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OF the many categories into which scientific knowledge has been arbitrarily 'divided, the one that has proved most. applicable in our attempts to gain an insight into the details of steelmaking processes is physical chemistry. To the young metallurgist who has only recently survived a college course in this subject, the application of its principles to reactions in liquid steel should not be difficult. The many excellent textbooks of physical chemistry provide ample material on the principles of this subject for the student of steelmaking processes. It is the purpose of this chapter to provide a concise review of the principles of physical chemistry that have proved useful in studies of steelmaking and at the same time to present some of the data that are essential to the application of physical chemistry to reactions at high temperatures. Certain parts of physical chemistry require rather formidable mathematics for their complete development, but in the main those applications in which we are here interested can be expressed in fairly simple terms. Many of the equations are logarithmic, and we shall use the symbols In X and log X to represent, respectively the natural and the common logarithm of X. The two are related-by In X = 2.303 log X. Logarithms may, be read from a good slide rule with sufficient accuracy for our purposes. In a few spots a knowledge of the calculus will be helpful. MATTER Innumerable forms of matter may, be recognized, and these may be converted by chemical processes into others, as ore, coke, and air are converted into iron, slag, and gas.. Whenever such a change occurs there is a corresponding change in the amount of energy associated with the matter. The process may require an input of energy, as in the electrolytic production of aluminum, or it may result in an output of energy, as in the combustion of fuel. The basic laws of the conservation of matter and of energy tell us that we cannot change the total amount of matter or the total amour t of energy.. When the fuel pile is used up, we realize that it has simply been converted into other forms of matter; .i.e., ash

Jan 1, 1964

By Carl Henrich

Aspen, the flourishing mountain- and mining-town of Pitkin county, Colorado, is located in the valley of the Roaring Fork, 11 miles above Glenwood springs, where that stream empties its waters into Grand river, a tributary of the Colorado. The Roaring Fork heads on the western slope of the Sawatch range near Grizzly peak, and runs in a general northwesterly direction to its junction with the Grand river. Of its numerous tributaries, Castle creek joins it just below the town of Aspen, the town being built on an extensive flat hounded on the northeast by the Roaring Fork and on the west by Castle creek. The latter heads at the junction of the Sawatch and the Elk mountains and flows northward between the two chains, until it empties into Roaring Fork. Opposite the town of Aspen, Hunter creek, coming westward from the western slope of Mount Massive, joins the Roaring Fork. About a mile north of Aspen, the bed of Hunter creek is at least 300 feet higher than that of the Roaring Fork at Aspen. Hunter creek forms thus, at its mouth, one of the best water-powers in Colorado. A portion of it is now utilized for electric lighting in Aspen, while in the near future, the whole of this magnificent natural power will be applied, through electric transmission, for hoisting, pumping and ventilating at different mines of the district. The mountain opposite the town of Aspen, on the east side of Hunter creek (which near its mouth flows southerly), is called Smuggler mountain, from the famous mine at the foot of it. On the other, or western, side of Hunter's creek (see map, Fig. I), a higher mountain rises, on the slope of which the regular dip of the Triassie or Upper Carboniferous red sandstone strata, alternating with white layers of the same rock, can be clearly seen from town. This mountain is called Red mountain, from the prevailing color of its rocky

