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J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—The fact that the experimental work has been applied to copper rather than iron and that the paper is presented to the Iron and Steel Division, I regard as rather significant. It shows the unity of metallurgy and the fallacy of trying to cut it up by metals. This result for the solubility of sulphur in molten copper correlates with Professor Schuhmann's finding that the published data on the other side of the copper-sulphur miscibility gap are also in error. I should like to ask the author to say a little bit more about the sulphur capacity of the slag. T. Rosenqvist (author's reply)-—I hope that Dr. Chipman will find the derivation of the expression for sulphur capacity more clearly explained in the printed version of the paper than in the oral discussion at the meeting. I feel that this quantity, which actually is the ratio of two activities, can be measured more easily than the individual activities. Even if the ratio CaO/CaS is chosen as the standard state, the expression can be used for any slag, even for slags completely free of lime, and it represents a way to put the desulphurizing power of all slag constituents into one bag. Some doubt has been expressed as to whether oxygen ions really exist in calcium oxide and in molten slags. From a thermodynamic view point that question is of minor importance. The term oxygen ion activity, or any activity for that matter, is defined rigorously by the equation: activity = exp u/RT, where u is the change in free energy connected with the transfer of one mol of ions from the standard state into the slag. Whatever happens to the ion in the slag is of no concern to the thermodynamicist. Regardless of whether the ion is "free" in the slag or not, or whether it is present in a very small amount, its activity can always be expressed, and for a thermo- dynamic calculation that is all we need. However, ionic activities will only be of some real value if they are simple functions of the slag composition, or can be measured easily. Concerning the real nature of the oxygen in the slag, my feeling is that the oxygen atom has a rather multiplex nature depending on how strongly it is tied by covalent forces or polarized by the other atoms or ions present. The oxides of iron, cobalt, and nickel differ from calcium oxide and blast furnace slags as to the amount of free electrons that can give rise to electronic conductivity. In slags we know that the conductivity is mostly ionic. The fact that reversible emf's can be obtained with oxygen electrodes in certain salt melts, indicates a significant amount of oxygen ions in these melts. But extended work, e.g. polaragraphic studies and measurements of transference number; are needed to obtain quantitative information about the real structure of the slags. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—-With reference to the ion, it might be well to remember Dr. Moses Gomberg. All of his life he had no use for the ionization theory and he contributed greatly to the field of chemistry on the assumption there was no such thing as ions. I do not think we have to worry about whether the oxygen is ionic or not. I think one thing specifically should be brought to your attention and this I think is one of the important contributions of Dr. Rosenqvist. He pointed out what we know as oxygen potentials or what is described as oxygen potentials. I have used this concept for a long period of time and I want to state that if this concept is properly applied, it vitiates much of what we have in the literature, or makes our usual ideas regarding oxidation seem primitive. That one thing is more valuable than almost all the rest of the discussion as a fundamental basis on which to build a reasonable in-

Jan 1, 1952

While coal was mined in New Mexico in 1860, production was on a small scale during the period considered here, and Table 77 contains all the data found. [ ]

Jan 1, 1942

By E. C. van Reuth

FIFTY-three alloys have been examined in the Fe-W and Co-W alloy systems in an attempt to verify the finding of o phases in these systems as reported by Goldschmidt.' The alloys were examined metallographically and by X-ray diffraction. The 10-g specimens were made by powder metallurgy techniques. Very fine, high-purity powders were compressed in a double-acting die at 120,000 psi after hydrogen reduction. All compacts were then sintered for 200 hr at 950°C in a helium atmosphere. Metallographic investigation and X-ray diffraction proved this time to be sufficient to allow complete homogenization before the subsequent high-temperature anneal. Each specimen was then sealed into an evacuated silica capsule and annealed at 1400"or 1500 C (except two) for 25 hr. (The 60 pct Fe and 55 pct Co alloys taken to 1610"and 1680°C respectively were held at these temperatures for 1hr. However, since these structures were at equilibrium before the anneal, and in view of their resultant structures, it is assumed that they reached equilib-

