is observed. Substances capable of adsorbing on the stainless steels, and hence accompanying the property of passivity, are typically oxygen, nitrites or chromates, but are not in any sense limited to these. Other elements and compounds can also chemisorb, and therefore may also play a major part in the mechanism of passivity in specific media. The mechanism of passivity based on chemisorption or activated adsorption begins with the interpretation Langmuir proposed for his experiments concerning adsorbed oxygen on tungsten.1 He found that adsorbed oxygen was tightly bound, remaining on the tungsten surface above temperatures at which WO3 rapidly volatilizes. The oxygen in such a state did not readily react with hydrogen even at

Jan 1, 1947

By R. C. Buehl, J. P. Morris

ACTIVITY values for sulphur dissolved in liquid iron and slags as functions of composition and temperature are needed in applying thermodynamics to sulphur-control problems in iron- and &apos; steel-making. The purpose of this investigation was to determine the effect of carbon on the activity of sulphur in the metal phase. The method employed was the same as that used in an earlier investigation&apos; concerning the effect of silicon on sulphur activity in liquid iron. A study was made of the conditions of equilibrium in the reaction between hydrogen gas and sulphur dissolved in iron-carbon alloys. The chemical equation for this reaction can be written as follows: S (in liquid Fe-C alloy) + H2 (gas) = H2S (gas). It was found that the activity coefficient of sulphur in liquid iron increases as the carbon content increases. At 2.3 pct carbon and 1600 °C, the activity coefficient of sulphur is twice its value in carbon-free iron, and at carbon saturation it is more than six times as great. The effect of temperature on sulphur activity was found to be small. Previous work on the reaction between hydrogen gas and sulphur dissolved in liquid iron has been reported by several investigators2,³,4 but only recently have studies been made of the effect of alloying elements. Silicon1 is known to have a pronounced influence on the activity of sulphur in iron, its effect being similar to that shown by carbon as described in the present report. Kitchener, Bockris, and Liber-man5 recently have published a preliminary report of their work on the effect of carbon on sulphur activity in iron. Their experiments were made at 1570°C and carbon saturation in the melt. Under these conditions they found that the activity coefficient of sulphur was approximately doubled by the presence of carbon. This is a much smaller effect than that found in the present work. Experimental Method: The apparatus and procedure were essentially the same as those used in the earlier investigation of the effect of silicon on sulphur activity.&apos; Briefly, the method was as follows: A molten iron-carbon alloy was brought to equilibrium at constant temperature with a mixture of H2 and H2S of constant composition by bubbling the gas through the metal. Samples of the melt were

Jan 1, 1951

By Eugene McAuliffe

IT is not possible to include in this paper, limited as it is in scope, the many diverse steps toward the reduction of mine accidents that are taken in the mines that produce the nation&apos;s coal. Every coal-producing state has enacted laws covering proper mining practices, and the major portion of these are directly related to the safety of the mine employees. The United States Bureau of Mines, the American Institute of Mining and Metallurgical Engineers, The American Mining Congress, a number of national, regional and state organizations, as well as the coal technical press, have covered time and time again all of the "do" and "don&apos;t" phases of mine operation that bear on the important question of mine and employee safety. Within the past 15 years The Union Pacific Coal Co. has attempted to put into practice in its mines in southern Wyoming these many good recommendations, finding some value in all, and yet, to secure substantial results, the management found it necessary to resort in the end to what might be referred to as "extra-territorial" methods. It is the writer&apos;s purpose to show in this paper that marked and even extraordinary betterment can be brought about when employer and employee work together with due sincerity. In presenting our own experi-ence, one that has been duplicated in so far as results are concerned on numerous other properties, no theory of perfection of management exists; on the other hand, our organization feels that as long as our record of accidents remains as shown by even our latest and best performance we still have far to go. Safety work in some form has been carried on in and about the mining properties of The Union Pacific Coal Co. since the first mine was opened at the now long-abandoned town of Carbon, Wyo., in 1868. On June 30, 1903, an explosion and subsequent mine fire occurred in mine No. 1 at Hanna, taking 169 lives, and a second explosion occurred in tile same mine on March 28, 1908, in which 59 additional lives were lost. Looking back with impartiality on the causes leading up to these two unfortunate disasters, we can only conclude that shooting from the solid, the absence of adequate ventilation, rock dusting, the use of water at the face to allay

Jan 1, 1938