Jan 1, 1889

By Ian Wark

SODIUM sulfide is used extensively to increase the recovery of oxidized copper and lead minerals by flotation, particularly when using xanthates as collectors. It is generally assumed that the sodium sulfide converts a film of the oxidized mineral to the sulfide, and that the xanthate, while not a very effective collector for the oxidized minerals, is a good collector for the sulfide. On the other hand, Taggart and his collaborators' claim that unless sulfide minerals are oxidized they cannot adsorb xanthates and do not float. Gaudin2 states that amyl xanthate, used in conjunction with sodium sulfide, gives better results than ethyl xanthate. Rabone3 and Mayer-Schranz4 agree that excess of sulfide functions as a depressant. Owing to the greater solubilities of the oxidized minerals than of the sulfides, the consumption of sodium sulfide is greater than that of most other flotation reagents, up to 10 lb. per ton of ore being used in some plants. Luyken and Bierbrauer5 recommend a water washing to remove soluble heavy metal salts; by this means sulfide consumption may be reduced. It was desirable to determine the limits of the sulfide concentrations between which contact is possible at surfaces of anglesite and cerussite in xanthate solutions. Similar determinations were desirable for the sulfide minerals with which the oxidized minerals are usually associated, since conditions should be chosen, if possible, so that the two types of mineral will float together. Because of the formation, especially in acid solutions, of hydrogen sulfide and of the hydrosulfide ion (HS-), the permissible limits of sulfide addition are obviously dependent upon the pH value. Sphalerite responds to ethyl xanthate only in the presence of an activator; for example, copper sulfate. It was necessary, therefore, to determine whether sodium sulfide interferes with the activation of sphalerite by copper sulfate. The combined effect of sulfide and copper sulfate was determined also for galena, chalcopyrite and pyrite.

Jan 1, 1936

By E. F. Bradley, R. I. Jaffee, H. R. Ogden, E. S. Bartlett, D. N. Williams

The mechanical properties of solid-solution-strengthened columbium alloys have been assessed as a function of alloying additions. Studies included the effects of tungsten, tantalum, molybdenum, and vanadium. Elevated temperature fabrication was required at alloying levels above about 15 pct W or 10 pct Mo. Tungsten, molybdenum, and vanadium additions increase tensile strength at room temperature and 2200°F, but tantalum additions exert little strengthening. Similarly, tungsten, molybdenum, and probably vanadium additions increase the ductile-to-brittle transition temperature, and tantalum additions decrease this parameter. The 2200°F stress-rupture strength is increased by tungsten and molybdenum additions; with 20 to 25 at. pct additions, 100-hr rupture strengths of 30,000 psi are obtainable. Small vanadium additions exhibit mild stress-rupture strengthening, and tantalum additions are innocuous. At 2500°F, tungsten additions retain stress-rutpure strengthening capability, but molybdenum additions are much less effective. Tantalum additions augment the stress-rupture strengthening of tungsten plus molybdenum additions at 2500°F. Of the refractory metals, columbium possesses specific potential for structural use in the temperature range from 2000" to about 2500°F. Desirable features of columbium are its good low-temperature ductility, ease of fabrication, oxidation mechanics (lack of a volatile oxide at moderate temperatures), good availability and reserves, and relatively low density. However, alloying is required to provide attractive strength at elevated temperatures. Published information concerning alloying be- havior of columbium relative to mechanical properties is sketchy, particularly in consideration for long-time applications at temperatures in excess of 2000°F. Only a few stress-rupture data at temperatures from 2000" to 2500°F have been reported;'-' these are too meager to allow rationalization of the effects of various alloying additions on creep or stress-rupture properties. Additional published data do, however, give some insight toward understanding of systematic alloying behavior for columbium relative to low-temperature strength4-' and ductility,' and elevated temperature tensile behavior.4,6 This paper is intended to augment previous knowledge, and to promote understanding of the alloying behavior of columbium for long-time structural service at elevated temperature. BASIC CONSIDERATIONS Solid-solution strengthening is recognized to be of prime importance in improving strength in columbium-base alloys. Other strengthening mechanisms may be (and are, in current alloys) used to augment solid-solution strengthening. As strengthening results primarily from lattice distortion, the strengthening effectiveness per atom depends upon atomic size mismatch between solvent and solute. Another factor in this regard is conformance to ideal solution behavior in the solid solution. Thus, for example, despite appreciable differences in the degree of mismatch between tungsten (5 pct), molybdenum (5 1/2 pct), and vanadium (7 1/2 pct) in solution in columbium, all are about equally effective in straining the columbium lattice at room temperature.'-' Similarly, tantalum additions do not strain the columbium lattice, and little strengthening is expected. Size effects being equal, maximum solution strengthening at high temperatures is anticipated to result from the addition of elements that increase the melting temperature of columbium. This expectation is based on an increase in the electronic bonding forces exhibited in the transition metal series as electronic structures approach those of the Group Vl metals. Of the metals that exhibit ex-