Jan 1, 1960

By Alexander Sattman, Anton Homatsch

Jan 1, 1894

By C. R. St. John, R. W. Lindsay, Charles R. Austin

MANY of the factors influencing the creep behavior of ferrous alloys have been investigated and reported upon in the literature, including such variables as grain size, steelmaking practice, nature and stability of the microstructure, and the effect of alloying elements in steels. However, with respect to the latter, the microstructures involved are usually heterogeneous and as a result the effect of the addition is related to its effects on the various phases present in the microstructure. In the instances where this structure consists of ferrite and carbide, the behavior of the alloy addition will be related to its action in strengthening ferrite and in opposing temperature softening of ferrite as well as coalescence of carbide. The present paper is the third in a series comprising a comprehensive review of investigations on the properties of iron binary alloys. 1.2 Its purpose is to describe the results of isolating one microstructural phase, namely ferrite, and studying its creep characteristics in both the unalloyed and alloyed conditions. This should aid in establishing to a large degree the importance of ferrite in the creep behavior of steels consisting of the previously mentioned ferrite-carbide aggregate. REVIEW OF PREVIOUS WORK In view of the fact that the present investigation deals only with the effects of silicon, manganese, chromium, molybdenum, nickel, and cobalt, and to a certain extent with the effects of carbon, the review of previous literature will be confined to these elements. Practically no references were encountered dealing with the influence of these elements on the creep characteristics of the isolated phase. However, various contributions have dealt with the creep behavior of low-carbon steels alloyed with the elements under consideration. A particularly concise review in this respect is given by Bullens (Battelle)3 and much of this material has been drawn upon. The definite improvement in creep resistance and high-temperature strength conferred by molybdenum is well known. Published suggestions by the A.S.M.E.4 permit of an increase of some 2000 to 5000 lb. per sq. in. in permissible design loads over a temperature range from 650° to 1000°F. as a consequence of additions of 0.40 to o.60 per cent of this element in carbon steels of the order of o.25 to o.35 per cent carbon content. Babcock and Wilcox Tube Co.5 has published data showing the pronounced increase in stress necessary to cause one per cent creep per 10,000 hr. when additions of 0.5 or 1 per cent molybdenum are made to a plain carbon steel. These data apply to temperatures over a range from 800° to 1000°F.

Jan 1, 1945

By George Sachs, S. M. Clark, George Espey

he tendency of a commercially drawn cartridge case to crack in the mercury test and the relation of cracking tendency to residual stress retained after drawing were studied. The fourth drawpiece (next to the final) of caliber 0.30 cartridge cases produced by Frankford Arsenal were selected as test pieces. These exhibited an exceptionally high cracking tendency, making a detailed study possible. To obtain fast cracking in the mercury test, about 0.0015 to 0.003 in. must be removed from the wall thickness of the drawpiece by pickling, and it must be subjected to the mercury test immediately after washing. Removal of the adhering mercury by annealing and subsequent squeezing of the case in a vise was used to reveal definitely the presence or absence of cracks. Various lots of apparently identically fabricated cases were shown to possess a different cracking tendency. Machining off or boring a hole in the base gradually reduced and eventually eliminated the cracking tendency. On the contrary, shortening of the wall (body) reduced the cracking tendency only if the wall became so short that the cracking zone was directly affected. By boring out the base and pickling from the outside and then splitting the resulting rings, it was possible to determine the approximate stress distribution in the base and in the adjacent part of the wall. Small compression stresses were present in the core and the major part of the base, while the surface of the base and the adjacent wall contained high circumferential tensile stresses. On the contrary, the wall when parted from the base contained only insignificant residual stress. The conception is advanced, that the stress distribution in a drawn cartridge case corresponds fundamentally to that of a tube (wall) shrunk on a disk (base). Such a stress distribution results from the tendency of the base to recover elastically by an increase in diameter from the biaxial compression during drawing while the wall exhibits little tendency to change its diameter after progressing through the die. This is confirmed by measurements which show the base diameter to be slightly larger than the wall diameter.