Jan 1, 1963

By Alwyn Birchmore Cox, Ian William Wark

Sodium sulfide is used extensively to increase the recovery of oxidized copper and lead minerals by flotation, particularly when using xanthates as collectors. It is generally assumed that the sodium sulfide converts a film of the oxidized mineral to the sulfide, and that the xanthate, while not a very effective collector for the oxidized minerals, is a good collector for the sulfide. On the other hand, Taggart and his collaborators1 claim that unless sulfide minerals are oxidized they cannot adsorb xanthates and do not float. Gaudin2 states that amyl xanthate, used in conjunction with sodium sulfide, gives better results than ethyl xanthate. Rabone3 and Mayer-Schranz4 agree that excess of sulfide functions as a depressant. Owing to the greater solubilities of the oxidized minerals than of the sulfides, the consumption of sodium sulfide is greater than that of most other flotation reagents, up to 10 lb. per ton of ore being used in some plants. Luyken and Bierbrauer5 recommend a water washing to remove soluble heavy metal salts; by this means sulfide consumption may be reduced. It was desirable to determine the limits of the sulfide concentrations between which contact is possible at surfaces of anglesite and cerussite in xanthate solutions. Similar determinations were desirable for the sulfide minerals with which the oxidized minerals are usually associated, since conditions should be chosen, if possible, so that the two types of mineral will float together. Because of the formation, especially in acid solutions, of hydrogen sulfide and of the hydrosulfide ion (HS-), the permissible limits of sulfide addition are obviously dependent upon the pH value. Sphalerite responds to ethyl xanthate only in the presence of an activator; for example, copper sulfate. It was necessary, therefore, to determine whether sodium sulfide interferes with the activation of sphalerite by copper sulfate. The combined effect of sulfide and copper sulfate was determined also for galena, chalcopyrite and pyrite.

Jan 1, 1939

By Ian William Wark, Alwyn Birchmore Cox

Sodium sulfide is used extensively to increase the recovery of oxidized copper and lead minerals by flotation, particularly when using xanthates as collectors. It is generally assumed that the sodium sulfide converts a film of the oxidized mineral to the sulfide, and that the xanthate, while not a very effective collector for the oxidized minerals, is a good collector for the sulfide. On the other hand, Taggart and his collaborators1 claim that unless sulfide minerals are oxidized they cannot adsorb xanthates and do not float. Gaudin2 states that amyl xanthate, used in conjunction with sodium sulfide, gives better results than ethyl xanthate. Rabone3 and Mayer-Schranz4 agree that excess of sulfide functions as a depressant. Owing to the greater solubilities of the oxidized minerals than of the sulfides, the consumption of sodium sulfide is greater than that of most other flotation reagents, up to 10 lb. per ton of ore being used in some plants. Luyken and Bierbrauer5 recommend a water washing to remove soluble heavy metal salts; by this means sulfide consumption may be reduced. It was desirable to determine the limits of the sulfide concentrations between which contact is possible at surfaces of anglesite and cerussite in xanthate solutions. Similar determinations were desirable for the sulfide minerals with which the oxidized minerals are usually associated, since conditions should be chosen, if possible, so that the two types of mineral will float together. Because of the formation, especially in acid solutions, of hydrogen sulfide and of the hydrosulfide ion (HS-), the permissible limits of sulfide addition are obviously dependent upon the pH value. Sphalerite responds to ethyl xanthate only in the presence of an activator; for example, copper sulfate. It was necessary, therefore, to determine whether sodium sulfide interferes with the activation of sphalerite by copper sulfate. The combined effect of sulfide and copper sulfate was determined also for galena, chalcopyrite and pyrite.