Jan 1, 1945

By H. Gisser

Recent experimental work has demonstrated (1)2 that ammonia and oxides of nitrogen are formed during the aging of smokeless powder. This is significant in connection with the problem of "season cracking," or stress corrosion of brass cartridge cases in view of other work(1) indicating that stressed and "stress- relieved" cases stored with small quantities of added ammonium nitrate crack on firing. The deterioration of stressed brass by ammonia has been known for some time(z) and it appears therefore that stress- corrosion cracking of brass cartridge cases is intimately associated with the so-called "powder volatiles," ammonia and oxides of nitrogen, both of which are decomposition products of smokeless powder. Working on the hypothesis that any barrier which prevents the powder volatiles from reaching the brass surface will reduce the incidence of stress-corrosion cracking, it was considered desirable to investigate the use of organic resin films to accomplish this purpose. The possibility of formation of ammonia within the nitrocellulose powder charge and by reduction of nitrogen oxides on the surface of the brass case requires that the barrier film be resistant both to ammonia and oxides of nitrogen. The film must also be impermeable to ammonium salts, either solid or in solution, since these salts and water necessarily appear within the powder charge. The usefulness of the

Jan 1, 1945

By Robert G. Peets

After 216 years, the end of operations at the Corn- wall mine can be foreseen within the next two decades. The story starts in 1732 when three sons of Wiliam Penn-John, Thomas, and Richard-deeded 9669 acres in the Province of Pennsylvania to a Joseph Turner, who assigned it to William Allen. In 1734 Peter Grubb, who had prospected for iron in the area, paid Allen £ 135 for 300 acres of this tract in what is now Lebanon County. In 1737 he was granted a warrant for 142.5 additional acres, which included three hills of outcropping magnetite described as "rich and abundant, forty feet deep, commencing two feet under the earth's surface." This seemingly inexhaustible reserve was to become one of the most valuable deposits in the U. S. before the ore-rich Lake Superior region was developed.

Jan 7, 1957

By W. F. Cloud

The data and information compiled under Part I of this report are the results of experiments performed in the petroleum engineering laboratory under the supervision of W. F. Cloud, Associate Professor of Petroleum Engineering and William Schriever, Professor of Physics, University of Oklahoma. Problems Being Studied Most of the time has been spent in trying to determine the rate of flow and pressure gradient in a 4-in. flow tube 10 ft. long, which was packed with sand of various grain sizes. To date, only two kinds of sand have been packed in this tube: 60 to 80-mesh Canadian river sand, 60 to 80-mesh and 80 to 100-mesh Simpson sand. The original intention was to follow the same procedure and use the same types of crude under identical saturation pressures of both air and gas, as well as unsaturated (dead) oil, flowing the various crudes through several different sizes of both Canadian river and Simpson (Wilcox) sands, but lack of time has prevented such an intensive study of the problem. Some additional time has been spent flowing saturated and unsaturated crudes, similar to those used in the 4-in. tube, through 1-in. tubes, one of which was 2 ft. long and one 5 ft. long. The results obtained have been checked against those obtained by using the 4-in. tube, to obtain the relation of diameter and length of tube to rate of flow in similar sands. Laboratory Equipment Saturation Tank.—A heavy steel cylindrical saturation tank, capacity about 42 gal. was mounted on a platform of bricks, then a galvanized tin temperature bath was built around the saturation tank. This contained