Jan 1, 1939

By Harry Roeser

Short cuts for determining the constants of oil decline curves, with the method of least squares as a starting point, are presented and applications made to practical examples. The nature of the raw data does not justify rigid adherence to the orthodox theory but does lend justification to convenient methods of approximation within reasonable limits. If the conventional form y = kxn were changed to y = k(x + c)', methods of determining the curves would be simplified and greater uniformity in calculated results would probably follow. As A result of the publication, several years ago, of some articles on determining the constants of empirical formulas, the determining the constant's of types of curves used for estimating the production decline of oil wells was brought to the writer for study. Methods requiring a minimum of time and labor and a maximum of rigor were sought, as it appeared that the nature of the data from which such curves are computed and the relative uncertainty of occurrence of the events predicted from them did not justify close adherence to the theory on which the solution of such problems is ordinarily based. The technical deficiencies of the solutions presented in this paper, from the standpoint of the method of least squares, are readily apparent to those familiar with that method, but their presentation in detail here is irrelevant to the subject matter. However, it is the author's conviction, after a rather exhaustive study of the problem, that the value of the solutions lose little by the approximate application of the conventional theory. It must be understood by those who use these formulas that the solutions herein given, and the formulas based on them, are merely facilities to aid the valuation engineer in forecasting future events. It is assumed, also, that before application is made of them, prescient judgment based on the circumstances in each case, shows that the forecast has some probability of realization. On this basis only will these formulas be found useful.

Jan 6, 1924

By Harry Roe

THE power drag scrapers and the slackline cableway excavator have been called "long-range excavators." Broadly, their field of usefulness is restricted to work in which their long range of action permits them to operate economically, and which other, possibly more conventional, excavating units cannot do. Both of these machines dig or lift material and transport it to a clumping point. They combine these two functions in a single machine, nearly always in a single straight-line motion. FIG. I.-SIMPLE FORM OF POWER DRAG SCRAPER. The purpose of this paper is to examine the important features that distinguish the machines in this group from each other, as well as from other groups.

Jan 1, 1937

By Henry Howe

THE data which are collected in Table 1 show that the ferrite of low-carbon steel and of electrolytic iron, like the network of hypo- and hyper-eutectoid carbon steel, inherits, either absolutely or relatively, the, grain size of the mother austenite from which it is born in cooling through the transformation range. This evidence is so abundant and concordant as to cast doubt on Prof. Jeffries' 1 hypothesis of what might be called reversed inheritance, by which he explains Mr. Ruder's observation2 that the grains of a "slug of pressed pure electrolytic iron powder"were coarser, perhaps 12,000,000µ2, after a 3-hr. exposure to 1000° C. than after a 3-hr. exposure to 1250-1300°, when they were about 35,000µs. His explanation implies a natural tendency of coarser austenite grains to yield finer ferrite ones than spring from finer austenite grains, so that the inheritance is reversed. What seems to me a simpler explanation is that the enormous grains which followed the 1000° heating were not inherited from the mother austenite, but were formed by the process of natal coarsening, by means of which Stead and Carpenter developed grains of this same order of magnitude in this same kind of material, on heating to 950° or to 1000°, the temperature used by Mr. Ruder, provided the exposure was not unduly prolonged, and it does not seem to have been in Mr. Ruder's case. That their coarsening was natal and not through inheritance is shown first by the fact that their grain coarseness was out of all proportion to their relatively low temperatures and short periods, and hence was very far in excess of the grain size which the mother austenite must have had, and second and more cogently by the fact that the shape of these coarsened grains was evidently determined by the temperature distribution which existed during and immediately after the Ar3 transformation, that during the passage from the gamma to the non-gamma state.