Jan 1, 1930

George IV. Goetz, Milwaukee, Wis.: Mr. Campbell deserves much credit for his interesting paper. The literature of the development of the open-hearth process is distributed in many technical journals, and is difficult of access to many engineers. Since the development of the basic process, the open-hearth furnace has been raised from a subsidiary to an independent position. Certain high grades of soft steel can be produced in the basic open-hearth furnace, which cannot be produced by any other known process. In the United States the charges for the acid process generally consist of either scrap and pig-iron or so-called wash-metal and scrap : the pig-and-ore process, as carried out in England, is practiced but very little. The introduction of the basic process has made it possible to use about four times as much pig-iron with scrap as can be used in the acid mixtures. The availability of a cheap pig-iron, very low in silicon and sulphur, and carrying several per cent. of manganese, is one of the reasons why the basic open-hearth process has developed so rapidly in Germany, as regards the output per furnace and the excellent quality of the material produced. The acid Bessemer steel has an inherent stiffness, which is plainly shown when spring steel is made by the Bessemer and by the openhearth processes. In order to get them of about equal stiffness, the open-hearth steel must have about 0.60 per cent. carbon ; whereas, the Bessemer steel must then have ahout 0.45 carbon, the remaining constituents being apparently about the same in each product. It has proved impracticable, with American coke-pig-iron, to interrupt blowing at a certain point in order to make hard steel; and experience has therefore shown that it is best to eliminate nearly all the carbon, and then to recarburize to the desired point. This practice

Jan 1, 1894

By T. D. Yensen

In the investigation of the magnetic properties of iron-nickel alloys,' it was found necessary in order to make the alloys forgeable, or malleable, to add small quantities of some other element. Iron-nickel alloys have been known for nearly a century, but have been made in commercial quantities only since 1885. Their remarkable mechanical properties were disclosed by Riley in 1889 and from that time on a large amount, of research work has been done both to discover new properties and to correlate the results obtained.2 Lately the Bureau of Standards has collected the published data in a special circular" giving in compact form an account of the properties of the iron-nickel alloys. It also contains a clear historical sketch of the development as well as a selected bibliography. The chief difficulty with the development of iron-nickel alloys was that the "pure" alloys do not forge readily. The addition of small amounts of manganese, however, made the alloys forgeable, and manganese has therefore come to be regarded as a necessary constituent of nickel steels. The present paper shows to what extent manganese is needed for various nickel contents and also what is the effect of other alloying elements on the forgeability. It also touches upon the cause of forgeability but refers to other sources for more exhaustive treatises on the subject. The alloys were prepared by melting electrolytic iron and electrolytic nickel with or without other alloying elements in the desired proportions in a magnesia crucible in a vacuum furnace under a pressure of 1 mm. mercury. The ingots, weighing about 2 kg., were allowed to cool in vacuo. If pipes or blowholes were present, the ingots were cut in such

Jan 1, 1922

By T. D. Yensen

In the investigation of the magnetic properties of iron-nickel alloys,' it was found necessary in order to make the alloys forgeable, or malleable, to add small quantities of some other element. Iron-nickel alloys have been known for nearly a century, but have been made in commercial quantities only since 1885. Their remarkable mechanical properties were disclosed by Riley in 1889 and from that time on a large amount, of research work has been done both to discover new properties and to correlate the results obtained.2 Lately the Bureau of Standards has collected the published data in a special circular" giving in compact form an account of the properties of the iron-nickel alloys. It also contains a clear historical sketch of the development as well as a selected bibliography. The chief difficulty with the development of iron-nickel alloys was that the "pure" alloys do not forge readily. The addition of small amounts of manganese, however, made the alloys forgeable, and manganese has therefore come to be regarded as a necessary constituent of nickel steels. The present paper shows to what extent manganese is needed for various nickel contents and also what is the effect of other alloying elements on the forgeability. It also touches upon the cause of forgeability but refers to other sources for more exhaustive treatises on the subject. The alloys were prepared by melting electrolytic iron and electrolytic nickel with or without other alloying elements in the desired proportions in a magnesia crucible in a vacuum furnace under a pressure of 1 mm. mercury. The ingots, weighing about 2 kg., were allowed to cool in vacuo. If pipes or blowholes were present, the ingots were cut in such