Jan 9, 1917

By Henry M. Bates, Roscoe Pound

Mr. Chairman and Gentlemen: I accepted your Chairman's invitation to speak to a group of experts in this field with the greatest hesitation, because I know little or nothing about it. Certainly I can make no detailed suggestions, or suggest planning along very definite lines. You cannot do that sort of thing in a vacuum, and as I have suggested, my knowledge of the whole oil problem is next to nothing. It is possible that as a student of our public law, constitutional law particularly, for a number of years, I have acquired a perspective that may enable me to offer, for what they are worth, some general thoughts on these problems. I think that nothing in the whole field of law requires more definitely and clearly the functional approach than does the problem of a sound legal solution of the difficulties of the oil and gas industry. The industry is dealing with substances that are peculiar, and one must know how those substances act and what has been the history of the industry, to undertake to make anything like specific suggestions. I certainly am not qualified.

Jan 1, 1935

By Robert H. Leach, C. H. Chatfield

This paper gives a brief summary of the process of manufacture of sterling silver, and some of its more important physical properties, as observed in conlmercial production of rolled sheet and wire. Although papers have been published by Turner and Smith,1 Rose,2 Sperry3 and Jordaq4 there are few technical data available, and unfortunately the time allowed for the preparation of this paper has not been sufficient to make it as comprehensive as the title might indicate. Analysis of Steeling Silver Fine or pure silver is too soft for coinage and the manufacture of articles in which strength and resistance to wear are desired. From the earliest times of which we have record, copper has been the metal generally used to harden silver. Analyses of coins and silver articles from ancient tombs show varying amounts of copper, and old Roman silver objects in the British Museum have approximately the same ana,lysis as our sterling. The first authentic record of the establishment of a standard alloy is during the reign of Henry I1 in England. During the twelfth and thirteenth centuries, the people in the Eastern Provinces of Germany had a reputation for the standard and purity of their silver coinage, and it is said that Henry II employed some of these Easterlings, as they were called, to improve and standardize the English coinage, which had become debased. The peculiar standard adopted is probably accounted for by the system of weights used. A troy pound contains

By Robert Leach

THIS paper gives a brief summary of the process of manufacture of sterling silver, and some of its more important physical properties, as observed in commercial production of rolled sheet and wire. Although papers have been published by Turner and Smith,1 Rose,2 Sperry3 and Jordan,4 there are few technical data available, and unfortunately the time allowed for the preparation of this paper has not been sufficient to make it as comprehensive as the title might indicate. ANALYSIS OF STERLING SILVER Fine or pure silver is too soft for coinage and the manufacture of articles in which strength and resistance to wear are desired. From the earliest times of which we have record, copper has been the metal generally used to harden silver. Analyses of coins and silver articles from ancient tombs show varying amounts of copper, and old Roman silver objects in the British Museum have approximately the same analysis as our sterling. The first authentic record of the establishment of a standard alloy is during the reign of Henry II in England. During the twelfth and thirteenth centuries, the people in the Eastern Provinces of Germany had a reputation for the standard and purity of their silver coinage, and it is said that Henry II employed some of these Easterlings, as they were called, to improve and standardize the English coinage, which had become debased. The peculiar standard adopted is probably accounted for by the system of weights used. A troy pound contains

Jan 1, 1928

By Price E. R.

The coal industry was beset with work stoppages and strikes throughout the year, and there was some loss in markets to oil and gas. These conditions, along with the mild decline in industrial activity, the steel strike, and the reduction in exports, contributed to an unfavorable year for the industry. All coal mines are working three days a week at the time of writing, and in estimating production for the year, it will be assumed that the mines will continue to work on that basis through December. Total production of bituminous coal in 1949 is estimated at 420 million tons, which is 179,518,229 tons under the production in 1948. Anthracite production is expected to reach 39,400,000 tons as compared with 57,139,948 tolls in 1948, a loss of 17,739,948 tons. Coal stocks, as of January 1, 1949, were 69,373,000 tons but at the end of the year will have dropped to approximately 22 million tons. Regardless of the difficulties during the current year, the industry has made substantial

Jan 1, 1950

By Emil Gathmann

Ik presenting this paper I will attempt to answer certain questions proposed at this meeting and describe and illustrate methods of producing sound steel in an economical and hence commercial manner, which are adaptable to the production of practically all steel manufacturers, by readily effected rational changes in the methods of casting, cooling, and subsequent handling of the ingots. In some of the high-grade mills of America, where it is essential to obtain perfectly sound billets or blooms, it is the practice to discard from 35 to 40 per cent. of the crop- or pipe-end, and even with this excessive discard, secondary pipe or shrinkage-cavities are frequently discovered during subsequent working of the blooms and billets into their various manufactured products. The usual discard of from 10 to 20 per cent, from the crop-end of the ingot, which is made by the present generally employed methods of form and solidifying of the castings, certainly does not give the slightest assurance of the saleable product being physically sound or chemically homogeneous. I am aware that in the past there has been and at the present time there still is a decided difference of expert opinion as to what constitutes physically sound steel. Physically sound steel, as I would classify it, must be free from blow-holes as well as pipe. The line of demarcation between harmless and harmful blow-holes is exceedingly difficult to define. It is certainly the better and safer practice to eliminate blow-holes from the saleable portion of the ingots and to form a well-defined shrinkage-cavity or pipe at the upper crop-end of ingot. The higher grades of steel are all piping-steels. Is not their superior physical quality due to this fact as well as to their better chemical composition ? Such

Jan 1, 1914

By S. J. Aparo

After surveying the beneficiation techniques in the Florida phosphate field, it is apparent that optimum beneficiation of this ore is a difficult task. Due to continually changing grade, size distribution and basic nature of the ore, there appears to be no universal technique nor a single reagent entirely satisfactory for achieving optimum metallurgy under these dynamic conditions. Although no major change in the basic flow sheet has been made in the last 20 years, there have been many refinements of the process in recent years which have helped increase production, improve recovery, lower unit cost of operation and make the beneficiation of lower grade deposits economically feasible. Among the significant changes is the use of larger plants and equipment which has helped to increase production significantly. The use of cyclones has facilitated and reduced the cost of slimes removal in these large plants. There have also been several new approaches to the flotation of coarse phosphate that are mentioned in the text of this paper. Lastly, significant improvements have also taken place in the area of flotation reagents.

Jan 1, 1970

By S. M. Moos, R. E. Dugger

In reviewing available vacuum filtration equipment in this paper, several types of filters have been included which are probably not familiar to operators in the mining industry. However, it was felt that these units might be of interest in the event that an application should arise for the filtration of a product in the future that does not exist today. In addition, exposure of our industry to equipment used in other industries might have a tendency to be thought provoking and perhaps lead to the development of equipment and/or applications in our industry which do not necessarily exist at this time. Most innovations in filtration equipment have been confined to the improvement or design change of components and accessories, particularly reflecting the availability of materials of construction that have been developed. Recent developments in the application of horizontal belt filters have been innovative. The application of this unit as a substitute for or an adjunct to thickeners in a CCD circuit can certainly be innovative and perhaps provide a basis for reduction in capital and operating costs in this area. For example, mill tails are generally pumped at the highest possible density that will adequately flow. Tailings ponds and dams with their attendant design requirements are based upon this estimated water volume. Availability of a much dryer, non-flowing filter cake opens up several new options for disposal. Considerable cost savings could result in the design and planning of disposal areas for containing dryer material. No attempt has been made in this paper to provide a manual for the operation of all of the many types of equipment that are available. Rather, the paper tries to present an overview. Fundamentals of Vacuum Filtration Filtration may be defined as the separation of solids from a liquid effected by passing the liquids through a porous medium. If the filtrate is induced to flow through the medium by hydrostatic head, we refer to it as gravity filtration. If we utilize super-atmospheric pressure upstream of the medium we call it pressure filtration and if sub-atmospheric pressure is applied downstream of the medium we call it vacuum filtration. Centrifugal filtration occurs when a centrifugal force is applied across the medium. Centrifuges will not be discussed in this paper. The process goal of filtration may be the production of dry solids where the cake is the valuable product, clarified liquid