Jan 1, 1922

By S. S. Clarke

LATE in 1942, the increasing demand for zinc, coupled with the growing shortage of miners and the knowledge that some abandoned mines would have to be reopened for prospecting and development, led to considerable thought as to the possibilities of further mechanization in order to conserve man power. The ore bodies, locally termed "sheet ground," are an important ore bed in some mines and are in the lower part of Boone formation of the Mississippian Series. Some mines contain interbedded layers of nearly pure galena and sphalerite in horizontal sheets ranging in thickness from a thin seam to several inches and is persistent over large areas. This type of ore body offered the best opportunity for study and experiments. The use of jumbo drill carriers was advanced but some doubt was expressed as to the adaptability of jumbos as then in use to mine headings as compared to post and arm mounting (Fig I). Another consideration was the introduction of truck haulage when several mines were trackless. A drill frame, built to carry 2 4-in. drifters, was mounted on a truck chassis. This design proved a failure as it was not rigid and the resiliency of the tires and springs allowed too much play. Long screw jacks were then used to hold the truck firmly in place, but placing the jacks and securing the truck required more effort and time than setting up post drills, so the truck carrier was abandoned. The use of a bull dozer underground had been under consideration for some time to be used in "brunoing" the broken dirt from behind pillars and other inaccessable places so the slusher drags could load without double dragging the dirt. A dozer with hydraulic blade lift was purchased and R. I. Tuthill, Superintendent of Section 30 Mines, suggested that a long drill arm be substituted for the blade, and the drills mounted on the cross member. The hydraulic lift would permit drilling holes at any required spacing. The "cat" was very mobile and answered the problem of a trackless mine. The initial tests showed that the "cat" would make a good carrier, but the hydraulic controls Were not positive enough to keep the drills in alignment while drilling. The next step was to build a small hoist. This hoist was attached to the power take-off on the "cat" and by means of sheaves and a double line of 3/8-in. hoist cable, a positive control for raising and lowering the boom was obtained. To avoid serious injuries to the drillers should the cable break, a safety chain was fastened to the drill boom and hooked into a slot in the back of the "cat" frame. A different power unit was obtained for the "cat," as a state law prohibited the use of internal combustion engines in mines. A custom machine shop had just placed on the market a small hoist powered by a Model A Ford engine that had been very ingeniously converted to a slide valve engine using compressed air. To use this unit on a "cat," our master mechanic de-

Jan 1, 1947

By Maurice Ewing

THE purpose of this paper is to present the results of the application of the earth-resistivity method of subsurface investigation to the problem of locating seams of anthracite coal beneath a mantle of soil and subsoil. Details are given of the successful use of this method in locating the outcrops of anthracite seams in actual prospecting. The presence of the outcrop of an anthracite seam is indicated at points where electrical resistivity tests showed relatively low readings. The reason for this is that in some localities the resistivity of anthracite was found to be about 0.0001 megohm-cm. compared to 1 to 200 megohm-cm. for shales and sandstones. For two reasons it is believed that the data sum-marized in this paper should be of particular interest. In the first place, most of the interpretations of the resistivity survey have been checked by subsequent drilling and some by the removal of the overburden and the exposing of the anthracite seams. It is infrequent that the oppor-tunity for checking results so thoroughly is given. In the second place, the fact that recent commentators1,2,3 on the application of geophysical methods to mining have concluded that direct prospecting for anthracite and other types of coal is not promising makes the good results obtained more significant. So far as the authors can learn, the only previous experiment with electrical methods in the Pennsylvania anthracite field was one made by Sherwin F. Kelly in 1922, when he used the self-potential method at Wilkes-Barre4. The profile he made does not show a very marked correlation with the geologic cross section. Kelly points out that stray currents from electric motors in the mines undoubtedly affected his results, but the experience of the present authors with stray currents from mining machinery suggests the possibility that the potentials measured by Kelly were due almost entirely to this effect.