Jan 1, 1980

By G. Bjorling

The opening oxidation of a hydrometallurgical treatment of natural sulphides must for several reasons be so controlled that a maximum of the sulphide sulphur is transformed into elemental. If the oxidation is performed at low pressure and moderate temperatures and with mild reagents such as diluted nitric acid (or ferric or cupric chloride) the just mentioned condition is realized and it has been found possible to conduct the reaction so that solutions are obtained from which the metals can be recovered and the reagents required for the dissolution are regenerated. Experiments in laboratory scale with nitric-acid promoted oxidation have shown that this method is applicable to several types of raw materials, and in combination with electrodialysis both for partial neutralization and for final regeneration of the circulating acid can the requirements of low consumption of chemical reagents and formation of harmless residues be well fulfilled. The metals can be recovered as cathodic deposits or as hydroxides, and the method should be applicable also for low grade ores and concentrates. Although oxidation of sulphides by ferric or cupric ions has the advantage that it can be performed in open vessels it seems well worth the complication of working with nitric acid promotion in a low-pressure autoclave. Also complex sulphidic, oxidic and metallic materials can be treated.

Jan 1, 1973

By D. Turnbull, J. H. Hollomon

THERE is a large body of evidence'" indicating that solidification during the liquid-solid transition is usually induced by heterogeneities present in the liquid. By dispersing liquid metals into small droplets, the impurities responsible for catalyzing solidification are isolated within a small number of these droplets. The effect of the foreign body therefore is restricted to a single drop by this technique. Thus upon cooling below the melting temperature, solidification is initiated by homogeneous nucleation in the majority of the droplets that do not contain impurities. In the case of solidification of liquid metals, the activation energy for nucleation is so great that its rate changes by orders of magnitude for a change in temperature of only several degrees centigrade.' Effectively homogeneous nucleation occurs at a critical temperature upon continuous cooling. Thus by microscopic observation of single particles during cooling, a temperature at which the rate of homogeneous nucleation becomes sensible can be determined.3 since at the temperatures at which nucleation occurs in the absence of impurities the rate of crystal growth is extremely rapid, the temperature at which the entire particle solidifies is very nearly the temperature at which the nucleation of the solidification occurs. Thus for liquids that freeze at high temperatures the onset of nucleation can be established by simply observing the temperature at which the marked heat evolution and increase in brightness of the particle occur. For liquids that freeze at lower temperatures the onset of nucleation can be determined by a rumpling and change in shape of the particle resulting from its solidification. The microscopic technique for observing the solidification of small particles has already been described." In earlier papers the nucleation of solidification of pure metals 5,6 and of alloy systems7 showing complete liquid and solid solubility have been described. In the present paper, the observations are extended to a simple eutectic system (Pb-Sn) where the possibility of the formation of two solid phases exists. Metals for the investigation were obtained from the American Smelting and Refining Co. in the form of pure lead and pure tin, 99.8 and 99.9 pct purity, respectively. An ingot of each of the pure metals was made into shot by heating the metals at a temperature about 50 °C in excess of the melting point and pouring the liquid slowly into a container of water at 15°C. Samples of the shotted pure metals were weighed out to make alloys containing 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, and 90 atomic pct Pb. Samples of each alloy were then melted in separate beakers. Each melt was poured through a pyrex funnel into a cylindrical mold (% in. ID). The casting solidified in 10 to 20 sec. The inside of the mold as well as the funnel through which the metal was poured were coated with graphite to eliminate adherence of the metal. Analyses were performed on some of the compositions and are given in Table I. The compositions also were checked for these samples and for those that were not analyzed by determining the spread between the liquidus and the solidus upon melting the small metal particles. These measurements agreed as well with the nominal compositions as the analyses listed above. Results The results of the supercooling experiments for the several alloys are summarized in Table II and plotted on the constitution diagram in Fig. 1. Data for the pure lead and pure tin were taken from earlier investigations. The values for the maximum supercooling of the several alloys are the average of several determinations on a number of drops of each alloy. The maximum value in any determination was within about 2 pct of the average. For the alloys containing from 20 to 60 atomic pct Sn, inclusive, two marked changes of the surface structure were observed upon cooling. At the higher temperature, after the first appearance of the solid phase it continued to grow slowly at a constant temperature and then stopped. At the lower temperature the alteration of surface structure was abrupt. For the alloys containing from 70 to 95 atomic pct Sn, inclusive, an abrupt change in surface structure was observed at a single critical temperature.