Jan 1, 1936

By R. U. Fitting, A. C. Bulnes

Field experience with limestone and sandstone production indicates the existence of wide differences between the reservoir behavior of these two types of formation. Little attention appears to have been given to the separate study of the flow of fluids and the retention of fluids in limestones. This paper presents data and arguments to demonstrate the existence of a difference between the two types of formation, and urges the separate intensive investigation of limestone reservoirs. AH experimental data presented pertain to dolomitic limestone formations in west Texas and New Mexico. Two kinds of Porous media are recognized— intergranular and intermediate. Intergranular rocks are those in which the porosity and permeability are determined by the geometrical properties and the sorting of the sedimentary units; intermediate rocks, those in which there is no direct relationship between grain properties and the porosity and permeability. Limestones in general are intermediate media. The partial relationship between porosity and permeability of any class of Porous media is represelried by an area of .finite extent and definite shape on the permeability-porosity plane. The horizontal and vertical variations of porosity and of permeability in limestone and sandstone formations are discussed and compared. Comparisons are made of connate-water content, the relative permeability-saturation relationship, and capillary phenomena in the two kinds of rocks. A number of tentative conclusions are drawn relative to the reservoir properties of lime- stones; in particular, (I) dolomitic limestones are oil bearing and apparently are oil productive in zones of permeability less than 0.1 millidarcyj and (2) primary depletion (by gas expansion) oil saturations may be lower in dolomitic limestones than in sandstones. Introduction It is well known that the reservoir performance of limestones displays numerous irregularities when compared with that of sandstones, and that the departures from "normal" behavior of limestones are more frequent and generally more marked than in sandstones. This is particularly true of fractured limestones and those that have undergone considerable development of secondary porosity' A review of the literature of production research published during the past 15 years reveals a startling absence of theoretical and experimental investigations directed specifically toward explaining and predicting the performance of limestone reservoirs, even. though such problems as the prediction of water encroachment and the estimation of ultimate recoveries continue at the "inspired guess" stage. By far the greater part of the experimental data reported pertain to measurements on sandstone core samples, while the theoretical studies, almost without exception, are developed from the assumption of an ideal porous medium and therefore seldom are applicable to limestone formations. The chief cause of this situation appears to be the common belief that, to all practical intents and purposes, sandstones and the majority of producing limestone formations

Jan 1, 1945

NEW MEMBERS The following list comprises the names of those persons who became members during the period of Nov. 10, 1917, to Dec. 10, 1917. ADAMS, LLOYD D Supt., Hoskins Mine, Mineral Point Zinc Co., Galena, Ill. ARMSTRONG, WILLIAM D., Min. Engr.. Empire Coal Co., 715 American Trust Bldg., Birmingham, Ala. BALL, TOM LEE, Efficiency Engr., Iron Mines Dept., Tennessee Coal, Iron &.R. R. Co., Bessemer, Ala. BENZIE, WILLIAM ROSE, Sec. & Treas., The Republic Coal Co., 901-2 Foster Bldg.,Denver, Colo. BERGSTROM, GUNNAR, Min. Engr.... Resident Mgr., Russian Dept., Swedish Diamond Rock Drilling Co., Slatawostowskaja Ulitza 6, Ekaterinburg, Russia. CADOT, J., Engr.,. Hardinge Conical Mill Co., Newhouse Bldg., Salt Lake City, Utah. COFFEY, GEORGE W 64 Santa Clara Ave., Oakland, Cal. CUTLER, WILLARD WALKER, JR Geol., Carter Oil Co., Tulsa, Okla.' . DANIEL, JOSEPH A., Min. Engr. & Geol., Hudson's Bay Co., Care The Institution of Mining & Metallurgy, 1 Finsbury Circus, London, E. C., England. EARDLEY, WALTER HAZEN, Cons. Engr., Chanute Spelter Co., 316 Frisco Bldg Joplin, Mo.

Jan 1, 1918

"Minerals in Transition" is the timely theme of this year's SME-AIME Fall Meeting and Exhibit, to be held September 10-12 at the Salt Palace, Salt Lake City, Utah. Approximately 2000 members and guests are expected to attend the meeting, which will include 117 technical papers, presented during 27 sessions. To complement the technical program, a record number of mining manufacturers and suppliers will be on hand to exhibit the latest in equipment innovation and professional services.