Jan 1, 1952

By W. H. Bassett

Beads of metal frequently appear at the ends of cast-copper wire bars and on the sides of wedge cakes near the top. These are richer in cuprous-oxide than the rest of the casting. A micrographical study of these exudations has been made. It is suggested that the material is forced through the surface while the copper is solidifying. If not eliminated in process of manufacture, it shows on the finished polished sheet copper in patches differing in color from the main body of the sheet. FIGURES 1 to 4 show the copper exudations, at different magnifications, as they appear on the ends of cast wire bars, and on the sides, usually near the top, of wedge cakes. Sometimes the exudations are in fine "drops;" at other times, large masses of the material are found. Microscopic examination of the copper exudation indicates that it is high in oxide and of eutectic proportions. Because of the difficulty of securing a suitable sample, the protuberances have not been analyzed chemically; but the spectroscope shows no indication that there are any more metallic impurities present than in the balance of the copper. The lowest copper plus silver content of the coppers studied for this? paper was 99.914 per cent.; the highest, 99.966 per cent.; so the oxygen content of the whole casting would be well under 0.07 per cent.

Jan 2, 1926

By J. D. Milburn, H. J. Hill

In quantitative interpretation of electrical logs the presence of clay minerals introduces an additional variable which further complicates an already complex problern. Although recognizing the difficulties introduced as a result of the heterogeneity of natural sediments and despite the present incomplete state of knowledge regarding electrochemical behavior of shales, dissemirzated clay minerals and concentrated electrolytes, it was felt that useful empirical correlations might be obtained from experimental investigation. Six typical sandstone formations, having a wide variety of petrophysical properties, were selected for the study. Approximately 45 samples from each formation were selected to satisfactorily represent the range of pore size distribution within the particular formation, As a matter of general interest, four limestone formations were also included in the investigation. Previously proposed equations relating to resistivity, SP and interrelationship of the two phenomena have, where possible, been tested with data obtained in this investigation. These equations do not satisfactorily describe experimental behavior of samples through all degrees of shaliness or throughout the range of brine solution resistivities normally encountered in logging practice. An empirical equation has been developed which quantitatively relates formation resistivity factor to satirrnting solution resistivity, porosity, and "effective clay content." This relation is indicated to be uniformly applicable to clean or shaly reservoir rocks. It is shown that both the SP and resistivity phenomena of shaly samples are related to the sample cation exchange capacity per unit pore volume. The independent chemical determination of this parameter is thus a means of determining the "effective clay content" of samples. Some implications regarding theory and electric log interpretation of shaly sands are discussed. INTRODUCTION The use of electrical resistivity logs as a means for estimating formation porosity is based upon the original work of Archie1. It was shown by empirical methods that the resistivity of a rock, when 100 per cent saturated with brine solution, could be related to rock porosity through the equation, F = Ro/ RW = f-m.......(1) where F, the formation resistivity factor, is defined as the ratio of the resistivity of the 100 per cent water saturated rock, Ro, to the saturating solution resistivity, Rw; f is the ratio of pore volume to bulk volume; and m is the slope of the average line when the data are plotted on log-log paper. This relation was established for relatively shale-free formations containing water having high salt concentrations, and under these conditions F may be considered constant for a given rock sample. Applications of Eq. 1 to interpretation of logs of shale-free formations has been quite successful when satisfactory formation water resistivity data could be obtained. The most readily available means of estimating formation water resistivity is the self-potential log. Conventional methods of SP log interpretation involve correct.

Jan 1, 1957