Jan 8, 1975

By G. W. Crane

When ore was discovered on the Tintic Standard property in the spring of 1916, new developments were immediately started both north and south of that property, on the supposition that in East Tintic the ore would be found to occur in northerly trending channels, similar to those so characteristic of the older camp. But 9 years of developments have failed to establish the existence of such a channel. This is due undoubtedly to important differences in the geology of the two camps, that were not recognized, and is indicative of the danger in the general tendency toward interpreting the geology of East Tintic too strictly in terms of that of the older camp. It should not be forgotten that while the two sections have had practically the same geological history, the net results of a long series of geologic processes have developed in them conditions that differ so widely and in so many particulars that the necessity of regarding them as essentially different districts seems apparent. In an effort to emphasize this fact, this paper is devoted chiefly to a comparison of the geological conditions as found in the two camps and is addressed more particularly to those familiar with the geology of the Tintic district. Following a short description of the several ore discoveries and of the Tintic Standard mine is a brief discussion of the evidence of ore channels in East Tintic. For my information regarding the Tintic Standard mine, I am indebted to the courtesy and generous assistance of Messrs. Wade and Snow of the Tintic Standard Mining Co. East Tintic District The Term East Tintic district is here used to represent that eastern part of the Tintic mining district lying between the productive portion of the old camp of Tintic on the west, the foot hills of Goshen Slope, on the east, the Denver and Rio Grande Railroad on the north, and Silver Pass on the south, all in Utah County. As represented by the geological map, Fig. 1, it includes an area about 4 miles wide, east and west, and 5 miles long, north and south, within which the Tintic Standard mine is about centrally located. The map is a compilation of data supplied, for the most part, by the Chief Consolidated Mining Co. and represents the

Jan 1, 1927

By John D. Verhoeven

A technique has been developed for carrying out normal freezing experiments with a current density of 2000 amp per sq cut passing through the solid-liquid interface. The equation relating the effective distribution coefficient to the equilibrium distribution coefficient in electric field-aided solidification, originally developed by Huckc et al.,1 has been modified for the case of concentrated solutions. Preliminary experiments on the Sn-Bi system give qualitative agreement with the equation. The data are analyzed by a slightly novel use of the normal freeze equation which allows one to determine the effective distribution coefficient more easily. Very extensive mixing in the liquid was found at these high current densities and it is postulated that the mixing results from a vertical component of the magnetic Lorentz force generated by the electric current. In the search for techniques of obtaining ultrahigh-purity metals the inefficient but very effective technique of electrotransport has received little attention. Electrotransport is most effective in the liquid state and a natural application, therefore, is to apply an electric field across the liquid zone of a zone-melting experiment. The present investigation was undertaken to study the effect of an electric field upon solidification of metals, so that the usefulness of electrotransport in such solidification experiments as zone melting could be determined. In zone-melting and normal-freezing experiments it is difficult to achieve complete mixing in the liquid in the immediate vicinity of the solidifying interface. Consequently a solute build-up will occur at the interface in the portion of the liquid where complete mixing does not occur (an equilibrium distribution coefficient, ko, less than one, and unidirectional atom motion will be implied throughout). This local solute build-up produces a corresponding rise in the solute concentration in the solid so that the ratio of the solute concentration between the solid and the bulk liquid is larger than the equilibrium distribution coefficient. This ratio is defined as the effective distribution coefficient, k,. The differential equation describing the solidification process may be derived by applying the continuity equation to an expression for the net solute flux at the interface. The solution to this differential equation then allows one to determine the solute distribution in the liquid and the relationship between k0 and ke. One of the most useful solutions to this equation was first derived by Burton, Prim, and Slichter,' in which they assumed that a) the equilibrium distribution of solute was maintained on the plane of the interface, 11) the solute build-up ahead of the interface in the liquid disappeared at a distance 6 from the interface, and c) the solute distribution in the liquid was invariant with time. The following well-known relation between ko and ke was then obtained, where R is the rate of solidification and D the diffusion coefficient of the solute in the liquid. This equation appears to correlate the data from a number of different types of solidification experiments very well. Application of an electric field across the solid-liquid interface can produce an additional flow of solute atoms as a result of the electrotransport. When the polarity of the field is such as to direct the electrotransport flux away from the interface the solute build-up may be diminished, even to the point of producing a solute depletion and a consequent ke smaller than ko. The quantitative description of this process and the resulting form of Eq. [I] was first given by Hucke et al.1* and then inde- where E is the electric-field intensity and U is the differential mobility, i.e., the velocity of the solute atoms with respect to the solvent atoms per unit electric field. Both authors follow the method of Burton, Prim, and Slichter in their derivation, the only difference being the additional electrotransport term in the flux equation. It has been pointed out1,3 that Eq. [2] predicts the possibility of a noticeable increase in the purification of materials by solidification in an electric field. The validity of Eq. 121 has not been checked experimentally and it is possible that other factors' arising from the presence of an electric field across

Jan 1, 1965

By A. S. Michaels, R. S. Timmins

A study of the effect upon oil recovery from an un-consolidated porous medium of chromatographic transport of selected reverse-wetting additives during water displacement is described. Flow tests were performed on hydrocarbon oil-saturated sand columns (containing connate water) into which small volumes of short-chain aliphatic amine solutions were introduced during water flooding. Concurrently, meusurements of oil-silica contact angles, oil-water interfacial tensions and oil-water distribution coefficients were measured us a function of additive concentration. Certain treatments were found to cause a slight reduction in oil recovery, while others produced a significant increase (up to 50 per cent of the normtzl irreducible rninimum oil saturation). Recovery eficiency was correlated most satisfactorily with the maximum degree of reverse wetting produced during additive transport; conditions which resulted in only mild oil wettability of the sand reduced recovery, while those favoring strong oil wetting increased recovery. A mechanism of reverse-wetting additive action during chromatographic transport is developed which ascribes the results to transient changes in oil-solid contact angle during flow, with consequent release of oil trapped by capillary forces. Implications of these observations with regard to improved waterflood efficiencies are discussed. INTRODUCTION The need for finding improved methods of oil production is amply illustrated by the large volume of oil considered economically unrecoverable by existing production practice. Water flooding has long been an excellent method of secondary recovery. However, even in those areas of a formation which are well swept by a water flood, 20 per cent or more of the oil remains trapped within the formation and is not recovered. This trapping of oil within the pores of the rock structure results primarily from interfacial forces. If these interfacial forces were altered, it is possible that the trapped oil could be released and recovered. The addition of surface-active agents to a water flood to alter the interfacial properties of the oil-water-solid system has received considerable attention as a method of increasing oil recovery. Studies of surfactant treatment have yielded varied and, in some cases, apparently conflicting results. Increased oil recovery using surface-active agents has been reported by a number of investigators. Others have found that use of surfactants in a water flood either has no effect upon oil recovery or decreases it. Since surface-active agents tend to alter the formation wettability and oil-water interfacial tension simultaneously, several investigators have tried to determine the role these two factors play in oil recovery. Data have been presented which indicate that the most desirable condition for the solid surface is strongly water-wet. Other results indicate that, although breakthrough recovery may be less, the greatest ultimate recovery is obtained when neutral wettability prevails.", " The desirability of low interfacial tension seems to depend upon the wettability of the formation. Reports of higher recoveries, when the interfacial tension is high in a water-wet system and low in an oil-wet system, are at odds with reports of increased recovery in water-wet systems when surfactants which decrease the interfacial tension are added to the water flood. A review of previous work studying the effects of using surface-active agents in a water flood shows that these agents produce widely different effects and that opinions as to the role of the various interfacial properties are diverse. The consensus, however, is that the interfacial properties are quite important in the displacement of oil from a porous medium by water. Even in those investigations where appreciable increases in oil recovery resulted from treatment with a surface-active agent, economic considerations generally made practical application of the treatment unattractive because surfactants tend to be adsorbed within the formation. This adsorption would necessitate using large quantities of surfactant if all of the flood water were treated to contain a given surfactant concentration, even if this concentration were quite low. Preston and Calhoun suggested that the principles of chromatography could be applied to the use of surface-active agents as a means of increasing oil recovery. A small volume of surface-active material is injec-